一种新型增韧剂的合成及其对环氧树脂的改性
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摘要
利用聚氨酯预聚物末端异氰酸根与环氧稀释剂中环氧基团之间的加成反应,合成了一种含有噁唑烷酮基团的环氧增韧剂OX-EPU,并采用红外和核磁共振谱图对产物分子结构进行了表征,证实该增韧剂合成成功。本文还将该增韧剂OX-EPU引入到环氧-胺固化体系中,并与市售聚氨酯改性环氧增韧剂(EPU)进行了比较。结果发现,两种增韧剂均能有效地改善树脂体系的冲击韧性,但EPU的引入明显降低了材料的耐热性能和拉伸强度,而OX-EPU却能保持材料良好的耐热和拉伸强度,适当的添加量可提高材料的机械性能。
In this work, a kind of polyurethane modified oxazolidone epoxy toughening agent OX-EPU was synthesized by the addition reaction between isocyanato-terminated polyurethane prepolymer and epoxy group of diluent agent, and characterized by FTIR and ~1H-NMR. The results confirm that synthesis of the toughening agent is successful. Besides, OX-EPU was introduced into the epoxy resin-amine curing system, and another marketed PU-modified toughening agent EPU was also adopted in parallel for comparison. The results show that, both the two toughening agents can effectively improve the toughness of the epoxy resin system, but the EPU obviously decreases the heat-resistant and tensile strength. However, OX-EPU can retain the excellent heat-resistant and tensile strength of the epoxy material, and even improve the mechanical property at proper adding amounts.
In this work, a kind of polyurethane modified oxazolidone epoxy toughening agent OX-EPU was synthesized by the addition reaction between isocyanato-terminated polyurethane prepolymer and epoxy group of diluent agent, and characterized by FTIR and ~1H-NMR. The results confirm that synthesis of the toughening agent is successful. Besides, OX-EPU was introduced into the epoxy resin-amine curing system, and another marketed PU-modified toughening agent EPU was also adopted in parallel for comparison. The results show that, both the two toughening agents can effectively improve the toughness of the epoxy resin system, but the EPU obviously decreases the heat-resistant and tensile strength. However, OX-EPU can retain the excellent heat-resistant and tensile strength of the epoxy material, and even improve the mechanical property at proper adding amounts.
引文
[1] 陈平,王德中. 环氧树脂及其应用[M]. 北京:化学工业出版社, 2004.
[2] SH Deng, XD Zhou, CJ Fan, et al. Release of Interfacial Thermal Stress and Accompanying Improvement of Interfacial Adhesion in Carbon Fiber Reinforced Epoxy Resin Composites: Induced by Diblock Copolymers[J]. Composite Part A: Applied Science and Manufacturing, 2012, 43(6): 990～996.
[3] 冯艳丽,彭秋柏,杜伟,王传忻.纳米增韧剂FORTEGRA202增韧环氧胶粘剂的研究[J].粘接,2014,(10):52～55.
[4] 刘方彪,王丹勇,等. 颗粒增强、增韧环氧树脂基复合材料制备研究进展[J]. 材料科学与工程学报,2014,32(4):613～618.
[5] VS Mathew, C Sinturel, SC George, S Thomas. Epoxy Resin/Liquid Natural Rubber System: Secondary Phase Separation and Its Impact on Mechanical Properties[J]. Journal of Material Science, 2010, 45(7): 1769～1781.
[6] CW Wise, WD Cook, AA Goodwin. CTBN Rubber Phase Precipitation in Model Epoxy Resins[J]. Polymer, 2000, 41(12): 4625～4633.
[7] 李晓辉,易红玲,等. 端环氧基聚氨酯的合成及其与环氧树脂共混物的性能[J]. 材料科学与工程学报, 2016, 34(1): 68～74.
[8] 徐亚娟,刘少兵. 热塑性树脂增韧环氧树脂研究进展[J]. 热固性树脂, 2010, 25(6): 43～47.
[9] 宫大军,魏伯荣.热致型液晶增韧环氧树脂的研究进展[J]. 化学与黏合, 2010, 32(6): 50～54.
[10] MF Zeng, XD Sun, HQ Xiao, et al. Investigation of Free Volume and the Interfacial, and Toughening Behavior for Epoxy Resin/Rubber Composites by Positron Annihilation[J]. Radiation Physics and Chemistry, 2008, 77(3): 245～251.
[11] 宋学政. 多官能团环氧树脂/热塑性树脂共混体系的相行为、形态结构、力学性能及固化反应研究[D]. 中国科学技术大学硕士学位论文,郭其鹏,安徽,中国科学技术大学, 2000(5).
[12] 张培培,陈有双,唐忠锋.聚氨酯改性环氧树脂的研究进展[J]. 中国涂料, 2010, 25(5): 27～30.
[13] H Harani, S Fellahi, M Bakar. Toughening of Epoxy Resin Using Synthesized Polyurethane Prepolymer Based on Hydroxyl- terminated Polyesters[J]. Journal of Applied Polymer Science, 1998, 70(13): 2603～2618.
[14] HH Wang, JC Chen. Toughening of Epoxy Resin by Reacting With Functional Terminated-polyurethanes[J]. Journal of Applied Polymer Science, 1995, 57(6): 671～677.
