DE4106355A1 - Poly-glyoxylate prepn. by polymerisation of 1-4 carbon alkyl ester(s) of glyoxylic acid - in presence of phosphorus pent:oxide, used as builders in detergents - Google Patents
Poly-glyoxylate prepn. by polymerisation of 1-4 carbon alkyl ester(s) of glyoxylic acid - in presence of phosphorus pent:oxide, used as builders in detergentsInfo
- Publication number
- DE4106355A1 DE4106355A1 DE19914106355 DE4106355A DE4106355A1 DE 4106355 A1 DE4106355 A1 DE 4106355A1 DE 19914106355 DE19914106355 DE 19914106355 DE 4106355 A DE4106355 A DE 4106355A DE 4106355 A1 DE4106355 A1 DE 4106355A1
- Authority
- DE
- Germany
- Prior art keywords
- formula
- polymerisation
- detergents
- alkyl
- prepn
- 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.)
- Withdrawn
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/06—Catalysts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/14—Polymerisation of single aldehydes not provided for in groups C08G2/08 - C08G2/12
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Polyglyoxylaten, die als charakteristische Strukturelemente Einheiten der FormelThe invention relates to a process for the preparation of polyglyoxylates, the units of the formula as characteristic structural elements
in der M=C₁- bis C₄-Alkyl, Alkalimetall-, Ammonium- und Alkanolamingruppen bedeutet, einpolymerisiert enthalten, durch Polymerisieren von Glyoxylaten der Formelin the M = C₁ to C₄ alkyl, alkali metal, ammonium and alkanolamine groups means contained in polymerized form by polymerizing Glyoxylates of the formula
in der M=C₁- bis C₄-Alkyl ist, in Gegenwart von Initiatoren und gegebenenfalls Hydrolysieren der Polyglyoxylsäureester mit Alkalimetallhydroxiden, Ammoniak oder Alkanolaminen.in which M = C₁ to C₄ alkyl, in the presence of initiators and optionally Hydrolyzing the polyglyoxylic acid esters with alkali metal hydroxides, Ammonia or alkanolamines.
Aus der JP-B-73/0 00 877 ist die Herstellung von Polyformaldehyd durch Polymerisieren von cyclischen Formaldehydoligomeren, wie Trioxan oder Tetraoxymethylen, unter Verwendung von Phosphorpentoxid in halogenierten oder nitrierten Kohlenwasserstoffen bekannt. Phosphorpentoxid wird in Mengen von 0,0001 bis 1 Gew.-%, bezogen auf das zu polymerisierende Formaldehydoligomere eingesetzt. Als inertes Verdünnungsmittel werden beispielsweise Di- und Trichlorethan, Nitroethan, Nitromethan oder Nitrobenzol in Mengen von 0,3 bis 20 Teilen pro Teil Formaldehydoligomer eingesetzt.From JP-B-73/0 00 877 is the production of polyformaldehyde Polymerization of cyclic formaldehyde oligomers, such as trioxane or Tetraoxymethylene, using phosphorus pentoxide in halogenated or nitrated hydrocarbons known. Phosphorus pentoxide is in Amounts from 0.0001 to 1 wt .-%, based on the formaldehyde oligomer to be polymerized used. As an inert diluent, for example Di- and trichloroethane, nitroethane, nitromethane or nitrobenzene in amounts of 0.3 to 20 parts per part of formaldehyde oligomer used.
