橡胶技术网

合成橡胶工业
CHINA SYNTHETIC RUBBER INDUSTRY
2010 Vol.33 No.1 P.11-15

 橡胶技术网

酸性膦酸酯钕盐催化丁二烯在苯乙烯溶剂中的选择性聚合

贾忠明　 张学全　 李杨　 董为民　 姜连升　 张春庆　 王玉荣　

摘　要：以酸性膦酸酯钕盐Nd(P_(507))_3(简称Nd)、氢化二异丁基铝(简称Al)和倍半乙基铝(简称Cl)为催化剂体系,研究了丁二烯在苯乙烯溶剂中的选择性聚合,考察了溶剂种类、Al/Nd、Cl/Nd及温度对聚合的影响.结果表明,该催化剂体系可在苯乙烯溶剂中实现丁二烯的选择性聚合,在Al/Nd(摩尔比)为10、Cl/Nd(摩尔比)为2.0及聚合温度为50 ℃的条件下,丁二烯的转化率可达90%以上;聚合物中苯乙烯链节的摩尔分数在4%以下,丁二烯链节的顺式-1,4-结构摩尔分数为90%左右,1,2-结构摩尔分数为4%左右.
关键词：苯乙烯;丁二烯;稀土催化剂;溶液聚合;微观结构;高抗冲聚苯乙烯
分类号：TQ325.2 　文献标识码：A
文章编号：1000-1255(2010)01-0011-05

Selective polymerization of butadiene in styrene catalyzed by neodymium phosphonate

Jia Zhongming（State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116012, China）　 Zhang Xuequan（Changchun Institute of Applied Chemistry, Chinese Academy of Science, Changchun 130022, China）　 Li Yang（State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116012, China）　 Dong Weimin（Changchun Institute of Applied Chemistry, Chinese Academy of Science, Changchun 130022, China）　 Jiang Liansheng（Changchun Institute of Applied Chemistry, Chinese Academy of Science, Changchun 130022, China）　 Zhang Chunqing（State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116012, China）　 Wang Yurong（State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116012, China）　

Abstract：The solution polymerization of 1,3-butadiene(Bd) was investigated in styrene (St) with the catalyst system comprised of neodymium phosphonate Nd(P_(507))_3(Nd),Al(i-Bu)_2H(Al) and Et_3Al_2Cl_3(Cl), the effects of solvent, Al/Nd, Cl/Nd and polymerization temperature on the polymerization of Bd were examined. The results indicated that the selective polymerization of Bd was achieved in St by the above catalyst. The polymer yield was up to 90% at 50 ℃, Al/Nd(mole ratio) of 10 and Cl/Nd(mole ratio) of 2.0. The produced polymer had mole fraction of 1,2-unit of 4%, mole fraction of cis-1,4-unit of 90% and mole fraction of St unit of bellow 4%.
Keywords：styrene; butadiene; rare earth catalyst; solution polymerization; microstructure; high impact polystyrene

基金项目：国家"八六三"计划资助项目(20774015);中国石油(天然气集团公司)中青年创新基金资助项目(07 E 1034).
作者简介：贾忠明(1983-),男,硕士研究生.
作者单位：贾忠明（大连理工大学,化工学院,精细化工国家重点实验室,辽宁,大连116012）　
　　　　　张学全（中国科学院,长春应用化学研究所,吉林,长春130022）　
　　　　　李杨（大连理工大学,化工学院,精细化工国家重点实验室,辽宁,大连116012）　
　　　　　董为民（中国科学院,长春应用化学研究所,吉林,长春130022）　
　　　　　姜连升（中国科学院,长春应用化学研究所,吉林,长春130022）　
　　　　　张春庆（大连理工大学,化工学院,精细化工国家重点实验室,辽宁,大连116012）　
　　　　　王玉荣（大连理工大学,化工学院,精细化工国家重点实验室,辽宁,大连116012）　

参考文献：

[1]李杨,王梅,刘宏海,等.高抗冲聚苯乙烯的研制[J].合成树脂及塑料,1997,14(3):10-11.
[2]Tung L H,Kirkby L L.Preparation of alkenyl aromatic monomer butadiene rubber:US,4311819[P].1982-01-19.
[3]Short J N,Hanmer R S,Okla B,et al.Polymerization of 1,3-butadiene to produce cis-1,4-polybutadiene in the presence of styrene monomer with an organometal and iodine containing catalyst followed by styrene polymerization:US,3299178[P].1967-01-17.
[4]Windisch H,Michels G,Obrecht W,et al.Method for polymerizing conjugated diolefins (diene) with catalysts based on cobalt compounds in the presence of vinylaromatic solvents:US,6310151[P].2001-10-30.
[5]Windisch H,Obrecht W,Michels G,et al.Method for polymerizing conjugated diolefins(dienes) with catalysts based on vanadium compounds in the presence of vinylaromatic solvents:US,6566465[P].2003-03-20.
[6]Hsieh H L,Yeh G H C.Olefin polymerization:US,4575538[P].1986-03-11.
[7]Windisch H,Obrecht W,Michels G,et al.Method for polymerizing conjugatediolefins(diene) with rare earth catalysts in the presence of vinylaromatic,solvents:US,0134999[P].2003-07-17.
[8]Hattori Y,Kitagawa Y.Prepolymerization process for produc-ing a conjugated diene compound prepolymer solution:US,5096970[P].1992-03-17.
[9]Friebe L,Nuyken O,Obrecht W.Neodymium-based Ziegler/Natta catalysts and their application in diene polymerization[J].Advances in Polymer Science,2006,204:1-154.
[10]Zhang Qisheng,Li Weishi,Shen Zhiquan.Copolymerization of butadiene and styrene with neodymium naphthenate based catalyst[J].European Polymer Journal,2002,38(5):869-873.
[11]王佛松,仲崇祺,谢德民,等.稀土催化双烯聚合中活性链端 anti-syn 异构化及聚合机理[J].科学通报,1983,28(19):1176-1179.

收稿日期：2008年10月29日

修稿日期：2009年10月30日

出版日期：2010年1月15日