CA2012475A1 - Diesters and their use in waxes - Google Patents
Diesters and their use in waxesInfo
- Publication number
- CA2012475A1 CA2012475A1 CA002012475A CA2012475A CA2012475A1 CA 2012475 A1 CA2012475 A1 CA 2012475A1 CA 002012475 A CA002012475 A CA 002012475A CA 2012475 A CA2012475 A CA 2012475A CA 2012475 A1 CA2012475 A1 CA 2012475A1
- Authority
- CA
- Canada
- Prior art keywords
- acid
- diester
- branched chain
- saturated
- carbon atoms
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
- C08L91/08—Mineral waxes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
Abstract
ABSTRACT
The invention provides a diester of the formula CH3(CH2)5CH(OCOR1)(CH2)10COOR22, in which R1 is a saturated, branched chain hydrocarbon radical having 15 to 21 carbon atoms and R2 is a saturated, branched chain hydrocarbon radical having 8 to 22 carbon atoms.
Preferably R1 is a methyl branched chain radical and contains 17 carbon atoms and statistically between 0.5 and 1.0 methyl side-chain per molecule, whereas R2 contains 18 to 22 carbon atoms with a C1-C8 , preferably C1 side-chain. The invention also provides a wax composition comprising a diester defined above optionally together with a hydrocarbon oil (C16-C32 and saturated), a C12-C22 optionally branched chain fatty acid and a monoester derived from a C18 to C22 fatty acid and a C12 to C22 alcohol. Furthermore the invention provides cosmetic preparations containing a wax composition as defined above.
The invention provides a diester of the formula CH3(CH2)5CH(OCOR1)(CH2)10COOR22, in which R1 is a saturated, branched chain hydrocarbon radical having 15 to 21 carbon atoms and R2 is a saturated, branched chain hydrocarbon radical having 8 to 22 carbon atoms.
Preferably R1 is a methyl branched chain radical and contains 17 carbon atoms and statistically between 0.5 and 1.0 methyl side-chain per molecule, whereas R2 contains 18 to 22 carbon atoms with a C1-C8 , preferably C1 side-chain. The invention also provides a wax composition comprising a diester defined above optionally together with a hydrocarbon oil (C16-C32 and saturated), a C12-C22 optionally branched chain fatty acid and a monoester derived from a C18 to C22 fatty acid and a C12 to C22 alcohol. Furthermore the invention provides cosmetic preparations containing a wax composition as defined above.
Description
7~ii 1~) DIESTERS ~ND T~IR ~SE IN WAXES
The invention relates to novel diestars and their use in waxes, more in particular in high performance waxes with beeswax-like properties. Beeswax is a nat:ural wax, which because of its special properties i5 o~ten used for cosmetic purposes and in medicine. It is self emulsifying after the addition of alkali and has an emollient effect on the skin giving a film permeable ~or moisture (ie. water vapour) and gas.
Several attempts have been made to prepare wax compositions having beeswax-like properties which ca~
serve as replacements or extenders for beeswax, however, no satisfactory composition has so far been developed.
Compon~nts which have been suggested for such wax compositions comprise: fatty acids, triglycerides, higher monoesters, oxidized microcrystalline wax, synthetic alcohols, Fischer-Tropsch wax etc .
More specifically EP-A-13 755 (Henkel) discloses a beeswax substitute comprising triglycerides of alpha-branched long chain carboxylic acids (so~called , .
The invention relates to novel diestars and their use in waxes, more in particular in high performance waxes with beeswax-like properties. Beeswax is a nat:ural wax, which because of its special properties i5 o~ten used for cosmetic purposes and in medicine. It is self emulsifying after the addition of alkali and has an emollient effect on the skin giving a film permeable ~or moisture (ie. water vapour) and gas.
Several attempts have been made to prepare wax compositions having beeswax-like properties which ca~
serve as replacements or extenders for beeswax, however, no satisfactory composition has so far been developed.
Compon~nts which have been suggested for such wax compositions comprise: fatty acids, triglycerides, higher monoesters, oxidized microcrystalline wax, synthetic alcohols, Fischer-Tropsch wax etc .
More specifically EP-A-13 755 (Henkel) discloses a beeswax substitute comprising triglycerides of alpha-branched long chain carboxylic acids (so~called , .
2~
Guerbet acids), paraffin oil, fatty acid etc. EP-A-182 355 ~Revlon) discloses certain ~sters of 12-hydroxystearic acid which have been esterified inter alia with unsaturated (1 to 3 double boncls), natural, S skraight chain fatty acids like oleic acid, linoleic acid, linolenic acid and a C5 to C22 a:Lcohol like octanol, isocetanol or isostearyl alcohol. These esters were used in cosmetic, household and pharmaceutical preparations together with other components such as mineral oil, fatty acids, glycerides etc~ Furthermore US~A-4 431 673 (Revlon) discloses cosmetic preparations comprising a long chain alkyl ester of a long chain aliphatic alcohol such as 2-octyldodecyl-12-stearoyloxystearate. Finally there is Seifen Oele Fette Wachse Volume 114 (1988) pp 547-552 summarizing analytical work on beeswax describing that the main fractions are: free fatty acids, paraffinic hydrocarbons, straight chain, simple esters and complex esters which are di-, tri- and higher esters derived from 15-hydroxypalmitic acid and which esters often still have free carboxylic or hydroxyl groups in the molecule. It is especially this group of complex esters which is held responsible for imparting moisture and oxygen permeability to beeswax. It is also clear from this article that despite a recent decline in the production of beeswax and great endeavours made no suikable replacement for beeswax has been commercially avail~ble so far.
