基于催化链转移聚合法MMA/MPS共聚物的制备及其表观催化链转移常数测定的研究

张冬; 王积毅; 陈 莉; 陈苏

doi:10.3724/SP.J.1105.2009.00651

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基于催化链转移聚合法MMA/MPS共聚物的制备及其表观催化链转移常数测定的研究

研究论文 | 更新时间：2021-03-19

- 基于催化链转移聚合法MMA/MPS共聚物的制备及其表观催化链转移常数测定的研究
- PREPARATION OF PMMA-co-PMPS COPOLYMERS VIA CATALYTIC CHAIN TRANSFER POLYMERIZATION TECHNIQUE AND EVALUATION OF THEIR APPARENT CHAIN TRANSFER CONSTANTS
- 高分子学报 2009年第7期页码：651-659
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- DOI：10.3724/SP.J.1105.2009.00651
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- 纸质出版日期：2009-7-20，
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张冬, 王积毅, 陈莉, 陈苏. 基于催化链转移聚合法MMA/MPS共聚物的制备及其表观催化链转移常数测定的研究[J]. 高分子学报, 2009,(7):651-659.

ZHANG Dong, WANG Jiyi, CHEN Li, CHEN Su. PREPARATION OF PMMA-co-PMPS COPOLYMERS VIA CATALYTIC CHAIN TRANSFER POLYMERIZATION TECHNIQUE AND EVALUATION OF THEIR APPARENT CHAIN TRANSFER CONSTANTS[J]. Acta Polymerica Sinica, 2009,(7):651-659.
张冬, 王积毅, 陈莉, 陈苏. 基于催化链转移聚合法MMA/MPS共聚物的制备及其表观催化链转移常数测定的研究[J]. 高分子学报, 2009,(7):651-659. DOI： 10.3724/SP.J.1105.2009.00651.

ZHANG Dong, WANG Jiyi, CHEN Li, CHEN Su. PREPARATION OF PMMA-co-PMPS COPOLYMERS VIA CATALYTIC CHAIN TRANSFER POLYMERIZATION TECHNIQUE AND EVALUATION OF THEIR APPARENT CHAIN TRANSFER CONSTANTS[J]. Acta Polymerica Sinica, 2009,(7):651-659. DOI： 10.3724/SP.J.1105.2009.00651.

摘要

以钴Ⅱ肟氟化硼络合物（CoBF）为催化剂，2

2′-偶氮二异丁腈（AIBN）为引发剂，实现了甲基丙烯酸甲酯（MMA）与γ-甲基丙烯酰氧基丙基三甲氧基硅烷（MPS）在6 0℃甲苯体系中的催化链转移聚合（catalytic chain transfer polymerization

CCTP），制备出末端含有双键的共聚物.利用核磁共振证明了其末端双键的存在，并通过热重分析证明CCTP 产物与自由基聚合产物的结构区别.用凝胶渗透色谱（GPC）对7种单体组成下不同催化剂CoBF用量的聚合产物进行分子量表征，结果表明以催化链转移聚合合成的共聚物具有分子量低及分子量分布较窄，且聚合物的分子量随着催化剂CoBF的增加呈明显下降趋势. 又分别采用了基于DPn(数均聚合度)、DPw(重均聚合度) 的Mayo方程和基于ΛP、ΛH 的链长分布方程计算出催化剂的表观链转移常数，发现基于DPw 的Mayo 方程和基于ΛP的链长分布方程的计算结果最为接近.并通过对共聚体系中不同单体组成的研究发现，催化剂表观链转移常数随着单体组成中MPS 的增加而增加.

Abstract

Catalytic chain transfer polymerization(CCTP) of methyl methacrylate(MMA) and γ-methacryloxypropyltrimethoxysilane (MPS) was perf orm ed using toluene as the solvent at 60℃ in the present of bis(boron difluorodim ethylglyoximate) cobaltate(Ⅱ)(CoBF) as catalytic chain transfer agent and AIBN as the initiator.Vinyl-terminated copolymers with low molecular weight were su ccessfully prepared by CCTP in this case. 1H-NMR was employed to prove the prese nce of vinyl unsaturated end groups of the as-prepared polymer.The effect of st ructure on thermal behavior was investigated by using thermogravimetry (TG) in n itrogen atmosphere.In contrast to PMMA-co-PMPS prepared in absence of CoBF

the differential thermogravimetry (DTG) curves of the copolymer synthesized by CCTP show that only one sharp peak appears at 283℃

which presents the degradation r e sulting from the random scission of the backbone and the terminal double bonds.G PC was carried out to analyze molecular weight information of copolymers synthes ized in different conditions.Results illuminated that average molecular weight decreased with the increase of CoBF.Apparent chain transfer constants (Ct) were determined with the conventional Mayo procedure based on number(Mn) and w eigh t(Mw) average molecular weights

and with chain length distribution procedu re ba sed on peak(ΛP) and high(ΛH) molecular weight slopes.It could be f ound that the apparent chain transfer constants determined fromMw and ΛP we re similar and much better than others.In addition

on the basis of different monomer feed compositions

we found that Ct values were increased with the concentration of MPS.

关键词

催化链转移聚合甲基丙烯酸甲酯γ-甲基丙烯酰氧基丙基三甲氧基硅烷链转移常数链长分布方程Mayo方程

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