Aus der EP-B 00 01 004 sind polymere Acetalcarboxylate bekannt, die durch Polymerisieren von Glyoxylsäureestern in Gegenwart von Initiatoren erhältlich sind. Diese Polymerisate enthalten als charakteristisches Merkmal mindestens 4 Einheiten der FormelFrom EP-B 00 01 004 polymeric acetal carboxylates are known which pass through Polymerization of glyoxylic acid esters in the presence of initiators are available. These polymers contain as a characteristic Characteristic at least 4 units of the formula
wobei M für Alkalimetall, Ammonium, C₁- bis C₄-Alkyl und Alkanolamingruppen steht. Die Herstellung der Polymeren ist jedoch aufwendig, weil man die Monomeren, d. h. die Formylester, zunächst durch Erhitzen der Halbacetalester von Glyoxylsäure in Gegenwart von Phosphorpentoxid herstellen und reinigen muß. Die gereinigten Aldehydester werden dann mit geeigneten Initiatoren polymerisiert, beispielsweise mit Bortrifluorid, Phosphorpentafluorid, Zinnchlorid, Aminen, Hydroxyl- und Cyanidionen oder mit Diethylnatriummalonat. Die so erhältlichen Polyglyoxylsäureester werden mit Alkalimetallbasen oder Ammoniak verseift. Man erhält dabei die entsprechenden Salze von Polyglyoxylsäuren. Diese Salze werden als biologisch abbaubare Zusätze für Waschmittel verwendet.where M is alkali metal, ammonium, C₁ to C₄ alkyl and alkanolamine groups stands. However, the preparation of the polymers is complex because the monomers, d. H. the formyl esters, first by heating the Semi-acetal ester of glyoxylic acid in the presence of phosphorus pentoxide must manufacture and clean. The cleaned aldehyde esters are then with suitable initiators polymerized, for example with boron trifluoride, Phosphorus pentafluoride, tin chloride, amines, hydroxyl and cyanide ions or with diethyl sodium malonate. The polyglyoxylic acid esters obtainable in this way are saponified with alkali metal bases or ammonia. You get the corresponding salts of polyglyoxylic acids. These salts are considered organic degradable additives used for detergents.
Die US-PS 42 33 423 betrifft die Stabilisierung eines Polyacetalcarboxylats in Gegenwart eines Säurekatalysators mit genügender Menge eines Acetals, das 3 bis 20 C-Atome besitzt. Der entstehende Alkohol wird durch den Zusatz von Molekularsieben oder von Phosphorpentoxid gebunden.The US-PS 42 33 423 relates to the stabilization of a polyacetal carboxylate in the presence of an acid catalyst with a sufficient amount of one Acetals, which has 3 to 20 carbon atoms. The alcohol produced is through the addition of molecular sieves or of phosphorus pentoxide.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung von Polyglyoxylaten durch Polymerisieren von Glyoxylsäureestern in Gegenwart von Initiatoren zur Verfügung zu stellen, bei dem direkt stabile Polyglyoxylate anfallen.The present invention has for its object a method for Production of polyglyoxylates by polymerizing glyoxylic acid esters in the presence of initiators, at which directly stable polyglyoxylates are obtained.
Die Aufgabe wird bei dem eingangs beschriebenen Verfahren dadurch gelöst, daß man als Polymerisationsinitiator Phosphorpentoxid einsetzt. Das Phosphorpentoxid wird in Mengen von 0,001 bis 15 Gew.-%, bezogen auf die Glyoxylate der Formel II angewendet. Die Polymerisation kann in Gegenwart oder auch in Abwesenheit von inerten Lösemitteln durchgeführt werden. Sofern man in einem inerten Lösemittel polymerisiert, betragen die Monomerkonzentrationen 1 bis 99%, vorzugsweise 5 bis 95 Gew.-%. Als inerte Lösemittel eignen sich Ether, Nitrile und/oder Chlorkohlenwasserstoffe. Besonders bevorzugt werden Dichlormethan, Tetrahydrofuran oder Acetonitril. Beim Polymerisieren in Dichlormethan liegen die Monomerkonzentrationen vorzugsweise bei 70 bis 90 Gew.-%, während sie in Tetrahydrofuran vorzugsweise 5 bis 50 Gew.-% betragen.The object is achieved in the method described at the outset by that phosphorus pentoxide is used as the polymerization initiator. The phosphorus pentoxide is in amounts of 0.001 to 15 wt .-%, based on the Glyoxylates of formula II applied. The polymerization can take place in the presence or can also be carried out in the absence of inert solvents. If you polymerize in an inert solvent, the monomer concentrations are 1 to 99%, preferably 5 to 95% by weight. As inert Solvents are suitable for ether, nitrile and / or chlorinated hydrocarbons. Dichloromethane, tetrahydrofuran or acetonitrile are particularly preferred. When polymerizing in dichloromethane, the monomer concentrations are preferably at 70 to 90% by weight while in tetrahydrofuran preferably 5 to 50% by weight.
