WO2015059084A1 - Polymérisation par précipitation en présence d'un groupe amine tertiaire et d'un anhydride - Google Patents

Polymérisation par précipitation en présence d'un groupe amine tertiaire et d'un anhydride Download PDF

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WO2015059084A1
WO2015059084A1 PCT/EP2014/072423 EP2014072423W WO2015059084A1 WO 2015059084 A1 WO2015059084 A1 WO 2015059084A1 EP 2014072423 W EP2014072423 W EP 2014072423W WO 2015059084 A1 WO2015059084 A1 WO 2015059084A1
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polymerization
acid
alkyl
composition
monomers
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PCT/EP2014/072423
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German (de)
English (en)
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Son Nguyen-Kim
Wolfgang Jahnel
Rolf Werner
Peter Hössel
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/14—Organic medium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/10—N-Vinyl-pyrrolidone

Definitions

  • the present invention relates to a process for producing a copolymer composition by radical copolymerization by the precipitation polymerization method in the presence of an adjuvant composition, to the copolymer composition obtainable by this process and to the use thereof.
  • Rheology modifiers which are often processed in solid, powdered form, are used in many technical fields, e.g. As the paints, papermaking, textile industry, hygiene, cosmetic and pharmaceutical agents used. Crosslinked polyacrylic acids are currently among the most widely used rheology modifiers.
  • WO 2007/010034 describes an ampholytic copolymer A) obtainable by free-radical copolymerization of a) at least one compound having a free-radically polymerizable,
  • WO 2007/012610 describes a silicone group-containing copolymer A) obtainable by free-radical copolymerization of a) at least one compound having a free-radically polymerizable,
  • WO 2007/010035 describes the use of an ampholytic copolymer which has a molar excess of anionogenic / anionic groups over cationogenic / cationic groups or which has a molar excess of cationogenic / cationic groups with respect to anionogenic / anionic groups and which can be obtained is characterized by radical copolymerization of a1) at least one compound with a free-radically polymerizable,
  • ampholytic copolymer can be prepared by radical copolymerization by the method of precipitation polymerization.
  • WO 2010/026178 relates to a process for the preparation of a crosslinked copolymer with anionogenic / anionic groups by free-radical copolymerization by the method of precipitation polymerization in the presence of glycerol monostearate.
  • WO 201 1/107460 relates to a process for preparing a crosslinked copolymer having anionogenic / anionic groups by free-radical copolymerization by the precipitation polymerization method in the presence of at least one compound having a block structure and comprising at least one hydrophobic block and at least one hydrophilic block and in the presence of at least one basic compound.
  • US 4,758,641 describes a process for the preparation of polymers of olefinically unsaturated C3-Cs carboxylic acids in a solvent selected from acetone and lower alkyl acetates and in the presence of a crosslinker.
  • US 4,692,502 describes a process for the polymerization of olefinically unsaturated carboxylic acids in an organic solvent and in the presence of ionic surfactants.
  • No. 4,526,937 describes a process for the precipitation polymerization of olefinically unsaturated carboxylic acids in the presence of polyoxyethylene-polyoxypropylene block copolymers having terminal OH groups and an HLB value of greater than 10.
  • No. 4,419,502 describes a process for the precipitation polymerization of olefinically unsaturated carboxylic acids in methylene chloride and in the presence of a polyoxyethylene alkyl ether and / or polyoxyethylene sorbitol ester having an HLB value of greater than 12.
  • EP 0 584 771 A1 describes a polymer of an olefinically unsaturated carboxylic acid and a steric stabilizer.
  • Suitable steric stabilizers are linear block copolymers and random comb polymers with hydrophilic and hydrophobic units.
  • US 4,375,533 describes a process for the polymerization of olefinically unsaturated carboxylic acids in a polymerization medium in which the carboxylic acid polymer is insoluble in the presence of a surfactant having an HLB value of less than 10.
  • No. 4,420,596 describes a process for the polymerization of olefinically unsaturated carboxylic acids in a polymerization medium which contains mineral spirits, in the presence of 1) a sorbitan ester, 2) a nonionic surfactant with an HLB Value of less than 10, which is an ester of glycerol or an alkylene glycol, and 3) a long-chain alcohol.
  • EP 1 209 198 A1 describes a polymer composition containing A) a crosslinked carboxyl group-containing polymer and B) at least one compound selected from esters of polyhydric alcohols with fatty acids and the alkylene oxide adducts thereof.
  • WO 2006/044193 describes a crosslinked copolymer based on a vinylamide and an unsaturated carboxylic acid and its use for modifying the rheological properties.
  • WO 91/00302 describes a process for preparing terpolymers of (i) a vinyllactam, (ii) a polymerizable carboxylic acid and (iii) a hydrophobic monomer in an aliphatic hydrocarbon as a solvent.
  • No. 5,191,043 describes a precipitation polymerization process in which a solvent mixture containing a saturated C 3 -C 10 -hydrocarbon and a secondary alcohol is used.
  • WO 99/29735 describes a process for the preparation of vinyl polymers in the presence of an oil as a solvent.
  • oils are silicone oils, light and heavy mineral oils and water-insoluble esters, specifically isopropyl palmitate and isopropyl myristate.
  • copolymer compositions obtained should be distinguished, in particular, by good redispersibility in both an aqueous medium and in an oil-containing medium.
  • a first aspect of the invention is a process for preparing a copolymer composition A) by free-radical copolymerization of a monomer composition
  • a monomer composition comprising a) at least one monomer selected from acrylic acid, salts of acrylic acid, methacrylic acid, salts of methacrylic acid and mixtures thereof, b) at least one free-radically polymerizable crosslinking compound which contains at least two ⁇ , ⁇ -ethylenically unsaturated double bonds per molecule, c) at least one ⁇ , ⁇ -ethylenically unsaturated amide group-containing compound, by the method of precipitation polymerization in the presence of an auxiliary composition H), containing
  • H1 at least one compound having at least one tertiary amino group
  • At least one further adjuvant H3) is additionally used which is selected from silicone group-containing surfactants, preferably polydialkylsiloxane-polyether copolymers, which may additionally have at least one amino group.
  • Another object of the invention is a copolymer composition A) as defined above and below, which is obtainable by this method.
  • a further subject of the invention is a cosmetic agent comprising A) at least one copolymer composition as defined above and below, B) at least one cosmetically acceptable active ingredient and
  • C) optionally at least one further cosme- tically acceptable excipient other than A) and B).
  • Another object of the invention is the use of a copolymer composition A), as defined above and hereinafter, for modifying the rheological properties of an aqueous or oil-containing composition.
  • Another object of the invention is the use of a copolymer composition A), as defined above and hereinafter, as an emulsifier or stabilizer for an emulsion.
  • a further subject of the invention is the use of a copolymer composition A), as defined above and hereinafter, for improving the redispersibility of a composition containing the copolymer compositions A) in an aqueous medium or in an oil-containing medium.
  • Another object of the invention is the use of a copolymer composition A), as defined above and hereinafter, as an adjuvant in cosmetics, as an adjuvant in the food industry, as an adjuvant in pharmacy, as a surface-active compound, as or in adhesives (n ) as well as in or coating agent (s) for the textile, paper, printing and leather industries.
  • a copolymer composition A as defined above and hereinafter, as an adjuvant in cosmetics, as an adjuvant in the food industry, as an adjuvant in pharmacy, as a surface-active compound, as or in adhesives (n ) as well as in or coating agent (s) for the textile, paper, printing and leather industries.
  • H2) at least one anhydride
  • Method according to embodiment 1, wherein additionally at least one further adjuvant H3) is used which is selected from silicone group-containing surfactants, preferably polydialkylsiloxane-polyether copolymers, which may additionally have at least one amino group.
  • silicone group-containing surfactants preferably polydialkylsiloxane-polyether copolymers, which may additionally have at least one amino group.
  • the monomer composition used to prepare the copolymer composition A) contains at least one amide group-containing monomer c) which is selected from ⁇ , ⁇ -ethylenically unsaturated amide group-containing compound of the general formula (II)
  • a process according to embodiment 4, wherein the compound of the general formula (II) is selected from N-vinylpyrrolidone, N-vinylcaprolactam and mixtures thereof.
  • the monomer composition used to prepare the copolymer composition A) contains at least one amide group-containing monomer c) which has a group of the formulas (IIIa) or (IIIb)
  • R a is H or C 1 -C 4 -alkyl
  • R b is H or C 1 -C 4 -alkyl, or
  • R a and R b together represent (CH 2) i- 4 .
  • the monomer composition used to prepare the copolymer composition A) comprises at least one monomer c) selected from N- (2-acryloxyethyl) imidazolidin-2-one and N- (2-methacryloxyethyl) imidazolidin-2-one on (2-ureidomethacrylate, UMA).
  • the monomer composition used to prepare the copolymer composition A) additionally comprises at least one compound d) other than the compounds a) having a free-radically polymerizable, ⁇ , ⁇ -ethylenically unsaturated double bond and at least one anionogenic and / or anionic one Contains groups per molecule, preferably selected from ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and mixtures thereof.
  • the monomer composition used to prepare the copolymer composition A) additionally comprises at least one compound e) having a free-radically polymerizable, ⁇ , ⁇ -ethylenically unsaturated double bond and at least one cationogenic and / or cationic groups per molecule contains.
  • component e) contains or consists of N-vinylimidazole.
  • the monomer composition used to prepare the copolymer composition A) additionally comprises at least one ether group-containing monomer f) selected from compounds of the general formulas IV a) and IV b)
  • H 2 C C-CX- (CH 2 -CH 2 -O) k (CH 2 -CH (CH 3 ) -O)
  • R 8 is hydrogen or C 1 -C 4 -alkyl, preferably methyl
  • R 9 is hydrogen, C 1 -C 30 -alkyl, C 2 -C 3 o-alkenyl or C 5 -C 8 -cycloalkyl,
  • X is O or a group of the formula NR 10 , in which R 10 is H, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • R 10 is H, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • H 2 C CC-O- (CH 2 -CH 2 -O) k (CH 2 -CH (CH 3 ) -O)
  • R 8 is hydrogen or methyl
  • R 9 is Ce-Cso-alkyl.
  • the monomer composition used to prepare the copolymer composition A) additionally contains at least one further monomer g) selected from gl) esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with C1-C30-alkanols,
  • esters of vinyl alcohol and allyl alcohol with C 1 -C 8 -monocarboxylic acids esters of vinyl alcohol and allyl alcohol with C 1 -C 8 -monocarboxylic acids, g 6) C 1 -C 30 -alkyl vinyl ethers,
  • a copolymer composition A) according to embodiment 30 in an aqueous or oily composition for modifying the rheological properties of this composition.
  • composition according to embodiment 35 in the form of a gel or dispersion.
  • Use of a copolymer composition A) obtainable by a process as defined in any of embodiments 1 to 29 for improving the redispersibility of a composition containing the copolymer compositions A) in an aqueous medium or in an oil-containing medium.
  • copolymer composition A) obtainable by a process as defined in any of embodiments 1 to 29 as an adjuvant in cosmetics, as an adjuvant in the food industry, as an adjuvant in the pharmaceutical industry.
  • zie as a surface-active compound, as or in adhesive (s) and as or in coating agent (s) for the textile, paper, printing and leather industries.
  • the HLB value hydrophilic lipophilic balance
  • a definition of the HLB value can be found in W.C. Griffin, J. Soc. Cosmetic Chem., Vol. 5, 249 (1954).
  • an experimental determination by the emulsion comparison method often succeeds.
  • the HLB value of the unknown surfactant is calculated according to the formula:
  • N weight percent of the surfactant whose HLB is to be determined, expressed as a decimal.
  • HLB values and methods for their determination are described in standard works, e.g. B. K. H. Schric, bases and formulations of cosmetics, Hüthig Verlag, 2nd ed., 1989.
  • the preparation of the copolymer compositions A) according to the invention is carried out by precipitation polymerization.
  • the monomers used are soluble in the reaction medium (monomer, solvent), but the corresponding polymer is not.
  • the resulting polymer becomes insoluble under the chosen polymerization conditions and precipitates out of the reaction mixture.
  • the inventive method itself is characterized by advantageous properties and also leads to copolymer compositions having particularly advantageous properties.
  • the precipitation polymers present in the polymer compositions according to the invention are distinguished by their capability as rheology modifiers (especially as thickeners).
  • a copolymer composition A which is readily redispersible in aqueous media and which, for. B. advantageous for the preparation of gel formulations.
  • a copolymer composition A is obtained which is readily redispersible in oil-containing media and z. B. advantageous for the preparation of oil formulations, especially oil-containing dispersions.
  • alkyl includes straight-chain and branched alkyl groups. These preferably include straight-chain or branched C 1 -C 30 -alkyl groups, particularly preferably C 1 -C 20 -alkyl groups. Suitable short-chain alkyl groups are, for. B. straight-chain or branched Ci-Cz-alkyl, preferably C1-C6-alkyl and particularly preferably Ci-C4-alkyl groups.
  • Suitable longer-chain Cs-Cso-alkyl or Cs-Cso-alkenyl groups are straight-chain and branched alkyl or alkenyl groups.
  • Suitable longer chain Cs-Cso-alkenyl groups include, for. B.
  • n-octenyl n-nonenyl, n-decenyl, n-undecenyl, n-dodecenyl, n-tridecenyl, n-tetradecenyl, n-pentadecenyl, n-hexadecenyl, n-heptadecenyl, n-octadecenyl, n-nonadecenyl, n-eicosenyl, n-docosenyl, n-tetracosenyl, hexacosenyl, triacontenyl, etc.
  • Cycloalkyl is preferably Cs-Cs-cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • Aryl includes unsubstituted and substituted aryl groups and is preferably phenyl, tolyl, xylyl, mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl,
  • Hetaryl mono-, bi- or trinuclear (monocyclic, bicyclic or tricyclic) aromatic ring system having 5 to 14 ring members, containing in addition to carbon atoms as ring members one, two, three or four heteroatoms selected from O, S and N as ring members.
  • copolymer compositions A) according to the invention can advantageously be formulated as gels under normal conditions (20 ° C.). "Gel-like consistency" show formulations which have a higher viscosity than a liquid and which are self-supporting, ie retain the shape given to them without a shape-stabilizing coating. However, in contrast to solid formulations, gel formulations can easily be deformed using shear forces.
  • the viscosity of the gel formers is preferably in a range of greater than 600 to about 60,000 mPas, more preferably from 6,000 to 30,000 mPas.
