1,3-二(2'-氨基亚乙基)-2-甲基咪唑溴盐与环氧树脂E-51的固化工艺

doi:10.7523/j.ucas.2022.049

中国科学院大学学报 ›› 2024, Vol. 41 ›› Issue (1): 42-49.DOI: 10.7523/j.ucas.2022.049

1,3-二(2'-氨基亚乙基)-2-甲基咪唑溴盐与环氧树脂E-51的固化工艺

苏泽^1,3, 白金虎², 吴琼³, 刘龙², 张延强^2,3

1. 郑州大学河南先进技术研究院, 郑州 450001;
2. 中国科学院过程工程研究所中国科学院粉体材料技术重点实验室, 北京 100190;
3. 郑州中科新兴产业技术研究院, 郑州 450000

收稿日期:2022-03-28 修回日期:2022-04-29 发布日期:2022-05-07
通讯作者: 刘龙，E-mail:lliu@ipe.ac.cn;张延强，E-mail:yqzhang@ipe.ac.cn
基金资助:
国家自然科学基金(22178359, 21878278)资助

Curing process of 1,3-di(2'-aminoethyl)-2-methylimidazolium bromide with epoxy resin E-51

SU Ze^1,3, BAI Jinhu², WU Qiong³, LIU Long², ZHANG Yanqiang^2,3

1. Henan Institute of Advanced Technology, Zhengzhou University, Zhengzhou 450001, China;
2. CAS Key Laboratory of Science and Technology on Particle Materials, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
3. Zhengzhou Institute of Emerging Industrial Technology, Zhengzhou 450000, China

Received:2022-03-28 Revised:2022-04-29 Published:2022-05-07

摘要/Abstract

摘要： 通过咪唑环上的季铵化反应，制备一种适用于环氧树脂的双氨基咪唑类离子液体固化剂1,3-二(2'-氨基亚乙基)-2-甲基咪唑溴盐(DAIL)。以环氧树脂E-51作为基体树脂，深入研究DAIL作为固化剂的固化工艺条件和固化物的性能。结果表明，DAIL可作为环氧树脂E-51的中温固化剂使用，二者的最佳质量比为DAIL∶E-51=20∶100，最佳固化温度范围为74~105 ℃，后固化温度为162 ℃，固化后的浇注体样条抗拉强度为159 MPa，弹性模量为2 281 MPa，断裂伸长率为12.8%，热分解温度为424.4 ℃。DMA分析表明DAIL/E-51浇注体最大损耗因子tan δ为0.56，玻璃转化温度θ_g为83 ℃，对应的贮存模量E为290 MPa，交联密度为30 149 mol·m^-3。该结果为高力学性能中温环氧树脂固化剂的使用提供了重要实验依据。

关键词: 1,3-二(2'-氨基亚乙基)-2-甲基咪唑溴盐, 环氧树脂, 固化剂, 固化原理, 固化动力学

Abstract: A diaminoimidazole ionic liquid curing agent, 1,3-di(2'-aminoethyl)-2-methylimidazolium bromide (DAIL) is prepared via quaternization of imidazole rings. With epoxy resin E-51 as matrix resin, the curing process conditions of DAIL as curing agent and the properties of cured products are studied in depth. The results show that DAIL can be used as a medium temperature curing agent for epoxy resins. The optimal ratio of the two is DAIL∶E-51=20∶100, the optimal curing temperature range is 74~105 ℃, and the post-curing temperature is 162 ℃. The tensile strength of the cured cast body splines is 159 MPa, the elastic modulus is 2 281 MPa, and the elongation at break is 12.8%, the thermal decomposition temperature is 424.4 ℃. DMA analysis shows that the maximum loss factor tanδ of the DAIL/E-51 cast body is 0.56, and the glass transition temperature θ_g is 83 ℃, the corresponding storage modulus E is 290 MPa, and the crosslinking density is 30 149 mol·m^-3. This study provides an important experimental basis for the use of high mechanical properties of medium temperature epoxy resin curing agent.

