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氯化稀土乙二醇二甲醚配合物催化丁二烯聚合

田林1,毕吉福2,吴广峰1*,张学全2*   

  1. (1.长春工业大学化学工程学院 长春 130012；2.中国科学院长春应用化学研究所 长春 130022)
  • 收稿日期:2012-02-28 修回日期:2012-04-25 出版日期:2013-01-10 发布日期:2013-01-10
  • 通讯作者: 张学全，研究员; Tel:0431-85262303; Fax:0431-85262253; E-mail:xqzhang@ciac.jl.cn; 研究方向：新型结构聚烯烃、聚双烯烃材料的合成

Studies on Butadiene Polymerization by Using Neodymium Chloride Ethylene Glycol Dimethyl Ether Complex as Catalyst

TIAN Lin1, BI Jifu2, WU Guangfeng1*, ZHANG Xuequan2*   

  1. (1.Department of Chemical Engineering,Changchun University of Technology,Changchun 130012,China;
    2.Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China)
  • Received:2012-02-28 Revised:2012-04-25 Published:2013-01-10 Online:2013-01-10
  • Contact: guangfeng wu

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被引次数

5 | 1

摘要： 以Nd2O3、(CH3)3SiCl和乙二醇二甲醚(DME)为原料，合成了NdCl3·2DME配合物，并将其用于催化丁二烯聚合。 考察了助催化剂种类与用量、陈化温度和聚合时间对聚合的影响。 结果表明，以烷基铝与MAO共同作为助催[JP2]化剂时具有高聚合活性，而单独以烷基铝或甲基铝氧烷(MAO)为助催化剂时聚合活性很低。 当n(Nd)∶n(AlR3)∶n(MAO)=1∶30∶45时，催化活性最高。 陈化温度对聚合活性、聚合物结构及相对分子质量均有较大的影响。 陈化温度过低或者过高，聚合活性、聚丁二烯cis-1,4含量和相对分子质量均降低；陈化温度为50 ℃时，具有最高聚合活性和最高cis-1,4含量。 NdCl3·2DME催化体系所得聚丁二烯的cis-1,4含量高达98.7%（IR）,而1,4-结构总含量高达99.6%（1H NMR）。

关键词: 丁二烯, 氯化稀土, 乙二醇二甲醚

Abstract: A neodymium chloride ethylene glycol dimethyl ether complex (NdCl3·2DME) was synthesized and used as catalyst for butadiene polymerization. The effects of concentrations of alkylaluminium(AlR3) and methylaluminoxane(MAO) cocatalysts, aging time and polymerization time on such polymerization were investigated. Results show that the as-prepared catalyst displays high activity when both AlR3 and MAO were used as cocatalysts, while the activity became much lower when AlR3 or MAO as cocatalyst was used respectively. The highest catalytic activity was observed with the molar ratio of n(Nd)∶n(AlR3)∶n(MAO) was 1∶30∶45. The catalytic activity, cis-1,4 content and molecular weight of the resulting polymer were much affected with variation of aging temperature of the catalyst system. The optimal aging temperature of the catalyst system was 50 ℃, while negative effect was observe when aging temperature was higher or lower. The contents of cis-1,4 and the total 1,4-unit of polybutadiene catalyzed by using current catalyst system were up to 98.7%(IR) and 99.6%(1H NMR), respectively.

Key words: butadiene, DME, rare earth chloride.

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