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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/2815—Monohydroxy compounds
  • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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  • C08G18/08—Processes
• • 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
  • A61K8/87—Polyurethanes
• • 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
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  • A61Q5/12—Preparations containing hair conditioners
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
  • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
  • C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
• • C—CHEMISTRY; METALLURGY
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3271—Hydroxyamines
  • C08G18/3275—Hydroxyamines containing two hydroxy groups
• • C—CHEMISTRY; METALLURGY
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
• • C—CHEMISTRY; METALLURGY
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4829—Polyethers containing at least three hydroxy groups
• • C—CHEMISTRY; METALLURGY
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4833—Polyethers containing oxyethylene units
• • C—CHEMISTRY; METALLURGY
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • C—CHEMISTRY; METALLURGY
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
• • C—CHEMISTRY; METALLURGY
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• • C—CHEMISTRY; METALLURGY
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  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
• • C—CHEMISTRY; METALLURGY
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  • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
• • C—CHEMISTRY; METALLURGY
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  • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
  • C08G83/002—Dendritic macromolecules
  • C08G83/003—Dendrimers
• • 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
  • A61K2800/48—Thickener, Thickening system
• • 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
  • A61K2800/544—Dendrimers, Hyperbranched polymers
• • A—HUMAN NECESSITIES
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  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q15/00—Anti-perspirants or body deodorants
• • 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
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q9/00—Preparations for removing hair or for aiding hair removal
  • A61Q9/04—Depilatories

Definitions

• the present invention relates to associative polyether-polyurethane thickeners in which dendritic polyether polyols are copolymerized, the preparation of these thickeners and their use, in particular in cosmetic preparations.
• Polyurethane-based associative thickeners are state of the art. They are described in detail, for example, in US 4,079,028 and in US 4,155,892.
• star-shaped products (group B) and “complex polymers” (group C) described in US Pat. No. 4,079,028 comprise polyurethanes in which polyhydric alcohols are copolymerized.
• polyhydric alcohols are low molecular weight compounds such as, for example, trimethylolpropane, pentaerythritol, sorbitol, erythritol, mannitol or dipentaerythritol.
• EP 1566393 (Cognis) describes thickeners based on an aqueous preparation of nonionic, water-dispersible or water-soluble polyurethanes which can be prepared by reacting (a) one or more polyfunctional isocyanates with (b) one or more polyether polyols , (c) one or more monofunctional alcohols and (d) if desired one or more polyfunctional alcohols, the compounds (d) containing no further functional groups apart from the OH groups.
• the polyfunctional alcohols (d) contain at least predominantly trifunctional alcohols, such as, for example, glycerol or preferably trimethylolpropane.
• EP 1765900 (Cognis) describes thickening agents based on an aqueous preparation of nonionic, water-dispersible or water-soluble polyurethanes of special structure. The particular structure of these polymers is due to the presence of allophanate bonds, which are generated by the use of an excess of isocyanate.
• component (a) it is possible to use hydrophilic polyols having at least 2 OH groups, which may also contain ether groups.
• EP 1584331 A1 (Shiseido) describes polyurethane thickeners for cosmetic preparations. The polyurethanes may also be branched. The underlying polyols and their alkoxylated derivatives are described in Sections [38] and [39].
• EP 725097 A1 also describes thickeners based on polyurethanes. Branches may optionally be introduced into the polyurethanes by component a4).
• A4) are 3 to 6-hydric alcohols of the molecular weight Weight range 92 to 600, preferably 92 to 400 and particularly preferably 92 to 200 such as glycerol, trimethylolpropane, pentaerythritol and / or sorbitol. Preferably, if any, glycerol or trimethylol propane is used.
• EP 978522 (National Starch) describes branched polyurethane thickeners having the following formula
• A is a hydrophilic polyol and is preferably selected from trimethylolpropane, [2-ethyl-2- (hydroxymethyl) -1, 3-propanediol], pentaerythritol, glycerin and sorbitol.
• WO 2009/101 141 A1 describes a process for preparing dendritic polyetherols by reacting at least one tri- or higher-functional alcohol and optionally further di- and / or monofunctional alcohols and / or modifying reagents with the aid of acidic catalysts. Furthermore, the use of these polyetherols is described as possible building blocks for the preparation of polyaddition or polycondensation polymers.
• DE 1021 1664 A1 describes the synthesis of hyperbranched polyglycerols by ring-opening polymerization of glycidol.
• Object of the present invention was to provide suitable for cosmetic applications thickener, which are distinguished from the known thickeners by
• the present invention relates to polymers comprising in copolymerized form
• R 1 is selected from C 6 -C 40 -alkyl, C 6 -C 40 -alkenyl, C 3 -C 10 -cycloalkyl, C 6 -C 30 -aryl, C 7 -C 40 -arylalkyl,
• R 2 is selected from C 2 -C 10 -alkylene, C 6 -C 10 -arylene, C 7 -C 10 -arylene, n 0 to 200
• the polymer according to the invention is water-soluble or water-dispersible.
• Water-soluble in the context of this invention means that at least 1 gram, preferably at least 10 grams of the substance known as water-soluble, ie for example the polymer according to the invention, in 1 liter of deionized water are clearly soluble to the human eye.
• Water-dispersible in the context of this invention means that at least 1 gram, preferably at least 10 grams of the substance known as water-dispersible, ie, for example, the polymer of the invention in 1 liter of deionized water without sediment with maximum average particle size 1 ⁇ are dispersible.
• the polymer according to the invention is uncrosslinked.
• uncrosslinked means that a degree of crosslinking of less than 15% by weight, preferably less than 10% by weight, in particular less than 5% by weight, determined via the insoluble fraction of the polymer, is present is.
• the insoluble fraction of the polymers is determined by extraction for four hours with the same solvent as used for gel permeation chromatography to determine the molecular weight distribution of the polymers, ie tetrahydrofuran, dimethylacetamide or hexafluoroisopropanol, depending on the solvent in which the polymer is more soluble, in a Soxhlet apparatus and after Dry the residue to constant weight Weigh the remaining residue.
• the polymer according to the invention is water-soluble or water-dispersible and uncrosslinked. a) polyisocyanate
• polyisocyanates are compounds having at least two to at most four isocyanate groups per molecule.
• Suitable polyisocyanates preferably contain on average 2 (diisocyanates) to at most 4 NCO groups per molecule, with diisocyanates being particularly preferred.
