Methods of preparing hydroxy functional vegetable oils

Abstract

There is disclosed a process for hydroxylating vegetable oils to create polyols suitable for use in polymer processes, particularly polyurethane processes. The process includes contacting a vegetable oil with hydrogen peroxide and an organic acid having 1-3 carbon atoms under conditions sufficient to oxidize carbon to carbon double bonds found in the vegetable oil. There is also disclosed a vegetable oil based polyol having an acid number of 2.0 mg KOH/g or less. The polyol contains 0.1% w/w or less water, 0.1% w/w or less of the organic acid used to prepare the polyol, and triglyceride groups having fatty acid moieties ranging from C 16 to C 18 . The fatty acid moieties contain pendant carboxylate groups having from 1 to 3 carbon atoms.

That which is claimed is: 
     
       1. A process for preparing a polyol having an acid number of not more than about 2 mg KOH/g, the process comprising the steps of:
 contacting a vegetable oil containing triglycerides with hydrogen peroxide and an organic acid having from 1 to 3 carbon atoms in the presence of water for a sufficient period of time, at a sufficient temperature, and at a sufficient pressure to hydroxylate carbon to carbon double bonds located along the fatty acid moieties of the triglycerides thereby forming a crude polyol product, 
 separating volatiles from the crude polyol product to achieve a semi-refined product, and 
 further reacting the semi-refined product at a sufficient temperature and under a sufficient vacuum to achieve a final polyol product having an acid number of not more than 2 mg KOH/g. 
 
     
     
       2. A process according to  claim 1  wherein the vegetable oil is selected from the group consisting of corn oil, palm oil, palm kernel oil, soybean oil, cottonseed oil, peanut oil, rapeseed oil, safflower oil, canola oil, olive oil, rice bran oil, jatropha oil, algae oil, and sunflower oil. 
     
     
       3. A process according to  claim 1  wherein the step of further reacting the semi-refined product comprises heating the semi-refined product at a temperature of at least approximately 170° C. under a vacuum to achieve a final polyol product having an acid number of not more than 2 mg KOH/g. 
     
     
       4. A process according to  claim 1  wherein the step of contacting a vegetable oil with hydrogen peroxide and an organic acid at a sufficient temperature to hydroxylate carbon to carbon double bonds comprises contacting the components at a temperature between about 50° C. and about 150° C. 
     
     
       5. A process according to  claim 1  wherein the molar ratio of organic acid to vegetable oil ranges from about 0.5/1 to about 10/1. 
     
     
       6. A process according to  claim 1  wherein the organic acid is acetic acid. 
     
     
       7. A process of according to  claim 1  wherein the molar ratio of hydrogen peroxide to vegetable oil ranges from about 0.1/1 to 6/1. 
     
     
       8. A process according to  claim 1  wherein the volatile separation step is conducted under a vacuum at a temperature less than about 170° C. and the further reaction step is conducted under a vacuum at a temperature between about 170° C. and about 270° C. 
     
     
       9. A continuous process for preparing a polyol having an acid number of not more than about 2 mg KOH/g, the process comprising the steps of:
 continuously charging a reactor with vegetable oil, hydrogen peroxide, and an organic acid having 1 to 3 carbon atoms wherein the charging is conducted at a temperature sufficient to initiate a reaction and at a flow rate that provides a residence time in the reactor sufficient to achieve a crude polyol product with an epoxide content less than or equal to 0.7 w/w of oxirane oxygen; 
 continuously transferring the crude polyol product from the reactor to a volatile separation step wherein the crude polyol product is subjected to heat while under vacuum wherein the heat and vacuum and residence time are sufficient to remove volatiles and achieve a semi-refined product; and 
 continuously transferring the semi-refined product of the volatile separation step to a further reaction step where the semi-refined product is subjected to heat while under a vacuum wherein the heat and vacuum and residence time are sufficient to achieve a final polyol product having an acid number of not more than 2 mg KOH/g. 
 
     
     
       10. A process according to  claim 9  wherein the vegetable oil is selected from the group consisting of corn oil, palm oil, palm kernel oil, soybean oil, cottonseed oil, peanut oil, rapeseed oil, safflower oil, canola oil, olive oil, rice bran oil, jatropha oil, algae oil, and sunflower oil. 
     
     
       11. A process according to  claim 9  wherein the further reaction step comprises heating the semi-refined product at a temperature of at least approximately 170° C. under a vacuum to achieve a final polyol product having an acid number of not more than 2 mg KOH/g. 
     
