Radical high polymerization of di-tert-butyl fumarate and novel synthesis of high molecular weight poly(fumaric acid) from its polymer
Radical high polymerization of di-tert-butyl fumarate and novel synthesis of high molecular weight poly(fumaric acid) from its polymer
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富马酸二叔丁酯的自由基高聚合及其聚合物合成高分子量聚富马酸的新方法
DOI：
10.1007/bf00255433
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发表时间：
1984
期刊：
影响因子：
3.2
通讯作者：
Shigeki Mori
中科院分区：
文献类型：
--
作者：
T. Otsu;T. Yasuhara;K. Shiraishi;Shigeki Mori
摘要
富马酸二叔丁酯（DtBF）在50 - 80°C下，以偶氮二异丁腈和过氧化苯甲酰为自由基引发剂时，容易发生均聚反应，生成一种刚性棒状聚合物——聚（叔丁氧羰基亚甲基），其数均分子量超过100,000。由此得到的无色粉末状聚合物可溶于苯、甲苯、四氯化碳和四氢呋喃，其甲苯溶液可制成透明薄膜或纤维。这种聚合物不熔融，但在180 - 190°C时会发生降解，定量地释放出异丁烯。剩余的聚合物经证实是纯的聚富马酸，即聚（羟基羰基亚甲基）。因此，发现聚（DtBF）在180 - 190°C的溶液中降解是合成高分子量聚富马酸的一种新途径。
SummaryDi-tert-butyl fumarate (DtBF) was found to homopolymerize easily with 1,1′-azobisisobutyronitrile and benzoyl peroxide as radical initiators at 50~80°C to give a nonflexible rod-like polymer, poly(tert-butoxycarbonylmethylene) with number-average molecular weight of more than 100,000. The colorless powderlike polymer thus obtained was soluble in benzene, toluene, carbon tetrachloride and tetrahydrofuran, and gave a transparent film or fiber from its toluene solution. This polymer did not melt, but it underwent degradation with a quantitative elimination of isobutene at 180~190°C. The remaining polymer was confirmed to be a pure poly(fumaric acid), poly(hydroxycarbonylmethylene). Therefore, the degradation of poly(DtBF) in solution at 180~190°C was found to be a new route for synthesizing of a high molecular weight poly(fumaric acid).