含氟聚氨酯二甲基丙烯酸酯为芯材的微胶囊制备及自修复性能

doi:10.16085/j.issn.1000-6613.2022-2188

摘要/Abstract

摘要：

首先自制了含氟聚氨酯二甲基丙烯酸酯（TFXPUA）大单体，然后采用界面聚合法制备了以TFXPUA、1,6-己二醇二丙烯酸酯（HDDA）、2-羟基-2-甲基-1-苯基-1-丙酮（HMPP）为芯材，聚氨酯为壁材的含氟聚氨酯微胶囊（MTFXPUA），再将其添加到水性聚氨酯中制备自修复涂膜及涂层。通过红外光谱（FTIR）、凝胶渗透色谱（GPC）、扫描电镜（SEM）、粒度分析（PSA）、接触角测试、拉伸试验、耐盐水浸泡实验以及电化学阻抗测试表征了TFXPUA以及MTFXPUA的化学结构、微观形貌、自修复及力学等性能。结果表明：含氟聚氨酯二甲基丙烯酸酯（TFXPUA）大单体成功制备，其数均分子量为14275。基于TFXPUA为芯材制得的含氟聚氨酯微胶囊（MTFXPUA）平均粒度为24.05μm，SEM结果表明MTFXPUA微胶囊在聚氨酯涂层中对微裂纹进行了良好自修复，随着TFXPUA中四氟对苯二甲醇（TFB）用量增加，MTFXPUA的修复处接触角、拉伸强度、在低频处阻抗值、Nyquist曲线半径呈现增大的趋势; 当TFB用量超过6%时，增加趋势变缓。TFB用量为6%时，修复处的接触角可达96.80°，修复后涂膜拉伸强度由17.94MPa增加到25.21MPa，基于含氟聚氨酯二甲基丙烯酸酯（TFXPUA）大单体制备的微胶囊对聚氨酯涂层具有良好的自修复性能，实现了对修复后材料的二次保护。

关键词: 含氟聚氨酯-丙烯酸酯, 大单体, 微胶囊, 自修复, 涂层

Abstract:

The fluoropolyurethane dimethacrylate (TFXPUA) macromonomer was prepared firstly. Then, the fluorinated polyurethane microcapsules (MTFXPUA) were prepared by interface polymerization with TFXPUA, 1,6-hexanediol diol acrylate (HDDA) and 2-hydroxy-2-methyl-1-phenyl-1-propanone(HMPP) as the core materials, and polyurethane as the wall material. MTFXPUA were added to waterborne polyurethane to prepare self-repairing films and coatings. The structure and properties of TFXPUA, MTFXPUA and the repaired polyurethane were characterized by Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), scanning electron microscopy (SEM), particle size analysis (PSA), contact angle test, tensile testing, salt water immersion test and electrochemical impedance. The results showed that TFXPUA macromonomer was prepared successfully and its number average molecular weight was 14275. The average particle size of fluorinated polyurethane microcapsules (MTFXPUA) based on TFXPUA as the core material was 24.05μm. The scanning electron microscope indicated that MTFXPUA had a good self-repairing effect on microcracks in polyurethane coating. With the increase of tetrafluoro benzenedimethanol (TFB) content in TFXPUA, the contact angle at the self-repairing site, tensile strength, impedance at low frequency and the radius of Nyquist curve of the waterborne polyurethane repaired by MTFXPUA increased. When TFB content exceeded 6%, the increase trend slowed down. When the amount of TFB was 6%, the water contact angle at the repair site could reach 96.80° and the tensile strength of the repaired film increased from 17.94MPa to 25.21MPa. Microcapsules based on fluoropolyurethane dimethacrylate (TFXPUA) macromonomer had good self-repairing performance for polyurethane coatings and realized the secondary protection of the repaired area.

Key words: fluorine polyurethane-acrylate, macromer, microcapsules, self-repairing, coating

中图分类号:

TQ031

辛华, 彭琪, 李阳帆, 张岩, 陈悦, 李新琦. 含氟聚氨酯二甲基丙烯酸酯为芯材的微胶囊制备及自修复性能[J]. 化工进展, 2023, 42(10): 5406-5413.

