Citation: Chanita Sungkapreecha, Walter W. Focke, René Androsch. Competition between Liquid-liquid De-mixing, Crystallization, and Glass Transition in Solutions of PLA of Different Stereochemistry and DEET[J]. Chinese Journal of Polymer Science, ;2020, 38(2): 174-178. doi: 10.1007/s10118-019-2314-0 shu

Competition between Liquid-liquid De-mixing, Crystallization, and Glass Transition in Solutions of PLA of Different Stereochemistry and DEET

a.
Interdisciplinary Center for Transfer-oriented Research in Natural Sciences, Martin Luther University Halle-Wittenberg, 06099 Halle/Saale, Germany
b.
University of Pretoria Institute for Sustainable Malaria Control and MRC Collaborating Centre for Malaria Research, Department of Chemical Engineering, University of Pretoria, Private Bag X20, Hatfield 0028, South Africa

Corresponding author: René Androsch, rene.androsch@iw.uni-halle.de
Received Date: 17 May 2019
Revised Date: 4 June 2019
Available Online: 26 July 2019

Liquid-liquid (L-L) de-mixing and vitrification of solutions of either crystallizable poly(L-lactic acid) (PLLA) or non-crystallizable poly(D/L-lactic acid) (PDLLA) with 50 m% N,N-diethyl-3-methylbenzamide (DEET) were analyzed by calorimetry and cloud-point measurements, which allows drawing conclusions about the effect of polymer stereochemistry on the phase behavior. Regardless of the PLA stereochemistry, vitrification of the solutions on fast cooling, hindering crystallization of PLLA, occurred below −20 °C and suppressed prior L-L de-mixing. The experimental results prove that crystallization in samples containing crystallizable PLLA, observed at around 55 °C on slow cooling, is not preceded by L-L de-mixing.
- Crystallization,
- PLA,
- DEET,
- Liquid-liquid phase separation,
- Thermally-induced phase separation (TIPS)
1. [1]
  Sungkapreecha, C.; Iqbal, N.; Gohn, A. M.; Focke, W. W.; Androsch, R. Phase behavior of the polymer/drug system PLA/DEET. Polymer 2017, 126, 116−125. doi: 10.1016/j.polymer.2017.08.031
2. [2]
  Sungkapreecha, C.; Beily, M. J.; Kressler, J.; Focke, W. W.; Androsch, R. Phase behavior of the polymer/drug system PLA/DEET: effect of PLA molar mass on subambient liquid-liquid phase separation. Thermochim. Acta 2018, 660, 77−81. doi: 10.1016/j.tca.2017.12.021
3. [3]
  Martínez-Pérez, C. A.; Olivas-Armendariz, I.; Castro-Carmona, J. S.; García-Casillas, P. E. Scaffolds for tissue engineering via thermally induced phase separation. Adv. Regenerative Med.: InTech 2011, 275−294.
4. [4]
  Lloyd, D. R.; Kinzer, K. E.; Tseng, H. S. Microporous membrane formation via thermally induced phase separation. I. Solid-liquid phase separation. J. Membr. Sci. 1990, 52, 239−261. doi: 10.1016/S0376-7388(00)85130-3
5. [5]
  Lloyd, D. R.; Kim, S. S.; Kinzer, K. E. Microporous membrane formation via thermally-induced phase separation. II. Liquid-liquid phase separation. J. Membr. Sci. 1991, 64, 1−11. doi: 10.1016/0376-7388(91)80073-F
6. [6]
  Katz, T. M.; Miller, J. H.; Hebert, A. A. Insect repellents: historical perspectives and new developments. J. Am. Acad. Dermatol. 2008, 58, 865−871. doi: 10.1016/j.jaad.2007.10.005
