利用超临界CO_2调控聚合物二元共混物的相形貌及力学性能
|
摘要
共混物的相态结构在很大程度上决定了共混物的物理性质。本工作以超临界CO_2为溶剂,通过改变工艺来调控聚丙烯(PP)/三元乙丙橡胶(EPDM)共混物的相形貌,进而利用动态力学分析(DMA)仪研究其力学行为。结果表明,利用CO_2在PP和EPDM基体中较大的溶解度和溶胀度差异,在CO_2环境下退火处理PP/EPDM,可以显著增加EPDM相体积分数,进而促使EPDM相形貌从海-岛状结构向双连续结构转变。力学性能测试结果表明,在相同EPDM含量下,真空热退火后材料性能并没有发生显著变化,而经过CO_2退火后材料的储能模量和损耗模量均有提高,这意味着材料的刚性和韧性都得到提升。
The dominating influence of phase morphology onto the final properties of polymer blends is proverbial.We herein employed supercritical carbon dioxide(CO_2)as the solution to adjust the phase morphology of polypropy-lene(PP)/ethylene-propylene-diene monomer(EPDM)blends,whose mechanical behavior was studied by using dynamic mechanical analysis(DMA).The results showed that the CO_2 treatment,owing to the carbon dioxide's solubility difference and swelling ratio difference in PP and EPDM matrices,could causes substantial increment of EPDM volume fraction,and in consequence,facilitates the transition of EPDM phase morphology in the polymer blends from an original sea-island structure to a co-continuous structure.The DMA test observed an inconspicuous performance change of the vacuum annealed blending material but definite storage modulus and loss modulus improvements of the supercritical CO_2 annealed PP/EPDM blends with the same EPDM content,indicating the promotion of both toughness and inflexibility.
The dominating influence of phase morphology onto the final properties of polymer blends is proverbial.We herein employed supercritical carbon dioxide(CO_2)as the solution to adjust the phase morphology of polypropy-lene(PP)/ethylene-propylene-diene monomer(EPDM)blends,whose mechanical behavior was studied by using dynamic mechanical analysis(DMA).The results showed that the CO_2 treatment,owing to the carbon dioxide's solubility difference and swelling ratio difference in PP and EPDM matrices,could causes substantial increment of EPDM volume fraction,and in consequence,facilitates the transition of EPDM phase morphology in the polymer blends from an original sea-island structure to a co-continuous structure.The DMA test observed an inconspicuous performance change of the vacuum annealed blending material but definite storage modulus and loss modulus improvements of the supercritical CO_2 annealed PP/EPDM blends with the same EPDM content,indicating the promotion of both toughness and inflexibility.
引文
1 Ou B L,Li D X.Latest research development of polypropylene/inorganic nanocomposites[J].Materials Review A:Review Papers,2008,22(3):32(in Chinese).欧宝立,李笃信.聚丙烯/无机纳米复合材料研究进展[J].材料导报:综述篇,2008,22(3):32.
2 Liu G Y,Qiu G X.Study on the mechanical and morphological properties of toughened polypropylene blends for automobile bumpers[J].Polymer Bulletin,2013,70(3):849.
3 He X F,Liu Y,Liu Y F,et al.Research progress of polypropylene modified by carbon nanotube[J].Materials Review A:Review Papers,2012,26(3):149(in Chinese).何小芳,刘源,刘玉飞,等.碳纳米管改性聚丙烯复合材料的研究进展[J].材料导报:综述篇,2012,26(3):149.
4 Hong Y,Qin Z,Min G,et al.Study on the phase structures and toughening mechanism in PP/EPDM/SiO2,ternary composites[J].Polymer,2006,47(6):2106.
5 Das D,Satapathy B K.Designing tough and fracture resistant polypropylene/multi wall carbon nanotubes nanocomposites by controlling stereo-complexity and dispersion morphology[J].Materials and Design,2014,54(54):712.
6 Liu G D,Qu X W,Yang L T,et al.Effect of interfacial forces and viscosity ratios on ternary polymer blends morphologies[J].Journal of Hebei University(Nature Science Edition),2000,20(1):44(in Chinese).刘国栋,瞿雄伟,杨丽庭,等.聚合物界面张力与粘度比对三元共混物形态结构的影响[J].河北大学学报(自然科学版),2000,20(1):44.
7 Menge H,Ilisch S,Aluas M.Investigation of physical-mechanical properties of PP/EPDM-compounds[J].Kautschuk Und Gummi Kunststoffe,2002,55(3):86.
8 Willemse R C,Boer A P D,Dam J V,et al.Co-continuous morphologies in polymer blends:A new model[J].Polymer,1998,39(39):5879.
