Abstract
The crystallization and melting behavior of polymers is of theoretical importance. In this work, poly(butylene succinate) (PBS) was selected as an example to study such behavior at low supercooling via introduction of the extended-chain crystal (ECC) of the same polymer as nucleating agent. The crystallization of PBS with its ECC as nucleating agent in a wide temperature range (90–127 °C) and the following melting behavior were studied. It is revealed that the melting point (Tm', for Tc≥113 °C) and the annealing peak temperature (Ta', for Tc=90–100 °C) show similar asymptotic behavior. Both Tm and Ta approach to a value of ca. 3.3 °C higher than the corresponding Tc when the crystallization time tc approaches the starting point. That is to say, the Hoffman-Weeks plot is parallel to Tm=Tc line. The crystallization line became parallel to the melting line when PBS was crystallized at Tc higher than 102 °C. Based on these results, we propose that the parallel relationship and the intrinsic similarity between the Ta and the Tm observed at the two ends of the Tc range could be attributed to the metastable crystals formed at the beginning of crystallization.
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References
Miyata, T.; Masuko, T. Crystallization behaviour of poly(tetramethylene succinate). Polymer 1998, 39, 1399–1404.
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, 605–13.
Park, J. W.; Kim, D. K.; Im, S. S. Crystallization behaviour of poly(butylene succinate) copolymers. Polym. Int. 0022, 51, 239–244.
Ye, H. M.; Tang, Y. R.; Xu, J.; Guo, B. H. Role of poly(butylene fumarate) on crystallization behaviour of poly(butylene succinate). Ind. Eng. Chem. Res. 2013, 52, 10682–10689.
Xu, J.; Heck, B.; Ye, H. M.; Jiang, J.; Tang, Y. R.; Liu, J.; Guo, B. H.; Reiter, R.; Zhou, D. S.; Reiter, G. Stabilization of nuclei of lamellar polymer crystals: insights from a comparison of the Hoffman-Weeks line with the crystallization line. Macromolecules 2016, 49, 2206–2215.
Hoffman, J. D. D. G. T.; Lauritzen, J. I., The rate of crystallization of linear polymers with chain folding. In Treatise on solid state chemistry, Hannay, N. B. Ed. Plenum Press, New York, 1976, Vol. 3.
Wunderlich, B., Crystal Melting. In Macromolecular physics, Academic Press, New York, 1980, Vol. 3.
Tang, Y. R.; Gao, Y.; Xu, J.; Guo, B. H. How to regulate the isothermal growth rate of polymer spherulite without changing its molecular composition? CrystEngComm 2015, 17, 6467–6470.
Toda, A.; Taguchi, K.; Nozaki, K.; Guan, X. C.; Hu, W. B.; Furushima, Y.; Schick, C. Crystallization and melting of poly(butylene terephthalate) and poly(ethylene terephthalate) investigated by fast-scan chip calorimetry and small angle X-ray scattering. Polymer 2020, 192, 122303.
Toda, A.; Taguchi, K.; Kono, G.; Nozaki, K. Crystallization and melting behaviours of poly(vinylidene fluoride) examined by fast-scan calorimetry: Hoffman-Weeks, Gibbs-Thomson and thermal Gibbs-Thomson plots. Polymer 2019, 169, 11–20.
Strobl, G. Colloquium: laws controlling crystallization and melting in bulk polymers. Rev. Mod. Phys. 2009, 81, 1287–1300.
Strobl, G. Crystallization and melting of bulk polymers: new observations, conclusions and a thermodynamic scheme. Prog. Polym. Sci. 2006, 31, 398–442.
Strobl, G. From the melt via mesomorphic and granular crystalline layers to lamellar crystallites: a major route followed in polymer crystallization? Eur. Phys. J. E 2000, 3, 165–183.
Heck, B.; Hugel, T.; Iijima, M.; Strobl, G. Steps in the formation of the partially crystalline state. Polymer 2000, 41, 8839–8848.
