茂金属聚乙烯共混体系流变性能研究
摘要
本论文借助Haake转矩流变仪、DSC、高级流变扩展系统ARES等现代化测试手段,对mPE/LDPE、PP/POE共混体系的剪切和拉伸流变性能进行了系统研究。
通过对mPE/LDPE共混体系的流变性能研究,发现在mPE基体中混入少量的LDPE,不仅可以明显降低mPE熔体的剪切粘度,提高其熔体剪切粘度对频率和温度的敏感性,而且使mPE/LDPE共混体系拉伸流变性能得到显著改善,熔体强度得到明显提高,进而改善了mPE的加工性能。
通过对PP/POE共混体系的流变性能研究,发现PP结构、POE含量均对共混体系流变性能有显著影响。PP/POE共混体系的剪切流变数据显示,PP和POE界面存在明显界面滑移现象,且这种滑移现象受PP和POE相容性的影响较大,其中PP1与POE之间界面滑移现象比PP2与POE之间界面滑移现象要更加明显。另外,拉伸流变试验数据显示,对于PP1/POE共混体系,当POE含量达到30%时,共混体系的拉伸粘度发生突变;对于PP2/POE共混体系,当POE含量达到10%时,共混体系的粘度曲线即发生明显变化。动态剪切流变试验数据显示,与PP2/POE共混体系相比,PP1/POE共混体系的线性粘弹区域较宽,其线性粘弹特征亦更明显。
上述实验结果的取得,对于进一步研究茂金属聚乙烯共混体系的流变性能—相态结构—力学性能的关系提供了重要的基础数据和理论指导,对茂金属聚乙烯及其共混体系加工与应用的发展具有一定的理论与实际意义。
The shear and extensional rheological properties of mPE/LDPE and PP/POE blend systems were systematically studied by means of a series of modern analysis technologies such as Haake rheometer, DSC, ARES rheometer.
Based on the study on rheological properties of mPE/LDPE blend systems, it was found that not only the shear viscosity decreased, but also the dependence of its shear viscosity on shear rate and temperature increased, and its extensional rheology and processibility were improved obviously after blending some LDPE with mPE.
By study on rheological properties of PP/POE blend systems, it was found that the structure of PP and content of POE had significant effect on rheological properties of blend systems. Shear rheological data of PP/POE showed that interfacial slip existed between PP and POE, which was greatly influenced by the compatibility of PP and POE, and interfacial slip between PP1and POE was more obvious than PP2 and POE. In addition, extensional rheological data indicated that extensional viscosity of PPl/POE blend systems changed greatly when content of POE amounted to 30%, while extensional viscosity curves of PP2/POE changed obviously when content of POE is only more than 10%. Data of dynamic shear rheometric tests displayed that not only linear viscoelasticity zone of PPl/POE blend systems was wider than PP2/POE, but also linear viscoelasticity phenomena was more obvious.
All the above experimental results and conclusions obtained would provide important basic data and theoretical guidance for further study on rheological properties, phase morphology and mechanical properties of metallocene polyethylene blend system, and have theoretical and practical significance for development and application of it.
通过对mPE/LDPE共混体系的流变性能研究,发现在mPE基体中混入少量的LDPE,不仅可以明显降低mPE熔体的剪切粘度,提高其熔体剪切粘度对频率和温度的敏感性,而且使mPE/LDPE共混体系拉伸流变性能得到显著改善,熔体强度得到明显提高,进而改善了mPE的加工性能。
通过对PP/POE共混体系的流变性能研究,发现PP结构、POE含量均对共混体系流变性能有显著影响。PP/POE共混体系的剪切流变数据显示,PP和POE界面存在明显界面滑移现象,且这种滑移现象受PP和POE相容性的影响较大,其中PP1与POE之间界面滑移现象比PP2与POE之间界面滑移现象要更加明显。另外,拉伸流变试验数据显示,对于PP1/POE共混体系,当POE含量达到30%时,共混体系的拉伸粘度发生突变;对于PP2/POE共混体系,当POE含量达到10%时,共混体系的粘度曲线即发生明显变化。动态剪切流变试验数据显示,与PP2/POE共混体系相比,PP1/POE共混体系的线性粘弹区域较宽,其线性粘弹特征亦更明显。
上述实验结果的取得,对于进一步研究茂金属聚乙烯共混体系的流变性能—相态结构—力学性能的关系提供了重要的基础数据和理论指导,对茂金属聚乙烯及其共混体系加工与应用的发展具有一定的理论与实际意义。
The shear and extensional rheological properties of mPE/LDPE and PP/POE blend systems were systematically studied by means of a series of modern analysis technologies such as Haake rheometer, DSC, ARES rheometer.
