 | 須藤 篤 （スドウ アツシ）
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Last Updated :2024/04/25
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新しい高分子素材の開発を行っています。特に、糖類などの天然物を原料とし、その化学構造を最大限生かすことで強度や耐熱性に優れた高分子素材の開発を目指しています。
研究者情報
学位
ホームページURL
J-Global ID
研究キーワード
- 高分子合成 Polymer Synthesis
現在の研究分野（キーワード）
- 新しい高分子素材の開発を行っています。特に、糖類などの天然物を原料とし、その化学構造を最大限生かすことで強度や耐熱性に優れた高分子素材の開発を目指しています。
研究分野
経歴
- 2016年04月 - 現在 近畿大学理工学部教授
- 2011年04月 - 2016年03月 近畿大学理工学部准教授
- 2007年04月 - 2011年03月 近畿大学分子工学研究所准教授
- 2006年04月 - 2007年03月 近畿大学分子工学研究所助教授
- 2002年04月 - 2006年03月 近畿大学分子工学研究所講師
- 1997年12月 - 2002年03月 東京工業大学資源化学研究所助手
- 1997年04月 - 1997年11月 東京工業大学資源化学研究所教務職員
学歴
所属学協会
研究活動情報
論文
- Atsushi Sudo; Akane Morihiro; Haruka OchiJournal of Polymer Science 62 7 1387 - 1393 2023年12月 [査読有り]
Abstract myo‐inositol, a naturally occurring cyclic hexaol, was converted into conformationally constrained diols 4 bearing two adamantane‐like components in the molecule. For the synthesis of 4, an orthoester derivative of myo‐inositol bearing an adamantane‐like rigid structure on which three hydroxyl groups were attached was used as the precursor. Two molecules of the orthoester were tethered via acetalization using two axially oriented hydroxyl groups, successfully constructing the core structure of 4. Polyaddition of 4 with diisocyanate was performed to obtain the corresponding polyurethanes, with glass transition temperatures (Tg) ranging from 150 to 210°C. - Shusuke Okamoto; Atsushi Sudo; Takeshi EndoPolymer Bulletin 2023年06月 [査読有り]
- Takeshi Endo; Morio Yonekawa; Atsushi SudoPolymer International 70 9 1176 - 1181 2021年09月 [査読有り]
- Shusuke Okamoto; Atsushi Sudo; Takeshi EndoJournal of Applied Polymer Science 138 22 50529 - 50529 2021年06月 [査読有り]
Reactive polyimides bearing a vinylcyclopropane (VCP) moiety in the main chain were successfully synthesized from the corresponding diamine with the VCP moiety. Their radical crosslinking using a dithiol proceeded with the radical ring-opening reaction (RROR) of the VCP moiety to afford the corresponding crosslinked polyimides with the C-C bonds in crosslinking moieties. Thermal properties of those crosslinked polyimides were evaluated by thermal gravimetry and differential scanning calorimetry. As a result, the increase of the crosslinking degree in the crosslinked polymer exhibited great residual weight at 600°C. In contrast, the tendency of the glass transition temperature was inverse because the increase in the amount of dithiol unit as a crosslinker would enhance the mitigation of the polymer packing structure and activates the mobility of polymer chains. - Kimikatsu Ikeya; Shusuke Okamoto; Atsushi SudoResults in Chemistry 3 100167 - 100167 2021年01月 [査読有り]
Myo-inositol, a naturally occurring cyclic compound obtained from rice bran, was transformed into a divinyl derivative bearing a rigid hexaoxadiamantane (HODAM) core composed of two orthoester moieties. The divinyl compound underwent radical polyaddition with dithiols to afford the corresponding semi-crystalline polythioethers, the melting temperatures (Tm) of which were above 240 °C. Furthermore, the divinyl compound was transformed into a HODAM-bearing diol via the radical addition of 2-mercaptoethanol to the vinyl groups. The diol product was used as a rigid monomer in polyurethane synthesis. The obtained polyurethanes exhibited glass transition temperatures (Tg) ranging from 55 to 110 °C. - Hiroyuki Ito; Atsushi SudoResults in Chemistry 3 100123 - 100123 2021年01月 [査読有り]
- Atsushi Sudo; Kyohei Nishiyama; Mika Morimoto; Shinichiro YamamotoJournal of Polymer Science 58 14 1973 - 1981 2020年07月 [査読有り]
- Shusuke Okamoto; Atsushi Sudo; Takeshi EndoJournal of Polymer Science 58 11 1601 - 1608 2020年06月 [査読有り]
A series of polyureas 5a-c bearing vinylcyclopropane (VCP) moiety in their main chains was synthesized by the polyaddition of diamine 2 bearing VCP moiety with diisocyanates. Upon treatment of polyurea 5b with thiols in the presence of azobisisobutyronitrile (AIBN), the VCP moieties in the polymer main chain efficiently reacted with the thiols via a sequence of the radical addition of thiol to the vinyl group and the ring opening of the cyclopropane ring, yielding the corresponding networked polymers 9-11. The thermogravimetric analysis of the networked polymers 9-11 revealed that their residual weight at 350 degrees C was higher than that of the precursor polyurea 5b. - Tomohiro Shimokawaji; Atsushi SudoJournal of Polymer Science 58 9 1229 - 1235 2020年05月 [査読有り]
Partially bio-based triepoxides, 1,3,5-tri-O-methyl-2,4,6-tri-O-(oxiran-2-yl-methyl)-myo-inositol (4) and 2,4,6-tri-O-(oxiran-2-yl-methyl)-myo-inositol 1,3,5-orthoacetate (5), were synthesized from naturally occurring myo-inositol. These two triepoxides differ from each other in terms of rigidity of the core structure; while the former triepoxide has a more flexible cyclohexane core, the latter has a highly rigid adamantane-like orthoester core. Triepoxide 5 readily reacted with nucleophilic monomers such as diamines, dithiol, and trithiol to yield networked polymers. The glass transition temperatures (T(g)s) of these polymers were higher than those of comparable networked polymers obtained by the polyaddition of triepoxide 4 with the same nucleophilic monomers, implying that the rigidity of the orthoester moiety contributed to the efficient restriction of the polymer chain in the synthesized networked polymers. - Atsushi Sudo; Tomoki Yamasaki; Takuro Yamashita; Dai IshidaJournal of Polymer Science Part A: Polymer Chemistry 57 24 2407 - 2414 2019年12月 [査読有り]
- Akira Yamauchi; Atsushi Sudo; Takeshi EndoJournal of Polymer Science Part A: Polymer Chemistry 57 21 2145 - 2148 2019年11月 [査読有り]
- Shusuke Okamoto; Atsushi Sudo; Takeshi EndoJournal of Polymer Science Part A: Polymer Chemistry 57 16 1723 - 1729 2019年08月 [査読有り]
Radical ring-opening polymerization of 1,1-dicyano-2-vinylcyclopropane 1 was performed in benzonitrile to find the corresponding homopolymer 2 soluble in organic solvents was successfully obtained while that in other solvents gave crosslinked and thus insoluble homopolymer. In addition, 1 underwent radical copolymerization with 1-cyano-1-ester-2-vinylcyclopropanes 3 and 4 to afford the corresponding copolymers 7 and 8. By increasing the content of the 1-derived unit in the resulting copolymers, the solubility of the copolymers in organic solvents became lower and the residual weights at 600 degrees C and their glass transition temperatures became higher. (c) 2019 Wiley Periodicals, Inc. - Yasuyuki Mori; Atsushi Sudo; Takeshi EndoJournal of Polymer Science Part A: Polymer Chemistry 57 14 1564 - 1568 2019年07月 [査読有り]
Oligo(spiroorthocarbonate)s 1, which were synthesized by the polycondensation of pentaerythritol derivatives with tetraethylorthocarbonate, were employed as comonomers in the cationic polymerization of epoxide initiated by sulfonium salt. In the copolymerization, the spiroorthocarbonate moiety of 1 underwent double ring-opening reaction, leading to the efficient diminution of the volume shrinkage upon the copolymerization. Thermal properties of the resulting networked polymers were evaluated by TGA. (c) 2019 Wiley Periodicals, Inc. - Synthesis of hydroxyl‐bearing polyurethanes from naturally occurring myo‐inositolSudo, A; Kaiba, KJ. Polym. Sci., Part A: Polym. Chem. 57 12 1358 - 1364 2019年05月 [査読有り]
- Takashi Doi; Tsutomu Shimokawa; Atsushi Sudo; Takeshi EndoJournal of Polymer Science Part A: Polymer Chemistry 57 4 531 - 538 2019年02月 [査読有り]
This article presents the effect of some ionic photochemical acid generators (PAGs) to inhibit the dissolution of hexafluoroisopropylalcohol (HFA)-containing polystyrene to an aqueous alkaline developer, which is a highly important effect in photoresist application to enhance resolution of patterning. The dissolution inhibiting factors and mechanisms were investigated by evaluating the solubility and the 1H-NMR analysis of OH proton in HFA moiety. The dissolution inhibition effect was enhanced when the structures of PAGs fulfill some requirements: (a) their anions should have higher basicity and smaller van der Waals volume; (b) their cations should be stabilized by conjugation with electron-rich aromatics. In the dissolution inhibition, the HFA moiety interacts with the anionic part of PAGs liberated from the electrostatic interaction with the counter cation. These interactions were predicted and quantified by DFT calculations using Gaussian 09, leading to the rational designs of PAGs with higher dissolution inhibiting effect in photoresist systems. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 531–538. - Yasuyuki Mori; Atsushi Sudo; Takeshi EndoJournal of Polymer Science Part A: Polymer Chemistry 57 7 792 - 798 2019年02月 [査読有り]
A series of soluble oligo(spiroorthocarbonate)s (OSOCs) were synthesized by polycondensation of tetraethylorthocarbonate with pentaerythritol derivatives. The pentaerythritol derivatives used herein were synthesized from pentaerythritol by attaching substituents on it to improve the solubility of themselves and the resulting OSOCs. The structures of the OSOCs were confirmed by NMR spectroscopy and MALDI-TOF mass analysis. (c) 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 792-798 - Taniguchi, A; Kaji, D; Hara, N; Murata, R; Akiyama, S; Harada, T; Sudo, A; Nishikawa, H; Imai, YRSC Adv. 9 4 1976 - 1981 2019年01月 [査読有り]
Solid-state organic fluorescent materials are important for the development of electroluminescent sensing devices. Herein, we report that N,N'-bis((R)-1-phenylethyl) perylene-3,4,9,10-tetracarboxylic diimide [(R,R)-BPP] and its antipode [(S,S)-BPP], which contain extended pi-electrons through planar perylenes, emit solid-state aggregation-induced-enhanced (AIEnh) circularly polarised luminescence (CPL) in inorganic (KBr) pellets and organic-polymer-film (PMMA- and myo-IPU-film) states; this CPL is difficult to observe in solution. These chiral perylene fluorophores emit AIEnh-CPL with high dissymmetry factors (g(CPL)) (up to 2.4 x 10(-3)) and high quantum yields (Phi(F), up to 0.43) in the three solid matrices. - Yoshiaki Kawaoka; Katsushige Koge; Atsushi Sudo; Takeshi EndoJournal of Polymer Science, Part A: Polymer Chemistry 56 18 2096 - 2102 2018年09月An efficient thermally latent initiation system using dual sulfonium salts, consisting S-benzylsulfonium salt 1 bearing SbF-6 counter anion and S,S-dimethylsulfonium salt 2 bearing CH3SO-4 counter anion, has been developed for the cationic polymerization of epoxides. Compared to the conventional system using 1 as a thermally latent initiator, the newly developed system allowed significant improvement of stability of epoxy formulations during storage at ambient temperature without sacrificing their curability at elevated temperatures. Such a remarkable performance is attributable to the nucleophilic attack of CH3SO-4 to cationic species formed unavoidably by the reaction of 1 with epoxide. Such entrapment of cationic species into the corresponding dormant led to the inhibition of undesirable chain growth of polymers during storage of epoxy formulations. In addition, the dormant can undergo dissociation at elevated temperature to give cationic species, which can readily initiate the polymerization of epoxide. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 2096–2102.
- Hara, N; Okazaki, M; Kitatobe, T; Tajima, N; Shizuma, M; Sudo, A; Fujihara, H; Fujiki, M; Imai, YChem. Lett. 47 9 1200 - 1202 公益社団法人 日本化学会 2018年07月 [査読有り]
Luminophores are key components in several optoelectronic applications and the development of methods for the synthesis of novel highly efficient luminophores is an important objective. Herein, new linear and hyperbranched polythiophenes bearing BINOL moieties through alkylene spacers were prepared by the electrochemical oxidation of the corresponding terthiophenes. These polythiophenes emitted orange-colored circularly polarized luminescence with dimensionless Kuhn's anisotropy factors, gCPL, of the order of 10−4 in chloroform in the photoexcited state.
- Radical polymerizations of two stereoisomeric trimethacrylates with rigid adamantane-like cores from naturally occurring myo-inositolOkamoto, S; Tanaka, K; Sudo, AJ. Polym. Sci., Part A: Polym. Chem. 56 15 1743 - 1748 2018年06月 [査読有り]
- Takuya Sato; Nobuyuki Hara; Nobuo Tajima; Atsushi Sudo; Michiya Fujiki; Yoshitane ImaiTetrahedron Letters 59 17 1619 - 1622 2018年04月 [査読有り]
Although chiral 1,1′-binaphthalene-2,2′-diyl-O,O-bis(N,N-dimethylthiocarbamate) (1) revealed no circularly polarized luminescence (CPL) signals, Newman–Kwart rearrangement of O-thiocarbamate groups at 1 yielded clear CPL signals from 1,1′-binaphthalene-2,2′-diyl-S,S-bis(N,N-dimethylthiocarbamate) (2), which acts as a CPL-gen molecule. - Shinya Maeda; Atsushi Sudo; Takeshi EndoJournal of Polymer Science, Part A: Polymer Chemistry 56 7 783 - 788 2018年04月 [査読有り]
Radical ring-opening polyaddition of bifunctional vinyloxirane with multifunctional thiols was investigated. The polyaddition proceeded smoothly via the ring-opening reaction of the oxirane moiety to afford the corresponding networked polymers bearing vinyl ether and sulfide moieties in the main chain. The thermal properties of the networked polymers and volume changes upon the polyaddition were investigated. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 783–788. - Shusuke Okamoto; Hiroki Tsujioka; Atsushi SudoChemistry Letters 47 3 369 - 372 2018年 [査読有り]
A perylene derivative bearing a urethane moiety served as an efficient photoredox catalyst for the reductive coupling of ketones and aldehydes under visible light, implicating that the urethane moiety captured substrates through hydrogen bonds to lower the LUMO levels of the captured substrates, thus promoting single electron transfer from the reductant anion radical of the perylene moiety to the substrates. - Naoya Takahashi; Shuhei Yamada; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 55 24 3996 - 4002 2017年12月 [査読有り]
Six 1,1-disubstituted vinylcyclopropanes (VCP) were synthesized from glycine and amino acids bearing hydrophobic moieties, l-alanine, l-valine, l-leucine, l-isoleucine, and l-phenylalanine. These VCP derivatives efficiently underwent radical ring-opening polymerization to afford the corresponding polymers bearing trans-vinylene moiety in the main chains and the amino acid-derived chiral moieties in the side chains. The polymers were film-formable, and in the films of polymers bearing the glycine- and alanine-derived side chains, presence of hydrogen bonding was confirmed by IR analysis. Thermogravimetric analysis of the polymers revealed that the temperatures of 5% weight loss were higher than 300 degrees C. Differential scanning calorimetry clarified that the polymers were amorphous ones showing glass transition temperatures in a range of 48-80 degrees C. (c) 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3996-4002 - Arata Yoshida; Atsushi SudoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 55 22 3798 - 3803 2017年11月 [査読有り]
Naturally occurring myo-inositol was developed into a highly rigid diol by converting its 3,4- and 1,6-vicinal diols in trans configuration into the corresponding butane-2,3-diacetals. The resulting diol bearing 6-6-6 fused ring system, in which conformational change is strictly suppressed, was combined with diisocyanates to perform polyadditions. The resulting polyurethanes were analyzed by differential scanning calorimetry, and it was found that their glass transition temperatures were much higher than those of the previously reported myo-inositol-derived polyurethanes, which were synthesized from a myo-inositol-derived diol bearing 5-6-5 fused ring system. (C) 2017 Wiley Periodicals, Inc. - Shusuke Okamoto; Risako Ariki; Hiroki Tsujioka; Atsushi SudoJOURNAL OF ORGANIC CHEMISTRY 82 18 9731 - 9736 2017年09月 [査読有り]
A simple, metal-free, and versatile approach to 1,2-diamines has been developed based on reductive coupling reactions of various imines, where perylene, an aromatic hydrocarbon, was used as a photoredox catalyst under visible light irradiation using a white light-emitting diode. The use of 1 mol % perylene enabled almost complete conversion of the 2 imines, leading to the formation of their corresponding 1,2diamines, which were isolated in good yields. The ratios between dl and meso diamines ranged from 31:69 to 82:18 depending on the substituents of the imines. - Isolation of Epimers in the Synthesis of Vinylcyclopropane Bearing Two Alanine Moieties and Their Radical Ring-Opening PolymerizationTakahashi, N; Sudo, A; Endo, TMacromolecules 50 15 5679 - 5686 2017年07月 [査読有り]
- Atsushi Sudo; Yugo Shirakawa; Tomio SakueJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 55 9 1524 - 1529 2017年05月 [査読有り]
myo-Inositol, a naturally occurring cyclic hexaol, was converted to 2,4,6-tri-O-allyl-myo-inositol and 1,2,3,4,5,6-hexa- O-allyl-myo-inositol. Polyaddition of the former product, a tri(allyl ether) bearing three hydroxyl groups, with dithiols yielded the corresponding networked polymers. Their glass transition temperatures (T(g)s) were higher than those of networked polymers formed by the polyaddition of 1,3,5-tri-Omethyl- 2,4,6-tri-O-allyl-myo-inositol. This implied the reinforcement of the networks by hydrogen bonding between the hydroxyl groups. Polyaddition of the latter product, a hexa(allyl ether), with dithiols yielded the corresponding networked polymers with much higher Tgs than those of all of the aforementioned networked polymers. This implied that efficient use of the hexafunctional monomer leads to the formation of more densely crosslinked polymers. (C) 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1524-1529 - T. Endo; A. SudoAdvanced and Emerging Polybenzoxazine Science and Technology 23 - 33 2017年02月 [査読有り]
Molecular designs of benzoxazines with enhanced reactivity are presented. The benzoxazines described herein undergo efficient ring-opening polymerization at lower temperatures than conventional benzoxazines. These benzoxazines with enhanced reactivities are categorized into two types: (1) benzoxazines activated by the neighboring-group participation of polar substituents and (2) benzoxazines activated by thioether moieties. - Takeshi Endo; Atsushi SudoHandbook of Telechelic Polyesters, Polycarbonates, and Polyethers 1 - 28 2017年01月In this chapter, the basic chemistry for the synthesis of telechelic polyesters and polycarbonates is discussed. It covers ionic, radical, and coordination ring-opening polymerizations, which are designed carefully so that they can proceed in a “living” fashion to give well-defined polymers with reactive termini useful for chain end functionalizations. For each polymerization system, typical examples useful for understanding the mechanism are selected and explained.
