单轴叶片挤出机加工的PS/HDPE合金形态结构及性能的研究
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摘要
为充分利用现有资源扩大高分子材料的应用领域,目前对聚合物进行共混改性的研究变得越来越活跃。当前,对不相容共混体系的改性研究主要侧重于研制新型的相容剂,而挤出共混设备对材料的聚集态结构、分散混合状况及材料的宏观力学性能也同样起着至关重要的作用。华南理工大学瞿金平教授最新研制的叶片挤出机彻底摒弃了基于剪切流变的螺杆挤出加工方式,通过采用正位移的输送原理及引入拉伸流场的作用方式,使得聚合物在叶片挤出机中具有热-机械历程短、降解程度小、物料混合效果好等特点。
本文通过选用PS/HDPE不相容的两相体系来研究叶片挤出机加工对共混物分散混合、微观相态、热行为及宏观力学性能的影响规律。为较好的开展实验研究工作,本文特从多个角度来进行考察,依次为:(1)分别选用纯PS及HDPE来分析物料在叶片及普通单螺杆挤出机中的降解及停留时间特性;(2)选用不同配比的PS/HDPE共混物经来研究在叶片挤出机的作用下分散相含量对体系相态及分散混合的影响规律;(3)选用低黏度比及高黏度比的PS/HDPE共混体系来研究不同拉伸流场强度对该体系分散混合状况及相转变速率的影响;(4)向PS/HDPE(30/70)体系中添加相容剂SEBS来分析叶片挤出机加工对体系相态及界面作用的影响。
研究表明:与螺杆挤出机相比,物料在叶片挤出机的塑化过程中降解程度较小、物料停留时间更短。经叶片挤出机加工的PS/HDPE的分散相平均粒径尺寸变得较小(约0.25~1um),分布较均匀,界面间的粘结作用较强。同时,共混物在较低的转速下微观相态结构由交错互锁的双连续相结构向“海岛结构转变”,且分散相平均尺寸进一步得到减小。另外,添加少量的SEBS可较好的对PS/HDPE(30/70)进行相容改性。
In order to fully utilize resources and expand the applications of polymer materials, it seems that the modification research of incompatible blends became more and more popular. At present, the modification of polymer blends focused primarily on developing new compatibilizers,while the blending equipments also act as the vital player in the course of polymer blends processing.Because it could improve the dispersing and mixing effect of dispersing phase materials in the two phase systems and influence the aggregation structures of polymer blends. Professor Qu Jinping,from South China University of Technology, developed a newly uniaxial vane extruder which completely abandoned the screw extruder based on shear flow field.The polymer heat-mechanical process became more shortly、the degree of degradation became more slightly and the effect of dispersing and mixing improved more obviously through the use of positive displacement conveying principle and the introduction of elongation flow field in the vane extruder.
In this paper, the PS/HDPE blends were selected to research the law of dispersing and mixing、micro-phase struture、thermal behaviors and macro-mechanical properties in the vane extruder.In order to precisely describle the micro-structure and properties of PS/HDPE blends in the vane extruder,the experiments were done from various perspectives as below respectively: (1) pure PS and HDPE were used to analyze the residence time and the degradation properties in the vane and screw extruders; (2) use the different mass proportions of PS/HDPE blends to study the law of dispersing and mixing and evolution rules of polymer blends phase strutures as the variation of dispersed phase content in the extruding process of vane extruder;(3) use the PS / HDPE blends of low viscosity and high viscosity ratio to study dispersion mixing status and rate of phase transformation in different flow field intensity; (4)add the compatibilizer SEBS in PS/HDPE(30/70) to analyze the phase structure and the interface adhension effect bettwen the dispersed and continuous phase.
The results show that: compared with the screw extruder, the molecular weight of PS decreased less、the residence time of HDPE in the vane extruder stayed shortly.The dispersed phase mean particle size of PS/HDPE blends became small(0.25um~1um),the distribution became homogeniusly by vane extruding processing . In the vane extruder, the phase evolution from“sea-island”structure to co-continous structure can be took place at low rotate speed,the“sea-island”structure formed as rotate speed increased and the dispersed mean particles became more small.the campatibilization of PS/HDPE(30/70) blends can been improved through adding little amount of SEBS .
