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Licensed Unlicensed Requires Authentication Published by De Gruyter June 23, 2016

Ethylene Methyl Acrylate Copolymer Toughened Poly(lactic acid) Blends: Phase Morphologies, Mechanical and Rheological Properties

L. Q. Xu, Y. Q. Zhao, R. Y. Chen, B. H. Kang and X. F. Peng


The ethylene methyl acrylate copolymer (EMA), for the first time, was melt blended with poly(lactic acid) (PLA) by a twin-screw extruder to toughen PLA. The phase morphologies, mechanical, and rheological properties of the PLA/EMA blends with six weight ratios were investigated. The results showed that the addition of EMA improves the toughness of PLA at the expense of the tensile strength, flexural strength and modulus to a certain degree, and results in the transition from brittle fracture of PLA into ductile fracture. The droplet-matrix morphology is observed in the PLA/EMA blends, in which the mean diameter of EMA droplets increases and its distribution widens gradually with increasing the EMA content. The PLA/EMA blends with three weight ratios (90/10, 80/20, and 70/30) display different characteristic linear viscoelastic properties in the low frequency region, which were investigated in terms of their complex viscosity, storage modulus, and Cole-Cole plots. The interfacial tension between the PLA and EMA is calculated using the Palierne model conducted on the 80/20 PLA/EMA blend, and the calculated result is 3.3 mN/m.

*Correspondence address, Mail address: Yong Qing Zhao, The Key Laboratory of Polymer Processing Engineering of Ministry of Education, South China University of Technology, Guangzhou 510640, Guangdong, PRC. E-mail:


Afrifah, K. A., Matuana, L. M., “Impact Modification of Polylactide with a Biodegradable Ethylene/Acrylate Copolymer”, Macromol. Mater. Eng., 295, 802811 (2010) 10.1002/mame.201000107Search in Google Scholar

Anderson, K. S., Hillmyer, M. A., “The Influence of Block Copolymer Microstructure on The Toughness of Compatibilized Polylactide/Polyethylene Blends”, Polymer, 45, 88098823 (2004) 10.1016/j.polymer.2004.10.047Search in Google Scholar

Borah, J. S., Chaki, T. K. and Sarkhel, G., “Simultaneous Effect of Organoclay and Controlled Peroxide Curing on Dielectric Properties and Flammability of LLDPE/EMA Blend”, Polym. Bull., 68, 22552267 (2012) 10.1007/s00289-012-0711-4Search in Google Scholar

Borah, J. S., Chaki, T. K., “Dynamic Mechanical, Thermal, Physico-Mechanical and Morphological Properties of LLDPE/EMA Blends”, J. Polym. Res., 18, 569578 (2011) 10.1007/s10965-010-9450-0Search in Google Scholar

Borah, J. S., Chaki, T. K., “Dynamic Rheological, Morphology and Mechanical Properties of Compatibilized LLDPE/EMA Blends”, J. Polym. Res., 18, 907916 (2011) 10.1007/s10965-010-9450-0Search in Google Scholar

Borah, J. S., Chaki, T. K., “Effect of Organo-Montmorillonite Addition on the Dynamic and Capillary Rheology of LLDPE/EMA Blends”. Appl. Clay. Sci., 5960, 4249 (2012)10.1016/j.clay.2012.02.007Search in Google Scholar

Borah, J. S., Chaki, T. K., “Exploring the Simultaneous Effect of Organoclay and Controlled Peroxide Curing on Thermal Stability of LLDPE/EMA Blend”, Thermochimica. Acta., 529, 4550 (2012) 10.1016/j.tca.2011.11.020Search in Google Scholar

Borah, J. S., Chaki, T. K., “Thermogravimetric and Dynamic Mechanical Analysis of LLDPE/EMA Blends”, J. Therm. Anal. Calorim., 105, 365373 (2011) 10.1007/s10973-011-1489-6Search in Google Scholar

Borah, J. S., Karak, N. and Chaki, T. K., “Effect of Organoclay Platelets on Morphology and Properties of LLDPE/EMA Blends”, Mat. Sci. Eng. A-Struct., 528, 28202830 (2011) 10.1016/j.msea.2010.12.067Search in Google Scholar

