分散相含量对乙烯-醋酸乙烯酯共聚物/聚丙烯原位微纤复合材料微纤形态、结晶行为及流变和力学性能的影响
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摘要
利用微纳层叠共挤出装置成功制得EVA/PP原位微纤复合材料(MFCs),并对其微纤形态、力学性能、结晶性能和流变行为进行了研究。结果表明:PP在EVA中能够形成微纤,且随PP含量增加,直径较大的微纤数量显著增多,MFCs的储能模量(G′)和损耗模量(G″)都相应增大。且当PP含量低于10%(质量分数,下同)时,复合材料体系是部分相容的,但当PP含量超过10%时,体系发生相分离现象。PP微纤能够有效提高EVA的拉伸强度。当PP含量为20%时,拉伸强度最大,为16.71MPa,比纯EVA树脂提高了42.9%。差示扫描量热法(DSC)测试显示PP微纤会阻碍EVA的结晶行为,使MFCs的结晶度降低。
A series of ethylene-vinyl acetate copolymer/polypropylene(EVA/PP)in-situ microfibrillar composites(MFCs)differed in dispersed phase(i.e.PP)content were prepared using a multistage stretching extruder with an assembly of laminatingmultiplying elements(LMEs),and the products' microfibers morphology,crystallization behaviors,mechanical and dynamic rheological performances were studied.The results showed that PP could form microfibers in situ in EVA,and more PP content would lead to obviously more large-diameter microfibers and higher storage modulus(G′)and loss modulus(G″)of the MFCs.The systems with PP contents below 10 wt% were partially compatible,while the phase separation occurred in systems with PP contents over10 wt%.PP microfibers could enhance the tensile performance of EVA effectively,as the EVA/20 wt%PP MFCs owned the maximum tensile strength of 16.71 MPa,which was 42.9% higher than that of pure EVA.We also observed an obstructive effect of PP microfibers on the crystallization behavior of EVA,which consequently attenuates the crystallinity of the MFCs.
A series of ethylene-vinyl acetate copolymer/polypropylene(EVA/PP)in-situ microfibrillar composites(MFCs)differed in dispersed phase(i.e.PP)content were prepared using a multistage stretching extruder with an assembly of laminatingmultiplying elements(LMEs),and the products' microfibers morphology,crystallization behaviors,mechanical and dynamic rheological performances were studied.The results showed that PP could form microfibers in situ in EVA,and more PP content would lead to obviously more large-diameter microfibers and higher storage modulus(G′)and loss modulus(G″)of the MFCs.The systems with PP contents below 10 wt% were partially compatible,while the phase separation occurred in systems with PP contents over10 wt%.PP microfibers could enhance the tensile performance of EVA effectively,as the EVA/20 wt%PP MFCs owned the maximum tensile strength of 16.71 MPa,which was 42.9% higher than that of pure EVA.We also observed an obstructive effect of PP microfibers on the crystallization behavior of EVA,which consequently attenuates the crystallinity of the MFCs.
引文
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17 Dong J H,Qi Y H,Wei L Q,et al.Research progress on in-situ fibrillation technology[J].Modern Chemical Industry,2015,35(2):23(in Chinese).董珈豪,戚远慧,韦良强,等.原位成纤技术研究进展[J].现代化工,2015,35(2):23.
18 Wang J,Zhang X,Zhao T,et al.Morphologies and properties of polycarbonate/polyethylene in situ microfibrillar composites prepared through multistage stretching extrusion[J].Journal of Applied Polymer Science,2014,131(131):2113.
19 Zhang D,He M,Qin S,et al.Rheology characterization,dynamic mechanical,thermal,and mechanical properties of LGF/TPU/PBT/PTW composites[J].Polymer Composites,2016,DOI:10.1002/PC.
20 Xu E H,Guo Q C,Chen L,et al.Effect of the desperation of hectorite on the rheological behaviors of nylon 6nanocomposites[J].Polymer Materials Science&Engineering,2015,31(9):69(in Chinese).许恩惠,郭前程,陈磊,等.锂皂石分散状态对尼龙6纳米复合材料流变行为的影响[J].高分子材料科学与工程,2015,31(9):69.
2 Yang G,Li Q C,Li Y M,et al.Capability and application of poly(ethylene-co-vinyl acetate)(EVA)[J].Chinese Journal of Colloid&Polymer,2009,27(3):45(in Chinese).杨钢,李启成,李雅明,等.乙烯-乙酸乙烯酯共聚物(EVA)的性能及应用[J].胶体与聚合物,2009,27(3):45.
3 Li X F,Huang L G,Hu H W,et al.Studies on rheological properties of ethylenevinyl-acetate copolymer[J].Polymer Materials Science&Engineering,2007,23(6):124(in Chinese).李新法,黄灵阁,胡宏伟,等.乙烯-醋酸乙烯共聚物的流变性能[J].高分子材料科学与工程,2007,23(6):124.
