4, 4'-二甲氧基二苯基氮氧自由基调控甲基丙烯酸甲酯聚合动力学研究

朱哲成; 单国荣

doi:10.11777/j.issn1000-3304.2017.16296

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4, 4'-二甲氧基二苯基氮氧自由基调控甲基丙烯酸甲酯聚合动力学研究

研究论文 | 更新时间：2021-03-19

- 4, 4'-二甲氧基二苯基氮氧自由基调控甲基丙烯酸甲酯聚合动力学研究
- Kinetics of Methyl Methacrylate Polymerization Mediated by 4, 4'-Dimethoxydiphenyl Nitroxide
- 高分子学报 2017年第6期页码：930-936
- 作者机构：
  
  化学工程联合国家重点实验室(浙江大学) 浙江大学化学工程与生物工程学院杭州 310027
- 作者简介：
  
  单国荣, E-mail:shangr@zju.edu.cn Guo-rong Shan, E-mail: shangr@zju.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2017.16296
  中图分类号：
- 纸质出版日期：2017-6，
  
  收稿日期：2016-9-21，
  
  修回日期：2016-10-26，
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朱哲成, 单国荣. 4, 4'-二甲氧基二苯基氮氧自由基调控甲基丙烯酸甲酯聚合动力学研究[J]. 高分子学报, 2017,(6):930-936.

Zhe-cheng Zhu, Guo-rong Shan. Kinetics of Methyl Methacrylate Polymerization Mediated by 4, 4'-Dimethoxydiphenyl Nitroxide[J]. Acta Polymerica Sinica, 2017,(6):930-936.
朱哲成, 单国荣. 4, 4'-二甲氧基二苯基氮氧自由基调控甲基丙烯酸甲酯聚合动力学研究[J]. 高分子学报, 2017,(6):930-936. DOI： 10.11777/j.issn1000-3304.2017.16296.

Zhe-cheng Zhu, Guo-rong Shan. Kinetics of Methyl Methacrylate Polymerization Mediated by 4, 4'-Dimethoxydiphenyl Nitroxide[J]. Acta Polymerica Sinica, 2017,(6):930-936. DOI： 10.11777/j.issn1000-3304.2017.16296.

摘要

合成了4

4'-二甲氧基二苯基氮氧自由基（DMDPN）和相应的烷氧基胺引发剂，用于甲基丙烯酸甲酯（MMA）的氮氧自由基调控聚合，研究了聚合过程中的动力学机理.通过电子自旋共振（ESR）表征，测定了DMDPN型烷氧基胺引发剂在100~120℃范围内的解离速率常数

，结果表明

符合阿伦尼乌斯公式（

），其活化能

为135.2 kJ·mol

-1

，指前因子

为3×10

.测定了末端官能团化聚合物PMMA-DMDPN的解离速率常数

，由于DMDPN中胺氧基团周围的空间位阻较小，受到前末端效应的影响较弱，

仅为

的6倍.采用间接法测定了110℃时增长自由基和DMDPN的结合速率常数

，并绘制了该温度下MMA/DMDPN聚合体系的Fischer相图，结果表明该聚合体系对应的

和

值处于相图的可控/“活性”区域内.

Abstract

Controlled/living radical polymerization (CLRP) is one of themost rapidly developingareas in polymer science. Amongthe various existing techniques

nitroxide-mediated polymerization (NMP) was the first to be proposed. Up to now

most of the nitroxides studied in NMP are dialkyl or alkyl-arylnitroxides

while the use of diarylnitroxides as control radicals has not been extensively studied. In this paper

4'-dimethoxydiphenyl nitroxide (DMDPN) and its corresponding alkoxyamine initiator were easily synthesized and used to mediate the polymerization of methyl methacrylate (MMA). DMDPN was highly stable at high temperature and the single electron delocalisation on the aromatic rings prevented the undesired hydrogen abstraction between the nitroxide and the propagating radical chain. The polymerization kinetics was monitored by gravimetric method while the molecular weight and the distribution of poly(methyl methacrylate) (PMMA) synthesized were determined by gel permeation chromatography (GPC).The dissociation rate constants (

) of the DMDPN-based alkoxyamine initiator wasdetermined by electron spin resonance (ESR) experiments performed at temperatures ranging from 100℃ to 120 ℃

yielded thefollowing Arrhenius parameters:

=135.2 kJ·mol

-1

and

=3×10

. The

value of macromolecular species was also determined at 110 ℃. As the low steric hindrance around the aminoxyl group in DMDPN

the penultimate unit effect

which was significant in a MMA/SG1(

tert

-butyl-

-(1-diethyl-phosphono-2

2-di-methylpropyl) nitroxide) system

had only a weak influence on

in the MMA/DMDPN system. A 6-fold increase of

between the DMDPN-based alkoxyamine initiator and PMMA-DMDPN macro-alkoxyamine was observed. A bulkpolymerization of MMA was performed at 110 ℃ using 1 mol% of DMDPN-based alkoxyamine in the presence of 0.5 mol% of the corresponding free nitroxide to determine the equilibrium constant

. The recombination rate constant (

) was then derived from the constant

. A Fischer's diagram for the polymerization of MMA at 110℃ was made and the values of

and

lied in the living and controlled area

proving the livingness of this polymerization system.

关键词

氮氧自由基调控聚合甲基丙烯酸甲酯4 4'-二甲氧基二苯基氮氧自由基动力学常数Fischer相图

Keywords

Nitroxide-mediated polymerizationMethyl methacrylate4 4'-Dimethoxydiphenyl nitroxideKinetic constantFischer's diagram

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