9 Willemse R C.Co-continuous morphologies in polymer blends:Stability[J].Polymer,1999,40(8):2175.
10 Jin K K,Lee S H,Hwang S H.Study on the thermoplastic vulcanizate using ultrasonically treated rubber powder[J].Journal of Applied Polymer Science,2003,90(9):2503.
11 Chung T S.The limitations of using Flory-Huggins equation for the states of solutions during asymmetric hollow-fiber formation[J].Journal of Membrane Science,1997,126(1):19.
12 Kong W L,Bao J B,Wang J,et al.Preparation of open-cell polymer foams by CO2,assisted foaming of polymer blends[J].Polymer,2016,90:331.
13 Areerat S,Funami E,Hayata Y,et al.Measurement and prediction of diffusion coefficients of supercritical CO2,in molten polymers[J].Polymer Engineering&Science,2004,44(10):1915.
14 Silva A L N D,Tavares M I B,Politano D P,et al.Polymer blends based on polyolefin elastomer and polypropylene[J].Journal of Applied Polymer Science,2015,66(10):2005.
15 Zhao J,Xu Z B,Feng L F.Influence of processing conditions on percolation threshold value and morphology of co-continuous PA6/PS blend[J].Journal of Materials Engineering,2006,2006(8):36(in Chinese).赵剑,许忠斌,冯连芳.PA6/PS双连续相的临界组分比及相形态研究[J].材料工程,2006,2006(8):36.
16 Willemse R C,Boer A P D,Dam J V,et al.Co-continuous morphologies in polymer blends:A new model[J].Polymer,1998,39(24):5879.
2 Liu G Y,Qiu G X.Study on the mechanical and morphological properties of toughened polypropylene blends for automobile bumpers[J].Polymer Bulletin,2013,70(3):849.
3 He X F,Liu Y,Liu Y F,et al.Research progress of polypropylene modified by carbon nanotube[J].Materials Review A:Review Papers,2012,26(3):149(in Chinese).何小芳,刘源,刘玉飞,等.碳纳米管改性聚丙烯复合材料的研究进展[J].材料导报:综述篇,2012,26(3):149.
4 Hong Y,Qin Z,Min G,et al.Study on the phase structures and toughening mechanism in PP/EPDM/SiO2,ternary composites[J].Polymer,2006,47(6):2106.
5 Das D,Satapathy B K.Designing tough and fracture resistant polypropylene/multi wall carbon nanotubes nanocomposites by controlling stereo-complexity and dispersion morphology[J].Materials and Design,2014,54(54):712.
6 Liu G D,Qu X W,Yang L T,et al.Effect of interfacial forces and viscosity ratios on ternary polymer blends morphologies[J].Journal of Hebei University(Nature Science Edition),2000,20(1):44(in Chinese).刘国栋,瞿雄伟,杨丽庭,等.聚合物界面张力与粘度比对三元共混物形态结构的影响[J].河北大学学报(自然科学版),2000,20(1):44.
7 Menge H,Ilisch S,Aluas M.Investigation of physical-mechanical properties of PP/EPDM-compounds[J].Kautschuk Und Gummi Kunststoffe,2002,55(3):86.
8 Willemse R C,Boer A P D,Dam J V,et al.Co-continuous morphologies in polymer blends:A new model[J].Polymer,1998,39(39):5879.
9 Willemse R C.Co-continuous morphologies in polymer blends:Stability[J].Polymer,1999,40(8):2175.
10 Jin K K,Lee S H,Hwang S H.Study on the thermoplastic vulcanizate using ultrasonically treated rubber powder[J].Journal of Applied Polymer Science,2003,90(9):2503.
11 Chung T S.The limitations of using Flory-Huggins equation for the states of solutions during asymmetric hollow-fiber formation[J].Journal of Membrane Science,1997,126(1):19.
12 Kong W L,Bao J B,Wang J,et al.Preparation of open-cell polymer foams by CO2,assisted foaming of polymer blends[J].Polymer,2016,90:331.
13 Areerat S,Funami E,Hayata Y,et al.Measurement and prediction of diffusion coefficients of supercritical CO2,in molten polymers[J].Polymer Engineering&Science,2004,44(10):1915.
14 Silva A L N D,Tavares M I B,Politano D P,et al.Polymer blends based on polyolefin elastomer and polypropylene[J].Journal of Applied Polymer Science,2015,66(10):2005.
15 Zhao J,Xu Z B,Feng L F.Influence of processing conditions on percolation threshold value and morphology of co-continuous PA6/PS blend[J].Journal of Materials Engineering,2006,2006(8):36(in Chinese).赵剑,许忠斌,冯连芳.PA6/PS双连续相的临界组分比及相形态研究[J].材料工程,2006,2006(8):36.
16 Willemse R C,Boer A P D,Dam J V,et al.Co-continuous morphologies in polymer blends:A new model[J].Polymer,1998,39(24):5879.