XIN Hua, PENG Qi, LI Yangfan, ZHANG Yan, CHEN Yue, LI Xinqi. Preparation and self-repairing performance of microcapsules with fluoropolyurethane dimethacrylate as the core[J]. Chemical Industry and Engineering Progress, 2023, 42(10): 5406-5413.

图/表 11

图1 TFXPUA的合成机理

图2 TFXPUA的GPC谱图

图3 MTFXPUA的红外谱

图4 MTFXPUA的SEM形貌图和粒度分布

图5 MTFXPUA/WPU复合涂膜修复前后SEM图

图6 MTFXPUA/WPU复合涂膜修复后修复处的接触角

图7 MTFXPUA/WPU复合涂膜修复后应力-应变

表1 MTFXPUA/WPU复合涂膜修复后的力学性能

项目	MPUA/WPU	MTF2PUA/WPU	MTF4PUA/WPU	MTF6PUA/WPU	MTF8PUA/WPU	MTF10PUA/WPU
拉伸强度/MPa	17.94	19.97	23.90	25.21	26.27	26.62
断裂伸长率/%	393.35	426.89	491.97	530.29	526.13	518.25

图8 MTFXPUA/WPU复合涂层修复处耐盐水浸泡光学照片

图9 MTFXPUA/WPU复合涂层电化学阻抗测试

表2 MTFXPUA/ WPU复合涂层修复后的电化学阻抗值(Z) (Ω·cm2)

MPUA /WPU	MTF2PUA /WPU	MTF4PUA /WPU	MTF6PUA /WPU	MTF8PUA /WPU	MTF10PUA /WPU
2.67×10⁵	3.81×10⁵	5.76×10⁵	8.97×10⁵	9.61×10⁵	1.04×10⁶

