EP1117696A1 - Procede de production de polymerisats reticules pulverulents - Google Patents

Procede de production de polymerisats reticules pulverulents

Info

Publication number
EP1117696A1
EP1117696A1 EP99932863A EP99932863A EP1117696A1 EP 1117696 A1 EP1117696 A1 EP 1117696A1 EP 99932863 A EP99932863 A EP 99932863A EP 99932863 A EP99932863 A EP 99932863A EP 1117696 A1 EP1117696 A1 EP 1117696A1
Authority
EP
European Patent Office
Prior art keywords
monomers
acid
weight
polymerization
quaternized
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99932863A
Other languages
German (de)
English (en)
Inventor
Volker Hildebrandt
Reinhold Dieing
Katrin Zeitz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1117696A1 publication Critical patent/EP1117696A1/fr
Withdrawn legal-status Critical Current

Links

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
    • 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
    • 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)
    • 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
    • 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
    • C08F2/06—Organic solvent
    • 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
    • A61K2800/542—Polymers characterized by specific structures/properties characterized by the charge
    • A61K2800/5426—Polymers characterized by specific structures/properties characterized by the charge cationic
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/20—Pills, tablets, discs, rods
    • A61K9/2004—Excipients; Inactive ingredients
    • A61K9/2022—Organic macromolecular compounds
    • A61K9/2027—Organic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyvinyl pyrrolidone, poly(meth)acrylates
    • 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 powdery, cationic, crosslinked polymers based on monoethylenically unsaturated monomers which contain a quaternized or guaternizable nitrogen atom by free-radical polymerization in supercritical carbon dioxide.
  • EP-A 220 603 describes a process for the production of 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 aids 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.
  • a 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 chemical chemistry can be formed.
  • 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 cationic crosslinked polymers based on monoethylenically unsaturated monomers which contain a quaternized or quaternizable nitrogen atom by radical-initiated polymerization which is characterized in that the polymerization in supercritical carbon dioxide as an inert diluent with mixing at temperatures from over 31 ° C to 150 ° C and pressures above 73 bar.
  • the polymerization is carried out under pressure in supercritical carbon dioxide as an inert diluent.
  • JA Hyatt, J. Org. Chem. 49, 5097-5101 (1984) reported on the properties of carbon dioxide in the liquid and in the supercritical state.
  • the critical point of carbon dioxide lies about 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 5 is that 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.
  • reaction temperature need not be kept constant; you can also set a step or ramp temperature profile. It is advisable to set temperatures in the range of 31 to 100 ° C at the beginning of the reaction.
  • the pressures are above 73 bar, preferably in the range of
  • the process according to the invention is preferably carried out in such a way that carbon dioxide in the solid, liquid or gaseous state is first used in pressure apparatus which are conventional per se in the reaction chamber
  • the carbon dioxide is converted into the supercritical state by increasing the pressure to values above 73 bar and the temperature above 31 ° C., then adjusting the reaction temperature and then metering in the starting materials.
  • the starting materials such as monomers, free radical initiators, crosslinking agents and, if appropriate, polymerization regulators, can be metered in individually or as mixtures. For example, it may be advisable to dissolve the radical initiators in the monomers. Which procedure you choose essentially depends on the solubility of the individual components among each other and in the diluent. However, the starting materials can also be introduced in whole or in part in the reaction space and then the carbon dioxide added. If desired, 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. Suitable are, for example, initiators which decompose into free radicals and which have half-lives of less than 3 hours at the temperatures chosen in each case. If the polymerization is carried out at different temperatures, by first polymerizing the monomers at a lower temperature and then polymerizing them at a significantly higher temperature, it is advantageous to use at least two different initiators, which have a sufficient decay rate in the temperature range selected 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 remove the heat generated during the polymerization, it is desirable that the printing apparatuses 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, multiple impulse counter-current, spiral stirrers) or blades.
  • the process according to the invention is particularly suitable for the production of powdered, cationic, crosslinked polymers.
  • powdery, cationic, crosslinked polymers are obtainable by free-radically initiated polymerization of
  • Suitable monomers (al) are selected from one of the following groups:
  • R 1 , R 2 and R 3 independently of one another are hydrogen, -CC 4 -alkyl or phenyl, preferably 2-methyl-N-vinyl imidazole or N-vinylimidazole
  • R 4 is a -C 24 alkyl, preferably N, N-diallyl-N-methylamine
  • diallylamines react under the polymerization conditions according to the invention with ring closure:
  • R 5 and R 6 are independently hydrogen or methyl
  • R 7 is a linear or branched C] _- C 4 alkylene radical
  • R 8 and R 9 are independently a C ⁇ -C 24 alkylene radical.
  • Suitable monomers of the general formula (III) are, for example, N, N-dimethylaminomethyl (meth) acrylate, N, N-diethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-diethylamino-butyl (meth) acrylate, N, N-dimethylaminohexyl (meth) acrylate, N, N-dimethylaminooctyl (meth) acrylate, N, N-dimethylamino dodecyl (meth) acrylate, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) butyl] methacrylamide, N-
  • Preferred monomers (al) are 3-methyl-1-vinylimidazolium chloride and methosulfate, dimethyldiallylammonium chloride and N, N-dimethylaminoethyl methacrylate and N- [3- (dimethylamino) propyl] methacrylamide, which are optionally quaternized by methyl chloride, dimethyl sulfate or diethyl sulfate were.
  • Particularly preferred monomers (al) are 3-methyl-1-vinylimidazolium chloride and methosulfate and dirnethyldiallylammonium chloride, 3-methyl-1-vinylimidazolium chloride and methosulfate are very particularly preferred.
  • Mixtures of the monomers (a1) can also be used.
