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 dispersants for detergents or cleaning agents or constituents thereof.
• water-soluble polymers in detergent and cleaning agent compositions which act as builders, lime soap dispersants or as incrustation inhibitors.
• Such polymers are described in EP-A-0 324 568. They are copolymers of (meth) acrylic acid and alkyl polyethylene glycol (meth) acrylates.
• the proportion by weight of alkyl polyalkylene glycols is 4 to 80% by weight, the proportion of unsaturated carboxylic acids 20 to 95% by weight.
• 0 to 30% by weight of other comonomers can be used.
• the copolymers described in the examples contain about 10 to 30% by weight of the alkylpolyalkylene glycols in copolymerized form.
• the polymers according to the prior art have too high charge densities due to the large proportions of polymerized carboxylic acids. Such polymers are incompatible with the detergent constituents, phase separations form and therefore the polymers according to the prior art also have no dispersing action. Polymers that do not contain carboxyl groups cannot be used for this purpose either because they have no dispersing properties. Effective polymers must show an affinity for the material to be dispersed.
• the object of the present invention is to provide polymers which can be used as dispersants in detergents and cleaning agents and constituents thereof. They should preferably show controllable dispersion behavior.
• the object is achieved according to the invention by using polymers a poly (meth) acrylic acid main chain in which, based on the main chain, 0 to 30% by weight of the (meth) acrylic acid basic building blocks by maleic acid (anhydride) - or fumaric acid basic building blocks or mixtures thereof and 0 to 10% by weight.
• % of the (meth) acrylic acid basic building blocks can be replaced by other copolymerizable ethylenic basic building blocks,
• poly (meth) acrylic acid or (meth) acrylic acid mean monomers or polymers of acrylic acid, methacrylic acid or mixtures thereof.
• maleic anhydride It includes maleic acid, maleic anhydride and mixtures thereof.
• the free carboxyl groups present in the polymer can be present 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, the carboxyl groups are wholly or partly in sodium or potassium salt form. The weight percentages are calculated based on the free carboxyl groups.
• the average molecular weights are based on the weight average molecular weight.
• Acrylic acid, methacrylic acid, optionally additionally fumaric acid, maleic acid or maleic anhydride can be used as monomers for the main chain.
• the proportion of maleic acid (anhydride), fumaric acid basic building blocks or mixtures thereof is 0 to 10% by weight.
• the main chain can also be free of these comonomers.
• 0 to 10% by weight, preferably 0 to 5% by weight, of the (meth) acrylic acid basic building blocks can be replaced by other, copolymerizable ethylenic basic building blocks. There can also be no such basic building blocks.
• 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.
• esters of (meth) acrylic acid such as methyl (meth) acrylate, butyl acrylate, ethylhexyl acrylate, styrene, acrylamide, lauryl acrylate, hydroxypropyl acrylate, hydroxy
• acrylic acid and basic methacrylic acid building blocks are used, their ratio can be varied within wide limits. There can also be only acrylic acid or methacrylic acid as basic building blocks in the main chain.
• the poly (meth) acrylic acid main chain is preferably composed of (meth) acrylic acid basic building blocks and 0 to 10% by weight of maleic acid (anhydride) basic building blocks.
• the C ⁇ _ 3 o-alkyl poly-C 2 . 4 -alkylene glycols are present 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 in copolymerized form.
• the alkylpolyalkylene glycols have Ci to C 3 -alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec. Butyl, tert. Butyl, hexyl, decyl, dodecyl, isotridecyl, octadecyl, stearyl or oleyl group.
• the alkyl groups can be linear or branched, they can be saturated or unsaturated.
• Preferred groups are Ci- ⁇ -alkyl groups, the methyl group is particularly preferred.
• alkylene oxide groups preferably 1 to 50 alkylene oxide groups, can be added per alkyl group.
• Ethylene oxide, propylene oxide or butylene oxide can be used as alkylene oxides.
• the mixing ratio of the alkylene oxides is arbitrary.
• the various alkylene oxides can be linked statistically or in blocks.
• the preferred alkylene oxide is ethylene oxide.
• the alkylpolyalkylene glycols can be prepared by all known alkoxylation methods which are known to the person skilled in the art.
• the alkyl polyalkylene glycols can also be referred to as polyalkylene glycol monoalkyl ethers.