Strobl, G. A thermodynamic multiphase scheme treating polymer crystallization and melting. Eur. Phys. J. E 2005, 18, 295–309.
Lv, Z. Y.; Zhang, M. C.; Zhang, Y.; Guo, B. H.; Xu, J. Study on melting and recrystallization of poly(butylene succinate) lamellar crystals via step heating differential scanning calorimetry. Chinese J. Polym. Sci. 2017, 35, 1552–1560.
Yao, S. F.; Chen, X. T.; Ye, H. M. Investigation of structure and crystallization behaviour of poly(butylene succinate) by Fourier transform infrared spectroscopy. J. Phys. Chem. B 2017, 121, 9476–9485.
Wei, Z. Y.; Yu, Y.; Zhou, C.; Zheng, L. C.; Leng, X. F.; Li, Y. Relationship between melting behaviour and morphological changes of semicrystalline polymers. J. Therm. Anal. Calorim. 2017, 129, 777–787.
Charlon, S.; Delbreilh, L.; Dargent, E.; Follain, N.; Soulestin, J.; Marais, S. Influence of crystallinity on the dielectric relaxations of poly(butylene succinate) and poly[(butylene succinate)-co-(butylene adipate)]. Eur. Polym. J. 2016, 84, 366–376.
Beckingham, B. S.; Ho, V.; Segalman, R. A. Formation of a rigid amorphous fraction in poly(3-(2′-ethyl)hexylthiophene). ACS Macro. Lett. 2014, 3, 684–688.
Wei, Z. Y.; Song, P.; Zhou, C.; Chen, G. Y.; Chang, Y.; Li, J. F.; Zhang, W. X.; Liang, J. C. Insight into the annealing peak and microstructural changes of poly(L-lactic acid) by annealing at elevated temperatures. Polymer 2013, 54, 3377–3384.
Bonnet, M.; Rogausch, K. D.; Petermann, J. The endothermic “annealing peak” of poly(phenylene sulphide) and poly(ethylene terephthalate). Colloid Polym. Sci. 1999, 277, 513–518.
Alizadeh, A.; Richardson, L.; Xu, J.; McCartney, S.; Marand, H.; Cheung, Y. W.; Chum, S. Influence of structural and topological constraints on the crystallization and melting behaviour of polymers 1. Ethylene/1-octene copolymers. Macromolecules 1999, 32, 6221–6235.
Marand, H.; Alizadeh, A.; Farmer, R.; Desai, R.; Velikov, V. Influence of structural and topological constraints on the crystallization and melting behaviour of polymers 2. Poly(arylene ether ether ketone). Macromolecules 2000, 33, 3392–3403.
Alizadeh, A.; Sohn, S.; Quinn, J.; Marand, H.; Shank, L. C.; Iler, H. D. Influence of structural and topological constraints on the crystallization and melting behaviour of polymers: 3. Bisphenol A polycarbonate. Macromolecules 2001, 34, 4066–4078.
Edling, H. E.; Vincent, M.; Marand, H.; Talley, S. J.; Barr, K.; Moore, R. B.; Turner, S. R. Synthesis and crystallization behaviour of rigid copolyesters with biphenyl-4,4′-dicarboxylate and 2,6-naphthalenedicarboxylate in the main chain. J. Polym. Sci., Part B Polly. Phys. 2019, 57, 973–980.
Furushima, Y.; Toda, A.; Rousseaux, V.; Bailly, C.; Zhuravlev, E.; Schick, C. Quantitative understanding of two distinct melting kinetics of an isothermally crystallized poly(ether ether ketone). Polymer 2016, 99, 97–104.
Jariyavidyanont, K.; Androsch, R.; Schick, C. Crystal reorganization of poly(butylene terephthalate). Polymer 2017, 124, 274–283.
