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
  • C08F6/00—Post-polymerisation treatments
  • C08F6/06—Treatment of polymer solutions
  • C08F6/12—Separation of polymers from solutions
• • 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
  • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
• • 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
  • C08F20/00—Homopolymers and 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
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/52—Amides or imides
  • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
  • C08F20/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-acryloylmorpholine
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
  • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations

Definitions

• the present invention relates to a process for the preparation of concentrates from copolymers based on acryloyldimethyltauric acid or salts thereof.
• copolymers based on acryloyldimethyltauric acid or salts thereof preferably prepared by precipitation polymerization and corresponding to the prior art are pulverulent substances with application disadvantages resulting therefrom. Pulverulent substances, in principle, hold the risk of dust explosion, and in addition the storage stability of the powders is adversely affected as a result of hygroscopicity.
• the dissolution operation (the polymers are preferably incorporated into aqueous media) is in most cases very time-consuming.
• the dissolution operation of the pulverulent products can, depending on the size of the batch, take an hour or more.
• incomplete dissolution/swelling of the pulverulent products is often observed, which leads to a reduction in the quality and stability of the end formulation (formation of lumps).
• the processing and/or use of the pulverulent products requires particular stirring and dispersion devices in order to dissolve, or to suspend, respectively, the polymers based on acryloyldimethyltauric acid or salts thereof.
• the object of the present invention was to develop a process for the preparation of polymer concentrates comprising polymers based on acryloyldimethyltauric acid or salts thereof.
• the polymer concentrates should, when present in highly concentrated liquid or liquid-disperse form, i.e. when the highest possible polymer content arises, have a low viscosity combined with high stability of the solution or dispersion.
• the invention provides a process for the preparation of concentrates in liquid or liquid-disperse form comprising
• X is a cation or a mixture of cations, and X consists of not more than 10 mol % of protons, and,
• the concentrates prepared according to the process of the invention comprise polymers comprising 98 to 99.5% by weight of units which have come from monomers of the formula (1) and 0.5 to 2% by weight of crosslinking structures which have come from monomers with at least two olefinic double bonds.
• the counterion X in the formula (1) is, in particular, a proton, a cation of an alkali metal, an equivalent of a cation of an alkaline earth metal or is an ammonium ion.
• Particularly preferred polymers are notable for the fact that 90 to 100 mol % of the cations X consist of ammonium ions and 0 to 10 mol % of protons.
• the monomers with at least two olefinic double bonds are preferably chosen from dipropyl glycol diallyl ether, polyglycol diallyl ether, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyloxyethane or other allyl or vinyl ethers of multifunctional alcohols, tetraethylene glycol diacrylate, triallylamine, trimethylolpropane diallyl ether, methylene bisacrylamide, divinylbenzene or trimethylolpropyl tri(meth)acrylate.
• the monomers with at least two olefinic double bonds lead to crosslinking structures during the polymerization.
• the concentrates prepared by the process according to the invention comprise polymers prepared by free-radical polymerization of 90-99.99% by weight of the compounds of the formula (1) and 0.01-10% by weight of one or more crosslinkers which contain at least two olefinic double bonds.
• these polymers are prepared by:
• the polymerization is carried out as a precipitation polymerization.
• the described polymers can be prepared by precipitation polymerization as follows.
• the reaction medium used is preferably a water-soluble alcohol or a mixture of two or more water-soluble alcohols having 1 to 4 carbon atoms, preferably tert-butanol, where the water content of the alcohol or alcohol mixture must not exceed 10% by weight.
• the type and amount of solvent has to be chosen such that the amount of 2-acrylamido-2-methylpropanesulfonic acid and/or salts thereof used is largely soluble or dispersible. Largely soluble or dispersible is understood as meaning that, even after scraping the stirrer, no solid material settles out of the solution or dispersion.
• the polymer which forms in the course of the reaction should, however, be largely insoluble in the chosen solvent (or solvent mixture).
