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WO2000005273A1 - Procede de production de polymerisats pulverulents reticules - Google Patents

Procede de production de polymerisats pulverulents reticules Download PDF

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Publication number
WO2000005273A1
WO2000005273A1 PCT/EP1999/004869 EP9904869W WO0005273A1 WO 2000005273 A1 WO2000005273 A1 WO 2000005273A1 EP 9904869 W EP9904869 W EP 9904869W WO 0005273 A1 WO0005273 A1 WO 0005273A1
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WIPO (PCT)
Prior art keywords
monomers
acid
carbon dioxide
vinyl
esters
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Application number
PCT/EP1999/004869
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German (de)
English (en)
Inventor
Volker Hildebrandt
Knut Breede
Katrin Zeitz
Original Assignee
Basf Aktiengesellschaft
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Publication date
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Publication of WO2000005273A1 publication Critical patent/WO2000005273A1/fr

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Classifications

    • 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
    • A61K8/81—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
    • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; 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
    • A61K8/8141—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
    • 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)
    • A61K8/8176—Homopolymers of N-vinyl-pyrrolidones. 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • 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
    • C08F2/04—Polymerisation in solution
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a process for the preparation of powdered polymers by radical polymerization of monoethylenically unsaturated monomers in supercritical carbon dioxide, if appropriate in the presence of crosslinking agents and substances which form free radicals, and the use of the polymers.
  • EP-A 220 603 describes a process for producing uncrosslinked powdery polymers based on N-vinyl monomers and / or ethylenically unsaturated carboxylic acid esters by radical polymerization in supercritical carbon dioxide.
  • EP-A 239 035 describes the preparation of crosslinked powdery polymers based on monoethylenically unsaturated carboxylic acids, their amides and / or esters by polymerization in supercritical carbon dioxide.
  • the reaction mixture and liquid carbon dioxide are generally placed in a pressure vessel and the supercritical state is then brought about by increasing the temperature and pressure.
  • the disadvantage of this is that, due to the non-uniform solubility of the monomers and crosslinking agents in the solvent, products with a non-uniform morphology or a non-uniform chemical composition can result. In individual cases, undesired bulk polymerization of the feed materials can occur before the substances are dissolved.
  • the object of the present invention was to find an improved process for the preparation of crosslinked polymers.
  • a process for the preparation of powdered polymers by free-radically initiated polymerization of monoethylenically unsaturated monomers selected from the group of monoethylenically unsaturated carboxylic acids, their amides and esters, the N, N-diallylairine and the N-vinyl monomers, or mixtures of these monomers , found in supercritical carbon dioxide as an inert diluent, which is characterized in that the carbon dioxide in the reaction space is first increased to supercritical state by increasing the pressure to pressures above 73 bar and temperatures greater than 31 ° C. and brought to a reaction temperature of up to 100 ° C, and then metered in the feed.
  • the polymerization is carried out under pressure in supercritical carbon dioxide as an inert diluent.
  • the critical point for carbon dioxide is then around 31 ° C and 73 bar.
  • the polymerization is preferably carried out under pressure in supercritical carbon dioxide at temperatures above about 31 ° C., the critical temperature of the carbon dioxide.
  • the upper limit for the preparation of the polymers is taken to be the temperature which is 10 ° C. above the beginning of the softening range of the respective resulting polymers.
  • the upper value for this temperature limit is 150 C for most polymers.
  • the polymerization is preferably carried out in the temperature range from 30 to 130 ° C.
  • the reaction temperature need not be kept constant; you can also set a step or ramp-shaped temperature profile. It is advisable to start the reaction
  • Set temperatures in the range of 31 to 100 C C.
  • the pressures are above 73 bar, preferably in the range from 80 to 300 bar, particularly preferably from 120 to 250 bar.
  • the process according to the invention is characterized in that carbon dioxide in a solid, liquid or gaseous state is initially introduced into the reaction chamber in conventional pressure apparatus, then by increasing the pressure to values above 73 bar and the temperature to values above 31 ° C. the carbon dioxide transferred to the supercritical state, then the reaction temperature is set and then the starting materials are metered in.
  • the supercritical carbon dioxide can also be introduced into the reaction space and then metered in.