- Atsushi Sudo; Shou SugitaJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 54 21 3436 - 3443 2016年11月 [査読有り]
A rigid diamine was synthesized from myo-inositol, a naturally occurring cyclic hexaol, and used as a monomer to synthesize polyamides. myo-Inositol was treated with 1,1-dimethoxycyclohexane to yield a bisketal bearing two hydroxyl groups, and from this bisketal, the target diamine was synthesized in three steps: (1) derivation of the diol into the corresponding bistriflate, (2) nucleophilic substitution of the bistriflate with sodium azide yielding a diazide, and (3) reduction of the diazide to the target diamine. The target diamine readily underwent polycondensation with dicarboxylic acid chloride in solution. The resulting polyamides, whose main chain inherited the rigid 5-6-5 system from the diamine monomers, have high glass transition temperatures. (C) 2016 Wiley Periodicals, Inc. - Yanmei Wang; Mika Kimura; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 54 16 2611 - 2617 2016年08月 [査読有り]
A new class of thermally latent initiators for the ring-opening polymerization of epoxides has been developed. The latent initiators developed herein were the hydroxylamides 1a, 1b, and 1c, which were synthesized from phthalide, 3-isochromanone, and cis-cyclohexahydrophthalide, respectively, by their ring-opening reactions with pyrrolidine. These hydroxylamides were designed so that their hydroxyl groups could attack the amide moiety intramolecularly upon heating, leading to ring closure and formation of the corresponding lactones while releasing pyrrolidine, the initiator for the anionic ring-opening polymerization of an epoxide. The temperatures at which this thermal dissociation occurred were strongly dependent on the hydroxylamide molecular structure. When using the hydroxylamides as thermally latent initiators, the polymerizations of bisphenol-A diglycidyl ether were investigated at various temperatures. This investigation clarified that the threshold temperature, that is, the temperature at which polymerization was initiated, increased in the order of 1a, 1b, and then 1c. (C) 2016 Wiley Periodicals, Inc. - Shinya Maeda; Atsushi Sudo; Takeshi EndoTETRAHEDRON LETTERS 57 10 1061 - 1065 2016年03月 [査読有り]
In this Letter, we report reversible addition and elimination of alcohols by acyclic vicinal tetracarbonyl compounds. First, the reversible fixation and release behavior of alcohols by an acyclic vicinal tetracarbonyl compound, 1,4-diphenyl-1,2,3,4-butanetetraone (DPBT) was investigated. On the basis of the results, the addition of alcohol to DPBT was carried out to provide the alcohol adduct of DPBT, which has a hemiacetal structure. Furthermore, we discovered the reaction of DPBT with 2 equi amount of methanol. (C) 2016 Published by Elsevier Ltd. - Shusuke Okamoto; Keita Kojiyama; Hiroki Tsujioka; Atsushi SudoCHEMICAL COMMUNICATIONS 52 76 11339 - 11342 2016年 [査読有り]
Perylene, a simple polycyclic aromatic hydrocarbon, was used as a photoredox catalyst to enable the reductive coupling reaction of aromatic aldehydes, ketones, and an imine under visible-light irradiation using a white LED. - Yamasaki, R; Sudo, A; Endo, TJ. Polym. Sci. Part A: Polym. Chem. 53 21 2462 - 2468 2015年11月 [査読有り]
A series of methacrylates bearing bicyclobis(gamma-butyrolactone) (BBL) moiety were synthesized and radically polymerized to afford the corresponding poly(methacrylate)s bearing BBL moiety in the side chain, with expecting that the high polarity and rigidity of BBL would be inherited by the polymers. The resulting polymers were soluble in polar aprotic solvents such as dimethyl sulfoxide and N,N-dimethylformamide because of the high polarity of the BBL moiety. The glass transition temperatures (T-g) of the polymers depended on the length of methylene linker that tethered the methacrylate and BBL moieties, making the use of shorter linkers lead to higher T(g)s. (C) 2015 Wiley Periodicals, Inc. - Makiuchi, N; Sudo, A; Endo, TJ. Polym. Sci. Part A: Polym. Chem. 53 22 2569 - 2574 2015年11月 [査読有り]
A series of N-aryl-N-pyridyl ureas were synthesized by the reactions of 4-aminopyridine (4AP) with the corresponding isocyanates such as phenyl isocyanate, 4-methylphenyl isocyanate, 4-methoxyphenyl isocyanate, 4-chlorophenyl isocyanate, 4-(trifluoromethyl)phenyl isocyanate, and 4-nitrophenyl isocyanate. Bulk polymerization of diglycidyl ether of bisphenol A (DGEBA) in the presence of the ureas as initiators was evaluated by differential scanning calorimetry (DSC) at a heating rate of 10 degrees C/min. The resulting DSC profiles indicated exothermic peaks above 140 degrees C, while the DSC profile measured for a formulation composed of DGEBA and pristine 4AP indicated an exothermic peak at around 120 degrees C, implying that the derivation of 4AP into the corresponding ureas is a useful strategy to achieve thermal latency. The peak top temperatures were correlated with the electron density of the aromatic ring of the ureas, that is, as the electron-withdrawing nature of the substituent on the aromatic ring became larger, the peak increases. (c) 2015 Wiley Periodicals, Inc. - Shusuke Okamoto; Shohei Onoue; Mami Muramatsu; Shimpei Yoshikawa; Atsushi SudoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 53 20 2411 - 2420 2015年10月 [査読有り]
Trimethacrylate and dimethacrylate with rigid adamantane-like cores were synthesized from myo-inositol orthoester, and their radical homopolymerization and copolymerization with methyl methacrylate (MMA) were investigated. The radical homopolymerization of trimethacrylate yielded a networked polymer with higher thermal stability than that of a networked polymer synthesized by radical homopolymerization of 1,3,5-cyclohexanetriol-derived trimethacrylate, demonstrating the effect of adamantane-like core rigidity on the increase in thermal stability. Further, dimethacrylate underwent cyclopolymerization, forming a macrocyclic structure in the repeating unit, as the two methacrylate groups were oriented axially from the rigid orthoester-core and thus located close to each other. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 2411-2420 - Tomoyuki Amako; Kazuki Nakabayashi; Atsushi Sudo; Michiya Fujiki; Yoshitane ImaiORGANIC & BIOMOLECULAR CHEMISTRY 13 10 2913 - 2917 2015年03月 [査読有り]
We investigated the ground- and photoexcited-state chiralities of two chiral fluorophores with a rigid framework embedded in two achiral polyurethanes as the solid matrices. As the fluorophores, we used two pairs of atropisomeric binaphthyl derivatives, (R)-(-)-1,1'-binaphthyl-2,2'-diyl hydrogen phosphate [(R)-1a] and (R)-(-)-(3,5-dioxa-4-phosphacyclohepta-[2,1-a:3,4-a']dinaphthalen-4-yl)-dimethylamine [(R)-1b], and for comparison, their optical antipodes (S)-1a and (S)-1b. As the solid matrices, we used two soluble achiral polyurethanes (2a and 2b) derived from the naturally occurring myo-inositol as the building block, because these polymers had a high glass transition temperature of similar to 150 degrees C. The chiral fluorophores in the polyurethanes emitted circularly polarised luminescence with a high circular anisotropy of similar to 0.6-1.5 x 10(-3). Regardless of the matrix, (R)- and (S)-1a had nearly mirror-image chiroptical properties in the ground and photoexcited states, as did (R) -and (S)-1b. - 吉田 新; 石田 大; 須藤 篤ネットワークポリマー 36 4 176 - 185 2015年 [査読有り]
- Makiuchi, Naoyuki; Sudo, Atsushi; Endo, Takeshiネットワークポリマー 36 6 277 - 281 2015年 [査読有り]
- 須藤 篤高分子論文集 72 5 232 - 242 2015年 [査読有り]
The target of the studies described herein is the development of high performance polymers from monosaccharides and myo-inositol. These naturally occurring cyclic polyols were functionalized via chemo(-) and regioselective reactions such as N-glycosilation, ketalization, and orthoesterification. The resulting derivatives bearing rigid cyclic structures and reactive groups were found to be useful monomers for synthesizing polymers with rigid cyclic structures in the main chains. The resulting polymers exhibited excellent heat resistance, proving the feasibility of our concept that the utilization of monosaccharides and myo-inositol as starting materials for polymer synthesis would emerge as a useful approach to high performance polymers. - Takeshi Endo; Atsushi SudoCONTROLLED RADICAL POLYMERIZATION, VOL 1: MECHANISMS 1187 19 - 50 2015年 [査読有り]
Radical ring-opening polymerization (radical ROP) has emerged as a useful tool for synthesizing polymers with main chains containing heteroatoms, which are difficult to be obtained by the chain polymerization of vinyl monomers. In this chapter, the structural characteristics of the cyclic monomers that can undergo radical ROPs, their respective polymerization mechanisms, their copolymerizations with conventional vinyl monomers for synthesizing degradable polymers, and their living/controlled radical ROPs for synthesizing functional materials are described. - Shusuke Okamoto; Shohei Onoue; Masakazu Kobayashi; Atsushi SudoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 52 24 3498 - 3505 2014年12月 [査読有り]
Two orthoester derivatives 1 and 2 that are easily accessible from naturally occurring myo-inositol were exploited as new triol- and diol-type monomers bearing a rigid adamantane-like structure to polyaddition with diisocyanates that gave the corresponding networked and linear polyurethanes. DSC analysis of the networked polyurethanes revealed their high glass transition temperatures ranging from 155 to 248 degrees C, suggesting the contribution of the rigidity of the adamantane-like structure introduced at the nodes of the networked polyurethanes 6. Besides, the polyaddition of 2 with diisocyanates gave the corresponding linear polyurethanes 4, of which glass transition temperatures were high, ranging from 105 to 177 degrees C, presumably by virtue of the rigidity of the adamantane-like structure introduced into the main chains. T(g)s of the networked polyurethanes 6 were higher than those of the linear polyurethanes 4. (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 3498-3505 - Naoyuki Makiuchi; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 52 17 2518 - 2522 2014年09月 [査読有り]
In this study, a series of urea-derivatives of 4-aminopyridine (4AP) were evaluated as thermally latent initiators for the anionic ring-opening polymerization of diglycidyl ether of bisphenol A (DGEBA). The urea-derivatives were synthesized by the reactions of 4AP with the corresponding iso(thio)cyanates (phenyl isocyanate, tert-butyl isocyanate, methylene diphenyl diisocyanate, and phenyl isothiocyanate). The ability of the urea-derivatives as latent initiators was investigated with differential scanning calorimetry (DSC): Upon heating formulations comprised of DGEBA and the urea-derivatives in a heating rate at 10 degrees C/min, the resulting DSC profiles indicated exothermic peaks to confirm that DGEBA underwent the polymerization efficiently. The corresponding DSC-peak top temperatures (T-peaktop) was higher than that observed for the formulation comprised of DGEBA and pristine 4AP, to clarify that the urea are useful initiators with thermal latency. A possible mechanism for the initiation step involves the thermal dissociation of the urea into 4AP and the corresponding isocyanates. 4AP thus generated readily initiated the ring-opening polymerization of epoxide. (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 2518-2522 - Asei William Kawaguchi; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 52 17 2523 - 2527 2014年09月 [査読有り]
Thiophenol and p-nitrothiophenol were evaluated as promoters for the ring opening polymerization of benzoxazine. The ring-opening polymerization of p-cresol type monofunctional N-phenyl benzoxazine 1a with 10 mol % of thiophenols proceeded at 150 degrees C, leading to the high conversion of 1a more than 95% within 5 h, whereas the polymerization of 1a without thiophenols did not proceed under the same conditions. The promotion effect of the thiophenols on curing of bisphenol-A type N-phenyl benzoxazine 1b was also investigated. In the differential scanning calorimetric (DSC) analysis of the polymerization of 1b at 150 degrees C without using any promoters, an exothermic peak attributable to the ring-opening reaction of benzoxazine was observed after 8 h. In contrast, in the DSC analysis of the polymerization of 1b with addition 20 mol % of p-nitrothiophenol, an exothermic peak was observed within 2 h, to clarify the significant promoting effect of p-nitrothiophenol. (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 2523-2527 - Atsushi Sudo; Taichi Sano; Makoto Harada; Dai IshidaACS MACRO LETTERS 3 8 808 - 812 2014年08月 [査読有り]
Dehydrating polycondensation of tetraol-type monomers derived from naturally occurring myo-inositol with 1,4-cyclohexanedione formed a series of oligo(spiroketal)s. One of the spiroketals had reactive allyl pendants, which were useful for side-chain modifications via thiol-ene chemistry. - Asei W. Kawaguchi; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 52 10 1448 - 1457 2014年05月 [査読有り]
We describe a new strategy for preparation of benzoxazine monomers based on in situ preparation of a thiol-functionalized benzoxazine and successive chemical modification of the thiol moiety. The thiol-functionalized benzoxazine can be prepared from its precursor bearing two benzoxazine moieties linked by disulfide bond. Reductive cleavage of the disulfide bond of the precursor with using triphenylphosphine as a reducing agent allows successful preparation of the thiol-functionalized benzoxazine. By performing this reduction process in the presence of epoxides and acrylates, the formation of the thiol moiety and its successive reaction with those electrophiles proceed efficiently to give the corresponding benzoxazines with sulfide moieties. The benzoxazine monomers thus prepared exhibit much higher polymerization ability than those without sulfide moiety. (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1448-1457 - Atsushi Sudo; Tomio SakueJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 52 8 1193 - 1199 2014年04月 [査読有り]
This paper deals with a triallyl monomer bearing a rigid adamantane-like core derived from myo-inositol, a naturally occurring cyclic hexaol. The core structure of the monomer can be readily constructed by orthoesterification of myo-inositol. The polyaddition of the triallyl monomer with dithiols based on the thermally induced radical thiol-ene reaction gives the corresponding networked polymers. These networked polymers exhibit much higher thermal stability than the comparative networked polymers obtained from a triallyl monomer bearing less rigid cyclohexyl core. (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1193-1199 - Asei William Kawaguchi; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 52 3 410 - 416 2014年02月 [査読有り]
1,3-benzoxazine 1, bearing 4-pyridyl moiety on the nitrogen atom, was synthesized from p-cresol, 4-aminopyridine, and paraformaldehyde. The efficient synthesis was achieved by adding acetic acid to suppress the strong basicity caused by the presence of 4-aminopyridine derivatives. Upon heating 1 at 180 degrees C, it underwent the thermally induced ring-opening polymerization. The resulting polymer was composed of two types of repeating unit, i.e., (1) Mannich-type one (-phenol-CH2-NR-CH2-) that can be expected from the general ring-opening polymerization of conventional benzoxazines and (2) a typical phenolic resin-type one (-phenol-CH2-phenol-) induced by release of 4-aminopyridine and paraformaldehyde (unit B). Another structural feature of the polymer was that it possessed a benzoxazine moiety at the chain end. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 410-416 - Yamada, S; Sudo, A; Goto, M; Endo, TRSC Advances 4 56 29890 - 29896 2014年 [査読有り]
A series of polypeptides have been synthesized from the corresponding N-phenoxycarbonyl derivatives of hydroxyl- or amino-functionalized alpha-amino acids such as L-serine, L-cysteine, L-threonine, L-tyrosine, L-glutamine, and L-asparagine. These derivatives are prepared by N-carbamylation of tetrabutylammonium salts of alpha-amino acids with diphenyl carbonate (DPC). The synthesis of polypeptides can be achieved by heating these N-phenoxycarbonyl derivatives at 60 degrees C in N,N-dimethylacetamide (DMAc) in the presence of n-butylamine through the polycondensation of the derivatives with accompanying elimination of phenol and CO2. The NMR and MALDI-TOF mass analyses of the resulting polypeptides revealed that n-butylamine was successfully incorporated into the chain end of the polypeptides. Molecular weights of the polypeptides were controlled by varying the feed ratio of the urethane derivatives to n-butylamine. The employment of an amine-terminated poly(ethylene glycol) in place of n-butylamine permitted the successful synthesis of the corresponding diblock copolymers composed of polyether and polypeptide segments. - Shuhei Yamada; Sudo Atsushi; Mitsuaki Goto; Takeshi EndoJournal of Polymer Science, Part A: Polymer Chemistry 51 21 4565 - 4571 2013年11月 [査読有り]
A facile and phosgene-free synthetic route to poly(l-tryptophan) 2 by the polycondensation of N-phenoxycarbonyl-l-tryptophan 1 is described. The monomer 1 was synthesized via the carbamylation of tetrabutylammonium salt of L-tryptophan with diphenyl carbonate. The polycondensation proceeded smoothly at 60 °C in N,N-dimethylacetamide in the presence of amines (n-butylamine, diethylamine, and triethylamine) along with the elimination of phenol and carbon dioxide. The structural analysis of the obtained 2 by Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry revealed that n-butylamine or diethylamine was successfully incorporated into the chain end of the polypeptide. Furthermore, we have demonstrated the synthesis of a diblock copolymer by utilizing amine-terminated poly(ethylene glycol) as a source of the polyether segment. The chain length of the polypeptide segment was controlled by varying feed ratio between 1 and the amino group of poly(ethylene glycol). © 2013 Wiley Periodicals, Inc. - エポキシドとCO2から得られる五員環カーボナートとアミンとの開環重付加によるネットワークポリヒドロキシウレタンの合成と熱挙動前田 真也; 須藤 篤; 遠藤 剛ネットワークポリマー 34 1 1 - 8 2013年11月 [査読有り]
二酸化炭素とエポキシドから五員環カーボナートを合成しアミンとの開環重付加反応によりネットワークポリヒドロキシウレタンを合成し、その熱挙動を明らかにした - Atsushi Sudo; Akane Suzuki; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 51 19 4213 - 4220 2013年10月 [査読有り]
Cationic copolymerization of n-butyl glycidyl ether (BGE) and 3-isochromanone (ICM) was investigated using trifluoromethanesulfonic acid (TfOH) as an initiator at 100 degrees C. In the copolymerization, the reactive site of ICM with the propagating cation was completely different from that in its homopolymerization: in the former, the propagating cation reacted with the carbonyl oxygen of ICM, while in the latter, the propagating cation reacted with the aromatic ring of ICM. In spite of the potential of ICM to undergo the homopolymerization, in the present copolymerization, ICM was consumed smoothly only in the presence of epoxide. As a result, the copolymerization proceeded in a statistic manner to afford the corresponding copolymer bearing ICM-derived ester linkages distributed in the main chain. Cationic copolymerization of bisphenol A-diglycidyl ether and ICM was also performed to synthesize the corresponding networked polymer. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4213-4220 - Hiroaki Oie; Atsushi Mori; Atsushi Sudo; Takeshi EndoJournal of Polymer Science, Part A: Polymer Chemistry 51 18 3867 - 3872 2013年09月 [査読有り]
ABSTRACT: A polyaddition system consisted of a bifunctional N-n-propyl benzoxazine and 2-methylresorcinol (MR) that proceeds at ambient temperature has been developed. In this system, the aromatic ring of MR acted as a bifunctional monomer, reacting with a two equivalent amount of benzoxazine moieties via their ring-opening reaction. The polyaddition gave the corresponding linear polymer bearing phenolic moieties bridged by Mannich-type linkage in the main chain. The linear polymer had a high glass transition temperature, which was comparable to that of the linear polybenzoxazine synthesized by the ring-opening polymerization of a monofunctional N-n-propyl benzoxazine. The employment of a bifunctional N-allyl benzoxazine in the polyaddition system resulted in the formation of the corresponding polymer with allyl pendants, which exhibited improved heat resistance due to its thermally induced crosslinking reaction. Copyright © 2013 Wiley Periodicals, Inc. - Atsushi Sudo; Yoshiya Shibata; Ayano MiyamotoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 51 18 3956 - 3963 2013年09月 [査読有り]
A bisketal of myo-inositol was used as a diol-type monomer for synthesis of polyurethanes. The monomer was obtained by treatment of myo-inositol with 1,1-dimethoxycyclohexane in the presence of p-toluenesulfonic acid as a catalyst. The ketalization resulted in the formation of a 5-6-5-fused ring system, which endowed the diol-type monomer with high rigidity. The diol readily reacted with diisocyanate to give the corresponding polyurethane, which exhibited excellent heat resistance due to the rigid 5-6-5 system in the main chain. (C) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3956-3963 - 山田 修平; 古賀 孝一; 須藤 篤; 後藤 光昭; 遠藤 剛Journal of Polymer Science Part A: Polymer Chemistry 51 17 3726 - 3731 wiley 2013年09月 [査読有り]
We report a useful synthetic method of polypeptides using a series of urethane derivative of -amino acids (l-leucine, l-phenylalanine, l-valine, l-alanine, l-isoleucine, l-methionine), which are readily synthesized by N-carbamoylation of tetrabutylammonium salts of -amino acids with diphenyl carbonate. Heating these urethane derivatives in N,N-dimethylacetamide in the presence of n-butylamine successfully gave the corresponding polypeptides with well-defined structures through polycondensation with the elimination of phenol and CO2. The matrix-assisted laser desorption/ionization time-of-flight mass spectrometry investigation showed that the resulting polypeptides had an n-BuNH2-incorporated initiating end and an amino group at propagating end. These results strongly indicated that primary amines served as an initiator in this polycondensation system. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3726-3731 - Xiang Dong Liu; Chun Hua Zhao; Atsushi Sudo; Takeshi EndoJournal of Polymer Science, Part A: Polymer Chemistry 51 16 3470 - 3476 2013年08月 [査読有り]
