EP3047003B1 - Verwendung modifizierter polyasparaginsäuren in spülmitteln - Google Patents

Verwendung modifizierter polyasparaginsäuren in spülmitteln Download PDF

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Publication number
EP3047003B1
EP3047003B1 EP14758978.2A EP14758978A EP3047003B1 EP 3047003 B1 EP3047003 B1 EP 3047003B1 EP 14758978 A EP14758978 A EP 14758978A EP 3047003 B1 EP3047003 B1 EP 3047003B1
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EP
European Patent Office
Prior art keywords
acid
weight
mol
modified polyaspartic
aspartic acid
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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.)
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EP14758978.2A
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German (de)
English (en)
French (fr)
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EP3047003A1 (de
Inventor
Jürgen Detering
Gazi TÜRKOGLU
Dietrich Fehringer
Heike Weber
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BASF SE
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BASF SE
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Priority to PL14758978T priority Critical patent/PL3047003T3/pl
Priority to EP14758978.2A priority patent/EP3047003B1/de
Publication of EP3047003A1 publication Critical patent/EP3047003A1/de
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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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • 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
    • C11D1/66—Non-ionic 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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

Definitions

  • the present invention relates to the use of modified polyaspartic acids in dishwashing agents, in particular as dispersants, deposit inhibitors and spot inhibitors.
  • Polymers obtained by free radical polymerization and made from carboxyl group-containing monomers have been an important component of phosphate-containing and phosphate-free automatic dishwashing agents for many years. With their dirt-dispersing and deposit-inhibiting effect, they make a significant contribution to the cleaning and rinsing performance of automatic dishwashing detergents. In this way, they ensure that no salt deposits from the hardness-forming calcium and magnesium ions remain on the dishes. Homo- and copolymers of acrylic acid are frequently used for this purpose.
  • a disadvantage of these polymers obtainable by free radical polymerization from carboxyl group-containing monomers is that they under aerobic conditions, such as are e.g. prevail in a municipal sewage treatment plant, are not biodegradable.
  • the molecular weights range between 2000-3000 g / mol or between 5000-6000 g / mol, depending on the manufacturing process. An adaptation of the polymer structure or the molecular weight to specific application requirements through targeted process changes is not possible or only possible to a very limited extent.
  • the object of the invention was therefore to provide polymers as detergent additives, in particular as an additive to phosphate-free detergent formulations for machine dishwashing, which can be used to inhibit deposits in water-bearing systems, are variably adjustable in their polymer structure and molecular weight and are biodegradable.
  • the molecular weight of the polymers can ideally be set between 1,000 and 10,000 g / mol.
  • the polyaspartic acid is initially obtained in salt form after the hydrolysis step with addition of a base, as the person skilled in the art can easily recognize.
  • the acid form of polyaspartic acid can easily be obtained by a further step of acidifying the salt, which can be carried out in a manner known to the person skilled in the art. Suitable acids for this include mineral acids, for example sulfuric acid or hydrochloric acid. If only the salt of polyaspartic acid is desired, for example as an intermediate stage, the step of subsequent acidification can be dispensed with.
  • polyaspartic acid is mentioned in connection with the present invention, its corresponding salts are accordingly also encompassed, as they are obtainable or are obtained by the mentioned subsequent acidification step and as recognized by the person skilled in the art.
  • the optional acidification of the salt of the modified polyaspartic acid can take place, for example, by adding a defined amount of a concentrated or dilute mineral acid such as sulfuric acid or hydrochloric acid to an aqueous sodium salt solution of the modified polyaspartic acid.
  • the acidification can also be done by treatment with an acidic ion exchanger such as Amberlite IR 120 (hydrogen form), by allowing the aqueous Na salt solution of the modified polyaspartic acid to flow over a column packed with the ion exchanger.
  • the bases used in the hydrolysis of the cocondensates in the production of the modified polyaspartic acids to be used according to the invention include: alkali and alkaline earth metal bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide; Carbonates such as soda and potassium carbonate; Ammonia and primary, secondary or tertiary amines; other bases with primary, secondary or tertiary amino groups.
  • alkali and alkaline earth metal bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide
  • Carbonates such as soda and potassium carbonate
  • Ammonia and primary, secondary or tertiary amines other bases with primary, secondary or tertiary amino groups.
  • Sodium hydroxide solution or ammonium hydroxide are preferred in connection with the present invention.
  • the modified polyaspartic acids to be used according to the invention are generally prepared via a polycondensation of aspartic acid with at least one carboxyl-containing compound (not aspartic acid) and subsequent hydrolysis of the cocondensates with the addition of a base as shown and described here above and below.
  • the production of such modified polyaspartic acids is also in DE 4221875.6 described by way of example.
  • the preparation of the modified polyaspartic acids to be used according to the invention is described by way of example below. This description of the manufacture must not be understood as limiting with regard to the modified polyaspartic acids to be used according to the invention.
  • the polyaspartic acids to be used according to the invention include, in addition to those which are produced according to the following description of the production, also those which can be produced by the following process.
  • the modified polyaspartic acids to be used according to the invention can be prepared, for example, by polycondensation of components (i) and (ii), ie aspartic acid and at least one carboxyl-containing compound in the molar ratios as described here.
  • the polycondensation can take place at temperatures from 100 to 270.degree. C., preferably from 120 to 250.degree. C., particularly preferably from 180 to 220.degree.
  • the condensation (tempering) is preferably carried out in vacuo or under an inert gas atmosphere (eg N 2 or argon).
  • the condensation can also take place under increased pressure or in a gas stream, for example carbon dioxide, air, oxygen or water vapor.
  • the reaction times depend on the reaction conditions chosen for the condensation generally between 1 minute and 50 hours, preferably between 5 to 8 hours.
  • the polycondensation can, for example, be carried out in the solid phase by first preparing an aqueous solution or suspension of aspartic acid and at least one carboxyl-containing compound (ii) and evaporating the solution to dryness. Condensation can already set in here.
