US3920569A - Detergent composition having substituted phthalic acid salt builder - Google Patents

Abstract

Salts of aromatic 1,2-dicarboxylic acids having hydrophobic groups attached to the benzene ring, especially alkali metal salts of C10-C20 alkyl and alkenyl phthalic acids, are used as detergency builders.

Description

United States Patent Carson et al.

[ Nov. 18, 1975 DETERGENT COMPOSITION HAVING SUBSTITUTED PHTHALIC ACID SALT BUILDER Inventors: Phillip Alfred Carson, Wirral; Peter Tissington, Laceby, both of England Assignee: Lever Bros. Co., New York, NY.

Filed: Feb. 9, 1973 Appl. No.: 330,894

Foreign Application Priority Data References Cited UNITED STATES PATENTS 3,692,684 9/1972 Hentschel 252/89 3,748,267 7/1973 Stokes 252/89 3,816,318 6/1974 Hentschel 252/89 OTHER PUBLICATIONS Ogami et al., Chem. Abs., 66, 7230, Abs. No. 76879b, (1967).

Primary Examiner-Benjamin R. Padgett Assistant Examiner-EL A. Miller Attorney, Agent, or Firm-James J. Farrell, Esq.

[57] ABSTRACT Salts of aromatic 1,2-dicarboxylic acids having hydrophobic groups attached to the benzene ring, especially alkali metal salts of C -C alkyl and alkenyl phthalic v .acids, are used as detergency builders.

3 Claims, No Drawings 1 DETERGENT COMPOSITION HAVING SUBSTITUTED Pl-ITI-IALIC ACID SALT BUILDER The invention relates to detergent compositions, and in particular to detergent compositions adapted for fabric washing.

Detergent compositions commonly incorporate synthetic detergent active compounds together with detergency builders. Conventional detergency builders are commonly inorganic materials, particularly condensed phosphates, for example sodium tripolyphosphate. It has, however, been suggested that the use of phosphate detergency builders can contribute to eutrophication problems. Alternative organic detergency builders which have been proposed, for example sodium nitrilotriacetate (NTA) and synthetic polyelectrolyte materials, tend to be more expensive or less efficient than the phosphate detergency builders, or otherwise unsatisfactory for one reason or another. For example NTA contains nitrogen which is alleged also to be a contributory factor in eutrophication and the synthetic polyelectrolyte builders proposed tend to be hygroscopic and largely non-biodegradable.

According to the present invention a detergent composition incorporates as a detergency builder a water soluble or dispersible salt of an aromatic 1,2-dicarboxylic acid having a hydrophobic group attached to the aromatic ring. These compounds broadly have the following formula:

wherein the groups R,, R R and R are hydrophobic groups, hydroxy groups or hydrogen atoms, at least one of the groups R,, R R and R being such a hydrophobic group, or at least two of the groups R R R and R being combined into a hydrophobic group. The preferred hydrophobic groups are alkyl and alkenyl groups, especially those containing about to carbon atoms in a single group on the benzene ring; if more than one hydrophobic group is present, the total number of carbon atoms in such groups would normally be higher, for example from about 14 to carbon atoms. If desired, the alkyl or alkenyl groups may contain hetero atoms, for example they may be joined to the benzene ring with ester or amide linkages in which the carbonyl groups bear the alkyl or alkenyl groups or ether linkages.

In the detergent compositions of the invention, the salts of the aromatic dicarboxylic acids act as detergency builders, generally by their forming insoluble salts with the calcium and magnesium-ions present in hard water. Additionally, the aromatic dicarboxylic acid detergency builders can have useful fabric softening properties in the wash.

The preferred detergency builders according to the present invention are salts of alkyl phthalic acids having the general formula:

coon

COOH

wherein R is an alkyl or alkenyl group containing from about 10 to 20 carbon atoms. One or more hydroxyl groups may also be present either in the benzene ring or in the alkyl group R, provided that this does not increase the solubilities of their salts excessively in relation to the alkyl chain length.

The majority of the detergency builders used in accordance with the present invention are believed to be novel compounds, but they can be prepared by conventional organic chemistry techniques. Specifically, for example, the alkyl phthalic acids may be made by oxidation of alkyl o-xylenes, for example with oxygen in the presence of catalysts such as cobaltous acetate or bromides such as manganese bromide; and the alkyl 0- xylenes can be prepared by Friedel-Crafts addition of an alkyl group to o-xylene. For safety, it should be mentioned that the oxidation reaction must be carefully controlled to prevent an explosion with the cobalt catalyst. In the case of carbalkoxy phthalic acids, where an alkyl chain is attached by an ester group to the benzene ring the compounds may be made by reaction of an acyl chloride with a hydroxyphthalic acid.

