Abstract
In this study, the isothermal crystallization kinetics and crystalline morphology of poly(butylene adipate-co-butylene 1,4-cyclohexanedicarboxylate) (PBAC), which refers to a copolyester containing a non-planar ring structure, were investigated by differential scanning calorimetry and polarized optical microscopy, and compared with those of neat poly(butylene 1,4-cyclohexanedicarboxylate) (PBC). The results indicate that the introduction of butylene adipate (BA) unit into PBAC did not change the intrinsical crystallization mechanism. But, the crystallization rate and ability, and equilibrium melting temperature of PBAC copolymers were reduced. All PBC and PBAC copolymers could only form high density of nucleation from melt at given supercooling, while no Maltese cross or ring-banded spherulites could be observed. PBAC copolymers with a high amount of BA unit became amorphous after quenching with liquid nitrogen from melt, while PBC and PBAC copolymers with a low amount of BA unit could still form a large amount of nuclei under the same treatment.
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References
Tserki, V.; Matzinos, P.; Pavlidou, E.; Vachliotis, D.; Panayiotou, C. Biodegradable aliphatic polyesters. part I. properties and biodegradation of poly(butylene succinate-co-butylene adipate). Polym. Degrad. Stab. 2006, 91, 367–376.
Gan, Z.; Kuwabara, K.; Abe, H.; Iwata, T.; Doi, Y. Metastability and transformation of polymorphic crystals in biodegradable poly(butylene adipate). Biomacromolecules 2004, 5, 371–378.
Xu, J.; Guo, B. H. Poly(butylene succinate) and its copolymers: research, development and industrialization. Biotechnol. J. 2010, 5(11), 1149–1163.
Gan, Z.; Abe, H.; Kurokawa, H.; Doi, Y. Solid-state microstructures, thermal properties, and crystallization of biodegradable poly(butylene succinate) (PBS) and its copolyesters. Biomacromolecules 2001, 2(2), 605–613.
Kint, D.; Munoz-Guerra, S. A review on the potential biodegradability of poly(ethylene terephthalate). Polym. Int. 1999, 48(5), 346–352.
Stein, R. S.; Misra, A. Morphological studies on polybutylene terephthalate. J. Polym. Sci. Polym. Phys. Ed. 1980, 18(2), 327–342.
Herrera, R.; Franco, L.; Rodríguez-Galán, A.; Puiggalí, J. Characterization and degradation behavior of poly(butylene adipate-co-terephthalate)s. J. Polym. Sci., Part A: Polym. Chem. 2002, 40(23), 4141–4157.
Yokouchi, M.; Sakakibara, Y.; Chatani, Y.; Tadokoro, H.; Tanaka, T. Structures of two crystalline forms of poly(buty1ene terephthalate) and reversible transition between them by mechanical deformation. Macromolecules 1975, 9, 266–273.
Kai, W.; Zhu, B.; He, Y.; Inoue, Y. Crystallization of poly(butylene adipate) in the presence of nucleating agents. J. Polym. Sci., Part B: Polym. Phys. 2005, 43(17), 2340–2351.
Yang, J.; Pan, P.; Dong, T.; Inoue, Y. Crystallization kinetics and crystalline structure of biodegradable poly(ethylene adipate). Polymer 2010, 51(3), 807–815.
Vasanthan, N.; Ozkaya, S.; Yaman, M. Morphological and conformational changes of poly(trimethylene terephthalate) during isothermal melt crystallization. J. Phys. Chem. B 2010, 114, 13069–13075.
Yang, J.; Pan, P.; Hua, L.; Xie, Y.; Dong, T.; Zhu, B.; Inoue, Y.; Feng, X. Fractionated crystallization, polymorphic crystalline structure, and spherulite morphology of poly(butylene adipate) in its miscible blend with poly(butylene succinate). Polymer 2011, 52(15), 3460–3468.
Chen, Y. A.; Wu, T. M. Crystallization kinetics of poly(1,4-butylene adipate) with stereocomplexed poly(lactic acid) serving as a nucleation agent. Ind. Eng. Chem. Res. 2014, 53, 16689–16695.
Milani, A.; Galimberti, D. Polymorphism of poly(butylene terephthalate) investigated by means of periodic density functional theory calculations. Macromolecules 2014, 47(3), 1046–1052.
