Abstract
This work establishes that the plasticization effect of a classical petrochemical plasticizer, dimethyl phthalate (DMP), on a polymer matrix, cellulose acetate (CA), is due to the development of intermolecular interactions of dipolar type. Plasticized cellulose acetate films are studied with regard to the interactions between the polymer and plasticizer at the macroscopic scale by thermogravimetric analysis and differential scanning calorimetry. At the molecular level, Fourier transform infrared spectroscopy and dielectric relaxation spectroscopy are used to elucidate the nature of interactions that are responsible for the plasticizing effects. These static and dynamic complementary analyses evidenced that DMP does not establish H-bonding interactions with the polymer chains of cellulose acetate but rather weaker interactions of dipolar type. These dipole–dipole interactions that develop between acetyl side groups of CA and the ester phthalate moieties of DMP increase the overall mobility of CA chains and also locally influence the molecular mobility and the water uptake tendency.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Alvarez F, Alegria A, Colmenero J (1991) Relationship between the time-domain Kohlrausch–Williams–Watts and frequency-domain Havriliak–Negami relaxation functions. Phys Rev B 44:7306–7312. doi:10.1103/PhysRevB.44.7306
Angell CA (1995) Formation of glasses from liquids and biopolymers. Science 267:1924–1935. doi:10.1126/science.267.5206.1924
Bao CY, Long DR, Vergelati C (2015) Miscibility and dynamical properties of cellulose acetate/plasticizer systems. Carbohydr Polym 116:95–102. doi:10.1016/j.carbpol.2014.07.078
Driessen WL, Everstijn PLA (1977) Dimethyl phthalate, a neutral bidentate oxygen-donor ligand to divalent metal ions. Z Naturforsch B 32:1284–1286
Einfeldt J, Kwasniewski A (2002) Characterization of different types of cellulose by dielectric spectroscopy. Cellulose 9:225–238
Einfeldt J, Meißner D, Kwasniewski A (2000) Comparison of the molecular dynamics of celluloses and related polysaccharides in wet and dried states by means of dielectric spectroscopy. Macromol Chem Phys 201:1969–1975. doi:10.1002/1521-3935(20001001)201:15<1969:AID-MACP1969>3.0.CO;2-L
Einfeldt J, Meißner D, Kwasniewski A (2001) Polymerdynamics of cellulose and other polysaccharides in solid state-secondary dielectric relaxation processes. Prog Polym Sci 26:1419–1472. doi:10.1016/S0079-6700(01)00020-X
Fulcher GS (1925) Analysis of recent measurements of the viscosity of glasses. J Am Ceram Soc 8:339–355. doi:10.1111/j.1151-2916.1925.tb16731.x
Guo Y, Wu P (2008) Investigation of the hydrogen-bond structure of cellulose diacetate by two-dimensional infrared correlation spectroscopy. Carbohydr Polym 74:509–513. doi:10.1016/j.carbpol.2008.04.005
Hassan-Nejad M, Ganster J, Bohn A et al (2009) Bio-based nanocomposites of cellulose acetate and nano-clay with superior mechanical properties. Macromol Symp 280:123–129. doi:10.1002/masy.200950614
Havriliak S, Negami S (1966) A complex plane analysis of α-dispersions in some polymer systems. Polym Sci Part C: Polym Symp 14:99–117. doi:10.1002/polc.5070140111
Heudorf U, Mersch-Sundermann V, Angerer J (2007) Phthalates: toxicology and exposure. Int J Hyg Environ Health 210:623–634. doi:10.1016/j.ijheh.2007.07.011
Johari GP, Goldstein M (1970) Viscous liquids and the glass transition. II. Secondary relaxations in glasses of rigid molecules. J Chem Phys 53:2372–2388. doi:10.1063/1.1674335
Johari GP, Goldstein M (1971) Viscous liquids and the glass transition. III. Secondary relaxations in aliphatic alcohols and other nonrigid molecules. J Chem Phys 55:4245–4252. doi:10.1063/1.1676742
Kaminski K, Kaminska E, Ngai KL et al (2009) Identifying the origins of two secondary relaxations in polysaccharides. J Phys Chem B 113:10088–10096. doi:10.1021/jp809760t
Kaminski K, Wlodarczyk P, Adrjanowicz K et al (2010) Origin of the commonly observed secondary relaxation process in saccharides. J Phys Chem B 114:11272–11281. doi:10.1021/jp1034773