• isocyanates examples which may be mentioned as suitable isocyanates are 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI), 4,4'-diphenyldimethylmethane diisocyanate, di- and tetraalkyldiphenylmethane diisocyanate, 4 , 4-Dibenzyldiisocyanat, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, the isomers of toluene diisocyanate (TDI), optionally in admixture, 1-methyl-2,4-diisocyanato-cyclohexane, 1, 6- diisocyanato-2 , 2,4-trimethylhexane,
• MDI 4,4'-diphenylmethane diisocyan
• the polymers according to the invention contain polymerized (condensed in) cycloaliphatic or aliphatic diisocyanate radicals, particularly preferably aliphatic diisocyanate radicals.
• condensed aliphatic diisocyanates 1, 4
• condensed cycloaliphatic diisocyanates are: isophorone diisocyanate (IPDI), 2-isocyanatopropylcyclohexyl isocyanate, 4-methylcyclohexane-1,3-diisocyanate (H-TDI) and 1,3-bis (isocyanatomethyl) cyclohexane.
• IPDI isophorone diisocyanate
• H-TDI 4-methylcyclohexane-1,3-diisocyanate
• 1,3-bis (isocyanatomethyl) cyclohexane 1,3-bis (isocyanatomethyl) cyclohexane.
• H 12-MDI or "saturated MDI” called diisocyanates such as 4,4'-methylene-bis (cyclohexyl isocyanate) (alternatively also called dicyclohexyl methane-4,4'-diisocyanate) or 2,4 ' -Methylenebis (cyclohexyl) diisocyanate may be contained as radicals in the polyurethanes of the invention.
• diisocyanates such as 4,4'-methylene-bis (cyclohexyl isocyanate) (alternatively also called dicyclohexyl methane-4,4'-diisocyanate) or 2,4 ' -Methylenebis (cyclohexyl) diisocyanate may be contained as radicals in the polyurethanes of the invention.
• a) comprises or comprises hexamethylene diisocyanate. In another preferred embodiment, a) is or comprises isophorone diisocyanate.
• R 1 is C 6 -C 40 -alkyl. In a preferred embodiment, this is a C6-C30-alkyl radical, more preferably a Ce-Cao-alkyl radical, and most preferably a Ci2-C3o-alkyl radical.
• R 1 is selected, for example, from radicals of linear or branched alkanes such as hexane, heptane, octane, 2-ethylhexane, nonane, decane, undecane, dodecane, tridecan, isotridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, noadecan , Eicosan, henicosan, docosan, tricosane, isotricosane, tetracosane, pentacosan, hexacosan, heptacosan, octacosan, nonacosan, triacontane, 2-octyldodecane, 2-dodecylhexadecane, 2-tetradecyloctadecane, 2-decyl
• R 1 is C 6 -C 40 alkenyl.
• Suitable C6-C4o-alkenyl radicals may be straight-chain or branched. These are preferably predominantly linear alkenyl radicals, as they also occur in natural or synthetic fatty acids and fatty alcohols and oxo alcohols, which are mono-, di- or polyunsaturated.
• n-hexenyl n-heptenyl, n-octenyl, n-nonenyl, n-decenyl, n-undecenyl, n-dodecenyl, n-tridecenyl, n-tetradecenyl, n-pentadecenyl, n-hexadecenyl, n-heptadecenyl , n-octadecenyl, n-nonadecenyl.
• R 1 is C 3 -C 3 cycloalkyl.
• Cycloalkyl is preferably cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
• R 1 is C 6 -C 30 -aryl.
• Aryl includes unsubstituted and substituted aryl groups and is preferably phenyl, tolyl, xylyl, mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl and especially phenyl, tolyl, xylyl or mesityl.
• R 1 is C 7 -C 40 arylalkyl.
• Arylalkyl represents groups which contain both alkyl and aryl radicals, these arylalkyl groups being linked either via the aryl or via the alkyl radical to the compound carrying them.
• R 1 may be an arylalkyl radical as described in EP 761780 A2, p. 4, Z. 53-55.
• R 2 in the general formula (I) is selected from -CH 2 -CH 2 -, -CH (CH 3) -CH 2 - and mixtures thereof, more preferably -CH 2 - CH 2 -.
• n is selected from the range 2 to 150.
• R 1 is a branched alkyl radical.
• the side chains of such branched alkyl radicals are likewise preferably alkyl radicals or alkenyl radicals, particularly preferably alkyl radicals, in particular unbranched alkyl radicals.
• the side chains of the branched alkyl radicals R 1 have a chain length of at most 6, preferably of at most 4 carbon atoms.
• the branches are significantly shorter than the main chain.
• each branch of R 1 has a chain length equal to at most half the chain length of the backbone of R 1 .
• the branches are significantly shorter than the main chain.
• the branched R 1 is iso- and / or neo-AI kylreste.
• R 1 radicals of isoalkanes are used as branched alkyl radicals. Particularly preferred is a Ci3-alkyl radical, in particular an iso-Ci3-alkyl radical.
• R 1 comprises branched alkyl radicals whose side chains have a chain length of at least 4, preferably of at least 6, carbon atoms.
• b) may also be a mixture of different alcohols.
• At least one alcohol b) is selected from alkoxylated alcohols.
• the ethylene oxide and propylene oxide units can be distributed randomly or in blocks.
• Suitable alcohols b) are, for example, the alkoxylated, preferably ethoxylated
• linear alcohols from natural sources or from the Ziegler synthesis reaction of ethylene in the presence of aluminum alkyl catalysts.
• suitable linear alcohols are linear C6-C o-3 alcohols, especially Ci2-C 3 o-alcohols.
• Particularly preferred alcohols are: n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, n-eicosanol, n-docosanol, n-tetracosanol, n-hexacosanol, n-octacosanol, and / or n-triacontanol, and mixtures of the aforementioned alcohols, for example NAFOL ® types such NAFOL ® 22+ (Sasol).
• Oxo alcohols are, for example, isoheptanol, isooctanol, isononanol, isodecanol, I-soundecanol, isotridecanol (for example Exxal® grades 7, 8, 9, 10, 11, 13).
• Particularly preferred alcohols are here: lsofol ® 12 (Sasol), Rilanit ® G16 (BASF SE). Alcohols which are obtained by Friedel-Crafts alkylation with oligomerized olefins and which then contain an aromatic ring in addition to a saturated hydrocarbon radical.
• Particularly preferred alcohols which may be mentioned here are: i-octylphenol and i-nonylphenol.
• R 4 , R 5 , R 7 and R 8 independently of one another have the meaning described in EP 761780 A2, p. 4, lines 45 to 58; R 4 , R 5 , R 7 and R 8 are independently of one another alkyl radicals having at least 4 carbon atoms and the total number of carbon atoms of the alcohols is at most 30,
• R 6 is an alkylene radical such as -CH 2 -, -CH 2 -CH 2 -, -CH 2 -CH (CH 3 ) -;
• 2-decyl-1-tetradecanol may be mentioned here as suitable alcohol.
