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
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
  • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
• • 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
  • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

• the invention relates to the use of certain polymers as controllable by pH Dispersants for detergents or cleaning agents or constituents thereof.
• the polymers of the prior art have too high charge densities due to the large proportions of copolymerized carboxylic acids. Such polymers are with the detergent ingredients incompatible, it form phase separations and therefore The polymers according to the prior art also do not have a dispersing effect. Polymers which do not contain carboxyl groups are also not for this purpose can be used because they have no dispersing properties. Effective polymers must show an affinity to the material to be dispersed.
• EP-A-0 754 712 relates to water-soluble polymers and detergent compositions containing them.
• the Water-soluble polymers can be used as dispersants be used.
• the polymers used are poly (meth) acrylic acids used with polyalhylene glycols are modified.
• In example 6 becomes a Maleic acid / acrylic acid copolymer with monomethoxypolyethylene glycol modified, the proportion on maleic acid basic building blocks approx. 29.3% by weight is.
• the object of the present invention is to provide polymers which are known as Dispersants used in detergents and cleaning agents and ingredients thereof can be. They should show a controllable by pH dispersion behavior.
• the object is achieved by the use of polymers of a poly (meth) acrylic acid backbone, in which, based on the main chain, 0 to 10 wt .-% of the (meth) acrylic acid basic building blocks by maleic acid (anhydride) - or fumaric acid Basic building blocks or mixtures thereof and from 0 to 10% by weight of the (meth) acrylic acid building blocks can be replaced by other copolymerizable ethylenic building blocks, and C 1-30 -alkylpoly-C 2-4 -alkylene glycols having an average molecular weight of 250 to 10,000 as side chains bonded to the main chain via ester groups, wherein, based on the polymer, 1 to 19% by weight of the main chain and 81 to 99% by weight of the side chains are present and this ratio and the average molecular weight of the side chains are selected so that free carboxyl groups are present in the polymer, as a controllable dispersant for washing or cleaning agents or constituents thereof, wherein the dispersing behavior
• maleic acid anhydride
• maleic acid includes maleic acid, maleic anhydride and mixtures thereof.
• the present in the polymer free carboxyl groups can in protonated form as free acid groups or in neutralized form. They can in particular be neutralized with ammonium, alkaline earth or alkali ions. In particular, lie the Carboxyl groups in whole or in part in sodium or potassium salt form before. The Calculation of the weight fractions based on the free carboxyl groups.
• the average molecular weights refer to the Weight average molecular weight.
• acrylic acid, methacrylic acid, optionally in addition fumaric acid, maleic acid or maleic anhydride can be used.
• fumaric acid building blocks or mixtures thereof is 0 to 10 wt .-%.
• the backbone may also be free of these comonomers.
• esters of (Meth) acrylic acid such as methyl (meth) acrylate, butyl acrylate, ethylhexyl acrylate, styrene, Acrylamide, lauryl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and N-vinylpyrrolidone.
• esters of (Meth) acrylic acid such as methyl (meth) acrylate, butyl acrylate, ethylhexyl acrylate, styrene, Acrylamide, lauryl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and N-vinylpyrrolidone.
• acrylic acid and basic methacrylic acid building blocks are used, their ratio can be be varied within wide limits. It can also only acrylic acid or methacrylic acid as Basic building blocks in the main chain are present.
• the poly (meth) acrylic acid backbone is of (meth) acrylic acid building blocks and 0 to 10 wt .-% of maleic acid (anhydride) basic building blocks.
• the C 1-30 -alkylpoly-C 2-4 -alkylene glycols are incorporated in copolymerized form in the polymers according to the invention in the form of acrylic acid esters, methacrylic acid esters or fumaric acid mono- or diesters or maleic acid mono- or diesters.
• the alkylpolyalkylene glycols have C 1 to C 30 alkyl groups such as, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec. Butyl, tert. Butyl, hexyl, decyl, dodecyl, isotridecyl, octadecyl, stearyl or oleyl.
• the alkyl groups may be linear or branched, they may be saturated or unsaturated.
• Preferred groups are C 1-6 -alkyl groups, especially preferred is the methyl group.
• alkylene oxide groups preferably from 1 to 50, can be used per alkyl group Alkylene oxide groups are present added.
• alkylene oxides ethylene oxide, Propylene oxide or butylene oxide can be used.
• the mixing ratio of Alkylene oxides is arbitrary.
• the various alkylene oxides can be random or be linked block by block.
• Preferred alkylene oxide is ethylene oxide.
• the production of Alkylpolyalkylene glycols can be prepared by all known methods of alkoxylation carried out, which are known in the art.