Based on the study on rheological properties of mPE/LDPE blend systems, it was found that not only the shear viscosity decreased, but also the dependence of its shear viscosity on shear rate and temperature increased, and its extensional rheology and processibility were improved obviously after blending some LDPE with mPE.
By study on rheological properties of PP/POE blend systems, it was found that the structure of PP and content of POE had significant effect on rheological properties of blend systems. Shear rheological data of PP/POE showed that interfacial slip existed between PP and POE, which was greatly influenced by the compatibility of PP and POE, and interfacial slip between PP1and POE was more obvious than PP2 and POE. In addition, extensional rheological data indicated that extensional viscosity of PPl/POE blend systems changed greatly when content of POE amounted to 30%, while extensional viscosity curves of PP2/POE changed obviously when content of POE is only more than 10%. Data of dynamic shear rheometric tests displayed that not only linear viscoelasticity zone of PPl/POE blend systems was wider than PP2/POE, but also linear viscoelasticity phenomena was more obvious.
All the above experimental results and conclusions obtained would provide important basic data and theoretical guidance for further study on rheological properties, phase morphology and mechanical properties of metallocene polyethylene blend system, and have theoretical and practical significance for development and application of it.
引文
[1]Robert T Sylvest,Gerald Lancaster,Stephen R Betso.New Elastomers from INSITE Technology,Molecular Architecture Control and Development Process Innovation,2nd International Congress on Metallocene Polymers,Metallocene' 96,Dusseldorf.Germany.March6-7,1996
[2]邹盛欧.茂金属聚乙烯开发近况[J].化工新材料,1997,5:3-6
[3]陈伟,景振华,王涛.茂金属聚合物催化剂及其聚乙烯的研究开发[J].合成树脂及塑料,1998,15(2):6-10
[4]Michael P.Plastics Engineering,1997,53(5):25
[5]王德禧,李蕴能,李兰等.茂金属聚合物进展[J].中国塑料,2000,14(2):12-17.
[6]李焉.茂金属聚烯烃的特性和应用[J].塑料,1999,28(3):1-7
[7]王金梅,吕兵,洪晓宇等.乙烯二聚共聚双功能均相催化体系的研究[J].石油炼制与加工,1995,26(12):26-28
[8]王海华,萧维,王峻沂.烯烃聚合反应茂金属催化剂的进展[J].合成树脂及塑料,1997,14(3):5-9
[9]陈伟,景振华.金属茂催化剂及其聚烯烃的研究开发[J].高分子通报,1997,35(1):54-58
[10]吴涛,袁绍彦,谢长琼等.茂金属聚乙烯与普通聚乙烯共混研究[J].工程塑料应用,2003,31(7):15-17
[11]闰明涛,高俊刚,李志庭.茂金属聚乙烯(mPE)/高压聚乙烯(HDPE)共混熔体的流变学[J].塑料工业,2001,29(4):37-39
[12]李代叙,雷军,周海英.HDPE/mLLDPE混炼后的性能与结构[J].现代塑料加工应用,2007,19(1):12-15
[13]占国荣等.mLLDPE与LDPE共混改善mLLDPE加工性能的研究[J].工程塑料应用,2004,32(1):28-30
[14]王穗禧,江梅,李兰等.聚丙烯及其改性技术[J].工程塑料应用,1998,26(4):26-30
[15]Engage POE,Product Information[J],DuPont Dow Elastomers,1998,9
[16]谢忠麟.聚丙烯的新型抗冲击改性剂POE[J].化工科技市场,1999(12):9-11
[17]Xiangfu Zhang,Fei Xie,et al.Effect of nucleating agent on the structure and properties of polypropylene/poly(ethylene-octene)blends[J].European Polymer Journal,2002(38):1-6
[18]Jinhai Yang,Yong Zhang,Yinxi Zhang.Brittle-ductile transition of PP/POE bends in both impact and high speed tensile test[J].Polymer,2003(44):5047-5052
[19]Kukaleva N,Jollands M,Cser F,et al.J Appl Polym Sci,2000,76:1011
[20]Paul S,Kale DD.Impact Modification of Polypropylene Copolymer with a Polyolefmic Elastomer[J].J Appl Polym Sci,2000,76(9):1480
[21]杨柳.PP/POE共混物性能分析[J].现代塑料加工应用,2004(16):21-24
[22]冯予星,刘力,张立群等.PP/POE共混合金的研究[J].工程塑料应用,1999,27(12):6-10
[23]毛立新,高翔,李淼等.茂金属聚烯烃弹性体增韧聚丙烯的研究[J].北京化工大学学 报,2003,30(1):24-28
[24]McNally T,McShane P,Nally G M,et al.Rheology,phase morphology,mechanical,impact and thermal properties of polypropylene/metallocene catalysed ethylene 1-octene copolymer blends[J].Polymer,2002,43:785-3793
