EP2657329B1 - Sequestriermittel zur Verwendung in Waschmitteln mit hoher Kalkbindungsfähigkeit - Google Patents

Sequestriermittel zur Verwendung in Waschmitteln mit hoher Kalkbindungsfähigkeit Download PDF

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Publication number
EP2657329B1
EP2657329B1 EP13164735.6A EP13164735A EP2657329B1 EP 2657329 B1 EP2657329 B1 EP 2657329B1 EP 13164735 A EP13164735 A EP 13164735A EP 2657329 B1 EP2657329 B1 EP 2657329B1
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Prior art keywords
terpolymer
acid
detergents
weight
sequestering agent
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English (en)
French (fr)
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EP2657329A1 (de
Inventor
Selahattin Serin
Hayrettin Avci
Ozgur Polat
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Viking Temizlik Ve Kozmetik Ueruenleri Pazarlama Sanayi Ticaret Anomim Sirketi
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Viking Temizlik Ve Kozmetik Ueruenleri Pazarlama Sanayi Ticaret Anomim Sirketi
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    • 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
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • 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
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate

Definitions

  • the present invention relates to polycarboxylate syntheses that are not harmful to the environment and comprising substituted groups such as sulfonate.
  • the present invention comprises terpolymers obtained from acrylic acid, maleic acid and sodium vinyl sulfonate and used in the production of cleaning products.
  • Detergents are chemicals having cleaning feature. Said products can be in the form of powder, liquid or cream. Many different chemicals are used in detergent manufacturing. Sequestering (chelating) agents are one of the most important chemicals used in the production of detergents. Following are used as the sequestering agents in powder detergents, liquid detergents and shampoos, respectively: Na 5 P 3 O 10 (sodium tripolyphosphate, STPP); K 5 P 3 O 10 (potassium tripolyphosphate, KTPP) and the carboxylates; and Na 4 -EDTA. In recent years, polycarboxylates are improved and started to be used in the detergent and textile industry. Polycarboxylates have superior properties compared to the known sequestering agents.
  • terpolymers are synthesized using acrylic acid, maleic acid and sodium vinyl sulfonate. When calcium binding capacity of these polymers is measured, better results as compared to the other sequestering agents available in the market are obtained.
  • Patent numbered US 3,635,915 describes polymerization of acrylic acid and maleic acid and investigation of utilization characteristics thereof as surface coating.
  • Patent numbered US 3,624,048 relates to the use of sulfonated polymaleic anhydride in detergents. Said invention describes various experiments being conducted in order to obtain sulfonated polymaleic anhydride in the presence of tetrachlorethylene by means of passing SO 3 gas.
  • Patent numbered US 3,903,039 relates to synthesis of terpolymers comprising sulfonate groups and utilization areas of said terpolymers.
  • isobutylene-cyclopentadiene copolymer is sulfonated in dioxane/SO 3 using pure hexane.
  • Patent numbered US 4,450,261 relates to low molecular weight styrene-maleic anhydride copolymers and sulfonated structures thereof.
  • the styrene-maleic anhydride copolymers obtained by said invention are synthesized using a variety of mercaptan chain transfer agents and the resulting copolymers are investigated.
  • Patent numbered US 4,709,091 relates to the production of polymaleic acid polymer. Synthesis of maleic acid copolymers with peroxide catalyst upon conducting neutralization thereof with alkali metal hydroxide or ammonia is investigated.
  • Patent numbered AU7778187 discloses styrene sulfonate/methyl styrene copolymer synthesis in styrene.
  • Patent numbered WO 91/17189 discloses calcium binding capacity of the polycarboxy compounds based on polysaccharide compounds and studies carried out on the usability thereof instead of phosphate in detergents.
  • Patent numbered US 5,135,677 relates to utilization of maleic acid polymers as water conditioners and detergent additives.
  • synthesis of polymaleic acid and maleic acid copolymers and role thereof in water conditioning are investigated.
  • Patent numbered US 2002/0035224 A1 relates to manufacturing and utilization methods of copolymers of acrylic-maleic acid (or salts thereof).
  • polymerization of maleic anhydride in the presence of acrylic acid and hydrogen peroxide catalyst and comparison of factors such as different pH and molecular weight are investigated.
