CA2363543C - Fatty amine derivatives of butylated hydroxy toluene for the protection of surfaces from physical and chemical degradation - Google Patents

Abstract

The present invention relates to novel antioxidant compounds to reduce the physical or chemical degradation or discoloration of surfaces, especially the fading of a variety of surfaces from sunlight, wherein the antioxidant compound is a derivative of butylated hydroxytoluene or sorbic acid and is selected from the group consisting of: (I), (II), (III), (IV), wherein each R1 and R3 is selected from the group consisting of hydroxy, methoxy, ethoxy, propoxy, butoxy, methyl, ethyl, propyl, straight or branched chained butyl groups, straight or branched chained amyl groups, and mixtures thereof; R2 is a hydroxy group; each R4 and R7 is selected from the group consisting of a saturated or unsaturated C1-C22, alkyl, aryl, cyclic alkyl group (which may be interrupted by an ester, amide, or ether group), hydrogen, and mixtures thereof; each R5, R6, R8, and R9 is selected from the group consisting of a saturated or unsaturated C1-C22, alkyl, aryl, cyclic alkyl group (which may be interrupted by an ester, amide, or ether group), and mixtures thereof; n is from 1 to 50; Y is a hydrogen or a methyl group; Z is a hydrogen or a methyl group; wherein the amino group of the compounds of formulas (I) to (IV) can be protonated or quaternized with R10X
where R10 is a hydrogen, a C1-C6 alkyl group, C1-C6 hydroxyl alkyl group, benzyl group and mixtures thereof; and X- is any compatible anion.

Description

FATTY AMINE DERIVATIVES OF BUTYLATED HYDROXY TOLUENE FOR
THE PROTECTION OF SURFACES FROM PHYSICAL AND CHEMICAL
DEGRADATION
s TECHNICAL FIELD
The present invention relates to novel, non-surface staining, light stable antioxidant compounds to reduce the fading, discoloration and degradation of various surfaces, i.e. fabrics, from sunlight. These antioxidant compounds are butylated hydroxytoluene and sorbic acid to derivatives, preferably containing at least one C8-C~ hydrocarbon fatty amine organic moiety and are either solid materials having a melting point of less than about 80°C, or are liquids at a temperature of less than about 40°C. Preferably these antioxidant compounds are incorporated into fabric softening compositions.
is BACK zRQUND OF THE INVENTION
Consumers worldwide experience color damage to their clothing, upholstery, the interior of their automobiles, etc., from exposure to the sun.
For example, color damage to clothing during drying and during wear is especially severe for those consumers living in tropical and subtropical 2o climates. Despite extensive efforts by the industry to develop light stable surfaces such as upholstery, and automobile interiors, to develop light stable dyes, after-treatments to improve light-fastness of dyes for textiles, and plastics which resist fading, the fading of surfaces from sunlight still remains a problem.
2s Antioxidant compounds are known in the art for various benefits. For example, EPA 273,011, Ravichandran et al., published (129188, Ciba -Geigy, teaches N,N-bis(hydroxyethyi)hydroxylamine esters to stabilize organic materials (i.e. organic polyolefins, elastomers and lubricating oils) against oxidative, thermal and actinic degradation.
3o U.S. Pat. No. 5,081,280, Takee et al., issued on Jan. 14, 1992, Yoshitomi Pharmaceutical Industries, Ltd., teaches a process for producing ester~ed, sterically hindered phenolic compounds as an antioxidant for organic materials with decreased reaction times and less discoloration of the compound. These compounds do not contain an amine function as do 3s the compounds of the present invention.
U.S. Pat. No. 3,330,859, Dexter et al., issued 7111167, Geigy _2_ Chemical Corporation, teaches sterically hindered phenolic carboxylic acid esters which are useful to stabilize organic materials such as organic polymers and copolymers, lubricating oils of the aliphatic ester type, hydrocarbon material such as gasoline, etc. These compounds do not s contain an amine function as do the compounds of the present invention.
U.S. Pat. No. 3,920,729, Sagawa, et al., issued Nov. 18, 1975, Sumitomo Chemical Co., Ltd,, teaches sterically hindered phenolic esterified isopropanolamines for the stabilization of organic substances, particularly polyolefins, halogenated vinyl polymers, copolymers of to halogenated vinyl and unsaturated polymerizable compound, copolymers of acrylonitrile, butadiene and styrene, polyurethane, polyamides, polyesters, polyacetals, polycarbonates, polystyrene and natural and synthetic rubber.
These compounds have methyl groups attached to the beta carbon atom with regard to the nitrogen atom, for enhanced thermal stability with reduced is blooming when mixed with a polyolefin.
U.S. Pat. No. 4,305,868, Wheeler et al., issued December 15, 1981, Uniroyla, Inc., teaches sterically hindered phenolic substituted esterbisamides as antioxidants useful for the protection of organic materials such as synthetic and natural rubbers, plastics and petroleum products 2o against oxidative degradation.
Furthermore, U.S. Pat. No. 4,900,469, Clorox, teaches antioxidants in detergents for bleach stability. Antioxidants have been used in softeners and detergents to prevent fabric yellowing and to control malodor. (See, JP
721116, 783, Kao. ) 2s Because antioxidant compounds are expensive, it is desirable to select and utilize the most efficient compounds in order to minimize the cost of formulating with these compounds.
However, it is now recognized that antioxidants adaptable for various other applications are not aMrays satisfactory for other applications such as 3o for use in foods (as a preservative), cosmetics (as a preservative), in rinse added fabric softener compositions, dryer added fabric softener compositions, detergents, fabric pretreatment or spray on products, hard surtace cleaners, compositions for use on floor coverings (i.e. carpet, vinyl), automotive upholstery, upholstery, hair care products, vinyl treatments and 3s plastics.

