基团转移聚合.pptVIP

乙烯基磷酸的稀土金属介导基团转移聚合（GTP） 高分子材料 田露 2015011001 主要内容 一、引言 二、乙烯基磷的自由基聚合与经典阴离子聚合 三、稀土金属介导的基团转移聚合 四、乙烯基磷酸的稀土金属介导基团转移聚合 五、表面引发GTP 六、聚乙烯基磷酸的合成 一、引言 近十几年来，聚合材料以其应用范围广泛占据了不可忽视的地位。由于聚合材料具有优良的使用性能，使其逐渐代替了传统原料，如木材、玻璃、陶瓷及金属。 本文通过将酯裂解反应与稀土金属介导的基团转移聚合（GTP）结合起来，制备出结构良好且具有高的分子量的聚乙烯基磷酸。 二、乙烯基磷的自由基聚合与经典阴离子聚合 ESI MS end-group analysis of vinylphosphonate oli- gomers, synthesized radically with different initiators, revealed that the initiation proceeds via chain transfer from initiator to monomer (hydrogen abstraction）. The underlying stability of the activated monomer radical and the readily occurring radical abstraction of the α -CH and side chain protons lead to rapid transfer reactions dominating the chain growth. 三、稀土金属介导的基团转移聚合 At the time,it was proposed that the trimethylsilyl group was transferring to a monomer as it was adding to the growing polymer chain end (Scheme 4 a), and therefore the new process was named GTP. 四、乙烯基膦的稀土金属介导基团转移聚合 In 2007, our group reported on catalytic polymerizations of dialkyl vinylphosphonates (alkyl = methyl, isopropyl) using rare earth metal complexes comprising monoden-tate σ -donor ligands (Scheme 6 , complex 1, 2a-d ). 五、表面引发GTP On basis of our studies on rare earth metal-mediated polymerization of vinylphosphonates，our group recently developed a surface-initiated group transfer polymerization (SI-GTP),which allows the covalent modification of solids with dense poly(vinylphosphonate) brushes. 六、聚乙烯基磷酸的合成 Direct GTP of vinylphosphonic acid is not possible, however, most applications of phosphonate-containing polymers are ascribed to the free acid. Therefore, simple polymer-analogous transformations of phosphonic esters to phosphonic acid are necessary. 1、Transesterification and Subsequent Hydrolysis 2、 Thermal Treatment * * “ ” 2016 “ ” * 含磷的聚合物，特别是含磷酸基团的部分，以其无卤阻燃性和质子传导特性受到广泛关注。含磷聚合物具有生物相容性好，毒性小，使其更多的应用于生物医药领域。 经由引发剂到单体的链转移(夺氢) The intramolecular hydrogen transfer from side group protons