Abstract
Swelling behaviour of poly(N-vinylcaprolactam) (PVC) and poly(N-vinylcaprolactam-co-itaconic acid) (P(VC-co-IA)) gels was investigated in different solvents (water, ethanol, methanol, isopropyl alcohol (IPA), chloroform, toluene, acetone) and in binary solvent mixtures (ethanol/chloroform, ethanol/methanol, IPA/chloroform, ethanol/water, IPA/water). Gels were synthesised in ethanol by the free radical cross-linking polymerisation method at 60°C for 24 h in the presence of azo-bis(isobutyronitrile) and allyl methacrylate as the initiator and cross-linker, respectively. And also, ethanol/distilled water mixture (ϕr = 4:1) was used as the synthesis medium to determine its effect on the swelling of gels. It was found that the presence of water in the synthesis medium significantly affected the equilibrium swelling value (ESV) and the swelling tendency of gels both in solvents and in solvent mixtures. All gels synthesised in ethanol showed the highest swelling in chloroform. The gels synthesised in the ethanol/water mixture displayed different swelling behaviour. In this case, while chloroform was still valid for maximum swelling of PVC, P(VC-co-IA) had the highest swelling in methanol. Solubility parameters of gels were predicted by the van Krevelen-Hoftyzer (VKH) and Hoy methods (group contribution methods) and theoretical calculations verified the experimental swelling order.
Similar content being viewed by others
References
Adamska, K., & Voelkel, A. (2006). Hansen solubility parameters for polyethylene glycols by inverse gas chromatography Journal of Chromatography A, 1132, 260–267. DOI: 10.1016/j.chroma.2006.07.066.
Bajpai, S. K., & Sonkusley, J. (2003). Dynamic release of riboflavin from a colon-targeted delivery device: an in vitro study Reactive & Functional Polymers, 55, 197–210. DOI: 10.1016/s1381-5148(02)00247-x.
Boyko, V. B. (2004). N-Vinylcaprolactam based bulk and microgels: Synthesis, structural formation and characterization by dynamic light scattering. Doctor rerum naturalium dissertation, Faculty of Mathematic and Natural Sciences, Dresden University of Technology, Dresden, Germany.
Brandrup, J., & Immergut, E. H. (Eds.) (1975). Polymer handbook (2nd ed.). New York, NY, USA: Wiley.
Bustamante, P., Navarro-Lupión, J., & Escalera, B. (2005). A new method to determine the partial solubility parameters of polymers from intrinsic viscosity. European Journal of Pharmaceutical Sciences, 24, 229–237. DOI: 10.1016/j.ejps.2004.10.012.
Cheng, S. C., Feng, W., Pashikin, I. I., Yuan, L. H., Deng, H. C., & Zhou, Y. (2002). Radiation polymerization of thermosensitive poly (N-vinylcaprolactam). Radiation Physics and Chemistry, 63, 517–519. DOI: 10.1016/s0969-806x(01)00638-7.
Çakal, E., & Çavuş, S. (2010). Novel poly(N-vinylcaprolactam-co-2-(diethylamino)ethyl methacrylate) gels: Characterization and detailed investigation on their stimuli-sensitive behaviors and network structure. Industrial & Engineering Chemistry Research, 49, 11741–11751. DOI: 10.1021/ie1007097.
Çavuş, S., & Çakal, E. (2012). Synthesis and characterization of novel poly(N-vinylcaprolactam-co-itaconic acid) gels and analysis of pH and temperature sensitivity. Industrial & Engineering Chemistry Research, 51, 1218–1226. DOI: 10.1021/ie2008746.
Çaykara, T., Özyürek, C., Kantoğlu, Ö., & Güven, O. (2002). Influence of gel composition on the solubility parameter of poly(2-hydroxyethyl methacrylate-itaconic acid) hydrogels. Journal of Polymer Science Part B: Polymer Physics, 40, 1995–2003. DOI: 10.1002/polb.10262.
Dalkas, G., Pagonis, K., & Bokias, G. (2006). Control of the lower critical solution temperature—type cononsolvency properties of poly(N-isopropylacrylamide) in water—dioxane mixtures through copolymerisation with acrylamide. Polymer, 47, 243–248. DOI: 10.1016/j.polymer.2005.10.115.
El-Hamshary, H. (2007). Synthesis and water sorption studies of pH sensitive poly(acrylamide-co-itaconic acid) hydrogels. European Polymer Journal, 43, 4830–4838. DOI: 10.1016/j.eurpolymj.2007.08.018.