[15] 陈伟明,王成忠,梁胜彪,杨小平. 新型噁唑烷酮环氧树脂的合成与性能研究[J]. 化学新型材料, 2005, 33(10):29～37.
[16] 陈健,杨云峰. 环氧树脂增韧改性研究进展[J]. 工程塑料应用, 2014, 42(5): 130～133.
[17] 陈庚,李镇江,等.缩水甘油封端聚氨酯的合成及其增韧改性环氧树脂的研究[J]. 工程塑料应用, 2012, 40(11): 16～18.
[18] 王成忠,石萌萌,黄丽. 噁唑烷酮环氧树脂的研究进展[J]. 高分子通报, 2012,(7): 43～50.
[19] HC Hsia, CCM Ma, MS Li, DS Chen. Glycidyl-terminated Polyurethane Modified Epoxy Resins: Mechanical Properties, Adhesion Properties, and Morphology[J]. Journal of Applied Polymer Science, 1994, 52(8): 1137～1151.
[20] YS Li, MS Li, CCM Ma, HC Hsia, DS Chen. Polyether and Polyester Polyol Based Glycidyl- Terminated Polyurethane Modified Epoxy Resins: Mechanical Properties and Morphology [J]. Polymer International, 1994, 35(4): 371～378.
[2] SH Deng, XD Zhou, CJ Fan, et al. Release of Interfacial Thermal Stress and Accompanying Improvement of Interfacial Adhesion in Carbon Fiber Reinforced Epoxy Resin Composites: Induced by Diblock Copolymers[J]. Composite Part A: Applied Science and Manufacturing, 2012, 43(6): 990～996.
[3] 冯艳丽,彭秋柏,杜伟,王传忻.纳米增韧剂FORTEGRA202增韧环氧胶粘剂的研究[J].粘接,2014,(10):52～55.
[4] 刘方彪,王丹勇,等. 颗粒增强、增韧环氧树脂基复合材料制备研究进展[J]. 材料科学与工程学报,2014,32(4):613～618.
[5] VS Mathew, C Sinturel, SC George, S Thomas. Epoxy Resin/Liquid Natural Rubber System: Secondary Phase Separation and Its Impact on Mechanical Properties[J]. Journal of Material Science, 2010, 45(7): 1769～1781.
[6] CW Wise, WD Cook, AA Goodwin. CTBN Rubber Phase Precipitation in Model Epoxy Resins[J]. Polymer, 2000, 41(12): 4625～4633.
[7] 李晓辉,易红玲,等. 端环氧基聚氨酯的合成及其与环氧树脂共混物的性能[J]. 材料科学与工程学报, 2016, 34(1): 68～74.
[8] 徐亚娟,刘少兵. 热塑性树脂增韧环氧树脂研究进展[J]. 热固性树脂, 2010, 25(6): 43～47.
[9] 宫大军,魏伯荣.热致型液晶增韧环氧树脂的研究进展[J]. 化学与黏合, 2010, 32(6): 50～54.
[10] MF Zeng, XD Sun, HQ Xiao, et al. Investigation of Free Volume and the Interfacial, and Toughening Behavior for Epoxy Resin/Rubber Composites by Positron Annihilation[J]. Radiation Physics and Chemistry, 2008, 77(3): 245～251.
[11] 宋学政. 多官能团环氧树脂/热塑性树脂共混体系的相行为、形态结构、力学性能及固化反应研究[D]. 中国科学技术大学硕士学位论文,郭其鹏,安徽,中国科学技术大学, 2000(5).
[12] 张培培,陈有双,唐忠锋.聚氨酯改性环氧树脂的研究进展[J]. 中国涂料, 2010, 25(5): 27～30.
[13] H Harani, S Fellahi, M Bakar. Toughening of Epoxy Resin Using Synthesized Polyurethane Prepolymer Based on Hydroxyl- terminated Polyesters[J]. Journal of Applied Polymer Science, 1998, 70(13): 2603～2618.
[14] HH Wang, JC Chen. Toughening of Epoxy Resin by Reacting With Functional Terminated-polyurethanes[J]. Journal of Applied Polymer Science, 1995, 57(6): 671～677.
[15] 陈伟明,王成忠,梁胜彪,杨小平. 新型噁唑烷酮环氧树脂的合成与性能研究[J]. 化学新型材料, 2005, 33(10):29～37.
[16] 陈健,杨云峰. 环氧树脂增韧改性研究进展[J]. 工程塑料应用, 2014, 42(5): 130～133.
[17] 陈庚,李镇江,等.缩水甘油封端聚氨酯的合成及其增韧改性环氧树脂的研究[J]. 工程塑料应用, 2012, 40(11): 16～18.
[18] 王成忠,石萌萌,黄丽. 噁唑烷酮环氧树脂的研究进展[J]. 高分子通报, 2012,(7): 43～50.
[19] HC Hsia, CCM Ma, MS Li, DS Chen. Glycidyl-terminated Polyurethane Modified Epoxy Resins: Mechanical Properties, Adhesion Properties, and Morphology[J]. Journal of Applied Polymer Science, 1994, 52(8): 1137～1151.
[20] YS Li, MS Li, CCM Ma, HC Hsia, DS Chen. Polyether and Polyester Polyol Based Glycidyl- Terminated Polyurethane Modified Epoxy Resins: Mechanical Properties and Morphology [J]. Polymer International, 1994, 35(4): 371～378.