  • Patent numbered US 2004/0014623 A1 discloses effects of polycarboxylic acid sequestering agents on different pH values. In addition, experiments are carried out in different types of detergent formulations.
  • Patent numbered WO 2005/090540 relates to synthesis of sulfonate/carboxylate polymers and the use of said polymers in the detergent formulations.
  • acrylic acid, styrene, sodium methallyl sulfonate and sodium phenyl methallyl ether compounds are used together for synthesis of said polymers.
  • Patent numbered WO 2011/061655 A2 discloses the matrix of the conversion of the sulfonate/carboxylate polymers into the solid state with sodium carbonate.
  • Patent numbered WO2008/017620 discloses a cleaning formulation for machine dishwashing, comprising 1 to 50 % by weight of one or more complexing agents from the group consisting of nitrilotriacetic acid, ethylenediaminetetraacetic acid, glycine-N,N-diacetic acid, glutamic acid-N,N-diacetic acid, minodisuccinate, hydroxyiminodisuccinate, S,S-ethylenediamine-disuccinate aspartic acid-diacetic acid, and the salts thereof; 1 to 15 % by weight nonionic surfectants; 0 to 30 % by weight of bleaches and optionally bleach activators: and 0 to 60 % by weight of one or more further additives, such as anionic or zwitterionic surfactants, bleach catalysts, alkali carriers, corrosion inhibitors, antifoams, dyes, fragrances, fillers, organic solvents and water.
  • the time needed for polymerization reactions are very
  • Another patent numbered WO2009/123322 relates to an automatic dishwashing composition
  • a builder and a water-soluble copolymer which comprises from about 30 to 60 mol% of the copolymer having a structural unit originating from a monoethylenic unsaturated dicarboxylic acid (or dicarboxylate) monomer having 4 to 6 carbon atoms or its anhydride at; from about 30 to 60 mol% of the copolymer having a structural unit originating from a monoethylenic unsaturated monocarboxylic acid (or monocarboxylate) monomer having 3 to 8 carbon atoms; and from about 5 to 15 mol% of the polymer having a structural unit originating from a monoethylenic unsaturated monomer having a sulfonic (or sulfonate) group; wherein the water-soluble copolymer has a weight average molecular weight of from about 1,000 to about 50,000 wherein the copolymer is polymerized with hydrogen peroxid
  • sequestering agents Na 5 P 3 O 10 (STPP), Na 4 -EDTA (sodium salt of ethylenediaminetetraacetic acid), citric acid, phosphonate (for example, DTPA: Diethylenetriaminepentaacetic acid) and polycarboxylates. Substances other than polycarboxylates pose a risk to the environment. Therefore, restrictions are brought on the use of sequestering agents.
  • the polycarboxylates available on the market are in the form of acrylic acid homopolymer (PA) and acrylic acid/maleic acid copolymer (PMA).
  • PA acrylic acid homopolymer
  • PMA acrylic acid/maleic acid copolymer
  • terpolymers containing sulfonate groups are also synthesized. Sulfonate groups are present in the terpolymer structures formed by using styrene sulfonic acid monomers.
  • sulfonate groups obtained in solvent medium by passing SO 3 gas are added to the structures (Patent numbered US 3,624,048 ).
  • solvents in industrial applications poses risks.
  • styrene sulfonic acid in synthesized terpolymers is environmentally risky.
  • Benzene ring is present in the styrene sulfonic acid structure.
  • Benzene is a biologically toxic compound. Therefore, the presence thereof in the biodegradation products is an undesired situation.
  • the present invention is developed by being inspired from existing situations and seeks to solve the above mentioned drawbacks.
  • the primary object of the present invention is to synthesize a polymer that can be used instead of sequestering agents in the production of cleaning products.
  • the present invention aims to obtain a sequestering agent that is not environmentally hazardous.
  • An object of the present invention is to obtain polymer structures having calcium binding capacity higher than that of the existing sequestering agents.
  • the present invention also aims to synthesize terpolymers using acrylic acid, maleic acid and sodium vinyl sulfonate.
  • Another object of the present invention is to synthesize polymers, biodegradation products of which are not toxic.
  • Another object of the present invention is to reduce the damage of the cleaning products to the environment.
  • Another object of the present invention is to increase the number of alternative substances that can be used instead of sequestering agents in the production of detergents.
  • Another object of the present invention is to produce cleaning products that are more environmentally friendly.