参考文献 25

1	雷瑞, 马养民, 杨秀芳. 醇酸树脂微胶囊的制备及环氧涂层自修复性能[J]. 化工进展, 2020, 39(7): 2782-2787.
	LEI Rui, MA Yangmin, YANG Xiufang. Self-healing performance of epoxy coating containing microencapsulated alkyd resin[J]. Chemical Industry and Engineering Progress, 2020, 39(7): 2782-2787.
2	HE Zhenglong, JIANG Shuai, LI Qifeng, et al. Facile and cost-effective synthesis of isocyanate microcapsules via polyvinyl alcohol-mediated interfacial polymerization and their application in self-healing materials[J]. Composites Science and Technology, 2017, 138: 15-23.
3	童晓梅, 郝芹芹, 闫子英, 等. 硅烷改性环氧树脂自修复微胶囊的制备及应用[J]. 化工进展, 2018, 37(9): 3555-3561.
	TONG Xiaomei, HAO Qinqin, YAN Ziying, et al. Preparation and application of epoxy resin self-healing microcapsules modified by silicone[J]. Chemical Industry and Engineering Progress, 2018, 37(9): 3555-3561.
4	冯建中, 明耀强, 张宇帆, 等. 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(1): 175-181.
	FENG Jianzhong, MING Yaoqiang, ZHANG Yufan, et al. Progress of research on encapsuled isocyanate self-healing polymeric materials[J]. Chemical Industry and Engineering Progress, 2016, 35(1): 175-181.
5	YAN Xiaoxing, ZHAO Wenting, WANG Lin. Preparation and performance of thermochromic and self-repairing dual function paint film with lac resin microcapsules and fluorane microcapsules[J]. Polymers, 2021, 13(18): 3109.
6	韩薇妍, 赵有玺, 龚平. 微胶囊结构与性能的研究进展[J]. 中国生物工程杂志, 2010, 30(1): 104-110.
	HAN Weiyan, ZHAO Youxi, GONG Ping. Development of the structures and characteristics of microcapsules[J]. China Biotechnology, 2010, 30(1): 104-110.
7	MEBARKI Noudjoub, ZIANE Hanifa, FAZOUANE Fethia, et al. Microencapsulation of Thymus fontanesii extracts in pectin/casein: Characterization, release behavior and storage stability[J]. Iranian Polymer Journal, 2021, 31(3): 301-316.
8	MOU Chuanlin, DENG Qizheng, HU Jiaxin, et al. Controllable preparation of monodisperse alginate microcapsules with oil cores[J]. Journal of Colloid and Interface Science, 2020, 569: 307-319.
9	WU Kaiyun, WEIZiyue, DONG Yuan, et al. One-pot efficient preparation of microcapsules based on photopolymerization for self-repairing coatings[J]. Physicochemical and Engineering Aspects, 2022, 642: 128660.
10	LI Panhua, GUO Wanchun, LU Zhang, et al. UV-responsive single-microcapsule self-healing material with enhanced UV-shielding SiO₂/ZnO hybrid shell for potential application in space coatings[J]. Progress in Organic Coatings, 2021, 151: 106046.
11	裴建新. 沥青裂缝自修复微胶囊的制备与表征[J]. 化工进展, 2016, 35(9): 2898-2904.
	PEI Jianxin. Preparation and properties of self-healing microcapsule for asphalt crack[J]. Chemical Industry and Engineering Progress, 2016, 35(9): 2898-2904.
12	TANG Chunxia, LI Yingzhan, Jason PUN, et al. Polydopamine microcapsules from cellulose nanocrystal stabilized Pickering emulsions for essential oil and pesticide encapsulation[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2019, 570: 403-413.
13	FATHABADI Hanieh Fathi, JAVIDI Mehdi. Self-healing and corrosion performance of polyurethane coating containing polyurethane microcapsules[J]. Journal of Coatings Technology and Research, 2021, 18(5): 1365-1378.
14	姚莉洁. 中空纤维自修复技术的研究进展[J]. 四川化工, 2014, 17(3): 16-18.
	YAO Lijie. Research progresses in hollow fiber self-healing technology[J]. Sichuan Chemical Industry, 2014, 17(3): 16-18.
15	Sándor KLING, Tibor CZIGÁNY. Damage detection and self-repair in hollow glass fiber fabric-reinforced epoxy composites via fiber filling[J]. Composites Science and Technology, 2014, 99: 82-88.
16	ZHANG Xiaolong, SU Junfeng, GUO Yandong, et al. Novel vascular self-nourishing and self-healing hollow fibers containing oily rejuvenator for bitumen[J]. Construction and Building Materials, 2018, 183: 150-162.
17	LEE Min Wook, AN Seongpil, YOON Sam S, et al. Advances in self-healing materials based on vascular networks with mechanical self-repair characteristics[J]. Advances in Colloid and Interface Science, 2018, 252: 21-37.
18	BURNWORTH Mark, TANG Liming, KUMPFER Justin R, et al. Optically healable supramolecular polymers[J]. Nature, 2011, 472(7343): 334-337.
19	ZHAO Xia, WEI Jinfei, LI Bucheng, et al. A self-healing superamphiphobic coating for efficient corrosion protection of magnesium alloy[J]. Journal of Colloid and Interface Science, 2020, 575: 140-149.
20	QIN Liming, CHEN Ning, ZHOU Xin, et al. A superhydrophobic aerogel with robust self-healability[J]. Journal of Materials Chemistry A, 2018, 6(10): 4424-4431.
21	XIE Zhulu, HU Benlin, LI Runwei, et al. Hydrogen bonding in self-healing elastomers[J]. ACS Omega, 2021, 6(14): 9319-9333.
22	ZHANG Yunpeng, YE Jiaofeng, QU Dongan, et al. Thermo-adjusted self-healing epoxy resins based on Diels–Alder dynamic chemical reaction[J]. Polymer Engineering & Science, 2021, 61(9): 2257-2266.
23	徐兴旺, 沈伟, 刘佳莉, 等. 基于双硫键自修复高分子材料研究进展[J]. 广东化工, 2017, 44(11): 124-126.
	XU Xingwang, SHEN Wei, LIU Jiali, et al. Research progress of self-healing polymer materials with thiol-disulfide exchange[J]. Guangdong Chemical Industry, 2017, 44(11): 124-126.
24	XU Yurun, CHEN Dajun. A novel self-healing polyurethane based on disulfide bonds[J]. Macromolecular Chemistry and Physics, 2016, 217(10): 1191-1196.
25	QU Qiqi, WANG Hua, HE Jing, et al. Synthesis and properties of responsive self-healing polyurethane containing dynamic disulfide bonds[J]. High Performance Polymers, 2021, 33(10): 1132-1140.

