Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/04—Carboxylic acids or salts thereof
  • C11D1/08—Polycarboxylic acids containing no nitrogen or sulfur
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2096—Heterocyclic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/24—Organic compounds containing halogen
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen

Definitions

• R is a hydrogen atom or an alkyl or substituted alkyl group containing from 6 to 20 carbon atoms
• R is an alkylene or substituted alkylene group containing from 0 to 4 carbon atoms and optionally incorporating hetero atoms as linking groups, the total number of carbon atoms in groups R, and R being from 6 to 20, one or both of X and Y being non-ionisable atoms or groups, any other being hydrogen
• n is O to 1, are disclosed.
• the present invention relates to detergent compositions, and particularly to detergent compositions adapted for fabric-washing.
• Detergent compositions for heavy-duty fabric washing in fabric-washing machines normally comprise as major ingredients detergent-active compounds and detergency builders.
• the most commonly used detergency builders are the condensed phosphates, particularly sodium tripolyphosphate, although other inorganic or organic materials, such as sodium nitrilotriacetate and sodium copolyethylene-maleate, have been proposed.
• R-CH(COOH) (CH -COOH wherein n is 0 or 1 and R is a primary or secondary straight-chain alkyl or alkenyl group containing from to 20 carbon atoms.
• R is a hydrogen atom or an alkyl or substituted alkyl group containing from 6 to 20, preferably from 10 "ice to 20, carbon atoms, R; is an alkylene or substituted alkylene group containing from O to 4, preferably 0 to 1, carbon atoms and optionally incorporating hetero atoms as linking groups, the total number of carbon atoms in groups R, and R being from 6 to 20, one or both of X and Y being non-ionisable atoms or groups, any other being a hydrogen atom, and n is 0 or 1.
• detergency builders of the invention are hereinafter referred to as substituted dicarboxylic acid salts.
• R and R are preferably linear.
• the preferred non-ionisable atoms or groups are halogen atoms, particularly chlorine or bromine, and hydroxy groups; the presence of any additional ionisable groups in the substituted dicarboxylic acids tends to detract from the detergency building properties of the substituted dicarboxylic acid salts.
• a detergent composition according to the invention comprises at least one detergent-active compound and at least one substituted dicarboxylic acid salt as defined above, the weight ratio of the detergent-active compound to the substituted dicarboxylic acid salt being within the range of about 10:1 to about 1:10.
• the substituted dicarboxylic acid salt is preferably an alkali-metal salt, such as a sodium, potassium or lithium salt, sodium salts being particularly preferred, but other cations, such as ammonium and substituted ammonium, may be used if desired.
• alkali-metal salt such as a sodium, potassium or lithium salt
• sodium salts being particularly preferred, but other cations, such as ammonium and substituted ammonium, may be used if desired.
• the weight ratio of the detergent-active compound to the substituted dicarboxylic acid salt is within the range of about 2:1 to about 1:4.
• the substituted dicarboxylic acid salt normally comprises at least about 5%, and preferably from about 20 to about 60%, by weight of the detergent composition,
• Substituted dicarboxylic acids according to the present invention can be prepared by addition to the double bond of an alkenyl malonic acid or its salt or an alkenyl succinic acid or its salt or anhydride.
• the addition reaction is accomplished using conventional techniques to give a variety of different groups X and Y in Formula I.
• X and Y may be the same group or different groups, and where they are different it will be appreciated that either of the different groups represented by X and Y in the Formula I may be nearer to the dicarboxylic head group in the molecule.
• Examples of different reagents which may be reacted with the appropriate starting materials, i.e. the alkenyl succinic or malonic acids or their salts or anhydrides, to give the various groups X and Y are shown in Table I below:
• the preferred starting materials which are used to prepare the substituted dicarboxylic acids of the present invention are alkenyl succinic acids or their salts or anhydrides which can be prepared by reaction between an olefin and maleic anhydride to give an alkenyl succinic anhydride, which can then be hydrolysed to give the acid and neutralised to give the salts if desired.
• the double bond in the alkenyl group is predominantly between the 5 and 6 carbon atoms, in which case R in Formula I contains only 1 carbon atom.
• R in Formula I contains only 1 carbon atom.
• a certain amount of migration of the double bond along the carbon chain can take place, either during the preparation of the alkenyl compound or during the reactions to form the compounds of the invention, so that R can contain up to about 4 carbon atoms.
