CA2025973A1

CA2025973A1 - Heavy duty laundry detergent

Info

Publication number: CA2025973A1
Application number: CA 2025973
Authority: CA
Inventors: Kim R. Smith; James E. Borland
Original assignee: Ethyl Corp
Current assignee: Albemarle Corp
Priority date: 1989-10-02
Filing date: 1990-09-21
Publication date: 1991-04-03
Also published as: JP2848536B2; EP0421327A1; JPH03179096A; DE69024305D1; DE69024305T2; EP0421327B1

Abstract

Abstract Free-flowing granular heavy duty laundry detergent is made by blending a composition to contain (i) a tert-amine oxide dihydrate having the formula R1R2R3NO.2H2O where R1 is a C8-24 alkyl, R2 is methyl, ethyl or a C8-24 alkyl and R3 is methyl or ethyl, (ii) a detergent builder (e.g. zeolite A) and optionally other conventional laundry detergent ingredients.

Description

EXPR~SS M~L Nl~ 00089s CASE: 6050 ,j JDO:kp HEAVY DUTY LAUNDRY DETERGENT

Backqround Trialkylamine oxides are known to be effective surfac-tants. Such amine oxides are made commercially by reacting a suitable trialkylamine with aqueous hydrogen peroxide. In this process the water content must be controlled to be at least 70 weight percent of the final composition or the reaction mass will gel and cannot be stirred. Such dilute aqueous solutions of trialkylamine oxide cannot be used to make a free-flowing granular laundry detergent by dry blending.

Esposita et al. U. S. 4,299,739 mention the desirability , of including tert-amine oxides in laundry detergents but offer no suggestion of how to tolerate the high water content.

Inamorato et al. U. S. 3,489,687 describe an attempt to make a granular free-flowing laundry detergent containing an amine oxide by adding an amount of an anhydrous salt, e.g., sodium sulfate and sodium tripolyphosphate to react with all the water in the amine oxide solution to form a friable mixed hydrated salt/amine oxide composition. However this necessitates 20 the addition of a salt composite rather than a discrete solid ,-amine oxide.

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According to the present invention, free-flowing granular heavy duty laundry detergent cor.taining a trialkylamine oxide surfactant can he macle by dry mixing a detergent alkylamine oxide dihydrate with a suitable laundry detergent builder and optionally other laundry detergent components.

2~2~973 Description of the Preferred Embodiments A preferred embodiment of the invention i5 a free-flowing heavy duty granular laundry detergent, said laundry detergent comprising (i) 1-30 weight percent of a discrete tert-amine oxide dihydrate having the formula RlR2R3No 2H2 wherein Rl is a C8_24 alkyl, R2 is methyl, ethyl or a C12_24 alkyl and R3 is methyl or ethyl and (ii) 10-50 weight percent o, a detergent builder.

An essential ingredient of the present heavy duty laundry detergent is the trialkylamine oxide dihydrate having the above formula RlR2R3NO-2H20. Such solid tert-amine dihydrates comprise about 1-50 weight percent of the detergent composition. More preferably the detergent comprises about 5-30 weight percent and most preferably 10-25 weight percent of the formulation.

The essential trialkylamine oxide dihydrates can be made by the process described in Application Serial No. 344,275, filed April 26, 1989. According to that process, the appropriate amine is reacted with at least a stoichiometric amount of concentrated ~(e.g., 50-70 weight percent active) hydrogen peroxide in an organic ester solvent (e.g., ethyl acetate) in an amount suffi-cient to maintain a fluid reaction mixture. Reaction temperatures of about 25-100C can be used. A preferred range is 60-75~C. Carbon dioxide can be injected to promote the reaction. Use of about 1.2 theories of 70 weight percent hydrogen peroxide results in a final reaction mixture which contains about 2 moles of water per mole of amine oxide. If more water than this is present, it should be distilled out to obtain a 2/1 water/amine oxide mole ratio. The organic ester solution can then be cooled causing the amine oxide dihydrate to 2~5~73 crystallize. Alternatively, the organic ester can be distilled out at atmospheric pressure or under vacuum to obtain the amine oxide dihydrate as the residue. It was surprisingly found that the tert-amine oxide dihydrate was not hygroscopic.

S Trialkylamines useful in making the tert-amine oxide dihydrate are those having the formula RlR2R3N wherein R1, R2 and R3 are as previously defined. Representative examples of these are:

octyl dimethylamine decyl dimethylamine dodecyl dimethylamine dodecyl diethylamine tetradecyl dimethylamine hexadecyl diethylamine octadecyl dimethylamine eicosyl dimethylamine docosyl dimethylamine tetracosyl dimethylamine dioctyl methylamine octyldecyl ethylamine didecyl methylamine decyl dodecyl methylamine didodecyl ethylamine ditetradecyl methylamine dihexadecyl methylamine eicosyldecyl methylamine ditetracosyl methylamine and the like including mixtures thereof.

