新型有机/无机复合紫外吸收剂的制备及其在PVC中的应用
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摘要
将全波段紫外吸收剂聚苯并咪唑(PBI)与纳米SiO_2复配制备了有机/无机复合紫外吸收剂,用于改善聚氯乙烯(PVC)的紫外老化性能。为了增强纳米SiO_2与PBI之间的相互作用,先用硅烷偶联剂γ-氨丙基三乙氧基硅烷对纳米SiO_2改性,产物命名为MSiO_2,然后将PBI涂覆到MSiO_2表面得到复合填料PBI@MSiO_2,最后将填料与PVC通过溶体共混制备复合材料。使用紫外-可见分光光度计和万能拉伸试验机等对复合材料的紫外吸收性能和力学性能等进行了表征和对比分析。结果表明,PBI@MSiO_2粒子显著改善了复合材料的紫外吸收性能,375nm处的紫外吸收率可达99%;并改善了复合材料的力学性能和屈服强度,当PBI@MSiO_2质量分数为6%时,复合材料屈服强度可达63.3MPa。
Poly(vinyl chloride)(PVC)is widely used in many fields due to its excellent non-flammable,corrosion and wear resistant properties.However,its thermal and optical stabilities are very poor which dramatically limit its outdoor application.The most effective way to improve PVC optical stability is the addition of light stabilizers.However,most of the currently used light stabilizers are poorly transparent which thereby restricts their use.In addition,most of the light stabilizers are small molecules,which are easily volatilized or migrated during their applications.In the present study,a novel organic/inorganic composite UV absorber was prepared by the combination of nano silica(SiO_2)with a panchromatic UV absorber polybenzimidazole(PBI),which was used to improve the UV resistance of PVC.In order to enhance the compatibility between nano SiO_2 and PBI,silane coupling agentγ-aminopropyltriethoxysilane was used to modify nano SiO_2(MSiO_2),after which PBI was coated onto the resultant MSiO_2(PBI@MSiO_2).The PVC/PBI@MSiO_2 composites were subsequently prepared by melt blending.The UV absorption,mechanical properties,morphology and thermal stability of the obtained composites were investigated and compared. The SEM observation reveals that PBI@MSiO_2 particles disperses homogenously in the PVC matrix,and the PVC/PBI@MSiO_2 composites exhibit excellent thermal stability,UV-aging resistance and good mechanical properties.In the presence of 6%(mass fraction)PBI@MSiO_2,the initial thermal decomposition temperature of the composite is significantly increased by about 34℃compared with that of pure PVC.Additionally,the UV-absorbance at 375 nm can reach 99%,and the yield strength is 63.3 MPa.
Poly(vinyl chloride)(PVC)is widely used in many fields due to its excellent non-flammable,corrosion and wear resistant properties.However,its thermal and optical stabilities are very poor which dramatically limit its outdoor application.The most effective way to improve PVC optical stability is the addition of light stabilizers.However,most of the currently used light stabilizers are poorly transparent which thereby restricts their use.In addition,most of the light stabilizers are small molecules,which are easily volatilized or migrated during their applications.In the present study,a novel organic/inorganic composite UV absorber was prepared by the combination of nano silica(SiO_2)with a panchromatic UV absorber polybenzimidazole(PBI),which was used to improve the UV resistance of PVC.In order to enhance the compatibility between nano SiO_2 and PBI,silane coupling agentγ-aminopropyltriethoxysilane was used to modify nano SiO_2(MSiO_2),after which PBI was coated onto the resultant MSiO_2(PBI@MSiO_2).The PVC/PBI@MSiO_2 composites were subsequently prepared by melt blending.The UV absorption,mechanical properties,morphology and thermal stability of the obtained composites were investigated and compared. The SEM observation reveals that PBI@MSiO_2 particles disperses homogenously in the PVC matrix,and the PVC/PBI@MSiO_2 composites exhibit excellent thermal stability,UV-aging resistance and good mechanical properties.In the presence of 6%(mass fraction)PBI@MSiO_2,the initial thermal decomposition temperature of the composite is significantly increased by about 34℃compared with that of pure PVC.Additionally,the UV-absorbance at 375 nm can reach 99%,and the yield strength is 63.3 MPa.
引文
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[10]梁乃强,房建华,郭晓霞,等.聚苯并咪唑-锂盐-聚乙二醇单甲醚共混全固态聚合物电解质的制备及性能[J].功能高分子学报,2017,30(2):168-174.
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[12] YUE Z Y,CAI Y B,XU S A.Proton conducting sulfonated poly(imide-benzimidazole)with tunable density of covalent/ionic cross-linking for fuel cell membranes[J].Journal of Power Sources,2015,286:571-579.
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[15]周超,陈丹丹,张侃,等.新型热固化型紫外光吸收剂的制备及其在PBO纤维上的应用[J].功能高分子学报,2015,28(3):319-324.
[16]杜鸿雁.纳米二氧化硅/PVC复合材料结构与性能研究[D].武汉:武汉理工大学,2004.
[17]徐守芳,陈雪花,李春忠.MMA接枝改性PVC/CaCO3纳米复合材料的力学性能[J].功能高分子学报,2005,18(3):378-382.
[18] SCHNEIDER P M,FOWLER W B.Band structure and optical properties of silicon dioxide[J].Physical Review Letters,1976,36(8):425-428.
[19] QIAN W, SHEN C H, GAO S J, et al. Phosphonic acid functionalized siloxane crosslinked with3-glycidoxyproyltrimethoxysilane grafted polybenzimidazole high temperature proton exchange membranes[J].Journal of Applied Polymer Science,2017,134(20):44818.
