新型阻燃线性低密度聚乙烯材料的制备及其性能研究
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摘要
针对目前阻燃聚乙烯材料使用过程中存在的阻燃性能不高以及耐水性差等问题,将一种双层包裹的聚磷酸铵(MCAPP)与三(2-羟乙基)异氰尿酸酯(THEIC)复配,结合紫外光交联的方法,制备新型无卤膨胀阻燃线性低密度聚乙烯复合材料(LLDPE)。利用傅里叶红外光谱、溶解度测试等对聚磷酸铵(APP)和MCAPP的结构和耐水性能进行表征。通过氧指数测试、热失重分析、扫描电镜等研究MCAPP与THEIC组成的膨胀阻燃剂(IFR)对LLDPE的阻燃性及热稳定性能的影响。结果表明:MCAPP被成功地制备,且相比未包裹的APP,MCAPP的水溶解性大幅降低,耐水性能提高。当质量分数为30%的IFR添加到LLDPE基体中,并经光强度为180W/m2的紫外光辐照交联后,此种新型LLDPE/MCAPP/THEIC阻燃体系具有比LLDPE/APP/THEIC体系更加优良的阻燃性能、耐水性能及热稳定性能。
In order to solve the problem of low flame retardancy and poor water resistance of flame retardant polyethylene materials,a novel halogen-free intumescent flame retardant linear low-density polyethylene(LLDPE)composites were prepared based on a double-microencapsulated ammonium polyphosphate(MCAPP)and tris(2-hydroxyethyl)isocyanurate(THEIC),through crosslinking by ultraviolet radiation.The chemical structure and water resistance of APP and MCAPP were studied through Fourier transform infrared spectroscopy(FT-IR)and water solubility.The synergistic effects between MCAPP and THEIC on the flame retardant properties and thermal stability of LLDPE were investigated by limiting oxygen index(LOI),thermogravimetric(TG)analysis and scanning electron microscope(SEM).The results showed that MCAPP was successfully obtained,and its solubility decreased greatly compared to that of pure APP with better water resistance.When IFR(MCAPP/THEIC)was introduced with 30%(mass fraction)loading into LLDPE matrix,and crosslinked by ultraviolet radiation with a light intensity of 180 W/m~2,LLDPE/MCAPP/THEIC showed more excellent flame retardant properties,water resistance and thermal stability than LLDPE/APP/THEIC.
In order to solve the problem of low flame retardancy and poor water resistance of flame retardant polyethylene materials,a novel halogen-free intumescent flame retardant linear low-density polyethylene(LLDPE)composites were prepared based on a double-microencapsulated ammonium polyphosphate(MCAPP)and tris(2-hydroxyethyl)isocyanurate(THEIC),through crosslinking by ultraviolet radiation.The chemical structure and water resistance of APP and MCAPP were studied through Fourier transform infrared spectroscopy(FT-IR)and water solubility.The synergistic effects between MCAPP and THEIC on the flame retardant properties and thermal stability of LLDPE were investigated by limiting oxygen index(LOI),thermogravimetric(TG)analysis and scanning electron microscope(SEM).The results showed that MCAPP was successfully obtained,and its solubility decreased greatly compared to that of pure APP with better water resistance.When IFR(MCAPP/THEIC)was introduced with 30%(mass fraction)loading into LLDPE matrix,and crosslinked by ultraviolet radiation with a light intensity of 180 W/m~2,LLDPE/MCAPP/THEIC showed more excellent flame retardant properties,water resistance and thermal stability than LLDPE/APP/THEIC.
引文
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[22] Li R M,Deng C,Deng C L,et al.An efficient method to improve simultaneously the water resistance,flame retardancy and mechanical properties of POE intumescent flame-retardant systems[J].RSC Advances,2015,5(21):16328-16339.
[2] Huang Y Q,Jiang S L,Wu L B,et al.Characterization of PPLLD/nano-SiO2composites by solid-state dynamic mechanical spectroscopy[J].Polym Test,2004,23(1):9-15.
[3] Li S C,Liu H,Zeng W.Effect of cross-linked PE-LLD/PP blend(PE-LLD-PP)as compatibilizer on morphology,crystallization behavior and mechanical property of PE-LLD/PP blends[J].Journal of Applied Polymer Science,2011,121(5):2614-1620.