  • the present invention in order to fulfill the objects mentioned above, relates to a sequestering agent used in the production of cleaning products, wherein it comprises maleic acid/acrylic acid/sodium vinyl sulfonate terpolymer.
  • the present invention in order to fulfill the objects mentioned above, relates to a sequestering agent obtaining method, wherein said terpolymer is obtained by the reaction of %5-30% by weight of maleic acid, %1-7% by weight of sodium vinyl sulfonate, and 30%-80% by weight of acrylic acid in the presence of 0.05%-5% by weight of a ammonium peroxydisulfate and 0.01%-2% by weight of an sodium bisulfite.
  • the present invention comprises terpolymers obtained from acrylic acid, maleic acid, sodium vinyl sulfonate and used in the production of cleaning products.
  • said terpolymers can be used as sequestering agents in the production of detergents.
  • calcium binding properties of the synthesized polymer structures and usability thereof in the liquid and powder detergent products in comparison with the known sequestering agents are investigated.
  • spray mixing process is used for investigation of the suitability of said polymer structures for powder detergents.
  • a laboratory scale reactor is designed and powder detergent production and appropriate utilization conditions of the investigated sequestering agents are determined in said reactor. Production trials and characteristics of the produced detergents are investigated.
  • Acrylic acid (C 3 H 4 O 2 )/maleic acid (C 4 H 4 O 4 )/sodium vinyl sulfonate (C 2 H 3 NaO 3 S) terpolymer is synthesized at a temperature of 90-95 °C by using an inhibitor and a peroxide based catalyst during the reaction time required for polymerization (1-3 hours).
  • Ammonium peroxydisulfate ((NH 4 ) 2 S 2 O 8 ) is used as the peroxide based catalyst and sodium bisulfite (NaHSO 3 ) is used as the inhibitor.
  • pH values of the Terpolymer 2 and Terpolymer 3 structures given above in Table 1 range between 1.5-2; pH value of the Terpolymer 1 ranges between 8.0-8.5. Solid materials present in the structures of said terpolymers (1, 2, 3) are in the range of 30%-40%.
  • Maleic acid/acrylic acid/sodium vinyl sulfonate terpolymers are polycarboxylates not posing an environmental risk and comprising substituted sulfonate groups (SO 3 ).
  • the main role of the polycarboxylates in the cleaning products is that they inhibit Ca 2+ , Mg 2+ , Fe 3+ , Cu 2+ and Zn 2+ ions. Inhibition is taking place by keeping and dispersing these ions in the cage. Calcium binding capacity of the polycarboxylates is higher than the other sequestering agents.
  • terpolymers according to the present invention can be used instead of the existing sequestering agents.
  • the calcium binding capacities of said terpolymers are compared with the existing sequestering agents, better results are obtained.
  • Calcium binding capacities of said polymer structures are calculated by complexometric titration. Using said titration method, iron and magnesium ion binding capacities of the terpolymer according to the present invention are measured. The measured values are given below in Table 3.
  • Table 3 Ca, Mg and Fe ion Binding Capacity of the Maleic Acid/Acrylic Acid/Sodium Vinyl Sulfonate Terpolymer Maleic Acid, Acrylic Acid, Sodium Vinyl Sulfonate Terpolymer (Terpolymer 2) Ca (mg/g, 20°C) Mg (mg/g, 20°C) Fe (mg/g, 20°C ) 257 152 116
  • Molecular weight and distribution of a polymer are very important in terms of material properties. Typically, as the molecular weight of the structure increases, the complexity and intermolecular attractive forces of the structure increase. This means a shift in many properties of the polymer. For the polymers, average molecular weight is used instead of molecular weight due to the fact that the polymers are composed of polymer chains of different lengths.
  • the molecular weights of the synthesized terpolymers according to the present invention are measured by Shimadzu brand GPC. The average molecular weights thereof range from 14000 to 16000 g/mol. The measured values are given below in Table 4.
  • Table 4 Average molecular weights of the synthesized terpolymers Substance Terpolymer 1 Terpolymer 2 Terpolymer 3 Average Molecular Weight (g/mol) 15473 14 613 14 822
  • the terpolymer according to the present invention has a maleic acid/acrylic acid/sodium vinyl sulfonate structure. In addition, it is a compound being soluble in water and having a high calcium binding capacity. Thus, detergents having a better calcium binding capacity are obtained.
  • maleic acid/acrylic acid/sodium vinyl sulfonate terpolymer not posing a risk in terms of international use and environment and comprising substituted sulfonate groups (SO 3 ) is synthesized.
  • Biodegradation products of the synthesized terpolymer are not toxic.
  • Calcium binding capacities of said water soluble polymer structures are high.

