Structure Analysis of Monomer and Polymer Crystals in the Photoinduced Solid-State Polymerization Reaction of Diethyl cis,cis-Muconate
Structure Analysis of Monomer and Polymer Crystals in the Photoinduced Solid-State Polymerization Reaction of Diethyl cis,cis-Muconate
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顺,顺-粘康酸二乙酯光诱导固相聚合反应中单体和聚合物晶体的结构分析
DOI：
10.1021/ma990876u
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发表时间：
1999
期刊：
影响因子：
5.5
通讯作者：
S. Aoki
中科院分区：
文献类型：
--
作者：
K. Tashiro;A. N. Zadorin;Seishi Saragai;T. Kamae;A. Matsumoto;Katsutaka Yokoi;S. Aoki
该固态聚合反应被推测为“拓扑化学”和“拓扑立构”反应。在局部化学聚合中，反应在晶格的结构约束下进行，因此所得聚合物具有高度受控的化学结构。5-17在拓扑异构反应中，子晶体相对于单体晶体以三维、特异性方式取向，即单晶到单晶反应。已知二乙炔的拓扑立构聚合是一个典型的例子。15-17在EMU的本发明的情况下，推测单体的晶格的对称性甚至在聚合反应之后被保留，并且原始单体的单晶形态实际上保留在聚合物产物中。1-4根据这些特征，推测EMU的固态聚合是如上所述的“拓扑化学”和“拓扑立构”反应。EMU单体也是重要的，因为EMU分子可以被认为是由“流行的”丁二烯和酯基组成的“正常”有机化合物之一。换句话说，EMU单体晶体的聚合机理的澄清将使我们有可能拓宽聚合反应的研究领域，这使得更容易控制一般聚合物物质的本体结构和相关物理性质。我们遇到了一堵硬墙，它干扰了我们阐明EMU单体的拓扑聚合反应机理的努力。这是因为聚合反应中的结构变化在聚合温度下在几十分钟的时间尺度内迅速发生。
This solid-state polymerization reaction was speculated to be a “topochemical” and a “topotactic” reaction. In the topochemical polymerization, the reactions progress under structural restraint by the crystal lattice, and so the resultant polymers have highly controlled chemical structures. 5-17 In the topotactic reaction, the daughter crystal is oriented in a three-dimensional, specfic manner with respect to the monomer crystal, that is, the single-crystal-to-single-crystal reaction. The topotactic polymerization of diacetylenes was already known as a typical example. 15-17 In the present case of EMU, the symmetry of the crystal lattice of monomers was speculated to be preserved even after the polymerization reaction and the single-crystalline morphology of the original monomer was actually retained in the polymer product. 1-4 From these characteristic features, the solid-state polymerization of EMU was speculated to be a “topochemical” and a “topotactic” reaction, as mentioned above. The EMU monomer is also important in the sense that the EMU molecule may be assumed to be one of the “normal” organic compounds consisting of “popular” butadiene and ester groups. In other words, a clarification of the polymerization mechanism of the EMU monomer crystal will give us a possibility to widen the research field of the polymerization reaction, which makes it easier to control the bulk structure and the related physical properties of the general polymer substances.Despite such an expectation, however, we had encountered a hard wall which disturbed our effort to clarify the mechanism of the topotactic polymerization reaction of the EMU monomer. This is because the structural change in the polymerization reaction occurs rapidly in a time scale of several tens of minutes under