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以甲基丙烯酸-2-羟乙酯和3-巯基丙酸经脱水酯化法合成了链转移剂单体甲基丙烯酸-3-巯基丙酰氧基乙酯(MMPOE)。以偶氮二异丁腈(AIBN)为引发荆,在MMPOE存在下进行丙烯腈和醋酸乙烯酯的常规自由基共聚反应合成支化聚(丙烯腈-醋酸乙烯酯)。用高效液相色谱、气相色谱、三检测凝胶渗透色谱(TD-GPC)和核磁共振谱(1H—NMR)对链转移剂单体、聚合反应过程和聚合物进行了表征分析。研究表明,以MMPOE为支化单体制得的支化聚(丙烯腈-醋酸乙烯酯),其支化程度随MMPOE的增加而提高;支化聚(丙烯腈-醋酸乙烯酯)的溶液黏度是相近分子量线型聚合物溶液黏度的20%~25%。

2- (3-mercaptopropionyloxy) ethyl methacrylate (MMPOE), a chain transter monomer, was synmesLzeu from α-methacrylate hydroxyethyl methacrylate and 3- mercaptopropionic acid. The polymerization of acrylonitrile (AN) and vinyl acetate (VAc) was carried out using MMPQE as the branching agent. Gas chromatography (GC), high-performance liquid chromatography (HPLC), proton nuclear magnetic resonance (1H-NMR) and tripledetection gel-permeation chromatography (TD-GPC) were used to characterize and analyze the chain transfer monomer, the polymerization and the resulting branched polymer. As expected, branched poly(AN-co-VAc) with high degree of branching was prepared, which has obviously low intrinsic viscosity and shear viscosity compared with its linear analogue. The viscosity of branched poly(AN-eo-VAc)s solution is only 20 % -25 % of that of their linear counterparts.

参考文献

[1] Liu QC;Xiong M;Cao M;Chen YM .Preparation of branched polyacrylonitrile through self-condensing vinyl copolymerization[J].Journal of Applied Polymer Science,2008(1):494-500.
[2] Bogdan Barboiu;Virgil Percec .Metal catalyzed living radical polymerization of acrylonitrile initiated with sulfonyl chlorides[J].Macromolecules,2001(25):8626-8636.
[3] Yang, HJ;Jiang, BB;Huang, WY;Zhang, DL;Kong, LZ;Chen, JH;Liu, CL;Gong, FH;Yu, Q;Yang, Y .Development of Branching in Atom Transfer Radical Copolymerization of Styrene with Triethylene Glycol Dimethacrylate[J].Macromolecules,2009(16):5976-5982.
[4] 黄文艳,杨宏军,龚海丹,刘春林,张东亮,杨扬,叶颖,蒋必彪.支化苯乙烯-丙烯腈共聚物合成与结构表征[J].高分子材料科学与工程,2010(01):9-11.
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