Processes of preparing estolide base oils and lubricants that include transesterification

Abstract

Provided herein are processes of producing estolide base oils, including the process comprising providing at least one fatty acid ester, and contacting the at least one fatty acid ester with at least one fatty acid to form an estolide base oil. Exemplary processes include the use of transesterification to form the at least one fatty acid ester and/or estolide base oil.

1 . A process of producing an estolide base oil comprising
 providing at least one fatty acid ester; and   contacting the at least one fatty acid ester with at least one fatty acid to form an estolide base oil.   
     
     
         2 . The process according to  claim 1 , wherein the at least one fatty acid ester is a fatty acid alkyl ester. 
     
     
         3 . The process according to  claim 2 , wherein the alkyl residue of the fatty acid alkyl ester is unsubstituted. 
     
     
         4 . The process according to any one of  claims 1 - 3 , wherein the fatty acid residue of the at least one fatty acid ester comprises at least one site of unsaturation. 
     
     
         5 . The process according to any one of  claims 1 - 4 , wherein the at least one fatty acid ester is monounsaturated. 
     
     
         6 . The process according to any one of  claims 1 - 5 , wherein the at least one fatty acid is saturated. 
     
     
         7 . The process according to any one of  claims 1 - 6 , wherein the contacting the at least one fatty acid ester with the at least one fatty acid occurs in the presence of at least one catalyst. 
     
     
         8 . The process according to  claim 7 , wherein the at least one catalyst is a Lewis acid. 
     
     
         9 . The process according to  claim 8 , wherein the at least one catalyst is a triflate. 
     
     
         10 . The process according to  claim 7 , wherein the at least one catalyst is a Bronsted acid. 
     
     
         11 . The process according to  claim 10 , wherein at least one catalyst is selected from one or more of hydrochloric acid, nitric acid, methanesulfonic acid, sulfuric acid, phosphoric acid, perchloric acid, triflic acid, or p-TsOH. 
     
     
         12 . The process according to any one of  claims 1 - 11 , wherein the process of producing the estolide base oil includes forming a covalent bond between an oxygen of a carboxylic group of the at least one fatty acid and a carbon of at least one site of unsaturation of the at least one fatty acid ester. 
     
     
         13 . A process of producing an estolide base oil comprising
 providing at least one first fatty acid ester;   transesterifying the at least one first fatty acid ester with at least one alcohol to provide at least one second fatty acid ester; and   contacting the at least one second fatty acid ester with at least one fatty acid to form an estolide base oil.   
     
     
         14 . The process according to  claim 13 , wherein the at least one fatty acid ester is a glyceride. 
     
     
         15 . The process according to  claim 14 , wherein the at least one fatty acid ester is selected from one or more of a monoglyceride, a diglyceride, or a triglyceride. 
     
     
         16 . The process according to any one of  claims 13 - 15 , wherein the fatty acid residue of the at least one fatty acid ester comprises at least one site of unsaturation. 
     
     
         17 . The process according to any one of  claims 13 - 16 , wherein the at least one alcohol is a monoalcohol. 
     
     
         18 . The process according to any one of  claims 13 - 17 , wherein the at least one second fatty acid ester is a fatty acid alkyl ester. 
     
     
         19 . The process according to any one of  claims 13 - 18 , wherein the fatty acid residue of the at least one second fatty acid ester is unsaturated. 
     
     
         20 . The process according to any one of  claims 13 - 19 , wherein the at least one second fatty acid ester is monounsaturated. 
     
     
         21 . The process according to any one of  claims 13 - 20 , wherein the at least one fatty acid is saturated. 
     
     
         22 . The process according to any one of  claims 13 - 21 , wherein the contacting the at least one second fatty acid ester with the at least one fatty acid occurs in the presence of at least one catalyst. 
     
     
         23 . The process according to  claim 22 , wherein the at least one catalyst is a Lewis acid. 
     
     
         24 . The process according to  claim 23 , wherein the at least one catalyst is a triflate. 
     
     
         25 . The process according to  claim 22 , wherein the at least one catalyst is a Bronsted acid. 
     