     
       12. A process according to  claim 9  wherein the molar ratio of organic acid to vegetable oil ranges from about 0.5/1 to about 10/1. 
     
     
       13. A process according to  claim 9  wherein the volatile separation step is conducted under a vacuum at a temperature less than about 170° C. and the further reaction step is conducted under a vacuum at a temperature between about 170° C. and about 270° C. 
     
     
       14. A process according to  claim 1  comprising the additional step of reacting the final polyol product with an isocyanate. 
     
     
       15. A process according to  claim 9  comprising the additional step of reacting the final polyol product with an isocyanate. 
     
     
       16. A process according to  claim 9  wherein the further reaction step is conducted in one or more pieces of equipment selected from the group consisting of a high temperature vacuum strip reactor, a wiped film evaporator, a counter current packed column, a distillation column, and a steam stripping vessel. 
     
     
       17. A vegetable oil based polyol having an acid number of 2.0 mg KOH/g or less and comprising 0.1% w/w or less water, 0.1% w/w or less of the organic acid used to prepare the polyol, and triglyceride groups having fatty acid moieties ranging from C 16  to C 18  wherein said fatty acid moieties contain pendant carboxylate groups having from 1 to 3 carbon atoms. 
     
     
       18. A vegetable oil based polyol according to  claim 17  wherein the vegetable oil is selected from the group consisting of corn oil, palm oil, palm kernel oil, soybean oil, cottonseed oil, peanut oil, rapeseed oil, safflower oil, canola oil, olive oil, rice bran oil, jatropha oil, algae oil, and sunflower oil. 
     
     
       19. A vegetable oil based polyol according to  claim 17  that has been reacted with polyurethane comprising a reaction product of the vegetable oil based polyol of claim 17 and an isocyanate. 
     
     
       20. A process for preparing a polyol having an acid number of not more than about 2 mg KOH/g, the process comprising the steps of:
 separating volatiles from a crude polyol product prepared from an epoxidized vegetable oil to achieve a semi-refined product, and   further reacting or purifying the semi-refined product at a temperature of at least approximately 170° C. under a vacuum to achieve a final polyol product having an acid number of not more than 2 mg KOH/g.    
     
     
       21. A process according to claim 20 wherein the volatile separation step is conducted under a vacuum at a temperature less than about 170° C. and the further reaction or purification step is conducted under a vacuum at a temperature between about 170° C. and about 270° C.  
     
     
       22. A process according to claim 20 wherein the further reaction step is conducted in one or more pieces of equipment selected from the group consisting of a high temperature vacuum strip reactor, a wiped film evaporator, a counter current packed column, a distillation column, and a steam stripping vessel.  
     
     
       23. A polyurethane comprising a reaction product of the polyol of claim 20 and an isocyanate.  
     
     
       24. A process for preparing a polyol having an acid number of not more than about 2 mg KOH/g, the process comprising the steps of:
 contacting an epoxidized vegetable oil containing triglycerides with an organic acid having from 1 to 3 carbon atoms for a sufficient period of time, at a sufficient temperature, and at a sufficient pressure to form hydroxyl groups from epoxide rings located along fatty acid moieties of the triglycerides thereby forming a crude polyol product,   separating volatiles from the crude polyol product to achieve a semi-refined product, and   further reacting and purifying the semi-refined product at a sufficient temperature and under a sufficient vacuum to achieve a final polyol product having an acid number of not more than 2 mg KOH/g; and wherein the epoxidized vegetable oil containing triglycerides has the following formula:   
       
         
           
           
               
               
           
         
         wherein the R and R 1  groups represent the fatty acid moieties of the triglycerides.  
       
     
     
       25. A process according to claim 24 wherein the further reaction or purification step comprises heating the semi-refined product at a temperature of at least approximately 170° C. under a vacuum to achieve a final polyol product having an acid number of not more than 2 mg KOH/g.  
     
     
       26. A process according to claim 24 wherein the volatile separation step is conducted under a vacuum at a temperature less than about 170° C. and the further reaction or purification step is conducted under a vacuum at a temperature between about 170° C. and about 270° C.  
     
     
       27. A process according to claim 24 wherein the further reaction step is conducted in one or more pieces of equipment selected from the group consisting of a high temperature vacuum strip reactor, a wiped film evaporator, a counter current packed column, a distillation column, and a steam stripping vessel.