Preparation and self⁃healing performance of pyridine⁃containing polyurethane

doi:10.19491/j.issn.1001-9278.2022.05.009

Abstract

Abstract:

To explore the effect of hydrogen bonds on the properties of polyurethane， two types of polyurethanes were synthesized using polytetrahydrofuran， isophorone diisocyanate， 4，4’?dihydroxybiphenyl， and N³，N⁵?bis（4?hydroxyphenyl）pyridine?3，5?diformamide as raw materials. Their chemical structure， thermal stability， mechanical properties， and self?healing properties were investigated by Fourier?transform infrared spectroscopy， thermogravimetry analysis， and a universal material testing machine. The results indicated that the two polyurethanes presented excellent self?healing performance， and both of them could completely self?heal the damages after healing at 60 ℃ for 30 min. As a chain extender， the polyurethane synthesized with N³，N⁵?bis（4?hydroxyphenyl）pyridine?3，5?dicarboxamide exhibited a better mechanical property than that with 4，4’?dihydroxybipheny， exhibiting higher tensile strength of 1.2 MPa， superior thermal stability with thermal degradation activation energy of 230.3 kJ/mol， and a higher carbon residual yield of 5 wt% at 800 oC.

Key words: pyridine, amide, H?bond, polyurethane, self?healing

CLC Number:

TQ323.8

LUO Jun, HUANG Hongsheng, YE Xiaolan, REN Jun, NIE Shengqiang, WANG Yi, ZHANG Chunmei, LIU Yuan. Preparation and self⁃healing performance of pyridine⁃containing polyurethane[J]. China Plastics, 2022, 36(5): 47-52.