  • the starting materials such as monomers, free radical initiators, crosslinking agents and optionally polymerization regulators can be metered in individually or as mixtures. For example, it may be advisable to dissolve the radical initiators in the compounds. Which procedure is chosen essentially depends on the solubility of the individual components among one another and in the diluent. If required, feedstocks can be metered in during the reaction (semi-batch procedure).
  • the polymerization reaction is started with the aid of polymerization initiators which break down into free radicals.
  • All initiators known for the polymerization of the monomers can be used.
  • Free radical initiators that have half-lives of less than 3 hours at the temperatures selected. If the polymerization is carried out at different temperatures, by polymerizing the monomers first at a lower temperature and then polymerizing them out at a significantly higher temperature, it is expedient to use at least two different initiators which have a sufficient rate of disintegration in the temperature range chosen in each case.
  • the polymerization reaction can be carried out batchwise or continuously with thorough mixing of the reactants in appropriately designed printing apparatuses. In order to dissipate the heat generated during the polymerization, it is desirable for the printing apparatus to have a cooling system. Of course, they must also be heatable in order to heat the reaction mixture to the temperature desired for the polymerization.
  • the pressure equipment should have mixing devices, e.g. Stirrers (blade, impeller, multi-stage impulse counterflow, spiral stirrers) or blades.
  • Powdered crosslinked or uncrosslinked polymers of the following composition can be prepared by the process according to the invention:
  • a monoethylenically unsaturated monomer selected from the group consisting of monoethylenically unsaturated carboxylic acids, their amides and / or their esters with amino alcohols, the N-N-diallylamines and N-vinyl monomers or mixtures of these monomers,
  • Monoethylenically unsaturated carboxylic acids come into consideration as monomers of group (a).
  • the most important representatives of this group are, for example, monoethylenically unsaturated C 3 - to Cs carboxylic acids, such as acrylic acid, methacrylic acid, vinyl acetic acid, itaconic acid, crotonic acid, alpha-methylcrotonic acid, alpha-ethyl acrylic acid, dimethylacrylic acid, alpha-chloro acrylic acid and Vinyl lactic acid.
  • the amides of monoethylenically unsaturated carboxylic acids for example acrylamide, methacrylamide, crotonic acid amide and itaconic acid amide, are also suitable.
  • the monomers of group (a) also include esters of monoethylenically unsaturated carboxylic acids and amino alcohols of the formula (I)
  • R 2 H, CK 2 , C 2 H 5 , C 3 H 7 .
  • These are preferably di-Ci to C 3 -alkylamino-C 2 to C 8 -alkyl acrylates or methacrylates.
  • Individual representatives of these monomers are, for example, dimethylaminoethyl acrylate, dirnethylaminoethyl methacrylate, diethylaminoethyl methacrylate, diethylaminoethyl acrylate, dipropylaminoethyl acrylate, dimethyl aminopropyl acrylate, dimethyl aminopropyl methacrylate, dimethyl aminopethyl acrylate, methyl amyl methacrylate, dimethylamethyl amyl methacrylate, dimethylamethyl amyl methacrylate, dimethylamethyl amyl methacrylate, dimethylamethyl amyl methacrylate,
  • N, N-diallylamines of the general formula (II) are also suitable.
  • R 4 is a -C 24 alkyl radical, preferably N, N-diaiiyl-N-methylamine.
  • diallylamines react under the polymerization conditions according to the invention with ring closure:
  • acrylic acid preference is given to using acrylic acid, methacrylic acid, acrylamide and / or methacrylamide. If acrylic acid is used as monomer (a), crosslinked polyacrylic acid is obtained by copolymerization with the monomers of group (b), and accordingly the use of acrylamide as monomer of group (a) provides crosslinked polyacrylic mide. Puts If mixtures of acrylic acid and acrylamide are used as monomers of group (a), crosslinked copolymers of acrylamide and acrylic acid are obtained in the copolymerization.
  • a further variation of the crosslinked copolymers is made possible by subjecting either acrylic acid additionally to the copolymerization in the presence of dimethylaminoethyl acrylate or acrylamide in the presence of dimethylaminoethyl acrylate together with the monomers (b) and optionally the monomers of group (c). Since the monomers of group (a) can be copolymerized with one another in any ratio, there are a variety of possible variations in the composition of the crosslinked copolymers.
  • N-vinyl monomers such as N-vinyl lactams, for example N-vinyl pyrrolidone or N-vinyl caprolactam, N-vinyl carboxamides which are derived from saturated ci to C 6 ⁇ carboxylic acids, for example N-vinyl formamide, N- Vinyl-N-methylformamide, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl propionamide, N-vinyl-N-methyl propionamide, N-vinyl butyramide or N-vinyl capronamide as well as N-vinyl imidazole and 2-methyl N-vinylimidazole.
  • N-vinyl lactams for example N-vinyl pyrrolidone or N-vinyl caprolactam
  • N-vinyl carboxamides which are derived from saturated ci to C 6 ⁇ carboxylic acids
  • N-vinyl formamide N-
  • Suitable crosslinkers are, for example, acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols.