本文通过选用PS/HDPE不相容的两相体系来研究叶片挤出机加工对共混物分散混合、微观相态、热行为及宏观力学性能的影响规律。为较好的开展实验研究工作,本文特从多个角度来进行考察,依次为:(1)分别选用纯PS及HDPE来分析物料在叶片及普通单螺杆挤出机中的降解及停留时间特性;(2)选用不同配比的PS/HDPE共混物经来研究在叶片挤出机的作用下分散相含量对体系相态及分散混合的影响规律;(3)选用低黏度比及高黏度比的PS/HDPE共混体系来研究不同拉伸流场强度对该体系分散混合状况及相转变速率的影响;(4)向PS/HDPE(30/70)体系中添加相容剂SEBS来分析叶片挤出机加工对体系相态及界面作用的影响。
研究表明:与螺杆挤出机相比,物料在叶片挤出机的塑化过程中降解程度较小、物料停留时间更短。经叶片挤出机加工的PS/HDPE的分散相平均粒径尺寸变得较小(约0.25~1um),分布较均匀,界面间的粘结作用较强。同时,共混物在较低的转速下微观相态结构由交错互锁的双连续相结构向“海岛结构转变”,且分散相平均尺寸进一步得到减小。另外,添加少量的SEBS可较好的对PS/HDPE(30/70)进行相容改性。
In order to fully utilize resources and expand the applications of polymer materials, it seems that the modification research of incompatible blends became more and more popular. At present, the modification of polymer blends focused primarily on developing new compatibilizers,while the blending equipments also act as the vital player in the course of polymer blends processing.Because it could improve the dispersing and mixing effect of dispersing phase materials in the two phase systems and influence the aggregation structures of polymer blends. Professor Qu Jinping,from South China University of Technology, developed a newly uniaxial vane extruder which completely abandoned the screw extruder based on shear flow field.The polymer heat-mechanical process became more shortly、the degree of degradation became more slightly and the effect of dispersing and mixing improved more obviously through the use of positive displacement conveying principle and the introduction of elongation flow field in the vane extruder.
In this paper, the PS/HDPE blends were selected to research the law of dispersing and mixing、micro-phase struture、thermal behaviors and macro-mechanical properties in the vane extruder.In order to precisely describle the micro-structure and properties of PS/HDPE blends in the vane extruder,the experiments were done from various perspectives as below respectively: (1) pure PS and HDPE were used to analyze the residence time and the degradation properties in the vane and screw extruders; (2) use the different mass proportions of PS/HDPE blends to study the law of dispersing and mixing and evolution rules of polymer blends phase strutures as the variation of dispersed phase content in the extruding process of vane extruder;(3) use the PS / HDPE blends of low viscosity and high viscosity ratio to study dispersion mixing status and rate of phase transformation in different flow field intensity; (4)add the compatibilizer SEBS in PS/HDPE(30/70) to analyze the phase structure and the interface adhension effect bettwen the dispersed and continuous phase.
The results show that: compared with the screw extruder, the molecular weight of PS decreased less、the residence time of HDPE in the vane extruder stayed shortly.The dispersed phase mean particle size of PS/HDPE blends became small(0.25um~1um),the distribution became homogeniusly by vane extruding processing . In the vane extruder, the phase evolution from“sea-island”structure to co-continous structure can be took place at low rotate speed,the“sea-island”structure formed as rotate speed increased and the dispersed mean particles became more small.the campatibilization of PS/HDPE(30/70) blends can been improved through adding little amount of SEBS .
