膦腈碱催化一步合成聚氧化苯乙烯大分子单体及其接枝共聚

徐炜琴; 梁天; 杨宏军; 薛小强; 黄文艳; 蒋其民; 蒋必彪

doi:10.11777/j.issn1000-3304.2018.18180

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膦腈碱催化一步合成聚氧化苯乙烯大分子单体及其接枝共聚

研究论文 | 更新时间：2021-01-26

- 膦腈碱催化一步合成聚氧化苯乙烯大分子单体及其接枝共聚
- One-step Synthesis of Poly(styrene oxide) Macromonomers Catalyzed by Phosphazene Base and Graft Copolymerization
- 高分子学报 2019年50卷第2期页码：118-123
- 作者机构：
  
  1.江苏省环境友好高分子材料重点实验室常州大学材料科学与工程学院江苏省光伏科学与工程协同创新中心　常州 213164
  2.常州大学怀德学院　靖江 214500
- 作者简介：
  
  E-mail: jiangbibiao@cczu.edu.cn Bi-biao Jiang, E-mail: jiangbibiao@cczu.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 21474010)资助项目()
- DOI：10.11777/j.issn1000-3304.2018.18180
  中图分类号：
- 纸质出版日期：2019-2，
  
  网络出版日期：2018-10-12，
  
  收稿日期：2018-8-13，
  
  修回日期：2018-9-5，
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徐炜琴, 梁天, 杨宏军, 薛小强, 黄文艳, 蒋其民, 蒋必彪. 膦腈碱催化一步合成聚氧化苯乙烯大分子单体及其接枝共聚[J]. 高分子学报, 2019,50(2):118-123.

Wei-qin Xu, Tian Liang, Hong-jun Yang, Xiao-qiang Xue, Wen-yan Huang, Qi-min Jiang, Bi-biao Jiang. One-step Synthesis of Poly(styrene oxide) Macromonomers Catalyzed by Phosphazene Base and Graft Copolymerization[J]. Acta Polymerica Sinica, 2019,50(2):118-123.
徐炜琴, 梁天, 杨宏军, 薛小强, 黄文艳, 蒋其民, 蒋必彪. 膦腈碱催化一步合成聚氧化苯乙烯大分子单体及其接枝共聚[J]. 高分子学报, 2019,50(2):118-123. DOI： 10.11777/j.issn1000-3304.2018.18180.

Wei-qin Xu, Tian Liang, Hong-jun Yang, Xiao-qiang Xue, Wen-yan Huang, Qi-min Jiang, Bi-biao Jiang. One-step Synthesis of Poly(styrene oxide) Macromonomers Catalyzed by Phosphazene Base and Graft Copolymerization[J]. Acta Polymerica Sinica, 2019,50(2):118-123. DOI： 10.11777/j.issn1000-3304.2018.18180.

摘要

以4-乙烯基苄醇(VBA)为引发剂，膦腈碱

-BuP

为催化剂，室温下催化氧化苯乙烯(SO)进行开环聚合一步合成聚氧化苯乙烯(PSO)大分子单体. PSO大分子单体与甲基丙烯酸甲酯(MMA)在不同温度下进行自由基共聚合成接枝共聚物. 用核磁(

H-NMR)、凝胶渗透色谱(GPC)、示差扫描量热仪(DSC)等对引发剂和聚合物结构及性能进行表征分析. 结果表明成功合成了功能引发剂VBA.

-BuP

能顺利催化SO聚合一步合成结构可控的PSO大分子单体，大分子单体PSO与MMA可以顺利共聚合成接枝共聚物. GPC和

H-NMR分析表明：合成的大分子单体中约有4.0%的惰性组分. DSC测得共聚物只有1个玻璃化转变温度，而且与理论计算值相吻合.

Abstract

Poly(styrene oxide) (PSO) macromonomers were synthesized in one step through the anionic ring-opening polymerization (ROP) of styrene oxide (SO) at room temperature

with 1-

tert

-butyl-4

4-tris(dimethylamino)-2

2-bis[tris(dimethylamino)-phosphoranylidenamino]-2Ʌ

4Ʌ

-catenadi-(phosphazene) (

-BuP

) as the catalyst

and 4-vinylbenzyl alcohol (VBA) as the functional initiator. The copolymerization of PSO macromonomers and methyl methacrylate (MMA) was carried out at different temperatures through free radical co-polymerization to prepare graft copolymers. The structures and properties of the functional initiator

the obtained macromonomers and the grafted copolymers were characterized by nuclear magnetic resonance spectroscopy (NMR)

gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). The results showed that functional initiator VBA was synthesized successfully. Super base

-BuP

displayed high catalytic activity for the ring-opening polymerization of SO

resulting in PSO macromonomers with polymerizable vinyl group

controlled molecular weight (

= 2700 – 11300 g/mol)

and narrow molecular weight distribution (

1.19). NMR measurement confirmed that the copolymerization of PSO macromonomers and MMA was carried out successfully to produce grafted copolymers. With the increase of copolymerization temperature

the conversion of MMA increased (

96%)

while the molecular weight of the copolymers decreased and the molecular weight distribution became narrow. The GPC curves of the product for the copolymerization before precipitation were bimodal

the molecular weight of the obtained polymers was low (6200 – 7800 g/mol) and the molecular weight distribution was wide (6.39 – 10.41). After precipitation

the GPC curves showed a unimodal signal

the molecular weight became larger (4.33 × 10

– 5.95 × 10

g/mol) and the molecular weight distribution became narrower (1.46 – 1.62). Integral calculation of the GPC curves and NMR measurement confirmed that there were about 3.8% – 4.6% inert components in the synthesized macromonomers. For the thermal analysis of PSO

PMMA-

-PSO and PMMA

the glass transition temperature (

) measured by DSC showed that the prepared grafted copolymer had only one

which was in good accordance with the theoretical value calculated according to the Fox equation. This result further proved that the graft copolymers were successfully prepared.

关键词

大分子单体接枝共聚膦腈碱一步法

Keywords

MacromonomerGraft copolymerizationPhosphazene baseOne-step method

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