• the starting material can be an alkenyl malonic acid and its salts or anhydride.
• These can be prepared by standard malonic ester synthesis techniques in which a sodium malonic acid diester is reacted with an alkenyl halide, for example chloride, to give the alkenyl malonic ester followed by conventional treatment to form the acid, anhydride or salt as desired.
• position of the double bond will depend on the position of the double bond in the alkenyl halide used.
• An alternative route for preparing an alkenyl malonic acid and its derivatives is by condensation of an aldehyde with a malonic acid diester in the presence of an amine; in this case the double bond is immediately adjacent to the malonic acid group.
• Substituted dicarboxylic acids according to the invention may also be prepared by reaction of a halogen with an alkyl succinic acid or alkyl malonic acid, in which case substitution tends to occur in the Ot-POSitiQIlS on the carbon chain.
• a detergent composition of the invention will contain at least one detergent-active compound.
• the substituted dicarboxylic acid salts of the invention themselves have some limited detergent-active properties, but as these salts are deliberately selected for use as precipitant detergency builders, for which purpose their parent substituted dicarboxylic acids must have water-insoluble calcium salts, these salts are not considered as detergentactive compounds for the purposes of this specification.
• the detergent-active content of the composition will generally be from about 5 to about 50%, preferably from about 5 to about 35%, and particularly preferably from about 10 to about by weight of the composition.
• detergent-active compound or compounds in the composition is not an essential feature of the invention: any of the detergent-active compounds conventionally incorporated in or proposed for use in detergent compositions may be used, and those skilled in the art of formulating detergent compositions will be familiar with these detergent-active compounds and the various amounts and combinations in which they may advantageously be used.
• the detergent-active compound or compounds may be anionic, nonionic, amphoteric or zwitterionic in character.
• Typical anionic detergent-active compounds are watersoluble or water-dispersible salts of various organic acids.
• the cations of such salts are generally alkali-metals, such as sodium and, less preferably, potassium, but other cations, such as ammonium and substituted ammonium, can be used if desired.
• alkyl benzene sulphonic acids the alkyl chains of which contain from about 8 to about 20 carbon atoms, such as p-dodecyl benzene sulphonic acid and linear alkyl (C benzene sulphonic acid; the mixtures of sulphonic acids obtained by reacting linear and branched olefins, particularly linear cracked-wax or Ziegler alpha-olefins, containing from about 8 to 22 carbon atoms, sulphur trioxide; alkyl sulphonic acids obtained by reacting alkanes containing from about 8 to about 22 carbon atoms with sulphur dioxide/oxygen or sulphur dioxide/chlorine (followed by hydrolysis in the latter case), or by the addition of bisulphite to olefins, particularly linear cracked-wax or Ziegler alpha-olefins, containing from about 8 to about 22 carbon atoms; alkyl s
• nonionic detergent-active compounds are: condensates of alkyl-phenols having an alkyl group (derived, for example, from polymerised propylene, diisobutylene, octene, dodecene or nonene) containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with about 5 to 25 moles of ethylene oxide per mole of alkyl-phenol; condensates containing from about 40% to about polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide with the reaction product of ethylenediamine and excess propylene oxide; condensates of linear or branched-chain aliphatic alcohols containing from 8 to 18 carbon atoms with ethylene oxide, e.g.
• R R R N- O long-chain tertiary amine oxides corresponding to the general formula R R R N- O, wherein R is an alkyl radical containing from about 8 to 18 carbon atoms and R and R are each methyl, ethyl or hydroxy ethyl radicals, such as dimethyldodecylamine oxide, dimethyloctylamine oxide, dimethylhexadecylamine oxide and N-bis (hydroxyethyl) dodecylamine oxide; long-chain tertiary phosphine oxides corresponding to the general formula RRRP O, wherein R is an alkyl, alkenyl or monohydroxyalkyl radical containing from 10 to 18 carbon atoms and R and R are each alkyl or monohydroxyalkyl groups containing from 1 to 3 carbon atoms, such as dimethyldodecylphosphine oxide, dimethylt
• amphoteric detergent-active compounds are: derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substitnents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilising group, such as sodium-3-dodecylaminopropionate, sodium 3 dodecylaminopropanesulphonate and sodium N-Z-hydroxydodecyl-N-methyl-taurate.
