SCI和EI收录∣中国化工学会会刊

›› 2014, Vol. 22 ›› Issue (9): 1046-1054.DOI: 10.1016/j.cjche.2014.06.030

• 材料与产品工程 • 上一篇    下一篇

In-situ IR Monitoring the Synthesis of Amphiphilic Copolymery P(HEMA-co-tBMA) via ARGET ATRP

Wenjing Lin1, Youqiang Yang1, Ruihao Chen1, Xiufang Wen1, Yu Qian1, Chengzhi Cai2, Lijuan Zhang1   

  1. 1 School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China;
    2 Department of Chemistry & Center for Materials Chemistry, University of Houston, Houston, TX 77204-5003, USA
  • 收稿日期:2013-07-03 修回日期:2013-11-01 出版日期:2014-09-28 发布日期:2014-11-04
  • 通讯作者: Lijuan Zhang
  • 基金资助:
    Supported by the National Natural Science Foundation of China (21176090, 21136003), Team Project of Natural Science Foundation of Guangdong Province (S2011030001366), Science and Technology Foundation of Guangdong Province (2012B050600010), and Fundamental Research Funds for the Central Universities (2013ZP0010).

In-situ IR Monitoring the Synthesis of Amphiphilic Copolymery P(HEMA-co-tBMA) via ARGET ATRP

Wenjing Lin1, Youqiang Yang1, Ruihao Chen1, Xiufang Wen1, Yu Qian1, Chengzhi Cai2, Lijuan Zhang1   

  1. 1 School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China;
    2 Department of Chemistry & Center for Materials Chemistry, University of Houston, Houston, TX 77204-5003, USA
  • Received:2013-07-03 Revised:2013-11-01 Online:2014-09-28 Published:2014-11-04
  • Supported by:
    Supported by the National Natural Science Foundation of China (21176090, 21136003), Team Project of Natural Science Foundation of Guangdong Province (S2011030001366), Science and Technology Foundation of Guangdong Province (2012B050600010), and Fundamental Research Funds for the Central Universities (2013ZP0010).

摘要: The amphiphilic copolymer poly(hydroxyethyl methacrylate-co-tert-butyl methacrylate) [P(HEMA-co-tBMA)] was synthesized by activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP), with the synthesis process monitored by in-situ infrared spectroscopy (IR). The molecular weight, chemical structure and characteristics of the copolymer were determined by 1H NMR, gas chromatography and gel permeation chromatography. The influences of various parameters on the living polymerization were explored. The molecularweight of the copolymer with narrowmolecularweight distribution (Mw/Mn b 1.50) increases approximately linearly with the monomer conversion, indicating a good control of polymerization. In the reaction temperature range from 50℃ to 90℃, the monomer conversion is higher at 60℃. The tBMA conversion rate decreases gradually with the increase of tBMA content, while the HEMA conversion is hardly affected by HEMA content. Weak polar solvent is more favorable to the polymerization compared to polar solvent. The molar ratio of reducing agent to catalyst has significant effect on the polymerization and increasing the amount of reducing agent will accelerate the reaction rate but causes wider molecular weight distribution. It is indicated that in-situ IR monitoring contributes to a more in-depth understanding of the mechanism of methacrylate monomer copolymerization.

关键词: In-situ IR monitoring, Amphiphilic copolymer, ARGET ATRP, Conversion rate

Abstract: The amphiphilic copolymer poly(hydroxyethyl methacrylate-co-tert-butyl methacrylate) [P(HEMA-co-tBMA)] was synthesized by activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP), with the synthesis process monitored by in-situ infrared spectroscopy (IR). The molecular weight, chemical structure and characteristics of the copolymer were determined by 1H NMR, gas chromatography and gel permeation chromatography. The influences of various parameters on the living polymerization were explored. The molecularweight of the copolymer with narrowmolecularweight distribution (Mw/Mn b 1.50) increases approximately linearly with the monomer conversion, indicating a good control of polymerization. In the reaction temperature range from 50℃ to 90℃, the monomer conversion is higher at 60℃. The tBMA conversion rate decreases gradually with the increase of tBMA content, while the HEMA conversion is hardly affected by HEMA content. Weak polar solvent is more favorable to the polymerization compared to polar solvent. The molar ratio of reducing agent to catalyst has significant effect on the polymerization and increasing the amount of reducing agent will accelerate the reaction rate but causes wider molecular weight distribution. It is indicated that in-situ IR monitoring contributes to a more in-depth understanding of the mechanism of methacrylate monomer copolymerization.

Key words: In-situ IR monitoring, Amphiphilic copolymer, ARGET ATRP, Conversion rate