Catalytic processes for preparing estolide base oils

Abstract

Provided herein are processes for preparing estolides and estolide base oils from fatty acid reactants utilizing catalysts. Further provided herein are processes for preparing carboxylic esters from at least one carboxylic acid reactant and at least one olefin.

1 . A process of producing an estolide base oil comprising:
 providing at least one first fatty acid reactant, at least one second fatty acid reactant, and a Lewis acid catalyst; and   oligomerizing the at least one first fatty acid reactant with the at least one second fatty acid reactant in the presence of the Lewis acid catalyst to produce an estolide base oil.   
     
     
         2 . The process according to  claim 1 , wherein the at least one first fatty acid reactant is selected from one or more unsaturated fatty acids, one or more unsaturated fatty acid oligomers, and combinations thereof. 
     
     
         3 . The process according to any one of  claims 1  and  2 , wherein the at least one second fatty acid reactant is selected from saturated and unsaturated fatty acids, saturated and unsaturated fatty acid oligomers, and combinations thereof. 
     
     
         4 . The process according to any one of  claims 1 - 3 , wherein the Lewis acid catalyst is a triflate. 
     
     
         5 . The process according to any one of  claims 1 - 4 , wherein the Lewis acid catalyst is selected from AgOTf, Cu(OTf) 2 , Fe(OTf) 2 , Fe(OTf) 3 , NaOTf, LiOTf, Yb(OTf) 3 , Y(OTf) 3 , Zn(OTf) 2 , Ni(OTf) 2 , Bi(OTf) 3 , La(OTf) 3 , Sc(OTf) 3 , and combinations thereof. 
     
     
         6 . The process according to any one of  claims 1 - 5 , wherein the Lewis acid catalyst is selected from Fe(OTf) 3 , Bi(OTf) 3 , Cu(OTf) 2 , and combinations thereof. 
     
     
         7 . The process according to any one of  claims 1 - 5 , wherein the Lewis acid catalyst is Bi(OTf) 3 . 
     
     
         8 . The process according to any one of  claims 1 - 5 , wherein the Lewis acid catalyst is Cu(OTf) 2 . 
     
     
         9 . The process according to any one of  claims 1 - 5 , wherein the Lewis acid catalyst is Fe(OTf) 3 . 
     
     
         10 . The process according to any one of  claims 1 - 3 , wherein the Lewis acid catalyst is at least one metal compound selected from cobalt compounds, nickel compounds, and combinations thereof. 
     
     
         11 . The process according to  claim 10 , wherein the Lewis acid catalyst is selected from Co(acac) 3 , CoCl 3 , NiCl 2 , Ni(acac) 2 , and combinations thereof. 
     
     
         12 . The process according to any one of  claims 1 - 11 , wherein the oligomerizing takes place in the presence of microwave radiation. 
     
     
         13 . The process according to any one of  claims 1 - 12 , wherein the oligomerizing is conducted in a microwave reactor. 
     
     
         14 . The process according to any one of  claims 1 - 13 , wherein the oligomerizing further comprises the presence of a Bronsted acid. 
     
     
         15 . The process according to  claim 14 , wherein the Bronsted acid is selected from hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, perchloric acid, triflic acid, p-TsOH, and combinations thereof. 
     
     
         16 . The process according to  claim 14 , wherein the Bronsted acid is a solid-supported acid. 
     
     
         17 . The process according to  claim 16 , wherein the Bronsted acid is selected from acid-activated clays. 
     
     
         18 . The process according to  claim 16  wherein the Bronsted acid is selected from acid-activated montmorillonite clays. 
     
     
         19 . The process according to  claim 13 , wherein the Bronsted acid is selected from acidic mesoporous materials. 
     
     
         20 . The process according to  claim 19 , wherein the Bronsted acid is selected from zeolite materials. 
     
     
         21 . The process according to any one of  claims 1 - 20 , wherein the oligomerizing is carried out at a temperature that is greater than 50° C. 
     
     
         22 . The process according to any one of  claims 1 - 21 , wherein the oligomerizing is carried out at a temperature range of 50° C. to 100° C. 
     
     
         23 . The process according to any one of  claims 1 - 22 , wherein the oligomerizing is carried out at a temperature range of 60° C. to 80° C. 
     
     
         24 . The process according to any one of  claims 1 - 23 , wherein the oligomerizing is carried out at a pressure of less than 1 atm absolute. 
     
     
         25 . The process according to any one of  claims 1 - 24 , wherein the oligomerizing is carried out at a pressure of less than 250 torr absolute. 
     
     
         26 . The process according to any one of  claims 1 - 25 , wherein the oligomerizing is carried out at a pressure of less than 100 torr absolute. 
     
     
         27 . The process according to any one of  claims 1 - 26 , wherein the oligomerizing is carried out at a pressure of less than 50 torr absolute. 
     