引文
[1]黄如注.相容剂的生产与应用[J].化工新型材料, 1992, (3): 30
[2] Locke C E, Paul D R. Graft copolymer modification of polyethylene-polystyrene blends.I. Graft preparation and characterization[J]. Journal of Applied Polymer Science, 1973,17(8): 2597-2617
[3] Locke C E, Paul D R. Graft copolymer modification of polyethylene-polystyrene blends.Ⅱ. Properties of modified blends[J]. Journal of Applied Polymer Science, 1973, 17(9): 2791-2800
[4] Ihab Kamel, Sueo Machi, Joseph Silverman Ihab Kamel. Radiation induced grafting ofstyrene vapor to polyethylene[J]. Journal of Polymer Science Part A-1: Polymer Chemistry, 1972, 10(4): 1019-1029
[5] Fayt R, Jér?me R, TeyssiéPh. Molecular design of multicomponent polymer systems.III.Comparative behavior of pure and tapered block copolymers in emulsification of blends of low-density polyethylene and polystyrene[J]. Journal of Polymer Science: Polymer Physics Edition, 2003, 20(12):2209-2217
[6] Fayt R, TeyssiéP H. Molecular design of multicomponent polymer systems.XVIII: Emulsification of high-impact polystyrene and low density polyethylene blends into high-impact alloys[J]. Journal of Applied Polymer Science, 2004, 30(16): 937-947
[7] Zden k Stary, Ivan Fortelny. Effect of the Molecular Structure of Ethene-Propene and Styrene-Butadiene Copolymers on compatibilizationef?ciency in Low-Density Polyethylene/Polystyrene Blends[J]. Journal of Applied Polymer Science, 2008,107(1): 174-186
[8]王国全.聚合物共混改性原理与应用[M].北京:中国轻工业出版社, 2007
[9]蒋果,黄汉雄.聚合物共混中的混沌混合[J].中国塑料, 2004, 18(3): 11-13
[10]汉森.塑料挤出技术[M]. (第二版).北京:中国轻工业出版社, 2001
[11] Isayev A I, Wong C M. Effect of Oscillations During Extrusion on Rheology and Mechanical Properties of Polymers[J]. Advances in Polymer Technology, 1990, 10(1): 31-45
[12] Jiang Long, Shen Kai zhi. A mandrel-rotating die to produce high-hoop-strength HDPE pipe by self-reinforcement[J].Journal of Applied Polymer Science, 1998, 69(2): 323-328
[13] Wong C M, Chen C H. Flow of Thermoplastics in an Annular Die Under Parallel Oscillation[J]. Polymer Engineering and Science, 1990, 30(24): 1374-1384
[14]瞿金平.电磁动态塑化挤出方法及设备[P].中国: 9010103410, 1992-11-25
[13] David B.塑料混合工艺及设备[M].詹茂盛.北京:化学工业出版社, 2002
[16] Serafim Bakalis. Velocity distributions and volume flow rates in the nip and translational regions of a co-rotating/self-wiping/twin-screw extruder[J]. Journal of Food Engineering, 2002, 5(4): 273-282
[17]刘廷华.双螺杆挤出可视化实验与非充满固体输送及熔融理论研究[D].北京:北京化工大学博士研究生学位论文, 1995
[18] Jassen L P B M.双螺杆挤出[M].耿孝正.北京:轻工业出版社, 1987
[19] Lagendijk R P, Hogt A H, Gotsis A D. Peroxydicarbonate modification of polypropylene and extensional flow properties[J]. Polymer, 2001, 42(25): 10035-10043
[20]李笑喃,刘鹏波.聚丙烯熔体拉伸流变行为的研究[J].塑料工业, 2007, 35(3):45
[21] Sabol, Baird. Morphology in blends of thermotropic liquid crystalline polymer and polypropylene[J]. International Polymer Processing, 1995, 10(2): 124-136
