聚丙烯增韧改性的研究
摘要
本文采用共混方法对聚丙烯(PP)进行了改性研究,通过添加成核剂、硫化方法,对EPDM、BR增韧PP体系的力学性能以及其结晶形态和结晶动力学做了较深入的研究,并用DSC、相差显微镜对增韧聚丙烯进行了分析。结果表明:橡胶的硫化,特别是与PP的接枝,大幅度提高了与PP间的相容性及对PP的成核作用;硫化体系比非硫化体系大幅度提高了改性PP的耐冲击强度,具有高流动,高抗冲性能;乙撑双硬脂酰胺为PP的良好成核剂,它对PP的屈服强度、室温缺口冲击强度有一定的提高,特别是室温无缺口冲击强度有很大的贡献,但对PP的耐低温冲击影响不大;乙撑双硬脂酰胺对PP/EPDM、PP/BR共混体系性能的影响是不相同,EPDM在高份数时,乙撑双硬脂酰胺对PP/EPDM体系体现出良好的成核作用,对冲击强度贡献很大,EPDM在低份数下,乙撑双硬脂酰胺起不到良好的成核作用;乙撑双硬脂酰胺对PP/BR共混体系有良好的成核作用,与没有成核剂的PP/BR共混体系相比,PP的耐冲击性得到较大幅度的提高;橡胶用量在低份数下(12phr以下),来源广、价格低的BR可以代替EPDM对PP的增韧改性,制备出的高抗冲PP材料;经在汽车工程材料上的实际应用,证明其性能完全满足汽车配件的使用要求。
In this paper, polypropylene(PP) was modificated in property by blending method. And mechanical property, crystalline morphology and crystallization kinetics were deeply studied about PP/EPDM and PP/BR systems where the rubber were vulcanized and the nucleator was adopted also. The toughened polypropylene was analysized by DSC and Phase differential micrographs technologies. The compatibility between rubber and PP and nuclearing effect were improved when the rubber was vulcanized and grafted into PP, sothat the modificatied PP possessinghigh flow behavior and high impact resilience. SF, which is the good nucleator, had an large contribution to hightened the yield strength and room temperature notch yield strength of PP, but had little impact on low temperature yield strength. The impacts were different, on which was nucleator put PP/EPDM and PP/BR systems. When the EPDM content is large, the nucleator had an good nuclearing function to PP/EPDM blend system. When the content is low, the function of nuclearitation is not good. Compared with the PP/BR system without nucleator, there was an good nuclearing function in PP/BR system with nucleator and the impact resilience of PP had been hightened extentedly. When the BR content is lower than 12 phr, the BR could instead of EDPM in fact of toughened modification to PP. It was proved that the fittings prepared by PP material of high impact resilience completely satisified the requirement of automobile industry.
In this paper, polypropylene(PP) was modificated in property by blending method. And mechanical property, crystalline morphology and crystallization kinetics were deeply studied about PP/EPDM and PP/BR systems where the rubber were vulcanized and the nucleator was adopted also. The toughened polypropylene was analysized by DSC and Phase differential micrographs technologies. The compatibility between rubber and PP and nuclearing effect were improved when the rubber was vulcanized and grafted into PP, sothat the modificatied PP possessinghigh flow behavior and high impact resilience. SF, which is the good nucleator, had an large contribution to hightened the yield strength and room temperature notch yield strength of PP, but had little impact on low temperature yield strength. The impacts were different, on which was nucleator put PP/EPDM and PP/BR systems. When the EPDM content is large, the nucleator had an good nuclearing function to PP/EPDM blend system. When the content is low, the function of nuclearitation is not good. Compared with the PP/BR system without nucleator, there was an good nuclearing function in PP/BR system with nucleator and the impact resilience of PP had been hightened extentedly. When the BR content is lower than 12 phr, the BR could instead of EDPM in fact of toughened modification to PP. It was proved that the fittings prepared by PP material of high impact resilience completely satisified the requirement of automobile industry.