• At least one alcohol b) is a mixture of ethoxylated linear Ci6-Ci8 fatty alcohols.
• Commercially such ethoxylated linear fatty alcohol for example, as Lutensol ® AT1 1 (BASF SE) available.
• At least one alcohol b) is selected from compounds having the structural formula RO (CH 2 CH 2 0) x H, wherein R is a linear C8-C 3 -alkyl radical, preferably linear Ci6-CI8 alkyl group, and x 2 is up to 30.
• at least one alcohol b) is selected from compounds having the structural formula RO (CH 2 CH 2 0) x H, wherein R is a linear C8-C 3 -alkyl radical, preferably linear C16 C18 alkyl and x is from 30 to 150.
• b) comprises a C 2 -C 3 -alcohol ethoxylated with 3 to 100 moles of ethylene oxide per mol.
• b) is selected from mixtures of ethoxylated linear and ethoxylated branched long-chain alcohols, in particular mixtures of the abovementioned types.
• b) is selected from ethoxylated 1SO-C13 oxo alcohols and mixtures thereof.
• ethoxylated alkyl-branched alcohol for example, as Lutensol TO10 ® (BASF SE) available.
• b) is selected from mixtures comprising ethoxylated C 16-18 fatty alcohols and ethoxylated C 3-3 oxo alcohols.
• b) is selected from the above-described alcohols of the general formulas (4) or (5) of EP 761780 A2, p.4 in their ethoxylated form.
• the polymers according to the invention contain in polymerized form at least one dendritic polyether polyol c).
• dendritic polyether polyols quite generally encompasses polyether polyols which have a branched structure and a high functionality.
• dendritic polymers include dendrimeric polyether polyols, hyperbranched polyether polyols and structures derived therefrom.
• Dendrimers are molecularly uniform macromolecules with a highly symmetric structure. They are structurally derived from star polymers, with the individual chains each branched in a star shape. Dendrimers arise from small molecules through a repetitive sequence of reactions, resulting in ever-increasing branches, each terminating with functional groups, which in turn are the starting point for further branching. Thus, with each reaction step, the number of monomer end groups increases, resulting in a spherical tree structure at the end. A characteristic feature of dendrimers is the number of reaction stages used to build them up, commonly referred to as "generations.” Due to their uniform structure, dendrimers generally have a very narrow molecular weight distribution.
• Preferred dendritic polyetherpolyols c) according to the invention are hyperbranched polyetherpolyols which are molecular and structurally nonuniform and have side chains of different length and branching as well as a molecular weight distribution.
• hyperbranched polymers reference is also made to PJ Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, No. 14, 2499.
• AB X monomers are suitable for the synthesis of hyperbranched polymers. These have two different functional groups A and B, which can react with each other to form a linkage.
• the functional group A is contained only once per molecule, the functional group B two or more times.
• the reaction of said AB x monomers with one another produces substantially uncrosslinked polymers with regularly arranged branching sites.
• the polymers have almost exclusively B groups at the chain ends. Further details can be found, for example, in Journal of Molecular Science, Rev. Macromol. Chem. Phys., C37 (3), 555-579 (1997).
• dendritic polyether polyols c) are polyether polyols which, in addition to the ether groups which form the polymer backbone, have on average at least 3, preferably at least 4, more preferably at least 5 and in particular at least 6 OH groups per molecule.
• the dendritic polyetherols c) of the present invention have on average not more than 500, preferably not more than 250, more preferably not more than 100, and in particular not more than 50 terminal or pendant functional OH groups per molecule.
• the dendritic polyether polyol c) is preferably a condensation product of on average at least 3, more preferably at least 4, in particular at least 5, and most preferably at least 6 di-, tri- or higher-functional alcohols.
• the dendritic polyether polyol c) is the condensation product of on average at least 3, particularly preferably at least 4, especially at least 5 and in particular at least 6 tri- or higher-functional alcohols.
• Preferred dendritic polyether polyols c) in the context of this invention are hyperbranched polyether polyols.
• Dendritic polyether polyols are preferably uncrosslinked polymer molecules having hydroxyl and ether groups which are either structurally and molecularly nonuniform (hyperbranched polyether polyols) or structurally and molecularly uniform (dendrimeric polyether polyols).
• Hyperbranched polyether polyols can be constructed starting from a central molecule analogously to dendrimers, but with nonuniform chain length of the branches. On the other hand, they can also have linear regions with functional side groups.
• hyperbranched means that the degree of branching (for the definition of the "degree of branching” see H. Frey et al., Acta Polym. 1997, 48, 30), ie the average number of dendritic linkages plus average number of end groups per molecule divided by the sum of the average number of dendritic, linear and terminal linkages per molecule multiplied by 100, 10 to 99.9%, preferably 20 to 99%, particularly preferably 20 to 95 % is.
• the hyperbranched polyether polyols c) used according to the invention preferably have a degree of branching of from 10 to 99.9%, preferably from 20 to 99%, particularly preferably from 20 to 95%.
• Dendrimer in the context of the present invention means that a polymer molecule has a degree of branching of more than 99.9 to 100%.
• DE 10307172 describes the polycondensation of glycerol in the presence of acidic catalysts, for example HCl, H 2 SO 4, sulfonic acid or H 3 PO 4.
• acidic catalysts for example HCl, H 2 SO 4, sulfonic acid or H 3 PO 4.
• WO 2004/074346 describes the alkaline polycondensation of glycerol and the subsequent reaction of the resulting condensation product under acidic conditions with a fatty alcohol. A polyglycerol modified with fatty alcohol is thereby obtained.
• Suitable dendritic polyether polyols c) are dendritic polyglycerols, ie hyperbranched polyglycerol and polyglycerol dendrimers.
• Suitable hyperbranched polyglycerols are, for example, glycidol-based polyglycerol ethers as described in DE 19947631 and DE 1021 1664. The preparation takes place by ring-opening reaction of glycidol, optionally in the presence of a polyfunctional starter molecule. These disclosures are referred to. Polyglycerol dendrimers are described, for example, by Haag et al., J. Am. Chem. Soc. 2000, 122, 2954-2955, to which reference is hereby made.
• dendritic polyether polyols c are also suitable in
• WO 00/56802 disclosed polyether polyols, to which reference is hereby made.
• the dendritic polyether polyols c) described therein are obtainable by ring-opening Polymerization of 1-ethyl-1-hydroxymethyl-oxetane with special catalysts.
