2003 年度実績報告書

重合時に非収縮性・膨張性を示すナノ材料の設計と合成システムの構築

研究課題

研究課題/領域番号	15350126
研究機関	山形大学
研究代表者	遠藤剛山形大学, 工学部, 教授 (40016738)
研究分担者	金澤昭彦山形大学, 工学部, 助教授 (80272714) 日野哲男山形大学, 大学院・理工学研究科, 助手 (50361275)
キーワード	ナノ材料 / 非収縮 / 膨張 / 三次元構造 / 体積収縮
研究概要	まずスピロオルトカーボナート(SOC)ないしはスピロオルトエステル(SOE)構造を持つビニル型モノマーを設計し、種々のコモノマーとの共重合反応を行うことにより、同構造を側鎖に有するコポリマーを合成し、その架橋反応と体積変化挙動を検討した。具体的には、合成したコポリマー中のコモノマーユニット、架橋基(SOCないしはSOE)、共重合組成比の影響を検討した。結果は以下の通りである。1)SOCの場合にはその重合時の体積膨張性に伴って共重合体中のSOC組成が高いほど架橋反応時の収縮が低減され、SOC組成の高いコポリマーでは膨張性が確認された。また、組成比と体積変化の関係の傾きはコモノマー構造の影響を大きく受けることも明らかとなった。2)SOEの場合にはその重合時の体積非収縮性により、共重合組成比に関わらず架橋時の体積変化が0〜4%程度と常に小さな値を示し、体積非収縮性を発現させるために組成比を厳密にコントロールする必要性がないことが明らかとなった。これにより、架橋体の他の物性をコントロールする上で架橋基以外の要因を主として考慮すれば良いことが分かる。また、SOCの高い体積膨張性に着目し、同構造のみからなるオリゴマーを合成し、その架橋反応についても検討した。このオリゴマーはその剛直な構造に基づいてナノレベルでの高い配向性を示すことから、CHOからなるポリマーとしては非常に高い密度を示す。これが架橋反応によりアモルファス化すると架橋により分子間が共有結合で結合されるにも関わらず、低密度化することが明らかとなった。また、SOC2量体の重合反応前後をSEMで観察したところ、部分的な架橋が進行した際には架橋前に存在した空隙が減少している様子が観察され、上記の現象を支持することができた。

研究成果
(17件)

すべてその他

すべて文献書誌 (17件)

[文献書誌] 山本進一: "Efficient Fixation of Carbon Dioxide into Poly(glycidyl methacrylate) Containing Pendant Crown Ether"Macromolecules. 36. 1514-1521 (2003)
[文献書誌] 須藤篤: "Highly Efficient Fixations of Carbon Dioxide and Carbon Disulfide by Cycloaddition to Aziridine under Atmospheric Pressure"Tetrahedron Letters. 44. 7889-7891 (2003)
[文献書誌] 西田治男: "Effect of Tin on Poly (L-lactic acid) Pyrolysis"Polymer Degradation and Stability. 81. 515-523 (2003)
[文献書誌] 高木幸治: "Allylnickel-Catalyzed Living Coordination Polymerization of Allenes with Ester Functionality"Polymer Bulletin. 50. 335-342 (2003)
[文献書誌] 永井篤志: "Controlled Cationic Ring-Opening Polymerization of 1,3-Oxazolidine-2-thione Derived from L-Seline"Macromolecules. 36. 9335-9339 (2003)
[文献書誌] 高橋栄治: "Photocationic and Radical Polymerizations of Epoxides and Acrylates by Novel Sulfonium Salts"Journal of Polymer Science Part A : Polymer Chemistry. 41. 3816-3827 (2003)
[文献書誌] 高橋栄治: "Novel N-Methylbenzothiazolium Salts as Hardeners for Epoxy and Acrylate Monomers"Journal of Polymer Science Part A : Polymer Chemistry. 41. 3828-3837 (2003)
[文献書誌] Yujiang Fan: "Racemization on Thermal Degradation of Poly (L-lactide) with Calcium Salt and Structure"Polymer Degradation and Stability. 80. 503-511 (2003)
[文献書誌] Yujiang Fan: "Control of Racemization for Feedstock recycling of PLLA"Green Chemistry. 5. 575-579 (2003)
[文献書誌] Yujiang Fan: "Pyrolysis Kunetics of Poly (L-lactide) with Carboxyl Acid and Carcium Salt End Structures"Polymer Degradation and Stability. 79. 547-562 (2003)
[文献書誌] Yujiang Fan: "Thermal Degradation of Poly (L-lactide) : Effect of Alkali Earth Metal Oxides For Selective L,L-Lactide Formation"Polymer. 45. 1197-1205 (2004)
[文献書誌] 須藤篤: "L-Tosylaziridine, A New Substrate for Chemical Fixation of Carbon Dioxide via Ring Expansion Reaction under Atmospheric Pressure"Tetrahedron Letters. 45. 1363-1365 (2004)
[文献書誌] 落合文吾: "Chemical Modification of Novel Alkyne-Containing Polymers Obtained by Radical Polymerization of Conjugated Enynes"Polymer Bulletin. 51. 263-269 (2004)
[文献書誌] 永井篤志: "Synthesis of Optically Active Polyurethane by Self-Polyaddition of Tyrosine Based Monomers"Journal of Polymer Science Part A : Polymer Chemistry. 42. 1143-1153 (2004)
[文献書誌] 山下陽一郎: "Deterionation Behavior of Cellulose Acetate Films in Acidic or Basic Aqueous Solutions"Journal of Applied Polymer Science. 91. 3354-3361 (2004)
[文献書誌] 須藤篤: "Controlled Depolymeization of Poly(5-ethyl-5-phenyl-1,3-dioxan-2-one) : Selective Liberation of Cyclic Carbonate Monomer from Polymer Chain Endo"Macromolecules. 37. 251-253 (2004)
[文献書誌] 遠藤剛: "A Novel Construction of A Reversible Fixation-Release System of Carbon Dioxide by Amidines and Their Polymers"Macromolecules. 37. 2007-2009 (2004)

