六咪唑环三磷腈的合成及其作为环氧树脂固化促进剂的性能
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摘要
利用六氯环三磷腈与咪唑发生亲核取代反应,合成六咪唑环三磷腈(HImCP);通过红外光谱、核磁共振~1H谱和~(31)P谱对其结构进行表征;进一步将其作为固化促进剂,加入双酚A型环氧树脂(E51)/甲基六氢苯酐(MHHPA)固化体系,通过凝胶时间和非等温DSC固化动力学分析研究体系的室温存储稳定性和高温固化反应活性,并考察固化物的力学性能和热性能。结果表明:相较于咪唑,HImCP是一种良好的潜伏性固化促进剂,当其添加量为1%(质量分数)时,E51/MHHPA体系具有较好的室温存储稳定性和高温固化活性;同时,得到的环氧树脂固化物表现出更高的拉伸强度、玻璃化转变温度和热稳定性。
Hexa(imidazolyl) cyclotriphosphazene(HImCP) was synthesized by nucleophilic substitution reaction of hexachlorocyclotriphosphazene with imidazole. The chemical structure was characterized by FT-IR,~1H-NMR, and ~(31)P-NMR. Then the as-prepared HImCP was utilized as curing catalyst for curing of diglycidylether of bisphenol A(E51)with methylhexahydrophthalic anhydride(MHHPA). Its influence on the storage stability at room temperature and curing activity at high temperature of E51/MHHPA system was studied by gelatum time and non-isothermal DSC analysis. The mechanical performance,glass-transition temperature(T_g),and thermostability of the obtained epoxy thermosets were also investigated. The results show that HImCP is a good latent curing catalyst contrast with unmodified imidazole. When the epoxy resin curing system contains 1%(mass fraction) of HImCP,it exhibits improved storage stability at room temperature as compared to that containing imidazole,as well as satisfied curing activity at high temperature. In addition,the obtained thermoset has higher tensile strength,T_g and thermostability than that resulted from imidazole.
Hexa(imidazolyl) cyclotriphosphazene(HImCP) was synthesized by nucleophilic substitution reaction of hexachlorocyclotriphosphazene with imidazole. The chemical structure was characterized by FT-IR,~1H-NMR, and ~(31)P-NMR. Then the as-prepared HImCP was utilized as curing catalyst for curing of diglycidylether of bisphenol A(E51)with methylhexahydrophthalic anhydride(MHHPA). Its influence on the storage stability at room temperature and curing activity at high temperature of E51/MHHPA system was studied by gelatum time and non-isothermal DSC analysis. The mechanical performance,glass-transition temperature(T_g),and thermostability of the obtained epoxy thermosets were also investigated. The results show that HImCP is a good latent curing catalyst contrast with unmodified imidazole. When the epoxy resin curing system contains 1%(mass fraction) of HImCP,it exhibits improved storage stability at room temperature as compared to that containing imidazole,as well as satisfied curing activity at high temperature. In addition,the obtained thermoset has higher tensile strength,T_g and thermostability than that resulted from imidazole.
引文
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[14] WEI W, YE W T, R L U, et al. Studies of selective detection of picric acid in solution phase using fluorescent polyphosphazene nanofibers[J]. Acta Polymerica Sinica, 2015,12:1477-1485.
[15] TOMUTA A M, FERNáNDEZ-FRANCOS X, FERRANDO F, et al. Enhanced chemical reworkability of DGEBA thermosets cured with rare earth triflates using aromatic hyperbranched polyesters (HBP) and multiarm star HBP-b-poly(ε-caprolactone) as modifiers[J]. Polymers for Advanced Technologies, 2013, 24(11): 962-970.
[16] YANG G, ZHENG B, YANG J, et al. Preparation and cryogenic mechanical properties of epoxy resins modified by poly (ethersulfone)[J]. Journal of Polymer Science Part A: Polymer Chemistry, 2008, 46(2): 612-624.
[17] LI S, CUI C, HOU H, et al. Synthesis and characterization of amino-terminated hyperbranched polymer and its effect on impact resistance of epoxy resin thermosets[J]. Colloid and Polymer Science, 2015, 293(9): 2681-2688.
