CA2141102A1 - Triglyceride oils thickened with estolides of hydroxy-containing triglycerides - Google Patents
Triglyceride oils thickened with estolides of hydroxy-containing triglyceridesInfo
- Publication number
- CA2141102A1 CA2141102A1 CA002141102A CA2141102A CA2141102A1 CA 2141102 A1 CA2141102 A1 CA 2141102A1 CA 002141102 A CA002141102 A CA 002141102A CA 2141102 A CA2141102 A CA 2141102A CA 2141102 A1 CA2141102 A1 CA 2141102A1
- Authority
- CA
- Canada
- Prior art keywords
- oil
- composition
- triglyceride
- carbon atoms
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/02—Natural products
- C10M159/08—Fatty oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
- C10M2207/402—Castor oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
- C10M2207/404—Fatty vegetable or animal oils obtained from genetically modified species
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/102—Polyesters
Abstract
A thickened composition is disclosed which comprises (A) at least one triglyceride estolide of the formula wherein R1 is an aliphatic group or an aliphatic group containing an ester moiety R2COO- with the proviso that at least one R1 is an aliphatic group containing the ester moiety, and contains from about 5 to about 23 carbon atoms, and R2 is a hydrocarbyl group containing from 1 to 100 carbon atoms and (B) at least one animal fat, vegetable oil or synthetic triglyceride oil of the formula
Description
214il~2 ,, Title: TRIGLYCERIDE OILS THICKENED WITH ESTOLIDES OF
HYDROXY-CONTAINING TRIGLYCERIDES
FIELD OF THE INVENTION
The present invention relates to the thickening of triglyceride oils by dissolving therein an estolide of a hydroxy-cont~ining triglyceride. In another embodiment the triglyceride oil is thickened through an ~l"ere~leli~lcation reaction by reacting the triglyceride oil with an estolide of a hydroxy-cont~inin~
triglyceride in the presence of a catalyst.
BACKGROUND OF THE INVENTION
Snccessful use of triglyceride oils as environmentally friendly, that is biodegradable, base fluids in industrial applications and also as a fuel additive when mixed with normally liquid fuels, is contingent upon increasing the viscosity of the triglyceride. In many industrial applications the triglyceride is too thin to be of value. In order to take advantage of the biodegradability of triglyceride oils, it becomes nPcess~ry to increase their viscosity.
U.S. Patent No. 844,426 (Twitchell, February 19, 1907) relates to a process for ,ll~ r~cturing certain organic products. One of the re~ct~nt.c contains an alcoholic hydroxyl, of which castor oil is cited, and the other reactant is a fatty acid such as stearic and oleic acids. The reaction takes place in the presence of a catalyst described as cont~inin~ a sulfa fatty acid group.
U.S. Patent No. 2,156,737 (Priester, May 2, 1939) relates to the preparation or production of lln~tnrated fatty acids of the type cont~ining two double bonds and to the preparation of an intermediate product from which said unsaturated fatty acids may be derived.
More particularly stated, this reference relates to a process for the preparation of 9, l l-oct~lec~liene l-acid from ricinoleic acid. The ricinoleic 21411~
acid is both pure ricinoleic acid or ricinoleic acid obtained from castor oil ofwhich the latter being obtained by the splitting up of castor oil.
U.S. Patent No. 2,049,072 (Mikesk~ et al, July 28, 1936) relates to the pl~a~ation of lubricants by blending with a mineral oil the product obtained 5 by esterification of hydroxy groups in natural or synthetic fatty acids or glycerides, with special rererel~ce to castor oil, with or without subsequent stabilizations of said esterified product as by hydrogenation.
U.S. Patent No. 2,652,410 (Cllnningh~m et al, September 15, 1953) relates to methods for re~cting alpha-hydroxy acids and/or estolides with 10 polyhydric alcohols. More particularly, this referellce relates to methods for e~,leliryh~g and dehydroxylating alpha-hydroxy acids and/or estolides such as are obtained by the controlled oxidation of paraffin wax.
U.S. Patent 2,877,181 (Dilworth et al, March 10, 1959) relates to anhydrous calcium fatty acid greases. More particularly, this lefe.ellce 15 discloses an additive that stabilizes anhydrous calcium fatty acid greases. This additive is an estolide and the estolides which act as stabilizers are intermolecular esters and polyesters of C10 to C24 hydroxy fatty acids having the general formula -O E
Il I
HO--C(CH2)2~CO--EI
R _n wherein R is an aliphatic hydrocarbon radical cont~ining 1 to 21 carbon atoms, x is an integer having a value to 1 to 21 and n is an integer having a value of 2 to about 12.
2 1 ~
U.S. Patent No. 4,582,715 (Volpenhein, April 15, 1986) relates to alpha acrylated glycerides of the formula:
H
~IC C 1 2 S O O o O=C
C=O C=O
EIC'Rl H l -Rl Hl -Rl O O O
wh~rein each Rl is a C,O-Cl4 aLkyl group and wherein each R2 is a Cl4-CI6 15 aliphatic group.
SUMMARY OF THE INVENTION
A composition is disclosed which comprises 214~
(A) at least one triglyceride estolide of the formula O
s O
Il 1 C~I--OC-R
o CEI~ OC R
wherein Rl is an aliphatic group or an aliphatic group cont~ining an ester moiety R2COO- with the proviso that at least one R' is an aliphatic group 15 cont~ining the ester moiety, and contains from about 5 to about 23 carbon atoms, and R2 is a hydrocarbyl group cont~ining from 1 to 100 carbon atoms and (B) at least one animal fat, vegetable oil or synthetic triglyceride oil of the formula Il c~ oc--R3 C~--OC-R
o OC--R
` ` 21411QZ
wherein R3, R4 and R5 are aliphatic groups or hydroxy cont~inin~. aliphatic groups that are saturated, monounsaturated, polyunsaturatedS or mixtures thereof, and contain from about 1 to about 23 carbon atoms.
S DETAILED DESCRIPTION OF THE INVENTION
(A) The Tri~lyceride Estolide An estolide is the product formed by the esterification reaction of a hydroxy-cont~ining fatty acid and a carboxylic acid.
The esterification to form the estolide occurs at a temperature of from ambient up to the decomposition temperature of any reactant or product.
Usually the upper temperature limit is not more than 150C and ~refelably not more than 120C. To shift the equilibrium to the right when forming an estolide, it is nPcess~ry to use either a large excess of carboxylic acid, or else remove water as it is formed. In either case, excess carboxylic acid or formed water can be removed by distillation.
As an example, under proper conditions the -OH from one ricinoleic acid molecule can react with the -COOH of another ricinoleic acid molecule to give an estolide:
OH
2 CH3 (CH2 )S CHCH2CH' CH(C~ 2 )7COOH
Il ' 0~
OC(C~I2)7CH=C~CH2CH(C}I2 )~ 3 CH3(cH2)scHclI2c~=cH(cEl2~7 214111~2 This estolide would continue to crosslink or react linearly at the unreacted -OHand -COOH sites to form a polyestolide.
In this invention, component (A) is a triglyceride estolide of the formula o Il 1 C~I2--OC-R
O `
Il 1 CH OC-R
Il 1 CH~ OC-R
wherein Rl is an aliphatic group or an aliphatic group cont~ining an ester moiety R2COO- with the proviso that at least one Rl is an ~liph~tic group cont~ining the ester moiety, and contains from about S to about 23 carbon atoms, and R2 is a hydrocarbyl group cont~ining from 1 to 100 carbon atoms.
The aliphatic group R' is aL~yl such as pentyl, heptyl, nonyl, undecyl, tridecyl, heptadecyl; aL~enyl cont~ining a single bond such as heptenyl, nonenyl, undecenyl, tridecenyl, heptadecenyl, nonadecenyl, heneicosenyl;
aL~enyl cont~ining 2 or 3 double bonds such as 8,11-hept~1ec-~lienyl and 8,11,14-hept~ec~trienyl. All isomers of these are included, but straight chain groups are preferred.
At least one of the Rl groups contains the ester moiety R2COO-. The residue of this R3 group (the Rl as described above less the hydrogen and also less the R2COO-) is still defined as an aliphatic group and as such is defined by 214110~
the parameters of the aliphatic groups above. An example of an R' cont~ining the ester moiety is r S
CH3CH2CII2CHCE~2 Removing the R2COO- from this structure gives CH3CH2CH2cj~c~2 as a residue which is defined as an aliphatic group.