  • Suitable reaction apparatus for the condensation are, for example, heating bands, kneaders, mixers, paddle dryers, extruders, rotary kilns and other heatable devices in which the condensation of solids can be carried out with removal of the water of reaction.
  • Polycondensates with a low molecular weight can also be produced in pressure-tight sealed vessels by not removing or only partially removing the water of reaction. Polycondensation can also be carried out using infrared radiation or microwave radiation.
  • An acid-catalyzed polycondensation for example with inorganic acids of phosphorus or sulfur or with hydrogen halides, is also possible. Such acid-catalyzed polycondensations are also in DE 4221875.6 described.
  • the molecular weight of the polyaspartic acid, obtained after hydrolysis of the polysuccinimide intermediate, can be controlled. It is therefore possible in the context of the present invention to produce modified polyaspartic acid to be used according to the invention by using methanesulfonic acid as an additive in addition to aspartic acid (i) and a carboxyl-containing compound (ii) in the polycondensation and then using the cocondensate obtained with a base as described here is hydrolyzed.
  • the molar ratio of aspartic acid (i) and a carboxyl-containing compound (ii) on the one hand to methanesulfonic acid on the other in the condensation step should be 200: 1 to 5: 1, preferably 100: 1 to 10: 1, particularly preferably 50: 1 to 12: 1.
  • 50 to 99 mol%, preferably 60 to 95 mol%, particularly preferably 80 to 95 mol% aspartic acid and 1 to 50 mol%, preferably 5 to 40 mol%, are particularly preferred for preparing the modified polyaspartic acid to be used according to the invention
  • 5 to 20 mol% of a carboxyl-containing compound is polycondensed with methanesulfonic acid in a ratio of 200: 1 to 5: 1, preferably 100: 1 to 10: 1, particularly preferably 50: 1 to 12: 1, as described here.
  • methanesulfonic acid is biodegradable.
  • the polycondensate is generally obtained in the form of the water-insoluble modified polyaspartimides, in a few cases in water-soluble form (e.g. in the polycondensation of L- Aspartic acid with citric acid).
  • the cocondensates of aspartic acid can be purified from the unreacted starting materials, for example, by adding the condensation product crushed and extracted with water at temperatures of 10 to 100 ° C. In the process, the unreacted starting materials are released and any methanesulfonic acid used is washed out. Unreacted aspartic acid can easily be removed by extraction with 1N hydrochloric acid.
  • Ammonia and primary, secondary or tertiary amines and other bases with primary, secondary or tertiary amino groups are also suitable as bases.
  • the amines can be bound to the polyaspartic acid in a salt-like or amide-like manner due to their high reactivity.
  • the treatment with bases gives partially or completely neutralized polycocondensates which, according to the use in the previous polycondensation, contain 50 to 99 mol% of aspartic acid according to (i) and 1 to 50 mol% of at least one carboxyl group-containing compound (ii) (with or without methanesulfonic acid in proportions as described here), in the form of the salts corresponding to the bases.
  • the modified polyaspartic acids to be used according to the invention or their salts can be used as an aqueous solution or in solid form, e.g. be used in powder or granular form.
  • the powder or granulate form can be obtained, for example, by spray drying, spray granulation, fluidized bed spray granulation, roller drying or freeze drying of the aqueous solution of polyaspartic acids or their salts.
  • the present invention also relates to detergent compositions, in particular detergent compositions suitable for automatic dishwashing, which, in addition to the modified polyaspartic acids described here and to be used according to the invention, also complexing agents, builders and / or co-builders, nonionic surfactants, bleaching agents and / or bleach activators, enzymes and possibly other additives such as solvents.
  • the modified polyaspartic acids described here and to be used according to the invention can be incorporated directly into the formulations (mixtures) in their various dosage forms by methods known to the person skilled in the art. Solid formulations such as powders, tablets, gel-like formulations and liquid formulations should be mentioned here.
  • the modified polyaspartic acids described here and to be used according to the invention can be used particularly advantageously in dishwasher detergents.
  • the detergent compositions according to the invention can be provided in liquid, gel-like or solid form, in one or more phases, as tablets or in the form of other dosage units, packaged or unpackaged.
  • modified polyaspartic acids described here and to be used according to the invention can be used both in multi-component product systems (separate use of detergent, rinse aid and regeneration substitute) and in detergents in which the functions of detergent, rinse aid and regeneration salt are combined in one product (e.g. 3- in-1 products, 6-in-1 products, 9-in-1 products, all-in-one products).
  • the detergent composition according to the invention is particularly suitable as a detergent composition for automatic dishwashing.
  • the dishwashing detergent composition according to the invention is therefore an automatic dishwashing detergent composition.
  • complexing agents (b) for example: nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, methylglycinediacetic acid, glutamic acid diacetic acid, iminodisuccinic acid, hydroxyiminodisuccinic acid, as well as their respective ethylenediamine diacetic acid.
  • Preferred complexing agents (b) are methylglycine diacetic acid and glutamic acid diacetic acid and their salts.
  • Particularly preferred complexing agents (b) are methylglycine diacetic acid and its salts. According to the invention, preference is given to 3 to 50% by weight of complexing agents (b).
  • water-soluble or water-insoluble substances can be used as builders and / or co-builders (c).
  • These can be low molecular weight carboxylic acids as well as their salts such as alkali citrates, in particular anhydrous trisodium citrate or trisodium citrate dihydrate, alkali succinates, alkali alonates, fatty acid sulfonates, oxydisuccinates, alkyl or alkenyl disuccinates, gluconic acids, tiacoacinate succinate, tiacoacinate, tiacoacinate, tiacoacinacetate, tiacoacinacetate, tiacoacinacetate, tiacinoacetate, tiacoylacetate, tiacinoacetate, tiacinate succinate, carboxymethyloyl acetate, carboxymethosuccinate, tiacinate succinate, tiacino
  • Bleach activators from the group consisting of multiply acylated alkylenediamines, particularly preferably TAED, N-acylimides, particularly preferably NOSI, acylated phenol sulfonates, particularly preferably n- or iso-NOBS, MMA, and TMAQ, are particularly suitable.
  • Bleach activators can be used in connection with the present invention in amounts of 0.1 to 30% by weight, preferably from 0.1 to 10% by weight, preferably from 1 to 9% by weight, particularly preferably from 1.5 to 8% by weight, based on the entire detergent composition can be used.
  • so-called bleach catalysts can also be incorporated into rinse aid particles.
  • Polymer 5b according to the invention This polymer was synthesized and worked up exactly as described in polymer 5, except that 4.81 g of methanesulfonic acid were also placed in the reactor.
  • the weight average molecular weight (Mw) of the modified polyaspartic acid was 6100 g / mol.
  • Polymer V1 (polyaspartic acid M):
  • Polymer V2 (polyaspartic acid T):