     
         26 . The process according to  claim 25 , wherein at least one catalyst is selected from one or more of hydrochloric acid, nitric acid, methanesulfonic acid, sulfuric acid, phosphoric acid, perchloric acid, triflic acid, or p-TsOH. 
     
     
         27 . The process according to any one of  claims 13 - 26 , wherein the process of producing the estolide base oil includes forming a covalent bond between an oxygen of a carboxylic group of the at least one fatty acid and a carbon of at least one site of unsaturation of the at least one fatty acid ester. 
     
     
         28 . A process of producing an estolide base oil comprising
 providing at least one unsaturated fatty acid glyceride;   transesterifying the at least one unsaturated fatty acid glyceride with at least one alcohol to provide at least one fatty acid alkyl ester having at least one site of unsaturation; and   contacting the at least one fatty acid ester with at least one fatty acid in the presence of a catalyst to provide an estolide base oil, wherein the process of producing the estolide base oil includes forming a covalent bond between an oxygen of a carboxylic group of the at least one fatty acid and a carbon of the at least one site of unsaturation of the at least one fatty acid alkyl ester.   
     
     
         29 . The process according to  claim 28 , wherein the at least one unsaturated fatty acid glyceride is a triglyceride. 
     
     
         30 . The process according to any one of  claims 28 - 29 , wherein the at least one unsaturated fatty acid glyceride is derived from a high-oleic vegetable oil. 
     
     
         31 . The process according to any one of  claims 28 - 30 , wherein the at least one alcohol is a monoalcohol. 
     
     
         32 . The process according to any one of  claims 28 - 31 , wherein the at least one alcohol is a branched or unbranched C 6 -C 12  monoalcohol. 
     
     
         33 . The process according to  claim 32 , wherein the at least one alcohol is 2-ethylhexanol. 
     
     
         34 . The process according to any one of  claims 28 - 33 , wherein the fatty acid residue of the at least one fatty acid alkyl ester comprises at least one site of unsaturation. 
     
     
         35 . The process according to any one of  claims 28 - 34 , wherein the at least one fatty acid alkyl ester is monounsaturated. 
     
     
         36 . The process according to any one of  claims 28 - 35 , wherein the alkyl residue of the at least one fatty acid alkyl ester is saturated and branched. 
     
     
         37 . The process according to any one of  claims 28 - 36 , wherein the at least one fatty acid is saturated. 
     
     
         38 . The process according to any one of  claims 28 - 37 , wherein the at least one fatty acid is a C 6 -C 14  fatty acid. 
     
     
         39 . The process according to any one of  claims 28 - 38 , wherein the at least one catalyst is a Lewis acid. 
     
     
         40 . The process according to  claim 39 , wherein the at least one catalyst is a triflate. 
     
     
         41 . The process according to any one of  claims 28 - 38 , wherein the at least one catalyst is a Bronsted acid. 
     
     
         42 . The process according to  claim 41 , wherein at least one catalyst is selected from one or more of hydrochloric acid, nitric acid, methanesulfonic acid, sulfuric acid, phosphoric acid, perchloric acid, triflic acid, or p-TsOH. 
     
     
         43 . The process according to any one of  claims 1 - 42 , wherein the estolide base oil comprises at least one compound selected from compounds of Formula I: 
       
         
           
           
               
               
           
         
         wherein 
         x is, independently for each occurrence, an integer selected from 0 to 20; 
         y is, independently for each occurrence, an integer selected from 0 to 20; 
         n is an integer greater than or equal to 0; 
         R 1  is an optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched; and 
         R 2  is an optionally substituted alkyl that is saturated or unsaturated, and branched or unbranched, 
         wherein each fatty acid chain residue of said at least one compound is independently optionally substituted. 
       
     
     
         44 . The composition according to  claim 43 , wherein
 x is, independently for each occurrence, an integer selected from 1 to 10;   y is, independently for each occurrence, an integer selected from 1 to 10;   n is an integer selected from 0 to 8;   R 1  is an optionally substituted C 1  to C 22  alkyl that is saturated or unsaturated, and branched or unbranched; and   R 2  is an optionally substituted C 1  to C 22  alkyl that is saturated or unsaturated, and branched or unbranched,   wherein each fatty acid chain residue is unsubstituted.   
     
