Abstract: The carboxyl-functionalized polybutadiene(PBu-COOH) was synthesized via a thiol-ene click-chemical method, and was subsequently used as a curing agent to produce a series of epoxy thermosets with different adding amount of PBu-COOH. The chemical structure of the resultant PBu-COOH was characterized by means of 1H NMR and Fourier transform infrared spectroscopy (FTIR). In addition, the curing mechanism of epoxy resin with the presence of PBu-COOH and chemical structure of epoxy thermosets were studied via FTIR. The thermal properties of polybutadiene and PBu-COOH were also obtained by differential scanning calorimetry (DSC). Our experiment confirmed the successful synthesis of PBu-COOH, and the higher glass transition temperature (Tg) of PBu-COOH compared with polybutadiene. The tentative curing mechanism of PBu-COOH is the cross-linking of epoxy resin through the ring-opening reaction between multi-carboxyl and epoxy groups which results in the generation of hydroxyl and ester groups. It was observed that a relatively low curing agent/resin mass ratio (3∶7) could make epoxy resin cross-link completely.
1 Goodman S H. Handbook of Thermoset Plastics[M].New Jersey:Noyes Publications,1998. 2 Pascault J P, Sautereau H, Verdu J, et al. Thermosetting polymers[M].New York:Marcel Dekker,2002:367. 3 May C A, Tanaka G Y. Epoxy resin chemistry and technology[M].New York:Marcel Dekker,1973. 4 Wang Honghua, Liu Xiaoqing, Liu Bo, et al. Synthesis of rosin-based flexible anhydride-type curing agents and properties of the cured epoxy[J].Polymer International,2009,58(12):1435. 5 Sylvain Caillol, Ghislain David, Bernard Boutevin, et al. Biobased thermosetting epoxy: Present and future[J].Chemical Reviews,2013,114:1082. 6 Li Chunmei, Tan Jiaojun, Gu Junwei, et al. Facile synthesis of imi-dazole microcapsules via thiol-click chemistry and their application as thermally latent curing agent for epoxy resins[J].Composites Science and Technology,2017,142:198. 7 Christopher N Kuncho, Daniel F Schmidt, et al. Effects of catalyst content, anhydride blending, and nanofiller addition on anhydride-cured epoxidized linseed oil-based thermosets[J].Industrial & Engineering Chemistry Research,2017,56:2558. 8 Sharpless K B, Kolb H C, Finn M G. Click chemistry: Diverse chemical function from a few good reactions[J].Angewandte Chemie International Edition,2001,40(11):2004. 9 Hoyle C E, Bowman C N. Thiol-ene click chemistry[J].Angewandte Chemie International Edition,2010,49(9):1540. 10 Xu Yuanhong, Xiong Xingquan, Cai Lei. Thiol-ene click chemistry[J].Progress in Chemistry,2012,24(2-3):385(in Chinese). 徐源鸿,熊兴泉,蔡雷.巯基-烯点击化学[J].化学进展,2012,24(2-3):385. 11 Boutevin G, Ameduri B, Boutevin B, et al. Synthesis and use of hydroxyl telechelic polybutadienes grafted by 2-mercaptoethanol for polyurethane resins[J].Applied Polymer Science,2000,75(13):1655. 12 JustynaJustynska, Helmut Schlaad. Modular synthesis of functional block copolymers[J].Macromolecular Rapid Communications,2004,25:1478. 13 Mao Shizhen, Wang Dehua. Study on two-dimensional NMR spectroscopy of high 1,2-polybutadiene[J].Acta Polymerica Sinica,1990(1):110(in Chinese). 毛诗珍,王德华.聚丁二烯的核磁共振二维谱研究[J].高分子学报,1990(1):110. 14 John L. Binder. Infrared spectra of polybutadienes[J].Rubber Che-mistry and Technology,1966,39(4):945. 15 Yan Fujiang, Guo Heying, Ni Shujie. Measure of CIS-structure content in BR[J].Tire Industry,2006,26(7):436(in Chinese). 闫福江,郭鹤莹,倪淑杰.BR中顺反结构含量的测定[J].轮胎工业,2006,26(7):436. 16 Yerabolu R, Kong J, Easton M, et al. Identification of protonated sulfone and aromatic carboxylic acid functionalities in organic molecules by using ion-molecule reactions followed by collisionally activated dissociation in a linear quadrupole ion trap mass spectrometer[J].Analytical Chemistry,2017,89(14):7398. 17 杨清芝.实用橡胶工艺学[M].第2版.北京:化学工业出版社,2005,23. 18 Jurgen E K Schawe.热分析应用手册—弹性体[M].陆立明,译.上海:东华大学出版社,2009:45. 19 Cordier P, Leibler L, et al. Self-healing and thermoreversible rubber from supramolecular assembly[J].Nature,2008,451:971. 20 Zheng Wei, Wu Youping, Yang Wei, et al. A combined experimental and molecular simulation study of factors influencing the selection of antioxidants in butadiene rubber[J].The Journal of Physical Chemistry B,2017,121:1413. 21 Spratte T, Plagge J, Wunde M,et al. Investigation of strain-induced crystallization of carbon black and silica filled natural rubber compo-sites based on mechanical and temperature measurements[J].Polymer,2017,115:12. 22 Gu Xiaoyu, Zhang Junying. Study on the curing mechanism of epo-xy/DICY system by FT-IR[J].Polymer Materials Science and Engineering,2006,5(22):182(in Chinese). 谷晓昱,张军营.用FT-IR研究双氰胺固化环氧树脂的反应机理[J].高分子材料科学与工程,2006,5(22):182. 23 Thomas Viail, Francois Tournihac, Simone Musso, et al. Control of reactions and network structures of epoxy thermosets[J].Progress in Polymer Science,2016,62:126.
渝公网安备50019002502923号 版权所有：《材料导报》编辑部
2018, Vol. 32 