The hydrocarbyl group R2 includes the following:
(1) Aliphatic hydrocarbongroups; thatis, alkyl groups suchas heptyl, nonyl, undecyl, tridecyl, heptadecyl; aLkenyl groups cont~ining a single double bond such as heptenyl, nonenyl, undecenyl, tridecenyl, isostearyl, heptadecenyl,heneicosenyl; aLkenyl groups cont~inin~ 2 or 3 double bonds such as 8,11-hept~dec~(lienyl and 8,11,14-hept~dec~trienyl. All isomers of these are included, but straight chain groups are preferred.
(2) Substituted aliphatic hydrocarbon groups; that is groups cont~inin~
non-hydrocarbon substituents which, in the context of this invention, do not alter the predomin~ntly hydrocarbon character of the group. Those skilled in the art will be aware of suitable substituents; examples are hydroxy, carbaLkoxy, (especially lower carbalkoxy) and alkoxy (especially lower alkoxy), the term, "lower" denoting groups cont~ining not more than 7 carbon atoms.
HYDROXY-CONTAINING TRIGLYCERIDES
FIELD OF THE INVENTION
The present invention relates to the thickening of triglyceride oils by dissolving therein an estolide of a hydroxy-cont~ining triglyceride. In another embodiment the triglyceride oil is thickened through an ~l"ere~leli~lcation reaction by reacting the triglyceride oil with an estolide of a hydroxy-cont~inin~
triglyceride in the presence of a catalyst.
BACKGROUND OF THE INVENTION
Snccessful use of triglyceride oils as environmentally friendly, that is biodegradable, base fluids in industrial applications and also as a fuel additive when mixed with normally liquid fuels, is contingent upon increasing the viscosity of the triglyceride. In many industrial applications the triglyceride is too thin to be of value. In order to take advantage of the biodegradability of triglyceride oils, it becomes nPcess~ry to increase their viscosity.
U.S. Patent No. 844,426 (Twitchell, February 19, 1907) relates to a process for ,ll~ r~cturing certain organic products. One of the re~ct~nt.c contains an alcoholic hydroxyl, of which castor oil is cited, and the other reactant is a fatty acid such as stearic and oleic acids. The reaction takes place in the presence of a catalyst described as cont~inin~ a sulfa fatty acid group.
U.S. Patent No. 2,156,737 (Priester, May 2, 1939) relates to the preparation or production of lln~tnrated fatty acids of the type cont~ining two double bonds and to the preparation of an intermediate product from which said unsaturated fatty acids may be derived.
More particularly stated, this reference relates to a process for the preparation of 9, l l-oct~lec~liene l-acid from ricinoleic acid. The ricinoleic 21411~
acid is both pure ricinoleic acid or ricinoleic acid obtained from castor oil ofwhich the latter being obtained by the splitting up of castor oil.
U.S. Patent No. 2,049,072 (Mikesk~ et al, July 28, 1936) relates to the pl~a~ation of lubricants by blending with a mineral oil the product obtained 5 by esterification of hydroxy groups in natural or synthetic fatty acids or glycerides, with special rererel~ce to castor oil, with or without subsequent stabilizations of said esterified product as by hydrogenation.
U.S. Patent No. 2,652,410 (Cllnningh~m et al, September 15, 1953) relates to methods for re~cting alpha-hydroxy acids and/or estolides with 10 polyhydric alcohols. More particularly, this referellce relates to methods for e~,leliryh~g and dehydroxylating alpha-hydroxy acids and/or estolides such as are obtained by the controlled oxidation of paraffin wax.
U.S. Patent 2,877,181 (Dilworth et al, March 10, 1959) relates to anhydrous calcium fatty acid greases. More particularly, this lefe.ellce 15 discloses an additive that stabilizes anhydrous calcium fatty acid greases. This additive is an estolide and the estolides which act as stabilizers are intermolecular esters and polyesters of C10 to C24 hydroxy fatty acids having the general formula -O E
Il I
HO--C(CH2)2~CO--EI
R _n wherein R is an aliphatic hydrocarbon radical cont~ining 1 to 21 carbon atoms, x is an integer having a value to 1 to 21 and n is an integer having a value of 2 to about 12.
2 1 ~
U.S. Patent No. 4,582,715 (Volpenhein, April 15, 1986) relates to alpha acrylated glycerides of the formula:
H
~IC C 1 2 S O O o O=C
C=O C=O
EIC'Rl H l -Rl Hl -Rl O O O
wh~rein each Rl is a C,O-Cl4 aLkyl group and wherein each R2 is a Cl4-CI6 15 aliphatic group.
SUMMARY OF THE INVENTION
A composition is disclosed which comprises 214~
(A) at least one triglyceride estolide of the formula O
s O
Il 1 C~I--OC-R
o CEI~ OC R
wherein Rl is an aliphatic group or an aliphatic group cont~ining an ester moiety R2COO- with the proviso that at least one R' is an aliphatic group 15 cont~ining the ester moiety, and contains from about 5 to about 23 carbon atoms, and R2 is a hydrocarbyl group cont~ining from 1 to 100 carbon atoms and (B) at least one animal fat, vegetable oil or synthetic triglyceride oil of the formula Il c~ oc--R3 C~--OC-R
o OC--R
` ` 21411QZ
wherein R3, R4 and R5 are aliphatic groups or hydroxy cont~inin~. aliphatic groups that are saturated, monounsaturated, polyunsaturatedS or mixtures thereof, and contain from about 1 to about 23 carbon atoms.
S DETAILED DESCRIPTION OF THE INVENTION
(A) The Tri~lyceride Estolide An estolide is the product formed by the esterification reaction of a hydroxy-cont~ining fatty acid and a carboxylic acid.
The esterification to form the estolide occurs at a temperature of from ambient up to the decomposition temperature of any reactant or product.
Usually the upper temperature limit is not more than 150C and ~refelably not more than 120C. To shift the equilibrium to the right when forming an estolide, it is nPcess~ry to use either a large excess of carboxylic acid, or else remove water as it is formed. In either case, excess carboxylic acid or formed water can be removed by distillation.
As an example, under proper conditions the -OH from one ricinoleic acid molecule can react with the -COOH of another ricinoleic acid molecule to give an estolide:
OH
2 CH3 (CH2 )S CHCH2CH' CH(C~ 2 )7COOH
Il ' 0~
OC(C~I2)7CH=C~CH2CH(C}I2 )~ 3 CH3(cH2)scHclI2c~=cH(cEl2~7 214111~2 This estolide would continue to crosslink or react linearly at the unreacted -OHand -COOH sites to form a polyestolide.
In this invention, component (A) is a triglyceride estolide of the formula o Il 1 C~I2--OC-R
O `
Il 1 CH OC-R
Il 1 CH~ OC-R
wherein Rl is an aliphatic group or an aliphatic group cont~ining an ester moiety R2COO- with the proviso that at least one Rl is an ~liph~tic group cont~ining the ester moiety, and contains from about S to about 23 carbon atoms, and R2 is a hydrocarbyl group cont~ining from 1 to 100 carbon atoms.
The aliphatic group R' is aL~yl such as pentyl, heptyl, nonyl, undecyl, tridecyl, heptadecyl; aL~enyl cont~ining a single bond such as heptenyl, nonenyl, undecenyl, tridecenyl, heptadecenyl, nonadecenyl, heneicosenyl;
aL~enyl cont~ining 2 or 3 double bonds such as 8,11-hept~1ec-~lienyl and 8,11,14-hept~ec~trienyl. All isomers of these are included, but straight chain groups are preferred.
At least one of the Rl groups contains the ester moiety R2COO-. The residue of this R3 group (the Rl as described above less the hydrogen and also less the R2COO-) is still defined as an aliphatic group and as such is defined by 214110~
the parameters of the aliphatic groups above. An example of an R' cont~ining the ester moiety is r S
CH3CH2CII2CHCE~2 Removing the R2COO- from this structure gives CH3CH2CH2cj~c~2 as a residue which is defined as an aliphatic group.