[25]Da Silva A L N,Tavares M I B,Politano D P,et al.Polymer blends based on polyolefm elastomer and polypropylene[J].J Appl Polym Sci,1997(66):2005-2014
[26]Paul S,Kale DD,Rheological study of polypropylene copolymer/polyolefinic elastomer blends[J].Journal of Applied Polymer Science,2002,84:665-671
[27]Ana Lucia N.Silva,Marisa C.G.Rocha,et al.Study of rheological behavior of elastomer/polypropylene blends[J].J.Polymer Testing,2002(21):259-293
[28]Monica F,Silvia E,Numa J,et al.Improvement of mechanical properties for PP/PS blends by in situ compatibilization Polymer 2005,46:6096-6101
[29]Bai S L,Sell S G,Hiver J M,et al.Polypropylene/polyamide 6/polyethylene-octene elastomer blends.Part 3:Mechanisms of volume dilatation during plastic deformation under uniaxial tension[J].Polymer,2005,46(17):6437-6446
[30]Litmanovich A D,Plate N A,Kudryavtsev Y V.Reactions in polymer blends:interchain effects and theoretical problems[J].Prog Polym Sci,2002,27(5):915.-970
[31]Sell S G,Bai S L,Hiver J M.Polypropylene/polyamide 6/polyethylene-octene elastomer blends.Part 2:volume dilatation during plastic deformation under uniaxial tension[J].Polymer,2004,45(17):5785-5792
[32]Puyvelde P V,Velankar S,Moldenaers P.Rheology and morphology of compatibilized polymer blends[J].Curr Opin Colloid In,2001,6(5-6):457-463
[33]Bai S L,Sell S G,Hiver J M,et al.Microstructures and mechanical properties of polypropylene/polyamide 6/polyethelene-octene elastomer blends[J].Polymer,2004,45(9):3063-3071
[34]沈家瑞,贾德民.聚合物共混物与合金[M].广州:华南理工大学出版社,1999,55-74
[35]G.Ronca,Thomas P Russell.Thermodynamics of phase separation in polymer mixtures [J].Macromolecules,1985,18(4):665-670
[36]Halfand M.J Chem Phys,1977,56:3592.
[37]周持兴,俞炜.聚合物流变实验与应用[M].上海:上海交通大学出版社,2003,142-143
[38]Bares J.Glass Transition of the Polymer Microphase[J].Macromolecules,1975,2:244.
[39]Diaz M F,Barbosa S E,Capiati N J.Polymer,2005,46:6096
[40]何慧,沈家瑞,黄庙由.合成橡胶工业,2000,23(3):117
[41]Adem E,Burillo G,Borja M V,et al.Nucl Phys B,2005,236:295
[42]Elmaghor F,张丽叶,励杭泉.合成橡胶工业,2002,25(1):43
[43]Elmaghor F,张丽叶,励杭泉.合成橡胶工业,2002,25(3):175
[44]Quintana S L,Rosales C,Mitre IJ.Polymer,2004,45:8041
[45]李忠明,谢邦互,黄锐等.材料研究学报,2005,19(1):8
[46]T.Alfrey,Jr.,W.J.Schrenk.Multipolymer Systems.Science,1980,208(4446):813
[47]R.Y.F.Liu,T.E.Bernal-Lara,A.Hiltner,et al.Polymer Interphase Materials by Forced Assembly.Macromolecules,2005,38(11):4819
[48]王明,沈佳斌,郭少云等.EPDM/PS交替多层复合材料的力学性能分析[J].复合材料学报,2007,24(6):36-43
[49]A.Valenza,G.Spadaro,D.Acierno.Dynamic rheological characterization of polyamide/modified polyolefin laminates[J].Colloid polym Sci,2000,278:986-992
[50]Rui Zhao,Christopher W Macosko.Slip at polymer-polymer interfaces:Rheological measurements on coextruded multilayers[J].J.Rheol.,2002,46(1):145-167
[51]K.Lamnawar,A.Maazouz.Rheolgical study of multilayer functionalized polymers:characterization of interdiffusion and reaction at polymer/polymer interface[J].Rheol Acta,2006,45:411-424
[52]L.JIANG,Y.C.LAM,J.ZHANG.Rheological Properties and Interfacial Slip of a Multilayer Structure Under Dynamic Shear[J].Journal of Polymer Science,2005,43:2683-2698
[53]N.P.ADHIKARI,J.L.GOVEAS.Effects of Slip on the Viscosity of Polymer Melts[J].Journal of Polymer Science,2004,42:1888-1904
[54]Sood R,Kulkami M G,Dutta A,et al.Viscosity of homogeneous polymer blends:An altered free-volume state model[J].Polymer Engineering and Science,1988,28(1):20-31
[2]邹盛欧.茂金属聚乙烯开发近况[J].化工新材料,1997,5:3-6
[3]陈伟,景振华,王涛.茂金属聚合物催化剂及其聚乙烯的研究开发[J].合成树脂及塑料,1998,15(2):6-10
[4]Michael P.Plastics Engineering,1997,53(5):25
[5]王德禧,李蕴能,李兰等.茂金属聚合物进展[J].中国塑料,2000,14(2):12-17.
