基于动态共价键自修复的光固化高分子材料研究进展

doi:10.16085/j.issn.1000-6613.2022-1608

摘要/Abstract

摘要：

光固化技术的高效、适应性广、经济、节能与环境友好等特点使得近年来光固化高分子材料在人类生产生活中被广泛应用。然而，光固化高分子材料的结构稳定性使得材料表面或内部一旦出现破损便难以修复，造成大量资源浪费与环境污染。动态共价键可以在外界刺激作用下（光照、加热等）发生可逆的断裂和重组，从而导致分子拓扑结构的动态调整，赋予光固化高分子材料结构可调整、可循环利用和自修复性能等。本文综述了近些年来基于酯键、Diels-Alder反应、二硫键、硼酸酯键、位阻脲键等可逆共价键自修复的光固化高分子材料设计与制备，对近年来不同类型动态共价键光固化高分子材料的优缺点和应用进行了评述，最后指出动态共价键光固化高分子材料力学性能的弱势以及基于动态共价键修复的单一性，并对该领域未来的研究方向作了展望。

关键词: 动态共价键, 修复, 光固化, 聚合物, 合成

Abstract:

Photocuring technology is highly efficient, adaptable, economical, energy-saving and environmentally friendly, making photocuring polymeric materials widely used in human production and life in recent years. However, the structural stability of Photocuring polymeric polymers makes it difficult to repair the materials once they are broken on the surface or inside, resulting in a large amount of wasted resources and environmental pollution. Dynamic covalent bonds can be reversibly broken and reorganized under the action of external stimuli (light, heating, etc.), which leads to dynamic adjustment of molecular topology and gives light-cured polymer materials structural adjustability, recyclability and self-healing properties. This paper reviewed the design and preparation of photocuring polymeric materials based on ester bonds, Diels-Alder reaction, disulfide bonds, borate ester bonds, site-resistant urea bonds and other reversible covalent bond self-repairs in recent years, summarized the advantages, disadvantages and applications of different types of dynamically covalently bonded photocuring polymeric materials in recent years, and finally pointed out the weaknesses of the mechanical properties of dynamically covalently bonded photocuring polymeric materials and the singularity of the former based on dynamically covalent bond repair, and gave an outlook on the future research directions in this field.

Key words: dynamic covalent bond, healing, photocuring, polymer, synthesis

中图分类号:

TB381

余希希, 张金帅, 雷文, 刘承果. 基于动态共价键自修复的光固化高分子材料研究进展[J]. 化工进展, 2023, 42(7): 3589-3599.

YU Xixi, ZHANG Jinshuai, LEI Wen, LIU Chengguo. Research progress of self-healing photocuring polymeric materials based on dynamic covalent bonds[J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3589-3599.

图/表 15

图1 基于酯键自修复的机理图[21]

图2 MG和CG的合成路线[15]

图3 HHTD的合成路线[29]

图4 UV固化丙烯酸封端聚氨酯树脂的合成路线[30]

图5 UV固化聚氨酯树脂的合成路线[31]

图6 两种硫醇单体的化学结构[32]

图7 DA单体的合成[33]

图8 基于双硫键自修复的机理图

图9 DTBO和DSPUA的合成路线[39]

图10 PUSA的合成路线[41]

图11 ACMO/TBMMA树脂的水解[46]

图12 PDMS-TA聚合物的制备[52]

图13 硼酸盐交联单元之间的动态交换与硼酸酯水解图示[55]

图14 基于CTO的UV固化低聚物的合成路线[63]

图15 氨基甲酸酯的解离交换机制[64]