7. [7]
  Roberts, J. R.; Reigart, J. R. Does anything beat DEET? Pediatr. Ann. 2004, 33, 443−453.
8. [8]
  Huggins, M. L. Solutions of long chain compounds. J. Chem. Phys. 1941, 9, 440−440.
9. [9]
  Flory, P. J. Thermodynamics of high polymer solutions. J. Chem. Phys. 1942, 10, 51−61. doi: 10.1063/1.1723621
10. [10]
  Shultz, A. R.; Flory, P. J. Phase equilibria in polymer-solvent systems. J. Am. Chem. Soc. 1952, 74, 4760−4767. doi: 10.1021/ja01139a010
11. [11]
  Shultz, A. R.; Flory, P. J. Phase equilibria in polymer-solvent systems. II. Thermodynamic interaction parameters from critical miscibility data. J. Am. Chem. Soc. 1953, 75, 3888−3892. doi: 10.1021/ja01112a005
12. [12]
  Mandelkern, L. Crystallization kinetics in high polymers. II. Polymer-diluent mixtures. J. Appl. Phys. 1955, 26, 443−451. doi: 10.1063/1.1722016
13. [13]
  Product information, Sulzer Chemtec Ltd. https://www.sulzer.com/-/media/files/products/polymer_production_technology/brochures/fact_sheet_polylactides.ashx?la=en: accessed 14/06/2019.
14. [14]
  Androsch, R.; Di Lorenzo, M. L.; Schick, C. Crystal nucleation of random L/D-lactide copolymers. Eur. Polym. J. 2016, 75, 474−485. doi: 10.1016/j.eurpolymj.2016.01.020
15. [15]
  Product information, Evonik Nutrition & Care GmbH; https://healthcare.evonik.com/product/health-care/en/products/biomaterials/resomer/pages/controlled-release.aspx: accessed 13/06/2019.
16. [16]
  Product information, Sigma-Aldrich Chemie GmbH; http://www.sigmaaldrich.com/catalog/product/aldrich/d100951: accessed 13/06/2019.
17. [17]
  Di Lorenzo, M. L.; Rubino, P.; Luijkx, R.; Hélou, M. Influence of chain structure on crystal polymorphism of poly(lactic acid). Part 1: effect of optical purity of the monomer. Colloid Polym. Sci. 2014, 292, 399−409. doi: 10.1007/s00396-013-3081-z
18. [18]
  Sungkapreecha, C.; Iqbal, N.; Focke, W. W.; Androsch, R. Crystallization of poly(L-lactic acid) (PLLA) in solution with the mosquito-repellent N,N-diethyl-3-methyl-benzamide (DEET). Polym. Cry. 2019, 2, e10029.
19. [19]
  Androsch, R.; Schick, C.; Di Lorenzo, M. L. Kinetics of nucleation and growth of crystals of poly(L-lactic acid). Adv. Polym. Sci. 2018, 279, 235−272.
20. [20]
  Androsch, R.; Schick, C. Interplay between the relaxation of the glass of random L/D-lactide copolymers and homogeneous crystal nucleation: evidence for segregation of chain defects. J. Phys. Chem. B 2016, 120, 4522−4528. doi: 10.1021/acs.jpcb.6b03022
21. [21]
  Righetti, M. C.; Gazzano, M.; Di Lorenzo, M. L.; Androsch, R. Enthalpy of melting of α′-and α-crystals of poly (L-lactic acid). Eur. Polym. J. 2015, 70, 215−220.
22. [22]
  Hu, W. B.; Mathot, V. B. F.; Frenkel, D. Lattice model study of the thermodynamic interplay of polymer crystallization and liquid-liquid demixing. J. Chem. Phys. 2003, 118, 10343−10348. doi: 10.1063/1.1572462
23. [23]
  Zha, L. Y.; Hu, W. B. Homogeneous crystal nucleation triggered by spinodal decomposition in polymer solutions. J. Phys. Chem. B 2007, 111, 11373−11378. doi: 10.1021/jp068431c
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1.
沈阳化工大学材料科学与工程学院沈阳 110142