[6]李焉.茂金属聚烯烃的特性和应用[J].塑料,1999,28(3):1-7
[7]王金梅,吕兵,洪晓宇等.乙烯二聚共聚双功能均相催化体系的研究[J].石油炼制与加工,1995,26(12):26-28
[8]王海华,萧维,王峻沂.烯烃聚合反应茂金属催化剂的进展[J].合成树脂及塑料,1997,14(3):5-9
[9]陈伟,景振华.金属茂催化剂及其聚烯烃的研究开发[J].高分子通报,1997,35(1):54-58
[10]吴涛,袁绍彦,谢长琼等.茂金属聚乙烯与普通聚乙烯共混研究[J].工程塑料应用,2003,31(7):15-17
[11]闰明涛,高俊刚,李志庭.茂金属聚乙烯(mPE)/高压聚乙烯(HDPE)共混熔体的流变学[J].塑料工业,2001,29(4):37-39
[12]李代叙,雷军,周海英.HDPE/mLLDPE混炼后的性能与结构[J].现代塑料加工应用,2007,19(1):12-15
[13]占国荣等.mLLDPE与LDPE共混改善mLLDPE加工性能的研究[J].工程塑料应用,2004,32(1):28-30
[14]王穗禧,江梅,李兰等.聚丙烯及其改性技术[J].工程塑料应用,1998,26(4):26-30
[15]Engage POE,Product Information[J],DuPont Dow Elastomers,1998,9
[16]谢忠麟.聚丙烯的新型抗冲击改性剂POE[J].化工科技市场,1999(12):9-11
[17]Xiangfu Zhang,Fei Xie,et al.Effect of nucleating agent on the structure and properties of polypropylene/poly(ethylene-octene)blends[J].European Polymer Journal,2002(38):1-6
[18]Jinhai Yang,Yong Zhang,Yinxi Zhang.Brittle-ductile transition of PP/POE bends in both impact and high speed tensile test[J].Polymer,2003(44):5047-5052
[19]Kukaleva N,Jollands M,Cser F,et al.J Appl Polym Sci,2000,76:1011
[20]Paul S,Kale DD.Impact Modification of Polypropylene Copolymer with a Polyolefmic Elastomer[J].J Appl Polym Sci,2000,76(9):1480
[21]杨柳.PP/POE共混物性能分析[J].现代塑料加工应用,2004(16):21-24
[22]冯予星,刘力,张立群等.PP/POE共混合金的研究[J].工程塑料应用,1999,27(12):6-10
[23]毛立新,高翔,李淼等.茂金属聚烯烃弹性体增韧聚丙烯的研究[J].北京化工大学学 报,2003,30(1):24-28
[24]McNally T,McShane P,Nally G M,et al.Rheology,phase morphology,mechanical,impact and thermal properties of polypropylene/metallocene catalysed ethylene 1-octene copolymer blends[J].Polymer,2002,43:785-3793
[25]Da Silva A L N,Tavares M I B,Politano D P,et al.Polymer blends based on polyolefm elastomer and polypropylene[J].J Appl Polym Sci,1997(66):2005-2014
[26]Paul S,Kale DD,Rheological study of polypropylene copolymer/polyolefinic elastomer blends[J].Journal of Applied Polymer Science,2002,84:665-671
[27]Ana Lucia N.Silva,Marisa C.G.Rocha,et al.Study of rheological behavior of elastomer/polypropylene blends[J].J.Polymer Testing,2002(21):259-293
[28]Monica F,Silvia E,Numa J,et al.Improvement of mechanical properties for PP/PS blends by in situ compatibilization Polymer 2005,46:6096-6101
[29]Bai S L,Sell S G,Hiver J M,et al.Polypropylene/polyamide 6/polyethylene-octene elastomer blends.Part 3:Mechanisms of volume dilatation during plastic deformation under uniaxial tension[J].Polymer,2005,46(17):6437-6446
[30]Litmanovich A D,Plate N A,Kudryavtsev Y V.Reactions in polymer blends:interchain effects and theoretical problems[J].Prog Polym Sci,2002,27(5):915.-970
