Article
  • Study on Crystallization Kinetics and Thermal Properties of PCF-co-EF/PLA Blends

  • Han Eol Kim and Byeong Uk Nam†

  • Dept. of Applied Chemical Engineering, Korea University of Technology and Education, 1600 Chungjeol-ro, Cheonan 31253, Korea

  • PCF-co-EF와 PLA 블렌드의 결정화 거동 및 열적 물성에 관한 연구

  • 김한얼 · 남병욱†

  • 한국기술교육대학교 응용화학공학과

Abstract

The goal of this study is to develop furan based bio-composites by blending poly(cyclohexylenedimethylene furandicarboxylate-co-ethylene furandicarboxylate) (PCF-co-EF) with poly(lactic acid) (PLA). Two types of PLA are used in this study and one is neat PLA mostly consisting of L-lactide (4032D) and the other is master batched PLA with various additives (3801X). The FE-SEM results showed sub-micron dispersion of the spherical domains in the blends, which indicates compatibility between PCF-co-EF and PLA. The thermal properties and non-isothermal crystallization kinetics shows that the PLA accelerates the rate of crystallization. Dynamic mechanical analysis showed compatibility of the blends and the improvement of ductility of the composites.


본 연구는 poly(cyclohexylenedimethylene furandicarboxylate-co-ethylene furandicarboxylate)(PCF-co-EF)와 poly(lactic acid)(PLA)를 블렌드하여 furan 기반의 바이오 복합재 개발을 목표로 하였다. PLA는 순수 PLA(4032D)와 첨가제가 마스터 배치된 PLA(3801X)를 사용하였다. FE-SEM을 통해 서브 마이크론의 구형 도메인 입자들이 복합재 내에 분산되어 있는 것을 통해 상용성을 확인하였고, 열적 물성 분석 및 비등온 결정화 거동 분석을 통해 PLA가 복합재의 결정화 속도를 가속시킨다는 것을 확인하였다. 또한 DMA를 이용한 동적 물성 측정을 통해 복합재의 상용성 및 연성의 향상을 확인하였다.


Keywords: poly(cyclohexylenedimethylene furandicarboxylate-co-ethylene furandicarboxylate), poly(lactic acid), polymer blend, crystallization kinetics, thermal properties