The hydrocarbyl group R2 includes the following:
(1) Aliphatic hydrocarbongroups; thatis, alkyl groups suchas heptyl, nonyl, undecyl, tridecyl, heptadecyl; aLkenyl groups cont~ining a single double bond such as heptenyl, nonenyl, undecenyl, tridecenyl, isostearyl, heptadecenyl,heneicosenyl; aLkenyl groups cont~inin~ 2 or 3 double bonds such as 8,11-hept~dec~(lienyl and 8,11,14-hept~dec~trienyl. All isomers of these are included, but straight chain groups are preferred.
(2) Substituted aliphatic hydrocarbon groups; that is groups cont~inin~
non-hydrocarbon substituents which, in the context of this invention, do not alter the predomin~ntly hydrocarbon character of the group. Those skilled in the art will be aware of suitable substituents; examples are hydroxy, carbaLkoxy, (especially lower carbalkoxy) and alkoxy (especially lower alkoxy), the term, "lower" denoting groups cont~ining not more than 7 carbon atoms.
(3) Hetero groups; that is, groups which, while having predomin~ntly aliphatic hydrocarbon character within the context of this invention, contain atoms other than carbon present in a chain or ring otherwise composed of 21~111)2 aliphatic carbon atoms. Suitable hetero atoms will be a~arelll to those skilled in the art and include, for example, oxygen, nitrogen and sulfur.
At least one of the R' groups is an aliphatic group cont~inin~ an ester moiety R2COO-. In a ~re~lled embodiment Rl is 2)n 2 ~ 2)S 3 Il o wherein n is from 5 to 13 and R2 is an aliphatic group cont~ining 1 to 23 carbon atoms, ~refelably from 4 to 18 carbon atoms.
The triglyceride estolide (A) is prepared by re-~ctin~ a triglyceride that contains at least one -OH group with a carboxylic acid R2COOH. At least 1 15 up to 3 -OH groups are present in the triglyceride. For each -OH group present, there is employed one mole of carboxylic acid.
~ ` 21~1iO2 Triglycerides cont~ining -OH groups occur in nature as castor oil wherein n is 7 and contains three -OH groups and lesquerella oil wherein n is 9 and contains two -OH groups.
O O~I
CH2oc(cEl2)7cEl~cRc~2c~(c~2 ) ~CH3 O OH
Il I
(CH2)7CH=CHCH2CH(CH2 ) SCH3 c~ro~ OIL
Il I
CH20C(CR2 )7C~=CHC~2C~(CII2 ) SCH3 O OH
Il I
CH2oc(c~I2)9cH~cHclI2~(c~2 ) ~CH3 CH OC(CH2)~CH=CH (CH2)7CH3 L~sQu~F~.~ o~
O O~I
~H20C(CH2)~C~=CHC~2~H(CH2 )SCE~3 The chemical profiles of castor oil and lesquerella oil show triglycerides other than those of the structures outlined above. A triglyceride of ricinoleic 20 acid is the predominate triglyceride of castor oil and is present at from 80-89 %
by weight. A triglyceride of 2 moles 14-hydroxy-11-eicosenoic acid and 1 mole 1 l-eicosenoic acid is the predominate triglyceride of lesquerella oil and is generally present in lesquerella oil in an amount in excess of 50% by weight.The carboxylic acid R2COOH reacted with the hydroxy-cont~inin~
25 triglyceride contains from 2 to 24 carbon atoms (acetic acid to tetracosanoicacid) including isomers and lm~ lration. Preferred carboxylic acids are the acids of butyric, caproic, caprylic, capric, lauric, myristic, p~lmitic, stearic, oleic, linoleic, and linolenic.
21~iiO~
The esterification to make the triglyceride estolide occurs by reacting a carboxylic acid with the hydroxy cont~ining triglyceride. pne mole of carboxylic acid is employed for every -OH group present in the hydroxy-containing triglyceride.
The following examples are illustrative of the preparation of triglyceride estolides wherein the carboxylic acid is a monocarboxylic acid. Unless otherwise indicated, all parts and percentages are by weight. Solvents may or may not be employed. Optimally, the obtained estolides are refined and bleached.
Example A-l Added to a 1 liter, 4 neck flask are 200 parts (0.19 moles) of castor oil, 74.2 parts (0.57 moles) heptanoic acid, 300 ml xylene and 2.5 parts para-toluenesulfonic acid. The contents are heated to 150C with stirring during which time water is azeotroped off. Xylene is stripped off using a nitrogen sweep and later to 12 millimeters mercury. The contents are filtered to give the desired product.
Example A-2 Lesquerella oil and heptanoic acid are reacted on a (1 -OH:l -COOH) basis. The lesquerella oil, heptanoic acid, para-toluenesulfonic acid and xyleneare added to a flask and the procedure of Example A-l is essentially followed.
The filtrate is the desired product.
Example A-3 Lesquerella oil and isostearic acid are reacted on a (1 -OH:l -COOH) basis. The lesquerella oil, isostearic acid, xylene and methanesulfonic acid areadded to a flask and the procedure of Example A-l is essentially followed. The filtrate is the desired product.
~ ` 214110~
Example A-4 Lesquerella oil and oleic acid are reacted on a (1 -OH: 1 - sCOOH) basis.
The lesquerella oil, oleic acid, xylene and meth~n~slllfonic acid are added to a flask and the procedure of Example A-l is essentially followed. The filtrate 5 is the desired product.
Mono carboxylic acids are also formed by the hydrolysis of a triglyceride.
CH2OC R~
o CH OC - l~b ~drol~d~ ~coo~ ~ ~bc ~cerol C~ 2 OC Re In the above reactions Ra~ Rb and RC are the same or dirrele~ and contain from 1 to 23 carbon atoms.
The following example is directed to the preparation of a triglyceride 20 estolide wherein the monocarboxylic acid is obtained from the hydrolysis of a triglyceride.
Example A-5 Added to a 12 liter, 4 neck flask are 3129 parts Sunyl 87, 3000 parts water and 1000 parts isopropyl alcohol. The mixture is heated to 60C and 25 added is 100 parts of a 50% aqueous solution of sodium hydroxide. The sodium hydroxide solution is added in 50 millimeter portions. This addition is exothermic and cooling is required to keep the reaction under control. At the end of this addition, the contents are pennitte~l to continue stirring for 6 hours.
2 1 ~
At 60C concentrated aqueous hydrochloric acid (37%) is slowly added until a pH of 2 is reached. At the end of this addition, the contents,are permittecl to stir for 30 more mimltes. Stirring is halted and the contents separate into layers. The bottom (aqueous) portion is removed and discarded and the S rem~in-ler of the contents is washed three times with 1000 parts hot water.
After the third wash, the water layer is removed and discarded and the contents are stripped and filtered to give a monocarboxylic acid mixture cont~ining 87%
oleic acid.
In a separate flask are added lesquerella oil and the 87% oleic acid on 10 a 1 -OH:l -COOH basis, along with para-toluenesulfonic acid and xylene.
The contents are heated to 150C with stirring while azeotroping off water.
The contents are then stripped and filtered to give the desired product.
(B) The Triglyceride Oil Component (B) of this invention is a triglyceride oil which is a natural 15 or synthetic oil of the formula o Il c~ oc--~--oc.i' O
Il CE~ OC--R
wherein R3, R4 and R5 are aliphatic hydrocarbyl groups cont~ining from about 1 to about 23 carbon atoms.
The term "hydrocarbyl group" as used herein denotes a radical having a carbon atom directly attached to the rem~inl1er of the molecule. The aliphatichydrocarbyl groups include the following:
2 1 ~ 2 (1) Aliphatic hydrocarbon groups; that is, alkyl groups such as heptyl, nonyl, undecyl, tridecyl, heptadecyl, nonadecenyl; alkenyl groups cont~inin~
a single double bond such as heptenyl, nonenyl, undecenyl tridecenyl, heptadecenyl, heneicosenyl; alkenyl groups cont~ining 2 or 3 double bonds such 5 as 8,1 l-heptadecadienyl and 8,11,14-heptadecatrienyl. All isomers of these are included, but straight chain groups are l,refelled.
