掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/D3PY01074K

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掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/D3PY01254A

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Poly(4-ethynylaniline) [poly(1)] coordinated to palladium nanoclusters (Pd NCs) were prepared. The coordination of Pd NCs was confirmed by X-ray photoelectron spectroscopy and scanning transmission electron microscopy. Pd NCs were coordinated with the benzene rings as well as amino groups of poly(1). Pd NCs were partly coordinated with the polymers, maintaining their original size to form the aggregates with sizes of several tens to hundreds nanometers. Pd NCs coordinated with poly(1) efficiently served as catalysts for the Mizoroki-Heck and Suzuki-Miyaura cross-coupling reactions.

DOI： 10.11364/networkedpolymer.44.6_275

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掲載種別：研究論文（学術雑誌）  

DOI： 10.1038/s41428-023-00822-4

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER  

The ring-opening metathesis polymerization (ROMP) of cyclic olefins with niobium(V) pentaalkoxide catalysts was studied. In the presence of zinc, benzylidene dichloride, and chlorotrimethylsilane, in situ niobium species was formed and ROMP reaction proceeded. Among niobium pentaalkoxide group, Nb(OEt)5 achieved the smallest dispersity value of the polymer and provided trans selective polynorbornene. In this paper, we discussed the role of additives and expected how the polymer was synthesized with Nb(OEt)5/TMSCl/Zn/PhCHCl2 system. We also elucidated the intermediate using some measurement.

DOI： 10.1016/j.mcat.2023.113393

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掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/pol.20220765

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掲載種別：研究論文（学術雑誌）  

DOI： 10.1038/s41428-023-00770-z

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

Trisubstituted 1,3,5-tri(benzimidazolyl)benzene derivatives were synthesized from ʟ-alanine, ʟ-valine, ᴅ-valine and glycine, and their self-assembling behavior and stimuli-response in solution and gel states were evaluated. Circular dichroism/UV-vis absorption spectroscopic and dynamic light scattering measurements revealed that the compounds formed H-aggregates via intramolecular hydrogen bonding and π-π stacking interactions in nonpolar solvents such as CHCl3, whereas collapse of the aggregates was confirmed by MeOH addition. Quantum mechanical calculations and molecular dynamics simulations also supported aggregation in CHCl3. Rheological analysis and morphology observation revealed the formation of a fibril like structure by further assembling of aggregates at a high concentration in CHCl3.

DOI： 10.1002/chem.202203703

PubMed

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

Platinum-containing macrocycles (platinacycles) have gained attention due to their unique photoelectric properties. In the present study, a novel conjugated platinacycle was synthesized by the dehydrochlorination coupling reaction of a bipyridine dichloroplatinum(II) complex and a 3,6-diethynylcarbazol derivative. The structure of the platinacycle was confirmed by 1H/13C, 1H-1H COSY, HMQC, HMBC, DEPT NMR spectroscopies in conjunction with DFT calculations, IR spectroscopy and MALDI-TOF mass spectrometry. The platinacycle exhibited a UV-vis absorption around 540 nm assignable to ligand-ligand charge transfer, and birefringence in DMF, possibly due to alignment of molecules.

DOI： 10.1039/d2dt03524c

PubMed

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER SCI LTD  

The polycondensation of N-((3,5-diamino)benzoyl)-L-alanine dodecyl ester (1L) with p-phthalaldehyde (2) was carried out to obtain poly(1L-2), a novel optically active polymer containing Schiff base moieties in the main chain. A series of analogous polymers with Schiff base moieties were also synthesized from N-((3,5-diamino) benzoyl)-D-alanine dodecyl ester (1D) and N-((3,5-diamino)benzoyl)glycine dodecyl ester (1G) with various feed ratios. The polymers exhibited CD signals assignable to exciton coupling-based chirality in CHCl3 depending on the feed molar ratios of 1L/1D and 1L/1G. Poly(1L-2) exhibited lyotropic liquid crystallinity in CHCl3 and THF.

DOI： 10.1016/j.polymer.2023.125703

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掲載種別：研究論文（学術雑誌）  

This study deals with chirality induction to the main chain of platinum (Pt)-containing aryleneethynylene polymers by ligand exchange reactions. The optically inactive polymers containing –(–C[tbnd]C–trans-Pt(PPh3)2–C[tbnd]C–)– moieties in the main chain undergo ligand exchange reactions with P-chiral diphosphines, (R,R)-BenzP* and (R,R)-QuinoxP* to give optically active polymers containing –(–C[tbnd]C–cis-Pt(P-chiral diphosphine)–C[tbnd]C–)– moieties. The ligand-exchanged polymers exhibit CD signals based on the conjugated main chain, indicating chirality induction to the main chain by the P-chiral ligands. The QuinoxP*-ligated polymers emit photoluminescence likely based on the transition from the QuinoxP* moieties. Quantum mechanical calculations predict reasonable CD, UV–vis absorption and photoluminescence spectra.

DOI： 10.1016/j.polymer.2022.125576

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掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society (ACS)  

DOI： 10.1021/acs.macromol.2c01882

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掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry (RSC)  

N-(3,5-Diaminobenzoyl)-l-alanine dodecyl ester dihydrochlorides underwent gelation in tetrahydrofuran and CHCl₃. The gel emitted blue fluorescence in the sol state and green fluorescence in the gel state.

DOI： 10.1039/d3sm00299c

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掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.macromol.2c00748

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掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.organomet.2c00173

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掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry (RSC)  

The cured resins of ethynylene-linked mono-, di- and tri-functional benzoxazines were thermally more stable than the resins obtained from the analogous benzoxazines without a triple bond.

DOI： 10.1039/d2py00840h

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DOI： 10.1021/acs.macromol.1c01773

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/D1SM01206A

PubMed

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DOI： 10.1021/acs.organomet.1c00435

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掲載種別：研究論文（学術雑誌）  

DOI： 10.1038/s41428-021-00568-x

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/d1py00665g

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.macromol.0c00911

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.macromol.0c00910

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.macromol.0c00096

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DOI： 10.1007/s00289-019-02798-9

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DOI： 10.1002/mame.201900282

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DOI： 10.1002/mame.201900275

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DOI： 10.1016/j.polymer.2019.05.072

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© The Royal Society of Chemistry. Polyacetylenes substituted with phenyl, N-tert-butoxycarbonyl-l-valine 4-anilide, and (S)-1-(acetoxy)ethyl groups with number-average molecular weights ranging from 3800 to 13 500 were synthesized by the polymerization of the corresponding acetylene monomers using [{1,1′-bis(diphenylphosphino)ferrocene}PdBr(C6H4-o-CH2OH)] as a catalyst. l-Lactide and γ-benzyl-l-glutamate N-carboxyanhydride were polymerized using the polyacetylenes as macroinitiators to obtain the block copolymers, some of which formed chiral secondary structures. A block copolymer consisting of helically twisted polyacetylene and α-helical peptide was successfully synthesized for the first time.

DOI： 10.1039/c8py00598b

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c7py01886j

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.macromol.7b02249

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.eurpolymj.2017.11.020

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記述言語：英語   出版者・発行元：合成樹脂工業協会  

CiNii Books

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記述言語：英語   出版者・発行元：日本接着学会  

CiNii Books

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Chiral compounds play a vital role in our lives because we are made up of chiral polymers. A strict rule of chirality synthesis is "to obtain one enantiomer of a new chiral product, one enantiomer of a chiral source is needed". If two enantiomers can be synthesized using a single chiral compound, we can both break the above rule and open up a more efficient route to useful chiral materials using a cheaper chiral source. Here we report the first example of double reversals of enantioselectivity in catalytic asymmetric polymerization of achiral monomers using a single isomer of simple chiral compounds as cocatalyst. Furthermore, we achieved this by changing only one achiral condition, that is, the amount of the chiral cocatalyst, without any other changes in the polymerization conditions. As a result, we easily and directly synthesized (+)- or (-)-polymer using a single chiral compound as a cocatalyst.

DOI： 10.1021/acs.macromol.7b01671

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.macromol.7b00779

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

The Sonogashira-Hagihara coupling polymerization of platinum-containing m,m-phenylene and p,p-phenylene-linked diethynyl monomers m,m-1 and p,p-1 with 1,4-dibromobenzene 2a, 1,4-dibromonaphthalene 2b and 9,10-dibromoanthracene 2c was carried out to obtain the corresponding platinum-containing polymers [poly(m, m-1-2a)-poly(m, m-1-2c)] and [poly(p, p-1-2a)-poly(p, p-1-2c)] with M-n's ranging from 4,300 to 28 000 in 24%-quantitative yields. The UV-vis absorption and emission properties of the formed polymers were measured in various solvents to examine the solvent effect on the optical properties. These polymers emitted fluorescence at 400-600 nm with 3.4-18.0% quantum yields in THF, CHCl3 and CH2Cl2. The fluorescence intensities of the polymers remarkably decreased upon raising the MeOH concentration in THF/MeOH mixtures, accompanying the formation of aggregates.

DOI： 10.1039/c5py01584g

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemical Society of Japan  

The dehydrochlorination coupling polymerization of N-(3,5-diethynylbenzoyl)-L-alanine dodecylamide 1 with platinum (Pt) chlorides having pyridine, bipyridine, and phenanthroline ligands 2a-2d gave novel optically active poly(phenyleneethynylene)s [poly(1-2a)-poly(1-2d)] bearing Pt in the main chains. The Z-average diameters of the polymers ranged from 453 to 1081 nm. Poly(1-2a) exhibited CD signals assignable to aggregates, and formed regulated twisted structures with height of 540 ± 70 nm and pitch of 62 ± 6 nm, which were confirmed by AFM measurements.

DOI： 10.1246/cl.160385

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記述言語：日本語   出版者・発行元：Japan Thermosetting Plastics Industry Association  

水素結合のエネルギーは，共有結合に比べて1 ～2 桁小さいことから，水素結合の切断・形成の制御により，外部刺激に応答してダイナミックに形態を転換させるネットワークポリマーを構築できる。本稿では，分子間水素結合によるネットワークポリマーの形成例，ならびに，筆者らが検討している分子内水素結合のネットワークにより高次構造を形成する，アミド基含有ポリアセチレンならびにポリフェニレンエチニレンについて解説する。

DOI： 10.11364/networkpolymer.36.148

CiNii Books

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その他リンク： https://jlc.jst.go.jp/DN/JLC/20011860769?from=CiNii

掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/chem.201590073

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記述言語：英語   掲載種別：研究論文（国際会議プロシーディングス）   出版者・発行元：WILEY-V C H VERLAG GMBH  

This article deals with (1) the controlled polymerization of an optically active phenylacetylene (PA) derivative using well defined rhodium (Rh) catalyst, [(nbd)Rh{C(Ph)=CPh2}(PPh3)] and the study on the molecular weight dependence of the chirality (degree of helix formation and predominance of one-handed helicity) of the formed polymers, (2) examination of the polymer end structures by matrix-assisted laser desorption/ionization time of flight (MALDI-TOF) mass spectrometry, (3) development of a novel Rh complex coordinated by a tridentate ligand, and [{nbd-(CH2)(4)PPh2}Rh{C(Ph)=CPh2}] and the polymerization of PA in a controlled manner.

DOI： 10.1002/masy.201400026

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemical Society of Japan  

The Sonogashira-Hagihara coupling polymerization of L- alanine-derived 2,5-dibromothiophene monomers 1a-1d with p- and m-diethynylbenzenes 2p and 2m gave novel optically active poly(thiophenyleneethynylene-phenyleneethynylene)s poly(1a-2p)-poly(1d-2m). p-Phenylene-linked poly(1b-2p)-poly(1d-2p) bearing amide-amide side chains exhibited CD signals based on chiral aggregates, while the m-phenylene-linked counterparts poly(1b-2m)-poly(1d-2m) exhibited no evidence of the formation of secondary structures. Poly(1a-2p) and poly(1a-2m) bearing amide-ester side chains exhibited no CD signal as well.

DOI： 10.1246/cl.150270

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

Block copolymers of N-tert-butoxycarbonyl-L-valine 4-ethynylanilide (1a) and N-tert-butoxycarbonylglycine 4-ethynylanilide (1b) with various compositions were synthesized by block copolymerization using a [(nbd)Rh{C(Ph)-CPh2}(PPh3)]/PPh3 catalyst. The block copolymers exhibited intense Cotton effects in the absorption region of the conjugated polyacetylene backbone in CHCl3, THF and DMF, indicating the formation of predominantly one-handed helical structures. Amplification of g values as a function of chiral unit content was observed in the block copolymers. The relationship between g/g(max) and molecular weight of the achiral block agreed with the predictions of the Ising model for a linear cooperative system, confirming the presence of chirality transfer from the chiral block to the achiral block.

DOI： 10.1039/c5py00743g

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemical Society of Japan  

Novel palladium complexes bearing a di-tert-butyl(4- substituted phenyl)phosphine ligand were synthesized and employed as catalysts for the polymerization of 1-chloro-2-(4- tert-butylphenyl)acetylene. Polymers were obtained as THFsoluble (weight-average molecular weights: 510059800) and insoluble parts, which were considered to be lower and higher molecular weight polyacetylenes. The catalytic activity increased as increasing the electron-withdrawing character of the substituent on the phosphine ligand.

DOI： 10.1246/cl.150457

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記述言語：日本語   掲載種別：研究論文（学術雑誌）   出版者・発行元：SOC POLYMER SCIENCE JAPAN  

This article overviews our recent research on the polymerization of substituted acetylenes by well-defined Pd catalysts. The authors synthesized a series of well-defined phosphine-ligated Pd complexes to polymerize substituted acetylene monomers. [(dppf)PdBr(R)]-type complexes [dppf = 1,1'-bis(diphenylphosphino)ferrocene; R = o-tolyl(1a), mesityl(1b), triphenylvinyl(1c), o-hydroxymethylphenyl(1d), p-cyanophenyl(1e) and p-nitrophenyl(1f) in combination with silver trifluoromethanesulfonate (AgOTf) were active for the polymerization of monosubstituted polar and apolar acetylene monomers [HC CPh(2), HC CCONHC4H9(3), HC CCO2C8H17(4), HC CCH2OCONHC6H13(5), HC CCH2OCO2C6H13(6) and HC CCH(CH3)OH(7)]. MALDI-TOF mass spectrometric and IR spectroscopic analyses of poly(2)-poly(7) confirmed the end-functionalization of the formed polymers by the "R" groups in the Pd catalysts. The polymerization of a disubstituted acetylene was achieved by bulky monophosphine-ligated Pd catalysts for the first time. The Pd catalysts were demonstrated to polymerize mono- and disubstituted acetylenes through an insertion mechanism.

DOI： 10.1295/koron.2014-0082

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

New ω-alkynamides, (S)-HC≡CCH2CONHCH2CH(CH3)CH2CH3 (1) and (S)-HC≡CCH2CH2CONHCH(CH3)CH2CH2CH2CH2CH3 (2) were synthesized and polymerized with a rhodium catalyst in CHCl3 to obtain cis-stereoregular poly(ω-alkynamide)s (poly(1) and poly(2)). Polarimetric, CD, and IR spectroscopic studies revealed that in solution the polymers adopted predominantly one-handed helical structures stabilized by intramolecular hydrogen bonds between the pendent amide groups. This behavior was similar to that of the corresponding poly(N-alkynylamide) counterparts (poly(3) and poly(4)) reported previously, whereas the helical senses were opposite to each other. The helical structures of the poly(ω-alkynamide)s were stable upon heating similar to those of the poly(N-alkynylamide)s, but the solvent response was completely different. An increase in MeOH content in CHCl3/MeOH resulted in inversion of the predominant screw-sense for poly(1) and poly(2). Conversely, poly(3) was transformed into a random coil, and poly(4) maintained the predominant screw-sense irrespective of MeOH content. The solvent dependence of predominant screw-sense for poly(1) and poly(2) was reasonably explained by molecular orbital studies using the conductor-like screening model (COSMO).

DOI： 10.1002/chem.201402628

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CHEMICAL SOC JAPAN  

The Sonogashira-Hagihara coupling polymerization of D-hydroxyphenylglycine-based diiodo monomers 1 and 2 with p-diethynylbenzene gave novel optically active poly(phenyleneethynylene)s 3 and 4 bearing perylene moieties with number-average molecular weights (M-n's) of 4800 and 3700 in 39% and 57% yields. The CD and UV-vis spectroscopic analysis revealed that polymer 3 formed folded helical structures in various solvents, while polymer 4 did not. UV-vis and fluorescence spectroscopic analysis indicated the presence of energy transfer from the phenyleneethynylene main chain to perylene side chains.

DOI： 10.1246/cl.140601

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Bulky monophosphine-ligated Pd complexes served as unprecedented admirable catalysts for the polymerization of a disubstituted acetylene. The moderately high polymer yields and cis content of the formed polyacetylene contrasted with those observed for traditional Mo catalyst-based polymer. These Pd catalysts are strong tools to promote the understanding of the structure-property relationships of disubstituted acetylenes.

DOI： 10.1021/mz400562m

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/ma401730e

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Novel optically active poly(m-phenyleneethynylene-aryleneethynylene)s bearing hydroxy groups with various arylene units {poly[(S)-/(R)-1-3a]-poly[(R)-1-3e] and poly[(S)-2-3a]} were synthesized by the Sonogashira-Hagihara coupling polymerization of 3,5-diiodo-4-hydroxy-C6H4CONHCH(CH3)COXC12H25 [(S)-/(R)-1 (X = O), (S)-2 (X = NH)] with HC C Ar-C CH [3a (Ar = 1,4-C6H4), 3b (Ar = 1,4-C6H4-1,4-C6H4-), 3c (Ar = 1,4-C6H4-1,4-C6H4-1,4-C6H4-), 3d (Ar = 2,5-dihexyl-1,4-C6H2), 3e (Ar = 2,5-didodecyl-1,4-C6H2)]. The yields and number-average molecular weights of the polymers were in the ranges 60-94% and 7,000-29,500 with no correlation between the yield and the M-n. Circular dichroism (CD), UV-vis, and fluorescence spectroscopic analyses indicated that poly[(S)-1-3a] poly[(S)-1-3c] and poly[(S)-2-3a] formed predominantly one-handed helical structures in THF, while poly[(S)-1-3d] and poly[(S)-1-3e] showed no evidence for forming chirally ordered structures. All polymers emitted blue fluorescence. The solution state IR measurement revealed the presence of intramolecular hydrogen bonding between the amide groups at the side chains of poly[(S)-1-2a]. The helical structures and helix-forming abilities of the polymers were analyzed by the molecular mechanics (MM), semiempirical molecular orbital (MO) and density functional theory (DFT) methods. Tube-like structures, presumably formed by perpendicular aggregation of the helical polymers, were observed by atomic force microscopy (AFM).

DOI： 10.1021/ma4017295

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This chapter overviews the development in the chemistry of polyacetylene and its derivatives, with a focus on polymerization catalysts for acetylene and its derivatives, controlled polymerization of acetylenes, new monomers and new polymers, and functions of substituted acetylene polymers. © 2012 Elsevier B.V. All rights reserved.

DOI： 10.1016/B978-0-444-53349-4.00088-1

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-BLACKWELL  

Novel optically active substituted acetylenes HC? CCH2CR1(CO2CH3)NHR2 [(S)-/(R)-1: R1 = H, R2 = Boc, (S)-2: R1 = CH3, R2 = Boc, (S)-3: R1 = H, R2 = Fmoc, (S)-4: R1 = CH3, R2 = Fmoc (Boc = tert-butoxycarbonyl, Fmoc = 9-fluorenylmethoxycarbonyl)] were synthesized from a-propargylglycine and a-propargylalanine, and polymerized with a rhodium catalyst to provide the polymers with number-average molecular weights of 240038,900 in good yields. Polarimetric, circular dichroism (CD), and UVvis spectroscopic analyses indicated that poly[(S)-1], poly[(R)-1], and poly[(S)-4] formed predominantly one-handed helical structures both in polar and nonpolar solvents. Poly[(S)-1a] carrying unprotected carboxy groups was obtained by alkaline hydrolysis of poly[(S)-1], and poly[(S)-4b] carrying unprotected amino groups was obtained by removal of Fmoc groups of poly[(S)-4] using piperidine. Poly[(S)-1a] and poly[(S)-4b] also exhibited clear CD signals, which were different from those of the precursors, poly[(S)-1] and poly[(S)-4]. The solution-state IR measurement revealed the presence of intramolecular hydrogen bonding between the carbamate groups of poly[(S)-1] and poly[(S)-1a]. The plus CD signal of poly[(S)-1a] turned into minus one on addition of alkali hydroxides and tetrabutylammonium fluoride, accompanying the red-shift of ?max. The degree of ?max shift became large as the size of cation of the additive. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

DOI： 10.1002/pola.25975

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A well-defined living polymerization catalyst, [(nbd)Rh{C(Ph)=CPh 2}(PPh3)]/PPh3, produced a series of amino acid based polyphenylacetylene derivatives having a wide range of molecular weights (Mn: 1500-128,800) with relatively narrow polydispersity. On the basis of the CD and UV-vis spectra of the obtained polymers measured in DMF, plotting the [Î] and Kuhn dissymmetry factor, g, against the molecular weight revealed that their predominantly one-handed helical conformation strongly depended on their molecular weights. © 2011 Wiley Periodicals, Inc.

DOI： 10.1002/pola.24941

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Novel polyphenylacetylene and polystyrene derivatives carrying L-proline moieties at the side chains were synthesized by the rhodium-catalyzed and radical polymerizations of the corresponding monomers. The polyphenylacetylene derivatives showed Cotton effects at the absorption region of the main chain, indicating that the polymers adopt helical conformations with predominantly one-handed screw sense. The polymers catalyzed the asymmetric aldol reactions of acetone with aromatic aldehydes, and cyclohexanone with p-nitrobenzaldehyde. The enantioselectivities largely depended on the reaction conditions. In the asymmetric aldol reaction of acetone with aromatic aldehydes, the R-enantiomeric products were predominantly obtained except the cases with the polymer catalyst in CHCl3. The ee of the products became higher as the reaction temperature was decreased. The polymeric catalysts were recoverable from the reaction mixture by filtration, and the recovered ones catalyzed the asymmetric aldol reaction of acetone with p-nitrobenzaldehyde without decreasing the product yield and ee. The ee was improved using the copolymers of L-proline-based and nonchiral monomers as catalysts. Copyright © 2011 Wiley Periodicals, Inc.

DOI： 10.1002/pola.24813

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The hydrosilylation polymerization of d-(-)-p-hydroxyphenylglycine-derived diethynyl monomers 1p and 1m with dihydrosilanes Si1 and Si2 was carried out using RhI(PPh3)3as a catalyst to give optically active novel poly(silylenevinylenephenyleneethynylene)s [(E)-poly(1p-Si1), (E)-poly(1p-Si2), (E)-poly(1m-Si1), (E)-poly(1m-Si2), and (Z)-poly(1p-Si1)] with number-average molecular weights ranging from 2800 to 17,000 in 41-92% yields. Polymers having (E)- and (Z)-olefin moieties were obtained, wherein the (E)-/(Z)-ratios depended on the reaction conditions. The UV-vis absorption edge of (E)-poly(1p-Si1) was positioned at a wavelength longer than that of (Z)-poly(1p-Si1), indicating that (E)-vinylene-linkage extends the conjugation more largely than the (Z)-counterpart. This was also confirmed by fluorescence spectroscopy. Alkaline hydrolysis of ester moieties of these polymers gave the corresponding polymers having carboxy groups. The (E)-polymers showed different solubility in hydrophobic solvents before and after hydrolysis, but the non-hydrolyzed and hydrolyzed (Z)-polymers exhibited the same solubility. © 2011 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.polymer.2011.06.010

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Progress in the polymerization of substituted acetylenes and the properties and functions of the formed polymers that have been synthesized in the past several years are surveyed. Polymerization catalysts for substituted acetylenes, new monomers and polymers, controlled polymerizations, and photoelectronic functions and separation membranes of substituted polyacetylenes are discussed. A focus is placed on the development of novel rhodium catalysts for the polymerization of phenylacetylenes, the helical structures of the polymers obtained from chiral monosubstituted acetylenes, and highly gas-permeable polymers prepared from disubstituted acetylenes, in which great advances have been made recently. © The Royal Society of Chemistry 2011.

DOI： 10.1039/c0py00333f

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The Sonogashira-Hagihara coupling polymerization of 3′,5′- diiodo-4′-hydroxy-N-α-tert-butoxycarbonyl-d-phenylglycine ethyl-, hexyl-, and laurylamides 1a-c with p-nonsubstituted, cyano, hexyl, and methoxy 3,5-diethynylazobenzenes 2a-d was carried out to obtain optically active novel poly(m-phenyleneethynylene) with Mwvalues in the range from 6900 to 15-400 in 62-84% yields. CD and UV-vis spectroscopic data indicated that the polymers adopted thermally stable helical conformations in CH2Cl2and N,N-dimethylformamide. Poly(1b-2a) further formed a chirally aggregated structure. The azobenzene moieties of the polymers underwent reversible photoisomerization upon UV- and visible-light irradiation, accompanying the changes of the higher-order structures. © 2011 American Chemical Society.

DOI： 10.1021/ma200281e

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Novel late transition metal catalysts for the controlled polymerization of acetylenic monomers are reported. Zwitterionic and cationic rhodium catalysts bearing tetrafluorobenzobarrelene (tfb) as a highly π-acidic diene showed excellent activity for the polymerization of acetylenic monomers. The activity values of (tfb)Rh[(η6-Ph)BPh3] and [(tfb)Rh(PPh3)2]BPh4are higher than those of the conventional analogues bearing 2,5-norbornadiene (nbd). The latter cationic tfb-rhodium catalyst achieves living polymerization of phenylacetylene and its ring-substituted derivatives in the presence of amines. The obtained polymers have a highly stereo-regulated main chain of cis-transoidal structure. The livingness of the polymerization of phenylacetylene with the binary catalyst composed of (tfb)Rh+[(η6-Ph)B-Ph3] and 'PrNH2was confirmed by the kinetic study and by multi-stage polymerization. Block copolymers were synthesized from two kinds of phenylacetylenes by using the present cationic rhodium catalyst. Well-defined palladium catalysts were developed, which enabled the synthesis of end-functionalized poly (phenylacetylene) s. The produced poly (phenyacetylene) has a hydroxymethylphenyl end group and thus can be applied as a macroinitiator to the synthesis of a block copolymer composed of poly (phenylacetylene) and poly(β-propiolactone) blocks. © 2011, The society of polymer science Japan.

DOI： 10.1295/koron.68.210

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Binary catalysts composed of cationic rhodium complexes, (tfb)Rh(L) 2 X (tfb: tetrafluorobenzobarrelene, L: phosphine ligand, X: counter anion), and i PrNH2 induced living polymerization of phenylacetylene and its ring-substituted derivatives. For instance, (tfb)Rh(PPh3) 2 BPh4 in conjunction with i PrNH 2 polymerized phenylacetylene in a living manner to yield poly(phenylacetylene) with narrow molecular weight distribution (M w /M n 1.09) quantitatively. The living nature was confirmed by kinetic plots of the polymerization. Nuclear magnetic resonance studies revealed that i PrNH 2 serves to dissociate the coordinating PPh 3 ligand of (tfb)Rh(L)2 X to form an initiating species. Block copolymers were synthesized by the sequential polymerization of different phenylacetylenes using the present catalyst. © The Society of Polymer Science, Japan (SPSJ). All rights reserved.

DOI： 10.1038/pj.2010.98

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This article reviews the development of catalysts for ring-opening metathesis polymerization (ROMP), synthesis of polymers bearing amino acids and peptides by ROMP of functionalized norbornenes, formation of aggregates and micelles, and applications of the polymers to medical materials. It also describes the control of monomer unit sequences, that is, living polymerization to synthesize block copolymers, and alternating copolymerization that is achieved on the basis of acid-base interactions. © The Society of Polymer Science, Japan (SPSJ) All rights reserved.

DOI： 10.1038/pj.2010.94

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End-functionalized poly(phenylacetylene)s were synthesized by the polymerization of phenylacetylene (PA) using the well-defined palladium catalysts represented as [(dppf)PdBr(R)] {dppf = 1,1′- bis(diphenylphosphino)ferrocene}. The Pd catalysts having a series of R groups such as o-tolyl, mesityl, C(Ph) CPh2, C6H4-o-CH2OH, C6H4-p-CN, and C6H4-p-NO2in conjunction with silver triflate polymerized PA to give end-functionalized poly(PA)s bearing the corresponding R groups in high yields. The results of IR and NMR spectroscopies and MALDI-TOF mass analyses proved the introduction of these R groups at one end of each polymer chain. The poly(PA) bearing a hydroxy end group was applied as a macroinitiator to the synthesis of a block copolymer composed of poly(PA) and poly(β-propiolactone) moieties. © 2010 Wiley Periodicals, Inc.