  • the monomers (a1) can either be used in quaternized form as monomers or polymerized non-quaternized, in which case the copolymer obtained is either quaternized or protonated.
  • the monomers can be used either as a dried substance or in the form of concentrated solutions in solvents suitable for the monomers, for example in polar solvents such as water, methanol, ethanol, acetone or electrolyte solutions.
  • mineral acids such as HC1, H 2 SO 4 and monocarboxylic acids, for example formic acid and acetic acid, dicarboxylic acids and polyfunctional carboxylic acids, are suitable for protonation
  • Oxalic acid and citric acid as well as all other proton donating compounds and substances that are able to protonate the corresponding nitrogen atom.
  • Water-soluble acids are particularly suitable for protonation.
  • the protonation of the polymer can either take place after the polymerization or in the formulation of the cosmetic preparation, in which a physiologically tolerable pH is generally set.
  • Protonation is understood to mean that at least some of the protonatable groups of the polymer, preferably 20 to 100%, are protonated, so that a total cationic charge of the polymer results.
  • alkyl halides with 1 to 24 C atoms in the alkyl group, e.g. Methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, propyl chloride, hexyl chloride, dodecyl chloride, lauryl chloride and benzyl halides, especially benzyl chloride and benzyl bromide.
  • Other suitable quaternizing agents are dialkyl sulfates, especially dimethyl sulfate or diethyl sulfate.
  • the quaternization of the basic monomers of the general formulas (I) to (III) can also be carried out with alkylene oxides such as ethylene oxide or propylene oxide in the presence of acids.
  • the quaternization of the monomer or a polymer with one of the quaternizing agents mentioned can be carried out by generally known methods.
  • Preferred quaternizing agents are: methyl chloride, dimethyl sulfate or diethyl sulfate.
  • Suitable monomers (a2) are N-vinyl lactams, e.g. N-vinyl piperidone, N-vinyl pyrrolidone and N-vinyl caprolactam, with N-vinyl pyrrolidone being preferred.
  • Suitable crosslinkers are, for example, acrylic esters, methacrylic esters, Allylether 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-ene-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
  • 2,2-bis [4- (2-hydroxypropyl) phenyl] propane diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 3-thio-pentane-l, 5-diol, and also polyethylene glycols, polypropylene glycols and polytetrahydrofurans with molecular weights of 200 to 10,000 in each case.
  • block copolymers of ethylene oxide or propylene oxide can also be used or
  • Copoly erisate containing ethylene oxide and propylene oxide groups incorporated are 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 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.
  • suitable crosslinkers 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, 1,6-diaminohexane, 1,2-dodecanediamine, piperazine, diethylenetriamine or isophoronediamine.
  • 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.
  • Triallylamine and triallylmonoalkylammonium salts e.g. Triallylmethylammonium chloride or methyl sulfate, suitable as a crosslinker.
  • 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.
  • crosslinkers are for example Alkylenglykoldi- (meth) acrylates such as ethylene glycol diacrylate, acrylate Ethylenglykoldimeth- dimethacrylate, tetraethylene glycol, acrylate Tetraethylenglykoldimeth-, diethylene glycol acrylate, Diethylenglykolmethacrylat, Vinylacryla, allyl acrylate, allyl methacrylate, divinyldioxane, pentaerythritol triallyl ether and mixtures of crosslinkers.
  • Alkylenglykoldi- (meth) acrylates such as ethylene glycol diacrylate, acrylate Ethylenglykoldimeth- dimethacrylate, tetraethylene glycol, acrylate Tetraethylenglykoldimeth-, diethylene glycol acrylate, Diethylenglykolmethacrylat, Vinylacryla, allyl acrylate, 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 crosslinking agent is poorly soluble in the reaction medium, it can be dissolved in a monomer or in a monomer mixture, or it can be metered in dissolved in a solvent. that 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.
  • N-vinyl acetamide N-methyl-N-vinyl acetamide, acrylamide, methacrylamide, N, N-dimethylacrylamide, N-methylol methacrylamide, N-vinyl formamide, N-vinyl oxazolidone, N-vinyl triazole.
  • the group of monomers (c) includes, for example, acrylonitrile, methacrylonitrile, acrylic acid and methacrylic acid esters, which are derived from monohydric Ci to Cig alcohols, hydroxy-C 2 -C 4 -alkyl esters of acrylic acid and methacrylic acid, Maleic anhydride, vinyl ester, 2-acrylamido-2-methylpropylsulfonic acid and / or vinyl phosphoric acid.
  • Esters of acrylic acid and methacrylic acid with fatty alcohol ethoxylates and fatty alcohol propoxylates are also 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 C 1 to C 2 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. If they are used for the modification of the copolymers from (a) and (b), the lower limit is 5% by weight, based on the monomer mixture. The sum of the percentages for the monomers (a), (b) and (c) is 100% in all cases.
  • 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 alkyl ethylene 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 or Ammonium peroxydisulfates, hydrogen peroxide, dibenzoyl peroxide, tert-butyl perpivalate, 2,2'-azobis (2,4-dimethylvaleronitrile), tert. -Butylperoxineodecanoate, tert-butyl-per-2-ethylhexanoate, di-tert. -butyl peroxide, tert.
  • alkali or Ammonium peroxydisulfates hydrogen peroxide
  • dibenzoyl peroxide tert-butyl perpivalate
  • tert. -Butylperoxineodecanoate tert-butyl-per-2-ethylhexanoate
  • redox coinitiators for example benzoin, dimethylaniline and organically soluble complexes and salts of heavy metals such as copper, cobalt, manganese, nickel and chromium or especially iron
  • the half-lives of the peroxides mentioned, especially the hydroperoxides can be reduced 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 you want to produce particularly low molecular weight copolymers, higher amounts of polymerization regulators are used, whereas 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, furthermore as detergent additives such as incrustation and color transfer inhibitors, as retention aids in papermaking, as flocculants in water treatment or for use in the field of Food technology, for example as a filter aid or complexing agent.
  • the polymers are also particularly suitable as thickeners and gelling agents in cosmetic formulations, especially for skin and hair cosmetic preparations such as hair treatments, hair lotions, hair rinses, hair emulsions, tip fluids, leveling agents for permanent waves, 'hot oil treatment' preparations, setting lotions or hair sprays, especially in skin and hair 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 feed materials were then metered in as a mixture in a single feed.
  • 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.

