异氰酸酯胶囊型自修复高分子材料研究进展

doi:10.16085/j.issn.1000-6613.2016.01.023

摘要/Abstract

摘要： 回顾了微胶囊型自修复高分子材料中双环戊二烯-Grubbs催化剂、聚二甲基硅氧烷-锡(铂)催化剂、环氧树脂-固化剂和异氰酸酯等自修复体系的研究现状,重点介绍了异氰酸酯胶囊型自修复材料的修复机理和研究新进展。异氰酸酯胶囊型自修复是通过异氰酸酯修复剂(主要是异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯及其三聚体等)潮固化来实现,并简要探讨了影响微胶囊自修复高分子材料自修复效果的主要因素(微胶囊的芯材、力学性能以及微胶囊与基材的相容性)。最后指出了微胶囊型自修复高分子材料今后的研究方向(建立自修复过程的模型,将微胶囊应用到存在一些如晶界、气孔等微结构的材料中)及其应用前景(提高航空航天和民用高铁等高速高风险项目的可靠性,开发自修复涂料、胶黏剂等)。

关键词: 微胶囊, 自修复, 高分子材料, 异氰酸酯

Abstract: This paper begins with a review of the research status of microcapsules-based self-healing polymeric materials including dicyclopentadiene-Grubbs catalyst, polydimethylsiloxane-tin (Pt) catalyst, epoxy-curing agent and isocyanate system. Self-healing mechanism and research progress of encapsuled isocyanate self-healing material are summarized. Self-healing function of particles encapsuled isocyanate actived through the curing process of isocyanate agent(mainly includes isophorone diisocyanate, hexamethylene diisocyanate and its trimer) healing in moisture environment. Following that, the factors (core material, mechanical property of microcapsules and its compatibility with substrate) influencing self-healing properties of microcapsules-based self-healing polymeric materials are briefly discussed. Finally, the future research directions, eg. establishment of self-healing process models and applications of microcapsules to material with microstructure such as grain boundary, porosity, are pointed out and the application prospects(improving the reliability of some high-speed high-risk projects such as aerospace and civil high-speed rail, self-healing coatings and adhesives development) of self-healing materials are exhibited.

Key words: microcapsules, self-healing, polymeric materials, isocyanate

中图分类号:

TB381

冯建中, 明耀强, 张宇帆, 郭浩槟, 黄凯鑫, 胡剑峰, 瞿金清. 异氰酸酯胶囊型自修复高分子材料研究进展[J]. 化工进展, 2016, 35(01): 175-181.

FENG Jianzhong, MING Yaoqiang, ZHANG Yufan, GUO Haobin, HUANG Kaixin, HU Jianfeng, QU Jinqing. Progress of research on encapsuled isocyanate self-healing polymeric materials[J]. Chemical Industry and Engineering Progree, 2016, 35(01): 175-181.

