Copolymerization of N-Vinyl Pyrrolidone with Functionalized Vinyl Monomers: Synthesis, Characterization and Reactivity Relationships

S. Vijaykumar; S. Prasannkumar; B. S. Sherigara; N. B. Shelke; Tejraj M. Aminabhavi; B. S. R. Reddy

Macromolecular Research, Vol.17, No.12, 1003-1009, December, 2009

S. Vijaykumar, S. Prasannkumar, B. S. Sherigara^†, N. B. Shelke¹, Tejraj M. Aminabhavi^{1, †}, and B. S. R. Reddy²

Department of Industrial Chemistry, Kuvempu University, Jnana Sahyadri, Shankaraghatta, Shimoga 577-451, India, Iran
¹Drug Delivery Division, Center of Excellence in Polymer Science, Karnatak University, Dharwad, 580-003, India, Iran
²Central Leather Research Institute Chennai, Adyar, Chennai 600-020, India, Iran

E-mail:,

Copolymers of N-vinylpyrrolidone (NVP) comonomer with styrene (St), hydroxypropyl methacrylate (HPMA) and carboxyphenyl maleimide (CPMI) were synthesized by free radical polymerization using 2,2'-azobisisobutyronitrile (AIBN) initiator in 1,4-dioxane solvent. The copolymers formed were characterized by FTIR, 1H NMR and 13C NMR techniques and their thermal properties were studied by DSC and TGA. Copolymer composition was determined by 1H NMR and/or by elemental analysis and monomer reactivity ratios (MRR) were estimated by the linear methods of Kelen-Tudos (K-T) and extended Kelen-Tudos (EK-T) and the non-linear approach. Copolymers of St and HPMA with NVP formed blocks of one of the monomer units, whereas alternating copolymers were obtained in CPMI-NVP, depending upon the side chain substitution. The MRR values are discussed in terms of monomer structural properties such as electronegativity and electron delocalization. The sequence distribution of monomers in the copolymers was studied by statistical method based on the average reactivity ratios obtained by EK-T method.

Keywords:N-vinyl-2-pyrrolidone;functionalized vinyl copolymers;reactivity ratios;Sequence distribution

[References]

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[Referenced By]

[1] Radic D, Gargallo L, Macromolecules, 30(4), 817 (1997)

[2] De Queiroz AAA, Vargas RR, Higa OZ, Ribeiro RR, Vitolo M, J. Appl. Polym. Sci., 84(4), 767 (2002)

[3] Bajpai SK, J. Appl. Polym. Sci., 83(8), 1717 (2002)

[4] Beitz T, Kotz J, Wolf G, Kleinpeter E, Friberg SE, J. Colloid Interface Sci., 240(2), 581 (2001)

[5] Basri M, Harun A, Ahmad MB, Razak CNA, Salleh AB, J. Appl. Polym. Sci., 82(6), 1404 (2001)

[6] Vijayasekaran S, Chirila TV, Hong Y, Tahija SG, Dalton PD, Constable IJ, McAllister IL, J. Biomater. Sci. Polym. Ed., 7, 685 (1996)

[7] Ranucci H, Spagnoli G, Sartore L, Bignottie F, Ferruti P, Macromol. Chem. Phys., 196, 763 (1995)

[8] Lee HY, Yu SA, Jeong KH, Kim YJ, Macromol. Res., 15(6), 547 (2007)

[9] Otagiri M, Imai T, Koinuma H, Matsumoro U, J. Pharm. Biomed. Anal., 7, 929 (1989)

[10] Mumper RJ, Duguid JG, Anwer K, Barron MK, Nitta H, Rolland AP, Pharm. Res., 13, 701 (1996)

[11] Reddy BSS, Arshady R, George M, Eur. Polym. J., 21, 511 (1985)

[12] Morariu S, Hulubei C, High Perform. Polym., 18, 185 (2006)

[13] Bauduin G, Boutevin B, Belbachir M, Meghabar R, Macromolecules, 28(6), 1750 (1995)

[14] Miller A, Szafko J, Turska E, J. Polym. Sci., 51, 15 (1977)

[15] Bajaj P, Sen K, Bahrami SH, J. Appl. Polym. Sci., 59(10), 1539 (1996)

[16] Soykan C, Coskun M, Ahmedzade M, Polym. Int., 49, 479 (2000)

[17] Kumar SV, Prasannakumar S, Musturappa TE, Mahadevan KM, Sherigara BS, J. Macromol. Sci. A, 44, 1161 (2007)

[18] Kelen T, Tudos F, J. Macromol. Sci. Chem., 1, 9 (1975)

[19] Kelen T, Tudos F, Foldes BT, Turcsanyi B, J. Macromol. Sci., 10, 1513 (1976)

[20] Dube M, Amin SR, J. Polym. Sci. Part A: Polym. Chem., 29, 703 (1991)

[21] Reo BS, J. Polym. Sci. Part C: Polym. Lett., 3, 26 (1998)

[22] Huglin MB, Khairou KS, Eur. Polym. J., 24, 239 (1988)

[23] Rosen S, Fundamental Principles of Polymeric Materials, John Wiley & Sons Inc., New York, 1993, pp 200-203.

[24] Gatica N, Fernandez N, Opazo A, Radic D, J. Chil. Chem. Soc., 50, 581 (2005)

[25] Mohammad TT, Massumeh H, J. Polym. Res., 11, 203 (2004)