The reaction between carbonyldiimidazole (CDI) and copper (II) nitrate produces a new Cu (II) complex with nitrate as the counter anion. TGA, UV, and FTIR analyses confirmed that the coordination number of CDI in this complex is two. The acceleration effect of the complex in epoxy-dicyandiamide (DICY) curing systems has been evaluated by DSC and TMA, and the increasing viscosity of the mixture was monitored during the storage. The results revealed that the complex is not only very effective for the acceleration of epoxy-DICY systems, leading to a rapid gelation within 21 min at 120°C, but it is also chemically stable at ambient temperature. This is reflected by the slow increase of viscosity of the accelerated curing systems stored at 35°C, even over 56 days. In addition, the effects of the [Cu(CDI)2]2+ complex with different counter anions, that is, bromide, chloride, nitrate, sulfate, phthalate, and acetate, were compared using a series of tests. By comparing with N,N-dimethyl-N′-phenylurea (fenuron), the widely used latent accelerator for DICY-epoxy curing systems, the complexes with bromide and nitride were found to be better, both regarding storage stability and for their acceleration effect. © 2013 Wiley Periodicals, Inc. - Masaki Moritsugu; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 51 12 2631 - 2637 2013年06月 [査読有り]
A series of networked polymers bearing isocyanurate moiety was synthesized by cyclotrimerization of diisocyanates, with employing methylenediphenyl 4,4-diisocyanate and 1,6-hexamethylenediisocyanate (HMDI) in several feed ratios. In spite of the large difference in intrinsic reactivity between these two diisocyanates, their coannulation proceeded efficiently by using sodium p-toluenesulfinate (pTolSO2Na) and 1,3-dimethyl-2-imidazolidinone as a catalyst and a solvent, respectively. The resulting networked polymers were transparent and exhibited excellent thermal stability. In addition, HMDI-rich feed ratios allowed for the formation of networked polymers with increased flexibility. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 26312637 - Hiroaki Oie; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 51 9 2035 - 2039 2013年05月 [査読有り]
A polybenzoxazine bearing allyl group in the side chain was synthesized by the ring-opening polymerization of N-allyl-benzoxazine and was crosslinked by the two different processes, (1) thermally induced oligomerization of the allyl side chains and (2) radical addition of dithiol (thiol-ene reaction) to the allyl side chains. The former process was promoted by adding 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane as a radical source, leading to the improved yield of the networked polymer isolated as acetone-insoluble fraction. The thiol-ene reaction with using 1,6-hexanedithiol was also an efficient method for crosslinking the polybenzoxazine. (c) 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013, 51, 2035-2039 - Atsushi Sudo; Shou SugitaJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 51 2 298 - 304 2013年01月 [査読有り]
A glucose-functionalized diamine was prepared and used as a new monomer for polyurea synthesis. The diamine was prepared by N-glycosylation of 1,6-hexamethylenediamine with D-glucose. Upon adding diisocyanates to the diamine, isocyanate reacted selectively with the amino groups, not with the hydroxyl groups of the glucose-derived structure, to give the corresponding polyureas. The polyureas exhibited highly hydrophilic nature due to the presence of the glucose-derived side chain. A ternary system consisting of the glucose-functionalized diamine, piperazine, and diisocyanate gave the corresponding polyureas, where content of the glucose-derived moiety was tunable by feed ratio between the diamine and piperazine. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013 - Asei William Kawaguchi; Atsushi Sudo; Takeshi EndoACS Macro Letters 2 1 1 - 4 2013年 [査読有り]
The reversible nature of the addition reaction of 1,3-benzoxazine and thiol at ambient temperature was discovered by investigating the reaction with using p-cresol-derived N-phenyl benzoxazine 1 and 1-octadecanethiol 2. The reaction was performed in several deuteriated media involving CDCl3 and CDCl3 + CD3OD, for monitoring their reaction by 1H NMR spectrometry. CDCl3 was a favorable solvent for the efficient progress of the reaction, and its combination with CD3OD allowed further acceleration of the reaction. In both cases, the reaction proceeded until conversion of 1 reached a certain ceiling value, to suggest that the reaction was reversible. This reversible nature was concretely confirmed by finding a dissociation reaction of isolated 3 into 1 and 2 in CDCl3. Analogously, a bisphenol A-derived bifunctional benzoxazine 4 and 1,6-hexanedithiol 5 underwent the polyaddition in CDCl3 + CD 3OD at ambient temperature to afford the corresponding polymer 6. Successful depolymerization of 6 into small fragments was achieved by dissolving 6 in CDCl3. © 2012 American Chemical Society. - 前田 真也; 須藤 篤; 遠藤 剛ネットワークポリマー 34 4 172 - 177 合成樹脂工業協会 2013年 [査読有り]
側鎖にカルボジイミドを有するポリマーをヨウ化サマリウムにより還元的カップリング反応を行ない、ネットワークポリマーを合成した - Atsushi Sudo; Takaaki Hamaguchi; Naoto Aoyagi; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 51 2 318 - 326 2013年01月 [査読有り]
A new trithiocarbonate 1 bearing two hydroxyl moieties was synthesized and employed as a RAFT agent for radical polymerization of vinyl monomers. 1 mediated RAFT polymerizations of styrene and ethyl acrylate to give the corresponding polymers with predictable molecular weights and narrow molecular weight distributions. Structural analyses of the polymers with NMR and MALDI-TOF mass techniques revealed that they were telechelic ones, of which both chain ends were endowed with hydroxyl groups inherited from trithiocarbonate 1. Usefulness of these telechelic polymers as polymeric diol-type building blocks was demonstrated in their polyaddition with diisocyanates, which gave the corresponding polyurethanes. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013 - Ohsawa, S; Morino, K; Sudo, A; Endo, TJ. Polym. Sci. Part A: Polym. Chem. 50 22 4666 - 4673 2012年11月 [査読有り]
A series of bicyclic bis(?-butyrolactone)s (BBL) bearing sulfide moiety 2 were readily synthesized from a precursor BBL bearing isopropenyl group 1. This efficient and versatile synthesis of 2 was achieved by a highly reliable radical addition reaction of thiols to the C-C double bond in the isopropenyl group 2 underwent anionic copolymerization with glycidyl phenyl ether in a 1:1 alternating manner to give a series of the corresponding polyester 3, of which side chains inherited the sulfide group from 2. The glass transition temperatures (Tg) of 3 showed clear dependence on the flexibility of the sulfide side chains. The scope of this copolymerization system was further expanded by synthesizing a bifunctional BBL 4 from 1 with using hexanedithiol and performing its copolymerization with bisphenol A diglycidyl ether 5. The copolymerization gave the corresponding networked polymer in high yield. During the copolymerization, the volume expanding nature of the double ring-opening reaction of 4 contributed to the efficient compensation of the intrinsic volume shrinkage of the ring-opening of epoxide to achieve a shrinkage-free curing system. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 - Hiroaki Oie; Atsushi Mori; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 50 22 4756 - 4761 2012年11月 [査読有り]
A highly efficient ring-opening addition reaction of benzoxazine at ambient temperature has been developed with 2-methylresorcinol as a nucleophilic reagent. In this reaction, 2-methylresorcinol reacted with two equivalent amount of benzoxazine to give the corresponding 1:2 adduct, demonstrating its potential as a bifunctional nucleophile. Based on this reaction, a new crosslinking system consisting of a polymer bearing benzoxazine moieties in the side chains and 2-methylresorcinol as a crosslinker has been performed to obtain the corresponding networked polymer. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 - Masaki Moritsugu; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 50 20 4365 - 4367 2012年10月 [査読有り]
- Takehito Dei; Kazuhide Morino; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 50 13 2619 - 2625 2012年07月 [査読有り]
Novel copolymers composed of a styrene (St) derivative bearing a vicinal tricarbonyl moiety and various vinyl monomers such as St, methyl methacrylate (MMA), and N-vinylpyrrolidone (NVP) were synthesized by (1) radical copolymerization of a St derivative with a 1,3-diketone structure with St, MMA, and NVP and (2) successive oxidation of the resulting copolymers with N-bromosuccinimide in DMSO to convert their 1,3-diketone moieties in the side chains into the corresponding vicinal tricarbonyl moieties. Their tricarbonyl moieties were readily hydrated in water-containing acetone to generate the corresponding copolymers bearing geminal diol structures in the side chains. On the other hand, heating the resulting copolymers bearing the geminal diol structures in vacuo-enabled successful recovery of the vicinal tricarbonyl moieties to demonstrate the reversible nature of this system. The hydration behavior in powdery state under air atmosphere saturated by water was also investigated. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 50: 2619-2625, 2012 - Morino, K; Sudo, A; Endo, TMacromolecules 45 11 4494 - 4499 2012年06月 [査読有り]
In this paper, we report reversible fixation and release of alcohols by a polystyrene derivative bearing acyclic vicinal tricarbonyl moieties (1) and its application to synthesis and reversible cross-linking-de-cross-linking system of a networked polymer. First the reversible fixation and release behavior of alcohols by an acyclic vicinal tricarbonyl compound, 1,3-diphenylpropanetrione (DPPT) as a model compound of 1 was investigated. On the basis of the results, the fixation of n-hexanol to 1 was carried out to provide the n-hexanol adduct of 1 (1-HexOH), which has a hemiacetal structure. On the other hand, heating 1-HexOH in vacua enabled successful recovery of 1 to demonstrate the reversible nature of this system. Furthermore, the reaction of 1 with 1,6-hexanediol proceeded smoothly to give networked polymer, which could be de-cross-linked by heating at 50 degrees C in DMSO/H2O mixture. This result indicates that a novel reversible cross-linking de-cross-linking system of networked polymer was constructed. - 前田 真也; 神田 隆行; 森野 一英; Kwang-Hoi Lee; 須藤 篤; 遠藤 剛ネットワークポリマー 33 3 116 - 122 合成樹脂工業協会 2012年05月 [査読有り]
- Asei W. Kawaguchi; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 50 8 1457 - 1461 2012年04月 [査読有り]
- Ohsawa, S; Barkakaty, B; Sudo, A; Endo, TJ. Polym. Sci. Part A: Polym. Chem. 50 7 1281 - 1289 2012年04月 [査読有り]
Bicyclobis(gamma-butyrolactone) (BBL) bearing methyl group 1a reacted with benzyl alcohol (BnOH) in the presence of p-toluenesulfonic acid (p-TsOH) through the double ring-opening of the bislactone structure to afford the corresponding adduct 2a bearing carboxyl group. The resulting carboxyl group underwent condensation with BnOH to afford the corresponding diester 3a. The second step was quite slow at ambient temperature; however, it was efficiently accelerated by elevating temperature to 120 degrees C or performing under reduced pressure at 80 degrees C to afford 3a in an excellent yield. Based on these results, the reaction of 1a with xylene-alpha,alpha-diol (XyD) was carried out in chlorobenzene at 120 degrees C to obtain the corresponding polyester bearing ketone group in the side chain. The condensation reaction in the second step was effectively promoted by simultaneous removal of water under reduced pressure. BBLs 1b and 1c bearing reactive groups, isopropenyl and chloromethyl, respectively, were also employed as monomers efficiently. Their reactions with XyD gave the corresponding reactive polyesters bearing methacryloyl and chloroacetyl moieties, respectively. (c) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 - CaiFei Wang; JiaQin Sun; XiangDong Liu; Atsushi Sudo; Takeshi EndoGREEN CHEMISTRY 14 10 2799 - 2806 2012年 [査読有り]
Two fully bio-based benzoxazine monomers, 3-furfuryl-8-methoxy-3,4-dihydro-2H-1,3-benzoxazine (Bzf) and 3-octadecyl-8-methoxy-3,4-dihydro-2H-1,3-benzoxazine (Bzs), have been successfully synthesized via a solventless method. Their structures have been confirmed by FTIR spectroscopy, NMR spectroscopy, and elemental analysis. Copolymerization of the monomers has been investigated by differential scanning calorimetry (DSC) measurements. The results reveal that they undergo homogeneous copolymerization when the Bzf-Bzs molar ratio exceeds 1 : 2. The furan moiety of Bzf was found to have beneficial effects on the copolymerization, including an accelerating effect on the curing process, improvement of the cross-linking density, and enhancement of the thermal properties of the copolymerized resins. Based on the mechanism of ring-opening polymerization of benzoxazines, these effects may be attributed to the electrophilic aromatic substitution of the furan ring structure. These findings have significant implications for the design of new fully bio-based polybenzoxazines with desirable properties. - Masaki Moritsugu; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 49 24 5186 - 5191 2011年12月 [査読有り]
Selective and quantitative cyclotrimerization of p-tolylisocyanate proceeded by using sodium p-toluenesulfinate as a catalyst and 1,3-dimethylimidazolidinone as a solvent. Exploitation of this system to the cyclotrimerization of methylene diphenyl 4,40-diisocyanate (MDI) permitted formation of the corresponding networked polymer, which was selectively consisted of isocyanurate moiety and thus exhibited excellent thermal stability. Utilization of phenyl isocyanate (PhNCO) as a comonomer with varying feed ratio [ MDI](0)/[PhNCO](0) allowed successful control of flexibility of the networked polymers, while retaining its high thermal stability. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 5186-5191, 2011 - Takeshi Ishikawa; Kazuhide Morino; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 49 24 5142 - 5151 2011年12月 [査読有り]
Here we report the incorporation of ketone groups into poly(4-hydroxystyrene)s main chain by radical copolymerization of O-protected hydroxystyrenes such as 4-ethoxyethoxystyrene and 4-acetoxystyrene with 2,2-diphenyl-4-methylene-1,3-dioxorane (DPMD) followed by removal of the protective groups and the photodegradable behavior of obtained copolymers. The copolymerization of O-protected hydroxystyrenes with DPMD gave the corresponding copolymers bearing DMPD-derived ketone groups in the main chain, of which content could be controlled by changing monomer feed ratio. The ethoxyethyl and acetyl groups of the obtained copolymers were completely removed under acidic and basic conditions, respectively, to afford poly(4-hydroxystyrene) s having ketone moieties in the main chain. The molecular weights of these copolymers decreased under photoirradiation due to the Norrish-type reactions of the ketone groups distributed in the main chain. These results demonstrate that poly(4-hydroxystyrene) s having ketone groups in the main chain possess good photo-scissibility. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 5142-5151, 2011 - Takeshi Ishikawa; Kazuhide Morino; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 49 21 4714 - 4720 2011年11月 [査読有り]
- Kubra Dogan Demir; Mehmet Atilla Tasdelen; Tamer Uyar; Asei William Kawaguchi; Atsushi Sudo; Takeshi Endo; Yusuf YagciJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 49 19 4213 - 4220 2011年10月 [査読有り]
A new class of polybenzoxazine/montmorillonite (PBz/MMT) nanocomposites has been prepared by the in situ polymerization of the typical fluid benzoxazine monomer, 3-pentyl-5-ol-3,4-dihydro-1,3-benzoxazine, with intercalated benzoxazine MMT clay. A pyridine-substituted benzoxazine was first synthesized and quaternized by 11-bromo-1-undecanol and then used for ion exchange reaction with sodium ions in MMT to obtain intercalated benzoxazine clay. Finally, this organomodified clay was dispersed in the fluid benzoxazine monomers at different loading degrees to conduct the in situ thermal ring-opening polymerization. Polymerization through the interlayer galleries of the clay led to the PBz/MMT nano-composite formation. The morphologies of the nanocomposites were investigated by both X-ray diffraction and transmission electron microscopic techniques, which suggested the partially exfoliated/intercalated structures in the PBz matrix. Results of thermogravimetric analysis confirmed that the thermal stability and char yield of PBz nanocomposites increased with the increase of clay content. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 4213-4220, 2011 - Atsushi Sudo; Hiroshi Yamashita; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 49 16 3631 - 3636 2011年08月 [査読有り]
p-Toluenesulfonic acid (TsOH) and several alkyl p-toluenesulfonates, that is, methyl p-toluenesulfonate (TsOMe), cyclohexyl p-toluenesulfonate (TsOCH), and neopentyl p-toluenesulfonate (TsONP), were evaluated as initiators for the ring-opening polymerization of benzoxazines. TsOH and TsOMe were highly efficient initiators that induced the polymerization at 60 and 80 degrees C, respectively. In contrast, TsOCH and TsONP did not initiate the polymerization below 100 degrees C, while they induced the polymerization at elevated temperatures, 120 and 150 degrees C, respectively. When TsOCH was used as an initiator, the corresponding polymerization rate was comparable to that observed for the polymerization with using TsOH as an initiator. These results suggested that neutral TsOCH and TsONP can be regarded as "thermally latent initiators," which underwent the thermal dissociation at the elevated temperatures to generate the corresponding alkyl cations and/or TsOH as the initiators of the polymerization. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 3631-3636, 2011 - Lee, K. H; 森野 一英; 須藤 篤; 遠藤 剛; Lee, H.-J; Kuramoto, K; Tanaka, Y; Okauchi, T; Tsuge, AJ. Polym. Sci. Part A: Polym. Chem. 49 16 3543 - 3549 2011年08月 [査読有り]
pi-Conjugated polymers, PTOTBT, PTEHTBT, and PTt-BTBT, composed of benzothiadiazole as an electron accepting unit and terthiophene as an electron donating unit in the backbone were prepared. PTOTBT, PTEHTBT, and PTt-BTBT contained side chain groups of n-octyl, 2-ethylhexyl, and t-butyl groups, respectively. Solubility, optical and thermal properties of the polymers showed strong dependences on their side chain groups. PTEHTBT having 2-ethylhexyl groups in the side chain exhibited absorption maximum (lambda(max)) at longer wavelength (565 nm) than PTOTBT (534 nm) and PTt-BTBT (495 nm). PTOTBT showed higher thermal stability than the others. The prepared polymers were employed to polymer solar cells (PSCs) with a configuration of ITO/PEDOT-PSS/polymer: PC61BH/LiF/Al. Power conversion efficiency of the PSC-based on PTEHTBT was 1.32%. (C) 2011 Wiley Periodicals, Inc. J PolymSci Part A: Polym Chem 49: 3543-3549, 2011 - Lee, K. H; 森野 一英; 須藤 篤; 遠藤 剛Polym. Bull. 67 2 227 - 236 2011年07月 [査読有り]
Novel pi-conjugated polymers composed of diester-subsituted bithiophene and dibenzothiophene (PDBT-DEBT) or N-alkyl carbazole (PCz-DEBT) were prepared via the Stille cross-coupling polymerization using Pd(0) catalyst. The structures of obtained polymers were confirmed by (1)H NMR and IR spectroscopies. Optical properties of the polymers were investigated by UV-vis and photoluminescence spectroscopies. The photoluminescence spectra of the polymers showed strong emission peaks in the green region. - Hiroaki Oie; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 49 14 3174 - 3183 2011年07月 [査読有り]
A polymer bearing 1,3-benzoxazine moiety in the side chain was synthesized successfully from poly(allylamine) based on a stepwise strategy consisted of three steps: (1) treatment of poly(allylamine) with salicylaldehyde to convert the amino group in the side chain into the corresponding o-(iminomethyl) phenol moiety, (2) reduction of the o-(iminomethyl) phenol to obtain the corresponding o-(aminomethyl) phenol moiety, and (3) formation of 1,3-benzoxazine moiety by the reaction of the o-(aminomethyl) phenol with formaldehyde. The content ratio of benzoxazine moieties and o-(aminomethyl) phenol moieties in the polymer were tunable by varying amount of formaldehyde. The presence of o-(aminomethyl) phenol moieties exhibited a significant promoting effect on the cross-linking reaction. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 3174-3183, 2011 - Atsushi Sudo; Atsushi Mori; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 49 10 2183 - 2190 2011年05月 [査読有り]
For the purpose of reducing the induction period of the ring-opening polymerization of N-methyl-1,3-benzoxazines, several urethanes were examined as promoters. The examined promoters 3a-d were the adducts of resorcinol and phenyl isocyanate, that of bisphenol A and phenyl isocyanate, that of resorcinol and butyl isocyanate, and that of 1,3-propanediol and phenyl isocyanate, respectively. The aromatic urethanes 3a and 3b, which were adducts of the phenolic compounds and phenyl isocyanate, exhibited significant promoting effects. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 2183-2190, 2011 - Takehito Dei; Kazuhide Morino; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 49 10 2245 - 2251 2011年05月 [査読有り]