     
         28 . The process according to any one of  claims 1 - 27 , wherein the oligomerizing is carried out at a pressure of less than 25 torr absolute. 
     
     
         29 . The process according to any one of  claims 1 - 28 , wherein the oligomerizing is carried out at a pressure of 1 torr absolute to 20 torr absolute. 
     
     
         30 . The process according to any one of  claims 1 - 29 , wherein the oligomerizing is carried out at a pressure of 5 torr absolute to 15 torr absolute. 
     
     
         31 . The process according to any one of  claims 1 - 30 , further comprising esterifying the estolide base oil to provide an esterified estolide base oil. 
     
     
         32 . The process according to any one of  claim 31 , wherein the esterifying is carried out in the presence of at least one alcohol. 
     
     
         33 . The process according to  claim 32 , wherein the esterification catalyst is selected from a Bronsted acid esterification catalyst, a Lewis acid esterification catalyst, and combinations thereof. 
     
     
         34 . The process according to  claim 33 , wherein the Bronsted acid esterification catalyst comprises a solid-supported acid. 
     
     
         35 . The process according to  claim 33 , wherein the Bronsted acid esterification catalyst is selected from acid-activated clays. 
     
     
         36 . The process according to  claim 33 , wherein the Bronsted acid esterification catalyst is selected from acid-activated montmorillonite clays. 
     
     
         37 . The process according to  claim 33 , wherein the Bronsted acid esterification catalyst is selected from acidic mesoporous materials. 
     
     
         38 . The process according to  claim 33 , wherein the Bronsted acid esterification catalyst is selected from zeolite materials. 
     
     
         39 . The process according to  claim 33 , wherein the Bronsted acid esterification catalyst is selected from hydrochloric acid, sulfamic acid, methylsulfamic acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, triflic acid, p-TsOH, and combinations thereof. 
     
     
         40 . The process according to  claim 33 , wherein the Lewis acid esterification catalyst is a triflate. 
     
     
         41 . The process according to  claim 40 , wherein the Lewis acid esterification catalyst is selected from AgOTf, Cu(OTf) 2 , Fe(OTf) 2 , Fe(OTf) 3 , NaOTf, LiOTf, Yb(OTf) 3 , Y(OTf) 3 , Zn(OTf) 2 , Ni(OTf) 2 , Bi(OTf) 3 , La(OTf) 3 , Sc(OTf) 3 , and combinations thereof. 
     
     
         42 . The process according to any one of  claims 1 - 41 , wherein the Lewis acid esterification catalyst is Bi(OTf) 3 . 
     
     
         43 . The process according to any one of  claims 1 - 41 , wherein the oligomerizing Lewis acid catalyst and the Lewis acid esterification catalyst are the same. 
     
     
         44 . The process according to any one of  claims 33 - 41 , wherein the Lewis acid esterification catalyst is at least one metal compound selected from titanium compounds, tin compounds, zirconium compounds, and hafnium compounds, and combinations thereof. 
     
     
         45 . The process according to  claim 44 , wherein the Lewis acid esterification catalyst is at least one titanium compound selected from TiCl 4 , Ti(OCH 2 CH 2 CH 2 CH 3 ) 4 , and combinations thereof. 
     
     
         46 . The process according to  claim 45 , wherein the Lewis acid esterification catalyst is Ti(OCH 2 CH 2 CH 2 CH 3 ) 4 . 
     
     
         47 . The process according to  claim 44 , wherein the Lewis acid esterification catalyst is at least one tin compound selected from Sn(O 2 CCO 2 ), SnO, SnCl 2 , and combinations thereof. 
     
     
         48 . The process according to  claim 47 , wherein the Lewis acid esterification catalyst is Sn(O 2 CCO 2 ). 
     
     
         49 . The process according to  claim 44 , wherein the Lewis acid esterification catalyst is at least one zirconium compound selected from ZrCl 4 , ZrOCl 2 , ZrO(NO 3 ) 2 , ZrO(SO 4 ), ZrO(CH 3 COO) 2 , and combinations thereof. 
     
     
         50 . The process according to  claim 49 , wherein the Lewis acid esterification catalyst is selected from ZrOCl 2 .8H 2 O and ZrOCl 2 .2THF. 
     
     
         51 . The process according to  claim 44 , wherein the Lewis acid esterification catalyst is at least one hafnium compound selected from HfCl 2 , HfOCl 2 , and combinations thereof. 
     
     
         52 . The process according to  claim 51 , wherein the Lewis acid esterification catalyst is selected from HfOCl 2 .2THF and HfOCl 2 .8H 2 O. 
     
     
         53 . The process according to any one of  claims 31 - 52 , wherein the esterifying takes place in the presence of microwave radiation. 
     
