担当区分：筆頭著者,　責任著者   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 (ACS)  

We synthesized two kinds of monocarbamothioates TZO(R) containing a thiazolidin-2-one (TZO) skeleton and TZD(R) containing a thiazolidine-2,4-dione (TZD) skeleton. In the reaction of TZO(R) and phenoxypropyrenesulfide (PPS) using tetrabutylammonium chloride (TBAC) as a catalyst in 1-methyl-2-pyrrolidinone at 60 °C, anionic ring-opening polymerization of PPS proceeded to give the corresponding linear polysulfides, polyPPS, with Mn = 75 860-206 700 (Mw/Mn = 1.54-1.73) in high yield. In contrast, in the reaction of TZD(R) and PPS, the continuous insertion reaction of PPS into TZD(R), i.e., living ring-expansion polymerization, occurred to afford cyclic polysulfides TZD(R)-c-poly(PPS)n with Mn = 1870-33 420 (Mw/Mn = 1.07-1.26) in high yield. The ring size could be controlled by the feed ratio of TZD(R)/PPS in the range of 1/5-1/100.

DOI： 10.1021/acs.macromol.0c00687

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担当区分：筆頭著者,　責任著者   記述言語：日本語   掲載種別：研究論文（学術雑誌）  

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Technical Association of Photopolymers, Japan  

© 2019SPST. We examined the synthesis and resist properties of tellurium-containing molecular resist materials. By the condensation reaction of anisol, phenol, and 2-phenylphenol with tellurium tetrachloride (TeCl4), dichloro di(4-hydroxyphenyl) telluride (CHPT), dichloro di(4-hydroxy-3-phenylbenz) telluride (CHBT), di(4-hydroxyphenyl) telluride (HPT), and di(4-hydoxy-3-phenylbenz) telluride (HBT) were synthesized. These were reacted with 2-methyl-2-adamantyl bromo acetate, yielding corresponding compounds CHPT-AD, CHBT-AD, HPT-AD, and HBT-AD, respectively. By the examination of resist properties (thickness loss property, resist sensitivity, and etching durability), CHBT-AD could be good candidate for higher resolution EUV resist material.

DOI： 10.2494/photopolymer.32.805

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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.orglett.9b03693

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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)  

<p>NORIA is a synthetic macrocycle consisting of twelve resorcinol rings. By cocrystallization of NORIA with benzene, NORIA organized one-dimensional array.</p>

DOI： 10.1039/d0ce00650e

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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  

We synthesized noria-containing cross-linking materials, Cross(Noria-MA-co-DM[n]m), by radical polymerization of a noria derivative with pendant methacryloyl groups (noria-MA) and α, ω-alkanedimethacrylamides (DM[n], n=3, 6, 12) at feed ratios of noria-MA/DM[n]=1/2.4, 1/12, and 1/24 (m=2.4, 12. and 24). Alkaline hydrolysis reaction of Cross(Noria-MA-co-DM[n]m) removed the noria moieties to give corresponding cross-linking materials, Cross-COOH-DM[n]m, containing noria-templated fixed cavities with pendant carboxylic acid groups. Among the noria-containing cross-linking materials, Cross(Noria-MA-co-DM[6]24) showed the greatest extent of removal of noria upon hydrolysis. Nitrogen and carbon dioxide absorption studies indicated that Cross(Noria-MA-co-DM[6]24) contains fixed cavities, whereas Cross-COOH-DM[6]24 does not in the solid (unswollen) state. Examination of the inclusion-complex-forming ability of the synthesized cross-linking materials using aqueous solutions of metal ions revealed that Cross-COOH-DM[6]24 has the greatest absorption capacity. These results indicate that Cross-COOH-DM[6]24 indeed contains noria-templated cavities that can accommodate metal ions in aqueous solution.

DOI： 10.1002/slct.201703099

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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  

We synthesized noria-containing cross-linking materials, Cross(Noria-MA-co-DM[n]m), by radical polymerization of a noria derivative with pendant methacryloyl groups (noria-MA) and α, ω-alkanedimethacrylamides (DM[n], n=3, 6, 12) at feed ratios of noria-MA/DM[n]=1/2.4, 1/12, and 1/24 (m=2.4, 12. and 24). Alkaline hydrolysis reaction of Cross(Noria-MA-co-DM[n]m) removed the noria moieties to give corresponding cross-linking materials, Cross-COOH-DM[n]m, containing noria-templated fixed cavities with pendant carboxylic acid groups. Among the noria-containing cross-linking materials, Cross(Noria-MA-co-DM[6]24) showed the greatest extent of removal of noria upon hydrolysis. Nitrogen and carbon dioxide absorption studies indicated that Cross(Noria-MA-co-DM[6]24) contains fixed cavities, whereas Cross-COOH-DM[6]24 does not in the solid (unswollen) state. Examination of the inclusion-complex-forming ability of the synthesized cross-linking materials using aqueous solutions of metal ions revealed that Cross-COOH-DM[6]24 has the greatest absorption capacity. These results indicate that Cross-COOH-DM[6]24 indeed contains noria-templated cavities that can accommodate metal ions in aqueous solution.

DOI： 10.1002/slct.201703099

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記述言語：英語   出版者・発行元：TECHNICAL ASSOC PHOTOPOLYMERS,JAPAN  

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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：TECHNICAL ASSOC PHOTOPOLYMERS,JAPAN  

Synthesis, physical properties, and resist properties of tellurium containing polymer with pendant adamantyl ester groups poly(Re-co-Te)-AD were examined, relevant to the application of resist material for extreme ultraviolet laser photolithography (EUVL) system. A tellurium containing polymer with pendant hydroxyl groups poly(Re-co-Te) was synthesized by the condensation reaction of resorcinol (Re) and tellurium tetrachloride (TeCl4), followed by the condensation reaction with adamantyl bromo acetate to give a corresponding polymer poly(Re-co-Te)-AD. Their physical properties (solubility, film-forming ability, thermal stability) and resist properties (thickness loss property after soaking in 2.38 wt% TMAH aq. solution, out-gassing on EUV exposure tool, and resist sensitivity under EUV exposure tool) were also examined.

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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：A V S AMER INST PHYSICS  

In this study, the authors examined the synthesis and resist performance of positive-tone chemically amplified molecular resist materials based on noria (water wheel in Latin) derivatives with pendant adamantyl ester (AD) groups (noria-AD) using an electron beam (EB) exposure tool. The physical properties of synthesized noria derivatives with various ratios of AD groups and their patterning properties were examined in an EB exposure tool. Furthermore, lithographic performances such as the etch durability and line width roughness of resist patterns were also investigated. These results showed that the physical properties and resist performance of the noria-AD were consistent with the ratio of AD groups, and noria derivatives have high potential to offer higher-resolution resist patterns for EB lithography. (C) 2016 American Vacuum Society.

DOI： 10.1116/1.4953068

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/pola.28095

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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  

Reaction of t-butylcalix[8]arene (BCA[8]) as an A8-type monomer with hexamethylene diisocyanate as a B2-type monomer was examined to afford only soluble polymers in high yields. Analysis by 1HNMR, IR, MALDI-TOF mass spectroscopy, and AFM indicated that the synthesized polymers consist of nanoscale-gel-shaped structures that contain fixed holes and cavities. We designated this class of polymers as botryosin, after the Greek word botrys, meaning a bunch of grapes. Examination of hostguest chemistry of the synthesized polymers revealed complexation with alkali metal ions.

DOI： 10.1246/cl.150840

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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：TECHNICAL ASSOC PHOTOPOLYMERS,JAPAN  

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記述言語：日本語   出版者・発行元：公益社団法人 応用物理学会  

DOI： 10.11470/jsapmeeting.2014.2.0_1440

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1246/cl.140497

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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  

Noria derivatives with pendant methoxy and adamantyl ester moieties (noria(MP)-AD(n)) were synthesized by the substitution reaction of noria analogues with 12 methoxy groups (noria(MP)) and 2-bromoacetyloxy-2-methyladamantane (BMA), and their degrees of introduction of adamantyl ester moieties (DI) could be controlled by the feed ratios of noria(MP) and BMA. The physical properties such as solubility, film-forming ability, and thermal stability of noriaMP-AD(n) were also examined to assess the suitability for application as extreme ultraviolet (EUV)-resist materials. The patterning property of noria(MP)-AD(18) (DI= 18) and noria(MP)-AD(54) (DI= 54) was investigated in an EUV-resist system, and noria(MP)-AD(18) yielded higher resolution than noriaMP-AD54, providing a clear line and space pattern with a resolution of 32 nm and a line-width roughness of 10.5 nm by exposure dose of 9.0 mJ/cm(2). (C) 2013 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.tsf.2013.02.016

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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  

To improve proton conduction at elevated temperatures, in situ impregnation of Nafion membranes has been carried out by infusing Noria "waterwheel" supramolecules, containing numerous hydroxyl terminal groups, into the ionic domains of Nafion via swelling in mixed methanol and dimethylacetamide solutions. Fourier transform infrared (FTIR) spectroscopy study reveals that interspecies hydrogen bonding occurs between hydroxyl groups of Noria and sulfonate groups of Nafion, which has facilitated retaining the modifier molecules within the membrane. Water uptake experiments exhibit that the impregnation of Noria into Nafion ionic domains suppresses the membrane swelling. The ion exchange capacity also increases upon this impregnation. The proton conductivity is reduced at low operating temperatures relative to neat Nafion due to the loss of hydronium ion transport. However, the proton conductivity of the Noria-impregnated membrane shows 60 % improvement over that of neat Nafion at elevated temperatures of 115 A degrees C. Of particular importance is that the Noria-impregnated membrane exhibits improved thermal, mechanical, and electrochemical stabilities with proton conductivity enhancement at elevated temperatures. Moreover, there is no noticeable difference in FTIR spectra before and after the proton fuel cell tests, indicating the improvement in the chemical stability of the Noria-impregnated membranes under the present proton fuel environment. It appears that these waterwheel supramolecules may have potential utility as high temperature electrolytes (or solid proton carriers) in proton fuel cells.

DOI： 10.1007/s10853-012-6681-y

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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：TECHNICAL ASSOC PHOTOPOLYMERS,JAPAN  

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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  

Polycondensation reaction of 1,3-dimethoxybenzene and TeCl4 was performed at a feed ratio of 1,3-DMB/TeCl4 = 1/10 without catalyst in 1,4-dioxane at 60 degrees C for 48h, affording poly(1,3-DMB-co-Te) with M-n = 45100 and M-w/M-n = 1.89 in 75% yield, with release of HCl. H-1 NMR, IR, and X-ray fluorescence spectroscopy indicated that poly(1,3-DMB-co-Te) had a partially branched skeleton. This polymer had good solubility, good film-forming ability, high thermal stability, and a high refractive index (1.769 at 0.6328 mu m).

DOI： 10.1246/cl.2011.762

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

Condensation reaction of 2-methylresorcinol and pyrogallol with 1,5-pentanedial [CH2(CH2CHO)2] in the presence of concentrated HCl in ethanol at 80 °C for 48 h proceeded according to a dynamic covalent chemistry (DC4) mechanism to afford the noria-like ladder-cyclic oligomers noriaMR and noriaPY, respectively. © 2011 The Chemical Society of Japan.

DOI： 10.1246/cl.2011.464

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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  

Polycarbosilanes were synthesized by hydrosilylation reaction of A(2) monomer containing bis Si-H moieties and B-n (n = 2 3 and 4) monomers containing di tri and tetra vinyl groups in the presence of Karstedt s catalyst The corresponding linear polycarbosilanes (LPC) and hyperbranched poly carbosilanes (HBPC) having M-n 2200-51 500 were obtained in 34-94% yield without any gel product The values of refractive index (n(D)) of the synthesized LPC and HBPC were in the range from 1 460 to 1 711 and were consistent with the structures of the synthesized products In the case of HBPC the values of nD increased with increase of number average molecular weight (K) molecular weight distribution (M-w/M-n) and glass transition temperature (T-g) apparently because of increased density due to the presence of microgels that is high refractive index hyperbranched carbosilanes could be synthesized by A(2) + B-n (n = 3 and 4) method (c) 2010 Wiley Periodicals Inc J Polym Sci Part A Polym Chem 48 5746-5751 2010

DOI： 10.1002/pola.24379

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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：NATURE PUBLISHING GROUP  

Hyperbranched polycarbonates (HBPCs) with M(n)=2.1-7.1 x 10(3) were synthesized by A(2)+B(3) polymerization using di-tert-butyl tricarbonate as the A(2) monomer and 1,1,1-tris(4-hydroxyphenyl)ethane as the B(3) monomer. A(2)+B(3) polymerization with different feed ratios was achieved, controlling the degree of branching (DB) and the ratio of terminal functional groups. The DB of the HBPCs is 0.5-0.7. The Boc-terminated PC was prepared by either a 1-pot or a 2-pot synthesis. In contrast, PC with terminal phenol groups was prepared by deprotection of Boc-terminated PC. Polymer Journal (2010) 42, 852-859; doi: 10.1038/pj.2010.82; published online 15 September 2010

DOI： 10.1038/pj.2010.82

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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：NATURE PUBLISHING GROUP  

Hyperbranched polysiloxanes were synthesized by polyhydrosilylation of silsesquioxane derivatives and vinyl derivatives in the presence of Karstedt&apos;s catalyst. The hyperbranched polymers (HBPs) with Mn=5.2x10(3)- 9.8x10(4) were soluble in common solvents and exhibited good thermal stability. HBPs based on double-decker-shaped silsesquioxane showed a large thermal-optical coefficient compared with the corresponding linear polymer. The refractive index values of the polymers obtained tended to decrease with the increasing structure size of the co-monomers. Polymer Journal (2010) 42, 799-803; doi:10.1038/pj.2010.79

DOI： 10.1038/pj.2010.79

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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：NATURE PUBLISHING GROUP  

The synthesis and photo-polymerization of hyperbranched polyesters (HBPEs) containing terminal methacryloyl groups (HBPE-MA) were examined. Polycondensations of 1,4-bis(chloromethyl) benzene with 1,3,5-benzenetricarboxylic acid using 1, 8-diazabicyclo[5.4.0] undec-7-ene as a base were performed to give the soluble HBPEs in satisfactorily high yields. Furthermore, HBPE-MA was synthesized by the reaction of HBPE with methacrylic acid. The photo-induced radical polymerization of HBPE-MA was performed in the presence of 2-methyl-1-[4-(methylthio) phenyl]-2-morpholinopropan-2-one (Irgacure 907), which acts as a photoinitiator in the solid film state and yields an insoluble cured film upon ultraviolet irradiation. Polymer Journal (2010) 42, 790-794; doi:10.1038/pj.2010.74

DOI： 10.1038/pj.2010.74

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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：JAPAN SOC APPLIED PHYSICS  

The synthesis and properties of noria derivatives containing oxetanyl groups were investigated for their application as negative-type extreme ultraviolet (EUV) resist materials. The solubility, film-forming ability, and photochemical reactivity were consistent with the structures of noria derivatives. The patterning properties of the synthesized noria derivatives were also examined using an EUV system, and patterns with 45 and 50 nm half-pitch resolution were obtained. (C) 2010 The Japan Society of Applied Physics

DOI： 10.1143/JJAP.49.06GF06

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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：TECHNICAL ASSOC PHOTOPOLYMERS,JAPAN  

The synthesis and properties of noria derivatives (noria-CHVE&apos;s) with pendant acetal moieties were examined for application as extreme ultraviolet (EUV)-resist materials. The reaction of noria and cyclohexyl vinyl ether was carried out in the presence of pyridinium p-toluenesulfonate as a catalyst, to give the corresponding noria-CHVE&apos;s with various degrees of introduction (DI) of cyclohexyl acetal moieties by adjusting the feed ratio of reactant and reaction time. The physical properties (solubility, thermal stability, and film-forming ability) of noria-CHVE&apos;s were consistent with the differences in DI values. The patterning properties of noria-CHVE(50) (DI = 50) and noria-CHVE(59) (DI = 59) were investigated in an EUV-resist system, and it was found that noria-CHVE(50) gave higher resolution than noria-CHVE(59), providing a clear line and space pattern with a resolution of 37.9 nm and a line-edge roughness (LER) of 7.2 nm.

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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 synthesis and properties of noria derivatives (noria-ADs) with pendant adamantate (AD) groups were examined to assess the suitability of these compounds for application as extreme ultraviolet (EUV)-resist materials. Noria-ADs with various degrees of introduction (DI) of AD were synthesized by adjusting the reactant feed ratio and reaction temperature. The differences in their physical properties (solubility, thermal stability, and film-forming ability) were consistent with the differences in DI values. The patterning properties of noria-AD(23) (DI = 23) and noria-AD(44) (DI = 44) were investigated in an EUV-resist system, and noria-AD(23) yielded higher resolution than noria-AD(44), providing a clear line and space pattern with a resolution of 26 nm and a line-edge roughness (LER) of 8.3 nm.

DOI： 10.1039/b925403j

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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 phase diagram of a mixture consisting of hyperbranched polyester (HBPEAc-COOH) and eutectic nematic liquid crystals (E7) has been established experimentally by means of differential scanning calorimetry and polarized optical microscopy subjected to prolonged annealing. The observed phase diagram is an upper azeotrope, exhibiting the coexistence of nematic + isotropic phase in the vicinity of 90 similar to 110 degrees C above the clearing temperature of neat E7 (60 degrees C). With decreasing temperature, a focal-conic fan shaped texture develops in the composition range of 63 similar to 93 wt % of the annealed E7/HBPEAc-COOH blends, suggestive of induced smectic phase in the mixture. Wide angle X-ray diffraction (WAXD) technique revealed the existence of higher order mesophase(s).

DOI： 10.1021/jp803893k

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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  

Olefin group-carrying styrene, 1-but-3-enyl-4-vinylbenznene (BVB), was polymerized via atom transfer radical polymerization (ATRP) initiated from C-methylcalix [4]resorcinarene-based multifunctional initiator (CRA-bib) at low conversion to produce star polymer [poly(BVB)] with narrow molecular weight distribution (M-w/M-n &lt; 1.35). The copolymerization of styrene (St) with poly(BVB) (M-n = 11,000, M-w/M-n = 1.23) as a macroinitiator afforded star block copolymer [poly(BVB-b-St)] with M-n = 35,000 and M-w/M-n = 1.44. The BVB layer of poly(BVB-b-St), located between the St shell and the CRA core, was crosslinked by olefin metathesis reaction of olefin groups o the BVB moieties. The removal of the CRA core of the crosslinked poly(BVB-b-St) by hydrolysis using KOH as a base gave polymeric hollow sphere [poly(cored crossBVB-b-St)] with good solubility in organic solvents. The morphological structure of the poly(cored crossBVB-b-St) showed spherical aggregates in THF by scanning electron microscopy (SEM). Furthermore, the nanocapsule structure of poly(cored crossBVB-b-St) with hollow spheres was found to be observed by transmission electron microscopy (TEM). (C) 2008 Wiley Periodicals, Inc.

