Modification And Photopolymerization Of Styrene Maleic Anhydride Compolymer

Photopolymerization is a high-efficiency,energy-saving,and environmentally-friendly high-tech with a controllable process and low temperature.The main properties of photocurable materials are related to the properties of oligomers,so the choice of oligomers is particularly important.Styrene-maleic anhydride copolymer(SMA)is a commonly used easily functionalized polymer with high gloss,abrasion resistance,good pigment compatibility and high reactivity of acid anhydride.It has applications in many fields such as automotive parts,dye dispersion,composite materials,fillers,and in recent years,the industrial production of SMA resin has been realized in China.However,SMA resin has high hardness and cannot continue to polymerize.These properties largely limit the application of SMA resin.In this paper,the flexible segment and polymerizable modification of the SMA resin are carried out to improve the flexibility of the SMA resin and endow it with photopolymerizable properties.The modified SMA resin is used as a special oligomer to study the photocuring properties,and the photopolymerization technology and SMA resin application is further developed.In this paper,the styrene-maleic anhydride copolymer can undergo ring-opening esterification reaction with the hydroxyl groups in the acid anhydride group,and SMA is modified step by step to optimize the modification conditions.Next,six modified SMA resins containing carbon-carbon double bonds were synthesized.Free radical photopolymerization technology was used to shape and process the modified SMA resin formulations,and the photocurable properties of the modified SMA resin formulations were further studied.(1)The SMA resin was modified with a long-chain fatty alcohol stearyl alcohol-the single hydroxyl flexible chain-in the solvent methyl ethyl ketone(MEK)to synthesize OSMA.The conditions of reaction temperature,reaction time,and catalyst Triethylamine(TEA)dosage are optimized.The optimal conditions for the modification with single hydroxyl flexible chain are reaction temperature 80?,reaction time 6 h,and catalyst trimethylamine(TEA)dosage 1%wt,Using hydroxyethyl methacrylate(HEMA)as the grafting monomer to synthesis the monohydroxyl polymerizable modification of OSMA in the solvent methyl ethyl ketone(MEK).The optimal conditions for the monohydroxyl polymerizable modification are reaction temperature 80?,reaction time 6 h,and catalyst trimethylamine(TEA)dosage 1%wt.With optimized modification conditions,EOSMA-1 and EOSMA-2 were synthesized by the SMA resin and different ratios(5:5,3:7)of long-chain fatty alcohol compound/hydroxyethyl acrylate(HEA),EMSMA were synthesized by SMA resin and polyethylene glycol monomethyl ether(mPEG)/hydroxyethyl acrylate(HEA),and EASMA were synthesized by SMA resin and fatty alcohol polyoxyethylene ether(AEO)/hydroxyethyl acrylate(HEA),and hydroxyethyl acrylate(HEA)modified SMA and styrene-maleic anhydride-butyl acrylate terpolymer(SMAB)resins respectively to synthesise E-SMA and E-SMAB.The thermal stability of six modified resins was analyzed by thermogravimetric analysis.Analysis shows that the mass loss of the six modified resins occurred only above 100? and have good thermal stability.The step-by-step graft modification scheme makes the SMA resin possess both flexible segments and polymerizable groups,which provides an idea for the multiple functionalization of SMA resin.(2)Six kinds of modified SMA resins are used as oligomers,and the reactive diluents propylene glycol diacrylate(DPGDA)and trimethylolpropane triacrylate(TMPTA)are used for photo-curing formula research.The resins with better solubility are selected DPGDA is used as a reactive diluent,and the formula composition is determined by viscosity test.The photocuring kinetics of the modified SMA resin formulation was studied by real-time infrared monitoring.The final conversion rate of carbon-carbon double bonds of EOSMA-1,EOSMA-2,EMSMA,and EASMA photocuring systems exceeded 84%at 90 mW/cm2,365 nm,15 s can be fully cured.The photocurable performance of modified SMA resin was systematically studied:the thermal stability,tensile mechanical properties,glass transition temperature(Tg),hydrophilicity and hydrophobicity of the modified SMA resin photocurable material were investigated.The six kinds of modified SMA resin light-curing materials have good thermal stability,and all have thermal weight loss above 167?.EMSMA and EASMA photocurable materials have the properties of high breaking elongation,high toughness value,high hydrophilicity and low glass transition temperature.The breaking elongation of the two is 12.76%,15.54%,toughness values is 42.0 MJ/m3,51.9 MJ/m3,glossiness of glass transition temperature is 45.5?,65.96?,water contact angle is 13.0°,5.5°,respectively.Investigate the gloss,hardness,flexibility,abrasion resistance,etc.of the modified resin light-cured coating.EMSMA and EASMA have high gloss,low hardness and good flexibility.Among them,EASMA has both high wear resistance and high flexibility,and the overall performance is the best.The photopolymerization technology has high molding processing efficiency and low cost for the modified SMA resin,which provides a new way for the industrial application of SMA resin.