Journal of Polymer Research

, Volume 18, Issue 5, pp 897–905 | Cite as

Modified acrylic-based superabsorbents with hydrophobic monomers: synthesis, characterization and swelling behaviors

  • Xingli Liu
  • Xiaolan Li
  • Zhiyong Lu
  • Xinping Miao
  • Yujun FengEmail author
Original Paper


A novel family of acrylic acid-based superabsorbent polymers (SAP-n) with controlled-absorption rate were synthesized via aqueous solution polymerization using K2S2O8/NaHSO3 as the redox initiators, N, N'-methylenebisacrylamide (NMBA) as the crosslinker, 2-methacryloyloxyethyl n-alkyl dimethyl ammonium bromide (CnDM, n = 4, 8, 12, 16) as the hydrophobic comonomers. The structures of the copolymers were elucidated by FT-IR and ionic chromatographic (IC) analysis respectively, and the swelling properties of the copolymers were examined. It was found that the water absorbency capacity either in distilled water or in 0.9% NaCl brine decreased with increasing hydrophobe length or content, and the water absorbency rate of SAP-n was as expected lower than that of SAP without hydrophobic monomer; in addition, water retention evaluation under different temperatures revealed that this kind of copolymers could absorb and retain large amount of water at room temperature and release it at high temperature.


Acrylic-based superabsorbents Hydrophobic monomer Swelling behaviors Controlled-absorption 



X. Liu gratefully acknowledges the financial support from the key project in natural sciences (09NZD002) of Southwest University for Nationalities, and Y. Feng thanks the financial supports from Sichuan Provincial Bureau of Science and Technology through its Distinguished Youth Fund (2010JQ0029) and application-oriented fundamental research program of (2008JY0002), as well as the opening fund from Sate Key Laboratory of Oil/Gas Reservoir Geology and Exploitation Engineering (PLN0605).


