Synthesis of Pyridine/Pyrrolimidine Cobalt/Nickel Complexes and Methyl Methacrylate Polymerization Catalyzed by Them

ZHU Xiao-yan; TAN Yin-yin; ZHENG Cheng-yu; ZHANG Qi; SUN Hao-tian; SU Bi-yun

doi:10.14028/j.cnki.1003-3726.2024.23.307

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Synthesis of Pyridine/Pyrrolimidine Cobalt/Nickel Complexes and Methyl Methacrylate Polymerization Catalyzed by Them

更新时间：2024-03-25

- Synthesis of Pyridine/Pyrrolimidine Cobalt/Nickel Complexes and Methyl Methacrylate Polymerization Catalyzed by Them
  增强出版
- Polymer Bulletin Vol. 37, Issue 4, Pages: 491-499(2024)
- 作者机构：
  
  西安石油大学油气田化学陕西省高校工程研究中心，西安　 710065
- 作者简介：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2024.23.307
  CLC：
- Received：05 September 2023，
  
  Accepted：2023-11-07，
  
  Published：20 April 2024
- 稿件说明：
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朱晓艳, 檀银银, 郑成宇, 张琦, 孙浩天, 苏碧云. 吡啶/吡咯亚胺型钴、镍配合物合成及其催化甲基丙烯酸甲酯聚合研究. 高分子通报, 2024, 37(4), 491–499

Zhu, X. Y.; Tan, Y. Y.; Zheng, C. Y.; Zhang Q.; Sun H. T.; Su, B. Y. Synthesis of pyridine/pyrrolimidine cobalt/nickel complexes and methyl methacrylate polymerization catalyzed by them. Polym. Bull. (in Chinese), 2024, 37(4), 491–499
朱晓艳, 檀银银, 郑成宇, 张琦, 孙浩天, 苏碧云. 吡啶/吡咯亚胺型钴、镍配合物合成及其催化甲基丙烯酸甲酯聚合研究. 高分子通报, 2024, 37(4), 491–499 DOI： 10.14028/j.cnki.1003-3726.2024.23.307.

Zhu, X. Y.; Tan, Y. Y.; Zheng, C. Y.; Zhang Q.; Sun H. T.; Su, B. Y. Synthesis of pyridine/pyrrolimidine cobalt/nickel complexes and methyl methacrylate polymerization catalyzed by them. Polym. Bull. (in Chinese), 2024, 37(4), 491–499 DOI： 10.14028/j.cnki.1003-3726.2024.23.307.

摘要

以冰醋酸/微波辐射催化2-乙酰基吡啶/吡咯与对苯二胺、卡巴肼发生Schiff碱缩合反应得到系列配体

L1~L4

，在甲醇/四氢呋喃中进一步与钴/镍氯化物反应获得配合物

1~8

。用元素分析、核磁氢谱、红外、紫外光谱和X-射线单晶衍射等手段对产物进行全面结构表征发现，配体

L1~L3

为二胺桥连的双亚胺吡啶/吡咯结构，

为单亚胺吡咯结构，配合物

1~6

均为双核配合物，而

7、8

为单核配合物。配体合成实验中发现

的产率最高，达到89.8%，说明苯胺与直链胺相比亲核性更强，更有利于产物的生成。通过系统研究配合物

1~8

对甲基丙烯酸甲酯(MMA)聚合催化行为与催化剂结构、聚合反应条件的关系发现，当聚合时间为6 h，温度为 90 ℃，单体与催化剂比例

(M)/

(Ni)为3000:1，主催剂和引发剂比例

(Ni)/

(AIBN)为2:1时，由2-乙酰基吡啶与对苯二胺缩合形成的双亚胺配体Ni(Ⅱ)配合物的催化活性最高，可达到4.3281×10

g∙mol

-1

∙h

-1

。

Abstract

A series of ligands

L1–L4

were synthesized by Schiff base condensation reaction of 2-acetylpyridine/pyrrole with

-phenylenediamine and carbazide catalyzed by glacial acetic acid/microwave radiation. Complexes

1–8

were further synthesized by reaction with cobalt/nickel chloride in methanol/tetrahydrofuran. The comprehensive structural characterization of the product was carried out using elemental analysis

nuclear magnetic resonance spectroscopy

infrared spectroscopy

ultraviolet spectroscopy

and X-ray single-crystal diffraction. It was found that the ligands

L1–L3

has a diamine bridged double imine pyridine/pyrrole structure

has a single imine pyrrole structure

and complexes

1–6

are all binuclear complexes

while complexes

and

are mononuclear. In the ligand synthesis experiment

it was found that the yield of

was the highest

reaching 89.8%

indicating that aniline has stronger nucleophilicity compared to linear amines and is more conducive to the generation of products. Through a systematic study of the relationship between the catalytic behavior of complexes

1–8

for the polymerization of methyl methacrylate (MMA) and the catalyst structure and polymerization reaction conditions

it was found that when the polymerization time was 6 h

the temperature was 90 ℃

the ratio of monomer to catalyst

(M)/

(Ni) was 3000:1

and the ratio of main catalyst to initiator

(Ni)/

(AIBN) was 2:1

the catalytic activity of the double imine ligand Ni(II) complex formed by the condensation of 2-acetylpyridine and

-phenylenediamine was the highest

reaching 4.3281×10

g∙mol

-1

∙h

-1

关键词

Keywords

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