  • the gels are hair gels.
  • water-soluble monomers and polymers are understood as meaning monomers and polymers which dissolve in water at at least 1 g / l at 20 ° C.
  • Water-dispersible monomers and polymers are understood as meaning monomers and polymers which decompose into dispersible particles with the aid of shearing forces, for example by stirring.
  • Hydrophilic monomers are preferably water-soluble or at least water-dispersible.
  • the copolymers contained in the copolymer compositions A) according to the invention are generally water-soluble.
  • the component a) used to prepare the copolymer compositions A) according to the invention is selected from acrylic acid, salts of acrylic acid, methacrylic acid, salts of methacrylic acid and mixtures thereof.
  • the component a) is preferably used in an amount of 10 to 99.89% by weight, based on the total weight of the monomers used for the polymerization (ie monomers a), monomers b), monomers c) and, if present, monomers d), e), f) and g) add up to 100% by weight).
  • the component a) in an amount of 15 to 89.9 wt .-%, based on the total weight of the used for the polymerization Monomers (ie, monomers a), b) and c) and, if present d), e) f) and g)) used.
  • component a) consists of acrylic acid or of at least one salt of acrylic acid or of a mixture of acrylic acid and at least one salt of acrylic acid.
  • component a) consists of a mixture of acrylic acid, methacrylic acid and / or at least one salt of (meth) acrylic acid.
  • Crosslinkers are preferably used in an amount of 0.01 to 5 wt .-%, particularly preferably 0.05 to 4 wt .-%, based on the total weight of the monomers used for the polymerization (ie monomers a), monomers b), monomers c ) and, if present, monomers d), e), f) and g) add up to 100% by weight).
  • Suitable crosslinkers b) are, for example, acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols.
  • the OH groups of the underlying alcohols may be completely or partially etherified or esterified; however, the crosslinkers contain at least two ethylenically unsaturated groups.
  • Examples of the underlying alcohols are dihydric alcohols such as
  • ethylene oxide or propylene oxide In addition to the homopolymers of ethylene oxide or propylene oxide also block copolymers of ethylene oxide or Propylene oxide or copolymers containing incorporated incorporated ethylene oxide and propylene oxide groups.
  • additional Basic alcohols having more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1, 2,5-pentanetriol, 1, 2,6-hexanetriol, cyanuric acid, sorbitans, sugars such as sucrose, glucose, mannose.
  • the polyhydric alcohols can also be used after reaction with ethylene oxide or propylene oxide as the corresponding ethoxylates or propoxylates.
  • the polyhydric alcohols can also initially be converted by reaction with epichlorohydrin into the corresponding glycidyl ethers. Preference is given to ethylene glycol di (meth) acrylate and polyethylene glycol di (meth) acrylates.
  • Further suitable crosslinkers b) are the vinyl esters or the esters of monohydric, unsaturated alcohols with ethylenically unsaturated C 3 -C 6 -carboxylic acids, for example acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid. Examples of such alcohols are allyl alcohol, 1-buten-3-ol, 5-hexene-1-ol, 1-octen-3-ol,
  • crosslinkers b) are (meth) acrylic esters, various esters of unsaturated carboxylic acids with the polyhydric alcohols described above, for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.
  • Suitable crosslinkers b) are also straight-chain or branched, linear or cyclic, aliphatic or aromatic hydrocarbons which have at least two double bonds which may not be conjugated in aliphatic hydrocarbons, eg. B. divinylbenzene, divinyltoluene, 1, 7-octadiene, 1, 9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes having molecular weights of 200 to 20,000.
  • crosslinkers b) are the acrylamides, methacrylamides and N-allylamines of at least difunctional amines.
  • amines are for example 1, 2-diaminoethane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane,
  • 1, 12-dodecanediamine, piperazine, diethylenetriamine or isophoronediamine are also suitable.
  • amides of allylamine and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least dibasic carboxylic acids, as described above.
  • crosslinkers b) are divinyldioxane, tetraallylsilane or tetravinylsilane.
  • mixtures of the abovementioned compounds c) can also be used.
  • Very particularly preferred crosslinkers b) are ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylates, pentaerythritol triallyl ether, methylenebisacrylamide, ⁇ , ⁇ '-divinylethyleneurea, triallylamine and triallylmonoalkylammonium salts.
  • the term "amide group-containing monomer” also includes urea group-containing monomers.
  • the component c) in an amount of 0.1 to 90 wt .-%, particularly preferably 1 to 85 wt .-%, in particular 5 to 80 wt .-%, based on the total weight of the monomers used for the polymerization (ie Monomers a), monomers b), monomers c) and, if present, monomers d), e), f) and g) add up to 100% by weight) are used.
  • the monomer composition used to prepare the copolymer composition A) preferably contains at least one amide group-containing monomer c) which is selected from ⁇ , ⁇ -ethylenically unsaturated amide group-containing compounds of the general formula (II)
  • Ci-C4-alkyl and the remaining radicals R 4 to R 6 are independently H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, wherein R 4 and R 5, together with the amide group to which they are attached, may also stand for a lactam having 5 to 8 ring atoms, wherein R 5 and R 6 together with the nitrogen atom to which they are attached, also for a five - can stand to seven-membered heterocycle.
  • the monomers c) of the formula (II) are preferably selected from primary amides of .alpha.,. Beta.-ethylenically unsaturated monocarboxylic acids, N-vinylamides of saturated monocarboxylic acids, N-vinyllactams, N-alkyl- and N, N-dialkylamides .alpha., .Beta.-ethylenically unsaturated monocarboxylic acids and mixtures thereof.
  • Preferred monomers c) are N-vinyl lactams and their derivatives, the z.
  • one or more Ci-C6-alkyl substituents such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc., may have. These include z. N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone,
  • N-vinyl-5-ethyl-2-pyrrolidone N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N- Vinyl 7-ethyl-2-caprolactam, etc.
  • N-vinylpyrrolidone and / or N-vinylcaprolactam.
  • Suitable monomers c) are furthermore acrylamide and methacrylamide.
  • Suitable monomers c) are furthermore methyl (meth) acrylamide, methylethacrylamide, ethyl (meth) acrylamide, ethylethacrylamide, n-propyl (meth) acrylamide, isopropyl (meth) acrylamide, n-butyl (meth) acrylamide, tert-butyl ( meth) acrylamide, tert-butylethacrylamide, n-pentyl (meth) acrylamide, n-hexyl (meth) acrylamide, n-heptyl (meth) acrylamide, n-octyl (meth) acrylamide, 1,1,3,3-tetramethylbutyl (meth) acrylamide,
  • Suitable monomers c) are furthermore piperidinyl (meth) acrylamide, morpholinyl (meth) acrylamide and mixtures thereof.
  • Suitable open-chain N-vinylamide compounds as monomers c) are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide,
  • N-vinyl-N-methylpropionamide N-vinyl-butyramide and mixtures thereof. Preference is given to using N-vinylformamide.
  • the monomer composition used to prepare the copolymeric composition A) contains at least one amide group-containing monomer c) which has a group of the formulas (IIIa) or (IIIb)
  • R a is H or C 1 -C 4 -alkyl, is H or C 1 -C 4 -alkyl, or
  • R a and R b together represent (CH 2) i- 4 .
  • the monomers c) of the formulas (IIIa) or (IIIb) are preferably selected from monomers having a group of the formulas (IIIa.1) or (IIIb.1)
  • Preferred as monomers c) are the compounds of the formula:
  • Suitable urea group-containing monomers c) are, for. N-vinyl or N-allyl urea or derivatives of imidazolidin-2-one. These include N-vinyl- and N-allylimidazolidin-2-one, N-vinyloxyethyl-imidazolidin-2-one,
  • Preferred urea group-containing monomers c) are
  • the amide group-containing monomers c which have a group of the formulas (IIIa) or (IIIb), in an amount of 0.1 to 20 wt .-%, particularly preferably 0.5 to 10 wt .-%, based on the total weight of the monomers used for the polymerization.
  • component d) comprises a compound which is different from the compounds of component a) and has a free-radically polymerizable, .alpha.,. Beta.-ethylenically unsaturated double bond and at least one anionogenic and / or anionic group Molecule can be used.
  • component d) is preferably used in an amount of from 0.1 to 40% by weight, particularly preferably from 0.5 to 25% by weight, based on the total weight of the monomers used for the polymerization ( ie monomers a), monomers b), monomers c) and, if present, monomers d), e), f) and g) add up to 100% by weight).
  • the compounds d) are selected from monoethylenically unsaturated carboxylic acids, phosphonic acids and mixtures thereof.
  • the monomers d) include monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 25, preferably 3 to 6, carbon atoms, which can also be used in the form of their salts or anhydrides. Examples thereof are ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and fumaric acid.
  • the monomers d) furthermore include the half-esters of monoethylenically unsaturated dicarboxylic acids having 4 to 10, preferably 4 to 6, carbon atoms, eg. B. of maleic acid such as monomethyl maleate.
  • the monomers d) also include monoethylenically unsaturated sulfonic acids and phosphonic acids, for example sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, vinyl phosphonic acid and allyl phosphonic acid.
  • the monomers d) also include the salts of the abovementioned acids, in particular the sodium, potassium and ammonium salts and the salts with amines.
  • the monomers d) can be used as such or as mixtures with one another. The stated proportions by weight are all based on the acid reforming.
  • component d) is selected from ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and mixtures thereof.
  • the monomer composition used to prepare the copolymer composition A) contains no monomer d).
  • the monomer composition used to prepare the copolymer composition A) may additionally contain at least one compound e) having a free-radically polymerizable, .alpha.,. Beta.-ethylenically unsaturated double bond and at least one cationogenic and / or cationic group per molecule.
  • the component e) in an amount of 0.01 to 50 wt .-%, preferably 0.1 to 40 wt .-%, particularly preferably 0.2 to 25 wt .-%, based on the total weight of monomers used for the polymerization (ie monomers a), monomers b), monomers c) and, if present, monomers d), e), f) and g) add up to 100% by weight).
  • copolymers present in the copolymer composition A) preferably have an excess of anionogenic and / or anionic groups. If, therefore, monomers e) are used, then preferably in amounts such that the copolymer in A) faces a molar excess of anionogenic / anionic groups cationogenic / cationic groups of at least 5: 1, preferably at least 10: 1.
  • the cationogenic and / or cationic groups of component e) are preferably nitrogen-containing groups, such as primary, secondary and tertiary amino groups, and quaternary ammonium groups.
  • the nitrogen-containing groups are tertiary amino groups or quaternary ammonium groups.
  • Charged cationic groups can be generated from the amine nitrogens either by protonation or by quaternization with acids or alkylating agents. These include z.
  • carboxylic acids such as lactic acid, or mineral acids such as phosphoric acid, sulfuric acid and hydrochloric acid, or as alkylating C1-C4 alkyl halides or sulfates such as ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate.
  • Protonation or quaternization can generally be carried out both before and after the polymerization.
  • component e) is selected from esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with aminoalcohols which may be mono- or dialkylated on the amine nitrogen, amides of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with diamines which contain at least one primary or secondary amino group, ⁇ , ⁇ -diallylamine, N, N-diallyl-N-alkylamines and derivatives thereof, vinyl- and allyl-substituted nitrogen heterocycles, vinyl- and allyl-substituted heteroaromatic compounds, and mixtures thereof.
  • Preferred monomers e) are the esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols.
  • Preferred amino alcohols are
  • esters which are mono- or dialkylated on the amine nitrogen by C 1 -C 8 -monosubstituted.
  • acid component of these esters are z.
  • Acrylic acid, methacrylic acid and mixtures thereof are preferably used as the acid component.
  • Preferred monomers e) are N-methylaminoethyl (meth) acrylate
  • N-ethylaminoethyl (meth) acrylate N- (n-propyl) aminoethyl (meth) acrylate
  • N- (tert-butyl) aminoethyl (meth) acrylate N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminomethyl (meth) acrylate,
  • the component e) consists only of
  • Suitable monomers e) are furthermore the amides of the abovementioned ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with diamines which have at least one primary or secondary amino group.
  • diamines having a tertiary and a primary or secondary amino group.
  • Preferred as monomers e) are z. N- [tert -butylaminoethyl] (meth) acrylamide, N- [2- (dimethylamino) ethyl] acrylamide, N- [2- (dimethylamino) ethyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide , N- [3- (Dimethylamino) propyl] methacrylamide, N- [4- (dimethylamino) butyl] acrylamide, N- [4- (dimethylamino) butyl] methacrylamide, N- [2- (diethylamino) ethyl] acrylamide, N - [4- (dimethylamino) cyclohexyl] acrylamide and N- [4- (dimethylamino) cyclohexyl] methacrylamide.
  • component e) comprises as vinyl-substituted heteroaromatic compound at least one N-vinylimidazole compound.
  • component e) is selected from N-vinylimidazole compounds and mixtures containing at least one N-vinylimidazole compound.
  • Suitable N-vinylimidazole compounds are compounds of the formula
  • R 1 to R 3 are independently hydrogen, Ci-C4-alkyl or phenyl.
  • R 1 to R 3 are hydrogen.
  • N-vinylimidazole compounds of the general formula (I) are also suitable.
  • R 1 to R 3 are independently hydrogen, Ci-C4-alkyl or phenyl.
  • Ph phenyl
  • monomer e) is 1-vinylimidazole (N-vinylimidazole) and are mixtures containing N-vinylimidazole.
  • Suitable monomers e) are also the compounds obtainable by protonation of the aforementioned N-vinylimidazole compounds. Suitable acids are those listed above.
  • Suitable monomers e) are also vinyl- and allyl-substituted nitrogen heterocycles, other than vinylimidazoles, such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and the salts thereof.
  • the monomer composition used to prepare the copolymer composition A) comprises, as monomer e), N-vinylimidazole or consists of N-vinylimidazole.
  • N-vinylimidazole in an amount of from 0.01 to 10% by weight, preferably from 0.1 to 8% by weight, based on the total weight of the monomer composition.
  • copolymer composition A) it is additionally possible to use at least one monomer f) which is different from the components a) to e) and is copolymerizable therewith.
  • Suitable monomers f) are selected from compounds of the general formulas IV a) and IV b)
  • H 2 C C-CX- (CH 2 -CH 2 -O) k (CH 2 -CH (CH 3 ) -O)
  • R 8 is hydrogen or C 1 -C 4 -alkyl, preferably methyl
  • R 9 is hydrogen, C 1 -C 30 -alkyl, C 2 -C 3 o-alkenyl or C 5 -C 8 -cycloalkyl,
  • X is O or a group of the formula NR 10 wherein R 10 is H, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • IV a) and IV b) k is preferably an integer from 1 to 500, in particular 3 to 250.