Schulz, M.; Seidlitz, A.; Petzold, A.; Thurn-Albrecht, T. The effect of intracrystalline chain dynamics on melting and reorganization during heating in semicrystalline polymers. Polymer 2020, 196, 122441.
Ye, H. M.; Wang, R. D.; Liu, J.; Xu, J.; Guo, B. H. Isomorphism in poly(butylene succinate-co-butylene fumarate) and its application as polymeric nucleating agent for poly(butylene succinate). Macromolecules 2012, 45, 5667–5675.
Ye, H. M.; Chen, X. T.; Li, H. F.; Zhang, P.; Ma, W. Z.; Li, B. T.; Xu, J. Industrializable and sustainable approach for preparing extended-chain crystals of biodegradable poly(butylene succinate) and their applications. Polymer 2019, 160, 93–98.
Ye, H. M.; Chen, X. T.; Liu, P.; Wu, S. Y.; Jiang, Z. Y.; Xiong, B. J.; Xu, J. Preparation of poly(butylene succinate) crystals with exceptionally high melting point and crystallinity from its inclusion complex. Macromolecules 2017, 50, 5425–5433.
Ichikawa, Y.; Kondo, H.; Igarashi, Y.; Noguchi, K.; Okuyama, K.; Washiyama, J. Crystal structures of α and β forms of poly(tetramethylene succinate). Polymer 2000, 41, 4719–4727.
Ichikawa, Y.; Kondo, H.; Igarashi, Y.; Noguchi, K.; Okuyama, K.; Washiyama, J. Crystal structures of α and β forms of poly(tetramethylene succinate). Polymer 2001, 42, 847–847.
Liu, G. M.; Zheng, L. C.; Zhang, X. Q.; Li, C. C.; Wang, D. J. Critical stress for crystal transition in poly(butylene succinate)-based crystalline-amorphous multiblock copolymers. Macromolecules 2014, 47, 7533–7539.
Liu, G. M.; Zheng, L. C.; Zhang, X. Q.; Li, C. C.; Jiang, S. C.; Wang, D. J. Reversible lamellar thickening induced by crystal transition in poly(butylene succinate). Macromolecules 2012, 45, 5487–5493.
Nikolic, M. S.; Djonlagic, J. Synthesis and characterization of biodegradable poly(butylene succinate-co-butylene adipate)s. Polym. Degrad. Stabil. 2001, 74, 263–270.
Schmidtke, J.; Strobl, G.; ThurnAlbrecht, T. A four-state scheme for treating polymer crystallization and melting suggested by calorimetric and small angle X-ray scattering experiments on syndiotactic polypropylene. Macromolecules 1997, 30, 5804–5821.
Strobl, G. R.; Schneider, M. Direct evaluation of the electron-density correlation-function of partially crystalline polymers. J. Polym. Sci., Part B: Polym. Phys. 1980, 18, 1343–1359.
Zhang, S. J.; Han, J. R.; Gao, Y.; Guo, B. H.; Reiter, G.; Xu, J. Determination of the critical size of secondary nuclei on the lateral growth front of lamellar polymer crystals. Macromolecules 2019, 52, 7439–7447.
Xu, Y. X.; Xu, J.; Sun, Y. B.; Liu, D. H.; Guo, B. H.; Xie, X. M. Crystallization behaviour of poly(butylene succinate-co-propylene succinate)s. Acta Polymerica Sinica (in Chinese) 2006, 1000–1006.
Yoo, E. S.; Im, S. S. Melting behaviour of poly(butylene succinate) during heating scan by DSC. J. Polym. Sci., Part B: Polym. Phys. 1999, 37, 1357–1366.
Wang, X. H.; Zhou, J. J.; Li, L. Multiple melting behaviour of poly(butylene succinate). Eur. Polym. J. 2007, 43, 3163–3170.
Yasuniwa, M.; Satou, T. Multiple melting behaviour of poly(butylene succinate). I. Thermal analysis of melt-crystallized samples. J. Polym. Sci., Part B: Polym. Phys. 2002, 40, 2411–2420.
