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Bulk polymer/solvent interactions for polyethylene and EVA copolymers, below their melting temperatures

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Abstract

In this work, the Flory–Huggins parameters corresponding to the amorphous phase of a polyethylene (PE) and two ethylene–vinyl acetate (EVA) copolymers (with 18 and 33 % vinyl acetate content, respectively) samples, with different solvents have been determined below the melting temperature of the polymers, in order to quantify the bulk interactions of these polymer/solvent systems. The employed solvents were a dispersion solvent (cyclohexane), a polar solvent (vinyl acetate) and an association solvent (methanol). Initially, the inverse gas chromatography measurements allowed obtaining the retention volumes, activity coefficients and overall Flory–Huggins parameters of every polymer/solvent system. According to these parameters, in all cases, the more compatible solvent was cyclohexane, so it was selected as the probe to calculate the percentages of crystallinity at room temperature, whose results were in agreement the literature data (35 % for PE, 29 % for EVA18, and 12 % for EVA33). The percentage of crystallinity allowed determining the amorphous Flory–Huggins parameters which are the ones which take into account just the bulk interactions in a polymer/solvent mixture. The Flory–Huggins parameter results show that, to accurately study the vapor–liquid equilibrium between a polymer and a solvent (bulk interactions), when the range of studied temperatures is below the melting point of the polymer, it is crucial to calculate the amorphous contribution (χ amorphous) on the overall Flory–Huggins parameter. In the case of this study, the lower the vinyl acetate content (higher crystallinity), the higher the difference between the overall and amorphous Flory–Huggins parameters is. Analyzing the interactions between the three polymeric materials and the solvents it can be noticed that, for the most compatible solvent (cyclohexane), χ amorphous represents the less contribution, or the highest correction, to the overall Flory–Huggins parameter (around 50 % for PE and EVA18, and 79 % for EVA33, the less crystalline polymer).

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References

  1. Chanda M, Roy SK (2008) Industrial polymers, specialty polymers, and their applications, vol 74. CRC Press, Boca Raton

    Book  Google Scholar 

  2. Harper CA, Petrie EM (2003) Plastic materials and processes: a concise encyclopedia. Wiley, New York

    Book  Google Scholar 

  3. Kawahara T, Hikasa T (2005) U.S. Patent No. 6,838,517. U.S. Patent and Trademark Office, Washington DC

  4. Paricaud P, Galindo A, Jackson G (2004) Modeling the cloud curves and the solubility of gases in amorphous and semicrystalline polyethylene with the SAFT-VR approach and Flory theory of crystallization. Ind Eng Chem Res 43(21):6871–6889

    Article  CAS  Google Scholar 

  5. Mathot VBF, Pijpers FJ (1983) Heat capacity, enthalpy and crystallinity for a linear polyethylene obtained by DSC. J Therm Anal Calorim 28(1):349–358

    Article  CAS  Google Scholar 

  6. Shi XM, Zhang J, Jin J, Chen SJ (2008) Non-isothermal crystallization and melting of ethylene-vinyl acetate copolymers with different vinyl acetate contents. Express Polym Lett 2(9):623–629

    Article  CAS  Google Scholar 

  7. Brandrup J, Immergut EH, Abe A, Bloch DR (eds) (1999) Polymer handbook, vol 89. Wiley, New York

    Google Scholar 

  8. Yazici O, Cakar F, Cankurtaran O, Karaman F (2009) Determination of crystallinity ratio and some physicochemical properties of poly(4-methyl-1-pentene). J Appl Polym Sci 113:901–906

    Article  CAS  Google Scholar 

  9. Conder JR, Young CL (1979) Physicochemical measurement by gas chromatography. Wiley, New York

    Google Scholar 

  10. Al-Ghamdi A, Melibari M, Al-Saigh ZY (2005) Characterization of environmentally friendly polymers by inverse gas chromatography: I amylopectin. J Polym Environ 13(4):319–327

    Article  CAS  Google Scholar 

  11. Rackett HG (1970) Equation of state for saturated liquids. J Chem Eng Data 15(4):514–517

    Article  CAS  Google Scholar 

  12. Tsonopoulos C (1975) An empirical correlation of second virial coefficients. AIChE J 20(2):263–272

    Article  Google Scholar 

  13. NIST Chemistry WebBook. http://webbook.nist.gov/chemistry/. Accessed July 2015

  14. Romdhane IH, Plana A, Hwang S, Danner RP (1992) Thermodynamic interactions of solvents with styrene–butadiene–styrene triblock copolymers. J Appl Polym Sci 45(11):2049–2056

    Article  CAS  Google Scholar 

  15. REPSOL-YPF catalogue. http://www.repsol.com/sa/herramientas/CatalogoQuimica/CatalogoQuimica.aspx. Accessed July 2015

  16. Gaur U, Wunderlich B (1980) The glass transition temperature of polyethylene. Macromolecules 13(2):445–446

    Article  CAS  Google Scholar 

  17. Sung YT, Kum CK, Lee HS, Kim JS, Yoon HG, Kim WN (2005) Effects of crystallinity and crosslinking on the thermal and rheological properties of ethylene vinyl acetate copolymer. Polymer 46(25):11844–11848

    Article  CAS  Google Scholar 

  18. Chen CT, Al-Saigh ZY (1989) Characterization of semicrystalline polymers by inverse gas chromatography. 1. Poly (vinylidene fluoride). Macromolecules 22(7):2974–2981

    Article  CAS  Google Scholar 

  19. Bieliński DM, Tranchida D, Lipiński P, Jagielski J, Turos A (2007) Ion bombardment of polyethylene—influence of polymer structure. Vacuum 81(10):1256–1260

    Article  Google Scholar 

  20. Anderson K (2012) Crystallinity and its impact on ethylene vinyl acetate copolymers. VitalDose Blog. http://www.vitaldose.com/blog/crystallinity-and-its-impact-on-ethylene-vinyl-acetate-copolymers/. Accessed July 2015

  21. Camacho J, Díez E, Ovejero G, Gómez L (2016) Inverse gas chromatography study of polyvinylacetate–solvent and polyethylene–solvent systems. Polym Eng Sci 56:36–43

    Article  CAS  Google Scholar 

  22. Camacho J, Díez E, Ovejero G, Díaz I (2013) Thermodynamic interactions of EVA copolymer solvent systems by inverse gas chromatography measurements. J Appl Polym Sci 128:481–486

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Grupo de Catálisis y Procesos de Separación (CyPS), Departamento de Ingeniería Química, Facultad de C. Químicas, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040, Madrid, Spain

    Javier Camacho, Eduardo Díez & Gabriel Ovejero

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  1. Javier Camacho
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  2. Eduardo Díez
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  3. Gabriel Ovejero
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Correspondence to Eduardo Díez.

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Camacho, J., Díez, E. & Ovejero, G. Bulk polymer/solvent interactions for polyethylene and EVA copolymers, below their melting temperatures. Polym. Bull. 74, 11–25 (2017). https://doi.org/10.1007/s00289-016-1694-3

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  • DOI: https://doi.org/10.1007/s00289-016-1694-3

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