  • I is an integer from 0 to 100.
  • R 8 in the formulas IV a) and IV b) is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
  • R 8 in the formulas IV a) and IV b) is hydrogen, methyl or ethyl.
  • R 9 is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 1, 1, 3,3- Tetramethylbutyl, ethylhexyl, n-nonyl, n-decyl, n-undecyl, tridecyl, myristyl, pentadecyl, palmityl, heptadecyl,
  • R 9 is cetyl (hexadecyl), stearyl (octadecyl) or cetearyl, ie a mixture of cetyl and stearyl.
  • X in the formula IV a) is O or NH.
  • Suitable polyether acrylates IV a) are, for.
  • Suitable polyetherols can easily be prepared by reacting ethylene oxide, 1,2-propylene oxide and / or epichlorohydrin with a starter molecule, such as water or a short-chain alcohol R 9 -OH.
  • the alkylene oxides can be used individually, alternately in succession or as a mixture.
  • the polyether acrylates IV a) can be used alone or in mixtures for the preparation of the polymers used according to the invention.
  • Suitable allyl alcohol alkoxylates IV b) are, for.
  • Suitable polyetherols can be easily prepared by reacting ethylene oxide, 1, 2-propylene oxide and / or epichlorohydrin with a Starter alcohol R 9 -OH are produced.
  • the alkylene oxides can be used individually, alternately in succession or as a mixture.
  • the allyl alcohol alkoxylates IV b) can be used alone or in mixtures for the preparation of the polymers used according to the invention.
  • H 2 C CC-O- (CH 2 -CH 2 -O) k (CH 2 -CH (CH 3 ) -O)
  • k and I independently of one another represent an integer from 0 to 100, the sum of k and I being at least 5,
  • R 8 is hydrogen or methyl
  • R 9 is Ce-Cso-alkyl.
  • k is preferably an integer from 5 to 100 and I is 0.
  • R 9 is cetyl, stearyl or cetearyl.
  • a mixture of a Ci8-22-alkyl-polyethylene glycol methacrylate with methyl methacrylate is commercially available under the name Plex-6877- ⁇ .
  • a mixture of a Ci6-i8-alkyl-polyethylene glycol methacrylate with methacrylic acid is commercially available under the name Lutencryl® 250 (C16-18 alkyl-PEG-methacrylate in methacrylic acid (50%)).
  • the component f) in an amount of 0.01 to 25 wt .-%, preferably 0.1 to 20 wt .-%, particularly preferably 0.2 to 15 wt .-%, based on the total weight of used for the polymerization, used (ie, the monomers a), monomers b), monomers c) and, if present, monomers d), e), f) and g) add up to 100 wt .-%).
  • the monomer composition used to prepare the copolymer composition A) may additionally contain, in copolymerized form, at least one further monomer g) other than the monomers a) to f).
  • the further monomer g) is preferably selected from gl) esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with C1-C30-alkanols,
  • Aminoalcohols having a primary or secondary amino group g4) urethane (meth) acrylates having alkylene oxide groups,
  • esters of vinyl alcohol and allyl alcohol with C 1 -C 8 -monocarboxylic acids esters of vinyl alcohol and allyl alcohol with C 1 -C 8 -monocarboxylic acids, g 6) C 1 -C 30 -alkyl vinyl ethers,
  • Suitable esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with C1-C30-alkanols are, for example, Methyl (meth) acrylate, methyl methacrylate, ethyl (meth) acrylate, ethyl ethacrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, tert-butyl ethacrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 1,1,3,3-tetramethylbutyl (meth) acrylate , Ethylhexyl (meth) acryl
  • n-undecyl (meth) acrylate tridecyl (meth) acrylate, myristyl (meth) acrylate,
  • the monomers gl) are advantageously suitable for modifying the properties of the copolymer composition A).
  • C 1 -C 4 -alkyl (meth) acrylates are characterized by a higher polarity and water solubility than alkyl (meth) acrylates having more than 4 carbon atoms in the alkyl radical.
  • Preferred monomers g1) are the esters of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic and dicarboxylic acids with C 1 -C 3 -alkanols, in particular methyl methacrylate.
  • Preferred monomers gl) are also the esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with C 8 -C 22 -alkanols, in particular stearyl (meth) acrylate, lauryl (meth) acrylate and mixtures thereof.
  • the monomer gl) is selected from C 1 -C 3 -alkyl (meth) acrylates, C 8 -C 22 -alkyl (meth) acrylates and mixtures thereof.
  • the component gl) is used in an amount of from 0.1 to 40% by weight, particularly preferably from 0.5 to 20% by weight, based on the total weight of the monomers used for the polymerization (ie monomers a) , Monomers b), monomers c) and, if present, monomers d), e), f) and g) add up to 100 wt .-%).
  • Monomer g2) Suitable additional monomers g2) are furthermore 2-hydroxyethyl acrylate,
  • the component g2) in an amount of 0.1 to 1 wt .-%, based on the total weight of the monomers used for the polymerization used (ie monomers a), monomers b), monomers c) and, if present Monomers d), e), f) and g) add up to 100% by weight).
  • Suitable additional monomers g3) are 2-hydroxyethylacrylamide,
  • the component g3) in an amount of 0.1 to 10 wt .-%, based on the total weight of the monomers used for the polymerization, used (ie monomers a), monomers b), monomers c) and, if present Monomers d), e), f) and g) add up to 100% by weight).
  • component g4 Suitable urethane (meth) acrylates with alkylene oxide groups g4) are described in DE 19838851 (component e2)), to which reference is made in its entirety. If present, component g4) is used in an amount of from 0.1 to 25% by weight, particularly preferably from 0.5 to 20% by weight, based on the total weight of the monomers used for the polymerization (ie monomers a) , Monomers b), monomers c) and, if present, monomers d), e), f) and g) add up to 100 wt .-%).
  • Suitable esters of vinyl alcohol with Ci-C3o monocarboxylic acid are, for. Vinyl formate, vinyl acetate, vinyl n-propionate, vinyl isopropanoate, vinyl n-butanoate, vinyl tert-butanoate, vinyl n-pentanoate, vinyl n-hexanoate, vinyl n-heptanoate, vinyl n-octanoate , Vinyl-1, 1, 3, 3-tetramethylbutanoate, vinyl-ethylhexanoate, vinyl-n-nonanoate, vinyl-n-decanoate, vinyl-n-undecanoate, vinyltridecanoate, vinylmyristanoate, vinylpentadecanoate, vinylpalmitanoate, vinylheptadecanoate, vinyloctadecanoate, vinylnonadecanoate, vinylarrachinanoate , Vinylbenhenanoate, vinyllignocerenanoate, vinylcerotinan
  • Preferred esters of vinyl alcohol with Ci-C3o monocarboxylic acid are, for.
  • the component g5) in an amount of 0.1 to 10 wt .-%, particularly preferably 0.5 to 20 wt .-%, based on the total weight of the monomers used for the polymerization, used (ie the monomers a ), Monomers b), monomers c) and, if present, monomers d), e), f) and g) add up to 100% by weight).
  • Suitable monomers of g6) are, for. B. n-octyl vinyl ether,
  • component g6 is used in an amount of from 0.1 to 10% by weight, based on the total weight of the monomers used for the polymerization (ie monomers a), monomers b), monomers c) and if present, monomers d), e), f) and g) add up to 100 wt .-%).
  • Monomer g7) Preferred vinylaromatics g7) are styrene, 2-methylstyrene, 4-methylstyrene,
  • Particularly preferred are styrene and 2-methylstyrene, especially styrene.
  • component g7) is used in an amount of from 0.1 to 10% by weight, based on the total weight of the monomers used for the polymerization (ie monomers a), monomers b), monomers c) and, if present , Monomers d), e), f) and g) add up to 100% by weight).
  • Preferred monomers g8) are vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.
  • the component g8) in an amount of 0.1 to 10 wt .-%, based on the total weight of the monomers used for the polymerization, used (ie, the monomers a), monomers b), monomers c) and, so far present, monomers d), e), f) and g) add up to 100 wt .-%).
  • the abovementioned monomers g) can each be used individually or in the form of any desired mixtures.
  • the component g) (ie, the sum of the monomer g1), g2), g3), g4), g5), g6), g7) and g8) in an amount of 0.1 to 40% by weight. %, based on the total weight of the monomers used for the polymerization (ie monomers a), monomers b), monomers c) and, if present, monomers d), e), f) and g) add up to 100 wt. -%).
  • a suitable amount for additional Monomers g) is in a range of 0.1 to 35 wt .-%, in particular 0.2 to 30 wt .-%, based on the total weight of the monomers used for the polymerization.
  • for the preparation of the copolymer composition A) based on the total weight of the monomers used for the polymerization, based on the total weight of the monomers used for the polymerization,
  • component c) preferably comprises at least 50% by weight, based on the total weight of component c), of vinylpyrrolidone, 2-ureidomethacrylate and / or vinylcaprolactam.
  • component c) comprises at least 50% by weight, based on the total weight of component c), of vinylpyrrolidone.
  • At least one crosslinking compound b 10 to 84.9% by weight of at least one ⁇ , ⁇ -ethylenically unsaturated amide group-containing compound c), 0 to 10% by weight, of at least one compound e) with a free-radically polymerizable, ⁇ , ⁇ -ethylenic unsaturated double bond and at least one cationogenic and / or cationic groups per molecule,
  • At least one compound f which is preferably selected from among Cs-C22-alkyl group-terminated polyether (meth) acrylates, with
  • At least one compound gl which is selected from esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with C1-C30 alkanols, preferably selected from Ci-C3-alkyl (meth) acrylates, C8 -C22-
  • At least one compound g6) which is selected from C8-C22-alkyl vinyl ethers used.
  • N-vinylimidazole as monomer e 1 to 10% by weight of N-vinylimidazole as monomer e), 0 to 20% by weight of at least one compound f) selected from C8-C22-alkyl-terminated polyether (meth) acrylates,
  • At least one compound gl which is selected from esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with C1-C30-
  • a preferred ester of an ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid with a Ci-C3o-alkanol is methyl methacrylate.
  • a mixture of a Ci8-22-Alkylpolyethylen- glycol methacrylate with methyl methacrylate is commercially available under the name Plex- 6877-0.
  • a mixture of a Ci6-i8-alkyl-polyethylene glycol methacrylate with methacrylic acid is commercially available under the name Lutencryl® 250 (50 wt .-% solution in methacrylic acid).
  • Excipient H1 compound having at least one tertiary amino group
  • the component H1) is preferably used in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on the monomer component a).
  • suitable cyclic amines which have at least one tertiary Aminofunkti- on, z.
  • B N-alkylimidazoles.
  • a preferred adjuvant H1) is N-methylimidazole.
  • suitable compounds having at least one tertiary amino group are, for.
  • Trialkanolamine such as triethanolamine, tri-n-propanolamine, tri-n-butanolamine, methyldiethanolamine, ethyldiethanolamine, ⁇ , ⁇ -dimethylethanolamine, N, N-dimethylpropanolamine, ⁇ , ⁇ -diethylethanolamine, etc.
  • Trialkanol- caused by manufacturing as further component (s) contain the corresponding dialkanolamine and / or monoalkanolamine. Such a mixture is also suitable in the method according to the invention.
  • Triethanolamine is preferably used as adjuvant H1).
  • the component H2) in an amount of 0.01 to 2 parts by weight, preferably 0.05 to 0.5 parts by weight, based on the total weight of the monomers used for the polymerization a) and c), and, if present, monomers d), e), f) and g) are used.
  • the auxiliary H2) is preferably selected from acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, acrylic anhydride, methacrylic anhydride, phthalic anhydride, etc.
  • the auxiliary H2) is in particular selected from acetic anhydride, succinic anhydride, methacrylic anhydride and mixtures thereof.
  • adjuvant H2 is a compound whose hydrolysis products are monomers in the context of the invention, such as. B. (meth) acrylic anhydride, the proportion of the hydrolysis product is attributed to the weight of the corresponding Monomerkompo- nente.
  • the component H3) in an amount of 0.1 to 30 parts by weight, preferably 0.5 to 15 parts by weight, based on the total weight of the monomers used for the polymerization a), b) and c) , and, if present, monomers d), e), f) and g) used.
  • Suitable silicone-containing surfactants are generally Polydi- alkylsiloxanes, especially polydimethylsiloxanes in which one or more alkyl groups have been replaced by lipophilic, hydrophilic ionic or nonionic radicals.
  • Suitable silicone-containing surfactants H3 are known under the INCI name dimethicone copolyols or silicone surfactants compounds such.
  • B. under the brand names Abil® (Fa. Th. Goldschmidt), Alkasil® (Fa. Rhöne-Poulenc), Silicone Polyol Copolymer® (Fa Genesee), Belsil® (Fa. Wacker), Silwet® ( from OSI) or Dow Corning (from Dow Corning). These include compounds with CAS numbers 64365-23-7; 68937-54-2; 68938-54-5; 68937-55-3.
  • a suitable commercially available compound is Belsil® DMC 6031.
  • Preferred silicone-containing surfactants H3) are polydialkylsiloxane-polyether copolymers, which may additionally have at least one amino group.
  • Preferred silicone compounds H3) are polysiloxanes of the general formula (E)
  • R n and R ° independently of one another represent alkyl, cycloalkyl, aryl or arylalkyl, Z 1 and Z 2 independently of one another represent radicals of the formula (F)
  • X 1 is O or N RP, where RP is hydrogen, alkyl, cycloalkyl or aryl.
  • the sum of u and v is selected so that the molecular weight of the polysiloxanes H1) is in a range of about 300 to 30,000.
  • the radicals R n and R ° are independently selected from among methyl, ethyl, cyclohexyl, phenyl and benzyl. More preferably, R n and R ° are both methyl.
  • c is an integer from 3 to 500, preferably 5 to 250, and u1 and u2 are independently from 2 to 500, especially 3 to 250, especially 5 to 100, stand.
  • Preferred silicone compounds H3) are furthermore selected from polysiloxanes of the general formula (G)
  • the radicals R q are each independently of one another alkyl, cycloalkyl or aryl, d is an integer from 2 to 1000, e is an integer from 2 to 100, f is an integer is from 2 to 8, and is OH, NHR r or a radical of the formula (F), as defined above, where R r is hydrogen, Ci-Cs-alkyl, Cs-Cs-cycloalkyl or a radical of the formula - (CH 2) w -NH 2, where w is an integer from 1 to 10, preferably 2 to 6, and mixtures thereof.
