可见光诱导苯乙烯的常温快速可逆加成-断裂链转移聚合

doi:10.7503/cjcu20170546

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (4): 800.doi: 10.7503/cjcu20170546

可见光诱导苯乙烯的常温快速可逆加成-断裂链转移聚合

罗菊香¹, 程德书¹, 李明春², 辛梅华²()

1. 三明学院资源与化工学院, 三明 365004
2. 华侨大学材料科学与工程学院, 厦门 361021

收稿日期:2017-08-08 出版日期:2018-04-10 发布日期:2017-12-05
作者简介:联系人简介: 辛梅华, 女, 博士, 教授, 主要从事高分子合成研究. E-mail:mhxin@hqu.edu.cn
基金资助:
国家自然科学基金(批准号: 51703120)、福建省中青年教师教育科研项目(批准号: JAT160453)、三明学院科学研究发展基金(批准号: B201602)和福建省教育厅科研项目(批准号: 2016038)资助

Visible Light Induced Rapid Reversible Addition-fragmentation Chain Transfer Polymerization(RAFT )of Styrene at Room Temperature^†

LUO Juxiang¹, CHENG Deshu¹, LI Mingchun², XIN Meihua^2,^*()

1. School of Resourses and Chemical Engineering, Sanming University, Sanming 365004, China
2. College of Material Science and Engineering, Huaqiao University, Xiamen 361021, China

Received:2017-08-08 Online:2018-04-10 Published:2017-12-05
Contact: XIN Meihua E-mail:mhxin@hqu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.51703120), the Education Research Found for Yong and Middle-aged Teachers in Fujian Province, China(No.JAT160453), the Scientific Research Development Fund of Sanming University, China(No.B201602) and the Project of Scientific Research of Fujian Education Department, China(No.2016038)

摘要/Abstract

摘要：

以商用蓝光发光二极管(LED)为可见光光源, 十二烷基-S'-(α,α'-二甲基-α″-乙酸)三硫代碳酸酯(DDMAT)为可逆加成-断裂链转移聚合(RAFT)试剂, 不加光引发剂或光催化剂, 实现了可见光诱导苯乙烯(St)的常温快速RAFT 聚合. 研究结果表明, 该聚合具有活性聚合的特征; 当光源关闭时, 聚合停止, 当光源开启时, 聚合进行, 且光的开关循环对聚合的活性没有影响. 通过原位核磁的方法对DDMAT的光致断裂和光致降解行为进行了研究, 该结果有助于进一步了解可见光诱导St的常温快速聚合的化学过程.

关键词: 可逆加成-断裂链转移聚合, 苯乙烯, 蓝光发光二极管, 动力学性能

Abstract:

The implementation of photoinitiators and photocatalysts-free visible light induced reversible addition-fragmentation chain transfer(RAFT) polymerization processes at room temperature has the potential to afford greener methodology to the preparation of polymeric materials. However, these previous works pointed out that photoinduced RAFT polymerization of styrene(St) at room temperature was very slowly even with exogenous photoinitiators or photocatalysts. In this work, we aim to overcome these drawbacks via the implementation of commercial blue light-emitting diodes(LEDs) as visible light source in the RAFT polymerization of St at room temperature with S-1-dodecyl-S'-(α,α'-dimethyl-α″-aceticacid)trithiocarbonate(DDMAT) as RAFT agent, without exogenous photoinitiators or photocatalysts. The polymerization rate was comparatively rapid and the results of polymerization kinetics of St show that the polymerization exhibits good living characteristics. Importantly, the polymerization could be instantly switch “On” or “Off ” in response to visible light, and the switching cycles of light had no effect on the living character of polymerization. Finally, the photo-fragmentation and photo-degradation of DDMAT were investigated by in situ ¹H NMR(nuclear magnetic resonance) spectroscopy. The detailed study provides a deeper understanding of the chemical processes of the polymerization method.

Key words: Reversible addition-fragmentation chain transfer(RAFT) polymerization, Styrene(St), Blue light-emitting diode(LED), Kinetics property

中图分类号:

O631

TrendMD:

罗菊香, 程德书, 李明春, 辛梅华. 可见光诱导苯乙烯的常温快速可逆加成-断裂链转移聚合. 高等学校化学学报, 2018, 39(4): 800.

LUO Juxiang, CHENG Deshu, LI Mingchun, XIN Meihua. Visible Light Induced Rapid Reversible Addition-fragmentation Chain Transfer Polymerization(RAFT )of Styrene at Room Temperature^†. Chem. J. Chinese Universities, 2018, 39(4): 800.

图/表 13

Scheme 1 Schematic of the visible light induced RAFT polymerization of St at room temperature

Fig.1 Absorption spectra of 0.1 mmol/L(A) and 5.0 mmol/L(B) DDMAT in ethanol

Fig.2 GPC trace of polystyrene(PSt) synthesized via visible light induced RAFT polymerization[St]0:[DDMAT]0=100:1, [M]0=48 mmol.

Fig.3 ln([M]0/[M]) as a function of time for the visible light induced RAFT polymerization of St

Fig.4 Mn and Mw/Mn versus conversion for visible light induced RAFT of St

Fig.5 GPC traces of PSt synthesized via RAFT polymerization

Fig.6 GPC traces for PSt-b-PBA(a) and PSt-TTC(b)

Fig.7 1H NMR spectrum of PSt-TTC

Fig.8 1H NMR spectrum of PSt-b-PBA polymer

Fig.9 Conversion as a function of time in “On/Off” experiment of visible light induced RAFT polymerization

Fig.10 Mn and Mw/Mn as a function of conversion in “On/Off” experiment of visible light induced RAFT polymerization

Fig.11 1H NMR spectra of 10 mmol/L(A) and 50 mmol/L(B) DDMAT solution before(a) and after the light radiation[30 min(b) and 60 min(c)]

Fig.12 1H NMR spectra of 50 mmol/L DDMAT solution before(a) and after(b) the light radiation

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可见光诱导苯乙烯的常温快速可逆加成-断裂链转移聚合

Visible Light Induced Rapid Reversible Addition-fragmentation Chain Transfer Polymerization(RAFT )of Styrene at Room Temperature^†

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可见光诱导苯乙烯的常温快速可逆加成-断裂链转移聚合

Visible Light Induced Rapid Reversible Addition-fragmentation Chain Transfer Polymerization(RAFT )of Styrene at Room Temperature†

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Visible Light Induced Rapid Reversible Addition-fragmentation Chain Transfer Polymerization(RAFT )of Styrene at Room Temperature^†