It is an object of the present invention to provide a suitable replacement for beeswax which is li~uicl at room temperature and which is of a good colour, is stable to oxidation and has the desirable qualities of moisture and oxygen permeability.
2~ 7~i ~ 3 - R7060 The present invention now provides a diester of the formula CH3(CH2)5CH(OCOR1)(CH2)1oCOOR2l in which R1 is a saturated, branched chain hydrocarbon radical having 15 to 21 carbon akoms and ~2 is a saturaked, branched chain hydrocarbon radical having 8 to 22 carbon atoms.
Diesters of this type are valuable constituents of high performance waxes as they can impart to a wax film properties like air and water permeability in combination with excellent emollient properties. They are alsv of a good colour, are stable to oxidation and exhibit low melting points, eg. below 0C. The above diesters are derived from 12-hydroxystearic acid, a saturated, branched chain C16 to C22 carboxylic acid and a C8 to C22 saturated, branched chain alcohol. The diesters can conveniently be prepared from the above three classes of compounds by esterification reactions. Suitable carboxylic acid skarking materials are e.g. isopalmitic acid/ isostearic acid, and isobehenic acid which acids can be obtained by reacting palmitoleic acid, oleic acid, erucic acid or mixtures thereof using a clay catalyst at temperatures of 240 to 280C for several hours undler steam pressure, skripping off the partly isomerized/
unpolymerized fraction which is then hydrogenated and (solvent) fra~tionated to yield a liquid, mixture of methyl branched chain saturated C1s to C22 ~atty`acids containing usually 0.5 to 1.0, preferably 0.6 to 0.9 mekhyl side-chain per molecule. Suitable alcohols are saturated branched chain C8-C22 alcohols as e.g.
2-ethylhexanol, isocetanol, Guerbet alcohols like 4-and/or 5-octyldodecanol, isopalmityl alcohol~ isostearyl alcohol, isobehenyl alcohol ekc. The lakter three alcohols can be prepared by reduction of the corresponding branched chain carboxylic acids.
12-Hydroxyskearic acid can technically be obkained by - : :
'7~i _ 4 - ~7060 hydrogenation of ricinoleic acidO Primary alcohols are preferred.
Preferably the diester according to the present invention satisfies the above formula in which R1 is a methyl branched chain radical eg. deri~ed from isopalmitic acid, isostearic acid or isobehenîc acid.
More preferably R1 contains 17 carbon atoms and statistically between 0.5 and 1.0, preferably between 0.6 and 0.9 methyl side-chain per molecule and is the hydrocarbyl group of technical isostearic acid. A diester in which R2 contains 18 to 22 carbon atoms with a C1-C~
side-chain is preferred. ~ore preferred is a diester in which the side-chain is a methyl group (from isopalmityl-, isostearyl- or isobehenyl alcohol)~
Diesters with excellent properties in waxes are those in which both R1 and R2 are both radicals derived ~rom isopalmitic, isostearic or isobehenic acid or alcohol with particular emphasis on those derived from isostearic acid. The diesters according to the present invention can be prepared by various methods known per se e.g. from 12-hydroxystearic acid, a suitable branched chain acid and alcohol or functional deriyatives thereof by esterification, inter-esterification or re-esterification techniques known in the art. One particularly attractive synthesis uses hydrogenated ricinoleic acid glycericles rich in glycerides of 12-hydroxyste~ric acid (hydrogenated castor oil or a fraction thereof) and esterifies the free hydroxyl groups thereof with a suitable branched chain acid using a tetraalkyl-titclnium or zirconium catalyst. Subsequently partial hydrolysis is effected by treatment with a weak alkaline aqueous solution such as aqueous sodium acetate, after which the glycerol is washed out. Then the reaction mixture is subjected to distillation and the (partial~ acidester so - 5 - ~70~0 obtained is esterified with a suitable branched chain alcohol whilst eliminating water of reaction. The diest~r can then be further purified e.g. by fractional.
distillation under vacuum.
The diesters according to the present invention are valuable ingredients in wax compositions and the invention provides wax compositions comprising such a diester in conjunction with other wax components.
Preferably the wax composition further comprises a hydrocarbon oil (C15-C32 and saturated), a C12-C22 preferably branched chain fatty acid and a monoester derived from a saturated, preferably branched chain, C18 to C22 fatty acid and a C12 to C22 branched chain alcohol.
Especially with diesters in which at least one C12 to C22 branched chain compound is derived from isostearic acid favourable properties are obtained in waxes.