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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)
EP14758978.2A 2013-09-16 2014-09-05 Verwendung modifizierter polyasparaginsäuren in spülmitteln Active EP3047003B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL14758978T PL3047003T3 (pl) 2013-09-16 2014-09-05 Zastosowanie zmodyfikowanych kwasów poliasparaginowych w środkach do zmywania
EP14758978.2A EP3047003B1 (de) 2013-09-16 2014-09-05 Verwendung modifizierter polyasparaginsäuren in spülmitteln

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP13184570 2013-09-16
EP14758978.2A EP3047003B1 (de) 2013-09-16 2014-09-05 Verwendung modifizierter polyasparaginsäuren in spülmitteln
PCT/EP2014/068924 WO2015036325A1 (de) 2013-09-16 2014-09-05 Verwendung modifizierter polyasparaginsäuren in spülmitteln

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Publication Number Publication Date
EP3047003A1 EP3047003A1 (de) 2016-07-27
EP3047003B1 true EP3047003B1 (de) 2020-11-11

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US (1) US9796951B2 (ru)
EP (1) EP3047003B1 (ru)
JP (1) JP2016536430A (ru)
KR (1) KR20160055917A (ru)
CN (1) CN105555931B (ru)
CA (1) CA2923744A1 (ru)
ES (1) ES2851207T3 (ru)
MX (1) MX2016003438A (ru)
PL (1) PL3047003T3 (ru)
RU (1) RU2665581C2 (ru)
WO (1) WO2015036325A1 (ru)

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WO2023114942A1 (en) 2021-12-16 2023-06-22 Nutrition & Biosciences USA 4, Inc. Compositions comprising cationic alpha-glucan ethers in aqueous polar organic solvents
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Also Published As

Publication number Publication date
EP3047003A1 (de) 2016-07-27
CN105555931A (zh) 2016-05-04
RU2016114687A (ru) 2017-10-23
RU2016114687A3 (ru) 2018-03-22
RU2665581C2 (ru) 2018-08-31
CA2923744A1 (en) 2015-03-19
US20160222322A1 (en) 2016-08-04
CN105555931B (zh) 2018-11-16
JP2016536430A (ja) 2016-11-24
MX2016003438A (es) 2016-07-21
US9796951B2 (en) 2017-10-24
WO2015036325A1 (de) 2015-03-19
ES2851207T3 (es) 2021-09-03
KR20160055917A (ko) 2016-05-18
PL3047003T3 (pl) 2021-05-04

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