A novel polymer bearing acyclic vicinal tricarbonyl moieties in the side chains was synthesized by (1) radical polymerization of a styrene derivative with a 1,3-diketone structure and (2) successive treatment of the resulting polystyrene derivative by N-bromosuccinimide to convert its 1,3-diketone moiety in the side chains into the corresponding vicinal tricarbonyl moiety. The tricarbonyl moiety was highly reactive with water to permit its rapid conversion into a geminal diol structure in water-containing acetone. On the other hand, heating the resulting polymer bearing the geminal diol structure under vacuum enabled successful recovery of the vicinal tricarbonyl moiety to demonstrate the reversible nature of this system, which allowed us to repeat the hydration-dehydration cycle without deteriorating the polymer structure. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 2245-2251, 2011 - 大澤 壮祐; 森野 一英; 須藤 篤; 遠藤 剛Macromolecules 44 7 1814 - 1820 2011年04月 [査読有り]
A novel bicyclic bis(gamma-butyrolactone), 2,8-dioxa-1-isopropenylbicyclo[3.3.0]octane-3,7-dione (2), was successfully synthesized by the reaction of 1,2,3-propanetricarboxylic acid and methacrylic anhydride at 140 degrees C in the presence of N,N-dimethyl-4-aminopyridine and CuCl(2). Anionic ring-opening copolymerization of 2 with glycidyl phenyl ether (GPE) using PPh(3) as an initiator proceeded in a 1:1 alternating manner to give the corresponding polyester 3 bearing alpha,beta-unsaturated ketone groups in the side chains. Prolongation of polymerization time resulted in the production of an insoluble networked copolymer due to reactions of the alpha,beta-unsaturated ketone groups in the side chains. In order to demonstrate the potential of the copolymer 3 as a reactive polymer, Michael addition of thiols to the alpha,beta-unsaturated ketone groups in the side chains was performed. - Yanmei Wang; Hisatoyo Morinaga; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 49 8 1881 - 1886 2011年04月 [査読有り]
A metharylate monomer having an octanal-derived bicyclo bisoxazolidine (BBOX) moiety was synthesized and was radically copolymerized with a methacrylate having a hydrophilic poly(ethylene glycol) chain to obtain an amphiphilic copolymer having the BBOX moieties as hydrophobic side chains. The BBOX moieties were stable for 7 days at pH 7.0, whereas they were gradually hydrolyze at pH 5.0 to release octanal continuously for 7 days, confirming the potential applicability of the copolymer to a polymeric pro-fragrance that can release aldehyde-type fragrance molecules slowly for a long period. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49:1881-1886, 2011 - Atsushi Sudo; Ryoichi Kudoh; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 49 7 1724 - 1729 2011年04月 [査読有り]
- Lee, K. H; 森野 一英; 須藤 篤; 遠藤 剛J. Polym. Sci. Part A: Polym. Chem. 49 6 1427 - 1433 2011年03月 [査読有り]
pi-Conjugated polymers, PBDT-CNETT and PBDT-CNECPDT, were prepared by the Stille cross-coupling polymerization. Optical and thermal properties of the obtained polymers were investigated by UV-vis spectroscopy and thermogravimetric analysis. PBDT-CNETT and PBDT-CNECPDT exhibited very narrow band gaps of 1.39 and 1.13 eV, respectively. Highest occupied molecular orbital energy levels estimated by surface analyzer were -5.17 and -5.11 eV for PBDT-CNETT and PBDT-CNECPDT, respectively. The solar cells based on these polymers wee evaluated with the cell configuration of ITO/PEDOT-PSS/polymer:PC(61)BH/LiF/Al. The power conversion efficiencies of the solar cells were estimated to be 1.57 and 0.16% for PBDT-CNETT and PBDT-CNECPDT, respectively. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 1427-1433, 2011 - Kwang-Hoi Lee; Kazuhide Morino; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 49 5 1190 - 1194 2011年03月 [査読有り]
Poly[(3-hexyliminomethyl)thiophene]s (P3HITs) were synthesized from the polymerizations of 2,5-dibromo-(hexyliminomethyl)thiophene and 5-bromo-2-iodo-3-(hexyliminomethyl)thiophene by Grignard metathesis method. The corresponding P3HITs with low regioregularity (70%) and high regioregularity (95%) were obtained, respectively. UV-vis and photoluminescence spectra of P3HIT were dependent on the regioregularity and solvent polarity. By hydrolysis of the imino groups in the side chains under acidic conditions, P3HIT was successfully converted into the polythiophene (P3TCHO) having aldehyde groups. This transformation was also performed facilely by exposing the P3HIT film to HCl gas to give the polythiophene having aldehyde moiety. The reverse way from aldehyde to imine was also successfully demonstrated by treating the film with triethylamine vapor. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 1190-1194, 2011 - Atsushi Sudo; Hidetada Morishita; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 49 5 1097 - 1103 2011年03月 [査読有り]
A norbornene monomer bearing cyclic dithiocarbonate moiety (NB-DTC) was successfully synthesized from the corresponding precursor having epoxy moiety by its reaction with carbon disulfide. NB-DTC underwent the ring-opening metathesis polymerization (ROMP) catalyzed by a ruthenium carbene complex to give the corresponding poly(norbornene). The dithiocarbonate moiety incorporated into the side chain of the obtained poly(norbornene) reacted with amine to afford the corresponding thiourethane moiety with thiol group, which underwent oxidative S-S coupling and/or addition reaction to the C-C double bond in the main chain, leading to formation of a cross-linked polymer. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 1097-1103, 2011 - Yanmei Wang; Hisatoyo Morinaga; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 49 3 596 - 602 2011年02月 [査読有り]
A new acid-labile polymer having acetal moieties in the main chain was synthesized by polycondensation of poly (ethylene glycol) (PEG) and lilial, an aldehyde widely used in fragrance applications. The hydrophobicity of the resulting acetal moiety and the hydrophilicity of the PEG chain allowed the polyacetal to exhibit amphiphilicity. The polyacetal derived from PEG having weight average molecular weight (M(w)) of 1000 (PEG1000) was soluble in water and self-associated to form associates in water. The polyacetals were hydrolyzed in acidic aqueous solutions to release hydrophobic lilial from the systems. The release rate of aldehyde from the polyacetal derived from PEG1000 was higher than that from the polyacetal derived from PEG having M(w) of 400 (PEG400). These results supported that the release rate of lilial can be controlled by the chain length of PEG, on which hydrophilicity of polyacetal depends. 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 596-602, 2011 - Atsushi Sudo; Yuan Zhang; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 49 3 619 - 624 2011年02月 [査読有り]
This article describes the anionic copolymerization of glycidyl phenyl ether (GPE) and 1,2-dihydro-3H-naphtho[2,1-b]pyran-3-one (DHNP), a six-membered aromatic lactone bearing naphthyl moiety. The copolymerization proceeded in a 1:1 alternating manner, to afford the corresponding polyester. The ester linkage in the main chain was cleavable by reduction with lithium aluminum hydride to give the corresponding diol that inherited the structure of the alternating sequence. The copolymerization ability of DHNP permitted its addition as a comonomer to an imidazole-initiated polymerization of bisphenol A diglycidyl ether. The resulting networked polymer, of which main chain was endowed with the DHNP-derived rigid naphthalene moieties, showed a higher glass transition temperature than that obtained similarly with using 3,4-dihydrocoumarin (DHCM) as a comonomer, an analogous aromatic lactone bearing phenylene moiety instead of naphthalene moiety of DHNP. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 619-624, 2011 - 遠藤 剛; 須藤 篤ネットワークポリマー 32 2 101 - 109 合成樹脂工業協会 2011年 [査読有り]
- Xiang Dong Liu; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 49 1 250 - 256 2011年01月 [査読有り]
Carbonyldiimidazole (CDI) was inventively used as an accelerator for the curing reaction of diglycidyl ether of bisphenol A (DGEBA) with dicyandiamide (DICY) and a high acceleration more effective than imidazole in double usage was observed. This result implies the accelerating role of CDI in the curing process is complex and involved not only the release of imidazole. To detail the accelerating mechanism of CDI, a series of curing reactions was studied by differential scanning calorimetry (DSC), NMR, IR, and viscosity monitoring. The results suggested that the accelerating mechanism of CD! involves (1) acylation of DICY with CDI to give the corresponding adduct with enhanced solubility, (2) the consequent release of imidazole that can react with epoxide, and (3) abstraction of proton of DICY by the alkoxide moiety to give the corresponding DICY anion endowed with enhanced nucleophilicity. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 250-256, 2011 - Kwang-Hoi Lee; Ho-Jin Lee; Kouji Kuramoto; Yohei Tanaka; Kazuhide Morino; Atsushi Sudo; Tatsuo Okauchi; Akihito Tsuge; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 49 1 234 - 241 2011年01月 [査読有り]
Soluble polythiophenes bearing strong electron withdrawing groups, dicyanoethenyl [-CH=C(CN)(2)] (PTDCN) and cyano-methoxycarbonylethenyl [-CH=C(CO(2)Me)CN] (PTCNME), in the side chains have been prepared. Optical band gaps calculated from onset absorption were 1.70 eV and 1.73 eV for PTDCN and PTCNME, respectively. Highest occupied molecular orbital energy levels measured with a surface analyzer (AC-2) were -5.53 eV and -5.29 eV for PTDCN and PTCNME, respectively, which were much lower than that of poly(3-hexylthiophene) (-4.81 eV). To investigate photovoltaic properties, bulk heterojunction polymer solar cells based on PTDCN and PTCNME were fabricated with a structure of ITO/PEDOT:PSS/active layer/LiF/AI, where the active layer was a blend film of polymer and [6,6]-phenyl C(61) butyric acid hexyl ester (PC(61)BH). Solar cell parameters were estimated from current density-voltage (J-V) characteristics under the illumination of AM1.5 at 100 mW/cm(2). The solar cell based on the blend film of PTCNME:PC(61)BH (1:1) showed power conversion efficiency (PCE) of 0.72% together with the open current voltage (V(oc)) of 0.61 V, the short current density (J(sc)) of 3.90 mA/cm(2), and the fill factor of 30.3%. The PCE of a solar cell fabricated from PTDCN in a similar way was 0.56%. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 234-241, 2011 - Balaka Barkakaty; Kazuhide Morino; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 49 2 545 - 549 2011年01月 [査読有り]
- 李 廣會; 森野 一英; 須藤 篤; 遠藤 剛Macromol. Chem. Phys. 211 23 2490 - 2496 2010年12月 [査読有り]
pi-Conjugated polymers composed of dialkoxybenzo[1,2-b: 4,5-b'] dithiophene and thiophenes bearing cyano-alkoxycarbonylethenyl [-CH C(CO(2)R) CN] and bis(alkoxycarbonyl) ethenyl groups [-CH=C(CO(2)R)(2)] were prepared. The optical properties of the obtained polymers were investigated by UV-vis and photoluminescence spectroscopy to demonstrate that the absorption maxima of the polymers were tunable by varying the substituent of thiophene unit. The photoluminescence wavelengths and intensities of the polymer in solution were significantly dependent on the polymer side chain. The HOMO energy level of the polymer was lowered by up to -5.51 eV by introducing electron-deficient cyano groups. Polymer solar cells based on the new polymers were fabricated to achieve a PCE of 1.90%. - Hiroaki Oie; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 48 23 5357 - 5363 2010年12月 [査読有り]
Thermally induced ring-opening polymerization of monofunctional N-allyl-1,3-benzoxazine 1a was compared with that of N-(n-propyl)-1,3-benzoxazine 1b to clarify an unexpected effect of allyl group to promote the polymerization, that is, in spite of the comparable bulkiness of allyl group to n-propyl group, the polymerization of 1a was much faster than that of 1b. Such a difference in polymerization rate was also observed similarly in the comparison of thermally induced polymerization of a bifunctional N-allyl-benzoxazine 2a with that of a bifunctional N-(n-propyl) analogue 2b. These observations implied a certain contribution of an electron-rich C-C double bond of the N-ally group to promotion of the ring-opening reaction of 1,3-benzoxazine into the corresponding zwitterionic species, which would involve a mechanism to stabilize the cationic part of the zwitterionic species based on "neighboring group participation" of the C-C double bond. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 5357-5363, 2010 - Xiang Dong Liu; Mika Kimura; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 48 23 5298 - 5305 2010年12月 [査読有り]
This report focuses on epoxy-dicyandiamide (DICY) curing system accelerated by N-aryl-N',N'-dialkyl urea, aiming at clarifying the accelerating mechanism and the relationship between accelerating effect and molecular structure of the accelerators. Nine N-aryl-N',N'-dialkyl ureas were synthesized and investigated with measurements of differential scanning calorimetry, thermo gravimetric/differential thermal analysis and NMR spectroscopy. The results revealed that the ureas released the corresponding secondary amines by the thermal dissociation in the presence of epoxide, which led to the formation of tertiary amines that catalyze the addition reaction of DICY to epoxide. Moreover, a tendency that the ureas able to release more compact amines exhibited higher acceleration effects was discovered. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 5298-5305, 2010 - Hisatoyo Morinaga; Hiroshi Morikawa; Atsushi Sudo; Takeshi EndoJournal of Polymer Science, Part A: Polymer Chemistry 48 20 4529 - 4536 2010年10月 [査読有り]
A new water-soluble poly(ethylene imine)-derivative having imidazolidine moieties was developed. With using branched poly(ethylene imine) (BPEI) as a precursor, it was modified by Michael addition reaction of its primary amino group to an acrylate having poly(ethylene glycol) (PEG) chain. The modified BPEI was reacted with octanal to give the corresponding BPEI derivative having octanal-derived imidazolidine moieties. The obtained polymer inherited the high hydrophilicity of the attached PEG chains to allow hydrolysis of the imidazolidine moieties under homogeneous conditions in aqueous media, leading to long-lasting release of octanal. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem. - Takeshi Ishikawa; Kazuhide Morino; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 48 19 4344 - 4350 2010年10月 [査読有り]
- Faruk Yilmaz; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 48 19 4178 - 4183 2010年10月 [査読有り]
A rapid cationic polymerization of cyclohexene oxide that completed within a few minutes was achieved by a new initiation system that involves (1) a copper-catalyzed reduction of benzoyl peroxide by an ascorbic acid derivative that generates free radicals and (2) capture of the radicals by allyl sulfonium salt having hexafluoroantimonate (SbF(6)(-)) as a counter anion, followed by fragmentation of sulfonium radical cation, from which a super acid HSbF(6) was produced to initiate the rapid polymerization. The key factor in designing an efficient allyl sulfonium salt was attachment of an electron withdrawing ester group at the allyl group, of which ability to stabilize the formed radical can enhance the efficiency in trapping radicals by the allylic salt. (c) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4178-4183, 2010 - 古賀 孝一; 須藤 篤; 遠藤 剛J.Polym.Sci. Part A: Polym. Chem. 48 19 4351 - 4355 2010年10月 [査読有り]
- Yanmei Wang; Hisatoyo Morinaga; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 48 17 3816 - 3822 2010年09月 [査読有り]
A polymer having acetal moiety in the side chain was synthesized by a reaction of 1,3-diol structure of poly(vinyl alcohol-co-N-vinylpyrrolidone) and octanal. The hydrophobicity of the resulting acetal moiety and the hydrophilicity of the pyrrolidone moiety allowed the polymer to exhibit amphiphilicity. The polymer released octanal by hydrolysis of the acetal side chains under acidic conditions. The release of octanal was enhanced by the increased hydrophilicity of the polymer because of the presence of pyrrolidone moiety. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3816-3822, 2010 - Atsushi Sudo; Hidetada Morishita; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 48 17 3896 - 3902 2010年09月 [査読有り]
A norbornene monomer bearing cyclic carbonate moiety (NB-CC) was successfully synthesized from the corresponding precursor having epoxy moiety by its reaction with carbon dioxide under atmospheric pressure, which was efficiently catalyzed by lithium bromide. NB-CC underwent the ring-opening metathesis polymerization (ROMP) catalyzed by a ruthenium carbene complex to give the corresponding poly(norbornene), of which side chain inherited the cyclic carbonate moiety from the monomer without any deterioration. The same ROMP system was applicable to the copolymerization of NB-CC and 5-butyl-2-norbornene (BNB), which afforded the corresponding copolymer with a composition ratio same as a feed ratio. In addition, by using a catalytic system consisted of palladium (II) acetate/tricyclohexylphosphine/triphenylcarbenium tetrakis(pentafluorophenyl)borate, the copolymerization of NB-CC and BNC proceeded successfully in a vinyl addition polymerization mode to give the corresponding poly(norbornene) having CC moiety in the side chain. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3896-3902, 2010 - Atsushi Sudo; Long-Chao Du; Shoji Hirayama; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 48 13 2777 - 2782 2010年07月 [査読有り]
Thermally induced polymerizations of a series of 1,3-benzoxazines with a variety of substituents on the nitrogen atom were investigated in detail, particularly in the following three aspects of the polymerization: (1) N-alkyl-1,3-benzoxazines are much more reactive than N-phenyl-1,3-benzoxazine. (2) The polymerization rate depended on the bulkiness of the N-substituent. The bulkier the substituent was, the slower the polymerization was. (3) The polymerizations accompanied weight loss due to the elimination of the corresponding imine (R-N = CH(2)), and its extent became larger when R was more bulky. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2777-2782, 2010 - 大澤 壮祐; 森野 一英; 須藤 篤; 遠藤 剛Macromolecules 43 8 3585 - 3588 2010年04月 [査読有り]
- Ryoichi Kudoh; Atsushi Sudo; Takeshi EndoMACROMOLECULES 43 3 1185 - 1187 2010年02月 [査読有り]
- 遠藤 剛; 落合 文吾; 須藤 篤未来材料 10 6 14 - 19 エヌ・ティー・エス 2010年 [査読有り]
- エポキシドとラクトン類との共重合反応を基盤とする新規硬化反応遠藤 剛; 須藤 篤未来材料 8 8 36 - 40 2010年 [査読有り]
- Balaka Barkakaty; Kazuhide Morino; Atsushi Sudo; Takeshi EndoGREEN CHEMISTRY 12 1 42 - 44 2010年 [査読有り]
A novel, efficient synthesis of cyclic carbonates from the reaction of epoxides and gaseous CO2 under mild conditions (1 atm, rt to 45 degrees C) was achieved in reasonable yields (65-83%) by using N-methyltetrahydropyrimidine (MTHP) that facilitated efficient delivery of CO2 from the gas phase to the reaction system. - Atsushi Sudo; Shoji Hirayama; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 48 2 479 - 484 2010年01月 [査読有り]
Acetylacetonato (acac) complexes of transition metals in the 4th period were examined as catalysts for the ring-opening polymerization of benzoxazine. This examination revealed that acac complexes of manganese, iron, and cobalt exhibited the highest activity, which was comparable or slightly higher than that exhibited by p-toluenesulfonic acid. By replacing acac ligand by hexafluoroacetylacetonato (F(6)-acac) ligand, the activity of manganese and iron complexes was remarkably enhanced. These metal F(6)-acac complexes were tolerant to moisture to allow their use under air without special caution. Another advantage was their negligible effect to promote unfavorable weight loss during the polymerization. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 479-484, 2010 - Kazuya Uenishi; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 47 24 6750 - 6757 2009年12月 [査読有り]
This article presents a route to a novel polyester having sequentially ordered two orthogonal reactive groups. The polyester was given by the imidazole-initiated alternating copolymerization or allyl glycidyl ether (AGE) and a bislactone 1. This copolymerization system is characterized by the following three reaction behaviors: (1) the selective participation of only one of the two lactone moieties of I to the copolymerization to give a linear polyester, and the consequent introduction of the second lactone into the side chain of the polyester, (2) the participation of the epoxy moiety in AGE to the copolymerization, and the consequent introduction of the carbon-carb on double bond into the side chain of the polyester, and (3) arrangement of the sequentially ordered two orthogonal reactive groups according to the alternating manner. The introduction of the two reactive groups to the side chain of the alternating copolymer allowed two routes of sequential chemoselective reactions: (A) The ring-opening reaction of the lactone moiety with n-propylamine and the following Pt-catalyzed hydrosilylation of the carbon-carbon double bond with dimethyl-phenylsilane and (B) the sequential reactions of the reverse order (C) 2009 Wiley Periodicals, Inc J Polym Sci Part A Polym Chem 47. 6750-6757, 2009 - 機能材料分野で活躍が期待されるモノマー遠藤 剛; 須藤 篤高分子 58 6 411 - 416 2009年12月 [査読有り]
- 須藤 篤; 木村 美華; Liu, X.-D; 遠藤 剛ネットワークポリマー 30 6 304 - 311 合成樹脂工業協会 2009年11月 [査読有り]
イソシアナートとアミンの反応によって得られるウレア類のエポキシ-ジシアンジアミド硬化系への加速効果を検討した。その結果、アミンに由来する部位が立体的に小さいほど加速効果が顕著になることが明らかになった。 - Hirokazu Okamura; Atushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 47 22 6163 - 6167 2009年11月 [査読有り]
Graft polymerization of ethyl acrylate and n-butyl acrylate onto surface of polypropylene (PP) beads (diameter: 3.2 mm) were carried out by using a redox system composed of triethylborane (Et(3)B) and molecular oxygen in air. The amounts of the grafted polymers increased by prolonging a period of soaking PP beads in a solution of Et3B in hexane, a less polar solvent of which affinity with PP would be higher than that of tetrahydrofuran, a highly polar solvent. These results implied that the present graft polymerization involved: (1) interpenetration of Et3B into the surface area with the aid of hexane as a solvent, (2) its aerobic oxidation to generate a radical species, (3) abstraction of proton from PP by the radical species, and (4) initiation of polymerization from the resulting radical on the PP surface. Besides the acrylates, acrylic acid, and glycidyl methacrylate were also grafted onto the surface of PP to endow it with carboxyl and epoxy moieties, respectively. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6163-6167, 2009 - Takeshi Endo; Atsushi SudoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 47 19 4847 - 4858 2009年10月 [査読有り]
