“可点击”丙烯酸酯聚合物的合成及其巯-炔光交联研究

doi:10.7517/j.issn.1674-0475.2018.01.008

影像科学与光化学 ›› 2018, Vol. 36 ›› Issue (1): 82-88.DOI: 10.7517/j.issn.1674-0475.2018.01.008

“可点击”丙烯酸酯聚合物的合成及其巯-炔光交联研究

税小川, 刘宇, 王跃川

四川大学高分子科学与工程学院高分子材料与工程国家重点实验室, 四川成都 610065

收稿日期:2017-02-18 修回日期:2017-04-05 出版日期:2018-01-15 发布日期:2018-01-15
通讯作者: 王跃川

Synthesis of “Clickable” Acrylate Polymers and Their Thiol-alkyne Photocrosslinking Reaction

SHUI Xiaochuang, LIU Yu, WANG Yuechuan

State Key Laboratory of Polymer Materials Engineering, College of Polymer Science and Engineering, Sichuan University, Chengdu 610065, Sichuan, P. R. China

Received:2017-02-18 Revised:2017-04-05 Online:2018-01-15 Published:2018-01-15

摘要/Abstract

摘要： 通过丙烯酰氯和1-乙炔基1-环己醇的酯化反应，制备了乙炔基功能化的丙烯酸酯功能单体1-乙炔基环己基丙烯酯（ECA）。以该单体与丙烯酸甲酯（MA）进行自由基聚合反应，合成了乙炔基功能化均聚物（PECA）和共聚物（PMA-co-PECA），用¹HNMR、FT-IR、GPC等对其结构进行了表征。结果表明：在自由基聚合过程中，ECA中的乙炔基得以保留，所得到的乙炔基功能化聚合物可溶于普通有机溶剂，如氯仿、二甲基亚砜、四氢呋喃、丙酮等。实时红外跟踪了PMA-co-PECA与三羟甲基丙烷三巯基丙酸酯经光引发的巯-炔反应，得到交联的聚合物网络，凝胶分数大于90%，表明聚合物链上保留的乙炔基与巯基的加成反应有较高的活性，可以通过硫醇-炔点击反应实现快速功能化。

关键词: 含炔基功能聚合物, 自由基聚合, 巯-炔点击反应, 光交联反应

Abstract: A acetylene functionalized acrylate monomer, 1-ethynylcyclohexyl acrylate(ECA), was prepared by the esterification of acryloyl chloride with 1-ethynyl 1-cyclohexanol. Then the acetylene functionalized polyacrylates PECA and PMA-co-PECA were synthesized through the free radical homopolymerization of ECA and copolymerization of ECA with methyl acrylate(MA).The structure of PECA and PMA-co-PECA were characterized by ¹HNMR, FTIR and GPC. The results suggest that the triple bonds were completely retained, and the resulting polymers were soluble in common solvents such as chloroform, dimethyl sulfoxide, tetrahydrofuran, acetone, etc. The thiol-yne reaction between PMA-co-PECA and trimethylolpropane tri(3-mercaptopropionate) (TMTP) was monitored by real-time IR, suggesting that the acetylene bearing polymers can be rapidly photocrosslinked and functionalized by thiol-alkyne reaction, and the bulk tertairy group does not affect the reactivity of the thiol-yne reaction.The gel fraction of the yeilding network was found to be more than 90%.

Key words: acetylene bearing polyacrylate, free radical polymerization, thiol-yne click chemistry, photocrosslinking reaction

税小川, 刘宇, 王跃川. “可点击”丙烯酸酯聚合物的合成及其巯-炔光交联研究[J]. 影像科学与光化学, 2018, 36(1): 82-88.

SHUI Xiaochuang, LIU Yu, WANG Yuechuan. Synthesis of “Clickable” Acrylate Polymers and Their Thiol-alkyne Photocrosslinking Reaction[J]. Imaging Science and Photochemistry, 2018, 36(1): 82-88.

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“可点击”丙烯酸酯聚合物的合成及其巯-炔光交联研究

Synthesis of “Clickable” Acrylate Polymers and Their Thiol-alkyne Photocrosslinking Reaction

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