Nach dem erfindungsgemäßen Verfahren werden Glyoxylate der FormelAccording to the method of the invention, glyoxylates of the formula
polymerisiert, in der M=C₁- bis C₄-Alkyl bedeutet. Vorzugsweise verwendet man als Monomer Glyoxylsäuremethylester und Glyoxylsäureethylester. Die bevorzugt in Betracht kommenden Initiatormengen an Phosphorpentoxid betragen 0,1 bis 10 Gew.-%, bezogen auf die Monomeren der Formel II. polymerized in which M = C₁ to C₄ alkyl. Preferably is used as the monomer glyoxylic acid methyl ester and glyoxylic acid ethyl ester. The preferred initiator amounts of phosphorus pentoxide amount to 0.1 to 10 wt .-%, based on the monomers of Formula II.
Die Monomeren der Formel II können gegebenenfalls mit anderen Aldehyd-Gruppen tragenden Verbindungen copolymerisiert werden, z. B. mit Verbindungen der FormelThe monomers of formula II can optionally with other aldehyde groups bearing compounds are copolymerized, e.g. B. with connections of the formula
in der
R=COOR¹, H, C₁-C₄-Alkyl
R¹=C₁- bis C₄-Alkyl, Alkali-, Ammonium- oder Alkanolamingruppe und
n=0-9in the
R = COOR¹, H, C₁-C₄ alkyl
R¹ = C₁ to C₄ alkyl, alkali, ammonium or alkanolamine group and
n = 0-9
Die Verbindungen der Formel III können mit den Verbindungen der Formel II in jedem beliebigen Verhältnis miteinander copolymerisiert werden. Weitere Comonomere für die Verbindungen der Formel II sind: C₁-C₄-Aldehyde, C₂-C₄-Alkylenoxide, Epihalogenhydride und Epoxibernsteinsäure.The compounds of formula III can with the compounds of formula II be copolymerized with each other in any ratio. Further Comonomers for the compounds of the formula II are: C₁-C₄ aldehydes, C₂-C₄ alkylene oxides, epihalohydrides and epoxy succinic acid.
Die nach dem erfindungsgemäßen Verfahren erhältlichen Polymerisate werden in Form der Alkali-, Ammonium- oder Alkanolamin-Salze als Builder in Waschmitteln verwendet. Überraschenderweise erhält man bei der Verwendung von Phosphorpentoxid als Katalysator stabile Polymere. Dies war aufgrund der Lehre der US-A-42 33 423 nicht zu erwarten, weil nach den dort gemachten Angaben Phosphorpentoxid als Agenz nur nach Abschluß der Polymerisation bei der Stabilisierung der Polymeren eingesetzt wird.The polymers obtainable by the process according to the invention are in the form of the alkali, ammonium or alkanolamine salts as a builder in Detergents used. Surprisingly, you get when using of phosphorus pentoxide as a catalyst stable polymer. This was due the teaching of US-A-42 33 423 is not to be expected, because according to those made there Information on phosphorus pentoxide as an agent only after completion of the polymerization is used in the stabilization of the polymers.
Die Prozentangaben in den Beispielen bedeuten Gew.-%. Die K-Werte wurden nach H. Fikentscher, Cellulosechemie, Band 13, 58 bis 64 und 71 bis 74 (1932) bei einer Temperatur von 25°C und einer Polymerkonzentration von 1% des Natriumsalzes der Polymeren in wäßriger Lösung bei pH 7 bestimmt.The percentages in the examples mean% by weight. The K values were according to H. Fikentscher, Cellulosechemie, Volume 13, 58 to 64 and 71 to 74 (1932) at a temperature of 25 ° C and a polymer concentration of 1% of the sodium salt of the polymers in aqueous solution at pH 7 determined.