  • the OH groups of the underlying alcohols can be wholly 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 1,2-ethanediol, 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, but-2-en-1,4-diol , 1, 2-pentanediol, 1, 5-pentanediol, 1, 2-hexanediol, 1, 5-hexanediol, 1, 10-decanediol, 1, 2-dodecanediol, 1, 12-dodecanediol, neopentyl glycol, 3-methylpentane -1, 5-diol, 2, 5-dodecanediol, 1, 12-dodecanediol, neopentyl glycol, 3-methylpentane -1, 5-diol, 2, 5-dodecanediol, 1, 12-dodecane
  • ethyl Lenoxide or propylene oxide can also be block copolymers of ethylene oxide or propylene oxide or copolymers which contain ethylene oxide and propylene oxide groups. builds included, used.
  • underlying alcohols with more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1,2, 5-pentanetriol, 1, 2, 6-hexanetriol, triethoxycyanuric acid, sorbitan, sugars such as sucrose, glucose, mannose.
  • the polyvalent ones Alcohols can also be used as the corresponding ethoxylates or propoxylates after reaction with ethylene oxide or propylene oxide.
  • the polyhydric alcohols can also first be converted into the corresponding glycidyl ethers by reaction with epichlorohydrin.
  • crosslinkers are the Vinylester or the esters of monohydric unsaturated alcohols with ethylenically unsaturated C ß -CG-carboxylic acids, for example acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.
  • examples of such alcohols are allyl alcohol, l-buten-3-ol, 5-hexen-l-ol, l-octen-3-ol, 9-decen-l-ol, dicyclopentenyl alcohol, 10-undecen-l-ol, cinnamon alcohol , Citronellol, crotyl alcohol or cis-9-octadecen-l-ol.
  • the monohydric, unsaturated alcohols can also be esterified with polybasic carboxylic acids, for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
  • polybasic carboxylic acids for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
  • esters of unsaturated carboxylic acids with the polyhydric alcohols described above, for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid, as crosslinking agents.
  • straight-chain or branched, linear or cyclic, aliphatic or aromatic hydrocarbons which have at least two double bonds which must not be conjugated to aliphatic hydrocarbons, e.g. Divinylbenzene, divinyltoluene, 1, 7-octadiene, 1, 9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes with molecular weights from 200 to 20,000.
  • crosslinking agents are the acrylic acid amides, methacrylic acid amides and N-allylamines of at least divalent amines.
  • amines are, for example, 1,2-diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane,
  • amides of allylamine and unsaturated carboxylic acids such as acrylic acids, methacrylic acid, itaconic acid, maleic acid, or at least dibasic carboxylic acids, as described above, are also suitable.
  • Triallylamine and trialiylmonoalkylammonium salts for example triallylmethylammonium chloride or methylsulfate, are also suitable as crosslinking agents.
  • N-vinyl compounds of urea derivatives at least dihydric amides, cyanurates or urethanes, for example urea, ethylene urea, propylene urea or tartaric acid diamide, e.g. N, N 'divinyl ethylene urea or N, N' divinyl propylene urea.
  • alkylenebisacrylamides such as methylenebisacrylamide and N, N '- (2,2-) butane and 1, 1' -bis- (3, 3 '-vinylbenzimidazolite-2-one) 1,4-butane.
  • crosslinking agents are, for example, alkylene glycol di (meth) acrylates, such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol acrylate, tetraethylene glycol dimethacrylate, diethylene glycol acrylate, diethylene glycol methacrylate, vinyl acrylate, allyl acrylate, plylyl methacrylate, allyl methacrylate and allyl methacrylate, allyl methacrylate and allyl methacrylate.
  • alkylene glycol di (meth) acrylates such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol acrylate, tetraethylene glycol dimethacrylate, diethylene glycol acrylate, diethylene glycol methacrylate, vinyl acrylate, allyl acrylate, plylyl methacrylate, allyl methacrylate and allyl methacrylate, ally
  • crosslinkers are divinyldioxane, tetraallylsilane or tetravinylsilane.
  • Crosslinking agents which are particularly preferably used are, for example, methylenebisacrylamide, triallylamine and triallylalkylammonium salts, divinylimidazole, N, N'-divinylethyleneurea, reaction products of polyhydric alcohols with acrylic acid or methacrylic acid, methacrylic acid esters and acrylic acid esters of polyalkylene oxides or polyhydric alcohols or with ethylene oxide and / Propylene oxide and / or epichlorohydrin have been implemented.
  • Methylene bisacrylamide, N, N'-divinylethylene urea and acrylic acid esters of glycol, butanediol, trimethylolpropane or glycerol or acrylic acid esters of glycol, butanediol, trimethylolpropane or glycerol reacted with ethylene oxide and / or epichlorohydrin are very particularly preferred as crosslinking agents.
  • the crosslinker is preferably soluble in the reaction medium. If the solubility of the crosslinking agent in the reaction medium is low, it can be dissolved in a monomer or in a monomer mixture or else added in solution in a solvent which mixes with the reaction medium. Those crosslinkers which are soluble in the monomer mixture are particularly preferred.
  • the solution viscosity of the polymers according to the invention can be influenced to a large extent by the content of crosslinking agent.
  • other ethylenically unsaturated monomers can be used in the copolymerization.
  • the group of monomers (c) includes, for example, acrylonitrile, methacrylonitrile, acrylic acid and methacrylic acid esters which are derived from monohydric - to -C 8 -alcohols, hydroxy-C 2 - to C 4 -alkyl esters of acrylic acid and methacrylic acid, maleic anhydride, Vinyl ester, 2-acrylamido-2-methylpropyl sulfonic acid and / or vinyl phosphoric acid.