DOI： 10.1002/pola.22824

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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  

Well-defined linear and star-shaped polystyrenes were synthesized, and the temperature dependence of their refractive index (n(D)) in the film state was examined. The values of n(D) decreased with increasing temperature, with an inflection at the glass-transition temperature (T-g). Above the T-g, the values of difference of n(D) between star-shaped polymer and linear polymer increased at elevated temperatures.

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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  

Reaction of resorcinol and 1,4-butanedial [(CH2)(2)(CHO)(2)] in the presence of concentrated HCl in ethanol at 80 degrees C for 48 h afforded a soluble polymer (CRA-polymer) in quantitative yield under thermodynamic control. Single X-ray crystal analysis revealed that the precursor product had cyclic structure, and TOF mass spectroscopy of CRA-polymer revealed a ladder structure with calixresorcinarene moieties in the main chain. The photoinduced deprotection reaction of CRA-polymer derivative (CRA-polymer-BOC) containing- tertbutyloxycarbonyl groups were examined in the film state in the presence of photoacid generator to produce the alkaline developable CRA-polymer with release of isobutylene and carbon dioxide.

DOI： 10.1021/ma7019573

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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/ma7026287

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記述言語：日本語   出版者・発行元：合成樹脂工業協会  

トリスエポキシ化合物と分子内にオキセタン残基を有するジカルボン酸化合物, メタクリル酸 (MAA), および3-カルボキシル3-エチルオキセタン (CEO) との重付加反応により, 主鎖および末端にオキセタニル基 (OX), 末端にメタクリロイル基 (MA) およびカルボキシル基 (CA) を有するハイブリッド型ハイパーブランチポリマー (HBP-OX-MA-CA) をワンポット反応により合成した。得られたHBP-OX-MA-CAの種々の架橋硬化反応【光カチオン重合, 光ラジカル重合, 熱硬化反応, デュアルキュアー型硬化反応 (光カチオン重合+光ラジカル重合, 光カチオン重合+熱硬化反応, または光ラジカル重合+熱硬化反応), ハイブリッド型硬化反応 (光カチオン重合+光ラジカル重合+熱硬化反応) 】は対応する開始剤を用いてフィルム状態で検討した。その結果, いずれの硬化反応も速やかに進行し, 溶媒に不溶の架橋硬化フィルムが得られることを明らかとした。それぞれの架橋反応で得られたフィルムのガラス転移温度 (<I>T</I><SUB>g</SUB>) は, 光カチオン重合, 光ラジカル重合, および熱硬化反応を単独で行った場合や, デュァルキュァー型硬化反応を行った場合と比較して, ハイブリット型硬化反応の場合, 架橋硬化物の<I>T</I><SUB>g</SUB>が最も高くなることが判明した。このことは, ハイブリット型硬化反応により架橋硬化フィルムの架橋密度が一層高くなることを示唆している。

DOI： 10.11364/networkpolymer1996.29.73

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その他リンク： https://jlc.jst.go.jp/DN/JALC/00315929454?from=CiNii

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 reaction of oxetanes using heteropolyacids as catalysts was examined. The reaction of 3-ethyl-3-phenoxymethyloxetane (EPMO) was examined using commercial heteropolyacid without any treatment (PW12-com.) as a catalyst at 80 degrees C in chlorobenzene for 12h, and the cationic ring-opening polymerization of EPMO proceeded smoothly to give the corresponding polyether poly(EPMO) in 89% yield. However, no polymer was obtained using treated heteropolyacid PW12-dry270 as a catalyst which is heated at 270 degrees C in vacuo before use. Furthermore, the cationic isomerization reaction of 3-acethyloxymethyl-3-ethyloxetane (AOEO) using PW12-dy270 was examined to give 4-ethyl-1-methyl-2,6,7-trioxabicyclo[2.2.2] octane (BOE) in 70% yield.

DOI： 10.1295/polymj.PJ2008080

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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  

A novel ladder-type cyclic oligomer (molecular water-wheel noria) derivative containing t-butyl ester groups was synthesized. This derivative (noria-COO(t)Bu) had good thermal stability, good solubility in common organic solvents, and good film-forming ability. The photo-induced deprotection (UV irradiation for 30 min followed by heating at 130 degrees C) of films of noria-COO(t)Bu was examined in the presence of a photo-acid generator, and it was found that deprotection of the t-butyl groups proceeded smoothly to give the corresponding carboxylic acid derivative (noria-COOH). Furthermore, when noria-COO(t)Bu(71) (ratio of t-butyl ester groups: 71%) was examined as an electron-beam resist material, a clear line and space pattern was obtained at a resolution of 70 nm.

DOI： 10.1039/b805394d

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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  

Thermal curing reactions of oxetane resins {mixtures of novolac type oxetane (PNOX) with 2,2'-bis[(3-ethyl-3-oxetanyl)methoxy}biphenyl (2,2'-BPOX) and mixtures of tris{4-[(3-ethyl-3-oxetanyl)methoxy]phenyl}methane (THPMOX) with 2,2'-BPOX with active diester, 4,4'-isopropylidenebis(2,6-dichlorophenyl diacetate) (IBDCPA) were examined using certain quaternary phosphonium salts as catalysts. The thermal curing reaction of oxetane resins with IBDCPA proceeded smoothly at 170-190 degrees C to produce insoluble gel products. However, the rate of gel production was strongly affected by catalyst concentration and reaction temperature, and gel products were obtained in the highest yield when the reaction was carried out at 190 degrees C in bulk using 7 mol % of tetraphenylphosphonium chloride (TPPC) as a catalyst. The glass transition temperatures (T-g)s and 5 weight-% of loss temperatures (T-d(5%))S of the resulting gel products were determined by DSC and TGA analysis, and it was found that their T(g)s and T(d)(5%)s were 97-118 degrees C and 374-380 degrees C, respectively, when the thermal curing reaction of oxetane resins PNOX/2,2'-BPOX with equivalent amount of cross-linker IBDCPA was performed using TPPC as a catalyst in bulk. On the other hand, the T(g)s and T-d(5%) s of gel products obtained from the reaction of oxetane resins THPMOX/2,2'-BPOX with IBDCPA using the same catalyst were 96-128 degrees C and 381-386 degrees C, respectively.

DOI： 10.1295/polymj.PJ2007171

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記述言語：日本語   出版者・発行元：合成樹脂工業協会  

DOI： 10.11364/networkpolymer1996.28.Supplement_65

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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：SPIE-INT SOC OPTICAL ENGINEERING  

In this contribution, we describe our efforts to develop novel chemically amplified molecular glass (MG) photoresists based on bulky phenol structures. In contrast to conventional polymeric materials, MG resists possess distinct advantages, such as smaller molecular size and uniformity in composition. A number of compounds which possess rigid aromatic backbones were synthesized in our laboratories and evaluated for electron beam lithography. Herein, two new MG photoresists are discussed in terms of their physical and lithographic properties. In the first section, we introduce tert-butoxycarbonyl (t-Boc) protected 'Noria-Boc' photoresists as a promising candidate for next generation lithographic technique. Noria-Boc was synthesized through a condensation reaction between resorcinol and 1,5-pentanedial. After protection with di-tert-butyl dicarbonate [(t-Boc(2)O], the cyclic, bulky and amorphous material was characterized by a high glass transition temperature (T-g &gt; 120 degrees C and excellent film-forming properties. Post-exposure bake at 140 degrees C was necessary to ensure complete development of the exposed area and produced sub-100 rim lines. In the second part, we describe the synthesis and lithographic evaluation of partially t-Boc-protected bulky phenol 'CRI'. CRI is also characterized by high glass transition temperature (T-g approximate to 130 degrees C) and good film-forming properties. Post-apply bake at 130 degrees C and post-exposure bake above 130 degrees C were necessary to ensure good contrast under deep UV (DUV) exposure conditions.

DOI： 10.1117/12.722919

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記述言語：日本語   出版者・発行元：合成樹脂工業協会  

オキセタニル基を有するビスエポキシ化合物とジカルボン酸化合物との重付加反応により, 主鎖にオキセタニル基, 側鎖に水酸基を有するポリエステル (P-OX) を合成し, この側鎖水酸基にメタクリロイル基, 或いはカルボキシル基の導入を検討した。その結果, カチオン重合性基とラジカル重合性基を有するデュアルキュアー型ポリマー (P-OX-MA) およびカチオン重合性基と熱硬化反応性基を有するデュアルキュアー型ポリマー (P-OX-CA) を合成した。P-OX-MAのカチオン重合は, 光酸発生剤を用いて薄膜中で検討し, ラジカル重合は光ラジカル開始剤を用いて同様に検討した。その結果, いずれの場合においても, 反応はよく進行し, 溶媒に不溶の硬化薄膜が得られた。また, 光酸発生剤および光ラジカル開始剤の両方を用いて反応を行い, 溶媒に不溶の硬化薄膜が得られることを明らかとした。次に, P-OX-CAの熱硬化反応は, 触媒としてテトラフェニルホスホニウムイオダイド (TPPI) を用いて同様に検討し, 溶媒に不溶の硬化薄膜が得られた。さらに, 光酸発生剤とTPPIの両方を用いて検討し, 硬化薄膜が得られることを明らかとした。得られたそれぞれの硬化薄膜の熱的特性 (<I>T</I><SUB>g</SUB>) は光カチオン重合, 光ラジカル重合および熱硬化反応を単独で行った場合と比較して, 硬化方法を併用させた場合高くなることが判明し, 硬化薄膜の密度がより高くなることが示唆された。

DOI： 10.11364/networkpolymer1996.28.19

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その他リンク： https://jlc.jst.go.jp/DN/JALC/00292209259?from=CiNii

記述言語：日本語   出版者・発行元：合成樹脂工業協会  

DOI： 10.11364/networkpolymer1996.28.Supplement_89

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記述言語：日本語   出版者・発行元：合成樹脂工業協会  

DOI： 10.11364/networkpolymer1996.28.Supplement_81

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記述言語：日本語   出版者・発行元：合成樹脂工業協会  

DOI： 10.11364/networkpolymer1996.28.Supplement_85

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記述言語：日本語   出版者・発行元：合成樹脂工業協会  

DOI： 10.11364/networkpolymer1996.28.Supplement_77

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記述言語：日本語   出版者・発行元：合成樹脂工業協会  

DOI： 10.11364/networkpolymer1996.27.Supplement_17

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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  

DOI： 10.1002/anie.200603013

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記述言語：日本語   出版者・発行元：合成樹脂工業協会  

DOI： 10.11364/networkpolymer1996.27.Supplement_13

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記述言語：日本語   出版者・発行元：合成樹脂工業協会  

側鎖にアゾベンゼン残基を有するポリマー類P-1～P-4と, 側鎖にアントラセン残基を有するポリマー類P-5～P-8を合成し, その光反応特性, 蓄熱特性, 光異性化反応の繰り返しによる耐久率の評価および光照射前後の屈折率変化について検討を行った。光異性化反応は, 光照射を250-W超高圧水銀灯を用いて行い, ポリマーのフィルム状態において検討した。その結果, アゾベンゼン残基を有するポリマーは約30秒でトランス体からシス体への異性化反応が進行し, アントラセン残基を有するポリマーは, 4～9分で二量化反応が進行することが判明した。また, アゾベンゼン残基を有するポリマーの蓄熱量は5～18kJ/mol, アントラセン残基を有するポリマーは, 4～27kJ/molであることが明らかとなった。さらに, 光照射前後による屈折率の測定を行った結果, アゾベンゼン残基を有するポリマーの屈折率変化は0.010～0.0l8, アントラセン残基を有するポリマーは, 0.052～0.075であった。アントラセン残基を有するポリマーの大きな屈折率変化は, 光照射により二量化反応が進行し, 架橋部位を形成することから, 光照射後のポリマーの密度が大きく変化したためと考えられる。

DOI： 10.11364/networkpolymer1996.27.10

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その他リンク： https://jlc.jst.go.jp/DN/JALC/00276293823?from=CiNii

記述言語：日本語   出版者・発行元：合成樹脂工業協会  

四員環環状エーテルであるオキセタンは適切な反応条件下で, 触媒として第四オニウム塩やクラウンエーテル錯体などを使用するとアシルクロリド, シリルクロリド, ホスホニルクロリド, 活性エステル, カルボン酸, チオール, フェノール, およびリン酸との付加反応が進行し, 対応する開環付加体が得られることを明らかにした。さらに, これらの新規反応を高分子合成や高分子反応に展開し, 適切な触媒と反応条件を選択することで, エポキシ類よりも高選択的に反応が進行することを明らかにした。さらに, これらの反応においてオキセタン類はエポキシ類にはないユニークな反応性を見出した。そこで, オキセタンの反応を基盤とした機能性ポリマー (オキセタン樹脂) の反応について検討を行い, オキセタン樹脂はエポキシ樹脂に代わる機能性材料として展開可能であることを明らかにした。

DOI： 10.11364/networkpolymer1996.27.38

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その他リンク： https://jlc.jst.go.jp/DN/JALC/00276293854?from=CiNii

記述言語：日本語   出版者・発行元：合成樹脂工業協会  

DOI： 10.11364/networkpolymer1996.26.Supplement_9

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記述言語：日本語   出版者・発行元：合成樹脂工業協会  

DOI： 10.11364/networkpolymer1996.26.Supplement_5

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記述言語：日本語   出版者・発行元：合成樹脂工業協会  

カリックスアレーン (CA) やシクロデキストリン (CD) は一分子内に多くの水酸基を有する環状化合物である。CAやCD類に関する研究はこれまで, ホスト・ゲスト分子挙動に関することが多く, これを機能性環状オリゴマーや高性能材料の合成原料として捉えることはほとんどなかった。しかし, これらのオリゴマーは環状であるが故に, 熱分解温度やガラス転移温度が高く, 構造によっては制膜性を有する。このことから, CAやCDの誘導体類は機能性材料として優れた特性を発現すると期待される。そこで, 最近, 筆者らはCAやCDの水酸基に様々な光反応性基として, ラジカル重合性基, カチオン重合性基, 光酸発生剤により分解される脱保護基の導入とその光反応性について検討を行った。その結果, 良好な耐熱性と制膜性および優れた光反応性を有していることが判明した。このことは, 優れたUV硬化樹脂やレジスト材料へ展開が可能であることを示した。さらに, 光異性化反応基を有するCA誘導体類の合成とその光反応性について検討した。それらは光異性化反応前後において非常に大きな屈折率変化を示すことが判明し, 光デバイス材料として展開が可能であると思われる。

DOI： 10.11364/networkpolymer1996.26.98

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その他リンク： https://jlc.jst.go.jp/DN/JALC/00251244291?from=CiNii

記述言語：日本語   出版者・発行元：合成樹脂工業協会  

DOI： 10.11364/networkpolymer1996.26.Supplement_13

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記述言語：日本語   出版者・発行元：合成樹脂工業協会  

DOI： 10.11364/networkpolymer1996.26.Supplement_17

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記述言語：日本語   出版者・発行元：合成樹脂工業協会  

DOI： 10.11364/networkpolymer1996.26.Supplement_1

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記述言語：日本語   出版者・発行元：合成樹脂工業協会  

DOI： 10.11364/networkpolymer1996.25.Supplement_115

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記述言語：日本語   出版者・発行元：合成樹脂工業協会  

DOI： 10.11364/networkpolymer1996.24.Supplement_153

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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  

As high performance UV-curing oligomers, certain calixarenes derivatives containing (meth)acrylate, vinyl ether, propargyl ether, oxetane, oxirane, or spiro ortho ester groups were synthesized by the reactions of calixarenes with (meth)acrylic acid derivatives, vinyl ether compounds, propargyl bromide, oxetane derivatives, epibromohydrin, and spiro ortho ester derivatives. It was found that most of the obtained calixarene derivatives containing polymerizable groups had excellent thermal stability and high photochemical reactivity.

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記述言語：日本語   出版者・発行元：合成樹脂工業協会  

DOI： 10.11364/networkpolymer1996.24.Supplement_149

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記述言語：日本語   出版者・発行元：合成樹脂工業協会  

DOI： 10.11364/networkpolymer1996.23.Supplement_191

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記述言語：日本語  

J-GLOBAL

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記述言語：日本語  

J-GLOBAL

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記述言語：日本語  

J-GLOBAL

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記述言語：日本語  

J-GLOBAL

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記述言語：日本語  

J-GLOBAL

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記述言語：日本語  

J-GLOBAL

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記述言語：日本語  

J-GLOBAL

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記述言語：日本語  

J-GLOBAL

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記述言語：英語   出版者・発行元：TECHNICAL ASSOC PHOTOPOLYMERS,JAPAN  

We synthesized tannic acid derivatives with pendant cyclohexyl acetal moieties (TA-CVEn), butyl acetal moieties (TA-BVEn), and adamantyl ester moieties (TA-AD(n)) by the reaction of tannnic acid (TA) with cyclohexyl vinyl ether (CVE), butyl vinyl ether (BVE), and adamantyl bromo acetate (AD) in various feeds ratios. The synthesized TA-CVEn, TA-BVEn, and TA-AD(n) had good solubility, good film-forming ability, and high thermal stability relevant to application of photolithography materials. However, only TA-BVE97 and TA-AD(74) can be used as positive-type photo-resist materials using 2.38 wt% TMAH aq. as developer due to the result of thickness loss property. Furthermore, their resist-sensitivity upon EUV exposure tool and etching durability were adequate and they have high potential as next-generation resist material for EUV photolithography.

DOI： 10.2494/photopolymer.31.221

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記述言語：英語   出版者・発行元：TECHNICAL ASSOC PHOTOPOLYMERS,JAPAN  

Synthesis, physical properties, and resist properties of tellurium containing polymer with pendant adamantyl ester groups poly(Re-co-Te)-AD were examined, relevant to the application of resist material for extreme ultraviolet laser photolithography (EUVL) system. A tellurium containing polymer with pendant hydroxyl groups poly(Re-co-Te) was synthesized by the condensation reaction of resorcinol (Re) and tellurium tetrachloride (TeCl4), followed by the condensation reaction with adamantyl bromo acetate to give a corresponding polymer poly(Re-co-Te)-AD. Their physical properties (solubility, film-forming ability, thermal stability) and resist properties (thickness loss property after soaking in 2.38 wt% TMAH aq. solution, out-gassing on EUV exposure tool, and resist sensitivity under EUV exposure tool) were also examined.

