Sains Malaysiana 46(12)(2017): 2433–2440

http://dx.doi.org/10.17576/jsm-2017-4612-19

 

Ammonium Persulfate-initiated Graft Copolymerization of Methacrylamide onto Chitosan: Synthesis, Characterization and Optimization

(Cangkukan Kopempolimeran Metakrilamida ke Kitosan oleh Ammonium Persulfat: Sintesis, Pencirian dan Pengoptimuman)

 

ZETTY AZALEA SUTIRMAN¹, MOHD MARSIN SANAGI^1,2*, AHMEDY ABU NAIM¹,

KHAIRIL JUHANNI ABD KARIM¹ & WAN AINI WAN IBRAHIM¹

 

¹Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor Darul Takzim, Malaysia

 

²Centre for Sustainable Nanomaterials, Ibnu Sina Institute for Scientific and Industrial Research

Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor Darul Takzim, Malaysia

 

Received: 11 September 2015/Accepted: 28 July 2016

 

ABSTRACT

Ammonium persulfate (APS)-initiated grafting of methacrylamide (MAM) onto chitosan was successfully prepared for the first time by free radical mechanism. Both chitosan and chitosan-graft-poly(methacrylamide) (chitosan-g-PMAM) were characterized using Fourier transform infrared spectroscopy (FTIR), solid state 13C NMR, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Important factors affecting graft copolymerization such as reaction time, temperature and concentrations of APS, MAM and chitosan were investigated and optimized to obtain maximum grafting parameters. The optimum values for grafting percentage and yield of graft copolymerization were achieved under the following conditions: chitosan (1 g), MAM (4 g), APS (0.6 g), time reaction (4 h) and temperature (70ºC).

 

Keywords: Ammonium persulfate; chitosan; free radical; graft copolymerization; methacrylamide

 

ABSTRAK

Cangkukan metakrilamida (MAM) kepada kitosan dimulakan oleh ammonium persulfat (APS) telah berjaya disediakan buat kali pertama melalui mekanisme radikal bebas. Kedua-dua kitosan dan kitosan-cangkuk-polimetakrilamida (kitosan-g-PMAM) telah dicirikan menggunakan spektrometri inframerah transformasi Fourier (FTIR), 13C NMR keadaan pepejal, analisis termogravimetri (TGA), kalorimetri imbasan kebedaan (DSC) dan mikroskopi imbasan elektron (SEM). Faktor penting dalam kopempolimeran cangkuk seperti masa tindak balas, suhu dan kepekatan APS, MAM dan kitosan telah dikaji dan dioptimum bagi memperoleh parameter cangkukan maksima. Peratus cangkukan dan perolehan tertinggi diperoleh dengan keadaan berikut: kitosan (1 g), MAM (4 g), APS (0.6 g), masa tindak balas (4 j) dan suhu (70ºC).

 

Kata kunci: Ammonium persulfat; kitosan; kopempolimeran cangkuk; metakrilamida; radikal bebas

REFERENCES

Ahmad, S.I., Radiman, S. & Ahmad, M.S. 2014. Sintesis nanozarah kuprum dalam larutan kitosan menggunakan kaedah sinaran gama. Sains Malaysiana 43(11): 1751-1759.

Akmaz, S., Dilaver Adgüzel, E., Yasar, M. & Erguven, O. 2013. The effect of ag content of the chitosan-silver nanoparticle composite material on the structure and antibacterial activity. Advances in Materials Science and Engineering 2013: 12-18.

Al-Karawi, A.J.M., Al-Qaisi, Z.H.J., Abdullah, H.I., Al- Mokaram, A.M.A. & Al-Heetimi, D.T.A. 2011. Synthesis, characterization of acrylamide grafted chitosan and its use in removal of copper(II) ions from water. Carbohydrate Polymers 83: 495-500.

Al Sagheer, F.A., Khalil, K.D. & Ibrahim, E.I. 2013. Synthesis and characterization of chitosan-g-poly(2-(furan-2-carbonyl)- acrylonitrile): Grafting of chitosan using a novel monomer prepared by a Baylis-Hillman reaction. European Polymer Journal 49: 1662-1672.

Athawale, V.D. & Padwaldesai, M.P. 1999. Free radical graft copolymerization of methacrylamide onto agar. European Polymer Journal 35: 1237-1243.

Bhattacharya, A. & Misra, B.N. 2004. Grafting: A versatile means to modify polymers: Techniques, factors and applications. Progress in Polymer Science (Oxford) 29: 767-814.

Burfield, D.R. & Ng, S.C. 1978. Persulphate initited graft copolymerization of methaacrylamide in natural rubber latex E --III. 14: 799-802.

