Study On Preparation And Modification Of The Copolymer Of Maleic Anhydride And Sesquiterpene From Turpentine

Heavy turpentine,which is mainly composed of longifolene and ?-caryophyllene,is a by-product in the production and processing of Masson pine oleoresin.As a kind of renewable resource,heavy turpentine has not been used with high added value,and it has been used as a fuel and low solvent for many times.In this study,a series of copolymers containing anhydride groups were prepared by copolymerization of heavy turpentine oil,including the main sesquiterpene,and maleic anhydride.Because of the high activity of the anhydride group,this kind of copolymer can be further modified,so as to provide a good research direction to improve the added value of heavy turpentine.In this study,the modification of heavy turpentine-maleic anhydride copolymer was taken as an example.By modifying the copolymer,the end group of ethylene was introduced.Then,the modification is applied to the field of UV curing.?-Caryophyllene-maleic anhydride copolymer(BCPMA)was synthesized by using ?-caryophyllene and maleic anhydride as raw material with di-tert-butyl peroxide(DTBP)as initiator and cyclohexanone as solvent.The effects of reaction temperature,reaction time,molar ratio of monomers,the amount of solvent and the amount of initiator on the yield of the copolymer were discussed.The structure of the polymer was characterized by FTIR,1HNMR,GPC and elemental analysis.Thermal stability of the polymer was determined by thermal gravimetric analysis(TG).The results show that when the conditions of reaction temperature 145?,reaction time 1h,molar ratio of maleic anhydride to ?-caryophyllene 2:1,mass ratio of cyclohexanone to ?-caryophyllene 2:1 and initiator dosage 4.5%,the yield of copolymer can reach 92.9%.The initial decomposition temperature of the copolymer is 370.6?,which indicates that it has high thermal stability.Heavy turpentine-maleic anhydride copolymer(HTPMA)was synthesized by using ?-caryophyllene and maleic anhydride as raw material with di-tert-butyl peroxide as initiator and cyclohexanone as solvent.The results of gas chromatography analysis of filtrate obtained from the bulk polymerization of heavy turpentine and maleic anhydride is that the reactivity of ?-caryophyllene and maleic anhydride is better than that of longifolene and maleic anhydride.The structure and properties of HTPMA were characterized by FT-IR,GPC,elemental analysis and TG analysis.The application of heavy turpentine maleic anhydride copolymer in the field of UV curing was studied.The HTPMA was further modified by 2-Hydroxyethyl acrylate and the polyester containing terminal vinyl group(HTMHA)was obtained.The FT-IR spectra showed that the anhydride groups of HTPMA were opened,and the terminal vinyl groups were successfully introduced.The performance of HTMHA UV curing film was tested.The results showed that the cured film had good flexibility and chemical resistance...