State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
赵骞(1982—),男,博士,副教授,qianzhao@zju.edu.cn
收稿:2019-05-13,
修回:2019-08-12,
纸质出版:2019-11-05
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陈峰, 候宇坤, 赵骞. 一种硼酸酯动态交联环氧树脂的合成与性能[J]. 化工学报, 2019, 70(11): 4449-4456
CHEN Feng, HOU Yukun, ZHAO Qian. Synthesis and properties of epoxy resin crosslinked by dynamic boronic ester bonds[J]. CIESC Journal, 2019, 70(11): 4449-4456
陈峰, 候宇坤, 赵骞. 一种硼酸酯动态交联环氧树脂的合成与性能[J]. 化工学报, 2019, 70(11): 4449-4456 DOI: 10.11949/0438-1157.20190503.
CHEN Feng, HOU Yukun, ZHAO Qian. Synthesis and properties of epoxy resin crosslinked by dynamic boronic ester bonds[J]. CIESC Journal, 2019, 70(11): 4449-4456 DOI: 10.11949/0438-1157.20190503.
利用巯基与环氧的点击反应,向环氧体系中引入二醇结构,并通过硼酸酯键对其进行交联,制备了一系列不同流变性能和玻璃化转变温度的可塑环氧树脂材料。研究了不同的配方对材料性能的影响,结果表明通过改变交联剂与动态链结的比例,体系的流变性能可以被调控;另一方面,改变软硬环氧组分的比例可以使材料的玻璃化转变温度在14.6~36.5℃之间调节。制备了该可塑环氧树脂与密胺通孔泡沫的复合材料,该材料具备良好的快速自黏结性能。材料断裂后,在10 s内即可达到最大黏结强度,且经多次拆卸-黏结循环后,黏结强度可以保持在约0.06 MPa。
A series of dynamic covalent polymer networks providing various rheological properties and glass transition temperatures were prepared
via
firstly introducing a diol group into an epoxy molecule through a thiol-epoxy click reaction and secondly crosslinking the diol groups by dynamic borate bonds. Effect of formulation on the properties of the materials was investigated. The rheological properties of the materials can be adjusted by tuning the ratio of the crosslinking agents and the exchangeable borate bonds. Glass transition temperature of the polymer can be adjusted from 14.6℃ to 36.5℃ by changing the ratio of the fed soft and hard epoxy components. A composite material is prepared by introducing the dynamic network into an open porous melamine foam. Such a composite can be rapidly self-welded in a few seconds after it had been cut. The welding performance is found to retain 0.06 MPa after 20 disassembling-bonding cycles
showing a good repeatability.
Zou W K , Dong J T , Luo Y W , et al . Dynamic covalent polymer networks: from old chemistry to modern day innovations [J]. Advanced Materials , 2017 , 29 ( 14 ): 1606100 .
Montarnal D , Capelot M , Leibler L , et al . Silica-like malleable materials from permanent organic networks [J]. Science , 2011 , 334 ( 6058 ): 965 - 968 .
Delpierre S , Willocq B , de Winter J , et al . Dynamic iminoboronate-based boroxine chemistry for the design of ambient humidity-sensitive self-healing polymers [J]. Chemistry - A European Journal , 2017 , 23 ( 28 ): 6730 - 6735 .
Lai J C , Mei J F , Jia X Y , et al . A stiff and healable polymer based on dynamic-covalent boroxine bonds [J]. Advanced Materials , 2016 , 28 ( 37 ): 8277 - 8282 .
Nicolaÿ R , Kamada J , van Wassen A , et al . Responsive gels based on a dynamic covalent trithiocarbonate cross-linker [J]. Macromolecules , 2010 , 43 ( 9 ): 4355 - 4361 .
Zheng P W , Mccarthy T J . A surprise from 1954: siloxane equilibration is a simple, robust, and obvious polymer self-healing mechanism [J]. Journal of the American Chemical Society , 2012 , 134 ( 4 ): 2024 - 2027 .
Cash J J , Kubo T , Bapat A P , et al . Room-temperature self-healing polymers based on dynamic-covalent boronic esters [J]. Macromolecules , 2015 , 48 ( 7 ): 2098 - 2106 .
Bao C Y , Jiang Y J , Zhang H Y , et al . Room-temperature self-healing and recyclable tough polymer composites using nitrogen-coordinated boroxines [J]. Advanced Functional Materials , 2018 , 28 ( 23 ): 1800560 .
Fang Z Z , Zheng N , Zhao Q , et al . Healable, reconfigurable, reprocessable thermoset shape memory polymer with highly tunable topological rearrangement kinetics [J]. ACS Applied Materials & Interfaces , 2017 , 9 ( 27 ): 22077 - 22082 .
Bao C Y , Guo Z W , Sun H X , et al . Nitrogen-coordinated boroxines enable the fabrication of mechanically robust supramolecular thermosets capable of healing and recycling under mild conditions [J]. ACS Applied Materials & Interfaces , 2019 , 11 ( 9 ): 9478 - 9486 .
Ying H , Zhang Y , Cheng J . Dynamic urea bond for the design of reversible and self-healing polymers [J]. Nature Communications , 2014 , 5 : 3218 .