DOI： 10.1002/pola.24366

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This article overviews the new aspects of transition metal catalysts for polymerization of substituted acetylene monomers. The activity of rhodium-based catalysts is enhanced by introducing a strongly π-acidic diene ligand, tetrafluorobenzobarrelene (tfb). Precise control of polymerization of phenylacetylenes is achieved by two types of rhodium catalysts bearing tfb. The activity of zwitterionic rhodium-type catalyst is also intensified by the introduction of tfb, which achieves a higher monomer consumption rate than that with the conventional rhodium catalyst. Disubstituted acetylenes with polar functional groups are polymerized by well-defined ruthenium carbene catalyst Phenylacetylenes having a coordinative substituent at the ortho position on its aromatic ring are efficiently polymerized by the ruthenium carbene catalyst to give the corresponding polymers in high yields.

DOI： 10.5059/yukigoseikyokaishi.68.1286

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-BLACKWELL  

Amino acid esters of ethyl cellulose [R' = H (1), CH3 (2), CH2CH(CH3)(2) (3), CH2CONH2 (4), CH2OCH2C6H5 (5, 5'), CH2CH2CH2CH2NHOCOC(CH3)(3) (6)] were synthesized in moderate to quantitative yields (30-99%) by the reaction of t-butoxy-carbonyl (t-Boc)-protected amino acids or an activated ester derivative with hydroxy groups of ethyl cellulose [EC, degree of substitution (DSEt), 2 69] The amino acid functionalities displaying varied chemical nature, shape, and bulk were used, and bulk of the substituent on the alpha-carbon of amino acids was elucidated to be of vital significance for the observed degree of incorporation (DSEst) H-1 NMR spectra were used to determine the degree of incorporation of amino acid moiety (DSEst), and almost complete substitution of the hydroxy protons was revealed in 1, 2, and 5' The onset temperatures of weight loss of 1-6 were 198-218 degrees C, indicating fair thermal stability The glass transition temperatures of the derivatized polymers were 30-40 degrees C lower than that of EC (T-g 131 degrees C, cf T-g, of 1-6, 93 5-103 degrees C). Free-standing membranes of EC and its amino acid esters (1, 2, 5, 5', and 6) were fabricated, and enhanced permselectivity for CO2/N-2 and CO2/CH4 gas pairs was discerned, when compared with EC (C) 2010 Wiley Periodicals, Inc J Polym Sci Part A Polym Chem 48 3986-3993, 2010

DOI： 10.1002/pola.24181

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A series of novel 1-methylpropargyl-N-alkylcarbamates, HC≡C-(R)- CH(CH3)OCONHCH2-CO2CH2CH 2CH3[(R)-1], HC≡C-(S)-CH(CH3)OCONHCH 2CO2CH2CH2CH3[(S)-1], HC≡C-(S)-CH(CH3)-OCONH-(R)-CH(CH3)CH 2CH2CH2CH2CH3[(S),(R)'-2] ,HC≡C-(S)-CH(CH3)OCONH-(R)-CH(CH3)CO 2-CH2CH2CH3[(S),(R)'-3], HC≡CCH2OCONH-(R)-CH(CH3)CO2CH 2CH2CH3[(R)'-4], HC≡CCH 2OCO-NH-(S)-CH(CH3)CO2CH2CH 2CH3[(S)'-4], and HC≡CCH2OCONHCH 2CO2CH2CH2CH3(5) were synthesized and polymerized using (nbd) Rh+[η6-C 6H5B-(C6H5)3] (nbd = 2,5-norbornadiene) as a catalyst. Substituted cis-stereoregular polyacetylenes with moderate molecular weights were obtained in good yields. Poly[(R)-1], poly[(S)-1], poly[(S),(R)'-2], and poly[(S),(R)'-3] exhibited large optical rotations (|[α]D| = 344°-508°), clear CD signals (Δε = 4.8-7.0 M-1cm-1) in CHCl3, and high viscosity indices (0.82-0.87), demonstrating the formation of helical structures with predominantly one-handed screw sense, which were stable up to 55 °C in the solvent. The solution state IR measurement confirmed the presence of intramolecular hydrogen bonding between the pendent carbamate groups of the polymers. Chiral amplification was observed in chiral/achiral [(S)-1/5] and R/S [(R)-1/(S)-1] copolymerizations. Conformational analysis revealed that the polymers adopt a tightly twisted helical conformation with a dihedral angle of 70° at the single bond on the main chain. The molecular mechanics calculation and X-ray diffraction measurement suggested that the diameter of the helix is 25 and 17 Å, respectively. © 2010 American Chemical Society.

DOI： 10.1021/ma100937k

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Novel conjugated polymers containing 3,9-carbazolylene and silylenevinylene moieties were synthesized by the hydrosilylation polymerization of 1,4-bis(3-ethynyl-9-carbazolyl)benzene (1) with various bis(hydrosilane)s or dihydrosilanes using a rhodium catalyst. Polymers with weight-average molecular weights ranging from 5400 to 20,000 were obtained in 55-97% yields by the polyaddition with a rhodium catalyst in toluene at 25 C for 24 h. All the polymers were soluble in CHCI3 and THF, and had predominantly řrans-structures. The polymers exhibited Amax at a longer wavelength region than 1, and emitted fluorescence in 14-50% quantumn yields. The polymers were oxidized and reduced in the region of 0.4-1.6 V, and thermally stable up to 200 °C under air. © 2010 Wiley Periodicals, Inc.

DOI： 10.1002/pola.23950

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Diarylacetylene monomers having trimethylsilyl groups and other substituents (substituted biphenyl, 1a and 1b; trimethylsilylmethylphenyl, 1c-e) were synthesized and polymerized with TaCl5-n-Bu4Sn catalyst to produce the corresponding poly(diarylacetylene)s (2a-d). Polymers 2a-c had high molecular weights and were soluble in common organic solvents. Free-standing membranes of 2a-c as well as previously reported 2f-h were prepared by the solution-casting method. Desilylation of these Si-containing polymer membranes was carried out with trifluoroacetic acid to afford 3a, 3b, and 3f-h. Upon desilylation, biphenyl-containing membranes became less permeable (3a, b), whereas fluorene-containing membranes became more permeable (3f-h). In particular, 3h exhibited extremely high gas permeability (PO2 = 9800 barrers), which is about the same as that of poly(1-trimethylsilyl-1-propyne). Desilylated membranes 3a and 3f-h showed different gas permeability from that of polymers 2i-k which have the identical chemical structures and obtained directly by the polymerization of the corresponding monomers. © 2010 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.polymer.2010.02.015

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Living polymerization of phenylacetylene (PA) was achieved with new catalyst systems composed of a cationic rhodium complex, [(tfb)Rh(PPh3)2]BPh4(2, tfb = tetrafluorobenzobarrelene) and amines as cocatalysts. Applying i-PrNH2as a cocatalyst, the PDI of the formed poly(PA) was as small as 1.09. Kinetic plots and multistage polymerization proved the livingness of the present polymerization. © 2010 The Chemical Society of Japan.

DOI： 10.1246/cl.2010.244

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Amino acid derived norbornene monomers having unprotected carboxy (1) and amino groups (2) and 7-oxanorbornene having ester groups (3) were block copolymerized using the Grubbs ruthenium complexes. In the combination of 1 and 2, block copolymers with number-average molecular weights ranging from 43 000 to 95 000 were obtained in good yields. Poly(1)75-block-Poly(2) 25 was soluble in 0.5 M NaOH(aq) but insoluble in 0.1 M HCl, while poly(l)25-block-poly(2)75 was soluble in 0.1 M HCl but insoluble in 0.5 M NaOH(aq). Thus, the block compositions remarkably affected the solubility of the copolymers in acidic and basic media. On the other hand, poly(2)62-block-poly(3)38 was soluble in H2O but insoluble in CH2Cl2 and CHCl3, while poly(2)38-block-poly(3)62 was soluble in CH 2Cl2 and CHCl3 but insoluble in H2O. In this monomer combination, the block compositions significantly affected the solubility of the copolymers in organic and aqueous media. 1H NMR spectroscopic, turbidity, and dynamic light scattering measurements revealed that poly(l)50-block-poly(2)50 formed micelles with a diameter around 130 nm in 0.5 M NaOH(aq). In a similar manner, it was revealed that poly(2)62-block-poly(3)38 and poty(2)3gblock-poly(3) 62 formed micelles with a diameter around 80 nm in H2O and reverse micelles with a diameter around 45 nm in CH2Cl2, respectively. © 2010 American Chemical Society.

DOI： 10.1021/ma902405g

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Diarylacetylene monomers containing substituted biphenyl (1a-f) and anthryl (1g) groups were synthesized and then polymerized with TaCl5-n- Bu4Sn catalyst to produce the corresponding poly(diarylacetylene)s (2a-g). Polymers 2a-f were soluble in common organic solvents such as cyclohexane, toluene, and chloroform. According to thermogravimetric analysis, the onset temperatures of weight loss of the polymers were over 400 °C in air, indicating considerably high thermal stability. Free-standing membranes 2a and 2c-e were prepared by the solution casting method. Desilylation of Si-containing membrane 2c was carried out with trifluoroacetic acid to afford 3c. All the polymer membranes, especially those having twisted biphenyl groups, exhibited high gas permeability; for example, their oxygen permeability (PO 2) values ranged from 130 to 1400 barrers. Membrane 2d having two chlorine atoms in the biphenyl group showed the highest gas permeability (PO2 = 1400 barrers) among the present polymers. © 2010 Wiley Periodicals, Inc.

DOI： 10.1002/pola.23836

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The Sonogashira-Hagihara polymerization of 3',5'-diiodo-N-α-tert-butoxycarbonyl-l-tyrosine methyl ester (1) and 3',5'-diiodo-N-α-tert-butoxycarbonyl-O-methyl-l-tyrosine methyl ester (2) with para-diethynylbenzene (3) was carried out to obtain optically active poly(m-phenyleneethynylene-p-phenyleneethynylene)s [poly(1) and poly(2)] with Mn's ranging from 9900 to 15,000 in 80-87% yields. Poly(1) exhibited intense CD signals in DMSO and THF, but did not in CH2Cl2, indicating that it took a predominantly one-handed helical conformation in the former two solvents. On the other hand, there was no evidence for poly(2) to take a helical structure in these solvents. Poly(1) turned the CD sign at 390 nm from plus to minus in DMSO/H2O = 9/1 (v/v) by the addition of NaOH. Alkaline hydrolysis of ester moieties of poly(1) and poly(2) gave the corresponding polymers having carboxy groups [poly(1a) and poly(2a)]. Poly(1a) and poly(2a) increased the CD intensity by the addition of NaOH. © 2010 Elsevier Ltd.

DOI： 10.1016/j.polymer.2010.03.048

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DOI： 10.1007/s00289-009-0121-4

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The polymerization of (2-isopropoxyphenyl)acetylene was investigated using a wide range of well-defined ruthenium-alkylidene complexes and related olefin metathesis initiators. In view of its superior activity, the second generation Hoveyda-Grubbs catalyst was singled out for further studies. Only phenylacetylenes ortho-substituted with alkoxy, ester, fluoro, and silyl groups afforded polymers with moderate molecular weights. They were characterized by various analytical techniques, and their properties were compared with those of samples prepared using Rh and W initiators. The Ru-based polymers possessed high trans contents and took a helical conformation with predominantly one-handed screw sense when chiral side-chains were present. © 2009 WILEY-VCH Verlag GmbH & Co. KGaA Weinheim.

DOI： 10.1002/macp.200900245

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

An N-monomethylated unsymmetrical diketopiperazine was synthesized from D-p-hydroxyphenylglycine and sarcosine, and condensed with trans-1,4-cyclohexanedicarboxylic acid to obtain the ester having diketopiperazine moieties at the both termini. Atomic force microscope measurement indicated that the ester formed a supramolecular structure aligned in a circular pattern based on hydrogen bonding between the amide groups of the diketopiperazine moieties.

DOI： 10.3987/COM-09-11762

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Novel conjugated polymers P1-P7 containing 3,9-linked carbazole units in the main chain were synthesized by the polycondensation of 3-ethynyl-9-(4-ethynylphenyl)carbazole (EEPCz) and dihaloarenes, and their optical and electrical properties were studied. Polymers with weight-average molecular weights of 4100-48,000 were obtained in 24-92% yields by the Sonogashira coupling polycondensation in tetrahydrofuran (THF)/Et3N at 30 or 50 °C for 48 h. All the polymers absorbed light around 350 nm. The polymers with electron-accepter units exhibited absorption bands originating from charge transfer. The polymers except the one containing azobenzenes emitted variously colored fluorescence with moderate quantum yields upon excitation at the absorption maxima. P1-P3 were oxidized around 0.6 V, and then reduced around 0.5 V. The conductivity of P3 was 1.1 × 10-14 S/cm at 103 V/cm. © 2009 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.polymer.2009.07.013

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Optically active 1-methylpropargyl esters bearing azobenzene groups, namely, (S)-(-)-3-methyl-3-{4-[4-(n-butyloxy)phenylazophenyl]carbonyl}oxy-1-propyne (1), (S)-(-)-3-methyl-3-{4-[4-(n-hexyloxy)phenylazophenyl]carbonyl}oxy-1-propyne (2), and (S)-(-)-3-methyl-3-{4-[-4-(n-octyloxy)phenylazophenyl]carbonyl}oxy-1-propyne (3) were synthesized and polymerized with Rh(+)(nbd)[eta(6)-C(6)H(5)B(-)(C(6)H(5))(3)] (nbd, norbornadiene) as a catalyst to afford the corresponding poly(1-methyloropargyl ester)s with moderate molecular weights (M(n) = 24,000-31,300) in good yields (79-84%). Polymers were soluble in common organic solvents including toluene, CHCl(3), CH(2)Cl(2), THF, and DMSO, whereas insoluble in diethyl ether, n-hexane, and methanol. Large optical rotations and strong CD signals demonstrated that all the polymers take a helical structure with a predominantly one-handed screw sense. The helical structure of the polymers changed with the addition of MeOH and heat. The trans-azobenzene of the polymer side chains isomerized. into cis on UV irradiation, which was accompanied with drastic helical conformational changes of the polymer backbone. The cis-azobenzene moiety reisomerized into trans on visible-light irradiation, which induced the recovery of chiral geometry of azobenzene moieties in the side chain. Conformational analysis revealed that the polymers form a tightly twisted right-handed helical structure with a dihedral angle of 70 degrees at the single bond of the main chain. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4749-4761, 2009

DOI： 10.1002/pola.23528

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The polymerization of 3′,5′-diiodo-4′-hydroxy-N-α- tert-butoxycarbonyl-D-phenylglycine ethyl-, hexyl-, and laurylamides 1-3 with p-diethynylbenzene was carried out to obtain optically active poly(m-phenyleneethynylene-p-phenyleneethynylene)s [poly(1) - poly(3)] with Mn's in the range from 6100 to 7300 in 79-82% yields. The specific rotation, CD, and UV - vis spectroscopic data revealed that poly(1) - poly(3) formed helices with predominantly one-handed screw sense. The presence of intramolecular hydrogen bonding formed between amide side groups was confirmed by solution-state IR spectroscopy. The helical structures were stable to heat and alkali metal hydroxides, while responsive to H2O and alkali metal alkoxides. © 2009 American Chemical Society.

DOI： 10.1021/ma900910k

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Diarylacetylenes having fluorenyl groups and other substituents (trimethylsilyl, t-butyl, bromine, fluorine) (1a-1) were polymerized with TaCl5-n-Bu4Sn. Monomers 1a-l produced high molecular weight polymers 2a-l (Mw 5.1 × 105-1.3 × 106) in 12-59% yields. All of the polymers were soluble in common organic solvents, and gave tough free-standing membranes by the solution casting method. The onset temperatures of weight loss of polymers 2a-l in air were over 400 °C, indicating considerably high thermal stability. All the polymer membranes showed high gas permeability; e.g., the oxygen permeability coefficient (PO2) of 2a was as large as 4800 barrers. Membrane 2d possessing two fluorine atoms at meta and para positions of the phenyl ring showed the highest oxygen permeability (PO2 = 6600 barrers) among the present polymers. © 2009 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.polymer.2009.06.064

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Amino acid derived norbornene monomers having carboxy (1) and amino groups (2) were synthesized and subjected to ring-opening metathesis copolymerization with various feed ratios using the Grubbs second generation ruthenium catalyst. The Mn's of the copolymers ranged from 5300 to 9400 (M w/Mn = 1.40-1.69). The monomer conversion and M n of the copolymer were maximized when the monomer feed ratio was 1:1. The monomer unit ratios in the copolymers were almost 1:1 at 10% conversion, irrespective of the feed ratios. The monomer reactivity ratios r1 and r2 were estimated to be 0.08 and 0.02, which confirmed that alternating copolymerization occurred. It is considered that alternating copolymerization is brought about by the acid-base interaction between the monomers and/or between the propagating polymer end and the incoming monomer. © 2009 American Chemical Society.

DOI： 10.1021/ja903248c

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Novel conjugated polymers containing 3,9- or 2,9-linked carbazole units in the main chain were synthesized by the polycondensation of ethynyl- and iodo-substituted 9-arylenecarbazolylene monomers, and their optical and electrical properties were studied. Polymers with weight-average molecular weights of 3400-12,000 were obtained in 76-99% yields by the Sonogashira coupling polycondensation in piperidine or tetrahydrofuran (THF)/piperidine at 30 °C for 48 h. All the 3,9-linked polymers absorbed light around 300 nm. The para-phenylene-linked polymer also absorbed light around 350 nm, while meto-phenylene-linked one did not. The 3,9-linked polymers absorbed light at a wavelength longer than the 2,9-linked one. The polymers emitted blue fluorescence with high quantum yields (0.21-0.78) upon excitation at the absorption maxima. The polymers were oxidized around 0.6 V, and reduced around 0.5 V. Poly(l) showed the dark conductivity of 3.7 x 10-11 S/cm (103 V/cm). © 2009 Wiley Periodicals, Inc.

DOI： 10.1002/pola.23431

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Zwitterionic Rh catalysts bearing a series of tetra fluorobenzobarrelene (tfb) ligands proved to be highly active in the polymerization of phenylacetylenes. The highest catalytic activity for the polymerization of phenylacetylene was observed with (tfb)Rh + [(η6-Ph) B-Ph3] (1). Catalyst 1 displayed higher activity to produce higher molecular weight polymer than the conventional nbd analogue, (nbd)Rh+[(η6-Ph)B-Ph3] (5, nbd = 2,5-norbornadiene). In the case of other zwitterionic Rh catalysts bearing polymethylated tfb ligands [tfb-Me2, 2; tfb-Me3, 3; tfb-Me4, 4], the catalytic activity tended to decrease with increasing number of the incorporated methyl groups. Catalyst 1 also showed high activity in the polymerization of phenylacetylene derivatives irrespective of electron-donating or -withdrawing nature of ring-substituents of the monomers. © 2009 American Chemical Society.

DOI： 10.1021/ma900293t

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

A diketopiperazine (DKP) having long alkyl chains was synthesized from D-p-hydroxyphenylglycine, and the formation of supramolecules was examined. The (1)H NMR and UV-vis spectroscopic measurements and molecular modeling have suggested that the DKP molecules are aligned based on hydrogen bonding between the amide groups, and there is no stacking between the phenyl groups.

DOI： 10.3987/COM-08-11635

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER SCIENCE SA  

Optically active N-propargylamicles polymerized with rhodium catalysts into helical polymers with predominantly one-handed screw sense. It was confirmed that hydrogen bonding between the amide groups in the side chains played an important role to stabilize the helical structure. Poly(1-methylpropargyl alcohol)s and the esters took helical structures stabilized by the steric effect of methyl group adjacent to the main chain. (C) 2009 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.synthmet.2009.01.002

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The ring-opening metathesis polymerization (ROMP) of norbornene derivatives 1-5 bearing oligomeric siloxane pendant groups was carried out with Grubbs 1st and 2nd generation, and Grubbs-Hoveyda ruthenium (Ru) catalysts. Monomer 1 gave high-molecular-weight polymers (Mnca. 27 000-180 000) in high yields (80-100%). Monomers 2-5 also polymerized with Ru carbene catalysts to give high-molecular-weight polymers (Mnca. 34 000-240 000) in high yields (66-100%). The onset temperatures of weight loss (T0) of the polymers were 180-250 °C. The glass transition temperatures (Tgs) of poly(1) and poly(2) bearing branched siloxane linkages were near or higher than room temperature (27 and 101 °C). Meanwhile, the Tgs of poly(3)-poly(5) bearing linear siloxane linkages were much lower (-115 to -23 °C), and decreased with increasing length of the siloxane linkages. Poly(1) and poly(2) were hydrogenated completely, which was confirmed by1H NMR spectroscopy. The free-standing membranes of poly(1) and poly(2) showed high gas permeability; especially poly(2) is the most permeable to various gases among ROMP-polynorbornene derivatives reported so far. © 2009 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.polymer.2009.01.039

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Amino acid-derived novel norbornene monomers (1a-2b) having nonprotected amino groups, together with tert-butoxycarbonyl (Boc) protected ones (1a-Boc-2b-Boc) were synthesized and polymerized by ring-opening metathesis polymerization using the Grubbs second generation ruthenium catalyst. The L-alanine-derived endo,endo-monomer la with amino groups gave no polymer, while the exo,exo-isomer 1b gave a polymer by raising the catalyst concentration. N-Methyl-L-alanine-derived 2a and 2b carrying secondary amino groups gave polymers in yields higher than 1a and 1b. On the other hand, Boc-protected 1a-Boc-2b-Boc gave the polymers in almost quantitative yields irrespective of the stereo structure (endo, exo) as well as the absence and presence of methyl group at the nitrogen atom. (1)H-(1)H COSY NMR spectroscopic analysis and molecular mechanics calculation indicated that the polymers were syndiotactic.

DOI： 10.1021/ma802243e

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

N,N'-bis-(L-4'-iodophenylalanine octyl ester)pyromellitic diimide (1) was synthesized, and the Sonogashira-Hagihara coupling polymerization of 1 with para-/meta-diethynylbenzenes (2p/2m) was carried out to obtain optically active phenyleneethynylene-based polyimides carrying ester groups [poly(1-2p) and poly(1-2m)] with number average molecular weights in the range from 4 900 to 19 700 in 68-80% yields. The polymers were satisfactorily converted into the corresponding polymers carrying free carboxy groups [poly(1-2p)' and poly(1-2m)'] by alkaline hydrolysis. All the polymers exhibited intense CD signals, indicating that they formed helices with predominantly one-handed screw sense. The helical conformations of the polymers were stable against heat. Poly(1-2p)' and poly(1-2m)' lost the one-handed helicity by the addition of NaOH, and the resultant polymer recovered the original conformation upon HCl addition.

DOI： 10.1002/macp.200800503

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

Chiral methylpropargyl ester monomers containing amino acid moieties, N-(tert-butoxycarbonyl)-L-alanine (R)-1-methylpropargyl ester (1), N-(benzyloxycarbonyl)-L-Valine (R)-1-methylpropargyl ester (2), and N-(tert-butoxycarbonyl)-L-O-cyclohexyl-L-glLitamic acid (R)-1-methylpropargyl ester (3) were synthesized and polymerized with (nbd)Rh(+)[eta(6)-C(6)H(5)B(-)(C(6)H(5))(3)] to give the corresponding polymers with number-average molecular weights ranging from 32 700 to 64 100 in 84-85% yields. The polymers were soluble in toluene, CHCl(3), CH(2)O(2), THF, DMF, and DMSO, but insoluble in hexane, diethyl ether, and MeOH. The specific rotation and circular dichroism (CD) spectroscopic studies revealed that poly(1)-poly(3) took predominantly one-handed helical structures in the solvents, wherein the degree of one-handedness and tightness of the helix depended on the solvent. The helical structure of the polymers was stable to the addition of MeOH and heat. (C) 2008 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.eurpolymj.2008.10.032

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Novel optically active phenylacetylenes having diketopiperizine were synthesized from L-phenylalanine and polymerized with a rhodium catalyst to obtain the polymers with number-average molecular weights over 10 000 in good yields. The CD and UV - vis spectra of the polymers indicated that they took helical structures with predominantly one-handed screw sense in DMF, while random coil Structures in CHCl(3). Addition of various Carboxylic acids such as trifluoroacetic acid to the polymer solution in CHCl(3) promoted the helical formation. Molecular mechanics calculation suggested that the most stable conformer was a right-handed helix accompanying tandem hydrogen-bonding strands between the amide groups.

DOI： 10.1021/ma8023552

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Optically active 1-methylpropargyl esters bearing various substituents were polymerized with [(nbd)Rh]+ [η6-C6H 5B(C6H5)3]- (nbd=norbornadiene) as a catalyst to afford the corresponding poly(1-methylpropargyl ester)s with moderate molecular weights in good yields. The polymers have a cis-stereoregular structure, which was determined by 1H NMR spectroscopy. Large optical rotations and clear CD signals demonstrated that all these polymers take on a helical structure with a predominantly onehanded screw sense. The polymers exhibited large viscosity indices in the range 1.14-1.75. Chiral amplification was observed in R/S copolymerization. Conformational analysis revealed that the polymers form a tightly twisted helical structure with a dihedral angle of 708 at the single bond of the main chain. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

DOI： 10.1002/asia.200800131

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Acetylenic monomers containing indan and other groups (1a-m) were polymerized with TaCl5-n-Bu4Sn catalyst to give high molecular weight polymers. Most polymers were soluble in common organic solvents including toluene and chloroform, and they afforded free-standing membranes by the solution casting method The onset temperature of weight loss of the polymers were over 400 °C, indicating high thermal stability. Despite the absence of bulky spherical groups, polymethylated indan-containing polymer membranes showed extremely high gas permeability. In particular, the oxygen permeability coefficients of polymers having 1,1,3,3-tetramethylindan and either p-fluorophenyl or p,m-difluorophenyl groups (2b and 2e) reached 17 900 and 18 700 barrers, respectively, which are even larger than that of the most permeable polymer known, poly(1-trimefhylsilyl-1-propyne) © 2008 American Chemical Society.

DOI： 10.1021/ma801845g

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記述言語：日本語   出版者・発行元：THE SOCIRETY OF RUBBER SCIENCE AND TECHNOLOGYY, JAPAN  

This article reviews the development of transition metal catalysts for substituted acetylenes. These catalysts enable us to synthesize a wide variety of substituted polyacetylenes, whose molecular weights and polydispersities can be controlled in some cases. Most of the polymers are soluble in common solvents and stable enough in the air unlike non-substituted polyacetylene. They exhibit interesting features and functions including helix formation, high gas permeability, and photoelectronic properties.

DOI： 10.2324/gomu.81.473

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その他リンク： https://jlc.jst.go.jp/DN/JALC/00321748056?from=CiNii

Novel acetylene monomers substituted with phenylethynylcarbazolyl groups, 3-[(4-octylphenyl)ethynyl]-9-propargylcarbazole (1), 3,6-bis[(4-octylphenyl)ethynyl]-9-propargylcarbazole (2), 9-(4-ethynylphenyl)-3-[(4-octylphenyl)ethynyl]carbazole (3), and 9-(4-ethynylphenyl)-3,6-bis[(4-octylphenyl)ethynyl]carbazole (4) were synthesized, and polymerized with Rh+(nbd)[η6-C6H5B-(C6H5)3] and WCl6-n-Bu4Sn catalysts. The corresponding polyacetylenes with number-average molecular weights ranging from 9200 to 94 000 were obtained in 20-98% yields. The IR spectra of the polymers revealed that acetylene polymerization took place at the terminal ethynyl group, while the ethynylene group remained intact. The UV-vis absorption band edge wavelengths of W-based poly(3) and poly(4) were longer than those of the other polymers. W-Based poly(4) emitted fluorescence with the highest quantum yield (41%). Poly(1) exhibited excimer-based fluorescence in dilute solution. © 2008 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.polymer.2008.08.028

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記述言語：日本語   掲載種別：研究論文（学術雑誌）   出版者・発行元：SOC SYNTHETIC ORGANIC CHEM JPN  

This article reviews the secondary structures, properties, and functions of helical polyacetylenes substituted with optically active groups, including cis-stereoregular poly (1-methylpropargyl ester) s, poly (N-alkynylamide) s, and poly (alkynamide) s synthesized by the polymerization using rhodium catalysts. The polymers take tightly twisted cis-cisoidal and loosely twised cis-transoidal helices according to the substituents and media, some of which undergo reversible transformation of helical sense with external stimuli such as temperature and pH. The helical polymers are applicable to chiral recognition materials and catalyts for asymmetric synthesis.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

L-glutamic acid diketopiperazine omega-alkenyl esters were synthesized and polymerized via acyclic diene metathesis polycondensation chemistry using ruthenium catalysts. The polycondensation of L-glutamic acid diketopiperazine omega-allyl ester (1) was unsuccessful, while the polycondensation Of L-glutamic acid diketopiperazine omega-homoallyl ester (2), -pentenyl ester (3), and -hexenyl ester (4) with Grubbs second-generation catalyst and Grubbs-Hoveyda catalyst satisfactorily proceeded to give the corresponding polymers. They exhibited melting temperatures around 150 degrees C, and possessed crystalline structures similar to that of polyethylene. Dynamic light scattering and differential scanning calorimetric measurements suggested that the polymers formed aggregates in N,N-dimethylformamide, presumably based on hydrogen bonding between diketopiperazine moieties.