This Highlight gives an overview of the recent progress in development of new ring-opening polymerizations (ROPs) and their applications to functional networked polymers in our group. The described ROPs involve thermally induced polymerization of 1,3-benzoxazine, anionic alternating copolymerizations of epoxides and lactones, and those exhibiting equilibrium nature. These ROPs were successfully applied to the syntheses of the relevant networked polymers, leading to their distinctive features such as high thermal stability, small volume shrinkage, and selective decrosslinking ability, which enabled design and development of next generation materials. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4847-4858,2009 - Atsushi Sudo; Kazuya Uenishi; Takeshi EndoPOLYMER INTERNATIONAL 58 9 970 - 975 2009年09月 [査読有り]
3,4-Dihydrocoumarin (DHCM) is an aromatic six-membered lactone, which does not undergo anionic homopolymerization. However, it does undergo copolymerization with an epoxide. The striking feature of this copolymerization is its 1 : 1 alternating nature, which allows for the formation of polyesters. In this mini-review, we describe the copolymerization behavior, the polymer structure and the advantages that can be achieved by addition of DHCM to the epoxy-imidazole curing system. Another focus is our development of DHCM analogues, which bring the advantages of DHCM to their applications as comonomers for the curing system. (c) 2009 Society of Chemical Industry - Koichi Koga; Atsushi Sudo; Haruo Nishida; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 47 15 3839 - 3844 2009年08月 [査読有り]
A new convenient synthesis of N-carboxyanhydrides (NCAs) of alpha-amino acids was achieved by selective cyclization of urethane derivatives of alpha-amino acids. The urethanes were readily synthesized via N-carbamoylation of alpha-amino acids by bis(4-nitrophenyl)carbonate quantitatively. These urethanes having 4-nitrophenoxy moiety were tolerant to air and moisture to allow their facile purification and storage. When the obtained urethanes were heated in 2-butanone at 60 degrees C, they underwent the selective cyclization via intramolecular nucleophilic attack of the carboxyl moiety to the urethane moiety with releasing 4-nitrophenol, leading to the successful formation of the corresponding NCAs. Addition of carboxylic acids remarkably stabilized the formed NCAs during the reaction, allowing their isolation in high yields. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3839-3844, 2009 - Hidetada Morishita; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 47 16 3982 - 3989 2009年08月 [査読有り]
A norbornene monomer carrying epoxy moiety 1 was successfully synthesized from 5-norbornene-2-carbardehyde by treating it with thioylide. With using a catalytic system consisted of palladium (II) acetate/tricyclohexylphosphine/triphenylcarbenium tetrakis(pentafluorophenyl)borate, homopolymerizations and copolymerization of 1 and 5-butyl-2-norbornene (BNB) were examined. The homopolymerization of I was slower than that of BNB presumably due to coordination of the epoxy moiety to the palladium-center in competition with the C-C double bond of norbornene. This deceleration became less significant in the copolyrnerizations with low initial feed ratios [1](0)/[BNB](0), leading to successful formation of the corresponding copolymers having a rigid poly(norbornene) main chain and epoxy moiety in the side chains, of which composition ratios agreed with the feed ratios. Influence of the epoxy moiety of 1 on its Pd-catalyzed addition polymerization was elucidated by studying the homopolymerization of BNB in the presence of 1,2-epoxyhexane. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3982-3989, 2009 - Hisatoyo Morinaga; Hiroshi Morikawa; Atsushi Sudo; Takeshi EndoJournal of Polymer Science, Part A: Polymer Chemistry 47 13 3241 - 3247 2009年07月 [査読有り]
A methacrylate having a hydrophilic poly(ethylene glycol) chain and 2-(N,N-dimethylamino)ethyl methacrylate were radically copolymerized to obtain a statistical hydrophilic copolymer having tertiary amino groups in the side chains. The obtained polymeric amine was quantitatively quaternarized by a benzyl chloride-type molecule having an acetal moiety derived from geraniol, which is a hydro-phobic alcohol widely used as a fragrance ingredient. The resulting copolymer, which had PEG chain and the quaternary ammonium moieties as hydrophiles and the ace-tal moieties as hydrophobes, exhibited amphiphilicity to form stable associates in water. The acetal moieties were stable for 30 days at pH 9, while they were gradually hydrolyzed at pH 4 to release geraniol continuously at least for 30 days, confirming the potential applicability of the copolymer to a controlled releasing system of functional molecules. © 2009 Wiley Periodicals, Inc. - Kazuya Uenishi; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 47 14 3662 - 3668 2009年07月 [査読有り]
A copolymerization of 10-methyl-2H,8H-benzo-[1,2-b:5,4-b']bipyran-2,8-dione (1) and glycidyl phenyl ether (GPE) was studied. 1 was a bislactone designed as a bifunctional analogue of 3,4-dihydrocoumarin (DHCM), of which anionic 1:1 alternating copolymerization with GPE has been reported by us, previously. This alternating nature was inherited by the present copolymerization of 1 and GPE, leading to an intriguing copolymerization behavior in contrast to the ordinary statistical copolymerizations of monofunctional monomers and bifunctional monomers usually controlled by the proportional dependence of the crosslinking density on the monomer feed ratio: (1) When the feed ratio [GPE](0)/[1](0) was 1, the two monomers underwent the 1:1 alternating copolymerization. In this case, I behaved as a monofunctional monomer, that is, only one of the two lactones in 1 participated in the copolymerization allowing the other lactone moiety to be introduced into the side chain almost quantitatively. (2) Increasing the feed ratio [GPE](0)/[1](0) to larger than 4 allowed almost all of the lactone moieties to participate in the copolymerization system to give the corresponding networked polymers efficiently. The compositions of the copolymers [GPE unit]/[1-derived acyclic ester unit] were always biased to smaller values than the feed ratios [GPE](0)/[lactone moiety in 1](0) by the intrinsic 1:1 alternating nature of the copolymerization. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3662-3668, 2009 - Ryoichi Kudoh; Atsushi Sudo; Takeshi EndoMACROMOLECULES 42 7 2327 - 2329 2009年04月 [査読有り]
- Akane Suzuki; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 47 8 2214 - U2 2009年04月 [査読有り]
- Atsushi Sudo; Yukio Isobe; Takeshi EndoJOURNAL OF APPLIED POLYMER SCIENCE 112 2 836 - 842 2009年04月 [査読有り]
A curing process of bisphenol-A diglycidyl ether using amine-carboxylic acid salts was studied with focusing on its small-volume shrinkage. The characteristic point of the curing process was the initial high-density created by strong interactions between the ionic species such as electro-statistic one and hydrogen-bonding, which disappeared on the consumption of these species by their reactions with the epoxide to give the low-density neutral polymers. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 112: 836-842, 2009 - Hisatoyo Morinaga; Hiroshi Morikawa; Yanmei Wang; Atsushi Sudo; Takeshi EndoMacromolecules 42 6 2229 - 2235 2009年03月 [査読有り]
Statistical amphiphilic copolymers of polymethacrylate having a lilial-derived acetal moiety as a hydrophobic side chain and poly(ethylene glycol) (PEG) as a hydrophilic side chain were synthesized with different unit ratios (3a (x:y = 100:0), 3b (x:y = 73:27), and 3c (x:y = 24:76)). In aqueous media the polymer 3c (x:y = 24:76) formed its micelles, whose particle diameter was ranged mainly from 10 to 220 nm and averaged diameter was 35 nm. Polymer 3c in aqueous media exhibited aggregation - dissociation behavior which was dependent sharply and reversibly on temperature in the presence of NaCl. The aggregation of the polymer micelles inhibited hydrolysis of the acid-labile acetal side chain and release of the resulting lilial, while its dissociation removed the inhibition. This responsive behavior by simply heating and cooling could control hydrolysis of the acid-labile acetal side chain and release of the resulting lilial. © 2009 American Chemical Society. - Daisuke Nagai; Asuka Fujii; Masayoshi Tanaka; Bungo Ochiai; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 47 6 1510 - 1521 2009年03月 [査読有り]
Anionic polymerization of methacrylates under sterically confined environment in a spherical beads-shaped networked. polystyrene (NwPS) matrix is described. The initiator used herein is a samarium (Sm) (III) enolate, which was formed by treatment of 2-bromoisobutylate immobilized in the side chain of NwPS with Sm (II) iodide. By using this NwPS-bound initiator, polymerization of a series of methacrylates (=solid-supported polymerization) was studied to find its two aspects: (1) In the early stages, the rate constant for each methacrylate was comparable to that for its conventional solution-phase polymerization using a Sm (III) enolate, suggesting that methacrylate can be efficiently supplied to the propagating end by its free permeation without any interference by the networked structure of the matrix. (2) After the early stages, the rate constant decreased remarkably, implying that permeation of methacrylate was sterically interfered by the formed poly(methacrylate) that filled the confined space in NwPS, as supported by a SEM image of the resulting beads, of which pores were filled with the formed polymers. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1510-1521, 2009 - Kazuya Uenishi; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 47 6 1661 - 1672 2009年03月 [査読有り]
An imidazole-initiated copolymerization of an aromatic bislactone, 10-methyl-2H,8H-benzo[1,2-b:5,4-b']bipyran-2,8-dione (1), and glycidyl phenyl ether (GPE) was investigated. In spite of the bifunctional nature of I that would potentially permit formation of networked and thus insoluble polymers upon its copolymerization, only one of the two lactone moieties of 1 exclusively underwent the copolymerization to give a linear polyester. Spectroscopic analysis of the polyester and its reductive scission into the corresponding fragment revealed that the polyester was formed by a 1:1 alternating copolymerization of GPE and the lactone moiety of 1. The other lactone in I that did not participate in the copolymerization was quantitatively incorporated into the side chain of the polyester as a reactive site, of which ring-opening reactions by amine and alcohol as nucleophilic reagents allowed chemoselective polymer reactions. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47:1661-1672,2009 - Atsushi Sudo; Ryoichi Kudoh; Hiroshi Nakayama; Kazuya Arima; Takeshi EndoMACROMOLECULES 41 23 9030 - 9034 2008年12月 [査読有り]
Polymerization behavior of N-phenylbenzoxazine in bulk was studies in detail to discover new reaction pathways: (1) formation of an intermediary polymer having N,O-acetal-type linkage in the main chain and (2) its rearrangement into Mannich-type linkage in the solid state. Efficient promotion of the main chain rearrangement was achieved by using a dual system composed of imidazole and sulfonic acid. - Zhang Yuan; 須藤 篤; 遠藤 剛ネットワークポリマー 29 1 23 - 30 合成樹脂工業協会 2008年12月 [査読有り]
- 亀井 康孝; 須藤 篤; 遠藤 剛Macromolecules 41 21 7913 - 7919 2008年11月 [査読有り]
A new synthetic method of polypeptide having defined terminal structures was established withusing an acyclic urethane of alpha-amino acid as a monomer. The urethane derivative presented herein is N-(4-nitrophenoxycarbonyl)-gamma-benzyl-L-glutamate, of which polymerization behavior in N,N-dimethylacetamide (DMAc) in the presence of various amines was examined. The polymerization was accelerated remarkably by adding butylamine so that it proceeded smoothly at 30 degrees C to afford the corresponding polycondensate, poly(gamma-benzyl-L-glutamate) (poly(BLG)). Detailed structural analysis of the obtained poly(BLG) with MALDI-TOF mass spectrometry revealed that butylamine was incorporated into the terminal of poly(BLG) and the other terminal was endowed with amino group. - Tetsuya Eguchi; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 46 19 6654 - 6659 2008年10月 [査読有り]
- Shimon Tanaka; Hyun-Kyoung Kim; Astushi Sudo; Haruo Nishida; Takeshi EndoMACROMOLECULAR CHEMISTRY AND PHYSICS 209 20 2071 - 2077 2008年10月 [査読有り]
A rapid and reversible aniscitropic photomechanical response of polymer film was achieved by using uniaxially stretched blend film composed of polycaprolactone and poly(vinyl ether) with azobenzene moiety (Azo-PVE) as a side chain. The photomechanical response behavior of the film was studied under a constant tensile stress. The deformation or recovery was rapidly completed within at most 0.1 min of UV + Vis light irradiation being switched on or off, respectively. The anisotropy of deformation was confirmed on a stretched film subjected to light irradiation. The deformation was observed as a contraction in a direction parallel to the stretching direction and as an elongation in the perpendicular direction. The anisotropy of the photoresponse was remarkably observed with increase in the stretching ratio, reflecting the binding between amorphous areas by Azo-PVE long chains. - Kazuya Uenishi; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 46 12 4092 - 4102 2008年06月 [査読有り]
Anionic copolymerizations of 3,4-dihydrocoumarin (DHCM) and a series of glycidyl ethers (n-butyl glycidyl ether, tert-butyl glycidyl ether, and allyl glycidyl ether) with 2-ethyl-4-methylimidazole as an initiator proceeded in a 1:1 alternating manner to give the corresponding polyesters, whose structures were confirmed by spectroscopic analyses and reductive scission of the ester bonds in the main chain with lithium aluminum hydride, followed by detailed analyses of the resulting fragments. The polyester obtained by the copolymerization of DHCM and allyl glycidyl ether inherited the allyl groups in the side chain, whose applicability to chemical modifications of the polyester was successfully demonstrated by a platinum-catalyzed hydrosilylation reaction. (c) 2008 Wiley Periodicals, Inc. - 亀井 康孝; 須藤 篤; 西田 治男; 菊川 清; 遠藤 剛Polymer Bulletin 60 5 625 - 633 2008年05月 [査読有り]
N-(4-Nitrophenoxycarbonyl)-gamma-benzyl-L-glutamate (1) was heated at 60 degrees C in N,N-dimethylacetoamide (DMAc) in the presence of p-(tert-butyl)phenylmethylamine (2) to afford poly(gamma-benzyl-L-glutamate) in high yield. H-1 NMR analysis of the obtained polymer revealed that the p-(tert-butyl)phenylmethyl group was successfully introduced into the polymer chain end. Under the same conditions, polycondensations of 1 in the presence of poly(ethylene glycol)s having amino terminals were performed. Both of the components were consumed quantitatively to afford the corresponding block copolymers having poly(gamma-benzyl-L-glutamate) and poly(ethylene glycol) segments. The molecular weights of the copolymers were controlled by the feed ratio [1](0)/[amino group in the macroinitiator](0). - Atsushi Sudo; Kazuya Uenishi; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 46 10 3447 - 3451 2008年05月 [査読有り]
- 亀井 康孝; 永井 篤志; 須藤 篤; 西田 治男; 菊川 清; 遠藤 剛Journal of Polymer Science Part A: Polymer Chemistry 46 8 2649 - 2657 2008年04月 [査読有り]
A series of activated urethane-type derivatives of gamma-benzyl-L-glutamate were synthesized, and their potential as monomers for polypeptide synthesis was investigated. The derivatives of the focus of this work were a series of N-aryloxycarbonyl-gamma-benzyl-L-glutamate 1, of which aryl groups were phenyl, 4-chlorophenyl, and 4-nitrophenyl. These urethanes 1 were reactive in polar solvents such as dimethylsulfoxide, N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMAc), and were efficiently converted into poly(gamma-benzyl-L-glutamate) (poly(BLG)) under mild conditions; at 60 degrees C without addition of any catalyst. Among the three urethanes, that having 4-nitrophenoxycarbonyl group le was the most reactive to give poly(BLG) efficiently, as was expected from the highly electron deficient nature of the nitrophenoxycarbonyl group. On the other hand, the urethane la having phenoxycarbonyl group was also efficiently converted into poly(BLG), in spite of the intrinsically less electrophilicity of the phenoxycarbonyl group. In addition, the successful formation of poly(BLG) by the reaction of 1a favored its diluted concentration (0.1 M) much more than 2.0 M, the optimum initial concentration for 1c. (1)H NMR spectroscopic analyses of the reactions in situ revealed that the predominant pathway from 1 to poly(BLG) involved the intramolecular cyclization of 1 into the corresponding N-carboxyanhydride, with release of phenol and its successive ring-opening polymerization with release of carbon dioxide. (c) 2008 Wiley Periodicals, Inc. - Atsushi Nagai; Yasutaka Kamei; Xiao-Shui Wang; Masaki Omura; Atsushi Sudo; Haruo Nishida; Eiichi Kawamoto; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 46 7 2316 - 2325 2008年04月 [査読有り]
The click-coupling reaction was applied to polycondensation, to synthesize a high-molecular weight prepolymer having benzoxazine moieties in the main chain. For the polycondensation, a bifunctional N-propargyl benzoxazine was synthesized from bisphenol A, propargylamine, and formaldehyde. The propargyl group was efficiently used for the copper(I)-catalyzed alkyne-azide "click" reaction with p-xylene-alpha,alpha'-diazide, to give the corresponding linear polycondensate having 1,2,3-triazole junctions. The polycondensation proceeded in N,N-dimethylformamide (DMF) at room temperature. By this highly efficient "click-" polycondensation reaction, the benzoxazine ring in the monomer was successfully introduced into the polymer main chain without any side reaction. The obtained polymer (=prepolymer) underwent thermal crosslinking to afford the corresponding product, which was insoluble in a wide range of organic solvents and exhibited higher thermal stability than the polymer before crosslinking. (C) 2008 Wiley Periodicals, Inc. - 亀井 康孝; 須藤 篤; 西田 治男; 菊川 清; 遠藤 剛Journal of Polymer Science Part A: Polymer Chemistry 46 7 2525 - 2535 2008年04月 [査読有り]
A series of activated urethane-type derivatives of alpha-amino acids were synthesized and applied to polypeptide synthesis. The urethane used herein, N-(4-nitrophenoxycarbonyl)-alpha-amino acids 1, were synthesized by N-carbamoylation of gamma-benzyl-L-glutamate, beta-benzyl-L-aspartate, L-leucine, L-phenylalanine, and L-proline, with 4-nitrophenyl chloroformate. When 1 was dissolved in N,N-dimethylacetamide (DMAc) and heated at 60 degrees C, it was smoothly converted into the corresponding polypeptides with releasing 4-nitrophenol and carbon dioxide. Spectroscopic analyses of the obtained polypeptides revealed that they were comparable with the authentic polypeptides synthesized by the ring-opening polymerizations of amino acid N-carbox-yanhydrides (NCAs). Besides the successful polycondensations of a series of 1, their polycondensations of 1a and other 1 were also successfully carried out to obtain the corresponding statistic copolypeptides. (C) 2008 Wiley Periodicals, Inc. - Atsushi Sudo; Suguru Motokucho; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 46 7 2588 - 2592 2008年04月 [査読有り]
- Yuan Zhang; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 46 5 1907 - 1912 2008年03月 [査読有り]
- Yukio Isobe; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 46 6 2305 - 2308 2008年03月 [査読有り]
- Daisuke Nagai; Asuka Fujii; Bungo Ochiai; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 46 6 1990 - 1997 2008年03月 [査読有り]
A new facile method for preparation of an amphiphilic block copolymer via a one-pot sequential atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) on solid support was developed. As a model homopolymerization for the solid-supported block copolymerization, ATRPs of MMA and HEMA in toluene and in 2-butanone/1-propanol solvent system were carried out, respectively. Crosslinked polystyrene beads bearing 2-bromoisobutyrate moieties successfully initiated the polymerizations of MMA and HEMA in controlled manner. On the basis of the successful results, the one-pot synthesis of amphiphilic block copolymer by changing the reaction medium was performed. After the ATRP of MMA in toluene at 90 degrees C for 1 h, the poly(MMA) formed on the beads were washed by continuous flow of 2-butanone/1-propanol under nitrogen with the aid of a glass filter in a U-shaped glass vessel. Then, 2-butanone/1-propanol, copper chloride (I), 2,2'-bipyridyl, and HEMA were added and heated at 50 degrees C for 48 h with shaking the vessel, followed by treatment with trifluoroacetic acid to isolate the well-defined amphiphilic block copolymer, poly(MMA-b-HEMA). These demonstrated the feasibility of the present strategy for well-defined synthesis of amphiphilic block copolymers via a one-pot procedure. (C) 2008 Wiley Periodicals, Inc. - 工藤 亮一; 須藤 篤; 遠藤 剛ネットワークポリマー 29 177 - 180 合成樹脂工業協会 2008年
- 須藤 篤; 遠藤 剛ネットワークポリマー 29 193 - 196 合成樹脂工業協会 2008年
- 森下 秀直; 須藤 篤; 遠藤 剛ネットワークポリマー 29 69 - 72 合成樹脂工業協会 2008年
- 遠藤 剛; 須藤 篤ネットワークポリマー 29 49 - 52 合成樹脂工業協会 2008年
- 須藤 篤; 永井 大介; 田中 正剛; 遠藤 剛ネットワークポリマー 29 57 - 60 合成樹脂工業協会 2008年
- 上西 和也; 須藤 篤; 遠藤 剛ネットワークポリマー 29 53 - 56 合成樹脂工業協会 2008年
- Fujita, Y; Koga, K; Kim, H. K; Wang, X. S; Sudo, A; Nishida, H; Endo, TJ. Polym. Sci. Part A: Polym. Chem. 45 22 5365 - 5369 2007年11月 [査読有り]
- Masashi Horikiri; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 45 20 4606 - 4611 2007年10月 [査読有り]