Keely CM, Zhang X, McBrierty VJ (1995) Hydration and plasticization effects in cellulose acetate: a solid-state NMR study. J Mol Struct 355:33–46. doi:10.1016/0022-2860(95)08865-S
Kohlrausch R (1854) Theorie des elektrischen Rückstandes in der Leidener Flasche. Ann Phys 167:56–82. doi:10.1002/andp.18541670103
Kudlik A, Tschirwitz C, Benkhof S et al (1997) Slow secondary relaxation process in supercooled liquids. EPL Europhys Lett 40:649. doi:10.1209/epl/i1997-00518-y
McBrierty VJ, Keely CM, Coyle FM et al (1996) Hydration and plasticization effects in cellulose acetate: molecular motion and relaxation. Faraday Discuss 103:255–268. doi:10.1039/FD9960300255
Meier MM, Kanis LA, de Lima JC et al (2004) Poly(caprolactone triol) as plasticizer agent for cellulose acetate films: influence of the preparation procedure and plasticizer content on the physico-chemical properties. Polym Adv Technol 15:593–600. doi:10.1002/pat.517
Murphy D, de Pinho MN (1995) An ATR–FTIR study of water in cellulose acetate membranes prepared by phase inversion. J Membr Sci 106:245–257. doi:10.1016/0376-7388(95)00089-U
Ngai KL (2011) Relaxation and diffusion in complex systems. Springer, New York
Ngai KL, Paluch M (2004) Classification of secondary relaxation in glass-formers based on dynamic properties. J Chem Phys 120:857–873. doi:10.1063/1.1630295
Petzold N, Schmidtke B, Kahlau R et al (2013) Evolution of the dynamic susceptibility in molecular glass formers: results from light scattering, dielectric spectroscopy, and NMR. J Chem Phys 138:12A510. doi:10.1063/1.4770055
Shahin Thayyil MS, Capaccioli S, Prevosto D, Ngai KL (2008) Is the Johari–Goldstein β-relaxation universal? Philos Mag 88:4007–4013. doi:10.1080/14786430802270082
Singh S, Li SS-L (2011) Phthalates: toxicogenomics and inferred human diseases. Genomics 97:148–157. doi:10.1016/j.ygeno.2010.11.008
Socrates G (2004) Infrared and Raman characteristic group frequencies: tables and charts, 3rd edn. Wiley, Chichester
Sousa M, Brás AR, Veiga HIM et al (2010) Dynamical characterization of a cellulose acetate polysaccharide. J Phys Chem B 114:10939–10953. doi:10.1021/jp101665h
Storey RF, Mauritz KA, Cox BD (1989) Diffusion of various dialkyl phthalate plasticizers in PVC. Macromolecules 22:289–294. doi:10.1021/ma00191a053
Stuart BH (2004) Infrared spectroscopy: fundamentals and applications. Wiley, Chichester
Tabb DL, Koenig JL (1975) Fourier transform infrared study of plasticized and unplasticized poly(vinyl chloride). Macromolecules 8:929–934. doi:10.1021/ma60048a043
Tamman G, Hesse W (1926) Die Abhängigkeit der Viskosität von der Temperatur bei Unterkühlten Flüssigkeiten. Z Anorg Allg Chem 156:245–257
Toprak C, Agar JN, Falk M (1979) State of water in cellulose acetate membranes. J Chem Soc Faraday Trans 1: Phys Chem Condens Phases 75:803–815. doi:10.1039/F19797500803
Ubbink J (2016) Structural and thermodynamic aspects of plasticization and antiplasticization in glassy encapsulation and biostabilization matrices. Adv Drug Deliv Rev 100:10–26. doi:10.1016/j.addr.2015.12.019
Vogel H (1921) Das Temperatur Abhängigkeitgesetz der Viskosität von Flüssigkeiten. Phys Z 22:645–646
Wübbenhorst M, van Turnhout J (2002) Analysis of complex dielectric spectra. I. One-dimensional derivative techniques and three-dimensional modelling. J Non-Cryst Solids 305:40–49. doi:10.1016/S0022-3093(02)01086-4
Acknowledgments
This work was supported by the region Nord-Pas de Calais (CPER 2011-2013).
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
10570_2016_1148_MOESM1_ESM.pdf
Online Resource 1H NMR spectra and analysis of CA/DMP (17%w/w) films annealed at 50 °C for 24 h, and DRS spectra of pure DMP recorded between -150 °C and 20 °C. (PDF 316 kb)
Rights and permissions
About this article
Cite this article
Benazzouz, A., Dudognon, E., Correia, N.T. et al. Interactions underpinning the plasticization of a polymer matrix: a dynamic and structural analysis of DMP-plasticized cellulose acetate. Cellulose 24, 487–503 (2017). https://doi.org/10.1007/s10570-016-1148-y
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-016-1148-y