DOI： 10.1021/ma800367z

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Di(iodophenyl)-substituted L-glutamic acid-derived benzenetetracarboxylic diimide (1) was synthesized, and the polycondensation of 1 with p-/m-diethynylbenzenes (2p/2m) was carried out to obtain optically active phenyleneethynylene-based polymers carrying ester-protected carboxy groups [poly(1-2p) and poly(1-2m)] with M(n)'s in the range from 6500 to 37 600 in 84-96% yields. The polymers were satisfactorily converted into the corresponding polymers [poly(1-2p)' and poly(1-2m)'] with free carboxy groups by alkaline hydrolysis. The polymer structures were characterized by IR, NMR, UV, and CD spectroscopies. All the polymers exhibited intense CD signals, indicating that they formed helices with predominantly one-handed screw sense. The helical structures of the polymers were stable against heat. Para-linked poly(1-2p) carrying ester-protected carboxy groups and poly(1-2p)' carrying free carboxy groups formed helices with opposite predominant helical senses each other, while their meta-linked counterparts [poly(1-2m) and poly(1-2m)'] formed helices with the same screw sense. Poly(1-2p)' lost the one-handed helicity by the addition of KOH, and the resultant polymer recovered the original conformation upon HCl addition. On the other hand, poly(1-2m)' kept stable by KOH addition.

DOI： 10.1021/ma800674f

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Copolymerization of ornithine- and lysine-derived N-propargylamides, N-alpha-tert-butoxycarbonyl-N-delta-fluorenylmethoxycarbonyl-L-ornithine N'-propargylamide (1), N-alpha-tert-butoxycarbonyl-N-epsilon-fluorenylmethoxycarbonyl-L-lysine N'-propargylamide (2), N-alpha-fluorenylmethoxycarbonyl-N-delta-tert-butoxycarbonyl-L-ornithine N'-propargylamide (3), and N-alpha-fluorenylmethoxycarbonyl-N-epsilon-tert-butoxycarbonyl-L-lysine N'-propargylamide (4) with dipropargyl adipate was carried out using (nbd)Rh+[eta(6)-C6H5B-(C6H5)(3)] as a catalyst in THF to obtain polymer gels in 80-93% yields. The gels adsorbed N-benzyloxycarbonyl L-alanine, N-benzyloxycarbonyl L-alanine methyl ester, and (S)-(+)-1-phenyl-1,2-ethanediol preferably than the corresponding optical isomers. The order of chiral discrimination was poly(l) > poly(4) > poly(2), poly(3) gels. The fluorenylmethoxycarbonyl groups of the gels could be partly removed by piperidine treatment, leading to increase of adsorptivity but decrease of chiral recognition ability. (C) 2008 Wiley Periodicals, Inc.

DOI： 10.1002/pola.22766

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Novel 4-ethynylphthaloyl amino acid esters carrying different terminal groups, 4-ethynylphthaloyl glycine (1S,2R,5S)-menthyl ester (1), 4-ethynylphthaloyl glycine (1R,2S,5R)-menthyl ester (2), 4-ethynylphthaloyl L-leucine methyl ester (3), 4-ethynylphthaloyl L-leucine (1S,2R,5S)-menthyl. ester (4), 4-ethynylphthaloyl L-leucine (1R,2S,5R)-menthyl ester (5) were synthesized and polymerized with a rhodium catalyst. Polymers with high molecular weights were obtained in 71-92% yields. The helical conformation of the polymers could be tuned by the chirality of the amino acid connected to the backbone, together with the chirality and bulkiness of the terminal pendent groups. (C) 2008 Wiley Periodicals, Inc.

DOI： 10.1002/pola.22772

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-BLACKWELL  

Amino acid-derived novel norbornene monomers were synthesized and polymerized with ruthenium catalysts. The polymerization rates were affected by the stereo structure of the monomers; exo,exo-NBL underwent ROMP faster to give the polymers in higher yields than the endo,exo-counterpart. The Grubbs 2nd generation catalyst was the most effective for the amino acid-based monomers. A polymer gel was synthesized by the copolymerization of exo,exo-NBL with 2.5 mol-% of bifunctional norbornene monomer. The gel adsorbed larger amounts of (R)-phenylalaninol and N-(benzyloxycarbonyl)alanine than those of the (S)-isomers.

DOI： 10.1002/macp.200700530

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The amino acid esters of hydroxypropyl cellulose (HPC) [R′ = H (2a), CH3(2b), CH2CH(CH3)2(2c), CH2CONH2(2d), CH2CH2CONH2(2e), CH2CH2CH2CH2NHOCOC(CH3)3(2f)] were synthesized in good yield by the reaction of t-butoxycarbonyl (t-Boc)-protected amino acids with hydroxy groups of HPC (1; molar substitution (MS), 4.61). The amino acid functionalities displaying varied chemical nature, shape, and bulk were utilized and the bulk of the substituent on the α-carbon of amino acids was elucidated to be of vital significance for the observed degree of incorporation (DSEst). The1H NMR spectra and elemental analysis were employed to determine the degree of incorporation of amino acid moiety (DSEst) and almost complete substitution of the hydroxy protons was revealed for 2a, 2b, and 2f. The presence of the peaks characteristic of the carbonyl group in the FTIR spectra furnished further evidence for the successful esterification of HPC. The starting as well as the resulting polymers (1 and 2a-f) were soluble in polar organic solvents; however, the esterification of 1 with bulky organic moieties resulted in an increased hydrophobicity as all of the amino acid-functionalized polymers (2a-f) were insoluble in water. The onset temperatures of weight loss of 2a-f were 175-230 °C, indicating fair thermal stability. The amino acid functionalization led to the enhanced polymer chain stiffness, and the glass transition temperatures of the derivatized polymers were 30-40 °C higher than that of 1 (Tg3.9 °C; cf. Tgof 2a-f, 35.1-43.3 °C). © 2008 Wiley Periodicals, Inc.

DOI： 10.1002/pola.22565

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：SPRINGER  

Novel phenylacetylenes carrying two amino acid moieties 1-3 were synthesized by the condensation of alanine, leucine, and phenylalanine with 4-ethynylphthalic anhydride. The corresponding polymers [poly(1)-poly(3)] with high molecular weights were obtained in 50-93% yields. The large specific rotations and intense CD signals indicated that poly(1)-poly(3) formed a helical structure with predominantly one-handed screw sense in CHCl(3). The helical conformation of the polymers was stable to heating but susceptible to MeOH.

DOI： 10.1007/s00289-007-0849-7

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N-Butynylamides, (S)-HC≡CCH2CH2NHCOCH 2CH(CH3)CH2CH3 (1), (R)-HC≡CCH2CH2-NHCOCH2CH(CH 3)CH2CH2CH2CH(CH3) 2 (2), (S)-HC≡CCH2CH2NHCOCH(CH 3)CH2CH2CH2CH2CH 2CH3 (3), (1S)-HC≡CCH2CH 2NHCOC9H13O2 (4, COC 9H13O2 = camphanyl), and HC≡CCH 2CH2NHCOCH2CH2CH2CH 2-CH3 (5) were polymerized with [(nbd)RhCl] 2-Et3N in CHCl3 to obtain cis-stereoregular poly(N-butynylamide)s [poly(1)-poly(5)]. CD and IR spectroscopic studies revealed that poly(1)-poly(4) having chiral substituents in the side chains took predominantly one-handed helical structure stabilized by intramolecular hydrogen bonds between the pendent amide groups in CHCl3. The helical structure of poly(1)-poly(3) was more stable to heating than that of the corresponding poly(N-propargylamide)s reported so far. In contrast, poly(4) having bulky lactone moieties changed the helical tightness according to temperature. The helical structure of poly(3) having α-methyl branch was much more stable to MeOH addition than that of poly(1) and poly(2) having β-methyl branch. The persistence length of the poly(N-butynylamide)s was nearly the same as that of poly(N-propargylcarbamate)s, but shorter than that of poly(N-propargylamide)s. Simulation of CD spectra was carried out for helical forms of a poly(N-butynylamide) to specify the asymmetric conformations. © 2008 American Chemical Society.

DOI： 10.1021/ma702316f

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Optically-active, novel N-propargylamides bearing hydroxy groups: (S)-HC≡CCH2NHCOCH (CH3)OH (1), (5)-HC≡CCH2NHCOCH(CH3)CH2OH (2), (S)-HC≡CCH2NHCOCH[CH(CH3)2]OH (3), (S)-HC≡CCH2NCOCH[CH2CH(CH3)2]OH (4), (S)-HC≡CCH2NHCOCH(C6H5)OH (5), and (S)-HC≡ CCH2NHCOCH(CH2C6H5)OH (6) were synthesized and polymerized with [(nbd)RhCl]2Et3N as a catalyst to obtain the corresponding polymers with moderate molecular weights (M̄n= 8 400 to 32 000) in 45 to 86% yields. Polarimetrie, circular dichroism (CD), and UV-vis spectroscopic analyses revealed that poly(1) and poly(6) took a helical structure with, predominantly, a one-handed screw sense.On the other hand, poly[(S)-HC≡CCH2OCOCH(CH3)OH] [poly(1′)], an ester analogue of poly(1), and poly(2)-poly(5) did not take a predominantly onehanded helical structure. © 2008 WILEY-VCH Verlag GmbH & Co. KGaA.

DOI： 10.1002/macp.200700374

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Amino acid derived novel norbornene monomers, N,N'-(exo-bicyclo[2.2.1]hept-5-en-2,3-diyldi-carbonyl) biS-L-leucine methyl ester (1) and N,N'-(exo-bicyclo[2.2.1]hept-5-en-2,3-diyldicarbonyl) biS-L-leucine (2) were synthesized and polymerized with Grubbs second generation ruthenium catalyst. The homopolymers, random, and block copolymers with number-average molecular weights ranging from 16 000 to 30 000 were obtained in good yields. The block copolymers with 1:2 unit ratios of 75:25, 62:38, and 50:50 were soluble in acetone, while the random copolymers with the same ratios were partly insoluble in the solvent. H-1 NMR, contact angle, dynamic light scattering, and atomic force microscopy measurements revealed that the block copolymer form micelles with a diameter around 100 nm in acetone consisting of a hydrophilic core of poly(2) and a hydrophobic shell of poly(1).

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：SOC POLYMER SCIENCE JAPAN  

A series of optically active novel O-acylated N-propargyllactamide derivatives, (S)-HC CCH2NHCOCH(CH3)OCOC2H5 (1), (S)-HC CCH2NHCOCH(CH3)OCO-n-C4H9 (2), (S)-HC CCH2NHCOCH(CH3)OCOC(CH3)(3) (3), (S)-HC=CCH2NHCOCH(CH3)OCOCH2Ph (4), (S)-HC CCH2NHCOCH(CH3)OCOCHPh2 (5), (S)-HC CCH2NHCOCH(CH3)OCOCPh3 (6), (S)-HC CCH2NHCOCH(CH3)OCO-1,4-C6H4-n-C6H13 (7), (S)-HC CCH2NHCOCH(CH3)OCOCH2CH2Ph (8) (S)HC CCH2NHCOCH(CH3)OCOCH2CH2CH2Ph (9), (S)-HC CCH2NHCOCH(CH2Ph)OCOC2H5 (10), and (S)-HC CCH2NHCOCH(CH2)Ph)OCO-1,4-C6H4-n-C6H13 (11) were synthesized and polymerized with [(nbd)RhCl](2)-Et3N as a catalyst to obtain the corresponding polymers with moderate molecular weights (M-n = 10 000-210 000) in 58-95% yields. Polarimetric, CID, UV-vis, and IR spectroscopic studies revealed that the polymers took helical structures with predominantly one-handed screw sense stabilized by intramolecular hydrogen bonding between the amide groups in the side chains in various solvents. The bulkiness of the substituents affected the degree of one-handedness, tightness and stability of helical structure of the polymers. Poly(7) formed a liquid crystal.

DOI： 10.1295/polymj.PJ2008089

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：SOC POLYMER SCIENCE JAPAN  

L-Glutamic acid-based novel dendritic phenylacetylene derivatives 1 and 2 were synthesized and polymerized with a rhodium catalyst to afford the corresponding polymers [poly(1) and poly(2)] with high molecular weights in 83-95% yields. Poly(1) formed a helical structure with predominantly one-handed screw sense in DPvIF, CHCl3, and MeOH, and poly(2) did in DMF. The helical conformation of poly(1) and poly(2) could be tuned by temperature. Poly(1) underwent solvent-driven helix-helix transition in CHCl3/DMF.

DOI： 10.1295/polymj.PJ2007159

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2,2,6,6-Tetramethyl-1-piperidinyloxy (TEMPO)- and 2,2,5,5-tetramethyl-1- pyrrolidinyloxy (PROXYL)-containing (R)-1-methylpropargyl TEMPO-4-carboxylate (1), CR)-1-methylpropargyl PROXYL-3-carboxylate (2), (rac)-1-methylpropargyl PROXYL-3-carboxylate (3), (S)-1-propargylcarbamoylethyl TEMPO-4-carboxylate (4), and (S)-1-propargyloxycarbonylethyl TEMPO-4-carboxylate (5) (TEMPO, PROXYL) were polymerized to afford novel polymers containing the TEMPO and PROXYL radicals at high densities. Monomers 1-3 and 5 provided polymers with moderate number-average molecular weights of 8200-140,900 in 49-97% yields in the presence of (nbd)Rh+[η6-C6H 5B-(C6H5)3], whereas 4 gave no polymer with this catalyst but gave polymers possessing low M n (3800-7500) in 56-61% yield with [(nbd)RhCl]2-Et 3N. Poly(1), poly(2), and poly(4) took a helical structure with predominantly one-handed screw sense in THF and CHCl3 as well as in film state. The helical structure of poly(1) and poly(2) was stable upon heating and addition of MeOH, whereas poly(4) was responsive to heat and solvents. All of the free radical-containing polymers displayed the reversible charge/discharge processes, whose capacities were in a range of 43.2-112 A h/kg. In particular, the capacities of poly(2)-poly(5)-based cells reached about 90-100% of the theoretical values regardless of the secondary structure of the polymer, helix and random. Poly(I), poly(2), and poly(4) taking a helical structure exhibited better capacity tolerance towards the increase of current density than non-helical poly(3) and poly(5) did. © 2007 Wiley Periodicals, Inc.

DOI： 10.1002/pola.22288

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Disubstituted acetylenes containing cyclohexyl groups (RC≡CC 6H4-p-cvclo-C6H11, R = Ph, p-Me 3SiPh, p-tert-BuMe2SiOPh, Me, Cl, 1a-e, respectively) were polymerized with Ta- or Mo-based catalyst, and 1a, 1c, and 1e provided high molecular weight polymers. Free-standing membranes of poly(1a) and poly(1c) were fabricated from toluene solution. Hydroxy-containing membrane poly(2c) was prepared by desilylation of siloxy-containing poly(lc) using trifluroacetic acid. According to thermogravimetric analysis (TGA), the produced polymers exhibited high thermal stability, and the onset temperatures of weight loss in air were ∼340°C The oxygen permeability coefficients of these membranes were in the range of 17-230 barrers. The point of poly(2c) in the P CO2 vs. PCO2/PCH4 plot were located above Robeson's upper bound. © 2007 The Society of Polymer Science.

DOI： 10.1295/polymj.PJ2007021

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Polymethylated poly(diphenylacetylene) derivatives, a new category of substituted polyacetylenes, were successfully synthesized, and proved to show extremely high gas permeability. © The Royal Society of Chemistry.

DOI： 10.1039/b712327b

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Pyrene-functionalized chiral methylpropargyl esters, (R)-3-butyn-2-yl-1-pyrenebutyrate [(R)-1], (S)-3-butyn-2-yl-1-pyrenebutyrate [(S)-1], (R)-3-butyn-2-yl-1-pyrenecarboxylate [(R)-2], and 3-butyn-2-yl-1-pyrenecarboxylate [(R,S)-2] were polymerized with (nbd)Rh+[η6-C6H5B-(C6H5)3] to obtain the corresponding polymers with moderate molecular weights (Mn: 10 500-66 500) in good yields (82-97%). All the polymers were soluble in CHCl3, CH2Cl2, and THF. The polarimetric and CD spectroscopic data indicated that poly[(R)-1], poly[(S)-1], and poly[(R)-2] existed in a helical structure with predominantly one-handed screw sense in these solvents. The helical structure of poly[(R)-1] and poly[(S)-1] was stable upon heating and addition of MeOH, while that of poly[(R)-2] changed upon MeOH addition. The copolymerization of (R)-1 with (S)-1 was also conducted to obtain the copolymers satisfactorily. Poly[(R)-1], poly[(S)-1], and poly[(R)-2] emitted fluorescence smaller than the corresponding racemic copolymers. The fluorescence intensity was tuned by the addition of MeOH to THF solutions of the polymers. © 2007 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.polymer.2007.09.012

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Carbazole-based novel hyperbranched conjugated polymers linked with triphenylamine and benzene moieties were synthesized by Sonogashira coupling polycondensation of N-octadecyl- and N-octyl-3,6-diethynylcarbazoles with tris(4-iodophenyl)amine and 1,3,5-tribromobenzene. Solvent-soluble polymers with number-average molecular weights in the range of 3500-21,000 were obtained in 48-66% yields. The UV-vis absorption bands of the polymers were red-shifted compared to that of carbazole, indicating the extension of conjugation length. The polymers emitted blue-green fluorescence with high quantum yields up to 67% in CHCl3. Poly(1/3) containing triphenylamine units emits visible light and shows unique solvatochromism. The polymers were electrochemically redox-active. © 2007 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.polymer.2007.09.011

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Optically active novel N-propargylamides bearing azobenzene, (R)-HC≡CCH2NHCOCH(CH3)O-1,4-C5H 4-N-N-C6H5 (1a), (R)-HC≡CCH 2NHCOCH(CH3)O-1,4-C6H4-N=N-1′, 4′-C6H4-n-hexyl (1b), (R)-HC≡ CCH 2NHCOCH(CH2C6H3)O-1,4-C 6H4-N-N-C6H5 (2a), (R)-HC≡CCH2NHCOCH(CH2C6H 5)O-1,4-C6H4-N-N-1′,4′-C 6H4-n-Hexyl (2b), and (R)-HC≡CCH 2NHCOCH(C6H5)O-1,4-C6H 4-N=N-C6H5 (3) were synthesized and polymerized with [(nbd)RhCl]2 as a catalyst to obtain the corresponding polymers with moderate molecular weights (Mn = 6900-44 000) in 46-99% yields. Polarimetrie, CD, UV-vis, NOE-NMR, and IR spectroscopic studies demonstrated that the resulting polymers took a helical structure with predominantly one-handed screw sense stabilized by intramolecular hydrogen bonding between the amide groups in the side chains in various solvents. The CD spectra simulated by molecular orbital calculation well agreed with the experimental ones, and indicated the arrangement of azobenzene moieties in a mutual chiral geometry of one-handed screw sense. The trans-azobenzene in the side chain isomerized into the cis form upon UV irradiation, while the helical structure of the main chain was not affected so much. The cis-azobenzene reisomerized into the trans form upon visible-light irradiation, which induced a recovery of chiral geometry of azobenzene moieties in the side chain. Poly(1b) formed a cholesteric liquid crystal. © 2007 American Chemical Society.

DOI： 10.1021/ma070917j

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Novel chiral acetylene monomers containing carbazole, 2-ethynyl-9-[(S)-2- methylbutoxycarbonyl]carbazole (1), 3-ethynyl-9-[(S)-2-methylbutoxycarbonyl] carbazole (2), 2-ethynyl-9-[(S)-2-methylbutyl]carbazole (3), and 2-ethynyl-9-[(S)-4-methylhexyl]carbazole (4) were synthesized and polymerized with [(nbd)RhCl]2 - Et3N. The corresponding polyacetylenes with number-average molecular weights ranging from 68,700 to 310,000 were obtained in good yields. Poly(1) exhibited a large specific rotation and an intense Cotton effect in toluene, indicating that it formed a helix with predominantly one-handed screw sense, while the other three polymers showed no evidence for taking a helical structure. Poly(1) largely decreased the CD intensity upon heating from -10 to 60°C Poly(1) showed a Cotton effect in film state in a manner similar to solution state. No chiral amplification was observed in the copolymerization of 1 with achiral 2-ethynyl-9-tert- butoxycarbonylcarbazole (5). © 2007 Wiley Periodicals, Inc.

DOI： 10.1002/pola.22203

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER SCI LTD  

Ornithine- and lysine-based novel N-propargylamides, N-alpha-tert-butoxycarbonyl-N-delta-fluorenylmethoxycarbonyl-L-ornithine-N'-propargylamide (1), N-alpha-tert-butoxycarbonyl-N-epsilon-fluorenylmethoxycarbonyl-L-lysine-N'-propargylamide (2), N-alpha-fluorenylmethoxycarbonyl-N-delta-tert-butoxycarbonyl-L-ornithine-N'-propargylamide (3), and N-alpha-fluorenylinethoxycarbonyl-N-epsilon-tert-butoxycarbonyl-L-lysine-N'-propargylamide (4) were synthesized and polymerized with a rhodium catalyst. Polymers with moderate molecular weights were obtained in good yields. Poly(1)-poly(4) showed strong Cotton effects in THF, whose sign and wavelength depended on the substituents. They were satisfactorily converted into the corresponding polymers [poly(1a) -poly (4a)] with free amino groups. Poly(1a) and poly(2a) also formed a helix, while poly(3a) and poly(4a) did not. Poly(1a) and poly(2a) decreased the CD intensity by the addition of m- and o-phthalic acids. (C) 2007 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.polymer.2007.08.062

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Novel chiral acetylene monomers containing cholesteryl groups, (R)-3-butyn-2-yl cholesteryl carbonate (1), (S)-3-butyn-2-yl cholesteryl carbonate (2), and propargyl cholesteryl carbonate (3) were synthesized and polymerized with (nbd)Rh+[η6-C6H 5B-(C6H5)3] to give the corresponding polymers with number-average molecular weights of 32 900-97 000 in 84-85% yields. Circular dichroism spectroscopic studies revealed that poly(1) and poly(2) predominantly took one-handed helical structure in CHCl3 and THF. The helical conformation was stable to heat and to addition of MeOH. The copolymerization of 1 and 2 was carried out with the rhodium catalyst to afford copolymers with number-average molecular weights ranging from 53 400 to 88 700 in 83-98% yields. The copolymer with a large diastereomeric excess showed a large specific rotation and an intense Cotton effect in THF, indicating that the predominance of one-handed helicity was high. Poly(l50-co-2 50) showed lyotropic liquid crystalline property. © 2007 WILEY-VCH Verlag GmbH & Co. KGaA.

DOI： 10.1002/macp.200700225

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Novel chiral acetylene monomers bearing carbazole and triphenylamine groups, namely, (S)-3-butyn-2-yl 2-(9-carbazolyl)ethyl carbonate (1) and (S)-3-butyn-2-yl 4-(diphenylamino)benzoate (2) were synthesized, and polymerized with Rh+(nbd)[η6-C6H5B-(C6H5)3] catalyst to give the corresponding polymers with moderate molecular weights (Mn 13.0 × 103 and 15.5 × 103) in good yields (86% and 88%). CD spectroscopic studies revealed that poly(1) and poly(2) took predominantly one-handed helical structure in CHCl3. The helical structures of poly(1) and poly(2) were very stable against heating and addition of MeOH. The solution of poly(1) and poly(2) emitted fluorescence in 0.52% and 7.2% quantum yields, which were lower than those of the corresponding monomers 1 and 2 (22.5% and 76.5%). The cyclic voltammograms of the polymers indicated that the oxidation potentials of the polymers were lower than those of the monomers. The polymers showed electrochromism and changed the color from pale yellow to pale blue by application of voltage, presumably caused by the formation of polaron at the carbazole and triphenylamine moieties. The onset temperatures of weight loss of poly(1) and poly(2) were 225 and 270 °C under air. © 2007 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.polymer.2007.06.011

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：TAYLOR & FRANCIS INC  

Aspartic and glutamic acid-based diketopiperazines, cyclo(L-asparaginyl-L-asparaginyl) (DKPD) and cyclo(L-glutaminyl-L-glutaminyl) (DKPE) were synthesized. Polycondensation of DKPD and DKPE with alpha,alpha'-dibromoxylenes was carried out using K2CO3 as a base in DNF to obtain polymers with weight-average molecular weights (M-w's) of 1100-3500. Furthermore, polycondensation of DKPE with various diamines was carried out using 4-[4,6-dimethoxy-1,3,5-triazin-2-yl]-4-methylmorpholinium chloride as a condensation agent in DMF to obtain polymers with M-w's of 1200-4100. The polymers were insoluble in common organic solvents except DMF.

DOI： 10.1080/10601320701406971

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

A novel optically active phenylacetylene derivative, N-(tert-butoxycarbonyl)-4-ethynyl-L-phenylalanine methyl ester (1), was synthesized from L-tyrosine and polymerized with a rhodium catalyst. The corresponding polymer [poly(l)] with a moderate molecular weight was obtained in a high yield. The alkaline hydrolysis of poly(l) gave poly[N-(tert-butoxycarbonyl)-4-ethynyl-L-phenylalanine] [poly(2)] carrying free carboxy groups. Polarimetric, CD, and UV-vis spectroscopy analyses revealed that poly(l) took a predominantly one-handed helical structure in MeOH and toluene, and poly(2) took a helical structure in MeOH. The secondary structures of poly(l) and poly(2) could be tuned with heat and solvents. (c) 2007 Wiley Periodicals, Inc.

DOI： 10.1002/pola.21936

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER SCI LTD  

Amino acid-derived novel norbornene diester derivatives, 5-norbornene-endo,endo-2,3-dicarboxylic acid bis((S)-2-N-(tert-butoxycarbonyl)aminopropyl) ester (1a), 5-norbomene-exo,exo-2,3-dicarboxylic acid bis((S)-2-N-(tert-butoxycarbonyl)aminopropyl) ester (1b), bis(N-alpha-(tertbutoxycarbonyl)-L-alanine) 5-norbomene-2,3-endo,endo-dimethyl ester (2a), bis(N-alpha-(tert-butoxycarbonyl)-L-alanine) 5-norbomene-2,3exo,exo-dimethyl ester (2b) were synthesized and polymerized by the Grubbs catalyst, 2nd generation. Ring-opening metathesis polymerization of the monomers satisfactorily proceeded to give the polymers with fairly high molecular weights in good yields. The polymerization rate was not affected by the stereostructure of the monomers, endo,endo- and exo,exo-, while largely affected by solvents. The order of polymerization rate was as follows: acetone-d(6) > benzene-d(6) > DMF-d(7) approximate to CD2Cl2 > CDCl3. (c) 2007 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.polymer.2007.04.014

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Novel acetylene monomers containing cholesteryl groups, N-cholesteryloxycarbonyl-2-ethynylcarbazole (1) and cholesteryl N-propargylcarbamate (2) were synthesized and polymerized with an Rh catalyst to give the corresponding polymers [poly(l) and poly(2)] with Mn of 22 600 and 26 600 in 56% and 95% yields, respectively. CD spectroscopic studies revealed that poly(l) and poly(2) took predominantly one-handed helical structure in CHCl3, THF, and toluene. The helical structure of poly(l) remarkably changed upon temperature, while that of poly(2) was stable against heating. The helix of poly(2) was relatively stable to the addition of MeOH, but largely affected by the composition of CHCl3 and toluene. PoIy(1) exhibited no clear oxidation peak, but a clear reduction peak at 0.65 V in cyclic voltammetry. Poly(1) and poly(2) showed liquid crystalline properties. © 2007 WILEY-VCH Verlag GmbH & Co. KGaA.