With regard to textiles, it has now been discovered that visible light is responsible for a significant amount of dye fading on clothing. For example, visible light has a higher contribution to fading than UV-A, which has a higher contribution to fading than UV-B. Antioxidants can provide broader sun-fade fabric protection for surfaces than sunscreen agents because antioxidant effectiveness is not dependent upon the absorption of light.
Therefore, an aspect of the present invention is to provide antioxidant compounds, effective at low levels, which will reduce the rate of degradation and/or discoloration (i.e. sun-fading) of a variety of surfaces.
SUMMARY OF THE INVENTION
The present invention relates to an antioxidant compound, to reduce the degradation or discoloration of surfaces from sunlight, selected from the group consisting of:
O ~ ~z (~lI) '''~:. '''~. c t)C»C:H~~ ~-- t~f '~
Ra ~>v>
z I
wherein R' is selected from the group consisting of a saturated or unsaturated C,-C22 alkyl, saturated or unsaturated C~-C22 aryl, saturated or unsaturated C,-C22 cyclic alkyl group (which may be interrupted by an ester, amide, or ether group), hydrogen, and mixtures thereof;
each R8, and R9 is selected from the group consisting of a saturated or unsaturated C~-C22 alkyl, saturated or unsaturated C~-C22 aryl, saturated or unsaturated C~-C2z cyclic alkyl group (which may be interrupted by an ester, amide, or ether group), and mixtures thereof;
n is from 1 to 50;
Z is a hydrogen or a methyl group;
wherein the amino group of the compounds of Formulas I to IV can be protonated or quantemized with R'°X where R'° is a hydrogen, a C,-C6 alkyl group, a C~-C6 hydroxyl alkyl group, benzyl group and mixtures thereof; and X- is an anion of a strong acid.
All percentages and ratios used herein are by weight of the total composition.

DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to novel antioxidant compounds to reduce the physical or chemical degradation or discoloration of surfaces, especially the fading of a variety of surfaces from sunlight, wherein the antioxidant compound is a non-surface staining, light stable compound, preferably containing at least one C$-C22 hydrocarbon fatty organic moiety, preferably at least one C~2-Cog hydrocarbon fatty organic moiety; wherein the antioxidant compound is a solid material having a melting point of less than about 80°C, preferably less than about 50°C, or a liquid at a temperature of less than about 40°C; preferably from about 0°C to about 25°C.
These antioxidant compounds are derivatives of butylated hydroxytoluene or sorbic acid and are selected from the group consisting of:

R~

R2 ~ ~ ~-(t)r~

nr) ~(~r'~l'R~ (nr) as () (M

2 wherein each R1 and R3 is selected from the group consisting of hydroxy, methoxy, ethoxy, propoxy, butoxy, methyl, ethyl, propyl, straight or branched chained butyl groups, straight or branched s chained amyl groups, and mixtures thereof, preferably straight or branched chained butyl groups, straight or branched chained amyl groups, and mixtures thereof, and more preferably "tert"-butyl groups;
R2 is a hydroxy group;
each R4 and R7 is selected from the group consisting of a saturated io or unsaturated C1-Cue, alkyl, aryl, cyclic alkyl group, (which may be interrupted by an ester, amide, or ether group), hydrogen, and mixtures thereof, preferably a methyl group;
each R5, R6, R8, and R9 is selected from the group consisting of a saturated or unsaturated C1-Cue, alkyl, aryl, cyclic alkyl group (which is may be interrupted by an ester, amide, or ether group), preferably a Cg to C22 alkyl group, more preferably a C12 to C1g alkyl group, and even more preferably a C12 to C14 alkyl group, and mixtures thereof;
n is from 1 to 50, preferably from 1 to 10, more preferably 1;
Y is a hydrogen or a methyl group; and Z is a hydrogen or a methyl group.
The amino group can be protonated or quaternized with R»X wherein R1~ is a hydrogen, a C1 to Cg alkyl group, a C1 to Cg hydroxy alkyl group, preferably a C1 to C3 alkyl group or hydroxy alkyl group, e.g. methyl (most s preferred), ethyl, propyl, hydroxyethyl, and the like, benzyl group, and mixtures thereof; and X- is the anion of a strong acid, for example chloride, bromide, methylsulfate, formats, sulfate, nitrate, and the like.
Preferably each R1 and R3 is a straight or branched chain butyl group to and mixtures thereof; R4 is a methyl group; R5 is selected from the group consisting of a saturated or unsaturated C12 to C18 alkyl group; and n is 1.
More preferably, each R1 and R3 is a "tert"-butyl group; R5 is selected from the group consisting of a saturated or unsaturated C12 to C14 alkyl group; and n is 1.
is An especially preferred compound of the present invention is 2-{N~
methyl-N-cocoamine)ethyl 3',5'-di-tert-butyl-4-hydroxybenzoate.
The antioxidant compounds of the present invention demonstrate light stability. "Light stable" means that the antioxidant compounds of the present invention do not discolor when exposed to either sunlight or Zo simulated sunlight for approximately 2 to 60 hours at a temperature of from about 25°C to about 45°C.
Antioxidant compounds and free radical scavengers can generally stabilize surfaces andlor protect dyes from degradation or discoloration by first preventing the generation of singlet oxygen and peroxy radicals, and is thereafter terminating the degradation pathways. Not to be limited by theory, a general discussion of the mode of action for antioxidants and free radical scavengers is disclosed in iGrk Othmer, The Encyclopedia of Chemical Technology, Volume 3, pages 128 - 148, Third Edition (1978), 3o Methods of Manufacture The following examples further destxibe and demonstrate embodiments within the scope of the present invention. The examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible 3s without departing from the spirit and scope of the invention.

-g.

