COORDINATION POLYMERIZATION OF 1,3-BUTADIENE WITH Ni(naph)2/A1R3/BF3·OEt2/DMEA/OctOH CATALYST SYSTEM

QIAO Yulu; ZHU Han; WU Yixian; WANG Jin; Xu Riwei; WU Guanying; YANG Wantai

doi:10.3724/SP.J.1105.2010.09204

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COORDINATION POLYMERIZATION OF 1,3-BUTADIENE WITH Ni(naph)2/A1R3/BF3·OEt2/DMEA/OctOH CATALYST SYSTEM

Research Article | 更新时间：2021-03-19

- COORDINATION POLYMERIZATION OF 1,3-BUTADIENE WITH Ni(naph)2/A1R3/BF3·OEt2/DMEA/OctOH CATALYST SYSTEM
- Acta Polymerica Sinica Issue 6, Pages: 640-646(2010)
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- DOI：10.3724/SP.J.1105.2010.09204
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- Published：20 June 2010，
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QIAO Yulu, ZHU Han, WU Yixian, WANG Jin, Xu Riwei, WU Guanying, YANG Wantai. COORDINATION POLYMERIZATION OF 1,3-BUTADIENE WITH Ni(naph)2/A1R3/BF3·OEt2/DMEA/OctOH CATALYST SYSTEM. [J]. Acta Polymerica Sinica (6):640-646(2010)
DOI：

QIAO Yulu, ZHU Han, WU Yixian, WANG Jin, Xu Riwei, WU Guanying, YANG Wantai. COORDINATION POLYMERIZATION OF 1,3-BUTADIENE WITH Ni(naph)2/A1R3/BF3·OEt2/DMEA/OctOH CATALYST SYSTEM. [J]. Acta Polymerica Sinica (6):640-646(2010) DOI： 10.3724/SP.J.1105.2010.09204.

摘要

在Ni(naph)2-AlR3-(BF3·OEt2)催化体系（简称Ni-Al-B）用于丁二烯（Bd）/己烷进行配位聚合体系中引入N

N二甲基乙醇胺（DMEA）和辛醇（OctOH），研究了DMEA/Ni摩尔比、B/Ni摩尔比和Al/Ni摩尔比对Bd聚合转化率、聚丁二烯（PB）产物的特性黏数、分子量、分子量分布及微观结构的影响，进一步探讨聚合反应动力学.结果表明，在镍系催化丁二烯聚合体系中引入一定量的DMEA和OctOH 后，可以提高顺-1

4微观结构含量至97.8%，降低1

2微观结构含量至约1.3%，提高分子量，使分子量分布变窄，并降低凝胶含量.进一步通过调节B/Ni及Al/Ni摩尔比值，可得到［η］为20 ~ 4.0 dL/g的高顺式PB.聚合速率对单体浓度呈现一级动力学关系

表观增长活化能为43.7 kJ·mol-1.

Abstract

The coordination polymerization of 1

3-butadiene was conducted with Ni(naph)2/A1R3/BF3·OEt2 catalyst system in the presence of N

N-dimethyl ethanolamine (DMEA) and octanol (OctOH) in hexane at 50℃.The effects of molar ratios of DMEA/Ni

B/Ni and Al/Ni on monomer conversion

intrinsic viscosity (［η］)

molecular weight

molecular weight distribution and microstructure of polybutadiene (PB) were investigated.The kinetic study was also conducted for this polymerization at different temperatures ranging from 20℃ to 50℃.The results showed that DMEA and OctOH played very important roles in modifying molecular weight

molecular weight distribution and microstructure.By comparison

the molecular weight of polybutadiene products could be greatly increased

molecular weight distribution narrowed and cis1

4 content of Bd units in polymer chain increased to 97.8% and 1

2-content decreased to 1.3% by introducing adequate amounts of DMEA and OctOH

leading to more crystalline and less gel content.Furthermore

the intrinsic viscosity (［η］) of polymer products could also be modulated by changing the molar ratios of B/Ni and Al/Ni in the range of 2.0 ~ 4.0 dL/g.The polymerization was in first order with respect to monomer concentration at different polymerization temperatures.The apparent activation energy for propagation was determined to be 43.7 kJ·mol-1.

关键词

镍系催化剂丁二烯微观结构顺丁橡胶

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Centre for Polymers from Renewable Resources, South China University of Technology

CSIRO, Materials Science and Engineering

College of Food Science, South China Agricultural University

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