Key words: 1,3-di (2'-aminoethyl)-2-methylimidazolium bromide, epoxy resin, curing agent, curing principle, curing kinetics

中图分类号:

苏泽, 白金虎, 吴琼, 刘龙, 张延强. 1,3-二(2'-氨基亚乙基)-2-甲基咪唑溴盐与环氧树脂E-51的固化工艺[J]. 中国科学院大学学报, 2024, 41(1): 42-49.

SU Ze, BAI Jinhu, WU Qiong, LIU Long, ZHANG Yanqiang. Curing process of 1,3-di(2'-aminoethyl)-2-methylimidazolium bromide with epoxy resin E-51[J]. Journal of University of Chinese Academy of Sciences, 2024, 41(1): 42-49.

参考文献

[1] 赵明，曹宇鑫，刘波，等. 聚硫醇表面功能化二硫化钼纳米片对环氧树脂胶粘剂的影响[J]. 中国胶粘剂, 2020, 29(12): 1-6. DOI:10.13416/j.ca.2020.12.002.
[2] 胡晓兰, 周川, 代少伟, 等. 氧化石墨烯改性不同表面性质的碳纤维/环氧树脂复合材料的微观形貌与动态热力学性能[J]. 复合材料学报, 2020, 37(5): 1070-1080. DOI:10.13801/j.cnki.fhclxb.20191021.001.
[3] 高宾, 赵彬, 王艳, 等. 高固体分低表面处理环氧涂料性能研究[J]. 中国涂料, 2020,35(3): 31-36. DOI: 10.13531/j.cnki.china.coatings.2020.03.007.
[4] 胡玉明. 环氧固化剂及添加剂[M]. 北京：化学工业出版社, 2011: 1-2.
[5] Maka H, Spychaj T, Pilawka R. Epoxy resin/ionic liquid systems: the influence of imidazolium cation size and anion type on reactivity and thermomechanical properties[J]. Industrial & Engineering Chemistry Research, 2012, 51(14): 5197-5206. DOI:10.1021/ie202321j.
[6] Jin F L, Li X, Park S J. Synthesis and application of epoxy resins: a review[J]. Journal of Industrial and Engineering Chemistry, 2015, 29: 1-11. DOI:10.1016/j.jiec.2015.03.026.
[7] Karel D. Network formation in curing of epoxy resins [J]. Advances in Polymer Science, 1986,78: 1-59. DOI:10.1007/BFb0035356.
[8] Natarajan M, Murugavel S C. Thermal stability and thermal degradation kinetics of bio-based epoxy resins derived from cardanol by thermogravimetric analysis[J]. Polymer Bulletin, 2017, 74(8): 3319-3340. DOI:10.1007/s00289-016-1885-y.
[9] 王伟. 环氧树脂固化技术及其固化剂研究进展[J]. 热固性树脂, 2001, 16(3): 29-33,37. DOI:10.3969/j.issn.1002-7432.2001.03.008.
[10] Lin J J, Speranza G P, Waddill H G. Synthesis and reactivity of mannich-derived polyoxyethylene amines as epoxy curing agents[J]. Journal of Applied Polymer Science, 1997, 66(12): 2339-2346. DOI:10.1002/(sici)1097-4628(19971219)66:12<2339:aid-app15>3.0.co;2-v.
[11] 祁小云, 谭硕望. 环氧树脂功能性固化剂的研究现状与进展[J]. 胶体与聚合物, 2005, 23(2): 37-38. DOI:10.13909/j.cnki.1009-1815.2005.02.015.
[12] Mori D I, Gin D L. Curable ionic liquid prepolymer-based ion gel coating system for toxic industrial chemical hazard mitigation on porous substrates[J]. Industrial & Engineering Chemistry Research, 2018, 57(47): 16012-16020. DOI:10.1021/acs.iecr.8b01292.
[13] Singh R P, Verma R D, Meshri D T, et al. Energetic nitrogen-rich salts and ionic liquids[J]. Angewandte Chemie International Edition, 2006, 45(22): 3584-3601. DOI:10.1002/anie.200504236.
[14] Scott M P, Rahman M, Brazel C S. Application of ionic liquids as low-volatility plasticizers for PMMA[J]. European Polymer Journal, 2003, 39(10): 1947-1953. DOI:10.1016/S0014-3057(03)00129-0.