Of the above, a still more preferred class of tert-amines consists of those in which Rl ic a linear C12_24 2~25~73 primary alkyl, R2 and R3 are methyl. Examples of these are:

n-dodecyl dimethylamine n-tetradecyl dimethylamine n-hexadecyl dimethylamine n-eicosyl dimethylamine n-docosyl dimethylamine n-tetracosyl dimethylamine and the like including mixtures thereof.

The following Examples show how to make the required trialkylamine oxide dihydrate.

Exam~le 1 In a 250 milliliter glass reaction flask was placed 100 grams of tetradecyldimethylamine (0.41 mole; amine value 230.0 mg KOH/g amine) and 0.5 gram (1.27 mmol) of diethylenetriaminepenta-acetic acid. This was heated with stirring to 65C and then 23 grams (0.47 mole) of 70 weight percent aqueous hydrogen peroxide was~added dropwise over a 15-minute period. The mixture was then heated to 76C and stirred at that temperature for seven hours.
As needed, ethyl acetate (34 mL) was added dropwise to the reaction mass in order to maintain a clear, gel-free liquid.
Analysis of the crude reaction mass showed 99 percent amine conversion by proton NMR. The crude reaction mass was added to 400 mL additional ethyl acetate. The solution was then cooled to 15C forming a non-hydroscopic white crystalline solid tetradecyl-dimethylamine oxide dihydrate in 86% recovered yield melting at about 41C.

2~973 Example 2 In a glass- reaction flask was placed 100 g tetradecyl dimethylamine and 0.5 g diethylenetriamine pentaacetic acid.
Carbon dioxide sparge into the liquid phase was started and the mixture was stirred and heated to 65C. The CO2 sparge was stopped and a CO2 gas phase was maintained over the reaction mixture. Dropwise feed of 70 weight percent aqueous hydrogen peroxide was started. At the same time, addition of ethyl acetate was commenced. After 10 minutes all the hydrogen peroxide and 28 mL of ethyl acetate had been added. Cooling was required to maintain the temperature under 75C. Heat was applied and the reaction continued for two more hours. Dropwise addition of ethyl acetate was continued for the first 19 minutes of the two-hour period. Total ethyl acetate feed was 43 mL. The reaction mixture-was a clear gel-free solution. The reaction mixture was analyzed by NMR showing a 100 percent amine conversion. The reaction mixture was poured into a flask containing 300 mL of ethyl acetate and cooled to 15C. Needle-like crystals of tetradecyl dimethyl-amine oxide dihydrate form (106 g) indicating a 87 percent yield.

The other essential ingredient in the present laundry detergent is at least one detergent builder. Detergent builders include sodium aluminum silicates (e.g. Zeolite A), sodium tripolyphosphate (STPP), sodium salt of nitrilotriacetic acid, sodium carbonate, sodium bicarbonate, sodium citrate, potassium carboxymethyloxymalonate, sodium carboxymethyloxy succinate, sodium salt of ethylenediaminepentaacetic acid (EDTA), sodium pyrophosphate and the like. Of the above the most preferred detergent builders are sodium carbonate, STPP and Zeolite A.

The amount of builder can vary from about 10 weight percent to 85 weight percent or more. A preferred amount is about 20-80 weight percent and most preferably 30-50 weight percent.

2 ~ 7 3 The laundry detergent can contain an additional surfactant other than the present tert-amine oxide dihydrate.
Examples of such surfactants are anionic, nonionic, amphoteric and cationic detergents.

Anionics include sodium, potassium, ammonium or alkyl-olammonium fatty acid soaps such as sodium salts of tallow fatty acids, coco fatty acids, oleic acid, stearic acid and the like.
Other very useful anionics are the sodium, potassium, ammonium and alkylolammonium salts of C10_16 alkyl benzenesulfonic acids such as sodium tridecylbenzenesulfonate. Likewise the sodium, potassium, ammonium and alkylolammonium salts of C12_16 alpha-olefin sulfonates and C12_16 alkylsulfates are useful.

Still another class of useful anionic surfactants comprises the alkali metal alkyl glyceryl ether sulfonates such as the C12_16 alkyl monoglyceride sulfonates and sulfates. Like-wise the alkali metal salts of C8_12 alkylphenyl polyethoxy-sulfonates and sulfates which contain about 5-10 ethyleneoxy units per molecule.

Other useful anionics include the water-soluble salts of 2-10 alkyl esters of C12_16 alpha-sulfonated fatty acids. Also water-soIuble salts of 2-acyloxyalkane-1-sulfonic acid which contain 2-9 carbon atoms in the aryl group are useful. Likewise fatty alcohol sulfates and ether sulfates are effective anionic surfactants. Also C12_18 alkyl polyethoxysulfates are useful co-surfactants.