[22] Keith Luker. Summary result of a novel single screw compounder[A]. Society of Plastics Engineers Annual Technical Conference: Plastics Encounter at ANTEC 2007, Conference Proceeding v1, 2007
[23] Carrot C, Guillet J, May J F. Molding of the conveying of Solid Polymer in the Feeding Zone of Intermeshing Co-rotating Twin Screw Extruder[J]. Polymer Engineering and Science, 1993, 33(11): 572-580
[24]周彦豪.高分子材料加工流变学[M].北京:北京化工学院, 1983
[25]耿孝正.塑料混合及连续混合设备[M].北京:中国轻工业出版社, 2008: 45-64
[26] Lca Manas-Zloczower, Z Tadmor. Mixing and Compounding of Polymers: Theory and Practice[M]. New York, 1994
[27] Paul D R.聚合物共混物:组成与性能[M].殷敬华.北京:科学出版社, 2004: 364-366
[28] Santana1 O O, Müllerl A J. Homogeneous nucleation of the dispersed crystallisable component of immiscible polymer blends[J]. Polymer Bulletin, 1994, 32(4): 471-477
[29] Bentley B J, Leal L G. An experimental investigation of drop deformation and breakup in steady, two-dimensional linear flows[J]. Journal of Fluid Mechanics, 1986, 167:241-283
[30] Elemans P H M, Bos H L, Janssen J M H. Transient phenomena in dispersive mixing[J]. Chemical Engineering Science, 1993, 48(2): 267-276
[31] Oswald, Menges G. Materials Science of polymers for engineers[M].Hanser, Munish, 1995
[32]祝卫国,汪传生.单螺杆挤出机分散混炼的改进[J].特种橡胶制品, 2003,24(4): 31-34
[33] Grace H P. Dispersion phenomena in high-viscosity immiscible fluid systems and application of static mixers as dispersion devices in such systems[J]. Chemical Engineering Communications, 1982, 14(3): 225-277
[34] Lagnado R R, Leal L G. The stability of two-dimensional linear flows[J]. Physics of Fluids, 1984, 27(5): 1094
[35] Stone H A. Dynamics of Drop Deformation and Breakup in Viscous Fluids[J]. Annual Review of Fluid Mechanics, 1984, 26(4): 65-102
[36] Rallison J M. The deformation of small viscous drops and bubbles in shear flows[J]. Annual Review of Fluid Mechanics, 1984, 16: 45-46
[37] Janseen J M H, Mejijer H E H. Droplet Breakup Mechanisms:Stepwise Equilibrium Versus Transient Dispersion[J]. Journal of Rheology, 1993, 37(4): 597-608
[38] Kang J,Simth T G. Study of Breakup Mechanisms in Cavity Flow[J]. AICHE Journal, 1996, 42(3): 649-659
[39] Scott C E, Macosko C W. Model Experiments Concerning Morphology Development during the Initial Stages of Polymer Blending[J]. Polymer Bulletin,1991, 26(3): 341-348
[40] Delpilar M, Noriega E.挤出过程的问题分析及解决方案[M].北京:化学工业出版社, 2003: 90-92
[41] Rauwendaal C.塑料挤出[M].北京:中国轻工业出版社, 1996: 235-244
[42] Han C D.聚合物加工流变学[M].北京:科学出版社, 1985
[43] Gramann P J, Davis B A,Osswald T A. A New Dispersive and Distributive Static Mixer for the Compounding of Highly Viscous Materials[A]. ANTEC Conference, New York, 1999
[44] Suzaka Y, Ooita. Mixing Device[P]. USP: 4334783, 1982-06-13
[45] Lechoslaw, Utracki A, Pierrofonds. Extensional Flow Mixer[P]. USP: 5451106, 1995-09-19
[46]黄磊,欧相麟.拉伸流场对聚合物填充体系的分散混合作用[J].中国塑料, 2006, 20(9): 54-58.
