POLYMERIZATION OF FUNCTIONALIZED NORBORNENES EMPLOYING MO(CH-T-BU)(NAR)(O-T-BU)2 AS THE INITIATOR
POLYMERIZATION OF FUNCTIONALIZED NORBORNENES EMPLOYING MO(CH-T-BU)(NAR)(O-T-BU)2 AS THE INITIATOR
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DOI：
10.1021/ma00016a003
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发表时间：
1991-08-05
期刊：
影响因子：
5.5
通讯作者：
GIBSON, VC
中科院分区：
文献类型：
--
作者：
BAZAN, GC;SCHROCK, RR;GIBSON, VC
以Mo(CH-t-Bu)(NaR)(O-t-Bu)2为引发剂，特别是在四氢呋喃中，可以使含酯、氰基、醋酸酯和相关官能团的降冰片烯以活性方式聚合，得到多分散度低至1.04的聚合物。聚(聚-顺-2，3-降冰片二醇二乙酸酯)(聚-6)、聚(脱-顺-2，7-降冰片二醇)(聚-7)和聚(脱-顺-O，O‘-异亚丙基-2，3-降冰片二醇)(聚-8)可以被水解制得含羟基的聚合物。Poly-6和Poly-7在摄氏300度以上会损失2当量的醋酸，从而得到黑色的难熔薄膜；在类似的条件下，类似的二元醇会损失2当量的水。在Mo-(CH-t-Bu)(NaR)(O-t-Bu)2中加入exo-cis-2，3-dichloro-endo-cis-2，3-(carbonyldioxy)norbornene(12)得到了一个可分离的四方锥体钼环丁烷配合物，其中约50%在室温下失去12而重新生成Mo(CH-t-Bu)(NaR)(O-t-Bu)2。用H-1核磁共振方法对含烷基钼端基的活性聚合物进行了表征。
Norbornenes containing esters, cyano, acetate, and related functionalities can be polymerized in a living manner employing Mo(CH-t-Bu)(NAr)(O-t-Bu)2 as the initiator, especially in THF, to give polymers with polydispersities as low as 1.04. Poly(exo-cis-2,3-norbornenediol diacetate) (poly-6), poly(exo-syn-2,7-norbornenediol diacetate) (poly-7), and poly(exo-cis-O,O'-isopropylidene-2,3-norbornendiol) (poly-8) can be hydrolyzed to give polymers containing hydroxyl groups in place of acetates. Poly-6 and poly-7 lose 2 equiv of acetic acid above 300-degrees-C to give black intractable films; the analogous diols lose 2 equiv of water under similar conditions. Addition of exo-cis-2,3-dichloro-endo-cis-2,3-(carbonyldioxy)norbornene (12) to Mo-(CH-t-Bu)(NAr)(O-t-Bu)2yields an isolable square-pyramidal molybdacyclobutane complex, approximately 50% of which loses 12 at room temperature to re-form Mo(CH-t-Bu)(NAr)(O-t-Bu)2. A block copolymer of 5-cyanonorbornene (5) and norbornene (100/100 equiv) was prepared. Living polymers containing molybdenum alkylidene end groups have been characterized by H-1 NMR methods.