Introduction

Recently, renewable resources have attracted attention due to growing concerns for environment and depletion of fossil-fuel resources. To keep a pace with social issues, plastic industries show their interests to replace traditional fossil-fuel based plastics with renewable resource based plastics. Among them, poly(ethylene furandicarboxylate) (PEF) has been considered as a suitable bio-alternative to replace the poly(ethylene terephthalate) (PET).1 In contrast to PET including terephthalic acid (TA) derived from fossil-fuel resources, PEF includes 2,5-furandicarboxylic acid (FDCA) which was selected by U.S Department of Energy as one of the important bio-based building blocks to play an important role in the green chemical industry.2 PEF has lower gas permeability for oxygen (O2) and carbondioxide (CO2) and easier processability related with its lower melting temperature (Tm) and higher glass transition temperature (Tg) than PET due to structural differences between FDCA and TA.3 Also, as it can be synthesized in a similar method to that of PET, it does not demand additional price when applying to PET manufacturing process. However, some drawbacks of PEF have been pointed out to its application. PEF shows brittle fracture behaviors that is caused by its rigid polymer chain and slower crystallization rate compared with that of PET. Moreover, its physical and thermal properties are still not enough to be commercialized, and its price is also not yet to be comparable to other bio-based plastics. Several researches have been proposed to solve drawbacks of PEF using long chain diol, such as propylene glycol,4 butylene glycol5-7 and hexylene glycol.8 With the incorporation of the long chain segment in the polymer chain, each furan based polyesters has a relatively low glass transition temperature, which could be considered as a brittle-to-ductile transition even if exact explanations are not mentioned. But, the longer the chain segment is, the more initial decomposition is expedited. Also, their low Tg according to chain length causes application limits in various area, and there is no effect on crystallization rate until C4 diol. Research on furan based polyesters is insufficient till now, moreover, researches on its copolymers or composites have been rarely tried. Poly(lactic acid), (PLA), is an aliphatic polyester thermoplastic that is derived from biomass through bioconversion and polymerization. It has been viewed as one of the most promising materials because of its excellent biodegradability, thermal plasticity, and superior mechanical properties comparable to those of commercial biodegradable polymers.9,10 However, the applications of PLA as common plastics have been limited due to its drawbacks, such as the inherent brittleness and poor thermal stability. Thus, many attempts have been made to obtain PLA with improved properties, and various PLA composites has been commercialized.11-13 The goal of this study is proposing a possibility of using new bio-composites based on furan based polyester as a promising alternative of fossil-based polyester. To solve some shortcomings of furan based-polyesters like slow crystallization rate, high cost and brittleness, PLA is melt blended with poly(cyclohexylenedimethylene furandicarboxylate-co-ethylene furandicarboxylate) (PCF-co-EF) which is a copolymer type of PEF. The reason for choosing PLA is its cost-effective performance compared with other commercial biodegradable polymers. Two types of PLA are used for blending; one is neat PLA mostly consisting of L-lactide and the other is master batched PLA with various additives. The neat PLA is selected for observing the compatibility and the property changes by PLA blending. Master batched PLA which has inorganic filler (talc) and additives is selected for observing the effects of inorganic filler as a crystallizer to accelerate the crystallization rate and the effects of additives as a plasticizer which is assumed to enhance the compatibility and ductility in PCF-co-EF/PLA blends system. The phase morphology, crystallization characteristics, thermal stability and relaxation transition behaviors of the blends were evaluated by field emission scanning electron microscopy (FE-SEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA).

