活性自由基聚合raft.pptxVIP

基于可逆加成-碎裂型链转移剂的活性自由基聚合;;;基于可逆加成-碎裂型链转移剂的活性自由基聚合;In 1986, CSIRO in Australia reported the use of PMMA macromonomers as chain transfer agents (CTAs) in radical polymerization. They called the process addition-fragmentation chain transfer (AFCT): ;;;;reversible addition-fragmentation chain transfer (RAFT) agent;Main equilibrium;Macromolecules 1998, 31, 5559-5562;RAFT聚合机理和动力学：;稳态与平衡：;;1. The initial RAFT agents 1 and the polymer RAFT agent 3 should have a reactive C=S double bond (high kadd). 2. The intermediate radicals 2 and 4 should fragment rapidly (high kβ, weak S–R bond) and give no side reactions.;;;d is the number of chains produced in a radical–radical termination event (d ～ 1.67 for MMA polymerization and ～1.0 for styrene polymerization) and f is the initiator efficiency.;（7）The fraction of living chains (L);The proportion of dead chains Dc：;测定：;测定：;The transfer constants of various RAFT agents have been measured in the range of 0.01 to above 1000 depending on the nature of Z, R, and type of monomer. It has been reported that to obtain narrow polydispersity polymers (Mw=Mn 1.5) in a batch process with degenerative chain transfer (e.g., RAFT process), the Ctr of the transfer agent should be greater than 2. However, this limitation can be overcome by the use of a monomer feed polymerization process to reduce the rate of propagation and thereby produce narrow polydispersity polymers from a less active CTA.;;;苯乙烯本体聚合(80℃)中的结果表明，相同R不同Z的RAFT试剂链转移常数按下面的次序递减:二硫代苯甲酸酯三硫代碳酸酯~脂肪二硫代羧酸酯黄原酸酯二硫代氨基甲酸酯。（最后两种基本不可控）;;当富电子原子（O/N)上有吸电子取代基，特别是可与O/N原子中孤对电子发生离域作用的取代基取代后，可以显著提高其转移常数。;R基团的影响：;不同R基团有如下递减规律: -C(alkyl)2CN,-C(Me)2Ar -C(Me)2(C=O)O(alkyl) -C(Me)2(C=O)NH(alkyl) -C(Me)2CH2C(Me)3≥ -C(Me)HPh -C(Me)3, -CH2ph，只有当 R=-C(Me)2Ph和-C(Me)2CN时才能得到可控的MMA聚合物。;;注意： R基团为-C(Me)2COOEt不能得到可控的MMA聚合物。这与ATRP、SFRP中的规律不同。;;;;;说明： 得到可控聚合物的分子量有上限。;;;;;;;;RAFT 可实现VAc的可控聚合，与VC一样，是重大突破。;注意R基：缺电子基团，应能保证快引发，个人认为是实现可控的另一个重要因素。;;;;;;;;;嵌段聚合物的制备：;星形聚合物的制备：;;;;;;聚合物RAFT 端基的脱除与转换：;;;;;;;;;;