(2) Substituted aliphatic hydrocarbon groups; that is groups cont~ining non-hydrocarbon substituents which, in the context of this invention, do not alter the predomin~ntly hydrocarbon character of the group. Those skilled in 10 the art will be aware of suitable substituents; examples are hydroxy, carbalkoxy, (especially lower carbalkoxy) and aLkoxy (especially lower alkoxy), the term, "lower" denoting groups cont~ining not more than 7 carbon atoms.
(3) Hetero groups; that is, groups which, while having predomin~ntly aliphatic hydrocarbon character within the context of this invention, contain 15 atoms other than carbon present in a chain or ring otherwise composed of aliphatic carbon atoms. Suitable hetero atoms will be apparent to those skilled in the art and include, for example, oxygen, nitrogen and sulfur.
Naturally occurring triglycerides are animal fat triglycerides and vegetable oil triglycerides. The synthetic triglycerides are those formed by the20 reaction of one mole of glycerol with three moles of a fatty acid or mixture of fatty acids. Preferred are vegetable oil triglycerides.
The groups R3, R4 and Rs may have an unsaturation content as low as 7-11 percent for coconut oil and as high as 100% for a synthetic triglyceride of glycerol and oleic acid. Generally the fatty acid moieties are such that the 25 triglyceride has a monounsaturated character of at least 60 percent, prefel~bly at least 70 percent and most preferably at least 80 percent. Normal sunflower oil has an oleic acid content of 25-30 percent. By genetically modifying the seeds of sunflowers, a sunflower oil can be obtained wherein the oleic content 2 1 ~ 2 is from about 60 percent up to about 90 percent. U.S. Patent Nos. 4,627,192 and 4,743,402 are herein incorporated by referellce for their disclosures directed to the preparation of high oleic sunflower oil. For example, a triglyceride comprised exclusively of an oleic acid moiety has an oleic acid 5 content of 100% and consequently a monoul~sa~u~ated content of 100% . Where the triglyceride is made up of acid moieties that are 70% oleic acid, 10%
stearic acid, 5% palmitic acid, 7% linoleic and 8% hexadecenoic acid, the monounsaturated content is 78%.
Naturally occurring triglycerides having utility in this invention are 10 exemplified by vegetable oils that are genetically modified such that they contain a higher than normal oleic acid content. That is, the Rl, R2 and R3 groups are heptadecenyl groups and the RlCOO-, R2COO- and R3Coo- that are ~ çh~l to the 1,2,3,-propanetriyl groups -CH2CHCH2- are the residue of an oleic acid molecule. Generally the fatty acid moieties are such that the 15 triglyceride has monounsaturated character of at least 60 percent, p~efe~ably 80 percent. Normal sunflower oil has an oleic acid content of 20-40 percent. By genetically modifying the seeds of sunflowers, a sunflower oil can be obtained wherein the oleic content is from about 60 percent up to about 90 percent.
U.S. Patent No. 4,627,192 and 4,743,402 are herein incorporated by reference 20 for their disclosures directed to the preparation of high oleic sunflower oil.
The prefel,ed triglyceride oils are genetically modified high oleic (at least 60 percent) acid triglyceride oils. Typical genetically modified high oleic vegetable oils employed within the instant invention are high oleic safflower oil, high oleic corn oil, high oleic rapeseed oil, high oleic sunflower oil, high 25 oleic soybean oil, high oleic cottonseed oil, high oleic lesquerella oil, high oleic meadowfoam oil and high oleic palm olein. A preferred high oleic vegetable oil is high oleic sunflower oil obtained from Heli~nthll~ sp. This product is available from SVO Enterprises, Eastlake, Ohio as SunylR high oleic sunflower ~ 211110~
oil. Sunyl 80 is a high oleic triglyceride wherein the acid moieties comprise 80 percent oleic acid. Another ~refel,ed high oleic vegetable oilr is high oleicrapeseed oil obtained from Brassica campestris or Brassica napus, also availablefrom SVO Enterprises as RSR high oleic rapeseed oil. RS 80 ~ignifi~s a 5 rapeseed oil wherein the acid moieties comprise 80 percent oleic acid.
It is to be noted the olive oil is excluded as a vegetable oil in this invention. The oleic acid content of olive oil typically ranges from 65-85 percent. This content, however, is not achieved through genetic modification, but rather is naturally occurring.
It is further to be noted that gen~tic~lly modified vegetable oils have high oleic acid contents at the expense of the di- and tri- ~ ated acids. A
normal sunflower oil has from 20-40 percent oleic acid moieties and from 50-70 percent linoleic acid moieties. This gives a 90 percent content of mono- and di- lln~ lrated acid moieties (20+70 or 40+50). Genetically modifying 15 vegetable oils generate a low di- or tri- unsaturated moiety vegetable oil. The gen~tic~lly modified oils of this invention have an oleic acid moiety:linoleic acid moiety ratio of from about 2 up to about 90. A 60 percent oleic acid moiety content and 30 percent linoleic acid moiety content of a triglyceride oilgives a ratio of 2. A triglyceride oil made up of an 80 percent oleic acid 20 moiety and 10 percent linoleic acid moiety gives a ratio of 8. A triglycerideoil made up of a 90 percent oleic acid moiety and 1 percent linoleic acid moiety gives a ratio of 90. The ratio for normal sunflower oil is 0.5 (30 percent oleic acid moiety and 60 percent linoleic acid moiety).
Non-genetically modified vegetable oils having utility in this invention are sunflower oil, safflower oil, corn oil, soybean oil, rapeseed oil, meadowfoam oil, lesquerella oil or castor oil.
-This first embodiment comprises an admixture of components (A) and (B). Typically the weight ratio of (A):(B)is from (1-99):(99-1~, plefelably from (10-90):(90-10) and most preferably from (40-60):(6040).
In the second embodiment, a reaction occurs between components (A) S and (B). The reaction is brought about by lltili7ing a catalyst. Components (A) and (B) are esters and the reaction of these components is an interesterification that produces various products according to the following reaction:
A B A A B --B
A+ B e~t A I s + B I --A
A B --B A --A B
(A) ~B) The catalyst is acidic, basic or en7ymatic. The basic catalyst comprises aL~ali or ~lk~lin~ earth metal aL~oxides cont~inin~ from 1 up to 6 carbon atoms.Pler~lled basic catalysts are sodium or potassium methoxide, calcium or magnesium methoxide, the ethoxides of sodium, pot~sillm, calcium or magnesium and the isomeric propoxides of sodium, pot~inm, calcium or 20 magnesium. The most prefelled basic catalyst is sodium methoxide. The acidic catalyst comprises mineral acids or organic acids cont~ining from 1 up to 6 carbon atoms. Preferred mineral acidic catalysts are hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid. Preferred organic acid catalystsare formic acid, acetic acid, propionic acid, the isomers of butyric acid, valeric 25 and caproic. The en_ymatic catalyst comprises the lipases and esterases.
Within this embodiment wherein a reaction occurs between components (A) and (B), the weight ratio of (A):(B)is from (1-99):(99-1), preferably from (10-90):(90-10) and most preferably from (40-60):(60-40).
21411~2 Example A-6 Added to a flask are 210 parts Sunyl 80 oil and 90 parts of the product of Example A-l. The contents are heated to 90C under 20 millimeters mercury. Sodium methoxide catalyst (1.3 parts) is slowly added and the vacuum reapplied. After 1.5 hours of reaction, 0.5 parts phosphoric acid is added to neutralize the catalyst. The contents are filtered to give the desired interesterified product.
In an even further embodiment, acids other than aliphatic mono-carboxylic acids may be reacted with the hydroxy cont~inin~ triglyceride to form an estolide. These may be aliphatic dicarboxylic acids or aryl mono-, di-or tri- carboxylic acids. Aliphatic dicarboxylic acids are of the formula HOOCCH=CHCOOH or HOOC(CH2)tCOOH wherein t is from zero up to 8.
Envisioned within the formula HOOCCH=CHCOOH are maleic acid and fumaric acid. The aliphatic dicarboxylic acids of interest are: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. One -COOH of component (B) is employed for each -OH group present within component (A).
The aryl carboxylic acids are of the formula Ar(COOH)x wherein Ar is a benzene or naphthalene nucleus and x is 1, 2 or 3. Aryl carboxylic acids having utility in this invention are benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2,3,-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, and the various isomers of the mono-, di- and tri- naphthoic acids. Again one -COOH of component (B) is employed for each -OH group present within component (A).