Claims (6)

  1. Verfahren zum Erlangen eines Sequestriermittels, dadurch gekennzeichnet, dass ein Terpolymer durch die Reaktion von 5-30 Gew.-% Maleinsäure, 1-7 Gew.-% Natriumvinylsulfonat und 30-80 Gew.-% Acrylsäure in der Anwesenheit von 0,05-5 Gew.-% Ammoniumperoxodisulfat und 0,01-2 Gew.-% Natriumbisulfit erlangt wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Reaktion bei einer Temperatur von 90-95 °C durchgeführt wird.
  3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass eine Durchführungsdauer der Reaktionszeit zwischen 1 und 3 Stunden ist.
  4. Sequestriermittel, das durch das Verfahren in Anspruch 1 erlangt werden kann.
  5. Sequestriermittel nach Anspruch 4, wobei Feststoffmaterialien im Terpolymer im Bereich von 30-40 % sind.
  6. Verwendung des Terpolymers nach Anspruch 4 in der Herstellung von Reinigungsprodukten als Sequestriermittel.
EP13164735.6A 2012-04-26 2013-04-22 Sequestriermittel zur Verwendung in Waschmitteln mit hoher Kalkbindungsfähigkeit Active EP2657329B1 (de)

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TR201204884 2012-04-26

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EP2657329B1 true EP2657329B1 (de) 2017-10-18

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Publication number Priority date Publication date Assignee Title
US10253280B2 (en) 2014-10-09 2019-04-09 Rohn And Haas Company Additive for reducing spotting in automatic dishwashing systems
US10144906B2 (en) 2014-10-09 2018-12-04 Rohm And Haas Company Additive for reducing spotting in automatic dishwashing systems

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US3635915A (en) 1969-11-28 1972-01-18 Deering Milliken Res Corp Copolymers of maleic acid and acrylic acid
US3624048A (en) 1970-05-18 1971-11-30 Fmc Corp Poly(maleic acid) sulfonates and their production
US3903039A (en) 1973-10-11 1975-09-02 Exxon Research Engineering Co Sulfonated terpolymers and uses thereof
DE3320864A1 (de) * 1983-06-09 1984-12-13 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von pulverfoermigen polymerisaten und deren verwendung
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