N-Methyl-N-{2-hydroxyethyl)cocoamine in the amount of 15.64 g (63.3 mmoi) is dissolved in 200 mL of dichloromethane and the resulting solution heated to 40°C. Following addition of triethylamine in the amount of 6.41 g s (63.3 mmol), 3,5-di-tert-butyl-4-hydroxybenzoyl chloride in the amount of 17.00 g (63.3 mmol) is added to the solution so as to maintain the reaction temperature at 35-40°C. The reaction mixture is stirred for an additional 2 h at 40°C and then cooled to room temperature. After stirring 16 h, the solution containing the reaction product is filtered and the filtrate to concentrated. The resulting residue is re-dissolved in 300 mL of chloroform and washed twice with two 50 mL aliquots of 50°~ K2C03 in water. The organic layer is separated, dried over MgS04, filtered, and concentrated.
The product is purified by column chromatography. Purity of the product is determined by thin layer chromatography and the structure confirmed by is 13C NMR.
EXAMPLE ~
N,N-Bis-(2-hydroxyethyl)-cocoamine in the amount of 22.09 g (78.1 mmol) and triethylamine in the amount of 15.79 g (156.3 mmol) are dissolved in 100 mL of dichloromethane. The resulting solution is treated with 3,5-di-2o tert-butyl-4-hydroxybenzoyl chloride in the amount of 42.00 g (156.3 mmoi) dissolved in 100 mL of dichloromethane. During addition the reaction temperature is maintained between 35-40°C. The reaction mixture is stirred for an additional 60 min at reftux and then cooled to room temperature. The mixture is filtered ~d the filtrate concentrated. The resulting residue is re-2s dissolved in 200 mL of dichloromethane and washed twice with two 100 mL
aliquots of 50% K2C03 in water, once with 100 mL of saturated NaHC03 solution in water, and once with 100 mL of brine. The organic layer is separated, dried over MgS04, filtered, and concentrated to give a viscous oil. Purity of the product is determined by thin layer chromatography and 3o the structure confirmed by 13C NMR.

N-Methyl-N-(2-hydroxyethyl)cocoamine in the amount of 36.28 g (144.0 mmol) and triethylamine in the amount of 14.62 g (144.0 mmol) are dissolved in 250 mL of dichloromethane. The resulting solution is treated 3s with 2,4-traps-tra»s-hexandienoyl chloride in the amount of 18.80 g (144.0 mmol). During addition, the reaction temperature is maintained between 35-40°C. The reaction mixture is stirred for an additional 2 h at reflux and then WO 96/03369 PCT/US9s108911 .g_ cooled to room temperature. The mixture is filtered and the filtrate concentrated. The resulting residue is re-dissolved in 300 mL of dichloromethane and washed twice with 200 mL of 50°~ K2C03 in water and twice with 200 mL of saturated NaHC03 solution in water. The organic s layer is separated, dried over MgS04, treated with activated charcoal, filtered, and concentrated to give an oil. Purity of the product is determined by thin layer chromatography and the structure confirmed by ~ 3C NMR.
COMPOSITIONS
The present invention also relates to a composition for decreasing to the physical or chemical degradation of surfaces, comprising:
(A) an effective amount of an antioxidant compound; and (B) an effective amount of a carrier material;
wherein the antioxidant compound is selected from the group consisting of:
r~ ~-c)~-~,'~ m cu) W)~f'~1~R' (III) Ra Ih) fN IM

