引用本文:
田林, 毕吉福, 吴广峰, 张学全. 氯化稀土乙二醇二甲醚配合物催化丁二烯聚合[J]. 应用化学,
2013, 30(1): 16-21.
doi:
DOI:10.3724/SP.J.1095.2013.20063
Citation: TIAN Lin, BI Jifu, WU Guangfeng, ZHANG Xuequan. Studies on Butadiene Polymerization by Using Neodymium Chloride Ethylene Glycol Dimethyl Ether Complex as Catalyst[J]. Chinese Journal of Applied Chemistry, 2013, 30(1): 16-21. doi: DOI:10.3724/SP.J.1095.2013.20063
Citation: TIAN Lin, BI Jifu, WU Guangfeng, ZHANG Xuequan. Studies on Butadiene Polymerization by Using Neodymium Chloride Ethylene Glycol Dimethyl Ether Complex as Catalyst[J]. Chinese Journal of Applied Chemistry, 2013, 30(1): 16-21. doi: DOI:10.3724/SP.J.1095.2013.20063
氯化稀土乙二醇二甲醚配合物催化丁二烯聚合
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,以烷基铝与甲基铝氧烷(MAO)共同作为助催化剂时具有高聚合活性,而单独以烷基铝或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)。
English
Studies on Butadiene Polymerization by Using Neodymium Chloride Ethylene Glycol Dimethyl Ether Complex as Catalyst
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 polymerization behaviors 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.
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Key words:
- butadiene
- / ethylene glycol dimethyl ether
- / rare earth chloride
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