DOI： 10.1002/macp.200600601

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Novel chiral N-propargylphosphonamidate monomers (HC≡CCH 2NHP (=O)R-O-menthyl, 1: R = CH3, 2: R = C 2H5, 3: R = n-C3H7, 4: R = Ph) were synthesized by the reaction of the corresponding phosphonic dichlorides with menthol and propargylamine. Pairs of diastereomeric monomers 1-4 with different ratios were obtained due to the chiral P-center and menthyl group. One diastereomer could be separated from another one in the cases of monomers 1 and 2. Polymerization of 1-4 with (nbd)Rh+[η6-C 6H6B-(C6H5)3] as a catalyst in CHCl3 gave the polymers with number-average molecular weights ranging from 5000 to 12,000 in 65-85%. Poly(1)-poly(4) exhibited quantitative cis contents, and much larger specific rotations than 1-4 did in CHCl3. The polymers showed an intense Cotton effect around 325 nm based on the conjugated polyacetylene backbone. It was indicated that the polymers took a helical structure with predominantly one-handed screw sense, and intramolecular hydrogen bonding between P=0 and N-H of the polymers contributed to the stability of the helical structure. Poly(1a) and poly(2a) decreased the CD intensity upon raising CH3OH content in CHCl 3/CH3OH. © 2006 Wiley Periodicals, Inc.

DOI： 10.1002/pola.21922

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The new carbazole-containing acetylene monomers, 2-ethynyl-9-tert- butoxycarbonylcarbazole (1) and 3-ethynyl-9-tert-butoxycarbonylcarbazole (2) were synthesized and polymerized with Rh (nbd)[n6-C6H 5B-(C6H5)3], [(nbd)RhCl]2-KN(SiMe3)2, and WCl 6-Ph4Sn catalysts. The corresponding polyacetylenes with number-average molecular weights ranging from 23 000 to 185000 were obtained in 80%-quantitative yields, except for the polymerization of 1 with W catalyst. Rh-based poly(1) showed UV-Vis absorption in the longer wavelength region than Rh-based poly(2). W-based poly(2) showed an absorption band edge at a wavelength longer than the Rh-based polymer. W-based poly(2) emitted fluorescence at 375 run upon excitation at 291 nm, while the Rh-based compound emitted almost no fluorescence. The polymers exhibited new absorption around 360-600 nm based on electrochemically doped species by application of an external voltage. © 2007 WILEY-VCH Verlag GmbH & Co. KGaA.

DOI： 10.1002/macp.200600423

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：TAYLOR & FRANCIS INC  

L-Serine-based hydroxy group-containing phenylacetylene, N-(alpha-tert-butoxycarbonyl)-L-serine 4-ethynylphenylamide (1), and the hydroxy group-protected counterpart, N-(alpha-tert-butoxycarbonyl)-O-trimethylsilyl-L-serine 4-ethynylphenylamide (2) were polymerized with (nbd)Rh+[eta(6) -C6H5B-(C6H5)(3)] as a catalyst to obtain the corresponding polymers [poly(1) and poly(2)] with moderate molecular weights in good yields. The polarimetric and CD spectroscopic data indicated that poly(1) existed in a helical conformation in DNIF, MeOH, and THF; and that poly(2) also took a one-handed helical structure in CHCl3 and toluene in addition to these solvents. The helical tightness of poly(2) depended on the polarity of the solvents. Upon heating, poly(1) and poly(2) slightly decreased the CD intensity in DMF, MeOH and THF, while poly(2) increased it in toluene. The helical conformation of poly(1) and poly(2) was stable by adding cyclohexane to THF.

DOI： 10.1080/10601320601188091

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(S)- and (R)-1-methylpropargyl alcohols [(5)-1 and (R)-1] and their ester derivatives (S)- and (R)-1-methylpropargyl hexanoates [(5)-2 and (R)-2] were polymerized using (nbd)Rh+[η6-C6H 5B-(C6H5)3] as catalyst to afford the corresponding substituted polyacetylenes with moderate molecular weights in good yields. The polymers possessed cis-stereoregular structures according to 1H NMR. Large optical rotations and clear CD signals demonstrated that these polymers took a helical structure with predominantly one-handed screw sense, stabilized by steric repulsion between the side chains containing chiral groups adjacent to the main chain. © 2007 American Chemical Society.

DOI： 10.1021/ma0629642

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Novel acetylene monomers containing carbazole with chiral menthyl and bornyl groups, 9-(1R,2S,5R)-menthyloxycarbonyl-2-ethynylcarbazole (1), 9-(1S,2R,5S)-menthyloxycarbonyl-2-ethynylcarbazole (2), 9-(1R,2S,5R)-menthyloxycarbonyl-3-ethynylcarbazole (3) and 9-(1S)-bornyloxycarbonyl-2-ethynylcarbazole (4) were synthesized and polymerized with a Rh catalyst to give the corresponding polymers [poly(1)-poly(4)] with moderate Mn value of (11.5-92.2) × 103 in good yields (77-89%). CD spectroscopic studies revealed that poly(1), poly(2) and poly(4) took predominantly one-handed helical structure in CHCl3, THF, toluene, and CH2Cl2, while poly(3) did not. Addition of methanol to CHCl3 solutions of poly(1) and poly(2) resulted in the formation of aggregates showing smaller CD signals at 275 and 320 nm. The helical structure of poly(1) and poly(2) was very stable against heating. The polymers emitted fluorescence in 0.40-2.90% quantum yields. Poly(4) exhibited an obvious oxidation peak at 1.10 V. The polymers were thermally stable below 300 °C. © 2006 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.polymer.2006.11.042

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Diphenylacetylenes containing both siloxy groups and halogen or methyl substituents (p-tert-BuMe2SiOC6H4C{triple bond, long}CC6H3R2, R = m,p-Cl,Cl; m,m-Cl,Cl; m,p-Br,Br; m,m-Br,Br; m,p-Me,Me; m,m-Me,Me, 1a-f, respectively) were polymerized with TaCl5-n-Bu4Sn catalyst to give high molecular weight polymers (2a-f) in good yields. Free-standing membranes were fabricated by casting from toluene solution. Desilylation of these siloxy group-containing polymer membranes with trifluoroacetic acid (TFA) afforded poly(diphenylacetylene) membranes having hydroxy groups (3a-f). Polymers 2a-f were soluble in low polar solvents such as toluene and CHCl3, while 3a-f were insoluble in these solvents. According to thermogravimetric analysis (TGA), 2a-f and 3a-f exhibited high thermal stability (T0 ∼340 and ∼390 °C, respectively). The gas permeability of the halogen-containing polymer membranes was higher than that of methyl group-containing ones. The PCO2/PN2 permselectivity ratios of polymer membranes 3a-f were in the range of 14-49. The points of 3a-f in the PCO2 vs PCO2/PN2 plot were located obviously above Robeson's upper bound. © 2006 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.polymer.2006.11.007

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The copolymerization of diastereomeric pairs of N-propargylphosphonamidate monomers 1-3 ((1R,2S,5R)-HC{triple bond, long}CCH2NHP({double bond, long}O)R-O-menthyl, 1: R = CH3, 2: R = C2H5, 3: R = n-C3H7) carrying P- and C-chiral centers was carried out with (nbd)Rh+[η6-C6H5B-(C6H5)3] as a catalyst in CHCl3 for 24 h to afford the copolymers with number-average molecular weights ranging from 1400 to 12 000 in 65-85% yields. The cis contents of the copolymers were above 80%. The copolymers consisting of a pair of diastereomeric monomer units with a large diastereomeric excess showed a large specific rotation and an intense Cotton effect in CHCl3, indicating that they take a helical conformation with predominantly one-handed screw sense. On the other hand, the copolymer with a small diastereomeric excess showed a small specific rotation and a CD signal. The copolymerization of P-(R)-1 (1a) with an achiral N-propargylphosphoramidate monomer, HC{triple bond, long}CCH2NHP({double bond, long}O)(OPh)2 (4) was also carried out with various feed ratios. Among the obtained copolymers with various compositions, poly(1a95-co-45) showed the largest specific rotation and CD intensity in CHCl3, and poly(1a50-co-450) did so in THF. The copolymers decreased the CD intensity upon raising the temperature. © 2006 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.polymer.2006.11.017

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Novel L-alanine and L-glutamic acid derivatized, carbazole-containing N-propargylamides [N-(9-carbazolyl)ethyloxycarbonyl-L-alanine N'-propargylamide and N-(9-carbazolyl)ethyloxycarbonyl-L-glutamic acid-gamma-benzyl ester N'-propargylamide] were synthesized and polymerized with (nbd)Rh+[eta(6)-C6H5B-(C6H5)(3)] (nbd = norbornadiene) as a catalyst to obtain the corresponding polymers with moderate molecular weights in high yields. Polarimetry, circular dichroism, and ultravioletvisible spectroscopy studies revealed that both poly[N-(9-carbazolyl)ethyloxycarbonyl-L-alanine N'-propargylamide] and poly[N-(9-carbazolyl)ethyloxycarbonyl-L-glutamic acid-gamma-benzyl ester IT-propargylamide] took a helical structure with a predominantly one-handed screw sense in tetrahydrofuran, CHCl3, and CH2Cl2. The helix content of poly[N-(9-carbazolyl)ethyloxycarbonyl-L-alanine N'-propargylamide] could be tuned by heat or the addition of a protic solvent, and the helical sense of poly[N-(9-carbazolyl) ethyloxycarbonyl-L-glutamic acid-gamma-benzyl ester N'-propargylamide] was inverted by heat in CHCl3 or in mixtures of tetrahydrofuran and CH2Cl2. Poly[N-(9-carbazolyl) ethyloxycarbonyl-L-alanine N'-propargylamide] and poly[N-(9-carbazolyl)ethyloxycarbonyl-L-glutamic acid-gamma-benzyl ester N'-propargylamide] also took a helical structure in film states. They showed small fluorescence in comparison with the monomers and redox activity based on carbazole. (c) 2006 Wiley Periodicals, Inc.

DOI： 10.1002/pola.21769

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Diphenylacetylene containing siloxy and halogen/alkyl groups (P-t-BuMe2SiO-C6H4C{triple bond, long}CC6H4-p-X, X = Cl, Br, I, Me, Et, 1b-f, respectively) were polymerized with TaCl5-n-Bu4Sn catalyst to provide high molecular weight polymers (2b-f) in good yields. These polymers afforded tough free-standing membranes by casting from toluene solution. Desilylation of these siloxy-containing polymer membranes was carried out with trifluoroacetic acid to give membranes of poly(diphenylacetylenes) having hydroxy and halogen/alkyl groups (3b-f). Polymers 2b-f were soluble in nonpolar solvents such as cyclohexane, toluene, and THF, while polymers 3b-f were insoluble in these solvents. The oxygen permeability coefficients (PO2) of membranes 2b-f and 3b-f were in the range of 140-280 and 12-190 barrers, respectively. The gas permeabilities of most membranes (2b-e and 3b-f) were higher than those of the corresponding polymer membranes without halogen/alkyl substituents (2a and 3a), suggesting that introduction of small spherical groups (halogen and methyl) into the polymers 2a and 3a enhances gas permeability. The incorporation of halogen atoms into the present membranes was more effective to improve gas permeability than methyl and ethyl groups. The points of 3b-e in the PC O2 versus PC O2 / PN2 and PC O2 / PC H4 plots were located obviously above Robeson's upper bound. © 2006 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.memsci.2006.09.017

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

The novel chiral phenylacetylene (1) functionalized with an L-lysine-based dendritic peptide was synthesized and polymerized with Rh catalysts to afford the corresponding polymer [poly(1)] with moderate molecular weights in good yields. Poly(1) was soluble in common organic solvents including DMF, THF, CHCl3, AcOEt, and MeOH. The polarimetric and CD spectroscopic data indicate that poly(1) exists in a helical structure with predominantly one-handed screw sense in THF and CHCl3, Poly(1) also assumes a helical structure in the solid state. This helical structure can be tuned by heat in CHCl3 or by addition of a protic solvent to CHCl3 solutions.

DOI： 10.1002/macp.200600259

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Phenylacetylene (PA) derivatives having two polar groups (ester, 2a-d; amide, 4) or one cyclic polar group (imide, 5a-c) were polymerized using (nbd)Rh+[(η6-C6H5)B-(C6H5)3] catalyst to afford high molecular weight polymers (∼1 × 106- 4 × 106). The hydrolysis of ester-containing poly(PA), poly(2a), provided poly(3,4-dicarboxy-PA) [poly (8)], which could not be obtained directly by the polymerization of the corresponding monomer. The solubility properties of the present polymers were different from those of poly(PA) having no polar group; that is, poly(2a)-poly(2d) dissolved in ethyl acetate and poly(4) dissolved in N,N-dimethylformamide, while poly(PA) was insoluble in such solvents. Ester-group-containing polymers [poly(2a)-poly(2d)] afforded free-standing membranes by casting from THF solutions. The membrane of poly(2a) showed high carbon dioxide permselectivity against nitrogen (PCO2/PN2= 62). © 2006 Wiley Periodicals, Inc.

DOI： 10.1002/pola.21667

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Novel diphenylacetylene monomers 1c-h possessing tert-butyl or trialkylsilyl and siloxy groups (p-R-C6H4C{triple bond, long}CC6H4-p-OSiMe2t-Bu: 1c R = t-Bu, 1e R = SiMe3, 1g R = SiMe2t-Bu; p-R-C6H4C{triple bond, long}CC6H4-m-OSiMe2t-Bu: 1d R = t-Bu, 1f R = SiMe3, 1h R = SiMe2t-Bu) were polymerized with TaCl5-n-Bu4Sn catalyst. Monomers 1c and 1e gave high molecular weight polymers in good yields. Free-standing membranes of polymers 2c-f were fabricated by casting from toluene solution. Desilylation of membranes of polymers 2c and 2d with trifluoroacetic acid (TFA) yielded poly(diphenylacetylenes) having tert-butyl and hydroxy groups (3c and 3d). Polymers 2c-f and 2h were soluble in nonpolar solvents such as hexane, cyclohexane and toluene, while 3c and 3d were insoluble in these solvents. According to thermogravimetric analysis (TGA), 2c-f, 3c and 3d exhibited high thermal stability. The gas permeability of all the membranes in the present study was much higher than that of the corresponding polymers without bulky groups, indicating that incorporation of bulky groups into the polymers improves the gas permeability. The PCO2/PN2 permselectivity ratios of polymers 3c and 3d were 23 and 14, respectively. The CO2 permeability and CO2/N2 permselectivity of 3c and 3d were positioned above Robeson's upper bound line. © 2006 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.memsci.2006.06.001

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Novel acetylene monomers containing N-phenyl-substituted carbazole (Cz) and triphenylamine (TPA) groups, namely, 3-ethynyl-9-phenylcarbazole (1) and p-(N,N-diphenylamino)phenylacetylene (2) were synthesized, and polymerized with several Rh-, W-, and Mo-based catalysts. Poly(1) and poly(2) with high number-average molecular weights (15 500-974 000) were obtained in good yields (77-97%), when [(nbd)RhCl]2-Et3N (nbd = norbornadiene) was used as a catalyst. The polymers exhibited UV-vis absorption peaks derived from the Cz and TPA moieties at 250-350 nm and polyacetylene backbone above 350 nm. The UV-vis absorption band edge wavelengths of the polymers were longer than those of the corresponding monomers. Poly(2) exhibited a UV-vis absorption peak at a longer wavelength than poly(1) did, which indicates that poly(2) has main chain conjugation longer than that of poly(1). The molecular weights and photoluminescence quantum yields of the polymers obtained by the polymerization using [(nbd)RhCl]2-Et3N were larger than those of the Rh+(nbd)[η6-C6H5B-(C6H5)3]-based counterparts. The cyclic voltammograms of the polymers indicated that they had clear electrochemical properties; the onset oxidation voltage of poly(1) was higher than those of N-alkyl-substituted Cz derivatives. The polymers showed electrochromism and changed the color from pale yellow to blue by application of voltage, presumably caused by the formation of charged polaron at the Cz and TPA moieties. The temperatures for 5% weight loss of the polymers were around 350-420 °C under air, indicating the high thermal stability. © 2006 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.polymer.2006.07.064

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A diastereomeric pair of novel N-propargylphosphonamidates, HC≡CCH2NHP(=O)(CH3)O-L-menthyl was synthesized by the successive condensations of methylphosphonic dichloride with L-menthol and propargylamine. The (R)-P-isomer (1a) was isolated, and the absolute configuration was determined by XRD. Polymerization of 1a, and a mixture of 1a and (S)-P-isomer (1b) was carded out with a zwitterionic Rh complex as acatalyst. cis-Stereoregular polymers with number-average molecular weights of 5 600-9 800 were obtained in good yields. Poly(1a) and poly(1a 29-co-1b71) exhibited large specific rotations (+408 and -146°), and intense Cotton effects ([θ] = +2.25 and -0.9 × 104deg · cm2 · dmol-1) based on the conjugated polyacetylene backbone around 325 nm in CHCl3, indicating that these polymers have helical structures, whose predominant helical senses are opposite. © 2006 WILEY-VCH Verlag GmbH & Co. KGaA.

DOI： 10.1002/marc.200600347

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Novel diphenylacetylenes with both trimethylsilyl groups and other substituents (R2C6H3C{triple bond, long}CC6H4-p-SiMe3, R = m,p-Cl,Cl, m,m-Cl,Cl, m,p-Br,Br, m,m-Br,Br, m,p-Me,Me, m,m-Me,Me, 1a-f, respectively) were polymerized with TaCl5-n-Bu4Sn to produce solvent-soluble polymers (2a-f). Most polymers (2a-e) had high molecular weight over 1 × 106, and gave free-standing membranes by the solution casting method. Desilylation of these Si-containing polymer membranes was carried out with trifluoroacetic acid (TFA), which afforded solvent-insoluble desilylated polymer membranes (3a-e). According to thermogravimetric analysis (TGA), both Si-containing and desilylated polymers showed high thermal stability (T0 ≥ 420 °C). The fractional free volume (FFV) of both Si-containing and desilylated polymer membranes (2a-d, 3a-d) were fairly large (ca. 0.27-0.32), while the FFVs of membranes (2e, 3e) were rather small (0.28 and 0.24). The oxygen permeability coefficients (PO2) of 2a was as high as 5400 barrers, which is the largest among all the poly(diphenylacetylene) derivatives. Polymers 2b-d also exhibited high oxygen permeability, and their desilylated ones 3b-d retained similar high oxygen permeability. On the other hand, the PO2 values of 2e and 3e were 1200 and 530 barrers, respectively, which are smaller than those of the halogen-containing polymers (2a-d and 3a-d). © 2006 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.memsci.2006.02.030

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Poly(diphenylacetylene)s having various silyl groups are soluble in common solvents, from whose membranes poly(diphenylacetylene) membranes can be obtained by desilylation. The oxygen permeability coefficients of the desilylated polymers are quite different from one another (120-3300 barrers) irrespective of the same polymer structure. When bulkier silyl groups are removed, the oxygen permeability increases to larger extents. Poly[1-aryl-2-p-(trimethylsilyl) phenylacetylene]s are soluble in common solvents, and afford free-standing membranes. These Si-containing polymer membranes are desilylated to give the membranes of poly[1-aryl-2-phenylacetylenels. Both of the starting and desilylated polymers show very high thermal stability and high gas permeability. 1-Phenyl-2-p-(f-butyldimethylsiloxy)phenylacetylene polymerizes into a high-molecular-weight polymer. This polymer is soluble in common organic solvents to provide a free-standing membrane. Desilylation of this membrane yields a poly(diphenylacetylene) having free hydroxyl groups, which is the first example of a highly polar group-carrying poly(diphenylacetylene). The P CO2/PCH4 and PCO2/ PN2, permselectivity ratios of poly(l-phenyl-2-p-hydroxylphenylacetylene) membrane are as large as 47.8 and 45.8, respectively, while keeping relatively high PCO, of 110 barrers. © 2006 Wiley Periodicals, Inc.

DOI： 10.1002/pola.21622

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The chiroptical properties of poly((S)-N-(3-butynyl)-3-methylpentanamide) (poly(1)) were studied, and the conformation was analyzed. Poly(1) exhibited a large specific rotation and Cotton effect in CHCl3, indicating that it took a helical structure with predominantly one-handed screw sense. From liquid state IR spectroscopic analysis along with molecular mechanics and semiempirical molecular orbital calculations, it was concluded that the helix was stabilized by intramolecular hydrogen-bonding strands between the amide groups of nth and (n+3)th units. © 2006 NIMS and Elsevier Ltd.

DOI： 10.1016/j.stam.2006.04.013

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Amino acid-derived novel norbornene derivatives, N,N '-(endo-bicyclo[2.2.1] hept-5-en-2,3-diyldicarbonyl) bis-L-alanine methyl ester (NBA), N, N '-(endo-bicyclo[2.2.1] hept-5-en-2,3-diyldicarbonyl) bis-L-leucine methyl ester (NBL), N,N '-(endo-bicyclo[2.2.1] hept-5-en-2,3-diyldicarbonyl) bis-L-phenylalanine methyl ester (NBF) were synthesized and polymerized using the Grubbs 2nd generation ruthenium (Ru) catalyst. Although NBA, NBL, and NBF did not undergo homopolymerization, they underwent copolymerization with norbornene (NB) to give the copolymers with M. ranging from 5200 to 38,100. The maximum incorporation ratio of the amino acid-based unit was 9%, and the cis contents of the main chain were 54-66%. (c) 2006 Wiley Periodicals, Inc.

DOI： 10.1002/pola.21580

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

2,2,6,6-Tetramethylpiperidine 1-oxyl (TEMPO)containing N-propargylamide HC=CCH2NHCO-4-TEMPO (1), propargyl ester HC=CCH2OCO-4-TEMPO (2), phenylacetylene derivative HC=CC6H3-3,4-(CO2-4-TEMPO)(2) (3), and norbornene diester monomers, NB-2,3-exo,exo-(CH(2)OCO4-TEMPO)(2) (4), NB-2,3-endo,exo-(COO-4-TEMPO)(2) (5a), NB-2,3-endo,endo-(COO-4-TEMPO)(2) (5b) (NB = norbornorbornene, TEMPO= 2,2,6,6-tetramethyl-1-piperidinyloxyl) were synthesized and polymerized with rhodium and ruthenium catalysts. Monomers 2, 5a, and 5b gave polymers with number-average molecular weights of 47000-185000 in 59-100% yields, while 1, 3, and 4 gave polymers insoluble in common organic solvents in 88-100% yields. The capacities of cells fabricated with poly(l), poly(2), and poly(3) were 67, 82, and 23 Ah . kg(-1) based on the weight, respectively. The capacity of poly(5a)-based cell reached the theoretical value (109 Ah . kg(-1)) of the polymer.

DOI： 10.1002/marc.200600286

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

A glutamic acid- and azobenzene-containing novel N-propargylamide, (S)-CH{triple bond, short}CCH2NHCOCH(CH2CH2CO2CH2C6H5)NHCO2CH2CH2-p-C6H4N{double bond, short}NC6H5 (1) was synthesized and polymerized with (nbd)Rh+[η6-C6H5B-(C6H5)3] as a catalyst to obtain the corresponding polymer [poly(1)] with the moderate number-average molecular weight of 12,200 in 93% yield. The chiroptical studies revealed that poly(1) took a helical structure in THF, CHCl3, CH2Cl2 and toluene. Poly(1) underwent solvent and heat-driven helix-helix transition. The trans-azobenzene of the side chain isomerized into cis upon UV-irradiation, accompanying decrease in helicity. The cis-azobenzene moiety reisomerized into trans upon visible-light irradiation, while the polymer did not recover the original helicity. © 2006 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.polymer.2006.02.022

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER SCI LTD  

Pyrene-functionalized chiral N-proparaylamide, (R)-HC=-CCH2NHCOCH(CH3)O-1,4-C6H4-OCO(CH2)(3)-1-pyrenyl (1) was polymerized with (nbd)Rh+[eta(6)-C6H5B-(C6H5)(3)] as a catalyst to obtain the corresponding polymer with a moderate weight in a good yield. Poly(l) was soluble in CHCl3. CH2Cl2, and THF The polarimetric and CD spectroscopic data indicated that poly(1) existed in a helical structure with predominantly one-handed screw sense in these solvents. The helical structure was stable upon heating and addition of MeOH. Poly(l) showed very large excimer-based fluorescence compared with 1. (c) 2006 Published by Elsevier Ltd.

DOI： 10.1016/j.polymer.2005.10.132

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Diphenylacetylenes possessing fluorine atom(s) and a siloxy group (1c-i) were polymerized with TaCl 5-n-Bu 4Sn. Monomers 1c-f having a siloxy group at the para position of a phenyl ring produced high molecular weight polymers (2c-f) in good yields. These polymers afforded tough free-standing membranes by casting their toluene solution. Desilylation of the polymer membranes was carried out with trifluoroacetic acid to give membranes of poly(diphenylacetylenes) having fluorine atoms and hydroxyl groups (3c-f). Polymers 2c-f were soluble in various organic solvents such as toluene, CHCl 3, and THF, while polymers 3c-f were insoluble in these solvents. All the polymers 2c-f and 3c-f exhibited high thermal stability. The gas permeability of most membranes in the present study (2d-f and 3c-f) were higher than those of the corresponding polymers without fluorine atoms (2a and 3a), indicating that incorporation of fluorine atoms into the polymers enhances gas permeability. The P CO2/P N2 permselectivity ratios of polymers 3c-f were as large as 36-48, and the points of 3c-f in the P CO2 vs P CO2/P N2 plot were located above Robeson's upper bound. © 2006 American Chemical Society.

DOI： 10.1021/ma052082n

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

Novel optically active amino acid based polyacetylenes bearing eugenol and fluorene moieties were synthesized, and their properties, including chiroptical ones, were analyzed. N-[1-(3,4-Dimethoxyphenyl)-2-propyloxycarbonyl]-L-alanine N′-propargylamide (1), N-[1-(3,4-dimethoxyphenyl)-2-propyloxycarbonyl]-L- alanine propargyl ester (2), N-(9-fluorenylmethoxycarbonyl)-L-alanine N′-propargylamide (3), and N-(9-fluorenylmethoxycarbonyl)-L-alanine propargyl ester (4) were polymerized with a rhodium-zwitterion catalyst in tetrahydrofuran to afford the corresponding polymers with moderate molecular weights ranging from 10,800 to 17,300 in good yields. Because of the large specific rotation and circular dichroism (CD) signal, it was concluded that the poly(N-propargylamide)s [poly(1) and poly(3)] took a helical structure with a predominantly one-handed screw sense. The solvent and temperature could tune the helical structure of poly(1). On the other hand, the poly(propargyl ester)s [poly(2) and poly(4)] exhibited only small specific rotations and CD signals. © 2005 Wiley Periodicals, Inc.

DOI： 10.1002/pola.21215

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Para-substituted 1-chloro-2-phenylacetylenes [ClC≡CC 6H4-p-R; R = F (1), Cl (2), Me (3), Br (4), I (5), CF 3 (6), SiMe3 (7), SiEt3 (8), Si(n-Pr) 3 (9), and Si(i-Pr)3 (10)] were polymerized with a catalyst generated by UV irradiation of Mo(CO)6 in CCl4 to provide the corresponding polymers. The formed polymers except poly(5) were soluble in common organic solvents and afforded free-standing membranes by the casting method except for poly(10) whose molecular weight was rather low. Compared to poly(1-chloro-2-phenylacetylene) (PCPA), all the polymers in this study exhibited high gas permeability. As the size of para-substituents increased, both the fractional free volume (FFV) and gas permeability increased and then decreased. Consequently, poly(6), which has a relatively bulky CF 3 group, showed the largest FFV (0.258) and the highest gas permeability (Po2 = 280 barrers). Poly(9) and poly(10) were more gas-permeable than PCPA despite their small FFV values and showed large diffusion coefficients, which might be due to large local mobility of the substituents. © 2006 American Chemical Society.

