Abstract
We successfully use a co-precipitation method to prepare inclusion complex between poly(butylene adipate) (PBA) chains (guest component) and urea molecules (host component). The PBA/urea inclusion complex is confirmed to adopt a hexagonal crystal modification with lattice parameters of a = 8.14 Å and c = 10.92 Å, and the interaction between PBA chains and urea is van der Waals force. The singly isolated PBA chains are suggested to take some gauche conformation, which is different from the all-trans conformation in β-form PBA. Furthermore, we employ the isolated PBA chains which are uniformly pre-established in a specific conformation in urea channels to regulate the crystal form of PBA for the first time. After removing the host urea molecules, the coalesced PBA chains are found to solely crystallize into α-form crystals at different coalescing temperatures. By comparing the FTIR spectra, it is found that PBA chains in inclusion complex plausibly contain some similar conformers as those in α-form crystal, which is suggested to be the intrinsic reason for the sole formation of α-form crystals. This research proves that inclusion complex can be used as a very effective method to regulate polymorphism of semi-crystalline polymers.
Similar content being viewed by others
References
Minke, R.; Blackwell, J. Polymorphic structures of poly(tetramethylene adipate). J. Macromol. Sci., Part B: Phys. 1979, 16(3), 407–417.
Minke, R.; Blackwell, J. Single crystals of poly(tetramethylene adipate). J. Macromol. Sci., Part B: Phys. 1980, 18(2), 233–255.
Gan, Z.; Kuwabara, K.; Abe, H.; Iwata, T.; Doi, Y. The role of polymorphic crystal structure and morphology in enzymatic degradation of melt-crystallized poly(butylene adipate) films. Polym. Degrad. Stab. 2005, 87(1), 191–199.
Song, Y. Y.; Ye, H. M.; Xu, J.; Hou, K.; Zhou, Q.; Lu, G. W. Stretch-induced bidirectional polymorphic transformation of crystals in poly(butylene adipate). Polymer 2014, 55(13), 3054–3061.
Pouget, E.; Almontassir, A.; Casas, M. T.; Puiggalí, J. On the crystalline structures of poly(tetramethylene adipate). Macromolecules 2003, 36(3), 698–705.
Iwata, T.; Kobayashi, S.; Tabata, K.; Yonezawa, N.; Doi, Y. Crystal structure, thermal behavior and enzymatic degradation of poly(tetramethylene adipate) solution-grown chain-folded lamellar crystals. Macromol. Biosci. 2004, 4(3), 296–307.
Noguchi, K.; Kondo, H.; Ichikawa, Y.; Okuyama K.; Washiyama, J. Molecular and crystal structure of poly(tetramethylene adipate) a form based on synchrotron X-ray fiber diffraction. Polymer 2005, 46(24), 10823–10830.
Gan, Z.; Kuwabara, K.; Abe, H.; Iwata, T.; Doi, Y. Metastability and transformation of polymorphic crystals in biodegradable poly(butylene adipate). Biomacromolecules 2004, 5(2), 371–378.
Gan, Z.; Abe, H.; Doi, Y. Temperature-induced polymorphic crystals of poly(butylene adipate). Macromol. Chem. Phys. 2002, 203(16), 2369–2374.
Woo, E. M.; Wu, M. C. Thermal and X-ray analysis of polymorphic crystals, melting, and crystalline transformation in poly(butylene adipate). J. Polym. Sci., Part B: Polym. Phys. 2005, 43(13), 1662–1672.
Liang, R.; Chen, Y. C.; Zhang, C. Q.; Yin, J.; Liu, X. L.; Wang, L. K.; Kong, R.; Feng, X.; Yang, J. J. Crystallization behavior of biodegradable poly(ethylene adipate) modulated by a benign nucleating agent: Zinc phenylphosphonate. Chinese J. Polym. Sci. 2017, 35(sn4), 558–568.
Tang, Y. R.; Xu, J.; Guo, B. H. Polymorphic behavior and enzymatic degradation of poly(butylene adipate) in the presence of hexagonal boron nitride nanosheets. Ind. Eng. Chem. Res. 2015, 54(6), 1832–1841.
Yang, J.; Liang, R.; Chen, Y.; Zhang, C.; Zhang, R.; Wang, X.; Kong, R.; Chen, Q. Using a self-assemblable nucleating agent to tailor crystallization behavior, crystal morphology, polymorphic crystalline structure, and biodegradability of poly(1,4-butylene adipate). Ind. Eng. Chem. Res. 2017, 56(28), 7910–7919.
Yang, J.; Pan, P.; Hua, L.; Zhu, B.; Dong, T.; Inoue Y. Polymorphic crystallization and phase transition of poly(butylene adipate) in its miscible crystalline/crystalline blend with poly(vinylidene fluoride). Macromolecules 2010, 43(20), 8610–8618.
Sun, X.; Pi, F.; Zhang, J.; Takahashi, I.; Wang, F.; Yan, S.; Ozaki, Y. Study on the phase transition behavior of poly(butylene adipate) in its blends with poly(vinyl phenol). J. Phys. Chem. B 2011, 115(9), 1950–1957.
Wang, H. J.; Feng, H. P.; Wang, X. C.; Guo, P. Y.; Zhao, T. S.; Ren, L. F.; Qiang, X. H.; Xiang, Y. H.; Yan, C. Effects of crystallization temperature and blend ratio on the crystal structure of poly(butylene adipate) in the poly(butylene adipate)/poly(butylene succinate) blends. Chinese J. Polym. Sci. 2014, 32(4), 488–496.