The invention also provides a wax composition which contains:
5 to 10 % ~w.w.~ of diester according to the general - formula specified above, ~5 to 80 % (w.w.) of monoester as define~ above, 5 to 20 % (w.w.) of hydrocarbon oil as defined above, 10 to 20 % (w.w.) of branched chain fatty acid as defined above.
Preferably the above composition is so compounded that the blend shows an acid value of 15 to 35 (most preferably from 17 to 22), an ester value of 65 to 85 .
(most preferably from 70 to 80) and an iodine value below .
Wax compositions described above are self-emulsifying upon addition of alkali or an alkanolamine and have good permeability for water vapour and air combined with good emollient functions so that they are valuable ingredients for cosmetic preparations and the invention thus also provides cosmetic and pharmaceutical preparations containing a wax composition as described above. Cosmetic and wax compositions described above combined excellent softening and emolliency on the skin and leave a film which is permeable for water vapour and ~as so that the ~kin with such a ~ilm continues to "breathe" and no bubbling of the film occurs. Also the diesters according to the present invention show excellent oxidative stability due to ~omplete saturation in combination with a remarkable low melting point necessary for good emolliency, good absorb~ncy and a good afterfeel. Usually the cosmetic preparations contain from 2 to 50, preferably from ~ to 12 % (w.w.~ of wax composition according to the present invention.
The invention is illustrated by the following examples.
Ex_mPle 1 Fir~t step:
Esterification of 12-hydroxystearic acid (A.V.=185;
OH.V.-153; S.V.=187; I.V.=~.2) with isostearyl alcohol ~A.V.= below 0.1; S.V.= below 1.0; OH.V.=204; I.V.=1.0;
colour below 20 APHA) and isostearic acid (A.V.C194;
S.V.=196; I.V.=1.3 ; colour 50-60 APHA).
_artin~ materials:
12-hydroxystearic acid 55% weight%
Isostearyl alcohol 42% weight~
p.toluenesulfonic acid (TSA) 0.16 weight%
Hypophosphorous acid 0.08 weight%
NaOH-solution (10%) 1.2 vol%
Activated carbon 0.6 weight~
Fullers earth 0.8 weight%
The mixture of 12-hydroxystearic acid, iso~tearyl alcohol, p.toluenesulfonic acid and hypophosphorous acid was heated to 120C. Esterification took place for E;iX
hours. After two hours of the esterification time, vacuum was applied using an oilpump (about 400 Pa). When the acid value (A.V.) was below 2, the product was refined by adding the NaOH-solution at a temperatur2 of 80C. After one hour agitation activated carbon and Fullers earth were added. Drying took 1.5 hours ~200 Pa)O Filtration was done with filter aid at a temperature of 60-70Co Properties of the diester obtained (A.V~- 0.1;
S.V.= 101; OH.V.= 81; I.V= 1.0; colour 300-400 APHA).
~2~75 SPcond st Raw materials:
Isostearyl-12-hydroxystearate 65.5 weight%
Isostearic acid22.7 weight~
Stannous-oxalate0.04 weight%
Phosphoric acid ~75%)0.13 weight~
Activated carbon10O7 weight%
Fullers earth 0.95 weight%
The mixture of isostearyl-12-h~droxy-stearate, isostearic acid and stannous-oxalate was heated to 23~C.
Esterification took place for five hours ~2.7 KPa). Ater five hours the acid value was found to be approximately 16. After another two hours of reaction at a higher temperature 245C, 2.7 lCpa~ the acid value had hardly changed and was found to be approximately 13.
; Esterification was stopped by adding th~ phosphoric acid at a temperature of 90C. ~he mixture was stirred for two hours (100 KPa). After adding the activa~ed carbon and ; Fullers earth the solution was dried for 1.5 hours at a ; temperature of 90C (at 200 Pa). Filtration was done with Supercel at a temperature of 70C. Properties of the diester obtained are A.V.= 11.7 5.V.= 117; OH.V= 9; I.V=
Guerbet acids), paraffin oil, fatty acid etc. EP-A-182 355 ~Revlon) discloses certain ~sters of 12-hydroxystearic acid which have been esterified inter alia with unsaturated (1 to 3 double boncls), natural, S skraight chain fatty acids like oleic acid, linoleic acid, linolenic acid and a C5 to C22 a:Lcohol like octanol, isocetanol or isostearyl alcohol. These esters were used in cosmetic, household and pharmaceutical preparations together with other components such as mineral oil, fatty acids, glycerides etc~ Furthermore US~A-4 431 673 (Revlon) discloses cosmetic preparations comprising a long chain alkyl ester of a long chain aliphatic alcohol such as 2-octyldodecyl-12-stearoyloxystearate. Finally there is Seifen Oele Fette Wachse Volume 114 (1988) pp 547-552 summarizing analytical work on beeswax describing that the main fractions are: free fatty acids, paraffinic hydrocarbons, straight chain, simple esters and complex esters which are di-, tri- and higher esters derived from 15-hydroxypalmitic acid and which esters often still have free carboxylic or hydroxyl groups in the molecule. It is especially this group of complex esters which is held responsible for imparting moisture and oxygen permeability to beeswax. It is also clear from this article that despite a recent decline in the production of beeswax and great endeavours made no suikable replacement for beeswax has been commercially avail~ble so far.
