纳米碳酸钙改性前端聚合双环戊二烯树脂性能研究

doi:10.19936/j.cnki.2096-8000.20250928.005

摘要/Abstract

摘要： 本文研究了纳米碳酸钙对前端聚合双环戊二烯树脂工艺性能、耐热性能及其力学性能的影响。结果表明,纳米碳酸钙的加入显著优化了双环戊二烯树脂的工艺窗口,其起始固化温度与峰值温度分别降低了16.16 ℃与13.92 ℃,室温凝胶时间延长至2.5 h以上。同时,纳米碳酸钙通过抑制高分子链段运动,将树脂的玻璃化转变温度(T_g)提升至127.9 ℃,增幅达33.79%。力学性能方面,当纳米碳酸钙含量为3wt%~4wt%时,树脂浇注体弯曲强度、拉伸模量与冲击强度分别达到60.53 MPa、1.90 GPa与4.84 kJ/m²,与纯树脂相比,分别提升13.27%、57.02%与9.09%,但过量纳米碳酸钙(>5wt%)会因为团聚形成的缺陷引发应力集中,从而导致力学性能下降。本研究可为设计兼具优良工艺性能和热机械性能的高性能前端聚合聚合物复合材料提供参考。

关键词: 纳米碳酸钙, 前端聚合, 聚双环戊二烯, 耐热性能, 力学性能, 工艺性能, 复合材料

Abstract: This study was systematically conducted to investigate the effects of nano-CaCO₃ modification on the processing, thermal stability, and mechanical properties of frontal-polymerized dicyclopentadiene (DCPD) resin. The results demonstrate that the incorporation of nano-CaCO₃ significantly optimized the processing window of DCPD resin. Thus, the initial curing temperature and peak curing temperature are decreased by 16.16 ℃ and 13.92 ℃, respectively, while the room-temperature gelation time extends beyond 2.5 h. Furthermore, as nano-CaCO₃ suppressed the mobility of molecular chain, the glass transition temperature (T_g) is elevated to 127.9 ℃, which is a 33.79% increase over that of the pure resin. Mechanically, the flexural strength, tensile modulus, and impact strength are improved to 60.53 MPa, 1.90 GPa and 4.84 kJ/m² with the optimal nano-CaCO₃ content (3wt%~4wt%), representing improvements of 13.27%, 57.02% and 9.09%, respectively. However, due to the stress concentration caused by the agglomeration of nano-CaCO₃ particles at high content (>5wt%), the mechanical properties of the DCPD resin are degraded. This work could provide insights for designing high-performance frontal-polymerized polymer composites with tailored processability and thermal-mechanical properties.

Key words: Nano-CaCO₃, frontal polymerization, dicyclopentadiene resin, thermal stability, mechanical properties, process optimization, composites

中图分类号:

TB332

李科辉, 张月尧, 宋龙杰, 杨莉玲, 陈丁丁, 邢素丽, 尹昌平, 唐俊. 纳米碳酸钙改性前端聚合双环戊二烯树脂性能研究[J]. 复合材料科学与工程, 2025, 0(9): 35-41.

LI Kehui, ZHANG Yueyao, SONG Longjie, YANG Liling, CHEN Dingding, XING Suli, YIN Changping, TANG Jun. Effects of nano calcium carbonate on the properties of frontal-polymerized dicyclopentadiene resin[J]. COMPOSITES SCIENCE AND ENGINEERING, 2025, 0(9): 35-41.

