Kinetics Study on Polyether Bulk End-cross-linking CuAAC Reaction

Ye-cheng Zou; Zheng-yang Qu; Jin-xian Zhai; Xiao-yan Guo; Rong-jie Yang

doi:10.11777/j.issn1000-3304.2016.15186

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Kinetics Study on Polyether Bulk End-cross-linking CuAAC Reaction

Research Article | 更新时间：2021-03-19

- Kinetics Study on Polyether Bulk End-cross-linking CuAAC Reaction
- Acta Polymerica Sinica Issue 2, Pages: 219-225(2016)
- 作者机构：
  
  北京理工大学材料学院,北京,100081
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2016.15186
  CLC：
- Published：20 February 2016，
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Ye-cheng Zou, Zheng-yang Qu, Jin-xian Zhai, Xiao-yan Guo, Rong-jie Yang. Kinetics Study on Polyether Bulk End-cross-linking CuAAC Reaction. [J]. Acta Polymerica Sinica (2):219-225(2016)
DOI：

Ye-cheng Zou, Zheng-yang Qu, Jin-xian Zhai, Xiao-yan Guo, Rong-jie Yang. Kinetics Study on Polyether Bulk End-cross-linking CuAAC Reaction. [J]. Acta Polymerica Sinica (2):219-225(2016) DOI： 10.11777/j.issn1000-3304.2016.15186.

摘要

采用原位红外光谱法研究了PTPEG/GAP反应动力学.利用PTPEG/GAP反应体系在2100 cm-1和1086 cm-1吸光度比值与反应时间的关系得到了PTPEG/GAP本体末端点击化学交联反应的动力学曲线. 曲线拟合表明

PTPEG/GAP本体末端交联反应过程分为明显的两个阶段;30 ℃时第一阶段反应动力学结束于535 min

40 ℃时为305 min

50 ℃时为295 min

60 ℃时为115 min. 黏度测试表明

PTPEG/GAP反应体系黏度() 随时间(t) 变化曲线呈L型;30 ℃时-t曲线拐点出现于540 min

40 ℃时为320 min

50 ℃时为305 min

60 ℃时为118 min

拐点前后分别对应PTPEG/GAP凝胶前、凝胶后状态;且-t曲线拐点时间与PTPEG/GAP第一阶段反应动力学结束时间相吻合. Arrhenius公式拟合表明

凝胶前

PTPEG/GAP末端点击化学交联反应表观活化能Ea1为(45.572.77)kJ/mol;凝胶后

表观活化能Ea2为(59.504.01)kJ/mol.

Abstract

In order to study the kinetic characters of bulk end-cross-linking CuAAC click reaction

in situ FTIR method was employed to investigate the kinetics of PTPEG/GAP bulk end-cross-linking CuAAC click reaction based on the spectral character of PTPEG and GAP.The kinetics curves of PTPEG/GAP bulk end-cross-linking CuAAC click reaction were obtained on the basis of the relationship of the absorbance ratio at 2100 cm-1 and 1086 cm-1 changing with time.The results of fitting curves indicated that during the whole reaction

two obvious stages were observed.At 30 ℃

40 ℃

50 ℃ and 60 ℃

the first stage ended at 535 min

305 min

295 min and 115 min

respectively.Shear viscosity () results showed that the curves of changed along with reaction time showed an L-like shape.At 30 ℃

40 ℃

50 ℃ and 60 ℃

the inflection point of -t curves appeared at 540 min

320 min

305 min and 118 min

respectively.The inflection point time of -t curves was consistent with the end time of first stage of the PTPEG/GAP.Arrhenius equation fitting results indicated that the activation energy of the first stage corresponding to the reaction before gelation of PTPEG/GAP was (45.572.77)kJ/mol while that of the second stage corresponding to the reaction after gelation was (59.504.01)kJ/mol.

关键词

点击化学端丙炔基聚乙二醇(PTPEG)本体末端交联光谱分析反应动力学

Keywords

Click chemistryPropargyl-terminated poly(ethylene glycol) (PTPEG)Bulk end-cross-linkingSpectral analysisReaction kinetics

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