• anionic water solubilising group such as sodium-3-dodecylaminopropionate, sodium 3 dodecylaminopropanesulphonate and sodium N-Z-hydroxydodecyl-N-methyl-taurate.
• Suitable zwitterionic detergent-active compounds are: derivatives of aliphatic quaternary ammonium compounds, sulphonium compounds and phosphonium compounds in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilising group, such as 3-(N,N-dimethyl-N-hexadecyl-ammonium) propane-l-sulphonate betaine, 3-(N,N-dimethyl-N-hexadecyl-ammonium)-2-hydroxypropane 1 sulphonate be taine, 3- (dodecylmethyl-sulphonium) propane 1 sulphonate betaine, and 3-(cetylmethylphosphonium) ethane sulphonate betaine.
• anionic water solubilising group such as 3-(N,N-dimethyl-N-hexadecyl-ammonium)
• the substituted dicarboxylic acid salts of the invention may comprise the whole of the detergency builder content of a detergent composition of the invention. However, if desired, mixtures of one or more of these salts with one or more known detergency builders may be used. As one of the objects of the invention is to provide an effective detergent composition containing either no phosphorus or at most only a low level of phosphorus, it is preferred that any such other detergency builders should not be phosphorus-containing compounds. Usually the total amount of detergency builders in a detergent composition of the invention will be from about 5 to about 70% by weight of the detergent composition. Many detergency builders are known, and those skilled in the art of formulating fabric-washing detergent compositions will he familiar with these materials.
• detergency builders examples include sodium tripolyphosphate; sodium orthophosphate; sodium pyrophosphate; sodium trimetaphosphate; sodium ethane-l-hydroxy-1,1-diphosphonate; sodium carbonate; sodium silicate; sodium citrate; sodium oxydiacetate; sodium nitrilotriacetate; sodium ethylenediaminetetraacetate; sodium salts of long-chain dicarboxylic acids, for instance straight chain (C to C succinic acids and malonic acids; sodium salts of alpha-sulphonated longchain monocarboxylic acids; sodium salts of polycarboxylic acids; i.e.
• acids derived from the polymerisation or copolymerisation of unsaturated carboxylic acids and unsaturated carboxy acid anhydrides such as maleic acid, acrylic acid, itaconic acid, methacrylic acid, crotonic acid and aconitic acid, and the anhydrides of these acids, and
• a detergent composition of the invention may contain any of the conventional detergent composition ingredients in any of the amounts in which such conventional ingredients are usually employed therein.
• additional ingredients are lather boosters, such as coconut monoethanolamide and palm kernel monoethanolamide; lather controllers; inorganic salts such as sodium sulphate and magnesium sulphate; bleaching agents such as sodium perborate, sodium percarbonate, trichloroisocyanuric acid, and sodium and potassium dichloroisocyanurates; antiredeposition agents, such as sodium carboxymethylcellulose; and, usually present only in minor amounts, perfumes, colourants, fluorescers, corrosion inhibitors, germicides and enzymes.
• a detergent composition of the invention can be prepared using any of the conventional manufacturing techniques commonly used or proposed for the preparation of detergent compositions, such as slurry-making followed by spray-drying or spray-cooling, and subsequent dry-dosing of sensitive ingredients not suitable for incorporation prior to the drying step.
• Other conventional techniques such as noodling, granulation, and mixing by fluidisation in a fluidised bed, may be utilised as and when necessary. Such techniques are familiar to those skilled in the art of detergent composition manufacture.
• a detergent composition of the invention may be prepared in any of the common physical forms associated with detergent compositions, such as powders, flakes, granules, noodles, cakes, bars and, in some cases, liquids.
• the product was hydrolysed by pouring it steadily into a 10% molar excess of a stirred solution of sodium hydroxide in alcohol (10% solution).
• the di-sodium salt which precipitated was filtered and washed with a little ethanol to remove excess base and coloured by-product to yield, on drying, a light brown product (226 g., 65% yield) of predominantly disodium 5,6-dichloro hexadecyl succinate, the carbon atoms being numbered along the longest chain.
• EXAMPLE 2 Preparation of disodium dihydroxy hexadecyl succinate To a solution of hexadecenyl succinic acid, prepared by conventional saponification and then acidification of 250 g. of the corresponding anhydride, were added formic acid ('850 ml.) and 30% hydrogen peroxide (75 ml.). The solution was stirred at 40 C. for 4 hours and was then basified with sodium hydroxide and warmed for 1 hour to hydrolyse the formate ester intermediate. The free acid was precipitated from solution by acidification with concentrated HCl and was filtered and dried.