[20]顾元松,陈莉,陈苏.纳米二氧化硅复合材料的研究进展[J].南京工业大学学报(自然科学版),2003,25(4):107-110.
[21] SOMBATSOMPOP N,CHAOCHANCHAIKUL K.Average mixing torque,tensile and impact properties,and thermal stability of poly(vinyl chloride)/sawdust composites with different silane coupling agents[J].Journal of Applied Polymer Science,2010,96(1):213-221.
[22] KRONGAUZ V V,LEE Y P,BOURASSA A.Kinetics of thermal degradation of poly(vinyl chloride)[J].Journal of Thermal Analysis&Calorimetry,2011,106(1):139-149.
[2] RABIE S T,NADA A A.Methyl methacrylate/2-hydroxyethyl methacrylate/N-hydroxyphenyl maleimide terpolymer as novel photostabilizer for rigid poly(vinyl chloride)[J].Polymer Bulletin,2013,70(7):1959-1976.
[3] GHAEBI MEHMANDOUST S,ALIZADEH R,BABALUO A A.Kinetic study of the poly(vinyl chloride)/titanium dioxide nanocomposites photodegradation under accelerated ultraviolet and visible light exposure[J].Polymers for Advanced Technologies,2014,25(8):799-808.
[4]刘天群,赵迪,李雪婷,等.包覆紫外线吸收剂奥克立林的纳米胶囊的制备及其性能[J].功能高分子学报,2018,31(2):175-180.
[5] LI M,LI G,JIANG J,et al.Ultraviolet resistance and antimicrobial properties of ZnO in the polypropylene materials:A review[J].Journal of Materials Science&Technology,2015,31(4):331-339.
[6] BRAUN D,RABIE S T,KHAIRELDIN N Y,et al.Preparation and evaluation of some benzophenone terpolymers as photostabilizers for rigid PVC[J].Journal of Vinyl&Additive Technology,2011,17(3):147-155.
[7] LIU Y X,LIU Y Y,LIN J J,et al.UV-protective treatment for Vectran?fibers with hybrid coatings of TiO2/organic UV absorbers[J].Journal of Adhesion Science&Technology,2014,28(18):1773-1782.
[8] QI L,DING Y F,DONG Q X,et al.UV photodegradation of polypropylene thick bars containing rutile-type TiO2nanorods[J].Chinese Journal of Polymer Science,2014,32(7):834-843.
[9] SHI Q F,GAO J Y,ZHAO D D,et al.Synergism effect between modified carbon black and organic ultraviolet absorber in polymer matrix for ultraviolet protection[J].Journal of Applied Polymer Science,2010,116(5):2566-2572.
[10]梁乃强,房建华,郭晓霞,等.聚苯并咪唑-锂盐-聚乙二醇单甲醚共混全固态聚合物电解质的制备及性能[J].功能高分子学报,2017,30(2):168-174.
[11] YUE Z Y,CAI Y B,XU S A.Phosphoric acid-doped cross-linked sulfonated poly(imide-benzimidazole)for proton exchange membrane fuel cell applications[J].Journal of Membrane Science,2016,501:220-227.
[12] YUE Z Y,CAI Y B,XU S A.Proton conducting sulfonated poly(imide-benzimidazole)with tunable density of covalent/ionic cross-linking for fuel cell membranes[J].Journal of Power Sources,2015,286:571-579.
[13] YUE Z Y,CAI Y B,XU S A.Phosphoric acid-doped organic-inorganic cross-linked sulfonated poly(imidebenzimidazole)for high temperature proton exchange membrane fuel cells[J].International Journal of Hydrogen Energy,2016,41(24):10421-10429.
[14]张晓丹.全波段紫外吸收剂的合成及其对聚氯乙烯(PVC)老化性能的研究[D].上海:华东理工大学,2018.
[15]周超,陈丹丹,张侃,等.新型热固化型紫外光吸收剂的制备及其在PBO纤维上的应用[J].功能高分子学报,2015,28(3):319-324.
[16]杜鸿雁.纳米二氧化硅/PVC复合材料结构与性能研究[D].武汉:武汉理工大学,2004.
[17]徐守芳,陈雪花,李春忠.MMA接枝改性PVC/CaCO3纳米复合材料的力学性能[J].功能高分子学报,2005,18(3):378-382.
[18] SCHNEIDER P M,FOWLER W B.Band structure and optical properties of silicon dioxide[J].Physical Review Letters,1976,36(8):425-428.
[19] QIAN W, SHEN C H, GAO S J, et al. Phosphonic acid functionalized siloxane crosslinked with3-glycidoxyproyltrimethoxysilane grafted polybenzimidazole high temperature proton exchange membranes[J].Journal of Applied Polymer Science,2017,134(20):44818.
[20]顾元松,陈莉,陈苏.纳米二氧化硅复合材料的研究进展[J].南京工业大学学报(自然科学版),2003,25(4):107-110.
[21] SOMBATSOMPOP N,CHAOCHANCHAIKUL K.Average mixing torque,tensile and impact properties,and thermal stability of poly(vinyl chloride)/sawdust composites with different silane coupling agents[J].Journal of Applied Polymer Science,2010,96(1):213-221.
[22] KRONGAUZ V V,LEE Y P,BOURASSA A.Kinetics of thermal degradation of poly(vinyl chloride)[J].Journal of Thermal Analysis&Calorimetry,2011,106(1):139-149.