参考文献 66

1	KIM Jin Seung, CHO Bong Sang, KWEON Jeong Ohk, et al. Preparation and properties of UV-curable di-functional sulfur-containing thioacrylate and thiourethane acrylate monomers with high refractive indices[J]. Progress in Organic Coatings, 2014, 77(11): 1695-1700.
2	BRETTERBAUER Klaus, HOLZMANN Claudia, RUBATSCHER Egon, et al. UV-curable coatings of highly crosslinked trimethylmelamine based acrylates and methacrylates[J]. European Polymer Journal, 2013, 49(12): 4141-4148.
3	UNNO Noriyuki, SATAKE Shin ichi, TANIGUCHI Jun. Super-resolution technique for nanoimprint mold using elastic UV-curable resin[J]. Microelectronic Engineering, 2013, 110: 167-172.
4	ZHENG Chao, LIU Guojun, HU Heng. UV-curable antismudge coatings[J]. ACS Applied Materials & Interfaces, 2017, 9(30): 25623-25630.
5	HAKEIM Osama Abdel, ARAFA Asmaa Ahmed, ZAHRAN Magdy Kandil, et al. Characterisation and application of pigmented UV-curable inkjet inks[J]. Pigment & Resin Technology, 2018, 47(2): 164-172.
6	SUGITA Hikaru, ITOU Keisuke, ITOU Yoshikazu, et al. Multi-acrylate-based UV-curable dismantlable adhesives[J]. International Journal of Adhesion and Adhesives, 2021, 104: 102758.
7	AGUIRRESAROBE Robert H, NEVEJANS Sil, RECK Bernd, et al. Healable and self-healing polyurethanes using dynamic chemistry[J]. Progress in Polymer Science, 2021, 114: 101362.
8	CHANG Kun, JIA Han, GU Shu-Ying. A transparent, highly stretchable, self-healing polyurethane based on disulfide bonds[J]. European Polymer Journal, 2019, 112: 822-831.
9	Saul UTRERA-BARRIOS, VERDEJO Raquel, LÓPEZ-MANCHADO Miguel A, et al. Evolution of self-healing elastomers, from extrinsic to combined intrinsic mechanisms: A review[J]. Materials Horizons, 2020, 7(11): 2882-2902.
10	陈兴幸, 钟倩云, 王淑娟, 等. 动态共价键高分子材料的研究进展[J]. 高分子学报, 2019, 50(5): 469-484.
	CHEN Xingxing, ZHONG Qianyun, WANG Shujuan, et al. Progress in dynamic covalent polymers[J]. Acta Polymerica Sinica, 2019, 50(5): 469-484.
11	LEE Sang Hyub, SHIN Se Ra, LEE Dai Soo. Self-healing of cross-linked PU via dual-dynamic covalent bonds of a Schiff base from cystine and vanillin[J]. Materials & Design, 2019, 172: 107774.
12	FAN Longfei, RONG Minzhi, ZHANG Mingqiu, et al. Repeated intrinsic self-healing of wider cracks in polymer via dynamic reversible covalent bonding molecularly combined with a two-way shape memory effect[J]. ACS Applied Materials & Interfaces, 2018, 10(44): 38538-38546.
13	XIANG Hongping, YIN Jingfeng, LIN Guanghong, et al. Photo-crosslinkable, self-healable and reprocessable rubbers[J]. Chemical Engineering Journal, 2019, 358: 878-890.
14	LIU Maochen, ZHONG Jiang, LI Zijian, et al. A high stiffness and self-healable polyurethane based on disulfide bonds and hydrogen bonding[J]. European Polymer Journal, 2020, 124: 109475.
15	WANG Shuaipeng, DAI Jinyue, TENG Na, et al. Synthesis of mechanically robust and self-healing UV-curable materials from renewable feedstock[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(45): 16842-16852.
16	WANG Shuaipeng, TENG Na, DAI Jinyue, et al. Taking advantages of intramolecular hydrogen bonding to prepare mechanically robust and catalyst-free vitrimer[J]. Polymer, 2020, 210: 123004.
17	ZHANG Biao, KOWSARI Kavin, SERJOUEI Ahmad, et al. Reprocessable thermosets for sustainable three-dimensional printing[J]. Nature Communications, 2018, 9(1): 1831.