The detergent compositions of the invention normally include in addition to the aromatic dicarboxylic acid detergency builders, one or more anionic, nonionic, amphoteric or zwitterionic detergent active compounds.

The synthetic detergent active compounds which can be used in the compositions of the invention are preferably anionic detergent active compounds, which are readily available and relatively cheap, and mixtures thereof. These compounds are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. Examples of such synthetic anionic detergent active compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating the higher (Cg- 18) alcohols produced by reducing the glycerides of tallow or coconut oil; sodium and potassium alkyl (C -C benzene sulphonates, particularly sodium linear secondary alkyl (C -C benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C -C fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid andneutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha-olefins (C -C with sodium bisulphite and those derived by reacting paraffins with S0 and Cl and then hydrolysing with a base to produce a random sulphonate; and olefin sulphonates, which term is used to cover the material made by reacting olefms, particularly alpha-ole- 3 fins, with S and then neutralising and hydrolysing the reaction product.

If desired, nonionic detergent active compounds may also be used. Examples include the reaction products of alkylcnc oxides, usually ethylene oxide, with alkyl (C -C phenols, generally 5 to 25 E0; i.c. 5 to 25 units of ethylene oxide per molecule; the condensation products of aliphatic (Cg-C13) alcohols with ethylene oxide, generally 6 to 30 E0, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine. Other socalled nonionic detergentactive compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.

Mixtures of detergent active compounds, for example mixed anionic or mixed anionic and nonionic compounds may be used in the detergent compositions, particularly to impart thereto controlled low sudsing properties. This is particularly beneficial for compositions intended for use in suds-intolerant automatic washing machines. Mixtures of amine oxides and ethoxylated nonionic compounds can also be beneficial.

Amounts of amphoteric or zwitterionic detergent active compounds can also be used in the compositions of the invention but this is not normally desired due to their relatively high cost. If any amphoteric or zwitterionic detergent active compounds are used it is generally in small amounts in compositions based on the much more commonly used anionic or nonionic detergent active compounds.

Many suitable detergent active compounds are commercially available and are described in the literature, for example in Surface Active Agents and Detergents" Vols 1 and 11 by Schwartz, Perry and Berch.

The amount of the synthetic detergent active compound or compounds used is generally in the range of from about to 50%, preferably about 15 to by weight of the compositions, depending on the desired properties.

The amount of the water-soluble or dispersible salt of the aromatic 1,2-dicarboxylic acids used as detergency builders in the compositions is normally within the range of about 15 to about 80%, preferably at least about 30% by weight, depending on the desired properties of the compositions. When the compositions are intended for use at lower concentrations, for example in the range from about 0.05 to about 0.2% w/v, as is often the case in automatic domestic washing machines, such as commonly used in North America, it is preferable to have higher amounts of the water-soluble salts of the aromatic dicarboxylic acids present, for example at least about and preferably -60% by weight. Although these amounts of the detergency builders have been expressed in terms of the amounts of salt used, it will be appreciated that the detergency builder may be in an acid or even anhydride form in the compositions'in some cases, provided that the salt is formed on dissolution of the composition in water, and this necessitates including alkaline salts in the detergent compositions. [t is however preferred to use the materials in a water-soluble salt form in the composition itself, the usual salts being the alkali metal salts, particularly the sodium, potassium or lithium salts, but ammonium or substituted ammonium salts for example the C -C alkyl and alkanol ammonium salts can be used if desired.

The ratio of the detergent active compound to the detergency builders is generally in the range of from 4 about 10:1 to 1:10, especially from about 3:1 to 1:5.

The aromatic dicarboxylic acid detergency builders of the present invention may be used as sole detergency builders or in admixture with amounts of other detergency builders. Examples of such conventional detergency builders include sodium nitrilotriacetate, sodium ethylene diamine tetraacetate, sodium alkenyl succinates, sodium sulpho fatty acids, sodium tripolyphosphate, sodium and potassium pyrophosphate, sodium orthophosphate, sodium carbonate and polyelectrolyte builders such as sodium polyacrylate, sodium polymaleate and sodium copolyethylene maleate.