• Largely insoluble is understood here as meaning that, in the course of the polymerization, a readily stirrable pasty polymer mass forms in which no lumps or agglutinations must form.
• the filtrate obtainable by filtering the paste with suction should have a solids content of at most 5% by weight. If the polymers are soluble in the chosen solvent or solvent mixture to a greater degree, clumping may arise during the drying of the polymer paste.
• the polymerization reaction itself is triggered in a manner known per se, e.g. by free-radical-forming compounds, such as azoic initiators (e.g. azobisisobutyronitrile), peroxides (e.g. dilauryl peroxide) or persulfates, in a suitable temperature interval from 20 to 120° C., preferably between 40 and 80° C., and is continued over a period of 30 minutes to several hours.
• free-radical-forming compounds such as azoic initiators (e.g. azobisisobutyronitrile), peroxides (e.g. dilauryl peroxide) or persulfates
• the polymer concentrates prepared by the process according to the invention also comprise one or more emulsifiers and/or a solvent or solvent mixture in the stated amount. If emulsifiers are used as the sole component II), the proportion of the solvent or solvent mixture is thus 0% and, accordingly, the proportion of the emulsifiers is 0% when the component II) consists only of a solvent or solvent mixture. Preference is given to using a mixture of emulsifier and solvent or solvent mixture as second component.
• Suitable emulsifiers are addition products of from 0 to 30 mol of alkylene oxide, in particular ethylene oxide, propylene oxide, butylene oxide, onto linear fatty alcohols having 8 to 22 carbon atoms, onto fatty acids having 12 to 22 carbon atoms, onto alkylphenols having 8 to 15 carbon atoms in the alkyl group and onto sorbitan esters; (C 12 -C 18 )-fatty acid mono- and diesters of addition products of from 0 to 30 mol of ethylene oxide onto glycerol; glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and optionally the ethylene oxide addition products thereof; addition products of from 15 to 60 mol of ethylene oxide onto castor oil and/or hydrogenated castor oil; polyol and, in particular, polyglycerol esters, such as, for example, polyglycerol polyricinoleate and polygly
• Further dispersion concentrates prepared by the process of the invention preferably comprise sorbitol esters prepared by reacting sorbitol with fatty acid methyl esters or fatty acid triglycerides.
• the fatty acid radical in the fatty acid methyl esters and fatty acid triglycerides generally contains 8 to 22 carbon atoms and can be straight-chain or branched, saturated or unsaturated. Examples of these are palmitic acid, stearic acid, lauric acid, linoleic acid, linolenic acid, isostearic acid or oleic acid.
• Suitable fatty acid triglycerides are all natural animal or vegetable oils, fats and waxes, for example olive oil, rapeseed oil, palm kernel oil, sunflower oil, coconut oil, linseed oil, castor oil, soybean oil, optionally also in refined or hydrogenated form. Since these natural fats, oils and waxes are normally mixtures of fatty acids of varying chain length, this also applies to the fatty acid radicals in the sorbitol esters used according to the invention.
• the sorbitol esters used according to the invention can also be alkoxylated, preferably ethoxylated.
• anionic emulsifiers such as ethoxylated and nonethoxylated mono-, di- or triphosphoric esters, but also cationic emulsifiers, such as mono-, di- and trialkyl quats and their polymeric derivatives.
• the concentrates prepared by the process according to the invention can comprise one or more solvents, preferably from the group of hydrocarbons, ester oils, vegetable oils and silicone oils.