[47]卜海涛,肖方成,欧相麟.拉伸流场对PP/纳米CaCO3填充体系分散混合的影响[J].塑料工业, 2008, 36(11): 35-38
[48]瞿金平.基于拉伸流变的高分子材料塑化输运方法及设备[P].中国: 200810026054.X, 2008
[49]岑丹涛.叶片泵单螺杆挤出机固体强制输送特性研究[D].广州:华南理工大学硕士研究生学位论文, 2008
[50]彭仕杰.聚合物熔体叶片正位移输送特性研究[D].广州:华南理工大学硕士研究生学位论文, 2008
[51]王彦岗.聚合物叶片挤出机正位移输送和塑化特性研究[D].广州:华南理工大学硕士研究生学位论文, 2008
[52]杨智韬.聚合物叶片挤出机熔体正位移输送与混合特性研究[D].广州:华南理工大学博士研究生学位论文, 2009
[53]游长江,石小华.嵌段共聚物增容剂对LDPE/PS分散相粒径的影响[J].合成橡胶工业, 1995, 18(6): 363-364
[2] Locke C E, Paul D R. Graft copolymer modification of polyethylene-polystyrene blends.I. Graft preparation and characterization[J]. Journal of Applied Polymer Science, 1973,17(8): 2597-2617
[3] Locke C E, Paul D R. Graft copolymer modification of polyethylene-polystyrene blends.Ⅱ. Properties of modified blends[J]. Journal of Applied Polymer Science, 1973, 17(9): 2791-2800
[4] Ihab Kamel, Sueo Machi, Joseph Silverman Ihab Kamel. Radiation induced grafting ofstyrene vapor to polyethylene[J]. Journal of Polymer Science Part A-1: Polymer Chemistry, 1972, 10(4): 1019-1029
[5] Fayt R, Jér?me R, TeyssiéPh. Molecular design of multicomponent polymer systems.III.Comparative behavior of pure and tapered block copolymers in emulsification of blends of low-density polyethylene and polystyrene[J]. Journal of Polymer Science: Polymer Physics Edition, 2003, 20(12):2209-2217
[6] Fayt R, TeyssiéP H. Molecular design of multicomponent polymer systems.XVIII: Emulsification of high-impact polystyrene and low density polyethylene blends into high-impact alloys[J]. Journal of Applied Polymer Science, 2004, 30(16): 937-947
[7] Zden k Stary, Ivan Fortelny. Effect of the Molecular Structure of Ethene-Propene and Styrene-Butadiene Copolymers on compatibilizationef?ciency in Low-Density Polyethylene/Polystyrene Blends[J]. Journal of Applied Polymer Science, 2008,107(1): 174-186
[8]王国全.聚合物共混改性原理与应用[M].北京:中国轻工业出版社, 2007
[9]蒋果,黄汉雄.聚合物共混中的混沌混合[J].中国塑料, 2004, 18(3): 11-13
[10]汉森.塑料挤出技术[M]. (第二版).北京:中国轻工业出版社, 2001
[11] Isayev A I, Wong C M. Effect of Oscillations During Extrusion on Rheology and Mechanical Properties of Polymers[J]. Advances in Polymer Technology, 1990, 10(1): 31-45
[12] Jiang Long, Shen Kai zhi. A mandrel-rotating die to produce high-hoop-strength HDPE pipe by self-reinforcement[J].Journal of Applied Polymer Science, 1998, 69(2): 323-328
[13] Wong C M, Chen C H. Flow of Thermoplastics in an Annular Die Under Parallel Oscillation[J]. Polymer Engineering and Science, 1990, 30(24): 1374-1384
[14]瞿金平.电磁动态塑化挤出方法及设备[P].中国: 9010103410, 1992-11-25
[13] David B.塑料混合工艺及设备[M].詹茂盛.北京:化学工业出版社, 2002
[16] Serafim Bakalis. Velocity distributions and volume flow rates in the nip and translational regions of a co-rotating/self-wiping/twin-screw extruder[J]. Journal of Food Engineering, 2002, 5(4): 273-282
[17]刘廷华.双螺杆挤出可视化实验与非充满固体输送及熔融理论研究[D].北京:北京化工大学博士研究生学位论文, 1995
[18] Jassen L P B M.双螺杆挤出[M].耿孝正.北京:轻工业出版社, 1987
[19] Lagendijk R P, Hogt A H, Gotsis A D. Peroxydicarbonate modification of polypropylene and extensional flow properties[J]. Polymer, 2001, 42(25): 10035-10043
[20]李笑喃,刘鹏波.聚丙烯熔体拉伸流变行为的研究[J].塑料工业, 2007, 35(3):45
[21] Sabol, Baird. Morphology in blends of thermotropic liquid crystalline polymer and polypropylene[J]. International Polymer Processing, 1995, 10(2): 124-136