As stated earlier, one way of shifting the equilibrium to the right is to employ excess carboxylic acid. After the estolide is formed the excess carboxylic acid can be distilled out or the carboxylic acid can be reacted with - - a basic compound to form a salt which is then separated out.
214ilO~
Examples of the formation of estolides lltili7ing aliphatic dicarboxylic acids or aryl mono-, di, or tri-carboxylic acids are as follows.
Example A-7 Added to a 2 liter, 4 neck flask are 457 parts lesquerella oil, 58 parts 5 fumaric acid, 4 parts meth~n~sulfonic acid and 250 parts xylene. The lesquerella oil and fumaric acid are charged on a 1 -OH:l -COOH basis.
Mixing is begun at room telll~elature and it is noted, that the fumaric acid remains insoluble. The contents are heated to effect solution. The temperature is increased to 150C and held for 16 hours during which time 9 ml of water 10 is obtained. Solvent is removed first by nitrogen sweeping and finally under vacuum of 25 millimeters mercury. At 70C the contents are filtered to give the desired product.
Example A-8 Following the procedure of Example A-7, 457 parts lesquerella oil, 54.6 15 parts adipic acid, 5 parts para-toluenesulfonic acid and 400 parts xylene arereacted at 150C. The contents are stripped and filtered to give the desired product.
Example A-9 The procedure of Example A-7 is repeated except that fumaric acid is 20 replaced with maleic acid.
Example A-10 Following the procedure of Example A-7, 457 parts lesquerella oil, 94 parts azelaic acid, 8 parts para-toluenesulfonic acid and 500 parts xylene are reacted at 150C. The contents are stripped and filtered to give the desired 25 product.
Example A-l l Following the procedure of Example A-7, 457 parts lesquerella oil, 84 parts phthalic acid, 7 parts para-toluenesulfonic acid and 400 parts xylene are 21~110~
reacted at 150C. The contents are stripped and filtered to give the desired product.
Example A-12 The procedure of Example A-l 1 is repeated except that phthalic acid is replaced with isophthalic acid.
Example A-13 The procedure of Example A-l 1 is repeated except that phthalic acid is replaced with terephthalic acid.
Example A-14 Following the procedure of Example A-7, 457 parts lesquerella oil, 105 parts hemimellitic acid, 10 parts para-toluenesulfonic acid and 500 parts xyleneare reacted at 150C. The contents are stripped and filtered to give the desiredproduct.
Example A-15 The procedure of Example A-14 is repeated except that hemimellitic acid is replaced with trimellitic acid.
Example A-16 The procedure of Example A-14 is repeated except that h~mimellitic acid is replaced with trimesic acid.
The below Table I outlines examples of this invention wherein components (A) and (B) are blended or reacted together according to the above ranges to effect solution. All parts are by weight.
TABLE I
THICKENING RESULTS OF VEGETABLE OILS MIXED OR REACTED WITH ESTOLIDES
EXAMI'L (A) ESTOLIDE (B) VEOETABLE OIL 40C VISCOSITY 100C VISCOSITY
E
I NONE 100 PARTS SUNYL 80 39.76 Cst 8.59 Cst 2 NONE 100 PARTS RS8036.96 8.29 3 10 PARTS PRODUCT OF EXAMPLE A-8 90 PARTS RS80 61.95 12.27 4 5 PARTS PRODUCT OF EXAMPLE A-7 95 PARTS SUNYL 80 49.09 10.3S
20 PARTS PRODUCT OF EXAMPLE A-7 80 PARTS SUNYL 80 98.S7 18.28 6 30 PARTS PRODUCT OF EXAMPLE A-7 70 PARTS SUNYL 80141.87 24.72 7 5 PARTS PRODUCT OF EXAMPLE A-8 95 PARTS SUNYL 80 46.54 9.73 8 10 PARTS PRODUCT OF EXAMPLE A-8 90 PARTS SUNYL 80 64.62 12.98 9 20 PARTS PRODUCTOF EXAMPLEA-8 80 PARTS SUNYL 80 M.01 14.32 10 30 PARTS PRODUCT OF EXAMPLE A-8 70 PARTS SUNYL 80107.66 18.51 11 5 PARTS PRODUCT OF EXAMPLE A-3 95 PARTS SUNYL 80 41.89 8.92 12 10 PARTS PRODUCT OF EXAMPLE A-3 90 PARTS SUNYL 80 44.53 9.31 13 20 PARTS PRODUCT OF EXAMPLE A-3 80 PARTS SUNYL 80 50.1 10.09 14 30 PARTS PRODUCTOF EXAMPLEA-3 70 PARTS SUNYL 80 S6.25 10.91 15 30 PARTS PRODUCT OF EXAMPLE A-l 70 PARTS SUNYL 80 5S.95 10.47 16~ 30 PARTS PRODUCT OF EXAMPLE A-l 70 PARTS SUNYL 80 50.67 10.11 ' Reacted as per E~ample A-6 21411~2 While the invention has been explained in relation to its prefelled embo liment~, it is to be understood that various modifications~ thereof will become apparent to those skilled in the art upon reading the specification.
Therefore, it is to be understood that the invention disclosed herein is intended S to cover such modifications as fall within the scope of the appended claims.
At least one of the R' groups is an aliphatic group cont~inin~ an ester moiety R2COO-. In a ~re~lled embodiment Rl is 2)n 2 ~ 2)S 3 Il o wherein n is from 5 to 13 and R2 is an aliphatic group cont~ining 1 to 23 carbon atoms, ~refelably from 4 to 18 carbon atoms.
The triglyceride estolide (A) is prepared by re-~ctin~ a triglyceride that contains at least one -OH group with a carboxylic acid R2COOH. At least 1 15 up to 3 -OH groups are present in the triglyceride. For each -OH group present, there is employed one mole of carboxylic acid.
~ ` 21~1iO2 Triglycerides cont~ining -OH groups occur in nature as castor oil wherein n is 7 and contains three -OH groups and lesquerella oil wherein n is 9 and contains two -OH groups.
O O~I
CH2oc(cEl2)7cEl~cRc~2c~(c~2 ) ~CH3 O OH
Il I
(CH2)7CH=CHCH2CH(CH2 ) SCH3 c~ro~ OIL
Il I
CH20C(CR2 )7C~=CHC~2C~(CII2 ) SCH3 O OH
Il I
CH2oc(c~I2)9cH~cHclI2~(c~2 ) ~CH3 CH OC(CH2)~CH=CH (CH2)7CH3 L~sQu~F~.~ o~
O O~I
~H20C(CH2)~C~=CHC~2~H(CH2 )SCE~3 The chemical profiles of castor oil and lesquerella oil show triglycerides other than those of the structures outlined above. A triglyceride of ricinoleic 20 acid is the predominate triglyceride of castor oil and is present at from 80-89 %
by weight. A triglyceride of 2 moles 14-hydroxy-11-eicosenoic acid and 1 mole 1 l-eicosenoic acid is the predominate triglyceride of lesquerella oil and is generally present in lesquerella oil in an amount in excess of 50% by weight.The carboxylic acid R2COOH reacted with the hydroxy-cont~inin~
25 triglyceride contains from 2 to 24 carbon atoms (acetic acid to tetracosanoicacid) including isomers and lm~ lration. Preferred carboxylic acids are the acids of butyric, caproic, caprylic, capric, lauric, myristic, p~lmitic, stearic, oleic, linoleic, and linolenic.
21~iiO~
The esterification to make the triglyceride estolide occurs by reacting a carboxylic acid with the hydroxy cont~ining triglyceride. pne mole of carboxylic acid is employed for every -OH group present in the hydroxy-containing triglyceride.
The following examples are illustrative of the preparation of triglyceride estolides wherein the carboxylic acid is a monocarboxylic acid. Unless otherwise indicated, all parts and percentages are by weight. Solvents may or may not be employed. Optimally, the obtained estolides are refined and bleached.
Example A-l Added to a 1 liter, 4 neck flask are 200 parts (0.19 moles) of castor oil, 74.2 parts (0.57 moles) heptanoic acid, 300 ml xylene and 2.5 parts para-toluenesulfonic acid. The contents are heated to 150C with stirring during which time water is azeotroped off. Xylene is stripped off using a nitrogen sweep and later to 12 millimeters mercury. The contents are filtered to give the desired product.