Figures/Tables 11

Fig.1. Synthesis equation of HPD

Fig.2. Synthesis equation of PPU and BPU

Fig.3. 1H?NMR spectrum of HPD

Fig.4. 13C?NMR spectrum of HPD

Fig.5. FTIR spectra of BPU and PPU

Fig.6. Peak fitting of carbonyl region of FTIR spectra of BPU and PPU

Fig.7. Stress?stain curves of BPU and PPU

Fig.8. TG and DTG curves of BPU and PPU at different heating rates

Fig.9. Thermal degradation kinetic curves of BPU and PPU

Fig.10. Stress?stain curves of PPU and BPU after self?healing

Fig.11. Photos of PPU and BPU before and after self?healing

References 15

1	杨洁，范建凤，索习东，等. 基于Diels⁃Alder反应的聚氨酯自修复材料设计及研究进展［J］. 聚氨酯工业， 2017， 32（4）：4⁃7.
	YANG J， FAN J F， SUO X D，et al. Research progress and material synthesis in self⁃healing polyurethane based on diels⁃alder reaction［J］. Polyurethane Industry， 2017， 32（4）：4⁃7.
2	NARDELI J V， FUGIVARA C S， TARYBA M， et al. Biobased self⁃healing polyurethane coating with Zn micro⁃flakes for corrosion protection of AA7475［J］. Chemical Engineering Journal， 2021， 404： 126478.
3	盛叶明，程波，卢珣. 基于多重可逆作用的自修复聚氨酯弹性体的制备及性能［J］. 高等学校化学学报， 2020， 41（3）：572⁃581.
	SHENG Y M， CHENG B， LU X. Research on self⁃healing polypolyurethane elastomer based on multiple reversible action［J］ Chemical Journal of Chinese Universities， 2020， 41（3）：572⁃581.
4	OUYANG C， ZHAO C， LI W， et al. Super⁃tough， self⁃healing polyurethane based on diels⁃alder bonds and dyna⁃mic zinc⁃ligand interactions［J］. Macromolecular Materials and Engineering， 2020， 305（6）： 2000089.
5	刘文俊，程原，赵本波，等. 异氰酸酯型微胶囊自修复涂料的研究进展［J］. 聚氨酯工业， 2020， 35（2）： 8⁃10.
	LIU W J， CHENG Y， ZHAO B B， et al. Synthesis and characterization of self⁃matting waterborne polyurethane resin for synthetic leather［J］. Polyurethane Industry， 2020， 35（2）： 8⁃10.
6	梁海先，肖长发，胡晓宇，等. 熔纺聚氨酯系中空纤维膜的压力响应性［J］. 高分子材料科学与工程， 2008， 24（12）： 130⁃133.
	LIANG H X， XIAO C F， HU X Y， et al. Pressure⁃responsibility of melt⁃spinning polyurethane based hollow fiber membrane［J］. Polymer Materials Science and Engineering， 2008， 24（12）： 130⁃133.
7	张志菲，赵树高，杨琨. 本征型自修复弹性体的研究进展［J］. 高校化学工程学报， 2018， 32（4）： 758⁃766.
	ZHANG Z F， ZHAO S G， YANG K. Research progress on intrinsic self⁃healing elastomer［J］. Chemical Journal of Chinese Universities， 2018， 32（4）： 758⁃766.
8	马振萍，米皓阳，王文志，等. 自修复聚氨酯弹性体的制备及性能研究［J］. 包装工程工程版， 2021， 42（3）： 69⁃77.
	MA Z P， MI H Y， WANG W Z， et al. Review on preparation and properties of self⁃healing PU elastomers［J］. Packaging Engineering， 2021， 42（3）： 69⁃77.
9	曹建诚，鲁富康，刘敬成，等. 基于 DA 反应的光固化自修复聚氨酯涂料及其性能研究［J］. 影像科学与光化学， 2018， 36（6）： 489⁃497.
	CAO J C， LU F K， LIU J C， et al. Preparation and proper⁃ties of UV⁃cured self⁃healing polyurethane coatings based on diels⁃alder reaction［J］. Imaging Science and Photochemis⁃try， 2018， 36（6）： 489⁃497.
10	宗泽，赵丹，董延茂，等. 自修复聚氨酯防水涂料的研究［J］. 化工新型材料， 2021， 49（3）： 212⁃215.
	ZONG Z， ZHAO D， DONG Y M， et al. Study of self⁃healing waterproof PU coating［J］. New Chemical Materials， 2021， 49（3）： 212⁃215.
11	ZHANG Y， ZHENG J， ZHANG X， et al. Dual dynamic bonds self⁃healing polyurethane with superior mechanical properties over a wide temperature range［J］. European Polymer Journal， 2022， 163： 110934.
12	WILLOCQ B， ODENT J， DUBOIS P， et al. Advances in intrinsic self⁃healing polyurethanes and related composi⁃tes［J］. RSC Advances， 2020， 10（23）： 13 766⁃13 782.
13	黄晓文，张士玉，赵凯锋，等. 含双硫键的自修复交联聚氨酯弹性体的合成与性能［J］. 高分子通报， 2018 （5）： 67⁃72.
	HUANG X W， ZHANG S Y， ZHAO K F， et al. Synthesis and characterization of cross⁃linked self⁃healable polyurethane elastomer containing disulfide bonds［J］. Chinese Polymer Bulletin， 2018， 5： 67⁃72.
14	杨一林，卢珣，王巍巍，等. 热可逆自修复聚氨酯弹性体的制备及表征［J］. 材料工程， 2017， 45（8）： 1⁃8.
	YANG Y L， LU X， WANG W W， et al. Preparation and characterization of thermally reversible self⁃healing polyurethane elastomer［J］. Journal of Materials Engineering， 2017， 45（8）： 1⁃8.
15	王玉龙，胡国胜，张静婷，等. 基于双硫键和氢键协效的高性能自修复聚氨酯脲的研制［J］. 化工进展， 2020， 40（1）： 324⁃331.
	WANG Y L， HU G S， ZHANG J T， et al. Development of self⁃healing poly（urethane urea） with high performances based on the synergistic effect of disulfide bonds and hydrogen bonds［J］. Chemical Industry and Engineering Progress， 2020， 40（1）： 324⁃331