In addition to the essential ingredients in the detergent compositions, other optional ingredients may be added, for example perfumes, colourants, fabric softening agents, fungicides, germicides, enzymes, fluorescent agents, antiredeposition agents such as sodium carboxymethylcellulose, hydrotropes, and in the case of liquid compositions opacifiers and organic solvents such as lower aliphatic alcohols. Other ingredients such as bleaches, for example sodium perborate with or without the presence of peracid precursors, chlorineliberating bleach compounds and inorganic salts such as sodium carbonate, sodium sulphate and sodium chloride may also be present if desired. The compositions also usually contain amounts of water, for example in the range offrom about 5 to 15% by weight in powdered detergent compositions.

The compositions, of the invention may be solid compositions, for example in powdered, granular or tablet form, semi-solid paste or gel compositions or they may be liquid compositions. The compositions can also be made by conventional processing techniques, for example by spray-drying aqueous slurries to give detergent powders. It is advantageous in this case to use the process described in the specification of our Belgian Pat. No. 769,827 in which relatively mild conditions are used in the spray-drying tower and the slurry is made under pressure with a low water content. This decreases the fire. hazard for making powders of high organic content.

While the compositions are of particular utility in the field of fabric washing they can also be used for general cleaning purposes or if desired for personal washing.

Compositions according to the invention are illustrated by the Examples below, in all of which parts are by weight except where otherwise indicated.

EXAMPLE 1 Propene-tetramer (42.0 g, 0.25 m) was added dropwise over one-half hour to a vigorously-stirred mixture of o-xylene (103 g, 1.00 M) and 93% sulphuric acid (200 g about 2 M) at 03, and the stirring was continued for a further 3 hours. The viscous, brown mass was poured onto ice (1 Kg), ether-extracted and the product was distilled to give unchanged xylene (92.1 g, 0.87 M; 87% recovery) and 1-dodecyl-3,4-dimethylbenzene (35.2 g, 0.13 M; 50%).

A mixture of the alkyl xylene (12.5 g, 0.05 M), a solution of MnBr Al-l o (2.86 g, 0.01 M) in glacial acetic acid (500 ml), and oxygen (20 atm) was heated at for 6 hours in a 1 liter stainless steel autoclave. Workup of the product gave alkyl xylene (5.50 g, 0.02 M; 44% recovery) and l-dodecylbenzene-3,4-dicarboxylic acid (8.01 g, 0.024 M; 50%). Spectroscopic and elemental analyses of the latter were consistent with the structure:

product.

Detergency builder Soil removal Sodium l-dodecylbenzene-3.4- 67 g 69 dlcarboxylate Sodium tripolyphosphate 82 66 The results indicate the compound to have some detergency building effect approching that of sodium tripolyphosphate.

Further tests showed the alkyl phthalic acid compound to have some fabric softening properties.

EXAMPLE 2 A commercial C vinylidene olefin (containing 9% internal olefin) (56.0 g, 0.25 M) was added dropwise over 1 hour to a vigorously stirred mixture of 93% sulphuric acid (cone. H 80. 49.0 g, 0.50 M, diluted to 93%) and o-xylene (106 g, 1.00 M) cooled to 5C. The mixture was allowed to warm to room temperature and the stirring continued for 4 hours. Work-upin the usual way afforded unchanged xylene (50.1 g, 0.47 M; 47% recovery) and the product l-hexadecyl-3,4- dimethylbenzene (70.1 g, 0.24 M; 97%).

A 750 ml autoclave was charged with a mixture of the alkyl xylene (15.0 g, 0.05 M), a solution of MnBr Al-l O (2.86 g, 0.01 M) in glacial acetic acid (500 ml), and oxygen atm). On heating, the pressure rose steadily to atm until the temperature reached 145150 when there was a rapid drop to 20 atm. After 3 hours at this temperature the pressure had dropped slowly to 15 atm. Isolated from the mixture were alkyl xylene (2.02 g, 0.01 M; 20% recovery) and a brown oil (13.5 g). The latter was found to comprise 82% of l-hexadecylbenzene-3,4-dicarboxylic acid (1 1.1 g, 0.03 M; 76% yield) having the structure below, with 12% of 1-hexadecyl-benzene-3 -methyl-4-carboxylic acid (1.62 g, 42 M moles; 10% yield).