It is an object of the present invention to provide a suitable replacement for beeswax which is li~uicl at room temperature and which is of a good colour, is stable to oxidation and has the desirable qualities of moisture and oxygen permeability.
2~ 7~i ~ 3 - R7060 The present invention now provides a diester of the formula CH3(CH2)5CH(OCOR1)(CH2)1oCOOR2l in which R1 is a saturated, branched chain hydrocarbon radical having 15 to 21 carbon akoms and ~2 is a saturaked, branched chain hydrocarbon radical having 8 to 22 carbon atoms.
Diesters of this type are valuable constituents of high performance waxes as they can impart to a wax film properties like air and water permeability in combination with excellent emollient properties. They are alsv of a good colour, are stable to oxidation and exhibit low melting points, eg. below 0C. The above diesters are derived from 12-hydroxystearic acid, a saturated, branched chain C16 to C22 carboxylic acid and a C8 to C22 saturated, branched chain alcohol. The diesters can conveniently be prepared from the above three classes of compounds by esterification reactions. Suitable carboxylic acid skarking materials are e.g. isopalmitic acid/ isostearic acid, and isobehenic acid which acids can be obtained by reacting palmitoleic acid, oleic acid, erucic acid or mixtures thereof using a clay catalyst at temperatures of 240 to 280C for several hours undler steam pressure, skripping off the partly isomerized/
unpolymerized fraction which is then hydrogenated and (solvent) fra~tionated to yield a liquid, mixture of methyl branched chain saturated C1s to C22 ~atty`acids containing usually 0.5 to 1.0, preferably 0.6 to 0.9 mekhyl side-chain per molecule. Suitable alcohols are saturated branched chain C8-C22 alcohols as e.g.
2-ethylhexanol, isocetanol, Guerbet alcohols like 4-and/or 5-octyldodecanol, isopalmityl alcohol~ isostearyl alcohol, isobehenyl alcohol ekc. The lakter three alcohols can be prepared by reduction of the corresponding branched chain carboxylic acids.
12-Hydroxyskearic acid can technically be obkained by - : :
'7~i _ 4 - ~7060 hydrogenation of ricinoleic acidO Primary alcohols are preferred.
Preferably the diester according to the present invention satisfies the above formula in which R1 is a methyl branched chain radical eg. deri~ed from isopalmitic acid, isostearic acid or isobehenîc acid.
More preferably R1 contains 17 carbon atoms and statistically between 0.5 and 1.0, preferably between 0.6 and 0.9 methyl side-chain per molecule and is the hydrocarbyl group of technical isostearic acid. A diester in which R2 contains 18 to 22 carbon atoms with a C1-C~
side-chain is preferred. ~ore preferred is a diester in which the side-chain is a methyl group (from isopalmityl-, isostearyl- or isobehenyl alcohol)~
Diesters with excellent properties in waxes are those in which both R1 and R2 are both radicals derived ~rom isopalmitic, isostearic or isobehenic acid or alcohol with particular emphasis on those derived from isostearic acid. The diesters according to the present invention can be prepared by various methods known per se e.g. from 12-hydroxystearic acid, a suitable branched chain acid and alcohol or functional deriyatives thereof by esterification, inter-esterification or re-esterification techniques known in the art. One particularly attractive synthesis uses hydrogenated ricinoleic acid glycericles rich in glycerides of 12-hydroxyste~ric acid (hydrogenated castor oil or a fraction thereof) and esterifies the free hydroxyl groups thereof with a suitable branched chain acid using a tetraalkyl-titclnium or zirconium catalyst. Subsequently partial hydrolysis is effected by treatment with a weak alkaline aqueous solution such as aqueous sodium acetate, after which the glycerol is washed out. Then the reaction mixture is subjected to distillation and the (partial~ acidester so - 5 - ~70~0 obtained is esterified with a suitable branched chain alcohol whilst eliminating water of reaction. The diest~r can then be further purified e.g. by fractional.
distillation under vacuum.
The diesters according to the present invention are valuable ingredients in wax compositions and the invention provides wax compositions comprising such a diester in conjunction with other wax components.
Preferably the wax composition further comprises a hydrocarbon oil (C15-C32 and saturated), a C12-C22 preferably branched chain fatty acid and a monoester derived from a saturated, preferably branched chain, C18 to C22 fatty acid and a C12 to C22 branched chain alcohol.
Especially with diesters in which at least one C12 to C22 branched chain compound is derived from isostearic acid favourable properties are obtained in waxes.
The invention also provides a wax composition which contains:
5 to 10 % ~w.w.~ of diester according to the general - formula specified above, ~5 to 80 % (w.w.) of monoester as define~ above, 5 to 20 % (w.w.) of hydrocarbon oil as defined above, 10 to 20 % (w.w.) of branched chain fatty acid as defined above.
Preferably the above composition is so compounded that the blend shows an acid value of 15 to 35 (most preferably from 17 to 22), an ester value of 65 to 85 .
(most preferably from 70 to 80) and an iodine value below .
