Syntheses And Application Of Non Isocyanate Polyurethane

Under the promotion of green chemistry non-isocyanate polyurethane (NIPU) havebeen attracting more attentions. The researches are mainly focused on the reaction of cycliccarbonate and amime. In this thesis, the recently researches about NIPU has been reviewed.The benign monomer4-(hydroxymethyl)-1,3-dioxolan-2-one was obtained from thereaction of renewable starting materials glycerol and dimethyl carbonate. Anionic andcationic polymerization of glycerol carbonate was preceded to give oligomer with etherunit due to decarboxylation, which reacted with dimethyl carbonate to produce linear bis(cyclic carbonate). The polymerization condition was explored. The preparation pathway ofmacromolecular diamine was investigated by the reaction of EPO3000terminated bymethoxycarbonyl group with1,6-hexanediamine.The esterification of cyclic glycerol carbonate with carbonyl chloride or anhydride toproduce bis (2-oxo-1,3-dioxolan-4-yl) methyl phthalate, hexane-1,6-diyl bis (2-oxo-1,3–dioxolan-4-yl) methyl diphthalate and bis (2-oxo-1,3-dioxolan-4-yl) methyl poly (1,6-hexanediyl adipate). The selectivity of cyclic carbonate containing ester group with primaryamine were examined using reaction of (2-oxo-1,3-dioxolan-4-yl) methyl benzoate with1-butylamine and benzylamine as the model. The intensity of carbonyl in cyclic carbonatewas monitored by FT-IR through the reaction process. The results of FT-IR and1H NMRshown that the amine selectively reacted with cyclic carbonate to form urethane. Noamidation reaction of amine with ester was observed. The ring opening reaction of bis(cyclic carbonate) with1,6-hexanediamine was further explored to learn the preparationpossibility of higher molecular weight non-isocyanate polyurethane. The obtained productwas characterized by the1H NMR, FT-IR, HSQC, GPC and MALDI-TOF analyses. TheGPC analysis showed that the number average weight of the oil was of the range of0.99to3.11*103, and the molecular weight distribution was of the range of1.50-2.30. Based on theanalysis of MALDI-TOF the obtained oil from the reaction of bis (2-oxo-1,3-dioxolan-4-yl)methyl phthalate with1,6-hexanediamine was a polyurethane oligomer with amino andhydroxyl as end groups. The polymer obtained by1,6-hexanediamine with polyester basedbis (cyclic carbonate) was a cyclic polyester-polyurethane oligomer. Those oligomerswould be a kind of useful starting materials for the higher molecular weight of polyurethane, polyester and so on. The unique structure of oligomer can increase theperformance tune ability of functional material.In addition, the copolymers with GC functional groups as side chain have beensynthesized by free radical polymerization of (Z)-4-oxo-4-(2-oxo-1,3-dioxolan-4-yl)methoxy)but-2-enoic acid with methyl acrylate and styrene. The high molecular weightpolyurethanes were obtained by ring-opening reaction of cyclic carbonate contentedcopolymer with amine.