Classifications

• • 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
  • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8141—Compositions of homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/817—Compositions of homopolymers or 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; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
  • A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/86—Polyethers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
• • 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
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
• • 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
  • C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
  • C08F271/02—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00 on to polymers of monomers containing heterocyclic 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/54—Polymers characterized by specific structures/properties

Definitions

• the present invention relates to cationically modified comb polymers based on acryloyldimethyltauric acid or acryloyldimethyltaurates.
• the visual appearance of a cream or lotion is influenced by the viscosity.
• the sensory properties such as consistency or distributability, determine the individual profile of a cosmetic product.
• the effectiveness of active substances (e.g. sun protection filters) and the storage stability of the formulation are closely related to the theological properties of the product.
• polyelectrolytes play a major role as thickeners and gelling agents.
• State of the art is in particular the polyacrylic acids based on poly (meth) acrylic acid and their water-soluble copolymers.
• the variety of possible structures and the associated diverse application possibilities are reflected in a large number of patent applications.
• a major disadvantage of thickeners based on poly (meth) acrylic acid is the strong pH dependence of the thickening performance. Sufficient viscosity is generally only achieved if the pH of the formulation is above pH 6, i.e. the poly (meth) acrylic acid is in neutralized form. Furthermore, the corresponding gels / formulation are sensitive to UV radiation and shear and also give the skin a sticky feeling. Since the thickeners are generally in acidic form, an additional neutralization step is also required in the formulation.
• Novel thickeners based on acryloyldimethyltauric acid or its salts were introduced to the market in the 1990s (EP-B-0 815 828, EP-B-0 815 844, EP-B-0 815 845, EP-B-0 829 258, EP-A-0 850 642 and EP-A-0 919 217). Both in the form of the pre-neutralized homopolymer and as corresponding copolymers ( ® ARISTOFLEX AVC CLARIANT GmbH), such thickeners are superior to the poly (meth) acrylate thickeners in many respects. They show an excellent property profile even in pH ranges below pH 6, i.e. a range in which conventional poly (meth) acrylate thickeners can no longer be used. High UV and shear stability, excellent viscoelastic properties, easy processing and a favorable toxicological profile of the main monomer give these thickeners a high application potential.
• the applicant has surprisingly managed to access new cationically modified comb polymers based on acryloyldimethyltauric acid (AMPS), which show very good thickening and emulsifying / dispersing properties with high pH stability.
• AMPS acryloyldimethyltauric acid
• the comb polymers according to the invention open up a broad spectrum of applications both in crosslinked and uncrosslinked form.
• the polymers according to the invention enable the user for the first time to combine the synergistic properties of hydrophobically modified anionic polymers with the known advantages of cationic charges.
• the invention relates to water-soluble or water-swellable copolymers, obtainable by radical copolymerization of
• the copolymers according to the invention preferably have a molecular weight of 10 3 g / mol to 10 9 g / mol, particularly preferably 10 4 to 10 7 g / mol, particularly preferably 5 * 10 4 to 5 * 10 6 g / mol.
• the Acryloyldimethyltauraten can be the inorganic or organic salts of Acryloyldimethyltaurinklare.
• the Li + , Na + , K + , Mg ++ , Ca ++ , Al +++ and / or NH 4 + salts are preferred.
• the monoalkylammonium, dialkylammonium, trialkylammonium and / or tetraalkylammonium salts, wherein the alkyl substituents independently of one another by amines can -hydroxyalkyl (C - - C 22) alkyl or (C ⁇ 0 C 2).
• one to three times ethoxylated ammonium compounds with different degrees of ethoxylation are preferred. It should be noted that mixtures of two or more of the above representatives are also within the meaning of the invention.
• the degree of neutralization of acryloyldimethyltauric acid can be between 0 and 100%, a degree of neutralization of above 80% is particularly preferred.
• the content of acryloyldimethyltauric acid or acryloyldimethyltaurates is at least 0.1% by weight, preferably 20 to 99.5% by weight, particularly preferably 50 to 98% by weight.
• All olefinically unsaturated, non-cationic monomers whose reaction parameters include copolymerization can be used as comonomers B) allow with acryloyldimethyltauric acid and / or acryloyldimethyltaurates in the respective reaction media.
• Preferred comonomers B) are unsaturated carboxylic acids and their anhydrides and salts, and also their esters with aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic alcohols with a carbon number of 1 to 22.
• Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, styrene sulfonic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and senecioic acid.
• Preferred counterions are Li + , Na + , K + , Mg ++ , Ca ++ , Al +++ , NH 4 + , monoalkylammonium, dialkylammonium, trialkylammonium and / or tetraalkylammonium radicals
• the alkyl substituents of the amines can independently of one another be (Ci - C 22 ) alkyl radicals or (C 2 - C ⁇ o) hydroxyalkyl radicals.
• the degree of neutralization of the carboxylic acids can be between 0 and 100%.
• N-vinylamides preferably N-vinylformamide (VIFA), N-vinylmethylformamide, N-vinylmethylacetamide (VIMA) and N-vinylacetamide; cyclic N-vinylamides (N-vinyllactams) with a ring size of 3 to 9, preferably N-vinylpyrrolidone (NVP) and N-vinylcaprolactam; Amides of acrylic and methacrylic acid, preferably acrylamide, methacrylamide, N, N-dimethyl-acrylamide, N, N-diethylacrylamide and N, N-diisopropylacrylamide; alkoxylated acrylic and methacrylamides, preferably hydroxyethyl methacrylate, hydroxymethyl methacrylamide, hydroxyethyl methacrylamide, hydroxypropyl methacrylamide and succinic acid mono- [2- (methacryloyloxy) ethy
• the proportion by weight of comonomers B), based on the total mass of the copolymers, can be 0 to 99.7% by weight and is preferably 0.5 to 80% by weight, particularly preferably 2 to 50% by weight.
• the macromonomers are at least simple olefinically functionalized polymers with one or more discrete repeat units and a number average molecular weight greater than or equal to 200 g / mol. Mixtures of chemically different macromonomers C) can also be used in the copolymerization.
• the macromonomers are polymeric structures which are composed of one or more repeating unit (s) and have a molecular weight distribution which is characteristic of polymers.
• Preferred macromonomers C) are compounds of the formula (I).
• R 1 represents a polymerizable function from the group of vinylically unsaturated compounds which are suitable for building polymer structures by radical means.
• a suitable bridging group Y is required to bind the polymer chain to the reactive end group.
• Preferred bridges Y are -O-, -C (O) -, -C (O) -O-, -S-, -O-CH 2 -CH (O -) - CH 2 OH, -O-CH 2 - CH (OH) -CH 2 O-, -O-SO 2 -O-, -O-SO 2 -O-, -O-SO-O-, -PH-, -P (CH 3 ) -, -PO 3 -, -NH- and -N (CH 3 ) -, particularly preferably -O-.
• the polymeric middle part of the macromonomer is represented by the discrete repeat units A, B, C and D.
• Preferred repeat units A, B, C and D are derived from acrylamide, methacrylamide, ethylene oxide, propylene oxide, AMPS, acrylic acid, methacrylic acid, methyl methacrylate, acrylonitrile, maleic acid, vinyl acetate, styrene, 1, 3-butadiene, isoprene, isobutene, diethylacrylamide and diisopropylacrylamide.
• the indices v, w, x and z in formula (I) represent the stoichiometric coefficients relating to the repeating units A, B, C and D.
• v, w, x. And z are independently 0 to 500, preferably 1 to 30, where the sum of the four coefficients must be> 1 on average.
• R 2 denotes a linear or branched aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (Ci-CsoJ hydrocarbon residue, OH, -NH 2 , -N (CH 3 ) 2 or is identical to the structural unit [-YR 1 ].
• Particularly preferred macromonomers C) are acrylic or methacrylic monofunctionalized alkyl ethoxylates of the formula (II).
• R 3 , R4, R 5 and R ⁇ independently of one another are hydrogen or n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (-C-C 3 o) hydrocarbon radicals.
• R 3 and R are preferably H or -CH 3 . particularly preferably H; R 5 is H or -CH 3 ; and R 6 is an n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C 1 -C 30 ) - carbon hydrogen rest.
• v and w are in turn the stoichiometric coefficients relating to the ethylene oxide units (EO) and propylene oxide units (PO), v and w are independently 0 to 500, preferably 1 to 30, the sum of v and w having to be ⁇ 1 on average.
• the distribution of the EO and PO units over the macromonomer chain can be statistical, block-like, alternating or gradient-like.
• Y stands for the bridges mentioned above.
