Abstract
Two isomeric polyesters, poly(1,6-hexamethylene adipate) (PHA) and poly(ɛ-caprolactone) (PCL), were each blended with amorphous poly(vinyl methyl ether) (PVME) and investigated and compared in the crystalline and amorphous phases. The amorphous phase, Tg, and crystalline morphology of the PVME/PHA blend were compared with those of classical PVME/PCL. Both blend systems exhibit a similar peculiar asymmetry with positive deviation in Tg-composition relationships, and both are similarly miscible, with the PVME/PHA blend exhibiting χ12=−0.21; for PVME/PCL, χ12=−0.20. These values indicate that both blends are similarly miscible but have only quite weak interactions in the amorphous phase. Neat PHA shows a regime-I to -II transition, but neat PCL exhibits a regime-II to -III transition. On blending with PVME (at 20 wt%), both PVME/PCL and PVME/PHA blends undergo changes in crystallization temperature (Tc). Dendritic spherulites in the high-Tc (46 °C or above)-crystallized PVME/PHA blend assume a straight-stalk pattern (chrysanthemum flower pestles or banana stems). In contrast to the similarities in amorphous-phase miscibility, the crystalline phases of these two blends differ significantly. When crystallized at high Tc (46 °C or above), the PVME/PCL (20/80) blend assumes a fluffy feather-like dendritic pattern, which is dramatically different from the straight-stalk dendrites in the PVME/PHA (20/80) blend.
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References
Yam, W. Y., Ismail, J., Kammer, H. W., Schmidt, H. & Kummerlöwe, C. Polymer blends of poly(ɛ-caprolactone) and poly(vinyl methyl ether)—thermal properties and morphology. Polymer 40, 5545–5552 (1999).
Guo, Q. Completely miscible ternary blends poly(hydroxyether of bisphenal-A)-poly(vinyl methyl ether)-poly(ɛ-caprolactone). Eur. Polym. J. 26, 1329–1332 (1990).
Oudhuis, A.A.C.M., Thiewes, H. J., van Hutten, P. F. & ten Brinke, G A comparison between the morphology of semicrystalline polymer blends of poly(ɛ-caprolactone)/poly(vinyl methyl ether) and poly(ɛ-caprolactone)/(styrene-acrylonitrile). Polymer 35, 3936–3942 (1994).
Bisso, G., Casarino, P. & Pedemonte, E. Thermodynamics of polymer blends based on poly(ɛ-caprolactone)/poly(vinyl methyl ether). Macromol. Chem. Phys. 200, 376–383 (1999).
Chiang, W. J. & Woo, E. M. Comparison of glass transition and interpretation on miscibility in blends of amorphous poly(vinyl methyl ether) with highly crystallizable versus less-crystallizable polyesters. J. Polym. Sci., Polym. Phys. B 45, 2899–2911 (2007).
Brode, G. L. & Koleske, J. V. Lactone polymerization and polymer properties. J. Macromol. Sci. Part A. 6, 1109–1144 (1972).
Wang, J., Cheung, M. K. & Mi, Y. Miscibility and morphology in crystalline/amorphous blends of poly(caprolactone)/poly(4-vinylphenol) as studied by DSC, FTIR, and 13C solid state NMR. Polymer 43, 1357–1364 (2002).
Yen, K. C., Mandal, T. K. & Woo, E. M. Enhancement of bio-compatibility via specific interactions in polyesters modified with a bio-resourceful macromolecular ester containing polyphenol groups. J. Biomed. Mater. Res. Part A 86, 701–712 (2008).
Robeson, L. M., Hale, W. F. & Merriam, C. N. Miscibility of the poly(hydroxy ether) of bisphenol A with water-soluble polyethers. Macromolecules 14, 1644–1650 (1981).
Pedrosa, P., Pomposo, J. A., Calahorra, E. & Cortazar, M. On the glass transition behavior, interaction energies, and hydrogen-bonding strengths of binary poly(p-vinylphenol)/polyether blends. Macromolecules 27, 102–109 (1994).
Chakraborty, S. S., Maiti, N., Mandal, B. M. & Bhattacharyya, S. N. Miscibility and phase diagrams for poly(vinyl methyl ether) and polyacrylate blend systems. Polymer 34, 111–114 (1993).
Mandal, T. K. & Woo, E. M. Marginal miscibility and solvent-dependent phase behavior in solution-blended poly(vinyl methyl ether)/poly(benzyl methacrylate). Macromol. Chem. Phys. 200, 1143–1149 (1999).
Flory, P. J. in Principles of Polymer Chemistry (ed. Flory, P.J.) Ch. XII (Cornell University Press, Ithaca, NY, USA, 1978).
Nishi, T. & Wang, T. T. Melting point depression and kinetic point effects of cooling on crystallization in poly(vinylidene fluoride)-poly(methyl methacrylate) mixtures. Macromolecules 8, 909–915 (1975).
Ahmad, H. & Yaseen, M. in Polymer Handbook (eds Brand, J., Immergut, E.H., Grulke, E.A.) Chap.VII, 706, (Wiley, New York, USA, 1999).
Woo, E. M., Mandal, T. K. & Lee, S. C. Relationships between ringed spherulitic morphology and miscibility in blends of poly(ɛ-caprolactone) with poly(benzyl methacrylate) versus poly(phenyl methacrylate). Colloid. Polym. Sci. 278, 1032–1042 (2000).
Chen, Y. F. & Woo, E. M. Growth regimes and spherulites in thin-film poly(ɛ-caprolactone) with amorphous polymers. Colloid. Polym. Sci. 286, 917–926 (2008).
Hoffman, J. D. Regime III crystallization in melt-crystallized polymers: the variable cluster model of chain folding. Polymer 24, 3–26 (1983).
Acknowledgements
This work was financially supported by a basic research grant (NSC-95 2221 E006 183 and NSC 96-2221-E-006-099-MY3) in consecutive years from National Science Council (NSC) of Taiwan.
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Woo, E., Chou, YH., Chiang, WJ. et al. Amorphous phase behavior and crystalline morphology in blends of poly(vinyl methyl ether) with isomeric polyesters: poly(hexamethylene adipate) and poly(ɛ-caprolactone). Polym J 42, 391–400 (2010). https://doi.org/10.1038/pj.2010.18
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DOI: https://doi.org/10.1038/pj.2010.18
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