2003 年度 実績報告書

重合時に非収縮性・膨張性を示すナノ材料の設計と合成システムの構築

研究代表者

遠藤 剛 山形大学, 工学部, 教授 (40016738)

研究成果

[文献書誌] 山本 進一: "Efficient Fixation of Carbon Dioxide into Poly(glycidyl methacrylate) Containing Pendant Crown Ether"Macromolecules. 36. 1514-1521 (2003)

[文献書誌] 須藤 篤: "Highly Efficient Fixations of Carbon Dioxide and Carbon Disulfide by Cycloaddition to Aziridine under Atmospheric Pressure"Tetrahedron Letters. 44. 7889-7891 (2003)

[文献書誌] 西田 治男: "Effect of Tin on Poly (L-lactic acid) Pyrolysis"Polymer Degradation and Stability. 81. 515-523 (2003)

[文献書誌] 高木 幸治: "Allylnickel-Catalyzed Living Coordination Polymerization of Allenes with Ester Functionality"Polymer Bulletin. 50. 335-342 (2003)

[文献書誌] 永井 篤志: "Controlled Cationic Ring-Opening Polymerization of 1,3-Oxazolidine-2-thione Derived from L-Seline"Macromolecules. 36. 9335-9339 (2003)

[文献書誌] 高橋 栄治: "Photocationic and Radical Polymerizations of Epoxides and Acrylates by Novel Sulfonium Salts"Journal of Polymer Science Part A : Polymer Chemistry. 41. 3816-3827 (2003)

[文献書誌] 高橋 栄治: "Novel N-Methylbenzothiazolium Salts as Hardeners for Epoxy and Acrylate Monomers"Journal of Polymer Science Part A : Polymer Chemistry. 41. 3828-3837 (2003)

[文献書誌] Yujiang Fan: "Racemization on Thermal Degradation of Poly (L-lactide) with Calcium Salt and Structure"Polymer Degradation and Stability. 80. 503-511 (2003)

[文献書誌] Yujiang Fan: "Control of Racemization for Feedstock recycling of PLLA"Green Chemistry. 5. 575-579 (2003)

[文献書誌] Yujiang Fan: "Pyrolysis Kunetics of Poly (L-lactide) with Carboxyl Acid and Carcium Salt End Structures"Polymer Degradation and Stability. 79. 547-562 (2003)

[文献書誌] Yujiang Fan: "Thermal Degradation of Poly (L-lactide) : Effect of Alkali Earth Metal Oxides For Selective L,L-Lactide Formation"Polymer. 45. 1197-1205 (2004)