18	LU Chuanwei, WANG Chunpeng, YU Juan, et al. Two-step 3D-printing approach toward sustainable, repairable, fluorescent shape-memory thermosets derived from cellulose and rosin[J]. ChemSusChem, 2020, 13(5): 854.
19	FENG Xiaming, LI Guoqiang. Versatile phosphate diester-based flame retardant vitrimers via catalyst-free mixed transesterification[J]. ACS Applied Materials & Interfaces, 2020, 12(51): 57486-57496.
20	ZHANG Jinshuai, HUANG Jia, ZHU Guoqiang, et al. Self-healing, recyclable, and removable UV-curable coatings derived from tung oil and malic acid[J]. Green Chemistry, 2021, 23(16): 5875-5886.
21	HUANG Jia, ZHANG Jinshuai, ZHU Guoqiang, et al. Self-healing, high-performance, and high-biobased-content UV-curable coatings derived from rubber seed oil and itaconic acid[J]. Progress in Organic Coatings, 2021, 159: 106391-106402.
22	黄佳, 张金帅, 朱国强, 等. 基于大豆油和衣康酸的自修复型紫外光固化涂料[J]. 涂料工业, 2021, 51(10): 44-53.
	HUANG Jia, ZHANG Jinshuai, ZHU Guoqiang, et al. Self-heal UV-curable coatings derived from soybean oil and itaconic acid[J]. Paint & Coatings Industry, 2021, 51(10): 44-53.
23	TURKENBURG D H, FISCHER H R. Diels-Alder based, thermo-reversible cross-linked epoxies for use in self-healing composites[J]. Polymer, 2015, 79: 187-194.
24	LIU Yingling, CHUO Tsai Wei. Self-healing polymers based on thermally reversible Diels-Alder chemistry[J]. Polymer Chemistry, 2013, 4(7): 2194-2205.
25	KROGSGAARD Marie, BEHRENS Manja A, PEDERSEN Jan Skov, et al. Self-healing mussel-inspired multi-pH-responsive hydrogels[J]. Biomacromolecules, 2013, 14(2): 297-301.
26	CANADELL Judit, GOOSSENS Han, KLUMPERMAN Bert. Self-healing materials based on disulfide links[J]. Macromolecules, 2011, 44(8): 2536-2541.
27	LI Qiutong, JIANG Miaojie, WU Gang, et al. Photothermal conversion triggered precisely targeted healing of epoxy resin based on thermoreversible Diels-Alder network and amino-functionalized carbon nanotubes[J]. ACS Applied Materials & Interfaces, 2017, 9(24): 20797-20807.
28	TURKENBURG Daniel H, DURANT Yvon, FISCHER Hartmut R. Bio-based self-healing coatings based on thermo-reversible Diels-Alder reaction[J]. Progress in Organic Coatings, 2017, 111: 38-46.
29	KE Xiaoxue, LIANG Hongbo, XIONG Lei, et al. Synthesis, curing process and thermal reversible mechanism of UV curable polyurethane based on Diels-Alder structure[J]. Progress in Organic Coatings, 2016, 100: 63-69.
30	AIZPURUA June, MARTIN Loli, Mercedes FERNÁNDEZ, et al. Recyclable, remendable and healing polyurethane/acrylic coatings from UV curable waterborne dispersions containing Diels-Alder moieties[J]. Progress in Organic Coatings, 2020, 139: 105460.
31	WANG Zhengyue, YANG Haitao, FAIRBANKS Benjamin D, et al. Fast self-healing engineered by UV-curable polyurethane contained Diels-Alder structure[J]. Progress in Organic Coatings, 2019, 131: 131-136.
32	WANG Zhengyue, LIANG Hongbo, YANG Haitao, et al. UV-curable self-healing polyurethane coating based on thiol-ene and Diels-Alder double click reactions[J]. Progress in Organic Coatings, 2019, 137: 105282.
33	LIU Jingcheng, ZHOU Zhen, SU Xunzheng, et al. Stiff UV-curable self-healing coating based on double reversible networks containing Diels-Alder cross-linking and hydrogen bonds[J]. Progress in Organic Coatings, 2020, 146: 105699.