Useful nonionics include polyethyleneoxy (5-10 units) C12_16 alcohols or C5_10 alkylphenols. Examples are poly-ethoxylated (5-9 units) dodecanol and polyethoxylated (5-9 units) nonylphenol. Cationic surfactants include quaternary ammonium, phosphonium and sulfonium compounds having at least one detergent 2 ~ 7 3 range, e.g. C12_18, alkyl group such as dodecyl dimethyl ammonium chloride.

Useful amphoteric surfactants include the C12_18 alkyl dimethyl betaines such as hexadecyl dimethylbetaine.

Other formulation components can include optical brightening agents, e.g.4,4'-bis(triazin-2-ylamino) stilbene-2,2'disulfonic acid, 2-(stilben-4-yl) napthotriazole, 2-(4-phenylstilben-4-yl)benzosazole, 1,4-bis(styryl)benzene, 1,3-di-phenyl-2-pyrazoline, and the like. The laundry detergent may also be formulated to contain dry peroxygen bleaches, e.g. sodium perborate; bleach activators, e.g. sodium Cg acyloxybenzene-sulfonate; and anti-redeposition agents, e.g. sodium polyacrylate.

Water soluble bulk fillers are routinely included in laundry detergents such as sodium sulfate. A typical laundry detergent formulation will contain about 5-50 weight percent filler to aid in handling.

A series of heavy duty laundry detergents formulations containing the present tert-amine oxide dihydrates is shown in the following table.

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Claims

1. A free-flowing heavy duty granular laundry detergent, said laundry detergent comprising (i) 1-30 weight percent of a discrete tert-amine oxide dihydrate having the formula R1R2R3NO?2H2O
wherein R1 is a C8-24 alkyl, R2 is methyl, ethyl or a C12-24 alkyl and R3 is methyl or ethyl and (ii) 10-50 weight percent of a detergent builder.

2. A laundry detergent of Claim 1 wherein R2 and R3 are methyl.

3. A laundry detergent of Claim 1 wherein R1 is a linear C12-24 alkyl group.

4. A laundry detergent of Claim 1 wherein said builder is selected from the group consisting of sodium tripolyphosphate, sodium carbonate, sodium nitrilotriacetate, sodium aluminum silicate, and mixtures thereof.

5. A laundry detergent of Claim 2 which includes at least one surfactant selected from anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants and mixtures thereof in addition to said tert-amine oxide dihydrate.

6. A laundry detergent of Claim 3 wherein said additional surfactant is an anionic surfactant.

7. A laundry detergent of Claim 4 wherein said anionic surfactant is sodium C10-18 alkylbenzene sulfonate.

8. A laundry detergent of Claim 3 wherein said additional surfactant includes a nonionic surfactant.

9. A laundry detergent of Claim 6 wherein said nonionic surfactant is a C6-12 alkyl phenol ethoxylate.

10. A laundry detergent of Claim 3 wherein said additional surfactant includes an amphoteric surfactant.

11. A laundry detergent of Claim 8 wherein said amphoteric surfactant is a C12-20 alkyl dimethylbetaine.

12. A laundry detergent of Claim 3 wherein said additional surfactant includes a cationic surfactant.

13. A laundry detergent of Claim 3 wherein said cationic surfactant is a C10-16 alkyl trimethylammonium chloride.

14. A laundry detergent of Claim 1 comprising:

(a) 5-30 weight percent tetradecyl dimethylamine oxide dihydrate, (b) 80 weight percent zeolite A, (c) 5-30 weight percent sodium alkylbenzene sulfonate, (d) 10-60% weight percent sodium carbonate.

15. A laundry detergent of Claim 1 comprising:

(a) 5-30 weight percent tetradecyl dimethylamine oxide dihydrate, (b) 70-95% sodium tripolyphosphate.

16. A process for making a free-flowing heavy duty granular non-hygroscopic laundry detergent, said process comprising dry mixing a discrete tert-amine oxide dihydrate having the formula R1R2R3NO?2H2O
wherein R1 is a C12-14 alkyl, R2 is methyl, ethyl or a C12-14 alkyl and R3 is methyl or ethyl with conventional laundry detergent components including a detergent builder.

17. A process of Claim 16 comprising dry mixing:

(a) 5-30 weight percent of a discrete solid non-hygro-scopic tetradecyl dimethylamine oxide dihydrate, (b) 20-80 weight percent of zeolite A, (c) 5-30 weight percent of a sodium C10-16 alkylbenzene sulfonate and (d) 10-60 weight percent of sodium carbonate.

18. A process of Claim 16 comprising dry mixing (a) 5-30 weight percent of a discrete solid non-hygro-scopic tetradecyl dimethylamine oxide dihydrate, (b) 20-80 weight percent of sodium tripolyphosphate, (c) 5-30 weight percent of a sodium C10-16 alkylbenzene sulfonate and (d) 10-60 weight percent of sodium carbonate.