[31]Sell S G,Bai S L,Hiver J M.Polypropylene/polyamide 6/polyethylene-octene elastomer blends.Part 2:volume dilatation during plastic deformation under uniaxial tension[J].Polymer,2004,45(17):5785-5792
[32]Puyvelde P V,Velankar S,Moldenaers P.Rheology and morphology of compatibilized polymer blends[J].Curr Opin Colloid In,2001,6(5-6):457-463
[33]Bai S L,Sell S G,Hiver J M,et al.Microstructures and mechanical properties of polypropylene/polyamide 6/polyethelene-octene elastomer blends[J].Polymer,2004,45(9):3063-3071
[34]沈家瑞,贾德民.聚合物共混物与合金[M].广州:华南理工大学出版社,1999,55-74
[35]G.Ronca,Thomas P Russell.Thermodynamics of phase separation in polymer mixtures [J].Macromolecules,1985,18(4):665-670
[36]Halfand M.J Chem Phys,1977,56:3592.
[37]周持兴,俞炜.聚合物流变实验与应用[M].上海:上海交通大学出版社,2003,142-143
[38]Bares J.Glass Transition of the Polymer Microphase[J].Macromolecules,1975,2:244.
[39]Diaz M F,Barbosa S E,Capiati N J.Polymer,2005,46:6096
[40]何慧,沈家瑞,黄庙由.合成橡胶工业,2000,23(3):117
[41]Adem E,Burillo G,Borja M V,et al.Nucl Phys B,2005,236:295
[42]Elmaghor F,张丽叶,励杭泉.合成橡胶工业,2002,25(1):43
[43]Elmaghor F,张丽叶,励杭泉.合成橡胶工业,2002,25(3):175
[44]Quintana S L,Rosales C,Mitre IJ.Polymer,2004,45:8041
[45]李忠明,谢邦互,黄锐等.材料研究学报,2005,19(1):8
[46]T.Alfrey,Jr.,W.J.Schrenk.Multipolymer Systems.Science,1980,208(4446):813
[47]R.Y.F.Liu,T.E.Bernal-Lara,A.Hiltner,et al.Polymer Interphase Materials by Forced Assembly.Macromolecules,2005,38(11):4819
[48]王明,沈佳斌,郭少云等.EPDM/PS交替多层复合材料的力学性能分析[J].复合材料学报,2007,24(6):36-43
[49]A.Valenza,G.Spadaro,D.Acierno.Dynamic rheological characterization of polyamide/modified polyolefin laminates[J].Colloid polym Sci,2000,278:986-992
[50]Rui Zhao,Christopher W Macosko.Slip at polymer-polymer interfaces:Rheological measurements on coextruded multilayers[J].J.Rheol.,2002,46(1):145-167
[51]K.Lamnawar,A.Maazouz.Rheolgical study of multilayer functionalized polymers:characterization of interdiffusion and reaction at polymer/polymer interface[J].Rheol Acta,2006,45:411-424
[52]L.JIANG,Y.C.LAM,J.ZHANG.Rheological Properties and Interfacial Slip of a Multilayer Structure Under Dynamic Shear[J].Journal of Polymer Science,2005,43:2683-2698
[53]N.P.ADHIKARI,J.L.GOVEAS.Effects of Slip on the Viscosity of Polymer Melts[J].Journal of Polymer Science,2004,42:1888-1904
[54]Sood R,Kulkami M G,Dutta A,et al.Viscosity of homogeneous polymer blends:An altered free-volume state model[J].Polymer Engineering and Science,1988,28(1):20-31