含双重动态键的可重加工及室温自修复聚氨酯弹性体
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摘要
通过同时向聚合物的主链和交联点引入2种动态共价键—Diels-Alder (D-A)键和二硫(S―S)键,制备了具有自修复、可重加工性能的聚氨酯(PU-SSDA)弹性体.一方面分布在主链和交联点的动态键使聚合物分子链通过可逆的断裂重组实现自修复,另一方面,交联的PU中同时存在线性的分子链,从而提高了断面间分子的运动性能,使被破坏的断面间迅速浸润,提高修复效率. PU-SSDA在室温下修复60 min的修复效率可达93%.此外,这些聚氨酯材料可以利用无溶剂一步法制备,作为环境友好材料具有广泛的应用潜力.
We synthesized a self-healing polyurethane elastomer(PU-SSDA) which displayed excellent healing efficiency at room temperature due to the synergistic contribution of dynamic covalent D-A bond and S–S bond.Mechanical and self-healing properties of the polyurethane elastomers were characterized by tensile test and threedimensional super depth of field microscope. The cross-linking structure of PU-SSDA is explored by extraction experiments, demonstrating that there are not only crosslinked structures but also linear molecular segments existed in the polyurethane elastomer. Mechanical properties of the PU-SSDA elastomer can be tuned by changing the cross-linking degree. As the crosslinking degree increases from 25% to 45%, the tensile strength increases from 2.9 MPa to 5.5 MPa while the elongation at break decreases from 795% to 304%. After optimization, when the crosslinking degree was 35%, the tensile strength was 3.7 MPa, the elongation at break was 606% and the repair efficiency could be restored to 93% after healing for 60 min at room temperature. Moreover, the healing efficiency still remains above 90% after 4 damage-healing cycles. In addition, the PU-SSDA elastomer can also be reprocessed by hot pressing at 120℃ . This excellent self-healing behavior and reprocessable property were attributed to the reversible fracture recombination reaction of dynamic D-A and S― S bonds and the quick infiltration of the linear polymer chains into damaged surface. The self-healing mechanism can be further confirmed by the dissolution experiments which showed that the PU-SSDA elastomer can be dissolved in DMF at 100 ℃ while the PU-control can only swell under the same conditions, demonstrating that the reversible cleavage and reformation of D-A and S―S bonds contribute a lot to the self-healing process. Due to the facile and friendly preparation method, fast self-healing behavior at room temperature and fully reprocessable properties, the asprepared polyurethane elastomers displayed wide potential applications such as protection coatings and wearable electronic devices.
We synthesized a self-healing polyurethane elastomer(PU-SSDA) which displayed excellent healing efficiency at room temperature due to the synergistic contribution of dynamic covalent D-A bond and S–S bond.Mechanical and self-healing properties of the polyurethane elastomers were characterized by tensile test and threedimensional super depth of field microscope. The cross-linking structure of PU-SSDA is explored by extraction experiments, demonstrating that there are not only crosslinked structures but also linear molecular segments existed in the polyurethane elastomer. Mechanical properties of the PU-SSDA elastomer can be tuned by changing the cross-linking degree. As the crosslinking degree increases from 25% to 45%, the tensile strength increases from 2.9 MPa to 5.5 MPa while the elongation at break decreases from 795% to 304%. After optimization, when the crosslinking degree was 35%, the tensile strength was 3.7 MPa, the elongation at break was 606% and the repair efficiency could be restored to 93% after healing for 60 min at room temperature. Moreover, the healing efficiency still remains above 90% after 4 damage-healing cycles. In addition, the PU-SSDA elastomer can also be reprocessed by hot pressing at 120℃ . This excellent self-healing behavior and reprocessable property were attributed to the reversible fracture recombination reaction of dynamic D-A and S― S bonds and the quick infiltration of the linear polymer chains into damaged surface. The self-healing mechanism can be further confirmed by the dissolution experiments which showed that the PU-SSDA elastomer can be dissolved in DMF at 100 ℃ while the PU-control can only swell under the same conditions, demonstrating that the reversible cleavage and reformation of D-A and S―S bonds contribute a lot to the self-healing process. Due to the facile and friendly preparation method, fast self-healing behavior at room temperature and fully reprocessable properties, the asprepared polyurethane elastomers displayed wide potential applications such as protection coatings and wearable electronic devices.
引文
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6Chen X X,Dam M A,Ono K,Mal A,Shen H B,Nutt S R,Sheran K,Wudl F.Science,2002,295(5560):1698-1702
7Liu Y L,Chen Y W.Macromol Chem Phys,2007,208(2):224-232
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13van Gemert G M L,Peeters J W,S?ntjens S H M,Janssen H M,Bosman A W.Macromol Chem Phys,2012,213(2):234-242
14Yang Li(杨莉).Ultra-fast Photoresponsive Shape Memory and Self-healing Polymeric Composites(近红外光快速响应的形状记忆自修复聚合物复合材料).Doctoral Dissertation of Sichuan University(四川大学博士学位论文),2017
15Wang Z H,Ying Y,Burtovyy R,Luzinov I,Urban M W.J Mater Chem A,2014,2(37):15527-15534
16Wang Z H,Urban M W.Polym Chem,2013,4(18):4897-4901
17Zhao J,Xu R,Luo G X,Wu J,Xia H S.J Mater Chem B,2016,4(5):982-989
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20Yoshie N,Saito S,Oya N.Polymer,2011,52(26):6074-6079
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23Yang Y L,Lu X,Wang W W.Mater Des,2017,127:30-36
24Lei Z Q,Xiang H P,Yuan Y J,Rong M Z,Zhang M Q.Chem Mater,2014,26(6):2038-2046
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26Lu Xili(卢锡立).Reprocessable Polymers Capable of Stimuli-controlled Shape Memory,Self-healing and Motion(具有刺激响应形状记忆、自修复或运动性能的可加工交联高分子材料).Doctoral Dissertation of Sichuan University(四川大学博士学位论文),2017