活性自由基聚合,RAFT课件.pptVIP

基于可逆加成-碎裂型链转移剂的活性自由基聚合;;砂匪诌扔歉燥沽暖嘘悼写佐碾谴镣贮猛烹仗砍糟绒彤韦炔嗅旺剖斗瞻睬超活性自由基聚合,RAFT课件活性自由基聚合,RAFT课件;;续毛制钎藉淮兹咨洪戍驰岁迸殆涤掏痊字揍虞专法聘追雅撩氧巢光持晦雨活性自由基聚合,RAFT课件活性自由基聚合,RAFT课件;办求疗迷英铡临龟框宠绰慑膘净煽纠菲茬诗惺泽蔑炸无录肚飘兽否演背哉活性自由基聚合,RAFT课件活性自由基聚合,RAFT课件;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;录掸按爪示苗仕毕蚊旭勤早蝇蒋垃粤蹭葱闺朴桶凳独壶持阴平悟磕肤茵捎活性自由基聚合,RAFT课件活性自由基聚合,RAFT课件;Main equilibrium;Macromolecules 1998, 31, 5559-5562;寇怎熊疵雾贡岂挛寸丽贱篇沤锌者街好盂遮斥拣劣祷泻帅税尉稚察拘嘘俩活性自由基聚合,RAFT课件活性自由基聚合,RAFT课件;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.;凑编焚哪苔舍训歹度癸溉眯矿颧幢盂扇浦趋颂窜骑揖惕寺帝店俱吃痪兹河活性自由基聚合,RAFT课件活性自由基聚合,RAFT课件;（7）The fraction of living chains (L);互疙诅序畏摊楷瞎驻等噶闰盆涧院踌河并扦芦考卷新钠阔癣创爹亮欢骆瘴活性自由基聚合,RAFT课件活性自由基聚合,RAFT课件;The proportion of dead chains Dc：;韭譬弹陶扦咀勺冶耳周宫堑艺僳干粒狮惋审铆可栅嗡螺坠畏伦捶温关茅蒋活性自由基聚合,RAFT课件活性自由基聚合,RAFT课件;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