Yasuniwa, M.; Tsubakihara, S.; Satou, T.; Iura, K. Multiple melting behaviour of poly(butylene succinate). II. Thermal analysis of isothermal crystallization and melting process. J. Polym. Sci., Part B: Polym. Phys. 2005, 43, 2039–2047.
Phillips, P. J.; Rensch, G. J. Crystallization studies of poly(epsilon-caprolactone). 2. Lamellar thickening and melting. J. Polym. Sci., Part B: Polym. Phys. 1989, 27, 155–173.
Cheng, S. Z. D.; Chen, J. H.; Barley, J. S.; Zhang, A. Q.; Habenschuss, A.; Zschack, P. R. Isothermal thickening and thinning processes in low-molecular-weight poly(ethylene oxide) fractions crystallized from the melt. 3. Molecular-weight dependence. Macromolecules 1992, 25, 1453–1460.
Marand, H.; Huang, Z. Y. Isothermal lamellar thickening in linear polyethylene: correlation between the evolution of the degree of crystallinity and the melting temperature. Macromolecules 2004, 37, 6492–6497.
Lee, Y. C.; Porter, R. S. Double-melting behaviour of poly(ether ether ketone). Macromolecules 1987, 20, 1336–1341.
Zhuravlev, E.; Schmelzer, J. W. P.; Wunderlich, B.; Schick, C. Kinetics of nucleation and crystallization in poly(epsilon-caprolactone) (PCL). Polymer 2011, 52, 1983–1997.
Furushima, Y.; Nakada, M.; Ishikiriyama, K.; Toda, A.; Androsch, R.; Zhuravlev, E.; Schick, C. Two crystal populations with different melting/reorganization kinetics of isothermally crystallized polyamide 6. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 2126–2138.
Konishi, T.; Sakatsuji, W.; Fukao, K.; Miyamoto, Y. Temperature dependence of lamellar thickness in isothermally crystallized poly(butylene terephthalate). Macromolecules 2016, 49, 2272–2280.
Furushima, Y.; Nakada, M.; Yoshida, Y.; Okada, K. Crystallization/melting kinetics and morphological analysis of polyphenylene sulfide. Macromol. Chem. Phys. 2018, 219, 7.
Strobl, G. The physics of polymers. Springer-Verlag, New York, 1997.
Doye, J. P. K.; Frenkel, D. Mechanism of thickness determination in polymer crystals. Phys. Rev. Lett. 1998, 81, 2160–2163.
Rottele, A.; Thurn-Albrecht, T.; Sommer, J. U.; Reiter, G. Thermodynamics of formation, reorganization, and melting of confined nanometer-sized polymer crystals. Macromolecules 2003, 36, 1257–1260. https://doi.org/10.1007/s10118-021-2530-2
Acknowledgments
This work was financially supported by the National National Science Foundation of China (Nos. U1862205, 51473085, and 21873054) and Tsinghua University Initiative Scientific Research Program (No. 20194180048). The authors wish to thank Prof. Wei Miao from School of Materials, Tsinghua University, who kindly offers great help in WAXD data analysis. We thank Dr. Ying Lu from Changchun Institute of Applied Chemistry, and Dr. Yu Wang from the Institute of Chemistry Chinese Academy of Sciences, for their valuable advice and discussion in data analyses of SAXS. The authors declare no conflict of interest.
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Melting and Annealing Peak Temperatures of Poly(butylene succinate) on the Same Hoffman-Weeks Plot Parallel to Tm=Tc Line
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Xie, ZN., Ye, HM., Chen, T. et al. Melting and Annealing Peak Temperatures of Poly(butylene succinate) on the Same Hoffman-Weeks Plot Parallel to Tm=Tc Line. Chin J Polym Sci 39, 745–755 (2021). https://doi.org/10.1007/s10118-021-2530-2
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DOI: https://doi.org/10.1007/s10118-021-2530-2