DOI： 10.1021/ma0519819

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掲載種別：研究論文（国際会議プロシーディングス）  

Novel chiral N-propargylphosphonamidate monomers 1-4 were synthesized and polymerized. The obtained polymers exhibited intense Cotton effect at the region of the absorption of polyacetylene backbone, indicating that they took a helical structure with predominantly one-handed screw sense.

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記述言語：日本語   掲載種別：研究論文（学術雑誌）   出版者・発行元：SOC POLYMER SCIENCE JAPAN  

The secondary structures of poly (N-propargylamides) were examined by the helical wormlike touched-bead model theory, molecular mechanics, and molecular orbital calculations along with exciton chirality method. The main-chain double bonds are slightly twisted from coplanarity to form a loose helix. Hydrogen bonds seem to be formed between the n th and (n + 2) th repeating units, giving two helically arranged hydrogen-bond strands around the helical backbone. The secondary structures of poly (N-alkynylamides) are influenced by the position of the chiral center and that of the amide group. The position of the chiral center mainly affects the helical pitch, which becomes short when the chiral center is positioned away from the main chain. The stability of the helical structure is also influenced by the position of the amide group. It is concluded that poly (N-propargylamides) with left-handed helical main chains display a minus Cotton effect around 390 nm.

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掲載種別：研究論文（国際会議プロシーディングス）  

N-Propargylamides 1-4 bearing phenyl groups were polymerized with a rhodium catalyst in chloroform to obtain the corresponding polymers with molecular weights in good yields. Although poly(2) only showed a weak Cotton effect, poly(1), poly(3) and poly(4) showed an intense Cotton effect at 383, 332 and 344 nm, respectively (Fig. 1). This result indicates that poly(1), poly(3) and poly(4) adopt a helical conformation with predominantly one-handed screw sense. Therefore, polymers with the substituent groups which provide steric repulsion form a helical conformation with predominantly one-handed screw sense. Furthermore, the λmax of poly(1) was observed at a wavelength longer than that of poly(4) by 51 nm, and the λmax of poly(4) was longer than that of poly(3) by 12 nm which indicates that poly(1) forms a looser helix than poly(4), and poly(4) forms a looser helix than poly(3), resulting in longer conjugation length.

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掲載種別：研究論文（国際会議プロシーディングス）  

N-Butynylamides 1-5 having various substituents were polymerized with [(nbd)RhCl]2-Et3N in CHCl3 to afford cis-stereoregular poly(N-butynylamides) with moderate molecular weights. CD and IR spectroscopic studies revealed that the polymers took helical conformation stabilized by intramolecular hydrogen bonds between the pendant amide groups in CHCl3. The helical structure of poly(1)-poly(3) was more stable to heating than that of the corresponding poly(N-propargylamides) reported so far. In contrast, poly(4) having bulky lactone moieties changed its helical pitch according to temperature. The helical structure of poly(2) having longer alkyl chain was more stable to the addition of methanol than that of poly(1). The persistence length of poly(N-butynylamides) was nearly the same as that of poly(N-propargylcarbamates), but shorter than that of poly(N-propargylamides).

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掲載種別：研究論文（国際会議プロシーディングス）  

N-Propargylamides 1-3 bearing benzene rings were polymerized with a rhodium catalyst in chloroform to obtain the corresponding polymers with molecular weights in good yields. Although poly(1) only showed a weak Cotton effect, poly(2) and poly(3) showed an intense Cotton effect at 332 and 344 nm, respectively (Fig. 1). This result indicates that poly(2) and poly(3) adopt a helical conformation with predominantly one-handed screw sense. The intensity of Cotton effect of poly(3) was larger than that of poly(2). It seems that poly(3) forms a helix more effeciently. Furthermore, the 0λmax of poly(3) was observed at a wavelength longer than that of poly (2) by 12 nm, which indicates that poly(3) forms a looser helix than poly(2), resulting in longer conjugation length.

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

The effect of hydroxyl group on the secondary structure of serine-based helical polyacetylenes was investigated. The structures of the polymers were examined by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy. It was found that derivating from the two conformers, the distance between the pendent groups becomes longer. It was confirmed that the hydroxyl groups greatly affect the secondary structures of the polymers, which was supported by liquid-state IR and molecular modeling studies.

DOI： 10.1021/ma051869a

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CHEMICAL SOC JAPAN  

An (L)-threonine-based helical poly(N-propargylamide)-Ru complex was synthesized, and used as a catalyst for hydrogen- transfer reaction of ketones. The enantiomeric excess (ee) values of the formed alcohols ranged from 12 to 36%. On the other hand, an Ru complex with a low-molecular-weight model ligand gave an alcohol with ee as low as 1.8%.

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Optically active N-propargylamides bearing a porphyrin group, (S)-HC=CCH2NHCOCH-(CH3)OCOR (1) and (S)-HC≡CCH 2NHCOCH(Ph)OCOR (2), where R = 4-(10,15,20-tris(4-tert-butylphenyl)- porphyrin-5-yl)phenyl, were polymerized with (nbd) Rh+[η6-C6H5B-(C 6H5)3] along with analogous monomers (S)-HC≡CCH2NHCOCH(CH3)OCOC6H 4-p-tert-Bu (3) and (S)-HC≡CCH2NHCOCH(Ph)OCOC 6H4-p-tert-Bu (4) for comparison to afford the corresponding polymers with moderate molecular weights (Mn = 17 000-24 000) in 28-76% yields. The 1H NMR spectra demonstrated that the resulting polymers had fairly stereoregular structures (cis content = 78-97%). CD and UV-vis spectroscopic studies revealed that poly(1)-poly(4) took one-handed helical structure. The relationship between the screw sense of poly-(N-propargylamides) and the sign of Cotton effect originating from the main chain was elucidated by comparison of the Cotton effects of either poly(1) and poly(3) or poly(2) and poly(4). It was concluded on the basis of the exciton chirality method along with molecular modeling study that the pendent porphyrins of poly(1) and poly(2) form right-handed helical arrays and that the main chains form a right-handed helix. © 2005 American Chemical Society.

DOI： 10.1021/ma051884f

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

Aspartic acid-based novel poly(TV-propargylamides), i.e., poly[N-(α-tert-butoxycarbonyl)-L-aspartic acid β-benzyl ester N'-propargylamide] [poly(1)] and poly[N(α-text-butoxycarbonyl)-L-aspartic acid α-benzyl ester N'-propargylamide] [poly(2)] with moderate molecular weights were synthesized by the polymerization of the corresponding monomers 1 and 2 catalyzed with (nbd)Rh+[η6-C6H 5B-(C6H5)3] in CHCl 3 at 30 °C for 2 h in high yields. The chiroptical studies revealed that poly(1) took a helical structure in DMF, while poly(2) did not in DMF but did in CH2Cl2 CHCl3, and toluene. The helicity of poly(1) and poly(2) could be tuned by temperature and solvents. Poly(2) underwent solvent-driven switch of helical sense, accompanying the change of the tightness © 2005 Wiley Periodicals, Inc.

DOI： 10.1002/pola.21001

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

Cyclopolymerization of amino acid-derived novel dipropargyl ester and dipropargylamide was carried out using a rhodium catalyst. Polymers with cyclized structures were obtained under certain conditions. The dipropargylamide polymer exhibited a large specific rotation and an intense Cotton effect around 300 nm based on the chiral higher order structure. It adsorbed N-benzyloxycarbonyl-L-alanine more than the D-isomer, and extracted Li +, Na+, K+, and Cs+ from water phase into CH2Cl2 phase. © Springer-Verlag 2005.

DOI： 10.1007/s00289-005-0445-7

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

L-Aspartic and L-glutamic acid-based novel N-propargylamides, (S)-HC≡CCH2NHCOCH(CH2COOcyclohexyl)NHCOOt-Bu (1) and (S)-HC≡CCH2NHCOCH(CH2CH2COOcyclohexyl) NHCOOt-Bu, were synthesized and polymerized using a rhodium catalyst. The corresponding polymers [poly(1) and poly(2)] with moderate molecular weights were obtained in good yields. CD and UV-vis spectroscopic analyses revealed that poly(1) and poly(2) took helical structures, whose tightness was different. The presence of intramolecular hydrogen bonding was confirmed by liquid-state IR spectroscopy. Poly(1a) and poly(2a) carrying free carboxyl groups were obtained by alkaline hydrolysis of poly(1) and poly(2). Poly(1a) did not form a helix, while poly(2a) formed a helix undergoing inversion of helical sense and change of tightness upon addition of KOH. © 2005 American Chemical Society.

DOI： 10.1021/ma051529p

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The polymerization of various silyl- and F-containing diphenylacetylenes (1a-k) with TaCl 5-n-Bu 4Sn provided high-molecular-weight polymers. Most polymers (2a-d, 2g, and 2h) were totally soluble in common organic solvents and afforded tough free-standing membranes by casting from toluene solution, while some polymers (2e, 2f, and 2i-k) were insoluble in any organic solvents. The onset temperatures of weight loss of polymers 2a-d in air were over 400°C, indicating very high thermal stability. The membranes of 2a-d were desilylated with trifluoroacetic acid to give desilylated polymer membranes 3a-d, which were insoluble in any solvents. The fractional free volumes (FFV) of the present membrane-forming trimethylsilyl and/or F-bearing polymers (2a-d and 3a-d) were ca. 0.28-0.31 and appreciably large, and they showed very high permeability (ca. 1400-14 000 barrers) to the six gases examined. The oxygen permeability coefficient (P o2) of 2a was as high as 2900 barrers, which is about twice that of poly[1-(p-trimethylsilyl)phenyl- 2-phenylacetylene]. The incorporation of F atoms into both poly[1-(p- trimethylsilyl)phenyl-2-phenylacetylene] and poly(diphenylacetylene) generally enhanced gas permeability. © 2005 American Chemical Society.

DOI： 10.1021/ma051445g

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

Poly(N-(α-tert-butoxycarbonyl)-L-aspartic acid β-cyclohexyl ester N′-propargylamide) [poly(1)] was synthesized by the polymerization of the corresponding monomer 1 catalyzed by (nbd) Rh+[η6-C6H5B-(C 6H5)3] in CH2Cl2 at 30°C for 2 h. Poly(1) was soluble in CH2Cl2, CHCl3, THF, and partly soluble in DMF. The specific rotation, CD, and UV-vis spectroscopic data revealed that poly(1) exists in a helical structure in CH 2Cl2, CHCl3, CHCl3/DMF, and CHCl3/MeOH, Poly(1) underwent thermo- and solvent-driven switch of helical sense, accompanying the change of tightness. © 2005 WILEY-VCH Verlag GmbH &amp
Co.

DOI： 10.1002/macp.200500129

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Optically active N-alkynylamides (S)-HC≡C(CH2) aNHCO(CH2)bCH(CH3)CH 2CH3 (1: a = 1, b = 0; 2: a = 1, b = 1; 3: a = 1, b = 2; 4: a = 1, b = 3; 5: a = 2, b = 0; 6: a = 2, b = 1; 7: a = 3, b = 0), having several numbers of methylene spacers between the ethynyl group and chiral carbon or amide group, and (S)-HC≡C(CH2)2OCOCH 2CH(CH3)CH2CH3 (8) were polymerized with (nbd)Rh+[η6-C6H5B --(C6H5)3] to afford the corresponding polymers with moderate molecular weights (Mn = 11 000-21 000) in 67-99% yields. The 1H NMR spectra demonstrated that the resulting polymers had stereoregular structures (cis content = 79-100%). CD, UV-vis, and IR spectroscopic studies revealed that the position of the amide group and chiral center strongly affects the pitch and stability of helical structure of the polymers, and intramolecular hydrogen bonding is formed between the amide groups in CHCl3. By comparison with the results of CD measurements and molecular orbital calculation, the sign of Cotton effect and the relationship between the screw sense of poly(N-propargylamides) was elucidated. © 2005 American Chemical Society.

DOI： 10.1021/ma050313k

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N-Propargylbenzamides 1-7 were polymerized with (nbd)Rh+[η 6-C6H5B-(C6H 5)3] to afford polymers with moderate molecular weights (Mn = 26000-51000) in good yields. The 1H NMR spectra demonstrated that the polymers have fairly stereoregular structures (81-88% cis). The optically active polymers, poly(1) and poly(2), were proven by their intense CD signals and large optical rotations to adopt a stable helical conformation with an excess of one-handed screw sense when heated in CHCl 3 or toluene. The sign of Cotton effect could be controlled by varying the content in the copolymers of either chiral bulky 1 and achiral nonbulky 3, or chiral nonbulky 2 and achiral bulky 7. The smaller the pendant group in the copolymerization of achiral monomers with 1, the more easily did the preferential helical sense change with the copolymer composition. However, the copolymers of chiral nonbulky 2 and achiral nonbulky 3 did not change the helical sense, irrespective of the composition. The free energy differences between the plus and minus helical states, as well as the excess free energy of the helix reversal, of those chiral-achiral random copolymers were estimated by applying a modified Ising model. © 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOI： 10.1002/chem.200401009

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Polymerization of several diphenylacetylene derivatives was carried out by using TaCl 5-n-Bu 4Sn as catalyst. C 6H 5C≡CC 6H 4-p-OSi(CH 3) 2t-Bu (3a) and C 6H 5C≡CC 6H 4-m-OSi(CH 3) 2t-Bu (3b) provided the corresponding polymers (poly(3a), poly(3b)) with high molecular weights in good yields, while p-t-Bu(CH 3) 2SiOC 6H 4C≡CC 6H 4-p-OSi(CH 3) 2t-Bu(3c), p-t-Bu(CH 3) 2SiOC 6H 4C≡CC 6H 4-m-OSi(CH 3) 2t-Bu (3d), and m-t-Bu(CH 3) 2SiOC 6H 4C≡CC 6H 4-m-OSi(CH 3) 2t-Bu (3e) did not satisfactorily. Desilylation of poly(3a) and poly(3b) membranes catalyzed by trifluoroacetic acid yielded poly(diphenylacetylenes) having free hydroxyl groups [poly(4a), poly(4b)], which are the first examples of highly polar group-carrying poly(diphenylacetylenes). Poly(3a) and poly(3b) dissolved in nonpolar solvents such as toluene and chloroform, while poly(4a) and poly(4b) were insoluble in these solvents. According to TGA in air, poly(3a) and poly(3b) were thermally fairly stable among substituted polyacetylenes, and poly(4a) and poly(4b) displayed even higher thermal stability. The P CO2/P CH4 and P CO2/P N2 permselectivity ratios of poly(4a) and poly(4b) membranes were as large as 13-46, while keeping relatively high P CO2 values. © 2005 American Chemical Society.

DOI： 10.1021/ma050566d

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cis-Stereoregular poly(N-propargylcarbamates) [poly(1)-poly(6)] were synthesized by the polymerization of the corresponding monomers [1: (S)-CH≡CCH2NHCOOCH(CH3)CH2CH 3;2: (S)-CH≡ CCH2NHCOOCH2CH(CH 3)CH2CH3; 3: (S)-CH≡CCH 2NHCOOCH2CH2CH(CH3)CH 2CH3; 4: (S)-CH≡ CCH2NHCOOCH 2CH2CH2CH(CH3)CH2CH 3; 5: (S)-CH≡CCH2NHCOOCH(CH3)CH 2CH2CH2CH2CH3; 6: (S)-CH≡CCH2NHCOOCH(CH3Ph] with a rhodium catalyst. Poly(2)-poly(6) took helical structure stabilized by intramolecular hydrogen bonding. They changed the conformation with temperature and addition of a polar solvent. Effects of the distance between the chiral center and main chain and the phenyl group were examined. 1H NMR and CD spectroscopic analyses revealed that the closer the distance between the chiral center and main chain, the more stable the helix and the rigid the polymer, i.e., poly-(5) > poly(2) > poly(3) > poly(4). When the distance between the chiral center and main chain was the same, the polymer without phenyl groups [poly(5)] was more rigid than the one with phenyl groups [poly-(6)], and the helical structure of the former was more stable. © 2005 American Chemical Society.

DOI： 10.1021/ma0502248

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Diphenylacetylenes having various silyl groups (PhC≡CC 6H4-SiR1R2R3, SiR 1R2R3 = p-SiMe3, p-SiMe 2i-Pr, p-SiEt3, p-SiMe2n-C8H 17, p-SiMe2n-C18H37, m-SiMe 3, m-SiMe2t-Bu, la-g, respectively) were polymerized with TaCl5-n-Bu4Sn catalyst to provide high molecular weight polymers. The formed polymers (2a-g) afforded tough free-standing membranes by casting from toluene solution. Desilylation of these Si-containing polymer membranes was carried out with trifluoroacetic acid. Para-substituted polymers (2a-e) underwent desilylation completely, while meta-subustituted polymers (2f and 2g) did not. According to thermogravimetric analysis (TGA), both Si-containing and desilylated polymers exhibited high thermal stability, and all the desilylated polymers showed practically the same onset temperature (∼480°C) of weight loss. The membranes of Si-containing polymers showed lower oxygen permeability as the silyl group became bulkier. The oxygen permeability coefficients (P(O2) 120-3300 barrers) of desilylated polymer membranes were quite different from each other irrespective of the same polymer structure. When bulkier silyl groups were removed, the oxygen permeability increased to larger extents. In ethanol/water pervaporation, both Si-containing and desilylated polymer membranes showed ethanol permselectivity, indicating that these membranes possess large excess free volumes. © 2005 American Chemical Society.

DOI： 10.1021/ma047632g

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER SCI LTD  

Homo- and copolymerizations of chiral amino acid-based N-propargylamides, i.e., N-(tert-butoxycarbonyl)-L-alanine N-t-propargylamide (LA) and N-(trifluoroacetyl)-L-valine N-t-propargylamide (FLV), were conducted with (nbd)Rh+[eta(6)-C6H5B-(C6H5)(3)] as a catalyst to afford the corresponding copolymers with moderate molecular weights in good yields. The CD and UV-Vis spectra showed that poly(LA) and poly(FLV) take helical structures with predominantly one-handed helices, whose CD signs are opposite. The helices of the homopolymers could be tuned by temperature and solvent. The specific rotation, CD and UV-Vis spectra showed that some of the copolymers underwent temperature- and solvent-induced helix inversion. (c) 2005 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.polymer.2005.02.072

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N-Propargyl-2-methyloctanamide, (1), N-propargyl-2-ethyloctanamide, (2), and N-propargyl-2-propyloctanamide, (3) were polymerized with (nbd)Rh +[η6-C6H5B--(C 6H5)3] as a catalyst to obtain the polymers with moderate molecular weights (Mn̄ = 15 000-57 000). The 1H NMR spectra demonstrated that the polymers had a stereoregular structure (cis = 100%). The polymers were proven to take a helical conformation with an excess of one-handed screw-sense in CHCl3, which was supported by their intense CD signals and large specific rotations. The signs of Cotton effects of poly(2) and poly(3) were dependent on the solvents used for CD measurement, while that of poly(1) was independent of the solvents. In CHCl3/THForCHCl3/toluene mixtures, the sign of Cotton effect of poly(2) was inverted with changing the solvent composition at 20°C, and the Cotton effects of poly(2) in CHCl3/toluene = 70/30 and CHCl3/THF = 80/20 were largely influenced by temperature. From the filtration and light scattering experiments of poly(2), the CD sign inversion was proved to be the screw sense inversion. © 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOI： 10.1002/macp.200400402

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掲載種別：研究論文（国際会議プロシーディングス）  

Optically active N-alkynylamides, (S)- HC=C(CH2) aNHCO(CH2)bCH(CH3)CH 2CH3 (a = 1-3, b = 0-3) having several numbers of methylene spacers between the ethynyl group and chiral carbon or amide group were polymerized with (nbd)Rh+[776-C6H5B - (C6H5)3] to afford the corresponding polymers with moderate molecular weights (Mn= 11 000-21 000) in 67-99% yields. The 1H NMR spectra demonstrated that the resulting polymers had stereoregular structures (cis content = 79-100%). CD, UV-vis, and IR spectroscopic studies revealed that the position of the amide group and chiral center strongly affects the pitch and stability of helical structure of the polymers, which intramolecular hydrogen bonding is always formed between the amide groups in CHCl3. By comparison with the results of CD measurements and molecular orbital calculation, the relationship between the sign of Cotton effect and the screw sense of poly(N-propargylamides) was elucidated.

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掲載種別：研究論文（国際会議プロシーディングス）  

Optically active N-alkynylamides, (S)-HC≡C(CH2) aNHCO(CH2)bCH(CH3)CH 2CH3 (a = 1-3, b = 0-3) having several numbers of methylene spacers between the ethynyl group and chiral carbon or amide group were polymerized with (nbd)Rh+[η6-C6H 5B-(C6H5)3] to afford the corresponding polymers with moderate molecular weights (Mn = 11 000-21 000) in 67-99% yields. The 1H NMR spectra demonstrated that the resulting polymers had stereoregular structures (cis content = 79-100%). CD, UV-vis, and IR spectroscopic studies revealed that the position of the amide group and chiral center strongly affects the tightness and stability of helical structure of the polymers, where intramolecular hydrogen bonding is always formed between the amide groups in CHCl3. By comparison with the results of CD measurements and molecular orbital calculation, the relationship between the sign of Cotton effect and the screw sense of poly(N-propargylamides) was elucidated.

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掲載種別：研究論文（国際会議プロシーディングス）  

In general, polymers carrying carbazole in the side chain or main chain exhibit photoconductivity photoluminescence, and electroluminescence, The present study deals with the polymerization of 9-t-butoxycarbonyl-(2 or 3)-ethynylcarbazole (1 or 2) and 9-((S)-2-methylbutoxycarbonyl)-(2 or 3)-ethynylcarbazole (8 or 4), with Rh and W catalysts, and examination of properties of the formed polymers, Poly(1)-poly(4) with high Mn (>100,000) were obtained in good yields (80-99%), They exhibited UV-vis absorption derived from the carbazole moiety and polyacetylene backbone, Poly(3) displayed intense CD signals in toluene, which indicates that it forms helix with predominantly one-handed screw sense.

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掲載種別：研究論文（国際会議プロシーディングス）  

We have reported that polyacetylenes carrying carbazole in the side chain exhibit photoconductivity, photoluminescence, and electroluminescence. The present study deals with the polymerization of 9-t-butoxycarbonyl-3- ethynylcarbazole, with an Rh catalyst, and examination of the properties of the formed polymers. Poly(1) with high Mn (>100,000) was obtained in good yields (80-99%) by the polymerization both in CH2Cl2 and THF. It exhibited UV-vis absorption maxima at 291 and 431 nm, and emission peaks at 314-315 and 354 nm or 404 nm by excitation at 291 nm in THF.

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Five novel N-propargylacetamide and -propaneamide monomers [HC≡CCH2NHCOR; 4: R = CH2C6H5, 5: R = CH(C6H5)26: R = CH2CH2C6H5, 7: R = CH2CH(C6H5)2, 8: R = CH2C(C6H5)3] were polymerized with a rhodium catalyst, (nbd)R+B-(C6H5)4(nbd = 2,5-norbornadiene), to provide polymers in 81-99% yields. Poly(4), poly(5), and poly(8) possessed low molecular weights (Mn= 3100-6100), presumably due to their low solubility in solvents, while poly(6) and poly(7) had moderate Mn's (15 000 and 16 700) and good solubility in several solvents including chloroform. The secondary structures of the five polymers in chloroform were investigated by UV-vis spectroscopy. Poly(4) adopted a helical structure to a certain extent, while poly(5)-poly(7) hardly did not. In contrast, poly(8) exhibited a UV-vis absorption peak around 365 nm, demonstrating that it invariably formed helices under the given conditions. Copolymers of monomer 8 with either chiral monomer 10 [HC≡CCH2NHCOCH(CH3)CHI2-CH3] or achiral monomers 1 [HC≡CCH2NHCOC(CH3)2C6H5] and 9 [HC≡CCH2NHCO(CH2)5CH3], i.e., poly(8-co-10)s, poly(8-co-1)s, and poly(8-co-9)s, showed good solubility and possessed higher Mn's than that of poly(8). Furthermore, with the increase of unit 8 in poly(8-co-10)s, poly(8-co-1)s, and poly(8-co-9)s, initial blue and then red shifts were observed in the λmaxof their UV-vis spectra and further in the CD signal of poly(8-co-10)s, demonstrating that all of these copolymers formed helices with different pitches, which depended on the compositions of the copolymers. Additionally, the sergeants and soldiers rule was observed in achiral/chiral poly(8-co-10)s.

DOI： 10.1021/ma048177r

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

Serine- and threonine-based acetylene monomers carrying hydroxyl group, N-tert-butoxycarbonyl-L-serine N′-propargylamide (1), N-teri- butoxycarbonyl-L-threoine N′-propargylamide (2), and their O-silylated monomers, N-tert-butoxycarbonyl-O-triethylsilyl-L-serine N′-propargylamide (8) and N-tert-butoxycarbonyl-O-triethylsilyl-L-threonine N′- propargylamide (4), were polymerized with a rhodium zwitterion catalyst in THF, MeOH, CH2Cl2, and toluene to afford the corresponding optically active poly-N-propargylamides) with moderate number-average molecular weights (4200-12 800) in good yields. The polymers exhibited large specific rotations (-172° to -955°) and clear CD signals at the absorption region of polyacetylene main chains. The CD signals of poly(1) and poly(2) appeared around 270-350 nm, while those of poly(3) and poly(4) appeared around 400 nm. It is considered that these polymers take helical structures with predominantly one-handed screw sense, whose helical pitches are different. The presence of intramolecular hydrogen bonding of poly(1) and poly(2) was confirmed by IR spectroscopy measured in CHCl3. Desilylation of poly(3) and poly(4) satisfactorily proceeded to afford the polymers exhibiting the same CD spectroscopic patterns as those of poly(1) and poly(2).

DOI： 10.1021/ma048391f

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Copolymerizations of 1-pyrenebutyric acid N-propargylamide (PY) with chiral amino acid-based N-propargylamides, N-(tert-butoxycarbonyl)-L-valine-N-propargylamide (LV) and N-(tert-butoxycarbonyl)-D-alanine-N-propargylamide (DA) were conducted with (nbd)Rh+[eta(6)-C6H5B-(C6H5)(3)] as a catalyst to obtain novel pyrene-functionalized helical poly(N-propargylamides). The controllable secondary structure of the copolymers by various compositions of the chiral amino acid units or solvent environment led to a controlled orientation of the side-chain pyrene. For instance, poly(PY30-co-LV70) exhibited a large specific rotation and a CD signal, while it emitted very weak fluorescence. On the other hand, poly(PY30-co-LV35-co-DA(35)) exhibited a small specific rotation and a CD signal, while it emitted fluorescence eight times larger than poly(PY30-co-LV70) did. The CD signal disappeared by the addition of MeOH to a THF solution of poly(PY30-co-LV70), while the fluorescence intensity increased.

DOI： 10.1021/ma048833n

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Copolymerizations of structurally different chiral amino acid-based N-propargylamides, N-(tert-butoxycarbonyl)-D-alanine-N-propargylamide (DA) with either N-(tert-butoxycarbonyl)-L-valine-N-propargylamide (LV) or N-(tert-butoxycarbonyl)-L-phenylalanine-N-propargylamide (LF), were conducted with (nbd)Rh+[eta(6)-C6H5B-(C6H5)(3)] as a catalyst to obtain the corresponding copolymers with moderate molecular weights in good yields. The specific rotation, CD, and UV-vis spectra showed that some of the copolymers underwent a helix-helix transition driven by temperature change. The transition of helix of poly(LV-co-DA) was much more obvious than that of poly(LF-co-DA). Poly(LV50-CO-DA(50)) underwent a solvent-induced helix-helix transition via random coil.

