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《合成橡胶工业》[ISSN:1000-1255/CN:62-1036/TQ]

期数:

2024年1期

页码:

12-17

栏目:

出版日期:

2024-01-15

文章信息/Info

Title:

Synthesis and 1,3-butadiene polymerization behavior of cobalt complexes containing benzotriazole-substituted pyridine ligands

文章编号:

1000-1255（2024）01-0012-06

作者:

郭姜文1; 王书唯1?鄢; 张松波2?鄢; 胡雁鸣2

1． 大连工业大学 纺织与材料工程学院，辽宁 大连 116034； 2． 中科院大连化学物理研究所 能源材料部，辽宁 大连 116023

Author(s):

GUO Jiang-wen1; WANG Shu-wei1; ZHANG Song-bo2; HU Yan-ming2

1. School of Textile and Material Engineering，Dalian Polytechnic University，Dalian 116034，China; 2. Division of Energy Materials，Dalian Institute of Chemical Physics of the Chinese Academy of Sciences，Dalian 116023，China

关键词:

苯并三氮唑; 聚丁二烯; 钴系催化剂; 取代基; 聚合温度

Keywords:

benzotriazole;  polybutadiene;  cobalt catalyst;  substituent;  polymerization temperature

分类号:

TQ 333.2

DOI:

DOI:10.19908/j.cnki.ISSN1000-1255.2024.01.0012

文献标识码:

A

摘要:

合成了苯并三氮唑取代吡啶配体的钴配合物，研究了助催化剂种类、取代基结构及聚合温度和时间对1,3-丁二烯聚合的影响。结果显示，经甲基铝氧烷活化后，配合物表现出较高的催化丁二烯聚合活性。配合物的活性取决于配体上吡啶2-位的取代基，其体积的增大导致活性降低，但与聚合物的顺式-1,4-结构选择性并无明显关联。其中，取代基为氢的钴配合物的活性和顺式-1,4-结构选择性最高，可制备出顺式-1,4-结构摩尔分数为94.0%、数均分子量达124.8×103 g/mol、分子量分布窄（多分散性指数2.0）的聚丁二烯。升高反应温度可明显提高聚合速率，在80 ℃的高温下聚合物收率仍可达93.6%，表明该催化剂体系具有很高的热稳定性。

Abstract:

A series of cobalt complexes contai-ning benzotriazole-substituted pyridine ligands were synthesized. The effects of the type of cocatalyst, substituent structure, and polymerization temperature and time on 1,3-butadiene polymerization were investigated. The results showed that after activation by methylaluminoxane, these complexes exhibited medium to high activities for 1,3-butadiene polyme-rization. The activity of the complex depended on the substituent at 2-position of pyridine on the ligand. An increment of the bulkiness of substituent resulted in a decrease in activity, but it was not significantly related to the cis-1,4- selectivity of the polymer. Among them, cobalt complex with hydrogen substituent group showed the highest activity and cis-1,4- selectivity, affording polybutadiene with predominant cis-1,4- unit mole fraction of 94.0%, a number average molecular weight of 124.8×103 g/mol, and a narrow molecualr weight distribution (polydispersity index 2.0). Raising the reaction temperature could significantly increase the polymerization rate, even at a high temperature of 80 ℃，the polymer yield remained up to 93.6%, implying the high thermal stability of the catalyst system.

参考文献/References

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备注/Memo

备注/Memo:

中国石油科技管理部资助项目（2019 F-26）。

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更新日期/Last Update: 1900-01-01