  • R r is hydrogen, Ci-Cs-alkyl, Cs-Cs-cycloalkyl or a radical of the formula - (CH 2) w -NH 2, where w is an integer from 1 to 10, preferably 2 to 6, and mixtures thereof.
  • suitable compounds of the formula (G) are the ethoxylated and / or propoxylated polydimethylsiloxanes of the general formula (G.1)
  • d is an integer from 2 to 1000, preferably 3 to 500, in particular 5 to 100
  • e is an integer from 2 to 100, preferably from 3 to 50, in particular from 4 to 20
  • f is an integer from 2 to 8
  • u and v independently of one another are an integer from 0 to 500, preferably 0 to 250, wherein the sum of u and v is> 1, preferably> 5, in particular 10.
  • Suitable compounds of the formula G.1 are obtainable under the name Wacker-Belsil® DMC 6031 and Pluriol® ST 4005 (BASF SE).
  • Preferred silicone compounds H3) are furthermore polysiloxanes having repeating units of the general formula (I)
  • d is an integer from 0 to 100
  • g is an integer from 1 to 8
  • R s and R 1 independently of one another are C 1 -C -alkylene, the sequence of the alkylene oxide units is arbitrary and e and f independently of one another are an integer from 0 to 200, the sum of r and s being> 0.
  • R s and R 1 are preferably, independently of one another, a C 2 -C 4 -alkylene radical.
  • R s and R 1 independently of one another represent a C 2 -C 3 -alkylene radical.
  • the molecular weight of the compound of formula (J) is in a range of about 300 to 100,000.
  • d is an integer of 1 to 20, such as. 2 to 10.
  • the end groups of the polysiloxanes having repeating units of the general formula (I) are selected from (CH 3) 3 SiO, H, C 1 -C 8 -alkyl and mixtures thereof.
  • a preferred alkyl end group is methyl.
  • Amino-containing compounds having repeating units of the general formula (I) preferably have an amine number in a range from about 2 to 50, in particular from 3 to 20.
  • Suitable alkoxylated Siloxanamine of formula J are, for. As described in WO-A-97/32917, which is incorporated herein by reference in its entirety. Commercially available compounds are z. B. the Silsoft brands of Momentive Performance Materials (formerly Witco), z. Silsoft A-843.
  • Preferred silicone compounds H3) are also available under the trade name Wetsoft® NE 810 and Wetsoft® NE 820 (Wacker). Preferred silicone compounds H3) are furthermore polysiloxanes having repeating units of the general formula (K)
  • R u is a Ci-Cs-alkylene radical
  • R v and R w are independently hydrogen, Ci-Cs-alkyl or Cs-Cs-cycloalkyl, the order of the siloxane units is arbitrary, h, i and k independently represent 0 to 100, wherein the sum of h, i and k is at least 3, I is an integer from 2 to 8,
  • Z 4 is a radical of the formula (F.1)
  • R x is hydrogen or a Ci-Cs-alkyl radical, and mixtures thereof.
  • the radical R u is preferably a C 2 -C 4 -alkylene radical.
  • R v and R w independently represent hydrogen or Ci-C 4 alkyl.
  • the sum of h, I and k is chosen such that the molecular weight of the compound of formula (K) is in a range of about 300 to 100,000, preferably 500 to 50,000.
  • the total number of alkylene oxide units of the radical of the formula (F.1), ie the sum of u and v, is preferably in a range from about 3 to 200, preferably 5 to 80.
  • the radical R x is preferably hydrogen or C 1 -C 4 -alkyl.
  • a suitable compound of the formula (K) is z.
  • Another preferred silicone compounds H3) is the compound with the INCI name Methoxy PEG / PPG-7/3 Aminopropyl Dimethicone. This is commercially available under the name ABIL® Soft AF 100 from Evonik Industries.
  • the component H4) in an amount of 0.1 to 15 parts by weight, particularly preferably 0.3 to 10 parts by weight, based on the total weight of the monomers used for the polymerization a), b) and c ), and, if present, monomers d), e), f) and g) are used.
  • the adjuvant H4) is preferably selected from nonionic surfactants having an HLB value of at most 7, in particular nonionic surfactants having an HLB value of at most 5.
  • Suitable nonionic surfactants as adjuvant H4) are preferably selected from alkoxylated primary Cs-Cso alcohols,
  • suitable alkoxylated primary alcohols preferably have 10 to 22 C-atoms, more preferably 12 to 20 C-atoms. They are preferably from 1 to 50, more preferably 1 to 30, such as. B. 2 to 20 moles alkoxylated alkoxide per mole of alcohol. For alkoxylation z.
  • They are preferably alcohols having linear or branched alkyl or alkenyl radicals, the latter also being able to have a plurality of nonadjacent double bonds.
  • alcohols in which the alcohol radical is methyl-branched linearly or in the 2-position or are mixtures of alcohols with linear and methyl-branched radicals, as are usually present in oxo alcohol radicals.
  • alkoxides especially ethoxylates with alcohols of native origin, and oxo alcohol alkoxylates and guerbet alcohol alkoxylates.
  • alkoxilates of alcohols obtainable by reduction of natural fatty acids and alcohol mixtures having 8 to 30, preferably 10 to 22, carbon atoms, eg.
  • n-decanol lauric alcohol, myristic alcohol, cetyl alcohol, stearic alcohol, oleic alcohol, lignoceryl alcohol, ceryl alcohol, etc.
  • the indicated degrees of alkoxylation each represent statistical averages which may be an integer or a fractional number for a particular product.
  • alkoxylated alcohols which have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • Alkoxylated alcohols containing EO and PO groups together in the molecule can also be used.
  • block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
  • H2 also mixed alkoxylated primary alcohols can be used, in which EO and PO units are not distributed in blocks, but statistically distributed.
  • Such products are for. B. by simultaneous action of ethylene and propylene oxide on primary alcohols available.
  • Suitable as adjuvant H4) esters of Cs-Cso-carboxylic acids with polyhydric alcohols are preferably derived from linear or branched, saturated or mono- or polyunsaturated carboxylic acids having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 C atoms in the alkyl or alkenyl radical, such as
  • Suitable polyhydric alcohols are preferably selected from straight-chain, branched or carbocyclic, saturated or unsaturated hydrocarbon compounds having at least three carbon atoms and at least three (esterifiable) hydroxyl groups.
  • Unsaturated hydrocarbon compounds may have one or more, preferably 1, 2 or 3 CC double bonds. geminal See such polyols are also usable.
  • the polyol is in particular a straight-chain or branched saturated hydrocarbon having 3 to 30 carbon atoms and 3 to 10 hydroxyl groups.
  • Preferred examples of useful polyols are: glycerol, di-, tri- and polyglycerols, low molecular weight partially or fully hydrolyzed polyvinyl acetate, 1, 2,4-butanetriol, trimethylolmethane, trimethylolethane, trimethylolpropane, trimethylolbutane, 2,2,4- Trimethyl-1, 3-pentanediol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, D-, L- and meso-erythritol, D- and L-arabitol, adonite, xylitol, sorbitol, mannitol, dulcitol, inositols and mixtures thereof.
  • auxiliary H4 alkoxylates of esters of Cs-C50-carboxylic acids with polyhydric alcohols.
  • the alkoxylation can be carried out with ethylene oxide, propylene oxide and / or butylene oxide.
  • Preferred alkylene oxide is ethylenoxide.
  • Another class of preferred nonionic surfactants which can be used as adjuvant H4) are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58 / 217598 or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533.
  • auxiliaries H4 are nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide and also fatty acid alkanolamides.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • auxiliaries H4 are polyhydroxy fatty acid amides of the formula (2),
  • R 17 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] represents a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (3)
  • R 18 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 19 is a linear, branched or cyclic alkylene radical having 2 to 8 carbon atoms or an arylene group having 6 to 8 carbon atoms, and
  • R 20 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, where Ci-C4-alkyl or
  • Phenyl radicals are preferred, and
  • [Z] 1 represents a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [Z] 1 is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted, for example, according to WO-A-95/07331, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired polyhydroxy fatty acid amides.
  • Suitable nonionic surfactants as adjuvant H4 are specific (HLB values and, if appropriate, brand name in brackets):
  • Polyoxyethylene sorbitol beeswax derivative (4.0; Atlas G-1727), Propylene glycol fatty acid ester (4.1, Emcol PM-50),
  • Sorbitan monostearate (4.7, Span 60 or Arlacel 60)
  • Sorbitan monopalmitate (6.7, Span 40 or Arlacel 40), and mixtures thereof.
  • Particularly suitable nonionic surfactants as adjuvant H4) are the Dehymuls® grades from COGNIS Care Chemicals. These include:
  • Dehymuls LE PEG-30 dipolyhydroxystearate
  • Dehymuls E mixture of higher molecular weight fatty acid esters, fatty acid salts and oil-binding additives; dicocoyl pentaerythrityl distearyl citrate and sorbitan sesquioleate and beeswax (cera alba) and aluminum stearate),
  • Dehymuls K (petrolatum and decyl oleate and dicocoyl pentaerythrityl distearyl citrate and sorbitan sesquioleate and microcrystalline wax (cera microcristallina) and mineral oil and beeswax (cera alba) and aluminum stearate),
  • Dehymuls PGPH polyglycerol-poly-12-hydroxystearic acid ester
  • Dehymuls SSO sorbitan sesquioleate
  • suitable nonionic surfactants as adjuvant H4 are the Hypermer® grades from ICI. These include:
  • Hypermer LP6 polymeric fatty acid ester, molecular weight (MW) about 4300
  • Hypermer LP7 Hypermer LP6
  • Hypermer B239 (block copolymer of a polyhydroxy fatty acid and polyethylene oxide, MW about 3500),
  • Hypermer B246 (block copolymer of a polyhydroxy fatty acid and polyethylene oxide, MW about 7500),
  • Hypermer B261 (block copolymer of a polyhydroxy fatty acid and polyethylene oxide, MW approx. 9600),
  • Hypermer E-464 (copolymer with a long hydrophobic alkylene chain and various anionic / nonionic hydrophiles, MW ca. 2300),
  • Hypermer A-109 block copolymer of a fatty acid or long-chain alkylene and EO
  • Hypermer A-409 block copolymer of a fatty acid or long-chain alkylene and EO.
  • sorbitan trioleate is used as adjuvant H4).
  • Sorbitan trioleate is commercially available under the trade name Span® 85.
  • a mixture of cetearyl glucoside and cetearyl alcohol is used as adjuvant H4).
  • Such a mixture is commercially available under the brand name Emulgade® PL 68/50.
  • the preparation of the copolymer composition A) takes place by the method of precipitation polymerization.
  • solvents are used in which the starting materials for the polymerization soluble and the resulting polymer are insoluble.
  • the polymerization takes place in an aprotic solvent or solvent mixture.
  • the polymerization is carried out in a mixture of a cosmetically acceptable oil body and a different aprotic solvent or solvent mixture.
  • a substantially anhydrous aprotic solvent or solvent mixture is used.
  • Essentially Anhydrous in the context of the invention means that the aprotic solvents or solvent mixtures are used in a technically available quality and are generally not subjected to removal of residual water.
  • essentially anhydrous is therefore understood water contents of up to 3% by weight, preferably up to 2% by weight, based on the total weight of the aprotic solvent or solvent mixture.
  • the water content is in a range of 0.05 to 2 wt .-%.
  • the anhydrides used according to the invention as auxiliary H2) effectively remove water introduced into the reaction mixture with the solvent.
  • Suitable solvents are, for example, aromatic hydrocarbons such as toluene, xylenes, benzene; aliphatic and cycloaliphatic hydrocarbons, such as n-alkanes or cyclohexane; Esters of acetic acid such as ethyl acetate or butyl acetate; Ether such.
  • the oil bodies are preferably selected from: vegetable oils, such as palm oil, rapeseed oil, castor oil, coconut oil, cod liver oil, corn oil, soybean oil, linseed oil, olive oil, peanut oil, safflower oil, sesame oil, grapefruit oil, basil oil, apricot oil, ginger oil, geranium oil, orange oil , Rosemary oil, macadamia oil, onion oil, tangerine oil, pine oil, sunflower oil, oxidized vegetable oils,
  • vegetable oils such as palm oil, rapeseed oil, castor oil, coconut oil, cod liver oil, corn oil, soybean oil, linseed oil, olive oil, peanut oil, safflower oil, sesame oil, grapefruit oil, basil oil, apricot oil, ginger oil, geranium oil, orange oil , Rosemary oil, macadamia oil, onion oil, tangerine oil, pine oil, sunflower oil, oxidized vegetable oils,
  • hydrogenated vegetable oils such as hydrogenated palm oil, hydrogenated rapeseed oil or hydrogenated soybean oil
  • Vegetable oil esters such as rapeseed oil methyl ester
  • animal oils such as lard oil, fish oils,
  • Silicone oils (cyclomethicones, silicon methicone types, etc.),
  • Paraffin oils, aromatic hydrocarbons and aromatic hydrocarbon mixtures e.g. Xylene, Solvesso 100, 150 or 200, and the like, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms,
  • Esters of linear or branched C6-C22 fatty acids with linear or branched C6-C22 fatty alcohols include z.
  • Erucyl behenate and erucyl erucate include, in particular, the esters of linear C6-C22 fatty acids with branched alcohols, in particular esters of 2-ethylhexanol,
  • Esters of linear and / or branched fatty acids with polyhydric alcohols such as, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, dimerdiol (dimeric fatty alcohols) or trimer triol) or guarenteed alcohols,
  • the oil body is preferably selected from vegetable oils such as palm oil, rapeseed oil, castor oil, coconut oil, cod liver oil, corn oil, soybean oil, linseed oil, olive oil, peanut oil, safflower oil, sesame seed oil, grapefruitol, basil oil, apricot oil, ginger oil, geranium oil, orange oil, rosemary oil, macadamia oil, Onion oil, tangerine oil, pine oil and sunflower oil.
  • vegetable oils such as palm oil, rapeseed oil, castor oil, coconut oil, cod liver oil, corn oil, soybean oil, linseed oil, olive oil, peanut oil, safflower oil, sesame seed oil, grapefruitol, basil oil, apricot oil, ginger oil, geranium oil, orange oil, rosemary oil, macadamia oil, Onion oil, tangerine oil, pine oil and sunflower oil.
