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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3784—(Co)polymerised monomers containing phosphorus

Definitions

• NTPP phosphates from other sources, such as fertilizers, faeces, soil erosion, etc. - contributes to the entry of phosphorus into the water. Excessive phosphorus concentrations, especially in stagnant and slow-flowing waters, can lead to symptoms of eutrophication.
• the task was therefore to find phosphate substitutes which improve the action of the builders system and thus the action of the detergent again.
• NTPP replacements e.g. Zeolite A, trisodium nitrilotriacetate and sodium citrate.
• Zeolite A trisodium nitrilotriacetate
• sodium citrate sodium citrate
• copolymers of the invention are preferably polymerized to give the copolymers used according to the invention.
• copolymers of the invention are preferably incorporated into the detergents and cleaning agents as builders or builders additives together with pentasodium triphosphate, zeolite A or trisodium nitrilotriacetate as further builders.
• acrylic acid, methacrylic acid, vinyl acetic acid or maleic anhydride are used as ethylenically unsaturated carboxylic acids or as their anhydrides
• 1-phenylvinyl-1-phosphonic acid or propene-2-phosphonic acid is preferably used as ethylenically unsaturated phosphonic acids.
• the copolymerization of other olefinically unsaturated compounds without carbon or phosphonic acid groups is not necessary, but e.g.
• Ethylene, butadiene, chloroprene, acrylamide, methacrylamide, acrylamidosulfonic acid, vinyl sulfonic acid, allylsulfonic acid, vinyl acetate, hydroxyethyl or propyl acrylate, vinyl glycol or (meth) acrylic acid methyl ester can be copolymerized.
• copolymers functioning as builders according to the invention also have the character of polymeric carboxylic acids and phosphonic acids and develop their excellent incrustation-inhibiting and dispersing properties with different builders systems, e.g. in combination with NTPP and zeolite A.
• the monomeric ethylenically unsaturated carboxylic acids are generally commercially available products; the monomeric ethylenically unsaturated phosphonic acids are simple and economical e.g. by reacting ketones with phosphorus trichloride (DE-OS 33 23 392) or with tetraphosphorus hexoxide (DE-OS 31 25 329 and DE-OS 32 10 419).
• DE-OS 18 01 411 describes the use of water-soluble salts of organic polymer compounds which contain phosphonic and carboxylic acid groups in the side chains as the sole builders in detergents and cleaning agents.
• Vinylphosphonic acid serves as the phosphonic acid monomer.
• the sole use of these builders is not economically feasible.
• the builders contained in the detergents and cleaning agents according to the invention can be incorporated into the detergents and cleaning agents in a customary manner by spray drying, mixing or spray mixing processes.
• Another advantage of the builders or builders additives according to the invention is their contribution to "anti-caking", i.e. to prevent segregation in detergent slurries that are rich in non-ionic surfactants.
• the washing and cleaning agents according to the invention are distinguished by excellent washing results. They have a very high calcium binding capacity as well as excellent dispersing and threshold effects, so that besides the incrustation-inhibiting effect they have to be attributed clear graying-inhibiting properties.
• the detergent and cleaning agent of the invention preferably contains anionic, zwitterionic (ampholytic) or nonionic in nature as surfactants.
• Nonionic surfactants are understood to mean those compounds which have an organic, hydrophobic group and a hydrophilic radical, for example the condensation products of alkylphenols or higher fatty alcohols with ethylene oxide, the condensation products of polypropylene glycol with ethylene oxide or propylene oxide, the condensation products of ethylene oxide with the reaction product from ethylenediamine and propylene oxide, as well as long-chain tertiary amine oxides
• Suitable builders for the detergents according to the invention are weakly acidic, neutral or alkaline inorganic or organic salts, in particular inorganic or organic complexing agents.
• Useful, weakly acidic, neutral or alkaline-reacting salts are, for example, the bicarbonates, carbonates or silicates of the alkalis, and also mono-, di- or trialkali orthophosphates.
• water-soluble salts of benzene, toluene or xylene sulfonic acid water-soluble salts of sulfoacetic acid, sulfobenzoic acid or salts of sulfodicarboxylic acids as well as the salts of acetic acid, lactic acid, citric acid, tartaric acid, oxydiacetic acid (HOOC-CH 2 -0-CH 2 -COOH) , Oxydisuccinic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, polyacrylic acid and polymaleic acid.
• acetic acid lactic acid, citric acid, tartaric acid, oxydiacetic acid (HOOC-CH 2 -0-CH 2 -COOH)