DOI： 10.2494/photopolymer.30.103

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記述言語：日本語   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：TECHNICAL ASSOC PHOTOPOLYMERS,JAPAN  

The requirements for next generation resist materials in extreme ultraviolet (EUV) lithography are very challenging. Therefore, the development of new resist materials has been expected to meet strict requirements. Molecular resists are promising resists owing to the small size of their building blocks. In this study, we examined lithographic performances, such as sensitivity and patterning, using noria derivative (noria-CHVEs, Resists 1-3) under EUV and a 75 keV electron beam (EB) exposure system. In particular, the effect of the protection ratio on the lithographic performances was studied by changing the protection ratio. The sensitivities of noria-CHVEs showed high values in the range between 1.8 and 3.0 mJ/cm(2). Resist 2 could provide a resist pattern with a higher resolution than Resists 1 and Resist 3, i.e., a semi-isolated pattern with a line width of 30 nm (pitch: 100 nm). These results indicate that the synthesized noria-CHVEs are promising EUV resist materials.

DOI： 10.2494/photopolymer.30.627

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記述言語：英語   出版者・発行元：SPIE-INT SOC OPTICAL ENGINEERING  

In this paper, we designed the synthesis of negative-type molecular resist materials for EB and EUVL exposure tools, and their properties were examined. The resist materials for EUVL have been required showing higher sensitivity for high throughput in the lithographic process, and expecting lower shot noise to improve a roughness. In EUVL process, the resist materials must be ionized by absorbing EUV to emit more secondary electrons. The EUV absorption of the synthesized resist materials was measured using their thin films on the silicon wafer, and it was observed that the ratio of EUV absorption of the synthesized resist was higher than in the comparison of that of PHS as a reference., i.e., 2.4 times higher absorption was shown. Furthermore, we examined the relationship between the ratios of EUV absorptions and functional groups of the resist materials. As the result, the sensitivity of resist materials under EUV exposure tool was consistent with their structures.

DOI： 10.1117/12.2280514

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© 2016 American Vacuum Society. In this study, the authors examined the synthesis and resist performance of positive-tone chemically amplified molecular resist materials based on noria (water wheel in Latin) derivatives with pendant adamantyl ester (AD) groups (noria-AD) using an electron beam (EB) exposure tool. The physical properties of synthesized noria derivatives with various ratios of AD groups and their patterning properties were examined in an EB exposure tool. Furthermore, lithographic performances such as the etch durability and line width roughness of resist patterns were also investigated. These results showed that the physical properties and resist performance of the noria-AD were consistent with the ratio of AD groups, and noria derivatives have high potential to offer higher-resolution resist patterns for EB lithography.

DOI： 10.1116/1.4953068

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記述言語：日本語   出版者・発行元：合成樹脂工業協会  

CiNii Books

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記述言語：日本語   出版者・発行元：日本接着学会  

CiNii Books

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J-GLOBAL

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記述言語：英語   出版者・発行元：TECHNICAL ASSOC PHOTOPOLYMERS,JAPAN  

© 2016SPST. We examined the condensation polymerization of t-butylcalix[8]arene (BCA[8]), p-t-butylcalix[4]arene (BCA[4]), and C-(4-t-butylbenz)calix[4]resorcinarene (BCRA[4]) with 1,3-adamantane dibromoacetate (ADB), yielding soluble polymers poly(BCA[8]-co-ADB), poly(BCA[4]-co-ADB), and poly(BCRA[4]-co-ADB), respectively. These polymers had good solubility, good film forming ability, and good thermal stability. It was anticipated that these polymers were applicable to positive-type resist materials. However, by the examination on the resist sensitivity using EUV exposure system, these polymers were applicable to negative type resist materials using THF as a developer. Furthermore, a negative clear resist pattern with 100nm resolution could be obtained by EB exposure system. These results indicated that poly(BCA[8]-co-ADB) and poly(BCRA[4]-co-ADB) have high potential to offer higher resolution negative pattern using EUV lithography system.

DOI： 10.2494/photopolymer.29.495

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記述言語：英語   出版者・発行元：CHEMICAL SOC JAPAN  

Reaction of t-butylcalix[8]arene (BCA[8]) as an As-type monomer with hexamethylene diisocyanate as a B-2-type monomer was examined to afford only soluble polymers in high yields. Analysis by 1H NMR, IR, MALDI-TOF mass spectroscopy, and AFM indicated that the synthesized polymers consist of nanoscale-gel-shaped structures that contain fixed holes and cavities. We designated this class of polymers as botryosin, after the Greek word botrys, meaning a bunch of grapes. Examination of host guest chemistry of the synthesized polymers revealed complexation with alkali metal ions.

DOI： 10.1246/cl.150840

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記述言語：英語   出版者・発行元：WILEY-BLACKWELL  

Polyaddition (A(n)+B-2) reactions of 1,1,1-tris(4-hydoxyphenyl) ethane (THPE; A(3)-type monomer), calix[4]resorcinarene (CRA[4]; A(8)-type monomer), -cyclodextrin (-CD; A(18)-type monomer), and -cyclodextrin (-CD; A(21)-type monomer) with 1,4-bis(4-vinyloxy)cyclohexane (BVOC; B-2-type monomer) afforded corresponding soluble hyperbranched polyacetals. The physical properties, including solubility, thermal stability, and film-forming ability, the ultraviolet-induced degradation reactivity, and the solubility-switch in an extreme ultraviolet (EUV) exposure tool indicated that poly(THPE-co-BVOC) and poly(CRA[4]-co-BVOC) are candidate next-generation photo-resists. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 2343-2350

DOI： 10.1002/pola.27686

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記述言語：英語   出版者・発行元：ELSEVIER SCIENCE BV  

Novel resist materials are required for lithographic processing with ionization radiation such as extreme ultraviolet (EUV) and electron beam (EB) exposure tools. In this study, we synthesized positive-tone chemically amplified molecular resist materials with pendant adamantyl ester (AD) and cyclohexyl 2-propyl ether moieties based on cyclic oligomers such as noria, calixarene dimer, cyclodextrin, and pillar[5]arene, and we examined the lithographic performances of sensitivity, etching durability, and patterning under EUV and EB exposure. We clarified that the sensitivity of the resist materials was consistent with the structure of the cyclic oligomers, i.e., the hole size of the molecular structure might be an important factor relevant to high-resolution resist materials. We found that chemically amplified molecular resists based on cyclic oligomers such as noria, calixarene dimer, cyclodextrin, and pillar[5]arene are promising candidates for higher-resolution resist materials. (C) 2014 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.mee.2014.11.002

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記述言語：英語   出版者・発行元：TECHNICAL ASSOC PHOTOPOLYMERS,JAPAN  

DOI： 10.2494/photopolymer.28.125

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記述言語：英語  

© 2014 The Chemical Society of Japan. We developed an epoxy thermosetting system based on a reaction of an epoxy resin and ε-caprolactam (ε-CL) in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a catalyst. Ring-opening copolymerization of epoxide groups and ε-CL proceeded at 170°C, affording gel products in high yields. The physical properties of the products were dependent on the feed ratios of the epoxy resin and ε-CL.

DOI： 10.1246/cl.140497

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記述言語：英語   出版者・発行元：WILEY-BLACKWELL  

We synthesized cyclic tetrathioesters containing thioester moieties at the o-position (o-CTE) and m-position (m-CTE) of an aromatic skeleton. The reaction of phenoxy propylenesulfide (PPS) with o-CTE and m-CTE was examined using tetrabutylammonium chloride as a catalyst in 1-methyl-2-pyrrolidinone, yielding the corresponding cyclic polysulfides poly[o-CTE(PPS)(n)] with M-n's=37,000-54,000 at 34-61% yields and poly[m-CTE(PPS)(n)] with M-n's=46,600-107,200 at 63-&gt;99% yields. Although the molecular weights of poly[o-CTE(PPS)(n)] could not be controlled, those of poly[m-CTE(PPS)(n)] could be controlled by the feed ratios of PPS and reaction temperature. Furthermore, the glass transition temperature (T-g) and thermal decomposition temperature (T-d(i)) of poly[m-CTE(PPS)(n)] increased with decreasing molecular weights. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 857-866

DOI： 10.1002/pola.27068

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記述言語：日本語   出版者・発行元：合成樹脂工業協会  

DOI： 10.11364/networkpolymer.35.2

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記述言語：英語   出版者・発行元：SPIE-INT SOC OPTICAL ENGINEERING  

Novel resist materials are required for lithographic processing with ionization radiation such as extreme ultraviolet (EUV) and electron beam (EB) exposure tool. In this study, we developed positive-tone chemically amplified molecular resists based on noria derivatives and calixarene derivatives and evaluated the lithographic performance using EUV and EB. We make clear that a small change in modification of noria resists can cause a significant change of sensitivity. Especially, it is useful for the improvement of resist sensitivities to use protecting groups such as 2-acetyloxy-2-methyladamantyl ester (AD) groups and ethoxy groups. Also, novel calixarene derivative such as pillar[5] arene protected by AD showed a semi-isolated pattern with the line width of 40 nm (pitch: 100nm). Noria derivatives and calixarene derivative resists were promising candidates because of high sensitivity, high resolution and etch durability similar to conventional resist such as ZEP 520A and UVIII.

DOI： 10.1117/12.2046595

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記述言語：英語   出版者・発行元：ELSEVIER SCIENCE SA  

Noria derivatives with pendant methoxy and adamantyl ester moieties (noria(MP)-AD(n)) were synthesized by the substitution reaction of noria analogues with 12 methoxy groups (noria(MP)) and 2-bromoacetyloxy-2-methyladamantane (BMA), and their degrees of introduction of adamantyl ester moieties (DI) could be controlled by the feed ratios of noria(MP) and BMA. The physical properties such as solubility, film-forming ability, and thermal stability of noriaMP-AD(n) were also examined to assess the suitability for application as extreme ultraviolet (EUV)-resist materials. The patterning property of noria(MP)-AD(18) (DI= 18) and noria(MP)-AD(54) (DI= 54) was investigated in an EUV-resist system, and noria(MP)-AD(18) yielded higher resolution than noriaMP-AD54, providing a clear line and space pattern with a resolution of 32 nm and a line-width roughness of 10.5 nm by exposure dose of 9.0 mJ/cm(2). (C) 2013 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.tsf.2013.02.016

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記述言語：日本語  

Research of the Kudo Group in Kansai University focuses on the synthesis of novel functional materials and refining their physical properties. The synthesis of non-linear polymers such as hyperbranched polymers, graft polymers, cyclic polymers, and star-shaped polymers and their physical properties are examined. Furthermore, new dynamic covalent chemistry systems are also examined for the synthesis of three dimensional cage molecules. The application for UV-curing materials, high-resolution resist materials, high-and low-refractive index materials, and refractive-index change materials are investigated using various synthesized functional polymers. Copyright ©2013 The Society of Polymer Science, Japan.

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記述言語：日本語   出版者・発行元：関西大学  

半導体集積回路（IC）は、最近20年の間に驚異的な進化を遂げ、高度情報化社会を牽引してきた。IT産業という言葉を定着させ、その発展を支えたのはICの進化のおかげであると断言しても過言ではない。ICを進化させたのは、フォトリソグラフィの発展により、レジストパターン幅を縮小させることに成功してきたからである。そのレジストパターンの発展も、いよいよ限界に近づき、分子レベルでのコントロールに迫ろうとしている。

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その他リンク： http://hdl.handle.net/10112/7512

記述言語：英語   出版者・発行元：CHEMICAL SOC JAPAN  

Condensation reaction of 2-methylresorcinol with m-benzenedicarbaldehyde in the presence of HCl as a catalyst in n-propanol at 90 degrees C for 48 h proceeded via a dynamic covalent chemistry (DCC) mechanism to afford a triple-ringed [14]arene in 52% yield.

DOI： 10.1246/cl.2012.699

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記述言語：日本語   掲載種別：書評論文，書評，文献紹介等   出版者・発行元：社団法人 有機合成化学協会  

A new dynamic covalent chemistry (DCC) system in the reaction of resorcinol and 1,5-pentanedial could be achieved, yielding a only soluble oligomer Noria (Noria means water wheel in Latin) in high yield, resembling a water-wheel in appearance. Application of the Noria derivatives with pendant photo-reactive groups were examined for UV-curing materials and photo-resist materials. The obtained Noria derivatives had good solubility, good film-forming ability, high thermal stability, and high photo-chemical reactivity. Furthermore, certain new ladder cyclic oligomers could be synthesized using a similar approach to that employed for the synthesis of Noria and their application as next generation resist materials was also investigated.

DOI： 10.5059/yukigoseikyokaishi.70.492

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記述言語：英語   出版者・発行元：WILEY-BLACKWELL  

A new synthetic strategy for polymers containing amino acids in the main chain was developed. Monomers N-oxetanylalanine (N-Oxe-Ala-COOH), N-oxetanylglutamic acid (N-Oxe-Glu-COOH), and N-oxetanyllysine (N-Oxe-Lys-COOH) containing both oxetanyl and carboxyl groups were synthesized, and self-polyaddition and self-copolyaddition of these monomers afforded the corresponding polymers containing amino acids in the main chain [poly(OxAla), poly(OxLys), poly(OxGlu), poly(OxAla-co-OxGlu), poly(OxGlu-co-OxLys), and poly(OxAla-co-OxLys)] with molecular weight in the range of 9206620, in satisfactory yields. The physical properties, such as solubility, glass transition temperature, and thermal stability, were consistent with the amount of carboxyl groups at the chain ends. Biodegradability of the polymers was examined by the biochemical oxygen demand method; the decomposition ratios of poly(OxAla) and poly(OxAla-co-OxGlu) were about 60%, whereas that of poly(OxGlu) was nearly 100% after 28 days. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 50: 458-465, 2012

DOI： 10.1002/pola.25053

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記述言語：日本語   掲載種別：書評論文，書評，文献紹介等  

A new dynamic covalent chemistry DCC system in the reaction of resorcinol and 1,5- pentanedial could be achieved, yielding a only soluble oligomer Noria Noria means water wheel in Latin in high yield, resembling a water-wheel in appearance. Application of the Noria derivatives with pendant photo reactive groups were examined for IJV curing materials and photo resist materials. The obtained Noria derivatives had good solubility, good film-forming ability, high thermal stability, and high photo-chemical reactivity. Furthermore, certain new ladder cyclic oligomers could be synthesized using a similar approach to that employed for the synthesis of Noria and their application as next generation resist materials was also investigated.

DOI： 10.5059/yukigoseikyokaishi.70.492

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記述言語：日本語   出版者・発行元：公益社団法人 日本化学会  

半導体集積回路(IC)は,最近20年の間に驚異的な進化を遂げ,高度情報化社会を牽引してきた。IT産業という言葉を定着させ,その発展を支えたのはICの進化のおかげであると断言しても過言ではない。ICを進化させたのは,フォトリソグラフィの発展により,レジストパターン幅を縮小させることに成功してきたからである。そのレジストパターンの発展も,いよいよ限界に近づき,分子レベルでのコントロールに迫ろうとしている。

DOI： 10.20665/kakyoshi.60.10_442

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記述言語：英語   出版者・発行元：TECHNICAL ASSOC PHOTOPOLYMERS,JAPAN  

DOI： 10.2494/photopolymer.25.587

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記述言語：英語   出版者・発行元：MDPI AG  

Nafion membranes were impregnated with photocurable supramolecules, viz., hyperbranched polyester having pendant functional carboxylic acid groups (HBPEAc-COOH) by swelling in methanol and subsequently photocured in-situ after drying. Structure-property relationships of the HBPEAc-COOH impregnated Nafion membranes were analyzed on the basis of Fourier transform infrared (FTIR) spectroscopy, solid-state nuclear magnetic resonance (SSNMR) and dynamic mechanical analysis (DMA). FTIR and SSNMR investigations revealed that about 7 wt % of HBPEAc-COOH was actually incorporated into the ionic domains of Nafion. The FTIR study suggests possible complexation via inter-species hydrogen bonding between the carboxylic groups of HBPEAc-COOH and the sulfonate groups of Nafion. The alpha-relaxation peak corresponding to the glass transition temperature of the ionic domains of the neat Nafion-acid form was found to increase from similar to 100 to similar to 130 degrees C upon impregnation with enhanced modulus afforded by the cured polyester network within the ionic domains. The AC impedance fuel cell measurement of the impregnated membrane exhibited an increasing trend of proton conductivity with increasing temperature, which eventually surpassed that of neat Nafion above 100 degrees C. Of particular importance is that the present paper is the first to successfully incorporate polymer molecules/networks into the Nafion ionic domains by means of impregnation with hyperbranched supramolecules followed by in-situ photopolymerization.

DOI： 10.3390/polym3042018

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記述言語：英語   出版者・発行元：JAPAN SOC APPLIED PHYSICS  

The synthesis and properties of water wheel-like cyclic oligomer (noria(PY)) derivatives (noria(PY)-ADs) with pendant adamantyl ester (AD) groups were examined for their application as extreme ultraviolet (EUV) resist materials. Noria(PY)-ADs with various degrees of introduction (DI values) of AD groups were synthesized by adjusting the reactant feed ratios and reaction concentration. Solubility, film-forming property, and thermal stability were consistent with differences in DI values. The patterning properties of noria(PY)-AD(25) (DI = 25%) were examined in an EUV resist system, and noria(PY)-AD(25) provided a clear line-and-space pattern with 30nm resolution and a line width roughness (LWR) of 11.3 nm. (C) 2011 The Japan Society of Applied Physics

DOI： 10.1143/JJAP.50.121602

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記述言語：英語   出版者・発行元：CHEMICAL SOC JAPAN  

Condensation reaction of 2-methylresorcinol and pyrogallol with 1,5-pentanedial [CH2(CH2CHO)(2)] in the presence of concentrated HCl in ethanol at 80 degrees C for 48 h proceeded according to a dynamic covalent chemistry (DCC) mechanism to afford the noria-like ladder-cyclic oligomers noria(MR) and noria(PY), respectively.

