极性单体锂系阴离子嵌段共聚物的合成与表征  

Synthesis and Characterization of Block Copolymers with PMMA Segment Initiated by Organic Lithium

作　　者：陈波[1] 王继铭[1] 束民泽 邹斌[1] 管涌[1] 郑安呐[1] 

机构地区：[1]华东理工大学材料科学与工程学院、上海市先进聚合物材料重点实验室、超细材料制备与应用教育部重点实验室,上海200237

出　　处：《高等学校化学学报》2014年第9期2007-2013,共7页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:50933002)资助~~

摘　　要：以酚锂作为副反应抑制剂,以正丁基锂或1,1-二苯基乙烯盖帽的正丁基锂为引发剂,通过顺次添加单体的方法,合成了结构明确的聚异戊二烯-b-聚甲基丙烯酸甲酯(PI-b-PMMA)和聚甲基丙烯酸正丁酯-b-聚甲基丙烯酸甲酯(PBMA-b-PMMA)2种嵌段聚合物.嵌段聚合反应中甲基丙烯酸甲酯(MMA)的转化率均高于90%,通过核磁图谱计算的链节摩尔比与理论设计值吻合.PI-b-PMMA和PBMA-b-PMMA的分子量分别达到4×104和1.6×104.在环己烷中,通过顺次添加单体的方法,合成了结构明确的聚苯乙烯-b-聚异戊二烯-b-聚甲基丙烯酸甲酯(PS-b-PI-b-PMMA)三嵌段共聚物,各单体的转化率均达到100%,并且产物中的链节摩尔比和理论设计值一致,最终产物的分子量达到7.4×104,分子量分布仅为1.28,为极性三嵌段热塑性弹性体以及有机玻璃透明增韧剂的工业化奠定了基础.Well-defined block copolymers polyisoprene-b-poly（ methyl methacrylate） （ PI-b-PMMA） and poly （ butyl methacrylate ）-b-poly （ methyl methacrylate ） （ PBMA-b-PMMA were synthesized in THF initiated by n-BuLi and DPHLi with the addition of P-Complex. The polymerizations were carried out under the conditions which could be achieved in industry through adding monomers by sequence. The conversion of MMA was higher than 90% both in PI-b-PMMA and PBMA-b-PMMA, and the molar ratios of each segment in block copolymers detected by 1 H NMR fit to those calculated. The Mn of PI-b-PMMA and PBMA-b-PMMA were 4. 0×104 and 1. 6 × 104, respectively. Well-defined triblock polymer PS-b-PI-b-PMMA was synthesized in cyclohexane under the condition which could be achieved in industry. The conversions of monomers were all completed, and the molar ratio in the final triblock polymer was consistent to the one calculated. The final Mn was 7. 4×104, and the molecular weight distribution（MWD） was only 1. 28.

关 键 词：阴离子活性聚合 酚锂 甲基丙烯酸甲酯 嵌段共聚物 

分 类 号：O632.1[理学—高分子化学]