• the resulting polymer backbone consists of trimethylolpropane units.
• dendritic polyether polyols c) are those described by Nishikubo et al., Polymer Journal 2004, 36 (5) 413, to which reference is hereby made.
• the dendritic polyether polyols c) described therein can be obtained by ring-opening polymerization of 3,3-bis (hydroxymethyl) oxetane.
• dendritic polyether polyols c) are the polyether polyols obtainable by joint ring-opening polymerization of 1-ethyl-1-hydroxymethyl-oxetane and 3,3-bis (hydroxymethyl) oxetane, as described by Chen et. al, J. Poly. Be. Part A: Polym. Chem. 2002, 40, 1991, which is incorporated herein by reference.
• Suitable dendritic hyperbranched polyether polyols are also described, for example, in WO 2009/101 141 A1.
• dendritic polyetherols are described by reacting at least one tri- or higher-functional alcohol and optionally further di- and / or monofunctional alcohols and / or modifying reagents with the aid of acidic catalysts.
• triols such as Tnmethylolmethan, trimethylolethane, trimethylolpropane (TMP), 1, 2,4-butanetriol, tris-hydroxymethyl isocyanurate, tris-hydroxyethyl isocyanurate (THEIC)
• Tnmethylolmethan, trimethylolethane, trimethylolpropane (TMP), 1, 2,4-butanetriol, tris-hydroxymethyl isocyanurate, tris-hydroxyethyl isocyanurate (THEIC) can be used.
• tetrols can be used, such as bis-trimethylolpropane (Di-TM P) or pentaerythritol.
• higher functional polyols such as bis-pentaerythritol (di-penta) or inositols can be used.
• alkoxylation products of the abovementioned alcohols and of glycerol preferably with 1 to 40 alkylene oxide units per molecule.
• Particularly preferred trifunctional and higher-functional alcohols are aliphatic alcohols and in particular those having primary hydroxyl groups, such as trimethylolmethane, trimethylolethane, trimethylolpropane, di-TM P, pentaerythritol, di-penta and their alkoxylates having 1 to 30 ethylene oxide units per molecule and also glycerol -Ethoxylates with 1 -30 ethylene oxide units per molecule.
• the tri- and higher-functional alcohols can also be used in mixture with difunctional alcohols.
• suitable compounds having two OH groups include ethylene glycol, diethylene glycol, triethylene glycol, 1,2- and 1,3-propanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1, 2, 1, 3 and 1, 4-butanediol, 1, 2-, 1, 3- and 1, 5-pentanediol, hexanediol, dodecanediol, cyclopentanediol, Cyclohexanediol, cyclohexanedimethanol, bis (4-hydroxycyclohexyl) methane, bis (4-hydroxycyclohexyl) ethane, 2,2-bis (4-hydroxycyclohexyl) propane, difunctional polyether polyols based on ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, or polytetrahydrofuran.
• the diols serve to fine tune the properties of the polyether polyol. If difunctional alcohols are used, the ratio of difunctional alcohols to the tri- and higher-functional alcohols is determined by the person skilled in the art according to the desired properties of the polyether. As a rule, the amount of difunctional or difunctional alcohols is 0 to 99 mol%, preferably 0-80, more preferably 0-75 mol% and very particularly preferably 0-50 mol% with respect to the total amount of all alcohols. It is also possible to obtain block copolyethers, for example diol-terminated polyethers, by alternating addition of tri- and higher-functional alcohols and diols during the course of the reaction.
• the dendritic polyether polyols c) are obtainable by condensation of at least one tri- or higher-functional alcohol and optionally further di- and / or monofunctional alcohols and / or modifying reagents with the aid of acidic catalysts.
• At least one dendritic polyether polyol c) is the condensation product of on average at least 3 di-, tri- or higher-functional alcohols.
• Preferred dendritic polyether polyols c) are obtainable by the acid-catalyzed polycondensation of trimethylolpropane.
• Preferred dendritic polyether polyols c) are obtainable by the acid-catalyzed polycondensation of trimethylolpropane, wherein at least a part of the OH groups of the trimethylolpropane is alkoxylated.
• Preferred dendritic polyether polyols c) are also obtainable by the acid-catalyzed polycondensation of pentaerythritol.
• Preferred dendritic polyether polyols c) are also obtainable by the acid-catalyzed polycondensation of pentaerythritol, where at least part of the OH groups of the pentaerythritol is alkoxylated.
• Preferred dendritic polyether polyols c) are also obtainable by the acid-catalyzed polycondensation of trimethylolpropane and triethylene glycol.
• Preferred dendritic polyether polyols c) are also obtainable by the acid-catalyzed polycondensation of trimethylolpropane and pentaerythritol.
• Preferred dendritic polyether polyols c) are also obtainable by the acid-catalyzed polycondensation of triethylene glycol and pentaerythritol.
• Preferred dendritic polyether polyols c) have a number average molecular weight Mn of at least 300 g / mol, preferably at least 400 g / mol, more preferably at least 500 g / mol.
• Suitable dendritic polyether polyols c) are also those dendritic polyether polyols c) which, in addition to the hydroxyl groups, contain further functional groups which are preferably obtained by modifying at least part of the hydroxyl groups.
• Such further functional groups include mercapto groups, primary, secondary or tertiary amino groups, ester groups, carboxylic acid groups or derivatives thereof, sulfonic acid groups or their derivatives, phosphonic acid groups or their derivatives, silane groups, siloxane groups, aryl radicals or short- or long-chain alkyl radicals.
• Modification reagents are used for modification. These are compounds which have at least one such additional functional group and at least one alcohol-reactive group.
• alcohol-reactive groups are isocyanate groups, acid groups, acid derivatives or epoxide groups.
• Compound c) can be modified prior to the polymerization by reacting at least a portion of its OH groups. This is possible either by the preparation of c) in the presence of modifying reagents or by the modification of compound c) after its preparation. Both possibilities are described in WO 2009/101 141, p. 8, Z.13 to p.9, Z.42, to which reference is hereby made.
• the modifying reagents can be added before or during the preparation of the polyether polyols c) starting from, for example, tri- or higher-functional alcohols. If the tri- or higher-functional alcohol or the alcohol mixture is reacted in the presence of modifying reagents in one step, a polyether polyol having randomly distributed functionalities other than hydroxyl groups is obtained.
• Such a functionalization can be achieved, for example, by addition of modifying reagents which contain mercapto groups, primary, secondary or tertiary amino groups, ester groups, carboxylic acid groups or derivatives thereof, sulfonic acid groups or derivatives thereof, phosphonic acid groups or their derivatives, silver groups, Siloxan groups, aryl radicals or short or long chain alkyl radicals.
