Mutual relation between microstructure and properties of bacterial copolyesters

细菌共聚酯微观结构与性能的相互关系

• 批准号: 11217205
• 负责人: YOSHIE Naoko
• 金额: $ 8.26万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11217205/
• 关键词: bacterial copolyesters; microstructure; structural transition; in situ observation of crystallization; cocrystallization; 微生物産生ポリエステル; 生分解性ポリマー; 顕微FTIR; ポリマーブレンド; 共結晶化; 結晶相分離; 結晶構造転移; 化学組成分布; 微細構造; 結晶相組成; 生分解ポリマー

Poly [(R)-3-hydroxybutyrate] [PHB] and its copolymers, which are produced from renewable resources by bacterial fermentation, attract widespread interest as biodegradable thermoplastics. In this project, mutual relation between microstructure and properties of bacterial copolyesters were analyzed. Properties of Polymeric materials are correlated with structures of diverse levels from atomic to macroscopic scales, this project was directed toward deep analysis of a copolyester, poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHB-HV), rather than shallow one of various coplyesters. We have achieved the following results.1. A speculer structural transition was found at ca. 10 mol% HV for PHB-HV with narrow chemical composition distribution.2. For PHB-HV with bimodal chemical composition distribution, the phase structure changes from perfect cocrystallization of all the PHB-HV chains, via crystallization of the PHB-HV with high HV content, to phase segregation preceding crystallization with the increase of the difference in the peak positions in composition distribution and/or the decrease of the crystallization temperature. Coincidentally various properties of PHB-HV remarkably changes.3. Through in situ observation of crystallization of PHB-HV with bimodal composition distribution by FTIR microscopy, the formation mechanism of the phases described above was demonstrated.

聚[(R)-3-羟基丁酸酯][PHB]及其共聚物是利用可再生资源通过细菌发酵生产的生物可降解热塑性塑料，引起了广泛的关注。本课题研究了细菌共聚酯的微观结构与性能之间的相互关系。高分子材料的性质与从原子尺度到宏观尺度的不同层次的结构有关，本项目旨在深入分析聚（3-羟基丁酸酯-co-3-羟基戊酸酯）（PHB-HV）共聚聚酯，而不是各种共聚聚酯的浅层分析。我们取得了以下成果：PHB-HV在约10 mol% HV时发生反射性结构转变，化学成分分布较窄。对于化学成分分布为双峰型的PHB-HV，随着成分分布峰位差的增大和/或结晶温度的降低，PHB-HV通过高HV含量的PHB-HV结晶，使PHB-HV各链完美共结晶，而相结构在结晶之前发生了相偏析。巧合的是，PHB-HV的各项性能发生了显著变化。通过FTIR显微镜对具有双峰组成分布的PHB-HV结晶过程的原位观察，论证了上述相的形成机理。

项目成果

N.Yoshie, M.Fujiwara, M.Ohmori, Y.Inoue: "Temperature dependence of cocrystallization and phase segregation in blends of poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate)"Polymer. 42. 8557-8563 (2001)

N.Yoshie、M.Fujiwara、M.Ohmori、Y.Inoue：“聚（3-羟基丁酸酯）和聚（3-羟基丁酸酯-co-3-羟基戊酸酯）共混物中共结晶和相分离的温度依赖性”聚合物。

N.Yoshie Y.Inoue: "Chemical composition distribution of bacterial copolyesters"Int. J. Biol. Macromol.. 25. 193-200 (1999)

N.Yoshie Y.Inoue：“细菌共聚酯的化学成分分布”Int。

T.Watanabe, Y.He, N.Asakawa, N.Yoshie, Y.Inoue: "Hydrogen-bonding interaction between poly(ε-caprolactone) and low molecular weight amino compounds"Polymer Int. 50. 463-468 (2001)

T.Watanabe、Y.He、N.Asakawa、N.Yoshie、Y.Inoue：“聚（ε-己内酯）和低分子量氨基化合物之间的氢键相互作用”Polymer Int. 50. 463-468 (2001)

Y.Wang, S.Yamada, N.Asakawa, T.Yamane, N.Yoshie, Y.Inoue: "Comonomer compositional distribution and thermal and morphological characteristics of bacterial Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)s with high 3-hydroxyvalerate content"Biomacromolecules.

Y.Wang、S.Yamada、N.Asakawa、T.Yamane、N.Yoshie、Y.Inoue：“细菌聚（3-羟基丁酸酯-co-3-羟基戊酸酯）的共聚单体组成分布以及热和形态特征，具有高

M.Saito, Y.Inoue, N.Yoshie: "Cocrystalllization and phase segregation of blend poly (3-hydroxybtyrrate) and poly (3-hydroxybutyrate-co-3-hydroxyvalerate)"Polymer. 42. 5573-5580 (2001)

M.Saito、Y.Inoue、N.Yoshie：“混合聚（3-羟基丁酸酯）和聚（3-羟基丁酸酯-co-3-羟基戊酸酯）的共结晶和相分离”聚合物。