EP2657329A1 - Sequestriermittel zur Verwendung in Waschmitteln mit hoher Kalkbindungsfähigkeit - Google Patents
Sequestriermittel zur Verwendung in Waschmitteln mit hoher Kalkbindungsfähigkeit Download PDFInfo
- Publication number
- EP2657329A1 EP2657329A1 EP13164735.6A EP13164735A EP2657329A1 EP 2657329 A1 EP2657329 A1 EP 2657329A1 EP 13164735 A EP13164735 A EP 13164735A EP 2657329 A1 EP2657329 A1 EP 2657329A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- terpolymer
- acid
- acrylic acid
- detergents
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003352 sequestering agent Substances 0.000 title claims abstract description 27
- 239000003599 detergent Substances 0.000 title description 26
- 102000005701 Calcium-Binding Proteins Human genes 0.000 title description 14
- 108010045403 Calcium-Binding Proteins Proteins 0.000 title description 14
- 229920001897 terpolymer Polymers 0.000 claims abstract description 57
- 239000011976 maleic acid Substances 0.000 claims abstract description 27
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 27
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 26
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 26
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 23
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 7
- 150000002978 peroxides Chemical class 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical group [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 26
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 abstract description 14
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229920005646 polycarboxylate Polymers 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 235000019832 sodium triphosphate Nutrition 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- -1 acrylic acid-sodium vinyl sulfonate-vinyl acetate Chemical compound 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000006065 biodegradation reaction Methods 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920000141 poly(maleic anhydride) Polymers 0.000 description 2
- 229920001444 polymaleic acid Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- ZVXSESPJMKNIQA-YXMSTPNBSA-N Lys-Thr-Pro-Pro Chemical compound NCCCC[C@H](N)C(=O)N[C@@H]([C@H](O)C)C(=O)N1CCC[C@H]1C(=O)N1[C@H](C(O)=O)CCC1 ZVXSESPJMKNIQA-YXMSTPNBSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000003926 complexometric titration Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000001177 diphosphate Substances 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Images
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
- C11D3/3757—(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. In said invention, 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). In said invention, 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.
- 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 peroxide based catalyst and 0.01 %-2% by weight of an inhibitor.
- 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.
- 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) 15 473 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.
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Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TR201204884 | 2012-04-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2657329A1 true EP2657329A1 (de) | 2013-10-30 |
| EP2657329B1 EP2657329B1 (de) | 2017-10-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| EP13164735.6A Active EP2657329B1 (de) | 2012-04-26 | 2013-04-22 | Sequestriermittel zur Verwendung in Waschmitteln mit hoher Kalkbindungsfähigkeit |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10144906B2 (en) | 2014-10-09 | 2018-12-04 | Rohm And Haas Company | Additive for reducing spotting in automatic dishwashing systems |
| US10253280B2 (en) | 2014-10-09 | 2019-04-09 | Rohn And Haas Company | Additive for reducing spotting in automatic dishwashing systems |
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| US3903039A (en) | 1973-10-11 | 1975-09-02 | Exxon Research Engineering Co | Sulfonated terpolymers and uses thereof |
| US4450261A (en) | 1983-02-22 | 1984-05-22 | National Starch And Chemical Corporation | Preparation of low molecular weight styrene-maleic anhydride copolymers and sulfonated copolymers 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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| AU7778187A (en) | 1986-09-02 | 1988-03-10 | Exxon Research And Engineering Company | Low and high temperature drilling fluids based on sulfonated terpolymer ionomers |
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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 |
| US4450261A (en) | 1983-02-22 | 1984-05-22 | National Starch And Chemical Corporation | Preparation of low molecular weight styrene-maleic anhydride copolymers and sulfonated copolymers thereof |
| DE3320864A1 (de) * | 1983-06-09 | 1984-12-13 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von pulverfoermigen polymerisaten und deren verwendung |
| US4640211A (en) | 1984-03-20 | 1987-02-03 | Schutz-Werke Gmbh & Co. Kg | Adjustment fixture for wishbone booms board-sailing devices |
| US4709091A (en) | 1984-04-06 | 1987-11-24 | Kao Corporation | Production of polymaleic acid |
| AU7778187A (en) | 1986-09-02 | 1988-03-10 | Exxon Research And Engineering Company | Low and high temperature drilling fluids based on sulfonated terpolymer ionomers |
| US5135677A (en) | 1988-04-11 | 1992-08-04 | Nippon Shokubai Co., Ltd. | Process for producing acid-type maleic acid polymer and water-treating agent and detergent additive containing said polymer |
| WO1991017189A1 (en) | 1990-04-27 | 1991-11-14 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Method for preparation of calcium-binding polycarboxy compounds based on polysaccharides, and replacements for phosphates in detergents, based on these polycarboxy compounds |
| WO1994001477A1 (de) * | 1992-07-03 | 1994-01-20 | Chemische Fabrik Stockhausen Gmbh | Copolymere der allyliminodiessigsäure mit ungesättigten carbonsäuren und deren verwendung als komplexbildner, peroxidstabilisatoren, builder in wasch- und reinigungsmitteln und dispergatoren |
| WO1996035728A1 (de) * | 1995-05-12 | 1996-11-14 | Stockhausen Gmbh & Co. Kg | Wasserlösliche copolymere und verfahren zu ihrer herstellung und ihre verwendung |
| EP0985690A2 (de) * | 1998-09-08 | 2000-03-15 | Nippon Shokubai Co., Ltd. | Acrylsäure-Maleinsäure Copolymer (oder seine Salze), Herstellungsverfahren und Verwendung und Verfahren zur Herstellung einer wässrigen Lösung eines Salzes von Maleinsäure mit niedrigem Verunreinigungsgehalt |
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| WO2005000020A2 (en) | 2003-06-23 | 2005-01-06 | Cognis Ip Management Gmbh | Alcohol alkoxylate carriers for pesticide active ingredients |
| WO2008017620A1 (de) * | 2006-08-10 | 2008-02-14 | Basf Se | Reinigungsformulierung für geschirrspülmaschinen |
| WO2009123322A1 (en) * | 2008-03-31 | 2009-10-08 | Nippon Shokubai Co., Ltd. | Automatic dishwashing composition containing a sulfonated copolymer |
| WO2011000020A1 (en) | 2009-06-12 | 2011-01-06 | Sbc Research Pty Ltd | Enhanced method of detection |
| WO2011061655A2 (en) * | 2009-11-23 | 2011-05-26 | Ecolab Inc. | Solidification matrix using a sulfonated/carboxylated polymer binding agent |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10144906B2 (en) | 2014-10-09 | 2018-12-04 | Rohm And Haas Company | Additive for reducing spotting in automatic dishwashing systems |
| US10253280B2 (en) | 2014-10-09 | 2019-04-09 | Rohn And Haas Company | Additive for reducing spotting in automatic dishwashing systems |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2657329B1 (de) | 2017-10-18 |
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