• modifying reagents which contain mercapto groups, primary, secondary or tertiary amino groups, ester groups, carboxylic acid groups or derivatives thereof, sulfonic acid groups or derivatives thereof, phosphonic acid groups or their derivatives, silver groups, Siloxan groups, aryl radicals or short or long chain alkyl radicals.
• Mercaptoethanol can be used as modification reagent for the modification with mercapto groups, for example.
• Tertiary amino groups can be produced, for example, by incorporation of amino-containing alcohols, such as triethanolamine, tripropanolamine, triisopropanolamine, N-methyldiethanolamine, N-methyldipropanolamine or N, N-dimethylethanolamine.
• amino-containing alcohols such as triethanolamine, tripropanolamine, triisopropanolamine, N-methyldiethanolamine, N-methyldipropanolamine or N, N-dimethylethanolamine.
• ester groups can be obtained by reacting the OH groups with lactones, especially with caprolactone. By reaction with long-chain alkanols or alkanediols, long-chain alkyl radicals can be introduced.
• dendritic polyether polyols c) are obtainable, for example, by reacting the dendritic polyether polyol in an additional process step with a modifying reagent which is reactive with the OH groups of the dendritic polyether polyol.
• the dendritic polyether polyols c) can be modified, for example, by adding modifying reagents containing acid, acid halide or isocyanate groups.
• Acid-containing dendritic polyether polyols c) are obtainable, for example, by reacting at least a portion of the OH groups with compounds containing anhydride groups.
• Ester-containing dendritic polyether polyols c) are obtainable, for example, by reacting at least part of the OH groups with caprolactone. The length of the ester chains can be controlled by the amount of caprolactone used.
• Dendritic polyetherols c) with polyalkylene oxide chains are obtainable by reacting the dendritic polyetherols c) with alkylene oxides, for example ethylene oxide, propylene oxide, butylene oxide or mixtures thereof.
• An object of the invention are polymers according to the invention, wherein the dendritic polyether polyol c) comprises polyalkylene oxide chains.
• the new polyurethane thickeners based on dendritic polyether polyols preferably have a large number of hydrophobic end groups, such as, for example, ethoxylated fatty residues, and therefore have a significantly higher thickening performance in comparison with the known polyurethane thickeners. d) From b) and c) different polyol
• the polymers according to the invention in copolymerized form contain at least one compound b) different from b) and c) with a molecular weight of at least 200 g / mol, preferably at least 1500 g / mol.
• Compound d) contains at least two OH groups per molecule and at least two groups selected from ether groups and ester groups.
• Compound d) is preferably selected from polyetherols, polyesterols and polyesteresterols.
• compound d) has a number-average molecular weight M n of from 1500 to 20 000 g / mol, preferably from 4000 to 12 000 g / mol.
• Suitable compounds d) are, for example, the polymerization products of ethylene oxide, its mixed or graft polymerization products and the polyethers obtained by condensation of polyhydric alcohols or mixtures thereof and those obtained by ethoxylation of polyhydric alcohols, amides, polyamides and aminoalcohols. Examples include polyethylene glycols, addition products of ethylene oxide with trimethylolpropane, EO-PO block copolymers, OH-terminated polyesters such as those of the polyfunctional polycaprolactone type.
• Preferred compounds d) are polyether polyols. These are polyols which contain at least two OH groups per molecule and at least two functions -O- (ether groups). As a rule, these polyether polyols are so highly hydrophilic that they are water-soluble at room temperature (20 ° C.).
• Particularly preferred compounds d) contain on average from 30 to 450 CH.sub.2CH.sub.2 O units (EO units) per molecule.
• Preferred compounds d) are therefore polyols of the general formula HO- (CH 2 -CH 2 -O) n -H, where n can assume the values 30 to 450. These are usually condensation products of the ethylene oxide with ethylene glycol or water.
• Preferred polyethylene glycols d) have a molecular weight M n in the range from 1500 to 20 000 g / mol, more preferably from 1500 to 12000 g / mol, in particular from 4000 to 12000 g / mol.
• Suitable compounds d) are also ethylene oxide-propylene oxide block copolymers such as EO-PO block copolymers of the general formula HO- (EO) m - (PO) n - (EO) oH, where m and o are independently integers in the range of 10 to 100, preferably from 20 to 80, n is an integer in the range from 5 to 50, preferably from 20 to 40, and wherein m, n and o are chosen such that HO- (EO) m- (PO) n - (EO) oH is water-soluble.
• the polyetherols d) have a molecular weight M n in the range of 1500 g / mol to 15000 g / mol.
• the polyetherols d) have a molecular weight M n in the range from 4000 g / mol to 12000 g / mol.
• the polyetherols d) have a molecular weight M n in the range from 200 g / mol to 1500 g / mol.
• the polyetherols d) have a molecular weight M n in the range of 6000 g / mol to 12000 g / mol.
• the polyetherols d) have a molecular weight M n in the range from 6000 g / mol to 10000 g / mol.
• the polyetherols d) have a molecular weight M n of about 10,000 g / mol.
• the polyetherols d) have a molecular weight M n of about 6000 g / mol.
• the polyetherols d) have a molecular weight M n of about 9000 g / mol.
• no compounds d) are used to prepare the polymers of the invention.
• polymers according to the invention with low melt viscosity are obtained, which can be handled well in pure form.
• the increase in viscosity results only after the addition of water.
• a readily manageable thickener precursor is first obtained, which has a thickening effect only when water is added, that is, for example when used in a cosmetic preparation.
• other compounds with isocyanate-reactive groups are used to prepare the polymers of the invention.
• the polymers according to the invention contain further compounds a) to d) which are different from one another in copolymerized form in the range from 1 to 9 groups which are reactive toward isocyanate groups per molecule.
• Compounds having isocyanate-reactive groups are preferably selected from compounds having hydroxyl groups such as alcohols, compounds having amino groups such as amines and compounds having hydroxyl groups and amino groups such as aminoalcohols.
• Suitable compounds e) with amino groups are, for example, ethylenediamine, diethylenetriamine and propylenediamine.
• Suitable compounds e) having hydroxyl groups and amino groups are, for example, ethanolamine and diethanolamine.