DOI： 10.1246/cl.2011.464

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記述言語：英語   出版者・発行元：NATURE PUBLISHING GROUP  

The characteristics of Noria analogs with 12 ethoxy groups and 12 hydroxy groups (Noria-OEt), which were synthesized by the condensation reaction of 3-ethoxyphenol with 1,5-pentanedial, were examined in detail. The solubility of the synthesized Noria-OEt in common organic solvents was better than that of Noria. In addition, Noria-OEt was soluble in 2.38wt% tetrametyl ammonium hydroxide (TMAH) aqueous as a developer. The thermal stability and mechanical properties were similar to those of Noria because of the ladder structure and amorphous characteristics, which means that the film-forming properties were confirmed. These characteristics are advantageous for use as a molecular glass photoresist. The patterning properties of the negative-type, alkaline developable, multicomponent photoresist based on Noria-OEt, with polyfunctional benzyl alcohols as a crosslinker and a photoacid generator, were evaluated with an extreme ultraviolet lithography system. This negative-type photoresist with 2,4-dihydroxymethyl-6-methylphenol as a crosslinker gave a resolution pattern of 35 nm half-pitch with 10.0 mJ cm(-2). Polymer Journal (2011) 43, 407-413; doi:10.1038/pj.2010.146; published online 9 February 2011

DOI： 10.1038/pj.2010.146

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記述言語：日本語   出版者・発行元：高分子学会  

The development of high resolution patterns (less than 22nm line and spaces) has been made by using an extreme ultraviolet (EUV) exposure system. To achieve higher resolution pattern, several molecular resist materials based on calixarene, low-molecular weight phenol resins, fullerene, and ladder cyclic oligomer (noria) have been investigated using EUV exposure system, and their resist patterns showed 22-50 nm resolutions. Furthermore, certain molecular glasses containing a photo-acid generator were examined and showed 50 nm resolution. Although, these molecular glasses showed high potential to give higher resolution patterns, their values of line-edge roughness were not enough. The further examination of the synthesis of new molecular glasses and EUV-exposure tools are under now consideration. © 2011 The Society of Polymer Science, Japan.

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記述言語：英語   出版者・発行元：NATURE PUBLISHING GROUP  

The simple polyaddition reaction to the preparation of a series of hyperbranched fluorinated polymers with different fluorine contents and comonomer structures was studied. The reaction solvent, N-methyl-2-pyrroridone, and o-dichlorobenzene were dried with CaH2and purified by distillation before use. Tetrabutylammonium bromide (TBAB) was crystallized from ethyl acetate. Bisphenol A and 4,4-biphenol were purified by recrystallization from ethyl acetate/hexane and ethanol/hexane, respectively.1H nuclear magnetic resonance (NMR) spectra were obtained using chloroform-d (CDCl3) or dimethyl sulfoxide-d6(DMSO-d6) ((CD3)2SO) as the solvent. The number-average molecular weight and molecular weight distribution values of the polymers were estimated. The1H NMR spectrum shows new signals around 3.92-4.04, 4.14-4.22 and 5.31-5.37 p.p.m., which are assignable to the methylene, methane, and hydoroxy groups of the obtained polymers by the ring opening of oxirane moieties.

DOI： 10.1038/pj.2010.134

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記述言語：英語   掲載種別：書評論文，書評，文献紹介等   出版者・発行元：TECHNICAL ASSOC PHOTOPOLYMERS,JAPAN  

Extreme ultraviolet (EUV) lithography systems can in principle provide extremely high resolution (line-and-space patterns with less than 22 nm separation) for fabrication of microelectronic devices. For this purpose, various molecular resist materials based on calixarene, low-molecular-weight phenol resins, fullerene, ladder cyclic oligomer (noria), and photo-acid generator-bonding molecules have been investigated, and have provided resist patterns with a resolution of 22 50 nm. Although these molecular glasses have the potential to give higher resolution patterns, their values of line-edge roughness remain too high at present. This review deals with the current status of molecular resists for EUV systems and prospects for further development.

DOI： 10.2494/photopolymer.24.9

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記述言語：英語   出版者・発行元：AMER CHEMICAL SOC  

The insertion reaction of propylene sulfide (PS) into p-tolylcarbamothioate (PTCT) was examined in the presence of tetrabutylammonium chloride (TBAC) in 1-methyl-2-pyrrolidinone at 60 degrees C in the feed ratio of PTCT/PS = 1/1-1/40, affording the corresponding polysulfides in satisfactory yields. It was found that the molecular weights (M-n's) coincided with the feed ratios PS and molecular dispersity ratios (M-w/M-n) were very narrow (M-w/M-n &lt; 1.10). i.e., this insertion reaction could be performed under the living system. Furthermore, the insertion living reaction of PS using tricarbamothioate was examined to give the controlled three-arms star-shaped polysulfides.

DOI： 10.1021/ma101969r

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記述言語：英語   出版者・発行元：NATURE PUBLISHING GROUP  

Hyperbranched polycarbonates (HBPCs) with M(n)=2.1-7.1 x 10(3) were synthesized by A(2)+B(3) polymerization using di-tert-butyl tricarbonate as the A(2) monomer and 1,1,1-tris(4-hydroxyphenyl)ethane as the B(3) monomer. A(2)+B(3) polymerization with different feed ratios was achieved, controlling the degree of branching (DB) and the ratio of terminal functional groups. The DB of the HBPCs is 0.5-0.7. The Boc-terminated PC was prepared by either a 1-pot or a 2-pot synthesis. In contrast, PC with terminal phenol groups was prepared by deprotection of Boc-terminated PC. Polymer Journal (2010) 42, 852-859; doi: 10.1038/pj.2010.82; published online 15 September 2010

DOI： 10.1038/pj.2010.82

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記述言語：英語   出版者・発行元：NATURE PUBLISHING GROUP  

The synthesis and photo-polymerization of hyperbranched polyesters (HBPEs) containing terminal methacryloyl groups (HBPE-MA) were examined. Polycondensations of 1,4-bis(chloromethyl) benzene with 1,3,5-benzenetricarboxylic acid using 1, 8-diazabicyclo[5.4.0] undec-7-ene as a base were performed to give the soluble HBPEs in satisfactorily high yields. Furthermore, HBPE-MA was synthesized by the reaction of HBPE with methacrylic acid. The photo-induced radical polymerization of HBPE-MA was performed in the presence of 2-methyl-1-[4-(methylthio) phenyl]-2-morpholinopropan-2-one (Irgacure 907), which acts as a photoinitiator in the solid film state and yields an insoluble cured film upon ultraviolet irradiation. Polymer Journal (2010) 42, 790-794; doi:10.1038/pj.2010.74

DOI： 10.1038/pj.2010.74

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記述言語：英語   出版者・発行元：NATURE PUBLISHING GROUP  

Calixarenes (CAs) are perfectly defined cyclic phenolic oligomers with potential applications as curing agents for polyfunctional epoxy resins to prepare cured epoxy resins with high glass transition temperature and high thermal stability. This paper explores the reaction mechanisms and optimal reaction conditions of CAs with epoxy groups by studying the model reactions of calix[4]resorcinarene (CRA), p-tert-butylcalix[n]arene (BCA[n], n=4, 6, 8) and their esterified derivatives with glycidyl phenyl ether (GPE). For reactions of completely esterified CRA with GPE, the optimum reaction conditions were determined as tetraphenylphosphonium chloride catalyst in chlorobenzene at 120 degrees C for 6 h. Under the above reaction conditions, the degree of introduction of GPE (D.I.) to CRA and its esterified derivatives was greater than 95%, whereas D.I.s were lower than 81% for BCA[n] (n=4, 6, 8) and their esterified derivatives. This difference in reactivity resulted from the difference in intermolecular hydrogen bonding and steric hindrance between CAs. These results indicate that CRA and its derivatives have great potential as curing agents for polyfunctional epoxy resins. Polymer Journal (2010) 42, 456-463; doi:10.1038/pj.2010.34

DOI： 10.1038/pj.2010.34

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS INC  

The acetyl esterified calixarene (CA) derivatives were prepared from calix[4]resorcinarene (CRA), and p-tert-butylcalixarene (BCA[n], n = 4, 6, 8), respectively. Using these CA derivatives as curing agents, the thermal curing reactions of two multifunctional epoxy resins (jER 828, 186 g/equiv., and ESCN, 193.7 g/equiv.) were investigated. The temperatures of glass transition (T(g)) and decomposition (T(d)(10%)) were measured by DSC and TGA, respectively. Based on the yields, T(g)s, and T(d)s of the thermal cured jER 828 epoxy resin with CRA-E100, the curing conditions were optimized to be tetrabutylphosphonium bromide (TBPB) as catalyst in NMP at 160 degrees C for 15 h. Under this curing condition, the cured materials of jER 828 or ESCN using various CA derivatives as curing agents were prepared. Except for BCA4 derivatives, the yields of thermal curing reaction were higher than 90%. T(g)s and T(d)(10%)s of the resultant cured materials were in the range of 113-248 degrees C and 363-404 degrees C, respectively. These results mean that the cured epoxy resins with excellent T(g)s were successfully formed by using CA derivatives as curing agents. It was also found that the T(g)s of cured epoxy resins were strongly affected by the degree of esterification of CA derivatives. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1931-1942, 2010

DOI： 10.1002/pola.23960

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記述言語：英語   出版者・発行元：AMER CHEMICAL SOC  

The synthesis, properties, and photocross-linking reactions of noria derivatives containing methacryloyl, vinyl ether, and oxetanyl groups to assess the suitability of these compounds for application as novel UV-curable materials, was reported. Tetrahydrofuran (THF), 1-methyl-2-pyrrolidinone (NMP), triethylamine (NEt3), glycidyl methacrylate, and 2-chloroethyl vinyl ether were dried over CaH2 and purified by distillation before use. Methacryloyl chloride was added slowly to a solution of noria in NEt3 at 25°C, and the resulting solution was stirred for 24 h and then concentrated in a rotary evaporator. Ethyl acetate was added to the residual mass, and the insoluble part was removed by filtration. The organic phase was washed with saturated aqueous sodium hydrogen carbonate, 1 N hydrogen chloride solution, and water. The obtained organic phase was dried over MgSO4 and concentrated in a rotary evaporator. In the case of noria-MA100, the photochemical radical polymerization of methacryloyl groups reached 24% after 400 s.

DOI： 10.1021/ma100527f

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記述言語：英語  

We have synthesized cyclodextrin (CD) derivatives with pendant norbornadiene (CD-NBD), with pendant azobenzene (CD-AZ), with pendant cinnamate (CD-CI), with pendant chalcone (CD-CH), and with pendant anthracene (CD-AT). In thin films of these CD derivatives under UV irradiation, photochemical isomerization of CD-NBD and CD-AZ, and photochemical dimerization of CD-CI, CD-CH, and CD-AT proceeded smoothly. The photochemical reactions were accompanied with large refractive index changes (ΔnD&#039;s) of 0.023-0.030 (CD-NBD), 0.015-0.023 (CD-AZ), 0.041-0.048 (CD-CI), 0.057-0.071 (CD-CH), and 0.062-0.083 (CD-AT), as determined by ellipsometry. © 2009 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.tsf.2009.09.023

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記述言語：英語   出版者・発行元：TECHNICAL ASSOC PHOTOPOLYMERS,JAPAN  

The synthesis and properties of noria derivatives (noria-CHVE&apos;s) with pendant acetal moieties were examined for application as extreme ultraviolet (EUV)-resist materials. The reaction of noria and cyclohexyl vinyl ether was carried out in the presence of pyridinium p-toluenesulfonate as a catalyst, to give the corresponding noria-CHVE&apos;s with various degrees of introduction (DI) of cyclohexyl acetal moieties by adjusting the feed ratio of reactant and reaction time. The physical properties (solubility, thermal stability, and film-forming ability) of noria-CHVE&apos;s were consistent with the differences in DI values. The patterning properties of noria-CHVE(50) (DI = 50) and noria-CHVE(59) (DI = 59) were investigated in an EUV-resist system, and it was found that noria-CHVE(50) gave higher resolution than noria-CHVE(59), providing a clear line and space pattern with a resolution of 37.9 nm and a line-edge roughness (LER) of 7.2 nm.

DOI： 10.2494/photopolymer.23.657

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記述言語：英語   出版者・発行元：JAPAN SOC APPLIED PHYSICS  

The synthesis and properties of noria derivatives containing oxetanyl groups were investigated for their application as negative-type extreme ultraviolet (EUV) resist materials. The solubility, film-forming ability, and photochemical reactivity were consistent with the structures of noria derivatives. The patterning properties of the synthesized noria derivatives were also examined using an EUV system, and patterns with 45 and 50 nm half-pitch resolution were obtained. (C) 2010 The Japan Society of Applied Physics

DOI： 10.1143/JJAP.49.06GF06

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記述言語：英語   出版者・発行元：ROYAL SOC CHEMISTRY  

The synthesis and properties of noria derivatives (noria-ADs) with pendant adamantate (AD) groups were examined to assess the suitability of these compounds for application as extreme ultraviolet (EUV)-resist materials. Noria-ADs with various degrees of introduction (DI) of AD were synthesized by adjusting the reactant feed ratio and reaction temperature. The differences in their physical properties (solubility, thermal stability, and film-forming ability) were consistent with the differences in DI values. The patterning properties of noria-AD(23) (DI = 23) and noria-AD(44) (DI = 44) were investigated in an EUV-resist system, and noria-AD(23) yielded higher resolution than noria-AD(44), providing a clear line and space pattern with a resolution of 26 nm and a line-edge roughness (LER) of 8.3 nm.

DOI： 10.1039/b925403j

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記述言語：英語   出版者・発行元：AMER CHEMICAL SOC  

Novel refractive index increase material based on polystyrenes with pendant bicyclo orthoester groups upon photoirradiation is analyzed. 1-Methyl-2-pyrrolidonone (NMP), dimethyl sulfoxide N,N-dimethylformamide (DMF), styrene, and 3-chloromethyl-3-ethyloxetane were dried over with CaH2 and purified by distillation before use. Infrared spectra were measured on a Thermo Electron model NICOLET 380 spectrometer. The refractive index of thin films spin-coated at about 0.1 μm thickness on silicon wafers was measured by ellipsometry at 0.6328 μm with a Gaertener Scientific Co. model L116C ellipsometer. The rate of photochemical reaction of the bicyclo ortho ester groups was measured by real-time IR spectroscopy. The resulting solution was washed with 1.0 N hydrogen chloride solution twice, and water three times. The organic phase was dried over with MgSO4 and concentrated in a rotary evaporator.

DOI： 10.1021/ma901060t

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS LTD  

Since dendritic polymers have excellent characteristic physical properties such as low viscosity, good solubility, and many functional groups, compared with corresponding linear polymers, they have been of great interest in the field of polymer chemistry. Among them, hyperbranched polymers have great possibility as high performance and new photo-curable polymers and oligomers in chemical industry. In this paper, we report the synthesis and photochemical reaction of certain hyperbranched polymers such as hyperbranched epoxy-methacrylate, hyperbranched oxetane-methacrylate, and hyperbranched polyurethane-methacrylate, and some physical properties of the resulting cured films. Copyright (C) 2009 John Wiley & Sons, Ltd.

DOI： 10.1002/pat.1377

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記述言語：日本語   出版者・発行元：神奈川大学工学部  

CiNii Books

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記述言語：英語   出版者・発行元：AMER CHEMICAL SOC  

The continuous insertion reaction of phenoxypropylenesulfide (PPS) into the thioester moieties of calixarene derivatives (cores) generated from p-tert-butylthiacalix[4] arene (BTC[4]), 2,9,14,20-tetramethylclix-[4] resorcinarene (CRA[4]), and 2,8,14,20-tetra(4-hydroxybenzen-1-yl)calix[4]resorcinarene {CRA(Ar-OH)[4]} proceeded smoothly with tetrabutylammonium chloride (TBAC) as a catalyst to give well-defined star-shaped polysulfides with 4. 9 and 12 arms, The arm length and Sulfur content of the star-shaped polysulfides were controlled by the feed ratio of PPS and core. The refractive-index values (n(D)&apos;s) of the synthesized star-shaped polysulfides were determined in the film state by means of ellipsometry; the n(D)&apos;s increased with increasing numbers of arms, length of arms, and sulfur content and with decreasing size of the core structure.

DOI： 10.1021/ma802042y

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記述言語：日本語   出版者・発行元：SOC POLYMER SCIENCE JAPAN  

The synthesis, physical property, and photo-induced deprotection reaction of noria derivative containing acetal moieties were examined. All the hydroxyl groups of noria were converted to acetal moieties, to afford the corresponding noria derivative (noria-Acetal). The thermal stability and solubility of noria-Acetal were good, respectively. Furthermore, the photo-induced deprotection reaction of noria-Acetal was examined in the presence of a photo-acid generator in the film state upon UV irradiation, and it was found that acetal groups were changed to carboxyl acid groups smoothly without further heating. It was expected that noria-Acetal would be applicable to next generation positive working photo-resist materials with high resolution for electron beam (EB) or extreme ultraviolet (EUV) resist systems.

DOI： 10.1295/koron.66.10

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記述言語：英語   出版者・発行元：SOC POLYMER SCIENCE JAPAN  

The synthesis and photopolymerization of hyperbranched polysulfides containing pendant methacryloyl groups (HBPS-MA) were examined. Polyadditions of 1,4-bis[(3-ethy-3-oxetanyl)methoxy]benzene (1,4-BEOMB) with thiocyanuric acid (TCA) were carried out to give the soluble hyperbranched polysulfides (HBPS) in satisfactory high yields. Then, we examined refractive index of the resulting HBPS. Furthermore, HBPS-MA was synthesized by the reaction of HBPS with methacrylic anhydride. The photo-initiated radical polymerization of HBPS-MA was performed in the presence of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-2-one (Irgacure 907 (R)) as a photoinitiator in the film state upon UV irradiation to afford the insoluble cured film.

DOI： 10.1295/polymj.PJ2009120

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記述言語：英語   出版者・発行元：SOC POLYMER SCIENCE JAPAN  

Novel photo-functional materials, such as refractive-index-changing materials, argon fluoride (ArF) resist materials, and electron beam (EB) resist materials, were designed based on the structures of calixarenes, cyclodextrin, and noria. The synthesis and refractive-index properties of calixarene derivatives containing photo-reactive groups, including azobenzene, norbornadiene, anthracene, cinnamate, and chalcone, were examined, and refractive-index changes (Delta n(D)&apos;S) of between 0.007 and 0.061. were observed. The synthesis and patterning properties of a single-layer ArF photoresist system of beta-CD derivative containing t-butyl ester and fluorine were examined, and a well-resolved 100 nm line and space pattern was obtained on a silicon wafer. A new ladder-like macrocycle, noria (water wheel in Latin), was also synthesized and its application as an EB resist material was examined. The noria derivatives noria-COO(t)Bu containing t-butyl ester groups, noria-BOC containing t-butyloxycarbonyl group, and noria-acetal containing acetal groups had good physical properties and photo-reactivity. EB-resist based on noria-COO(t)Bu and noria-BOC provided clear line and space patterns at a resolution of 70 and 50 nm, respectively.