DOI： 10.1021/ma048834f

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The stability of several poly(N-propargylamides) was investigated in solution and in solid state on the basis of molecular weight change with time, and further their thermal stability was investigated by TGA. When the stability of poly(N-propargylamides) with varying pendent groups was compared, polymers with pendent groups of moderate size showed the highest stability in solution. Too short and too bulky pendent groups were not favorable for the stability of polymers. When poly(N-propargylheptanamide) (poly(6)) was stored in THF as solution at -20°C in the absence of oxygen in dark, its degradation rate was the lowest. The degradation rate of poly(6) depended on the solvents used, which may be related to different solubility of oxygen in these solvents. Polymers with high cis contents degraded faster than polymers with low cis contents did. Addition of TEMPO and DPPH into the poly(6)/THF solution more or less depressed the degradation of poly(6). The degradation of polymer main chain in solution was always accompanied by the decrease of cis content, i.e. geometric isomerization from cis- to trans-structure. When the polymers were stored in the solid state at -20°C, the polymers having alkyl pendent groups with moderate length were more stable than those with bulky pendent groups. Geometric isomerization occurred along with degradation in the solid state as well. © 2004 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.polymer.2004.08.066

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Novel poly(aryleneethynylenes) and poly(aryleneimines) containing carbazole units in the main chain were synthesized by polycondensation of diethynylcarbazoles with dihaloarenes, or diformylcarbazole with phenylenediamines, and their general properties were studied. The polymers with Mw = 2700-33 700 were obtained in 60-100% yields. Compared to carbazole, the UV-vis absorption of the polymers was red-shifted, which indicates the extension of conjugation length. Excited at the absorption maxima, the polymers containing ethynylene moieties showed blue or green emission with high fluorescence quantum yields (6-86%) in the solution state, while in the film state, they exhibited fluorescence at longer wavelength, which suggests the formation of excimers. On the contrary, the polymers having imine moieties showed emission with low fluorescence quantum yields (<1%).

DOI： 10.1021/ma049391i

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N-Propargylamides with one, two, and three phenyl groups at the α-position of the carboxyl group [HC=CCH2NHCOR; 1, R = C(CH3)2C6H5; 2, R = CCH 3(C6H5)2; 3, R = C(C 6H5)3] were polymerized with a rhodium catalyst, (nbd)Rh+B-(C6H5) 4 (nbd = 2,5-norbornadiene), to obtain the corresponding polymers in 85-91% yields. Poly(1) possessed a moderate molecular weight (Mn = 6300) and was thoroughly soluble in chloroform and dichloromethane. On the other hand, poly(2) and poly(3) were not totally soluble in the solvents. The M n's of chloroform-soluble parts were less than 3000. The secondary structure of these three polymers in chloroform was examined by UV-vis spectroscopy with varying temperature. It was found that only poly(1) could adopt helical conformation even at 60 °C. By the copolymerization of either monomer 2 or 3 with HC≡CNH2CO(CH2)4H (4), the solubility of the polymers was effectively improved, and the M n's were remarkably increased. When the content of unit 4 in poly-(2-co-4)s was 25% and above, the copolymers could form helical conformation with different degrees, among which poly(20.40-co-40.60) showed the largest helicity. When the content of unit 4 of poly(3-co-4)s exceeded 95%, the copolymer took helical structure partly.

DOI： 10.1021/ma0492317

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

This study examined the synthesis of copolymers of an alanine-derived chiral N-propargylamide [N-(tert-butoxycarbonyl)-L-alanine N′- propargylamide] with an azobenzene-containing N-propargylamide [N-4-(phenylazo)benzoyl-L-alanine N′propargylamide] and the transformation of the higher order structure of the copolymers by photoirradiation. The trans-azobenzene moiety of the copolymers isomerized into the cis one, which was accompanied by the transformation of the helical structure into a random state by UV irradiation. Visible-light irradiation induced the reisomerization of cis-azoberizene into the trans one, but it did not induce the recovery of the higher order structure. © 2004 Wiley Periodicals, Inc.

DOI： 10.1002/pola.20374

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：SPRINGER  

This work deals with the synthesis and characterization of novel eugenol-based polymers. The polymerization of 2-methoxy-4-propenyl-1-prop-2-ynyloxybenzene (1) with Rh, Mo, and W catalysts gave the corresponding polyacetylene [poly(1)], while that using BF3 catalyst gave poly(1)', without affecting the triple bond. A novel cross-linked polyacetylene was synthesized from poly (1)' with [(nbd)RhC1](2)-Et3N catalyst.

DOI： 10.1007/s00289-004-0272-2

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A variety of novel N-propargylsulfamide monomers (HC≡CCH 2NHSO2R) with alkyl (1-4) or aryl groups (5-10) were polymerized with a Rh catalyst, (nbd)Rh+B-(C 6H5)4 (nbd = 2,5-norbornadiene), to provide polymers with moderate molecular weights (3000-15 000) in good yields (above 80%). Polymerization of monomer 4 (R = -(CH2)7CH 3) at -15°C yielded a stereoregular polymer whose cis content was nearly 100%, while the cis content remained 79% at 30°C. Thus, the stereoregularity of the polymer largely depended on polymerization temperature. On the other hand, polymerization solvents hardly affected stereoregularity. Copolymerization of monomer 4 and N-propargylamide monomer 11 afforded copolymers with various compositions in high yields (above 87%), and the cis contents of the resultant copolymers were located between those of the corresponding homopolymers. The presence of intramolecular hydrogen bonding between the neighboring sulfamide groups was confirmed by IR spectroscopy measured in chloroform, suggesting that these types of polymers with appropriate substitutents also have the potential to form helices under suitable conditions like poly(N-propargylamides).

DOI： 10.1021/ma049739+

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N-Propargylamides with bulky pendent groups [HC≡CCH2NHCOR, 9: R = CH2C(CH3)3, 10: R=C(CH 3)3 11: R = C(CH3)2CH 2CH2CH3,12: R = CH(CH2CH 3)2, 13: R = CH(CH2CH2CH 3)2] were polymerized with a rhodium catalyst, (nbd)Rh+B-(C8H5)4 (nbd = 2,5-norbornadiene), to obtain the polymers in 80-92% yields. Poly(11) and poly(12) possessed moderate molecular weights (Mn ≥ 10 000) and were totally soluble in a few solvents including chloroform. On the other hand, the Mn values of poly(9), poly(10), and poly(13) were no more than 5000, and these polymers were not completely soluble in any solvents. The conformational transition behavior of these polymers was examined by temperature-variable UV-vis spectroscopy in chloroform solution, which revealed that poly(10) - poly(13) could form dynamically stable helical conformation even at 60°C. By copolymerizations of monomers 9 and 10 with monomer 4, HC≡CCH2NHCO(CH2)4H, the solubility of the polymers was effectively improved and almost all the copolymers totally dissolved in chloroform, while the molecular weights of the copolymers increased up to 18 600-45 000. Moreover, the helix contents of poly(40.63-co- 90.37) and poly(40.40-co-100.60) were the highest among the two series of (co)polymers, respectively. It is concluded that the copolymerization of 9 and 10 with 4 effectively decreased the steric repulsion between the crowded side chains, which probably allowed the copolymers to take helical conformation efficiently.

DOI： 10.1021/ma049321b

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

N-Propargylamide-terminated peptide-based macromonomers with a degree of polymerization ranging from 4 to 40 were synthesized by the polymerization of γ-benzyl and γ-stearyl-L-glutamate-N-carboxy anhydrides initiated with propargylamine. The macromonomers took an α-helical structure, which was confirmed by signals at 208 and 220 nm in CD spectra. The macromonomers were subjected to polymerization and copolymerization with an alanine-derived N-propargylamide [N-(tert-butoxycarbonyl)-L-alanine-N′-propargylamide] catalyzed with (2,5-norbornadiene)-Rh+[η6-C 6H5B-(C6H5)3]. It was confirmed through a CD spectroscopic study that the copolymer obtained from the copolymerization of the γ-stearyl-L-glutamate-based macromonomer with the alanine-derived N-propargylamide had a helical polyacetylene main chain and helical polypeptide side chains.

DOI： 10.1002/mabi.200400019

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The polymerization of N-propargylamides (HC=CCH2NHCOR, R = i-Pr (1), i-Bu (2), or n-Pen (3)) with a Rh vinyl complex (4) was examined. The polymerization of 2 in chloroform in the presence of triphenylphosphine yielded polymer with a relatively narrow molecular weight distribution (Mn = 17 300, Mw/Mn = 1.36). The first-order plot based on the time profile of polymerization at 0°C was linear, and the second monomer feed was also consumed completely in multistage polymerization. These results indicate that this polymerization has a livinglike nature. Further, a block copolymer was successfully prepared from monomers 2 and 3.

DOI： 10.1021/ma035818u

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Copolymerization of two N-propargylamides bearing pendent groups with different lengths [monomer 4, HC≡CCH2NHCO(CH2) 4H; monomer 8, HC≡CCH2NHCO(CH2) 8H] was carried out and the conformational transition behavior of copolymers with different compositions was examined systematically. The copolymers could form relatively stable helices even though both of the corresponding homopolymers, poly(4) and poly(8), could not take a stable helical conformation under the same conditions. The helix content of copolymers reached a maximum when the content of monomer 8 was 61%. These results are explained in terms of the idea that the copolymers have higher cis-content and that the intramolecular hydrogen bonding is more effective in these copolymers compared with the corresponding homopolymers.

DOI： 10.1002/macp.200400001

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

A novel, water-soluble Rh complex, (nbd)Rh[PPh2(m-NaOSO2C6H4)] [C(Ph)=CPh2] (1) was synthesized by the reaction of [(nbd)RhCl](2), Ph2P(m-NaOSO2C6H4) and Ph2C=C(Ph)Li, whose structure was determined by NMR and IR spectroscopies. The Rh catalyst 1 induced the polymerization of phenylacetylene (PA) in water to give two kinds of polymers; one was soluble in organic solvents such as tetrahydrofuran (THF) and CHCl3, and the other was insoluble in common organic solvents. The polymerization of sodium p-ethynylbenzoate (p-NaOCO-PA) homogeneously proceeded with 1 in water at 60 degreesC to give the polymer in high yield. Poly(p-NaOCO-PA) was treated with 1 N HCl and then reacted with (CH3)(3)SiCHN2 to obtain poly(p-MeOCO-PA). The methyl-esterified polymer was insoluble in THF and CHCl3, which suggests that the formed poly(p-MeOCO-PA) has cis-cisoidal structure. The polymer obtained from the polymerization of [p-CH3(OCH2CH2)(2)O2CC6H4]C=CH with 1 in water was soluble in methanol, ethanol, and THF, and partly soluble in water. (C) 2004 Wiley Periodicals, Inc.

DOI： 10.1002/pola.11035

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

A novel branched polycarbonate with a hydroxyl group at the chain end was synthesized by the copolymerization of glycidol with carbon dioxide (CO,). The copolymerization was carried out with 5 mol % of an alkali metal halide or quaternary ammonium salt as a catalyst under atmospheric CO2. The obtained poly(glycidol-co-carbon dioxide) was O-benzoylated and O-silylated, and the corresponding polymers were analyzed with IR, size exclusion chromatography, C-13 NMR, and Si-29 NMR. The IR spectroscopy analysis of the O-benzoylated polymer revealed that the maximum incorporation degree of the carbonate group was 90% (i.e., the CO2/glycidol composition ratio was 0.9:1.0). The incorporation of CO, as a carbonate unit was also confirmed by the treatment of this polymer with n-butylamine, which caused the aminolysis of the carbonate and led to degraded products. (C) 2004 Wiley Periodicals, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Novel carbazole-containing polymers, i.e., poly(3,6-di-tert-butyl-N-(p-ethynylphenyl)carbazole) [poly(t-Bu(2)CzPA)] and poly(N-(p-ethynylbenzoyl)carbazole) [poly(CzCOPA)] were synthesized by the polymerization of the corresponding carbazole-containing acetylene monomers using [(norbornadiene)-RhCl](2)-Et3N, WCl6-n-Bu4Sn, and WCl4 catalysts. The UV-vis absorption band edge wavelengths of the polymers obtained by the polymerization with W catalysts were longer than those of the Rh-based polymers. The photoluminescence quantum yield of the W-based poly(t-Bu(2)CzPA) was 55%, while that of the Rh-based one was as low as 3.6%. The photocurrent of poly(t-Bu(2)CzPA) was 40-50 times higher than the dark current. Poly(t-Bu2CzPA) in conjunction with iridium complexes exhibited electroluminescence (13-18 cd/m(2)).

DOI： 10.1021/ma035972g

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N-Propargylamides having pendent groups with different lengths (HC≡CCH2NHCOR, R = (CH2)nH, n = 1-8) were polymerized in the presence of a Rh catalyst [(nbd)Rh+B -(C6H5)4; nbd = 2,5-norbornadiene] to obtain polymers with moderate molecular weight and high stereoregularity [poly(1)-poly(8)] in high yields. The conformational transition behavior of the resultant polymers was investigated by measuring UV-vis spectra in chloroform solution at different temperatures. Among the examined polymers, poly(5) and poly(6) took a stable helical conformation at relatively high temperatures, and their helical contents were the highest. Poly(2)-poly(4), which bear shorter alkyl pendent chains, did not exist in stable helical conformation owing to the lack of chain flexibility and the intermolecular hydrogen bonding. Poly(1) was not completely soluble in any solvents. Poly(7) and poly(8), which contain longer pendent chains, took helical conformation only at low temperatures because of the lower cis content of the polymer main chain. Both ΔH and ΔS for the conformational transition from random coil to helix assumed negative values, which also greatly depended on the length of the pendent groups. Whereas the helical conformation of poly(5) and poly(6) was readily generated in chloroform, neither THF nor toluene was favorable for helix formation.

DOI： 10.1021/ma035735d

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Novel acetylene monomers containing carbazolymethyl groups, 3,5-bis[(3,6-di-t-butyl)carbazolylmethyl]-1-ethynylbenzene (1), 3-(3,6-di-t-butyl)carbazolylmethyl-1-ethynylbenzene (2), and 4-(3,6-di-t-butyl)carbazolylmethyl-1-ethynylbenzene (3) were synthesized, and polymerized with [(nbd)RhCl]2-Et3N, Rh+(nbd) [η6-C6H5B-(C6H 5)3], and WCl6-n-Bu4Sn catalysts. The corresponding polyacetylenes with number-average molecular weights ranging from 1600 to 115,000 were obtained in 18%-quantitative yields. The UV-vis absorption band edge wavelengths of the polymers obtained with W catalyst were longer than those of the Rh-based polymers. The photoluminescence quantum yields of the W-based polymers were 1.1-3.1%, while those of the Rh-based ones were 0.18-4.1%. © 2004 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.polymer.2004.09.047

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Novel sulfonium salts, 1-naphthylmethyl-, cinnamyl-, 9-fluorenyl tetramethylene sulfonium hexafluoroantimonates, and dimethylsulfonium hexafluoroantimonates, were synthesized by the reaction of tetrahydrothiophene and dimethylsulfide with the corresponding bromides or chloride, followed by anion exchange with KSbF6. These sulfonium salts polymerized epoxy monomers at a temperature lower than previously reported for benzyltetramethylenesulfonium hexafluoroantimonate. They initiated radical photopolymerization as well as cationic polymerization. The photopolymerization was accelerated by the addition of aromatic compounds such as p-methoxyphenol, 4-methoxy-1-naphthol, 2-ethyl-9,10-dimethoxyanthracene, N-ethylcarbazole, and phenothiazine as photosensitizers. (C) 2003 Wiley Periodicals, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Elsevier BV  

Polyacetylenes having carboxyl and/or amino groups in the side chain were synthesized by the polymerization of N-(2-propynyloxycarbonyl)-L-alanine (1) and L-alanine N-propargylamide (2) catalyzed with a rhodium cation complex. Poly(10.5-co-20.5) exhibited a larger CD signal than the homopolymers. The polymer mixtures obtained by the polymerization of 1 in the presence of poly(2), and those obtained by the polymerization of 2 in the presence of poly(1) showed specific rotations larger than calculated. The polymerization of propargylamine in the presence of poly(1) did not exhibit significant effect, while the polymer mixtures obtained by the polymerization of propiolic acid in the presence of poly(2) exhibited [α]D of positive sign, although poly(2) alone exhibited [α]D of negative sign. © 2003 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.polymer.2003.11.044

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Marcel Dekker Inc.  

This work deals with the synthesis of a novel polyacetylene containing eugenol moieties, and characterization of the general properties of the formed polymer. The polymerization of 4-allyl-2-methoxy-1-prop-2-ynyloxybenzene (1) with [(nbd)RhCl]2 and (nbd)Rh+[η6-C 6H5B-(C6H5)3] catalysts gave the polymer [poly(1)] with number-average molecular weights ranging from 12,100 to 31,400 in good yields. With MoCl5 as a catalyst, poly(1) was obtained in a poor yield. Employment of n-Bu 4Sn as a cocatalyst was effective to increase the polymer yield. W catalysts were not effective to the polymerization of 1. Poly(1) was soluble in common organic solvents, film-forming, and thermally stable up to 150°C. Poly(1) exhibited the UV-VIS absorption maxima at 280 nm, and broad absorption assignable to a conjugated polyacetylene main chain at 300-450 nm.

DOI： 10.1081/MA-120027299

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

Achiral N-propargylamides, i.e., N-propargyl-3-methylbutanamide (1), N-propargyl-2-ethylbutanamide (2), and N-propargyl-3,3-dimethylbutanamide (3), were polymerized with (nbd)Rh+[η6-C6H5B- (C6H5)] to afford polymers with moderate molecular weights (Mn = 6000-22000) in good yields. The 1H NMR and UV-vis spectra demonstrated that the polymers, poly(1)-poly(3), have stereoregular structures (cis = 100%) and equally populated right- and left-handed helical conformation. A predominant helix sense was induced in these polymers by the addition of chiral alcohols or amine, which was confirmed by CD and UV-vis spectroscopies. 1H NMR and CD spectroscopic studies strongly suggested that the poly(N-propargylamides) interacted with the chiral alcohols by hydrogen bonding at the amide groups of the polymer side chain. Chiral terpenes could also induce single-handed helical conformation. It is likely that hydrophobic interaction led to the one-handed helical conformation in the case of the chiral terpenes because the addition of n-hexane decreased the CD signal.

DOI： 10.1021/ma030324i

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

N-Propargylcarbamates (2, HCdropCCH(2)NHCO(2)R), where R = i-Bu (2a) or (S)-CH2CH(CH3)C2H5 (2b), were polymerized in the presence of a Rh catalyst, [(nbd)RhCl](2)-Et3N, in CHCl3, giving stereoregular cis polymers as slightly yellow solids in good yields. The H-1 NMR spectra of poly(2) showed very broad signals at ambient temperature, indicating the limited mobility of the main chain. IR spectroscopic study of the polymers in CHCl3 revealed that most of the pendant carbamate groups participate in intramolecular hydrogen bonds. The chiral polymer from 2b exists in a helical conformation with an excess of one-handed screw sense, which was supported by the very large optical rotation ([U](D) = +777degrees) and intense CD effects ([theta]max = 81 700 deg cm(2) dmol(-1)). A Rh-based polymer from the corresponding chiral carbonate monomer, (S)-HdropCCH(2)OCO(2)CH(2)CH(CH3)C2H5 (3), obtained as a viscous oil, showed much poorer chiroptical properties ([alpha](D) = + 13.8degrees), meaning that the intramolecular hydrogen bonds rigidify the polymer backbone and simultaneously induce and stabilize the helical conformation of poly(2). The contribution of the hydrogen bonds to the secondary structure was also supported by variation in the CD and UV-vis spectra of poly(2) upon the addition of methanol.

DOI： 10.1021/ma0209085

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

The present study deals with the synthesis and polymerization of novel amino acid-derived acetylene monomers, N-(tert-butoxycarbonyl)-L-alanine N′-propargylamide (L-1A), N-(tert-butoxycarbonyl)-L-alanine N′-methyl-N′-propargylamide (N-Me-L-1A), and N-(tert-butoxycarbonyl)-L-alanine propargyl ester (L-1E) and the analysis of the properties of the formed polymers. The monomers were synthesized by the condensation of N-(tert-butoxycarbonyl)-L-alanine with propargylamine, N-methylpropargylamine, and propargyl alcohol in 50, 89, and 72% yields, respectively. They satisfactorily underwent polymerization with (nbd)Rh+[η6-C6H5B- (C6H5)3] as a catalyst ([M]0/[Cat] = 10-200) in THF and CH2Cl2 at 0-50°C to afford the corresponding polymers with Mn's in the range 1 × 104-2 × 105. Poly(L-1A) exhibited a large specific rotation {[α]D = -1349° (CH2Cl2)} and a CD signal ([θ]max = -3.2 × 104 deg cm2 dmol-1 (CHCl3)), suggesting that it takes a helical conformation. On the other hand, poly(N-Me-1A) and poly(L-1E) showed no evidence of a helical structure. The helical structure of poly(L-1A) was deformed by the addition of MeOH.

DOI： 10.1021/ma021738z

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

The present study deals with the copolymerization of an amino acid-based acetylene, N-(tert-butoxycarbonyl)-L-alanine N'-propargylamide (L-1A) with the optical isomer (D-1A), achiral hexanoic acid N-propargylamide (2A), and pivalic acid N-propargylamide (3A), and chiroptical properties of the copolymers. The copolymerization catalyzed by (nbd)Rh+[eta(6)-C6H5B-(C6H5)(3)] afforded copolymers with number-average molecular weights over 104 in good yields. Nonlinear relationships were observed in the specific rotation and CD and UV-vis spectroscopies with respect to the L-1A content in feed. For instance, poly(L-1A-co-D-1A)s incorporated with 12.5% of either optical isomer (75% ee) exhibited almost the same optical properties as those of the homopolymers. Chiral amplification was observed in the copolymerization of L-1A with the achiral monomers. The specific rotation of poly(L-1A-co-2A) with 45% L-1A unit was practically the same as that of poly(L-1A). The copolymers of L-1A and 3A with an L-1A content in feed as low as 12% exhibited nearly the same helix content as the homopolymer of L-1A did.

DOI： 10.1021/ma021432s

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Five novel carbazole-containing polymers, i.e., poly(3,6-di-tert-butyl-9-prop-2-ynylcarbazole) [poly(t-Bu(2)CzPr)], poly(9-but-2-ynylcarbazole) [poly(CzBu)], poly(3,6-di-tert-butyl-9-but-2-ynylcarbazole) [poly(t-Bu(2)CzBu)], poly(9-(4-ethynylphenyl)carbazole) [poly(p-CzPA)], and poly(9-(4-prop-1-ynylphenyl)carbazole) [poly(p-CzPPr)] were synthesized by the polymerization of the corresponding carbazole-containing acetylene monomers using [(norbornadiene)RhCl](2)-Et3N, WCl6, MoCl5, TaCl5, and NbCl5 in conjunction with Sn, Bi, Sb, and Si cocatalysts and W(CO)(6)-hv/CCl4 catalysts. The UV-vis absorption band edge wavelengths of poly(t-Bu(2)CzPr) and poly(p-CzPA) were longer than those of the corresponding polymers substituted by methyl group at the main chain, poly(t-Bu(2)CzBu) and poly(p-CzPPr), respectively. The band edge wavelengths of phenylene-spacer-containing polymers, poly(p-CzPA) and poly(p-CzPPr), were longer than those of methylene-spacer-containing polymers, poly(t-Bu(2)CzPr) and poly(t-Bu(2)CzBu), respectively. Poly(p-CzPA) obtained by WCl6-n-Bu4Sn-catalyzed polymerization exhibited UV-vis absorption apparently at a longer wavelength than the MoCl5-n-Bu4Sn-based counterpart did. Poly(t-Bu(2)CzPr) showed photoconductivity. The temperatures for 5% weight loss of the polymers were around 300-350 degreesC under air.

DOI： 10.1021/ma021686d

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

A samarium enolate, supported on a crosslinked polystyrene resin, successfully initiated the living anionic polymerization of allyl methacrylate (AMA) to afford the corresponding poly(AMA) with well-controlled molecular weights. Diblock, triblock, and tetrablock copolymerizations with methyl methacrylate (MMA) were also successfully performed. The formed polymers, supported on the resin by a benzyl ester linker, were quantitatively isolated from the resin by selective cleavage of the linker with trifluoroacetic acid (TFA). Allyl ester in the side chain was not affected by this isolation step. The allyl group of the immobilized poly(AMA-b-MMA) on the resin was transformed into a 2,3-dihydroxypropyl group by osmium oxidation. The resulting copolymer was isolated by TFA treatment of the resin, and it showed amphiphilicity. In both the polymerization and side-chain modification, the formed polymers were easily washed from excess reagents only by filtration, and this demonstrated the feasibility of the automated synthesis of functional polymers based on this solid-supported polymerization technique. (C) 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 853-860, 2003.

DOI： 10.1002/pola.10626

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/ma0257292

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/pola.10573

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

The polymerization of isobutyl vinyl ether (IBVE) and tert-butyl vinyl ether (TBVE) was carried out with metallocene and nonmetallocene catalysts, and the stereoregularity of the formed polymers was examined with C-13 NMR spectroscopy. IBVE afforded polymers with 63-68% dyad isotacticity by polymerization with mixtures of metallocene catalysts and methyl aluminoxane as a cocatalyst in toluene as a solvent. However, TBVE yielded polymers with 47-52% dyad isotacticity (21-28% triad isotacticity) under the same conditions, the isotacticity being lower than that of poly(isobutyl vinyl ether) (PIBVE). Nonmetallocene catalysts, including Ti, Zr, and Hf complexes with two phenoxy imine chelate ligands, provided PIBVE and poly(tert-butyl vinyl ether) with 63-68 and 45-51% dyad isotacticity, respectively. (C) 2002 Wiley Periodicals, Inc.

DOI： 10.1002/pola.10483

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Aldol-type reactions of a samarium enolate at the propagating end of living anionic poly-(MMA) with aldehydes were carried out. The enolate underwent aldol-type end-capping reaction with 3-phenylpropanal to give the corresponding samarium alkoxide at the polymer terminal. Successive treatment of the alkoxide with benzoyl chloride resulted in its benzoylation. End-capping reaction with 2-phenylpropanal also smoothly proceeded to give the poly(MMA) having the corresponding secondary alkoxide at the terminal. Its benzoylation was not successful; however, an intramolecular reaction of the terminal alkoxide with the methyl ester moiety of the penultimate MMA unit predominantly proceeded to give the corresponding poly(MMA) having a lactone moiety at its terminal. In addition, a terminal samarium enolate of a living poly(MMA), which was supported on polystyrene beads by a benzoyl ester-type linker, reacted with the aldehydes to afford the end-capped poly(MMA), which could be efficiently isolated from the beads by selective cleavage of the linker by trifluoroacetic acid treatment.

DOI： 10.1021/ma0121060

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

A novel five-membered cyclic thiocarbonate bearing adamantane moiety, 4,6-dioxatetracyclo-[6.3.1.1.O-3,10(3,7)]tridecane-5-thione (1), was synthesized from 1,2-adamantanediol and thiophosgene in the presence of pyridine. Monomer 1 underwent cationic ning-opening polymerization initiated by triethyloxonium tetrafluoroborate (Et3OBF4), methyl trifluoromethanesulfonate (TfOMe), trifluoromethanesulfonic acid (TfOH), and H2O with 2 mol % of boron trifluoride etherate (BF3OEt2) in CH2Cl2 at 30 degreesC to afford the polythiocarbonate by isomerization of the thiocarbonyl group into a carbonyl group with selective ring-opening direction. The number-average molecular weight and polydispersity of the polymer obtained by polymerization with H2O/BF3OEt2 were 10 600 and 1.44, respectively. The temperature with 5% weight loss of the obtained polymer was 338 degreesC. Monomer I expanded as large as 14% during the polymerization.

DOI： 10.1021/ma012094i

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Anionic copolymerization of ethylphenylketene (EPK) with 4-(tert-butyldimethylsilyloxy)benzaldehyde (SiO-BA) was carried out using butyllithium as an initiator in THF at -40 degreesC. The copolymerization proceeded via 1:1 alternation, generating the corresponding polyester having silyl protected phenol moiety in the side chain quantitatively. By addition of lithium chloride to the polymerization system, the polymerization proceeded in a living fashion to afford the corresponding polyester having narrow molecular weight distribution (M-w/M-n < 1.2). Treatment of the obtained polymer with tetrabutylammonium fluoride in the presence of acetic acid resulted in complete removal of the silyl group without main chain degradation to afford polyester having phenol moiety, which was soluble in methanol. Thermal degradability of the polyester with phenol moiety Was considerably higher than that of the silyl-protected polymer, suggesting that the acidity of the phenol moiety would promote thermal dissociation of the polyester main chain.

DOI： 10.1021/ma011928u

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

This article reviews recent topics in the controlled synthesis of polycarbonates and polylactones with small polydispersity indices by activated monomer cationic ring-opening polymerizations, especially with new initiator systems, such as alcohol/protonic acid and boron alkoxide/protonic acid. (C) 2002 Wiley Periodicals, Inc.

