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    张新慧, 白静, 史子兴, 钟蔚华. 硼酯交联增强聚合物的制备和表征[J]. 功能高分子学报, 2019, 32(4): 479-485. doi: 10.14133/j.cnki.1008-9357.20181203001
    引用本文: 张新慧, 白静, 史子兴, 钟蔚华. 硼酯交联增强聚合物的制备和表征[J]. 功能高分子学报, 2019, 32(4): 479-485. doi: 10.14133/j.cnki.1008-9357.20181203001
    ZHANG Xinhui, BAI Jing, SHI Zixing, ZHONG Weihua. Preparation and Characterization of Boron Ester Cross-Linked Enhanced Polymers[J]. Journal of Functional Polymers, 2019, 32(4): 479-485. doi: 10.14133/j.cnki.1008-9357.20181203001
    Citation: ZHANG Xinhui, BAI Jing, SHI Zixing, ZHONG Weihua. Preparation and Characterization of Boron Ester Cross-Linked Enhanced Polymers[J]. Journal of Functional Polymers, 2019, 32(4): 479-485. doi: 10.14133/j.cnki.1008-9357.20181203001

    硼酯交联增强聚合物的制备和表征

    Preparation and Characterization of Boron Ester Cross-Linked Enhanced Polymers

    • 摘要: 首先以甲基丙烯酸乙酰乙酸乙二醇酯(AAEM)和丙烯酸正丁酯(BA)为单体,以偶氮二异丁腈为引发剂,通过共聚反应得到共聚物PABn;然后利用该共聚物分子链上的β-二酮基团与伯胺间的缩合反应接枝邻二羟基,制备了含有邻二羟基的丙烯酸酯共聚物PABn-2OH;最后通过PABn-2OH的邻二羟基与硼酸反应形成硼酯键交联共聚物PABn-2OH-B。通过拉伸和动态力学测试分析了PABn-2OH和PABn-2OH-B的力学性能及其影响因素。结果表明:邻二羟基的引入不仅可以通过共聚物之间的氢键增强膜的力学性能,还为硼酸水溶液进入聚合物网络提供了通道;PABn-2OH浸泡于硼酸水溶液中发生硼酯交联反应后其力学性能显著增强,硼发挥着类似于植物中矿物质的“矿化作用”;硼酯在酸/碱条件下的可逆反应可用来调控和设计交联聚合物的形状记忆特性。

       

      Abstract: A series of copolymers with β-diketone groups (PABn) were synthesized by free radical copolymerization using 2-(acetoacetyloxy) ethyl methacrylate (AAEM) and N-butyl acrylate (BA) as monomers, and azobisisobutyronitrile (AIBN) as the initiator. Then the adjacent dihydroxyl groups were attached to the copolymers to give rise to PABn-2OH via the reaction between β-diketone and primary amines. Finally, with the addition of boric acid, a series of crosslinked copolymers (PABn-2OH-B) were obtained via boron esterification. The mechanical properties of PABn-2OH and PABn-2OH-B samples and the influence factors were studied by tensile measurements and dynamic mechanical tests. It was shown that the compositions of copolymer, the content of adjacent dihydroxyl and crosslinking density presented significant impacts on the mechanical performances. The presence of dihydroxyl groups can not only effectively improve the mechanical properties via the hydrogen bonds among copolymers, but also provide accesses for boric acid into the polymer network to form crosslinked inorganic-organic hybrids connected by boron esterification bonds. In this context, soaking of PABn-2OH in aqueous solution of boric acid could form boron ester cross-linking, resulting in significant mechanical enhancement with only 1% mass fraction of boron in PABn-2OH-B samples, which was analogous to the mineralization process of mineral elements in plants. Inspired by the phenomenon in nature, the mechanical properties of copolymer were effectively tailored via controlling the content of hydroxyl groups and their reactions with boric acid. Furthermore, the boron ester bonds were reversible in acid and base solution, and various shape transformations could be realized via controlling the environmental pH.

       

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