Borah, J. S., Naskar, K. and Chaki, T. K., “Covulcanization of LLDPE/EMA Blends Using Dicumyl Peroxide”, J. Appl. Polym. Sci., 123, 502509 (2012) 10.1002/app.34472Search in Google Scholar

Bousmina, M., “Effect of Interfacial Tension on Linear Viscoelastic Behavior of Immiscible Polymer Blends”, Rheol. Acta., 38, 251254 (1999) 10.1007/s003970050175Search in Google Scholar

Chopra, D., Kontopoulou, M., Vlassopoulos, D. and Hatzikiriakos, S. G., “Effect of Maleic Anhydride Content on the Rheology and Phase Behavior of Poly(styrene-co-maleic anhydride)/Poly(methyl methacrylate) Blends”, Rheol. Acta., 41, 1024 (2002) 10.1007/s003970200001Search in Google Scholar

Feng, F., Ye, L., “Morphologies and Mechanical Properties of Polylactide/Thermoplastic Polyurethane Elastomer Blends”, J. Appl. Polym. Sci., 119, 27782783 (2011) 10.1002/app.32863Search in Google Scholar

Ferry, J. D., “Viscoelastic Properties of Polymers”, 3rd Edition, Wiley, New York (1980)Search in Google Scholar

Graebling, D., Muller, R. and Palierne, J. F., “Linear Viscoelastic Behavior of Some Incompatible Polymer Blends In the Melt. Interpretation of Data with A Model of Emulsion of Viscoelastic Liquids”, Macromolecules, 26, 320329 (1993) 10.1021/ma00054a011Search in Google Scholar

Gupta, B., Revagade, N. and Hilborn, J., “Poly(lactic acid) Fiber: An Overview”, Prog. Polym. Sci., 32, 455482 (2007) 10.1016/j.progpolymsci.2007.01.005Search in Google Scholar

Gururajan, G., Froude, V., RiuttaS., Thomas, A., Gao, I., Samuels, S. L., Massouda, D. F., Weinberg, M. and Ogale, A. A., “Effect of Poly(ethylene methyl acrylate) Copolymer on Thermal, Morphological, and Mechanical Properties of Polypropylene Copolymer Blown Films”, J. Appl. Polym. Sci., 107, 25002508 (2008) 10.1002/app.27275Search in Google Scholar

Han, J. J., Huang, H. X., “Preparation and Characterization of Biodegradable Polylactide/Thermoplastic Polyurethane Elastomer Blends”, J. Appl. Polym. Sci., 120, 32173223 (2011) 10.1002/app.33338Search in Google Scholar

Ho, C. H., Wang, C. H., Lin, C. I. and Lee, Y. D., “Synthesis and Characterization of TPO-PLA Copolymer and its Behavior as Compatibilizerfor PLA/TPO Blends”, Polymer, 49, 39023910 (2008) 10.1016/j.polymer.2008.06.054Search in Google Scholar

Jašo, V., Cvetinov, M., Rakić, S. and Petrović, Z. S., “Bio-Plastics and Elastomers from Polylactic Acid/Thermoplastic Polyurethane Blends”, J. Appl. Polym. Sci., 131, 41104 (2014) 10.1002/app.41104Search in Google Scholar

Jiang, L., Wolcott, M. P. and Zhang, J., “Study of Biodegradable Polylactide/Poly(butylene adipate-co-terephthalate) Blends”, Biomacromolecules, 7, 199207 (2006) 10.1021/bm050581qSearch in Google Scholar PubMed

Koning, C., Van Duin, M., Pagnoulle, C. and Jerome, R., “Strategies for Compatibilization of Polymer Blends”, Prog. Polym. Sci., 23, 707757 (1998) 10.1016/S0079-6700(97)00054-3Search in Google Scholar

Li, K., Peng, J., TurngL.S. and HuangH.X., “Dynamic Rheological Behavior and Morphology of Polylactide/Poly(butylenes adipate-co-terephthalate) Blends with Various Composition Ratios”, Adv. Polym. Tech., 30, 15057 (2011) 10.1002/adv.20212Search in Google Scholar

