增韧剂对PC/PBT合金性能的影响
|
摘要
研究了三种不同类型增韧剂乙烯–丙烯酸丁酯–甲基丙烯酸缩水甘油酯共聚物(PTW)、甲基丙烯酸甲酯–丁二烯–苯乙烯共聚物(MBS)和乙烯–辛烯共聚物(POE)对聚碳酸酯/聚对苯二甲酸丁二酯(PC/PBT)合金力学性能、熔体流动速率(MFR)、热性能和结晶与熔融行为的影响。结果表明:对于PC/PBT (质量比为65/35)合金,当增韧剂添加量为5份时,PC/PBT合金综合性能最优。三种类型的增韧剂都能显著改善PC/PBT合金的冲击性能,当增韧剂添加量在2～5份时,PC/PBT合金发生脆韧转变。MBS增韧PC/PBT合金的拉伸强度和弯曲强度保持率最高,分别为94.0%和92.6%,但热变形温度降低到105.7℃;PTW增韧PC/PBT合金的拉伸强度和弯曲强度保持率最低,分别为84.3%和80.7%,其优势是对热变形温度基本无影响,但对PC/PBT合金MFR的降低最严重;PTW和POE增韧PC/PBT合金的耐湿热老化性远优于MBS增韧PC/PBT合金。三种类型的增韧剂对PC/PBT合金中的PBT相结晶性均有不同程度的阻碍作用,MBS增韧PC/PBT合金的结晶度最高,为35.73%,POE增韧PC/PBT合金的结晶度为30.21%,PTW增韧PC/PBT合金的结晶度最低,为24.95%。
The effects of three different types of toughening agents ethylene-butyl acrylate-glycidyl methacrylate copolymer(PTW),methyl methacrylate-butadiene-styrene copolymer(MBS) and ethylene-octylene copolymer(POE) on the mechanical properties,melt flow rate(MFR),thermal properties and crystallization and melting behaviors of polycarbonate(PC)/polybutylene terephthalate(PBT) alloy were studied. The results show that,for the PC/PBT(mass ratio of 65/35) alloy,the combination properties are the best when the amount of toughening agent is 5 phr. The three kinds of toughening agents can remarkably improve the impact performance of PC/PBT alloy,the brittle and ductile transition is occurred when the dosage of toughening agent is 2–5 phr. The retention rates of the tensile strength and flexural strength of the MBS toughened PC/PBT alloy are the highest,94% and 92.6% respectively,but the thermal deformation temperature is decreased to 105.7℃. The PTW toughened PC/PBT alloy has the lowest tensile strength and flexural strength retention rates,84.3% and 80.7% respectively,the advantage of which is no effect on the thermal deformation temperature,but the reduction of the MFR is most serious to PC/PBT alloy. The heat and humidity aging properties of PTW and POE toughened PC/PBT alloys are much better than the MBS toughened PC/PBT alloy,and the three types of toughening agents have different degrees of obstruction to the crystallization of the PBT phase in PC/PBT alloy. The crystallinity of MBS toughened PC/PBT alloy is the highest,it is 35.73%,for POE toughened PC/PBT alloy,the crystallinity is 30.21%,and the crystallinity is 24.95% for PTW toughened PC/PBT alloy which is the lowest.
The effects of three different types of toughening agents ethylene-butyl acrylate-glycidyl methacrylate copolymer(PTW),methyl methacrylate-butadiene-styrene copolymer(MBS) and ethylene-octylene copolymer(POE) on the mechanical properties,melt flow rate(MFR),thermal properties and crystallization and melting behaviors of polycarbonate(PC)/polybutylene terephthalate(PBT) alloy were studied. The results show that,for the PC/PBT(mass ratio of 65/35) alloy,the combination properties are the best when the amount of toughening agent is 5 phr. The three kinds of toughening agents can remarkably improve the impact performance of PC/PBT alloy,the brittle and ductile transition is occurred when the dosage of toughening agent is 2–5 phr. The retention rates of the tensile strength and flexural strength of the MBS toughened PC/PBT alloy are the highest,94% and 92.6% respectively,but the thermal deformation temperature is decreased to 105.7℃. The PTW toughened PC/PBT alloy has the lowest tensile strength and flexural strength retention rates,84.3% and 80.7% respectively,the advantage of which is no effect on the thermal deformation temperature,but the reduction of the MFR is most serious to PC/PBT alloy. The heat and humidity aging properties of PTW and POE toughened PC/PBT alloys are much better than the MBS toughened PC/PBT alloy,and the three types of toughening agents have different degrees of obstruction to the crystallization of the PBT phase in PC/PBT alloy. The crystallinity of MBS toughened PC/PBT alloy is the highest,it is 35.73%,for POE toughened PC/PBT alloy,the crystallinity is 30.21%,and the crystallinity is 24.95% for PTW toughened PC/PBT alloy which is the lowest.
