Processes for preparing polytrimethylene ether glycol
View Patent ↗Provided are processes for preparing low molecular weight polytrimethylene ether glycol by acid catalyzed polycondensation, neutralization, removal of unreacted monomer, and contact with filter aid. The processes can avoid hydrolysis and yet provide product substantially free of catalyst derived end groups.
1. A process of making low molecular weight polytrimethylene ether glycol comprising the steps of:
(a) polycondensing an initial mixture comprising 1,3-propanediol and sulfuric acid at a temperature of at least about 150° C. to obtain a first reaction mixture;
(b) adding to the first reaction mixture (i) alumina, (ii) silica based filter aid, and optionally (iii) activated carbon black at temperature greater than about 120° C. and less than about 200° C. to form a second reaction mixture;
(c) distilling the second reaction mixture at a pressure of about 1 to about 40 torr and a temperature of about 120° C. to about 200° C. to obtain a third reaction mixture and a distillate containing 1,3-propanediol; and
(d) filtering the third reaction mixture at a temperature of about 70° C. to about 100° C. to obtain polytrimethylene glycol of number average molecular weight from about 200 to about 500 which contains less than about 0.5 weight % 1,3-propanediol and has an acid number of less than 0.05 mg KOH/g and a turbidity of less than about 1 NTU.
2. The process of claim 1 wherein the distillate containing 1,3-propanediol from step (c) is recycled to the initial mixture of step (a).
3. The process of claim 1 wherein the third reaction mixture contains less than about 1% by weight 1,3-propanediol.
4. The process of claim 1 wherein step (d) is repeated.
5. The process of claim 1 wherein the amount of sulfuric acid in step (a) is less than about 0.3% by weight.
6. The process of claim 1 wherein the polytrimethylene ether glycol has a molecular weight of from about 200 to about 300.
7. The process of claim 1 wherein the initial mixture contains recovered 1,3-propanediol.
8. The process of claim 1 wherein step (c) is performed at about 120 to about 180° C. and the total combined amount of alumina and silica is less than about 5% by weight of the first reaction mixture.
9. The process of claim 8 wherein the weight ratio of alumina to silica is within the range from 2:1 to 3:1.