Androsch, R.; Rhoades, A. M.; Stolte, I.; Schick, C. Density of heterogeneous and homogeneous crystal nuclei in poly(butylene terephthalate). Eur. Polym. J. 2015, 66, 180–189.
Cui, Z.; Qiu, Z. Thermal properties and crystallization kinetics of poly(butylene suberate). Polymer 2015, 67, 12–19.
Park, S. S.; Chae, S. H.; Im, S. S. Transesterification and crystallization behavior of poly(butylene succinate)/poly(butylene terephthalate) block copolymers. J. Polym. Sci., Part A: Polym. Chem. 1998, 36(1), 147–156.
Nikolic, M. S.; Djonlagic, J. Synthesis and characterization of biodegradable poly(butylene succinate-co-butylene adipate)s. Polym. Degrad. Stab. 2001, 74, 263–270.
Kuwabara, K.; Gan, Z.; Nakamura, T.; Abe, H.; Doi, Y. Crystalline/amorphous phase structure and molecular mobility of biodegradable poly(butylene adipate-co-butylene terephthalate) and related polyesters. Biomacromolecules 2002, 3(2), 390–396.
Cranston, E.; Kawada, J.; Raymond, S.; Morin, F. G.; Marchessault, R. H. Cocrystallization model for synthetic biodegradable poly(butylene adipate-co-butylene terephthalate). Biomacromolecules 2003, 4, 995–999.
Gan, Z.; Kuwabara, K.; Yamamoto, M.; Abe, H.; Doi, Y. Solid-state structures and thermal properties of aliphatic-aromatic poly(butylene adipate-co-butylene terephthalate) copolyesters. Polym. Degrad. Stab. 2004, 83, 289–300.
Ren, M.; Song, J.; Song, C.; Zhang, H.; Sun, X.; Chen, Q.; Zhang, H.; Mo, Z. Crystallization kinetics and morphology of poly(butylene succinate-co-adipate). J. Polym. Sci., Part B: Polym. Phys. 2005, 43(22), 3231–3241.
Shi, X. Q.; Ito, H.; Kikutani, T. Characterization on mixed-crystal structure and properties of poly(butylene adipate-co-terephthalate) biodegradable fibers. Polymer 2005, 46, 11442–11450.
Qiu, Z.; Yan, C.; Lu, J.; Yang, W.; Ikehara, T.; Nishi, T. Various crystalline morphology of poly(butylene succinate-co-butylene adipate) in its miscible blends with poly(vinylidene fluoride). J. Phys. Chem. B 2007, 111(11), 2783–2789.
Hwang, S. Y.; Jin, X. Y.; Yoo, E. S.; Im, S. S. Synthesis, physical properties and enzymatic degradation of poly(oxyethylene-b-butylene succinate) ionomers. Polymer 2011, 52(13), 2784–2791.
Ojijo, V.; Sinha Ray, S.; Sadiku, R. Role of specific interfacial area in controlling properties of immiscible blends of biodegradable polylactide and poly[(butylene succinate)-co-adipate]. ACS Appl. Mater. Interfaces 2012, 4(12), 6690–6701.
Wang, X.; Shi, J.; Chen, Y.; Fu, Z.; Shi, Y. Nonisothermal crystallization kinetics of poly(butylene adipate-co-terephthalate) Copolyester. China Pet. Process. Petrochemical Technol. 2012, 14(1), 74–79.
Dil, E. J.; Carreau, P. J.; Favis, B. D. Morphology, miscibility and continuity development in poly(lactic acid)/poly(butylene adipate-co-terephthalate) blends. Polymer 2015, 68, 202–212.
Liu, F.; Zhang, J.; Wang, J.; Liu, X.; Zhang, R.; Hu, G.; Na, H.; Zhu, J. Soft segment free thermoplastic polyester elastomers with high performance. J. Mater. Chem. A 2015, 3, 13637–13641.
Brunelle, D. J.; Jang, T. Optimization of poly(1,4-cyclohexylidene cyclohexane-1,4-dicarboxylate) (PCCD) preparation for increased crystallinity. Polymer 2006, 47(11), 4094–4104.