[15] Rahmathullah M A M, Jeyarajasingam A, Merritt B, et al. Room temperature ionic liquids as thermally latent initiators for polymerization of epoxy resins[J]. Macromolecules, 2009, 42(9): 3219-3221. DOI:10.1021/ma802669k.
[16] Ostrowska S, Markiewicz B, Wąsikowska K, et al. Epoxy resins cured with ionic liquids as novel supports for metal complex catalysts[J]. Comptes Rendus-Chimie, 2013, 16(8): 752-760. DOI:10.1016/j.crci.2012.12.005.
[17] 高升, 刘龙, 张延强, 等. 3-(2-氨基-2-氧乙基)-1-丁基咪唑二氰胺盐对环氧树脂(E-51)的固化工艺[J]. 中国科学院大学学报, 2020, 37(3): 289-294. DOI:10.7523/j.issn.2095-6134.2020.03.001.
[18] Jiang Z Y, Wang Q C, Liu L, et al. Dual-functionalized imidazolium ionic liquids as curing agents for epoxy resins[J]. Industrial & Engineering Chemistry Research, 2020(59): 3024-3034. DOI:10.1021/acs.iecr.9b06574.
[19] Liu L, Gao S, Jiang Z Y, et al. Amide-functionalized ionic liquids as curing agents for epoxy resin: preparation, characterization, and curing behaviors with TDE-85[J]. Industrial & Engineering Chemistry Research, 2019, 58(31): 14088-14097. DOI:10.1021/acs.iecr.9b01888.
[20] Zhang J Z, Cai J, Dong H F, et al. A novel dual amino-functionalized cation-tethered ionic liquid for CO₂ capture[J]. Industrial & Engineering Chemistry Research, 2013, 52(17): 5835-5841. DOI:10.1021/ie4001629.
[21] 汪多仁.环氧树脂的合成与应用[J].热固性树脂, 2001, 16(1): 42-45. DOI:10.13650/j.cnki.rgxsz.2001.01.013.
[22] Tan X, Zeng L M, Liao Q L, et al. Model-fitting kinetic analysis of novel phosphorus-containing curing agent for epoxy resin[J]. Thermochimica Acta, 2017, 657: 197-202. DOI:10.1016/j.tca.2017.10.001.
[23] Kissinger H E. Reaction kinetics in differential thermal analysis[J]. Analytical Chemistry, 1957, 29(11): 1702-1706. DOI:10.1021/ac60131a045.
[24] Opfermann J, Kaisersberger E. An advantageous variant of the Ozawa-Flynn-Wall analysis[J]. Thermochimica Acta, 1992, 203: 167-175. DOI:10.1016/0040-6031(92)85193-Y.
[25] Chen M F, Zhou Q, Ni L Z, et al. Synthesis, cure kinetics, and thermal properties of a novel boron-silicon hybrid polymer[J]. Journal of Thermal Analysis and Calorimetry, 2013, 114(3): 1317-1324. DOI:10.1007/s10973-013-3148-6.
[26] 阳富强, 吴超, 石英. 热重与差示扫描量热分析法联用研究硫化矿石的热性质[J]. 科技导报, 2009, 27(22): 66-71. DOI:10.3321/j.issn:1000-7857.2009.22.015.
[27] Mąka H, Spychaj T, Zenker M. High performance epoxy composites cured with ionic liquids[J]. Journal of Industrial and Engineering Chemistry, 2015, 31: 192-198. DOI:10.1016/j.jiec.2015.06.023.

1,3-二(2'-氨基亚乙基)-2-甲基咪唑溴盐与环氧树脂E-51的固化工艺

Curing process of 1,3-di(2'-aminoethyl)-2-methylimidazolium bromide with epoxy resin E-51

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 1

编辑推荐

Metrics

本文评价

访问统计

联系我们