聚苯乙烯基发泡木塑复合材料的制备和性能
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摘要
本文采用偶氮二甲酰胺作为发泡剂、木粉和聚苯乙烯树脂为主要原料,通过自由发泡挤出成型法制备聚苯乙烯基发泡木塑复合材料。研究了木粉粒径和成核剂对泡孔形态、泡孔分布、力学性能和表观密度的影响；偶联剂对复合材料界面相容性的改善；模口的温度和熔体粘度的关系；弹性体SBS对复合材料缺口冲击强度的影响；聚乙烯含量对聚乙烯-聚苯乙烯基发泡木塑复合材料力学性能的影响。
结果表明：较小粒径(如80-120目)的木粉能够赋予复合材料更好的泡孔形态、更大的泡孔、密度、更均匀的泡孔分布和更高的力学强度(与采用40-80目木粉的复合材料相比,弯曲强度和拉伸强度分别提高了21.9%和47%)；1200目滑石粉是适宜的成核剂,能有效地提高泡孔的密度,降低复合材料的表观密度；偶联剂马来酸酐接枝聚苯乙烯的添加,不仅改善了发泡复合材料的力学性能,而且使泡孔的平均直径更小,而加入硅烷偶联剂的发泡复合材料的泡孔平均直径较大,力学性能表现较差,但具有较低的表观密度；随着模口温度的升高聚合物熔体的粘度下降,聚合物的自由体积增大,导致复合材料的泡孔尺寸增长和泡孔密度提高,最终降低了复合材料的表观密度；弹性体SBS能够提高复合材料的缺口冲击强度,(SBS含量为10%时,复合材料的缺口冲击强度最高)同时也降低了复合材料的弯曲和拉伸强度；随着聚乙烯含量的不断上升复合材料的弯曲和拉伸强度均有提高,并且泡孔形态也得到改善,当聚乙烯含量超过30%时,复合材料各方面的性能均开始下降。
In this paper the foamed polystyrene (PS) based wood plastic composites, which using azodicarbonamide (AC) as blowing agent, wood flour and PS as main materials, were prepared by free foaming method. The effects of wood flour particle size and nucleating agent on cell morphology, cell distribution and mechanical properties of the composites; effects of coupling agent on the interface compatibility; the relationship between temperature of mold and melt; effects of elastomer SBS on notched impact strength of the composites; effects of content of polyethylene on the mechanical properties of the polyethylene/polystyrene/wood composites were studied
The results showed that when the wood flour particle size is 80-120 mesh, the composites have better cell morphology, higher cell density, smaller cell size, much more uniform cell distribution, and the flexural strength and tensile strength were increased by 21.9% and 47% compared to the composites containing 40-80 mesh wood flour. The 1200 mesh talc was a promising nucleating agent, which could effectively increase the cell density and decrease the apparent density of composites. For the foamed composites with PS-g-MAH, the mechanical properties were improved, and the average diameter of the cell became much smaller, and for that with the silane coupling agent, the average diameter of the cell was bigger, and the mechanical properties behaved poorly, but the apparent density was lower. As the die temperature increased, the viscosity of the polymer melt decreased, and the free volume increased, thus result in the increasing of cell dimension and cell density of the composites, which finally decreased the apparent density of the composites; SBS can enhance the notched impact strength of the composites (when SBS content was 10%,the notched impact strength of composites was best), but it will decrease the flexural strength and tensile strength at the same time; with increasing the amount of the polyethylene, the flexural strength and tensile strength of the composites both enhanced, and the morphology of the cell also improved, when polyethylene content was more than 30%, all the performances of the composites decreased
结果表明：较小粒径(如80-120目)的木粉能够赋予复合材料更好的泡孔形态、更大的泡孔、密度、更均匀的泡孔分布和更高的力学强度(与采用40-80目木粉的复合材料相比,弯曲强度和拉伸强度分别提高了21.9%和47%)；1200目滑石粉是适宜的成核剂,能有效地提高泡孔的密度,降低复合材料的表观密度；偶联剂马来酸酐接枝聚苯乙烯的添加,不仅改善了发泡复合材料的力学性能,而且使泡孔的平均直径更小,而加入硅烷偶联剂的发泡复合材料的泡孔平均直径较大,力学性能表现较差,但具有较低的表观密度；随着模口温度的升高聚合物熔体的粘度下降,聚合物的自由体积增大,导致复合材料的泡孔尺寸增长和泡孔密度提高,最终降低了复合材料的表观密度；弹性体SBS能够提高复合材料的缺口冲击强度,(SBS含量为10%时,复合材料的缺口冲击强度最高)同时也降低了复合材料的弯曲和拉伸强度；随着聚乙烯含量的不断上升复合材料的弯曲和拉伸强度均有提高,并且泡孔形态也得到改善,当聚乙烯含量超过30%时,复合材料各方面的性能均开始下降。
In this paper the foamed polystyrene (PS) based wood plastic composites, which using azodicarbonamide (AC) as blowing agent, wood flour and PS as main materials, were prepared by free foaming method. The effects of wood flour particle size and nucleating agent on cell morphology, cell distribution and mechanical properties of the composites; effects of coupling agent on the interface compatibility; the relationship between temperature of mold and melt; effects of elastomer SBS on notched impact strength of the composites; effects of content of polyethylene on the mechanical properties of the polyethylene/polystyrene/wood composites were studied