  • a particularly preferred oil body is soybean oil.
  • Another particularly preferred oil body is the ester of linear or branched C6-C22 fatty acids with ethylene glycol and / or propylene glycol.
  • the oil body is Waglinol® 2/7680 (INCI: propylene glycol dicaprylate / caprate).
  • the polymerization according to the first embodiment is preferably carried out in ethyl acetate or in a mixture of cyclohexane and ethyl acetate.
  • the ratio of cyclohexane to ethyl acetate is preferably in a range of 45:55 to 55:45.
  • the polymerization according to the second embodiment preferably takes place in a mixture of soybean oil and ethyl acetate.
  • the ratio of soybean oil to ethyl acetate is preferably in a range of 1: 3 to 3: 1, more preferably 1: 2 to 2: 1.
  • the polymerization according to the second embodiment is preferably carried out in a mixture of esters of linear or branched C 6 -C 22 fatty acids with ethylene glycol and / or propylene glycol and ethyl acetate.
  • the ratio of ester of linear or branched fatty acids with ethylene glycol and / or propylene glycol to ethyl acetate is preferably in the range of 1: 5 to 5: 1.
  • the polymerization takes place in a mixture of Waglinol® 2/7680 (INCI: propylene glycol dicaprylate / caprate) and ethyl acetate.
  • Waglinol® 2/7680 ICI: propylene glycol dicaprylate / caprate
  • the ratio of Waglinol® 2/7680 (INCI: propylene glycol dicaprylate / caprate) to ethyl acetate is preferably in the range of 1: 5 to 5: 1.
  • the precipitation polymerization is usually carried out at temperatures of 40 to 100 ° C, preferably 50 to 95 ° C, in particular 60 to 90 ° C.
  • the precipitation polymerization is usually carried out at pressures of 1 to 15 bar, in particular 1 to 6 bar. If the polymerization is not carried out under elevated pressure, the solvent or solvent mixture determined by the corresponding boiling temperatures, the maximum reaction temperature.
  • the monomers can be polymerized by means of free-radical initiators.
  • the customary peroxo and / or azo compounds can be used, for example alkali metal or ammonium peroxidisulfates, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide,
  • Diisopropyl peroxydicarbamate bis (o-toluoyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, tert-butyl peroctoate, dilauroyl peroxide, tert-butyl perisobutyrate, tert-butyl peracetate, di-tert-amyl peroxide, tert-butyl hydroperoxide, 2,2 ' Azo-bis-isobutyronitrile, azo-bis (2-amidinopropane) dihydrochloride, azobis (2,4-dimethylvaleronitrile) or
  • initiator mixtures or redox initiator systems such as. B.
  • At least two free-radical initiators are used for the preparation of the copolymers according to the invention, which are essentially independent of each other. allow for slow initiation in at least two phases.
  • copolymers can be achieved with particularly low residual monomer contents.
  • at least two initiators whose decomposition temperatures differ from one another by at least 10 ° C. are preferably used.
  • the decomposition temperature is defined as the temperature at which 50% of the molecules decompose into free radicals within 2.5 hours.
  • the copolymerization in this procedure is carried out until completion of the precipitation of the copolymer at a temperature greater than or equal to the lower decomposition temperature and less of the higher decomposition temperature, and after the precipitation further reaction takes place at a temperature greater than or equal to the higher decomposition temperature.
  • the process according to the invention preferably comprises a first polymerization phase at a first polymerization temperature and a second polymerization phase at a second polymerization temperature above the first polymerization temperature, at least two initiators being used for the polymerization, of which
  • Half-times at the first polymerization temperature differ so that at least one of these initiators during the first polymerization phase decomposes into free radicals and at least one of these initiators during the first polymerization phase substantially does not decompose into radicals and during the second polymerization phase decomposes into free radicals.
  • the second polymerization phase essentially begins after precipitation of the copolymer.
  • “Substantially" after precipitation of the copolymer is understood to mean that the copolymer is preferably at least 80% by weight, preferably at least 90% by weight, in particular at least 95% by weight, based on the total weight of the copolymer , in precipitated form.
  • the half-life of an initiator can be determined by conventional methods known to those skilled in the art, such as. In the publication "Initiators for high polymers", Akzo Nobel, No. 10737.
  • the half-life of the first polymerization initiator at the first polymerization temperature and the second polymerization initiator at the second polymerization temperature is in a range of about 1 minute to 3 hours, more preferably 5 minutes to 2.5 hours. If desired, shorter half-lives z. From 1 second to 1 minute or longer half lives than 3 hours, as long as it is ensured that the initiator (s) decomposing at the higher temperature essentially decomposes into free radicals during the second polymerization phase.
  • the initiator system used contains at least two initiators whose decomposition temperatures differ by at least 15 ° C from each other.
  • the initiator which decomposes at the lower temperature preferably has a decomposition temperature of 50 to 100 ° C on.
  • the decomposing at the higher temperature initiator preferably has a decomposition temperature of 80 to 150 ° C.
  • the precipitation polymerization is preferably carried out in such a way that a part of the solvent or solvent mixture is initially introduced, heated and the polymerization is carried out by addition of initiator, monomer (s), crosslinker, auxiliaries (in each case possibly dissolved in the same or a different solvent or solvent mixture). If the polymerization takes place in a mixture of a cosmetically acceptable oil body and a different aprotic solvent or solvent mixture, the aprotic solvent or solvent mixture other than the oil body is preferably separated off after the polymerization.
  • the auxiliary H2) is preferably added in the course of the polymerization, the addition beginning with the beginning of the polymerization.
  • the adjuvant H1) (compound having at least one tertiary amino group) is preferably added in the course of the polymerization, with the addition beginning at the beginning, in the course of or only after the end of the polymerization.
  • component H3) is preferably added after the start of the polymerization.
  • the component H4) is preferably initially charged at least in part before the beginning of the polymerization.
  • H4) are particularly preferably initially charged before the beginning of the polymerization.
  • the addition is preferably carried out after at least 90% of the monomers have reacted.
  • the precipitated polymer is isolated from the reaction mixture following polymerization.
  • any general method that can be used to isolate the polymers in conventional precipitation polymerization is suitable. Such methods are for. As filtration, centrifugation, evaporation of the solvent or combinations of these methods.
  • polymers, the polymerization being carried out in an aprotic solvent or solvent mixture are isolated from the reaction mixture after the polymerization.
  • the copolymer composition may be subjected to purification if desired. This serves z. B. for the separation of unpolymerized components and / or at least a portion of the excipients.
  • the copolymer composition A) is isolated after the precipitation polymerization and subjected to washing with a liquid washing medium.
  • Suitable washing media are in principle the same solvents as are suitable for the polymerization. For easier drying of the polymers, it is recommended, however, low-boiling solvents such. B acetone, to use.
  • the copolymer composition A) may be subjected to a treatment with a washing medium one or more times in succession.
  • the copolymer composition is brought into intimate contact with the washing medium in a suitable device and the washing medium is subsequently separated from the copolymer composition.
  • Suitable devices are for. B. stirred tank.
  • the treatment with the washing medium can be carried out in the container used for the polymerization.
  • the separation of copolymer and washing medium takes place z. B. by filtration or centrifugation.
  • the filtration can be carried out under pressure increased on the polymer side or reduced on the outlet side.
  • the reaction mixture is subjected to a partial or complete solvent exchange with the precipitated polymer following the polymerization.
  • polymers in which the polymerization takes place in an aprotic solvent or solvent mixture are subjected to a partial or complete solvent exchange after the polymerization.
  • the aprotic solvent or solvent mixture is preferably partially or completely replaced by at least one cosmetically acceptable oil body.
  • the solvent exchange is carried out by distillation.
  • a portion of the aprotic solvent or solvent mixture is first removed by distillation.
  • the proportion of the solvent or solvent mixture initially removed by distillation is preferably from 5 to 95% by weight, more preferably from 10 to 90% by weight, in particular from 20 to 80% by weight, based on the total amount of the aprotic solvent or solvent mixture.
  • at least one oil body is added.
  • the choice of the aprotic solvent or solvent mixture and the oil body is then carried out in accordance with a sufficient difference in the boiling points.
  • ethyl acetate is used as the aprotic solvent and at least one vegetable oil is used as the oil body.
  • ethyl acetate is used as the aprotic solvent and soybean oil is used as the oil body.
  • soybean oil is used as the oil body.
  • aprotic solvent ethyl acetate and oil body Waglinol is used as the aprotic solvent ethyl acetate and oil body Waglinol.
  • a mixture of a cosmetically acceptable oil body and a different aprotic solvent or solvent mixture is used to prepare the copolymer composition A). Then the aprotic solvent or solvent mixture is partially or completely removed following the polymerization. Preferably, the removal of the aprotic solvent or solvent mixture is carried out by distillation. The choice of the aprotic solvent or solvent mixture and the oil body is then carried out in accordance with a sufficient difference in the boiling points.
  • ethyl acetate is used as the aprotic solvent and at least one vegetable oil is used as the oil body.
  • ethyl acetate is used as the aprotic solvent and soybean oil is used as the oil body.
  • ethyl acetate is used as aprotic solvent and waglinol as oil body.
  • Copolymer Composition A further subject matter of the invention is the copolymer composition A) obtainable by the process described above.
  • copolymer composition A also encompasses the products obtained therefrom by at least one workup and / or purification step. Suitable work-up and purification steps are, for example, washing, drying and shaping.
  • the copolymer composition A) is preferably in the form of a powder or an oil dispersion.
  • the copolymer composition A) according to the invention may contain at least one further component in addition to the polymer particles obtained in the precipitation polymerization. This includes at least one of the adjuvants H1) and / or H2).
  • the adjuvants H1) and / or H2) can, if desired, be partly or completely removed from the copolymer composition A), for example. By at least one washing step, as previously described.
  • A) may obtain the adjuvant (s) H3) as further component.
  • a specific embodiment is therefore a copolymer composition A) which contains at least one component H3).
  • A) then contains preferably at least one component H3) in an amount of 0.01 to 15 wt .-%, particularly preferably 0, 1 to 10 wt .-%, based on the total weight of the copolymer composition A).
  • the adjuvant H3) may have an advantageous effect on the performance properties of the copolymer composition A), z. Example by increasing the dissolution rate or reduced dust formation.
  • the adjuvants H 1), H 2) and / or H 3) may also have an advantageous effect on one or more other performance properties of the copolymer composition A), eg. By promoting low-crystallinity products or control of particle size, molecular weight, morphology, etc.
  • the adjuvants H 1), H 2) and / or H 3) can also have an advantageous effect on one or more other performance properties of formulations of the copolymer composition A). So z. B. the presence of at least one of these adjuvants advantageously affect the clarity of formulated with A) gels.
  • copolymer compositions A) according to the invention and the copolymers contained therein are distinguished by their pH-dependent solubility.
  • the anionic groups (acid groups) of the copolymers contained in the copolymer compositions A) can be partially or completely neutralized with a base.
  • a base for the neutralization of the polymers, alkali metal bases such as caustic soda, potassium hydroxide, soda, sodium bicarbonate, potassium carbonate or potassium hydrogencarbonate and alkaline earth metal bases such as calcium hydroxide, calcium oxide, magnesium hydroxide or magnesium carbonate and amines can be used. Suitable amines are, for.
  • C 1 -C 6 -alkylamines preferably n-propylamine and n-butylamine, dialkylamines, preferably diethylpropylamine and dipropylmethylamine, trialkylamines, preferably triethylamine and triisopropylamine.
  • amino alcohols for.
  • Tri- alkanolamines such as triethanolamine
  • Alkyldialkanolamine such as methyl or ethyldiethanolamine
  • dialkylalkanolamines such as dimethylethanolamine and 2-amino-2-methyl-1 - propanol.
  • the neutralization of the acid groups can also be carried out with the aid of mixtures of several bases.
  • the copolymers contained in the copolymer composition A) are advantageously suitable for modifying the rheological properties of aqueous compositions. It may be z. B. be an aqueous active or gratuitstoffzusammen arrangement. In general, they may be, for example, cosmetic compositions, pharmaceutical compositions, hygiene products, paints, compositions for the paper industry and the textile industry. In a preferred embodiment, the compositions contain at least one water-soluble or at least water-dispersible active or effect substance. Of course, the copolymers contained in the copolymer composition A) are also suitable for modifying the rheological properties of compositions containing at least one water-insoluble (hydrophobic) active or effect substance.
  • Modification of rheological properties is widely understood in the context of the present invention.
  • the copolymers contained in the copolymer composition A) are generally suitable for thickening the consistency of aqueous compositions in a wide range. Depending on the basic consistency of the liquid compositions, depending on the amount of copolymer used, as a rule, flow properties can be achieved from low viscosity to solid (in the sense of "no longer flowing”). Under “modification rheological properties” is therefore u. a. Increasing the viscosity of liquids, improving the thixotropic properties of gels, the solidification of gels and waxes, etc. understood.
  • the compositions according to the invention are preferably suitable for the formulation of aqueous cosmetic and pharmaceutical products.
  • the copolymer composition A) are generally clear.
  • the compositions can be formulated in the form of clear gels.
  • the copolymer compositions A) prepared in the presence of the adjuvant system of the invention are distinguished by advantageous rheological properties. Further control of the rheology-modifying properties can take place via the type and amount of the monomers used to prepare the copolymer compositions A). This applies especially to the type and amount of crosslinker used c). This also applies specifically to the use of surface-active monomers in the production of A), such as. B. the polyether acrylates IV c) or Allylalkoholalkoxilate IV d).
  • a 0.2% strength by weight aqueous solution of a copolymer composition A) generally has a viscosity in the range from 5000 to 15000 mPa.s (values determined by means of Brookfield viscometer at 23 ° C. and 100 s -1 ).
  • a 0.5% strength by weight aqueous solution of a copolymer composition A) generally has a viscosity in the range from 20,000 to 60,000 mPa.s (values determined by means of Brookfield viscometer at 23 ° C. and 100 s -1 ).
  • the copolymer compositions A) are suitable both for preparing homogeneous-phase aqueous compositions and for formulating heterogeneous phase compositions which additionally comprise at least one water-insoluble (hydrophobic) liquid or solid compound.
  • "Homogeneous phase compositions” have only a single phase regardless of the number of their constituents.
  • Heterogeneous phase compositions are disperse systems of two or more immiscible components.
  • copolymer compositions A) can be used both in the water phase and in the oil phase.
  • heterogeneous liquid / liquid compositions contain the copolymer compositions A) substantially in the water phase.