[2] YE W T, WEI W, FEI X M, et al. Six-arm star-shaped polymer with cyclophosphazene core and poly(ε-caprolactone) arms as modifier of epoxy thermosets[J]. Journal of Applied Polymer Science, 2016, 134(2): 44384-44393.
[3] FEI X M, WEI W, TANG Y, et al. Simultaneous enhancements in toughness, tensile strength and thermal properties of epoxy-anhydride thermosets with a carboxyl-terminated hyperbranched polyester[J]. European Polymer Journal, 2017, 90: 431-441.
[4] NORRIS B C, SHEPPARD D G, HENKELMAN G, et al. Kinetic and thermodynamic evaluation of the reversible N-heterocyclic carbene-isothiocyanate coupling reaction: applications in latent catalysis[J]. Journal of Organic Chemistry, 2011, 76(1):301-304.
[5] WAN Y J, TANG L C, GONG L X, et al. Grafting of epoxy chains onto graphene oxide for epoxy composites with improved mechanical and thermal properties[J]. Carbon, 2014, 69(2):467-480.
[6] TOMUTA A M, RAMIS X, FERNáNDEZ-FRANCOS X, et al. New chemically reworkable epoxy coatings obtained by the addition of polyesters with star topologies to diglycidyl ether of bisphenol a resins[J]. Progress in Organic Coatings, 2013, 76(11):1616-1624.
[7] SHIN M J, SHIN Y J, HWANG S W, et al. Microencapsulation of imidazole curing agent by solvent evaporation method using W/O/W emulsion[J]. Journal of Applied Polymer Science, 2013, 129(3): 1036-1044.
[8] WEI W, LU R J, YE W T. Liquid marbles stabilized by fluorine-bearing cyclomatrix polyphosphazene particles and their application as high-efficiency miniature reactors[J]. Langmuir,2016,32(7): 1707-1715.
[9] WANG W, DI N, CAO W R, et al. Cure kinetics of epoxy resin using 1,2,4,5-benzenetetracarboxylic acid/2-ethyl-4-methylimidazole salt as a latent hardener[J]. Material Research Innovations, 2016, 19(Suppl 8):502-507.
[10] MIN J S, SHIN Y J, HWANG S W, et al. Microencapsulation of imidazole curing agent by solvent evaporation method using W/O/W emulsion[J]. Journal of Applied Polymer Science, 2013, 129(3):1036-1044.
[11] FUENSANTA M, GRAU A, ROMERO-SáNCHEZ M D, et al. Effect of the polymer shell in imidazole microencapsulation by solvent evaporation method[J]. Polymer Bulletin, 2013, 70(11):3055-3074.
[12] ARIMITSU K, FUSE S, KUDO K, et al. Imidazole derivatives as latent curing agents for epoxy thermosetting resins[J]. Materials Letters, 2015, 161:408-410.
[13] YEN W P, CHEN K L, YEH M Y, et al. Investigation of soluble PEG-imidazoles as the thermal latency catalysts for epoxy-phenolic resins[J]. Journal of the Taiwan Institute of Chemical Engineers, 2015, 59:98-105.
[14] WEI W, YE W T, R L U, et al. Studies of selective detection of picric acid in solution phase using fluorescent polyphosphazene nanofibers[J]. Acta Polymerica Sinica, 2015,12:1477-1485.
[15] TOMUTA A M, FERNáNDEZ-FRANCOS X, FERRANDO F, et al. Enhanced chemical reworkability of DGEBA thermosets cured with rare earth triflates using aromatic hyperbranched polyesters (HBP) and multiarm star HBP-b-poly(ε-caprolactone) as modifiers[J]. Polymers for Advanced Technologies, 2013, 24(11): 962-970.
[16] YANG G, ZHENG B, YANG J, et al. Preparation and cryogenic mechanical properties of epoxy resins modified by poly (ethersulfone)[J]. Journal of Polymer Science Part A: Polymer Chemistry, 2008, 46(2): 612-624.
[17] LI S, CUI C, HOU H, et al. Synthesis and characterization of amino-terminated hyperbranched polymer and its effect on impact resistance of epoxy resin thermosets[J]. Colloid and Polymer Science, 2015, 293(9): 2681-2688.