• Oxydisuccinic acid 1,2,3,4-cyclopentanetetracarboxylic acid
• polyacrylic acid and polymaleic acid polymaleic acid.
• the weakly acidic metaphosphates and the alkaline polyphosphates, in particular tripolyphosphate, are also suitable as complex-forming framework substances. They can be replaced in whole or in part by organic complexing agents.
• Organic complexing agents include, for example, nitrilotriacetic acid, ethylenediaminetetra acetic acid, N-hydroxyethylethylenediamine triacetic acid, polyalkylene-polyamine-N-polycarboxylic acids and other known organic complexing agents, it also being possible to use combinations of different complexing agents.
• Detergent additives according to the invention include products such as the alkali or ammonium salts of sulfuric acid, silica, carbonic acid, boric acid, alkylene, hydroxyalkylene or aminoalkylenephosphonic acid, as well as bleaching agents, stabilizers for peroxide compounds (bleaching agents) and water-soluble organic complexing agents.
• the bleaching agents include sodium perborate mono- or tetrahydrate, the alkali salts of peroxomono- or peroxodisulfuric acid, the alkali salts of peroxodiphosphoric acid (Fi 4 P 2 0 8 ).
• water-soluble, precipitated magnesium silicate acts as a stabilizer for these bleaches.
• Organic complexing agents are the alkali salts of iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, methylenediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid and nitrilotrismethylenephosphonic acid.
• Washing aids that increase the dirt-carrying capacity of washing liquors, such as carboxymethyl cellulose, carboxymethyl starch, methyl cellulose or copolymers of maleic anhydride with methyl vinyl ether, foam regulators, such as mono- and dialkyl phosphoric acid esters with 16 to 20 carbon atoms in the alkyl radical, and optical brighteners, disinfectants and / or proteolytic enzymes additional components of the softening detergent.
• the product obtained is 952 g of an aqueous, viscous solution which, according to 31 P-NMR spectroscopy, is free of monomeric 1-phenyl-vinyl-1-phosphonic acid.
• Example 2 In an apparatus analogous to Example 1, 240 g (3.3 mol) of acrylic acid and 40.3 g (0.33 mol) of propene-2-phosphonic acid are boiled in 500 ml of water. The polymerization is started by adding 5 ml of 5% potassium peroxydisulfate solution as a radical initiator. After 15 min. 780 g of a viscous, colorless solution are obtained, the residual monomer content of propene-2-phosphonic acid being determined by 31 P-NMR spectroscopy. 90% of the phosphonic acid used is polymer-bound.
• the amount of complexing agent was determined in the form of the sodium salt present at pH 10, which is required to redissolve a given amount of freshly precipitated CaC0 3 precipitate.
• this method can also be used at elevated temperatures. If the solution remains clear at 60 ° C in the same proportions as at 20 ° C, the 20 ° C value also applies to the elevated temperature.
• the method has an error of the order of ⁇ 5% because the titration rate influences the titration result.
• the resulting Numerical values therefore only give an indication of the magnitude of the calcium binding capacity. In general, calcium binding capacity decreases with increasing temperature. The results are shown in Table I.
• the threshold effect can be made visible by scattered light measurement (TYNDALL effect).
• the assessment is based on the following grading scale
• EMPA cotton as in Example 6 was washed 25 times at 60 ° C and 18 ° d with a test detergent B of the following composition (dosage 160 g, only plain wash):
• the inorganic tissue incrustation was determined by ashing at 800 ° C. The experiment was repeated in the presence of 1.6% by weight of copolymer according to Example 2, based on the amount of detergent, whereby almost the same reduction in tissue incrustation was achieved as by adding 3.1% by weight of sodium nitrilotriacetate (NTA) (Table II).
• NTA sodium nitrilotriacetate
• test detergent B by adding 1.6% by weight of copolymer acrylic acid-1-phenylvinyl-1-phosphonic acid (ACS / PVP; molar ratio 10: 1) (Table II).

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)

Applications Claiming Priority (2)

Publications (1)

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ID=6236213

Family Applications (1)

Country Status (6)

Cited By (11)

Families Citing this family (2)

• 1984
  • 1984-05-18 DE DE19843418494 patent/DE3418494A1/de not_active Withdrawn
• 1985
  • 1985-05-04 EP EP85105456A patent/EP0161596A2/fr not_active Withdrawn
  • 1985-05-15 NO NO851975A patent/NO851975L/no unknown
  • 1985-05-15 DK DK217185A patent/DK217185A/da not_active Application Discontinuation
  • 1985-05-17 JP JP60104154A patent/JPS60255899A/ja active Pending
  • 1985-05-17 ES ES543261A patent/ES8607379A1/es not_active Expired

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