Landscapes

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

Abstract

L'invention concerne un procédé de production de polymérisats cationiquement réticulés pulvérulents, à base de monomères monoéthyléniquement insaturés qui contiennent un atome d'azote quaternisé ou pouvant être quaternisé. Ce procédé se caractérise en ce que la polymérisation s'effectue dans du dioxyde de carbone surcritique, en tant qu'agent de dilution, avec mélange à des températures pouvant aller de 31 °C à 150 °C et sous des pressions supérieures à 73 bars.
EP99932863A 1998-07-24 1999-07-12 Procede de production de polymerisats reticules pulverulents Withdrawn EP1117696A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19833287A DE19833287A1 (de) 1998-07-24 1998-07-24 Verfahren zur Herstellung von pulverförmigen vernetzten Polymerisaten
DE19833287 1998-07-24
PCT/EP1999/004868 WO2000005274A1 (fr) 1998-07-24 1999-07-12 Procede de production de polymerisats reticules pulverulents

Publications (1)

Publication Number Publication Date
EP1117696A1 true EP1117696A1 (fr) 2001-07-25

Family

ID=7875131

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99932863A Withdrawn EP1117696A1 (fr) 1998-07-24 1999-07-12 Procede de production de polymerisats reticules pulverulents

Country Status (6)