34	JIA Han, GU Shuying. A near infrared induced self-healable composite based on disulfide bonds for flexible electronics[J]. Journal of Polymer Research, 2020, 27(10): 1-13.
35	WAN Ting, CHEN Dajun. Synthesis and properties of self-healing waterborne polyurethanes containing disulfide bonds in the main chain[J]. Journal of Materials Science, 2017, 52(1): 197-207.
36	MICHAL Brian T, JAYE Colin A, SPENCER Emily J, et al. Inherently photohealable and thermal shape-memory polydisulfide networks[J]. ACS Macro Letters, 2013, 2(8): 694-699.
37	OTSUKA Hideyuki, NAGANO Shinsuke, KOBASHI Yasuharu, et al. A dynamic covalent polymer driven by disulfidemetathesis under photoirradiation[J]. Chemical Communications, 2010, 46(7): 1150-1152.
38	HAN Guang, NIE Juyin, ZHANG Huiqi. Facile preparation of recyclable photodeformable azobenzene polymer fibers with chemically crosslinked networks[J]. Polymer Chemistry, 2016, 7(32): 5088-5092.
39	ZHAO Dongli, LIU Shanshan, WU Yefei, et al. Self-healing UV light-curable resins containing disulfide group: Synthesis and application in UV coatings[J]. Progress in Organic Coatings, 2019, 133: 289-298.
40	ZHAO Dongli, DU Zhukang, LIU Shanshan, et al. UV light curable self-healing superamphiphobic coatings by photopromoted disulfide exchange reaction[J]. ACS Applied Polymer Materials, 2019, 1(11): 2951-2960.
41	LI Xinpan, YU Ran, HE Yangyang, et al. Self-healing polyurethane elastomers based on a disulfide bond by digital light processing 3D printing[J]. ACS Macro Letters, 2019, 8(11): 1511-1516.
42	ZHANG Manwen, TAO Xinglin, YU Ran, et al. Self-healing, mechanically robust, 3D printable ionogel for highly sensitive and long-term reliable ionotronics[J]. Journal of Materials Chemistry A, 2022, 10(22): 12005-12015.
43	ZHONG Ye, XU Yufang, ANSLYN Eric V. Studies of reversible conjugate additions[J]. European Journal of Organic Chemistry, 2013, 2013(23): 5017-5021.
44	YU Kunhao, XIN An, DU Haixu, et al. Additive manufacturing of self-healing elastomers[J]. NPG Asia Materials, 2019, 11: 7.
45	CHENG Kezi, CHORTOS Alex, LEWIS Jennifer A, et al. Photoswitchable covalent adaptive networks based on thiol-ene elastomers[J]. ACS Applied Materials & Interfaces, 2022, 14(3): 4552-4561.
46	MIAO Jiatao, GE Meiying, WU Yadong, et al. 3D printing of sacrificial thermosetting mold for building near-infrared irradiation induced self-healable 3D smart structures[J]. Chemical Engineering Journal, 2022, 427: 131580.
47	WANG Zhanhua, GANGARAPU Satesh, ESCORIHUELA Jorge, et al. Dynamic covalent urea bonds and their potential for development of self-healing polymer materials[J]. Journal of Materials Chemistry A, 2019, 7(26): 15933-15943.
48	ZHANG Qi, SHI Chenyu, QU Dahui, et al. Exploring a naturally tailored small molecule for stretchable, self-healing, and adhesive supramolecular polymers[J]. Science Advances, 2018, 4(7): eaat8192.
49	ZHANG Qi, DENG Yuanxin, LUO Hongxia, et al. Assembling a natural small molecule into a supramolecular network with high structural order and dynamic functions[J]. Journal of the American Chemical Society, 2019, 141: 12804-12814.
50	DENG Yuanxin, ZHANG Qi, FERINGA Ben L, et al. Toughening a self-healable supramolecular polymer by ionic cluster-enhanced iron-carboxylate complexes[J]. Angewandte Chemie, 2020, 132(13): 5316-5321.