In einem 100-ml-Einhalskolben wurden unter Argon 2,0 g (14,1 mmol, 8 Gew.-%) Phosphorpentoxid vorgelegt und 50 ml Tetrahydrofuran unter Rühren zugegeben. Anschließend wurden 20 ml (24,9 g, 238,3 mmol) Glyoxylsäure-methylester langsam zugetropft und die Reaktionsmischung 72 h bei Raumtemperatur belassen. Danach wurden 2 ml Ethylvinylether zugefügt und 30 min gerührt. Anschließend gab man 10 ml 0,1 N Natronlauge und 1,5 g Natriumcarbonat zu und ließ weiter 30 min rühren. Es wurde vom Produkt abdekantiert und das Lösemittel im Vakuum abdestilliert. Das Produkt wurde aus Methanol ausgefällt, nochmals in Wasser gelöst und aus Aceton umgefällt, sowie getrocknet. Es besaß einen K-Wert von 29,6. In a 100 ml single-necked flask, 2.0 g (14.1 mmol, 8 wt .-%) phosphorus pentoxide and 50 ml of tetrahydrofuran under Stirring added. Then 20 ml (24.9 g, 238.3 mmol) of methyl glyoxylate slowly added dropwise and the reaction mixture for 72 h Leave room temperature. Then 2 ml of ethyl vinyl ether was added and Stirred for 30 min. Then 10 ml of 0.1 N sodium hydroxide solution and 1.5 g were added Sodium carbonate and allowed to stir for a further 30 min. It was from the product decanted and the solvent distilled off in vacuo. The product was precipitated from methanol, redissolved in water and reprecipitated from acetone, as well as dried. It had a K value of 29.6.
In der in Beispiel 1 beschriebenen Apparatur wurden 4,5 ml Dichlormethan und 0,2 g (1,4 mmol, 1,1 Gew.-%) Phosphorpentoxid unter Argon vorgelegt und die Mischung auf 0°C abgekühlt. Anschließend wurden langsam 15 ml (18,7 g oder 212,2 mmol) Glyoxylsäure-methylester langsam zugetropft. Aufgrund der starken Viskositätszunahme wurden weitere 4,5 ml Dichlormethan zugegeben. Es wurde 2 h bei 0°C polymerisiert und danach 10 ml Dimethoxymethan zugefügt und weitere 2 h nachgerührt. Man ließ die Reaktionsmischung 18 h bei 0°C stehen und gab danach unter Kühlen 25 ml 10 N Natronlauge zu. Nach Erwärmen auf Raumtemperatur wurde noch 2 h gerührt, dann 40 ml Methanol zugefügt und noch 5 h gerührt. Das weiße Produkt wurde abfiltriert und getrocknet. Es besaß einen K-Wert von 25,1.In the apparatus described in Example 1, 4.5 ml of dichloromethane and 0.2 g (1.4 mmol, 1.1 wt .-%) of phosphorus pentoxide under argon and the mixture cooled to 0 ° C. Then 15 ml (18.7 g or 212.2 mmol) methyl glyoxylic acid slowly added dropwise. Due to the strong increase in viscosity, a further 4.5 ml dichloromethane admitted. The mixture was polymerized at 0 ° C. for 2 h and then 10 ml Dimethoxymethane added and stirred for a further 2 h. The reaction mixture was left Stand at 0 ° C for 18 h and then gave 25 ml of 10 N with cooling Caustic soda too. After warming to room temperature, stirring was continued for 2 h, then 40 ml of methanol were added and the mixture was stirred for a further 5 h. The white product was filtered off and dried. It had a K value of 25.1.
