柔性主链的支化结构对冲击硬化材料性能的影响

doi:10.11944/j.issn.1000-0518.2019.10.190026

摘要/Abstract

摘要：

以羟基封端的二甲基甲基乙烯基(硅氧烷与聚硅氧烷)(C=C—PDMS—OH)为接枝主链 ,将单氢化端基二甲基硅氧烷(H-PDMS)作为接枝支链,通过卡斯特催化剂催化二者间的硅氢化反应形成具有瓶刷结构的柔性主链(Brush PDMS-OH)。再通过三甲氧基硼氧六环(TMOB)的动态交联和异佛尔酮二异氰酸酯扩链剂(IPDI)的稳态化学交联,制备主链带有支化链的冲击硬化材料(Brush Impact Hardening Polymer,B-IHP)。通过核磁共振波谱仪(NMR)、傅里叶变换红外光谱仪(FTIR)和流变仪等测试手段对材料结构和性能进行表征。结果表明,B-IHP具有良好的机械性能和冲击硬化性能,拉伸强度达到9.8 MPa,冲击硬化值达到3500以上。 B-IHP具有良好的自愈合性能,愈合效率可达95%以上,愈合时间仅为6 h。该柔性主链的支化结构可以明显降低主链发生链缠结的相对分子质量阈值,提升材料的冲击硬化性能和自愈合能力。

关键词: 接枝, 冲击硬化, 自愈合

Abstract:

Hydroxyl-terminated dimethylmethylvinyl(siloxane and polysiloxane) (C=C—PDMS—OH) was used as the graft branched chain to form a flexible main chain (Brush PDMS-OH) with bottle brushes by hydrogenation of H-PDMS with the caster catalyst. Brush impact hardening polymer (B-IHP) with branched chains was prepared by dynamic cross-linking of trimethoxyboroxyhexacyclic (TMOB) and stable chemical cross-linking by isophorone diisocyanate extender (IPDI). The structure and properties of the material were characterized by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectrometer (FTIR) and rheometer. The results show that B-IHP has good mechanical properties and impact hardening properties. Its tensile strength can reach 9.8 MPa and impact hardening value can reach more than 3500. B-IHP has good self-healing performance, the healing efficiency can reach more than 95%, and the healing time is only 6 hours. The results show that the branched structure of flexible main chain can significantly reduce the relative molecular mass threshold of chain entanglement and improve the impact hardening and self-repairing ability of materials.

Key words: grafting, impact hardening, self-healing

邓裕坤, 梁学称, 裴小鹏, 翟侃侃, 王超, 张百超, 白云刚, 张文德, 谭颖, 王丕新, 徐昆. 柔性主链的支化结构对冲击硬化材料性能的影响[J]. 应用化学, 2019, 36(10): 1155-1164.

DENG Yukun, LIANG Xuechen, PEI Xiaopeng, ZHAI Kankan, WANG Chao, ZHANG Baichao, BAI Yungang, ZHANG Wende, TAN Ying, WANG Pixin, XU Kun. Influence of Branched Structures in Flexible Main Chain on the Properties of Impact Hardening Materials[J]. Chinese Journal of Applied Chemistry, 2019, 36(10): 1155-1164.