A bifunctional cyclic five-membered dithiocarbonate (DTC), having a bisphenol A structure, was found to be an effective accelerator for a epoxy-amine curing system comprised of bisphenol A diglycidyl ether and amine-terminated polypropylene glycol. The acceleration effect was evaluated by monitoring the time-dependence of the storage modulus of the reaction mixture with a dynamic mechanical analyzer. The reactions involved in the curing system were investigated in detail by performing a series of model reactions using the corresponding monofunctional monomers. This investigation revealed that (1) DTC reacted with amine rapidly, (2) the reaction afforded the corresponding adduct having a thiourethane and thiol moieties, and (3) the thiol reacted rapidly with epoxide. The thiourethane moiety incorporated into the resulting adduct effectively catalyzed the reaction of epoxide and amine, and this catalysis was the predominant mechanism for the acceleration effect arisen by the addition of DTC. (c) 2007 Wiley Periodicals, Inc. - Kazuya Uenishi; Atsushi Sudo; Takeshi EndoMACROMOLECULES 40 18 6535 - 6539 2007年09月 [査読有り]
This paper describes the alternating character in the copolymerization of glycidyl phenyl ether (GPE) and 3,4-dihydrocoumarin (DHCM) by 2-ethyl-4-methylimidazole (EMI) as an initiator. DHCM, which is an aromatic lactone that does not undergo its homopolymerization under anionic conditions, underwent the copolymerization with GPE by EMI. In the present copolymerization, formation of the GPE-DHCM alternating sequence and that of the GPE-GPE sequence competed, and the former was always the predominant one. The maximum content of the alternating sequence (90%) was achieved when the feed ratio GPE/DHCM was 1. The obtained copolymer was a polyester, for which the ester linkage was cleavable by reduction with lithium aluminum hydride. The resulting compound inherited the structure of the alternating sequence, and its high yield (90%) supported the high alternating character of the copolymerization. - Atsushi Sudo; Kazuya Uenishi; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 45 16 3798 - 3802 2007年08月 [査読有り]
- Bungo Ochiai; Tomomi Nagasawa; Yasuhiro Asano; Daisuke Nagai; Atsushi Sudo; Takeshi EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 45 13 2820 - 2826 2007年07月 [査読有り]
Thermal behaviors were monitored by infrared thermographic analysis in the copolymerization of a spiroorthoester and a bifunctional oxetane with thermally latent initiators [benzyl tetrahydrothiophenium hexafluoroantimonate (BTHT) and benzyl 4-hydroxyphenyl methyl sulfonium hexafluoroantimonate (BPMS)]. The copolymerization with BPMS increased the temperature during the copolymerization more than that with BTHT, whereas the exothermicities were lowered with the increase in the initial feed ratio of the spiroorthocarbonate monomer. The high exothermicity in the copolymerization with BPMS is ascribable to the faster propagation of the oxetane monomer with a high heat of polymerization, and this is supported by model reactions and computational calculation. (c) 2007 Wiley Periodicals, Inc. - Kazuya Uenishi; Hiroshi Morikawa; Atsushi Sudo; Takeshi EndoJournal of Polymer Science, Part A: Polymer Chemistry 45 6 1170 - 1176 2007年03月 [査読有り]
The application of siloxane oligomer 1 to the precoating of an inorganic surface with a crosslinked polysiloxane layer having five-membered cyclic dithiocarbonate (DTC) moiety by curing reaction, is described. The DTC moiety can undergo cascade reactions with both amines and electrophillic reagents, which are commonly used components of adhesives based on polyaddition chemistry. The curing reaction could be performed on a quartz surface to coat it with a crosslinked polysiloxane layer having DTX moiety. The layer inherits the high reactivity of DTC with amine, which allows the demonstration of cascade reactions consisting of the ring-opening reaction of DTC and the successive addition reaction of the resulting thiol with epoxide in the coating layer. This method has the ability of achieving high adhesion through the combination of this precoating technique with epoxy-amine two-component adhesives. - 平山 正次; 須藤 篤; 遠藤 剛ネットワークポリマー 28 211 - 212 合成樹脂工業協会 2007年
- 須藤 篤; 鈴木 茜; 遠藤 剛ネットワークポリマー 28 5 - 8 合成樹脂工業協会 2007年
- 江口 哲也; 須藤 篤; 遠藤 剛ネットワークポリマー 28 165 - 168 合成樹脂工業協会 2007年
- 上西 和也; 須藤 篤; 遠藤 剛ネットワークポリマー 28 1 - 4 合成樹脂工業協会 2007年
- 田中 斎文; 松本 幸三; 須藤 篤; 西田 治男; 遠藤 剛; Hyun-Kyoung Kimネットワークポリマー 28 161 - 164 合成樹脂工業協会 2007年
- 張 淵; 須藤 篤; 遠藤 剛ネットワークポリマー 28 9 - 12 合成樹脂工業協会 2007年
- Horikiri, M; Sudo, A; Endo, TNetwork Polymer 28 3 74 - 81 合成樹脂工業協会 2007年 [査読有り]
- Motokucho, S; Sudo, A; Endo, TJ. Polym. Sci. Part A: Polym. Chem. 45 19 4459 - 4464 2007年 [査読有り]
- Daisuke Nagai; Atsushi Sudo; Takeshi EndoMACROMOLECULES 39 26 8898 - 8900 2006年12月 [査読有り]
- Yukio Isobe; Atsushi Sudo; Takeshi EndoMacromolecules 39 23 7783 - 7785 2006年11月 [査読有り]
A new thermoresponsive system which is prepared by mixing β-cyclodextrins (CD) with a poly (propylene glycol) with amino groups in both terminals was investigated. The thermoresponsive behavior of the system was confirmed by repeatable and keen response of its viscosity and transmittance of visible light to repeated heating-and-cooling cycles. The family of supramolecules represented by the term 'pseudo-polyrotaxane (PPRtx) inherit the intrinsic nature of the inclusion complexes between formation and dissociation. The results show that the PPRtx composed of CD and polyethers can be formed spontaneously upon mixing the two components at ambient temperature by appropriate design of the terminal functionality of the polyether. The thermoresponse of the PPRtx is highly sensitive to the thermal stimuli, allowing to design various systems with thermoswitching behavior. - Yukio Isobe; Atsushi Sudo; Takeshi EndoMACROMOLECULES 39 23 7783 - 7785 2006年11月 [査読有り]
- Suguru Motokucho; Atsushi Sudo; Takeshi EndoJournal of Polymer Science, Part A: Polymer Chemistry 44 21 6324 - 6331 2006年11月 [査読有り]
A polymer having a trithiocarbonate moiety in its main chain was synthesized with a cyclic, five-membered dithiocarbonate as a building block. The trithiocarbonate in the polymer acted as a reversible addition-fragmentation chain transfer reagent to mediate a controlled insertion polymerization of styrene into the polymer main chain, giving the corresponding sequence-ordered polymer having a well-defined polystyrene segment in the main chain. During the polymerization, the polystyrene segment in the main chain gained its molecular weight, which maintained a linear relationship with the conversion of styrene. The insertion polymerization of styrene was induced not only thermally but also by ultraviolet irradiation. This photoinduced polymerization was well controlled by the trithiocarbonate moiety to give the corresponding polymer, whose structure was virtually the same as that obtained by the thermal polymerization. © 2006 Wiley Periodicals, Inc. - XS Wang; HK Kim; Y Fujita; A Sudo; H Nishida; T EndoMACROMOLECULES 39 3 1046 - 1052 2006年02月 [査読有り]
Polyrotaxanes with a low threading ratio of alpha-cyclodextrin (alpha-CD) on a poly(ethylene glycol) chain effectively acted as both the relaxation and reinforcing reagents in Novolac-type epoxy resin. The polyrotaxanes were incorporated into the epoxy resin during the curing process to produce transparent and rigid epoxy resin/polyrotaxane (E/PR) alloys. From dynamic mechanical analysis (DMA) of the E/PR alloys, it was found that the polyrotaxane contributed not only as a stress-relaxation component but also as a reinforcing modifier in the epoxy resin matrix. The morphology and chemical Structures of polyrotaxanes in the epoxy resin matrices were assumed to be in a nanoscale dispersion, forming an interpenetrate network structure with multi crosslinking bonds on threaded alpha-CDs. This assumption was made based on their transparency, differential scanning calorimetry, small-angle X-ray scattering, and DMA analyses. This is the first report on the unique properties of polyrotaxanes added in a rigid matrix. - 上西 和也; 須藤 篤; 遠藤 剛ネットワークポリマー 27 157 - 160 合成樹脂工業協会 2006年
- 須藤 篤; 上西 和也; 堀切 雅史; 遠藤 剛ネットワークポリマー 27 153 - 156 合成樹脂工業協会 2006年
- 精密開環重合遠藤 剛; 須藤 篤未来材料 6 8 26 - 36 2006年 [査読有り]
- Y Itagaki; A Sudo; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 44 1 681 - 685 2006年01月 [査読有り]
- K Uenishi; A Sudo; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 43 24 6492 - 6502 2005年12月 [査読有り]
Poly(thiourethane)s having a siloxane moiety in the side chain were synthesized with a 5-membered cyclic dithiocarbonate (DTC) having a siloxane group as a building block. The synthetic pathway consisted of (1) an addition reaction of the DTC with diamines and (2) polyaddition reactions of the resulting dithiols with diisocyanates. The siloxane moiety in the polymer side chain underwent a self-condensation reaction upon exposure to moisture, and this led to a successful crosslinking reaction of the poly(thiourethane). The crosslinking on a silicate surface was accompanied by condensation between the siloxane side chain of the polymer and the silanol group on the surface, giving the corresponding surface that was permanently coated with the crosslinked polymer. (c) 2005 Wiley Periodicals, Inc. - K Uenishi; A Sudo; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 43 21 5119 - 5126 2005年11月 [査読有り]
A new efficient and straightforward method to convert amines into siloxane-thiol hybrid molecules was developed. The method relies on the nucleophilic addition of amines to a cyclic dithiocarbonate having siloxane moiety (DTC-Si), and the successive ring-opening reaction of the dithiocarbonate moiety to give the corresponding acyclic thiourethane having a thiol moiety. Based on this method, amine-terminated poly(propylene glycol) was successfully transformed into the corresponding polyether having thiol-terminals and siloxane groups. In the presence of moisture, the alkoxysilyl moiety underwent condensation reaction to make the polyether cured into a transparent resin having solvent-resistance. Addition of bisphenol A diglycidyl ether (Bis A-DGE) to the curing process resulted in two simultaneous reactions, i.e., (1) condensation of siloxane part and (2) addition reaction of the thiol terminal and the epoxide group. When this curing process was carried out on a glass surface, the siloxane part reacted with silanol group on the surface, forming a coating layer having excellent mechanical toughness graded as maximum 7H by pencil toughness test (JIS-K5400). (c) 2005 Wiley Periodicals, Inc. - K Uenishi; A Sudo; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 43 19 4422 - 4430 2005年10月 [査読有り]
A novel 5-membered cyclic dithiocarbonate (DTC) having a siloxane moiety, 5-(3-trimethoxysilylpropyloxymethyl)-1,3-oxathiolane-2-thione, was synthesized from the corresponding epoxide precursor by its cycloaddition with carbon disulfide. The siloxane group underwent condensation reaction by the treatment with water and a basic or acidic catalyst, to afford the corresponding oligomer having siloxane main chain and DTC pendant. The resulting oligomer was liquid and soluble in organic solvents such as THF and chloroform. Treatment of the oligomer with amines resulted in selective ring-opening reaction of the DTC group, generating a thiol group, which underwent oxidative coupling reaction to make the oligomer successfully cured. (c) 2005 Wiley Periodicals, Inc. - HK Kim; XS Wang; Y Fujita; A Sudo; H Nishida; M Fujii; T EndoMACROMOLECULAR CHEMISTRY AND PHYSICS 206 20 2106 - 2111 2005年10月 [査読有り]
Light-induced reversible changes in elasticity of semi-interpenetrating network (semi-IPN) films hearing azobenzene moieties were achieved under both ultraviolet and visible light irradiation. The semi-IPN film was prepared by a cationic copolymerization of azobenzene-containing vinyl ethers in a linear polycarbonate (PC) film as a matrix. When the irradiation was switched on and off, the semi-IPN film showed rapid reversible deformation with the same behavior occurring over a range of wavelengths, including both the UV and visible regions. The observed reversible deformation of the film was attributed to the decrease in the film's elasticity, which was assumed to be caused by the frequent trans-cis cycling isomerization of azobenzene moieties taking place during the UV and visible light irradiation. This cycling makes it difficult for the azobenzene groups to aggregate, thus hindering their ability to function as pseudo-crosslinking points. - S Motokucho; Y Itagaki; A Sudo; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 43 16 3711 - + 2005年08月 [査読有り]
A novel 5-membered cyclic dithiocarbonate (DTC) having a hydroxy group, 5-hydroxymethyl-1,3-oxathiolane-2-thione (DTC-OH), was synthesized from glycidol. On the basis of the highly efficient reaction of its hydroxyl group with isocyanate, a polyurethane having isocyanate terminals was modified with DTC-OH into a new type of polyurethane prepolymer having DTC-terminals, which was highly reactive with amines but tolerant to moisture. - HK Kim; XS Wang; Y Fujita; A Sudo; H Nishida; M Fujii; T EndoPOLYMER 46 16 5879 - 5883 2005年07月 [査読有り]
A new material with photomechanical switching ability was developed. The material is a binary polymer blend composed of a poly(vinylether) having azobenzene moiety in the side chain and a polycarbonate as a matrix. Upon switching UV-irradiation on and off, the developed polymer blend showed deformation that was both rapid and reversible. This observed photomechanical effect is attributed to a reversible modulus change in the polymer blend, arising from an UV-controlled isomerization of the azobenzene moiety, causing a switching behavior between its highly aggregated and dissociated states. These two states are the physical crosslinking and decrosslinking of the polymer chains. (c) 2005 Elsevier Ltd. All rights reserved. - HK Kim; XS Wang; Y Fujita; A Sudo; H Nishida; M Fujii; T EndoMACROMOLECULAR RAPID COMMUNICATIONS 26 13 1032 - 1036 2005年07月 [査読有り]
A novel semi-interpenetrating polymer network (semi-IPN) with photomechanical switching ability was developed by a cationic copolymerization of azobenzene containing vinyl ethers in a matrix of a linear polycarbonate (PC). The semi-IPN film showed reversible deformation upon switching the UV irradiation on and off and responded with unprecedented rapidity. The photomechanical effect is attributed to a reversible change between the highly aggregated and dissociated states of the azobenzene groups. - H Morikawa; A Sudo; H Nishida; T EndoJOURNAL OF APPLIED POLYMER SCIENCE 96 2 372 - 378 2005年04月 [査読有り]
The copolymerization of epoxides and a six-membered cyclic carbonate, 5,5-dimethyl-1,3-dioxan-2-one (DM6CC), was carried out with 1,8-diazabicyclo[5.4.0]undec-7-ene as an initiator. In the copolymerization of glycidyl phenyl ether (GPE) and DM6CC, DM6CC remarkably accelerated the polymerization rate of GPE and also effectively suppressed chain-transfer reactions, which occur in the homopolymerization of the epoxide. This suppression resulted in the formation of the corresponding copolymer with a higher molecular weight. Similar effects of DM6CC were also observed in a curing system with a Novolac-type multifunctional epoxide (Novolac glycidyl ether). The curing reaction of the epoxide in the presence of DM6CC smoothly proceeded and yielded the corresponding networked polymer, showing a decrease in the volume shrinkage as the DM6CC content increased. (C) 2005 Wiley Periodicals, Inc. - H Morikawa; A Sudo; H Nishida; T EndoMACROMOLECULAR CHEMISTRY AND PHYSICS 206 5 592 - 599 2005年03月 [査読有り]
To clarify the cationic copolymerization behavior of epoxide and cyclic carbonate, the copolymerization behavior of glycidyl phenyl ether (GPE) with seven-membered cyclic carbonate (7CC) was carried out using methyl trifluoromethanesulfonate (MeOTf) as a cationic initiator. The addition of 7CC accelerated the consumption rate of GPE, and the resulting copolymers were richer in 7CC-derived unit compared to the feed ration of 7CC. During the copolymerization, a large amount of five-membered cyclic carbonate having a phenoxymethyl group (PM-5CC) was produced as a by-product, which suggests the corresponding spiroorthocarbonate was formed as an intermediate and that residual oxytetramethylene (OTM) unit was incorporated into the copolymer sequence. From H-1 NMR analysis, it was found that the copolymers had a statistically random sequence consisting of GPE, 7CC, and OTM units. - 金 〓〓; 須藤 篤; 西田 治男; 遠藤 剛ネットワークポリマー 26 45 - 48 合成樹脂工業協会 2005年
- 磯部 行夫; 須藤 篤; 遠藤 剛ネットワークポリマー 26 153 - 156 合成樹脂工業協会 2005年
- 上西 和也; 須藤 篤; 遠藤 剛ネットワークポリマー 26 165 - 168 合成樹脂工業協会 2005年
- 王 暁水; 須藤 篤; 西田 治男; 遠藤 剛ネットワークポリマー 26 161 - 164 合成樹脂工業協会 2005年
- 落合 文吾; 淺野 育洋; 永井 大介; 長澤 智三; 遠藤 剛; 須藤 篤ネットワークポリマー 26 173 - 176 合成樹脂工業協会 2005年
- 堀切 雅史; 須藤 篤; 遠藤 剛ネットワークポリマー 26 157 - 160 合成樹脂工業協会 2005年
- D Nagai; A Sudo; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 42 21 5384 - 5388 2004年11月 [査読有り]
Anionic copolymerization of ethylphenylketene with benzaldehyde with butyllithium or diethylzinc as the initiator proceeded in a perfect 1:1 alternating manner to produce the corresponding polyester, whose repeating unit had two adjacent chiral centers. The relative stereochemistry between these two chiral centers was successfully controlled by the addition of (S,S)-(-)-2,2'-isopropylidenebis(4-tert-butyl-2-oxazoline), producing the corresponding polyester that had excellent diastereoselectivity (erythro-configuration : threo-configuration = 4:96). The diastereomeric ratio was determined by high-performance liquid chromatography analysis of the diol, which was obtained by reductive degradation of the polyester while maintaining the configuration of the repeating unit. (C) 2004 Wiley Periodicals, Inc. - Tanaka,M; Sudo,A; Endo,TJ. Polym. Sci. Part A: Polym. Chem. 42 19 5026 - 5029 2004年10月 [査読有り]
- Tanaka,M; Sudo,A; Endo,TJ. Polym. Sci., Part A: Polym. Chem. 42 17 4417 - 4423 2004年09月 [査読有り]
A solid-supported samarium enolate successfully initiated the polymerization of 2-(trimethylsilyloxy)ethyl methacrylate (TMS-HEMA) through the living anionic process. In addition, the silyl group was readily removed by treatment of the beads with a weak acid to afford the corresponding well-defined poly(methacrylate) having a hydroxyethyl group in the side chain (PHEMA). The hydroxyl group of the immobilized PHEMA on the beads was successfully acetylated to give poly(2-acetoxyethyl methacrylate), which could be quantitatively isolated from the beads by trifluoroacetic acid treatment. Moreover, the hydroxyl group of the immobilized PHEMA could be utilized as an initiator for acid promoted ring opening polymerization of lactone to yield the corresponding graft copolymer. In this method, the residual and excess reagents could be removed by filtration, which demonstrated the applicability of the present technique to a novel method for construction of functional polymers. (C) 2004 Wiley Periodicals, Inc. - S Motokucho; A Sudo; F Sanda; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 42 10 2506 - 2511 2004年05月 [査読有り]
A novel branched polycarbonate with a hydroxyl group at the chain end was synthesized by the copolymerization of glycidol with carbon dioxide (CO,). The copolymerization was carried out with 5 mol % of an alkali metal halide or quaternary ammonium salt as a catalyst under atmospheric CO2. The obtained poly(glycidol-co-carbon dioxide) was O-benzoylated and O-silylated, and the corresponding polymers were analyzed with IR, size exclusion chromatography, C-13 NMR, and Si-29 NMR. The IR spectroscopy analysis of the O-benzoylated polymer revealed that the maximum incorporation degree of the carbonate group was 90% (i.e., the CO2/glycidol composition ratio was 0.9:1.0). The incorporation of CO, as a carbonate unit was also confirmed by the treatment of this polymer with n-butylamine, which caused the aminolysis of the carbonate and led to degraded products. (C) 2004 Wiley Periodicals, Inc. - A Sudo; Y Morioka; F Sanda; T EndoTETRAHEDRON LETTERS 45 7 1363 - 1365 2004年02月 [査読有り]
Al-Tosvlaziridine was found to be a useful substrate for cycloaddition reaction with carbon dioxide. The reaction was successfully catalyzed by lithium bromide under atmospheric pressure to give the corresponding five-membered cyclic urethane, N-tosyl-1,3-oxazolidin-2-one. selectively. It was found that electron-donating nature of the substituent at 2-position of N-tosylaziridine accelerated the reaction, and this tendency allowed Lis to estimate the reaction mechanism. (C) 2003 Elsevier Ltd. All rights reserved. - A Sudo; K Kataoka; F Sanda; T EndoMACROMOLECULES 37 2 251 - 253 2004年01月 [査読有り]
- A Sudo; Y Morioka; E Koizumi; F Sanda; T EndoTETRAHEDRON LETTERS 44 43 7889 - 7891 2003年10月 [査読有り]
Cycloaddition of aziridine with carbon dioxide was successfully catalyzed by alkali metal halide or tetraalkylammonium halide to give the corresponding 5-membered cyclic urethane, 1,3-oxazolidin-2-one, selectively. The reaction can be performed at ambient temperature under atmospheric pressure. Analoguous reaction of aziridine with carbon disulfide also successfully gave the corresponding 5-membered cyclic dithiourethane, 1,3-thioxazolidine-2-thione. (C) 2003 Published by Elsevier Ltd. - D Nagai; A Sudo; T EndoMACROMOLECULES 36 9 3061 - 3065 2003年05月 [査読有り]
Copolymerization of ethylphenylketene with benzaldehyde by butyllithium proceeded in a perfect 1:1 alternating manner to afford the corresponding polyester, of which the repeating unit has two adjacent chiral centers. The relative stereochemistry between these two chiral centers was controlled by solvents (tetrahydrofuran or toluene) and additives such as (-)-sparteine or diethylzinc, and the resulting diastereoselectivity, erythro-configuration:threo-configuration, was controlled in a range of 80:20 to 12:88. These diastereomeric ratios were determined by HPLC analysis of the diols, which were obtained by reductive degradation of the polyester with maintaining the configuration of the repeating unit. The more polar diol was converted to the corresponding cyclic carbonate, and a single crystal of it was successfully analyzed by X-ray crystallography to determine its configuration as a threo one. The threo-rich polymer was less soluble, more thermally degradable, and denser than the erythro-rich polymer. - M Tanaka; A Sudo; F Sanda; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 41 6 853 - 860 2003年03月 [査読有り]
