Abstract
Hydrogels with high water uptake were prepared by ionizing radiation induced crosslinking in aqueous solutions of four cellulose derivatives (carboxymethylcellulose sodium salt—CMC-Na, methylcellulose—MC, hydroxyethylcellulose—HEC and hydroxypropylcellulose—HPC). The gel fraction increased with absorbed dose, while water uptake decreased. At high polymer concentrations lower gel fractions were found due to the lower polymer chain mobility and inhomogeneity at low water content. The swelling rate gradually slowed down after 4–5 h. CMC and HEC gels reached equilibrium after 24 h, while HPC and MC gels required longer immersion times. Gels showed second-order swelling kinetics in water. The mechanism of the water diffusion proved to be anomalous. In pure water, CMC gels showed the highest, while HPC and MC gels the lowest water uptake. The derivatives had different sensitivities to ionic strength in the swelling solution. The salt type also proved to be a significant factor at uniform ionic strength. Thus different cellulose derivative based gels may be preferred at various applications depending on the environment.
Similar content being viewed by others
References
Anbergen U, Oppermann W (1990) Elasticity and swelling behaviour of chemically crosslinked cellulose ethers in aqueous systems. Polymer 31(10):1854–1858. doi:10.1016/0032-3861(90)90006-K
BeMiller JN, Whistler RL (1993) Industrial gums: polysaccharides and their derivatives, 3rd edn. Academic Press, New York
Cai J, Zhang L (2006) Unique gelation behavior of cellulose in NaOH/urea aqueous solution. Biomacromolecules 7(1):183–189. doi:10.1021/bm0505585
Chang C, Zhang L (2011) Cellulose-based hydrogels: present status and application prospects. Carbohydr Polym 84:40–53. doi:10.1016/j.carbpol.2010.12.023
Charlesby A (1955) The degradation of cellulose by ionizing radiation. J Polym Sci 15(79):263–270. doi:10.1002/pol.1955.120157921
Clough RL (2001) High-energy radiation and polymers: a review of commercial processes and emerging applications. Nucl Instr Meth Phys Res B 185(1–4):8–33. doi:10.1016/S0168-583X(01)00966-1
Convay BE (1981) Ionic hydration in chemistry and biophysics. Elsevier, New York
Das R, Panda AB, Pal S (2012) Synthesis and characterization of a novel polymeric hydrogel based on hydroxypropyl methyl cellulose grafted with polyacrylamide. Cellulose 19:933–945. doi:10.1007/s10570-012-9692-6
Dastidar TG, Netravali AN (2012) ‘Green’ crosslinking of native starches with malonic acid and their properties. Carbohydr Polym 90(4):1620–1628. doi:10.1016/j.carbpol.2012.07.041
El-Din HMN, Alla SGA, El-Naggar AWM (2010) Swelling and drug release properties of acrylamide/carboxymethyl cellulose networks formed by gamma irradiation. Radiat Phys Chem 79(6):725–730. doi:10.1016/j.radphyschem.2010.01.011
Fei B,Wach RA, Mitomo H, Yoshii F, Kume T (2000) Hydrogel of biodegradable cellulose derivatives. I. Radiation-induced crosslinking of CMC. J Appl Polym Sci 78(2):278–283. doi:10.1002/1097-4628(20001010)78:2<278::AID-APP60>3.0.CO;2-9
Furusawa K, Dobashi T, Morishita S, Oyama M, Hashimoto T, Shinyashiki N, Yagihara S, Nagasawa N (2005) Structural and kinetic modification of aqueous hydroxypropylmethylcellulose (HPMC) induced by electron beam irradiation. Physica A: Stat Mech Applic 353:9–20. doi:10.1016/j.physa.2004.12.068
Ganji F, Vasheghani-Farahani S, Vasheghani-Farahani E (2010) Theoretical description of hydrogel swelling: a review. Iranian Polym J 19(5):375–398
Haque A, Morris ER (1993) Thermogelation of methylcellulose. Part I: molecular structures and processes. Carbohydr Polym 22(3):161–173. doi:10.1016/0144-8617(93)90137-S
Ibrahim SM, Salmawi KME, Zahran AH (2007) Synthesis of crosslinked superabsorbent carboxymethylcellulose/acrylamide hydrogels through electron-beam irradiation. J Appl Polym Sci 104:2003–2008. doi:10.1002/app.25916
Ishii D, Tatsumi D, Matsumoto T, Murata K, Hayashi H, Yoshitani H (2006) Investigation of the structure of cellulose in LiCl/DMAc solution and its gelation behavior by small-angle X-ray scattering measurements. Macromol Biosci 6(4):293–300. doi:10.1002/mabi.200500231
Kadokawa J, Murakami M, Kaneko Y (2008) A facile preparation of gel materials from a solution of cellulose in ionic liquid. Carbohydr Res 343:769–772. doi:10.1016/j.carres.2008.01.017
Kim J, Lee KW, Hefferan TE, Currier BL, Yaszemski MJ, Lu L (2008) Synthesis and evaluation of novel biodegradable hydrogels based on poly(ethylene glycol) and sebacic acid as tissue engineering scaffolds. Biomacromolecules 9(1):149–157. doi:10.1021/bm700924n
