化学学报 ›› 2011, Vol. 69 ›› Issue (15): 1817-1823. 上一篇    下一篇

研究论文

超支化聚苯乙烯-线型聚苯乙烯-超支化聚甲基丙烯酸甲酯三嵌段聚合物的合成与表征

孔立智*,1,2, 乔华明1, 蒋必彪1   

  1. (1常州大学材料科学与工程学院 常州 213164)
    (2常州大学化工设计研究院 常州 213016)
  • 投稿日期:2010-12-25 修回日期:2011-04-19 发布日期:2011-04-30
  • 通讯作者: 孔立智 E-mail:lzkong@cczu.edu.cn
  • 基金资助:

    江苏省自然科学基金;常州大学科技创新基金

Synthesis and Characterization of Hyperbranched Polystyrene- Linear Polystyrene-Hyperbranched Poly(Methyl Methacrylate) Triblock Copolymers

Kong Lizhi*,1,2; Qiao Huaming1; Jiang Bibiao1   

  1. (1 Department of Materials Science and Engineering, Changzhou University, Changzhou 213164)
    (2 Institute of Chemical Design & Research, Changzhou University, Changzhou 213016)
  • Received:2010-12-25 Revised:2011-04-19 Published:2011-04-30
  • Contact: Kong Lizhi E-mail:lzkong@cczu.edu.cn

合成了超支化聚苯乙烯-线型聚苯乙烯-超支化聚甲基丙烯酸甲酯三嵌段聚合物(HPS-b-LPS-b-HPMMA). 首先分别合成了带有炔基和溴的三硫代碳酸酯(ATC和BTC), 然后通过苯乙烯(St)的可逆加成-断裂链转移(RAFT)聚合, 制得端炔基和端基溴的线型聚苯乙烯大分子RAFT试剂, 然后将大分子RAFT试剂的溴末端转化为叠氮末端. 接着在大分子RAFT试剂存在情况下, 通过自缩合原子转移自由基共聚合(SCATRCP)分别制得端炔基超支化聚苯乙烯-线型聚苯乙烯(HPS-b-LPS)和端叠氮基超支化聚甲基丙烯酸甲酯-线型聚苯乙烯(HPMMA-b-LPS)两嵌段聚合物. 最后将两种两嵌段聚合物通过点击(click)反应偶合, 得到不对称的超支化-线型-超支化三嵌段聚合物HPS-b-LPS-b-HPMMA. 核磁共振氢谱(1H NMR)、凝胶渗透色谱(GPC)结果表明, 所得产物分子量可控, 得到了预期结构的聚合物.

关键词: 可逆加成-断裂链转移聚合, 点击反应, 超支化聚合物, 嵌段聚合物

Hyperbranched polystyrene-linear polystyrene-hyperbranched poly(methyl methacrylate) triblock polymer (HPS-b-LPS-b-HPMMA) was synthesized by following steps: First of all, two kinds of trithiocarbonates with a alkynyl group or bromide atom (ATC and BTC) were synthesized. Then reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene (St) was carried out to obtain linear polystyrene macro-RAFT agents with terminal alkynyl group and bromine. Bromine end of the macro-RAFT agent was replaced by azide group. Then, in the presence of the macro-RAFT agents, self-condensing atom transfer radical copolymerization (SCATRCP) of St/CMS or MMA/BPPM was carried out to obtain hyperbranched PSt-linear PSt (HPS-b-LPS) with terminal alkynyl group and hyperbranched PMMA-linear PSt (HPMMA-b-LPS) with terminal azido group. Finally, two kinds of diblock copolymer were coupled by click reaction to get hyperbranched-linear-hyperbranched triblock polymer (HPS-b-LPS-b-HPMMA). 1H NMR, GPC results showed that the final polymer with the controlled molecular weight and the expected structure was obtained.

Key words: reversible addition-fragmentation chain transfer (RAFT), click reaction, hyperbranched polymer, block polymer

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