Berti, C.; Celli, A.; Marchese, P.; Marianucci, E.; Barbiroli, G.; Di Credico, F. Influence of molecular structure and stereochemistry of the 1,4-cyclohexylene ring on thermal and mechanical behavior of poly(butylene 1,4-cyclohexanedicarboxylate). Macromol. Chem. Phys. 2008, 209(13), 1333–1344.
Gigli, M.; Lotti, N.; Vercellino, M.; Visai, L.; Munari, A. Novel ether-linkages containing aliphatic copolyesters of poly(butylene 1,4-cyclohexanedicarboxylate) as promising candidates for biomedical applications. Mater. Sci. Eng. C Mater. Biol. Appl. 2014, 34, 86–97.
Gigli, M.; Lotti, N.; Gazzano, M.; Siracusa, V.; Finelli, L.; Munari, A.; Dalla Rosa, M. Fully aliphatic copolyesters based on poly(butylene 1,4-cyclohexanedicarboxylate) with promising mechanical and barrier properties for food packaging applications. Ind. Eng. Chem. Res. 2013, 52(36), 12876–12886.
Commereuc, S.; Askanian, H.; Verney, V.; Celli, A.; Marchese, P.; Berti, C. About the end life of novel aliphatic and aliphatic-aromatic (co)polyesters after UV-weathering: structure/degradability relationships. Polym. Degrad. Stab. 2013, 98(7), 1321–1328.
Berti, C.; Binassi, E.; Celli, A.; Colonna, M.; Fiorini, M.; Marchese, P.; Marianucci, E.; Gazzano, M.; Credico, F. D. I.; Brunelle, D. J. Poly(1,4-cyclohexylenedimethylene 1,4-cyclohexanedicarboxylate): influence of stereochemistry of 1,4-cyclohexylene units on the thermal properties. J. Polym. Sci., Part B: Polym. Phys. 2008, 46, 619–630.
Chen, L. P.; Yee, A. F.; Goetz, J. M.; Schaefer, J. Molecular structure effects on the secondary relaxation and impact strength of a series of polyester copolymer glasses. Macromolecules 1998, 31(16), 5371–5382.
Gong, Y.; Hu, C. W.; Li, H.; Huang, K. L.; Tang, W. Isomer transformation and photoluminescence in novel coordination polymers constructed from 1,4-cyclohexanedicarboxylic acid and imidazole. J. Solid State Chem. 2005, 178(10), 3152–3158.
Liu, F.; Qiu, J.; Wang, J.; Zhang, J.; Na, H.; Zhu, J. Role of cis-1,4-cyclohexanedicarboxylic acid in the regulation of the structure and properties of a poly(butylene adipate-co-butylene 1,4-cyclohexanedicarboxylate) copolymer. RSC Adv. 2016, 6(70), 65889–65897.
Qiu, J.; Liu, F.; Zhang, J.; Na, H.; Zhu, J. Non-planar ring contained polyester modifying polylactide to pursue high toughness. Compos. Sci. Technol. 2016, 128, 41–48.
Celli, A.; Marchese, P.; Sullalti, S.; Berti, C.; Barbiroli, G. Eco-friendly poly(butylene 1,4-cyclohexanedicarboxylate): relationships between stereochemistry and crystallization behavior. Macromol. Chem. Phys. 2011, 212(14), 1524–1534.
Acknowledgments
This work was financially supported by the National Natural Science Foundation of China (No. 51503217), Zhejiang Province Public Welfare Project (No. 2017C31081), the Open Project Program of MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Zhejiang University (No. 2016MSF001), and Youth Innovation Promotion Association CAS (No. 2017339).
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Isothermal Crystallization Kinetics and Crystalline Morphologies of Poly(butylene adipate-co-butylene 1,4-cyclohexanedicarboxylate) Copolymers
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Liu, F., Chi, DQ., Na, HN. et al. Isothermal Crystallization Kinetics and Crystalline Morphologies of Poly(butylene adipate-co-butylene 1,4-cyclohexanedicarboxylate) Copolymers. Chin J Polym Sci 36, 756–764 (2018). https://doi.org/10.1007/s10118-018-2051-9
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DOI: https://doi.org/10.1007/s10118-018-2051-9