SiO_2/Zn_2SnO_4/环氧丙烯酸酯涂层的阻燃性能
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摘要
为了探究复合纳米颗粒对环氧丙烯酸酯(EA)涂层阻燃性能的影响,以十六烷基三甲基溴化铵(CTAB)和正硅酸乙酯(TEOS)为原料合成了介孔二氧化硅纳米颗粒,以ZnCl_2和SnCl4·5H_2O为原料合成了锡酸锌(Zn_2SnO_4)纳米颗粒,将它们复合制成了介孔二氧化硅/锡酸锌复合纳米颗粒(SiO_2/Zn_2SnO_4),并用X射线粉末衍射仪(XRD)、透射电镜(TEM)对其表征。将所制的纳米颗粒(介孔SiO_2、Zn_2SnO_4、SiO_2/Zn_2SnO_4)与丙烯酸、丙烯酰胺、EA复合,经UV光固化制备出3种涂层(SiO_2/EA、Zn_2SnO_4/EA、SiO_2/Zn_2SnO_4/EA),通过紫外-可见光谱仪、差示扫描量热仪(DSC)及氧指数测定仪等对涂层的透光率、热稳定性、阻燃性能进行测试。结果表明:SiO_2/Zn_2SnO_4/EA涂层的综合性能较佳,当SiO_2/Zn_2SnO_4质量分数为4.85%时,该涂层的热稳定性及阻燃性能最佳,其极限氧指数、燃烧级别、残炭率(500℃下马弗炉煅烧)和硬度分别为31、V-0、17.32%及6H。
To explore the effect of composite nanoparticles on the flame retardancy of epoxy acrylate(EA) coating, mesoporous silica nanoparticle was synthesized by using cetyltrimethylammonium bromide (CTAB) and tetraethoxysilane(TEOS) as raw materials, and zinc stannate nanoparticle was synthesized based on ZnCl_2 and SnCl4· 5H2 O as raw materials. Then mesoporous silica/zinc stannate nanoparticle complex was prepared by compounding them, and the above nanoparticles were characterized by X-raypowder diffractometer(XRD) and transmission electron microscope(TEM). Three kinds of compositecoatings(SiO_2/EA, Zn_2SnO_4/EA, SiO_2/Zn_2SnO_4/EA) were prepared by UV curing method through mixing theabove prepared nanoparticles(mesoporous SiO_2, Zn_2SnO_4, SiO_2/Zn_2SnO_4), acrylic acid, acrylamide with EA,and the transmittance, thermal stability and flame retardancy of the coating were measured by UV-visspectrometer, differential scanning calorimeter(DSC) and oxygen index tester. The results showed that thecomprehensive properties of SiO_2/Zn_2SnO_4/EA coatings were superior. When the mass percent content ofSiO_2/Zn_2SnO_4 was 4.85%, the thermal stability and flame retardancy of the coating are the best. The coating’s limiting oxygen index,combustion grade,carbon residue rate(calcined in muffle furnace at500℃)and hardness were 31,V-0,17.32%and 6H,respectively.
To explore the effect of composite nanoparticles on the flame retardancy of epoxy acrylate(EA) coating, mesoporous silica nanoparticle was synthesized by using cetyltrimethylammonium bromide (CTAB) and tetraethoxysilane(TEOS) as raw materials, and zinc stannate nanoparticle was synthesized based on ZnCl_2 and SnCl4· 5H2 O as raw materials. Then mesoporous silica/zinc stannate nanoparticle complex was prepared by compounding them, and the above nanoparticles were characterized by X-raypowder diffractometer(XRD) and transmission electron microscope(TEM). Three kinds of compositecoatings(SiO_2/EA, Zn_2SnO_4/EA, SiO_2/Zn_2SnO_4/EA) were prepared by UV curing method through mixing theabove prepared nanoparticles(mesoporous SiO_2, Zn_2SnO_4, SiO_2/Zn_2SnO_4), acrylic acid, acrylamide with EA,and the transmittance, thermal stability and flame retardancy of the coating were measured by UV-visspectrometer, differential scanning calorimeter(DSC) and oxygen index tester. The results showed that thecomprehensive properties of SiO_2/Zn_2SnO_4/EA coatings were superior. When the mass percent content ofSiO_2/Zn_2SnO_4 was 4.85%, the thermal stability and flame retardancy of the coating are the best. The coating’s limiting oxygen index,combustion grade,carbon residue rate(calcined in muffle furnace at500℃)and hardness were 31,V-0,17.32%and 6H,respectively.
引文
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[19] TENG Z G, SU X D, ZHENG Y Y, et al. Mesoporous silica hollowspheres with ordered radial mesochannels by a spontaneous self-transformation approach[J]. Chemistry of Materials, 2013, 15(1):98-105.
[20] LIU C H, CHEN H Y, REN Z, et al. Controlled synthesis and structuretunability of photocatalytically active mesoporous metal-basedstannate nanostructures[J]. Applied Surface Science, 2014, 296(30):53-60.
[21] PETSOM A, ROENGSUMRAN S, ARIYAPHATTANAKUL A, et al.An oxygen index evaluation of flammability for zinc hydroxystannateand zinc stannate as synergistic flame retardants for acrylonitrile-butadiene-styrene copolymer[J]. Polymer Degradation and Stability,2003, 80(1):17-22.