• the alkylpolyalkylene glycols can also be used as Polyalkylenglykolmonoalkylether be called.
• the side chains used are preferably C 1-6 -alkylpolyethylene glycols, in particular methylpolyethylene glycols.
• the average molecular weight of the side chains is 250 to 10,000, preferably 500 to 2,000, especially 750 to 1,500.
• the polymer Preferably in the polymer 5 to 15 wt .-% of the main chain and 85 to 95 wt.% Are of the side chains.
• the polymers used according to the invention are known per se.
• DE-A-196 53 524 is the use of such polymers as additives in described mineral building materials.
• inventively usable Polymers and processes for their preparation described In addition to the following Manufacturing methods can also be used in DE-A-196 53 524 and EP-A-0 324 568 described manufacturing process for the polymers are carried out.
• the reactive dispersants of the invention have two different Molecular segments, carboxylates (A) and alkylpolyalkylene glycols (B).
• A carboxylates
• B alkylpolyalkylene glycols
• the molecular units A have adsorbing properties, that is, by the Interaction of the molecular unit A in the polymer with the particle surface the polymer is adsorbed on the surface.
• the molecular units A are depending on the pH of the Medium of carboxylic acids or carboxylate groups.
• the molecular units B of the polymers have desorbing properties. This means, that these units have little or no interaction with the particle surface received. These molecular units are solvated by water and pull that Polymer molecule away from the particle surface back into the aqueous solution. This is synonymous with a dilution effect. As units of the group B become Polyalkylene glycol units used.
• the adsorbing force can be increased during use by increasing the number of the adsorbing groups is increased or the number of desorbing groups is lowered.
• the lowering of the alkylpolyalkylene units is carried out by chemical Cleavage reactions in which the groups are removed from the polymer molecule. There in detergents, the pH is usually above 7, such a cleavage reaction by alkaline hydrolysis of the ester bonds occur. As a result, the alkylpolyalkylene glycols become cleaved from the polymers of the invention, and from a Ester group is generated a carboxylic acid or a carboxylate group.
• the changes in the dispersing behavior have e.g. Influence on that Crystallization behavior of inorganic or organic particles or crystals.
• the viscosity of solid suspensions of organic or inorganic solids by programmable reactivity with respect to cleavage
• the alkylpolyalkylene glycol groups are influenced in a targeted manner. It is for example possible that the viscosity of a solid slurry increases during the course of the application, decreases, passes through a maximum or remains constant. This behavior can be through simultaneous use of two or more different reactive dispersants be targeted.
• slurry means an aqueous slurry or dispersion of Detergents or cleaning ingredients, wherein at least one ingredient is not dissolved but present dispersed. So that part of the ingredients can be solved and part of the Ingredients are dispersed.
• the slurry is an aqueous mixture the constituents of detergents and cleaners understood in the manufacture is generated by solid detergents and cleansers to the ingredients as well as possible to mix.
• a special case is when at the same time during the dispersion Crystallization process takes place.
• the adsorbed polymer parts grow in the Crystal lattice of the solid and lost the dispersion.
• the effectiveness is lost in this case as time progresses as the polymer is consumed.
• new dispersant-active polymer again and again is reproduced. This can be done by desorbing groups existing reactive polymers are constantly split off.
• Such Effects are also combined in a polymer.
• Different reactivity can be found in a polymer molecule can be incorporated by e.g. the desorbing groups once strongly reactive and once unreactive or poorly reactive. During the Application, the particularly reactive groups can be split off, while the non-reactive groups are retained.
• Such Differentiation can be achieved, for example, by the Alkylpolyalkylenglykoltechniken ester-like to copolymerized methacrylic acid, Acrylic acid, fumaric acid mono- or diesters or maleic mono- or diesters bound.
• the esters are differentially susceptible to hydrolysis. The have the highest susceptibility to hydrolysis, e.g.
• methacrylic esters, Fumaric monoester or Maleinkladoester lower susceptibility to hydrolysis have.
• alkylpolyalkylene glycols are ester-like with acrylic acid, Methacrylic acid, fumaric acid or maleic acid are bound, they are different quickly split off again. At other conditions of the surrounding environment can turn out change the order of reactivity so that e.g. Methacrylic ester faster be cleaved as acrylic acid ester or maleic acid monoester.
• the polymers of the invention as dispersants for the preparation of Solid suspensions used, it may, depending on the composition of the polymers Viscosity remain constant, increase or decrease during the course of the application. It can also be during the application of a minimum or maximum viscosity form when the viscosity first increases and then decreases again or vice versa. Such maxima or minima usually occur when there are two or more effects overlap.