A samarium enolate, supported on a crosslinked polystyrene resin, successfully initiated the living anionic polymerization of allyl methacrylate (AMA) to afford the corresponding poly(AMA) with well-controlled molecular weights. Diblock, triblock, and tetrablock copolymerizations with methyl methacrylate (MMA) were also successfully performed. The formed polymers, supported on the resin by a benzyl ester linker, were quantitatively isolated from the resin by selective cleavage of the linker with trifluoroacetic acid (TFA). Allyl ester in the side chain was not affected by this isolation step. The allyl group of the immobilized poly(AMA-b-MMA) on the resin was transformed into a 2,3-dihydroxypropyl group by osmium oxidation. The resulting copolymer was isolated by TFA treatment of the resin, and it showed amphiphilicity. In both the polymerization and side-chain modification, the formed polymers were easily washed from excess reagents only by filtration, and this demonstrated the feasibility of the automated synthesis of functional polymers based on this solid-supported polymerization technique. (C) 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 853-860, 2003. - F Sanda; T Kaizuka; A Sudo; T EndoMACROMOLECULES 36 4 967 - 968 2003年02月 [査読有り]
- A Sudo; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 41 1 116 - 118 2003年01月 [査読有り]
- A Sudo; R Iinuma; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 40 20 3455 - 3459 2002年10月 [査読有り]
- A Sudo; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 40 18 3103 - 3111 2002年09月 [査読有り]
End-capping reactions of a living polyester, obtained by anionic polymerization of ethylphenylketene (EPK), were carried out. As end-capping reagents, electrophiles such as alkyl halide and acyl halide were successfully used. Reactivity of the terminal enolate and the resulting terminal structures were elucidated by model reactions, using lithium enolates having low molecular weights, obtained by an equimolar reaction of EPK with butyllithium. Polymerization of EPK by lithium alkoxide and the subsequent clad-capping reaction afforded the corresponding polyester having functional groups at both chain ends and a narrow molecular weight distribution. (C) 2002 Wiley Periodicals, Inc. - Tanaka, M; Sudo, A; Sanda, F; Endo, TMacromolecules 35 18 6845 - 6850 2002年08月 [査読有り]
Aldol-type reactions of a samarium enolate at the propagating end of living anionic poly-(MMA) with aldehydes were carried out. The enolate underwent aldol-type end-capping reaction with 3-phenylpropanal to give the corresponding samarium alkoxide at the polymer terminal. Successive treatment of the alkoxide with benzoyl chloride resulted in its benzoylation. End-capping reaction with 2-phenylpropanal also smoothly proceeded to give the poly(MMA) having the corresponding secondary alkoxide at the terminal. Its benzoylation was not successful; however, an intramolecular reaction of the terminal alkoxide with the methyl ester moiety of the penultimate MMA unit predominantly proceeded to give the corresponding poly(MMA) having a lactone moiety at its terminal. In addition, a terminal samarium enolate of a living poly(MMA), which was supported on polystyrene beads by a benzoyl ester-type linker, reacted with the aldehydes to afford the end-capped poly(MMA), which could be efficiently isolated from the beads by selective cleavage of the linker by trifluoroacetic acid treatment. - D Nagai; H Kuramoto; A Sudo; F Sanda; T EndoMACROMOLECULES 35 16 6149 - 6153 2002年07月 [査読有り]
Anionic copolymerization of ethylphenylketene (EPK) with 4-(tert-butyldimethylsilyloxy)benzaldehyde (SiO-BA) was carried out using butyllithium as an initiator in THF at -40 degreesC. The copolymerization proceeded via 1:1 alternation, generating the corresponding polyester having silyl protected phenol moiety in the side chain quantitatively. By addition of lithium chloride to the polymerization system, the polymerization proceeded in a living fashion to afford the corresponding polyester having narrow molecular weight distribution (M-w/M-n < 1.2). Treatment of the obtained polymer with tetrabutylammonium fluoride in the presence of acetic acid resulted in complete removal of the silyl group without main chain degradation to afford polyester having phenol moiety, which was soluble in methanol. Thermal degradability of the polyester with phenol moiety Was considerably higher than that of the silyl-protected polymer, suggesting that the acidity of the phenol moiety would promote thermal dissociation of the polyester main chain. - A Sudo; Y Iitaka; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 40 11 1912 - 1917 2002年06月 [査読有り]
- S Motokucho; A Sudo; F Sanda; T EndoCHEMICAL COMMUNICATIONS 17 17 1946 - 1947 2002年 [査読有り]
A polymer having a trithiocarbonate moiety in the main chain was applied as a polymeric precursor to the synthesis of a sequence ordered polymer by insertion polymerization of styrene into the main chain by a RAFT mechanism. - A Sudo; M Sato; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 39 21 3789 - 3796 2001年11月 [査読有り]
A polymer with a 2-azetidinone moiety in its main chain was efficiently synthesized by [2 + 2] cycloaddition of bisimine with bisketene. The bisketene was easily prepared by dehydrochlorination of the corresponding dicarboxylic acid chloride and was used without purification. The treatment of the obtained polymer with lithium aluminum hydride resulted in a reductive ring-opening reaction of the 2-azetidinone moiety in the main chain that gave the corresponding linear polyamine with hydroxymethyl side chains. (C) 2001 John Wiley & Sons, Inc. - D Nagai; A Sudo; F Sanda; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 39 13 2078 - 2084 2001年07月 [査読有り]
A living anionic alternating copolymerization of ethylphenylketene (EPK) with 4-methoxybenzaldehyde (MBA) was achieved. When n-butyllithium was added to a mixture of EPK and MBA in tetrahydrofuran at -40 degreesC in the presence of an excess amount of lithium chloride, the copolymerization of these monomers proceeded via complete 1:1 alternating manner to afford the polymer with a narrow molecular weight distribution. A linear relationship was observed between the molecular weight and the monomer/initiator ratio, keeping a narrow molecular weight distribution. The structure of the obtained polymer was determined to be a polyester by IR spectroscopy together with the reductive degradation of the polymer by lithium aluminum hydride, which quantitatively afforded the corresponding diol to the repeating unit of the expected polyester structure. Both conversions of EPK and MBA agreed to a first-order kinetic equation with linear evolution between the molecular weight and conversion. These observations along with the successful results in two-stage polymerization indicate that the present copolymerization proceeded through a living mechanism. (C) 2001 John Wiley & Sons, Inc. - A Sudo; S Uchino; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 39 13 2093 - 2102 2001年07月 [査読有り]
Novel ketenes, (4-chlorophenyl)ethylketene and (4-bromophenyl)ethylketene, were synthesized by dehydrochlorination of 2-(4-halophenyl)butanoyl chlorides, and their anionic polymerizations by lithium (4-methoxyphenoxide) in tetrahydrofuran at -20 degreesC were carried out to afford the corresponding polyesters with narrow molecular weight distributions (weight-average molecular weight/number-average molecular weight < 1.3) quantitatively. Polymerizations with various feed ratios afforded the corresponding polyesters with predictable molecular weights and narrow molecular weight distributions. Kinetic studies of the polymerizations at -78 degreesC revealed that the polymerization rates were apparently larger than that of ethylphenylketene, which is considered to be responsible for the enhanced electrophilicities of the monomers via the introduction of electron-negative halogen atoms. Monomer conversion agreed with the first-order kinetic equation. These results strongly support the living mechanism of this polymerization. The obtained polyesters were modified by a palladium-catalyzed coupling reaction of the side-chain 4-halophenyl group with 4-methoxyphenylboronic acid, demonstrating their potential as reactive polymers. (C) 2001 John Wiley & Sons, Inc. - A Sudo; S Uchino; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 39 10 1596 - 1600 2001年05月 [査読有り]
A novel ketene, ethyl(4-methoxyphenyl)ketene (EMPK), was synthesized by the dehydrochlorination of 2-(4-methoxyphenyl)butanoyl chloride. The anionic polymerizations of EMPK by butyllithium in tetrahydrofuran at -20 degreesC were carried out with a varying feed ratio to give the corresponding polyesters having predictable molecular weights and narrow molecular weight distributions, quantitatively. The selective formation of the polyester was confirmed by IR analysis, and the reductive degradation of the polymer was supported by lithium-aluminium hydride. The second feed of the monomer (after the first stage of polymerization) resulted in the formation of the polymer with the expectedly increased molecular weight and low polydispersity to strongly support the living mechanism of this polymerization. (C) 2001 John Wiley & Sons, Inc. - Gao, X; A Sudo; Y Nakamura; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 39 6 800 - 806 2001年03月 [査読有り]
A tetrahydrofuran (THF)-containing network polymer was prepared by the radical suspension copolymerization of a styrene (St)-type monomer with THF moiety, St, p-chloromethylstyrene, and divinylbenzene in a biphasic medium consisting of water and monochlorobenzene in the presence of acacia gum as a suspension stabilizer. The diameters of the obtained polymer beads ranged from 100 to 200 mum. The obtained network polymer showed higher swelling abilities in various organic solvents than a similarly prepared network polymer without THF moiety, and it was stable under oxidative, reductive, and basic conditions. In its derivations to polystyrene-based resins with thioether alcohol and hydroxyl moiety, remarkable accelerations of reactions were observed as a result of the introduction of THF moiety. (C) 2001 John Wiley & Sons, Inc. - Gao, X; A Sudo; Y Nakamura; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 39 6 800 - 806 2001年03月 [査読有り]
A tetrahydrofuran (THF)-containing network polymer was prepared by the radical suspension copolymerization of a styrene (St)-type monomer with THF moiety, St, p-chloromethylstyrene, and divinylbenzene in a biphasic medium consisting of water and monochlorobenzene in the presence of acacia gum as a suspension stabilizer. The diameters of the obtained polymer beads ranged from 100 to 200 mum. The obtained network polymer showed higher swelling abilities in various organic solvents than a similarly prepared network polymer without THF moiety, and it was stable under oxidative, reductive, and basic conditions. In its derivations to polystyrene-based resins with thioether alcohol and hydroxyl moiety, remarkable accelerations of reactions were observed as a result of the introduction of THF moiety. (C) 2001 John Wiley & Sons, Inc. - Gao, X; A Sudo; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 39 4 453 - 458 2001年02月 [査読有り]
A method to control the copolymer composition in suspension polymerizations of monomers with different polarity was studied: the copolymerization of a styrene-type monomer having THF moiety (1) with styrene (feed ratio 1 : 1) was carried out at 85 degreesC using benzoyl peroxide (BPO) in a suspension system consisting of water and monochlorobenzene. The copolymerization was greatly affected by a mixture ratio of suspension system, and when the H2O : PhCl ratio was 7 : 1 (v/v), 1 and St were consumed almost at the same rate, which suggested the formation of a random copolymer with uniform composition. The copolymer was proven to have an identical structure as expected, and a composition ratio of 1 : 1 by H-1 NMR analysis and elemental analysis. (C) 2001 John Wiley & Sons, Inc. - Nagai, D; Sudo, A; Sanda, F; Endo, TJ. Network Polym., Jpn. 22 25 - 30 2001年 [査読有り]
- A Sudo; K Igarashi; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 38 23 4200 - 4205 2000年12月 [査読有り]
- Gao, X; A Sudo; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 38 14 2536 - 2542 2000年07月 [査読有り]
A series of novel polyesters containing dioxane moieties in their main chains were synthesized by the bulk polycondensation of trans-2,5-bis-(hydroxymethyl)-1,4-dioxane with various aliphatic dicarboxylic acid chlorides. The obtained polyesters, analyzed by differential thermal analysis, possessed crystallinity, the melting point of which exhibited a weak odd- even effect on the methylene unit number and a small decreasing trend with an increase in the methylene unit number. These properties were compared with those of similar polyesters bearing cyclohexane moieties, and it was found that the rigidity of the dioxane moiety plays an important role in enhancing the effective packing of the corresponding polymers. (C) 2000 John Wiley & Sons, Inc. - A Sudo; S Uchino; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 38 7 1073 - 1082 2000年04月 [査読有り]
A living polymerization of ethylphenylketene (EPK) was accomplished. When polymerization of EPK was carried out with butyllithium as an initiator in tetrahydrofuran (THF) at -20 degrees C, EPK was completely consumed within 5 min, and the corresponding polyester with narrow molecular weight distribution (M-w/M-n similar to 1.1) was obtained almost quantitatively. Kinetic study of the polymerization at -78 degrees C revealed that conversion of EPK agreed with the first-order kinetic equation, and that M-n of the polymer increased in virtually direct proportion to the conversion. Along with these results, successful results in postpolymerization at -20 degrees C strongly supported living mechanism of the present polymerization. Further, lithium alkoxides having a methoxy group, styryl moiety, and nitroxyl radical, also successfully initiated polymerization of EPK to afford the corresponding polymers having functional initiating ends. In the polymerization with varying feed ratio [EPK](o)/[initiator](o), the linear relationship between the feed ratio and M-n of the obtained polymer was observed, while maintaining narrow M-w/M-n. (C) 2000 John Wiley & Sons, Inc. - M Tanaka; A Sudo; F Sanda; T EndoCHEMICAL COMMUNICATIONS 24 2503 - 2504 2000年 [査読有り]
A resin-supported samarium enolate successfully initiated the living anionic polymerization of methacrylates to afford the corresponding homopolymer as well as block copolymer with well-controlled molecular weights, which could be quantitatively isolated from the resin, so demonstrating the applicability of the present technique for solid supported construction of macromolecular architectures. - A Sudo; K Nishimura; Y Nakamura; T EndoJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 37 24 4483 - 4486 1999年12月 [査読有り]
- A Sudo; S Uchino; T EndoMACROMOLECULES 32 5 1711 - 1713 1999年03月 [査読有り]
- A Sudo; T EndoMACROMOLECULES 31 22 7996 - 7998 1998年11月 [査読有り]
- 西郷 和彦; 須藤 篤; 橋本 幸彦有機合成化学協会誌 56 5 386 - 394 1998年05月 [査読有り]
In recent years, the development of chiral auxiliaries has been attracting much attention. Although many of these are usually derived from natural chiral compounds, limitations in their structural modification are sometimes an obstacle to achieve an efficient asymmetric process. This problem would be solved by using non-natural chiral compounds due to their two favorable characteristics in contrast to natural products and their derivatives: 1) Both enantiomers are readily available and can be used in asymmetric reactions. 2) The structure can be freely designed. In the preparation of well-designed, non-natural chiral auxiliaries, the optical resolution of their racemic modifications is thought to be one of the most practical methods. In this context, the development of an efficient method for the optical resolution of a racemic modification is considered to be essential. We have been carrying out a study which was coherent with the design, optical resolution, and application of non-natural chiral auxiliaries. In this review we would like to describe our recent results concerning the development of new non-natural chiral auxiliaries as well as their application to asymmetric syntheses. - A Sudo; H Yoshida; K SaigoTETRAHEDRON-ASYMMETRY 8 19 3205 - 3208 1997年10月 [査読有り]
Enantiopure 2-[2-(diphenylphosphino)phenyl] oxazoline, derived from a nonnatural amino alcohol, cis-2-amino-3,3-dimethyl-1-indanol, was found to be an efficient ligand for the rhodium-catalyzed enantioselective hydrosilylation of ketones. (C) 1997 Elsevier Science Ltd. - A Sudo; K SaigoJOURNAL OF ORGANIC CHEMISTRY 62 16 5508 - 5513 1997年08月 [査読有り]
A chiral amino alcohol, cis-2-amino-3,3-dimethyl-1-indanol (2), was converted into the corresponding enantiomerically pure phosphorus-containing oxazoline 4. Oxazoline 4 was found to be an efficient ligand for palladium-catalyzed enantioselective allylic amination reactions: In the amination reaction of (E)-1,3-diphenyl-2-propen-1-yl acetate (7a), 4 was found to be more efficient than the similar ligands 1a-c, derived from valinol, tert-leucinol, etc. Other 1,3-bis(p-substituted aryl)-2-propen-1-yl acetates were also converted to the corresponding amines in a similar manner and with excellent enantioselectivity. In the amination reaction of 1-alkyl-3,3-diphenyl-2-propen-1-yl acetates 11, the correponding amines 12 were obtained with excellent enantioselectivity when acetic acid was added to the reaction system. - A Sudo; K SaigoCHEMISTRY LETTERS 1 97 - 98 1997年 [査読有り]
The chiral oxazolidinone, derived from cis-2-amino-3,3-dimethyl-1-indanol, was found to be an efficient chiral auxiliary in the asymmetric Diels-Alder reaction. - K Saigo; Y Hashimoto; K Kinbara; A SudoPROCEEDINGS OF THE INDIAN ACADEMY OF SCIENCES-CHEMICAL SCIENCES 108 6 555 - 573 1996年12月 [査読有り]
The review describes the mechanism of chiral discrimination of racemic amines upon crystallization and the induction of chirality in organic reactions by using them as chiral auxiliaries. In order to form conglomerates, which can be resolved into the two enantiomers upon alternative seeding, both formation and packing of 2(1)-columns are essentially very important. On the other hand, in order to achieve high efficiency in resolution through diastereomeric salt formation, which is the most practical method, one of a pair of diastereomeric salts derived from a racemic amine and an enantiomerically pure resolving agent should at least have two 2(1)-columns and planar boundary surfaces in its crystal structure. On the basis of this knowledge, we developed several artificial chiral auxiliaries such as erythro-2-amino-1,2-diphenylethanol, cis-2-amino-1-acenaphthenol, and cis-2- amino-3,3-dimethyl-1-indanol. These were found to be very efficient chiral auxiliaries in asymmetric inductions: alkylation of chiral imines, catalytic borane-reduction, and alkylation of chiral N-acylated oxazolidinone. - A Sudo; K SaigoTETRAHEDRON-ASYMMETRY 7 10 2939 - 2956 1996年10月 [査読有り]
The chiral amino alcohol, cis-2-amino-3,3-dimethyl-1-indanol was synthesized and resolved. Its oxazolidinone derivative was found to be a highly efficient chiral auxiliary in diastereoselective alkylation, acylation, bromination, and hydroxylation reactions. Copyright (C) 1996 Elsevier Science Ltd - K Saigo; Y Hashimoto; A SudoZHURNAL ORGANICHESKOI KHIMII 32 2 249 - 258 1996年 [査読有り]
- A SUDO; K SAIGOTETRAHEDRON-ASYMMETRY 6 9 2153 - 2156 1995年09月 [査読有り]
The chiral amino alcohol, cis-2-amino-3,3-dimethyl-1-indanol was synthesized and resolved. Its oxazolidinone derivative was found to be a highly efficient chiral auxiliary in an asymmetric alkylation reaction. - A SUDO; M MATSUMOTO; Y HASHIMOTO; K SAIGOTETRAHEDRON-ASYMMETRY 6 8 1853 - 1856 1995年08月 [査読有り]
The chiral amino alcohol, cis-2-amino-1-acenaphethenol, was resolved via its (R)-2-phenylpropionic acid salt. This amino alcohol was used as the precursor of a chiral oxazaborolidine, which was an efficient chiral catalyst in the asymmetric reduction of prochiral ketones. - Y HASHIMOTO; K TAKAOKI; A SUDO; T OGASAWARA; K SAIGOCHEMISTRY LETTERS 3 235 - 236 1995年03月 [査読有り]
The chiral imines prepared from an artificial chiral auxiliary, erythro-2-amino-1,2-diphenylethanol, and various aldehydes, reacted with organolithium reagents to give the corresponding chiral amines with excellent diastereofacial selectivity. - A SUDO; Y HASHIMOTO; H KIMOTO; K HAYASHI; K SAIGOTETRAHEDRON-ASYMMETRY 5 7 1333 - 1346 1994年07月 [査読有り]
The chiral amino alcohol, cis-2-amino-1-acenaphthenol, was synthesized, and resolved by a simple procedure. This new chiral amino alcohol was converted into an oxazoline derivative and applied as a chiral auxiliary to the diastereoselective [2,3]-Wittig rearrangement. - S SHIMADA; Y HASHIMOTO; A SUDO; M HASEGAWA; K SAIGOJOURNAL OF ORGANIC CHEMISTRY 57 26 7126 - 7133 1992年12月 [査読有り]
The Lewis acid-promoted reactions of 2,2-dialkoxycyclopropanecarboxylic esters 4a-c with aldehydes and unsymmetrical ketones to give gamma-lactones were investigated. TiBr, is an excellent catalyst and gives cis 3,4-substituted gamma-lactones in good yields with high diastereoselectivity. SnBr4 promotes the reaction of 4a-c with aldehydes with high cis-selectivity, but does not promote the reaction of 4a with unsymmetrical ketones. ZrCl4 is moderately trans-selective in the reaction of 4a with aldehydes, while being moderately cis-selective in the reaction of 4a with unsymmetrical ketones. Cis-gamma-lactones can be converted into their trans-isomers by treatment with NaOEt in EtOH. - Shimada, S; Saigo, K; Abe, M; Sudo, A; Hasegawa, MChem. Lett. 8 8 1445 - 1448 1992年08月 [査読有り]
In the presence of titanium(IV) bromide, N-tosyl aldimines smoothly reacted with ketene bis(trimethylsilyl) acetals at low temperature, and upon esterification anti-beta-amino esters were obtained selectively.
