Preparation Of Fully Bio-based UV-Cured Non-Isocyanate Polyurethanes

Polyurethane is the most common polymer material in our life,widely used in adhesives,coatings,low speed tire,car cushion etc.In order to further deepen the research and application of NIPU,we use renewable resource as the basic material and synthesised various kinds of functional small molecule compounds.Then we use the situ polymerization and ring opening polymerization UV-curing technology to verified their special function.prepolymer,and UV-curing the prepolymer,then we prepared two kinds of cardanol-based UV-cured polyurethane.The main content of this thesis include:1.Fully bio-based non-isocyanate polyurethane?NIPU?was facilely prepared by self-condensation of primary amide of ricinoleic acid under oxidation conditions.The resulting linear urethane oligomer?Mn=1307 Da?as a viscous liquid was further cured under UV light irradiation to afford a polymer film with hardness of lower than2B.Infrared spectra as well as changes of polymer appearance proved crosslinking of the linear NIPU.Hardness of UV-cured film was promoted to 4H when a certain amount of cardanol was added to the linear urethane oligomer,accompanied by manifest improvement of resistance to chemical media such as aqueous HCl,EtOH,toluene and THF.2.Eugenol epoxy resin was synthesized by the reaction of eugenol.The difunctional five-membered cyclic carbonate and dithiocarbonate 4 were successfully synthesized by the reaction of epoxide 1 with carbon dioxide and carbon disulfide respectively.The ring opening reactions of 3 with p-phenylenediamine were carried out in dimethyl sulfoxide at 100?for 48h to produce the corresponding poly?hydroxyurethane?s quantitatively.The ring opening reactions of 4 with p-phenylenediamine produced the corresponding poly?thiourethane?s quantitatively.The obtained poly?hydroxyurethane?s were thermally more stable than the analogous poly?thiourethane?s,probably because of less thermal stability of thiourethane moiety than hydroxyurethane moiety.we preparation cardanol-based UV-cured resins via3.UV-curing the prepolymer.The NIPUs exhibited T_g from-32^-25?and T_d above 200?.The studies showed that:The product have the most favorable overall performance when the mole ratio of cardanol-to-poly?thiourethane?s is 2:1.4.Eugenol,a relatively cheap and abundant renewable resource,is used to design terminal diene compounds.Thiol-ene click reactions between the terminal diene intermediates and 1,6-hexanedithiol afford the corresponding oligomers with molecularmass of about 1.3 kDa.The ring opening reactions of 7 with p-phenylenediamine produced the corresponding poly?thiourethane?s quantitatively.amount of cardanol was added to the linear urethane oligomer,via further cured under UV light irradiation,crosslinking reactions of cardanol with prepolymer.The NIPUs exhibited Tg from-36^-23?and Td above 180?.The polymer with highest stiffness was produced in the mole ratio of cardanol to poly?thiourethane?s is 2:1.