Cheba, B.A. 2011. Chitin and chitosan : Marine biopolymers with unique properties and versatile applications. Journal of Biotechnology & Biochemistry 6: 149-153.

Don, T.M. & Chen, H.R. 2005. Synthesis and characterization of AB-crosslinked graft copolymers based on maleilated chitosan and N-isopropylacrylamide. Carbohydrate Polymers 61: 334-347.

Hatada, K., Kitayama, T. & Ute, K. 1983. Determination of tacticity of polymethacrylamide by C-13 NMR spectroscopy. Polymer Bulletin 9: 241-244.

Heux, L., Brugnerotto, J., Desbrières, J., Versali, M.F. & Rinaudo, M. 2000. Solid state NMR for determination of degree of acetylation of chitin and chitosan. Biomacromolecules 1: 746-751.

Islam, M., Masum, S., Rahman, M.M., Islam, A. & Shaikh, A.A. 2011. Preparation of chitosan from shrimp shell and investigation of its properties. International Journal of Basic & Applied Sciences 11(1): 77-80.

Konaganti, V.K., Kota, R., Patil, S. & Madras, G. 2010. Adsorption of anionic dyes on chitosan grafted poly(alkyl methacrylate)s. Chemical Engineering Journal 158: 393-401.

Kuo, S.W., Kao, H.C. & Chang, F.C. 2003. Thermal behavior and specific interaction in high glass transition temperature PMMA copolymer. Polymer 44: 6873-6882.

Liu, J., Wen, X.Y., Lu, J.F., Kan, J. & Jin, C.H. 2014. Free radical mediated grafting of chitosan with caffeic and ferulic acids: Structures and antioxidant activity. International Journal of Biological Macromolecules 65: 97-106.

Misra, B.N., Mehta, I.K. & Khetarpal, R.C. 1984. Grafting onto cellulose. VIII. Graft copolymerization of poly(ethylacrylate) onto cellulose by use of redox initiators. Comparison of initiator reactivities. Journal of Polymer Science: Polymer Chemistry Edition 22: 2767-2775.

Mun, G.A., Nurkeeva, Z.S., Dergunov, S.A., Nam, I.K., Maimakov, T.P., Shaikhutdinov, E.M., Lee, S.C. & Park, K. 2008. Studies on graft copolymerization of 2-hydroxyethyl acrylate onto chitosan. Reactive and Functional Polymers 68: 389-395.

Nandi, G., Patra, P., Priyadarshini, R., Kaity, S. & Ghosh, L.K. 2015. Synthesis, characterization and evaluation of methacrylamide grafted gellan as sustained release tablet matrix. International Journal of Biological Macromolecules 72: 965-974.

Sadeghi, M., Ghasemi, N. & Soliemani, F. 2012. Graft copolymerization methacrylamide monomer onto carboxymethyl cellulose in homogeneous solution and optimization of effective parameters. World Applied Sciences Journal 16: 119-125.

Shanmugapriya, A. 2011. Optimization of ceric ammonium nitrate initiated graft copolymerization of acrylonitrile onto chitosan. Journal of Water Resource and Protection 03: 380-386.

Singh, V., Sharma, A.K. & Sanghi, R. 2009a. Poly(acrylamide) functionalized chitosan: An efficient adsorbent for azo dyes from aqueous solutions. Journal of Hazardous Materials 166: 327-335.

Singh, V., Sharma, A.K., Tripathi, D.N. & Sanghi, R. 2009b. Poly(methylmethacrylate) grafted chitosan: An efficient adsorbent for anionic azo dyes. Journal of Hazardous Materials 161: 955-966.

Singh, V., Tiwari, A., Tripathi, D.N. & Sanghi, R. 2006a. Microwave enhanced synthesis of chitosan-graft-polyacrylamide. Polymer 47: 254-260.

Singh, V., Tiwari, A., Pandey, S. & Singh, S.K. 2006b. Microwave-accelerated synthesis and characterization of potato starch-g-poly(acryiamide). Starch/Staerke 58: 536-543.

Stawski, D. & Połowiński, S. 2005. Polymerization of itaconic acid. Polimery/Polymers 50: 118-122.

Zakaria, S., Chin, H.C., Wan Ahmad, W.H., Kaco, H., Soon, W.C. & Chin, H.C. 2015. Mechanical and antibacterial properties of paper coated with chitosan. Sains Malaysiana 44(6): 905-911.

Zohuriaan-mehr, M.J. 2005. Advances in chitin and chitosan modification through graft copolymerization: A comprehensive review. Polymer Journal 14: 235-265.

 

 

*Corresponding author; email: marsin@kimia.fs.utm.my