Method for preparing polymethylols
The present invention relates to a process for distilling an aqueous polymethylol mixture which comprises a polymethylol of the formula (I) (HOCH 2 ) 2 —C—R 2 (I) in which each R is independently a further methylol group or an alkyl group having 1 to 22 carbon atoms or an aryl or aralkyl group having 6 to 22 carbon atoms, a tertiary amine, water and the adduct of tertiary amine and formic acid (amine formate), which comprises performing the distillation in a distillation column which is connected at the bottom to an evaporator, the bottom temperature being above the evaporation temperature of the monoester of formic acid and polymethylol (polymethylol formate) which forms during distillation. The present invention further relates to a composition comprising polymethylol and 1 to 10 000 ppm by weight of polymethylol formate, and to the use thereof.
1. A process for distilling an aqueous polymethylol mixture comprising a polymethylol of the formula (I)
in which each R is independently a further methylol group or an alkyl group having 1 to 22 carbon atoms or an aryl or aralkyl group having 6 to 22 carbon atoms, a tertiary amine,
water and
the adduct of tertiary amine and formic acid (amine formate), wherein the aqueous polymethylol mixture is obtained in a multistage reaction involving, in stage a), condensing alkanals in an aldol reaction with formaldehyde in the presence of tertiary amines as a catalyst to give methylolalkanals of the formula (II) where each R is independently a further methylol group or an alkyl group having 1 to 22 carbon atoms or an aryl or aralkyl group having 6 to 22 carbon atoms
and then, in stage b), distillatively separating the reaction mixture obtained from stage a) into bottoms comprising predominantly compounds of the formula (II), and a top stream comprising low boilers, and, in stage c hydrogenatingthe bottoms discharge from stage b), wherein the reaction discharge from the hydrogenation (stage c)) is an aqueous polymethylol mixture which comprises a polymethylol of the formula (I) and the aqueous polymethylol mixture is purified by removing low boilers from the polymethylol compound by distillation, wherein the distillation is performed in a distillation column which is connected at the bottom to an evaporator, the temperature at the bottom of the column being above the evaporation temperature of the monoester of formic acid and polymethylol (polymethylol formate) which forms during the distillation and wherein the reflux at the top of the column is adjusted such that the predominant amount of the polymethylol formate is retained in the column, and discharged from the bottom of the evaporator is a discharge which comprises predominantly the polymethylol compound.
2. The process according to claim 1 , wherein the aqueous polymethylol mixture comprises
20 to 90% by weight of polymethylol (I),
0 to 5% by weight of methanol,
0 to 5% by weight of tertiary amine,
0 to 5% by weight of organic secondary compounds,
0.01 to 5% by weight of the adduct of tertiary amine and formic acid (amine formate), and the remainder water.
3. The process according to claim 1 , wherein the polymethylol is neopentyl glycol, trimethylolpropane, pentaerythritol, trimethylolethane, or trimethylolbutane.
4. The process according to claim 3 , wherein the polymethylol is neopentyl glycol.
5. The process according to claim 1 , wherein the tertiary amine is triethylamine, tri-n-propylamine, tri-n-butylamine, or trimethylamine.
6. The process according to claim 4 , wherein the tertiary amine is trimethylamine.
7. The process according to claim 5 , wherein the tertiary amine is trimethylamine.
8. The process according to claim 1 , wherein the pressure at the top of the column is 0.001 to 0.9 bar, the column further comprises a condenser, and the operating temperature of the condenser is in the range from 0 to 80° C.
9. The process according to claim 1 , wherein the temperature of the bottom of the column is 10% to 50% above the boiling temperature of the polymethylol formate.
10. The process according to claim 1 , wherein the distillation column further comprises a condenser, and more than 30% by weight condensate obtained in the condenser is recycled into the distillation column.
11. The process according to claim 1 , wherein the distillation column has 5 to 30 theoretical plates.
12. The process according to claim 1 , wherein the distillation column has internals for increasing the separating performance and the aqueous polymethylol mixture is fed in within a spatial region between ¼ and ¾ of the theoretical plates of the distillation column.
13. The process according to claim 1 , wherein tertiary amine is added to the bottoms discharge from stage b).
14. The process according to claim 1 , wherein the bottoms discharge from the distillation of the aqueous polymethylol mixture is separated into a top stream comprising polymethylol, and a bottom stream comprising higher-boiling organic components.