     
         54 . The process according to any one of  claims 31 - 53 , wherein the esterifying is conducted in a microwave reactor. 
     
     
         55 . The process according to any one of  claims 1 - 54 , wherein said process is a continuous flow process. 
     
     
         56 . A continuous process of producing an estolide base oil comprising:
 providing at least one first fatty acid reactant, at least one second fatty acid reactant, and an oligomerization catalyst; and   continuously oligomerizing the at least one first fatty acid reactant with the at least one second fatty acid reactant in the presence of the oligomerization catalyst to produce an estolide base oil.   
     
     
         57 . The process according to  claim 56 , wherein the at least one first fatty acid reactant and the oligomerization catalyst are continuously provided. 
     
     
         58 . The process according to any one of  claims 56  and  57 , wherein the at least one first fatty acid reactant and the at least one second fatty acid reactant are continuously oligomerized in a reactor. 
     
     
         59 . The process according to  claim 58 , wherein the reactor is equipped with a heat source. 
     
     
         60 . The process according to any one of  claims 58  and  59 , wherein the reactor is a microwave reactor. 
     
     
         61 . The process according to any one of  claims 58 - 60 , wherein the reactor is a continuous stirred tank reactor. 
     
     
         62 . The process according to any one of  claims 56 - 61 , wherein the oligomerizing produces one or more first estolides. 
     
     
         63 . The process according to any one of  claims 56 - 62 , further comprising removing at least a portion of one or more first estolides from the reactor. 
     
     
         64 . The process according to  claim 63 , further comprising transferring at least a portion of the one or more first estolides that have been removed back to the reactor or to a secondary reactor for continued oligomerization, wherein said continued oligomerization provides one or more second estolides. 
     
     
         65 . The process according to  claim 64 , wherein the one or more second estolides have an EN that is greater than the EN of the one or more first estolides. 
     
     
         66 . The process according to any one of  claims 64  and  65 , further comprising transferring at least a portion of the one or more first estolides, and optionally at least a portion of the one or more second estolides, to a separation unit for separation into one or more estolide products. 
     
     
         67 . The process according to  claim 66 , wherein the separation is accomplished by distillation, phase separation, chromatography, membrane separation, affinity separation, solvent extraction, or combinations thereof. 
     
     
         68 . The process according to  claim 58 , wherein the reactor is a column reactor. 
     
     
         69 . The process according to  claim 68 , wherein the reactor is a vertical column reactor. 
     
     
         70 . The process according to any one of  claims 68  and  69 , wherein the reactor comprises a first reaction stage. 
     
     
         71 . The process according to any one of  claims 68 - 70 , wherein the reactor comprises two or more reaction stages. 
     
     
         72 . The process according to  claim 71 , wherein temperatures differ at two or more of the reaction stages. 
     
     
         73 . The process according to any one of  claims 70 - 72 , wherein the oligomerization catalyst is present in one or more of the reaction stages. 
     
     
         74 . The process according to any one of  claims 70 - 73 , wherein the at least one first fatty acid reactant and the oligomerization catalyst are present in the first reaction stage. 
     
     
         75 . The process according to any one of  claims 70 - 74 , wherein at least a portion of the oligomerizing takes place at the first reaction stage. 
     
     
         76 . The process according to any one of  claims 70 - 75 , wherein the oligomerizing provides an initial oligomerized product. 
     
     
         77 . The process according to  claim 76 , further comprising transferring at least a portion of the initial oligomerized product to at least one second reaction stage. 
     
     
         78 . The process according to any one of  claims 76  and  77 , further comprising separating the portion of the initial oligomerized product into one or more first estolides and one or more second estolides. 
     
     
         79 . The process according to  claim 78 , wherein the one or more second estolides have an EN that is greater than the EN of the one or more first estolides. 
     
     
         80 . The process according to any one of  claims 78  and  79 , further comprising transferring at least a portion the one or more first estolides to the first reaction stage for continued oligomerization. 
     
     
         81 . The process according to any one of  claims 78 - 80 , further comprising removing at least a portion of the one or more second estolides from the reactor. 
     
     
         82 . The process according to any one of  claims 56 - 81 , wherein the oligomerization catalyst is selected from a Bronsted acid, a Lewis acid, and combinations thereof. 
     
     
         83 . The process according to  claim 82 , wherein the Lewis acid catalyst is a triflate. 
     
     
         84 . The process according to  claim 83 , wherein the Lewis acid catalyst is selected from AgOTf, Cu(OTf) 2 , Fe(OTf) 2 , Fe(OTf) 3 , NaOTf, LiOTf, Yb(OTf) 3 , Y(OTf) 3 , Zn(OTf) 2 , Ni(OTf) 2 , Bi(OTf) 3 , La(OTf) 3 , Sc(OTf) 3 , and combinations thereof. 
     