The results showed that when the wood flour particle size is 80-120 mesh, the composites have better cell morphology, higher cell density, smaller cell size, much more uniform cell distribution, and the flexural strength and tensile strength were increased by 21.9% and 47% compared to the composites containing 40-80 mesh wood flour. The 1200 mesh talc was a promising nucleating agent, which could effectively increase the cell density and decrease the apparent density of composites. For the foamed composites with PS-g-MAH, the mechanical properties were improved, and the average diameter of the cell became much smaller, and for that with the silane coupling agent, the average diameter of the cell was bigger, and the mechanical properties behaved poorly, but the apparent density was lower. As the die temperature increased, the viscosity of the polymer melt decreased, and the free volume increased, thus result in the increasing of cell dimension and cell density of the composites, which finally decreased the apparent density of the composites; SBS can enhance the notched impact strength of the composites (when SBS content was 10%,the notched impact strength of composites was best), but it will decrease the flexural strength and tensile strength at the same time; with increasing the amount of the polyethylene, the flexural strength and tensile strength of the composites both enhanced, and the morphology of the cell also improved, when polyethylene content was more than 30%, all the performances of the composites decreased
引文
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[7]常怀春,张来启,宋楠楠,孙青峰,许秋菊,微发泡PVC／木粉复合仿木材料的制备及工艺研究[J].辽宁大学学报,2008,35(2)：139-142
[8]宋永明,肖泽芳,王清文,木粉／再生聚苯乙烯复合材料的动态机械性质分析[J].东北林业大学报,2004,32(5)：29-31
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[10]杨治伟,王国全,侯宇峰等.纳米氧化锌／AC复合发泡剂在PP发泡中的应用研究[J].塑料,2003,32(3)：25-28.
[11]陈立军,陈焕钦.活性物质对AC发泡剂性能的影响研究及其活化机理[J].绝缘材料,2005,1：30-32.
[12]王清文,王伟宏,郭垂根等.木塑复合材料与制品.北京：化学工业出版社,2007：73-75.
[13]OksmanK,Clemons C. Mechanical, Properties and Morphology of Impact Modified Pol-ypropylene-Wood Flour Composites[J].Journal of Applied Polymer Science,1998(67): 1503-1506
[14]周兴平,谢孝林,LIR.KY,硅烷偶联剂处理对SF／PP结构和性能的影响[J].木材科学与工艺,2005,13(3)：329-333
[15]FemandaMB, Coutinho TH, Polypropylene-Wood Fiber Composites:Effect of Treatment and Mixing Conditions on Mechanical Properties [J].Journal of Applied Polymer Science, 1997(65):1227-1235
[16]王君,木塑复合材料界面化学及材料性能研究.北京林业大学硕士论文
[17]秦特夫,阎吴鹏,木材表面非极性化原理的研究-木材乙酰化过程中化学官能团的变化[J].木材工业,1999,13(4)：17-23
[18]Mankikadan R C, Nair S M, Sabu T, et al, Tensile Properties of Short Sisal Fiber Reinfor-ced Polystyrene Composites[J].Journal of Applied Polymer Science,1996(60):1483-1497
[19]Maldas D, Kokta B V, Daneault C, Influence of Coupling and Treatments on the Mechanical Properties of Cellulose Fiber-Polystyrene Composites[J].Journal of Applied Polymer Science,1989(37):751-775
[20]姜峰,木塑复合材料增韧性能研究.中国林业科学院论文
[21]L A Utraeki, T V Khanh, I S Miles et al. Multicompoment Polymer Systems[J].Polymer science and Technology Series,1992(70)
[22]王经武.塑料改性技术.北京：化学工业出版社,2004：261-289
[23]季根忠,刘维民,齐陈泽等.刚性粒子增韧聚合物机理研究[J].高分子通报,2005,1：50-53
[24]刘英俊,刘伯元.塑料填充改性.北京：中国轻工业出版社,1998：121-128
[25]漆宗能,马永梅,张世民等.纳米塑料[J].石化技术与应用,2001,19(5)：336-339
[26]罗忠富,黄锐.无机纳米粒子填充聚合物的研究进展[J]功能高分子学报,1998,11(4)：555-560
[27]N M Stark, R E Rowlands. Effects of Wood Fiber Characteristics On Mechanical Prop-erties Of Wood/Polypropylene Composites[J].Wood and Fiber Science,2003,35(2):167-174
[28]史学涛,弹性体包覆无机刚性粒子增韧聚丙烯研究.西北工业硕士论文
[29]白晓艳,低发泡PVC／木粉研究.东北林业大学硕士论文
[30]高达利.微孔泡沫塑料发泡过程及以纳米粒子为载体插层制备微发泡剂的研究.北京化工大学硕士论文.
