Year 2016, Volume 3 , Issue 3, Pages 607 - 622 2017-01-08


Erhan BAT [1]

Hydroxyethyl methacrylate (HEMA) based hydrogels have found increasing number of applications in areas such as chromatographic separations, controlled drug release, biosensing, and membrane separations. In all these applications, the pore size and pore interconnectivity are crucial for successful application of these materials as they determine the rate of diffusion through the matrix. 2-Hydroxyethyl methacrylate is a water soluble monomer but its polymer, polyHEMA, is not soluble in water. Therefore, during polymerization of HEMA in aqueous media, a porous structure is obtained as a result of phase separation. Pore size and interconnectivity in these hydrogels is a function of several variables such as monomer concentration, cross-linker concentration, temperature etc. In this study, we investigated the effect of monomer concentration, graphene oxide addition or clay addition on hydrogel pore size, pore interconnectivity, water uptake, and thermal properties. PolyHEMA hydrogels have been prepared by redox initiated free radical polymerization of the monomer using ethylene glycol dimethacrylate as a cross-linker. As a nanofiller, a synthetic hectorite Laponite® XLG and graphene oxide were used. Graphene oxide was prepared by the Tour Method. Pore morphology of the pristine HEMA based hydrogels and nanocomposite hydrogels were studied by scanning electron microscopy. The formed hydrogels were found to be highly elastic and flexible. A dramatic change in the pore structure and size was observed in the range between 22 to 24 wt/vol monomer at 0.5 % of cross-linker. In this range, the hydrogel morphology changes from typical cauliflower architecture to continuous hydrogel with dispersed water droplets forming the pores where the pores are submicron in size and show an interconnected structure. Such controlled pore structure is highly important when these hydrogels are used for solute diffusion or when there’s flow through monolithic hydrogels. These robust hydrogels may be useful in separation and biomedical applications.
hydrogels, hydroxyethyl methacrylate, porous polymers, nanocomposites
  • Wu D, Xu F, Sun B, Fu R, He H, Matyjaszewski K. Design and Preparation of Porous Polymers. Chemical Reviews. 2012;112(7):3959-4015.
  • Okay O. Macroporous copolymer networks. Progress in Polymer Science. 2000;25(6):711-79.
  • Benes MJ, Horak D, Svec F. Methacrylate-based chromatographic media. Journal of Separation Science. 2005;28(15):1855-75.
  • Khutoryanskaya OV, Mayeva ZA, Mun GA, Khutoryanskiy VV. Designing Temperature-Responsive Biocompatible Copolymers and Hydrogels Based on 2-Hydroxyethyl(meth)acrylates. Biomacromolecules. 2008;9(12):3353-61.
  • Hradil J, Horak D. Characterization of pore structure of PHEMA-based slabs. Reactive & Functional Polymers. 2005;62(1):1-9.
  • Vianna-Soares CD, Kim CJ, Borenstein MR. Manufacture of porous cross-linked HEMA spheres for size exclusion packing material. Journal of Porous Materials. 2003;10(2):123-30.
  • Vidaurre A, Cortazar IC, Meseguer JM. Water sorption properties of poly(ethyl acrylate-co-hydroxyethyl methacrylate) macroporous hydrogels. Macromolecular Symposia. 2003;200:283-90.
  • Antonietti M, Caruso RA, Goltner CG, Weissenberger MC. Morphology variation of porous polymer gels by polymerization in lyotropic surfactant phases. Macromolecules. 1999;32(5):1383-9.
  • Liu Q, Hedberg EL, Liu ZW, Bahulekar R, Meszlenyi RK, Mikos AG. Preparation of macroporous poly(2-hydroxyethyl methacrylate) hydrogels by enhanced phase separation. Biomaterials. 2000;21(21):2163-9.
  • Kumar A, Tyagi P, Singh H, Kumar Y, Lahiri SS. Synthesis and characterization of a porous poly(hydroxyethylmethacrylate-co-ethylene glycol dimethacrylate)-based hydrogel device for the implantable delivery of insulin. Journal of Applied Polymer Science. 2012;126(3):894-905.
  • Dziubla TD, Torjman MC, Joseph JI, Murphy-Tatum M, Lowman AM. Evaluation of porous networks of poly(2-hydroxyethyl methacrylate) as interfacial drug delivery devices. Biomaterials. 2001;22(21):2893-9.
  • Galperin A, Smith K, Geisler NS, Bryers JD, Ratner BD. Precision-Porous PolyHEMA-Based Scaffold as an Antibiotic-Releasing Insert for a Scleral Bandage. Acs Biomaterials-Science & Engineering. 2015;1(7):593-600.
  • Horak D, Kroupava J, Slouf M, Dvorak P. Poly(2-hydroxyethyl methacrylate)-based slabs as a mouse embryonic stem cell support. Biomaterials. 2004;25(22):5249-60.
  • Horak D, Hlidkova H, Hradil J, Lapcikova M, Slouf M. Superporous poly(2-hydroxyethyl methacrylate) based scaffolds: Preparation and characterization. Polymer. 2008;49(8):2046-54.
  • Arslantunali D, Budak G, Hasirci V. Multiwalled CNT-pHEMA composite conduit for peripheral nerve repair. Journal of Biomedical Materials Research Part A. 2014;102(3):828-41.
  • Studenovska H, Slouf M, Rypacek F. Poly(HEMA) hydrogels with controlled pore architecture for tissue regeneration applications. Journal of Materials Science-Materials in Medicine. 2008;19(2):615-21.
  • Dalaran M, Emik S, Guclu G, Iyim TB, Ozgumus S. Removal of acidic dye from aqueous solutions using poly(DMAEMA-AMPS-HEMA) terpolymer/MMT nanocomposite hydrogels. Polymer Bulletin. 2009;63(2):159-71.
  • Gupta VK, Tyagi I, Agarwal S, Sadegh H, Shahryari-ghoshekandi R, Yari M, et al. Experimental study of surfaces of hydrogel polymers HEMA, HEMA-EEMA-MA, and PVA as adsorbent for removal of azo dyes from liquid phase. Journal of Molecular Liquids. 2015;206:129-36.
  • Andac M, Galaev IY, Denizli A. Molecularly imprinted poly(hydroxyethyl methacrylate) based cryogel for albumin depletion from human serum. Colloids and Surfaces B-Biointerfaces. 2013;109:259-65.
  • Marcano DC, Kosynkin DV, Berlin JM, Sinitskii A, Sun ZZ, Slesarev A, et al. Improved Synthesis of Graphene Oxide. Acs Nano. 2010;4(8):4806-14.
Journal Section Articles

Author: Erhan BAT


Application Date : September 1, 2016
Acceptance Date : September 30, 2020
Publication Date : January 8, 2017

Vancouver Bat E . HYDROXYETHYL METHACRYLATE BASED NANOCOMPOSITE HYDROGELS WITH TUNABLE PORE ARCHITECTURE. Journal of the Turkish Chemical Society Section A: Chemistry. 2017; 607-622.