• C 6 alkylpolyethylene glycols, in particular methyl polyethylene glycols, are preferably used as side chains.
• the average molecular weight of the side chains is 250 to 10,000, preferably 500 to 2,000, in particular 750 to 1,500.
• DE-A-196 53 524 describes the use of such polymers as additives in mineral building materials.
• This document describes polymers which can be used according to the invention and processes for their preparation. In addition to the production processes below, the production processes for the polymers described in DE-A-196 53 524 and EP-A-0 324 568 can also be carried out.
• the reactive dispersants according to the invention have two different molecular segments, carboxylates (A) and alkyl polyalkylene glycols (B).
• A carboxylates
• B alkyl polyalkylene glycols
• the molecular units A have adsorbing properties, that is to say that the interaction of the molecular unit A in the polymer with the particle surface adsorbs the polymer on its surface.
• the molecular units A are 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. These molecular units are solvated by water and pull the polymer molecule back into the aqueous solution away from the particle surface. This is equivalent to a thinning effect. Group B polyalkylene glycol units are used. Two forces act on the polymer: an adsorbing force and a desorbing force that maintain balance during use.
• the adsorbing force can be increased during use by increasing the number of adsorbing groups or decreasing the number of desorbing groups.
• the alkylpolyalkylene units are lowered by chemical cleavage reactions in which the groups are removed from the polymer molecule. Since the pH value in detergents is usually above 7, such a cleavage reaction can occur through alkaline hydrolysis of the ester bonds. As a result, the alkyl polyalkylene glycols are split off from the polymers according to the invention, and a carboxylic acid or a carboxylate group is produced from an ester group.
• the number of carboxylic acid groups is increased during use, while the number of alkylpolyalkylene oxide side chains is reduced in the polymers according to the invention.
• the dispersing properties of the polymers are changed during use over time. This property can also be referred to as a time-controlled or controllable dispersant (dispersibility which can be changed by pH).
• the changes in the dispersing behavior have e.g. Influence on the crystallization behavior of inorganic or organic particles or crystals.
• the viscosity of solid suspensions of organic or inorganic solids can be influenced in a targeted manner by programmable reactivity with regard to the elimination of the alkylpolyalkylene glycol groups. It is possible, for example, that the viscosity of a solid slurry increases, decreases, goes through a maximum or remains constant in the course of the application. This behavior can be specifically adjusted by the simultaneous use of two or more differently reactive dispersants.
• slurry means an aqueous slurry or dispersion of detergent or cleaning agent ingredients, with at least one ingredient not being dissolved but being dispersed. This means that some of the ingredients can be dissolved and some of the ingredients can be dispersed.
• the slurry is an aqueous mixture understood the constituents of detergents and cleaning agents that are produced in the manufacture of solid detergents and cleaning agents in order to mix the ingredients as well as possible.
• a special case is when a crystallization process takes place simultaneously during the dispersion.
• the adsorbed polymer parts grow into the crystal lattice of the solid and are lost in the dispersion.
• the effectiveness is lost as time progresses because the polymer is consumed.
• Such effects can also be combined in one polymer.
• Different reactivities can be built into a polymer molecule by, for example, binding the desorbing groups once strongly reactive and once unreactively or less reactive.
• the particularly reactive groups can be split off during use, while the non-reactive groups are retained.
• Such a differentiation can be achieved, for example, by having the alkyl polyalkylene glycol units bonded in ester form to polymerized methacrylic acid, acrylic acid, fumaric acid mono- or diesters or maleic acid mono- or diesters.
• the esters are susceptible to hydrolysis in different ways.
• acrylic acid esters, fumaric acid diesters and maleic acid diesters are most susceptible to hydrolysis in one case at high pH values, while methacrylic acid esters, fumaric acid monoesters or maleic acid monoesters are less susceptible to hydrolysis have.
• methacrylic acid esters, fumaric acid monoesters or maleic acid monoesters are less susceptible to hydrolysis have.
• the alkyl polyalkylene glycols are bound in an ester-like manner to acrylic acid, methacrylic acid, fumaric acid or maleic acid, they are split off again at different speeds. In other conditions of the surrounding environment, the order of reactivity can change, so that methacrylic acid esters, for example, are split faster than acrylic acid esters or maleic acid monoesters.
• the viscosity can remain constant depending on the composition of the polymers, increase or decrease in the course of use.