[31]吴舜英,滕建新,李及珠,刘小平.微孔发泡塑料动态成核机理的研究[J].中国塑料,2001,15(2)：43
[32]Colton J S, Suh N P[J].Polymer,1987,27:500.
[33]Wang J, Cheng X G, Yuan MJ, et al[J].Polymer,2001,42:8265.
[34]Wang J, Cheng X G, Zheng XJ, et al[J].Polymer,2003,41:368.
[35]顾书英,任杰,朱立华,低发泡PS熔体流变特性及其制品泡孔结构[J].建筑材料学报,2002,5(4)：342-346
[36]John Z.LU, Qinglin Wu,Ioan Negulescu,Wood-Fiber/High Density Polyethylene Compo-sites:Coupling Agent Performance[J].Applied Polymer Science,2005,96:93-102
[37]宋永明,木粉／再生聚苯乙烯复合材料的增韧改性研究.东北林业大学硕士论文.2004.
[38]Magnus Bengtsson, Nicole M.Stark. Durability and mechanical properties of silane cross-linked [J]. Composites Science and Technology.2007,67:2728-2738
[39]翟文涛,余坚,何嘉松,超临界流体制备微发泡聚合物材料的研究进展[J].高分子通报,2009,3：1-10
[40]李兰杰,刘得志,木粉粒径对木塑复合材料性能的影响[J].现代塑料加工,2005,17(5)：21-24
[41]于慧洁,郭奕崇,信春玲,何亚东,聚苯乙烯微发泡挤出成型研究[J].塑料,2007,36(5)：66-70
[42]周持兴.聚合物流变实验与应用.上海：上海交通大学出版社,2003：52～56
[2]温安华,薛平,贾明印,微发泡木塑复合材料的研究进展[J].塑料工业,2006,34(6)：1-4
[3]Doroudiani S,Chaffey C E,Kortschot M T,Polymer[J].2002,40(8):723
[4]Zhou J H, Hanna M,Starch/Staerke[J].2004,56(10):484
[5]Matnana L.M, Mengelogln F.Microcellula foaming of impact-modlifier in rigid PVC wood-fiber composites [J]. Journal of Vinyl Additive Technology 2001,7(2):67～75.
[6]H.Lin,S.Minda,Z.Chinoen. Mechanical characterization of microcellular foaming PVC/W-ood-flour composites [J]. Polym Research,2001,8:241.
[7]常怀春,张来启,宋楠楠,孙青峰,许秋菊,微发泡PVC／木粉复合仿木材料的制备及工艺研究[J].辽宁大学学报,2008,35(2)：139-142
[8]宋永明,肖泽芳,王清文,木粉／再生聚苯乙烯复合材料的动态机械性质分析[J].东北林业大学报,2004,32(5)：29-31
[9]Rizvi G, Matuana L M, Polymer[J].2000,40(10):21-24
[10]杨治伟,王国全,侯宇峰等.纳米氧化锌／AC复合发泡剂在PP发泡中的应用研究[J].塑料,2003,32(3)：25-28.
[11]陈立军,陈焕钦.活性物质对AC发泡剂性能的影响研究及其活化机理[J].绝缘材料,2005,1：30-32.
[12]王清文,王伟宏,郭垂根等.木塑复合材料与制品.北京：化学工业出版社,2007：73-75.
