Novel Spherulitic Structures of Polyorganophosphazenes in Relation to Their Polymorphism

聚有机磷腈的新型球晶结构及其多晶型性

• 批准号: 06453151
• 负责人: MASUKO Toru
• 金额: $ 4.48万
• 依托单位: Yamagata University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 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-06453151/
• 关键词: Polyorganophosphazene; Polymer spherulite; Crystal modification; Mesomorphic state; Depolarization light intensity; Birefringence; Polarized infrared absorption spectra; 熱解析; 脱偏光強度測定

Crystallizable polyorganophosphazenes (POP) have so-called T (1) transitions at which the polymer changes from its 3-D crystalline state to the 3-D mesomorphic structre (the delta phase). The transition generally locates between the glass transition temperature and the melting point. In this research, isothermal crystallization kinetics of two types of polyphosphazenes from their delta phase have been invesigated, and resultant spherulitic structures of POP's are examined in terms of their polymorphism mainly by optical microscopy, high temperature x-ray diffraction and thermal analysis. The results obtained are summarized as follows :(1)When the poly [bis (3,4-dimethylphenoxy) phosphazene] (PB (dM) PP)films heated at 140ﾟC were cooled down to various isothermal temperatures, T_c, A-type spherulites (more than 100mum in diameter) and B-type spherulites sppeared independently. According to relative amount of the two types of spherulites in the sample, the T_c range can be divided into three regions.The relationship between the types of PB (dM) PP spherulite and its crystal forms was examined in detail using x-ray diffraction. The A-type spherulite is composed of the alpha-form crystal (Pbcn) and the B-type spherulites of the beta-form (also orthorhombic).(3) We tried to identify the direction of the c axis located in the B-type spherulite using polarized infrared spectra of the sample, but failed to determine the exact direction, since the polarlzed infrared spectra indicated were the same characteristics between the direction paralell to the spherulite radius and that vertival to it. These findings require more x-ray diffraction data by microbeam experiments. The works along this linewill be continued in future.(4) Morpholigocal features of poly [bis (4-ethylphenoxy) phosphazene] were also investigated in a similar manner as those for PB (dM) PP,and the results showed considerably diffrent crystallization mechanism from that of PB (dM) PP.

可结晶的聚有机磷腈（POP）具有所谓的T（1）转变，在该转变处聚合物从其3-D结晶状态转变为3-D介晶结构（δ相）。转变通常位于玻璃化转变温度和熔点之间。本文研究了两种聚磷腈从δ相等温结晶的动力学，并通过光学显微镜、高温X射线衍射和热分析等方法研究了聚磷腈的球晶结构。（1）聚[双（3，4-二甲基苯氧基）磷腈]（PB（dM）PP）薄膜在140 ℃加热后，冷却到不同的等温温度，T_c、A型球晶（直径大于100 μ m）和B型球晶独立地展开。根据PB（dM）PP中两种球晶的相对含量，将其T_c范围分为三个区域，并利用X射线衍射方法详细研究了PB（dM）PP球晶类型与其晶型之间的关系。A型球晶由α型晶体（PbCN）和β型（也是正交晶系）的B型球晶组成。(3)我们试图用样品的偏振红外光谱来确定B型球晶中c轴的方向，但由于偏振红外光谱所显示的球晶半径方向与球晶半径垂直方向具有相同的特征，因此未能确定准确的c轴方向，这一发现需要更多的微束X射线衍射数据。今后将继续沿着这条路线开展工作。(4)聚[双（4-乙基苯氧基）磷腈]的形态结构与PB（dM）PP相似，但结晶机理与PB（dM）PP有很大不同。

项目成果

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K.Yonetake: "Growth of Liquid Crystal in Poly[[6-(4'-cyanobiphenyl-4-oxy)hexyl]methylsiloxane]" Polym.J.27. 1157-1159 (1995)

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