Radical copolymerization of N-isopropylacrylamide with anhydrides of maleic and citraconic acids

Dincer S., Koseli V., Kesim H., Rzaev Z., Piskin E.

EUROPEAN POLYMER JOURNAL, vol.38, no.11, pp.2143-2152, 2002 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 38 Issue: 11
  • Publication Date: 2002
  • Doi Number: 10.1016/s0014-3057(02)00127-1
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.2143-2152
  • Hacettepe University Affiliated: Yes


Radical-initiated copolymerization of N-isopropylacrylamide (NIPA) with maleic (MA) and citraconic (CA) anhydrides was carried out in the presence of 2,2'-azobisisobutyronitrile (AIBN) as an initiator in 1,4-dioxane at 65 degreesC under nitrogen atmosphere. Structure and monomer unit compositon of the copolymers obtained from a wide range of monomer feed were determined by elemental analysis (content of N for NIPA units), Fourier transform infrared and H-1 NMR spectroscopy. Monomer reactivity ratios for NIPA (M-1)-MA (M-2) and NIPA (M-1)-CA (M-2) pairs were determined by Kelen-Tudos (KT) and non-linear regression (NLR) methods using elemental and H-1 NMR spectroscopy analyses data. They are r(1) = 0.45 and r(2) = 0.08 (KT, N analysis), r(1) = 0.44 and r(2) = 0.10 (KT, H-1 NMR), r(1) = 0.45 and r(2) = 0.078 (NLR) for NIPA-MA monomer pair and r(1) = 0.52 and r(2) = 0.02, r(1) = 0.44 and r(2) = 0.04, r(1) = 0.51 and r(2) = 0.014 for NIPA-CA monomer pair, respectively. Observed tendency towards alternating copolymerization at less than or equal to50 mol%. NIPA concentration in monomer feed and relatively high activity of NIPA growing radical was explained by H-bond formation between C=O (anhydride) and NH (amide) fragments during chain growth reactions. Intrinsic viscosity, molecular weight and thermal behaviour of the synthesized copolymers were found to depend on the type of comonomer and the amount of NIPA units in the copolymers. These functional amphiphilic copolymers containing anion- and cation-active groups show both temperature and pH sensitivity and can be used for biological purposes as physiologically active macromolecular systems. (C) 2002 Elsevier Science Ltd. All rights reserved.