Preparation of aliphatic oligocarbonate polyols
View Patent ↗The present invention relates to an improved process for preparing aliphatic oligocarbonate polyols by transesterifying dimethyl carbonate (DMC) with an aliphatic polyol component.
1. A process for preparing oligocarbonate polyols, comprising
A) reacting dimethyl carbonate with a polyol component, in the presence of an ytterbium compound transesterification catalyst, at pressures of atmospheric pressure to 6 bar and temperatures of between 100 to 170° C.,
wherein step A) comprises n≧2 successive substeps A i ) in which i takes values of 1 to n, and in each substep A i ), a pressure 1 p i of between 3 to 6 bar is established in the reactor, a portion x i of the total amount of dimethyl carbonate is added to the liquid phase of the reaction mixture and, after a reaction time t i at a temperature T i , the methanol formed in the reaction is removed from the reaction mixture by distillation in the form of a gaseous methanol/dimethyl carbonate mixture, in the course of which the pressure is reduced, at constant temperature T i , from 1 p i to a pressure 2 p i , and in the last substep A n ), the portion x n still absent from the total amount is added and the pressure 2 p n at the end of the substep is atmospheric pressure; and
B) reducing the pressure further until a pressure of ≦100 mbar has been attained, passing an inert gas stream into the reaction mixture, such that further methanol/dimethyl carbonate mixture is distilled off in parallel, and such that the temperature of the reaction mixture does not exceed 195° C.
2. The process according to claim 1 , wherein the transesterification catalyst is ytterbium(III) acetylacetonate.
3. The process according to claim 1 , wherein the transesterification catalyst is chosen from ytterbium(III) heptadionate, ytterbium(III) acetylacetonate and ytterbium(III) chloride.
4. The process according to claim 1 , wherein the polyol component is 1,6-hexanediol.
5. The process according to claim 1 , wherein the polyol component is chosen from 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,12-dodecanediol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, trimethylolpropane, pentaerythritol, bis(2-hydroxyethyl) ether, bis(6-hydroxyhexyl) ether, diols prepared by reducing dimerized unsaturated fatty acids (“dimer diols”), short-chain C 2 or C 3 polyether diols having a number-average molecular weight of <500 g/mol, short-chain C 4 polyether diols having a number-average molecular weight of <700 g/mol and mixtures thereof.