Study On Synthetic Technology Of Grafting Anthraquinone As Redox Mediator

The purpose of this paper is to immobilize anthraquinone moleculars onto carrer materials by chemical grafting methods based on the relevant chemical reactions of the substituents on anthraquinone.The strongly acidic cation exchange resin and cellulose were used as carriers to graft anthraquinone.The synthesis processes were studied and optimized respectively.The structure and properties of the modified materials were investigated thoroughly.In this paper,2-amino anthraquinone was immobilized on ion exchange resin firstly.Anthraquinone functional resin(AFR)was synthesized using a series of chemical reactions.Fourier transform infrared spectroscopy(FT-IR)and Thermogravimetric analysis(TGA)were used to characterize the AFR.Catalytic activity and reusability of AFC on biological reduction of NaNO3 were investigated and compared with the ones of another quinonly resin prepared by physical adsorption method.The results showed that the optimal condition for the synthesis processes of AFR were as follows:001*7 resin sulfonyl chloride modified by SOCl2,KOH:-NH2:-SO2Cl=4:2:1,and immobilization reation time for 4 h at 80℃.The grafting rate and anthraquinone content of AFR were 92.7%and 3.45mmol/g in above conditions.FT-IR result showed that quinonyl groups were successfully immobilized on resin with carbanyl group and secondary amino group detected.According to TGA curves,it showed that novel immobilized redox mediator maintain a good thermal stability below 100℃ meetting the application requirements.Biological reduction rates of NaNO3 increased by 2.8 times and the degradation rate of NaNO3 reached 95%after AFR(92.7%)added.Further more,the properties of AFR(92.7%)retained the same during 8-time successive repeated experiments,but another quinonly resin physical adsorption method lost its catalytic activity at 4-time successive repeated experiments.The anthraquinone functional cellulose(AFC)was fabricated by the reaction of chloridized cellulose and 2-amino anthraquinone.The cellulose was modified by thionyl chloride dissolved in[AMIM]Cl ionic liquid as solvent.The results showed that the optimal condition for the synthesis processes of AFC were as follows:the molar ratio of SOCl2:-OH=2:1 and immobilization reation time for 4 h at 80℃.The substitution degree of chloridized cellulose was 1.89 in above conditions.The grafting rate of AFR was 136%with a content of 6.09 mmol/g for anthraquinone group when the molar ratio of-Cl:-NH2:KOH was 1:1.6:2.56 and the experiment was carried out at 100℃ for 6 h.The property、composition、morphology and structure of materials were determined and analyzed by means of FT-IR、HNMR、EDS and SEM.The results showed that AFC had carbonyl group and secondary amine group,and its surface morphology became coarse.The prepared AFC could serve as membrane material of Anthraquinone immobilized functional membrane and had a potential on certain practical application because of its high content of anthraquinonyl.