Li L, Thangamathesvaran PM, Yue CY, Tam KC, Hu X, Lam YC (2001) Gel network structure of methylcellulose in water. Langmuir 17(26):8062–8068. doi:10.1021/la010917r
Liu P, Zhai M, Li J, Peng J, Wu J (2002) Radiation preparation and swelling behavior of sodium carboxymethyl cellulose hydrogels. Radiat Phys Chem 63:525–528. doi:10.1016/S0969-806X(01)00649-1
Liu P, Peng J, Li J, Wu J (2005) Radiation crosslinking of CMC-Na at low dose and its application as substitute for hydrogel. Radiat Phys Chem 72:635–638. doi:10.1016/j.radphyschem.2004.03.090
Mischnick P, Momcilovic D (2010) Chemical structure analysis of starch and cellulose derivatives. Adv Carbohydr Chem Biochem 64:117–210. doi:10.1016/S0065-2318(10)64004-8
Narjary B, Aggarwal P, Singh A, Chakraborty D, Singh R (2012) Water availability in different soils in relation to hydrogel application. Geoderma 187–188:94–101. doi:10.1016/j.geoderma.2012.03.002
Pekel N, Yoshii F, Kume T, Güven O (2004) Radiation crosslinking of biodegradable hydroxypropylmethylcellulose. Carbohydr Polym 55:139–147. doi:10.1016/j.carbpol.2003.08.015
Qin X, Lu A, Zhang L (2013) Gelation behavior of cellulose in NaOH/urea aqueous system via crosslinking. Cellulose 20:1669–1677. doi:10.1007/s10570-013-9961-z
Richter A, Paschew G, Klatt S, Lienig J, Arndt KF, Adler HJP (2008) Review on hydrogel-based pH sensors and microsensors. Sensors 8(1):561–581. doi:10.3390/s8010561
Rička J, Tanaka T (1984) Swelling of ionic gels: quantitative performance of the Donnan theory. Marcomolecules 17:2916–2921. doi:10.1021/ma00142a081
Rosén O, Sjöström J, Piculell L (1998) Responsive polymer gels based on hydrophobically modified cellulose ethers and their interaction with ionic surfactants. Langmuir 14:5795–5801. doi:10.1021/la971168+
Saglam A, Yalçinkaya Y, Denizli A, Arica MY, Genç Ö, Bektas S (2002) Biosorption of mercury by carboxymethylcellulose and immobilized Phanerochaete chrysosporium. Microchem J 71(1):73–81. doi:10.1016/S0026-265X(01)00142-4
Schott H (1992) Kinetics of polymers and their gels. J Pharm Sci 81(5):467–470. doi:10.1002/jps.2600810516
Seki Y, Altinisik A, Demircioğlu B (2014) Carboxymethylcellulose (CMC)-hydroxyethylcellulose (HEC) based hydrogels: synthesis and characterization. Cellulose. doi:10.1007/s10570-014-0204-8
Tan R, She Z, Wang M, Fang Z, Liu Y, Feng Q (2012) Thermo-sensitive alginate-based injectable hydrogel for tissue engineering. Carbohydr Polym 87(2):1515–1521. doi:10.1016/j.carbpol.2011.09.048
Uraki Y, Imura T, Kishimoto T, Ubukata M (2006) Body temperature-responsive gels derived from hydroxypropylcellulose bearing lignin II: adsorption and release behavior. Cellulose 13:225–234. doi:10.1007/s10570-005-9032-1
Wach RA, Mitomo H, Yoshii F, Kume T (2002) Hydrogel of radiation-induced crosslinked hydroxypropylcellulose. Macromol Mater Eng 287:285–295. doi:10.1002/1439-2054(20020401)287:4<285:AID-MAME285>3.0.CO;2-3
Wach RA, Mitomo H, Nagasawa N, Yoshii F (2003a) Radiation crosslinking of carboxymethylcellulose of various degree of substitution at high concentration in aqueous solution of natural pH. Radiat Phys Chem 68:771–779. doi:10.1016/S0969-806X(03)00403-1
Wach RA, Mitomo H, Nagasawa N, Yoshii F (2003b) Radiation crosslinking of methylcellulose and hydroxyethylcellulose in concentrated aqueous solutions. Nucl Instr Methods Phys Res B 211:533–544. doi:10.1016/S0168-583X(03)01513-1
Wach RA, Rokita B, Bartoszek N, Katsumura Y, Ulanski P, Rosiak JM (2014) Hydroxyl radical-induced crosslinking and radiation-initiatied hydrogel formation in dilute aqueous solutions of carboxymethylcellulose. Carbohydr Polym 112:412–415. doi:10.1016/j.carbpol.2014.06.007
Yang S, Fu S, Liu H, Zhou Y, Li X (2011) Hydrogel based on carboxymethyl cellulose for removal heavy metal ions. J Appl Polym Sci 119(2):1204–1210. doi:10.1002/app.32822
Yoshii F, Zhao L, Wach RA, Nagasawa N, Mitomo H, Kume T (2003) Hydrogels of polysaccharide derivatives crosslinked with irradiation at paste-like condition. Nucl Instrum Methods Phys Res B 208:320–324. doi:10.1016/S0168-583X(03)00624-4
Acknowledgments
The authors thank the Hungarian Science Foundation (NK 105802) for partial support, and Eva Horvathne Koczog for technical assistance.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Fekete, T., Borsa, J., Takács, E. et al. Synthesis of cellulose derivative based superabsorbent hydrogels by radiation induced crosslinking. Cellulose 21, 4157–4165 (2014). https://doi.org/10.1007/s10570-014-0445-6
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-014-0445-6