参考文献

[1] 李思超,韩朋,许华平. 自修复高分子材料[J]. 化学进展,2012, 24(7):1346-1352.
[2] 汪海平,容敏智,章明秋. 微胶囊填充型自修复聚合物及其复合材料[J]. 化学进展,2010,22(12):2397-2407.
[3] 李海燕,张丽冰,王俊. 本征型自修复聚合物材料研究进展[J]. 化工进展,2012,31(7):1549-1554.
[4] ZHANG W,DUCHET J,GERARD J F. Self-healable interfaces based on thermo-reversible Diels-Alder reactions in carbon fiber reinforced composites[J]. Journal of Colloid and Interface Science, 2014,430:61-68.
[5] ENGEL T,KICKELBICK G. Furan-modified spherosilicates as building blocks for self-healing materials[J]. European Journal of Inorganic Chemistry,2015,2015(7):1226-1232.
[6] BRANCART J,SCHELTJENS G,MUSELLE T,et al. Atomic force microscopy-based study of self-healing coatings based on reversible polymer network systems[J]. Journal of Intelligent Material Systems and Structures,2014,25(1):40-46.
[7] YUAN C E,RONG M Z,ZHANG M Q. Self-healing polyurethane elastomer with thermally reversible alkoxyamines as crosslinkages[J]. Polymer,2014,55(7):1782-1791.
[8] YUAN C E,ZHANG M Q,RONG M Z. Application of alkoxyamine in self-healing of epoxy[J]. Journal of Materials Chemistry A,2014, 2:6558-6566.
[9] ZHANG Z P,RONG M Z,ZHANG M Q. Room temperature self-healable epoxy elastomer with reversible alkoxyamines as crosslinkages[J]. Polymer,2014,55(16):3936-3943.
[10] WHITE S R,SOTTOS N R,GEUBELLE P H,et al.Autonomic healing of polymer composites[J]. Nature,2001,409:794-797.
[11] RULE J D,BROWN E N,SOTTOS N R,et al.Wax-protected catalyst microspheres for efficient self-healing materials[J]. Advanced Materials,2005,17(2):205-208.
[12] KAMPHAUS J M,RULE J D,MOORE J S,et al. A new self-healing epoxy with tungsten (Ⅵ) chloride catalyst[J]. Journal of the Royal Society Interface,2008,5(18):95-103.
[13] KELLER M W,WHITE S R,SOTTOS N R. A self-healing poly(dimethyl siloxane) elastomer[J]. Advanced Functional Materials,2007,17(14):2399-2404.
[14] KELLER M W,WHITE S R,SOTTOS N R.Torsion fatigue response of self-healing poly(dimethylsiloxane) elastomers[J]. Polymer,2008, 49(13/14):3136-3145.
[15] BEIERMANN B A,KELLER M W,SOTTOS N R. Self-healing flexible laminates for resealing of puncture damage[J]. Smart Materials Structures,2009,18(8):1-7.
[16] GUADAGNO L,RAIMONDO M,NADDEO C,et al. Healing efficiency and dynamic mechanical properties of self-healing epoxy systems[J]. Smart Materials and Structures,2014,23(4):045001.
[17] YE X J,SONG Y X,ZHU Y,et al. Self-healing epoxy with ultrafast and heat-resistant healing system processable at elevated temperature[J]. Composites Science and Technology,2014,104:40-46.
[18] YUAN X H,SU Q,HAN L Y,et al. Preparation and performance of self-healing epoxy composites by microcapsulated approach[J]. Key Engineering Materials,2014,636:73-77.
[19] ZHANG H,YANG J L. Development of self-healing polymers via amine-epoxy chemistry:Ⅰ. properties of healing agent carriers and the modelling of a two-part self-healing system[J]. Smart Materials and Structures,2014,23(6):065003.
[20] ZHANG H,YANG J L. Development of self-healing polymers via amine-epoxy chemistry:Ⅱ. systematic evaluation of self-healing performance[J]. Smart Materials and Structures,2014,23(6):065004.
[21] Chowdhury R A,Hosur M V,Nuruddin M,et al. Self-healing epoxy composites:preparation,characterization and healing performance[J]. Journal of Materials Research and Technology,2015,4(1):33-43.
[22] KHOEE S,KACHOEI Z. Design and development of novel reactive amine nanocontainers for a self-healing epoxy adhesive:self-repairing investigation using the lap shear test[J]. RSC Advances,2015,5(27):21023-21032.
[23] CREDICO B D,LEVI M,TURRI S. An efficient method for the output of new self-repairing materials through a reactive isocyanate encapsulation[J]. European Polymer Journal, 2013, 49(9):2467-2476.
[24] YANG J L,KELLER M W,MOORE J S,et al. Microencapsulation of isocyanates for self-healing polymers[J]. Macromolecules,2008, 41(24):9650-9655.
[25] WANG W,XU L K,LI X B,et al. Self-healing properties of protective coatings containing isophorone diisocyanate microcapsules on carbon steel surfaces[J]. Corrosion Science,2014,80:528-535.
[26] WANG W,XU L K,LI X B,et al. Self-healing mechanisms of water triggered smart coating in sea water[J]. Journal of Materials Chemistry A,2014,2(6):1914-1921.
[27] HUANG M X,YANG J L. Facile microencapsulation of HDI for self-healing anticorrosion coatings[J]. Journal of Materials Chemistry,2011,21(30):11123-11130.
[28] HUANG M X,YANG J L. Salt spray and EIS studies on HDI microcapsule-based self-healing anticorrosive coatings[J]. Progress in Organic Coatings,2014,77(1):168-175.
[29] WU G,AN J L,TANG X Z,et al. A versatile approach towards multifunctional robust microcapsules with tunable,restorable,and solvent-proof superhydrophobicity for Self-Healing and self-cleaning coatings[J]. Advanced Functional Materials,2014,24(43):6751-6761.
[30] WU G,AN J L,SUN D W,et al. Robust microcapsules with polyurea/silica hybrid shell for one-part self-healing anticorrosion coatings[J]. Journal of Materials Chemistry A,2014,2(30):11614-11620.
[31] SUN D W,AN J L,WU G,et al. Double-layered reactive microcapsules with excellent thermal and non-polar solvent resistance for self-healing coatings[J]. Journal of Materials Chemistry A,2014, 3(8):4435-4444.
[32] WANG W,XU L K,SUN H Y,et al. Spatial resolution comparison of AC-SECM with SECM and their characterization of self-healing performance of hexamethylene diisocyanate trimer microcapsule coatings[J]. Journal of Materials Chemistry A,2015,3(10):5599-5607.
[33] HILLEWAERE X K D,TEIXEIRA R F A,NGUYEN L T T,et al. Autonomous self-healing of epoxy thermosets with thiol-isocyanate chemistry[J]. Advanced Functional Materials,2014,24(35):5575-5583.
[34] 曲爱兰. 仿生自修复防腐涂层的研究进展[J]. 涂料工业,2012,42(4):71-75.
[35] 张伟,辛毅,张纾,等. 自修复微胶囊制备及微纳力学性能[J].化工学报,2008,59(6):1595-1599.
[36] RULE J D,SOTTOS N R,WHITE S R. Effect of microcapsule size on the performance of self-healing polymers[J].Polymer,2007,48(12):3520-3529.
[37] 赵钊,计宏伟,陈金龙,等. 自修复体系中微胶囊壁材力学性能的测试与表征[J]. 实验力学,2013,28(5):580-585。
[38] HU J F,CHEN H Q,ZHANG Z B.Mechanical Properties of melamine formaldehyde microcapsules for self-Healing materials[J]. Materials Chemistry and Physics,2009,118(1):63-70.
[39] KESSLER M R,WHITE S R. Self-activated healing of delamination damage in woven composites[J]. Composites Part A,2001,32(5):683-699.
[40] WANG R G,LI H Y,LIU W B,et al. Surface modification of poly(urea-formaldehyde) microcapsules and the effect on the epoxy composites performance[J]. Journal of Macromolecular Science,Part A:Pure and Applied Chemistry,2010,47(10):991-995.