DOI： 10.1002/pola.10289

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CHEMICAL SOC JAPAN  

Six-membered cyclic thiocarbonate derivatives, 5,5-(bicyclo[2.2.1]hept-2-en-5,5-ylidene)-1,3-dioxane-2-thione (1) and 5,5 -(bicyclo [2.2.1]heptan-5,5-ylidene)-1,3-dioxane-2-thione (2) underwent anionic ring-opening polymerization initiated by 1,8diazabicyclo[5.4.0]-7-undecene (DBU) to afford polythiocarbonates accompanying 12.3 and 12.6% volume expansion, respectively.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Three- and four-armed star-shaped poly(epsilon-caprolactone)s were synthesized from trimethylolpropane and pentaerythritol as initiators using fumaric acid as an activator of the monomer, respectively. Star-shaped poly(E-caprolactone)s could be satisfactorily obtained, which was confirmed by size exclusion chromatography equipped with low-angle laser light scattering and viscometer detectors. Comparing the melting points among the polymers with similar molecular weights, the order was as follows: linear poly(epsilon-caprolactone) > three-armed poly(epsilon-caprolactone) > four-armed poly(epsilon-caprolactone). On the other hand, poly(epsilon-caprolactone)s with similar arm length showed similar melting points irrespective of the arm numbers. Thermal decomposition temperature of poly(epsilon-caprolactone)s increased with the arm number.

DOI： 10.1021/ma011341f

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Novel phosphates, O-p-(hydroxymethyl)benzyl O,O-diethyl phosphate (1) and O-(2-bromoisobutyryloxymethyl)benzyl O,O-diethyl phosphate (2) were synthesized by the reaction of diethyl phosphorochloridate with 1,4-benzenedimethanol and the successive reaction with 2-bromoisobutyryl bromide in the presence of triethylamine and submitted to the polymerization of epsilon -caprolactone and methyl methacrylate as the initiators. They afforded phosphate end-functional poly(epsilon -caprolactone) and poly(methyl methacrylate) with controlled molecular weights and polydispersity ratios by living ring-opening polymerization and samarium-induced polymerization. The polymerization of glycidyl phenyl ether (GPE) was carried out with the phosphate end-functional polymers as the latent polymeric initiators in the presence of ZnCl2. The polymerization of GPE did not proceed below 90 degreesC, but it rapidly proceeded to afford poly(GPE) above the temperature. (C) 2001 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Five-member cyclic dithiocarbonates were synthesized by the reactions of carbon disulfide with benzoic, p-anisic, p-chlorobenzoic, 1-naphthalenecarboxylic, p-nitrobenzoic, and p-(tert-butyl)benzoic glycidyl esters, and their cationic ring-opening polymerizations were carried out with methyl trifluoromethane sulfonate and trifluoromethane sulfonic acid as initiators at room temperature to 80 degreesC. Polymers with number-average molecular weights of 3400-24,900 were obtained in high yields, and their structures were estimated by NMR and IR spectroscopy. The monomers showed a clear difference in the polymerization rate according to the substituents. The rate of polymerization decreased in the order of p-chlorobenzoic benzoic > 1-naphthalenecarboxylic > p-nitro-benzoic > p-tert-butylbenzoic > p-anisic. The data of the reaction kinetics, NMR studies, and molecular orbital calculations proved a plausible mechanism involving the participation of p-substituted benzoyloxymethyl groups to stabilize the cationic propagating end. The polymers showed decomposition temperatures with 5% weight loss ranging from 200 to 260 degreesC. No glass-transition temperatures for the polymers were observed below 200 degreesC by differential scanning calorimetry. (C) 2001 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

The cysteine-bridged macrocycles, 22-32-membered cyclic dimers could be synthesized with a high reagent concentration (1 M) in excellent yields by the oxidation of the cysteine-based Compounds having dithiol groups. (C) 2001 Elsevier Science Ltd. All rights reserved.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

This article deals with the self-polyaddition of 3-(1,3-dioxan-2-one-5-yl)propyl 2-(9-fluorenylmethoxycarbonylamino)ethyl thioether by the deprotection of the 9-fluorenylmethyoxycarbonyl (Fmoc) group with NN-diisopropylethylamine, 4-(dimethylamino)pyridine, or triethylamine as a novel synthetic method of a polyhydroxyurethane. The polymer with higher yields and M-n's was obtained by using N,N-diisopropylethylamine and 4-(dimethylamino)pyridine than triethylamine. Fmoc deprotection and stability of the cyclic carbonate group were elucidated to optimize the condition by using the model compounds, 3-cyclohexylpropyl 2-(9-fluorenylmethoxycarbonylamino)ethyl thioether and 3-(1,3-dioxan-2-one-5-yl)propyl ethyl thioether.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

DOI： 10.1021/ma010653f

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

We carried out the polyaddition of dye-embedded diols with diisocyanates to obtain novel nonlinear optical (NLO) polyurethanes, where the NLO units were embedded in the polymer backbone. The obtained polymers showed high glass-transition temperatures (138-184 degreesC) and thermal stability (temperature of 10% weight loss under nitrogen = 227-287 degreesC). The h maximum of the polymers was 521-556 nm. (C) 2001 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/ma001993o

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-BLACKWELL  

The alkali hydrolysis of poly(2,2-dimethyl-5-methylene-1,3-dioxolan-4-one) and poly(2,2-dimethyl-5-methylene-1,3-dioxolan-4-one-co-styrene) was carried out with a sodium hydroxide solution (40%) in tetrahydrofuran at room temperature to obtain poly(alpha -hydroxyacrylic acid) or poly(alpha -hydroxyacrylic acid-co-styrene) with number-average molecular weights of 39,000-73,000 in 41-86% yields. The styrene unit in the hydrolyzed copolymer hindered the formation of a lactone ring. (C) 2001 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/pola.1108

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

This work deals with the cationic ring-opening polymerization of the ester-substituted cyclic carbonates 5-methyl-5-benzoyloxymethyl-1,3-dioxan-2-one (CC1) and 4-benzoyloxymethyl-1,3-dioxan-2-one (CC4). The polymerization was carried out with trifluoromethanesulfonic acid, methyl trifluoromethanesulfonate, boron trifluoride etherate, or methyl iodide as the initiator. The reactivity of CC1 and CC4 was higher than that of 5,5-dimethyl-1,3-dioxan-2-one, which had no ester moiety. These results suggest that this ring-opening polymerization was accelerated by the intramolecular ester group. CC1 showed a higher polymerizability than CC4, affording a polymer with a higher molecular weight. Additionally, using methyl iodide as the initiator was effective for increasing the molecular weight of the obtained polycarbonate and decreasing decarboxylation. (C) 2001 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

alpha -Methyl glutamic acid (L-D)-, (L-D)-, (D-L)-, and (D-D)-gamma -dimers were synthesized from L- and D-glutamic acids, and the obtained dimers were subjected to polycondensation with 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 1-hydroxybenzotriazole hydrate as condensation reagents. Poly-gamma -glutamic acid (gamma -PGA) methyl ester with the number-average molecular weights of 5000 similar to 20,000 were obtained by polycondensation in N,N-dimethylformamide in 44 similar to 91% yields. The polycondensation of (L-L)- and (D-D)-dimers afforded the polymers with much larger /[alpha](D)(30)/ compared with the corresponding dimers. The polymer could be transformed into gamma -PGA by alkaline hydrolysis or transesterification into alpha -benzyl ester followed by hydrogenation. (C) 2001 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Synthesis and anionic ring-opening polymerization of L-serine (Ser)- and L-threonine (Thr)based cyclic carbonates, (2-oxo[1,3]dioxan-5-yl)carbamic acid benzyl ester (Z-S-CC), (4-methyl-2-oxo[1,3]dioxan-5-yl)carbamic acid benzyl ester (Z-T-CC), and (4-methyl-2-oxo [1,3] dioxan-5-yl)carbamic acid tert-butyl ester (Boc-T-CC), were examined. The monomers were synthesized by reaction of triphosgene with the corresponding diols obtained by reduction of N-benzyloxycarbonyl-L-serine (Z-Ser), N-benzyloxycarbonyl-L-threonine (Z-Thr), and N-tert-butoxycarbonyl-L-threonine (Boc-Thr). Their ring-opening polymerizations were carried out with tert-BuOK, tert-BuOLi, and n-BuLi as initiators (2-10 mol %) in tetrahydrofuran (THF) at -78 to -30 degreesC for 1 h to obtain the corresponding polycarbonates. Poly(Z-T-CC) and poly(Boc-T-CC) showed inverted specific rotations with respective to the monomers. The small increase of the absolute values suggested the absence of higher-order structures. The polymers showed three different diads in the ratio of 1:8:1, which agreed well with the value expected from the equimolar reaction of the monomer with tert-BuOK. The polymers underwent cleavage of the Z and Boc groups by hydrogenation and acid treatment, respectively to afford the corresponding polycarbonates with free amino groups.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/ma000759v

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

The radical polyaddition of N-4-vinylbenzoyl-L-cysteine methyl eater (VCM) was carried out in the presence of 2,2'-azobisisobutyronitrile (AIBN, 3 mol %) as an initiator in dimethyl formamide (DMF) with monomer concentrations of 0.5 and 1.0 M at 60 degreesC for 20 h under nitrogen atmosphere to afford the corresponding polymers [poly(VCM), PVCM] with number-average molecular weights (M-n)'s of 5300 and 18,000 in 92 and 95% yields, respectively. The obtained polymers had a heterotelechelic structure with thiol and olefin end moieties. The radical polymerization of methyl methacrylate and trityl methacrylate was carried out in the presence of PVCM with AIBN (3 mol %) as an initiator in DMF at 60 degreesC for 20 h to afford the block copolymers with M-n values in the range of 13,000-26,800 in good yields. PVCM [M-n = 18,000; polydispersity (M-w/M-n) = 1.56] was treated with 4 equiv of NaOH aq. (1.0 M) to afford the polymer having carboxyl groups in the side chain with a M-n of 17,300 and M-w/M-n of 1.88 in 95% yield and was also oxidized to polysulfoxide and polysulfone with 4 equiv of H2O2 per sulfide unit in CH2Cl2 (1.0 M) for 20 h. (C) 2000 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

The reaction of six- and five-membered cyclic carbonates, 5-(2-propenyl)-1,3-dioxan-2-one (1) and 4-(3-butenyl)-1,3-dioxolan-2-one (2) with hexylamine and benzylamine was carried out in N,N-dimethylacetamide at 30, 50, and 70 degreesC. The six-membered cyclic carbonate 1 proceeded quantitatively with hexylamine at 30 degreesC for 24 h, while the five-membered cyclic carbonate 2 converted in 34%. The reaction rate constants at 50 degreesC are evaluated as follows; 1.42 L/mol.h (1 with hexylamine) > 0.29 L/mol.h (1 with benzylamine) > 0.04 L/mol.h (2 with hexylamine) > 0.01 L/mol.h (2 with benzylamine). The activation energies in the reactions of 1 and 2 with hexylamine were estimated to be 10.1 and 24.6 kJ/mol, respectively. The ring-strain energy was calculated by the semi-empirical method using the PM3 Hamiltonian. The ring-strain energy of the six-membered cyclic carbonate was 2.86 kcal/mol larger than that of five-membered one. (C) 2000 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Novel phosphonamidates, O-tert-butyl P-phenyl 1-piperidinyl phosphonamidate (1), O-tert-butyl P-phenyl N,N-diethyl phosphonamidate (2), O-tert-butyl P-phenyl 1-morpholinyl phosphonamidate (3), O-tert-butyl P-phenyl N-methyl-N-phenyl phosphonamidate (4), O-2-phenylpropyl P-phenyl 1-piperidinyl phosphonamidate (5), and O-1-phenylethyl P-phenyl 1-piperidinyl phosphonamidate (6) were synthesized from phenylphosphonic dichloride with the corresponding amines, followed by reaction with 2-methyl-2-propyl alcohol, 2-phenylpropyl alcohol, or 1-phenylethyl alcohol in the presence of sodium hydride. Their initiator activities were examined in the polymerization of GPE. GPE did not react with 1-4 below 110 degreesC, but it smoothly polymerized above 110 degreesC to afford the polymer with M-n of (0.7-1.4) x 10(3). The polymerization of GPE did not proceed with 5 and 6 below 90 and 170 degreesC, respectively, but proceeded rapidly above those temperatures. The phosphonamidates 1-6 served as thermally latent anionic initiators in the polymerization of GPE. The activities of 1-6 were affected by the decomposition rates of the ester parts and the basicity of the corresponding amines. The initiating species were identified as the amines by a N-15-labeled NMR experiment.

DOI： 10.1021/ma001175w

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Cationic ring-opening polymerization of epsilon -thionocaprolactone was examined. The corresponding polythioester with the number-average molecular weight (M-n) of 57,000 was obtained in the polymerization with 1 mol % of BF3 . OEt2 as an initiator in CH2Cl2 at 28 degreesC for 5 h with quantitative monomer conversion. The M-n of the polymer increased with the solvent polarity and monomer-to-initiator ratio. No polymerization took place below -30 degreesC, and the monomer conversion and M-n of the polymer increased with the temperature in the range of -15 to 28 degreesC. The increase of initial monomer concentration was effective to improve the monomer conversion and the M-n of the obtained polymer. (C) 2000 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Novel aliphatic aminimides were synthesized from the corresponding carboxylic acid esters, 1,1-dimethylhydrazine, and epoxides in 54-95% yields. Bulk polymerization of glycidyl phenyl ether (GPE) with 3 mol % of the aminimides was evaluated by DSC as a model process for curing of epoxy resin. All the aminimides showed no exothermic DSC peak below 120 degrees C but showed sharp exothermic peaks above 137 degrees C, indicating good thermal latency. Good relationships were observed between the calculated bond length from the carbonyl carbon to the ct-carbon of the aliphatic group (R-C), DSC onset temperatures, and the thermal dissociation temperatures (T-d's) of the aminimides. The aminimide with a longer R-C bond length showed lower T-d and DSC onset temperature, that is, higher activity. (C) 2000 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

The initiating species of phosphonic acid esters serving as thermally latent initiators was investigated in the cationic polymerization of glycidyl phenyl ether (GPE). O, O-Di-t-butyl phenylphosphonate (1H) dissociated into phenylphosphonic acid and isobutene on heating to 150 degrees C. H-2 NMR spectroscopic study was carried out to examine the alkyl initiating species in the cationic polymerization of GPE with O, O-di-t-butyl-d(9) phenylphosphonate (1D) in the presence of ZnCl2. A signal based on the t-butyl-d(9) group was observed in the obtained polymer. The cationic polymerization of GPE with phosphonic acid was carried out to examine the proton initiating species at 170 degrees C. GPE was converted quantitatively to the corresponding. It was suggested that both the alkyl cation and the proton serve as the initiating species in the cationic polymerization of GPE.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

S-tert-Butyl-P-phenyl-l-piperidinyl phosphonamidodithioate (1) served as a novel thermally latent anionic initiator in the polymerization of glycidyl phenyl ether. (C) 2000 Published by Elsevier Science Ltd.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

A bifunctional five-membered cyclic carbonate was synthesized from carbon dioxide and diglycidyl terephthalate, and its polyaddition with alkyl diamines were carried out in DMF at room temperature to obtain the corresponding poly(hydroxyurethane)s with M(n)s in the range of 6300-13200 in good yields. The structures of the obtained polymers were confirmed by IR and NMR spectroscopy and their glass-transition and decomposition temperatures were observed at 3-29 degrees C and 182-277 degrees C, respectively. (C) 2000 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Activated monomer cationic ring-opening polymerization of epsilon-caprolactone (epsilon-CL) and delta-valerolactone (delta-VL) and the synthesis of di- and triblock copolymers of a seven-membered cyclic carbonate (7CC) and these lactones initiated with n-butyl alcohol/HCl . Et2O and H2O/HCl . Et2O were carried out to obtain the corresponding homopolymers and block copolymers with narrow polydispersity ratios in one pot quantitatively. The molecular weights of the obtained polymers could be controlled with the feed ratio of the monomer and initiator.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

Communication: Ring-opening polymerization of a seven-membered cyclic carbonate, 1,3-dioxepan-2-one, was investigated with a novel initiator system, BCl3-HCl . Et2O. Addition of HCl . Et2O promoted the polymerization even at 0 degrees C to produce the corresponding polycarbonate with controlled molecular weight and narrow polydispersity ratio (<1.2).

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Controlled ring-opening polymerization of a seven-membered cyclic carbonate, 1,3-dioxepan-2-one (7CC), with H2O/HCl.Et2O initiator system was investigated. The molecular weight (M-n) of the obtained polymer could be controlled by the amount of H2O in the range of 10(3)-10(4) maintaining a low polydispersity ratio (M-w/M-n = 1.11-1.17). The second portion of the monomer after completion of the first polymerization was converted quantitatively to give the corresponding polymer with a low M-w/M-n. The kinetic and H-1 NMR spectroscopic studies suggested that the nucleophilic attack of H2O to the monomer activated with hydrogen chloride afforded alpha-hydroxyl-omega-carbonic acid, followed by decarboxylation reaction to give alpha,omega-dihydroxyl compound. It was suggested that the chain growth in this system was the attack of the terminal hydroxyl group to the monomer activated with hydrogen chloride.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Ring-opening polymerization of cyclic carbonates (1,3-dioxepan-2-one and 5,5-dimethyl-1,3-dioxan-2-one)with triethyl and triisopropyl berates as initiators promoted by hydrogen chloride was carried out. The molecular weights of the obtained polymers could be controled by the amount of alkylborates, and their polydispersity ratios were small (similar to 1.15). The polymerization obeyed good first-order kinetics throughout the reaction. After the monomers were completely consumed, the polymerization proceeded again quantitatively when the same amount of monomers were introduced into the polymerization mixtures. H-1 and C-13 NMR spectroscopic studies suggested that the polymerization proceeded in a living manner via insertion of the monomer to the boron-oxygen bond.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

The cationic polymerization of glycidyl phenyl ether (GPE) was examined with novel phosphonic acid esters, O,O-di-p-methylbenzyl phenylphosphonate (la), O,O-dibenzyl phenylphosphonate (1b), and O,O-di-p-nitrobenzyl phenylphosphonate (Ic), as initiators. GPE did not convert with 1a-c even at 210 degrees C in the absence of ZnCl2. In the presence of ZnCl2 along with phosphonic acid esters la, Ib, and Ic, the polymerization of GPE did not proceed below 90, 130, and 170 degrees C, respectively, but it rapidly proceeded to afford polyGPE with M-n of 2500-5000 above those temperatures. It was found that la, Ib, and Ic seri ed as thermally latent initiators in the polymerization of GPE in the presence of ZnCl2. Electron-donating substituents on the benzyl group of the phosphonic acid esters increased the initiator activity. The initiation species was identified as a benzyl cation by C-13-labeled experiments.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

This article deals with cationic ring-opening polymerization of spiro orthoesters, depolymerization of the obtained polymers, and its application to chemical recycling systems. Further, we describe novel living cationic ring-opening polymerization of a cyclic dithiocarbonate based on neighboring group participation.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

The syntheses and cationic ring-opening polymerizations of the seven-membered cyclic carbonates having phenyl and methyl groups were carried out, and the substituent effect on the polymerization behavior was examined. The cyclic carbonate (2) carrying a phenyl group in position 4 was transformed into the corresponding polycarbonate containing a small amount of a polyether unit by an accompanying elimination of 2-phenyl-tetrahydrofuran (5) by using TfOMe and TfOEt as initiators. When TfOH and SnCl4 were used as the initiators, the main product was not the polymer but compound 5. It was confirmed that the unit sequence of poly(2) was completely controlled by the stabilization effect of the phenyl group on the propagating cation. Namely, the cationic polymerization of 2 proceeded via the selective cleavage of the bond between the benzyl carbon and the ether oxygen with forming a stable benzyl cation. Using cyclic carbonates carrying a phenyl group in position-5 (3) and a methyl group in position-4 (4) lead to the corresponding polycarbonates in good yields without elimination of tetrahydrofuran derivatives under any conditions. In these cases, the unit sequences could not be controlled. We have demonstrated that the cationic polymerization behavior of seven-membered cyclic carbonates is dramatically affected by the substituents and their positions.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CHEMICAL SOC JAPAN  

S,S-Di-t-butyl phenylthiophosphonate (1) served as a novel thermally latent initiator in the polymerization of glycidyl phenyl ether (GPE) in the presence of ZnCl2.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Di-2,2,2-trichloroethyl cis-epoxysuccinate, di-2-cyanoethyl cis-epoxysuccinate, and di-2-methoxyethyl cis-epoxysuccinate were synthesized, and the substituent effect of the epoxysuccinates on the polycondensation with diamine was studied. The order of reactivities of the epoxysuccinates with m-xylylenediamine was as follows: di-trichloroethyl ester much greater than di-cyanoethyl ester > di-methoxyethyl ester, such was also confirmed by the model reaction of the epoxysuccinate with benzylamine. H-1 NMR and IR spectroscopic study and ab initio calculation also well explained the reactivity order. (C) 2000 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

The electrophilic reactions of five-membered cyclic dithiocarbonates were studied. They afforded the isomers and polymers depending on the substituents.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Polyaddition of bifunctional spiro orthoesters (SOEs) with bifunctional acid chlorides tvas examined to develop zero-shrinkage polymerization. The polyaddition afforded the corresponding polyether-esters by repeating the addition reaction accompanying the double ring-opening isomerization of the SOE moiety in a manner similar to the reaction of monofunctional SOEs with acid chlorides. The polyaddition accompanied a slight shrinkage or expansion in volume. (C) 2000 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Synthesis and radical polyaddition behavior of N-methacryloyl-L-cysteine methyl ester (MA-C-M), N-4-pentenoyl-L-cysteine methyl ester (P-C-M), and N-4-vinylbenzoyl-L-cysteine methyl ester (V-C-M) were examined. Although MA-C-M afforded a cross-linked polymer and P-C-M did not polymerize at 60 degrees C, V-C-M polymerized satisfactorily to afford the corresponding polysulfide with M-n's in the range 7000-23 000 in good yields. The molecular weight of poly(V-C-M) increased after post-polymerization, indicating the telechelic structure with mercapto and olefin moieties at the polymer ends. The specific rotation and CD spectrospecific analysis suggested that poly(V-C-M) had some higher order structures.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Novel phosphonic acid esters, O,O-di-1-phenylethyl phenylphosphonate (1), O,O-di-tert-butyl phenylphosphonate (2), and O,O-dicyclohexyl phenylphosphonate (3), were synthesized from phenylphosphonic dichloride and the corresponding alcohols. The phenylphosphonic esters 1-3 decomposed into phenylphosphonic acid and the corresponding olefins by heating at 150-170 degrees C. Their initiator activities were examined in the cationic polymerization of glycidyl phenyl ether (GPE). They converted GPE only 4% even at 190 degrees C in the absence of ZnCl2. In the presence of ZnCl2 along with 1-3, GPE did not convert below 90 degrees C in the case of 1 and 2, and below 140 degrees C in the case of 3, but it rapidly converted to afford polyGPE with M-n of 2000-7000 above those temperatures. It was found that 1-3 served as thermally latent initiators in the polymerization of GPE in the presence of ZnCl2.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

A spiro orthoester having an ester moiety, 2-acetoxymethyl-1,4,6-trioxaspiro[4.6] undecane (4) was synthesized, and its cationic polymerization and depolymerization of the obtained polymer (5) were carried out. The monomer 4 underwent cationic polymerization with a cationic catalyst to afford the corresponding poly(cyclic orthoester) 5, The obtained polymer 5 could be depolymerized with a cationic catalyst to regenerate the monomer 4 in an excellent yield. Further, bifunctional spiro orthoesters (6, 8, 9) having diester moieties were synthesized from terephthalic acid, succinic acid, and 1,4-cyclohexanedicarboxylic acid, and their acid-catalyzed reversible crosslinking-decrosslinking was examined. The bifunctional monomer 6 derived from terephthalic acid underwent cationic crosslinking to afford the corresponding network polymer (7), which could be also depolymerized to regenerate the original bifunctional monomer 6, (C) 1999 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Cationic ring-opening polymerization of a cyclic carbonate carrying an exomethylene moiety, 5-methylene-1,3-dioxan-2-one (ExTMC), was carried out, and its behavior was compared with a cyclic carbonate having no exomethylene group, 1,3-dioxan-2-one (TMC). ExTMC afforded the polymers with larger molecular weights than TMC under any conditions. The observed molecular weights of the polymers agreed well with the calculated ones in the polymerization of ExTMC with TfOH at 0 degrees C. A linear relationship was observed between the conversion and number-average molecular weight of the polymer obtained in the polymerization of ExTMC, which could not be observed in the polymerization of TMC. After ExTMC was completely converted, the polymerization took place again when the same amount of ExTMC was introduced into the polymerization mixture, The effect of the exomethylene group on the polymerization behavior was analyzed by an ab initio molecular orbital calculation to determine the possibility of the presence of an allylic cationic intermediate. It was suggested that the stabilization of the propagating cation by the exomethylene group caused the living character of the cationic polymerization of ExTMC. Furthermore, a block copolymer of ExTMC with a vinyl ether was synthesized as an application of the pseudo-living polymerization of ExTMC.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

The synthesis and radical polymerization of N-methacryloyl-S-trityl-L-cysteine methyl ester [MA-C(Trt)-M] were examined. The radical polymerization was carried out at 60 degrees C far 20 h in the presence of 2,2'-azoisobutyronitrile (AIBN) in benzene, PhCl, and N,N-dimethylformamide (DMF) to afford the corresponding polymer with (M) over bar(n)'s in the range of 13 200-130 000 in good yields. In the radical copolymerizations of MA-C(Trt)-M with methyl methacrylate and trityl methacrylate, the specific rotations of the copolymers showed maximum values with MA-C(Trt)-M contents of 60 and 80 mol-%, respectively. The polymers were treated with HBr/CH3CO2H (30 wt.-%) to afford the trityl group-free polymers, which were insoluble in solvents due to the oxidative crosslinking reaction between the thiol groups.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

Synthesis and radical ring-opening polymerization behavior of 1-phenyl-2-vinylcyclopropane (PhVCP) were examined. PhVCP was synthesized by the coupling reaction of butadiene with phenyldiazomethane, where cis and trans isomers were obtained with the ratio 78:22. Radical polymerization of PhVCP was carried out in bulk at 60-180 degrees C with 2,2'-azoisobutyronitrile, benzoyl peroxide, or di-tert-butyl peroxide as initiator to obtain a 1,5-ring-opened polymer with (M) over bar(n) approximate to 1900. When PhVCP was polymerized in the presence of 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO), (M) over bar(n) of the obtained polymer increased with time. The radical polymerizability of PhVCP is much lower compared with that of styrene. From the molecular-orbital calculation of both monomers, it has been suggested that this is not caused by an electronic factor of the vinyl group but by side reactions such as the abstraction of a hydrogen atom from the allylic position of PhVCP.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

Polyaddition of bifunctional bicycle ortho esters (BOEs) with bifunctional acid chlorides were carried out to afford quantitatively the corresponding polymers via a double ring-opening isomerization process. Polyaddition of bifunctional BOEs with a trifunctional acid chloride, 1.3.5-benzenetricarbonyl chloride, also proceeds satisfactorily to yield crosslinked polymers quantitatively The mixtures of BOEs and acid chloride show zero to low shrinkage (0.6%) during the polyaddition reaction.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

