Citation: MIAO Zhongshuo, MEN Yongfeng. Crystallization and Melting Behaviors of Poly(1, 4-cyclohexylene Dimethylene Terephthalate) Studied by Fast-Scan Calorimetry[J]. Chinese Journal of Applied Chemistry, ;2020, 37(6): 642-649. doi: 10.11944/j.issn.1000-0518.2020.06.190359 shu

Crystallization and Melting Behaviors of Poly(1, 4-cyclohexylene Dimethylene Terephthalate) Studied by Fast-Scan Calorimetry

MIAO Zhongshuo ^1,2 ,
MEN Yongfeng ^1,,

a.
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
b.
University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: MEN Yongfeng, men@ciac.ac.cn
Received Date: 30 December 2019
Revised Date: 9 February 2020
Accepted Date: 10 March 2020

Fund Project: the National Science Fund for Distinguished Young Scholars 51525305Supported by the National Science Fund for Distinguished Young Scholars(No.51525305)

Figures(6)

The crystallization and melting behavior of poly(1, 4-cyclohexylene dimethylene terephthalate) (PCT) was studied by fast scanning calorimetry (FSC) combined with traditional differential scanning calorimetry (DSC) in the range of near glass transition temperature and melting temperature (100~270 ℃). The crystallization rate of PCT is faster when the supercooling degree is larger. FSC can effectively inhibit the crystallization of PCT during the cooling process while the traditional DSC can avoid the influence of sample degradation on the experimental results under the lower supercooling degrees. The combination of FSC and DSC can well measure the crystallization kinetics of PCT. The experimental results show that the crystallization rate is the fastest at 175 ℃. FSC is also used to measure the melting point dependence of heating rate after isothermal crystallization, and calibrated on the basis of the modeling of melting kinetics for the determination of the melting point at zero heating rate T_m. The Hoffman-Weeks plot of T_m against T_c with the intersection of T_c=T_m suggested the equilibrium melting point T_m^o≅315 ℃ of chain-extended infinite-size crystals of PCT.
- poly(1, 4-cyclohexylene dimethylene terephthalate),
- isothermal crystallization,
- fast scanning calorimetry,
- zero-entropy production melting point,
- lamella
1. [1]
  Kibler C J, Bell A, Smith J G. Polyesters of 1, 4-Cyclohexanedimethanol[J]. J Polym Sci Part A:Polym Chem, 1964,2(13):2115-2125.
2. [2]
  Wunderlich B. Crystal Nucleation, Growth, Annealing[J]. Macromol Phys, 1976,2:214-227.
3. [3]
  Hoffman J D, Davis G T, Lauritzen J I, et al. The Rate of Crystallization of Linear Polymers with Chain Folding[M]//N.B. Hannay. Treatise on Solid State Chemistry. New York-London, 1976, 3: 497-614.
4. [4]
  Wunderlich B. Crystal Melting[M]. New York:Macromolecular Physics Academic Press, 1980, 3.
5. [5]
  Schick C, Mathot V. Fast Scanning Calorimetry[M]. Switzerland:Springer, 2016.
6. [6]
  Toda A, Androsch R, Schick C. Feature Article:Insights into Polymer Crystallization and Melting from Fast Scanning Chip Calorimetry[J]. Polymer, 2016,91:239-263. doi: 10.1016/j.polymer.2016.03.038
7. [7]
  Toda A, Taguchi K, Nozaki K. Melting Behaviors of Polyethylene Crystals:An Application of Fast-Scan DSC[J]. Polymer, 2014,55:3186-3194. doi: 10.1016/j.polymer.2014.05.009
8. [8]
  Toda A, Yamada K, Hikosaka M. Superheating of the Melting Kinetics in Polymer Crystals:A Possible Nucleation Mechanism[J]. Polymer, 2002,43:1667-1679. doi: 10.1016/S0032-3861(01)00733-9
9. [9]
  Toda A, Taguchi K, Nozaki K. Fast Limiting Behavior of the Melting Kinetics of Polyethylene Crystals Examined by Fast-Scan Calorimetry[J]. Thermochim Acta, 2019,677:211-216. doi: 10.1016/j.tca.2018.12.024
