Monomer-to-Polymer Phase Transition of Diacetylenes with gamma-Rays

伽马射线下丁二炔单体到聚合物的相变

基本信息

批准号：
62540239
负责人：
MATSUYAMA Tomochika
金额：
$ 0.38万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1987
资助国家：
日本
起止时间：
1987 至 1989
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-62540239/
关键词：
Diacetylene Polydiacetylene Topochemical polymerization Oriented polymers Color change Solid state polymerization Single crystals of polymers First order phase transition 放射線重合相転移ジアセチセン DCH TCDU 共役系高分子単結晶

项目摘要

1. The monomer crystal of 1,6-di(N-carbazolyl)-2,4-hexadiyne (DCH) has the lattice parameters which predict a low reactivity in solid state polymerization. Despite the prediction, DCH monomer crystals can be converted to fully conjugated polymer crystals upon exposure to gamma-rays. This is due to the transformation of the crystal from a less-reactive phase to a more-reactive phase at the level of about 30% polymerization. This phase transformation is abruptly achieved without destruction of the crystal. The fact implies that a topochemical 1,4-addition reaction leading to the polymerization under gamma-irradiation proceeds homogeneously in both phases by the formation of solid solutions.2. The crystal of DCH monomer undergoes inherent phase transition (IPT). It has been determined that the temperature and the heat of IPT are 148K and 1.2 kcal/mol in as-grown DCH crystals, respectively. When the crystals were gamma-irradiated at room temperature, it was found that all lattice parameter … More s change gradually with gamma-ray dosage in the aforementioned less-reactive phase. In addition to the above fact it was also found in the less-reactive phase that the transition point of IPT is shifted to the temperature side lower than 148K with decreasing the heat of IPT under gamma-irradiation and that the color of the crystal is red below and blue above the temperature of IPT. The temperature shift of IPT, the decrement of heat for IPT and the color change at IPT are interpreted in terms of the concept of strain field induced by the formation of polymers within the monomer columns.3. The asymmetric monomers of 1-(N-carbazolyl)-6-(4'-methyl terephthaloyl)- 2,4-hexadiyne and 1-(N-carbazolyl)-6-(2',4'-dinitrophenyl ether)-2,4- hexadiyne were synthesized. Their crystal structures were determined with x-ray diffraction analysis. The present crystals showed neither topochemical polymerization nor phase transition. The non-polymerizability of the crystals is explained with monomer packing parameters and is consistent with the Baughman's model. Less

1。1,6-Di（N-甲基唑基）-2,4-己二二烷（DCH）的单体晶体具有晶格参数，可预测固态聚合的反应性较低。尽管进行了预测，但在暴露于伽马射线后，DCH单体晶体可以转换为完全共轭的聚合物晶体。这是由于在约30％聚合的水平下，晶体从反应较低的相变为更反应性的相。突然实现了这种相变，而不会破坏晶体。事实表明，座垫的1,4个成熟反应导致γ辐射下聚合在两个阶段的形成固体溶液中同质进行。2。 DCH单体的晶体经历了继承相变（IPT）。已经确定，在生长的DCH晶体中，IPT的温度和热量分别为148K和1.2 kcal/mol。当晶体在室温下被伽马射照时，发现所有晶格参数……在priore较低反应性相位的伽马射线剂量逐渐变化。除了上述事实外，还发现IPT的过渡点转移到低于148K的温度侧，而在γ-辐射下的IPT热量降低，并且晶体的颜色在IPT的温度以下，蓝色的颜色在IPT的温度以下。 IPT的温度转移，IPT的热量减少和IPT的颜色变化是根据单体柱中聚合物形成的应变场概念来解释的。3。 1-（N-甲基唑基）-6-（4'-甲基terephathaloyl）的不对称单体-2,4-己二二酯和1-（N-甲基唑基）-6-（2'，4'-二硝基苯基乙醚）-2,4- hExadiyne合成了。通过X射线衍射分析确定它们的晶体结构。目前的晶体既不显示拓扑化学聚合也不显示相变。晶体的非聚合性用单体堆积参数解释，并且与鲍曼的模型一致。较少的