  • copolymer compositions A) according to the invention are generally suitable for the preparation of active or effect compositions comprising A) at least one copolymer composition as defined above,
  • Active ingredients for cosmetics eg hair or skin cosmetics
  • pharmaceuticals eg hair or skin cosmetics
  • hygiene products e.g., a pharmacological action in an organism, a cleaning and / or disinfecting effect, a modification of a textile material, for.
  • a specific property for example, color pigments for make-up or emulsion paints, are often formulated and applied in the form of aqueous active or F Stammstoffzusammen deren.
  • the active and effect compositions according to the invention contain the copolymer compositions A), preferably in an amount of from 0.01 to 50% by weight, particularly preferably from 0.05 to 30% by weight, in particular from 0.1 to 20% by weight on the total weight of the agent.
  • the copolymer compositions according to the invention exhibit good application-technical properties, even in small quantities, eg. B. a good thickening effect.
  • the active ingredient and effect composition according to the invention contain Polymer component A) in an amount of 0.1 to 5 wt .-%, based on the total weight of the composition.
  • Components B) and C) are selected according to the desired area of use of the composition.
  • typical use components eg certain pharmaceutical agents
  • they are z. B. selected from carriers, excipients, emulsifiers, surfactants, preservatives, fragrances, of component A) different thickeners, polymers, gelling agents, dyes, pigments, light stabilizers, bodying agents, antioxidants, defoamers, antistatic agents, resins, solvents, solubilizers, neutralizing agents , Stabilizers, sterilants, blowing agents, drying agents, opacifiers, etc.
  • compositions comprise a carrier component C) selected from water, hydrophilic carriers other than water, and mixtures thereof.
  • Suitable hydrophilic carrier C) are z.
  • compositions of the invention may be used as active ingredient, for. B. as a cosmetic and / or pharmaceutical active ingredient B) (as well as optionally as excipient C)), at least one polymer which differs from the inventive copolymer compositions A).
  • active ingredient B a cosmetic and / or pharmaceutical active ingredient B
  • excipient C at least one polymer which differs from the inventive copolymer compositions A).
  • polymers which differs from the inventive copolymer compositions A include, in general, anionic, cationic, amphoteric and neutral polymers.
  • anionic polymers are copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes, eg. B. Luviset PUR® Fa. BASF, and polyureas.
  • Particularly suitable polymers are copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (for example Luvimer® 100P), copolymers of ethyl acrylate and methacrylic acid (for example Luvimer® MAE), copolymers of N-tert-butylacrylamide, ethyl acrylate , Acrylic acid (Ultrahold® 8, strong), copolymers of vinyl acetate, crotonic acid and optionally further vinyl esters (eg Luviset® brands), maleic anhydride copolymers, optionally reacted with alcohol, anionic polysiloxanes, eg. Carboxy-functional, t-butyl acrylate, methacrylic acid (eg Luviskol® VBM), copolymers of acrylic acid and methacrylic acid with hydrophobic monomers, such as e.g. B.
  • An example of an anionic polymer is furthermore the methyl methacrylate / methacrylic acid / acrylic acid / urethane acrylate copolymer available under the name Luviset® Shape (INCI name: Polyacrylate-22).
  • anionic Polymers are also vinyl acetate / crotonic acid copolymers, such as those sold under the names Resyn® (National Starch) and Gafset® (GAF) and vinylpyrrolidone / vinyl acrylate copolymers, available for example under the trademark Luviflex® (BASF).
  • Further suitable polymers are the vinylpyrrolidone / acrylate terpolymer available under the name Luviflex® VBM-35 (BASF) and sodium sulfonate-containing polyamides or sodium sulfonate-containing polyesters.
  • vinylpyrrolidone / ethyl methacrylate / methacrylic acid copolymers such as those sold by Stepan under the names Stepanhold-Extra and -R1 and the Carboset® grades from BF Goodrich.
  • Suitable cationic polymers are, for. As cationic polymers called Polyquaternium INCI, z. B. Copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® FC, Luviquat® HM, Luviquat® MS, Luviset Clear®, Luviquat® Supreme®, Luviquat® Care), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat® PQ 1 1), copolymers of N-
  • Vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® Hold); cationic cellulose derivatives (polyquaternium-4 and -10), acrylamidocopolymers (polyquaternium-7) and chitosan.
  • Suitable cationic (quaternized) polymers are also Merquat® (polymer based on dimethyldiallylammonium chloride), Gafquat® (quaternary polymers formed by reaction of polyvinylpyrrolidone with quaternary ammonium compounds), polymer JR (hydroxyethylcellulose with cationic groups) and cationic polymers on vegetable Base, z.
  • guar polymers such as the Jaguar® brands of Fa. Rhodia.
  • Very particularly suitable polymers are neutral polymers, such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate, polysiloxanes, polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone, polyethyleneimines and their salts, polyvinylamines and their salts, cellulose derivatives, Polyaspartic acid salts and derivatives.
  • neutral polymers such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate, polysiloxanes, polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone, polyethyleneimines and their salts, polyvinylamines and their salts, cellulose derivatives, Polyaspartic acid salts
  • Suitable polymers are also nonionic, water-soluble or water-dispersible polymers or oligomers, such as polyvinyl caprolactam, z. B. Luviskol® Plus (BASF SE), or polyvinylpyrrolidone and copolymers thereof, in particular with vinyl esters, such as vinyl acetate, z. Luviskol® VA 37, VA 55, VA 64, VA 73 (BASF SE); Polyamides, z. B. based on itaconic acid and aliphatic diamines, as z. B. in DE-A-43 33 238 are described.
  • nonionic, water-soluble or water-dispersible polymers or oligomers such as polyvinyl caprolactam, z. B. Luviskol® Plus (BASF SE), or polyvinylpyrrolidone and copolymers thereof, in particular with vinyl esters, such as vinyl acetate, z. Luviskol® VA 37, VA 55, VA 64, VA 73 (BASF SE
  • Suitable polymers are also amphoteric or zwitterionic polymers, such as those available under the names Amphomer® (National Starch) octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate 2-hydroxypropyl methacrylate copolymers and zwitterionic polymers, as disclosed for example in German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451. Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali metal and ammonium salts are preferred zwitterionic polymers.
  • zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are commercially available under the name Amersette® (AMERCHOL), and copolymers of hydroxyethyl methacrylate, methyl methacrylate, ⁇ , ⁇ -dimethylaminoethyl methacrylate and acrylic acid (Jordapon®).
  • Suitable polymers are also nonionic, siloxane-containing, water-soluble or
  • dispersible polymers e.g. As polyether siloxanes, such as Tegopren® (Goldschmidt) or Belsil® (Wacker).
  • compositions according to the invention comprise at least one polymer which differs from the polymers contained in the copolymer compositions A) and which acts as a thickener.
  • Suitable polymeric thickeners are, for example, optionally modified polymeric natural substances (carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose and the like) as well as synthetic polymeric thickeners (polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides). These include the polyacrylic and polymethacrylic compounds, some of which have already been mentioned above, for example the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkylene polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name: carbomer). Such polyacrylic acids are u. a.
  • Carbopol ® available, z. Carbopol 940 (molecular weight about 4,000,000), Carbopol 941 (molecular weight about 125,000) or Carbopol 934 (molecular weight about 3,000,000).
  • acrylic acid copolymers which are obtainable, for example, from Rohm & Haas under the trade names Aculyn® and Acusol®, eg. The anionic non-associative polymers Aculyn 22, Aculyne 28, Aculyn 33 (crosslinked), Acusol 810, Acusol 823 and Acusol 830 (CAS 25852-37-3).
  • associative thickeners for. B. based on modified polyurethanes (HEUR) or hydrophobically modified acrylic or methacrylic acid copolymers (HASE thickener, high alkali swellable emulsion).
  • the amount of additional thickener used is preferably in a range of 0.001 to 10 wt .-%, preferably 0.1 to 5%, based on the total weight of the composition.
  • effect substances which can be formulated as aqueous active substance composition according to the invention are dyes: z.
  • a compilation of suitable disperse dyes can be found, for example, in Ullmanns Enzyklopadie der ischen Chemie, 4th Edition, Vol. 10, pp. 155-165 (see also Vol. 7, pp.
  • Disperse dyes and solvent dyes which are suitable according to the invention comprise a wide variety of different chromophore classes of dyes, for example anthraquinone dyes, monoazo and disazo dyes, quinophthalones, methine and azamethine dyes, naphthalimide dyes, naphthoquinone dyes and nitro dyes.
  • disperse dyes which are suitable according to the invention are the disperse dyes of the following Color Index list: CI Disperse Yellow 1 - 228, CI Disperse Orange 1 - 148, CI Disperse Red 1 - 349, CI Disperse Violet 1 - 97, CI Disperse Blue 1 - 349, CI Disperse Green 1 - 9, CI Disperse Brown 1 - 21, CI Disperse Black 1 - 36.
  • solvent dyes suitable according to the invention are the compounds of the following Color Index list: CI Solvent Yellow 2 - 191, CI Solvent Orange 1 - 1 13, CI Solvent Red 1 - 248, CI Solvent Violet 2 - 61, CI Solvent Blue 2 - 143, CI Solvent Green 1 - 35, CI Solvent Brown 1 - 63, CI Solvent Black 3 - 50.
  • Dyes which are suitable according to the invention are also derivatives of naphthalene, of anthracene, of perylene, of terrylene, of quaterrylene, as well as diketopyrrolopyrrole dyes, perinone dyes, coumarin dyes, isoindoline and isoindolinone dyes, porphyrin dyes, phthalocyanine and naphthalocyanine dyes.
  • the active ingredient and effect compositions according to the invention may also contain conventional surface-active substances and other additives.
  • Surfactants include surfactants, dispersing aids and wetting agents.
  • the other additives include, in particular, thickeners, defoamers, preservatives, antifreeze agents, stabilizers, etc.
  • anionic, cationic, nonionic and amphoteric surfactants are usable, wherein polymer surfactants and surfactants with heteroatoms are included in the hydrophobic group.
  • the anionic surfactants include, for example, carboxylates, especially alkali, alkaline earth and ammonium salts of fatty acids, eg. B. potassium stearate, which are commonly referred to as soaps; glutamates; Sarcosinates, e.g.
  • the cationic surfactants include, for example, quaternized ammonium compounds, in particular alkyltrimethylammonium and dialkyldimethylammonium compounds.
  • Nonionic surfactants include, for example:
  • Fatty alcohol polyoxyethylene esters for example lauryl alcohol polyoxyethylene ether acetate,
  • Alkyl polyoxyethylene and polyoxypropylene ethers e.g. From iso-tridecyl alcohol and fatty alcohol polyoxyethylene ether,
  • Alkylaryl alcohol polyoxyethylene ethers e.g. Octylphenol polyoxyethylene ethers, alkoxylated animal and / or vegetable fats and / or oils, for example, corn oil ethoxylates, castor oil ethoxylates, tallow fatty ethoxylates,
  • Glycerol esters such as glycerol monostearate
  • Alkylphenol alkoxylates such as, for example, ethoxylated isooctyl, octyl or nonylphenol, tributylphenol polyoxyethylene ethers,
  • sorbitol esters such as, for example, sorbitan fatty acid esters (sorbitan monooleate, sorbitan tristearate), polyoxyethylene sorbitan fatty acid esters, alkyl polyglycosides, N-alkylgluconamides,
  • alkyl methyl alkyl methyl, Alkyldimethylphosphine oxides, such as, for example, tetradecyldimethylphosphine oxide.
  • amphoteric surfactants include, for example, sulfobetaines, carboxybetaines and alkyldimethylamine oxides, e.g. B. tetradecyldimethylamine oxide.
  • surfactants which are to be mentioned as examples here are perfluorosurfactants, silicone surfactants, phospholipids, such as lecithin or chemically modified lecithins, amino acid surfactants, eg. B. N-lauroylglutamate.
  • the alkyl chains of the surfactants listed above are linear or branched radicals of usually 8 to 20 carbon atoms.
  • the active or effect compositions according to the invention may contain water-soluble salts as component B) and / or C), eg. B. NaCl.
  • the active or effect compositions according to the invention may contain organic solvents, oils and / or fats for some applications. Preferred are such solvents, oils and / or fats that are environmentally friendly or biocompatible. These include z. B .:
  • Paraffin oils aromatic hydrocarbons and aromatic hydrocarbon mixtures, e.g. Xylenes, Solvesso 100, 150 or 200, and the like, phenols and alkylphenols, e.g. Phenol, hydroquinone, nonylphenol, etc., ketones with more than 4 C atoms such as cyclohexanone, isophorone, acetophenone, acetonaphthone,
  • Alcohols with more than 4 C atoms such as acetylated lanolin alcohol, cetyl alcohol, 1-decanol, 1-heptanol, 1-hexanol, isooctadecanol, isopropyl alcohol, oleyl alcohol, benzyl alcohol,
  • Carboxylic acid esters eg., dialkyl adipate, such as
  • Phthalic acid bis (2-ethylhexyl) esters alkyl acetates (also branched alkyl groups), such as ethyl acetate and ethyl acetoacetate, stearates such as butyl stearate, glycerol monostearate, citrates such as acetyltributyl citrate, furthermore cetyl octanoate, methyl oleate, methyl p-hydroxybenzoate, methyl tetradecanoate , Propyl p-hydroxybenzoate, methyl benzoate, lactic acid esters, such as isopropyl lactate, butyl lactate and 2-ethylhexyl lactate,
  • Vegetable oils such as palm oil, rapeseed oil, castor oil and derivatives thereof, such.
  • hydrogenated vegetable oils such as hydrogenated palm oil, hydrogenated rapeseed oil, hydrogenated soybean oil,
  • oils such as lard oil, fish oils,
  • Dialkylamides medium to long chain fatty acids eg. B. Hallcomide, as well
  • Vegetable oil esters such as rapeseed oil methyl ester.
  • copolymer compositions A) can be used together with conventional compressors. These include the aforementioned polymers acting as thickeners. These also include polysaccharides and organic layer minerals such as Xanthan Gum ® (Kelzan ® from. Kelco), Rhodopol ® 23 (Rhone Poulenc) or VEE gum ® (from RT Vanderbilt) or Attaclay ® (Engelhardt).
  • Xanthan Gum ® Kelzan ® from. Kelco
  • Rhodopol ® 23 Rhone Poulenc
  • VEE gum ® from RT Vanderbilt
  • Attaclay ® Engelhardt
  • Suitable thickening agents are also organic natural thickeners (agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein) and inorganic thickeners (polysilicic acids, clay derivatives such as montmorillonite , Zeolites, silicic acids).
