POLYMERS OF CARBONIC-ACID .11. REACTIONS AND POLYMERIZATIONS OF ALIPHATIC CYCLOCARBONATES WITH BORON HALOGENIDES

被引:59
作者
KRICHELDORF, HR
WEEGENSCHULZ, B
机构
[1] Institut für Technische und Makromolekulare Chemie, Universität Hamburg, 20146 Hamburg
关键词
D O I
10.1021/ma00074a022
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Neopentylene carbonate (NPC) and trimethylene carbonate (TMC) were reacted with BF3.OEt2, BCl3, and BBr3 under various conditions. When the cyclocarbonates and boron halogenides were combined in equimolar amounts at 20-degrees-C in chloroform, crystalline complexes were formed in the cases of TMC-BF3, NPC-BCl3, and NPC-BBr3. Depending on the reaction conditions, BCl3 and BBr3 react with both cyclocarbonates by ring opening and halogen transfer without initiating polymerization. In contrast BF3.OEt2 and its TMC complex are effective initiators, and polymerizations in bulk may yield polycarbonates in yield >95% and with high molecular weights (M(w) > 10(5)). However, all polycarbonates contain ether groups, and the molar fraction of ether groups increases with the temperature. This observation and the acceleration of the polymerization in polar solvents suggest a cationic mechanism
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页码:5991 / 5998
页数:8
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