• the solvents used according to the invention include oils, such as hydrocarbon oils with linear or branched, saturated or unsaturated C 7 -C 40 -carbon chains, for example vaseline, dodecane, isododecane, cholesterol, lanolin, hydrogenated polyisobutylenes, docosanes, hexadecane, isohexadecane, paraffins and isoparaffins;
• oils such as hydrocarbon oils with linear or branched, saturated or unsaturated C 7 -C 40 -carbon chains, for example vaseline, dodecane, isododecane, cholesterol, lanolin, hydrogenated polyisobutylenes, docosanes, hexadecane, isohexadecane, paraffins and isoparaffins;
• oils of vegetable origin in particular liquid triglycerides, such as sunflower oil, corn oil, soybean oil, rice oil, jojoba oil, babusscu oil, pumpkin oil, grapeseed oil, sesame oil, walnut oil, apricot oil, macadamia oil, avocado oil, sweet almond oil, lady's smock oil, castor oil, olive oil, peanut oil, rapeseed oil and coconut oil;
• liquid triglycerides such as sunflower oil, corn oil, soybean oil, rice oil, jojoba oil, babusscu oil, pumpkin oil, grapeseed oil, sesame oil, walnut oil, apricot oil, macadamia oil, avocado oil, sweet almond oil, lady's smock oil, castor oil, olive oil, peanut oil, rapeseed oil and coconut oil;
• oils of animal origin preferably beef tallow, perhydrosqualene, lanolin
• synthetic oils such as purcellin oil, linear and/or branched fatty alcohols and fatty acid esters, preferably Guerbet alcohols having 6 to 18, preferably 8 to 10, carbon atoms; esters of linear (C 6 -C 13 )-fatty acids with linear (C 6 -C 20 )-fatty alcohols; esters of branched (C 6 -C 13 )-carboxylic acids with linear (C 6 -C 20 )-fatty alcohols, esters of linear (C 6 -C 18 )-fatty acids with branched alcohols, in particular 2-ethylhexanol; esters of linear and/or branched fatty acids with polyhydric alcohols (such as, for example, dimerdiol or trimerdiol) and/or Guerbet alcohols; alcohol esters of C 1 -C 10 -carboxylic acids or C 2 -C 30 -dicarboxylic acids, C 1 -C 30 -carboxylic mono
• waxes such as beeswax, paraffin wax or microwaxes, optionally in combination with hydrophilic waxes, such as, for example, cetylstearyl alcohol; fluorinated and perfluorinated oils;
• monoglycerides of C 1 -C 30 -carboxylic acids diglycerides of C 1 -C 30 -carboxylic acids, triglycerides of C 1 -C 30 -carboxylic acids, for example triglycerides of caprylic/capric acids, ethylene glycol monoesters of C 1 -C 30 -carboxylic acids, ethylene glycol diesters of C 1 -C 30 -carboxylic acids, propylene glycol monoesters of C 1 -C 30 -carboxylic acids, propylene glycol diesters of C 1 -C 30 -carboxylic acids, and also propoxylated and ethoxylated derivatives of the abovementioned classes of compounds.
• Suitable silicone oils are dimethylpolysiloxanes, cyclomethicones, polydialkylsiloxanes R 3 SiO(R 2 SiO) x SiR 3 , in which R is methyl or ethyl, particularly preferably methyl, and x is a number from 2 to 500, for example the dimethicones available under the trade names VICASIL (General Electric Company), DOW CORNING 200, DOW CORNING 225, DOW CORNING 200 (Dow Corning Corporation); trimethylsiloxysilicates [(CH 2 ) 3 SiO) 1/2 ]X[SiO 2 ] y , where x is a number from 1 to 500 and y is a number from 1 to 500; dimethiconols R 3 SiO[R 2 SiO] x SiR 2 OH and HOR 2 SiO[R 2 SiO] x SiR 2 OH, where R is methyl or ethyl and x is a number up to 500,
• the concentrates prepared by the process according to the invention consist of dispersions of the polymers in a liquid matrix comprising oil, emulsifier, dispersant and/or water. Preference is also given here to liquid-disperse forms with the highest possible polymer content and low viscosity coupled with high stability of the dispersion. In the concentrates according to the invention, preference is given to using oils, emulsifiers and dispersants which are acceptable in cosmetic, pharmaceutical and dermatological formulations.
• the invention further also provides the concentrates obtainable by the process according to the invention.