  1. 1.
    Kazanskii KS, Dubrovskii SA (1992) Chemistry and physics of agricultural hydrogels. Adv Polym Sci 104:97–133Google Scholar
  2. 2.
    Buchholtz F, Peppas N (1994) Superabsorbent polymers. ACS Symposium Series 573; Am Chem Soc: Washington, DCGoogle Scholar
  3. 3.
    Buchholz FL, Graham AT (1998) Modern superabsorbent polymer technology. Wiley-Vch, New YorkGoogle Scholar
  4. 4.
    Mohan YM, Murthy PS, Raju KM (2005) Synthesis, characterization and effect of reaction parameters on swelling properties of acrylamide-sodium methacrylate superabsorbent copolymers. React Funct Polym 63:11–26CrossRefGoogle Scholar
  5. 5.
    Kellenberger S (1989) Absorbent products contaning hydrogels with abilitiy to swell against pressure. EP 339461Google Scholar
  6. 6.
    James R, Samuel C, Steve L, John P (2002) Absorbent stuctures with integral layer of superabsorbent polymer particels. US 6403857Google Scholar
  7. 7.
    Kosemund K, Schlatter H, Ochsenhirt JL, Krause EL, Marsman DS, Erasala GN (2009) Safety evaluation of superabsorbent baby diapers. Regul Toxicol Pharm 53:81–89CrossRefGoogle Scholar
  8. 8.
    Buchholz FL (2006) Model of liquid permeability in swollen composites of superabsorbent polymer and fiber. J Appl Polym Sci 102:4075–4084CrossRefGoogle Scholar
  9. 9.
    Weerawarna S (2009) Biodegradable superabsorbent particles. US 20090325797Google Scholar
  10. 10.
    Park TG (1999) Temperature modulated protein release from pH/temperature-sensitive hydrogels. Biomaterials 20:517–521CrossRefGoogle Scholar
  11. 11.
    Seki Y, Torgursul A, Yurdakoc K (2007) Preparation and characterization of poly(acrylic acid)-iron rich smectite superabsorbent composites. Polym Adv Technol 18:477–482CrossRefGoogle Scholar
  12. 12.
    Omidian H, Rocca JG, Park K (2005) Advances in superporous hydrogels. J Control Release 102:3–12CrossRefGoogle Scholar
  13. 13.
    Yao KJ, Zhou WJ (1994) Synthesis and water absorbency of the copolymer of acrylamide with anionic monomers. J Appl Polym Sci 53:1533–1538CrossRefGoogle Scholar
  14. 14.
    Wu L, Liu M (2008) Preparation and characterization of cellulose acetate-coated compound fertilizer with controlled-release and water-retention. Polym Adv Technol 19:785–792CrossRefGoogle Scholar
  15. 15.
    Zheng T, Liang YH, Ye SH, He ZY (2009) Superabsorbent hydrogels as carriers for the controlled-release of urea: experiments and a mathematical model describing the release rate. Biosyst Eng 102:44–50CrossRefGoogle Scholar
  16. 16.
    Raju KM, Raju MP, Mohan YM (2003) Synthesis of superabsorbent copolymers as water manageable materials. Polym Int 52:768–772CrossRefGoogle Scholar
  17. 17.
    Raju KM, Raju MP (2001) Synthesis and swelling properties of superabsorbent copolymers. Adv Polym Tech 20:146–154CrossRefGoogle Scholar
  18. 18.
    Weaver M. (1976) Highly absorbent strach-containing polymeric compositions. US 3981100Google Scholar
  19. 19.
    Kohls SJ, Baker DD, Kremer DA, Dawson JO (1999) Water-retentive polymers increase nodulation of actinorhizal plants inoculated with Frankia. Plant Soil 214:105–115CrossRefGoogle Scholar
  20. 20.
    Zheng YA, Wang AQ (2009) Study on superabsorbent composite. XX. Effects of cation-exchanged montmorillonite on swelling properties of superabsorbent composite containing sodium humate. Polym Compos 30:1138–1145CrossRefGoogle Scholar
  21. 21.
    Lionetto F, Sannino A, Maffezzoli A (2005) Ultrasonic monitoring of the network formation in superabsorbent cellulose based hydrogels. Polymer 46:1796–1803CrossRefGoogle Scholar
  22. 22.
    Rogers JV, Richter WR, Choi YW, Judd AK (2009) Use of superabsorbent polymer gels for surface decontamination of Bacillus anthracis spores. Lett Appl Microbiol 48:180–186CrossRefGoogle Scholar
  23. 23.
    Seungkoo K, Scott J (2005) Superabsorbent polymer. US 20050090586Google Scholar
  24. 24.
    Zohuriaan-Mehr MJ, Kabiri K (2008) Superabsorbent polymer materials: a review. Iran Polym J 17:451–477Google Scholar
  25. 25.
    Weir JL, Wilson LR, Weir J, Wilson L, Weir L, Wilson R (2002) Preparation of water-swellable, water-insoluble polymer, for personal care articles, comprises contacting polyvalent metal salt solution with polymer to give required absorption rate index. US 6433058Google Scholar
  26. 26.
    Jockusch S, Turro NJ, Mitsukami Y, Matsumoto M, Iwamura T, Lindner T, Flohr A, di Massimo G (2009) Photoinduced surface crosslinking of superabsorbent polymer particles. J Appl Polym Sci 111:2163–2170CrossRefGoogle Scholar
  27. 27.
    Wilson LR, Wilson L (2004) Preparation of polymer particles for absorbent articles such as diaper, involves polymerizing monomer in presence of covalent crosslinking agent and polyvalent metal coordination compound. US 6716929Google Scholar
  28. 28.
    Kiatkamjornwong S (2007) Superabsorbent polymers and superabsorbent polymer composites. ScienceAsia 33:39–43CrossRefGoogle Scholar
  29. 29.
    Chang K, Reed PE (2009) Expandable polymeric microparticle composition used for modifying water permeability of subterranean formation including sandstone for recovering hydrocarbon fluids, comprises interpenetrating polymer network consisting of labile polymers. WO 2009131982Google Scholar
  30. 30.
    Atkins JM, Chang K, Doucette CC, Street JP (2009) Composition useful in tertiary oil recovery process comprises highly cross linked expandable polymeric microparticle, and non-labile and labile crosslinking agent. US 2009264325Google Scholar