引文
1 许健南.塑料材料.北京:中国轻工业出版社,1999:73~74
2 上海科学技术情报研究所.聚丙烯的发展及其应用.上海:上海科学技术情报研究所,1977:10~29
3 朱炤男．聚丙烯塑料的应用与改性．北京：中国轻工业出版社，1982:20~47
4 何叶力,李力,关肇基.聚丙烯树脂的加工与应用.北京:中国石化出版社,2000:163~194
5 辛浩波,邓涛,邓本成.塑料合金及塑橡共混改性.北京:中国轻工业出版社,2000,221～240
6 崔科增,张雷.中国聚丙烯市场现状和前景.中国塑料,2004,18(11):9～15
7 高春雨.世界聚丙烯工业的发展趋势.塑料加工应用,2001,4:63～67
8 刘英俊.聚丙烯塑料改性及应用进展.工程塑料应用,1995,23(5):49~54
9 刘英俊,王锡臣.改性塑料行业指南.北京:中国轻工业出版社,2000:23~25
10 王喜,齐泮仑,王鹤庆.国外聚丙烯新产品的开发.中国石油和化工,2004,
5:38~41
11 崔小明.国外聚丙烯新产品研发进展.周年塑料,2004,22(5):35~37
12 Norton D R,Keller A.Spherulitic and Lamellar Morphology of Melt-crystallized Isotactic Polypropylene.Polymer,1985,26(5):704~716
13 Khanna Y P.Rheological Mechanism and Overview of Nucleated Crystallization Kinetics.Macromolecules,1993,26(14):3639~3643
14 Uenoyama M,Shukushima S,Hayami H,et al.Development of Radiation cross-linked Polypropylene.SEI Technical Review,2002,(54):10~11
15 李馥梅.工程化聚丙烯研究与应用新近展.中国塑料,2001,6:34~36
16 李玮,刘佑习.聚丙烯的改性.高分子材料科学与工程.1997,13(6):9~14
17 王国全,王秀芬.聚合物改性.北京:中国轻工业出版社,2000:78~91
18 徐光景.聚丙烯共混改性影响因素初探.塑料,1998,27 (6):27~32
19 张青松.PP/UHMWPE 共混合金增韧增强机理研究.菏泽学院学报,2004,26(4):36~40
20 杨军等.PP/UHMWPE 原位成纤复合材料的混炼及成型工艺研究.中国塑料,1999,11:34~36
21 Fu Qiang,Wang Guiheng.Polymer Eng&Sci.,1992,32(1):94~97
22 吴永刚,马懿,李敬泽.无机刚性粒子增韧 PP 的研究.中国塑料,1999,13(4):29~33
23 赵贵哲,刘亚青.纳米 SiO2 增强增韧聚丙烯(PP)的研究.吉林大学学报(工学版),2005,35(2):205~209
24 Tabtian G A,Vebables R.The Performance of Selected Unsaturated Coatings for Calcium Carbonate Filler in Polypropylene.European Polymer Journal,2000,36:137~141
25 Judeinstein P,Sanchez C.Hybrid Organic-Inorganic Materials:a Land of Multi-Disciplinarity.J Mater Chem,1996,6(4):511~517
26 Dirix Y,Bastiansen C,Caseri W.Preparation,Structure and Properties of Uniaxially Oriented Polyethylene-Silver Nanocomposites.Materials Science,1999(34):3859~3864
27 邓本诚,李俊山.橡胶塑料共混改性.北京:中国石化出版社,1996:589~594
28 张立红.高流动抗冲共聚聚丙烯开发进展.合成树脂及塑料,2003,20(5):48~51
29 James Kersting R.Development of UNIPOLTM+ PP High Melt Flow Rate Polypropylene Impact Copolymers with Improve Impact Stiffness Balance.In:Polyolefins XII,Houston,Texas:2000:109~124
30 Phillips R,Herbert G,News J,et al.Polymer Eng. & Sci.,1994,(34):1731-1743
31 Harris J E.Industry Trends in Polypropylene.In:Polyolefins XII,Houston,Texas:2000:175~187
