【作者】 沈大娲；

【导师】 付志峰；

【作者基本信息】 北京化工大学 ， 材料物理与化学， 2002， 硕士

【摘要】 本论文采用原子转移自由基聚合与缩合聚合相结合的方法，合成了形如PSt-b-PC-b-PSt、PC-g-PSt以及（PSt）₂PC（PSt）₂的三种聚苯乙烯与聚碳酸酯的共聚物。并通过¹H NMR、GPC以及溴含量测定等方法验证了其结构。 用双酚A与溴异丁酰溴反应得到了2-（4-羟基-苯基）-2-（4-α-溴代异丁酸基-苯基）丙烷；用1，1，1-三（4-羟基苯基）乙烷与溴异丁酰溴反应得到了1，1-二（4-羟基-苯基）-1-（4-α-溴代异丁酸基-苯基）乙烷和1-（4-羟基-苯基）-1，1-二（4-α-溴代异丁酸基-苯基）乙烷。通过¹H NMR验证了其结构。 在双酚A与三光气缩聚的反应体系中，以2-（4-羟基-苯基）-2-（4-α-溴代异丁酸基-苯基）丙烷作为封端剂，得到两端各带有一个溴异丁酸酯基的聚碳酸酯（Ⅰ）；以1-（4-羟基-苯基）-1，1-二（4-α-溴代异丁酸基-苯基）乙烷作为封端剂，得到两端各带有两个溴异丁酸酯基的聚碳酸酯（Ⅱ）；以1，1-二（4-羟基-苯基）-1-（4-α-溴代异丁酸基-苯基）乙烷作为共聚单体，得到主链上带有溴异丁酸酯侧基的聚碳酸酯（Ⅲ）。并通过GPC、¹H NMR和溴含量测定验证了其结构。北京化工大学硕士学位论文由I引发苯乙烯的原子转移自由基聚合，得到了Pst一b一PC一b一Pst;由n引发苯乙烯的原子转移自由基聚合，得到了Pc一g一Pst;由m引发苯乙烯的原子转移自由基聚合，得到了伊st)ZPc（Pst）2。通过GPc、’H NMR验证了它们的结构。将聚碳酸酷链水解后，得到的聚苯乙烯段分子量随转化率线性增长，分子量分布均较窄（MW/Mn<1.3）。先用官能性化合物引发苯乙烯的原子转移自由基聚合，得到大分子封端剂或大分子单体，再进行双酚A与三光气的缩合聚合，也可以得到pst一b一PC一b一PSt和pC一g一PSt。更多还原

【Abstract】 In the present dissertation, three copolymers with well-defined architectures, PSt-b-PC-b-PSt, PC-g-PSt and (PSt)2PC(PSt)2 were synthesized by the combination of condensation polymerization and atom transfer radical polymerization(ATRP).In the first part of this dissertation, 2-(4-hydroxyphenyl)-2-(4-(a-bromoisobutyryloxy)phenyl)propane (I) was synthesized by reacting bisphenol A with a-bromo isobutyryl bromide and purified by column chromatogram. Then, polycarbonate with one bromoisobutyrylate groups at each end was prepared by using I as the end-capping agent in the condensation polymerization of bisphenol A with triphosgene. Its molecular weight and structure were determined by GPC, ]H NMR or bromide content analysis. Lastly, this difounctional polycarbonate was used as the macroinitiator for the ATRP of styrene to prepare triblock copolymer of PSt-b-PC-b-PSt. In order to confirm the blocking polymerization was a controlled/living process, the dependence of molecular weight of polystyrene outer block on monomer conversion was investigated through the hydrolysis of the polycarbonate central block by potassium hydroxide.In the second part of this dissertation, a functional polycarbonate was prepared through copolymerization of triphosgene with bisphonel A and l,l-bis-(4- hydroxyphenyl)-!-(4-(a-bromoisobutyryloxy)phenyl) ethane, which was syhthesized by reacting 1,1 ,l-tris(4-hydroxyphenyl)ethane with ct-bromo isobutyryl bromide. Then, ATRP of styrene was carried out in the presence of the above functional polycarbonate, resulting a graft copolymer of PC-g-PSt.In the last part of the dissertation, another functional polycarbonate was synthesized by using l-(4- hydroxyphenyl)-1,1-bis(4-(a-bromoisobutyryloxy)phenyl)ethane as an end-capping agent. Due to that polycarbonate obtained above had two bromoisobutyrylate groups at each end, (PSt)2PC(PSt)2 could be generated with the polycarbonate as an initiator in the ATRP of styrene.更多还原