Wax compositions described above are self-emulsifying upon addition of alkali or an alkanolamine and have good permeability for water vapour and air combined with good emollient functions so that they are valuable ingredients for cosmetic preparations and the invention thus also provides cosmetic and pharmaceutical preparations containing a wax composition as described above. Cosmetic and wax compositions described above combined excellent softening and emolliency on the skin and leave a film which is permeable for water vapour and ~as so that the ~kin with such a ~ilm continues to "breathe" and no bubbling of the film occurs. Also the diesters according to the present invention show excellent oxidative stability due to ~omplete saturation in combination with a remarkable low melting point necessary for good emolliency, good absorb~ncy and a good afterfeel. Usually the cosmetic preparations contain from 2 to 50, preferably from ~ to 12 % (w.w.~ of wax composition according to the present invention.
The invention is illustrated by the following examples.
Ex_mPle 1 Fir~t step:
Esterification of 12-hydroxystearic acid (A.V.=185;
OH.V.-153; S.V.=187; I.V.=~.2) with isostearyl alcohol ~A.V.= below 0.1; S.V.= below 1.0; OH.V.=204; I.V.=1.0;
colour below 20 APHA) and isostearic acid (A.V.C194;
S.V.=196; I.V.=1.3 ; colour 50-60 APHA).
_artin~ materials:
12-hydroxystearic acid 55% weight%
Isostearyl alcohol 42% weight~
p.toluenesulfonic acid (TSA) 0.16 weight%
Hypophosphorous acid 0.08 weight%
NaOH-solution (10%) 1.2 vol%
Activated carbon 0.6 weight~
Fullers earth 0.8 weight%
The mixture of 12-hydroxystearic acid, iso~tearyl alcohol, p.toluenesulfonic acid and hypophosphorous acid was heated to 120C. Esterification took place for E;iX
hours. After two hours of the esterification time, vacuum was applied using an oilpump (about 400 Pa). When the acid value (A.V.) was below 2, the product was refined by adding the NaOH-solution at a temperatur2 of 80C. After one hour agitation activated carbon and Fullers earth were added. Drying took 1.5 hours ~200 Pa)O Filtration was done with filter aid at a temperature of 60-70Co Properties of the diester obtained (A.V~- 0.1;
S.V.= 101; OH.V.= 81; I.V= 1.0; colour 300-400 APHA).
~2~75 SPcond st Raw materials:
Isostearyl-12-hydroxystearate 65.5 weight%
Isostearic acid22.7 weight~
Stannous-oxalate0.04 weight%
Phosphoric acid ~75%)0.13 weight~
Activated carbon10O7 weight%
Fullers earth 0.95 weight%
The mixture of isostearyl-12-h~droxy-stearate, isostearic acid and stannous-oxalate was heated to 23~C.
Esterification took place for five hours ~2.7 KPa). Ater five hours the acid value was found to be approximately 16. After another two hours of reaction at a higher temperature 245C, 2.7 lCpa~ the acid value had hardly changed and was found to be approximately 13.
; Esterification was stopped by adding th~ phosphoric acid at a temperature of 90C. ~he mixture was stirred for two hours (100 KPa). After adding the activa~ed carbon and ; Fullers earth the solution was dried for 1.5 hours at a ; temperature of 90C (at 200 Pa). Filtration was done with Supercel at a temperature of 70C. Properties of the diester obtained are A.V.= 11.7 5.V.= 117; OH.V= 9; I.V=
3; viscosity 40C, 65.4 mm /s. Glc. C18 6%; C36 29%; ~54 65%; C72 19%. Further purification of the diester was effected by fractional distillation under vacuum recovering a predominantly C54-C72 fraction followed by HPLC to r~cover the pure diester~
Example 2 EskeriEication of 12-hydroxystearic acid with isostearic acid and isostearyl alcohol.
. ~ .
: `
Fir t ste~:
Raw materials-12-hydroxystearic acid ~027.0 g Isostearic acid 3505 982~1 g p.toluenesulfonicacid 3.2~ g Hypophosphorous acid 1.60 g The mixture of 12-hydroxystearic acid, isostearic acid, p.TSA and hypophosphorous was heated to 120C.
Esterification took place for 5.5 hours (200 Pa). After the first reaction step it was not necessary to refine or filtrate the product because of the reuse of the cat:alyst in the second step.
Second step:
Raw materials:
12-isostearylstearic acid 1810 g Isostearyl alcohol 1147.8 g NaOH-solution (33%) 3.0 g Activated carbon 17.7 g Fullers earth 23.6 g ~/
Decalite ~Filter aid) 10 g Catalyst from first ~tep The mixture of 12-isostearylstearic acid and isostearyl alcohol was heated to 120C. Esterification took place for 10.5 hours (200 Pa)O When the acid value was below 2, the NaOH-solution was added at a temperature o~ 90C. After half an hour agitation activated carbon, Decalite and Fullers earth were added. Drying took 1.5 hours (half an hour at 100 KPa and one hour at 250 Pa).
Filtraticn was done with filter aid at a temperature of 60C. Properties of ~he dies~er obtained areo AoV~=lo 2;
.