[13]OksmanK,Clemons C. Mechanical, Properties and Morphology of Impact Modified Pol-ypropylene-Wood Flour Composites[J].Journal of Applied Polymer Science,1998(67): 1503-1506
[14]周兴平,谢孝林,LIR.KY,硅烷偶联剂处理对SF／PP结构和性能的影响[J].木材科学与工艺,2005,13(3)：329-333
[15]FemandaMB, Coutinho TH, Polypropylene-Wood Fiber Composites:Effect of Treatment and Mixing Conditions on Mechanical Properties [J].Journal of Applied Polymer Science, 1997(65):1227-1235
[16]王君,木塑复合材料界面化学及材料性能研究.北京林业大学硕士论文
[17]秦特夫,阎吴鹏,木材表面非极性化原理的研究-木材乙酰化过程中化学官能团的变化[J].木材工业,1999,13(4)：17-23
[18]Mankikadan R C, Nair S M, Sabu T, et al, Tensile Properties of Short Sisal Fiber Reinfor-ced Polystyrene Composites[J].Journal of Applied Polymer Science,1996(60):1483-1497
[19]Maldas D, Kokta B V, Daneault C, Influence of Coupling and Treatments on the Mechanical Properties of Cellulose Fiber-Polystyrene Composites[J].Journal of Applied Polymer Science,1989(37):751-775
[20]姜峰,木塑复合材料增韧性能研究.中国林业科学院论文
[21]L A Utraeki, T V Khanh, I S Miles et al. Multicompoment Polymer Systems[J].Polymer science and Technology Series,1992(70)
[22]王经武.塑料改性技术.北京：化学工业出版社,2004：261-289
[23]季根忠,刘维民,齐陈泽等.刚性粒子增韧聚合物机理研究[J].高分子通报,2005,1：50-53
[24]刘英俊,刘伯元.塑料填充改性.北京：中国轻工业出版社,1998：121-128
[25]漆宗能,马永梅,张世民等.纳米塑料[J].石化技术与应用,2001,19(5)：336-339
[26]罗忠富,黄锐.无机纳米粒子填充聚合物的研究进展[J]功能高分子学报,1998,11(4)：555-560
[27]N M Stark, R E Rowlands. Effects of Wood Fiber Characteristics On Mechanical Prop-erties Of Wood/Polypropylene Composites[J].Wood and Fiber Science,2003,35(2):167-174
[28]史学涛,弹性体包覆无机刚性粒子增韧聚丙烯研究.西北工业硕士论文
[29]白晓艳,低发泡PVC／木粉研究.东北林业大学硕士论文
[30]高达利.微孔泡沫塑料发泡过程及以纳米粒子为载体插层制备微发泡剂的研究.北京化工大学硕士论文.
[31]吴舜英,滕建新,李及珠,刘小平.微孔发泡塑料动态成核机理的研究[J].中国塑料,2001,15(2)：43
[32]Colton J S, Suh N P[J].Polymer,1987,27:500.
[33]Wang J, Cheng X G, Yuan MJ, et al[J].Polymer,2001,42:8265.
[34]Wang J, Cheng X G, Zheng XJ, et al[J].Polymer,2003,41:368.
[35]顾书英,任杰,朱立华,低发泡PS熔体流变特性及其制品泡孔结构[J].建筑材料学报,2002,5(4)：342-346
[36]John Z.LU, Qinglin Wu,Ioan Negulescu,Wood-Fiber/High Density Polyethylene Compo-sites:Coupling Agent Performance[J].Applied Polymer Science,2005,96:93-102
[37]宋永明,木粉／再生聚苯乙烯复合材料的增韧改性研究.东北林业大学硕士论文.2004.
[38]Magnus Bengtsson, Nicole M.Stark. Durability and mechanical properties of silane cross-linked [J]. Composites Science and Technology.2007,67:2728-2738
[39]翟文涛,余坚,何嘉松,超临界流体制备微发泡聚合物材料的研究进展[J].高分子通报,2009,3：1-10
[40]李兰杰,刘得志,木粉粒径对木塑复合材料性能的影响[J].现代塑料加工,2005,17(5)：21-24
[41]于慧洁,郭奕崇,信春玲,何亚东,聚苯乙烯微发泡挤出成型研究[J].塑料,2007,36(5)：66-70
[42]周持兴.聚合物流变实验与应用.上海：上海交通大学出版社,2003：52～56