Example A-2 Lesquerella oil and heptanoic acid are reacted on a (1 -OH:l -COOH) basis. The lesquerella oil, heptanoic acid, para-toluenesulfonic acid and xyleneare added to a flask and the procedure of Example A-l is essentially followed.
The filtrate is the desired product.
Example A-3 Lesquerella oil and isostearic acid are reacted on a (1 -OH:l -COOH) basis. The lesquerella oil, isostearic acid, xylene and methanesulfonic acid areadded to a flask and the procedure of Example A-l is essentially followed. The filtrate is the desired product.
~ ` 214110~
Example A-4 Lesquerella oil and oleic acid are reacted on a (1 -OH: 1 - sCOOH) basis.
The lesquerella oil, oleic acid, xylene and meth~n~slllfonic acid are added to a flask and the procedure of Example A-l is essentially followed. The filtrate 5 is the desired product.
Mono carboxylic acids are also formed by the hydrolysis of a triglyceride.
CH2OC R~
o CH OC - l~b ~drol~d~ ~coo~ ~ ~bc ~cerol C~ 2 OC Re In the above reactions Ra~ Rb and RC are the same or dirrele~ and contain from 1 to 23 carbon atoms.
The following example is directed to the preparation of a triglyceride 20 estolide wherein the monocarboxylic acid is obtained from the hydrolysis of a triglyceride.
Example A-5 Added to a 12 liter, 4 neck flask are 3129 parts Sunyl 87, 3000 parts water and 1000 parts isopropyl alcohol. The mixture is heated to 60C and 25 added is 100 parts of a 50% aqueous solution of sodium hydroxide. The sodium hydroxide solution is added in 50 millimeter portions. This addition is exothermic and cooling is required to keep the reaction under control. At the end of this addition, the contents are pennitte~l to continue stirring for 6 hours.
2 1 ~
At 60C concentrated aqueous hydrochloric acid (37%) is slowly added until a pH of 2 is reached. At the end of this addition, the contents,are permittecl to stir for 30 more mimltes. Stirring is halted and the contents separate into layers. The bottom (aqueous) portion is removed and discarded and the S rem~in-ler of the contents is washed three times with 1000 parts hot water.
After the third wash, the water layer is removed and discarded and the contents are stripped and filtered to give a monocarboxylic acid mixture cont~ining 87%
oleic acid.
In a separate flask are added lesquerella oil and the 87% oleic acid on 10 a 1 -OH:l -COOH basis, along with para-toluenesulfonic acid and xylene.
The contents are heated to 150C with stirring while azeotroping off water.
The contents are then stripped and filtered to give the desired product.
(B) The Triglyceride Oil Component (B) of this invention is a triglyceride oil which is a natural 15 or synthetic oil of the formula o Il c~ oc--~--oc.i' O
Il CE~ OC--R
wherein R3, R4 and R5 are aliphatic hydrocarbyl groups cont~ining from about 1 to about 23 carbon atoms.
The term "hydrocarbyl group" as used herein denotes a radical having a carbon atom directly attached to the rem~inl1er of the molecule. The aliphatichydrocarbyl groups include the following:
2 1 ~ 2 (1) Aliphatic hydrocarbon groups; that is, alkyl groups such as heptyl, nonyl, undecyl, tridecyl, heptadecyl, nonadecenyl; alkenyl groups cont~inin~
a single double bond such as heptenyl, nonenyl, undecenyl tridecenyl, heptadecenyl, heneicosenyl; alkenyl groups cont~ining 2 or 3 double bonds such 5 as 8,1 l-heptadecadienyl and 8,11,14-heptadecatrienyl. All isomers of these are included, but straight chain groups are l,refelled.
(2) Substituted aliphatic hydrocarbon groups; that is groups cont~ining non-hydrocarbon substituents which, in the context of this invention, do not alter the predomin~ntly hydrocarbon character of the group. Those skilled in 10 the art will be aware of suitable substituents; examples are hydroxy, carbalkoxy, (especially lower carbalkoxy) and aLkoxy (especially lower alkoxy), the term, "lower" denoting groups cont~ining not more than 7 carbon atoms.
(3) Hetero groups; that is, groups which, while having predomin~ntly aliphatic hydrocarbon character within the context of this invention, contain 15 atoms other than carbon present in a chain or ring otherwise composed of aliphatic carbon atoms. Suitable hetero atoms will be apparent to those skilled in the art and include, for example, oxygen, nitrogen and sulfur.
Naturally occurring triglycerides are animal fat triglycerides and vegetable oil triglycerides. The synthetic triglycerides are those formed by the20 reaction of one mole of glycerol with three moles of a fatty acid or mixture of fatty acids. Preferred are vegetable oil triglycerides.
The groups R3, R4 and Rs may have an unsaturation content as low as 7-11 percent for coconut oil and as high as 100% for a synthetic triglyceride of glycerol and oleic acid. Generally the fatty acid moieties are such that the 25 triglyceride has a monounsaturated character of at least 60 percent, prefel~bly at least 70 percent and most preferably at least 80 percent. Normal sunflower oil has an oleic acid content of 25-30 percent. By genetically modifying the seeds of sunflowers, a sunflower oil can be obtained wherein the oleic content 2 1 ~ 2 is from about 60 percent up to about 90 percent. U.S. Patent Nos. 4,627,192 and 4,743,402 are herein incorporated by referellce for their disclosures directed to the preparation of high oleic sunflower oil. For example, a triglyceride comprised exclusively of an oleic acid moiety has an oleic acid 5 content of 100% and consequently a monoul~sa~u~ated content of 100% . Where the triglyceride is made up of acid moieties that are 70% oleic acid, 10%
stearic acid, 5% palmitic acid, 7% linoleic and 8% hexadecenoic acid, the monounsaturated content is 78%.
Naturally occurring triglycerides having utility in this invention are 10 exemplified by vegetable oils that are genetically modified such that they contain a higher than normal oleic acid content. That is, the Rl, R2 and R3 groups are heptadecenyl groups and the RlCOO-, R2COO- and R3Coo- that are ~ çh~l to the 1,2,3,-propanetriyl groups -CH2CHCH2- are the residue of an oleic acid molecule. Generally the fatty acid moieties are such that the 15 triglyceride has monounsaturated character of at least 60 percent, p~efe~ably 80 percent. Normal sunflower oil has an oleic acid content of 20-40 percent. By genetically modifying the seeds of sunflowers, a sunflower oil can be obtained wherein the oleic content is from about 60 percent up to about 90 percent.
U.S. Patent No. 4,627,192 and 4,743,402 are herein incorporated by reference 20 for their disclosures directed to the preparation of high oleic sunflower oil.
The prefel,ed triglyceride oils are genetically modified high oleic (at least 60 percent) acid triglyceride oils. Typical genetically modified high oleic vegetable oils employed within the instant invention are high oleic safflower oil, high oleic corn oil, high oleic rapeseed oil, high oleic sunflower oil, high 25 oleic soybean oil, high oleic cottonseed oil, high oleic lesquerella oil, high oleic meadowfoam oil and high oleic palm olein. A preferred high oleic vegetable oil is high oleic sunflower oil obtained from Heli~nthll~ sp. This product is available from SVO Enterprises, Eastlake, Ohio as SunylR high oleic sunflower ~ 211110~
oil. Sunyl 80 is a high oleic triglyceride wherein the acid moieties comprise 80 percent oleic acid. Another ~refel,ed high oleic vegetable oilr is high oleicrapeseed oil obtained from Brassica campestris or Brassica napus, also availablefrom SVO Enterprises as RSR high oleic rapeseed oil. RS 80 ~ignifi~s a 5 rapeseed oil wherein the acid moieties comprise 80 percent oleic acid.
It is to be noted the olive oil is excluded as a vegetable oil in this invention. The oleic acid content of olive oil typically ranges from 65-85 percent. This content, however, is not achieved through genetic modification, but rather is naturally occurring.