.2~
~ 10 - R7060 S.V~=107; I.V.=1.1; OH.V.=14; Viscosity 40C 52.3 ~m2/s and a pour point -34C. &lc. 6% C18, 44% C36, 51% C54/
21% C72~ Further purification of the diester was effected by molecular distillation.
Example 3 A wax composition was prepared by mixing the following ingredients:
15% (w.w.) Paraffin oil (C16-C32 5aturated) 10% (w.w.) Isostearic acid (as in Example 1) 65% (w.w.~ Isostearyl isostearate (A.V.= 0.1;
S.V.= 106; I.V.= 1.8, Colour 80 APHA) 10% (w.w.) Isostearyl-12-isostearoyl stearate obtained according to Example 1 The liquid wax so obtained had an A.V.= 20.2; S.V.=
101, and a melting point of below 20C and did not show any crystallization when kept at 4C for 6 hours.
Example 4 The wax obtained according to the previous example was emulsified by preparing an oil phase consisting of ll parts of the wax according to Example 3 and adding 40 parts of paraffine oil (also described in Example 3) and preparing a water phase consisting of 0.5 part triethanolamine and 48.5 parts of demineralized water. A
cold cream base was thus prepared by homogeni2ing the quantities oil phase and water phase mentioned above with a high speed mixer (10 seconds 3,000 rpm~.
.
~ 2~
~ R7060 Exam~e 5 ~ wax preparation we prepared by heating and mixing the following ingredients~
14% (w.w.) of paraffin oil as in Example 3 9% (w.w.) of isostearic acid as in Example 1 63% (w.wO) Cetearyl stearate 10% (w.w.) Isostearyl-12-isostearoyl stearate 4% (w.w.) Hexaglyceryl dioleate (hexaglycerol esterified with 2 moles of oleic acid) The wax so obtained had a higher melting point than the wax of Example 3 and remained substantially amorphous upon storage.
Example 6 The wax prepared according to Example 5 was emulsified by first preparing an oily phase consisting of 17.5 parts (w.w) of the wax of Example 2 2.5 parts (w.w) of ozokerite 1 part (w.w. )of paraffin ~m.p. 50-52C) l part (WDW. ) Of lanoline 52 parts (w.w.) of paraffin oil (C16-C3~3 which oil phase was emul~ified at 65C in a water phase consisting of 25.5 parts of water and 0.75 part of borax at 3000 rpm for 5 seconds. The cream so obtained ~howed good emolliency, a pleasant skinfeel and was easy to spread. Upon perspiring no bubbles occurred.
:l5 , , - 12 ~ ~7060 Example 7 A thixotropic day cream was prepaxed by heating and mixing an oil phase consisting of:
9 parts (w.w.) of wax composition o~ Examp].e 5 5 parts (wOw.) of paraffin oil of Example 3 2 parts (w.w.~ of lanolin 2 parts (w.w.) of sorbitan monostearate 1 part (w.w.) of castor oil with a water phase consisting of 78 parts (w.w.)of water 1 par~ (w.w.)of glycerol ~ part (w.w.)of POE-20 sorbitan monostearate 0.2 part (w.w.~of triethanolamine.
~o The thixotropic cream so obtained had a good skinfeel. The lipid film on the skin was permeable for air and water vapour and no bubble formation of the lipid film was observed.
Example 8 A skin mil~ was prepared by heating and mixing 6 parts (w.w.) wax of Example 3 2.2 parts (w.w.) ceteareth-6 2O2 parts (w.w.) ceteareth-25 1 part (w.w.) cPteareth alcohol 2 parts (w.w.) almond oil -~5 2 parts (w.w~) of avacado oil 0.5 parts (w.w.-) acetylated lanolin as the oil phase with a wat~r phase con~isting of 2 parts of glycerol, 1 part (w.wc) propylene glycol, 0~5 part ~w.w.) of p.hydroxybenzoic acid and 80.6 parts (w.w~) o~
demineralized water.
: 15 : 30
Example 2 EskeriEication of 12-hydroxystearic acid with isostearic acid and isostearyl alcohol.
. ~ .
: `
Fir t ste~:
Raw materials-12-hydroxystearic acid ~027.0 g Isostearic acid 3505 982~1 g p.toluenesulfonicacid 3.2~ g Hypophosphorous acid 1.60 g The mixture of 12-hydroxystearic acid, isostearic acid, p.TSA and hypophosphorous was heated to 120C.
Esterification took place for 5.5 hours (200 Pa). After the first reaction step it was not necessary to refine or filtrate the product because of the reuse of the cat:alyst in the second step.
Second step:
Raw materials:
12-isostearylstearic acid 1810 g Isostearyl alcohol 1147.8 g NaOH-solution (33%) 3.0 g Activated carbon 17.7 g Fullers earth 23.6 g ~/
Decalite ~Filter aid) 10 g Catalyst from first ~tep The mixture of 12-isostearylstearic acid and isostearyl alcohol was heated to 120C. Esterification took place for 10.5 hours (200 Pa)O When the acid value was below 2, the NaOH-solution was added at a temperature o~ 90C. After half an hour agitation activated carbon, Decalite and Fullers earth were added. Drying took 1.5 hours (half an hour at 100 KPa and one hour at 250 Pa).