[22] Keith Luker. Summary result of a novel single screw compounder[A]. Society of Plastics Engineers Annual Technical Conference: Plastics Encounter at ANTEC 2007, Conference Proceeding v1, 2007
[23] Carrot C, Guillet J, May J F. Molding of the conveying of Solid Polymer in the Feeding Zone of Intermeshing Co-rotating Twin Screw Extruder[J]. Polymer Engineering and Science, 1993, 33(11): 572-580
[24]周彦豪.高分子材料加工流变学[M].北京:北京化工学院, 1983
[25]耿孝正.塑料混合及连续混合设备[M].北京:中国轻工业出版社, 2008: 45-64
[26] Lca Manas-Zloczower, Z Tadmor. Mixing and Compounding of Polymers: Theory and Practice[M]. New York, 1994
[27] Paul D R.聚合物共混物:组成与性能[M].殷敬华.北京:科学出版社, 2004: 364-366
[28] Santana1 O O, Müllerl A J. Homogeneous nucleation of the dispersed crystallisable component of immiscible polymer blends[J]. Polymer Bulletin, 1994, 32(4): 471-477
[29] Bentley B J, Leal L G. An experimental investigation of drop deformation and breakup in steady, two-dimensional linear flows[J]. Journal of Fluid Mechanics, 1986, 167:241-283
[30] Elemans P H M, Bos H L, Janssen J M H. Transient phenomena in dispersive mixing[J]. Chemical Engineering Science, 1993, 48(2): 267-276
[31] Oswald, Menges G. Materials Science of polymers for engineers[M].Hanser, Munish, 1995
[32]祝卫国,汪传生.单螺杆挤出机分散混炼的改进[J].特种橡胶制品, 2003,24(4): 31-34
[33] Grace H P. Dispersion phenomena in high-viscosity immiscible fluid systems and application of static mixers as dispersion devices in such systems[J]. Chemical Engineering Communications, 1982, 14(3): 225-277
[34] Lagnado R R, Leal L G. The stability of two-dimensional linear flows[J]. Physics of Fluids, 1984, 27(5): 1094
[35] Stone H A. Dynamics of Drop Deformation and Breakup in Viscous Fluids[J]. Annual Review of Fluid Mechanics, 1984, 26(4): 65-102
[36] Rallison J M. The deformation of small viscous drops and bubbles in shear flows[J]. Annual Review of Fluid Mechanics, 1984, 16: 45-46
[37] Janseen J M H, Mejijer H E H. Droplet Breakup Mechanisms:Stepwise Equilibrium Versus Transient Dispersion[J]. Journal of Rheology, 1993, 37(4): 597-608
[38] Kang J,Simth T G. Study of Breakup Mechanisms in Cavity Flow[J]. AICHE Journal, 1996, 42(3): 649-659
[39] Scott C E, Macosko C W. Model Experiments Concerning Morphology Development during the Initial Stages of Polymer Blending[J]. Polymer Bulletin,1991, 26(3): 341-348
[40] Delpilar M, Noriega E.挤出过程的问题分析及解决方案[M].北京:化学工业出版社, 2003: 90-92
[41] Rauwendaal C.塑料挤出[M].北京:中国轻工业出版社, 1996: 235-244
[42] Han C D.聚合物加工流变学[M].北京:科学出版社, 1985
[43] Gramann P J, Davis B A,Osswald T A. A New Dispersive and Distributive Static Mixer for the Compounding of Highly Viscous Materials[A]. ANTEC Conference, New York, 1999
[44] Suzaka Y, Ooita. Mixing Device[P]. USP: 4334783, 1982-06-13
[45] Lechoslaw, Utracki A, Pierrofonds. Extensional Flow Mixer[P]. USP: 5451106, 1995-09-19
[46]黄磊,欧相麟.拉伸流场对聚合物填充体系的分散混合作用[J].中国塑料, 2006, 20(9): 54-58.
[47]卜海涛,肖方成,欧相麟.拉伸流场对PP/纳米CaCO3填充体系分散混合的影响[J].塑料工业, 2008, 36(11): 35-38
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[49]岑丹涛.叶片泵单螺杆挤出机固体强制输送特性研究[D].广州:华南理工大学硕士研究生学位论文, 2008
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