参考文献

[1] 李青彬, 韩永军, 燕青芝, 等. 波聚合体系、引发、过程及应用[J]. 化学进展, 2014, 26(7): 1202-1213.
[2] 陈苏. 前端聚合[M]. 北京: 化学工业出版社, 2013.
[3] ROBERTSON I D, YOURDKHANI M, CENTELLAS P J, et al. Rapid energy-efficient manufacturing of polymers and composites via frontal polymerization[J]. Nature, 2018, 557(7704): 223-227.
[4] ZHANG T, XU N, YIN W, et al. Energy-efficient frontal polymerization of poly(DCPD-co-TCPD) with improving thermomechanical properties and chemical resistance[J]. Materials Today Communications, 2024, 40: 109494.
[5] 李然, 郭安儒, 吴文敬, 等. 纳米无机填料改性酚醛树脂基防热复合材料烧蚀性能研究现状[J]. 复合材料科学与工程, 2020(6): 114-120.
[6] 余明, 李晓玲, 徐晓辉, 等. 纳米改性环氧树脂基中子屏蔽材料研究与设计[J]. 舰船科学技术, 2022, 44(14): 35-39.
[7] 王泽龙. 无机纳米填料改性聚丙烯的研究进展[J]. 化纤与纺织技术, 2021, 50(6): 40-41.
[8] 李孟宇, 马雅婷, 赵蕾, 等. 纳米SiO₂改性环氧树脂复合材料的热稳定性及使用寿命[J]. 复合材料学报, 2017, 34(11): 2421-2427.[9] 孙正, 刘力源, 刘德博, 等. 纳米改性连续纤维增强热塑性树脂复合材料及其力学性能研究进展[J]. 复合材料学报, 2019, 36(4): 771-783.
[10] FENNER J S, DANIEL I M. Hybrid nanoreinforced carbon/epoxy composites for enhanced damage tolerance and fatigue life[J]. Composites Part A: Applied Science and Manufacturing, 2014, 65: 47-56.
[11] 胡雅. 石墨烯改性树脂材料的研究进展[J]. 民用飞机设计与研究, 2024(1): 86-94.
[12] 张翼清, 初立秋, 金剑, 等. 纳米碳酸钙改性聚丙烯的性能与增韧机理[J]. 合成树脂及塑料, 2023, 40(2): 1-5.
[13] 熊欣, 李亚东. 纳米碳酸钙填充改性环氧树脂植筋胶力学性能研究[J]. 科学技术创新, 2021(3): 171-173.
[14] 耿立艳, 张辰威, 刘文博, 等. CF/纳米SiO₂改性树脂复合材料界面性能研究[J]. 玻璃钢/复合材料, 2012(2): 60-63.
[15] 吕津辉. 纳米碳酸钙改性技术研究进展及代表性应用综述[J]. 中国粉体工业, 2021(2): 12-18.
[16] 李旭阳, 陈国伟, 高喜平, 等. 前沿聚合法制备聚双环戊二烯/纳米碳酸钙复合材料[J]. 高分子材料科学与工程, 2015, 31(9): 173-177, 183.
[17] ALAM M A, ARIF S, ANSARI A H. Mechanical and morphological study of synthesized PMMA/CaCO₃ nano composites[C]//IOP Conference Series: Materials Science and Engineering. Bristol, UK: IOP Publishing, 2017, 225(1): 012222.
[18] HAGITA K, MORITA H. Effects of polymer/filler interactions on glass transition temperatures of filler-filled polymer nanocomposites[J]. Polymer, 2019, 178: 121615.
[19] 顾达. 纳米碳酸钙的合成、表面改性及在聚合物改性中的应用[C]//全国碳酸钙行业技术经济交流暨筹备成立中国无机盐工业协会碳酸钙分会会议. 北京: 中国无机盐工业协会, 2001: 48-56.
[20] TONOYAN A O, MINASYAN A H, VARDERESYAN A Z, et al. Influence of shrinkage of polymer on the stationarity of propagation of frontal polymerization heat waves[J]. Journal of Polymer Engineering, 2019, 39(8): 769-773.
[21] KUMAR A, GAO Y, GEUBELLE P H. Analytical estimates of front velocity in the frontal polymerization of thermoset polymers and composites[J]. Journal of Polymer Science, 2021, 59(11): 1109-1118.
[22] GARY D P, BYNUM S, THOMPSON B D, et al. Thermal transport and chemical effects of fillers on free-radical frontal polymerization[J]. Journal of Polymer Science, 2020, 58(16): 2267-2277.
[23] GROCE B R, LANE E E, GARY D P, et al. Kinetic and chemical effects of clays and other fillers in the preparation of epoxy-vinyl ether composites using radical-induced cationic frontal polymerization[J]. ACS Applied Materials and Interfaces, 2023, 15(15): 19403-19413.
[24] DAVTYAN S P, TONOYAN A O, VARDERESYAN A Z, et al. Frontal copolymerization in the presence of nano-particles[J]. European Polymer Journal, 2014, 57: 182-186.
[25] 张哲轩, 周洋, 李润丰, 等. 纳米碳酸钙——生产、改性和应用[J]. 材料导报, 2023, 37(增刊2): 162-171.
[26] RUIU A, SANNA D, ALZARI V, et al. Advances in the frontal ring opening metathesis polymerization of dicyclopentadiene[J]. Journal of Polymer Science, Part A: Polymer Chemistry, 2014, 52(19): 2776-2780.
[27] 严玉茹, 李会录, 王超, 等. 填料增强改性环氧树脂力学性能的研究进展[J]. 绝缘材料, 2024, 57(6): 1-8.
[28] 曹万荣, 符开斌, 狄宁宇, 等. 无机纳米粒子增韧改性环氧树脂的研究进展[J]. 绝缘材料, 2009(6): 31-35.