新規置換ポリメチレンの合成とキャラクタリゼ-ション

1991 Fiscal Year Annual Research Report

• Project/Area Number: 01430019
• Research Institution: Osaka City University
• Principal Investigator: 大津 隆行 大阪市立大学, 工学部, 教授 (00046864)
• Co-Investigator(Kenkyū-buntansha): 松本 章一 大阪市立大学, 工学部, 助手 (00183616) ; 圓藤 紀代司 大阪市立大学, 工学部, 講師 (10047409) ; 山田 文一郎 大阪市立大学, 工学部, 助教授 (50047198)
• Keywords: ラジカル重合 / 1,2ー二置換エチレン / フマル酸ジアルキル / Nー置換マレイミド / イタコン酸誘導体 / 剛直高分子 / 熱安定性 / 気体分離膜

Research Abstract

フマル酸ジアルキルの重合では、かさ高い置換基による立体障害が予想されるがポリマ-が得られる。回転セクタ-法、ESRによるラジカルの定量にもとづく方法および生長ラジカルの捕捉による方法で決定した素反応速度定数の絶対値によれば、生長は立体障害により明らかに遅くなるが停止はさらに抑制されるため重合が可能となる。各速度定数は非常に小さな値であるが、ポリマ-ラジカルの定常状態濃度はESRにより容易に検出されるほど高く、生長および停止の速度はビニル重合とあまり変わらない。かさ高い置換基による立体障害は、アゾニトリルを開始剤とする重合で一次ラジカルのモノマ-への付加を遅くするため、かなりの一次ラジカル停止が起こる。また、モノマ-のエステルアルキル基の生長における立体効果は、ポリマ-のタクチシチ-の決定によっても明らかにした。種々のNー置換マレイミドについて置換基の構造と重合の関係を明らかにし、生成ポリマ-のキャラクタリゼ-ションを行なった。Nーアルキルおよびフェニルマレイミドは熱安定性にすぐれ極性溶媒にのみ溶解するポリマ-を生成するが、Nー(oー置換フェニル)マレイミドでは重合性が変わるばかりでなくポリマ-が非極性溶媒にも溶解する。また、Nー長鎖アルキルマレイミドのポリマ-の気体分離膜としての性能を評価し、Toが高く透過速度の大きいことを明らかにした。さらに、Nートリアルキルシリルマレイミドを合成し重合したが、このポリマ-は酸加水分解でポリマレイミドに変換できる。その他の1,2ーに置換エチレンとしてクロトン酸エステル、ケイ皮酸エステル、ソルビン酸エステルなどの重合を行いポリマ-のキャラクタシゼ-ションを行なった。さらに、イタコン酸誘導体の重合による置換ポリメチレンの合成も行なった。

