A Novel Approach To The Synthesis Of Nonisocyanate Polyurethane

Polyurethanes(PUs) are widely used in daily life for their excellent properties and molding advantages, as yet domestic markets for the PU products has huge developing potential. The conventional way to the synthesis of PU has many disadvantages and makes against the environment protection, so we attempt to study on the new way to synthesize a novel PU generation, nonisocyanate polyurethane (NIPU), which shows a better performance and saves the cost. Besides, it has little pollution and does little harm to the health of workers. In this subject, NIPU synthesized from macromolecule amine and small molecule cyclic carbonate was researched.1. The amine-terminated polyether (ATPE) was synthesized through methylsulfonyl chloride method. Firstly, methylsulphonate polyether was obtained by reaction of high reactive polyether polyols with methylsulfonyl chloride, and then the methylsulphonate polyether reacted with ammonia or methyl amine to form amine-terminated polyether. Different reaction conditions were discussed in the second step of this reaction and the products were confirmed by 1HNMR analysis. The studies showed that, the optimal reaction temperature is 130℃, the optimal ratio of raws is 5:1 and the optimal reation time is 5h.2. The amine-terminated polyether (ATPE) was synthesized through chlorohydrination method in two steps. Firstly, vic-chlorohydrins-terminated polyether was obtained through high reactive polyether polyols reacting with epichlorohydrin catalyzed by double metal cyanide catalyst (DMC). Then, vic-chlorohydrins-terminated polyether (CHTPE) reacted with ammonia to form amine-terminated polyether. We found the rules of controlling graft numbers of epichlorohydrin and amine value of the product quantitatively, according to that, we studied the effect factors of this reaction. The results showed that the optimal reaction temperature is 110℃, the ratio of raws is 5:1, the reation time is 6h. Structure of the product was signified by 1HNMR spectra.3. The synthesis of cyclic carbonate from carbon dioxide and small molecule epoxides was researched, including glycol diglycidyl ether and trimethylolpropane triglycidyl ether. In further we studied the effect factors of this reaction. The results indicated that, in the condition of 100℃and 2.0Mpa, using tetrabutylammonium iodide as catalyst, the glycol diglycidyl ether was reacted in the highest yields, and in the condition of 120℃and 2.0Mpa, using tetrabutylammonium iodide as catalyst, the trimethylolpropane triglycidyl ether was reacted in the highest yields. Structure of the product was signified by FT-IR and 1HNMR spectra.4. Nonisocyanate polyurethanes (NIPU) were obtained by amine-terminated polyether and small molecule cyclic carbonate when cyclic carbonate-to-amine ratio is 1:1. The target product was signified by FT-IR spectra.The research showed that, the amine-terminated polyether from methylsulfonyl chloride method was low active and could not reacted with cyclic carbonate to obtain NIPU; while the amine-terminated polyether from chlorohydrination method was more active to synthesize NIPU.