32 张爱民,施楣梧,徐僖.微波技术在聚合物加工中的应用.塑料工业,1996,5:55~59
33 姜洪,张联盟.原位复合技术在新材料制备中应用评述.国外建材科技,2002,23(1):1~4
34 陈晓蕾,王汝,杨贵忠.聚丙烯物理改性的研究进展.塑料科技,2004,159(1):49~52
35 舒文艺.聚合物互穿网络技术在高分子合金中的应用.塑料,1994,23(1):29~35
36 晋日亚,王培霞.聚丙烯改性研究进展.中国塑料,2001,15(2):20~23
37 Lotz B.αand βPhases of Isotactic Polypropylene:A Case of Growth Kinetics ‘Phase Reentrancy’in Polymer Crystallization.Polymer,1998,39(19):4561~ 4567
38 Kim Y C,Kim C Y,Kim S C.Crystallization Characteristics of Isotactic Polypropylene With and Without Nucleating Agent.Polymer Eng.& Sci.,1991,31(14):1009~1014
39 李尹熙,骆秀云.汽车塑料应用手册.北京:机械工业出版社,1989:47~85
40 赵全友等.PP/共聚PP/POE汽车保险杆专用料的研制.工程塑料应用,2001,11:5~7
42 窦强等.聚丙烯蓄电池外壳专用料的配制.中国塑料,2000,14(1):38~41
43 李霞梅,唐小平,姚亮红等.汽车零部件用聚丙烯塑料的开发.塑料科技,2002,149(3):60~65
44 E.H.Merz.J.Polym.Sci.1956,22,325~328
45 S.Newman.J.Appl.Polym Sci.1965,9(6):2297~2230
46 J.A.Schmitt.J.Appl.Polym.Sci.1960,3(5):132~135
47 R.P.Kambour.L.Polym.Sci.1973,A27,1393~1395
48 C.G.Bragaw.Multicomponent Polymer Systems.Robert Ed.1971,99:86～97
49 韩明哲,周豪,刘家伟.成核剂在聚丙烯改性中的协同效应.中国塑料,2003,17(7):69~71
50 张丽英,武志军,张浩.成核剂对聚丙烯结晶形态及力学性能的影响.合成树脂及塑料,2004,4:1210~1238
51 刘保成,李荣勋,刘光烨.成核剂对耐候性聚丙烯性能的影响.塑料工业,2004,32(4):38~42
2 上海科学技术情报研究所.聚丙烯的发展及其应用.上海:上海科学技术情报研究所,1977:10~29
3 朱炤男．聚丙烯塑料的应用与改性．北京：中国轻工业出版社，1982:20~47
4 何叶力,李力,关肇基.聚丙烯树脂的加工与应用.北京:中国石化出版社,2000:163~194
5 辛浩波,邓涛,邓本成.塑料合金及塑橡共混改性.北京:中国轻工业出版社,2000,221～240
6 崔科增,张雷.中国聚丙烯市场现状和前景.中国塑料,2004,18(11):9～15
7 高春雨.世界聚丙烯工业的发展趋势.塑料加工应用,2001,4:63～67
8 刘英俊.聚丙烯塑料改性及应用进展.工程塑料应用,1995,23(5):49~54
9 刘英俊,王锡臣.改性塑料行业指南.北京:中国轻工业出版社,2000:23~25
10 王喜,齐泮仑,王鹤庆.国外聚丙烯新产品的开发.中国石油和化工,2004,
5:38~41
11 崔小明.国外聚丙烯新产品研发进展.周年塑料,2004,22(5):35~37
12 Norton D R,Keller A.Spherulitic and Lamellar Morphology of Melt-crystallized Isotactic Polypropylene.Polymer,1985,26(5):704~716
13 Khanna Y P.Rheological Mechanism and Overview of Nucleated Crystallization Kinetics.Macromolecules,1993,26(14):3639~3643
14 Uenoyama M,Shukushima S,Hayami H,et al.Development of Radiation cross-linked Polypropylene.SEI Technical Review,2002,(54):10~11
15 李馥梅.工程化聚丙烯研究与应用新近展.中国塑料,2001,6:34~36
16 李玮,刘佑习.聚丙烯的改性.高分子材料科学与工程.1997,13(6):9~14
17 王国全,王秀芬.聚合物改性.北京:中国轻工业出版社,2000:78~91
18 徐光景.聚丙烯共混改性影响因素初探.塑料,1998,27 (6):27~32
19 张青松.PP/UHMWPE 共混合金增韧增强机理研究.菏泽学院学报,2004,26(4):36~40
20 杨军等.PP/UHMWPE 原位成纤复合材料的混炼及成型工艺研究.中国塑料,1999,11:34~36