4 Fu M.Research of EVA modified by blending[D].Guangzhou:Guangdong University of Technology,2014(in Chinese).付蒙.EVA的共混改性研究[D].广州:广东工业大学,2014.
5 Gabor Kiss.In situ composites:Blends of isotropic polymers and thermotropic liquid crystalline polymers[J].Polymer Engineering&Science,1987,27(6):410.
6 Weiss R A,Wansoo Huh,Nicolais L.Novel reinforced polymers based on blends of polystyrene and a thermotropic liquid crystalline polymer[J].Polymer Engineering&Science,1987,27(9):684.
7 Li Z M,Quan H,Yang M B,et al.Research advance in thermoplastics/thermoplastics in-situ microfibrillar reinforced blends[J].China Plastics,2005(10):1(in Chinese).李忠明,权慧,杨鸣波,等.TP/TP原位微纤化共混物的研究进展[J].中国塑料,2005(10):1.
8 Huang Ying,He Yadong,Ding Weidan,et al.Improved viscoelastic,thermal,and mechanical properties of in situ microfibrillar polypropylene/polyamide 6,6composites via direct extrusion using a triple-screw extruder[J].RSC Advances,2017,7(9):5030.
9 Jayanarayanan K,Sabu Thomas,Kuruvilla Joseph.Morphology,static and dynamic mechanical properties of in situ microfibrillar composites based on polypropylene/poly(ethylene terephthalate)blends[J].Composites Part A Applied Science&Manufacturing,2008,39(2):164.
10 Xu H S,Li Z M,Yang S Y,et al.Rheological behavior comparison between PET/HDPE and PC/HDPE microfibrillar blends[J].Polymer Engineering&Science,2005,45(9):1231.
11 Yi X,Xu L,Wang Y L,et al.Morphology and properties of isotactic polypropylene/poly(ethylene terephthalate)in situ microfibrillar reinforced blends:Influence of viscosity ratio[J].European Polymer Journal,2010,46(4):719.
12 Sun X,Yu Q,Shen J,et al.In situ microfibrillar morphology and properties of polypropylene/polyamide/carbon black composites prepared through multistage stretching extrusion[J].Journal of Materials Science,2013,48(3):1214.
13 Li T,Li J,Zhang Y Q,et al.Structure and properties of(PP+EVOH)PP barrial prepared by microlayer coextrusion[J].Acta Polymerica Sinica,2009,1(12):1226(in Chinese).李婷,李姜,张玉清,等.微层共挤出(PP+EVOH)/PP阻隔材料的结构与性能研究[J].高分子学报,2009,1(12):1226.
14 Wang M,Guo S Y.Stratified fuctional composites with micrometer or nanometer scale thickness prepared by a new processing technology[J].Engineering Plastics Application,2008,36(11):83(in Chinese).王明,郭少云.微纳多层功能复合材料的制备新技术[J].工程塑料应用,2008,36(11):83.
15 Dong J,Qi Y,Sun J,et al.In situ fibrillation of poly(trimethylene terephthalate)in polyolefin elastomer through multistage stretching extrusion[J].Journal of Applied Polymer Science,2016,133(33):43797.
16 Li Z M,Yang W,Xie B H,et al.Theoretical consideration of the droplet-fiber transition in blends and preparation of in-situ microfiber-contained polymer blends[J].Polymer Materials Science&Engineering,2003,19(5):168(in Chinese).李忠明,杨伟,谢邦互,等.GEP/PO原位微纤化共混物的制备[J].高分子材料科学与工程,2003,19(5):168.
17 Dong J H,Qi Y H,Wei L Q,et al.Research progress on in-situ fibrillation technology[J].Modern Chemical Industry,2015,35(2):23(in Chinese).董珈豪,戚远慧,韦良强,等.原位成纤技术研究进展[J].现代化工,2015,35(2):23.
18 Wang J,Zhang X,Zhao T,et al.Morphologies and properties of polycarbonate/polyethylene in situ microfibrillar composites prepared through multistage stretching extrusion[J].Journal of Applied Polymer Science,2014,131(131):2113.
19 Zhang D,He M,Qin S,et al.Rheology characterization,dynamic mechanical,thermal,and mechanical properties of LGF/TPU/PBT/PTW composites[J].Polymer Composites,2016,DOI:10.1002/PC.
20 Xu E H,Guo Q C,Chen L,et al.Effect of the desperation of hectorite on the rheological behaviors of nylon 6nanocomposites[J].Polymer Materials Science&Engineering,2015,31(9):69(in Chinese).许恩惠,郭前程,陈磊,等.锂皂石分散状态对尼龙6纳米复合材料流变行为的影响[J].高分子材料科学与工程,2015,31(9):69.