CH;,(CH).|- CH Huclmi CO H . 6 x predominantly 5 y predominantly 7 The alkyl phthalic acid prepared as above was evaluated for its'detergency building properties using the test conditions described for- Example 1, with the following results.

Detergency builder Soil removal (71) Sodium l-hexadecylbenzene-3A- 76 76 dicarboxylate Sodium tripolyphosphate 79 71 EXAMPLE 3" Nonadec-l-ene-3-ol was prepared from hexadecyl magnesium bromide and acrolein in ether. The unsaturated alcohol g) was heated with anhydrous potassium hydrogen sulphate (68 g) at for. 2 hours under reduced pressure, and the product was treated with water, extracted with ether and dried. Evaporation of the ether then gave a mixture of cisand transnonadeca-1,3-diene. Equimolar proportions of maleic anhydride and the diene prepared as above were then heated under reflux in benzene for 6 hours after which the solvent was removed by distillation under reduced pressure. After washing the Diels-Alder reaction product with petroleum ether (4060), the product (1 1.5

g) was dehydrogenated with selenium dioxide (4.9 g) in boiling acetic anhydride for 6 hours. The precipitated selenium was removed by filtration and the filtrate was evaporated to give a red-brown product 3-pentadecyl phthalic anhydride, which was heated under reflux for 4 hours in a sodium hydroxide solution to yield the disodium salt.

The disodium 3-pentadecyl phthalate prepared as described above was tested for detergency builder properties in the standard test described in Example 1 above (using 25H water) with the following results at the product concentrations shown (with the same ratio of alkyl benzene sulphonatezbuilder).

Detergency builder 7: detergency for product concentration Disodium 3-pentadecyl 8 64 73 phthalate Sodium tripolyphosphate 46 70 76 Equivalence with the sodium tripolyphosphate is shown for the new detergency builder according to the invention at the higher product concentrations.

EXAMPLE 4 4 a solution of magnesium myristyl bromide. The solution of furfuryl bromide prepared as above was added with the Grignard reagent solution, again at a rate maintaining reflux, after which the mixture was cooled, poured onto ice and acidified with dilute sulphuric acid. The ethereal extract was washed, dried and then distilled under reduced pressure to give four fractions, one of which boiling at l30-l50C (at 0.8 mm Hg) was identified as pentadecyl furan. Dimethyl acetylene dicarboxylate (2].4 g) and pentadecyl furan (42 g) prepared as above were reacted at l for 8 hours and then cooled to l0, diluted with 1,2-dichloroethane and acidified with cone. sulphuric acid (6.4 g). The mixture was warmed to diluted with water, ether extracted and then worked up to give the 3-hydroxy-6- pentadecyl phthalic acid, which was neutralised with sodium hydroxide solution at 20C for 2 hours to give the disodium salt.

The disodium-3-hydroxy-6-pentadecyl phthalate was evaluated as a detergency builder using the procedure described in Example 1 with the following results:

7c detergency at 0.l71 builder concentration This result compares favourably with the result of 65.3% for sodium tripolyphosphate under comparable conditions.

What we claim is:

l. A detergent composition comprising an anionic, nonionic, amphoteric or zwitterionic detergent active compound and as a detergency builder a water soluble or dispersible salt of a substituted phthalic acid having the formula:

' COOH R (COO) COOH wherein R is a C ,C alkyl or alkenyl group and n is 0 or 1, the ratio of the detergent active compound to the detergency builder being'from about 10:1 to 1:10.

2. A detergent composition according to claim 1,

wherein the alkyl or alkenyl group is attached directly to the benzene ring.

3. A detergent composition according to claim 1, wherein the detergency builder is used in the form of the sodium salt.

Claims (3)

1. A DETERGENT COMPOSITION COMPRISING AN ANIONIC NONIONIC AMPHOTEERIC OR ZWITTERIONIC DETERGENT ACTIVE COMPOUND AND AS A DETERGENCY BUILDER A WATER SOLUBLE OR DISPERSIBLE SALT OF A SUBSTITUTED PHTHALIC ACID HAVING THE FORMULA:

2. A detergent composition according to claim 1, wherein the alkyl or alkenyl group is attached directly to the benzene ring.

3. A detergent composition according to claim 1, wherein the detergency builder is used in the form of the sodium salt.