Research Products

• [Publications] A.Matsumoto: "Synthesis and Characterization of Thermally Stable Polymers throguh Anionic Polymerization of tertーButyl Crotonate" Polym.J.23. 211-218 (1991)
• [Publications] B.Yamada: "Spin Trapping of Propagating Radicals Derived from Dialkyl Fumarates" J.Polym.Sci.:Part A:Polym.Chem.29. 637-642 (1991)
• [Publications] J.ーZ.Yang: "Study on Radical Polymerization Reactivity of αーAlkyl βーMethyl Itaconates" Makromol.Chem.,Rapid Commun.12. 205-209 (1991)
• [Publications] T.Otsu: "Increase in Thermal Stability of Vinyl Polymers through Radical Copolymerization with NーCyclohexylmaleimide" Polym.Intnl.25. 179-184 (1991)
• [Publications] B.Yamada: "Effects of Chain Length and Size of Alkyl Group in Redical Polymerization of Dialkyl Fumarate as Studied by Electron Paramagnetic Resonance Spectroscopy" Makromol.Chem.192. 1829-1833 (1991)
• [Publications] T.Otsu: "Radical Polymerization of Itaconic Anhydride and Raaction of the Resulting Polymers with Amines and Alcohols" Polym.Intnl.25. 245-251 (1991)
• [Publications] A.Matsumoto: "Synthesis of Substituted Polymethylenes by Radical Polymerization of N,N,N',N'ーTetraalkylfumaramides and Their Characterization" J.Polym.Sci.:Part A:Polym.Chem.29. 1697-1706 (1991)
• [Publications] A.Matsumoto: "Synthesis of Substituted Polymethylens by Radical Polymerization of Alkyl N,NーDialkylfumarates and Maleamates:Relativei Reactiuity of the Isomers" J.Polym.Sci.:Part A:Polym.Chem.29. 1707-1715 (1991)
• [Publications] A.Matsumoto: "Gas Permeation Behavior through Poly(Nーnーalkylmaleimide)Membranes" Polym.J.23. 1371-1375 (1991)
• [Publications] J.ーZ.Yang: "Terpolymerization Behavior of Citraconic Anhydride,Styrene,and Isobutyl Vinyl Ether" Polym.Bull.26. 509-512 (1991)
• [Publications] B.Yamada: "Contribution of Primary Radical Termination to Radical Polymerization of Diethyl Fumarate Estimated from Absolute Rate Constants" Polym.Bull.26. 543-548 (1991)
• [Publications] T.Otsu: "Synthesis of Alternating Copolymers from NーAlkylcitoraconamides and αーMethylstyrene" Polym.Commun.32. 528-529 (1991)
• [Publications] A.Matsumoto: "Synthesis of Substituted Polymethylene by Radical Polymerization of N,N,N',N'ーTetraethylmaleamide as an Acyclic cisー1,2ーDisubstituted Ethylene" Polym.Commun.32. 530-532 (1991)
• [Publications] A.Matsumoto: "Synthesis and Thermal Properties of Poly(adamantyl Sorbate)" Makromol.Chem.,Rapid Commun.12. 681-685 (1991)
• [Publications] A.Matsumoto: "Synthesis and Radical Polymerization of Adamantylーcontaining Maleic and Fumaric Esters Leading to Formation of Thermally Stable Poly(substituted methylene)s with a Rigid Chain Structure" Chem.Lett.1991. 1361-1364 (1991)
• [Publications] B.Yamada: "Steric Environments of Radicals Produced by Addition of tertーButoxy Radicals to Dialkyl Maleates as Studied by Spin Trapping with 2,4,6ーTriーtertーbutylnitrosobenzene" Makromol.Chem.192. 1931-1940 (1991)
• [Publications] B.Yamada: "Determination of Absolute Rate Constants for Radical Polymerization of Diisopropyl Fumarate Based on a Quantitative Scavenge of Propagating Radical" Polymer. 32. 1892-1896 (1991)
• [Publications] M.Yoshioka: " ^<13>CーNuclear Magnetic Resonance Study on Stereoregularity of Poly(dialkyl fumarate)s Bearing tertーButyl Ester Group" Polymer. 32. 2741-2746 (1991)
• [Publications] M.Yoshioka: "meso and racemo Additions in Propagation for Radical Polymerization of Dialkyl Fumarates.I.Stereoregularity of Poly(dialkyl fumarate)s" Polym.J.23. 1191-1196 (1991)
• [Publications] J.ーZ. Yang: "Alternating Copolymers from Radical Copolymerization of Citraconic Derivatives with Isobutyl Vinyl Ether" Polym.Intnl.26. 63-68 (1991)
• [Publications] J.ーZ.Yang: "Reactivity of Citraconic Anhydride,NーAlkylcitroaconimides,Dialkyl Citraconates and Dialkyl Mesaconates in Radical Copolymerization with Vinyl Acetate and Characterization of the Resulting Copolymers" Europ.Polym.J.27. 1081-1086 (1991)
• [Publications] M.Yoshioka: "meso and racemo Additions in Propagation for Radical Polymerization of Dialkyl Fumarates.II.Determination of the Absolute Rate Constants" Polym.J.23. 1249-1252 (1991)
• [Publications] J.ーZ.Yang: "Radical Copolymerization of Citoraconic Anhydride with Styrene and Terpolymerization of Citraconic Anhydride and Maleic Anhydride with Styrene" Macromolecules. 25. 102-107 (1992)
• [Publications] M.Yoshioka: "Kinetic Studies on the Radical Polymerization of Isopropyl tertーButyl Fumarate Initiated with 2,2'ーAzobis(isobutyronitrile)and Dimethyl 2,2'ーAzobis(isobutyrate):Rates of Addition and Termination of the Primary Radical" Macromolecules. 25. 559-562 (1992)
• [Publications] T.Otsu: "Effect of the Substituents on Radical Copolymerization of Dialkyl Fumarates with Some Vinyl Monomers" J.Polym.Sci.:Part A:Polym.Chem.
• [Publications] A.Matsumoto: "Synthesis of Substituted Polymethylenes from Alkyl Cinnamates Bearing Bulky Alkyl Group" Europ.Polym.J.
• [Publications] T.Otsu: "Synthesis of Substituted Polymethylenes from Acenaphthylene by Radical Polymerization and Copolymerization" J.Appl.Polym.Sci.
• [Publications] A.Matsumoto: "Synthesis and Radical Polymerization of Itaconates Containing an Adamantyl Ester Group" Bull.Chem.Soc.,Jpn.
• [Publications] T.Otsu: "Synthesis and Characterization of Polymers form Itaconic Acid Derivatives" Makromol Chem.,Symp.
• [Publications] B.Yamada: "Elucidation of Steric Effect in Radical Polymerization of Dialkyl Fumarates by Spin Trapping with 2,4,6ーTriーtertーbutylnitrosobenzene" Polymer.
• [Publications] T.Otsu: "Determination of Absolute Rate Constants for Raidcal Polymerization of Dialkyl Itaconates with Various Ester Groups by Electron Spin Resonance Spectroscopy" Macromolecules.
• [Publications] M.Yoshioka: "Kinetic Studies on Radical Polymerization of Dicyclohexyl Fumarate with Azo Initiators" Europ.Polym.J.
• [Publications] T.Otsu: "“Fast"Radical Polymerization of Sterically Hindered Dialkyl Fumarates as 1,2ーDisubstituted Ethylenes"," Macromolecules.
• [Publications] M.Yoshioka: "Reactivity of Primary Radical in Polymeriation of Dialkyl Fumarates Initiated with Dimethyl 2,2'ーAzobisisobutyrate and 2,2'ーAzobisーisobutyrontrile" Macromolecules.
• [Publications] T.Otsu: "Radcial Polymerization of Isoporpyl tertーButyl Fumarate and Maleate,and Characterization of the Resultant Polymers" J.Polym.Sci.:Part A:Polym.Chem.
• [Publications] M.Yoshioka: "Opening Mode in the Propagation of Dialkyl Fumarates and Maleates as 1,2ーDisubstituted Ethylenes in Radical Polymerization" Macromolecules.
• [Publications] T.Otsu: "Radical Polymerization and Copolymerization of Bisl3ーtrisー(trimethylsiloxy)silypropyl) Fumarate" Makromol.Chem.