参考文献

[1]	SONG Xiaobang,JIN Limin,WANG Chunxia.Comparative Analysis of Impact Resistance Between Unidirectional Composite and Pure Resin Material[J]. J Text Res,2012,33(6):15-19(in Chinese). 宋孝浜,金利民,王春霞. 单向复合材料及纯树脂材料抗冲击性能的比较[J]. 纺织学报,2012,33(6):15-19.
[2]	WEI Rubin,ZHAI Wen,LI Feng,et al. Application of High Efficiency Impact Resistant Composites in Bulletproof and Explosionproof Shelter[J]. Eng Plast Appl,2016,44(4):131-135(in Chinese). 魏汝斌,翟文,李锋,等. 高效抗冲击复合材料在防弹防爆方舱中的应用[J]. 工程塑料应用,2016,44(4):131-135.
[3]	GU Yaxin,WANG Hongmei,LIU Genhua,et al. Effect of Two Types of Elastomers on Low Temperature Impact Resistance of PPR Materials[J]. China Plast Ind,2016,44(12):18-22(in Chinese). 谷亚新,王洪梅,刘根华,等. 两种弹性体对PPR材料低温抗冲击材料的影响[J]. 塑料工业,2016,44(12):18-22.
[4]	YANG Chang,WANG Jinxiang,DENG Hui.The Impact of New Composite Protective Material Impact Resistance Caused by the Raw Material[J]. J Funct Mater Dev,2017,23(5):100-104(in Chinese). 杨昶,王劲翔,邓辉. 原料对新型复合材料抗冲击性能的影响[J]. 功能材料与器件学报,2017,23(5):100-104.
[5]	Chen L,Revel S,Morris K,et al. Low Molecular Weight Gelator-Dextran Composites[J]. Chem Comm,2010,46(36):6738-6740.
[6]	ZHANG Yunlu.Influence of Interleaved Polyester Fibres to Carbon Fibre Composite on Impact Resistance[J]. Aero Wea,2018,6(3):88-92(in Chinese). 张云露. 聚酯纤维插层对碳纤维复合材料抗冲击性能的影响[J]. 航空兵器,2018,6(3):88-92.
[7]	YANG Deqing,WU Binghong,ZHANG Xiangwen.Anti-Explosion and Shock Resistance Performance of Sandwich Defensive Structure with Star-Shaped Auxetic Material Core[J/OL].Explos Shock Waves,2019,39(6):065102(in Chinese). 杨德庆,吴秉鸿,张相闻. 星型负泊松比超材料防护结构抗暴抗冲击性能研究[J/OL]. 爆炸与冲击,2019,39(6):065102.
[8]	Maranzano B J,Wagner N J.The Effects of Particle Size on Reversible Shear Thickening of Concentrated Colloidal Dispersions[J]. J Chem Phys,2001,114(23):10514-10528.
[9]	Lee Y S,Wetzel E D,Wagner N J.The Ballistic Impact Characteristics of Kevlar Woven Fabrics Impregnated with a Colloidal Shear Thickening Fluid[J]. J Mater Sci,2003,38(13):2825-2833.
[10]	Lee Y P,Cheah S J,Ogilvie J F.Strengths of Absorption Features in Vibration-Rotational Band v=6←v=0 of 14N16OX2Πr in the near Infrared Region[J]. Infrared Phys Technol,2003,44(3):199-205.
[11]	Alderson A,Evansr K E.Molecular Origin of Auxetic Behavior in Tetrahedral Framework Silicates[J]. Phys Rev Lett,2002,89(22):55031-55034.
[12]	Evans K E,Alderson A.Auxetic Materials:Functional Materials and Structures from Lateral Thinking[J]. Adv Mater,2000,12(9):617-627.
[13]	Zhou C,Wang B,Zhang F T.Micro-Gels for Impact Protection[J]. J Appl Polym Sci,2013,130(4):2345-2351.
[14]	Pritchard R H,Lava P,Debruyne D.Precise Determination of the Poisson Ratio in Soft Materials with 2D Digital Image Correlation[J]. Soft Matter,2013,9(26):6037-6045.
[15]	Cauvin S,Liles D,Robson S,et al. Emulsions of Dilatant Organopolysilosanes:USP,0033627[P],2011.
[16]	ZHOU Chao,WANG Bo,XU Kun,et al. The Synthesis and Appication of Novel Anti-impact Protective Microgel[J]. Funct Mater,2013,12(44):1745-1749(in Chinese). 周超,王博,徐昆,等. 新型冲击材料的合成及应用性能研究[J]. 功能材料,2013,12(44):1745-1749.
[17]	LIU Xiaoke,YU Kejing,QIAN Kun.Preparation and Mechanical Performance of Shear Thickenning Glue/Polyurethane Foam Composites[J]. Mater Rep B:Res Pap,2018,32(9):3255-3260(in Chinese). 刘小可,俞科静,钱坤. 剪切增稠胶/聚氨酯泡沫复合材料的制备与力学性能[J]. 材料导报B:研究篇,2018,32(9):3255-3260.
[18]	XIA Yanli,YU Kejing,QIAN Kun,et al. Structure and Properties of Novel Impact Resistance and Energy-Absorbing Material STG[J]. Aero Mater Technol,2018,12(2):40-44(in Chinese). 夏艳丽,俞科静,钱坤,等. 新型抗冲击吸能材料STG的结构与性能分析[J]. 宇航材料工艺,2018,12(2):40-44
[19]	DENG Yukun,QIN Xiangge,XU Kun,et al. Sythesis and Property of Impact Hardening Materials with New Chain Extender IPDI[J]. New Chem Mater,2016,44(2):126-128(in Chinese). 邓裕坤,秦湘阁,徐昆,等. 加入新型扩链剂IPDI的冲击硬化材料的合成与性能研究[J]. 化工新型材料,2016,44(2):126-128.