  • organic natural thickeners agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein
  • inorganic thickeners polysilicic acids, clay derivatives such as montmorillonite , Zeolites, silicic acids.
  • Further thickeners are the polysaccharides and heteropolysaccharides, in particular the polysaccharide gums, for example gum arabic, agar, alginates, carrageenes and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, eg. B. propoxylated guar, and their mixtures.
  • Other polysaccharide thickeners are, for example, starches of various origins and starch derivatives, eg.
  • thickeners it is also possible to use phyllosilicates. These include, for example, available under the trade name Laponite ® magnesium or sodium magnesium phyllosilicates from Solvay Alkali and the magnesium silicates from Süd-Chemie.
  • the amount of additional thickener used is preferably in a range of 0.001 to 10 wt .-%, preferably 0.1 to 5%, based on the total weight of the composition.
  • suitable antifoam agents are, for example, silicone emulsions (such as, for example, silicone ® SRE, from Wacker, or Rhodorsil ® from Rhodia), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof.
  • Bactericides may be added to stabilize the compositions of the invention against attack by microorganisms. Suitable bactericides are play as Proxel ® from. ICI or Acetide ® RS from. Thor Chemie and Kathon ® MK from Rohm & Haas.
  • Suitable antifreeze are organic polyols, eg. As ethylene glycol, propylene glycol or glycerol. These are usually given in quantities of not more than
  • the proportion thereof of various volatile organic compounds is preferably not more than 1 wt .-%, in particular not more than 1000 ppm.
  • the active compound compositions of the invention may contain 1 to 5 wt .-% buffer, based on the total amount of the formulation prepared, for pH regulation, wherein the amount and type of buffer used depends on the chemical properties of the active ingredient or the active ingredients.
  • buffers are alkali salts of weak inorganic or organic acids such. For example, phosphoric acid, boric acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid and succinic acid.
  • the copolymer compositions according to the invention are used as component in a cosmetic agent. As described above, they can serve to modify the rheological properties of a cosmetic agent based on an aqueous medium.
  • Another object of the invention is a cosmetic agent containing
  • Component C) optionally at least one further cosmetically acceptable excipient other than A) and B).
  • Component C) preferably comprises at least one cosmetically or pharmaceutically acceptable carrier.
  • the carrier component C) is selected from i) water, ii) water-miscible organic solvents, preferably C 2 -C 4 alkanols, in particular ethanol,
  • oils iii) oils, fats, waxes,
  • Suitable components C) are the aforementioned organic solvents, oils and fats.
  • cosmetically acceptable oil or fat components C are described in Karl-Heinz Schmann, bases and formulations of cosmetics, 2nd edition, Verlag Hüthig, Heidelberg, pp. 319-355, to which reference is made here.
  • the cosmetic agents according to the invention may be skin-cosmetic, hair-cosmetic, dermatological, hygienic or pharmaceutical agents. Because of their thickening properties, the above-described copolymer compositions A) are particularly suitable as additives for hair and skin cosmetics. They are especially suitable for the formulation of gels.
  • the agents according to the invention are preferably in the form of a gel, foam, spray, ointment, cream, emulsion, suspension, lotion, milk or paste. If desired, liposomes or microspheres can also be used.
  • the copolymer compositions are also particularly suitable as emulsifier or stabilizer for emulsions.
  • the cosmetically active agents according to the invention may additionally contain cosmetically and / or dermatologically active active substances and effect substances as well as auxiliaries.
  • the previously mentioned active ingredients B) and auxiliaries C) are suitable.
  • the cosmetic compositions according to the invention preferably comprise at least one copolymer composition A) as defined above, at least one carrier C as defined above and at least one different constituent thereof, which is preferably selected from cosmetically active ingredients, emulsifiers, Surfactants, preservatives, perfume oils, additional thickeners, hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, light stabilizers, bleaches, gelling agents, conditioners, tinting agents, tanning agents, dyes, pigments, consistency regulators, humectants, restoats, collagen, Protein hydrolysates, lipids, antioxidants, defoamers, antistatic agents, emollients and plasticizers.
  • cosmetically active ingredients emulsifiers, Surfactants, preservatives, perfume oils, additional thickeners, hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, light stabilizers, bleaches
  • Suitable cosmetically and / or dermatologically active agents are, for.
  • tanning agents As skin and hair pigmenting agents, tanning agents, bleaching agents, keratin-hardening substances, antimicrobial agents, light filter agents, repellents, hyperemic substances, keratolytic and keratoplastic substances, Antischuppenwirkstof- fe, anti-inflammatory drugs, keratinizing substances, antioxidant or as Radical scavengers active ingredients, skin moisturizing or moisturizing substances, moisturizing agents, deodorizing agents, sebostatic agents, plant extracts, antierythym matically or antiallergically active agents and mixtures thereof.
  • Artificial skin tanning agents that are suitable for tanning the skin without natural or artificial irradiation with UV rays, z.
  • Suitable keratin-hardening substances are generally active ingredients, as used in antiperspirants, such as.
  • Antimicrobial agents are used to destroy or inhibit their growth microorganisms and thus serve both as a preservative and as a deodorizing substance, which reduces the formation or intensity of body odor. These include z.
  • preservatives known in the art such as p-hydroxybenzoic acid, imidazolidinyl urea, formaldehyde, sorbic acid, benzoic acid, salicylic acid, etc.
  • deodorizing substances are, for.
  • Suitable light filtering agents are substances that absorb UV rays in the UV-B and / or UV-A range. Suitable UV filters are those mentioned above. Also suitable are p-aminobenzoic acid esters, cinnamic acid esters, benzophenones, camphor derivatives and UV-radiation-stopping pigments, such as titanium dioxide, talc and zinc oxide.
  • Suitable repellents are compounds capable of preventing or repelling certain animals, particularly insects, from humans. This includes z. B.
  • Suitable hyperemic substances which stimulate the circulation of the skin are, for.
  • essential oils such as mountain pine, lavender, rosemary, juniper berry, horse chestnut extract, birch leaf extract, hay flower extract, ethyl acetate, camphor, men thol, peppermint oil, rosemary extract, eucalyptus oil, etc.
  • Suitable keratolytic and keratoplastic substances are for.
  • Suitable antidandruff agents are, for.
  • the cosmetic agents according to the invention may contain as cosmetic active ingredient (as well as optionally as adjuvant) at least one cosmetically or pharmaceutically acceptable polymer which differs from the copolymer compositions A) according to the invention.
  • cosmetically or pharmaceutically acceptable polymer which differs from the copolymer compositions A) according to the invention.
  • These include, in general, anionic, cationic, amphoteric and neutral polymers.
  • anionic, cationic, amphoteric and neutral polymers are fully incorporated herein by reference.
  • the agents according to the invention are a skin cleanser.
  • Preferred skin cleansing agents are soaps of liquid to gelatinous consistency, such as transparent soaps, luxury soaps, de-soaps, cream soaps, baby soaps, skin soaps, abrasive soaps and syndets, pasty soaps, greases and washing pastes, liquid detergents, shower and bath preparations such as washing lotions, shower baths and gels , Bubble baths, oil baths and scrub preparations, shaving foams, lotions and creams.
  • the agents according to the invention are cosmetic agents for the care and protection of the skin, nail care preparations or preparations for decorative cosmetics.
  • suitable skin cosmetic agents are, for.
  • Means for use in decorative cosmetics include, for example, masking pens, theatrical paints, mascara and eye shadows, lipsticks, kohl pencils, eyeliners, rouges, powders, and eyebrow pencils.
  • the copolymer compositions A) can be used in nasal strips for pore cleansing, in anti-acne agents, repellents, shaving agents, depilatories, personal care products, foot care products and in baby care.
  • the skin care compositions according to the invention are in particular W / O or O / W skin creams, day and night creams, eye creams, face creams, anti-aging creams. creams, moisturizing creams, bleaching creams, vitamin creams, skin lotions, body lotions and moisturizing lotions.
  • the copolymer composition can contribute to moisturizing and conditioning the skin and to improving the feel on the skin.
  • the copolymer composition according to the invention in certain formulations a considerable improvement in the skin compatibility can be achieved.
  • Skin cosmetic and dermatological compositions preferably contain at least one copolymer composition A) in a proportion of about 0.001 to 30% by weight, preferably 0.01 to 20% by weight, very particularly preferably 0.1 to 12% by weight, based on the total weight of the agent.
  • compositions of the invention in a form suitable for skin care, such. B. as a cream, foam, gel, pen, mousse, milk, spray (pump spray or propellant spray) or lotion can be applied.
  • skin cosmetic preparations may contain other active ingredients and adjuvants customary in skin cosmetics, as described above.
  • These preferably include emulsifiers, preservatives, perfume oils, cosmetic active ingredients such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol, light stabilizers, bleaching agents, tanning agents, collagen, protein hydrolysates, stabilizers, pH regulators, dyes , Salts, thickeners, gelling agents, bodying agents, silicones, humectants, moisturizers and other common additives.
  • emulsifiers emulsifiers, preservatives, perfume oils, cosmetic active ingredients such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol, light stabilizers, bleaching agents, tanning agents, collagen, protein hydrolysates, stabilizers, pH regulators, dyes , Salts, thickeners, gelling agents, bodying agents, silicones, humectants, moisturizers and other common additives.
  • Preferred oil and fat components of the skin cosmetic and dermatological agents are the aforementioned mineral and synthetic oils, such as.
  • mineral and synthetic oils such as.
  • silicone oils and aliphatic hydrocarbons having more than 8 carbon atoms animal and vegetable oils, such as.
  • sunflower oil coconut oil, avocado oil, olive oil, lanolin, or waxes, fatty acids, fatty acid esters, such as.
  • C6-C3o fatty acids such as. As jojoba oil, fatty alcohols, Vaseline, hydrogenated lanolin and acetylated lanolin and mixtures thereof.
  • the skin cosmetic and dermatological preparations may additionally contain conditioning substances based on silicone compounds.
  • Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes or silicone resins.
  • the preparation of the cosmetic or dermatological preparations is carried out by customary methods known to the person skilled in the art.
  • the cosmetic and dermatological agents are preferably in the form of emulsions, in particular as water-in-oil (W / O) or oil-in-water (O / W) emulsions.
  • W / O water-in-oil
  • O / W oil-in-water
  • Emulsions are prepared by known methods.
  • the emulsions generally contain conventional constituents, such as fatty alcohols, fatty acid esters and, in particular, fatty acid triglycerides, fatty acids, lanolin and derivatives thereof, natural or synthetic oils or
  • a suitable emulsion for.
  • a skin cream, etc. generally contains an aqueous phase which is emulsified by means of a suitable emulsifier in an oil or fat phase.
  • a copolymer composition A) can be used.
  • Preferred fat components which may be included in the fat phase of the emulsions are: hydrocarbon oils such as paraffin oil, purcellin oil, perhydrosqualene and solutions of microcrystalline waxes in these oils; animal or vegetable oils, such as sweet almond oil, avocado oil, calophilum oil, lanolin and derivatives thereof, castor oil, seed oil, olive oil, jojoba oil, karite oil, hoplostethus oil; Mineral oils whose beginning of distillation under atmospheric pressure at about 250 ° C and the distillation end point at 410 ° C, such. Vaseline oil; Esters of saturated or unsaturated fatty acids, such as alkyl myristates, e.g.
  • the fat phase may also contain other oil-soluble silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane and the silicone glycol copolymer, fatty acids and fatty alcohols.
  • waxes can be used, such as. Carnauba wax, candililla wax, beeswax, microcrystalline wax, ozokerite wax and Ca, Mg and Al oleates, myristates, linoleates and
  • an emulsion of the invention may be present as O / W emulsion.
  • Such an emulsion usually contains an oil phase, emulsifiers that stabilize the oil phase in the water phase, and an aqueous phase that is usually thickened.
  • Suitable emulsifiers are preferably O / W emulsifiers, such as polyglycerol esters, sorbitan esters or partially esterified glycerides into consideration.
  • the agents according to the invention are a shower gel, a shampoo formulation or a bathing preparation.
  • Such formulations contain at least one copolymer composition A) and usually anionic surfactants as base surfactants and amphoteric and / or nonionic surfactants as cosurfactants.
  • suitable active ingredients and / or adjuvants are generally selected from lipids, perfume oils, dyes, organic acids, preservatives and antioxidants, as well as thickeners / gelling agents, skin conditioners and humectants.
  • formulations preferably contain from 2 to 50% by weight, preferably from 5 to 40% by weight, particularly preferably from 8 to 30% by weight of surfactants, based on the total weight of the formulation.
  • the shower gel / shampoo formulations additional thickeners, such.
  • sodium chloride PEG-55, propylene glycol oleate, PEG-120-Methylglucose dioleate and others, as well as preservatives, other active ingredients and excipients and water contained.
  • the agents according to the invention are a hair treatment agent.
  • Hair treatment agents according to the invention preferably contain at least one copolymer composition A) in an amount in the range of about 0.01 to
  • the hair treatment compositions according to the invention are in the form of a hair mousse, hair gel, shampoos, shower gels.
  • the hair cosmetic preparations can be sprayed as (aerosol) spray, (aerosol) foam,
  • Hairsprays include both aerosol sprays and pump sprays without propellant gas.
  • Hair foams include both aerosol foams and pump foams without propellant gas.
  • Hair sprays and hair foams preferably comprise predominantly or exclusively water-soluble or water-dispersible components. If the compounds used in the hair sprays and hair foams according to the invention are water-dispersible, they can be used in the form of aqueous microdispersions with particle diameters of usually 1 to 350 nm, preferably 1 to 250 nm. The solids contents of these preparations are usually in a range of about 0.5 to 20 wt .-%.
  • the hair treatment agent is in the form of a gel. In a further preferred embodiment, the hair treatment agent is in the form of an emulsion. Preference is given here to the use in surfactant-containing formulations.
  • the hair cosmetic formulations according to the invention comprise a) from 0.05 to 5% by weight, preferably from 0.1 to 3% by weight, of at least one copolymer composition A), b) from 20 to 99.95% by weight of water or water / alcohol mixture, c) 0 to 70% by weight of at least one surfactant,
  • alcohol all alcohols customary in cosmetics are to be understood, for.
  • ethanol isopropanol, n-propanol.
  • the proportion of alcohols b) in the hair cosmetic formulations of the invention is preferably 0 to 20 wt .-%.