[2] XING W Y, HU Y, SONG L, et al. Thermal degradation andcombustion of a novel UV curable coating containing phosphorus[J].Polymer Degradation and Stability, 2009, 94:1176-1182.
[3] CHEN X L, HU Y, JIAO C M, et al. Preparation and thermalproperties of a novel flame-retardant coating[J]. Polymer Degradationand Stability, 2007, 92:1141-1150.
[4] KARATAS S, HOSG?R Z, KAYAMAN-APOHAN N, et al.Preparation and characterization of phosphine oxide containingorganosilica hybrid coatings by photopolymerization and sol-gelprocess[J]. Progress in Organic Coatings, 2009, 65:49-55.
[5] CHEN X L, SONG L, HU Y. Flammability and thermal degradation ofepoxy acrylate modified with phosphorus-containing compounds[J].Journal of Applied Polymer Science, 2010, 115:3332-3338.
[6] LIANG H B, SHI W F. Thermal behaviour and degradation mechanismof phosphate di/triacrylate used for UV curable flame-retardantcoatings[J]. Polymer Degradation and Stability, 2004, 84:525-532.
[7] KAHRAMAN M V, KAYAMAN-APOHAN N, ARSU N, et al. Flameretardance of epoxy acrylate resin modified with phosphorus containingcompounds[J]. Progress in Organic Coatings, 2004, 51(3):213-219.
[8] HORROCKS A R, SMART G, KANDOLA B, et al. Zinc stannateinteractions with flame retardants in polyamides, Part1:Synergies withorganobromine-containing flameretardants in polyamides 6(PA6)and6.6(PA6.6)[J]. Polymer Degradation and Stability, 2012, 97(12):2503-2510.
[9] YANG L, SHI C L. Effect of zinc hydroxystannate coated M-HOSwhisker on flame retardant properties of flexible PVC[J]. ProcediaEngineering, 2018, 211:901-905.
[10] ZOU H, WU S S, SHEN J. Polymer/silica nanocomposites:preparation,characterization, properties, and applications[J]. Chemical Reviews,2008, 108:3893-3957.
[11]杨磊,陈建芳,杨建建,等.新型含Si环氧丙烯酸酯纳米涂层的制备及性能[J].化工进展, 2012, 31(2):378-382.YANG L, CHEN J F, YANG J J, et al. Preparation of novel UV-curingSi-containing EA nanocoating and its performance[J]. Chemical Industry and Engineering Progress, 2012, 31(2):378-382.
[12]杨磊,许湧深,邱守季,等.微滴乳液聚合制备PDMS/SiO2纳米复合材料[J].化工学报, 2013, 64(4):1473-1477.YANG L, XU Y S, QIU S J, et al. Preparation of PDMS/SiO2nanocomposites miniemulsion polymerization[J]. Journal of ChemicalIndustry and Engineering, 2013, 64(4):1473-1477.
[13]王孝龙,纪全,孔庆山,等.溶胶-凝胶法制备PET/SiO2纳米复合材料及其TG、DSC分析[J].化工学报, 2007, 58(11):2926-2931.WANG X L, JI Q, KONG Q S, et al. Poly(ethylene terephthalate)/SiO2nanocomposites prepared by sol-gel method and their TG&DSCanalysis[J]. Journal of Chemical Industry and Engineering, 2007, 58(11):2926-2931.
[14] EMRE Basyürk, TüLAY?nan, ATTILA Güng?r. Flame retardant UV-curable acrylated epoxidized soybean oil based organic-inorganichybrid coating[J]. Progress in Organic Coatings, 2013, 76(6):985-992.
[15] SUN Y L, YANG B J, ZHANG S X, et al. Cucurbit
[7]urilpseudorotaxane-based photoresponsive supramolecular nanovalve[J].Chemistry-A European Journal, 2012, 18(30):9212-9216.
[16] TUNCOLU I G, ACIKSARI C, SUVACI E, et al. Synthesis of Zn2SnO4powders via hydrothermal method for ceramic targets[J]. Journal of theEuropean Ceramic Society, 2015, 35(14):3885-3892.
[17]江曙东.介孔二氧化硅的功能化改性及其环氧树脂复合材料的热解与燃烧性能研究[D].合肥:中国科学技术大学, 2015.JIANG S D. Functionalization of mesoporous silica and study onthermal stability and combustion properties of epoxy composites[D].Hefei:University of Science and Technology of China, 2015.
[18] YAN N, WANG F, ZHONG H, et al. Hollow porous SiO2nanocubestowards high-performance anodes for Lithium-ion batteries[J].Scientific Reports, 2013, 3:1568-1574.
[19] TENG Z G, SU X D, ZHENG Y Y, et al. Mesoporous silica hollowspheres with ordered radial mesochannels by a spontaneous self-transformation approach[J]. Chemistry of Materials, 2013, 15(1):98-105.
[20] LIU C H, CHEN H Y, REN Z, et al. Controlled synthesis and structuretunability of photocatalytically active mesoporous metal-basedstannate nanostructures[J]. Applied Surface Science, 2014, 296(30):53-60.
[21] PETSOM A, ROENGSUMRAN S, ARIYAPHATTANAKUL A, et al.An oxygen index evaluation of flammability for zinc hydroxystannateand zinc stannate as synergistic flame retardants for acrylonitrile-butadiene-styrene copolymer[J]. Polymer Degradation and Stability,2003, 80(1):17-22.