• R 1 is selected from C 6 -C 40 -alkyl, preferably C 12 -C 30 -alkyl,
• R 2 is selected from -CH 2 -CH 2 -, CH (CH 3) -CH 2 - and mixtures thereof, preferably - 3 to 100, preferably 10 to 20,
• R 1 is selected from linear and / or branched Ci2-C3o-alkyl
• R 2 is -CH 2 -CH 2 -
• the polymers according to the invention comprise components a), b) and c) preferably in the following ratios (mol to mol):
• polymers according to the invention contain compound (d) in copolymerized form: a: b of 10: 1 to 1: 1, 9; preferably 5: 1 to 1: 1
• b c from 25: 1 to 1: 1; preferably 10: 1 to 1, 5: 1
• a: b from 1.5: 1 to 1: 1, 9; preferably 1, 2: 1 to 1: 1, 5
• compound e is preferably copolymerized in such an amount that from 0 to 50 mol%, particularly preferably from 0 to 25 mol%, very particularly preferably from 0 to 10 mol% all of the isocyanate-reactive groups of components b) to e) of e).
• e) is copolymerized in such an amount that from 0 to 1 mol% of all isocyanate-reactive groups of components b) to e) of e) originate.
• no compound e) is copolymerized.
• Another object of the present invention are methods for preparing the polymers of the invention.
• the individual reaction steps are provided with Roman numerals. Steps with higher digits are performed in time after lower-digit steps.
• the components a) to e) can be polymerized in the presence of a solvent other than a) to e).
• solvent is meant a compound which is inert to a) to e), in which the starting compounds a) to e), the resulting intermediates and the polymers according to the invention are soluble.
• Soluble means that at least 1 g, preferably at least 10 g of the relevant compound in 1 liter of solvent under standard conditions for the human eye is clearly resolved.
• Suitable solvents are xylene, toluene, acetone, tetrahydrofuran (THF), butyl acetate, N-methylpyrrolidone and N-ethylpyrrolidone.
• the polymers according to the invention are prepared from the compounds a) to e) essentially in the absence of solvents.
• Substantially in the absence of solvents means that with respect to the total amount of compounds a) to e), the polymerization in the presence of less than 10 wt .-%, preferably less than 5 wt .-% of a different from a) to e) Solvent is carried out.
• Preferred catalysts are zinc carboxylates, in particular selected from zinc 2-ethylhexanoate, zinc n-octanoate, zinc n-decanoate, zinc neodecanoate, zinc ricinoleate and zinc stearate. Especially preferred is zinc neodecanoate.
• Suitable catalysts include (alkaline) salts of inorganic acid or of carboxylic acids such as potassium salts of acetic acid, citric acid, lactic acid, oxalic acid. It is preferred according to the invention for all the compounds used in the process to be substantially free of water. "Essentially anhydrous" means that the water content of all the compounds used in the process is less than 5% by weight, preferably less than 1% by weight, particularly preferably is less than 0.1 wt .-%, based on the total amount of the respective compound.
• Group-containing compounds are brought into contact, are common and known in the art.
• Step IV) takes place after step III).
• An object of the invention is a process for the preparation of the polymers according to the invention comprising the steps
• the polymer obtainable by this particular embodiment preferably has, based on its total weight, less than 5% by weight, more preferably less than 1% by weight and in particular 0% by weight, of compound d) in copolymerized form.
• the NCO value (isocyanate content) was determined titrimetrically in accordance with DIN 53185.
• Polymer-analogous Modification of the Polymers according to the Invention The dendritic polyether polyol c) comprises, in a preferred embodiment, free OH groups after the polymerization. These cause an increased in comparison with conventional associative thickeners solubility of the polymers of the invention in polar solvents, especially in alcohols and water.
• the free OH groups of the copolymerized compound c) also have a positive influence on the structure and the visual appearance of the preparations containing the polymers according to the invention.
• the invention thus also relates to polymers according to the invention in which in the range from 5 to 95% of the OH groups present before the polymerization in c) are present even after the polymerization as OH groups.
• sufficient thickening effect can already be achieved from a conversion of only 5 mol% of the originally present in c) OH groups, ie at 95 mol% OH groups still present.
• the invention also relates to polymers according to the invention in which in the range from 75 to 95% of the OH groups present in the c) before the polymerization also exist after the polymerization as OH groups.
• the invention furthermore relates to polymers which are obtainable by the reaction of at least part of the free OH groups of the copolymerized compound c) of the polymer according to the invention with compounds which are reactive toward OH groups.
• the polymerized-in compound c) can be modified by reacting the polymer according to the invention in an additional process step with suitable modifying reagents which can react with the OH groups of c).
• the remaining OH groups of copolymerized compound c) can be modified, for example, by adding modifying reagents containing acid, acid halide or isocyanate groups.
• Functionalization of the copolymerized compound c) with acid groups can be carried out, for example, by reacting their OH groups with compounds containing anhydride groups.
• Ester groups can be subsequently introduced, for example, by reaction with caprolactone. The length of the ester chains can be controlled by the amount of caprolactone used.
• the copolymerized compounds c) can also be functionalized by reaction with alkylene oxides, for example ethylene oxide, propylene oxide, butylene oxide or mixtures thereof.
• the invention also provides polymers obtainable by functionalization of the polymerized-in compound c) with OH-reactive substances which, in addition to at least one group which is reactive toward OH groups, comprise further groups such as carboxylate, sulfonate, diol or polyol.
• the invention also provides polymers obtainable by functionalizing the polymerized-in compound c) with OH-reactive substances which, in addition to at least one group which is reactive toward OH groups, comprise sugar molecules.
• the invention also relates to polymers obtainable by functionalization of the polymerized-in compound c) with OH-reactive substances which, in addition to at least one group which is reactive towards OH groups, comprise polar polymer chains such as, for example, polyacrylic acid chains or polyalkylene glycol chains.
• the invention also provides polymers obtainable by functionalizing the polymerized-in compound c) with OH-reactive substances which, in addition to at least one group which is reactive toward OH groups, comprise nonpolar polymer chains such as, for example, polyisobutene chains.
• the invention also relates to polymers obtainable by functionalization of the polymerized-in compound c) with OH-reactive substances which, in addition to at least one group which is reactive toward OH groups, comprise silicone chains.
• the invention also provides polymers obtainable by functionalization of the polymerized-in compound c) with OH-reactive substances which, in addition to at least one group which is reactive toward OH groups, comprise amphiphilic surfactant chains.
• Functional groups such as carboxylate, sulfonate, diol, sugar, polar and non-polar polymer chains, surfactant chains can thus be bonded via a hydroxyl group or an amino group to the copolymerized, NCO-functionalized compound c).
• the invention also relates to the use of the polymers according to the invention for the preparation of aqueous preparations.