Imbernon L , Oikonomou E K , Norvez S , et al . Chemically crosslinked yet reprocessable epoxidized natural rubber via thermo-activated disulfide rearrangements [J]. Polymer Chemistry , 2015 , 6 ( 23 ): 4271 - 4278 .
Jin K L , Li L Q , Torkelson J M . Recyclable crosslinked polymer networks via one-step controlled radical polymerization [J]. Advanced Materials , 2016 , 28 ( 31 ): 6746 - 6750 .
Xiang H P , Yin J F , Lin G H , et al . Photo-crosslinkable, self-healable and reprocessable rubbers [J]. Chemical Engineering Journal , 2019 , 358 : 878 - 890 .
Ogden W A , Guan Z B . Recyclable, strong, and highly malleable thermosets based on boroxine networks [J]. Journal of the American Chemical Society , 2018 , 140 ( 20 ): 6217 - 6220 .
Ferry J D . Viscoelastic Properties of Polymers [M]. 3rd ed . New York : John Wiley & Sons Inc ., 1981 .
Liu Y J , Tang Z H , Chen Y , et al . Programming dynamic imine bond into elastomer/graphene composite toward mechanically strong, malleable, and multi-stimuli responsive vitrimer [J]. Composites Science and Technology , 2018 , 168 : 214 - 223 .
Liu H C , Zhang H , Wang H , et al . Weldable, malleable and programmable epoxy vitrimers with high mechanical properties and water insensitivity [J]. Chemical Engineering Journal , 2019 , 368 : 61 - 70 .
Boland C S , Khan U , Ryan G , et al . Sensitive electromechanical sensors using viscoelastic graphene-polymer nanocomposites [J]. Science , 2016 , 354 ( 6317 ): 1257 - 1260 .
Liang J , Zhang X H . Rheological properties of SP in shock transmission application [J]. Journal of Materials in Civil Engineering , 2014 , 27 ( 9 ): 04014250 .
Golinelli N , Spaggiari A , Dragoni E . Mechanical behaviour of magnetic silly putty: viscoelastic and magnetorheological properties [J]. Journal of Intelligent Material Systems and Structures , 2017 , 28 ( 8 ): 953 - 960 .
Ivanov A E , Larsson H , Galaev I Y , et al . Synthesis of boronate-containing copolymers of N,N -dimethylacrylamide, their interaction with poly(vinyl alcohol) and rheological behaviour of the gels [J]. Polymer , 2004 , 45 ( 8 ): 2495 - 2505 .
He L H , Fullenkamp D E , Messersmith P B , et al . pH responsive self-healing hydrogels formed by boronate-catechol complexation [J]. Chemical Communications , 2011 , 47 ( 26 ): 7497 - 7499 .
Cromwell O R , Chung J , Guan Z B . 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 .
Rottger M , Domenech T , Leibler L , et al . High-performance vitrimers from commodity thermoplastics through dioxaborolane metathesis [J]. Science , 2017 , 356 ( 6333 ): 62 - 65 .
Zhang Q , Anastasaki A , Li G Z , et al . Multiblock sequence-controlled glycopolymers via Cu(0)-LRP following efficient thiol–halogen, thiol-epoxy and CuAAC reactions [J]. Polymer Chemistry , 2014 , 5 ( 12 ): 3876 - 3883 .
Yoshimura Y , Yamazaki Y , Saito Y , et al . Synthesis of 1-(5,6-dihydro-2H-thiopyran-2-yl)uracil by a Pummerer-type thioglycosylation reaction: the regioselectivity of allylic substitution [J]. Tetrahedron , 2009 , 65 ( 45 ): 9091 - 9102 .
Brändle A , Khan A . Thiol–epoxy ‘click polymerization: efficient construction of reactive and functional polymers [J]. Polymer Chemistry , 2012 , 3 ( 12 ): 3224 - 3227 .
Binder S , Gadwal I , Bielmann A , et al . Thiol-epoxy polymerization via an AB monomer: synthetic access to high molecular weight poly(β-hydroxythio-ether)s [J]. Journal of Polymer Science Part A: Polymer Chemistry , 2014 , 52 ( 14 ): 2040 - 2046 .
Brooks W L A , Sumerlin B S . Synthesis and applications of boronic acid-containing polymers: from materials to medicine [J]. Chemical Reviews , 2016 , 116 ( 3 ): 1375 - 1397 .
Duncan T T , Berrie B H , Weiss R G . Soft, peelable organogels from partially hydrolyzed poly(vinyl acetate) and benzene-1,4-diboronic acid: applications to clean works of art [J]. ACS Applied Materials & Interfaces , 2017 , 9 ( 33 ): 28069 - 28078 .
Angelova L V , Leskes M , Berrie B H , et al . Selective formation of organo, organo-aqueous, and hydro gel-like materials from partially hydrolysed poly(vinyl acetate)s based on different boron-containing crosslinkers [J]. Soft Matter , 2015 , 11 ( 25 ): 5060 - 5066 .
Yesilyurt V , Webber M J , Appel E A , et al . Injectable self-healing glucose-responsive hydrogels with pH-regulated mechanical properties [J]. Advanced Materials , 2016 , 28 ( 1 ): 86 - 91 .
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