  31. 31.
    Mudiyanselage TK, Neckers DC (2008) Highly absorbing superabsorbent polymer. J Polym Sci Pol Chem 46:1357–1364CrossRefGoogle Scholar
  32. 32.
    Pourjavadi A, Barzegar S (2009) Synthesis and evaluation of pH and thermosensitive pectin-based superabsorbent hydrogel for oral drug delivery systems. Starch-Stärke 61:161–172CrossRefGoogle Scholar
  33. 33.
    Campan R, Cazaux F, Coqueret X (2002) Controlled swelling of poly(hydroxyethyl methacrylate) hydrogels by photochemical grafting of hydrophobic acrylates. Macromol Mater Eng 287:924–930CrossRefGoogle Scholar
  34. 34.
    Omidian H, Hashemi SA, Sammes PG, Meldrum I (1999) Modified acrylic-based superabsorbent polymers dependence on particle size and salinity. Polymer 40:1753–1761CrossRefGoogle Scholar
  35. 35.
    Lu H, Feng Y (2008) Study on associative polymerizable inverse microemulsion. J Macromol Sci Part A-Pure Appl Chem 45:372–380CrossRefGoogle Scholar
  36. 36.
    Lu H, Feng Y (2007) Synthesis, characterization and kinetics of hydrophobically associating polyacrylamide. E-Polymers no.099. 1-13Google Scholar
  37. 37.
    Lee WF, Yang LG (2004) Superabsorbent polymeric materials. XII. Effect of montmorillonite on water absorbency for poly(sodium acrylate) and montmorillonite nanocomposite superabsorbents. J Appl Polym Sci 92:3422–3429CrossRefGoogle Scholar
  38. 38.
    Pourjavadi A, Amini-Fazl MS (2007) Optimized synthesis of carrageenan-graft-poly(sodium acrylate) superabsorbent hydrogel using the Taguchi method and investigation of its metal ion absorption. Polym Int 56:283–289CrossRefGoogle Scholar
  39. 39.
    Liu ZX, Miao YG, Wang ZY, Yin GH (2009) Synthesis and characterization of a novel super-absorbent based on chemically modified pulverized wheat straw and acrylic acid. Carbohydr Polym 77:131–135CrossRefGoogle Scholar
  40. 40.
    Qi XH, Liu MZ, Zhang F, Chen ZB (2009) Synthesis and properties of poly(sodium acrylate-co-2-acryloylamino-2-methyl-1-propanesulfonic acid)/attapulgite as a salt-resistant superabsorbent composite. Polym Eng Sci 49:182–188CrossRefGoogle Scholar
  41. 41.
    Flory PJ (1953) Principles of polymer chemistry. Cornell University Press, IthacaGoogle Scholar
  42. 42.
    Schulz DN, Bock J, Valint PL Jr (1994) In: Dupin P, Bock J, Davis R, Schulz DN, Thies C (eds) Macromolecular complexes in chemistry and biology, Chapt 1. Springer-Verlag, BerlinGoogle Scholar
  43. 43.
    Candau F, Selb J (1999) Hydrophobically-modified polyacrylamides prepared by micellar polymerization. Adv Colloid Interface Sci 79:149–172CrossRefGoogle Scholar
  44. 44.
    Feng Y, Billon L, Grassl B, Khoukh A, Francois J (2002) Hydrophobically associating polyacrylamides and their partially hydrolyzed derivatives prepared by post-modification. 1. Synthesis and characterization. Polymer 43:2055–2064CrossRefGoogle Scholar
  45. 45.
    Li X, Liu X, Chen Q, Wang Y, Feng Y (2010) Hydrophobically associating polyacrylamides prepared by inverse suspension polymerization: synthesis, characterization and aqueous solution properties. J Macromol Sci Part A-Pure Appl Chem 27:358–367CrossRefGoogle Scholar
  46. 46.
    Zhou WL, Zhang YA, Jin KM et al (2009) Synthesis and characterization of functionalized acrylic-acrylamide-based superabsorbent gels. J Appl Polym Sci 114:2828–2836CrossRefGoogle Scholar
  47. 47.
    Marandi GB, Hariri S, Mahdavinia GR (2009) Effect of hydrophobic monomer on the synthesis and swelling behaviour of a collagen-graft-poly[(acrylic acid)-co-(sodium acrylate)] hydrogel. Polym Int 58:227–235CrossRefGoogle Scholar
  48. 48.
    Ma JT, Liang B, Cui P, Dai H, Huang RH (2003) Dilute solution properties of hydrophobically associating polyacrylamide: fitted by different equations. Polymer 44:1281–1286CrossRefGoogle Scholar
  49. 49.
    Omidian H, Hashemi SA, Sammes PG, Meldrum I (1998) A model for the swelling of superabsorbent polymers. Polymer 39:6697–6704CrossRefGoogle Scholar
  50. 50.
    Kairi K, Omidian H, Hashemi SA, Zohuriaan-mehr MJ (2003) Synthesis of fast-swelling superabsorbent hydrogels: effect of crosslinker type and concentration on porosity and absorption rate. Eur Polym J 39:1341–1348CrossRefGoogle Scholar
  51. 51.
    Pourjavadi A, Barzegar S, Mahdavinia GR (2006) MBA-crosslinked Na-Alg/CMC as a smart full-polysaccharide superabsorbent hydrogels. Cabohydr Polym 66:386–395CrossRefGoogle Scholar
  52. 52.
    Liu PS, Li L, Zhou NL, Zhang J, Wei SH, Shen J (2007) Waste polystyrene foam-graft-acrylic acid/montmorillonite superabsorbent nanocomposite. J Appl Polym Sci 104:2341–2349CrossRefGoogle Scholar
  53. 53.
    Bhardwaj AK, Shainberg I, Goldstein D, Warrington DN, Levy GJ (2007) Water retention and hydraulic conductivity of cross-linked polyacrylamides in sandy soils. Soil Sci Soc Am J 71:406–412CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2010

Authors and Affiliations

  • Xingli Liu
    • 1
  • Xiaolan Li
    • 2
    • 3
  • Zhiyong Lu
    • 2
  • Xinping Miao
    • 1
  • Yujun Feng
    • 2
    Email author
  1. 1.College of Chemistry and Environmental Protection EngineeringSouthwest University for NationalitiesChengduPeople’s Republic of China
  2. 2.Chengdu Institute of Organic ChemistryChinese Academy of SciencesChengduPeople’s Republic of China
  3. 3.The Graduate School of the Chinese Academy of SciencesBeijingPeople’s Republic of China

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