• a minimum or maximum viscosity can also develop during use if the viscosity first increases and then decreases again, or vice versa. Such maxima or minima usually occur when two or more effects overlap.
• the polymers according to the invention can be prepared in various ways using free-radical polymerization initiators and optionally regulators. Two ways are described below as examples.
• the molecular weights of the polymers according to the invention are preferably between 1,000 and 200,000.
• a homo- or copolymer which has a molecular weight between 1,000 and 100,000.
• the polycarboxylic acids can be prepared by all known methods of solution, bulk, precipitation or emulsion polymerization.
• 1 to 19% by weight of the polycarboxylic acids are esterified with 81 to 99% by weight of alkyl polyalkylene glycols by known methods in the form of a polymer-analogous reaction.
• the polymers according to the invention can, if appropriate, be converted into an aqueous solution with water and neutralized as the alkali or alkaline earth metal or ammonium salt.
• an ester of the unsaturated carboxylic acids is first prepared with the alkyl polyalkylene glycols and these esters are radically copolymerized with unsaturated carboxylic acids.
• esters obtained are polymerized by the customary and known methods of bulk, solution, emulsion or precipitation polymerized.
• An aqueous solution is preferably prepared.
• the neutralized alkali, alkaline earth or ammonium salt form can be produced.
• an esterification product can be produced from 10 parts of acrylic acid and 81 parts of methyl polyethylene glycol with a molecular weight of 1,000, which is then copolymerized with 9 parts of acrylic acid.
• an esterification product can be prepared from 19 parts of acrylic acid and 81 parts of methyl polyethylene glycol with a molecular weight of 1,000 and polymerized.
• an esterification product can be prepared from 10 parts of acrylic acid and 81 parts of methyl polyethylene glycol with a molecular weight of 1,000 and then copolymerized with 9 parts of methacrylic acid.
• an esterification product can be produced from 10 parts of acrylic acid, 9 parts of methacrylic acid and 81 parts of methyl polyethylene glycol with a molecular weight of 1,000 and then polymerized.
• the polymers according to the invention are not subject to any restrictions with regard to the production methods.
• the person skilled in the art knows the details and various variations via the radical polymerizations and via esterifications, so that details need not be given here.
• the polymers used according to the invention are preferably used in slurries of detergent or cleaning agent components in the production of solid detergents or cleaning agents. They serve in particular to reduce the viscosity of the slurry.
• the invention also relates to washing or cleaning agents containing at least one surfactant, at least one builder and, based on the washing or cleaning agent, 0.2 to 10% by weight of at least one polymer, as described above. Further ingredients and their amounts are described, for example, in EP-A-0669958 and the literature cited therein.
• the invention also relates to a method for producing solid washing or cleaning agents by mixing at least one surfactant, at least one builder and optionally further conventional ingredients with water to form a slurry and subsequent drying of the slurry, the mixing in the presence of 0.2 to 10% by weight, based on the solid ingredients of the washing or cleaning agent, of at least one polymer, as described above is described, is executed.
• the following polymers can be prepared by route 1, route 2 or another method:
• the polymers according to the prior art have charge densities which are too high due to the large proportions of more than 20% by weight of copolymerized carboxylic acids. Such polymers are incompatible with the detergent components and therefore do not have a dispersing effect on an aqueous slurry. Polymers which do not contain carboxyl groups, i.e. which consist of a homopolymer of polyalkylene glycol monoacrylates, cannot be used for this purpose either, since they have no dispersing properties.
• the polymers to be used according to the invention are important auxiliaries in the production of phosphate-reduced and phosphate-free washing and cleaning agents. By using these aids, it is possible to raise the slurry concentration in the crutcher to at least 80% by weight. This means better economy through cheaper utilization of the spray tower and a saving in energy because less water has to be evaporated.
• the homogenizing and viscosity-reducing effect of the polymers to be used according to the invention is illustrated by viscosity measurements on detergent formulations. A slurry of 80% by weight detergent constituents and 18% by weight water is used as the detergent slurry at 60 ° C.
• the detergent for making the slurry was composed as follows:
• the polymer lowers the viscosity of the detergent slurry from 30,000 mPas (without additive) to 10,000 mPas after 10 minutes, to 5,000 mPas after 20 minutes and to 2,000 mPas after 50 minutes.
• polymers according to the invention are effective agents for producing 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)
• Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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