  • esters of acrylic acid and methacrylic acid with fatty alcohol ethoxylates and fatty alcohol propoxylates are suitable, the fatty alcohol component having 10 to 20 carbon atoms and the ethylene oxide or propylene oxide content being 1 to 20 mol%.
  • Such alcohol components are obtained, for example, by reacting CI Q to C 2 o fatty alcohols with ethylene oxide and / or propylene oxide and esterifying the alkoxylated fatty alcohols obtained with acrylic acid or methacrylic acid.
  • the use of these comonomers results in crosslinked copolymers which have a high resistance to electrolytes.
  • the monomers of group (c) are used in an amount of 0 to 30, and preferably up to 15% by weight.
  • esters of acrylic acid and methacrylic acid are, for example, methyl acrylate, ethyl acrylate, methyl methacrylate, 2-ethylhexyl acrylate, stearyl acrylate, stearyl methacrylate and the acrylic acid esters of the isomeric butyl alcohols.
  • Hydroxy-C 2 to C 4 -alkyl esters of acrylic acid and methacrylic acid are, for example, hydroxyethyl acrylates, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl methacrylate.
  • vinyl esters vinyl acetate and vinyl propionate are preferably used.
  • Other suitable monomers are olefins such as ethylene or propylene, styrene and alkylethylene glycol acrylates or methacrylates with 1 to 50 ethylene glycol units.
  • Water-soluble and water-insoluble peroxo and / or azo compounds can be used as initiators for the radical polymerization, for example alkali metal or ammonium peroxydisulfates, hydrogen peroxide, dibenzoyl peroxide, tert-butyl perpivalate, tert. -Butyi-per-2-ethylhexanoate, 2, 2 '-azo-bis (2, 4-dimethylvaleronitrile), tert. -Butyl peroxineodecanoate, di-tert. -butyl peroxide, tert.
  • redox coinitiators for example benzoin, dimethylaniline and organically soluble complexes and salts of heavy metals such as copper, cobalt, manganese, nickel and chromium or in particular iron
  • the half-lives of the peroxides mentioned, in particular the hydroperoxides can be reduced , so that, for example, tert. -Butyl hydroperoxide in the presence of 5 ppm copper (II) acetylacetonate is already effective at 100 ° C.
  • the polymerization can optionally also be carried out in the presence of polymerization regulators in order to regulate the molecular weight of the polymers. If particularly low molecular weight copolymers are to be produced, higher amounts of polymerization regulators are used, while only small amounts of polymerization regulators are used for the production of high molecular weight copolymers or the absence of these substances is used.
  • Suitable polymerization regulators are, for example, 2-mercapto-ethanol, mercaptopropanols, mercaptobutanols, thioglycolic acid, N-dodecyl mercaptan, tert.
  • the polymerization regulators are used in an amount of 0 to 10, preferably 0 to 5% by weight, based on the monomers used.
  • the polymers obtainable by the process according to the invention are suitable for use as viscosity modifiers (emulsifiers and dispersing assistants), as W / O and O / W emulsifiers and generally as process aids, finishing aids or as superabsorbents, and furthermore as detergent additives such as incrustation and Color transfer inhibitors, as retention aids in paper manufacture, as flocculants in water treatment or for use in the field of food technology, for example as filter aids or complexing agents.
  • viscosity modifiers emulsifiers and dispersing assistants
  • W / O and O / W emulsifiers and generally as process aids, finishing aids or as superabsorbents
  • detergent additives such as incrustation and Color transfer inhibitors
  • retention aids in paper manufacture as flocculants in water treatment or for use in the field of food technology, for example as filter aids or complexing agents.
  • the polymers are particularly suitable as thickeners and gelling agents in cosmetic formulations, especially hair cosmetic preparations such as hair treatments, hair lotions, hair rinses, hair emulsions, tip fluids, leveling agents for perms, 'hot oil treatment' preparations, setting lotions or hair sprays, especially in conditioners.
  • hair cosmetic preparations such as hair treatments, hair lotions, hair rinses, hair emulsions, tip fluids, leveling agents for perms, 'hot oil treatment' preparations, setting lotions or hair sprays, especially in conditioners.
  • the hair cosmetic preparations can be applied as a spray, foam, gel, gel spray or mousse.
  • the polymers are also suitable as auxiliaries in pharmaceutical formulations, for example as tablet disintegrants.
  • the polymers produced according to the invention are white, free-flowing powders with a uniform morphology, which have practically no tendency to stickiness.
  • Carbon dioxide was placed in an autoclave and brought to the supercritical state and to the reaction temperature by increasing the pressure and temperature.
  • the starting materials were then metered in as a mixture in a single feed over the course of 10 minutes.
  • the reaction mixture was stirred at 600 rpm.
  • the residence time in the reactor was 10 hours.
  • the mixture was then cooled to room temperature and let down. Loose, white powders were obtained, which had no tendency to aggregate, with particle sizes in the range from 10 to 500 ⁇ m.