     
         85 . The process according to  claim 84 , wherein the Lewis acid catalyst is selected from Fe(OTf) 3 , Bi(OTf) 3 , Cu(OTf) 2 , and combinations thereof. 
     
     
         86 . The process according to  claim 85 , wherein the Lewis acid catalyst is Bi(OTf) 3 . 
     
     
         87 . The process according to  claim 85 , wherein the Lewis acid catalyst is Cu(OTf) 2 . 
     
     
         88 . The process according to  claim 85 , wherein the Lewis acid catalyst is Fe(OTf) 3 . 
     
     
         89 . The process according to  claim 82 , wherein the Lewis acid catalyst is a metal compound selected from cobalt compounds, nickel compounds, and combinations thereof. 
     
     
         90 . The process according to  claim 89 , wherein the Lewis acid catalyst is selected from Co(acac) 3 , CoCl 3 , NiCl 2 , Ni(acac) 2 , and combinations thereof. 
     
     
         91 . The process according to  claim 82 , wherein the Bronsted acid is selected from hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, perchloric acid, triflic acid, p-TsOH, and combinations thereof. 
     
     
         92 . The process according to  claim 82 , wherein the Bronsted acid is a solid-supported acid. 
     
     
         93 . The process according to  claim 82 , wherein the Bronsted acid is selected from acid-activated clays. 
     
     
         94 . The process according to  claim 82 , wherein the Bronsted acid is selected from acid-activated montmorillonite clays. 
     
     
         95 . The process according to  claim 82 , wherein the Bronsted acid is selected from acidic mesoporous materials. 
     
     
         96 . The process according to  claim 82 , wherein the Bronsted acid is selected from zeolite materials. 
     
     
         97 . The process according to any one of  claims 56 - 96 , wherein the oligomerizing is carried out at a temperature that is greater than 50° C. 
     
     
         98 . The process according to any one of  claims 56 - 97 , wherein the oligomerizing is carried out at a temperature range of 50° C. to 100° C. 
     
     
         99 . The process according to any one of  claims 56 - 98 , wherein the oligomerizing is carried out at a temperature range of 60° C. to 80° C. 
     
     
         100 . The process according to any one of  claims 56 - 99 , wherein the oligomerizing is carried out at a pressure of less than 1 atm absolute. 
     
     
         101 . The process according to any one of  claims 56 - 100 , wherein the oligomerizing is carried out at a pressure of less than 250 torr absolute. 
     
     
         102 . The process according to any one of  claims 56 - 101 , wherein the oligomerizing is carried out at a pressure of less than 100 torr absolute. 
     
     
         103 . The process according to any one of  claims 56 - 102 , wherein the oligomerizing is carried out at a pressure of less than 50 torr absolute. 
     
     
         104 . The process according to any one of  claims 56 - 103 , wherein the oligomerizing is carried out at a pressure of less than 25 torr absolute. 
     
     
         105 . The process according to any one of  claims 56 - 104 , wherein the oligomerizing is carried out at a pressure of 1 torr absolute to 20 torr absolute. 
     
     
         106 . The process according to any one of  claims 56 - 105 , wherein the oligomerizing is carried out at a pressure of 5 torr absolute to 15 torr absolute. 
     
     
         107 . The process according to  claim 58 , wherein the reactor is a plug flow reactor. 
     
     
         108 . The process according to any one of  claims 56 - 107 , wherein the oligomerizing takes place in the presence of microwave radiation. 
     
     
         109 . The process according to any one of  claims 56 - 108 , further comprising esterifying the estolide base oil to produce an esterified estolide base oil. 
     
     
         110 . The process according to  claim 109 , wherein the esterifying takes place in the presence of at least one alcohol and an esterification catalyst. 
     
     
         111 . The process according to any one of  claims 109  and  110 , wherein the esterifying takes place in the presence of microwave radiation. 
     
     
         112 . A process of producing a carboxylic acid ester, comprising:
 providing at least one carboxylic acid reactant, at least one olefin, and a Bismuth catalyst; and   reacting the at least one carboxylic acid reactant with the at least one olefin in the presence of the Bismuth catalyst to produce a carboxylic acid ester.   
     
     
         113 . The process according to  claim 112 , wherein the at least one carboxylic acid reactant is selected from aliphatic carboxylic acids, aromatic carboxylic acids, and combinations thereof. 
     
     
         114 . The process according to any one of  claims 112  and  113 , wherein the at least one olefin is selected from aliphatic olefins, aromatic olefins, and combinations thereof. 
     
     
         115 . The process according to any one of  claims 112 - 114 , wherein the Bismuth catalyst is Bi(OTf) 3 . 
     
     
         116 . The process according to any one of  claims 112 - 115 , wherein the reacting takes place in the presence of microwave radiation.