DOI： 10.1295/polymj.PJ2009086

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記述言語：英語   出版者・発行元：TECHNICAL ASSOC PHOTOPOLYMERS,JAPAN  

DOI： 10.2494/photopolymer.22.73

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記述言語：英語   出版者・発行元：ROYAL SOC CHEMISTRY  

An environmentally friendly development process using supercritical carbon dioxide (scCO(2)) was applied to a novel molecular glass resist made from a molecular waterwheel ('Noria'), and patterned by electron-beam (EB) lithography. The physical and lithographic properties of a Noria derivative, tert-butoxycarbonylprotected Noria ('Noria-BOC'), were examined to evaluate it as a next-generation resist in terms of its solubility, film-forming ability, thermal stability, photosensitivity, and patterning properties. FT-IR spectra and contrast curve studies revealed the good photo-induced deprotection reactivity of Noria-BOC and the excellent negative-tone characteristics of scCO(2) development, respectively. The EB-patterning of Noria-BOC followed by development in scCO(2) gave clear lithographic patterns with sub-100 nm resolution.

DOI： 10.1039/b821475a

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記述言語：日本語   出版者・発行元：公益社団法人 高分子学会  

ビスフェノール A ビス(クロロホルメート)(BABC)と 1,1,1-トリス(4-ヒドロキシフェニル)エタン(THPE)との反応をピリジン存在下，THF 中，25℃，3 時間の条件で行い，対応する可溶性のハイパーブランチポリカーボネート(HBPC)を高収率で合成した．次に，得られた HBPC と無水メタクリル酸との反応をピリジン中，25℃，12 時間の条件で行い，末端にメタクリロイル基を有するハイパーブランチポリカーボネート(HBPCMA)を合成した．HBPCMA の光ラジカル重合は，3 wt%の光ラジカル重合開始剤を添加した HBPCMA のフィルムを作製し，光源として 250-W 超高圧水銀灯を用いて光照射を行った．その結果，光ラジカル重合は容易に進行し，光照射 15 分でのメタクリロイル基の反応率は 28%に達した．同様に，末端にメタクリロイル基を有する直鎖状ポリカーボネート(LPCMA)を合成し，その光ラジカル重合についても検討を行った．その結果，同様の光照射条件下での LPCMA 中のメタクリロイル基の反応率は 13%であった．このことは，HBPCMA は LPCMA と比較して優れた光重合特性を有することを示唆している．次に，HBPCMA および LPCMA の光ラジカル重合前後の屈折率測定を行った結果，HBPCMA の光ラジカル重合前後の屈折率変化(&amp;Delta;&lt;i&gt;n&lt;/i&gt;&lt;sub&gt;D&lt;/sub&gt;)は 0.007 あったのに対して，LPCMA は 0.004 であり，光ラジカル重合前後で，HBPCMA は LPCMA と比較して大きな屈折率変化を示すことも判明した．&lt;br&gt;

DOI： 10.1295/koron.66.36

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記述言語：日本語   出版者・発行元：SOC POLYMER SCIENCE JAPAN  

Synthesis and functionalization of hyperbranched polycarbonate (HBPC) were examined. The reaction of bisphenol A bis(chloroformate) (BABC) and 1,1,1-tris (4-hydroxyphenyl) ethane (THPE) performed in the presence of pyridine in THF gave soluble hyperbranched polycarbonate in high yields. Furthermore, the reaction of the resulting HBPC with methacrylic anhydride was carried out in pyridine to produce the photo-curable hyperbranched polycarbonate (HBPCMA) with methacryloyl groups at the ends of the polymer chains. The photo-initiated radical polymerization of HBPEMA was examined in the presence of photo-initiator in the film state upon UV irradiation, and it was found that the photo-initiated radical polymerization proceeded smoothly to give the cured films. It was also observed that the rate of the photo-radical polymerization of hyperbranched polymer was higher than that of a linear polymer. Furthermore, it was found that the change in the refractive index before and after photo-curing reaction of HBPCMA was larger than that of a linear polymer.

DOI： 10.1295/koron.66.36

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記述言語：日本語   出版者・発行元：公益社団法人 高分子学会  

アセタール残基を有する noria(ラダー型環状オリゴマー)誘導体(noria-Acetal)の合成と，その物理的特性，および光脱保護反応性について詳細に検討した．noria のヒドロキシル基のすべてを &lt;i&gt;t&lt;/i&gt;-ブチルエステル基，カルボキシル基の順に変換し，最後にアセタール基に変換することで，noria-Acetal を合成した．得られた noria-Acetal は一般的な有機溶媒に容易に溶解し，良好な製膜性と高い耐熱性を有することを明らかとした．noria-Acetal の光脱保護反応は，光酸発生剤を含有させた薄膜に光照射を行い検討した．その結果，アセタール基はカルボキシル基に変換され，光照射後の薄膜は 2.38 wt%のテトラメチルアンモニウムハイドライド水溶液に可溶であった．これらのことは，noria-Acetal は次世代ポジ型レジスト材料として応用展開が可能であることを示唆した．&lt;br&gt;

DOI： 10.1295/koron.66.10

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS INC  

The synthesis and self-polyaddition of new monomers, o-, m-, and p-[(3-ethyloxetane-3-yl)metlioxyetliyl]benzoic acid (o-EOMB, m-EOMB, and p-EOMB) containing both oxetanyl groups and carboxyl groups were examined. The reactions of o-EOMB, m-EOMB, and p-EOMB in the presence of tetraphenylphosphonium bromide as a catalyst in o-dichlorobenzene at 150-170 degrees C resulted in self-polyaddition to give the corresponding hetero-telechelic polymers poly(o-EOMB), poly(m-EOMB), and poly(p-EOMB) with M(n)s = 14,500-33,400 in satisfactory yields. The M(n) of poly (o-EOMB) decreased at higher reaction temperatures than 150 degrees C, unlike those of poly(m-EOMB) and poly(p-EOMB), possibly due to inter- or intraester exchange side reactions. It was also found that the thermal properties and solubilities of these polymers were supposed with the proposed structures. (C) 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7835-7842, 2008

DOI： 10.1002/pola.23088

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記述言語：日本語   出版者・発行元：化学工業社  

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記述言語：英語   出版者・発行元：SPIE-INT SOC OPTICAL ENGINEERING  

Polymers are attractive materials for optical waveguide applications due to their low cost, easy processibility and good flexibility. One of the highest priorities in the improvement of polymer optical waveguides is to develop new polymer materials possessing low optical loss, thermal stability, and refractive index controllability. Here, we present promising optical waveguide materials, i.e. calixarene polymers, which possess good optical and thermal properties. Calixarene polymer optical waveguides showed low optical loss (less than 1 dB/cm at 1.3 mu m) and good thermal stability (5 wt% loss temperature : higher than 300 degrees C). The control of refractive index of calixarene polymers was also achieved by copolymerization of calixrene with other comonomer. Calixarene molecules are originally known as an inclusion compound in host-gesut chemistry, which can bind various metal ions and organic molecules. Thus, we also investigated the binding property of calixarene polymer against trivalent europium(Eu3+) complex which possesses excellent luminescent characteristics. An interaction, i.e. coordination structure, is established between calixarene polymer and Eu complex, which results in an effective suppression of concentration quenching of Eu complex.

DOI： 10.1117/12.763211

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DOI： 10.1021/ma800287j

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We found new reactions of oxetanes with many reagents such as acyl chlorides, silyl chlorides, phosphonyl chlorides, alkyl chlorides, aryl esters, thio esters, phosphonic acids, carboxylic acids, thiols, and phenols using suitable quaternary onium salts or crown ether complexes as catalysts. More recently, we also found an anionic ring-opening polymerization of certain oxetane monomers such as (3-methyl-3-hydroxymethyl)oxetane and (3-ethyl-3-hydroxymethyl)oxetane, which have hydroxyl groups, catalyzed by potassium tert-butoxide and 18-crown-6-ether complex, and an anionic ring-opening alternating co-polymerization of oxetane monomers with cyclic carboxylic anhydrides. These reaction systems have also been applied to the synthesis of new functional polymers. In this article, we would like to introduce the application of these reaction systems for the synthesis of high performance new photo-curable polymers and oligomers containing pendant or terminal (meth)acryloyl groups. © 2007 Materials Research Society.

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記述言語：英語   出版者・発行元：AMER CHEMICAL SOC  

The thioacyl group transfer (TAGT) polymerization of propylene sulfide (PS) by using dithiocarbonyl compounds as initiator and the synthesis of AB diblock polymers by the combination of reversible addition-fragmentation chain transfer (RAFT) and TAGT polymerizations have been demonstrated. Ring-opening polymerization of PS was conducted with benzyl dithiobenzoate (BDB) and benzyl 1-pyrrolecarbodithioate (BPC) as initiators in the presence of tetraphenylphosphonium salts as catalysts. The synthesis of diblock copolymers using PS was conducted by the polymerizations of PS using the BDB-terminated polystyrene and BPC-terminated poly(N,N-dimethyl acryamide) (PolyDMAm) as macroinitiators in the presence of tetraphenylphosphonium chloride (TPPC). This approach is proving to be a promising approach to design macromolecular architecture, such as block copolymer with a versatile combination of functional blocks.

DOI： 10.1021/ma071533w

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS INC  

The polyaddition of fluorine-containing bis(epoxide)s and fluorine-containing triazine di(aryl ether)s were examined to give the corresponding fluorine-containing poly(cyanurate)s. It was observed that the synthesized fluoropolymers had good thermal stabilities and good film-forming properties. The glass transition temperatures (T-g's) and refractive-indices (n(D)'S) of synthesized polymers were determined by differential scanning calorimetry and ellipsometry, respectively, and it was found that the values of T-g's and n(D)'S were supported by their fluorine containing ratios and skeletons. (c) 2007 Wiley Periodicals, Inc.

DOI： 10.1002/pola.22191

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記述言語：日本語  

CiNii Books

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記述言語：英語   出版者・発行元：AMER CHEMICAL SOC  

The synthesis and photopolymerization of alkaline-developable hyperbranched polyurethane (HBPUMA-COOH) were examined. The reaction of dicyclohexylmethane 4,4'-diisocyanate (CMDI) and trimethylolpropane (TMP) in the presence of 2-methacryloyloxyethyl isocyanate (MOI) was carried out to give the soluble hyperbranched polyurethane (HBPUMA) with terminal methacryloyl groups in satisfactory yield. After that, HBPUMA-COOH was synthesized by the reaction of HBPUMA and cis-1,2,3,6-tetrahydrophthalic anhydride (THPA). The photoradical polymerization of HBPUMA-COOH was examined in the presence of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-2-one (Irgacure 907) as a photoinitiator in the film state upon UV irradiation to afford the corresponding cured film quantitatively. It was found that the tensile strength of the resulting cured film of HBPUMA-COOH was higher than those of the HBPUMA and linear one. The negative patterning property of HBPUMA-COOH also had 5 mu m line and space pattern resolution by UV irradiation with 150 mJ/cm(2). Furthermore, it was cleared that the photocured HBPUMA and HBPUMA-COOH showed very low birefringence.

DOI： 10.1021/ma062381s

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS INC  

The ring-opening copolymerization of a glycidyl ester derivative having a benzophenone group and the donor-acceptor norbornadiene (D-A NBD) dicarboxylic acid, 5-(4-methoxyphenyl)-1,4,6,7,7-pentamethyl-2,5-norbornadiene-2,3-dicarboxylic acid, monoglycidyl ester derivatives with D-A NBD dicarboxylic anhydride using tetraphenylphosphonium bromide as a catalyst proceeded smoothly to give novel self-photosensitizing NBD polymers in good yields. The molecular weight of these polyesters was about 4,000, and lower than that of analogous NBD polymers having no benzophenone group. All the synthesized NBD polymers isomerized smoothly to the corresponding quadricyclane (QC) polymers upon UV irradiation in tetrahydrofuran (THF) solution and in the film state. The rate of the photoisomerization of the D-A NBD moieties in these polymers was higher than that of the D-A NBD moieties in the polymer having rto photosensitizing group. Furthermore, the rate of the photoisomerization of the D-A NBD moieties in these polymers was also higher than that of the NBD polymer with low molecular weight photosensitizer in dilute solution. The photo-irradiated polymers having QC moieties released thermal energies of 146-180 J/g. The D-A NBD moieties contained in these NBD polymers possessed fair to good fatigue resistance. The degradation of the NBD moieties in these polymers was 15-30% after 50 repeated cycles of interconversion. (c) 2007 Wiley Periodicals, Inc.

DOI： 10.1002/pola.22052

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記述言語：日本語   出版者・発行元：公益社団法人 高分子学会  

ハイパーブランチポリマーの末端,あるいは側鎖に光重合反応性基とアルカリ現像性基を有するハイブリッド型ハイパーブランチポリマーの合成法とその反応特性,および得られた硬化物の物性について紹介する。

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS INC  

This paper reports new addition reactions of oxetalies with certain protonic reagents such as carboxylic acid, phenol, and thiol, and with certain aprotic reagents such as acyl chloride, thioester, phosphonyl dichloride, silyl chloride, and chloroformate using quaternary onium salts as catalysts. The kinetic study of the addition reactions of oxetanes was also investigated. These new addition reactions were applicable to the synthesis of new polymers. These polyaddition systems could also construct both polymer main chains and reactive side chains. The alternating copolymerization of oxetanes with carboxylic anhydride was performed. Furthermore, it was found that anionic ring-opening polymerization of oxetanes containing hydroxy groups proceeded to afford the hyperbranched polymer (HBP) with an oxetanyl group and many hydroxy groups at the ends of the polymer chains. Alkali developable photofunctional HBPs were synthesized by the polyaddition of bis(oxetane)s or tris(oxetane)s, and their patterning properties were examined, too. The photo-induced cationic polymerization of the polymers with pendant oxetanyl groups and the thermal curing reactions of polyfunctional oxetanes (oxetane resins) were also examined to give the crosslinking materials quantitatively. (c) 2007 Wiley Petiodicals, Inc.

DOI： 10.1002/pola.21828

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS INC  

The ring-crossover polymerization of cyclic dithioester 1 was performed in the presence of quaternary onium salts as catalysts at 70-150 degrees C for 24 h in NMR It was found that predictable cyclic polymers with the same repeating structures as 1 were obtained with M(n)s in the range between 700 and 3,500, quantitatively. It was observed that intermolecular and intramolecular thioester-exchange reactions proceeded between cyclic monomer 1 and resulting cyclic polymers under thermodynamic control to give a lower-molecular-weight cyclic polymer with a lower polydispersity ratio (M-n = 2,400, M-w/M-n = 1.70). (c) 2006 Wiley Periodicals, Inc.

DOI： 10.1002/pola.21850

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記述言語：英語  

Synthesis and properties of alkaline-developable hyperbranched polymers containing both methacryloyl groups and carboxyl groups were examined. The synthesized photo-functional hyperbranched polymers showed high photo-chemical reactivities, fine solubilities, good film-forming properties, and good thermal properties. These indicated that hyperbranched polymers with terminal photo-polymerizable groups were applicable to new UV curing materials. Furthermore, the cured films obtained from the photo-functional hyperbranched polymers had high tensile strength and lower birefringence compared to linear ones. The negative resist composed of photo-functional hyperbranched polymers also showed better resolution. © 2007, The Society of Polymer Science, Japan. All rights reserved.

DOI： 10.1295/kobunshi.56.334

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Octa-arms and dodeca-arms star-shaped polysulfides poly(PPS(n)-BCA[8]core), poly(PPS(n)-CRAcore), poly(PPS(n)-CRAPhCore) with high refractive-indices (nDS) were synthesized by the radiating from p-t-butylcalix[8]arene derivative, c-methylcalix[4]arene derivative, and c-phenylcalix[4]arene derivative as cores. It was found that the order of the values of nDS of resulting polysulfides are as follows: poly(PPS(n)-CRAPhCore) &gt; poly(PPS(n)-CRAcore) &gt; poly(PPS(n)-BCA[8]core). These mean that nDS are supported by their compact structures and high segment densities.

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Well-defined star-shaped polymers were synthesized by atom transfer radical polymerization of MMA and St radiating from calixarene derivative as a core. The polymerization was performed in the presence of CuCl/bpy as a catalyst to afford the star-shaped polymers with narrow molecular weight distribution. The refractive-indices properties of the synthesized star-shaped polymers and corresponding linear polymers were examined in the film states at several temperatures. The linear relationships between the refractive-indices values (n Ds) and temperatures were observed. It was found that n Ds of star-shaped polymers were higher than those of corresponding linear ones at higher glass transition temperature.

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The reaction of 3-ethyl-3-phenoxymethyloxetane (EPMO) and 3-acetyloxymethyl-3-ethyloxetane (AOEO) were examined using tungsto phosphoric acid (PW12) as a hetero polyacid catalyst at 80°C in chlorobenzene for 24 h. It was found that cationic polymerization of EPMO proceeded smoothly to give the corresponding polymer with high molecular weight in satisfactory high yield and inter-molecular reaction of AOEO proceeded to give the corresponding bicyclo ortho ester compound selectively. These results mean that reaction of oxetanes using PW12 has been affected strongly by the structure of oxetane.

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The polyaddition of 3,3-bis(4-carboxylphenyloxymethyl)oxetane (CPOMO) and 1,3,5-trisglycidyloxybenzene (TGOB) was carried out in the presence of tetrabutylammoniumbromide(TBAB) at 90°C for 7 h to afford the hyperbranched polymer (HBP) with Mn = 7,200 in 81% yield. The reaction of HBP with methacrylic anhydride was performed to give the corresponding polymer (HBP-MA) with both methacryloyl and oxetanyl groups. The photo-polymerization of HBP-MA was performed in the film state using photo-radical initiator or photo-acid generator. Furthermore, the reaction of HBP with tetrahydrophthalic anhydride was performed to give the corresponding polymer (HBP-CA) with both carboxyl and oxetanyl groups. The thermal curing reaction of HBP-CA was performed in the film state using tetraphenylphosphonium iodide (TPPI). Furthermore, the thermal properties of resulting cured films were examined.

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The synthesis and photo-induced deprotection reaction of Noria derivatives with pendant t-butyloxy carbonyl groups, t-butyl ester groups, and acetal groups were examined. The synthethesized Noria derivatives had good film-forming properties and good solubilities. It was observed that the photo chemical reaction of Noria derivatives proceeded in the film states to give the corresponding products which are soluble in aqueous alkaline solution.

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We examined the syntheses and optical properties of novel refractive-index change materials based on cyclodextrins (CDs) containing certain photo-reactive groups. The photochemical reaction of obtained CD-derivatives was examined in the film state upon UV irradiation. It was found that the large refractive-index changes (Δn = 0.015-0.083) occurred before and after photochemical reaction.

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Synthesis and properties of the hyperbranched poly(ester)s containing methacryloyl groups (HBPEMA) were examined. Hyperbranched polyester containing oxetanyl groups (HBPE) was synthesized by the polyaddition of 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene (BEOB) with trimesic acid (TMA) using tetraphenylphosphonium chloride (TPPC) as a catalyst. HBPEMA was prepared by the addition reaction of the synthesized HBPE with methacrylic acid (MAA). The photo-initiated radical polymerization of the obtained HBPEMA was examined in the presence of photo-initiator in the film state upon UV irradiation, and it was found that the photo-initiated radical polymerization proceeded smoothly to give the cured films. It was observed that the rate of the photo-radical polymerization of hyperbranched polymer was higher than that of linear one. It was found that the birefringence of the cured film of hyperbranched polyester was lower than those of the corresponding linear ones.