Filtraticn was done with filter aid at a temperature of 60C. Properties of ~he dies~er obtained areo AoV~=lo 2;
.
.2~
~ 10 - R7060 S.V~=107; I.V.=1.1; OH.V.=14; Viscosity 40C 52.3 ~m2/s and a pour point -34C. &lc. 6% C18, 44% C36, 51% C54/
21% C72~ Further purification of the diester was effected by molecular distillation.
Example 3 A wax composition was prepared by mixing the following ingredients:
15% (w.w.) Paraffin oil (C16-C32 5aturated) 10% (w.w.) Isostearic acid (as in Example 1) 65% (w.w.~ Isostearyl isostearate (A.V.= 0.1;
S.V.= 106; I.V.= 1.8, Colour 80 APHA) 10% (w.w.) Isostearyl-12-isostearoyl stearate obtained according to Example 1 The liquid wax so obtained had an A.V.= 20.2; S.V.=
101, and a melting point of below 20C and did not show any crystallization when kept at 4C for 6 hours.
Example 4 The wax obtained according to the previous example was emulsified by preparing an oil phase consisting of ll parts of the wax according to Example 3 and adding 40 parts of paraffine oil (also described in Example 3) and preparing a water phase consisting of 0.5 part triethanolamine and 48.5 parts of demineralized water. A
cold cream base was thus prepared by homogeni2ing the quantities oil phase and water phase mentioned above with a high speed mixer (10 seconds 3,000 rpm~.
.
~ 2~
~ R7060 Exam~e 5 ~ wax preparation we prepared by heating and mixing the following ingredients~
14% (w.w.) of paraffin oil as in Example 3 9% (w.w.) of isostearic acid as in Example 1 63% (w.wO) Cetearyl stearate 10% (w.w.) Isostearyl-12-isostearoyl stearate 4% (w.w.) Hexaglyceryl dioleate (hexaglycerol esterified with 2 moles of oleic acid) The wax so obtained had a higher melting point than the wax of Example 3 and remained substantially amorphous upon storage.
Example 6 The wax prepared according to Example 5 was emulsified by first preparing an oily phase consisting of 17.5 parts (w.w) of the wax of Example 2 2.5 parts (w.w) of ozokerite 1 part (w.w. )of paraffin ~m.p. 50-52C) l part (WDW. ) Of lanoline 52 parts (w.w.) of paraffin oil (C16-C3~3 which oil phase was emul~ified at 65C in a water phase consisting of 25.5 parts of water and 0.75 part of borax at 3000 rpm for 5 seconds. The cream so obtained ~howed good emolliency, a pleasant skinfeel and was easy to spread. Upon perspiring no bubbles occurred.
:l5 , , - 12 ~ ~7060 Example 7 A thixotropic day cream was prepaxed by heating and mixing an oil phase consisting of:
9 parts (w.w.) of wax composition o~ Examp].e 5 5 parts (wOw.) of paraffin oil of Example 3 2 parts (w.w.~ of lanolin 2 parts (w.w.) of sorbitan monostearate 1 part (w.w.) of castor oil with a water phase consisting of 78 parts (w.w.)of water 1 par~ (w.w.)of glycerol ~ part (w.w.)of POE-20 sorbitan monostearate 0.2 part (w.w.~of triethanolamine.
~o The thixotropic cream so obtained had a good skinfeel. The lipid film on the skin was permeable for air and water vapour and no bubble formation of the lipid film was observed.
Example 8 A skin mil~ was prepared by heating and mixing 6 parts (w.w.) wax of Example 3 2.2 parts (w.w.) ceteareth-6 2O2 parts (w.w.) ceteareth-25 1 part (w.w.) cPteareth alcohol 2 parts (w.w.) almond oil -~5 2 parts (w.w~) of avacado oil 0.5 parts (w.w.-) acetylated lanolin as the oil phase with a wat~r phase con~isting of 2 parts of glycerol, 1 part (w.wc) propylene glycol, 0~5 part ~w.w.) of p.hydroxybenzoic acid and 80.6 parts (w.w~) o~
demineralized water.
: 15 : 30
Claims (10)
1. A diester of the formula CH3(CH2)5CH(OCOR1)(CH2)10COOR2, characterized in that R1 is a saturated, branched chain hydrocarbon radical having 15 to 21 carbon atoms and R2 is a saturated, branched chain hydrocarbon radical having 8 to 22 carbon atoms.
2. A diester according to claim 1 characterized in that R1 contains 17 carbon atoms and statistically between 0.5 and 1.0 methyl side-chain per molecule.
3. A diester according to claim 1 characterized in that R2 contains 18 to 22 carbon atoms with C1-C8 side-chain.
4. A diester according to claim 1 in which both R1 and R2 are radicals derived from isostearic acid.
5. A wax composition characterized in that it comprises a diester according to claim 1.
6. A wax composition according to claim 5 characterized in that it further comprises a hydrocarbon oil (C16-C32 and saturated), a C12-C22 fatty acid and a monoester derived from a saturated, C18 to C22 fatty acid and a C12 to C22 branched chain, alcohol.