• the preparation of the polymers of the invention can in various ways and Way using radical polymerization initiators and optionally Controllers take place. Two ways are described below by way of example.
• the molecular weights of the polymers according to the invention are preferably between 1,000 and 200,000.
• the Molar weight between 1,000 and 100,000 has.
• the production of polycarboxylic acids can by all known methods of solution, substance, precipitation or Emulsion polymerization take place.
• 1 to 19 wt .-% the polycarboxylic acids with 81 to 99 wt .-% alkylpolyalkylene glycols according to known Esterified methods in the form of a polymer-analogous reaction.
• the polymers according to the invention can be mixed with water in an aqueous solution be transferred and neutralized as alkali or alkaline earth or ammonium salt.
• inventive Polymers are first an ester of unsaturated carboxylic acids with the Alkylpolyallcyenglykolen prepared and these esters are unsaturated with Radicals copolymerized carboxylic acids.
• an aqueous solution is prepared neutralized alkali, alkaline earth or ammonium salt form.
• an esterification product can be prepared and polymerized.
• an esterification product can be produced and then polymerized.
• the polymers according to the invention are not subject to any manufacturing methods Restrictions. About the radical polymerizations and about esterification knows the expert the details and different variations, so that details are not here must be executed.
• the polymers used according to the invention are preferably used in slurries of Detergents or Detergents In the Preparation of Solid Detergents Detergents used. They serve in particular for reducing the viscosity of the slurries.
• the invention also relates to detergents or cleaners containing at least one Surfactant, at least one builder and, based on the washing or cleaning agent, 0.2 to 10 wt .-% of at least one polymer, as described above.
• Other ingredients and their amounts are described, for example, in EP-A-0669958 and US Pat cited literature.
• the invention also relates to a process for the preparation of solid washing or Detergents by mixing at least one surfactant, at least one builder and optionally further customary ingredients with water to form a slurry and subsequent drying of the slurries, wherein the mixing in the presence of 0.2 to 10% by weight, based on the solid ingredients of the washing or cleaning agent, at least one polymer, as described above, is carried out.
• Proportion of unsaturated carboxylic acid copolymerized in the polymer according to the invention (% by weight)
• Proportion of alkylpolyalkylene glycol in the polymer according to the invention (% by weight) Molar weight of the polymer according to the invention (weight average) 10 acrylic acid 90 methylpolyethylene glycol molecular weight 1,500 20,000 1 acrylic acid 99 methyl polyethylene glycol molecular weight 8,000 12,000 19 acrylic acid 81
• the polymers of the prior art have too high charge densities due to the large proportions of more than 20 wt .-% of copolymerized carboxylic acids. Such Polymers are incompatible with the detergent ingredients and therefore act also not dispersing on an aqueous slurry. Polymers that have no Contain carboxyl groups, ie from a homopolymer of Polyalkylenglykolmonoacrylaten exist are also not for this purpose can be used because they have no dispersing properties.
• a polymer with molecular weight (weight average) 24,500, by Esterification of 85% by Weight of Methylpolyethylene Glycol With Molar Mass 1000 With 10% by Weight Acrylic acid and 5 wt .-% methacrylic acid and subsequent polymerization and Neutralization was prepared as an aqueous sodium salt solution was added to 2 wt .-% (solid) added to the detergent slurry.
• polymers according to the invention are effective agents for Production of detergents.

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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)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
• Macromonomer-Based Addition Polymer (AREA)

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Publications (2)

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• 2000
  • 2000-06-09 DE DE10028216A patent/DE10028216A1/de not_active Withdrawn
• 2001
  • 2001-06-06 ES ES01956458T patent/ES2247151T3/es not_active Expired - Lifetime
  • 2001-06-06 CA CA002410445A patent/CA2410445A1/en not_active Abandoned
  • 2001-06-06 JP JP2002502061A patent/JP2003535962A/ja not_active Withdrawn
  • 2001-06-06 AT AT01956458T patent/ATE303430T1/de not_active IP Right Cessation
  • 2001-06-06 MX MXPA02011120A patent/MXPA02011120A/es active IP Right Grant
  • 2001-06-06 EP EP01956458A patent/EP1287105B1/de not_active Expired - Lifetime
  • 2001-06-06 DE DE50107292T patent/DE50107292D1/de not_active Expired - Fee Related
  • 2001-06-06 US US10/297,490 patent/US6878683B2/en not_active Expired - Fee Related
  • 2001-06-06 WO PCT/EP2001/006394 patent/WO2001094518A1/de not_active Ceased
  • 2001-06-06 AU AU2001278440A patent/AU2001278440A1/en not_active Abandoned

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