Claims (4)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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DE19914106355 DE4106355A1 (en) | 1991-02-28 | 1991-02-28 | Poly-glyoxylate prepn. by polymerisation of 1-4 carbon alkyl ester(s) of glyoxylic acid - in presence of phosphorus pent:oxide, used as builders in detergents |
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DE19914106355 DE4106355A1 (en) | 1991-02-28 | 1991-02-28 | Poly-glyoxylate prepn. by polymerisation of 1-4 carbon alkyl ester(s) of glyoxylic acid - in presence of phosphorus pent:oxide, used as builders in detergents |
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DE4106355A1 true DE4106355A1 (en) | 1992-09-03 |
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DE19914106355 Withdrawn DE4106355A1 (en) | 1991-02-28 | 1991-02-28 | Poly-glyoxylate prepn. by polymerisation of 1-4 carbon alkyl ester(s) of glyoxylic acid - in presence of phosphorus pent:oxide, used as builders in detergents |
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Cited By (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5856288A (en) * | 1996-04-26 | 1999-01-05 | Nippon Shokubai Co., Ltd. | Polyalkylene glycol-polyglyoxylate block copolymer, its production process and use |
US6031132A (en) * | 1997-12-18 | 2000-02-29 | Nippon Shokubai Co., Ltd. | Amide-group-containing polyacetal and its production process and use |
US6235704B1 (en) | 1997-07-30 | 2001-05-22 | Basf Aktiengesellschaft | Solid textile detergent formulation based on glycin-N and N-Diacetic acid derivatives |
EP1127903A1 (en) * | 2000-02-28 | 2001-08-29 | Nippon Shokubai Co., Ltd. | Production process for glyoxylic acid (salt)-based polymer |
US7074749B2 (en) | 2000-06-16 | 2006-07-11 | Basf Aktiengesellschaft | Oxoalcohol-based detergent |
EP2083067A1 (en) | 2008-01-25 | 2009-07-29 | Basf Aktiengesellschaft | Use of organic complexing agents and/or polymeric compounds containing carbonic acid groups in a liquid washing or cleaning agent compound |
WO2010070088A1 (en) | 2008-12-18 | 2010-06-24 | Basf Se | Surfactant mixture comprising branched short-chained and branched long-chained components |
WO2011003904A1 (en) | 2009-07-10 | 2011-01-13 | Basf Se | Surfactant mixture having short- and long-chained components |
WO2011098571A1 (en) | 2010-02-12 | 2011-08-18 | Basf Se | Use of a copolymer as a thickener in liquid detergents having lower graying tendency |
WO2011117350A1 (en) | 2010-03-25 | 2011-09-29 | Basf Se | Electrochemical textile-washing method |
WO2011157777A1 (en) | 2010-06-17 | 2011-12-22 | Basf Se | Polymers comprising saccharide side groups and use thereof |
WO2012095482A1 (en) | 2011-01-13 | 2012-07-19 | Basf Se | Use of optionally oxidized thioethers of polyalkylene glycols in detergents and cleaning agents |
WO2012095481A1 (en) | 2011-01-13 | 2012-07-19 | Basf Se | Use of optionally oxidized thioethers of alcohol alkoxylates in detergents and cleaning agents |
US8232356B2 (en) | 2007-11-14 | 2012-07-31 | Basf Se | Method for producing a thickener dispersion |
WO2012171849A1 (en) | 2011-06-15 | 2012-12-20 | Basf Se | Branched polyesters with sulfonate groups |
US8524649B2 (en) | 2007-08-03 | 2013-09-03 | Basf Se | Associative thickener dispersion |
US8846599B2 (en) | 2011-06-15 | 2014-09-30 | Basf Se | Branched polyesters with sulfonate groups |
WO2015000969A2 (en) | 2013-07-03 | 2015-01-08 | Basf Se | Use of a gel-like polymer composition which can be obtained by polymerizing an acid group-containing monomer in the presence of a polyether compound in formulations for automatic dishwashing |
US8951955B2 (en) | 2011-01-13 | 2015-02-10 | Basf Se | Use of optionally oxidized thioethers of alcohol alkoxylates in washing and cleaning compositions |
US8987183B2 (en) | 2011-01-13 | 2015-03-24 | Basf Se | Use of optionally oxidized thioethers of polyalkylene oxides in washing and cleaning compositions |
US9435073B2 (en) | 2010-03-25 | 2016-09-06 | Basf Se | Electrochemical textile-washing process |
WO2017158002A1 (en) | 2016-03-16 | 2017-09-21 | Basf Se | Washing- and cleaning-active polymer films, process for the production thereof and use thereof |
EP3287476A1 (en) * | 2016-08-25 | 2018-02-28 | Covestro Deutschland AG | Method for the preparation of polyoxymethylene block copolymers |
WO2018109201A1 (en) | 2016-12-16 | 2018-06-21 | Basf Se | Washing and cleaning multi-layer films, method for the production and use thereof |