Eroğlu, M. S., Baysal, B. M., & Güven, O. (1997). Determination of solubility parameters of poly(epichlorohydrin) and poly(glycidyl azide) networks. Polymer, 38, 1945–1947. DOI: 10.1016/s0032-3861(96)00720-3.
Hansen, C. M. (1967). The three dimensional solubility parameter and solvent diffusion coefficient: Their importance in surface coating formulation. PhD. thesis, Technical University of Denmark, Kgs. Lyngby. Copenhagen, Denmark: Danish Technical Press.
Hansen, C. M. (2007). Hansen solubility parameters: A user’s handbook (2nd ed.). Boca Raton, FL, USA: CRC Press.
Hildebrand, J. H., & Scott, R. L. (1950). The solubility of non-electrolytes (3rd ed.). New York, NY, USA: Reinhold.
Hore, M. J. A., Hammouda, B., Li, Y., & Cheng, H. (2013). Co-nonsolvency of poly(n-isopropylacrylamide) in deuterated water/ethanol mixtures. Macromolecules, 46, 7894–7901. DOI: 10.1021/ma401665h.
Hoy, K. L. (1970). New values of the solubility parameters from vapor pressure data. Journal of Paint Technology, 42, 76–118.
Jagur-Grodzinski, J. (2010). Polymeric gels and hydrogels for biomedical and pharmaceutical applications. Polymers for Advanced Technologies, 21, 27–47. DOI: 10.1002/pat.1504.
Jun, L., Bochu, W., & Yazhou, W. (2006). Thermo-sensitive polymers for controlled-release drug delivery systems. International Journal of Pharmacology, 2, 513–519. DOI: 10.3923/ijp.2006.513.519.
Just, S., Sievert, F., Thommes, M., & Breitkreutz, J. (2013). Improved group contribution parameter set for the application of solubility parameters to melt extrusion. European Journal of Pharmaceutics and Biopharmaceutics, 85, 1191–1199. DOI: 10.1016/j.ejpb.2013.04.006.
Katime, I., Velada, J. L., Novoa, R., Díaz de Apodaca, E., Puig, J., & Mendizabal, E. (1996). Swelling kinetics of poly(acrylamide)/poly(mono-n-alkyl itaconates) hydrogels. Polymer International, 40, 281–286. DOI: 10.1002/(SICI)1097-0126(199608)40:4<281∷AID-PI555>3.0.CO;2-H.
King, M. B. (1969). Phase equilibrium in mixtures. Oxford, UK: Pergamon Press.
Krušić, M. K., Ilić, M., & Filipović, J. (2009). Swelling behaviour and paracetamol release from poly(N-isopropylacrylamide-itaconic acid) hydrogels. Polymer Bulletin, 63, 197–211. DOI: 10.1007/s00289-009-0086-3.
Mark, J. E. (Ed.) (2007). Physical properties of polymers handbook (2nd ed.). New York, NY, USA: Springer.
Meaurio, E., Cesteros, L. C., Katime, I. (1998). Study of the solvent role on complexation in systems poly(mono n-alkyl itaconate)/tertiary polyamide. Polymer, 39, 379–385. DOI: 10.1016/s0032-3861(97)00271-1.
Nasimova, I. R., Makhaeva, E. E., & Khokhlov, A. R. (2001). Poly(N-vinylcaprolactam) gel/organic dye complexes as sensors for metal ions in aqueous salt solutions. Journal of Applied Polymer Science, 81, 3238–3243. DOI: 10.1002/app.1778.
Nurkeeva, Z. S., Mun, G. A., Khutoryanskiy, V. V., Kan, V. A., Zotov, A. A., & Shaikhutdinov, E. M. (2000). Interactions of linear and cross-linked polyacrylic acid with polyvinyl ether of ethyleneglycol in some aliphatic alcohols. Polymer Bulletin, 44, 563–568. DOI: 10.1007/s002890070079.
Osada, Y., Gong, J. P., & Tanaka, Y. (2004). Polymer gels. Journal of Macromolecular Science, Part C: Polymer Reviews, 44, 87–112. DOI: 10.1081/mc-120027935.
Özdemir, C., & Güner, A. (2007). Solubility profiles of poly(ethylene glycol)/solvent systems, I: Qualitative comparison of solubility parameter approaches. European Polymer Journal, 43, 3068–3093. DOI: 10.1016/j.eurpolymj.2007.02.022.