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The synthesis of the photo-functional star-shaped polysulfides [star-PPS(n)-co-MPS(m)] radiating from the p-t-butylcalix[8]arene derivative (BTC-BCA[8]) as a core was examined. The continuous insertion reaction of 3-phenoxypropyrenesulfide and 3-methacryloyloxypropyrenesulfide into thioester moieties of BTC-BCA[8] initiator was performed in the presence of tetrabutylammoniumcloride as a catalyst to afford the corresponding star-PPS(n)-co-MPS(m) quantitatively. Furthermore, the values of refractive-indices of star-PPS(n)-co-MPS(m) were examined in the film state before and after photochemical reaction.

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The ring-crossover polymerization of cyclic dithioester (CDE), cyclic tetrathioester (CTE), and cyclic hexathioester (CHE) were examined using tetrabutylammonium chloride (TBAC) as a catalyst at 70°C for 24 h in NMP. It was obtained that cyclic polymers were obtained from CDE and CTE with M ns in the range of 900-5800 in 90-97% yields. The structures of the resulting cyclic polymers were confirmed by 1H NMR and MALDI-TOF mass spectroscopy. However, the cyclic polymer was not obtained by this reaction of CHE.

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Thermal curing reaction of oxetane resin (PNOX) and 2,2-bis[(3- ethyloxetane-3-yl)methoxy] biphenyl (2,2&#039;-BPOX) with active ester was examined in the presence of quaternary onium salt as a catalyst for 18 h, affording the corresponding gel products in high yields. Furthermore, the thermal properties of the resulting gel products were examined by DSC and TGA. It was observed that the glass transition temperatures and yields of cured materials decreased with increasing the feed ratios of 2,2&#039;- BPOX on the thermal curing reaction. However, their thermal decomposition temperatures were constant in all the cured materials.

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The well-defined star-polymers were synthesized by the atom-transfer radical polymerization of glycidyl methacrylate using calixarene-derivative as a core. The reaction of synthesized star-polymers with 3-phenyl-2,5-norbornadien was carried out in the presence of TBAB at 70°C for 48 h in NMP, affording the corresponding star-polymers containing norbornadiene moieties in the side chain. Furthermore, the refractive-index properties of the resulting star-polymers were examined in the film state before and after photo-irradiation, and it was found that large refractive-index changes occurred.

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The addition reaction of AB2 building block containing two oxetanyl groups with acyl chloride was carried out using t-butylammonium chloride as a catalyst, to afford the corresponding ester compounds with pendant chloromethyl groups. According to the similar manner of this reaction system, we synthesized dendron and dendrimer with internary chloromethyl groups.

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The synthesis and refractive-index property of the graft-polysulfides were examined. The radical polymerization of well-defined macromonomers containing styrene moieties at the end and sulfur atoms was carried out with AIBN as an initiator, affording the corresponding graft-polysulfides. Furthermore, the refractive-index property of the resulting graft-polysulfides was examined in the film state by ellipsometry.

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記述言語：日本語   掲載種別：書評論文，書評，文献紹介等   出版者・発行元：社団法人 有機合成化学協会  

This article reports new ring-opening reactions of oxetane compounds with certain reagents such as acyl chlorides, carboxylic esters, phenols, and carboxylic acids using certain quaternary onium salts as catalysts. Reaction behavior of oxetanes was investigated based on kinetic study. These new reactions of oxetanes were also successfully applied to polymer synthesis. Polymers containing pendant reactive groups were obtained by polyaddition of bis (oxetane) s with certain difunctional monomers such as dicarboxylic chlorides, bis (phenol) s, or dicarboxylic acids. The reaction of oxetanes with cyclic carboxylic anhydrides proceeded in alternating ring-opening copolymerization mode to give copolymers with A-B sequence. The authors found new anionic ring-opening polymerization of oxetanes containing pendant hydroxyl groups using appropriate catalyst system. Hyperbranched polymers containing hydroxyl groups were prepared by the reactions of oxetanes. Alkali developable photopolymers were also obtained by the chemical modification of the hyperbranched polymers. The reactions of oxetanes with certain reagents were also useful for thermal curing reaction providing oxetane resins.

DOI： 10.5059/yukigoseikyokaishi.64.934

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS INC  

The syntheses and properties of hyperbranched poly(o-hydroxyamide) [poly(HAB-BCC)-ABP], poly[o-(t-butoxycarbonyl)amide] [poly(HAB-BOC)-ABP-t-BOC], and polybenzoxazole [poly(HAB-cycloBCC)] were examined. Poly(HAB-BCC)-ABP was obtained from the polycondensation reaction of 3,3-dihydroxy-4,4'-diaminobiphenyl (HAB) as an A(2)-monomer and 1,3,5-benzenetricarboxylchloride (BCC) as a B-3-monomer with 2-amino-4-t-butylphenol (ABP) in NMP in the presence of pyridine for 24 h. The reaction of poly(HAB-BCC)-ABP and di-t-buthylcarbonate (DiBOC) was performed to obtain the corresponding poly(HAB-BCC)-ABP-t-BOC with pendant t-BOC groups. The thermal cyclodehydration of poly(HAB-BOC)-ABP-t-BOC was carried out in the film sate at 400 degrees C, affording the poly(HAB-cyclo-BCC) in quantitative yield. Furthermore, the solubilities and thermal properties of these polymers were examined. (c) 2006 Wiley Periodicals, Inc.

DOI： 10.1002/pola.21449

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記述言語：英語   出版者・発行元：AMER CHEMICAL SOC  

We succeeded in the synthesis of certain poly(silsesquioxane)s (poly(SCC)) with excellent refractive indices properties, which have pendant norbornadiene (NBD), azobenzene (AZ), and anthracene (AT) moieties. The photochemical reactions of the obtained poly(SCC) derivatives were examined in the film state upon UV irradiation, and it was found that poly(SCC) derivatives with NBD groups, AZ groups, and AT groups had large change in values of the refractive index (Delta n(D)'s) before and after photoirradiation which were in the range of 0.050-0.073, 0.007-0.009, and 0.094-0.116, respectively.

DOI： 10.1021/ma052147m

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記述言語：英語   出版者・発行元：SOC POLYMER SCIENCE JAPAN  

Hyperbranched poly(ester)s with many pendant primary hydroxy groups were prepared in 21-84% yields by polyadditions of certain bis(oxetane)s such as 1,4-bis[(3-ethyl-3-oxetanylmethoxymethyl)]benzene (BEOB), 1,2-bis [(3-ethy-3-oxetanyl) methoxy] benzene (1,2-BEOMB), 1,3-bis[(3-ethy-3-oxetanyl)methoxy]benzene (1,3-BEOMB), 1,4-bi s [(3-ethy-3-oxetanyl)methoxy] benzene (1,4-BEOMB), 4,4-bis[(3-ethyl-3-oxetanyl)methoxy]biphenyl (4,4'-BEOBP), 3,3',5,5'-tetramethyl-[4,4'-bis(3-ethyl-3-oxetanyl)methoxy]biphenyl (TM-BEOBP) with 1,3,5-benzenetricarboxylic acid (TMA) using tetraphenylphosphonium chloride (TPPQ as a catalyst in NMP at 140 degrees C for 12 h. Resulting polymers were insoluble in water; however, these polymers were soluble in 2.3% tetramethylammonium hydroxide aqueous solution. These polymers were also Soluble in dioxane, THF, MEK, and aprotic polar solvents. The glass transition temperatures (T(g)s) of these polymers were 59-131 degrees C.

DOI： 10.1295/polymj.38.145

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記述言語：英語   出版者・発行元：SOC POLYMER SCIENCE JAPAN  

The hyperbranched poly(ester)s with pendant primary hydroxy, methacryloyl, and oxetanyl groups were synthesized by the one-pot method for the polyaddition of bis(oxetane)s with 1,3,5-benzenetricarboxylic acid (TMA) and methacrylic acid (MA) in the presence of tetraphenylphosphonium chloride (TPPC) as a catalyst. A alkaline-developable photo-reactive hyperbranched polymer (P-4b) was prepared by the addition reaction of the synthesized hyperbranched poly(ester) P-4a with cis-1,2,3,6-tetrahydrophthalic anhydride (THPA). A resist composed of 58 wt% P-4b, 12 wt% dilute monomer, 5 wt% Irgacure907 (R) as a photo-initiator, 24 wt% epoxy resin, and 1wt% dicyandiamide achieved a resolution of a 55 pm line pattern and a 27 mu m space pattern by UV irradiation (1000 mJ) when 6 mu m thick film is used.

DOI： 10.1295/polymj.38.447

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記述言語：英語   出版者・発行元：SOC POLYMER SCIENCE JAPAN  

Octa-arms star-shaped polysulfides poly(PPS(n)-BCA[8](core)) (n = 5, 10, 15, 20, 30, 40, 50, 60, and 70) with high refractive-index were synthesized by the radiating from p-t-butylcalix[8]arene derivative as a core. The continuous insertion reaction of 3-phenoxypropyrenesulfide (PPS) into thioester moieties of BCA[8]-core was perfomerd in the presence of TBAC as a catalyst to afford the star-shaped polymers poly(PPS(n)-BCA[8](core)) quantitatively. The arm-lengths of poly(PPS(n)-BCA[8](core)) were controlled by the feed ratios of [PPS]/[(BCA[8]-core) x 8]. The refractive-indices values (n(D)s) of poly(PPS(n)-BCA[8](core)) increased with their sulfur contents. Furthermore. we examined the n(D)s of the linear polymers poly(PPS(n)-Bphe) which skeletons are almost the same as the star-shaped polymers poly(PPS(n)-BCA[8](core)). It was found that n(D)s of star-shaped polymer were higher than those of linear ones due to their compact structures and high segment densities.

DOI： 10.1295/polymj.38.289

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The copolymerization of 3-methacryloyloxypropylenesulfide (MPS) and 3-pheoxypropylenesulfide (PPS) using o-DiCTE as an initiator was carried out using tetra butylammonium chloride (TBAC) as a catalyst at 70 °C for 96 h in NMP (0.05 mol/L), affording cyclic polysulfides containing methacryloyl groups (M nS = 2000 - 14200) in 91-95 % yields. The copolymerization of MPS and PPS using o-OMe-DiLTE as an initiator was also carried out under the same condition, affording linear polysulfides containing methacryloyl groups (M nS = 900 - 8800) in 91-95 % yields. Photo-initiated radical polymerization of the obtained polysulfides was examined in the film state, to give the cured materials. Furthermore the reflactive-indeices values of the obtained polysulfides were examined before and after photo-irradiation.

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This article deals with synthesis and photo-reactive properties of polysilsesquioxanes containing pendant photo-reactive groups. The reaction of poly(p-chloromethyl)phenyl silsesquioxane with various compounds containing photo-chemical isomerizable groups was carried out in the presence of tetrabutyl ammoniumubromide (TBAB) as a PTC or 1,8-diazabicyclo[5.4.0] undec-7-ene(DBU) as a base affording the corresponding polymers containing photo-reactive groups in 51∼81 % yields. Furthermore, the refractive indices values of resulting polymers before and after photo-irradiation were examined.

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The polyaddition of 3,3-bis(4-carboxylphenyloxymethyl)oxetane (CPOMO) and bisphenol A diglycidylether (BPGE) was carried out in the presence of tetrabutylammonium bromide (TBAB) at 90°C for 24 h to afford the polymer (P-1) with Mn = 14600, Mw / Mn = 1.68 in 91% yield. The polymer reaction of P-1 with methacrylic anhydride was performed using NEt3 at 40°C for 24 h to give the corresponding polymer (P-1′) with both methacryloyl and oxetanyl groups. The photochemical reaction of P-1′ was performed in the film state using photo-radical initiator or photo-acid generator, affording the cured materials. Furthermore, the thermal properties of resulting cured films were examined.

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We have found a new dynamic covalent chemistry system for the formation of ladder macrocycle. The reaction of resorcinol and 1,5-pentanedial [(CH2)3(CHO)2] was performed in the presence of conc. HCl in ethanol at 80°C for 48 h, affording a soluble cyclic oligomer under thermo dynamic control in good yield. The resulting oligomer was referred to as Noria, because its structure confirmed by single crystal X-ray analysis looks like a water-wheel. Noria had double cyclic rings, 24 hydroxy groups, 6 cavities in the side, and a large hydrophobic hole in a molecule. Furthermore, we examined the photochemical reaction and extraction of synthesized Noria-derivatives.

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The cationic ring-opening copolymerization of poly(EHMO)-Ac with BEOMB was carried out in the presence of BF 3OEt 2 as an initiator in CH 2Cl 2 at 0°C for 24 h and corresponding dendritic polymers, poly(poly(EHMO)-Ac-co-BEOMB) with number-average molecular weights of 6400-26700 were obtained in 59-61 % yields. The poly(poly(EHMO)-Ac-co-BEOMB) was treated with alkaline solution to obtain the corresponding polymer, poly(poly(EHMO)-co-BEOMB) containing many hydroxyl groups. Furthermore, the reaction of poly(poly(EHMO)-co-BEOMB) with methacrylic anhydride in the presence of pyridine were performed to afford the poly(poly(EHMO)-co-BEOMB)-MA with pendant methacryloyl groups. The photo-initiated radical polymerization of poly(poly(EHMO)-co-BEOMB)-MA was examined using Irgacure 907® as an initiator in the film state, affording the crosslinked polymer.

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The ring-expansion reaction of cyclic dithioester compound (CDE) was carried out using tetrabutylammonium chloride (TBAC) as a catalyst at 70°C for various time in NMP (0.5 mol/L), affording corresponding cyclic polymers with M ns = 2100 - 3500, M w/M n = 1.4-4.8 in 91-95% yields. It was observed that M ns of resulting polymers increased gradually with reaction time. The polymer with the highest M n was obtained after 96 h. After that, the reduction of M ns was observed with reaction time increased. It was suggested that an intermolecular ring-crossover reaction occurred between the thioester moieties of CDE.

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The synthesis and self-polyaddition of novel monomers containing oxetanyl and carboxyl groups were examined. The reactions of 3-ethyl-3- hydroxymethyloxetane(EHO) and certain acid anhydrides were carried out in THF in the presence NEt3 at 50°C for 24 h to give the corresponding monomers containing oxetanyl and carboxyl groups. The self-polyaddition of the obtained monomers was carried out using TPPB as a catalyst in o-dichlorobenzene at 170°C for 24 h, affording the corresponding polymers with Mn = 2800-36000 in 89-97 % yields.

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Syntheses and properties of the hyperbranched poly(ester)s containing methacryloyl groups (HBPEMA) and hyperbranched poly(urethane)s containing methacryloyl groups (HBPUMA) were examined. HBPEMA was prepared by the polyaddition of bisphenol-A diglycidyl ether (BPGE) with trimesic acid (TMA) and methacrylic acid (MA) using tetrabutylammonium chloride (TBAC) as a catalyst in one-pot method. HBPUMA was synthesized by the polyaddition of 4,4&#039;-diisocyanate (CMDI) with trimethylol propane (TMP) and 2-methacryloyloxyethyl isocyanate (MOI) using dibutyltin dilaurate (DBTDL) as a catalyst in one-pot method. The photo-initiated radical polymerizations of the obtained HBPEMA and HBPUMA were examined in the presence of photo-initiator in the film state upon UV irradiation, and it was found that the photo-initiated radical polymerizations proceeded smoothly to give the cured films. It was observed that photo-reactivity of the hyperbranched polymers were higher than those of linear ones.

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The reaction of 3,3′-dihydroxybenzidine and trimesic acid was carried out using (2,3-dihydro-2-thioxo-3-benzoxazolyl)phosphonate (DBOP) in the presence of NEts in NMP at r.t. for 24 h, to afford the hyperbranched poly(o-hydroxyamide) (HBPHA) in good yield. The reaction of the obtained HBPHA with methacrylic anhydride or di-t-butyl dicarbonate afforded the corresponding hyperbranched poly(amide)s containing photo-polymerization groups (HBPHA-MA) or photo-deprotection groups (HBPHA- t-BOC), respectively. Furthermore, the photo-chemical reaction and thermal cyclization reaction of HBPHA-MA and HBPHA- t-BOC were examined in the film state to give the hyperbranched polybenzoxazoles (HBPBO).

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We examined the syntheses of new sulfur containing star-shaped polymers with controlled the arm length by the insertion reaction of 3-phenoxypropyrene sulfide (PPS) into the calixarenes(BCA[8], CRA[4], CRAPh[4])-based tioesters. The reaction of thioesters and PPS was carried out in the presence of tetrabutylammonium chloride(TBAC) as a catalyst at 90°C for 24h in NMP, affording the star-shaped polymers. Furthermore, the refractive-indices values (nDs) of resulting star-shaped polymers were examined in the film state. Those nDs were observed in the order of star-CRA Ph&gt; star-CRA&gt; star-BCA due to their compact structures and high segment densities.

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The reaction of resorcinol with 1,4-butanedial was carried out in the presence of conc.HCl as a catalyst in ethanol at 80°C for 24 h, affording the corresponding polymers with Mn = 3700-10700 and M w/Mn = 1.2-3.1 in 12-29 % yields. The structure of the obtained polymers was confirmed by 1H NMR and MALDI-TOF-MS spectra. It was indicated that the obtained polymers had ladder skeletones and calixarene moieties in the main chain.

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The synthesis and self-polyaddition of novel monomers containing both oxetanyl and carboxyl groups were examined. The reactions of 3-ethyl-3-chloromethyloxetane(ECO) and o,m,p-rhydroxybenzoic acid were carried out in NMP in the presence TBAB at 80°C for 24 h to give the corresponding ethers containing both oxetanyl and carboxyl groups. The self-polyaddition of the obtained o-EOMBA, m-EOMBA, p-EOMBA was carried out using TPPB as a catalyst in o-dichlorobenzene at 150°C for 24 h, affording the corresponding polymers with Mns = 13000 - 33000 (Mw/Mn= 1.2 - 2.3) in 84-95% yields.

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The reaction of resorcinol and 1,5-dialdehyde was performed in the presence of HCl as a catalyst in ethanol at 80°C for 48 h to afford the cyclic oligomer (Noria) containing many hydroxy groups. The Noria-derivative containing carbonate group and tertr-butyl ester group were synthesized. Furthermore, photo-induced deprotection of the synthesized Noria-derivatives was examined in the film states using photo-acid generator to give corresponding Noria-derivatives which are soluble in aqueous alkaline solution.