Country Link
US (1) US6482917B1 (fr)
EP (1) EP1117696A1 (fr)
JP (1) JP2002521505A (fr)
CN (1) CN1311798A (fr)
DE (1) DE19833287A1 (fr)
WO (1) WO2000005274A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10237378A1 (de) * 2002-08-12 2004-03-11 Basf Ag Vernetzte kationische Copolymere mit Reglern und ihre Verwendung in haarkosmetischen Zubereitungen
US7837742B2 (en) * 2003-05-19 2010-11-23 The Procter & Gamble Company Cosmetic compositions comprising a polymer and a colorant
EP1863858A1 (fr) * 2005-03-18 2007-12-12 Basf Aktiengesellschaft Polymeres cationiques utilises comme epaississants de compositions aqueuses et alcooliques
ATE510861T1 (de) * 2006-09-21 2011-06-15 Basf Se Kationische polymere als verdicker für wässrige und alkoholische zusammensetzungen
CN105254781B (zh) * 2015-11-19 2018-01-02 湖北鄂皖高新科技有限公司 一种利用超临界二氧化碳制备离聚体的方法
JP7132316B2 (ja) * 2020-12-28 2022-09-06 高圧ガス工業株式会社 二液型硬化性組成物

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3665594D1 (en) * 1985-10-22 1989-10-19 Basf Ag Process for preparing powdery polymers
DE3609829A1 (de) 1986-03-22 1987-09-24 Basf Ag Verfahren zur herstellung von pulverfoermigen vernetzten copolymerisaten
DE19505750A1 (de) 1995-02-20 1996-08-22 Basf Ag Agglomerierte, feinteilige, vernetzte Vinylimidazol-Copolymerisate, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19546698A1 (de) 1995-12-14 1997-06-19 Basf Ag Copolymerisate aus Carbonsäuren und mehrfach olefinisch ungesättigten Carbonsäurederivaten und ihre Verwendung als Verdickungs- oder Dispergiermittel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0005274A1 *

Also Published As

Publication number Publication date
JP2002521505A (ja) 2002-07-16
US6482917B1 (en) 2002-11-19
WO2000005274A1 (fr) 2000-02-03
CN1311798A (zh) 2001-09-05
DE19833287A1 (de) 2000-01-27

Similar Documents

Publication Publication Date Title
DE4435423A1 (de) Verfahren zur Herstellung einer wäßrigen Polymerisatdispersion
DE2103898A1 (de) Quaternare Copolymere
EP0239035A2 (fr) Procédé de préparation de copolymères réticulés à particules fines et leur usage
DE2924663A1 (de) Verfahren zur herstellung einer waessrigen dispersion aus wasserloeslicher polymermasse
EP0544158B1 (fr) Usage de homo- ou copolymères à base de 1-vinylimidazoles quaternisé comme polyélectrolytes organiques
DE69108218T2 (de) Kationische Copolymere, Emulsionen und deren Verwendung.
DE19731764A1 (de) Vernetzte kationische Copolymere
EP0301447A2 (fr) Polymères de sels insaturés d'ammonium quaternaire alkoxylé, leur préparation et leur utilisation
DE3049178A1 (de) "verfahren zum verdicken von waessrigen systemen"
EP1117696A1 (fr) Procede de production de polymerisats reticules pulverulents
WO2005108445A1 (fr) Procede pour produire des polymeres formes principalement de vinylformamide
DE10241296A1 (de) Verwendung von vernetzten kationischen Polymerisaten in der Kosmetik
DE69311867T2 (de) Verfahren zur Herstellung von Carboxylgruppen enthaltende vernetzte Polymere
EP0073296B1 (fr) Procédé de préparation de dispersions de résines synthétiques acryliques
EP0220603B1 (fr) Procédé de préparation de polymères en forme de poudre
DE3321372A1 (de) Verfahren zur herstellung von acrylamid-polymerisaten
EP0009186A1 (fr) Azo-diisobutyryl-(N,N'-hydroxyalkyl)-amidines, leur préparation et utilisation comme initiateurs de polymérisation, comme agents réticulants et comme agents gonflants
EP1658314B1 (fr) Utilisation d'acide 2-hydroxy-2-sulfinato-acetique ou de ses sels en tant qu'initiateur dans des emulsions eau dans l'huile
DE10208361A1 (de) Verfahren zur Herstellung einer wässrigen thermisch härtbaren Polymerdispersion
DE19731907A1 (de) Vernetzte kationische Copolymere mit N-Vinylimidazolen
WO2000005273A1 (fr) Procede de production de polymerisats pulverulents reticules
DE102006055473A1 (de) Verfahren zur Herstellung von Pfropfcopolymeren auf Basis von Polyethern
DE19600405A1 (de) Verfahren zur Herstellung von wasserunlöslichen Polymerisaten
DE2324204C2 (de) Verfahren zur Herstellung von Ionenaustauschern
EP3063191B1 (fr) Polymères contenant du s-vinylthioalkanole

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20010104

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20030505