Li, R. M., Yu, W. and Zhou, C. X., “Phase Behavior and its Viscoelastic Responses of Poly(methyl methacrylate) and Poly(styrene-co-Maleic Anhydride) Blend Systems”, Polym. Bull., 56, 455466 (2006) 10.1007/s00289-005-0499-6Search in Google Scholar

Ma, P., Hristova-Bogaerds, D. G., Goosssens, J. G. P., SpoelstraA.B., Zhang, Y. and Lemstra, P. J., “Toughening of Poly(lactic acid) by Ethylene-Co-Vinyl Acetate Copolymer with Different Vinyl Acetate Contents”, Eur. Polym. J., 48, 146154 (2012) 10.1016/j.eurpolymj.2011.10.015Search in Google Scholar

Nampoothiri, K. M., Nair, N. R. and John, R. P., “An Overview of the Recent Developments in Polylactide (PLA) Research”, Bioresource. Technol., 101, 84938501 (2010) 10.1016/j.biortech.2010.05.092Search in Google Scholar

Omonov, T. S., Harrats, C., Moldenaers, P. and Groeninckx, G., “Phase Continuity Detection and Phase Inversion Phenomena in Immiscible Polypropylene/Polystyrene Blends with Different Viscosity Ratios”, Polymer, 48, 59175927 (2007) 10.1016/j.polymer.2007.08.012Search in Google Scholar

Oyama, H. T., “Super-Tough Poly(lactic acid) Materials: Reactive Blending with Ethylene Copolymer”, Polymer, 50,747–751 (2009) 10.1016/j.polymer.2008.12.025Search in Google Scholar

Palierne, J. F., “Linear Rheology of Viscoelastic Emulsions with Interfacial Tension”, Rheol. Acta., 29, 204214 (1990) 10.1007/BF01331356Search in Google Scholar

Park, S. B., Hwang, S. Y., Moon, C. W., Im, S. S. and Yoo, E. S., “Plasticizer Effect of Novel PBS Ionomer in PLA/PBS Ionomer Blends”, Macromol. Res., 18, 463471 (2010) 10.1007/s13233-010-0512-2Search in Google Scholar

Peón, J., Vega, J. F., Del Amo, B. and Martnez-Salazer, J., “Phase Morphology and Melt Viscoelastic Properties in Blends of Ethylene/Vinyl Acetate Copolymer and Metallocene-Catalysed Linear Polyethylene”, Polymer, 44, 29112918 (2003) 10.1016/S0032-3861(03)00176-9Search in Google Scholar

Pesneau, I., Champagne, M. F. and HuneaultM.A., “PP/EMA TPV: Dynamic Cross-Linking through an Alcoholysis Reaction”, Polym. Eng. Sci., 42, 20162031 (2002) 10.1002/pen.11093Search in Google Scholar

Poomalai, P., Varghese, T. O. and Siddaramaiah, “Ethylene Methacrylate (EMA) Co-Polymer Toughened Polymethyl Methacrylate Blends: Physico-Mechanical, Optical, Thermal and Chemical Properties”, Polym. Plast. Technol., 48, 958965 (2009) 10.1080/03602550902996685Search in Google Scholar

Ren, J., Fu, H. Y., Ren, T. B. and Yuan, W. Z., “Preparation, Characterization and Properties of Binary and Ternary Blends with Thermoplastic Starch, Poly(lactic acid) and Poly(butylene adipate-co-terephthalate)”, Carbohyd. Polym., 77, 576582 (2009) 10.1016/j.carbpol.2009.01.024Search in Google Scholar

Shibata, M., Inoue, Y. and Miyoshi, M., “Mechanical Properties, Morphology, and Crystallization Behavior of Blends of Poly(L-lactide) with Poly(butylene succinate-co-L-lactate) and Poly(butylene succinate)”, Polymer, 47, 35573564 (2006) 10.1016/j.polymer.2006.03.065Search in Google Scholar

