Competition in Crystallization between Different Components and Formation of Concentric Double Spherulites in Block Copolymers

嵌段共聚物中不同组分之间的结晶竞争与同心双球晶的形成

• 批准号: 09650991
• 负责人: SHIOMI Tomoo
• 金额: $ 2.37万
• 依托单位: Nagaoka University of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09650991/
• 关键词: Crystallization; Spherulite; Concentric circles; Block copolymer; Poly (epsilon-caprolactone); Poly (ethylene glycol); Long spacing

A unique morphology of spherulites, namely double spherulites like concentric circles, was observed for poly(epsilon-caprolactone)-block-poly(ethylene glycol)-block-poly(epsilon-caprolactone) (PCL-PEG-PCL) triblock copolymers, ABA-2 and ABA-3, with PCL compositions of 66 and 60 wt%, respectively. The inside and outside spherulites in the concentric spherulites were those of PCL and PEG, respectively. In formation of the conceniric spherulites, the spherulites of the PCL component first occurred necessarily and grew, and then the PEG spherulite developed from the growth front of the PCL spherulite. Any nucleation of the PEG spherulite prior to that of PCL was not observed. In the triblock copolymers, ABA-1 and ABA-4, with PCL compositions of 83 and 34 wt%, respectively, no concentric spherulites were observed but a usual single spherulite was formed ; in ABA-1 only PCL spherulites was formed while only PEG spherulite was observed in ABA-4. Two melting peaks appeared for ABA-2 and ABA-3 in which the concentric spherulites was observed. The SAXS curves also had two kinds of peaks due to alternating structure of the crystal lamella and amorphous layer for both ABA-2 and ABA-3. The long spacing estimated from the peak position suggested that the amorphous chains of the counter component existed between the crystal lamella.

对于聚（ε-己内酯）-嵌段-聚（乙二醇）-嵌段-聚（ε-己内酯）（PCL-PEG-PCL）三嵌段共聚物阿坝-2和阿坝-3（PCL组成分别为66和60wt%），观察到独特的球晶形态，即像同心圆的双球晶。同心球晶中的内球晶和外球晶分别是PCL和PEG的球晶。在球晶的形成过程中，PCL组分的球晶首先必然出现并长大，然后PEG球晶从PCL球晶的生长前沿发展而来。没有观察到PEG球晶在PCL之前的任何成核。在三嵌段共聚物中，阿坝-1和阿坝-4，与PCL的组合物分别为83和34重量%，没有观察到同心球晶，但通常的单球晶形成;在阿坝-1中，只有PCL球晶形成，而只有PEG球晶在阿坝-4中观察到。阿坝-2和阿坝-3出现两个熔融峰，其中观察到同心球晶。阿坝-2和阿坝-3的SAXS曲线也有两种峰，这是由于晶体片层和非晶层的交替结构。从峰位估计的长间距表明，晶体片层之间存在的反组分的非晶链。

项目成果

塩見友雄: "多相高分子の結晶化の特性" 日本ゴム協会誌. 71. 209-216 (1998)

Tomoo Shiomi：“多相聚合物的结晶特性”日本橡胶协会杂志 71. 209-216 (1998)。

塩見 友雄: "多相高分子の結晶化の特性" 日本ゴム協会誌. 71・4(予定). (1998)

Tomoo Shiomi：“多相聚合物的结晶特性”日本橡胶协会杂志71・4（预定）。

塩見 友雄: "多相高分子の結晶化の特性" 日本ゴム協会誌. 71. 209-216 (1998)

Tomoo Shiomi：“多相聚合物的结晶特性”日本橡胶协会杂志 71. 209-216 (1998)。

T.Shiomi, K.Imai, K.Takenaka, H.Hayashi, Y.Tezuka: "Appearance of Double Spherulites like Concentric Circles for Poly (epsilon-caprolactone) -blocsk-Poly (ethyleneglycol) -block-Poly (epsilon-caprolactone)" Macromolecules. in press.

T.Shiomi、K.Imai、K.Takenaka、H.Hayashi、Y.Tezuka：“聚（ε-己内酯）-blocsk-聚（乙二醇）-block-聚（ε-己内酯）的同心圆双球晶外观

塩見友雄: "高分子多相系の結晶化" 繊維学会誌(繊維と工業). 55・3発表予定. (1998)

Tomoo Shiomi：“聚合物多相体系的结晶”日本纤维科学技术学会杂志（纺织工业）预定于3月55日发表。（1998年）。