The Study on Crystallization Behavior of Bacterially Synthesized Copolyesters by High-Resolution Solid-State NMR

高分辨率固体核磁共振研究细菌合成共聚酯的结晶行为

• 批准号: 06651043
• 负责人: INOUE Yoshio
• 金额: $ 1.28万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06651043/
• 关键词: Solid State NMR; Polymer Crystal; Biodegadable Polymer; Copolyester; Copolymer; 固体NMR

In this study, composition dependence of crystallization behavior of some bacterial copolyesters has been studied by high-resolution solid state C-13 NMR,DSC,and polarized microscopy.The crystalline states of bacterial poly (3-hydroxybutyrate-co-4-hydroxybutyrate) (P3HB-4HB) with a wide range of 4HB contents were investigated. It was demostrated that P3HB-4HB can not form isomorphic crystals because of the extent of the structural difference between the 3HB and 4HB units.Crystal isomorphism of chemically synthesized poly (ethylene terephthalate-co-1,4-cyclohexenedimethylene terephthalate) (PET-CHT) was analyzed. It was found that cocrystallization of the both monomer units is realized to some extent for the copolymers with high CHT unit content.The composion distribution of bacterial poly (3-hydroxybutyrate-co-3-hydroxyvalerate) was found to be extremely broad and it attects significantly the crystallization behavior.The solid state structure of bacterial poly (3-hydroxybutyrate-co-3-hydroxypropionate) (P3HB-3HP) with 3HP content ranged from 0 to 37mol% was also studied. It was found that the crystalline region was composed of only the 3HB unit, suggesting that the cocrystallization does not occur in P3HB-3HP.

本文采用固体高分辨C-13 NMR、DSC和偏光显微镜研究了几种细菌共聚酯的结晶行为与组成的关系，并研究了不同4-羟基丁酸酯含量的细菌聚（3-羟基丁酸酯-co-4-羟基丁酸酯）（P3 HB-4 HB）的结晶状态。结果表明，P3 HB-4 HB不能形成同晶型晶体，这是由于3 HB和4 HB结构差异的程度不同所致，并对化学合成的聚对苯二甲酸乙二醇酯-co-1，4-环己烯二亚甲基对苯二甲酸酯（PET-CHT）的晶体同晶性进行了分析。结果表明，当CHT单元含量较高时，两种单体单元在一定程度上实现了共结晶。（3-羟基丁酸酯-co-3-羟基戊酸酯）的结晶范围非常宽，对结晶行为有显著影响。研究了3-羟基丁酸酯-3-羟基丙酸酯共聚物（P3 HB-3 HP），其3-羟基丁酸酯含量为0 ~ 37mol%。结果表明，P3 HB-3 HP的结晶区仅由3 HB单元组成，这表明在P3 HB-3 HP中没有发生共结晶。

项目成果

Masafumi ICHIKAWA: "Morphological Study of Bacterial Poly(3-hydroxybutrate-co-3-hydroxypropionate)" Macromol. Chem. Phys.(印刷中).

Masafumi ICHIKAWA：“细菌聚（3-羟基丁酸酯-co-3-羟基丙酸酯）的形态学研究”Macromol。

Naoko YOSHIE: "NMR Study on Isomorphous Behavior in Random Copolyesters : Poly- (ethyleneterephthalate-co-1,4-cyclohexylenedimethyleneterephthalate)" Polymer. 35. 1931-1935 (1994)

Naoko YOSHIE：“无规共聚酯同晶行为的核磁共振研究：聚（对苯二甲酸乙二醇酯-共-1,4-环己基二亚甲基对苯二甲酸酯）”聚合物。

Masafumi ICHIKAWA: "Morphological Study of Bacterial Poly (3-hydroxybutyrate-co-3-hydroxypropionate)" Macromol.Chem.Phys.

Masafumi ICHIKAWA：“细菌聚（3-羟基丁酸酯-co-3-羟基丙酸酯）的形态学研究” Macromol.Chem.Phys。

Hidenori Satoh: "Hydrolytic Degradation of Blends of Poly(3-hydroxybutyrate)with Poly(3-hydroxybutyrate-co-3-hydroxybutyrate)" POLYMER. 35. 286-290 (1994)

Hidenori Satoh：“聚（3-羟基丁酸酯）与聚（3-羟基丁酸酯-co-3-羟基丁酸酯）共混物的水解降解”聚合物。

Kazuhiro NAKAMURA: "A Structural Study on the Crystalline State of Bacterial Copolyester Poly (3-hydroxybutyrate-co-4-hvdroxybutvrate)" Polymer. 35. 193-197 (1994)

Kazuhiro NAKAMURA：“细菌共聚酯聚（3-羟基丁酸酯-co-4-羟基丁酸酯）结晶状态的结构研究”聚合物。