• Particularly preferred macromonomers C) have the following structure according to formula (II):
• the molecular weight of the macromonomers C) is preferably 200 g / mol to 10 6 g / mol, particularly preferably 150 to 10 4 g / mol and particularly preferably 200 to 5000 g / mol.
• the proportion by weight of the macromonomer F) is based on
• Total mass of the copolymers 0.1 to 99.8% by weight, particularly preferably 2 to 90% by weight and particularly preferably 5 to 80% by weight.
• the copolymers contain at least one cationic comonomer D) in their structure.
• Suitable comonomers D) are all olefinically unsaturated monomers with a cationic charge which are capable of forming copolymers in the selected reaction media with acryloyldimethyltauric acid or its salts. The resulting distribution of the cationic charges over the chains can be statistical, alternating, block-like or gradient-like.
• the cationic comonomers D) also include those which carry the cationic charge in the form of a betaine structure.
• Comonomers D) in the sense of the invention are also amino-functionalized precursors which can be converted into their corresponding quaternary derivatives by polymer-analogous reactions (e.g. reaction with DMS).
• Particularly preferred comonomers D) are diallyldimethylammonium chloride (DADMAC), [2- (methacryloyloxy) ethyl] trimethylammonium chloride (MAPTAC), [2- (acryloyloxy) ethyl] trimethylammonium chloride, [2-methacrylamidoethyl] trimethylammonium chloride, [2- (acrylamido) ethyl] trimethylammonium chloride, N-methyl-2-vinylpyridinium chloride and / or N-methyl-4-vinylpyridinium chloride.
• the proportion by weight of the comonomers D), based on the total mass of the copolymers, is 0.1 to 99.8% by weight, preferably 0.5 to 30% by weight and particularly preferably 1 to 20% by weight.
• the copolymerization is carried out in the presence of at least one polymeric additive E), the additive E) being added to the polymerization medium in whole or in part in solution before the actual copolymerization.
• the use of several additives E) is also according to the invention.
• Crosslinked additives E) can also be used.
• additives E) or their mixtures only have to be wholly or partly soluble in the chosen polymerization medium.
• additive E) has several functions. On the one hand, it prevents the formation of over-crosslinked polymer fractions in the copolymer being formed in the actual polymerization step and, on the other hand, additive E) is statistically attacked by active radicals in accordance with the generally known mechanism of graft copolymerization. As a result, depending on the additive E), more or less large amounts of it are incorporated into the copolymers.
• suitable additives E) have the
• additives E) are homopolymers and copolymers which are soluble in water and / or alcohols. Copolymers are also to be understood as meaning those with more than two different types of monomers. Homo- and copolymers are particularly preferred as additives E)
• Particularly preferred additives E) are polyvinyl pyrrolidones (such as ® K15, K20 * 6 and ® K30 from BASF), poly (N-vinylformamides), poly (N-vinylcaprolactams) and Copolymers of N-vinylpyrrolidone, N-vinylformamide and / or acrylic acid, which can also be partially or completely saponified.
• polyvinyl pyrrolidones such as ® K15, K20 * 6 and ® K30 from BASF
• poly (N-vinylformamides) poly (N-vinylcaprolactams)
• Copolymers of N-vinylpyrrolidone, N-vinylformamide and / or acrylic acid which can also be partially or completely saponified.
• the molecular weight of the additives E) is preferably 10 2 to 10 7 g / mol, particularly preferably 0.5 * 10 4 to 10 6 g / mol.
• the amount of polymeric additive E) used is, based on the total mass of the monomers to be polymerized during the copolymerization, preferably 0.1 to 90% by weight, particularly preferably 1 to 20% by weight and particularly preferably 1.5 to 10% by weight .-%.
• the copolymers according to the invention are crosslinked, i.e. they contain comonomers with at least two polymerizable vinyl groups.
• Preferred crosslinkers are methylene bisacrylamide; methylenebismethacrylamide; Esters of unsaturated mono- and polycarboxylic acids with polyols, preferably diacrylates and triacrylates or methacrylates, particularly preferably butanediol and ethylene glycol diacrylate or methacrylate, trimethylolpropane triacrylate (TMPTA) and trimethylolpropane trimethacrylate (TMPTMA); Allyl compounds, preferably allyl (meth) acrylate, triallyl cyanurate, maleic acid diallyl ester, polyallyl ester, tetraallyloxyethane, triallylamine, tetraallylethylene diamine; Allyl esters of phosphoric acid; and / or vinylphosphonic acid derivatives.