[1]	WEI Simiao, SHAO Lushan, XU Zhun, LIU Yanting, ZHAO Siheng, XU Bo. Flame⁃retardant performance of PA6 modified with hypophosphite/siloxane bi⁃functional compound and diethyl aluminum hypophosphite compound [J]. China Plastics, 2022, 36(7): 129-135.
[2]	ZHU Zixuan, LIU Haifen, FAN Jiazhao, LI Huafeng, WANG Lixin. Research progress of adhesive materials and co⁃extrusion adhesion technology for photovoltaic backsheet [J]. China Plastics, 2022, 36(7): 174-186.
[3]	LI Kaize, XIN Yong. Properties of thermoplastic polyurethane composites modified with carbon nanotubes [J]. China Plastics, 2022, 36(6): 1-5.
[4]	CHEN Liang, ZHANG Pingbo, JIANG Pingping, BAO Yanmin, GAO Xuewen, XIA Jialiang. Preparation and properties of self⁃healing waterborne polyurethane based on disulfide bonds [J]. China Plastics, 2022, 36(6): 46-53.
[5]	WANG Jinye, TANG Bohu, YANG Lining, XIE Meng, GUO Zechao, YANG Guang. Study on multi⁃jet⁃fusion forming process of PA12 parts [J]. China Plastics, 2022, 36(6): 81-86.
[6]	FENG Xiu, SHEN Ying, XU Sheng. Synthesis and application of pentavalent organic bismuth for polyurethane [J]. China Plastics, 2022, 36(5): 104-109.
[7]	CHEN Sheng, LIANG Yingchao, WU Fangjuan, FANG Hui, FAN Xinfeng, CHEN Hui, WANG Yonggang. Preparation and interfacial modification of polyamide 6/bidirectional warp⁃knitted glass fiber composites [J]. China Plastics, 2022, 36(5): 24-28.
[8]	LEI Jingfa, SHEN Qiang, LIU Tao, SUN Hong, YIN Zhiqiang. Influence of fused deposition process parameters on static and dynamic mechanical properties of thermoplastic polyurethane elastomer [J]. China Plastics, 2022, 36(5): 29-35.
[9]	XU Rongxia, WEI Gang, WEI Lilan, WU Jiecui, JIANG Yujiang. Friction and wear properties of PE⁃UHMW modified with nano⁃SiO₂ and PA6 [J]. China Plastics, 2022, 36(4): 47-52.
[10]	LI Suyuan, LIU Huipeng, GONG Shun, HUANG Guotao, LI Yucai, WU Xin, DENG Jianping, PAN Kai. Preparation and characterization of EVA foaming materials modified with thermoplastic polyamide elastomer [J]. China Plastics, 2022, 36(4): 6-14.
[11]	ZHANG Jiufu, LUO Kaiqiang, XU Jun, GUO Baohua. Study on comprehensive properties and influencing factors of long glass fiber reinforced PA66 composites [J]. China Plastics, 2022, 36(3): 1-8.
[12]	ZHANG Shucheng, TANG Wenbin, YU Tianjiao, XU Zhenzhen, XING Jian. Preparation and properties of polyurethane foams with different contents of polyether polyol [J]. China Plastics, 2022, 36(3): 104-109.
[13]	LI Zeyang, CEN Lan, CHEN Sheng, CHEN Weijie, DU Binghua, ZHANG Ershuai. Preparation and properties of XNBR/PA12 thermoplastic elastomer [J]. China Plastics, 2022, 36(3): 15-20.
[14]	HU Huanbo, WU Wei, LI Ning, ZHAO Tianyu, ZOU Zhiqiang. Preparation and properties of TPEE/P（AA⁃co⁃AM） water absorbent elastomer [J]. China Plastics, 2022, 36(3): 9-14.
[15]	LI Bo, GONG Jun, JIN Xueyi, MENG Xiaoyu. Effect of carbon nanotube modification method on properties of polyamide 11 [J]. China Plastics, 2022, 36(2): 61-66.