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The ring-expansion reaction of equimolar cyclic dithioester DTE with 3-phenoxypropyrene sulfide (PPS) (cyclic dithioester 1/ PPS = 1/2) was examined in the presence of TBAC as a catalyst in NMP for 24 h. It was found that intermolecular ester-exchange reaction occurred during the insertion reaction of PPS into cyclic dithioesters, and cyclic polymers with Mns = 3600 - 8900 were obtained in 80 - 96% yields. The structures of the obtained cyclic polymers were confirmed by the 1H NMR, 13C NMR, IR, and MALDI TOF-MS spectroscopy. The continuous insertion reaction of excess PPS into cyclic dithioester (cyclic dithioester 1 / PPS =1/10- 1/50) was also examined, and it was found that the insertion reaction proceeded quantitatively to afford the corresponding cyclic polysulfides in satisfactory yields.

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Tetra-arms star-shaped polysulfides (star-TCA(n)) (n = 10, 20, 30, 40, and 50) were synthesized by the radiating from p-t-butylthiacalix[4]arene derivative (BTA-TCA) as a core. The continuous insertion reaction of 3- phenoxypropyrenesulfide (PPS) into thioester moieties of BTA-TCA-core was performed in the presence of TBAC as a catalyst at 90°C in NMP for 24 h, to afford the corresponding star-shaped polymers star-TCA(n) with Mns = 1400 -7800, Mw / Mn = 1.2-1.8. The arm-length of star-TCA(n) could be controlled by the feed ratios of PPS and BTA-TCA. It was observed that the refractive-indices values (nDs) of star-TCA(n)s were independent on Mns and dependent on the sulfur-contents ratios.

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The reaction of resorcinol and 1,5-dialdehyde was performed in the presence of HC1 as a catalyst in ethanol at 80°C for 48 h to afford novel cyclic oligomer (Noria) containing many hydroxy groups. The Noria-derivatives containing radical polymerizable groups and cationic polymerizable groups were synthesized. Furthermore, the photochemical reaction of synthesized Noria-derivatives was examined in the film states using photo-radical initiator or photo-acid generator to give the corresponding cured materials, respectively. It was found that the obtained cured materials had high thermal stabilities.

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We examined the syntheses of new sulfur containing twelve-arm star-shaped polymers with controlled the arm length by the insertion reaction of 3-phenoxypropyrene sulfide (PPS) into the C-4-hydroxyphenyl-calixresorcin[4] arene(Ph-CRA[4])-based tioesters (BTA-Ph-CRA[4]). The reaction of BTA-Ph-CRA[4] and PPS was carried out in the presence of tetrabutylammonium chloride(TBAC) as a catalyst at 90°C for 24h in NMP, affording the star-shaped polymers (star-Ph-CRA(n)s). Furthermore the refractive-indices values (nDs) of resulting star-Ph-CRA(n)s were examined in the film state. It was observed that nDs increased with sulfur-content ratios of the star-Ph-CRA(n)s.

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Photo Optical Effect of some photochromic dyes was investigated with Michelson&#039;s interferometer to determine physical and optical parameters for their reactions. The factors for their high efficiency was found to be those quantum yield, absorption wavelength, specific molar volume, and free volume of the matrices.

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記述言語：日本語   出版者・発行元：高分子刊行会  

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS INC  

Hyperbranched polyesters with terminal methacryloyl groups (HBPEAc) were synthesized by the one-pot polyaddition of bisphenol A diglycidyl ether and trimesic acid in the presence of methacrylic acid with a number-average molecular weights of 5100-7700 in 70-83% yields. The photoradical polymerization of HBPEAc was examined in the presence of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-2-one (Irgacure 907 (R)) as a photoinitiator in the film state upon UV irradiation to afford the corresponding cured films quantitatively. The crosslinking densities of the cured films of HBPEAc were higher than those of the corresponding linear ones, and birefringence cannot be detected for the cured films of HBPEAc because of their random structures. Furthermore, an alkaline-developable hyperbranched polyester containing pendant carboxyl groups (HBPEAc-COOH) was prepared by the addition reaction of HBPEAc with cis-1,2,3,6-tetrahydrophthalic anhydride, and its patterning properties were examined to give the resolution of a 55-mu m-line and 275-mu m-space pattern by UV irradiation with 700 mJ/cm(2). (c) 2005 Wiley Periodicals, Inc.

DOI： 10.1002/pola.20957

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS INC  

The ring-opening copolymerization of donor-acceptor norbornadiene (D-A NBD) dicarboxylic acid monoglycidyl ester derivatives with D-A NBD dicarboxylic acid anhydride was performed with tetraphenylphosphonium bromide as a catalyst in toluene to produce new norbornadiene (NBD) polyesters containing D-A NBD moieties in the main chain and in the side chain in one step in good yields. The photoisomerization of the D-A NBD moieties in these polyesters proceeded very smoothly to give the corresponding quadricyclane groups. Because these NBD polyesters contained many NBD moieties in the polymer chain, they had the highest capacity for heat storage in the D-A NBD polymers reported so far. The stored thermal energy of the irradiated polyesters was evaluated by differential scanning calorimetry analysis to be approximately 150-190 J/g. (c) 2005 Wiley Periodicals, Inc.

DOI： 10.1002/pola.20911

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記述言語：英語   出版者・発行元：AMER CHEMICAL SOC  

The ring-expansion reaction of equimolar cyclic dithioester 1 with 3-phenoxypropyrene sulfide (PPS) (cyclic dithioester 1/PPS = 1/2) was examined in the presence of TBAC as a catalyst in NMP for 24 h. It was found that intermolecular ester-exchange reaction occurred during the insertion reaction of PPS into cyclic dithioesters, and cyclic polymers with M(n)s = 3600-8900 were obtained in 80-96% yields. The structures of the obtained cyclic polymers were confirmed by the H-1 NMR, C-13 NMR IR, and MALDI TOF-MS spectroscopy. The continuous insertion reaction of excess PPS into cyclic dithioester (cyclic dithioester 1/PPS = 1/50) was also examined, and it was found that the insertion reaction proceeded quantitatively to afford the corresponding cyclic polysulfide with M. = 42 000 and M-w/M-n = 4.50 in a 96% yield.

DOI： 10.1021/ma047642h

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS INC  

The thermal curing reaction of polyfunctional oxetanes (oxetane resins) such as tris [4-(3-ethyloxetane-3-yl)methoxyphenyl] methane (TEOMP) and 1,3,5-tris(3-ethyl-3-oxetanylmethoxy)benzene with certain polyfunctional phenols was performed in bulk with quaternary onium salts as catalysts. The reaction proceeded smoothly at 180-220 degrees C and produced insoluble gel products, and the rate of gel production increased with the reaction temperature. The rate of the addition reaction of TEOMP with 3,3',5,5'-tetrachlorobisphenol A was also measured by IR spectroscopy, and the rate of reaction was proportional to the product of the oxetane concentration and the catalyst concentration in the film state. Furthermore, the glass-transition temperatures and 5 and 10 wt % weight-loss temperatures of the resulting gel products were confirmed with differential scanning calorimetry and thermogravimetric analysis, and the glass-transition temperatures and 5 wt % weight-loss temperatures were 127-162 degrees C and 323-351 degrees C, respectively. (c) 2005 Wiley Periodicals, Inc.

DOI： 10.1002/pola.20586

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記述言語：英語   出版者・発行元：CHEMICAL SOC JAPAN  

In this paper, we describe the syntheses, properties, and photo-induced deprotection of beta-CD derivatives containing t-butyl ester groups and fluorine atoms. The beta-CD derivative was obtained from the reaction of beta-CD and t-butyl-alpha(trifluoromethyl)acrylate. The obtained P-CD derivative had excellent solubility, good film-forming property, high thermal stability, and good transmittance with the VUV spectra. When the photo-chemical reaction of the beta-CD derivative was performed with a photo acid generator in the film state upon UV irradiation, it was found that the photoinduced deprotection of t-butyl ester groups and decomposition of acetal moieties of gluconopyranose unit proceeded smoothly. Furthermore, we examined the patterning property of the beta-CD derivative as the photo resist using triphenylsulfonium fluorosulfonate as a photo acid generator, and 2-heptanone as the solvent. From this result, it was observed that the resolution of a 100 nm line and space pattern could be obtained.

DOI： 10.1246/bcsj.78.731

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記述言語：英語   出版者・発行元：SOC POLYMER SCIENCE JAPAN  

The synthesis and photochemical valence isomerization of polymers containing donor-acceptor type norbornadiene (D-A NBD) residues in both main and side chains, by the polyaddition of 5-(4-methoxyphenyl)1,4,6,7,7-pentamethyl-2,5-norbornadiene-2,3-dicarboxylic acid diglycidyl ester (D-A NDGE) with terephthaloyl chloride follows by substitution reactions of the resulting polymer with potassium 5-(4-methoxyphenyl)-1,4,6,7,7-pentamethyl -3-methylester-2,5-NBD-2-carboxylate, potassium 5-(4-methoxyphenyl)-1,4,6,7,7-pentamethyl-3-(N,N-dipropylcarbamoyl) -2,5-NBD-2-carboxylate, and potassium 5-(4-methoxyphenyl)-1,4,6,7,7-pentamethyl-3-(N-methyl-N-phenylcarbamoyl)-2,5-NBD-2-carboxylate, respectively. The photochemical valence isomerization of the synthesized poly(ester)s (P-1-P-4, and P-5a-c) was examined in tetrahydrofuran solution or in the film state upon irradiation with a 500-W xenon lamp, and it was found that each photochemical reaction proceeded very smoothly. It was also observed that the rate of the photochemical reaction of the NBD polymers increased efficiently by the addition of 4,4'-bis(diethylamino)benzophenone (BEBP) as a photo-sensitizer in the film state. The stored thermal energies of the irradiated polymers were evaluated by DSC analysis to be 75-153 J/g.

DOI： 10.1295/polymj.37.246

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記述言語：英語   出版者・発行元：CHEMICAL SOC JAPAN  

The synthesis and photoinduced deprotection reaction of calix[4]resorcinarene derivatives with pendant acetal moieties were examined. C-methyl[(methoxymethylcarbonyl)oxy]calix[4]resorcinarene (CRA-Acetal) and C-4-hydroxy-phenyl[(methoxymethyicarbonyl)oxy]calix[4]resorcinarene (CRA(ph)-Acetal) were prepared from C-methylcalix[4]resorcinarene (CRA) and C-4-hydroxyphenylcalix[4]resorcinarene (CRA(ph)). The synthesized CRA-Acetal and CRA(ph)-Acetal had good solubilities, good film-forming properties, and high thermal stabilities. The photoinduced deprotection reaction of CRA-Acetal and CRA(ph)-Acetal was examined in the presence of bis[4-(diphenylsulfonio)phenyl] sulfide (DPSP) as a photo-acid generator in the film state upon UV irradiation. It was found that the deprotection reaction of acetal groups of CRA-Acetal and CRA(ph)-Acetal proceeded smoothly without further heating to produce the corresponding calixarene derivatives, CRA-COOH and CRA(ph)-COOH with carboxylic acid groups.

DOI： 10.1246/bcsj.77.2109

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS INC  

Hyperbranched polyimides (HBPI)s with high glass-transition temperatures and excellent thermal stability were synthesized through the reaction of commercially available carboxylic acid dianhydrides with tris[4-(4-aminophenoxy)phenyl]ethane (TAPE). In particular, hyperbranched polyimide HBPI(TAPE-DSDA), prepared through the reaction of TAPE with 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), showed higher thermal stability and good solubility. Furthermore, alkaline-developable, photosensitive HBPI(TAPE-DSDA)-MA-CA was prepared through the reaction of HBPI(TAPE-DSDA) with glycidyl methacrylate with tetrabutylammonium bromide as a catalyst in N-methyl-2-pyrrolidinone (NMP) followed by the addition reaction of cis-1,2,3,6-tetrahydrophthalic anhydride with triphenylphosphine as a catalyst in NMP. The glass-transition temperatures of HBPI(TAPE-DSDA)MA-CA were greater than 300 degreesC. A resist composed of 74 wt% HBPI(TAPE-DSDA)MA-CA, 22.2 wt% trimethylpropane triacrylate, and 3.8 wt% Irgacure 907 as a photoinitiator achieved a resolution of a 55-mum line pattern and a 275-mum space pattern by UV irradiation (1000 mJ/cm(2)). (C) 2004 Wiley Periodicals, Inc.

DOI： 10.1002/pola.20239

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS INC  

The anionic ring-opening polymerization of oxetanes containing hydroxyl groups was carried out with potassium tert-butoxide as an initiator in the presence of 18-crown-6-ether in N-methylpyrrolidinone at 180 degreesC; it yielded corresponding multifunctional hyperbranched polymers: poly(3-ethyl-3-hydroxymethyloxetane)s, with number-average molecular weights of 2200-4100 in 83-95% yields, and poly(3-methyl-3-hydroxymethyloxetane)s, with number-average molecular weights of 4600-5200 in 70-95% yields. The synthesized poly(3-ethyl-3-hydroxymethyloxetane)s and poly(3-methyl-3-hydroxymethyloxetane)s were hyperbranched polyethers containing an oxetane moiety and many hydroxy groups at the ends. The postpolymerization of poly(3-ethyl-3-hydroxymethyloxetane)s was performed in the presence of potassium tert-butoxide and 18-crown-6-ether in N-methylpyrrolidinone at 180 degreesC; it yielded corresponding polymers with higher molecular weights in good yields. The cationic polymerization of poly(3-ethyl-3-hydroxymethyloxetane) derivatives was carried out with boron trifluoride etherate as an initiator and was followed by alkaline hydrolysis; this yielded a new branched polymer, a poly(hyperbranched polyether), with many pendant hydroxy groups. (C) 2004 Wiley Periodicals, Inc.

DOI： 10.1002/pola.20236

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記述言語：英語   出版者・発行元：CHEMICAL SOC JAPAN  

We have examined the synthesis of cyclic oligomers with pendant norbornadiene (NBD) moieties based on the calixarenes [p-tert-butylcalix[8]arene (BCA), p-methylcalix[6]arene (MCA), calix[4]resorcinarene (CRA), 2,8,14,20-tetra-decylcalix[4]resorcinarene (CRA(10)), and 2,8,14,20-tetrakis(p-hydroxyphenyl)calix[4]resorcinarene (CRA(ph))]. The photochemical valence isomerization of the obtained calixarene derivatives containing NBD moieties proceeded very smoothly to afford the corresponding quadricyclane (QC) moieties, and it was found that the large refractive-index changes (Deltan's = 0.028-0.061) before and after photo-isomerization.

DOI： 10.1246/bcsj.77.1415

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS INC  

Fluorine-containing polyethers with pendant hydroxyl groups were synthesized by the polyaddition of fluorine-containing bis(epoxide)s with certain fluorine-containing diols with quaternary onium salts as catalysts. When the polyaddition was performed with 2,2',6,6'-tetrafluoro-4,4'-biphenol diglycidiyl ether and 2,2',6,6'-tetrafluoro-4,4'-biphenol, the corresponding polyether with pendant hydroxyl groups was successfully obtained in good yield. The polyaddition of certain fluorine-containing bis(epoxide)s with diols also proceeded in bulk to provide the corresponding fluorine containing polyethers with high molecular weights. These polyethers were highly transparent at 157 nm for 0.1 mum thickness, with their transmittance of 14-75% at 157 nm. (C) 2004 Wiley Periodicals, Inc.

DOI： 10.1002/pola.20074

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記述言語：英語   出版者・発行元：CHEMICAL SOC JAPAN  

The syntheses and photoinduced deprotection reactions of calix[4]resorcinarene derivatives with pendant t-butyl ester moieties were examined. Calix[4]resorcinarenes, 1a-1h, were prepared by the condensation reaction of resorcinol with certain aldehydes in the presence of hydrochloric acid as a catalyst in ethanol at 80 degreesC for 30 min in good yields. The substitution reaction of 1a-1h with t-butyl bromoacetate using cesium carbonate as a base and tetrabutylammonium bromide (TBAB) as a phase transfer catalyst was performed to afford the corresponding calix[4]resorcinarene derivatives, 2a-2h with pendant t-butyl ester groups. It was found that 2a, 2e, 2f, 2g, and 2h had film forming properties. The photoinduced deprotection reaction of calixarene derivatives 2a, 2e, 2f, 2g, and 2h was examined in the presence of bis-[4-(diphenylsulfonio)phenyl] sulfide (DPSP) as a photoacid generator in the film state upon UV irradiation for 5 min followed by heating at 170 C. It was found that the deprotection reaction of the t-butyl ester groups of 2a, 2e, 2f, 2g, and 2h proceeded smoothly to produce the corresponding calixarene derivatives, 3a, 3e, 3f, 3g, and 3h with carboxylic acid groups, quantitatively.

DOI： 10.1246/bcsj.77.819

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記述言語：英語  

A facile synthesis of N-carboxyanhydrides and poly(α-amino acid) using di-tert-butyltricarbonate (DBTC) is discussed. A one-pot synthesis of poly(amino acid) from an amino acid and DBTC as a dehydrating agent is also discussed. It is found that ring-opening polymerization of α-amino acid-N-carboxyanhydrides (NCA) is advantageous over the polycondensation because ring-opening polymerization, which is a chain polymerization is capable of providing polypeptides with precise topology. Results show that the system is suitable to synthesize NCA and poly(amino acid) from amino acids having acid-sensitive protecting groups.

DOI： 10.1021/ma0498464

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS INC  

The synthesis and self-polyaddition of the optically active monomers I-T(L)-M and I-T(D)-M bearing both isocyanate and hydroxyl groups were examined. I-T(L)-M and I-T(D)-M were synthesized by reactions of L- and D-tyrosine methyl ester, T(L)-M and T(D)-M, with di-tert-butyltricarbonate, respectively. The self-polyaddition of I-T(L)-M and I-T(D)-M proceeded smoothly with triethylamine or tert-butyllithium as the initiator in tetrahydrofuran, affording the optically active linear polyurethanes poly[I-T(L)-M] and poly[I-T(D)-M] with specific head-to-tail structures, where the number-average molecular weights ranged from 10,000 to 20,000 in excellent yields. The optical properties suggested the idea that poly[I-T(L)-M] and poly[I-T(D)-M] should have some higher order structures. (C) 2004 Wiley Periodicals, Inc.