7. A wax composition according to claim 6 characterized in that the fatty acid and/or the monoester is derived from isostearic acid.
8. A wax composition according to claim 6 characterized in that it contains:
5 to 10 % (w.w.) of the diester 55 to 80 % (w.w.) of the monoester 5 to 20 % (w.w.) of the hydrocarbon oil 10 to 20 % (w.w.) of the fatty acid
5 to 10 % (w.w.) of the diester 55 to 80 % (w.w.) of the monoester 5 to 20 % (w.w.) of the hydrocarbon oil 10 to 20 % (w.w.) of the fatty acid
9. A process for preparing a diester according to claim 1 characterized in that 12-hydroxystearic acid, a C16 to C22 branched chain carboxylic acid and a C8 to C22 primary alcohol and/or functional derivative of the above compounds are converted into a diester by a method known per se.
10. A cosmetic preparation characterized in that it contains from 2 to 50% (w.w.) of a wax composition according to claim 6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP89200768.3 | 1989-03-23 | ||
| EP89200768 | 1989-03-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2012475A1 true CA2012475A1 (en) | 1990-09-23 |
Family
ID=8202347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002012475A Abandoned CA2012475A1 (en) | 1989-03-23 | 1990-03-19 | Diesters and their use in waxes |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5104586A (en) |
| EP (1) | EP0389269B1 (en) |
| JP (1) | JPH02273645A (en) |
| AT (1) | ATE89813T1 (en) |
| CA (1) | CA2012475A1 (en) |
| DE (1) | DE69001698T2 (en) |
| DK (1) | DK0389269T3 (en) |
| ES (1) | ES2042209T3 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE39218E1 (en) | 1994-09-30 | 2006-08-01 | L'oreal | Anhydrous and water-resistant cosmetic compositions |
| US5645632A (en) * | 1996-02-14 | 1997-07-08 | Union Camp Corporation | Diesters of polymerized fatty acids useful in formulating hot-melt inks |
| US5837223A (en) * | 1996-08-12 | 1998-11-17 | Revlon Consumer Products Corporation | Transfer resistant high lustre cosmetic stick compositions |
| US6350889B1 (en) | 1999-06-24 | 2002-02-26 | Arizona Chemical Company | Ink jet printing compositions containing ester-terminated dimer acid-based oligo (ester/amide) |
| JP3437494B2 (en) * | 1999-07-01 | 2003-08-18 | カネボウ株式会社 | Novel α-hydroxy fatty acid derivative and composition for external use |
| US6355261B1 (en) | 1999-12-02 | 2002-03-12 | The C. P. Hall Company | Ultraviolet radiation absorbing waxes useful in cosmetic compositions |
| DE10341025A1 (en) * | 2003-09-03 | 2005-03-31 | Cognis Deutschland Gmbh & Co. Kg | Emollient mixture for cosmetic and pharmaceutical formulations |
| CN114644557A (en) * | 2022-03-24 | 2022-06-21 | 华南理工大学 | Preparation method of isostearyl alcohol isostearate |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2856277A1 (en) * | 1978-12-27 | 1980-07-17 | Henkel Kgaa | BEE WAX REPLACEMENT |
| US4431673A (en) * | 1980-05-02 | 1984-02-14 | Revlon, Inc. | Cosmetic compositions |
| US4464908A (en) * | 1982-08-12 | 1984-08-14 | The United States Of America As Represented By The United States Department Of Energy | Solar-powered turbocompressor heat pump system |
| US4567037A (en) * | 1984-11-20 | 1986-01-28 | Revlon, Inc. | Fatty acid diesters |
| US4867965A (en) * | 1986-10-02 | 1989-09-19 | Revlon, Inc. | Fatty acid diesters |
-
1990
- 1990-03-19 CA CA002012475A patent/CA2012475A1/en not_active Abandoned
- 1990-03-21 ES ES199090303055T patent/ES2042209T3/en not_active Expired - Lifetime
- 1990-03-21 AT AT90303055T patent/ATE89813T1/en not_active IP Right Cessation
- 1990-03-21 EP EP90303055A patent/EP0389269B1/en not_active Expired - Lifetime
- 1990-03-21 DK DK90303055.9T patent/DK0389269T3/en active
- 1990-03-21 DE DE90303055T patent/DE69001698T2/en not_active Expired - Fee Related
- 1990-03-22 JP JP2073162A patent/JPH02273645A/en active Pending
- 1990-03-23 US US07/497,848 patent/US5104586A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0389269B1 (en) | 1993-05-26 |
| US5104586A (en) | 1992-04-14 |
| EP0389269A1 (en) | 1990-09-26 |
| JPH02273645A (en) | 1990-11-08 |
| DE69001698D1 (en) | 1993-07-01 |
| ATE89813T1 (en) | 1993-06-15 |
| ES2042209T3 (en) | 1993-12-01 |
| DE69001698T2 (en) | 1993-10-07 |
| DK0389269T3 (en) | 1993-08-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |