丙烯酸酯乳液原位接枝共混高抗冲聚氯乙烯的制备与性能
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摘要
首先以丙烯酸丁酯、甲基丙烯酸甲酯为单体,1,4-丁二醇二甲基丙烯酸酯为交联剂,烯丙氧基壬基酚聚氧乙烯醚硫酸铵为反应型乳化剂,聚苯乙烯乳液为种子乳液,通过种子乳液聚合工艺,制得了粒径约200 nm且窄粒径分布的丙烯酸酯共聚物(ACR)乳液。然后将该ACR乳液直接加入氯乙烯的悬浮聚合体系中,制得了ACR乳液原位悬浮接枝共混型高抗冲聚氯乙烯(PVC)复合树脂。用红外光谱、差示扫描量热仪、扫描电子显微镜对树脂结构和形貌等进行了表征;考察了不同聚合温度下所得的ACR乳液对最终PVC复合树脂力学性能的影响;考察了悬浮聚合工艺中ACR乳液的加料顺序对悬浮聚合稳定性、PVC复合树脂的颗粒形态和力学性能的影响。结果表明,所得PVC复合树脂由ACR、氯乙烯在ACR上接枝所得共聚物及PVC均聚物组成,该原位增韧PVC复合树脂的抗冲性能提高非常显著。尤其是70℃乳液聚合所得ACR乳液用于氯乙烯的悬浮聚合,且当ACR质量分数为6.0%时的PVC复合树脂的缺口冲击强度可达常规SG-5型PVC树脂的7.4倍。此外,在氯乙烯单体液滴分散好后再加ACR乳液进行悬浮聚合,所得PVC复合树脂的颗粒形态和抗冲性能较好,且聚合过程中无粘釜、无粘轴现象。
Latices of acrylate copolymer resin(ACR) with the particle size about 200 nm and relatively narrow distribution was prepared through emulsion polymerization with butyl acrylate and methyl methacrylate as monomer,1,4-butanediol dimethacrylate as crosslinker,allyloxmethyl nonylphenol ether sulfates as reactive emulsifier,and polystyrene latex as seed latex. Then,high impact polyvinyl chloride was obtained through acrylate latex in situ suspension graft copolymerization with vinyl chloride and blending. The structure and morphology of ACR-g-PVC were characterized by infrared spectroscopy,differential scanning calorimeter and scanning electron microscope. Effect of kinds of ACR latices,which were prepared at different temperatures of emulsion polymerization,on mechanical properties of ACR-g-PVC resin,and effect of ACR latex feeding sequence on stability of suspension polymerization,morphology and mechanical properties of ACR-g-PVC resin were investigated. The results show that PVC composite resin is composed of copolymer formed by vinyl chloride grafting on the ACR,homopolymer of vinyl chloride and ACR. Impact strength of PVC composite resin is improved remarkably by suspension graft copolymerization of ACR latex and vinyl chloride. When the mass fraction of ACR latex is 6.0%,the notched impact strength of the ACR-g-PVC resin is 7.4 times that of unmodified SG-5 PVC resin. Besides,if ACR latex is added after vinyl chloride monomer is dispersed well in situ suspension polymerization,the particle shape and impact strength of ACR-g-PVC resin are better than those of ACR latex added before. The most important thing is that no sticking kettle and shaft problem are found.
Latices of acrylate copolymer resin(ACR) with the particle size about 200 nm and relatively narrow distribution was prepared through emulsion polymerization with butyl acrylate and methyl methacrylate as monomer,1,4-butanediol dimethacrylate as crosslinker,allyloxmethyl nonylphenol ether sulfates as reactive emulsifier,and polystyrene latex as seed latex. Then,high impact polyvinyl chloride was obtained through acrylate latex in situ suspension graft copolymerization with vinyl chloride and blending. The structure and morphology of ACR-g-PVC were characterized by infrared spectroscopy,differential scanning calorimeter and scanning electron microscope. Effect of kinds of ACR latices,which were prepared at different temperatures of emulsion polymerization,on mechanical properties of ACR-g-PVC resin,and effect of ACR latex feeding sequence on stability of suspension polymerization,morphology and mechanical properties of ACR-g-PVC resin were investigated. The results show that PVC composite resin is composed of copolymer formed by vinyl chloride grafting on the ACR,homopolymer of vinyl chloride and ACR. Impact strength of PVC composite resin is improved remarkably by suspension graft copolymerization of ACR latex and vinyl chloride. When the mass fraction of ACR latex is 6.0%,the notched impact strength of the ACR-g-PVC resin is 7.4 times that of unmodified SG-5 PVC resin. Besides,if ACR latex is added after vinyl chloride monomer is dispersed well in situ suspension polymerization,the particle shape and impact strength of ACR-g-PVC resin are better than those of ACR latex added before. The most important thing is that no sticking kettle and shaft problem are found.
引文
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[2]Shu H D,Liu K,Liu F,et al.Improving mechanical properties of poly(vinyl chloride)by doping with organically functionalized reactive nanosilica[J].J.Appl.Polym.Sci.,2013,129:2931-2939.
[3]Pan M W,Xing S N,Yuan J F,et al.Synthesis and characterization of poly(butyl acrylate-co-ethylhexyl acrylate)/poly(vinyl chloride)[P(BA-EHA)/PVC]novel core-shell modifier and its impact modification for a poly(vinyl chloride)-based blend[J].Polym.Eng.Sci.,2010,50:1085-1094.
[4]Jiang H Y,Liu B J,Deng Y J,et al.High-efficiency impact modifier prepared by coagulation emulsion polymerization through internal voiding toughening mechanism[J].Polym.Adv.Technol.,2015,26:182-189.
[5]任济民,张宁,包永忠,等.以PVC为外壳层的ACR抗冲改性剂的合成及其对PVC的增韧作用[J].塑料工业,2011,39(2):90-93.Ren J M,Zhang N,Bao Y Z,et al.Synthesis of ACR impact modifier with PVC shell and its toughening efficiency on PVC[J].China Plastics Industry,2011,39(2):90-93.
[6]夏宇正,赵秋颖,石淑先,等.氯乙烯悬浮聚合用ACR乳液及抗冲PVC树脂的制备[J].聚氯乙烯,2015,43(11):17-22.Xia Y Z,Zhao Q Y,Shi S X,et al.Preparation of ACR emulsions for vinyl chloride suspension polymerization and impact PVC resins[J].Polyvinyl Chloride,2015,43(11):17-22.
[7]Yuan J F,Pan M W,Wang X M,et al.Dynamic mechanical,rheological,and morphological studies of polyacrylate-graft-poly(vinyl chloride)suspension resin[J].Polym.Eng.Sci.,2007,47:996-1003.
[8]潘明旺,张留成,张健,等.ACR/VC乳液共聚树脂的制备及其结构与性能[J].石油化工,2002,31(12):983-987.Pan M W,Zhang L C,Zhang J,et al.Preparation and structure&properties of ACR-VC resin[J].Petrochemical Technology,2002,31(12):983-987.
[9]曹同玉,刘庆普,胡金生.聚合物乳液合成原理性能及应用[M].北京:化学工业出版社,2007:360.