[4]郝冬梅,林倬仕,陈涛,等.EP微胶囊化APP对阻燃PP性能的影响[J].现代塑料加工应用,2008,20(4):37-40.
[5] Saihi D,Vroman I,Giraud S.Microencapsulation of ammonium polyphosphate with a polyurethane shell.PartⅠ:coacervation technique[J].Reactive and Functional Polymers,2005,64(3):127-138.
[6] Saihi D,Vroman I,Giraud S.Microencapsulation of ammonium polyphosphate with a polyurethane shell.PartⅡ:interfacial polymerization technique[J].Reactive and Functional Polymers,2006,66:1118-1125.
[7]孙才英,李斌.MA异氰酸酯改性APP及其在LLDPE中耐水性的评价[J].应用化学,2007,24(4):434-438.
[8]张延奎,吴昆,张卡,等.双层包裹聚磷酸铵微胶囊合成及其在环氧树脂中阻燃研究[J].高分子学报,2012(7):759-765.
[9]张琪,刘娟,孙立婧,等.APP对硬质聚氨酯-酰亚胺泡沫泡孔结构及力学性能的影响[J].塑料,2015,44(5):7-10.
[10] Ni J X,Song L,Hu Y,et al.Preparation and characterization of microencapsulated ammonium polyphosphate with polyurethane shell by in situ polymerization and its flame retardance in polyurethane[J].Polymers for Advanced Technologies,2009,20(12):999-1005.
[11] Wu K,Song L,Wang Z Z,et al.Microencapsulation of ammonium polyphosphate with PVA-melamine-formaldehyde resin and its flame retardance in polyphosphate[J].Polymers for Advanced Technologies,2008,19(12):1914-1921.
[12] Wu K,Wang Z Z,Hu Y.Microencapsulated ammonium polyphosphate with urea-melamine-formaldehyde shell:preparation,characterization,and its flame retardance polypropylene[J].Polymers for Advanced Technologies,2008,19(8):1118-1125.
[13] Nie S B,Hu Y,Song L,et al.Synergistic effect between a char forming agent(CFA)and microencapsulated ammonium polyphosphate on the thermal and flame retardant properties of polypropylene[J].Polymers for Advanced Technologies,2008,19(8):1077-1083.
[14] Bai P,Li B,Gao S L.Investigation on flame retardancy and antidripping of new intumescent flame retardant polypropylene film[J].Polymers&Polymer Composites,2010,18:495-502.
[15] Hu X P,Li Y L,Wang Y Z.Synergistic effect of the charring agent on the thermal and flame retardant properties of polyethylene[J].Macromolecular Materials and Engineering,2004,289:208-212.
[16] Li B,Xu M J.Effect of a novel charring-forming agent on flame retardancy and thermal degradation of intumescent flame retardant polypropylene[J].Polymer Degradation and Stability,2006,91(6):1380-1386.
[17] Li B,He J,Guan L M,et al.A novel intumescent flame-retardant system for flame-retarded LLDPE/EVA composites[J].Journal of Applied Polymer Science,2009,114(6):3626-3635.
[18] Chen W Y,Yuan S S,Liu G S,et al.Effect of charring agent THEIC on flame retardant properties of polypropylene[J].Journal of Applied Polymer Science,2015,132(1):41214.
[19] Ni J X,Tai Q L,Lu H D,et al.Microencapsulated ammonium polyphosphate with polyurethane shell:preparation,characterization,and its flame retardance in polyurethane[J].Polymers for Advanced Technologies,2010,21(6):392-400.
[20] Brown N M D,Hewitt J A,Meenan B J.X-ray-induced beam damage observed during X-ray photoelectron spectroscopy(XPS)studies of palladium electrode ink materials[J].Surf Interface Anal,1992,18:187-198.
[21] Shih P Y,Yung S W,Chin TS.Thermal and corrosion behavior of P2O5-Na2O-CuO glasses[J].Journal of Non-Cryst Solids,1998,224:143-152.
[22] Li R M,Deng C,Deng C L,et al.An efficient method to improve simultaneously the water resistance,flame retardancy and mechanical properties of POE intumescent flame-retardant systems[J].RSC Advances,2015,5(21):16328-16339.