• Preparations which contain at least 5% by weight, in particular at least 20% by weight, very particularly preferably at least 30% by weight and most preferably at least 70% by weight of water are preferred.
• preparations containing not more than 95% by weight, more preferably not more than 90% by weight and in particular not more than 85% by weight of water may be, for example, solutions, emulsions, suspensions or dispersions.
• auxiliaries for example dispersants and / or stabilizers
• surfactants for example dispersants and / or stabilizers
• preservatives for example anti-foaming agents
• fragrances wetting agents
• UV filters pigments
• emollients active ingredients
• other thickeners dyes
• plasticizers humectants and / or other polymers.
• Another object of the invention are cosmetic preparations containing at least one inventive polymer.
• Preference for use in cosmetic preparations is given to polymers according to the invention which are prepared without using a tin-containing catalyst.
• polymer-like polar modified polymers according to the invention preferably leads to more stable emulsions.
• An object of the present invention is the use of polymer-analogous polar modified polymers according to the invention to increase the compatibility with polar solvents such as low molecular weight monohydric alcohols such. Ethanol or low molecular weight polyhydric alcohols such as propylene glycol or glycerol.
• polymer-analogous polar modified polymers according to the invention for increasing the solubility of finely water-soluble ingredients such as, for example, hydrophilic UV filters.
• Another object of the present invention is the use of polymer-polymer polar modified polymers according to the invention for increasing the water-binding capacity in the preparation and after application to the skin (use of the polymers according to the invention as a moisturizer).
• Another object of the present invention is the use of the polymer analog nonpolar modified polymers of the invention to increase the compatibility with non-polar liquid phases such as cosmetic oils and silicone oils.
• the present invention likewise relates to the use of polymer-analogously non-polar modified polymers according to the invention for increasing the solubility of limited oil-soluble constituents, for example hydrophobic UV filters.
• a further subject of the present invention is the use of polymer-analogously modified polymers according to the invention for improving the dispersibility of particles in the preparation.
• Another object of the present invention is a method for improving the feel of the skin, characterized in that the skin is brought into contact with a preparation comprising a polymer-analogous non-polar modified polymer according to the invention.
• theological behavior can be adjusted due to the case.
• the polymers according to the invention can generally be used instead of the associative thickeners known from the prior art for cosmetic preparations.
• Cosmetic preparations containing an associative thickener based on polyurethane are described in detail in WO 2009/135857, p.
• Preparations according to the invention are the preparations described in WO 2009/135857, pp. 87 to 11, with the proviso that the preparations according to the invention contain a polymer according to this invention instead of the polyurethane thickeners designated there.
• the determination of the molecular weight of the polyether polyol PE.1 was carried out by GPC in hexafluoroisopropanol + 0.05% trifluoroacetic acid potassium salt as solvent, standard: PMMA.
• the OH number was determined in accordance with DIN 53240, Part 2.
• the polymerization was carried out in a 4-liter four-neck glass flask equipped with a stirrer, reflux condenser and a vacuum-assisted distillation column.
• the mixture of 1250.4 g of pentaerythritol (9.00 mol), 1393.3 g of triethylene glycol (9.00 mol) and 6.8 g of trifluoromethanesulfonic acid was evacuated and slowly heated to 200 ° C. by means of an oil bath at a pressure of 200 mbar. After reaching the reaction temperature, the reaction mixture was stirred for 4 h. Thereafter, the reaction mixture was allowed to cool under vacuum. For neutralization, 8.0 g of ethanolic KOH (5 molar) was added to the reaction solution and stirred for 2 hours.
• the product was stripped at 130 ° C and a reduced pressure of up to 100 mbar for 4 h.
• the polymer solution was cooled to 50 ° C (internal temperature) and treated with 89 mg of acetic acid dissolved in 5 ml of xylene, to neutralize the previously quantitatively determined amount of potassium acetate in polyethylene glycol.
• acetic acid dissolved in 5 ml of xylene
• zinc neodecanoate TIB ® Cat 616, TIB Chemicals, Mannheim, Germany
• polymerization was started, and the batch at an internal temperature of 50 ° C to an isocyanate content of 0.40%.
• the viscosity of a 10% strength aqueous solution of the branched polyether polyurethane A.1 was 15,000 mPa * s (shear rate 100 1 / s) or 7,000 mPa * s (shear rate 350 l / s).
• Synthesis Example 2 Preparation of a polymer according to the invention containing a hyperbranched polyether polyol, degree of functionalization of the OH groups 50% (A.2)
• the viscosity of a 10% aqueous solution of the branched polyether polyurethane A.2 was 25,000 mPa * s (shear rate 100 1 / s) or 12,000 mPa * s (shear rate 350 1 / s).
• the viscosity of a 5% aqueous solution of the branched polyether polyurethane A.1 was 9200 mPa * s (shear rate 100 1 / s) and 4600 mPa * s (shear rate 350 1 / s).
• Synthesis Example 4 Preparation of a polymer of the invention containing a hyperbranched polyether polyol of functionalization of the OH groups of 50% (A.4) 120.00 g Polyethylene glycol Pluriol E6000 ® (BASF SE, molecular weight 6000 g / mol) were dissolved in 467.00 g of xylene under Dissolved nitrogen in a 2 liter polymerization reactor (plane glass vessel with anchor stirrer). After heating the solution to about 140 ° C (internal temperature), 200 g of xylene were distilled off. The water content of the reaction mixture was then only about 100 ppm.
• BASF SE molecular weight 6000 g / mol
• the polymer solution was cooled to 50 ° C (internal temperature) and treated with 89 mg of acetic acid dissolved in 5 ml of xylene, to neutralize the previously quantitatively determined amount of potassium acetate in polyethylene glycol.
• acetic acid dissolved in 5 ml of xylene
• zinc neodecanoate TIB Kat 616, TIB Chemicals, Mannheim
• isophorone diisocyanate dissolved in 10 ml of xylene
• the viscosity of a 5% aqueous solution of the branched polyether polyurethane A.4 was 8200 mPa * s (shear rate 100 1 / s) and 3500 mPa * s (shear rate 350 1 / s).
• Synthesis Example 5 Preparation of a polymer according to the invention comprising a hyperbranched polyether polyol, degree of functionalization of the OH groups 50% (A.5)
• the viscosity of a 10% aqueous solution of the branched polyether polyurethane A.5 was 6700 mPa * s (shear rate 100 1 / s) and 4600 mPa * s (shear rate 350 1 / s).