• EXAMPLE 4 Preparation of disodium epoxy hexadecyl succinates 150 g. of m-chloroperbenzoic acid were dissolved in diethyl ether and this solution was added to a stirred solution of 250 g. of hexadecenyl succinic anhydride in ether/ chloroform (1:3) so that the temperature remained at 25 C. The reaction was continued for 17 hours (overnight) before the excess per-acid was destroyed by the addition of a aqueous solution of sodium bisulphite. The solution was then washed rapidly in turn with 5% aqueous sodium carbonate solution, water, and brine before drying the organic layer with anhydrous sodium sulphate and removing the solvent. The yield was 142 g. of predominantly disodium 5,6-epoxy hexadecyl succinic anhydride which was subsequently hydrolysed to the disodium salt.
• EXAMPLE 5 Preparation of disodium bromo-hydroxy hexadecyl succinates
• the dicarboxylic acid formed by hydrolysis of 50 g. of hexadecenyl succinic anhydride was dissolved in water and a dilute solution of bromine (12.5 g.) in 500 ml. of water was added at 20 C. The whole solution was kept at 20 C. for 2 hours and was then neutralised with sodium hydroxide and evaporated to dryness. Analysis indicated the product was 70% bromohydrin and 30% dibromo compounds.
• EXAMPLE 6 Preparation of disodium hydroxy hexadecyl malonate 23 g. of sodium was dissolved in 600 ml. of dry ethanol and 160 g. of diethyl malonate added at 50 C. The mixture was stirred for minutes then 240 g. of dry hexadecane 1,2-epoxide were added. The mixture was gently refluxed for 2 /2 hours and allowed to cool. The precipitated product was removed by filtration and was heated for 1 hour with a slight excess of aqueous caustic soda. The solution was filtered and the filtrate evaporated to dryness.
• Discs of desized cambric cotton were solid with a radioactive synthetic sebum deposited on the discs to the level of 1.5% from diluted benzene solution. After drying, the soiled discs were washed in the detergent solution containing 0.05% weight by volume of sodium dodecyl benzene sulphonate (prepared from sulphonated DOB 055 ex Shell Chemicals Ltd.), 0.025% of alkaline silicate and an amount of a selected detergency builder at 45 C. for 10 minutes in 25 H water at pH 10 using a repeatable degree of agitation at 70 cycles per minute. The percentage detergency of each material was determined by counting the radio-activity of each washed cotton disc before and after washing and the detergency was calculated by the equation:
• A is the corrected radio-active count before washing and A is the corrected radio-active count after washing.
• R is a linear alkyl group
• R is an alkylene group containing either 0 or 1 carbon atom
• R and R contain together 14 carbon atoms
• X and Y are selected from the group of non-ionisable atoms or groups consisting of hydrogen, chlorine, bromine, hydroxy and nitro (provided that both X and Y cannot be hydrogen), and n is 0 or 1;
• the weight ratio of said detergent-active compound and said dicarboxylic acid salt being from about 1: 10 to about 10:1.
• a detergent composition according to claim 1 wherein said dicarboxylic acid salt comprises from about 20 to about 60% by weight of the detergent composition.

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• Chemical & Material Sciences (AREA)
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• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Detergent Compositions (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Cited By (5)

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• 1970
  • 1970-12-04 GB GB5764770A patent/GB1342360A/en not_active Expired
• 1971
  • 1971-11-30 CA CA128,934A patent/CA939580A/en not_active Expired
  • 1971-12-01 ZA ZA718053A patent/ZA718053B/xx unknown
  • 1971-12-01 DE DE19712159435 patent/DE2159435A1/de active Pending
  • 1971-12-02 NL NL7116552A patent/NL7116552A/xx unknown
  • 1971-12-02 AT AT1037471A patent/AT321436B/de not_active IP Right Cessation
  • 1971-12-02 ES ES397615A patent/ES397615A1/es not_active Expired
  • 1971-12-02 US US00204348A patent/US3725286A/en not_active Expired - Lifetime
  • 1971-12-02 IT IT70970/71A patent/IT943163B/it active
  • 1971-12-03 BE BE776259A patent/BE776259A/fr unknown
  • 1971-12-03 FR FR7143530A patent/FR2117379A5/fr not_active Expired

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