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Grafting of Methyl Methacrylate onto Starch Initiated by Ceric Ion as an Initiator in Presence of Nitric Acid as Activator

Abdurahman Abuabdalla Khalifa

Abstract


Natural polymers with improved structure have been securing increasing value in the industry as they
are abundant, cheap, and biodegradable. Graft copolymerization is one of the effective ways to
enhance the properties of natural polymers. Starch based graft copolymers are becoming increasingly
important due to their remarkable adhesion, high water absorbency, and biodegradability. Methyl
methacrylate (MMA) grafted onto starch by using the ceric ammonium nitrate (CAN) as a redox
initiator in the presence of nitric acid in aqueous medium to form grafted copolymer (Starch-g-
PMMA) was investigated. The grafting reaction was carried out under stream of nitrogen gas. The
impact of different reaction parameters to achieve the highest percent grafting (%G) has been studied
by determining the initiator concentration, monomer concentration, time (hours), nitric acid
concentration, and polymerization temperature. The % G was found to be 97%. Evidence of grafting
was characterized and confirmed by Fourier transform infrared spectroscopy (FTIR). The peaks at
1736.70 cm-1 and 3449.78 cm-1 indicates that MMA has been successfully grafted to starch. %G was
found to be decreased at higher than 70°C, after 2 hours of reaction time, with an increase of MMA
monomer concentration, initiator concentration, and with HNO3 concentration. The highest percent
grafting was obtained at the parameters of 1 g starch, 70°C, 2 hours, 2 mmol CAN, 140 mmol MMA
and 0.4 mmol HNO3.


Keywords


Ceric ammonium nitrate, FTIR, grafting, methyl methacrylate, starch

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References


Ojogbo E, Ogunsona EO, Mekonnen TH. Chemical and physical modifications of starch for renewable polymeric materials. Materials Today Sustainability. 2020; 7–8: 100028.

Zhang L, Gao J, Tian R, et al. Graft mechanism of acrylonitrile onto starch by potassium permanganate. Journal of Applied Polymer Science. 2003; 88 (1): 146–152.

Tolvanen P, Mäki-Arvela P, Sorokin AB, et al. Kinetics of starch oxidation using hydrogen peroxide as an environmentally friendly oxidant and an iron complex as a catalyst. Chemical Engineering Journal. 2009; 154 (1–3): 52–59.

Mostafa KM. Graft polymerization of acrylic acid onto starch using potassium permanganate acid (redox system). Journal of Applied Polymer Science. 1995; 56(2): 263–269. 5. Celik M, Sacak M. Synthesis and characterization of starch‐poly (methyl methacrylate) graft copolymers. Journal of Applied Polymer Science. 2002; 86(1): 53–57.

Manoj Kumar, P Nayak. Grafting vinyl monomers onto chitosan:IV: Graft copolymerized of acrylic acid onto chitosan using ceric ammonium nitrate as the initiator—characterization and antimicrobial activities. Materials Sciences and Applications. 2011; 2(12): 1741. 7. Bharti S, Mishra S. Synthesis, characterization and application of polymethyl methacrylate grafted oatmeal: a potential flocculant for wastewater treatment. International Journal of Environmental Research. 2016; 10(1): 169–178. 8. Young Austin H. Starch: Chemistry and Technology. 2nd ed. Amsterdam: Elsevier; 1984.

Azudin MN, Kelvin LET. An Evaluation of the Quality of Sago Starch Produced in Sarawak, Malaysia 1990. Proceeding of the Fourth International Sago Symposium. Kuching, Sarawak, Malaysia: Sago Congresses. 1991. August 6–9. pp. 149–152. 10. Govindasamy S, Campanella OH, Oates CG. The single screw extruder as a bioreactor for sago starch hydrolysis. Food Chemistry. 1997; 60 (1): 1–11.

Wang WJ, Powell AD, Oates CG. Sago starch as a biomass source: raw sago starch hydrolysis by commercial enzymes. Bioresource Technology. 1996; 55(1): 55–61.

Lagos A Reyes. Grafting onto chitosan. I. Graft copolymerization of methyl methacrylate onto chitosan with Fenton’s reagent (Fe2+−H2O2) as a redox initiator. Journal of Polymer Science Part A: Polymer Chemistry. 1988; 26(4): 985–991.

Jayakumar R, Prabaharan M, Reis RL, et al. Graft copolymerized chitosan—present status and applications. Carbohydrate Polymers. 2005; 62(2): 142–158.

Guthrie JT, Tune PD. The preparation, characterization, and application of cellulose–MMA graft copolymers. I. The aqueous‐based preparation of cellulose–MMA graft copolymers. Journal of Polymer Science Part A: Polymer Chemistry. 1991; 29(9): 1301–1312. 15. Trimnell D, Fanta GF, Salch JH. Graft polymerization of methyl acrylate onto granular starch: comparison of the Fe+2/H2O2 and ceric initiating systems. Journal of Applied Polymer Science. 1996; 60(3): 285–292.

Kojima K, Yoshikuni M, Suzuki T. Tributylborane‐initiated grafting of methyl methacrylate onto chitin. Journal of Applied Polymer Science. 1997; 24(7): 1587–1593.

Misra BN, Mehta IK, Dogra R. Grafting onto wool. VII. Ceric ion‐initiated graft copolymerization of vinyl monomers. Comparison of monomer reactivities. Journal of Applied Polymer Science. 1980; 25(2): 235–241.

Yazdani‐Pedram M, Retuert J. Homogeneous grafting reaction of vinyl pyrrolidone onto chitosan. Journal of Applied Polymer Science. 1997; 63(10): 1321–1326.

Kang BG, Yoon SH, Lee SH, et al. Studies on the physical properties of modified starch‐filled HDPE film. J. Appl. Polym. Sci. 1996; 60 (11): 1977–1984.


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