21 Fu Qiang,Wang Guiheng.Polymer Eng&Sci.,1992,32(1):94~97
22 吴永刚,马懿,李敬泽.无机刚性粒子增韧 PP 的研究.中国塑料,1999,13(4):29~33
23 赵贵哲,刘亚青.纳米 SiO2 增强增韧聚丙烯(PP)的研究.吉林大学学报(工学版),2005,35(2):205~209
24 Tabtian G A,Vebables R.The Performance of Selected Unsaturated Coatings for Calcium Carbonate Filler in Polypropylene.European Polymer Journal,2000,36:137~141
25 Judeinstein P,Sanchez C.Hybrid Organic-Inorganic Materials:a Land of Multi-Disciplinarity.J Mater Chem,1996,6(4):511~517
26 Dirix Y,Bastiansen C,Caseri W.Preparation,Structure and Properties of Uniaxially Oriented Polyethylene-Silver Nanocomposites.Materials Science,1999(34):3859~3864
27 邓本诚,李俊山.橡胶塑料共混改性.北京:中国石化出版社,1996:589~594
28 张立红.高流动抗冲共聚聚丙烯开发进展.合成树脂及塑料,2003,20(5):48~51
29 James Kersting R.Development of UNIPOLTM+ PP High Melt Flow Rate Polypropylene Impact Copolymers with Improve Impact Stiffness Balance.In:Polyolefins XII,Houston,Texas:2000:109~124
30 Phillips R,Herbert G,News J,et al.Polymer Eng. & Sci.,1994,(34):1731-1743
31 Harris J E.Industry Trends in Polypropylene.In:Polyolefins XII,Houston,Texas:2000:175~187
32 张爱民,施楣梧,徐僖.微波技术在聚合物加工中的应用.塑料工业,1996,5:55~59
33 姜洪,张联盟.原位复合技术在新材料制备中应用评述.国外建材科技,2002,23(1):1~4
34 陈晓蕾,王汝,杨贵忠.聚丙烯物理改性的研究进展.塑料科技,2004,159(1):49~52
35 舒文艺.聚合物互穿网络技术在高分子合金中的应用.塑料,1994,23(1):29~35
36 晋日亚,王培霞.聚丙烯改性研究进展.中国塑料,2001,15(2):20~23
37 Lotz B.αand βPhases of Isotactic Polypropylene:A Case of Growth Kinetics ‘Phase Reentrancy’in Polymer Crystallization.Polymer,1998,39(19):4561~ 4567
38 Kim Y C,Kim C Y,Kim S C.Crystallization Characteristics of Isotactic Polypropylene With and Without Nucleating Agent.Polymer Eng.& Sci.,1991,31(14):1009~1014
39 李尹熙,骆秀云.汽车塑料应用手册.北京:机械工业出版社,1989:47~85
40 赵全友等.PP/共聚PP/POE汽车保险杆专用料的研制.工程塑料应用,2001,11:5~7
42 窦强等.聚丙烯蓄电池外壳专用料的配制.中国塑料,2000,14(1):38~41
43 李霞梅,唐小平,姚亮红等.汽车零部件用聚丙烯塑料的开发.塑料科技,2002,149(3):60~65
44 E.H.Merz.J.Polym.Sci.1956,22,325~328
45 S.Newman.J.Appl.Polym Sci.1965,9(6):2297~2230
46 J.A.Schmitt.J.Appl.Polym.Sci.1960,3(5):132~135
47 R.P.Kambour.L.Polym.Sci.1973,A27,1393~1395
48 C.G.Bragaw.Multicomponent Polymer Systems.Robert Ed.1971,99:86～97
49 韩明哲,周豪,刘家伟.成核剂在聚丙烯改性中的协同效应.中国塑料,2003,17(7):69~71
50 张丽英,武志军,张浩.成核剂对聚丙烯结晶形态及力学性能的影响.合成树脂及塑料,2004,4:1210~1238
51 刘保成,李荣勋,刘光烨.成核剂对耐候性聚丙烯性能的影响.塑料工业,2004,32(4):38~42