Liang, Z.; Pan, P.; Zhu, B.; Inoue, Y. Isomorphic crystallization of poly(hexamethylene adipate-co-butylene adipate): regulating crystal modification of polymorphic polyester from internal crystalline lattice. Macromolecules 2010, 43(15), 6429–6437.
Zhao, L.; Gan, Z. Effect of copolymerized butylene terephthalate chains on polymorphism and enzymatic degradation of poly(butylene adipate). Polym. Degrad. Stab. 2006, 91(10), 2429–2436.
Sun, Y.; Li, H.; Huang, Y.; Chen, E.; Zhao, L.; Gan, Z.; Yan, S. Epitaxial crystallization of poly(butylene adipate) on highly oriented polyethylene thin film. Macromolecules 2005, 38(7), 2739–2743.
Ning, Z. B.; Nielsen, R.; Zhao, L. F.; Yu, D. H.; Gan, Z. H. Influence of teflon substrate on crystallization and enzymatic degradation of polymorphic poly(butylene adipate). Chinese J. Polym. Sci. 2014, 32(9), 1243–1252.
Tang, Y. R.; Li, T.; Ye, H. M.; Xu, J.; Guo, B. H. The effect of polymer-substrate interaction on the nucleation property: comparing study of graphene and hexagonal boron nitride nanosheets. Chinese J. Polym. Sci. 2016, 34(8), 1021–1031.
Imai, M.; Kaji, K.; Kanaya, T.; Sakai, Y. Ordering process in the induction period of crystallization of poly(ethylene terephthalate). Phys. Rev. B 1995, 52(17), 12696.
Wang, C. X.; Zhang, X. C.; Song, Y. Y.; Zhou, Q.; Ye, H. M. Regulating the polymorphism behaviour and crystal transformation of poly(butylene adipate) by incorporating butylene fumarate units into the crystal lattice. RSC Adv. 2016, 6(1), 607–616.
Song, Y. Y.; Ye, H. M.; Meng, X. Y.; Zhou, Q.; Lu, G. W. Novel polymorphism behavior of poly(butylene adipate) in its nanocomposites with carbon nanofibers. RSC Adv. 2015, 5(124), 102384–102391.
Ye, H. M.; Song, Y. Y.; Meng, X.; Zhou, Q. Fractionated crystallization, polymorphism and crystal transformation of poly(butylene adipate) confined in electrospun immiscible blend fibers with polystyrene. RSC Adv. 2016, 6(61), 55961–55969.
Lu, J.; Mirau, P. A.; Tonelli, A. E. Chain conformations and dynamics of crystalline polymers as observed in their inclusion compounds by solid-state NMR. Prog. Polym. Sci. 2002, 27(2), 357–401.
Gurarslan, A.; Shen, J.; Tonelli, A. E. Behavior of poly(e-caprolactone)s (PCLs) coalesced from their stoichiometric urea inclusion compounds and their use as nucleants for crystallizing PCL melts: Dependence on PCL molecular weights. Macromolecules 2012, 45(6), 2835–2840.
Zhong, Z.; Yang, X.; Guo, B. H.; Xu, J., Huang, Y. Dissolution behavior of the crystalline inclusion complex formed by the drug diflunisal and poly(e-caprolactone). Cryst. Growth Des. 2016, 17(1), 355–362.
Ye, H. M.; Chen, X. T.; Liu, P.; Wu, S. Y.; Jiang, Z.; Xiong, B.; Xu, J. Preparation of poly(butylene succinate) crystals with exceptionally high melting point and crystallinity from its inclusion complex. Macromolecules 2017, 50(14), 5425–5433.
Ye, H. M.; Song, Y. Y.; Xu, J.; Guo, B. H.; Zhou, Q. Melting behavior of inclusion complex formed between polyethylene glycol oligomer and urea. Polymer 2013, 54(13), 3385–3391.
Chenite, A.; Brisse, F. Structural investigations of ureaaliphatic polyester adducts. Macromolecules 1993, 26(12), 3055–3061.
Smith, A. E. The crystal structure of the urea-hydrocarbon complexes. Acta Crystallogr. 1952, 5(2), 224–235.
Meaurio, E., López-Rodríguez, N.; Sarasua, J. R. Infrared spectrum of poly(L-lactide): application to crystallinity studies. Macromolecules 2006, 39(26), 9291–9301.
Meaurio, E., Zuza, E., López-Rodríguez, N.; Sarasua, J. R. Conformational behavior of poly(L-lactide) studied by infrared spectroscopy. J. Phys. Chem. B 2006, 110(11), 5790–5800.
Ma, W.; Zhang, J.; Wang, X. Formation of poly(vinylidene fluoride) crystalline phases from tetrahydrofuran/N,Ndimethylformamide mixed solvent. J. Mater. Sci. 2008, 43(1), 398–401.
Yan, C.; Zhang, Y.; Hu, Y.; Ozaki, Y.; Shen, D.; Gan, Z.; Yan, S.; Takahashi, I. Melt crystallization and crystal transition of poly(butylene adipate) revealed by infrared spectroscopy. J. Phys. Chem. B 2008, 112(11), 3311–3314.
Acknowledgments
This work was financially supported by the National Natural Science Foundation of China (No. 21674128) and China University of Petroleum (Beijing).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Ye, HM., Chen, XT., Liu, P. et al. Prominently Promoting the Formation of Poly(butylene adipate) α-Form Crystals by Coalescing from Inclusion Complex. Chin J Polym Sci 36, 866–870 (2018). https://doi.org/10.1007/s10118-018-2095-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10118-018-2095-x