[1]	王鑫, 王兵兵, 杨威, 徐志明. 金属表面PDA/PTFE超疏水涂层抑垢与耐腐蚀性能[J]. 化工进展, 2023, 42(8): 4315-4321.
[2]	刘战剑, 付雨欣, 任丽娜, 张曦光, 袁中涛, 杨楠, 汪怀远. 超疏水涂层在防腐阻垢领域研究进展[J]. 化工进展, 2023, 42(6): 2999-3011.
[3]	孙闫晨昊, 王维, 李一喆, 祝妍妮, 刘学武, 张大为. 橘皮油微胶囊制备及其产品质量评价[J]. 化工进展, 2023, 42(5): 2626-2637.
[4]	何阳, 李思盈, 李传强, 袁小亚, 郑旭煦. 热还原氧化石墨烯/环氧树脂复合涂层的防腐性能[J]. 化工进展, 2023, 42(4): 1983-1994.
[5]	席慧敏, 钱坤, 俞科静, 李杰, 张中威, 熊自明, 张耀良. 基于二硫键和氢键的自修复聚氨酯弹性体的制备、改性及其应用[J]. 化工进展, 2023, 42(2): 934-943.
[6]	胡锦健, 李龙, 董子靖. 碳纳米材料在PU纱线基柔性应变传感器中的应用[J]. 化工进展, 2023, 42(2): 872-883.
[7]	郝旭波, 牛宝联, 郭昊天, 徐祥和, 张忠斌, 李应林. 相变微胶囊改性及其在光热转换中的应用[J]. 化工进展, 2023, 42(2): 854-871.
[8]	顾海洋, 王冬, 宗永忠, 付少海. 制革污泥蛋白质基生物质棉织物阻燃涂层的制备与阻燃性能[J]. 化工进展, 2023, 42(2): 641-649.
[9]	刘洋, 赵恒, 李倩, 辛虎, 李杏涛. 全氟聚醚聚合物及其功能复合材料的研究进展[J]. 化工进展, 2023, 42(1): 321-335.
[10]	王乔逸, 陆少锋, 师文钊, 洪勋, 姚东霞, 张领. 界面聚合聚脲/聚氨酯复合壳体香精微胶囊的制备及性能[J]. 化工进展, 2022, 41(8): 4432-4440.
[11]	詹洵, 陈健, 杨兆哲, 吴国民, 孔振武, 沈葵忠. 纳米纤维素构建超疏水材料研究进展[J]. 化工进展, 2022, 41(8): 4303-4313.
[12]	郭制安, 隋智慧, 李亚萍, 徐逸坤, 孙芳, 赵欣. 相变双向调温纺织材料制备技术研究进展[J]. 化工进展, 2022, 41(7): 3648-3659.
[13]	朱雪丹, 姚亚丽, 马利利, 王嘉鑫, 杨杰, 彭磊, 何金梅, 屈孟男. 聚氯乙烯基超疏水材料的制备及应用研究进展[J]. 化工进展, 2022, 41(7): 3676-3688.
[14]	何美莹, 岳学杰, 张涛, 邱凤仙. 红外辐射调控原理及其在热管理应用中的材料研究进展[J]. 化工进展, 2022, 41(7): 3719-3730.
[15]	李博申, 魏铭, 胡瑶瑶, 董月林, 董群锋, 杨立峰. 改性h-BN/聚氨酯丙烯酸酯涂料的制备与性能[J]. 化工进展, 2022, 41(6): 3194-3202.