引文
[1]刘小林.丙烯酸漆对PC/PBT共混物性能和微观结构的影响[J],塑料工业,2016,44(6):77-81,88.Liu Xiaolin.Effect of acrylic paint on properties and microstructure of PC/PBT blend[J].China Plastics Industry,2016,44(6):77-81,88.
[2]曾晓强,曹长林,陈昌禧,等.强韧化PBT/PC共混物的制备与性能[J],中国塑料,2015,29(4):82-87.Zeng Xiaoqiang,Cao Changlin,Chen Changxi,et al.Preparation and properties of strengthened and toughened PBT/PC blends[J].China Plastics,2015,29(4):82-87.
[3]刘旭,田小艳,汤粤豫,等.我国PC/PBT合金材料的市场需求及制备技术现状[J],广东化工,2015,42(21):94,117.Liu Xu,Tian Xiaoyan,Tang Yueyu,et al.Market demand and the preparation technology of PC/PBT alloy materials in china[J],Guangdong Chem,2015,42(21):94,117.
[4]李文强.汽车用PC/PBT合金材料性能的研究[D].上海:东华大学,2014年.Li Wenqiang.Study on properties of PC/PBT alloy used for automotive[D].Shanghai:Donghua University,2014.
[5]Okamoto M,Shinoda Y.Toughening mechanism in a ternary polymer alloy:PBT/PC/rubber system[J].Polymer,2009,34(23):4 868-4 873.
[6]金祖铨,吴念.聚碳酸酯树脂及应用[M].北京:化学工业出版社,2009.Jin Zuquan,Wu Nian.Polycarbonate resin and application[M].Beijing:Chemical Industry Press,2009.
[7]袁志伟,彭汉,黄文娴.PC/PBT合金增韧研究[J].合成材料老化与应用.2011,40(4):26-30.Yuan Zhiwei,Peng Han,Huang Wenxian.Study on toughening of PC/PBT alloy[J].Synthetic Materials Aging and Application,2011,40(4):26-30.
[8]孙树林,童艳玲,邹德音,等.核壳结构改性剂对PBT/PC共混物的增韧作用[J].高分子材料科学与工程.2011,27(12):52-55.Sun Shulin,Tong Yanling,Zou Deyin,et al.Toughening of PBT/PC blends with core-shell modifier[J].Polymer Materials Science and Engineering,2011,27(12):52-55.
[9]魏刚,彭娅,龙盛如,等.PBT/PC/E-MA-GMA三元共混体系的力学性能与亚微相态[J].合成树脂及塑料,2006,23(5):61-64,69.Wei Gang,Peng Ya,Long Shengru,et al.Mechanical properties and sub-microscopic phase state of ternary system of PBT/PC/E-MA-GMA[J].China Synthetic Resin and Plastics.2006,23(5):61-64,69.
[10]Bai Huiyu,Zhang Yong,Zhang Yinxi,et al.Toughening modification of PBT/PC blends with PTW and POE[J].Journal of Applied Polymer Science,2006,101:54-62.
[11]Kalkar A K,Siesler H W,Pfeifer F,et al.Molecular orientation and relaxation in PBT/PC blends[J].Polymer,2003,44:7 251-7 264.
[12]吕通建,段伟,李文龙,等.KTR-6C对PC/PBT共混体系性能的影响[J].塑料工业,2006,34(4):20-22.Lyu Tongjian,Duan Wei,Li Wenlong,et al.Effect of KTR-6Con property of PC/PBT alloy[J].China Plastics Industry,2006,34(4):20-22.
[13]吴承旭,周健,李雪飞,等.PBT/PC合金塑料的性能与微观结构[J].化工学报,2010,61(6):1 571-1 576.Wu Chengxu,Zhou Jian,Li Xuefei,et al.Properties and microstructure of polybutylene terephthalate/polycarbonate alloy plastics[J].CIESC Journal.2010,61(6):1 571-1 576.
[14]朱亚峰.乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯三元共聚物对PC/PBT共混体系性能的影响[J].塑料工业,2009,37(S1):51-53.Zhu Yafeng.Effect of AX8900 on the properties of PC/PBTblends[J].China Plastics Industry,2009,37(S1):51-53.
[15]Emiliano L,Jozesf K K.Impact modification of PA6 and PBTby epoxy-functionalized rubbers[J].Macromolecular Symposia,2003,202:59-66.
[16]Tsai C H,Chang F C.Polymer blends of PBT and PP compatibilized by ethylene-co-glycidyl metharylate copolymers[J].Journal of Applied Polymer Science,1996,61:321-323.
[17]Balakrishnan S,Neelakantan N R,Saheb D N,et al.Rheological and morphological behabiour of blends of polycarbonate with unmodified and maleic anhydride grafted ABS[J].Polymer,1998,39:5 765-5 771.
[18]陈玉君,候巩.聚对苯二甲酸丙二酯的热降解性能研究[J].聚酯工业,2005,18(2):27-30.Chen Yujun,Hou Gong.Study on heat degradation of polytirmethylent terephthalate[J].Polyester Industry,2005,18(2):27-30.
