Synthesis And Characterization Of Bio-based Non-isocyanate Polyurethane Hybrids Through A Non-isocyanate Route

In this paper,we demonstrate a facile route to prepare bis(2,3-dihydroxypropyl)ether dicarbonate(DGDC)from biomass diglycerol and dimethyl carbonate(DMC).The obtained bis(cyclic carbonate)monomer can be subsequently applied for the preparation of linear and cross-linked non-isocyanate polyurethanes.Then,we mixed an epoxy resin(1,4-butanediol diglycidyl ether)and DGDC,and react them with diethylenetriamine or triethylene tetramine to prepare hybrid non-isocyanate polyurethane(HNIPU).Finally,we synthesized two difurfuryl diamines from furfurylamine and aldehydes or acetone.By reacting them with DGDC,a series of full bio-bassed HNIPUs were prepared.The structure,thermal and mechanical properties of the obtained polymers were investigated.1.We used biomass diglycerol to react with dimethyl carbonate and prepared DGDC using K2CO3 as catalyst at 70 'C for 24 h.the yield is up to 79%.The structure of DGDC was confirmed by infrared and nuclear magnetic characterization.DGDC was reacted with diamines or triamines,and linear and cross-linked NIPUs were prepared through green channels.The prepared NIPU has low thermal stability and low Tg.The tensile strength and elongation of the Cross-linked NIPUs were compared by changing the ratios of diamine and trimethylamine and the type of diamine.The tensile strength of the Cross-linked NIPU-5 was 15.76 MPa,and the elongation was up to 284%.2.A series of thermosetting HNIPU materials were obtained by mixing DGDC and epoxy resin(1,4-butanediol diglycidyl ether)as A component and reacting with B component(diethylenetriamine,triethylene tetramine).The thermal properties,dynamic mechanical properties and physical mechanical properties were investigated.TGA tests show that the introduction of the epoxy resin can improve the initial decomposition temperature of HNIPU from 10 to 40 ?,and the DMA test showed that Tg was 0 to 40 ?.The crosslinking density of the series HNIPU materials was calculated by using the elastic theory of elastomer,and its range was 247-4827mol/m3,and the tensile strength was up to 18-24Mpa,and the elongation of the fracture was 64-66%.3.To obtain bio-based amines,we used biomass furan methylamine to react with acetaldehyde and acetone,respectively,under 6 mol/L HCL at 40?,and prepared acetaldehyde difurfuryl diamine(CH3-DFDA)and acetone difurfuryl diamine(DIFFA).The yield is 67%and 80%,respectively.The synthesized DIFFA and CH3-DFDA were confirmed by infrared and nuclear magnetic characterization.4.A series of bio-bassed HNIPU materials were obtained by mixing DGDC and epoxy resin(1,4-butanediol diglycidyl ether)as A component,and reacting with B component(CH3-DFDA or DIFFA).The tensile strength is between 20.3-22.7Mpa and the elongation of fracture is between 170.7-294.5%.The crosslinking density was 227-2795mol/m3.