References
  • 1. L. Wu, R. Mincheva, Y. Xu, J. M. Raquez, and P. Dubois, Biomacromolecules, 13, 2973 (2012).
  •  
  • 2. T. Werpy and G. Peterson, Top Value Added Chemicals from Biomass, U.S. Department of Energy, Washington DC, 2004.
  •  
  • 3. S. Burgess, J. Leisen, B. Kraftschik, C. Mubarak, R. Kriegel, and W. Koros, Macromolecules, 47, 1383 (2014).
  •  
  • 4. M. Vannini, P. Marchese, A. Celli, and C. Lorenzettib, Green Chem., 17, 4162 (2015).
  •  
  • 5. J. Ma, Y. Pang, M. Wang, J. Xu, H. Ma, and X. Nie, J. Mater. Chem., 22, 3457 (2012).
  •  
  • 6. J. Zhu, J. Cai, W. Xie, P. H. Chen, M. Gazzano, M. Scandola, and R. A. Gross, Macromolecules, 46, 796 (2013).
  •  
  • 7. B. Wu, Y. Xu, Z. Bu, L. Wu, B. G. Li, and P. Dubois, Polymer, 55, 3648 (2014).
  •  
  • 8. G. Z. Papageorgiou, V. Tsanaktsis, D. G. Papageorgiou, K. Chrissafis, S. Exarhopoulos, and D. N. Bikiaris, Eur. Polym. J., 67, 383 (2015).
  •  
  • 9. J. M. Raquez, Y. Habibi, M. Murariu, and P. Dubois, Prog. Polym. Sci., 38, 1504 (2013).
  •  
  • 10. L. Shen, J. Haufe, and M. K. Patel, Product Overview and Market Projection of Emerging Bio-based Plastics. PRO-BIP 2009, Final Report, Report Commissioned by European Polysaccharide Network of Excellence (EPNOE) and European Bioplastics, Group Science, Technology and Society, Universiteit Utrecht, The Netherlands, 2009.
  •  
  • 11. H. Liu and J. Zhang, J. Polym. Sci., Part B: Polym. Phys., 49, 1051 (2011).
  •  
  • 12. R. M. Taib, Z. A. Ghaleb, and Z. A. Mohd Ishak, J. Appl. Polym. Sci., 123, 2715 (2012).
  •  
  • 13. R. M. Taib, H. M. Hassan, and Z. A. Mohd Ishak, Polym. Plast. Technol., 53, 199 (2014).
  •  
  • 14. J. D. Hoffman and J. J. Weeks, J. Res. Natl. Bur. Stand. Sect A, 66, 13 (1962).
  •  
  • 15. A. Jeziorny, Polymer, 19, 1142 (1978).
  •  
  • 16. I. Aravind, A. Boumod, Y. Grohens, and S. Thomas, Ind. Eng. Chem. Res., 49, 3873 (2010).
  •  
  • 17. H. Xiao, W. Lu, and J. T. Yeh, J. Appl. Polym., 112, 3754 (2009).
  •  
  • 18. R. Elenga, R. Seguela, and F. Rietsch, Polymer, 32, 1975 (1991).
  •  
  • 19. S. Karrad, J. M. L. Cuesta, and A. Crespy, J. Matl. Sci., 33, 453 (1998).
  •  
  • 20. J. Garcia-Martinez, O. Laguna, S. Areso, and E. P. Collar, J. Appl Polym. Sci., 81, 625 (2001).
  •  
  • 21. J. D. Menczel, L. Judovits, R. B. Prime, H. E. Bair, M. Reading, and S. Swier, “Differential Scanning Calorimetry (DSC)”, in Thermal Analysis of Polymers: Fundamentals and Applications, J. D. Menczel and R. B. Prime, Editors, John Wiley & Sons Inc., Chapter 2 (2009).
  •  
  • 22. M. Liu, Q. Zhao, Y. Wang, C. Zhang, Z. Mo, and S. Cao, Polymer, 44, 2537 (2003).
  •  
  • 23. M. C. Righetti and M. Pizzoli, Macromol. Chem. Phys., 199, 2063 (1998).
  •  
  • 24. M. Avrami, J. Chem. Phys., 8, 212 (1939).
  •  
  • 25. M. Avrami, J. Chem. Phys., 9, 177 (1941).
  •  
  • 26. T. Ozawa, Polymer, 12, 150 (1971).
  •  
  • 27. J. J. Kolstad, J. Appl. Polym. Sci., 62, 1079 (1996).
  •  
  • 28. T. Wan, L. Chen, Y. Chua, and X. Lu, J. Appl. Polym. Sci., 94, 1381 (2004).
  •  
  • 29. H. Zou, L. Wang, C. Yi, and H. Gan, Polym. Int., 60, 1349 (2011).
  •  
  • 30. R. P. Chartoff, J. D. Menczel, and S. H. Dillman, “Dynamic Mechanical Analysis”, in Thermal Analysis of Polymers: Fundamentals and Applications, J. D. Menczel and R. B. Prime, Editors, John Wiley & Sons Inc., Chapter 5 (2009).
  •  
  • 31. H. R. Kim, B. U. Nam, and Y. H. Kim, WIT Transact. Eng. Sci., 88, 648 (2014).
  •  
  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 0379-153X(Print)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2023 Impact Factor : 0.4
  • Indexed in SCIE

This Article

  • 2018; 42(4): 610-619

    Published online Jul 25, 2018

  • 10.7317/pk.2018.42.4.610
  • Received on Nov 21, 2017
  • Revised on Jan 5, 2018
  • Accepted on Feb 19, 2018

Correspondence to

  • Byeong Uk Nam

  • Dept. of Applied Chemical Engineering, Korea University of Technology and Education, 1600 Chungjeol-ro, Cheonan 31253, Korea

  • E-mail: bunam@kut.ac.kr
  • ORCID:
    0000-0001-5248-7349