New aspect of cationic ring-opening polymerization of seven-membered spiroorthocarbonates: synthesis and polymerization of substituted 1,6,8,13-tetraoxaspiro[6.6]tridecanes
New aspect of cationic ring-opening polymerization of seven-membered spiroorthocarbonates: synthesis and polymerization of substituted 1,6,8,13-tetraoxaspiro[6.6]tridecanes
复制标题
七元螺原碳酸酯阳离子开环聚合新进展：取代1,6,8,13-四氧螺[6.6]十三烷的合成与聚合
DOI：
10.1021/ma00182a008
复制
发表时间：
1988
期刊：
影响因子：
5.5
通讯作者：
T. Endo
中科院分区：
文献类型：
--
作者：
T. Takata;T. Endo
合成了两种新的具有螺[6.6]十三烷骨架的螺环单体--螺原碳酸酯（SOC，7和8），并研究了它们在阳离子条件下的聚合行为。通过阳离子开环聚合，SOC 7和8得到结构明显不同的聚合物，聚碳酸酯9和聚（醚-碳酸酯）12，取决于SOC的结构，但与溶剂无关（氯苯、二氯乙烷、硝基苯）、催化剂（BF 3 OEt 2、Ph 3 C + BF 4-、PhCH 2S + CH 2CH 2CH 2CH 2 SbF 6-）和温度（从室温到120和150 C）。基于SOC之间结构的差异，结果表明两个可区分的聚合过程，推测由增长的阳离子物种的反应位点的亲电性或消除的部分的离开能力控制。
Two new spirocyclic monomers, spiroorthocarbonates (SOCs, 7 and 8) having spiro [6.6] tridecane skeletons, were synthesized and their polymerizationbehavior was studied under cationic conditions. By cationic ring-opening polymerization, SOCs 7 and 8 afforded clearly structure-different polymers, polycarbonate 9 and poly (ether-carbonate) 12, respectively, depending on the structure of SOC, but independent of solvent (chlorobenzene, ethylene dichloride, nitrobenzene), catalyst (BF3OEt2, Ph3C+ BF4", PhCH2S+ CH2CH2CH2CH2 SbF6-), and temperature (from room temperature to 120 and 150 C). On the basis of the difference of the structures between the SOCs, the results suggested two distinguishable polymerization courses controlled presumably by the electrophilicity of the reaction site of the propagating cationic species or the leaving ability of the eliminated moiety.