Preparation And Properties Of Terpene-based Cyclic Carbonate And Nonisocvanate Polyurethane

In this paper, a novel terpinene-maleic ester-type cyclic carbonate (TCC) was synthesizedby terpinene-maleic ester-type epoxy resin (TME) reacted with CO2. The synthesizeddifunctional cyclic carbonate was used to synthesize nonisocyanate polyurethanes (NIPU) bypolyaddition with diamines such as1,2-ethanediamine (EDA),1,6-hexamethylene diamine(HMDA), triethylenetetramine (TETA) tetraethylenepentamine (TEPA) and isophoronediamine (IPDA). TCC modified with epoxide resin E-51was used to synthesize hybridnonisocyanate polyurethane(HNIPU) by curing with polyamines hardeners.The main contents and conclusions of this paper were listed as follows:1. A novel biomass terpene-based cyclic carbonate was prepared by treatment ofterpene-based epoxy resin with carbon dioxide in the conjunctional catalysis oftriethylbenzylammonium and ethylene glycol without any organic solvent. The effects of thedosage of catalyst, carbon dioxide pressure, reaction temperature and time on the reaction wereinvestigated. The cyclocarbonate value of the product was obtained by the method ofpotentiometric titration. The results showed that the cyclocarbonate value of the product was0.267mol/100g, the conversion of terpene-based epoxy resin and the selectivity for cycliccarbonate were as high as99.7%and94.0%under optimum conditions (catalyst concentration1.0%, CO2pressure1.5MPa, reaction temperature130℃and reaction time7h) respectively.The chemical structure of the novel terpene-based cyclic carbonate was characterized by GPC,FT-IR, MS,1H NMR and13C NMR.2. The crosslinking reaction kinetic of TCC with HMDA was investigated by FT-IRmethod. The kinetic equation of the crosslinking reaction system was obtained.The kinetic equation of TCC/HMDA system: 3. NIPU was synthesized by TCC reacted with difunctional primary amines. The synthesized NIPU was characterized by FT-IR analysis. The results showed that the formation of amide functions was strongly affected by the temperature of polymerization, amide linkages were not observed when the temperature of polymerization was over120℃. The polymer with highest glass transition temperature was produced in the stoichiometric molecular ratio of carbonate to amine. The linear NIPUs exhibited Tg from13to64℃and Td above300℃.4. The hybrid nonisocyanate polyurethane coating was synthesized by TCC/E-51reacted with difunctional primary amines at90℃for3h and then at140℃for4h. The microphase separation took place when the dosage of E-51up to60%by weight based on the weight of TCC, which was characterized by FT-IR and SEM analysis to the coating.HNIPU has many eximious properties, such as good impact strength, flexibility, adhesion, water resistance and ethanol resistance compared with the NIPU. The properties of the composite products are closely related to the dosage of E-51. The pencil hardness, flexibility, adhesion, water-resistance and ethanol-resistance properties of the composite products increase with the dosage of E-51.