• Synthesis Example 6 Preparation of a polymer of the invention containing a hyperbranched polyether polyol of functionalization of the OH groups of 50% (A.6) 374.00 g Lutensol ® AT25 (BASF SE) were dissolved in 374.00 g of acetone under nitrogen in a 2-liter Polymerization reactor (plane glass vessel with anchor stirrer) solved. Now, the polymer solution was heated to 50 ° C (internal temperature) and treated with 259 mg of acetic acid to neutralize the previously quantitatively determined amount of potassium acetate in Luten sol ® .
• the solvents xylene and THF were subsequently substantially removed by vacuum distillation at elevated temperature (about 60 ° C.) (residual content ⁇ 100 ppm) and the residue was dissolved in 610.9 g of water.
• the aqueous solution of 7.58 g of the preservative Euxyl K701 ® and 80 mg of the stabilizer 4-hydroxy-TEMPO were added subsequently.
• the viscosity of a 10% aqueous solution of the Functionalized, branched polyether polyurethane A.7 was 36,000 mPa * s (shear rate 100 1 / s) (viscosity at shear rate 350 1 / s not measurable).
• TMP 1,1,1-tris (hydroxymethyl) propane
• the solvents xylene and THF were subsequently largely removed by vacuum distillation at elevated temperature (about 60 ° C) (residual content ⁇ 100 ppm) and the residue dissolved in 577.1 g of water.
• the aqueous solution of 7.22 g of the preservative Euxyl K701 ® and 70 mg of the stabilizer 4-hydroxy-TEMPO were added subsequently.
• the viscosity of a 5% aqueous solution of the branched polyether polyurethane A.8 was 12500 mPa * s (shear rate 100 l / s) and 7500 mPa * s (shear rate 350 l / s).
• the viscosity of a 10% aqueous solution of the branched polyether polyurethane A.9 was 27000 mPa * s (shear rate 100 1 / s) (viscosity at shear rate 350 1 / s not measurable).
• the cosmetic preparations were prepared by adding the water phase B to the oil phase A and then adding the obtained O / W emulsion with the preservative (phase C).
• the ® on a Cremophor A6 / A25 basis based formulations were obtained FA.1 -FA.1 .1 .9 (Tab. 1) and based on a stearate based formulations FA.2.1 -FA.2.9 (Tab. 4).
• Phase B each one of the polymers A.1 -A.9 0.5 g
• Comparative Example FA.1 .8 very poor (gritty) despite high viscosity.
• the polymer according to the invention with completely reacted OH groups A.3 achieves the highest viscosity (30.0 Pa * s), ie the same value as polymer A.8.
• the corresponding preparation FA.1 .8, however, has a much worse structure; the structure of the preparation FA.1 .3 is significantly better due to the copolymerized hyperbranched polyether polyol.
• the corresponding linear comparison structure A.9 gives a viscosity (FA.1.9) of 20.0 Pa * s and is thus comparable to the viscosity of the polymer A.2 (FA.1.2) with 19.2 Pa * s.
• the decisive advantage of the polymer A.2 according to the invention compared to A.9 is comparable viscosity in the possibility of functionalization and tailoring of the polymer architecture, since even 50% of the originally present OH groups of copolymerized compound c) are present as OH groups.
• the structures A.2, A.3 (according to the invention) and A.8 (not according to the invention) allow similar viscosities of the cosmetic preparations of about 9 Pa * s.
• the polymer A.2 according to the invention can be subsequently modified in contrast to A.8.
• the structure of the preparation obtainable with polymer A.3 is significantly better than that obtained with A.8.
• the polymers A.1, A.2, A.3, A.4, A.5, A.6 or A.7 as well as combinations thereof of the respective emulsion can also be obtained after combination of water and oil phase at 60-80 ° C or the cooled emulsion at about 40 ° C are added.
• the invention also relates to the subsequent addition of the polyurethanes obtainable according to the invention to a cosmetic preparation in order to adjust the desired viscosity.
• phase D (if needed) and cool to about 40 ° C while stirring.
• phase E successively to the emulsion and cool to room temperature while stirring. Homogenise briefly.
• O / W emulsions comprising polymer A.1
• O / W emulsions containing one or more of the polymers A.2, A.3, A.4, A.5, A.6 or A.7 are also prepared.
• hydrodispersions comprising one or more of the polymers A.2, A.3, A.4, A.5, A.6 or A.7 are also prepared.
• Zinc oxide 5.0 10.0 2.0 3.0
• Pre-swell cellulose (if needed) in water then add the remaining ingredients of phase D and heat to 80 ° C.
• solid-stabilized emulsions comprising polymer A.1
• solid-stabilized emulsions containing one or more of the polymers A.2, A.3, A.4, A.5, A.6 or A.7 are also prepared.
• Triethanolamine 1 0 0.25 2.0 2.0 4.0
• Glycerol monostearate SE 1 0 3.0 1, 5 1, 5
• sunscreen creams containing one or more of the polymers A.2, A.3, A.4, A.5, A.6 or A.7 are also prepared.
• silicone emulsions comprising polymer A.1
• silicone emulsions containing one or more of the polymers A.2, A.3, A.4, A.5, A.6 or A.7 are also prepared.
• Alpha hydroxy acids lactic acid, citric acid, malic acid, glycolic acid
• Beta hydroxy acid Salicylic acid pH value> 3
• phase A and B separately to approx. 80 ° C. If necessary, adjust the pH of phase B to> 3 with NaOH. Stir phase B into phase A, homogenize briefly. Cool to about 40 ° C with stirring, add the components of phase D in succession, homogenize again.
• hydroxycarboxylic acid cream containing polymer A.1 hydroxycarboxylic creams containing one or more of the polymers A.2, A.3, A.4, A.5, A.6 or A.7 are also prepared.
• emulsions with deodorant active ingredient containing polymer A.1 are also prepared.
• depilatory cream containing polymer A.1 depilatory creams containing one or more of the polymers A.2, A.3, A.4, A.5, A.6 or A.7 are also prepared.
• fragrance qsqsqsqs dye qsqsqsqs
• Conditioning polymer is understood to mean polyquaternium-7, PQ-10, PQ-16, PQ-39, PQ-44, PQ-46, PQ-67, guar hydroxypropyltrimonium chlorides, PQ-87, and combinations thereof.
• conditioner shampoos containing one or more of the polymers A.2, A.3, A.4, A.5, A.6 or A.7 are also prepared.
• conditioning polymer is meant polyquaternium-7, PQ-10, PQ-16, PQ-39, PQ-44, PQ-46, PQ-67, guar hydroxypropyltrimonium chlorides, PQ-87 and combinations thereof.
• hair conditioners containing one or more of the polymers A.2, A.3, A.4, A.5, A.6 or A.7 are also prepared.

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