[文献書誌] 須藤 篤: "L-Tosylaziridine, A New Substrate for Chemical Fixation of Carbon Dioxide via Ring Expansion Reaction under Atmospheric Pressure"Tetrahedron Letters. 45. 1363-1365 (2004)

[文献書誌] 落合 文吾: "Chemical Modification of Novel Alkyne-Containing Polymers Obtained by Radical Polymerization of Conjugated Enynes"Polymer Bulletin. 51. 263-269 (2004)

[文献書誌] 永井 篤志: "Synthesis of Optically Active Polyurethane by Self-Polyaddition of Tyrosine Based Monomers"Journal of Polymer Science Part A : Polymer Chemistry. 42. 1143-1153 (2004)

[文献書誌] 山下 陽一郎: "Deterionation Behavior of Cellulose Acetate Films in Acidic or Basic Aqueous Solutions"Journal of Applied Polymer Science. 91. 3354-3361 (2004)

[文献書誌] 須藤 篤: "Controlled Depolymeization of Poly(5-ethyl-5-phenyl-1,3-dioxan-2-one) : Selective Liberation of Cyclic Carbonate Monomer from Polymer Chain Endo"Macromolecules. 37. 251-253 (2004)

[文献書誌] 遠藤 剛: "A Novel Construction of A Reversible Fixation-Release System of Carbon Dioxide by Amidines and Their Polymers"Macromolecules. 37. 2007-2009 (2004)

2003 年度実績報告書

遠藤剛山形大学, 工学部, 教授 (40016738)

[文献書誌] 山本進一: "Efficient Fixation of Carbon Dioxide into Poly(glycidyl methacrylate) Containing Pendant Crown Ether"Macromolecules. 36. 1514-1521 (2003)

[文献書誌] 須藤篤: "Highly Efficient Fixations of Carbon Dioxide and Carbon Disulfide by Cycloaddition to Aziridine under Atmospheric Pressure"Tetrahedron Letters. 44. 7889-7891 (2003)

[文献書誌] 西田治男: "Effect of Tin on Poly (L-lactic acid) Pyrolysis"Polymer Degradation and Stability. 81. 515-523 (2003)

[文献書誌] 高木幸治: "Allylnickel-Catalyzed Living Coordination Polymerization of Allenes with Ester Functionality"Polymer Bulletin. 50. 335-342 (2003)

[文献書誌] 永井篤志: "Controlled Cationic Ring-Opening Polymerization of 1,3-Oxazolidine-2-thione Derived from L-Seline"Macromolecules. 36. 9335-9339 (2003)

[文献書誌] 高橋栄治: "Photocationic and Radical Polymerizations of Epoxides and Acrylates by Novel Sulfonium Salts"Journal of Polymer Science Part A : Polymer Chemistry. 41. 3816-3827 (2003)

[文献書誌] 高橋栄治: "Novel N-Methylbenzothiazolium Salts as Hardeners for Epoxy and Acrylate Monomers"Journal of Polymer Science Part A : Polymer Chemistry. 41. 3828-3837 (2003)

[文献書誌] 須藤篤: "L-Tosylaziridine, A New Substrate for Chemical Fixation of Carbon Dioxide via Ring Expansion Reaction under Atmospheric Pressure"Tetrahedron Letters. 45. 1363-1365 (2004)

[文献書誌] 落合文吾: "Chemical Modification of Novel Alkyne-Containing Polymers Obtained by Radical Polymerization of Conjugated Enynes"Polymer Bulletin. 51. 263-269 (2004)

[文献書誌] 永井篤志: "Synthesis of Optically Active Polyurethane by Self-Polyaddition of Tyrosine Based Monomers"Journal of Polymer Science Part A : Polymer Chemistry. 42. 1143-1153 (2004)

[文献書誌] 山下陽一郎: "Deterionation Behavior of Cellulose Acetate Films in Acidic or Basic Aqueous Solutions"Journal of Applied Polymer Science. 91. 3354-3361 (2004)

[文献書誌] 須藤篤: "Controlled Depolymeization of Poly(5-ethyl-5-phenyl-1,3-dioxan-2-one) : Selective Liberation of Cyclic Carbonate Monomer from Polymer Chain Endo"Macromolecules. 37. 251-253 (2004)

[文献書誌] 遠藤剛: "A Novel Construction of A Reversible Fixation-Release System of Carbon Dioxide by Amidines and Their Polymers"Macromolecules. 37. 2007-2009 (2004)