Ozmen, M. M., & Okay, O. (2003). Swelling behavior of strong polyelectrolyte poly(N-t-butylacrylamide-co-acrylamide) hydrogels. European Polymer Journal, 39, 877–886. DOI: 10.1016/s0014-3057(02)00356-7.
Poling, B. E., Prausnitz, J. M., & O’Connell, J. P. (2001). The properties of gases and liquids (5th ed.). New York, NY, USA: McGraw-Hill.
Price, G. J., & Shillcock, I. M. (2002). Inverse gas chromatographic measurement of solubility parameters in liquid crystalline systems. Journal of Chromatography A, 964, 199–204. DOI: 10.1016/s0021-9673(02)00651-9.
Ravindra, R., Krovvidi, K. R., & Khan, A. A. (1998). Solubility parameter of chitin and chitosan. Carbohydrate Polymers, 36, 121–127. DOI: 10.1016/s0144-8617(98)00020-4.
Schenderlein, S., Lück, M., & Müller, B. W. (2004). Partial solubility parameters of poly(d,l-lactide-co-glycolide). International Journal of Pharmaceutics, 286, 19–26. DOI: 10.1016/j.ijpharm.2004.07.034.
Schmaljohann, D. (2006). Thermo- and pH-responsive polymers in drug delivery. Advanced Drug Delivery Reviews, 58, 1655–1670. DOI: 10.1016/j.addr.2006.09.020.
Sevgili, L. M., Toprak, S., & Çavuş, S. (2015). Swelling of N-vinylcaprolactam-dodecyl methacrylate gel in heptane + toluene mixtures. Chemical Papers, 69, 668–678. DOI: 10.1515/chempap-2015-0073.
Shah, S., Pal, A., Gude, R., & Devi, S. (2010). Synthesis and characterization of thermo-responsive copolymeric nanoparticles of poly(methyl methacrylate-co-N-vinylcaprolactam). European Polymer Journal, 46, 958–967. DOI: 10.1016/j.eurpolymj.2010.01.005.
Small, P. A. (1953). Some factors affecting the solubility of polymers. Journal of Applied Chemistry, 3, 71–80. DOI: 10.1002/jctb.5010030205.
Tang, Y., Zhang, S., Wang, M., Zhu, J., Sun, T., & Jiang, G. (2014). A glucose-based diblock copolymer: synthesis, characterization and its injectable/temperature-sensitive behaviors. Journal of Polymer Research, 21, 390. DOI: 10.1007/s10965-014-0390-y.
Thorne, J. B., Vine, G. J., & Snowden, M. J. (2011). Microgel applications and commercial considerations. Colloid and Polymer Science, 289, 625–646. DOI: 10.1007/s00396-010-2369-5.
Tomić, S. L., & Filipović, J. M. (2004). Synthesis and characterization of complexes between poly(itaconic acid) and poly(ethylene glycol). Polymer Bulletin, 52, 355–364. DOI: 10.1007/s00289-004-0298-5.
Troy, D. B. (Ed.) (2006). Remington: The science and practice of pharmacy (21st ed.). Philadelphia, PA, USA: Lippincott Williams & Wilkins.
van Krevelen, D. W., & te Nijenhuis, K. (2009). Properties of polymers: Their correlation with chemical structure; their numerical estimation and prediction from additive group contribution (4th ed.). Amsterdam, The Netherlands: Elsevier.
Verheyen, S., Augustijns, P., Kinget, R., & Van den Mooter, G. (2001). Determination of partial solubility parameters of five benzodiazepines in individual solvents. International Journal of Pharmaceutics, 228, 199–207. DOI: 10.1016/s0378-5173(01)00838-9.
Zafar, Z. I., Malana, M. A., Pervez, H., Shad, A., & Momma, K. (2008). Synthesis and swelling kinetics of a cross-linked pH-sensitive ternary copolymer gel system. Polymer(Korea), 32, 219–229.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Rights and permissions
About this article
Cite this article
Çavuş, S., Çakal, E. & Sevgili, L.M. Solvent dependent swelling behaviour of poly(N-vinylcaprolactam) and poly(N-vinylcaprolactam-co-itaconic acid) gels and determination of solubility parameters. Chem. Pap. 69, 1367–1377 (2015). https://doi.org/10.1515/chempap-2015-0153
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1515/chempap-2015-0153