DOI： 10.1002/pola.11047

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS INC  

The polyaddition of bis(oxetane)s 1,4-bis[(3-ethyl-3-oxetanylmethoxymethyl)]benzene (BEOB), 4,4'-bis [(3-ethyl-3-oxetanyl)methoxyl benzene (4,4'-BEOBP), 1,4-bis[(3-ethy-3-oxetanyl)methoxyl -benzene (1,4-BEOMB), 1,2-bis[(3-ethyl-3-oxetanyl)methoxy]benzene (1,2-BEOMB), 4,4-bis[(3-ethyl-3-oxetanyl)methoxy]biphenyl (4,4'-BEOMB), 3,3',5,5'-tetramethyl-[4,4'-bis(3-ethyl-3-oxetanyl)methoxy]biphenyl (TMBEOBP) with active diesters di-s-phenylthioterephthal ate (PTTP), di-s-phenylthioisoterephthalate (PTIP), 4,4'-di(p-nitrophenyl)terephthalate (NPTP), 4,4'-di(p-nitrophenyl)isoterephthalate (NPIP) were carried out in the presence of tetraphenylphosphonium chloride (TPPC) as a catalyst in NMP for 24 h, affording corresponding polyesters with M.'s in the range 2200-18,200 in 41-98% yields. The obtained polymers would soluble in common organic solvents and had high thermal stabilities. (C) 2004 Wiley Periodicals, Inc.

DOI： 10.1002/pola.11057

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記述言語：英語   出版者・発行元：SOC POLYMER SCIENCE JAPAN  

Polyadditions of certain bis(oxetane)s such as 1,4-bis[(3-ethyl-3-oxetanylmethoxymethyl)]benzene (BEOB), 1,4-bis[(3-ethy-3-oxetanyl)methoxy] benzene (1,4-BEOMB), 4,4'-bis[(3-ethyl-3-oxetanyl)methoxy] benzene (4,4'-BEOBP), 2,2'-bis[(3-ethyl-3-oxetanyl)methoxy] biphenyl (2,2'-BEOBP), 3,3',5,5-tetramethyl-[4,4'-bis(3-ethyl-3-oxetanyl)methoxy]biphenyl (TM-BEOBP) with such active bis(ester)s as 4,4'-isopropylidenebis(2,6-dichlorophenyl diacetate) (IBDPA), 4,4'-isopropylidene-bis(2,6-dichlorophenyl dibenzoate) (IBDPB) and 4,4'-isopropylidenebis(2,6-dichlorophenyl di-2,4-dichlorobenzate) (IBDPD) were examined in the presence of tetraphenylphosphonium chloride (TPPC) as a catalyst in DMAc at 160degreesC for 96h, and it was found that corresponding polyethers with M(n)s in the range 7200-17400 were obtained in 91-99% yields. The all obtained polymers would soluble in common organic solvents.

DOI： 10.1295/polymj.36.841

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記述言語：英語   出版者・発行元：SOC POLYMER SCIENCE JAPAN  

Fluorine-containing poly(acetal)s were synthesized by the polyaddition of bisphenol AF (BPAF) with divinyl ether compounds. It was found that the poly(acetal) (PA-1) with a number average molecular weights of 4400 was obtained in 71% yield by the polyaddition of BPAF with ethylene glycol divinyl ether (EGDVE) using I mol % of pyridinium p-toluene sulfonate (PTS) as a catalyst in THF at room temperature for 24 h. Furthermore, the polyaddition of BPAF with other divinyl ether compounds were also carried out to give corresponding poly(acetal)s (PA-2-PA-3) in appropriate reaction conditions. It was also found that the photoinduced depolymerization of the resulting poly(acetal)s proceeded using photo-acid generator (PAG) by the photo-irradiation in the film state. It was found that transmittance of PA-1 was 39% at 157 nm for 0.1 mum thickness.

DOI： 10.1295/polymj.36.531

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記述言語：英語   出版者・発行元：SOC POLYMER SCIENCE JAPAN  

The anionic ring-opening polymerization of 3,3-bis(hydroxymethyl)oxetane (BHO) was carried out using t-BuOK as an initiator in the presence of 18-crown-6-ether (18-C-6) in NMP at 180 degreesC, affording the corresponding hyperbranched polyethers, poly(BHO)s containing an oxetanyl group and many hydroxyl groups at the ends in 83-98% yields. Since the resulting poly(BHO)s were insoluble in common organic solvents, the poly(BHO)s were treated with acetic anhydride to obtain poly(BHO-Ac)s containing acetyl groups at the ends. The M,,s and degree of branching (DB) of poly(BHO-Ac)s were in the range of 2600-4400 estimated by SEC and 0.09-0.55 calculated by C-13 NMR spectroscopy, respectively. The cationic copolymerization of poly(BHO-Ac) and 3-ethyl-3-phenoxymethyloxetane (EPO) was examined using BF3OEt2 as an initiator in CHCl3 at 0 degreesC for 24 h, affording pseudo dendritic polymers, poly[poly(BHO-Ac)/EPO]s with M-n = 11000-15000 in 58-65% yields. Furthermore, the obtained poly[poly(BHO-Ac)/ EPO] was hydrolyzed with KOH to afford the poly[poly(BHO)/EPO] containing many hydroxyl groups.

DOI： 10.1295/polymj.36.413

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記述言語：英語   出版者・発行元：SOC POLYMER SCIENCE JAPAN  

Fluorine-containing poly(ether)s with pendant primary hydroxyl groups were synthesized by the poly-addition of bisphenol AF di(3-ethyl-3-oxetanylmethyl ether) (BPAFEO) with bisphenol AF (BPAF) using quaternary onium salts, crown ether complexes or organic bases as catalysts. When the polyaddition was performed with co-catalysts such as tetraphenylphosphonium chloride (TPPC) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) without solvent at 190degreesC for 120h, the corresponding poly(ether)s pendant primary hydroxyl groups were successfully obtained in good yield. The polyaddition of various bis(oxetane)s with BPAF also proceeded in bulk to provide the corresponding poly(ether)s. It was found that these poly(ether)s are highly transparent at 157 nm, and transmittance of poly(ether)s were determined to be 34-55 % at 157 nm for 0.1 mum thickness.

DOI： 10.1295/polymj.36.114

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記述言語：英語   出版者・発行元：AMER CHEMICAL SOC  

The cationic ring-opening polymerization of a 1,3-oxazolidine-2-thione derivative (S-L) from L-serine was examined. SL was synthesized by the reaction of L-serine methyl ester hydrochloride with carbon disulfide and hydrogen peroxide in the presence of triethylamine. Cationic polymerizations using methyl trifluoromethanesulfonate (TfOMe), trifluoromethanesulfonic acid (TfOH), and boron trifluoride etherate (BF3.OEt2) as initiators gave polymers with polythiourethane structures in quantitative yields. The obtained polymers showed inverted specific rotations with respect to the monomer, where the large increase of the absolute values suggested the possibility of high-order structures. The molecular weight of the polymer was controlled by the feed ratio of SL to TfOMe and its distribution was constantly narrow (M-w/M-n &lt; 1.14), supporting the controlled character of the polymerization. The reaction mechanism was examined for TfOMe. According to NMR spectroscopic experiments, the polymerization with TfOMe proceeds via an active chain end mechanism in which the protonated cyclic endo iminothiocarbonate 2 is the active species. The propagation step involves a nucleophilic attack of S-L to the active species.

DOI： 10.1021/ma030320d

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記述言語：日本語  

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS INC  

The synthesis of polyesters with pendant oxetane groups by the chemoselective alternating copolymerization of 3-ethyl-3-(glycidyloxymethyl)oxetane (EGMO) with carboxylic anhydride and the photochemical reaction of the resulting polymer was examined. The alternating copolymerization of EGMO with phthalic anhydride proceeded chemoselectively with quaternary onium salts under appropriate reaction conditions, and the corresponding soluble polymers with pendant oxetane groups with number-average molecular weights of 4700-7200 were obtained in 72-87% yields. Furthermore, the photochemical reaction of the resulting polymers was examined with certain photoacid generators in the film state upon UV irradiation, and it was found that the photocrosslinking reaction of the pendant oxetane groups proceeded smoothly to give the insoluble polymers. (C) 2003 Wiley Periodicals, Inc.

DOI： 10.1002/pola.10734

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記述言語：日本語   出版者・発行元：公益社団法人 高分子学会  

DOI： 10.1295/kobunshi.52.340

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS INC  

The synthesis and optical properties of polyesters with pendant fluorinated phenoxy groups were examined. The polyaddition of bisphenol AF diglycidyl ether (1) with fluorine-containing terephtalates (2a-f) was carried out with tetrabutylphosphonium chloride (TBPC) as the catalyst in chlorobenzene to afford the corresponding polyesters with number-average molecular weights (M-n's) ranging from 15,200 to 30,000 in 88-96% Yields. Furthermore, the polyaddition of 1 with isophthalate 2g and phthalate 2h also produced high-molecular-weight polyesters with M-n's = 22,700 and 22,600 in 88 and 84% yields, respectively. The linear relationship was observed between the fluorine contents and refractive indices of the obtained polyesters. (C) 2002 Wiley Periodicals, Inc.

DOI： 10.1002/pola.10563

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記述言語：英語   出版者・発行元：NATURE PUBLISHING GROUP  

The synthesis of a hetero telechelic hyperbranched polyether was studied. The anionic ring-opening polymerization of 3-ethyl-3-(hydroxymethyl)oxetane (EHO) using potassium tert-butoxide as an initiators was also discussed. It was found that the dendritic unit ratios and thermal stabilities of poly(EHO) decreased with (number-average molecular weight) Mns.

DOI： 10.1295/polymj.35.88

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記述言語：英語   掲載種別：書評論文，書評，文献紹介等   出版者・発行元：SOC POLYMER SCIENCE JAPAN  

This paper reviews our recent studies on the syntheses and functions of novel calixarene derivatives with excellent thermal stability as high performance materials. Calixarene derivatives containing protective groups such as tert-butoxycarbonyl (t-Boc), trimethylsilyl (TMS), and cyclohexenyl (CHE) groups were successfully prepared by the reaction of certain calixarenes, p-methylcalix[6]arene (1a), p-tert-butylcalix[8]arene (1c), and C-methylcalix[4]resorcinarene (1d) with the corresponding protecting reagents. Calixarene containing radically polymerizable groups such as methacryloyl groups and cationic polymerizable groups such as propargyl, vinyl ether groups were prepared in good yields. Calixarene derivatives containing cyclic ethers such as oxirane, oxetane, and spiro orthoesters were also prepared. Calixarene derivatives thus obtained had good film forming property and thermal stability. It was proved that the photoinduced deprotection of the calixarene derivatives containing protective groups in the presence of a photo-acid generator proceeded easily to give the corresponding calixarenes with phenol groups. Photoinitiated polymerization of the calixarenes with various polymerizable groups using suitable photoinitiators in the film state proceeded efficiently to produce crosslinked films. Furthermore, thermal curing of epoxy resins with calixarenes (1a, le, 1d), and calixarenes containing active ester groups using certain catalysts were studied to found that the calixarenes were useful curing agents for epoxy resins.

DOI： 10.1295/polymj.35.213

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記述言語：日本語   出版者・発行元：社団法人 日本印刷学会  

This review deals with the syntheses and photochemical reactions of the certain calixarene derivatives containing (meth) acrylate, vinyl ether, propargyl ether, oxetane, oxirane, spiro ortho ester, cyclohexenyl ether, trimethylsilyl ether, and tert-butoxycarbonyl groups. These calixarene derivatives were synthesized by substitution and addition reactions of hydroxyl groups of calixarenes such as &lt;i&gt;p&lt;/i&gt;-&lt;i&gt;tert&lt;/i&gt;-butyl-calix [8] arene, &lt;i&gt;p&lt;/i&gt;-methyl-calix [6] arene, and calix [4] resorcinarene. Most of the obtained calixarene derivatives had high &lt;i&gt;T&lt;/i&gt;gs, excellent thermal stabilities, and good film forming properties. Furthermore, calixarene derivatives had also high photochemical reactivity, when the photochemical reactions of calixarene derivatives were carried out in the film state upon UV irradiation.

DOI： 10.11413/nig1987.39.394

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS INC  

The polyaddition of 4,4'-bis[(3-ethyl-3-oxetanyl)methoxy]biphenyl (4,4'-BEOBP) and phenylphosphonic dichloride (PPDC) with quaternary onium salts as catalysts proceeded under mild reaction conditions to afford a polymer containing phosphorous atoms in its main chain. A polyphosphonate with a high number-average molecular weight (10,300) was obtained by the reaction of 4,4'-BEOBP and PPDC in the presence of tetraphenylphosphonium chloride (TPPC) in o-dichlorobenzene at 130 degreesC for 24 h. The structure of the resulting polymer was confirmed with IR, H-1 NMR, and P-31 NMR spectroscopy. Furthermore, it was proved that the polyaddition of certain bis(oxetane)s with phosphonic dichlorides proceeded smoothly to give corresponding polyphosphonates with TPPC as the catalyst. (C) 2002 Wiley Periodicals, Inc.

DOI： 10.1002/pola.10436

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記述言語：英語  

O-Methacryloyl-N-(tert-butoxycarbonyl)-β-hydroxyaspartic acid dimethyl ester was synthesized by methyl esterification of β-hydroxyaspartic acid, followed by protection of the amino group with the tert-butoxycarbonyl group and then the reaction of the hydroxyl group with methacryloyl chloride. The monomer efficiently underwent radical polymerization to afford the corresponding polymer with a number-average molecular weight of 42,000 in good yields. The alkaline hydrolysis of the polymer occurred not only at the methyl ester but also at the ester moiety between the main and side chains of the polymer. The methyl ester-free polymer gradually released β-hydroxy-aspartic acid moiety in a phosphate buffer solution with pH = 7.3 and 7.8. © 2002 Wiley Periodicals, Inc. J. Polym. Sci. Part A: Polym. Chem.

DOI： 10.1002/pola.10363

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記述言語：英語   掲載種別：研究発表ペーパー・要旨（国際会議）   出版者・発行元：AMER CHEMICAL SOC  

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記述言語：英語   掲載種別：研究発表ペーパー・要旨（国際会議）   出版者・発行元：AMER CHEMICAL SOC  

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS INC  

New photoreactive calixarene derivatives containing Spiro ortho ester groups (calixarenes 3a-3c) were synthesized by the reaction of 2-bromomethyl-1,4,6-trioxaspiro[4.4]nonane with 2,8,14,20-tetramethyl-4,6,10,12,16,18,22,24-octakis(carboxymethoxy)calix[4]resorcinarene, 5,11,17,23,29,35-hexamethyl-37,38,39,40,41,42-hexakis(carboxymethoxy)calix[6]arene, and 5,11,17,23,29,35,41,47-octa-tert-butyl-49,50,51,52, 53,54,55,56-octakis-(carboxymethoxy)calix[8]arene, which were prepared by the reaction of C-methylcalix[4]resorcinarene,p-methylcalix[6]arene, and p-tert-butylcalix[S] arene, respectively. The thermal stability of the obtained calixarene derivatives containing Spiro ortho ester groups was examined with thermogravimetric analysis, and it was found that these calixarene derivatives had good thermal stability. The photoinitiated cationic polymerization of Spiro ortho ester groups in calixarene derivatives 3a-3c was examined with certain photoacid generators in the film state. Interestingly enough, the reaction of calixarene derivatives did not proceed with only photoirradiation; however, the reaction proceeded smoothly when the photoirradiation was followed by heating. Furthermore, calixarene 3a, composed of a C-methylcalix[4]resorcinarene structure, showed the highest photochemical reactivity in this reaction system. (C) 2002 Wiley Periodicals, Inc.

DOI： 10.1002/pola.10207

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS INC  

The synthesis and characterization of the fluoropolymers poly1a-1d and poly2a-2d with pendant hydroxyl groups were examined. The polyaddition of bis(epoxide)s [2,2'-bis(4-glycidyletherphenyl)hexafluoropropane and bisphenol A diglycidyl ether] with dicarboxylic acids (tetrafluoroterephthalic acid and terephthalic acid) and diols [2,2'-bis(4-hydroxyphenyl)hexafluoropropane, 2,2',3,3',5,5',6,6'-octafluoro-4,4'-biphenol, 1,4-bis(hexafluorohydroxyisopropyl)benzene, and 1,3-bis(hexafluorohydroxyisopropyl)benzene] was carried out at 50-100 degreesC for 6-48 h in the presence of quaternary onium salts (tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylphosphonium bromide, and tetrabutylphosphonium chloride; 2.5 mol %) as catalysts in dimethyl sulfoxide, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dioxane, diglyme, o-dichlorobenzene, chlorobenzene, and toluene to afford the corresponding polymers, poly1a-1d and poly2a-2d, with number-average molecular weights of 11,000-59,400 in 45-97% yields. The solubility of the obtained polymers was good, and their thermal stability might be assumed from their structures. A linear relationship was observed between the contents of the fluorine atoms and the refractive indices. (C) 2002 Wiley Periodicals, Inc.

DOI： 10.1002/pola.10197

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記述言語：英語   出版者・発行元：AMER CHEMICAL SOC  

DOI： 10.1021/ma020106+

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記述言語：英語   出版者・発行元：TECHNICAL ASSOC PHOTOPOLYMERS,JAPAN  

Synthesis and photocrosslinking reaction of hyperbranched polyimide containing methacryloyl groups at the ends were examined. The reaction of tris(2-aminoethyl)amine with 3,3',4,4'-benzophenone tetracarboxylic dianhydride produced the hyperbranched polyimide [HBPI(TAEA-BTDA)] with carboxylic acid at the ends. The hyperbranched polyimide containing methacryloyl groups at the ends (P-1 - P-3) were obtained by the reaction of HBPI(TAEA-BTDA) with glycidyl methacrylate. The photocrosslinking reaction of P-1, P-2, and P-3 with a 10 wt% photoinitiator proceeded smoothly to afford the crosslinking polymers in the film state.

DOI： 10.2494/photopolymer.15.185

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記述言語：英語   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.

DOI： 10.1016/S0040-4039(01)01584-2

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記述言語：英語   出版者・発行元：AMER CHEMICAL SOC  

Synthesis and self-polyaddition of optically active monomers derived from tyrosine was discussed. The tyrosine-based monomer, L-tyrosine methyl ester [I-T(L)-M] having isocyanate and hydroxyl groups was synthesized by the reaction of tyrosine methyl ester and (BOC)2C)3in chloroform. Results indicated that no side product could be formed and I-T(L)-M was stable at room temperature in the solution, but I-T(L)-M could not be isolated by recrystallization and distillation.

DOI： 10.1021/ma0101456

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記述言語：英語   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.

DOI： 10.1002/1099-0518(20010101)39:1<23::AID-POLA30>3.0.CO;2-4

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記述言語：英語   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.

DOI： 10.1021/ma991005n

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記述言語：日本語  

CiNii Books

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記述言語：英語   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.

DOI： 10.1002/(SICI)1521-3935(19990501)200:5<1232::AID-MACP1232>3.0.CO;2-U

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記述言語：日本語   会議種別：公開講演，セミナー，チュートリアル，講習，講義等  

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