10. [10]
  Minakov A A, Wurm A, Schick C. Superheating in Linear Polymers Studied by Ultrafast Nanocalorimetry[J]. Eur Phys J E, 2007,23:43-53. doi: 10.1140/epje/i2007-10173-8
11. [11]
  Toda A. Heating Rate Dependence of Melting Peak Temperature Examined by DSC of Heat Flux Type[J]. J Therm Anal Calorim, 2016,123:1795-1808. doi: 10.1007/s10973-015-4603-3
12. [12]
  Gradys A, Sajkiewics P, Adamovsky S. Crystallization of Poly(Vinylidene Fluoride) During Ultra-Fast Cooling[J]. Thermochim Acta, 2007,461:153-157. doi: 10.1016/j.tca.2007.05.023
13. [13]
  Toda A, Konishi M, Schick C. An Evaluation of Thermal Lags of Fast-Scan Microchip DSC with Polymer Film Samples[J]. Thermochim Acta, 2014,589:262-269. doi: 10.1016/j.tca.2014.05.038
14. [14]
  Lee Y, Porte R S. Double-Melting Behavior of Poly(ether ether ketone)[J]. Macromolecules, 1987,20:1336-1341. doi: 10.1021/ma00172a028
15. [15]
  Chen H S, Porter R S. Melting Behavior of Poly(Ether Ether Ketone) in Its Blends with Poly(Ether Imide)[J]. J Polym Sci B Polym Phys, 1993,31:1845-1850. doi: 10.1002/polb.1993.090311217
16. [16]
  Santis F D, Adamovsky S, Schick C. Isothermal Nanocalorimetry of Isotactic Polypropylene[J]. Macromolecules, 2007,40:9026-9031. doi: 10.1021/ma071491b
17. [17]
  Silvestre C, Cimmino S, Schick C. Isothermal Crystallization of Isotactic Poly(Propylene) Studied by Superfast Calorimetry[J]. Macromol Rapid Commun, 2007,28:875-881. doi: 10.1002/marc.200600844
18. [18]
  Rhoades A M, Williams J L, Androsch R. Crystallization Kinetics of Polyamide 66 at Processing-Relevant Cooling Conditions and High Supercooling[J]. Thermochim Acta, 2015,603:103-109. doi: 10.1016/j.tca.2014.10.020
19. [19]
  Toda A, Taguchi K, Sato K. Melting Kinetics of It-Polypropylene Crystals over Wide Heating Rates[J]. J Therm Anal Calorim, 2013,113:1231-1237. doi: 10.1007/s10973-012-2914-1
20. [20]
  Zhuravlev E, Wunderlich B, Schick C. Kinetics of Nucleation and Crystallization in Poly(ε-Caprolactone)(PCL)[J]. Polymer, 2011,52:1983-1997. doi: 10.1016/j.polymer.2011.03.013
21. [21]
  Androsch R, Rhoades A M, Schick C. Density of Heterogeneous and Homogeneous Crystal Nuclei in Poly(Butylene Terephthalate)[J]. Eur Polym J, 2015,66:180-189. doi: 10.1016/j.eurpolymj.2015.02.013
22. [22]
  Konishi T, Sakatsuji W, Fukao K. Temperature Dependence of Lamellar Thickness in Isothermally Crystallized Poly(Butylene Terephthalate)[J]. Macromolecules, 2016,49:2272-2280. doi: 10.1021/acs.macromol.6b00126
23. [23]
  Furushima Y, Toda A, Androsch R. Two Crystal Populations with Different Melting/Reorganization Kinetics of Isothermally Melt Crystallized Polyamide 6[J]. J Polym Sci B Polym Phys, 2016,54:2126-2138. doi: 10.1002/polb.24123
24. [24]
  Xu J, Heck B, Reiter G. Stabilization of Nuclei of Lamellar Polymer Crystals:Insights from a Comparison of the Hoffman-Weeks Line with the Crystallization Line[J]. Macromolecules, 2016,49:2206-2215. doi: 10.1021/acs.macromol.5b02123
25. [25]
  Wang J, Li Z, Hu W B. Comparing Crystallization Rates Between Linear and Cyclic Poly(Epsilon-Caprolactones) via Fast-Scan Chip-Calorimeter Measurements[J]. Polymer, 2015,63:34-40. doi: 10.1016/j.polymer.2015.02.039
26. [26]
  Minakov A A, Schick C, Martino G. Isothermal Reorganization of Poly(Ethylene Terephthalate) Revealed by Fast Calorimetry[J]. Faraday Discuss, 2005,128:261-270. doi: 10.1039/B403441D
27. [27]
  Marand H, Xu J, Srinivas S. Determination of the Equilibrium Melting Temperature of Polymer Crystals:Linear and Nonlinear Hoffman-Weeks Extrapolations[J]. Macromolecules, 1998,31:8219-8229. doi: 10.1021/ma980747y
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