• TMPTA Trimethylolpropane triacrylate
• the proportion by weight of crosslinking comonomers, based on the total mass of the copolymers, is preferably up to 20% by weight, particularly preferably 0.05 to 10% by weight and particularly preferably 0.1 to 7% by weight.
• Solvents are used which are largely inert with respect to radical polymerization reactions and advantageously allow the formation of medium or high molecular weights.
• Water is preferred; lower alcohols; preferably methanol, ethanol, propanols, iso-, sec- and t-butanol, particularly preferably t-butanol; Hydrocarbons with 1 to 30 carbon atoms and mixtures of the aforementioned compounds.
• the polymerization reaction is preferably carried out in the temperature range between 0 and 150 ° C., particularly preferably between 10 and 100 ° C., both under normal pressure and under elevated or reduced pressure. If necessary, the polymerization can also be carried out under a protective gas atmosphere, preferably under nitrogen.
• High-energy electromagnetic radiation, mechanical energy or the usual chemical polymerization initiators such as organic peroxides, e.g. Benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dilauroyl peroxide or azo initiators, e.g. Azodiisobutyronitrile (AIBN) can be used.
• organic peroxides e.g. Benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dilauroyl peroxide or azo initiators, e.g. Azodiisobutyronitrile (AIBN)
• AIBN Azodiisobutyronitrile
• inorganic peroxy compounds such as (NH 4 ) 2 S 2 ⁇ 8 , K 2 S 2 O 8 or H 2 O 2 , optionally in combination with reducing agents (e.g. sodium bisulfite, ascorbic acid, iron (II) sulfate etc.) or redox systems which contain an aliphatic or aromatic sulfonic acid (eg benzenesulfonic acid, toluenesulfonic acid, etc.) as the reducing component.
• reducing agents e.g. sodium bisulfite, ascorbic acid, iron (II) sulfate etc.
• redox systems which contain an aliphatic or aromatic sulfonic acid (eg benzenesulfonic acid, toluenesulfonic acid, etc.) as the reducing component.
• the polymerization reaction can e.g. be carried out as precipitation polymerization, emulsion polymerization, bulk polymerization, solution polymerization or gel polymerization.
• Precipitation polymerization preferably in tert-butanol, is particularly advantageous for the property profile of the copolymers according to the invention.
• the multifunctional polymers according to the invention have a great variety of structures and consequently a wide range of potential uses which can be tailored to almost any problem in which interface or surface effects play a role.
• the term "tailor-made polymers” describes the possibilities that this new class of polymers offers the user.
• the presence of cationic charges in the polymer structure makes it possible to exploit adhesion effects against anionic surfaces in a targeted manner.
• the polymer was prepared in tert-butanol by the precipitation process.
• the monomers were initially introduced into t-butanol, the reaction mixture was rendered inert, and the reaction was then heated to 60 ° C. by adding
• the polymer showed a viscosity of 11,000 mPas in 1% solution in distilled water.
• the polymer was made in water by the gel polymerization process.
• the monomers were dissolved in water, the reaction mixture 5 was rendered inert, and the reaction was then initiated after heating to 70 ° C. by adding sodium peroxodisulfate.
• the polymer gel was then crushed and the polymer isolated by vacuum drying.
• the polymer was made in water by the emulsion process.
• the monomers were emulsified in a water / cyclohexane using Span 80 ® , the reaction mixture was rendered inert with N 2 and then the reaction after heating to 60 ° C. by adding sodium peroxodisulfate started.
• the polymer emulsion was then evaporated (cyclohexane acted as a tug for water) and the polymer isolated.
• the polymer was tert in the precipitation process. Butanol made. The monomers were initially introduced into t-butanol, the reaction mixture was rendered inert, and the reaction was then initiated after heating to 68 ° C. by adding AIBN. The polymer was isolated by suction extraction of the solvent and subsequent vacuum drying.
• the polymer was made by the solution method in water. The monomers were dissolved in water, the reaction mixture was rendered inert, and the reaction was then initiated by heating to 55 ° C. using an iron (II) sulfate / H 2 O 2 redox couple. The polymer solution was then evaporated and the polymer was then isolated by vacuum drying.
• the polymer was tert in the precipitation process. Butanol made. The monomers were initially charged in t-butanol, the reaction mixture was rendered inert, and the reaction was then initiated after heating by adding DLP. The polymer was isolated by suction extraction of the solvent and subsequent vacuum drying.

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