     
         45 . The process according to any one of  claims 43 - 44 , wherein
 x+y is, independently for each chain, an integer selected from 13 to 15; and   n is an integer selected from 0 to 6.   
     
     
         46 . The process according to any one of  claims 43 - 45 , wherein R 2  is an unsubstituted alkyl that is saturated or unsaturated, and branched or unbranched 
     
     
         47 . The process according to any one of  claims 43 - 46 , wherein R 2  is a branched or unbranched C 1  to C 20  alkyl that is saturated or unsaturated. 
     
     
         48 . The process according to  claim 47 , wherein R 2  is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, undecanyl, dodecanyl, tridecanyl, tetradecanyl, pentadecanyl, hexadecanyl, heptadecanyl, octadecanyl, nonadecanyl, and icosanyl, which are saturated or unsaturated and branched or unbranched. 
     
     
         49 . The process according to  claim 47 , wherein R 2  is selected from C 6  to C 12  alkyl. 
     
     
         50 . The process according to  claim 49 , wherein R 2  is 2-ethylhexyl. 
     
     
         51 . The process according to any one of  claims 43 - 50 , wherein R 1  is a branched or unbranched C 1  to C 20  alkyl that is saturated or unsaturated. 
     
     
         52 . The process according to  claim 51 , wherein R 1  is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, undecanyl, dodecanyl, tridecanyl, tetradecanyl, pentadecanyl, hexadecanyl, heptadecanyl, octadecanyl, nonadecanyl, and icosanyl, which are saturated or unsaturated and branched or unbranched. 
     
     
         53 . The process according to  claim 51 , wherein R 1  is selected from unsubstituted C 7  to C 17  alkyl that is unbranched and saturated or unsaturated. 
     
     
         54 . The process according to  claim 51 , wherein R 1  is selected from C 13  to C 17  alkyl that is unsubstituted, unbranched, and saturated or unsaturated. 
     
     
         55 . The process according to  claim 53 , wherein R 1  is selected from saturated C 7  alkyl, saturated C 9  alkyl, saturated C 11  alkyl, saturated C 13  alkyl, saturated C 15  alkyl, and saturated or unsaturated C 17  alkyl, which are unsubstituted and unbranched. 
     
     
         56 . The process according to  claim 54 , wherein R 1  is selected from saturated C 13  alkyl, saturated C 15  alkyl, and saturated or unsaturated C 17  alkyl, which are unsubstituted and unbranched. 
     
     
         57 . The process according to any one of  claims 43 - 47 , wherein R 1  and R 2  are independently selected from optionally substituted C 1  to C 18  alkyl that is saturated or unsaturated, and branched or unbranched. 
     
     
         58 . The process according to any one of  claims 43 - 47 , wherein R 1  is selected from optionally substituted C 7  to C 17  alkyl that is saturated or unsaturated, and branched or unbranched; and R 2  is selected from an optionally substituted C 3  to C 20  alkyl that is saturated or unsaturated, and branched or unbranched. 
     
     
         59 . The process according to any one of  claims 43 - 58 , wherein x is, independently for each occurrence, an integer selected from 7 to 8. 
     
     
         60 . The process according to any one of  claims 43 - 59 , wherein y is, independently for each occurrence, an integer selected from 7 to 8. 
     
     
         61 . The process according to any one of  claims 1 - 2  and  4 - 12 , wherein the at least one fatty acid ester is a glyceride, and the estolide base oil is an esto-glyceride. 
     
     
         62 . The process according to  claim 61 , wherein the at least one fatty acid ester is selected from one or more of a monoglyceride, a diglyceride, or a triglyceride. 
     
     
         63 . The process according to any one of  claims 61 - 62 , further comprising transesterifying the esto-glyceride with at least one alcohol to provide an esterified estolide base oil. 
     
     
         64 . The process according to  claim 63 , wherein the at least one alcohol is a monoalcohol. 
     
     
         65 . The process according to any one of  claims 63 - 64 , wherein the at least one alcohol is branched. 
     
     
         66 . The process according to  claim 65 , wherein the at least one alcohol is 2-ethylhexanol.