WO2018109200A1 (en) | 2016-12-16 | 2018-06-21 | Basf Se | Multi-layered film , method for the production and use thereof |
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-
1991
- 1991-02-28 DE DE19914106355 patent/DE4106355A1/en not_active Withdrawn
Cited By (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5856288A (en) * | 1996-04-26 | 1999-01-05 | Nippon Shokubai Co., Ltd. | Polyalkylene glycol-polyglyoxylate block copolymer, its production process and use |
US6235704B1 (en) | 1997-07-30 | 2001-05-22 | Basf Aktiengesellschaft | Solid textile detergent formulation based on glycin-N and N-Diacetic acid derivatives |
US6031132A (en) * | 1997-12-18 | 2000-02-29 | Nippon Shokubai Co., Ltd. | Amide-group-containing polyacetal and its production process and use |
EP1127903A1 (en) * | 2000-02-28 | 2001-08-29 | Nippon Shokubai Co., Ltd. | Production process for glyoxylic acid (salt)-based polymer |
US6576714B2 (en) | 2000-02-28 | 2003-06-10 | Nippon Shokubai Co., Ltd. | Production process for glyoxylic acid (salt)-based polymer |
US7074749B2 (en) | 2000-06-16 | 2006-07-11 | Basf Aktiengesellschaft | Oxoalcohol-based detergent |
US8524649B2 (en) | 2007-08-03 | 2013-09-03 | Basf Se | Associative thickener dispersion |
US8232356B2 (en) | 2007-11-14 | 2012-07-31 | Basf Se | Method for producing a thickener dispersion |
EP2083067A1 (en) | 2008-01-25 | 2009-07-29 | Basf Aktiengesellschaft | Use of organic complexing agents and/or polymeric compounds containing carbonic acid groups in a liquid washing or cleaning agent compound |
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WO2011003904A1 (en) | 2009-07-10 | 2011-01-13 | Basf Se | Surfactant mixture having short- and long-chained components |
US8865639B2 (en) | 2010-02-12 | 2014-10-21 | Basf Se | Use of a copolymer as thickener in liquid detergents having lower graying tendency |
WO2011098571A1 (en) | 2010-02-12 | 2011-08-18 | Basf Se | Use of a copolymer as a thickener in liquid detergents having lower graying tendency |
US9435073B2 (en) | 2010-03-25 | 2016-09-06 | Basf Se | Electrochemical textile-washing process |
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US8951955B2 (en) | 2011-01-13 | 2015-02-10 | Basf Se | Use of optionally oxidized thioethers of alcohol alkoxylates in washing and cleaning compositions |
US8987183B2 (en) | 2011-01-13 | 2015-03-24 | Basf Se | Use of optionally oxidized thioethers of polyalkylene oxides in washing and cleaning compositions |
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US8846599B2 (en) | 2011-06-15 | 2014-09-30 | Basf Se | Branched polyesters with sulfonate groups |
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US10655088B2 (en) | 2013-07-03 | 2020-05-19 | Basf Se | Solid polymer composition obtained by polymerization of an acid group-containing monomer in the presence of a polyether compound |
US10323215B2 (en) | 2013-07-03 | 2019-06-18 | Basf Se | Solid polymer composition obtained by polymerization of an acid group containing monomer in the presence of a polyether compound |
WO2017158002A1 (en) | 2016-03-16 | 2017-09-21 | Basf Se | Washing- and cleaning-active polymer films, process for the production thereof and use thereof |
US10822443B2 (en) | 2016-03-16 | 2020-11-03 | Basf Se | Washing- and cleaning-active polymer films, process for the production thereof and use thereof |
EP3287476A1 (en) * | 2016-08-25 | 2018-02-28 | Covestro Deutschland AG | Method for the preparation of polyoxymethylene block copolymers |
WO2018109201A1 (en) | 2016-12-16 | 2018-06-21 | Basf Se | Washing and cleaning multi-layer films, method for the production and use thereof |
WO2018109200A1 (en) | 2016-12-16 | 2018-06-21 | Basf Se | Multi-layered film , method for the production and use thereof |
WO2019048474A1 (en) | 2017-09-06 | 2019-03-14 | Basf Se | Washing- and cleaning-active polymer films, process for their production and their use |
WO2020011627A1 (en) | 2018-07-11 | 2020-01-16 | Basf Se | Process for preparing stable polymers containing vinylimidazole |
WO2020035567A1 (en) | 2018-08-16 | 2020-02-20 | Basf Se | Water-soluble polymer films of ethylene oxide homo- or copolymers, calendering process for the production thereof and the use thereof |
WO2020249706A1 (en) | 2019-06-14 | 2020-12-17 | Basf Se | Aqueous polymer dispersions suitable as opacifiers in liquid formulations |
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