書籍
- Encyclopedia of Polymeric Nanomaterials (Editors: Shiro Kobayashi, Klaus Müllen) Free-Radical Ring-Opening PolymerizationTakeshi Endo; Atsushi Sudo (担当:分担執筆範囲:Free-Radical Ring-Opening Polymerization)Springer 2015年 ISBN: 9783642296475 2676 811-818
- 高分子架橋の反応･構造制御 事例集遠藤 剛; 須藤 篤 (担当:分担執筆範囲:第２章第１節 架橋化合物の分子量、立体構造、配列の制御)技術情報協会 2014年01月 ISBN: 9784861045172 729
- 第７版 化学便覧 応用化学編第Ⅰ分冊須藤 篤 (担当:分担執筆範囲:Ⅱ編第5章3節-8)丸善出版 2014年01月 ISBN: 9784621087596 854 318-319
- 電子部品用 機能性粘着・接着剤須藤 篤 (担当:分担執筆範囲:第5章3節-8)シー・エム・シー出版 2013年08月 ISBN: 9784781308128 269 119-125
- 高分子基礎科学One Point 2 精密重合Ⅱ須藤 篤 (担当:分担執筆範囲:第４章 イオン・配位・開環・逐次重合 pp54-69)共立出版株式会社 2013年03月 ISBN: 9784320044364 138 54-69
- 「高分子の合成」下巻遠藤 剛; 須藤 篤 (担当:分担執筆範囲:第Ⅳ編「開環重合」)講談社サイエンティフィク 2010年04月 ISBN: 9784061543621 915 459-568
- ゲルコントロール－ゲルの上手な作り方とゲル化の抑制遠藤 剛; 須藤 篤 (担当:分担執筆範囲:第５章ゲル化の基礎とその基盤となる重合反応)株式会社 情報機構 2009年06月 ISBN: 9784904080214 685 549-570
- 総説エポキシ樹脂（最近の進歩Ⅰ）遠藤 剛; 須藤 篤 (担当:分担執筆範囲:第２章（硬化剤・硬化触媒・硬化システム）エポキシドの共重合にもとづく新規硬化反応)エポキシ樹脂技術協会 2009年03月 ISBN: 9784990015060 456 43-48
- ＵＶ硬化におけるプロセスの最適化遠藤 剛; 須藤 篤 (担当:分担執筆範囲:17章「モノマー設計による硬化収縮対策」)サイエンス＆テクノロジー株式会社 2008年04月 ISBN: 9784907002411 307 202-208
- 反応性高分子の新展開須藤 篤; 永井 大介; 遠藤 剛 (担当:分担執筆範囲:第５章「易分解性ポリエステルの合成と応用」)シーエムシー出版 2005年05月 ISBN: 4882314983 266 74-85
講演・口頭発表等
- Development of Functional Polymers with the Aid of MALDI-TOF MS [Invited, Invited8] [招待講演]Sudo, A19th Asia-Pacific International Symposium on Microscale Separations and Analysis 2023 (APCE 2023), Kuala Lumpur Convention Centre, Malaysia 2023年10月
- 米糠成分myo-イノシトールを原料とするエポキシ樹脂の開発 [招待講演]須藤 篤技術情報協会セミナー 2023年08月 公開講演，セミナー，チュートリアル，講習，講義等
- 高分子合成と反応(2)−各重合法の特徴、高分子の構造制御、高分子反応− [招待講演]須藤 篤第57回高分子の基礎と応用講座 2023年06月 公開講演，セミナー，チュートリアル，講習，講義等
- Reductive Coupling Polymerization of Dialdehydes and Diimines Driven by Visible Light Irradiation [Poster]Sudo, A; Tanaka, H; Yoneda; M; Ayabe, SAdvanced Polymers via Macromolecular Engineering 2023 2023年04月
- 高分子化学再入門～モノマーの構造と重合法の関係～ [招待講演]須藤 篤情報機構セミナー 2023年03月 公開講演，セミナー，チュートリアル，講習，講義等
- 米糠成分イノシトールを原料とするエポキシ樹脂の開発 [招待講演]須藤 篤エポキシ樹脂技術協会 第45回公開技術講座 2022年08月 口頭発表（招待・特別）
- エポキシ樹脂 [招待講演]須藤 篤日本接着学会 第25回接着入門講座 「接着の科学と技術～接着原理・表面処理から原材料の基礎まで～」 2022年07月 公開講演，セミナー，チュートリアル，講習，講義等
- 米糠成分myo-イノシトールを原料とする高分子合成 [招待講演]須藤 篤接着・接合技術コンソーシアム 第15回企業ワークショップ（産業技術総合研究所） 2021年12月 口頭発表（招待・特別）
- 天然化合物myo-イノシトールを用いた高分子合成 [招待講演]須藤 篤日本接着学会西部支部 第１回西部支部講演会 2021年07月 口頭発表（招待・特別）
- Polyion Complexation of Phytic Acid and Polyamines [Invited, OSM4] [招待講演]Sudo, Ath Asian Conference on Coordination Chemistry 2019 (ACCC7 2019), Putra World Trade Centre, Kuala Lumpur 2019年10月
- ADMET Polymerization of Divinyl Compounds Bearing Rigid Skeletons Derived from Naturally Occurring myo-Inositol [Poster, 7P-T1-031a]Akiyama, S; Tsumura, A; Sudo, AThe 12th SPSJ International Polymer Conference (IPC2018), Hiroshima 2018年12月
- Synthesis of Polymers Bearing Rigid Diamantane-like Components from Naturally Occurring myo-Inositol [Poster, 7P-T1-043a]Ikeya, K; Okamoto, S; Sudo, AThe 12th SPSJ International Polymer Conference (IPC2018), Hiroshima 2018年12月
- Synthesis of Ladder Polymers by Polycondensation of myo-Inositol-derived Tetrasilylethers with Diketones [Poster, 7P-T1-042b]Matsumoto, Y; Kirimura, S; Sudo AThe 12th SPSJ International Polymer Conference (IPC2018), Hiroshima 2018年12月
- Development of Rigid Rod-like Polymers from Naturally Occurring myo-Inositol [Oral, 6E03]Sudo, A; Kirimura, S; Okamoto, S; Ikeya, KThe 12th SPSJ International Polymer Conference (IPC2018), Hiroshima 2018年12月
- 米糠成分myo-イノシトールを原料とする高分子合成 [招待講演]須藤 篤和歌山化学交流会 2018年10月 公開講演，セミナー，チュートリアル，講習，講義等
- 高分子合成と反応（２）各重合法の特徴、高分子の構造制御、高分子反応 [招待講演]須藤 篤第52回高分子の基礎と応用講座 2018年06月 公開講演，セミナー，チュートリアル，講習，講義等 高分子学会関西支部
- エポキシ樹脂の反応機構と耐熱性向上 [招待講演]須藤 篤エポキシ樹脂の高耐熱化技術 2018年02月 公開講演，セミナー，チュートリアル，講習，講義等 技術情報協会
- 米糠成分myo-イノシトールを原料とする高性能高分子の開発 [招待講演]須藤 篤高分子同友会・関西勉強会 2018年01月 公開講演，セミナー，チュートリアル，講習，講義等 大阪YMCA 高分子同友会
- 高分子合成と反応（２） ―各重合法の特徴、高分子の構造制御、高分子反応― [招待講演]須藤 篤第52回高分子の基礎と応用講座 2017年06月 公開講演，セミナー，チュートリアル，講習，講義等 花王株式会社大阪事業所 高分子学会関西支部
- Development of High Performance Polymers from Naturally Occurring Myo-Inositol [通常講演]須藤 篤The 12th International Conference on Advanced Polymers via Macromolecular Engineering (APME2017) 2017年05月 口頭発表（一般）
- エポキシ樹脂の反応機構 [招待講演]須藤 篤エポキシ樹脂技術協会 定例講演会 2017年04月 公開講演，セミナー，チュートリアル，講習，講義等 大阪市立工業研究所 エポキシ樹脂技術協会
- エポキシ樹脂の反応機構 [招待講演]須藤 篤次世代接着材料研究会PartⅥ 第１回例会 2016年06月 公開講演，セミナー，チュートリアル，講習，講義等 積水化学工業株式会社 京都研修センター 日本接着学会 次世代接着材料研究会
- myo-イノシトールを出発原料とするネットワークポリマーの合成 [招待講演]須藤 篤高分子学会「精密ネットワークポリマー研究会-接着と塗装研究会 合同研究会」 2014年11月 口頭発表（招待・特別） 東京理科大学森戸記念館
- 天然の環状化合物を原料とする高性能高分子の開発 [招待講演]須藤 篤高分子学会「第82回高分子若手研究会[関西]」 2014年07月 公開講演，セミナー，チュートリアル，講習，講義等 六甲YMCA
- 開環重合による新規高分子材料の設計と応用 [招待講演]須藤 篤未踏科学技術協会「未踏科学サマー道場」 2013年08月 公開講演，セミナー，チュートリアル，講習，講義等 湘南国際村センター
- RAFT重合法に基づく末端官能基化ポリマーの精密合成 [招待講演]須藤 篤日本接着学会「次世代接着材料研究会」 2010年04月 公開講演，セミナー，チュートリアル，講習，講義等 大阪YMCA
- Ring-opening Polymerizations of Cyclic Monomers Derived from Phenols and Their Applicarions [招待講演]須藤 篤The 6th International Workshop on Future Molecular Systems 2009 2009年05月 口頭発表（招待・特別）
- エポキシとラクトンの共重合法の開発と硬化系への応用 [招待講演]須藤 篤東京工業大学理工学部応用化学科講演会 2009年01月 口頭発表（招待・特別） 東京工業大学
- Development of a Novel Alternating Copolymerization and Properties of the Obtained Alternating Copolymers [招待講演]Sudo, A; Endo, TSecond International Conference on Polymer Blends and Composites 2008年09月 口頭発表（招待・特別）
- Development of new copolymerization of epoxide with lactone-derivatives and its application to synthesis of networked polymers [招待講演]Sudo, A; Endo, TAdvances in Epoxy Chemistry, Materials & Surface Science 2008年08月 口頭発表（招待・特別） University of Limerick
- 超分子系の熱解離挙動に基づくエポキシ硬化系の制御 [招待講演]須藤 篤高分子学会「08-1精密ネットワークポリマー研究会」 2008年04月 公開講演，セミナー，チュートリアル，講習，講義等 東京工業大学
- エポキシ硬化材料のための新規反応系の開発 [招待講演]須藤 篤エポキシ樹脂技術協会「エポキシ樹脂セミナー」 2006年12月 公開講演，セミナー，チュートリアル，講習，講義等 ホテルグランドヒル市谷
- Synthesis and Polymerization of Benzoxazine Derivative [招待講演]Sudo, A; Endo, TBaekeland 2009, Second International Symposium on Thermosets 2006年06月 口頭発表（招待・特別） Antalya, Turkey
- エポキシ硬化のための新規反応系の開発 [招待講演]須藤 篤分子工学研究会「分子工学研究会講演会」 2006年06月 公開講演，セミナー，チュートリアル，講習，講義等 新横浜国際ホテル
- ケテンとアルデヒドの交互共重合によるポリエステルの精密合成 [招待講演]須藤 篤; 遠藤 剛高分子学会中国四国支部「愛媛地区高分子懇話会」 2004年02月 口頭発表（招待・特別） 愛媛大学
- 不溶性担体上での精密重合－高分子合成の新しいツールとして－ [招待講演]須藤 篤; 遠藤 剛高分子学会九州支部「有機材料研究会」 2003年09月 公開講演，セミナー，チュートリアル，講習，講義等 九州大学
MISC
- Takeshi Endo; Atsushi Sudo Biomedicines 8 (9) 2020年09月
- Takeshi Endo; Atsushi Sudo Polymer International 69 (3) 219 -227 2020年03月
- 遠藤剛; 須藤篤 ネットワークポリマー論文集 39 (6) 2018年
- 高野祐樹; 原伸行; 谷口彩乃; 須藤篤; 藤木道也; 今井喜胤 日本化学会春季年会講演予稿集(CD-ROM) 97th ROMBUNNO.3PA‐099 2017年03月
- 遠藤 剛; 須藤 篤 ネットワークポリマー = Journal of network polymer, Japan 38 (1) 29 -38 2017年
- Takeshi Endo; Atsushi Sudo MOLECULES 21 (12) 2016年12月
- 高野祐樹; 北村沙也香; 飼馬康平; 原田拓典; 須藤篤; 藤木道也; 今井喜胤 シンポジウム「モレキュラー・キラリティー」講演要旨集 2015 217 (JA),216 (EN) 2015年06月
- Shuhei Yamada; Atsushi Sudo; Mitsuaki Goto; Takeshi Endo JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 53 (6) 829 -829 2015年03月
- 尼子智之; 中林和輝; 須藤篤; 藤木道也; 今井喜胤 基礎有機化学討論会要旨集 25th 278 2014年08月
- 尼子智之; 須藤篤; 藤木道也; 今井喜胤 光化学討論会要旨集(CD-ROM) 2014 ROMBUNNO.2P036 2014年
- 遠藤 剛; 須藤 篤 川村理研報告 (21) 3 -12 2011年
- 遠藤 剛; 須藤 篤; 古賀 孝一 JSRテクニカルレビュー (117) 1 -8 2010年03月
- 須藤 篤; 遠藤 剛 色材協會誌 81 (12) 531 -533 2008年12月
- Living cationic ring-opening polymerization of five-membered cyclic dithiocarbonate controlled by neighboring group participation of carbamate groupSuguru Motokucho; Atsushi Sudo; Takeshi Endo Annals of The Molecular Engineering Institute Kinki University 8 1 -2 2008年
- A New Series of Cyclic 5-Membered Dithiocarbonates Having Urethane Tether: Application as an Adhesion Promoter to Epoxy-amine Curing System.Atsushi Sudo; Suguru Motokucho; Takeshi Endo Annals of The Molecular Engineering Institute Kinki University 8 1 -2 2007年
- Polymer having a trithiocarbonate moiety in the main chain: application to reversible addition-fragmentation chain transfer controlled thermal and photoinduced monomer insertion polymerizationsSuguru Motokucho; Atsushi Sudo; Takeshi Endo Annals of The Molecular Engineering Institute Kinki University 7 92 -99 2007年
- Synthesis of a novel cyclic 5-membered dithiocarbonate (DTC) having hydroxy group and its application to terminal functionalization of polyurethane.Motokucho, Suguru; Itagaki, Yoshiteru; Sudo, Atsushi; Endo, Takeshi Annals of The Molecular Engineering Institute Kinki University 6 164 -170 2006年
- Cyclic Dithiocarbonate Having Urethane Structure: Synthesis and Application to Polymer SynthesisSuguru Motokucho; Atsushi Sudo; Takeshi Endo 8th SPSJ International Polymer Conference 1 527 -527 2005年
- 須藤 篤; 遠藤 剛 日本接着学会年次大会講演要旨集 37 1 -4 1999年06月
- A Sudo; K Saigo TETRAHEDRON-ASYMMETRY 7 (3) 619 -619 1996年03月
受賞
- 2013年10月 合成樹脂工業協会 第63回ネットワークポリマー講演討論会 学術賞
受賞者: 須藤 篤 - 2007年10月 合成樹脂工業協会 第57回ネットワークポリマー講演討論会 学術奨励賞
受賞者: 須藤 篤
共同研究・競争的資金等の研究課題
- 日本学術振興会：科学研究費助成事業研究期間 : 2021年04月 -2024年03月代表者 : 須藤 篤本研究の最終的な目標は「可視光利用にもとづく高耐熱性高分子の開発」であり、その実現のための手段として、これまで申請者が開発したイミン類の可視光駆動型の還元的カップリング系に着目した。この系は、光レドックス触媒としてペリレンを用いたメタルフリーな反応系であり、申請者が独自に開発したものである。 研究は３つのサブテーマからなり、サブテーマ１では還元的カップリング系をジイミンの反応に適用することでポリアミンを合成すること、サブテーマ２では得られたポリアミンの物性を評価すること、サブテーマ３ではポリアミンの化学修飾による耐熱性向上を検討する。以下、今年度の成果である。 サブテーマ１．昨年度、電子供与性基をもつベンズアルデヒド誘導体から合成したジイミンは、カップリング重合しないという問題が明らかになった。そこで、今年度はその問題を解決を目指した。重合系に酢酸を添加したところ、メチル基やメトキシ基をもつジイミンであっても重付加が進行し、対応するポリアミンを得ることに成功した。 サブテーマ２．昨年度に続き、得られたポリアミンの示差走査熱量測定を行い、それらのガラス転移温度が110～160 ℃と比較的高いことを確認した。 サブテーマ３．今年度から検討を開始した。カップリング重合によって得られる高分子は、その繰り返し単位中に1,2-ジアミン構造をもつことから、アルデヒドとの縮合やホスゲン誘導体との縮合によって5員環構造に誘導できると考えた。そこで、ポリアミンのモデル化合物となる1,2-ジアミンを合成し、アルデヒドとの縮合反応を検討した。その結果，dl体の1,2-ジアミンは反応するものの、meso体は反応しないことが明らかになった。一方、トリホスゲンとの反応は、ジアミンの立体構造の影響を受けることなく効率よく進行することが明らかになった。
- 米糠成分イノシトールを原料とする反応性ラダー高分子の開発科学研究費補助金：基盤研究(C)研究期間 : 2018年04月 -2021年03月代表者 : 須藤 篤
- 米糠成分イノシトールを原料とする剛直棒状かつ主鎖分解性をもつ高分子の開発科学研究費補助金：基盤研究(C)研究期間 : 2015年04月 -2018年03月代表者 : 須藤 篤
- 単糖類を原料とする剛直・易分解性高分子の開発科学研究費補助金：基盤研究(C)研究期間 : 2012年04月 -2015年03月代表者 : 須藤 篤
- 日本学術振興会：科学研究費助成事業研究期間 : 2009年 -2011年代表者 : 遠藤 剛; 須藤 篤; 森野 一英; 古荘 義雄隣接トリカルボニル基を側鎖にもつポリスチレン誘導体を設計・合成した。そのRedox特性を利用した反応を検討する過程において、隣接トリカルボニル基に水やモノアルコールが無触媒下、室温で付加することを見いだした。この付加反応は可逆的であり、これらの付加体を減圧下で加熱すると元の隣接トリカルボニルポリマーが定量的に回収できることもわかった。同様にジオールを用いるとアルコール付加体部位が架橋点となり、各種溶媒に不溶のネットワークポリマーが生成した。一方、このネットワークポリマーをDMSO/H_2O(9/1, v/v)中で撹拌した後、減圧下で加熱して揮発性分を留去することにより、元の隣接トリカルボニルポリマーをほぼ定量的に回収した。
- ケテンとアルデヒドのリビング交互共重合に基づくポリエステルの精密合成科学研究費補助金：基盤研究(C)研究期間 : 2001年04月 -2003年03月代表者 : 須藤 篤
- ケテン類を用いた高歪環状骨格を有する新規機能性高分子の立体選択的合成科学研究費補助金：奨励研究(A)研究期間 : 1999年04月 -2001年03月代表者 : 須藤 篤
- 日本学術振興会：科学研究費助成事業研究期間 : 1999年 -1999年代表者 : 遠藤 剛; 須藤 篤ケテン類の重合について詳細に検討した結果,アルキルリチウムによるエチルフェニルケテンのアニオン重合がリビング的に進行し,対応するポリエステルが定量的に得られることを見出した。得られるポリエステルの分子量はケテンと開始剤の量比によって制御することができ,また分子量分布は1.1程度と狭いものであった。 このリビング性に基づき,種々の官能基を有するリチウムアルコキシドによる開始反応を行ない,重合のリビング活性末端をさまざまな求電子剤を用いてエンドキャッピングすることにより,両末端が官能基化された分子量分布の狭いポリエステルが得られた。 さらにアルコキシ基・クロロ基・ブロモ基によって置換されたフェニル基を有するケテン類のアニオン重合を行なったところ,開始剤としてアルキルリチウムもしくはリチウムアルコキシドを用いることにより重合はリビング的に進行し,対応する分子量分布の狭いポリエステルが得られた。特にブロモフェニル基を有するケテンの重合によって得られたポリエステルは,その側鎖のブロモフェニル基の遷移金属触媒によるカップリング反応によってさまざまな機能性ポリエステルヘと変換することができた。 以上のように,本研究によってケテン類のリビングアニオン重合が達成され,このことにより種々の機能性ポリエステルの精密合成が可能となった。
- 日本学術振興会：科学研究費助成事業研究期間 : 1998年 -1998年代表者 : 遠藤 剛; 須藤 篤ケテン類は,その重合によりカルボニル基もしくはエキソメチレン基を有する高分子を与えることから有用なモノマーとして期待されるが,合成や反応制御が困難なことから重合挙動の詳細な研究は行なわれていない。そこで本研究では,ケテン類の特異な反応性を利用した高分子合成法の開拓の一環として,そのリビング重合の開拓を目的に種々検討を行った。 まず,エチルフェニルケテンの重合を種々の条件下で行なった結果,アルキルリチウムを開始剤として用いることにより重合がリビング的に進行し,エキソメチレン基を有するポリエステルがほぼ定量的に得られることを見出した。本重合のリビング性を利用することにより種々のブロック共重合体の合成も可能である。また,種々の官能基を有するアリールアルキルケテンの重合もリビング的に進行することを見出した。 さらに,ケテン上にシリル基を導入し,そのd^*軌道による成長末端の安定化に基づくリビング重合系を設計した。アルキルリチウムによるシリルケテンのアニオン重合を行なった結果,約5量体のオリゴエステルが得られた。本重合系では高分子量体は得らないものの,得られるオリゴマーの分子量分布は極めて狭いことから,シリル基の導入がケテンの重合反応に対して大きく影響することがわかった。 アリールアルキルケテンおよびシリルケテンは合成および取扱いが容易であり,置換基導入等の自由度が大きい。このような観点からも本研究で開発されたケテン類のリビング重合は,種々の機能性ポリエステルの精密重合法として極めて有用であるといえる。