It is further to be noted that gen~tic~lly modified vegetable oils have high oleic acid contents at the expense of the di- and tri- ~ ated acids. A
normal sunflower oil has from 20-40 percent oleic acid moieties and from 50-70 percent linoleic acid moieties. This gives a 90 percent content of mono- and di- lln~ lrated acid moieties (20+70 or 40+50). Genetically modifying 15 vegetable oils generate a low di- or tri- unsaturated moiety vegetable oil. The gen~tic~lly modified oils of this invention have an oleic acid moiety:linoleic acid moiety ratio of from about 2 up to about 90. A 60 percent oleic acid moiety content and 30 percent linoleic acid moiety content of a triglyceride oilgives a ratio of 2. A triglyceride oil made up of an 80 percent oleic acid 20 moiety and 10 percent linoleic acid moiety gives a ratio of 8. A triglycerideoil made up of a 90 percent oleic acid moiety and 1 percent linoleic acid moiety gives a ratio of 90. The ratio for normal sunflower oil is 0.5 (30 percent oleic acid moiety and 60 percent linoleic acid moiety).
Non-genetically modified vegetable oils having utility in this invention are sunflower oil, safflower oil, corn oil, soybean oil, rapeseed oil, meadowfoam oil, lesquerella oil or castor oil.
-This first embodiment comprises an admixture of components (A) and (B). Typically the weight ratio of (A):(B)is from (1-99):(99-1~, plefelably from (10-90):(90-10) and most preferably from (40-60):(6040).
In the second embodiment, a reaction occurs between components (A) S and (B). The reaction is brought about by lltili7ing a catalyst. Components (A) and (B) are esters and the reaction of these components is an interesterification that produces various products according to the following reaction:
A B A A B --B
A+ B e~t A I s + B I --A
A B --B A --A B
(A) ~B) The catalyst is acidic, basic or en7ymatic. The basic catalyst comprises aL~ali or ~lk~lin~ earth metal aL~oxides cont~inin~ from 1 up to 6 carbon atoms.Pler~lled basic catalysts are sodium or potassium methoxide, calcium or magnesium methoxide, the ethoxides of sodium, pot~sillm, calcium or magnesium and the isomeric propoxides of sodium, pot~inm, calcium or 20 magnesium. The most prefelled basic catalyst is sodium methoxide. The acidic catalyst comprises mineral acids or organic acids cont~ining from 1 up to 6 carbon atoms. Preferred mineral acidic catalysts are hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid. Preferred organic acid catalystsare formic acid, acetic acid, propionic acid, the isomers of butyric acid, valeric 25 and caproic. The en_ymatic catalyst comprises the lipases and esterases.
Within this embodiment wherein a reaction occurs between components (A) and (B), the weight ratio of (A):(B)is from (1-99):(99-1), preferably from (10-90):(90-10) and most preferably from (40-60):(60-40).
21411~2 Example A-6 Added to a flask are 210 parts Sunyl 80 oil and 90 parts of the product of Example A-l. The contents are heated to 90C under 20 millimeters mercury. Sodium methoxide catalyst (1.3 parts) is slowly added and the vacuum reapplied. After 1.5 hours of reaction, 0.5 parts phosphoric acid is added to neutralize the catalyst. The contents are filtered to give the desired interesterified product.
In an even further embodiment, acids other than aliphatic mono-carboxylic acids may be reacted with the hydroxy cont~inin~ triglyceride to form an estolide. These may be aliphatic dicarboxylic acids or aryl mono-, di-or tri- carboxylic acids. Aliphatic dicarboxylic acids are of the formula HOOCCH=CHCOOH or HOOC(CH2)tCOOH wherein t is from zero up to 8.
Envisioned within the formula HOOCCH=CHCOOH are maleic acid and fumaric acid. The aliphatic dicarboxylic acids of interest are: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. One -COOH of component (B) is employed for each -OH group present within component (A).
The aryl carboxylic acids are of the formula Ar(COOH)x wherein Ar is a benzene or naphthalene nucleus and x is 1, 2 or 3. Aryl carboxylic acids having utility in this invention are benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2,3,-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, and the various isomers of the mono-, di- and tri- naphthoic acids. Again one -COOH of component (B) is employed for each -OH group present within component (A).
As stated earlier, one way of shifting the equilibrium to the right is to employ excess carboxylic acid. After the estolide is formed the excess carboxylic acid can be distilled out or the carboxylic acid can be reacted with - - a basic compound to form a salt which is then separated out.
214ilO~
Examples of the formation of estolides lltili7ing aliphatic dicarboxylic acids or aryl mono-, di, or tri-carboxylic acids are as follows.
Example A-7 Added to a 2 liter, 4 neck flask are 457 parts lesquerella oil, 58 parts 5 fumaric acid, 4 parts meth~n~sulfonic acid and 250 parts xylene. The lesquerella oil and fumaric acid are charged on a 1 -OH:l -COOH basis.
Mixing is begun at room telll~elature and it is noted, that the fumaric acid remains insoluble. The contents are heated to effect solution. The temperature is increased to 150C and held for 16 hours during which time 9 ml of water 10 is obtained. Solvent is removed first by nitrogen sweeping and finally under vacuum of 25 millimeters mercury. At 70C the contents are filtered to give the desired product.
Example A-8 Following the procedure of Example A-7, 457 parts lesquerella oil, 54.6 15 parts adipic acid, 5 parts para-toluenesulfonic acid and 400 parts xylene arereacted at 150C. The contents are stripped and filtered to give the desired product.
Example A-9 The procedure of Example A-7 is repeated except that fumaric acid is 20 replaced with maleic acid.
Example A-10 Following the procedure of Example A-7, 457 parts lesquerella oil, 94 parts azelaic acid, 8 parts para-toluenesulfonic acid and 500 parts xylene are reacted at 150C. The contents are stripped and filtered to give the desired 25 product.
Example A-l l Following the procedure of Example A-7, 457 parts lesquerella oil, 84 parts phthalic acid, 7 parts para-toluenesulfonic acid and 400 parts xylene are 21~110~
reacted at 150C. The contents are stripped and filtered to give the desired product.
Example A-12 The procedure of Example A-l 1 is repeated except that phthalic acid is replaced with isophthalic acid.
Example A-13 The procedure of Example A-l 1 is repeated except that phthalic acid is replaced with terephthalic acid.
Example A-14 Following the procedure of Example A-7, 457 parts lesquerella oil, 105 parts hemimellitic acid, 10 parts para-toluenesulfonic acid and 500 parts xyleneare reacted at 150C. The contents are stripped and filtered to give the desiredproduct.
Example A-15 The procedure of Example A-14 is repeated except that hemimellitic acid is replaced with trimellitic acid.
Example A-16 The procedure of Example A-14 is repeated except that h~mimellitic acid is replaced with trimesic acid.
The below Table I outlines examples of this invention wherein components (A) and (B) are blended or reacted together according to the above ranges to effect solution. All parts are by weight.
TABLE I
THICKENING RESULTS OF VEGETABLE OILS MIXED OR REACTED WITH ESTOLIDES
EXAMI'L (A) ESTOLIDE (B) VEOETABLE OIL 40C VISCOSITY 100C VISCOSITY
E
I NONE 100 PARTS SUNYL 80 39.76 Cst 8.59 Cst 2 NONE 100 PARTS RS8036.96 8.29 3 10 PARTS PRODUCT OF EXAMPLE A-8 90 PARTS RS80 61.95 12.27 4 5 PARTS PRODUCT OF EXAMPLE A-7 95 PARTS SUNYL 80 49.09 10.3S
20 PARTS PRODUCT OF EXAMPLE A-7 80 PARTS SUNYL 80 98.S7 18.28 6 30 PARTS PRODUCT OF EXAMPLE A-7 70 PARTS SUNYL 80141.87 24.72 7 5 PARTS PRODUCT OF EXAMPLE A-8 95 PARTS SUNYL 80 46.54 9.73 8 10 PARTS PRODUCT OF EXAMPLE A-8 90 PARTS SUNYL 80 64.62 12.98 9 20 PARTS PRODUCTOF EXAMPLEA-8 80 PARTS SUNYL 80 M.01 14.32 10 30 PARTS PRODUCT OF EXAMPLE A-8 70 PARTS SUNYL 80107.66 18.51 11 5 PARTS PRODUCT OF EXAMPLE A-3 95 PARTS SUNYL 80 41.89 8.92 12 10 PARTS PRODUCT OF EXAMPLE A-3 90 PARTS SUNYL 80 44.53 9.31 13 20 PARTS PRODUCT OF EXAMPLE A-3 80 PARTS SUNYL 80 50.1 10.09 14 30 PARTS PRODUCTOF EXAMPLEA-3 70 PARTS SUNYL 80 S6.25 10.91 15 30 PARTS PRODUCT OF EXAMPLE A-l 70 PARTS SUNYL 80 5S.95 10.47 16~ 30 PARTS PRODUCT OF EXAMPLE A-l 70 PARTS SUNYL 80 50.67 10.11 ' Reacted as per E~ample A-6 21411~2 While the invention has been explained in relation to its prefelled embo liment~, it is to be understood that various modifications~ thereof will become apparent to those skilled in the art upon reading the specification.
