端基功能化聚烯烃的合成与应用  

Synthesis and Applications of Chain End Functionalized Polyolefins

作　　者：张勇杰[1,2] 李化毅[1] 董金勇[1] 胡友良[1] 

机构地区：[1]中国科学院化学研究所分子科学中心中国科学院工程塑料重点实验室,北京100190 [2]中国科学院大学,北京100049

出　　处：《化学进展》2014年第1期110-124,共15页Progress in Chemistry

基　　金：国家自然科学基金项目(No.51343006)资助~~

摘　　要：端基功能化聚烯烃(Cef-PO)在聚烯烃改性和构筑复杂结构聚合物方面有着重要应用。可通过控制烯烃配位聚合过程中的自发链转移反应,得到端基不饱和聚烯烃;或通过引入硼烷、磷烷、苯乙烯及其衍生物/氢气等链转移剂得到不同反应性基团封端的聚烯烃;再经进一步基团转化反应,得到多种不同性能的Cef-PO。另外,活性配位聚合过程中,通过对活性增长聚烯烃链选择性封端处理,或使用功能化的催化剂,也可以用来制备Cef-PO。通过配位链转移聚合,即聚烯烃链在催化剂金属中心和烷基金属链转移剂之间快速可逆链转移的聚合过程,可以直接得到具有高度反应活性的碳-金属键封端的聚烯烃,经化学转化得到CefPO。此外,叶立德活性聚合、共轭二烯烃的阴离子活性聚合和环烯烃的开环易位聚合也可以用来制备CefPO。向其他聚合方式(活性自由基聚合、活性阴离子聚合等)的转换及与点击化学的结合是Cef-PO应用的明显特点。Cef-PO的应用包括作为聚合物的改性剂以及用于合成具有复杂结构的聚合物。Chain end functionalized polyolefins（ Cef-POs） are of great importance in macromolecular design and polyolefin modifications. By utilizing self-induced chain transfer reactions（ to β-H,e. g.） or using chain transfer agents such as borane, phosphine and styrene（ and its derivatives） / H 2 in olefin coordination polymerization,unsaturated bond and reactive group terminated polyolefins can be obtained,respectively. Successive chemical modification of chain-end group results in various Cef-POs. Given the status of ＂one polymer chain per catalyst＂in living coordination polymerization of olefin,Cef-POs can also be obtained by endcapping living chains and / or applying functionalized living catalysts. The problem of low catalyst efficiency encountered in living coordination polymerization can be w ell solved by coordinative chain transfer polymerization（ CCTP）,a process involving rapid and reversible chain transfer reactions betw een the catalyst（ active species） and the chain transfer agent（ usually in the form of a main group metal alkyl）. CCTP generates polyolefin capped by carbon-metal bond,w hich is highly reactive and can be modified into versatile terminal groups. In addition,living polymerization of Ylides,living anionic polymerization of butadiene and ring-opening metathesis polymerization of cycloolefine are alternative approaches to synthesize（ analogues of） Cef-PEs. The applications of Cef-POs,featured by transformation reaction from metallocene to other polymerization（ living anionic polymerization,＂controlled / living ＂ radical polymerization,ring-opening polymerization,etc.） and combination w ith click chemistry,include tw o main aspects： polymer modification and synthesis of topological polymer.

关 键 词：聚烯烃 端基功能化 链转移反应 活性聚合 配位链转移聚合 

分 类 号：O632.1[理学—高分子化学] O631.5[理学—化学]