硼酯交联增强聚合物的制备和表征
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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PAB_n;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PAB_n-2OH;最后通过PAB_n-2OH的邻二羟基与硼酸反应形成硼酯键交联共聚物PAB_n-2OH-B。通过拉伸和动态力学测试分析了PAB_n-2OH和PAB_n-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;PAB_n-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。
A series of copolymers with β-diketone groups(PAB_n) were synthesized by free radical copolymerization using2-(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 PAB_n-2 OH via the reaction between β-diketone and primary amines. Finally, with the addition of boric acid, a series of crosslinked copolymers(PAB_n-2 OH-B) were obtained via boron esterification. The mechanical properties of PAB_n-2 OH and PAB_n-2 OH-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 PAB_n-2 OH 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 PAB_n-2 OH-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.
A series of copolymers with β-diketone groups(PAB_n) were synthesized by free radical copolymerization using2-(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 PAB_n-2 OH via the reaction between β-diketone and primary amines. Finally, with the addition of boric acid, a series of crosslinked copolymers(PAB_n-2 OH-B) were obtained via boron esterification. The mechanical properties of PAB_n-2 OH and PAB_n-2 OH-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 PAB_n-2 OH 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 PAB_n-2 OH-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.
引文
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[23]SELF J L,DOLINSKI N D,ZAYAS M S,et al.Br?nsted-acid-catalyzed exchange in polyester dynamic covalent networks[J].ACSMacro Letters,2018,7(7):817-821.
[2]ANTONIETTI M.Mesocrystals and Nonclassical Crystallization[M].HoboKen,New Jersey:Wiley,2008.
[3]MEYERS M A,MCKITTRICK J,CHEN P.Structural biological materials:Critical mechanics-materials connections[J].Science,2013,339(6121):773-779.
[4]WEGST U G K,BAI H,SAIZ E,et al.Bioinspired structural materialsc[J].Nature Materials,2014,14(1):23-36.
[5]LEI Z,WANG Q,SUN S,et al.A bioinspired mineral hydrogel as a self-healable,mechanically adaptable Ionic skin for highly sensitive pressure sensing[J].Advanced Materials,2017,29(22):1700321.
[6]SPRINGSTEEN G,WANG B.A detailed examination of boronic acid-diol complexation[J].Tetrahedron,2002,58(26):5291-5300.
[7]AND J P,MATYJASZEWSKI K.Synthesis of nanocomposite organic/inorganic hybrid materials using controlled“living”radical polymerization[J].Chemistry of Materials,2001,13(10):3436-3448.
[8]CHEN Y,QIAN W,CHEN R,et al.One-pot preparation of autonomously self-healable elastomeric hydrogel from boric acid and random copolymer bearing hydroxyl groups[J].ACS Macro Letters,2017,6(10):1129-1133.
[9]BLEVINS D G,LUKASZEWSKI K M.Boron in plant structure and function[J].Annual Review of Plant Physiology&Plant Molecular Biology,2003,49(49):481-500.
[10]AN Z,COMPTON O C,PUTZ K W,et al.Bio-inspired borate cross-linking in ultra-stiff graphene oxide thin films[J].Advanced Materials,2011,23(33):3842-3846.
[11]ROTTGER M,DOMENECH T,LEIBLER R,et al.High-performance vitrimers from commodity thermoplastics through dioxaborolane metathesis[J].Science,2017,356(6333):62-65.
[12]YIN Y,LI J,LIU Y,et al.Starch crosslinked with poly(vinyl alcohol)by boric acid[J].Journal of Applied Polymer Science,2010,96(4):1394-1397.
[13]TILLET G,BOUTEVIN B,AMEDURI B.Chemical reactions of polymer crosslinking and post-crosslinking at room and medium temperature[J].Progress in Polymer Science,2011,36(2):191-217.
[14]MAGNET S,GUILLOT J,GUYOT A,et al.Crosslinking ability of styrene-butyl acrylate copolymer latices functionalized with glycidyl methacrylate[J].Progress in Organic Coatings,1992,20(92):73-80.
[15]蒋姗,黄天涯,王伟,等.共聚物Poly(DMAEMA-co-TPE-a)的合成及pH敏感荧光多孔光纤制备[J].功能高分子学报,2017,30(1):103-109.
[16]NASIRI M,SAXON D J,REINEKE T M.Enhanced mechanical and adhesion properties in sustainable triblock copolymers via noncovalent interactions[J].Macromolecules,2018,51(7):2456-2465.
[17]SCHIFF H.Mittheilungen aus dem universit?tslaboratorium in pisa:Untersuchungenüdas chinolin[J].Justus Liebigs Annalen Der Chemie,1864,131(1):112-117.
[18]CROMWELL O R,CHUNG J,GUAN Z.Malleable and self-healing covalent polymer networks through tunable dynamic boronic ester bonds[J].Journal of the American Chemical Society,2015,137(20):6492-6495.
[19]WANG C,LIU N,ALLEN R,et al.A rapid and efficient self-healing thermo-reversible elastomer crosslinked with graphene oxide[J].Advanced Materials,2013,25(40):5785-5790.
[20]DENISSION W,DROESBEKE M,NICOLA R,et al.Chemical control of the viscoelastic properties of vinylogous urethane vitrimers[J].Nature Communications,2017,8:14857.
[21]SIMS M B,LESSARD J J,BAI L,et al.Functional diversification of polymethacrylates by dynamicβ-ketoester modification[J].Macromolecules,2018,51(16):6380-6386.
[22]何晴,白静,史子兴,等.基于Diels-Alder反应的热可逆交联聚醚胺的制备和表征[J].功能高分子学报,2018,31(2):140-146.
[23]SELF J L,DOLINSKI N D,ZAYAS M S,et al.Br?nsted-acid-catalyzed exchange in polyester dynamic covalent networks[J].ACSMacro Letters,2018,7(7):817-821.