Shibata, M., Teramoto, N. and Inoue, Y., “Mechanical Properties, Morphologies, and Crystallization Behavior of Plasticized Poly(L-lactide)/Poly(butylene succinate-co-L-lactate) Blends”, Polymer, 48, 27682777 (2007) 10.1016/j.polymer.2007.02.065Search in Google Scholar

Simoes, C. L., Viana, J. C. and Cunha, A. M., “Mechanical Properties of Poly(epsilon-caprolactone) and Poly(lactic acid) Blends”, J. Appl. Polym. Sci., 112, 345352 (2009) 10.1002/app.29425Search in Google Scholar

Su, Z. Z., Li, Q. Y., Liu, Y. J., Hu, G. H. and Wu, C. F., “Compatibility and Phase Structure of Binary Blends of Poly(lactic acid) and Glycidyl Methacrylate Grafted Poly(ethylene octane)”, Eur. Polym. J., 45, 24282433 (2009) 10.1016/j.eurpolymj.2009.04.028Search in Google Scholar

Wang, R. Y., Wang, S. F., Zhang, Y., Wan, C. Y. and Ma, P. M., “Toughening Modification of PLLA/PBS Blends via In Situ Compatibilization”, Polym. Eng. Sci., 49, 2633 (2009) 10.1002/pen.21210Search in Google Scholar

Wu, D. F., Zhang, Y. S., Yuan, L. J., Zhang, M. and Zhou, W. D., “Viscoelastic Interfacial Iroperties of Compatibilized Poly(epsilon-caprolactone)/Polylactide Blend”, J. Polym. Sci., Part B: Polym. Phys., 48, 756765 (2010) 10.1002/polb.21952Search in Google Scholar

Xu, L. Q., Huang, H. X., “Relaxation Behavior of Poly(lactic acid)/Poly(butylene succinate) Blend and a New Method for Calculating its Interfacial Tension”, J. Appl. Polym. Sci., 125, E272–E277 (2012) 10.1002/app.36910Search in Google Scholar

Yeh, J. T., Tsou, C. H., Huang, C. Y., Chen, K. N., Wu, C. S. and Chai, W. L., “Compatible and Crystallization Properties of Poly(lactic acid)/Poly(butylene adipate-co-terephthalate) Blends”, J. Appl. Polym. Sci.116, 680687 (2010)Search in Google Scholar

Yokohara, T., Yamaguchi, M., “Structure and Properties for Biomass-Based Polyester Blends of PLA and PBS”, Eur. Polym. J., 44, 677685 (2008) 10.1016/j.eurpolymj.2008.01.008Search in Google Scholar

Zhang, J. W., Jiang, L. and Wolcott, M. P., “Study of Biodegradable Polyactide/Poly(butylene adipate-co-terephthalate) Blends”, Biomacromolecules, 7, 199207 (2006) 10.1021/bm050581qSearch in Google Scholar PubMed

Zhang, J. W., Liu, H. Z., “Research Progress in Toughening Modification of Poly(lactic acid)”, J. Polym. Sci., Part B: Polym. Phys., 49, 10511083 (2011) 10.1002/polb.22283Search in Google Scholar

Zhang, N. W., Wang, Q. F., Ren, J., and Wang, L., “Preparation and Properties of Biodegradable Poly(lactic acid)/Poly(butylene adipate-co-terephthalate) Blend with Glycidyl Methacrylate as Reactive Processing Agent”, J. Mater. Sci., 44, 250256 (2009) 10.1007/s10853-008-3049-4Search in Google Scholar

Zhao, Y. Q., Chen, F. Q., Wu, Z. H., Feng, Y. H. and Qu, J. P., “Morphology, Mechanical, and Rheological Properties of Poly(lactic acid)/Ethylene Acrylic Acid Copolymer Blends Processing via Vane Extruder”, J. Appl. Polym. Sci., 131, 40146 (2014) 10.1002/app.40146Search in Google Scholar

Received: 2015-09-13
Accepted: 2016-02-20
Published Online: 2016-06-23
Published in Print: 2016-07-30

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