公开(公告)号：US5468785A

公开(公告)日：1995-11-21

申请号：US228302

申请日：1994-04-15

申请人： Michael P. Greuel ,  Labros D. Arvanitopoulos ,  H. James Harwood

发明人： Michael P. Greuel ,  Labros D. Arvanitopoulos ,  H. James Harwood

IPC分类号： C08F2/38 ,  C08F2/50 ,  C08F4/44 ,  C08F293/00 ,  C08F2/48 ,  C08F18/08 ,  C08F20/18

CPC分类号： C08F2/38 ,  C08F2/50 ,  C08F293/005 ,  Y10S522/904

摘要： The invention relates to the use of cobaloximes and related cobalt(II) complexes which have essentially planar equatorially coordinated ligands and a pair of axially coordinated ligands which have at least one carbon-cobalt bond, as photoinitiators for free radical polymerizations. By selection of the appropriate cobaloximes and related complexes, it is possible to prepare polymers which have useful terminal functionality at both the head and the tail ends of the growing polymer chain. The process also teaches the photochemical polymerization and copolymerizations whereby the alkyl cobaloximes and related compounds, which are used as the photoinitiators, have alkyl groups, which may in essence, be polymers with carbon-cobalt chain ends, thereby allowing grafting reactions to occur to the polymer backbone.While it is possible to synthesize the cobaloxime and related compounds initially, for subsequent addition to a monomer, it is also taught within this invention that the cobalt complex can be prepared "in-situ", such as by the routes which include: (1) Cobalt-hydride plus monomer addition; (2) free radical initiator plus monomer plus cobalt complex, the ratio of free radical initiator to cobalt complex being essentially 1:1; and (3) the reaction of Co(II) with an alkyl halide.

摘要翻译： 本发明涉及使用具有基本上平面的赤道配位配体的钴胂和相关的钴（II）络合物，以及具有至少一个碳 - 钴键的一对轴向配位的配体作为自由基聚合的光引发剂。 通过选择合适的咔唑和相关络合物，可以制备在生长的聚合物链的头末端和尾端具有有用的末端官能团的聚合物。 该方法还教导了光化学聚合和共聚，其中用作光引发剂的烷基钴胂和相关化合物具有烷基，其实质上可以是具有碳 - 钴链端的聚合物，从而允许接枝反应发生在 聚合物骨架。 尽管最初可以合成共咔唑和相关化合物，但是为了随后添加到单体中，本发明还教导了钴络合物可以“原地”制备，例如通过以下途径制备：（1 ）钴氢化物加单体添加; （2）自由基引发剂加单体加钴络合物，自由基引发剂与钴络合物的比例基本上为1:1; 和（3）Co（II）与烷基卤的反应。