Preparation and characteristics of cationic starches

: 159-165
Ivano-Frankivsk National Technical University of Oil and Gas;LLC "SCIENTIFIC AND TECHNICAL FIRM" BIPEX LTD "
Lviv Polytechnic National University
Lviv Polytechnic National University
Lviv Polytechnic National University
Lviv Polytechnic National University

The aim of the work was to improve and simplify the method of obtaining cationic starches with a high degree of substitution using triethylamine and epichlorohydrin as starting reagents, research and optimization the conditions for the process of cationation of starch by a semi-dry method. Cationic starch with ammonium fragments, 3-chloro-2-hydroxypropyltrietilammonium chloride was obtained by the interaction of an amine reagent with corn starch in the presence of NaOH by a semi-dry manner.

The amine reactant 3-chloro-2-hydroxypropyltriethylammonium chloride was obtained by the one-pot interaction of triethylamine with HCl followed by the reaction with epichlorohydrin in the presence of cetyltrimethylammonium bromide as a catalyst. Cationic starches with the degree of substitution of hydrogen atoms in OH groups of starch (DS) 0.02 ÷ 0.45 was obtained by the interaction of 3-chloro-2-hydroxypropyltrietilammonium chloride with corn starch in the presence of sodium hydroxide. The molar ratio of sodium hydroxide to the amine reagent and the ratio of the amine reagent to starch (D-glucopiranose unite) in the starting reaction mixture on the DS was investigated. It was shown that cationized starch with the highest degree of substitution was formed at the optimal starting molar ratio of sodium hydroxide to amine reactant equal to 1,2 -2,0. Increasing the ratio of the amine reagent to starch with the sodium hydroxide content being less than optimal increases the DS significantly. The structure of the amine reagent and the cationic starch was confirmed by IR spectroscopy. The content of ammonium fragments in the cationic starch was calculated on the nitrogen content determined by the Kjeldahl method. The greatest efficiency of the reaction of corn starch cationization in the investigated range from 1.0 to 6.0 was observed at the molar ratio of the amine reagent: starch = 1.0.

1. Vida Zargar, Morteza Asghari, & Amir Dashti. (2015). A Review on Chitin and Chitosan Polymers: Structure, Chemistry, Solubility, Derivatives, and Applications ChemBioEng Rev 2, 1-24.
2. Kriazhev, V. N., Romanov, V. V.,& Shyrokov, V. A. (2010). Poslednye doslyzhenyia khymyy y tekhnolohyy proyzvodnыkh krakhmala. Khymyia  rastytelnoho sыria, (1), 5-12.
3. Prado, H. J., & Matulewicz, M. S. (2014). Cationization of polysaccharides: A pass to greener darivatives with many industrial applications. Europian Polymer Journal (52), 53-75.
4. Baek, K., Yang, J. S., Kwon, T. S., Yang, J. W., & Yang, Ji-Won (2007). Cationic starch-enhanced ultrafiltration for Cr (VI) removal. CBE-Journal Papers, 206, 245-250.
5. Ching Ting Tsao, Chih Hao Chang, Yu Yung Lin, Ming Fung Wu, Jaw-Lin Wang, Jin Lin Han, & Kuo Huang Hsieh (2010). Antibacterial activity and biocompatibility of a chitosan-c-poly (glutamic acid)  polyelectrolyte complex hydrogel. Carbohydrate Research, 345, 1774-1780.
6. Butrym, S. M., Butrym, N. S., Byldiukevych, T. D., & Yurkshtovych, T. L. (2010). Sposob poluchenyia katyonnoho krakhmala. Pat. BY 12847, MPK S 08V 31/100. 28.02.2010.
7. Sableviciene, D., Klimaviciute, R., Bendoraitiene, J., & Zemaitaitis, A. (2005). Flocculation properties of hight substituted cationic starches. Colloids and surfaces A: Physicochem. Tng. Aspects,
259, 23-30.
8. Popadyuk, N., Zholobko, O., Donchak, V., Harhay, H., Budishevska, O., Voronov, A., Kohut, A., & Voronov, S. (2014). Ionically and Covalently Crosslinked Hydrogel Particles Based on Chitosan and
Poly (ethylene glycol). Chemistry and Chemical Thechnology, 8(2), 171-176.
9. Pi-xinWang, Xiu-liWu, Xue Dong-hua, Xu Kun, Tan Ying, Du Xi-bing, & Li Wen-bo. (2009). ER, % 165 Preparation and characterization of cationic corn starch with a high degree of substitution in dioxane-THFwater media. Carbohydrate Research, 344, 851-855.
10. Lytviak, V. V., & Kanarskyi, A. V. (2016). Osobennosty katyonyzatsyy α-D-hliukopyranozы krakhmala v polozhenyy3S atoma (N-3-khloro-2-hydroksypropyl)-N, N, N-trymetylammonyi khlo-rydom. Plastycheskye massы, 7-8, 27-31.
11. Khalil, M. I., Farag and, S., & Hushem, A.(1993) Preparation fnd Characterization of SomeCationic Starches. Journal Starch/stärke, 45 (6), 226-231.
12. Cheronys, N., & Ma, T. S. (1973) Mykro- ypolumykro metodы orhanycheskoho funktsyonalnohoanalyza. M.: Khymyia, 576.
13. Pat. CN1187484A, China. Inventor YangJinzong Zhang Yonghua Yan Xiujun Wan YongxiangDing Wenguang (1997). Process for synthesizing 3-chloro-2-hydroxypropyl-trimethyl mmoniumchloride.
14. Khalil, M. I. & Farag Dokki, A. (1998).Preparation of Some Cationic Starches using the DryProcess. Journal Starch/stärke, 50(6), 267-271.<267::AID-STAR267>3.0.CO;2-W
15. Kazytsыna, L. A., & Kupletskaia, N. B.(1971). Prymenenye UF-, YK- y YaMR-spektroskopyy v orhanycheskoi khymyy. - M: Vыsshaiashkola, 264.
16. Kizil, J. & Seetharaman, K. (2002).Characterization of Irradiated Starches by Using FTRamanand FTIR Spectroscopy. Journal of Agricultureand food chemistry, 50, 3912-3918.
17. Pereira, A. G., Paulino, A. T., Rubira, A. F.,& Muniz, E. C. (2010). Polymer-polymer miscibility inPEO/cationic starch and PEO/hydrophobic starch bland.eXPRESS Polymer Letters, 4(8), 488-499.
18. Fanga, J. M., Fowlera, P. A., Sayersb, C. &Williams P. A. (2004). The chemical modification of arange of starches under aqueous reaction conditions.Carbohydrate Polymers, 55, 283-289.
19. Chun Bei Huang, Robert Jeng, Mohini Sain,Bradley A. Saville & Martin Hubbes. (2006).Production, characterization, and mechanicalpropertiesof starch modified by Ophiostoma spp.Bioresources, 1(2), 257-269.
20. Lovkys, Z. V., Lytviak, V. V., & Petiu-shev N. N. (2007). Tekhnolohyia krakhmala y krakhmalo-produktov: ucheb. posob., RUP "Nauchno-praktyches-kyi tsentr Natsyonalnoi akademyy nauk Belarusypo prodovolstvyiu. - Mynsk: Asobnы, 178.
21. Quanxiao Liu, Jinli Li, & Wencai Xu.(2010). Application of Cationic Starch with HighDegree of Substitution in Packaging Paper from High Yield Pulp. Scientific Research. Proceedings of the 17th IAPRI World Conference on Packaging, 35-38.