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Abstract

L'invention concerne un procédé de production de polymérisats pulvérulents par polymérisation radicalaire de monomères monoéthyléniquement insaturés, choisis dans le groupe des acides carboxyliques monoéthyléniquement insaturés, de leurs amides et esters, des N, N-diallylamines et des monomères de N-vinyles, ou bien de mélanges de ces monomères, en présence de réticulants et à l'aide de dioxyde de carbone surcritique comme solvant inerte. Ce procédé se caractérise en ce que l'on fait prendre d'abord au dioxyde de carbone, dans la chambre de réaction, son état surcritique en élevant la pression à une valeur supérieure à 73 bars et en le portant à une température de réaction pouvant aller jusqu'à 100 DEG C, et en ce que l'on ajoute ensuite, de façon dosée, les substances utilisées.
PCT/EP1999/004869 1998-07-23 1999-07-12 Procede de production de polymerisats pulverulents reticules WO2000005273A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19833285A DE19833285A1 (de) 1998-07-23 1998-07-23 Verfahren zur Herstellung von pulverförmigen vernetzten Polymerisaten
DE19833285.8 1998-07-24

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1201682A1 (fr) * 2000-10-31 2002-05-02 E.I. Du Pont De Nemours And Company Procédé de fabrication d'une poudre de polymère utilisant un fluide supercritique
EP2447286A1 (fr) * 2010-11-01 2012-05-02 The Procter & Gamble Company Procédé utilisant un milieu supercritique pour produire des polymères

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0239035A2 (fr) * 1986-03-22 1987-09-30 BASF Aktiengesellschaft Procédé de préparation de copolymères réticulés à particules fines et leur usage
CA1274942A (fr) * 1985-09-20 1990-10-02 Wilfred G. Sertage, Jr. Polymerisation de l'acide acrylique

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1274942A (fr) * 1985-09-20 1990-10-02 Wilfred G. Sertage, Jr. Polymerisation de l'acide acrylique
EP0239035A2 (fr) * 1986-03-22 1987-09-30 BASF Aktiengesellschaft Procédé de préparation de copolymères réticulés à particules fines et leur usage

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1201682A1 (fr) * 2000-10-31 2002-05-02 E.I. Du Pont De Nemours And Company Procédé de fabrication d'une poudre de polymère utilisant un fluide supercritique
US6828363B2 (en) 2000-10-31 2004-12-07 E.I. Du Pont De Nemours And Company Process for the preparation of powder coating compositions
EP2447286A1 (fr) * 2010-11-01 2012-05-02 The Procter & Gamble Company Procédé utilisant un milieu supercritique pour produire des polymères
WO2012061210A1 (fr) * 2010-11-01 2012-05-10 The Procter & Gamble Company Procédés utilisant un milieu supercritique pour produire des polymères
US9006366B2 (en) 2010-11-01 2015-04-14 The Procter & Gamble Company Processes using supercritical medium to produce polymers

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