A REVERSE ATRP PROCESS CATALYZED BY NICKEL-BASED (NiCl2/PPh3) SYSTEM

QIN Dongqi; QIN Shuhui; QIU Kunyuan

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A REVERSE ATRP PROCESS CATALYZED BY NICKEL-BASED (NiCl2/PPh3) SYSTEM

Research Article | 更新时间：2021-03-19

- A REVERSE ATRP PROCESS CATALYZED BY NICKEL-BASED (NiCl2/PPh3) SYSTEM
- Acta Polymerica Sinica Issue 1, Pages: 108-112(2002)
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- Published：20 February 2002，
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QIN Dongqi, QIN Shuhui, QIU Kunyuan. A REVERSE ATRP PROCESS CATALYZED BY NICKEL-BASED (NiCl2/PPh3) SYSTEM. [J]. Acta Polymerica Sinica (1):108-112(2002)
DOI：

QIN Dongqi, QIN Shuhui, QIU Kunyuan. A REVERSE ATRP PROCESS CATALYZED BY NICKEL-BASED (NiCl2/PPh3) SYSTEM. [J]. Acta Polymerica Sinica (1):108-112(2002) DOI：

摘要

以2

3-二氰基-2

3-二苯基丁二酸二乙酯 (DCDPS)/NiCl2/PPh3为引发体系

首次利用Ni2+和Ni+之间的变价关系

研究了乙烯基单体的反向ATRP .结果表明

苯乙烯 (St)的聚合具有活性自由基聚合的特征

所得PSt的分子量随转化率的增加而增加

并且制得的PSt可以作为大分子引发剂进行扩链反应 .但该引发体系引发甲基丙烯酸甲酯(MMA)聚合时没有活性自由基聚合特征

PMMA的分子量与转化率基本无关

但分子量分布窄Mw/Mn=1.19.

Abstract

Radical polymerization of styrene and methyl methacrylate was investigated using a nickel-based initiating system

i．e．DCDPS／NiCl2／PPh3

in which diethyl 2

3-dicyano-2

3-diphenyl-succinate (DCDPS) is a hexa-substituted ethane thermal iniferter and the nickel based catalyst reacted from Ni2+ to Ni1+．The polymerization of styrene (St) was successfully controlled in bulk at 120℃．The kinetics studies showed that the kinetics is first order in monomer．The number average molecular weight Mn increased linearly with conversion from 57100 to 126000

and the molecular weight distributions(Mw／Mn) were around l.5 as the monomer conversion was increased from 38％ to 86％．Well defined polystyrene with α-(carbethoxycyanophenyl)methyl-ω-chlorine end groups was obtained from the polymerization of St with DCDPS／NiCl2／PPh3 initiating system

and the polymerization proceeded via reverse ATRP．While the polymerization behavior of methyl methacrylate (MMA) initiated with the same system was absolutely different．The molecular weights of so-obtained PMMA did not increase with the monomer conversions and at the same time the molecular weight distributions kept narrow (Mw／Mn=1.19) during the polymerization．

关键词

活性自由基聚合NiCl2PPh323二氰基23二苯基丁二酸二乙酯(DCDPS)甲基丙烯酸甲酯(MMA)苯乙烯(St

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