The reaction of bicycle ortho esters (BOEs) with acid chlorides was examined. The BOEs readily reacted with acid chlorides to give the corresponding adducts via ring-opening isomerization. The order of the reactivities of the acid chlorides is as follows, sebacoyl chloride greater than or equal to adipoyl chloride > succinyl chloride and 1,3,5-benzenetricarbonyl chloride > isophthaloyl chloride greater than or equal to benzoyl chloride. It is considered that the ring-opening isomerization of the BOEs with acid chlorides proceeds by a similar mechanism as that of the homopolymerization of the BOEs.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Graft polymerization of glycidyl phenyl ether (GPE) and alternating graft copolymerization of GPE-succinic anhydride (SA) onto a polymer-supported aminimide were examined. The polymer-supported aminimide was synthesized by radical polymerization of 1,1-dimethyl-1-(2-hydroxy-3-(4-vinylbenzyloxy)propyl)amine 2-benzoylimide, which was prepared by the reaction of methyl benzoate with equimolar amounts of 1,1-dimethyl hydrazine and 4-glycidylmethylstyrene. This aminimide could initiate the polymerization of GPE and alternating copolymerization of GPE with SA to give the corresponding graft copolymers. (C) 1999 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Synthesis and radical polymerization of a proline-substituted acrylamide, N-methacryloyl-L-proline methyl ester (A-P-M) were carried out. The isomerization of A-P-M between s-cis and a-trans forms of A-P-M was analyzed by H-1 NMR spectroscopy and molecular dynamics simulation, and the effect of the cis-trans isomerization on the radical polymerization of A-P-M was examined. The content of s-cis form of h-P-M increased with the NMR measuring temperature. The radical polymerization of A-P-M at higher temperature afforded the polymer with a higher s-cis content and a lower absolute value of specific rotation. It was suggested that the s-cis/s-trans ratio and the tacticity of the polymer affected the optical properties.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Syntheses and radical polymerizations of methaerylamides having (L)leucine and N-methyl-(L)-leucine methyl ester structures in the side chains N-methacryloyl-(L)-leucine methyl ester (MA-L-M) and N-methyl-N-methacryloyl-(L)-leucine methyl ester (N-Me-MA-L-M) were carried out. The monomers were prepared by the reactions of methacryloyl chloride with the corresponding amino acid methyl esters. Radical polymerizations were carried out in the presence of appropriate initiators at 60 degrees C and 120 degrees C. MA-L-M afforded the corresponding polymer with M(n)s 38,000 similar to 372,000 in high yields, while N-Me-MA-L-M afforded a trace amount of polymer at 60 degrees C and in a low yield even at 120 degrees C. Both inversion and increase of absolute value of specific rotation were observed in the transformation from MA-L-M (+1.3 degrees C) to poly(MA-L-M) (-35.7 degrees C). Changes in the CD spectral pattern and the conformation of the leucine moiety were confirmed from the monomer to polymer. (C) 1998 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

The anionic ring-opening polymerization of six-membered cyclic carbonates having aromatic substituents, 5-methyl-5-phenyl-1,3-dioxan-2-one (1) and 5,5-diphenyl-1,3-dioxan-2-one (2), was carried out. The anionic homopolymerization of 1 readily proceeds to afford the corresponding polycarbonate, while 2 showed only a slight homopolymerizability. This is due to a rapid back biting reaction of the propagating polymer end to form 2. The conformational restriction of the adduct of 2 with an alkoxide, originating from the electrostatic repulsion between the alkoxide anion and the pi electrons of the aromatic rings, might cause the rapid back biting reaction. The anionic copolymerization of 2 with 5,5-dimethyl-1,3-dioxan-2-one (3) proceeds to afford the copolymer. The anionic ring-opening polymerization of 1 was confirmed to be an equilibrium polymerization. Monomer 1 was regenerated up to the equilibrium monomer concentration by depolymerization of poly(1). A volume expansion (10.8%) was observed during the polymerization of 1.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Ring-opening reactions of 1,3-dioxepan-2-one (1) and 1,3-dioxan-2-one (2) with several alcohols were examined. The reactions proceeded without trifluoroacetic acid (TFA) in low conversions, while they proceeded smoothly with TFA to afford the ring-opened adducts and oligomers. Ring-opening polymerizations of 1 and 2 were also carried out by alcohol-acid catalysts to afford the corresponding polycarbonates ((M) over bar(n) = 2500-6800). The molecular weights increased with increase of the conversions of 1 and 2. The observed polymerization rates of 1 and 2 were determined as 24.4 x 10(-6) and 0.8 x 10(-6) s(-1), respectively. Mechanistic aspects were studied by NMR spectroscopy. The methylene protons alpha and beta to the carbonate moieties shifted to lower fields in 0.06-0.11 ppm in the H-1-NMR spectra by the addition of TFA. Downfield shifts of the carbonyl carbon signals of 1 and 2 were observed in 3.94-4.15 ppm in the C-13-NMR spectra. These results strongly suggest that the cyclic carbonates are activated by TFA. (C) 1998 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Synthesis and radical polymerization of a novel optically active methacrylate, (S)-2-tert-butoxycarbonylamino-3-phenylpropyl methacrylate (MA-F-BOC), were examined. MA-F-BOC was synthesized from methacrylic acid and N-protected (L)-phenylalaninol. Radical polymerization of MA-F-BOC quantitatively afforded the corresponding polymethacrylate with a relatively high molecular weight. Radical copolymerizations of MA-F-BOC were carried out with styrene and acrylamide to afford the copolymers. Radical polymerization of MA-F-BOC in the presence of n-butanethiol afforded the oligomers, whose degrees of polymerizations were 3.3-8.0. The BOC group was completely cloven with HBr to afford the corresponding optically active polymeric amine quantitatively. (C) 1998 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Synthesis and radical polymerization of novel vinylcyclopropanes; 1-carboethoxy-2-trimethylsilyl-2-vinylcyclopropane (1a) and 1-carboethoxy-2-(1-trimethylsilyl)-vinylcyclopropane (1b), were examined. la and 1b were prepared by the coupling reaction of 2-trimethylsilylbutadiene with ethyl diazoacetate, which was prepared from glycine ethyl ester hydrochloride. The radical polymerization of 1a and 1b was carried out at 60 degrees C in bulk for 40 h in the presence of 2,2'-azobis(isobutyronitrile) (5 mol % vs. monomer). Poly(1) consisted of a 1,5-ring-opened unit. Desilylation reaction of poly(1) proceeded quantitatively in aqueous hydrochloric acid. (C) 1998 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

Novel one-pot syntheses of sulfur-containing polymers from a five-membered cyclic dithiocarbonate (5-phenoxymethyl-1,3-oxathiolane-2-thione (1)) and diamines were examined. Polydisulfides with (M) over bar(n) 5400 similar to 15 800 were obtained in the oxidation polymerizations of dithiols 2, which were obtained in situ by the reactions of 1 and diamines. When 1,12-dodecanediamine was employed, a polydisulfide with relatively high (M) over bar(n) was obtained, while in the case of m-xylylenediamine, the polymerization was accompanied by intermolecular cyclization to give a polydisulfide with low (M) over bar(n). Polythiourethanes with (M) over bar(n) 6 500 similar to 17 200 were obtained in the polyaddition of 2 with 4,4'-methylenebis(phenyl isocyanate). The yields and (M) over bar(n) values increase with increasing methylene chain length of 2. Polythioethers with (M) over bar(n) 2 600 similar to 19 900 were obtained by the polycondensations of 2 with alpha,alpha'-dibromo-p-xylene. The glass transition temperature (T-g) of the polymer decreases with increasing methylene chain length in the main chain.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Anionic equilibrium polymerization behavior of several six-membered cyclic carbonates was examined. The conversions of the monomers reached a constant below 100%, and the final conversion decreased in the order of 1,3-dioxan-2-one (1) > 5,5-dimethyl-1,3-dioxan-2-one (2) > 5,5-diethyl-1,3-dioxan- 2-one (3) greater than or equal to 5-methyl-5-phenyl-1,3-dioxan-2-one (4) > 5-ethyl-5-phenyl-1,3-dioxan-2-one (5). The reactions of 2,2-disubstituted-1,3-propanediols were carried out with phosgene dimer to find that the cyclic carbonate (5) was formed quantitatively in the reaction of 2-ethyl-2-phenyl-1,3-propanediol, while the corresponding polycarbonate was formed in the reaction of 2,2-diethyl-1,3-propanediol in 24% yield besides 3. Thermodynamic parameters were estimated in the anionic ring-opening polymerizations of cyclic carbonates (1-5) by Dainton's equation. The obtained Delta H-p value in the ring-opening polymerization of each cyclic carbonate reflected the polymerizability. Molecular orbital calculations of the model compounds of the polymers were carried out to fmd that the polymerizabilities of the cyclic carbonates correlated with the stabilities of the corresponding polymer structures. The concentrations of the monomers formed in the depolymerizations well agreed with the equilibrium monomer concentrations in the anionic ring-opening polymerizations.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Novel one-pot syntheses of sulfur-containing polymers from a bifunctional five-membered cyclic dithiocarbonate (1a) were carried out. Polythiourethanes were obtained by the polyaddition of 4,4'-methylenebis(phenyl isocyanate), tolylene 2,6-diisocyanate, and hexamethylene diisocyanate with a dithiol(2a) obtained by the reaction of 1a and benzylamine under mild conditions. Polythioesters were also obtained by the polycondensation of terephthaloyl and succinyl chlorides with 2a. Further, polythioether was obtained by the polycondensation of alpha,alpha'-dibromo-p-xylene with 2a. (C) 1998 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

The selective cationic isomerizations and ring-opening polymerizations of cyclic five-membered dithiocarbonates(la, 5-phenoxymethyl-1,3-oxathiolane-2-thione; Ib, 5-methyl-1,3-oxathiolane-2-thione; Ic, 5-ethyl-1,3-oxathiolane-2-thione; Id, 5-chloromethyl-1,3-oxathiolane-2-thione) have been achieved by the selection of the catalysts, which have enabled the first facile preparations of 1,3-dithiolan-2-one derivatives (2a-d) and polydithiocarbonates (P1a-d). The mechanism of the selectivity was elucidated by the H-1 and C-13 NMR spectroscopic analyses for their reaction intermediates. The initiation steps of the reactions of la with TfOEt or TfOH were different, wherein the formation of the cyclic carbenium ion (6) via the ethylation of TfOEt on the thiocarbonyl sulfur and the oxonium cation (7) via the protonation of TfOH on the ether oxygen were observed, respectively. The cation 7 might not be electrophilic enough to be attacked by the monomer (1), which could explain the fact that the results in the reaction of 1 selectively gave the isomer with TfOH. The polymerization and isomerization should proceed predominantly via 6 and 7, respectively. The reactivities of 1a-d decreased in the order of Ib congruent to 1c > 1a > 1d, which showed good agreement with the H-1 NMR chemical shifts of the methine protons of 6a-d.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

The syntheses and cationic polymerizations of seven-membered cyclic sulfites having phenyl (7PhCS), benzo (7BnCS), and cyclohexane (7CyCS) groups were examined. 7PhCS and 7CyCS underwent complete elimination of SO2 to afford the corresponding tetrahydrofuran derivatives under the cationic conditions. On the other hand, 7BnCS underwent cationic polymerization in the presence of cationic initiators such as TfOH, TfOMe, SnCl4, TsOMe, and MeI in bulk or chlorobenzene to afford the corresponding polymer with (M) over bar(n) 950-8700 without desulfoxylation. The benzo group was operative for polymerization and suppression of desulfoxylation. The polymerization of 7BnCS did not show equilibrium character. The steric hindrance of the benzene ring might be effective to suppress a back-biting reaction. The volume expansion during the polymerization of 7BnCS was 8.57%. This might be caused by the larger dipole-dipole interactions between the monomers and smaller ones between the polymers.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

Synthesis and cationic ring-opening polymerization of a seven-membered cyclic carbonate, 1,3-dioxepan-2-one (1), were examined. The cationic ring-opening polymerization of 1 proceeded without decarboxylation at 20 degrees C to give the corresponding polycarbonate, differently from a six-membered cyclic carbonate (2), for which polymerization is generally accompanied by partial elimination of carbon dioxide. The observed polymerization rate of 1 in nitrobenzene was about 1.3 times faster than that in dichloromethane. The observed pseudo first-order polymerization rate constants of 1 and 2 at 20 degrees C were determined to be 4.15 x 10(-4) and 4.16 x 10(-6) s(-1), respectively. The observed polymerization rate of 1 was 100 times larger than that of 2. The activation energies in the polymerization of 1 and 2 were estimated to be 6.27 and 8.52 kcal/mol, respectively.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：SOC POLYMER SCIENCE JAPAN  

The synthesis and radical ring-opening polymerizations of vinylcyclopropanes bearing six-, seven-, and eight-membered cyclic thioacetal moieties, 1-vinyl-4,8-dithiospiro[2.5]octane (4), 1-vinyl-4,9-dithiospiro[2.6]nonane (5), and 1-vinyl-4,10-dithiospiro[2.7]decane (6) were carried out. Monomers 4-6 were prepared by reactions of 1,1-dichloro-2-vinylcyclopropane and corresponding dithiols in N,N-dimethylformamide (DMF) in the presence of a base. Radical polymerizations of 4, 5, and 6 were carried out at 60, 80, and 120 degrees C for 20 h in the presence of an appropriate initiator (3 mol% vs. monomer) to obtain polymers with M-n 600-3100, mainly consisting of a 1,5-ring-opened unit and a unit with no olefinic moiety.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Cationic ring-opening polymerization behavior of a seven-membered cyclic sulfite (1)was examined. 1 was prepared by the reaction of 1,4-butanediol with SOCl2 in 58% yield. The cationic polymerization of 1 was carried out at 0, 25, 60, or 100 degrees C with trifluoromethanesulfonic acid (TfOH), methyl trifluoromethanesulfonate (TfOMe), BF3 . OEt2, SnCl4, methyl p-toluenesulfonate (TsOMe), or MeI as an initiator in bulk under a nitrogen atmosphere to afford the polymer with (M) over bar(n) 1000-10,400. The order of activities of the initiators for 1 was as follows, TfOH congruent to TfOMe > SnCl4 > BF3 . OEt2 > TsOMe congruent to MeI. The polymerization of 1 with TfOMe afforded a poly(sulfite) below 25 degrees C, but afforded a polymer containing an ether unit at 60 degrees C, which was formed by a desulfoxylation. The higher the activity of the initiator was, the more easily the desulfoxylation occurred. We expected volume expansion on polymerization because cyclic sulfites have large dipole moment values, but it turned out that 1 showed 4.34% shrinkage on polymerization. (C) 1997 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：HUTHIG & WEPF VERLAG  

Syntheses and radical polymerizations of methacrylamides derived from optically active amino alcohols were carried out. The monomers were prepared by condensation of optically active amino alcohols and methacrylic acid using 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC . HCl). Radical polymerizations of the monomers were carried out in the presence of 2,2-azoisobutyronitrile (AIBN) (3 mol-%) in methanol and N,N-dimethylformamide (DMF) as solvents, resulting with good yields in polymers with (M) over bar(n)'s in the range 17 800-81 000. The monomer reactivity ratios of N-(1-hydroxy-4-methyl-2-pentyl)methacrylamide (MA-Lol) and methyl methacrylate (MMA) in the copolymerization were estimated to be 0.50 and 2.38, respectively. The lower reactivity of MA-Lol in comparison with MMA is similar to common methacrylamide derivatives. The hydrophilicity of the polymers was evaluated by the heat of fusion of water using differential scanning calorimetry (DSC). The determined order poly(MA-Aol) > poly(MA-Lol) > poly(MA-Fol) reflects the bulkiness of the side chains.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Syntheses and radical polymerizations of several (meth)acrylamides having L-amino acid moieties were examined. The monomers were prepared by the reactions of L-amino acid ester hydrochlorides with (meth) acryloyl chloride in the presence of triethylamine in satisfactory yields. Radical polymerizations of the monomers were carried out in the presence of AIBN (1 mol %) in bulk and in several solvents to afford the corresponding polymers in satisfactory yield. The glass transition temperatures and specific rotations of the polymers depended on the substituents of the L-amino acid moieties. Nearly the same specific rotations were observed for the monomers and the model compounds of the polymer units, N-pivaloyl amino acid methyl esters. On the contrary, the specific rotations of the polymers shifted to the negative direction in ca. 30 degrees. The interaction between the polymer side chains might affect the changes in the specific rotations from monomers to polymers. (C) 1997 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Syntheses and radical ring-opening polymerizations of vinylcyclopropanone derivertives having cyclic six-membered acetal, exomethylene, and phenyl groups; 1-vinyl-6-methylene-4,8-dioxaspiro[2.5]octane (2b), 1-vinyl-5,7-dimethyl-6-methylene-4,8-dioxaspiro[2.5]octane (2c), 1-vinyl-5-phenyl-4,8-dioxaspiro[2.5] octane (2d), and 1-vinyl-5,7-diphenyl-4,8-dioxaspiro[2.5]octane (2e), were carried out. The monomers were prepared by reactions of 1,1-dichloro-2-vinylcyclopropane and the corresponding diols in DMF in the presence of sodium hydride. Radical polymerizations of 2b-2e were carried out at 60, 80, and 120 degrees C in the presence of an appropriate initiator (3 mol % vs. monomer) in degassed sealed ampoules for 20 h. Although colorless transparent polymers ((M) over bar(n) 2300-13,500) were isolated by preparative HPLC for the most monomers, a crosslinked polymer was obtained in the case of 2b. The structures of the polymers were determined to consist of single and double ring-opening units. The content of the double ring-opened unit was 25-75% by comparison of LR spectra to a model compound. It is suggested that the double ring-opened propagating chain end is stabilized by the substituents on the cyclic acetal rings. The two-center energies of the cyclopropane ring and activation energy of ring-opening calculated by molecular orbital methods may explain the selectivity in the cleavage of the cyclopropane ring, and the degree of double ring-opening. (C) 1997 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER SCIENCE BV  

Crosslinked poly(cyclic orthoester)s prepared by radical additions of poly(cyclic orthoester)s possessing exomethylene groups and dithiols efficiently depolymerized to bifunctional spiro orthoesters in the presence of trifluoroacetic acid in dichloromethane. Furthermore, the dithiol-linked bifunctional spiro orthoester monomers prepared by the radical additions of spiro orthoester possessing exomethylene group and dithiols afforded the corresponding crosslinked polymers in the presence of trifluoroacetic acid as a catalyst in bulk condition. The quantitative depolymerization of the obtained crosslinked polymer afforded the corresponding bifunctional monomer in dichloromethane at room temperature. Meanwhile, an acid-catalyzed reversible crosslinking-depolymerization of a polymer having a spiro orthoester group in the side chain was carried out. The copolymer obtained by the radical copolymerization of 2-methylene-1,4,6-trioxaspiro[4.6]undecane with acrylonitrile was treated with trifluoroacetic acid in dichloromethane at 10 degrees C to afford the crosslinked polymer quantitatively. The crosslinked polymer was then treated with trifluoroacetic acid at a low concentration in dichloromethane at room temperature to recover the original polymer.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：HUTHIG & WEPF VERLAG  

Syntheses of poly(ester-amide)s derived from optically active amino alcohols are described. Poly(ester-amide)s with (M) over bar n 8,700 similar to 27,200 were obtained by the polycondensations of hydroxycarboxylic acids derived from maleic or succinic acid, and by those of dicarboxylic acids and diols' derived from dicarboxylic acids and optically active amino alcohols using EDC . HCl in satisfactory yields. The radical additions of ethanethiol or mercaptoethanol to the polymers derived from maleic anhydride proceeded smoothly in satisfactory incorporation ratios (43 similar to 98%). The polymer obtained from succinic anhydride and 2-aminoethanol showed hydrolytic degradability. The Tg of the polymer derived from leucinol showed even-odd effect with increase of methylene chain length of dicarboxylic acids.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：SPRINGER VERLAG  

Syntheses and radical ring-opening polymerization of 1,1-bis(hydroxymethyl)-2-vinylcyclopropane (1a) and 1,1-bis(methoxymethyl)-2-vinylcyclopropane (1b) were examined. Novel polymers bearing hydroxyl and methyl ether moieties in the side chains as well as olefinic moieties in the main chain were obtained. The main structure of the polymers, obtained by radical polymerization, originated from the cleavage of the cyclopropane ring near the hydroxymethyl or methoxymethyl groups. The difference in the two-center energies and bond orders of the C-C bonds of the cyclopropane ring well explained the selectivity in the direction of the cleavage. The number-average molecular weights ((M) over bar(n)) of poly(1a) and poly(1b) were 94200 and 11200 in the polymerization in bulk at 60 degrees C, respectively. The intermolecular hydrogen bonding of la might increase the radical polymerizability. The oxygen permeability of poly(1a) was 6.19 mL.20 mm.m(-2).day(-1).atm(-1) at 35 degrees C, demonstrating that poly(1a) could be a good oxygen barrier material.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：HUTHIG & WEPF VERLAG  

The synthesis and radical polymerization behavior of a novel methacrylate having a peptide moiety, N-benzyloxycarbonyl-L-leucyl-L-alanylglycine 2-methacryloyloxyethyl ester (1), are described. 1 shows radical polymerizability in spite of the bulky peptide moiety. Only the ester group near the peptide moiety of poly(1) could be hydrolyzed selectively and completely in the hydrolysis of poly(1) in an alkaline solution.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Anionic ring-opening polymerization of a seven-membered cyclic carbonate, 1,3-dioxepan-2-one (1), was carried out to observe that the higher the polymerization temperature and lower the initial monomer concentration were, the lower the yield and molecular weight, and wider the molecular weight distribution of the obtained polymers were. The back-biting reaction and the formation of cyclic oligomers of 1 were observed during the polymerization of 1. The relative polymerization rate of 1 was about 35 times faster than that of six-membered carbonate, 1,3-dioxan-2-one (3). The Delta Hps of 1 and 3 estimated by MO (PM3) calculations were -9.8 and -4.4 kcal/mol, respectively. 1 could easily undergo the ring-opening polymerization based on larger ring strain. (C) 1997 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：HUTHIG & WEPF VERLAG  

A variety of cyclic carbonates was shown to undergo volume expansion on polymerization. The degree of volume expansion, which was measured by the density gradient tube method, was ranging from 1.1% to 7.7%. The volume expansion was examined by assuming a change in molecular interaction such as dipole moment between monomer and polymer states.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CHEMICAL SOC JAPAN  

Acid-catalyzed reversible crosslinking-decrosslinking of polymers having spiro orthoester groups in the side chains was carried out. The copolymers obtained by the radical copolymerizations of 2-methylene-1,4,6-trioxaspiro[4.6] undecane with acrylonitrile, methyl, cyclohexyl, and 2-ethylhexyl acrylates were treated with trifluoroacetic acid (5 mol%) at -10 degrees C for 1 h in CH2Cl2 (4.2 M) to afford the crosslinked polymers in 69-99% yields. The crosslinked polymers were then treated with trifluoroacetic acid at a low concentration (0.1 M) in CH2Cl2 at room temperature for 1 h to give the original polymers in 55-99% yields. These results strongly support the conclusion that the acid-catalyzed reversible crosslinking-decrosslinking of the polymers possessing the spiro orthoester groups in the side chains could be constructed.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Syntheses and radical polymerization behavior of methacrylamides having peptide moieties, N-(methacryloylglycyl)-L-leucyl-L-alanine methyl ester (MA-GLA-M) and N-(methacryloyl-beta-alanyl)-L-leucyl-L-alanine methyl ester (MA-beta LA-M), were examined. Radical polymerizations of MA-GLA-M and MA-beta LA-M in the presence of AIBN (1 mol %) in DMF (1.0 mol/L) afforded the corresponding polymers (poly(MA-GLA-M) and poly(MA-beta LA-M)) in nearly quantitative conversions with <(M)over bar (ns)> 68000 and 69000, respectively. An increase of the absolute value of molecular rotation on the transformation from MA-GLA-M (-126.0 degrees) and MA-beta LA-M (-132.9 degrees) to poly(MA-GLA-M) (-176.5 degrees) and poly(MA-beta LA-M) (-242.1 degrees) could be observed. The radical polymerizability of MA-beta LA-M in MeOH was suggested to be lower than that of MA-GLA-M. The CD patterns of poly(MA-GLA-M) and poly(MA-beta LA-M) were similar to those of the corresponding model compounds.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：HUTHIG & WEPF VERLAG  

Synthesis and cationic polymerization of a novel vinyl ether with an L-proline moiety, N-carbobenzoxy-L-proline 2-vinyloxyethyl ether (ZProVE), were carried out. ZProVE was prepared by the condensation of N-carbobenzoxy-L-proline and 2-hydroxyethyl vinyl ether. Cationic polymerization of ZProVE was carried out in dichloromethane at -50, -20 degrees C, or room temperature. The number-average molecular weight ((M) over bar(n)) of the polymer obtained in the polymerization at -50 degrees C was 44900, and the [alpha](D)(23) value of the polymer was -36.1 degrees, which was somewhat larger (more positive) than that of ZProVE (-46.4 degrees). Cationic copolymerizations of ZProVE and isobutyl vinyl ether proceeded readily to afford the corresponding copolymers. Alkaline hydrolysis of poly(ZProVE) afforded poly(hydroxyethyl vinyl ether).

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Syntheses and polycondensations of optically active hydroxycarboxylic acids prepared from acid anhydrides and aminoalcohols were carried out. Novel polymers with (M) over bar(n) 9900-27,200 were obtained by the polycondensations of hydroxycaboxylic acids derived from maleic or succinic acid using 1.2 eq. of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC . HCl) in DMF (2M) at room temperature for 8 h in satisfactory yields. Meanwhile, a hydroxycarboxylic acid obtained from phthalic acid afforded no polymer but a phthalimide derivative. The radical additions of ethanethiol or mercaptoethanol with the polymers derived from maleic anhydride proceeded smoothly in satisfactory incorporation ratios (65-98%), respectively. The polymer obtained from succinic anhydride and 2-aminoethanol showed hydrolytic degradability. (C) 1997 John Wiley & Sons, Inc.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Syntheses and radical copolymerization behavior of N-methacryloyl-L-leucine methyl ester (MA-(L)-L-M) and its optical isomer (MA-(D)-L-M) have been examined. From their melting points and crystal X-ray analysis, MA-(L)-L-M and MA-(D)-L-M might be suggested to form a racemic compound associated at the amide moiety by a hydrogen bond. Radical copolymerizations of MA-(L)-L-M and MA-(D)-L-M were carried out using AIBN as an initiator (1 mol %) in chlorobenzene (1 M) to afford the corresponding copolymers as n-hexane-insoluble pacts with <(M)over bar (n)>, 77 000-120 000. The conversions of the monomers were almost quantitative in any case. The T-g of the copolymer having an equimolar ratio of L- and D-units was lower than those of the corresponding homopolymers. while the solubility of the copolymer in ether was higher than those of the homopolymers. The total rate of radical copolymerization of MA-(L)-L-M and MA-(D)-L-M was smaller than those of the homopolymerizations of the both monomers.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Synthesis and radical polymerization of methacrylamide having an L-leucyl-L-alanine methyl ester structure, N-methacryloyl-L-leucyl-L-alanine methyl ester (MA-LA-M), were carried out. Radical polymerization of MA-LA-M in the presence of AIBN (1 mol %) in chlorobenzene (1.0 mol/L) afforded the corresponding polymer (poly(MA-LA-M)) with M(n) 196 000. The 10% weight loss temperature of poly(MA-LA-M) under nitrogen was 300 degrees C. Increase of the absolute value of specific rotation in the transformation from MA-LA-M (-48.0 degrees) to poly(MA-LA-M) (-76.5 degrees) could be observed. The rate of radical polymerization of MA-LA-M was 4-6 times larger than that of N-methacryloyl-L-leucine methyl ester (MA-L-M) in benzene-d(6) (1.0 mol/L), whereas the activation energy (E(a)) of MA-LA-M (51.4 kJ/mol) was larger than that of MA-L-M (29.7 kJ/mol). The absolute value of the activation entropy (Delta S-double dagger) in the radical polymerization of MA-LA-M (-144 J/(K . mol)) was smaller than that of MA-L-M (-221 J/(K . mol)). These parameters for the both monomers were nearly equal in the polymerizations in DMSO-d(6). From the IR and H-1 NMR analyses, MA-LA-M in benzene might be suggested to be more strongly aggregated each other by intermolecular hydrogen bonds than MA-L-M.

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS INC  

Synthesis and radical ring-opening polymerization of vinylcyclopropane bearing six-membered cyclic acetal moiety, 1-vinyl-4,8-dioxaspiro[2.5]octane (1), were carried out. 1 was prepared by the reaction of 1,1-dichloro-2-vinylcyclopropane and 1,3-propanediol in DMF in the presence of a base. Radical polymerization of 1 was carried out in the presence of an appropriate initiator (3 mol % vs. 1) at 60 and 120 degrees C in degassed sealed ampoules for 20 h. A colorless transparent viscous polymer was obtained by the isolation with preparative HPLC. The structure of poly(1) was determined to consist of two 1,5-ring-opened units and a unit bearing no olefinic moiety. The difference of the activation energies for the ring opening reaction of the cyclopropane ring calculated by the molecular orbital method could explain the selectivity in the direction of the cleavage of the cyclopropane ring. Acid hydrolysis of poly(1) afforded the corresponding polyketone in quantitative conversion. (C) 1996 John Wiley & Sons, Inc.

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