[2]曾晓强,曹长林,陈昌禧,等.强韧化PBT/PC共混物的制备与性能[J],中国塑料,2015,29(4):82-87.Zeng Xiaoqiang,Cao Changlin,Chen Changxi,et al.Preparation and properties of strengthened and toughened PBT/PC blends[J].China Plastics,2015,29(4):82-87.
[3]刘旭,田小艳,汤粤豫,等.我国PC/PBT合金材料的市场需求及制备技术现状[J],广东化工,2015,42(21):94,117.Liu Xu,Tian Xiaoyan,Tang Yueyu,et al.Market demand and the preparation technology of PC/PBT alloy materials in china[J],Guangdong Chem,2015,42(21):94,117.
[4]李文强.汽车用PC/PBT合金材料性能的研究[D].上海:东华大学,2014年.Li Wenqiang.Study on properties of PC/PBT alloy used for automotive[D].Shanghai:Donghua University,2014.
[5]Okamoto M,Shinoda Y.Toughening mechanism in a ternary polymer alloy:PBT/PC/rubber system[J].Polymer,2009,34(23):4 868-4 873.
[6]金祖铨,吴念.聚碳酸酯树脂及应用[M].北京:化学工业出版社,2009.Jin Zuquan,Wu Nian.Polycarbonate resin and application[M].Beijing:Chemical Industry Press,2009.
[7]袁志伟,彭汉,黄文娴.PC/PBT合金增韧研究[J].合成材料老化与应用.2011,40(4):26-30.Yuan Zhiwei,Peng Han,Huang Wenxian.Study on toughening of PC/PBT alloy[J].Synthetic Materials Aging and Application,2011,40(4):26-30.
[8]孙树林,童艳玲,邹德音,等.核壳结构改性剂对PBT/PC共混物的增韧作用[J].高分子材料科学与工程.2011,27(12):52-55.Sun Shulin,Tong Yanling,Zou Deyin,et al.Toughening of PBT/PC blends with core-shell modifier[J].Polymer Materials Science and Engineering,2011,27(12):52-55.
[9]魏刚,彭娅,龙盛如,等.PBT/PC/E-MA-GMA三元共混体系的力学性能与亚微相态[J].合成树脂及塑料,2006,23(5):61-64,69.Wei Gang,Peng Ya,Long Shengru,et al.Mechanical properties and sub-microscopic phase state of ternary system of PBT/PC/E-MA-GMA[J].China Synthetic Resin and Plastics.2006,23(5):61-64,69.
[10]Bai Huiyu,Zhang Yong,Zhang Yinxi,et al.Toughening modification of PBT/PC blends with PTW and POE[J].Journal of Applied Polymer Science,2006,101:54-62.
[11]Kalkar A K,Siesler H W,Pfeifer F,et al.Molecular orientation and relaxation in PBT/PC blends[J].Polymer,2003,44:7 251-7 264.
[12]吕通建,段伟,李文龙,等.KTR-6C对PC/PBT共混体系性能的影响[J].塑料工业,2006,34(4):20-22.Lyu Tongjian,Duan Wei,Li Wenlong,et al.Effect of KTR-6Con property of PC/PBT alloy[J].China Plastics Industry,2006,34(4):20-22.
[13]吴承旭,周健,李雪飞,等.PBT/PC合金塑料的性能与微观结构[J].化工学报,2010,61(6):1 571-1 576.Wu Chengxu,Zhou Jian,Li Xuefei,et al.Properties and microstructure of polybutylene terephthalate/polycarbonate alloy plastics[J].CIESC Journal.2010,61(6):1 571-1 576.
[14]朱亚峰.乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯三元共聚物对PC/PBT共混体系性能的影响[J].塑料工业,2009,37(S1):51-53.Zhu Yafeng.Effect of AX8900 on the properties of PC/PBTblends[J].China Plastics Industry,2009,37(S1):51-53.
[15]Emiliano L,Jozesf K K.Impact modification of PA6 and PBTby epoxy-functionalized rubbers[J].Macromolecular Symposia,2003,202:59-66.
[16]Tsai C H,Chang F C.Polymer blends of PBT and PP compatibilized by ethylene-co-glycidyl metharylate copolymers[J].Journal of Applied Polymer Science,1996,61:321-323.
[17]Balakrishnan S,Neelakantan N R,Saheb D N,et al.Rheological and morphological behabiour of blends of polycarbonate with unmodified and maleic anhydride grafted ABS[J].Polymer,1998,39:5 765-5 771.
[18]陈玉君,候巩.聚对苯二甲酸丙二酯的热降解性能研究[J].聚酯工业,2005,18(2):27-30.Chen Yujun,Hou Gong.Study on heat degradation of polytirmethylent terephthalate[J].Polyester Industry,2005,18(2):27-30.