is wherein each R~ and R3 is selected from the group consisting of hydroxy, methoxy, ethoxy, propoxy, butoxy, methyl, ethyl, propyl, straight or branched chained butyl groups, straight or branched chained amyl groups, and mixtures thereof, preferably straight or branched chained butyl groups, straight or branched chained amyl groups, and mixtures thereof, and more preferably "tart"-butyl groups;
R2 is a hydroxy group;
each R4 and R~ is selected from the group consisting of a saturated s or unsaturated C1-C22, alkyl, aryl, cyclic alkyl group (which may be interrupted by an ester, amide, or ether group), hydrogen, and mixtures thereof, preferably a methyl group;
each R5, Rs, R8, and R9 is selected from the group consisting of a saturated or unsaturated C1-C22, alkyl, aryl, cyclic alkyl group (which io may be interrupted by an ester, amide, or ether group), preferably a Cg to C~ alkyl group, more preferably a C12 to C18 alkyl group, and even more preferably a C12 to C14 alkyl group, and mixtures thereof;
n is from 1 to 50, preferably from 1 to 10, more preferably 1;
Y is a hydrogen or a methyl group; and is Z is a hydrogen or a methyl group.
The amino group can be protonated or quatemized with R~ OX wherein R10 is a hydrogen, a C1 to Cg alkyl group, a C1 to C6 hydroxy alkyl group, preferably a C1 to C3 alkyl group or hydroxy alkyl group, e.g. methyl (most preferred), ethyl, propyl, hydroxyethyl, and the like, benzyl group, and 2o mixtures thereof; and X' is the anion of a strong acid, for example chloride, bromide, methylsutfate, formats, sulfate, nitrate, and the like.
The carrier andlor diluent employed in the instant compositions is a non-toxic, non-irritating substance which when mixed with the antioxidant 2s compound, promotes the deposition of the antioxidant compound onto surfaces. The compositions of the present invention preferably comprise from about 25°~ to about 95°~, preferably from about 50°~
to about 90°~6 of a liquid carrier. Preferably the carrier andlor diluent is primarily water due to its fow cost relative availability, safety, and environmental compatibility.
3o The level of water in the liquid carrier is at least about 50°~, preferably at least about 60°~, by weight of the carrier. Mixtures of water and low molecular weight, e.g., <100 glmol, organic solvent, e.g., lower alcohol such as ethanol, propanol, isopropanol or butanol are useful as the carrier liquid.
Low molecular weight alcohols include monohydric, dihydric (glycol, etc.) 3s trihydric {glycerol, etc.), and higher polyhydric (polyols) alcohols.

Claims (7)

WHAT IS CLAIMED IS.

1. An antioxidant compound, to reduce the degradation or discoloration of surfaces from sunlight, selected from the group consisting of:

wherein R7 is selected from the group consisting of a saturated or unsaturated C22 alkyl, saturated or unsaturated C6-C22 aryl, saturated or unsaturated C3-cyclic alkyl group (which may be interrupted by an ester, amide, or ether group), hydrogen, and mixtures thereof:

each R8, and R9 is selected from the group consisting of a saturated or unsaturated C1-C22 alkyl, saturated or unsaturated C6-C22 aryl, saturated or unsaturated cyclic alkyl group (which may be interrupted by an ester, amide, or ether group), and mixtures thereof;

n is from 1 to 50;
Z is a hydrogen or a methyl group;

wherein the amino group of the compounds of Formulas III or IV can be protonated or quarterized with R10X where IR10 is a hydrogen, a C1-C6 alkyl group, a C1-C6 hydroxyl alkyl group, benzyl group and mixtures thereof and X- is an anion of a strong acid.

2. The antioxidant compound of Claim 1 wherein the antioxidant compound is a solid material having a melting point of less than 80°C or a liquid at a temperature of less than 40°C.

3. The antioxidant compound of Claim 1 wherein the antioxidant compound is a solid material having a melting point of less than 50°C or a liquid at a temperature of 0°C to 25°C.

4. The antioxidant compound of Claim 3 wherein the compound is 2-(N-methyl-N-cocoamino)ethyl 2,4-trans-trans-hexandienoyl.

5. The antioxidant compound of Claim 1 wherein R7 is a methyl group; each R8, and R9 is selected from the group consisting of a saturated or unsaturated C12 to alkyl group, and mixtures thereof; and n is 1.

6. The antioxidant compound of Claim 5 wherein each R8, and R9 is selected from the group consisting of a saturated or unsaturated C12 to C14 alkyl group, and mixtures thereof.

7. A composition for decreasing the physical or chemical degradation of surfaces, comprising:
(A) an effective amount of the antioxidant compound of Claim 1; and (B) an effective amount of a carrier material.