Therefore, it is to be understood that the invention disclosed herein is intended S to cover such modifications as fall within the scope of the appended claims.
Claims (29)
1. A composition, comprising;
(A) at least one triglyceride estolide of the formula wherein R1 is an aliphatic group or an aliphatic group containing an ester moiety R2COO- with the proviso that at least one R1 is an aliphatic group containing the ester moiety, and contains from about 5 to about 23 carbon atoms, and R2 is a hydrocarbyl group containing from 1 to 100 carbon atoms and (B) at least one animal fat, vegetable oil or synthetic triglyceride oil of the formula wherein R3, R4 and R5 are aliphatic groups or hydroxy containing aliphatic groups that are at least 60 percent monounsaturated and further wherein an oleic acid moiety:linoleic acid moiety ratio is from about 2 up to about 90, andcontain from about 1 to about 23 carbon atoms.
(A) at least one triglyceride estolide of the formula wherein R1 is an aliphatic group or an aliphatic group containing an ester moiety R2COO- with the proviso that at least one R1 is an aliphatic group containing the ester moiety, and contains from about 5 to about 23 carbon atoms, and R2 is a hydrocarbyl group containing from 1 to 100 carbon atoms and (B) at least one animal fat, vegetable oil or synthetic triglyceride oil of the formula wherein R3, R4 and R5 are aliphatic groups or hydroxy containing aliphatic groups that are at least 60 percent monounsaturated and further wherein an oleic acid moiety:linoleic acid moiety ratio is from about 2 up to about 90, andcontain from about 1 to about 23 carbon atoms.
2. The composition of claim 1 wherein the triglyceride of (B) is a vegetable oil triglyceride.
3. The composition of claim 2 wherein R3, R4 and R5 independently contain from about 5 to about 23 carbon atoms.
4. The composition of claim 1 wherein the vegetable oil triglyceride comprises sunflower oil, safflower oil, corn oil, soybean oil, rapeseed oil, meadowfoam oil, lesquerella oil, castor oil or genetically modified sunflower oil, safflower oil, corn oil, soybean oil, rapeseed oil, lesquerella oil or meadowfoam oil.
5. The composition of claim 2 wherein R3, R4 and R5 independently contain from about 11 to about 21 carbon atoms.
6. The composition of claim 1 wherein the vegetable oil triglyceride has at least 70 percent monounsaturated character.
7. The composition of claim 1 wherein the monounsaturation of R3, R4 and R5 is a residue of oleic acid.
8. The composition of claim 1 wherein one of the R1 groups is an aliphatic group containing from 9 to 19 carbon atoms, the remaining R1 groups are R2 is an aliphatic group containing from 1 to 23 carbon atoms and n is from 5 to 13.
9. The composition of claim 8 wherein R2 is a heptadecenyl group.
10. The composition of claim 8 wherein R2 is an isostearyl group.
11. The composition of claim 1 wherein R1 is R2 is an aliphatic group containing from 3 to 17 carbon atoms and n is from 5 to 13.
12. The composition of claim 11 wherein R2 is a heptadecenyl group.
13. The composition of claim 11 wherein R2 is an isostearyl group.
14. The composition of claim 1 wherein (A) is an estolide of lesquerella oil or genetically modified lesquerella oil wherein R2 is an alkyl group containing from 3 to 17 carbon atoms and (B) is a high oleic sunflower oil containing at least 75 percent oleic unsaturation.
15. The composition of claim 1 wherein the weight ratio of (A):(B) is from (1-99):(99-1).
16. The composition of claim 1 optionally utilizing (C) an acidic, basic or enzymatic catalyst.
17. The composition of claim 16 wherein the catalyst is an acidic catalyst.
18. The composition of claim 16 wherein the catalyst is a basic catalyst.
19. The composition of claim 16 wherein the catalyst is an enzymatic catalyst.
20. A composition, comprising;
(A) at least one triglyceride estolide prepared by reacting a triglyceride containing -OH functionality with a carboxylic acid of the formula R2COOH, HOOCCH=CHCOOH, HOOC(CH2)tCOOH, or Ar(COOH)x or esters thereof wherein R2 is a hydrocarbyl group containing from 1 to 100 carbon atoms, t is from zero up to 8, Ar is a benzene or naphthalene nucleus and x is 1, 2 or 3 and (B) at least one animal fat, vegetable oil or synthetic triglyceride oil of the formula wherein R3, R4 and R5 are aliphatic groups or hydroxy containing aliphatic groups that are at least 60 percent monosaturated and further wherein an oleic acid moiety:linoleic acid moiety ratio is from about 2 up to about 90 and contain from about 1 to about 23 carbon atoms.
(A) at least one triglyceride estolide prepared by reacting a triglyceride containing -OH functionality with a carboxylic acid of the formula R2COOH, HOOCCH=CHCOOH, HOOC(CH2)tCOOH, or Ar(COOH)x or esters thereof wherein R2 is a hydrocarbyl group containing from 1 to 100 carbon atoms, t is from zero up to 8, Ar is a benzene or naphthalene nucleus and x is 1, 2 or 3 and (B) at least one animal fat, vegetable oil or synthetic triglyceride oil of the formula wherein R3, R4 and R5 are aliphatic groups or hydroxy containing aliphatic groups that are at least 60 percent monosaturated and further wherein an oleic acid moiety:linoleic acid moiety ratio is from about 2 up to about 90 and contain from about 1 to about 23 carbon atoms.
21. The composition of claim 20 wherein t is from 2 to 8.
22. The composition of claim 20 wherein Ar is a benzene nucleus and x is 1.
23. The composition of claim 20 wherein HOOCCH=CHCOOH is fumaric acid.
24. The composition of claim 20 wherein t is 4.
25. The composition of claim 20 wherein the triglyceride of (B) is a vegetable oil triglyceride.
26. The composition of claim 20 wherein R3, R4 and R5 independently contain from about 11 to about 21 carbon atoms.
27. The composition of claim 20 wherein the vegetable oil triglyceride comprises sunflower oil, safflower oil, corn oil, soybean oil, rapeseed oil, meadowfoam oil, lesquerella oil, castor oil, or genetically modified sunflower oil, safflower oil, corn oil, soybean oil, rapeseed oil, lesquerella oil or meadowfoam oil.
28. A lubricant composition comprising from about 0.01 percent to about 30 percent by weight of the composition of claim 1.
29. A lubricant composition comprising from about 0.01 percent to about 30 percent by weight of the composition of claim 20.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/187,889 | 1994-01-28 | ||
| US08/187,889 US5427704A (en) | 1994-01-28 | 1994-01-28 | Triglyceride oils thickened with estolides of hydroxy-containing triglycerides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2141102A1 true CA2141102A1 (en) | 1995-07-29 |
Family
ID=22690912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002141102A Abandoned CA2141102A1 (en) | 1994-01-28 | 1995-01-25 | Triglyceride oils thickened with estolides of hydroxy-containing triglycerides |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US5427704A (en) |
| EP (1) | EP0665285A3 (en) |
| CA (1) | CA2141102A1 (en) |
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| US5976560A (en) * | 1998-01-30 | 1999-11-02 | Han; Nam Fong | Vegetable derived petroleum jelly replacement |
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-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5976560A (en) * | 1998-01-30 | 1999-11-02 | Han; Nam Fong | Vegetable derived petroleum jelly replacement |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0665285A2 (en) | 1995-08-02 |
| EP0665285A3 (en) | 1995-09-20 |
| US5427704A (en) | 1995-06-27 |
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