• the concentrates according to the invention are suitable as thickener, consistency-imparting agent, emulsifier, solubilizer, dispersant, slip agent, adhesive, conditioner and/or stabilizer in an excellent manner for the formulation of cosmetic, pharmaceutical and dermatological compositions, in particular of oil-in-water emulsions in the form of creams, lotions, cleansing milk, cream gels, spray emulsions, e.g. body lotions, after sun lotions, sun screen compositions and deodorant sprays.
• the invention further also provides cosmetic, pharmaceutical and dermatological preparations comprising a concentrate according to the invention.
• the polymer concentrates according to the invention are used in the cosmetic, pharmaceutical and dermatological preparations in amounts by weight of from 0.01 to 10% by weight, preferably 0.1 to 5% by weight, particularly preferably 0.5 to 3% by weight, based on the finished compositions.
• the cosmetic, pharmaceutical and dermatological preparations may comprise anionic, cationic, nonionic, zwitterionic and/or amphoteric surfactants, and also further auxiliaries and additives, cationic polymers, film formers, superfatting agents, stabilizers, biogenic active ingredients, glycerol, preservatives, pearlizing agents, dyes and fragrances, solvents, opacifiers, and also protein derivatives, such as gelatin, collagen hydrolysates, natural and synthetic-based polypeptides, egg yolk, lecithin, lanolin and lanolin derivatives, fatty alcohols, silicones, deodorizing agents, substances with a keratolytic and keratoplastic action, enzymes and carrier substances.
• antimicrobially active agents can be added to the compositions according to the invention.
• the cosmetic, pharmaceutical and dermatological preparations can comprise organic solvents.
• suitable organic solvents are all mono- or polyhydric alcohols. Preference is given to using alcohols having 1 to 4 carbon atoms, such as ethanol, propanol, isopropanol, n-butanol, isobutanol, tert-butanol, glycerol and mixtures of said alcohols.
• Further preferred alcohols are polyethylene glycols with a relative molecular mass below 2000.
• polyethylene glycol with a relative molecular mass between 200 and 600 and in amounts up to 45% by weight and of polyethylene glycol with a relative molecular mass between 400 and 600 in amounts of from 5 to 25% by weight is preferred.
• suitable solvents are, for example, triacetin (glycerol triacetate) and 1-methoxy-2-propanol.
• the tert-butanol residues are removed from the mixture. It must be ensured that although the applied vacuum permits the removal of the tert-butanol by distillation, it does not exceed the corresponding boiling temperature of the solvent at this pressure. After the tert-butanol has been separated off, the mixture is cooled and the product is removed from the flask.
• the tert-butanol residues are removed from the mixture. It must be ensured that although the applied vacuum permits the removal of the tert-butanol by distillation, it does not exceed the corresponding boiling temperature of the solvent at this pressure. After the tert-butanol has been separated off, the mixture is cooled and the product is removed from the flask.
• the figures given in table 1 are % by weight.
• the dispersion concentrates B and D were prepared analogously to A, but varying the emulsifiers and oils.
• Hostacerin DGI Polyglyceryl-2 Sesquiisostearate Hostaphat KL 340 D Trilaureth-4 Phosphate Emulsogen SRO Rapeseed Oil Sorbitol Esters Myritol 318 Caprylic/Capric Triglyceride

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• Health & Medical Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Animal Behavior & Ethology (AREA)
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• Veterinary Medicine (AREA)
• Chemical Kinetics & Catalysis (AREA)
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• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Epidemiology (AREA)
• Birds (AREA)
• Dermatology (AREA)
• Cosmetics (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 2003
  • 2003-04-03 DE DE10315183A patent/DE10315183A1/de not_active Withdrawn
• 2004
  • 2004-03-26 DE DE502004011717T patent/DE502004011717D1/de not_active Expired - Lifetime
  • 2004-03-26 EP EP04007372A patent/EP1464659B1/de not_active Expired - Fee Related
  • 2004-03-26 ES ES04007372T patent/ES2349408T3/es not_active Expired - Lifetime
  • 2004-04-02 US US10/817,364 patent/US20040260010A1/en not_active Abandoned

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