申请人:Rizzardo Ezio
公开号:US09340498B2
公开(公告)日:2016-05-17
A method of preparing polymer, the method comprising polymerizing one or more ethylenically unsaturated monomers of formula (I)
where U is selected from H, C1-C4 alkyl or halogen; V is halogen or of the form O-G where G is selected from —C(O)R1 and —R1, or V is of the form NGGa where G is as defined above and Ga is selected from H and R1, G and Ga form together with N a heterocyclic ring, or V is of the form CH2Gb where Gb is selected from H, R1, OH, OR1, NR12, PR12, P(O)R12, P(OR1)2, SR1, SOR1, and SO2R1; and where the or each R1 is independently selected from optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted arylalkyl, optionally substituted heteroarylalkyl, optionally substituted alkylaryl, optionally substituted alkylheteroaryl, and an optionally substituted polymer chain,
under the control of a RAFT agent of formula (II) or (III),
where Y is a Lewis base moiety and Y* is an n-valent Lewis base moiety; X is O or NR1, R1 is as defined above or forms together with Y or Y* and N a heterocyclic ring; m is an integer ≧1; n is an integer ≧2; and where R* is a m-valent radical leaving group that affords R*. which initiates free radical polymerization of the one or more ethylenically unsaturated monomers of formula (I), and R is a free radical leaving group that affords R. which initiates free radical polymerization of the one or more ethylenically unsaturated monomers of formula (I).
一种制备聚合物的方法,包括在RAFT试剂的控制下聚合一个或多个式(I)的乙烯基不饱和单体,其中U从H、C1-C4烷基或卤素中选择;V为卤素或形式为O-G的形式,其中G从—C(O)R1和—R1中选择,或V为形式为NGGa的形式,其中G如上所定义,Ga从H和R1中选择,G和Ga与N一起形成杂环环,或V为形式为CH2Gb的形式,其中Gb从H、R1、OH、OR1、NR12、PR12、P(O)R12、P(OR1)2、SR1、SOR1和SO2R1中选择;其中每个R1独立地从可选取代的烷基、可选取代的烯基、可选取代的炔基、可选取代的芳基、可选取代的杂芳基、可选取代的碳环基、可选取代的杂环基、可选取代的芳基烷基、可选取代的杂芳基烷基、可选取代的烷基芳基、可选取代的烷基杂芳基和可选取代的聚合物链中独立选择;RAF试剂的式(I)或(III),其中Y是一个Lewis碱基团,Y*是一个n价Lewis碱基团,X为O或NR1,R1如上所定义或与Y或Y*和N一起形成杂环环,m为一个≧1的整数,n为一个≧2的整数,其中R*是一个m价基团离去基团,提供R*,它引发式(I)的一个或多个乙烯基不饱和单体的自由基聚合,R是一个自由基离去基团,提供R,它引发式(I)的一个或多个乙烯基不饱和单体的自由基聚合。