51	ZHANG Qi, DENG Yuanxin, SHI Chenyu, et al. Dual closed-loop chemical recycling of synthetic polymers by intrinsically reconfigurable poly(disulfides)[J]. Matter, 2021, 4(4): 1352-1364.
52	SIEREDZINSKA Bianka, ZHANG Qi, VAN DEN BERG Keimpe J, et al. Photo-crosslinking polymers by dynamic covalent disulfide bonds[J]. Chemical Communications, 2021, 57(77): 9838-9841.
53	RÖTTGER M, DOMENECH T, VAN DER WEEGEN R, et al. High-performance vitrimers from commodity thermoplastics through dioxaborolane metathesis[J]. Science, 2017, 356(6333): 62-65.
54	LIU Zhu, XIAO Dingshu, LIU Guocong, et al. Self-healing and reprocessing of transparent UV-cured polysiloxane elastomer[J]. Progress in Organic Coatings, 2021, 159: 106450.
55	ROBINSON Lindsay L, SELF Jeffrey L, FUSI Alexander D, et al. Chemical and mechanical tunability of 3D-printed dynamic covalent networks based on boronate esters[J]. ACS Macro Letters, 2021, 10(7): 857-863.
56	LAI Jiancheng, MEI Jinfeng, JIA Xiaoyong, et al. A stiff and healable polymer based on dynamic-covalent boroxine bonds[J]. Advanced Materials, 2016, 28(37): 8277-8282.
57	PENG Shuqiang, WANG Zian, LIN Jinbin, et al. Tailored and highly stretchable sensor prepared by crosslinking an enhanced 3D printed UV-curable sacrificial mold[J]. Advanced Functional Materials, 2021, 31(10): 2008729.
58	WANG Sheng, MA Songqi, LI Qiong, et al. Facile preparation of polyimine vitrimers with enhanced creep resistance and thermal and mechanical properties via metal coordination[J]. Macromolecules, 2020, 53(8): 2919-2931.
59	ZHANG Yanfeng, YING Hanze, HART Kevin R, et al. Malleable and recyclable poly(urea-urethane) thermosets bearing hindered urea bonds[J]. Advanced Materials, 2016, 28(35): 7646-7651.
60	ZHANG Qiang, WANG Shujuan, RAO Bin, et al. Hindered urea bonds for dynamic polymers: An overview[J]. Reactive and Functional Polymers, 2021, 159: 104807.
61	JIANG Liang, LEI Yuan, XIAO Yao, et al. Mechanically robust, exceptionally recyclable and shape memory cross-linked network based on reversible dynamic urea bonds[J]. Journal of Materials Chemistry A, 2020, 8(42): 22369-22378.
62	Sungwoo JUN, KIM Sun Ok, LEE Hee Jin, et al. Transparent, pressure-sensitive, and healable e-skin from a UV-cured polymer comprising dynamic urea bonds[J]. Journal of Materials Chemistry A, 2019, 7(7): 3101-3111.
63	ZHANG Jinshuai, SHANG Qianqian, HU Yun, et al. Castor-oil-based UV-curable hybrid coatings with self-healing, recyclability, removability, and hydrophobicity[J]. Progress in Organic Coatings, 2022, 165: 106742.
64	HAMACHI Leslie S, Daniel A RAU, ARRINGTON Clay B, et al. Dissociative carbamate exchange anneals 3D printed acrylates[J]. ACS Applied Materials & Interfaces, 2021, 13(32): 38680-38687.
65	ZHENG Ning, FANG Zizheng, ZOU Weike, et al. Thermoset shape-memory polyurethane with intrinsic plasticity enabled by transcarbamoylation[J]. Angewandte Chemie International Edition, 2016, 55(38): 11421-11425.
66	DELEBECQ Etienne, PASCAULT Jean Pierre, BOUTEVIN Bernard, et al. On the versatility of urethane/urea bonds: Reversibility, blocked isocyanate, and non-isocyanate polyurethane[J]. Chemical Reviews, 2013, 113(1): 80-118.

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