  • constituents are understood to include the additives customary in cosmetics, for example antifoams, surface-active compounds, d. H. Surfactants, emulsifiers, foaming agents and solubilizers.
  • the surface-active compounds used can be anionic, cationic, amphoteric or neutral.
  • Other common ingredients may also be z.
  • perfume oils, opacifiers, active ingredients, UV filters, care agents such as panthenol, collagen, vitamins, protein hydrolysa- te, alpha- and beta-hydroxycarboxylic acids, stabilizers, pH regulators, dyes, viscosity regulators, gel formers, salts , Humectants, moisturizers, complexing agents and other common additives.
  • Hair polymers are all styling and conditioner polymers known in cosmetics, which can be used in combination with the copolymer composition A) used according to the invention, if very special properties are to be set.
  • Suitable conventional hair cosmetic polymers are, for example, the abovementioned cationic, anionic, neutral, nonionic and amphoteric polymers, to which reference is made here.
  • the preparations may additionally contain conditioning substances based on silicone compounds.
  • Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyaryl siloxanes, polyethersiloxanes, silicone resins or dimethicone copolyols (CTFA) and amino-functional silicone compounds such as amodimethicones (CTFA).
  • copolymer compositions according to the invention are particularly suitable as thickeners in hairstyling preparations, in particular hair foams and hair gels.
  • emulsifiers all emulsifiers commonly used in hair foams can be used.
  • Suitable emulsifiers may be nonionic, cationic or anionic or amphoteric.
  • a preparation suitable for styling gels according to the invention can be composed, for example, as follows:
  • the proportion of alcohols c) in the styling gel formulations according to the invention is preferably 0 to 20 wt .-%.
  • copolymer compositions A) according to the invention are also suitable for shampoo formulations.
  • Preferred shampoo formulations comprise: a) 0.05-10% by weight of the copolymer composition A) obtainable by the process according to the invention,
  • Suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosines, acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefin sulfonates, especially the alkali and alkaline earth metal salts, e.g. As sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts.
  • alkali and alkaline earth metal salts e.g. As sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts.
  • the alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1 to 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units in the molecule.
  • Suitable z Sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium lauroyl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium dodecyl benzene sulfonate, triethanolamine dodecyl benzene sulfonate.
  • Suitable amphoteric surfactants are, for. Alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines, alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates or
  • cocodimethylsulfopropyl betaine cocodimethylsulfopropyl betaine, lauryl betaine, cocamidopropyl betaine or sodium cocamphopropionate can be used.
  • Suitable nonionic surfactants are, for example, the reaction products of aliphatic alcohols or alkylphenols having 6 to 20 C atoms in the alkyl chain, which may be linear or branched, with ethylene oxide and / or propylene oxide.
  • the amount of alkylene oxide is about 6 to 60 moles per mole of alcohol.
  • alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, alkylpolyglycosides or sorbitan ether esters are also suitable.
  • the shampoo formulations may contain conventional cationic surfactants, such as.
  • quaternary ammonium compounds for example Cetyltrimethylammoni- umchlorid.
  • Conventional conditioning agents in combination with the copolymer compositions A) can be used in the shampoo formulations to achieve certain effects.
  • these include, for example, the abovementioned cationic polymers with the name Polyquaternium according to INCI, in particular copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® FC, Luviquat® HM, Luviquat® MS, Luviquat® Care), copolymers of N-vinylpyrrolidone / Dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat® PQ 11), copolymers of N-vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® Hold); cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamide copolymers (Polyquaternium
  • protein hydrolysates can be used, as well as conditioning substances based on silicone compounds, for example polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes or silicone resins.
  • silicone compounds for example polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes or silicone resins.
  • suitable silicone compounds are dimethicone copolyols (CTFA) and amino-functional silicone compounds. fertilize like Amodimethicone (CTFA).
  • CTFA dimethicone copolyols
  • quaternaryl derivatives such as guar hydroxypropyltrimonium chloride (INCI) can be used.
  • copolymer compositions A) according to the invention are particularly suitable for oil-containing formulations.
  • copolymer compositions A) to be used according to the invention are also suitable for use in modifying the rheological properties in pharmaceutical preparations of any kind.
  • Preferred agents which comprise the copolymer composition A) obtainable by the process according to the invention are:
  • Another object of the invention is the use of a copolymer composition A), as defined above, as an adjuvant in pharmacy.
  • C) optionally at least one further pharmaceutically acceptable excipient other than A) and B).
  • compositions C) are the excipients known to be useful in the pharmaceutical, food technology and related fields, in particular those listed in relevant pharmacopoeias (eg DAB, Ph. Eur., BP, NF) and other excipients whose properties are physiological application.
  • Suitable auxiliaries C) may be: lubricants, wetting agents, emulsifying and suspending agents, preserving agents, antioxidants, anti-irritants, chelating agents, emulsion stabilizers, film formers, gelling agents, odor masking agents, resins, Hydrocolloids, solvents, solubilizers, neutralizing agents, permeation accelerators, pigments, quaternary ammonium compounds, lipid and superfatting agents, ointment, cream or oil bases, silicone derivatives, stabilizers, sterilants, blowing agents, drying agents, opacifiers, additional thickeners, waxes, plasticizers , White oils.
  • a related embodiment is based on expert knowledge, as shown for example in Fiedler, HP Lexicon of excipients for pharmacy, cosmetics and related fields, 4th ed., Aulendorf: ECV Editio-Kantor-Verlag, 1996.
  • the active ingredients may be mixed or diluted with a suitable excipient.
  • Excipients may be solid, semi-solid or liquid materials which may serve as a vehicle, carrier or medium for the active ingredient. If desired, the admixing of further auxiliaries takes place in the manner known to the person skilled in the art. In particular, these are aqueous solutions or solubilisates for oral or parenteral administration.
  • copolymer composition to be used according to the invention are also suitable for use in oral dosage forms such as tablets, capsules, powders, solutions.
  • oral dosage forms such as tablets, capsules, powders, solutions.
  • they can provide the poorly soluble drug with increased bioavailability.
  • emulsions for example fat emulsions, can be used in addition to solubilisates.
  • compositions of the abovementioned type can be obtained by processing the pharmaceutical compositions A) to be used according to the invention by conventional methods and using known and new active compounds.
  • the content of copolymer A) in the pharmaceutical compositions is in the range from 0.01 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight .-%, based on the total weight of the agent.
  • all pharmaceutical active ingredients and prodrugs are suitable for the production of the pharmaceutical agents according to the invention.
  • These include benzodiazepines, antihypertensives, vitamins, cytostatic drugs - especially taxol, anesthetics, neuroleptics, antidepressants, antibiotics, antifungals, fungicides, chemotherapeutics, urologics, antiplatelet agents, sulfonamides, spasmolytics, hormones, immunoglobulins, sera, thyroid drugs, psychotropic drugs, Parkinson's and other antihyperkinetics, Ophthalmics, neuropathy preparations, calcium metabolism regulators, muscle relaxants, anesthetics, lipid-lowering drugs, liver therapeutics, coronary agents, cardiac drugs, immunotherapeutics, regulatory peptides and their inhibitors, hypnotics, sedatives, gynecologics, gout, fibrinolytics, enzyme preparations and transport proteins.
  • teines enzyme inhibitors, emetics, circulation-promoting agents, diuretics, diagnostics, corticoids, cholinergics, biliary tract therapies, antiasthmatics, broncholytics, beta-receptor blockers, calcium antagonists, ACE inhibitors, arteriosclerotic agents, antiphlogistics, anticoagulants, antihypotonics, antihypoglycemics, antihypertensives, antifibrinolytics, antiepileptics, antiemetics , Antidotes, antidiabetics, antiarrhythmics, antianemics, antiallergic drugs, anthelmintics, analgesics, analeptics, aldosterone antagonists, weight loss agents.
  • suitable active pharmaceutical ingredients are in particular the active substances mentioned in paragraphs 0105 to 0131 of US 2003/0157170.
  • the copolymer compositions A) to be used according to the invention are also suitable in the foodstuffs sector for modifying the rheological properties.
  • the invention therefore also relates to food-grade preparations which contain at least one of the copolymer compositions A) to be used according to the invention.
  • Food preparations are in the context of the present invention, dietary supplements such. As food-containing preparations and dietary foods to understand.
  • the abovementioned copolymer compositions A) are also suitable for modifying the rheological properties of feed additives for animal nutrition.
  • copolymer compositions A) are suitable for preparing aqueous preparations of dietary supplements such as water-insoluble vitamins and provitamins such as vitamin A, vitamin A acetate, vitamin D, vitamin E, tocopherol derivatives such as tocopherol acetate and vitamin K.
  • Another object of the invention is the use of a copolymer composition A), as defined above, as auxiliaries in pharmacy, preferably as or in coating agent (s) for solid dosage forms, for modifying rheological properties, as a surface-active compound, as or in adhesive (s) and as or in coating agent (s) for the textile, paper, printing and leather industries.
  • a copolymer composition A as defined above, as auxiliaries in pharmacy, preferably as or in coating agent (s) for solid dosage forms, for modifying rheological properties, as a surface-active compound, as or in adhesive (s) and as or in coating agent (s) for the textile, paper, printing and leather industries.
  • Lutencryl® 250 LUMA MAS (weight ratio 1: 1)
  • Emulgade PL 68/50 Mixture of alkyl (Ci6-i8) -polyglucoside and
  • Pentaerythritol triallyl ether 1 65 g
  • the product obtained after cooling to room temperature, was filtered off and washed twice with ethyl acetate. Thereafter, the moist product was dried in an oven at about 70 ° C for 20 h.
  • H1 1 triethanolamine, [relative to AS + MAS]
  • H2 2) acetic anhydride, based on the total weight of the monomer composition of AS, VP, MAS, LUMA and, if used, VI,
  • Emulgade® PL 68/50 based on 100% by weight of the monomer composition
  • Example 15 Distilled off 100 ° C under atmospheric pressure. Then, feed 5 was added at a bath temperature of 100 ° C., and the remaining ethyl acetate was distilled off in vacuo (about 10-20 mbar). A fine about 30% oil dispersion was obtained.
  • the precipitation polymer of Example 15 were prepared in Table III.
  • Feeders the template was heated to about 70 ° C under IS -passing and stirring at 250 rpm. Thereafter, the feed of feed 1, feed 2 and feed 3 was started at this temperature. Feed 1 and feed 2 were metered in over 3 hours and feed 3 in 5 hours, during which the first turbidity was observed within about 15 to 25 minutes , 2 h after the addition of feed 3 had ended, the reaction mixture was heated to 75 ° C. and polymerized with stirring at 75 ° C. over a period of 3 hours. Thereafter, the reaction mixture was heated to 80 ° C and polymerized for a further 10 h with stirring. Thereafter, the ethyl acetate was distilled off at an external temperature of 100 ° C in vacuo. An approximately 30% oil dispersion was obtained.
  • the precipitation polymers obtained by the method B or C are listed in Table III.
  • Table IV lists homogenizing data.
  • H1 1 triethanolamine, [relative to AS + MAS]
  • H2 2) acetic anhydride, based on the total weight of the monomer composition of AS, VP, VI, MAS, and LUMA
  • Emulgade® PL 68/50 based on the total weight of the monomer composition
  • Example 12 was repeated except that the ethyl acetate was replaced with soybean oil. There was no stable dispersion. After about 4 h at room temperature, phase separation occurred.
  • Example 12 was repeated except that the ethyl acetate was replaced with Waglinol. There was no stable dispersion. After about 4 h at room temperature, phase separation occurred.
  • Example 13 was repeated, but the ethyl acetate was replaced with soybean oil. There was no stable dispersion. After about 4 h at room temperature, phase separation occurred.
  • Example 13 was repeated except that the ethyl acetate was replaced with Waglinol. There was no stable dispersion. After about 4 h at room temperature, phase separation occurred.
  • Phases 1 and 2 were homogenized separately with stirring; This gave a cla res, thick gel (thickener phase) and a Festigerphase. Thereafter, the setting phase was slowly stirred into the thickening phase to give a nearly clear, firm gel.
  • Analogous hair gels are prepared with the copolymers of Examples 2, 3 and 4.
  • Cremophor ® A6 3.3 Ceteareth-6 (and) stearyl alcohol Cremophor ® A25 3.3 Ceteareth-25
  • Vitamin E acetate 1, 0 tocopheryl acetate
  • Glycerol monostearate s.e. 5.0 glyceryl stearate

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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)
  • Cosmetics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un procédé de préparation d'une composition copolymère A) par copolymérisation radicalaire d'une composition monomère comprenant a) au moins un monomère choisi parmi l'acide acrylique, les sels de l'acide acrylique, l'acide méthacrylique, les sels de l'acide méthacrylique, et leurs mélanges, b) au moins un composé de réticulation polymérisable par voie radicalaire qui contient au moins deux doubles liaisons α, β-éthyléniquement insaturées par molécule, c) au moins un composé α, β-éthyléniquement insaturé contenant un groupe amide, selon le procédé de polymérisation par précipitation en présence d'une composition adjuvante H) contenant H1) au moins un composé comportant au moins un groupe amino tertiaire, et H2) au moins un anhydride. En outre, la présente invention concerne la composition copolymère pouvant être obtenue par ce procédé et sont utilisation.
PCT/EP2014/072423 2013-10-21 2014-10-20 Polymérisation par précipitation en présence d'un groupe amine tertiaire et d'un anhydride WO2015059084A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019176977A1 (fr) * 2018-03-15 2019-09-19 東亞合成株式会社 Procédé de production de fines particules polymères
CN112920349A (zh) * 2021-01-26 2021-06-08 嘉兴学院 一种含硅聚合物助剂及其制备方法
CN116478340A (zh) * 2023-04-26 2023-07-25 石家庄华莱鼎盛科技有限公司 钻井液用降滤失剂羧羟基超支化聚合物

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019176977A1 (fr) * 2018-03-15 2019-09-19 東亞合成株式会社 Procédé de production de fines particules polymères
CN112920349A (zh) * 2021-01-26 2021-06-08 嘉兴学院 一种含硅聚合物助剂及其制备方法
CN116478340A (zh) * 2023-04-26 2023-07-25 石家庄华莱鼎盛科技有限公司 钻井液用降滤失剂羧羟基超支化聚合物
CN116478340B (zh) * 2023-04-26 2023-09-12 石家庄华莱鼎盛科技有限公司 钻井液用降滤失剂羧羟基超支化聚合物

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