Classifications

• • 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
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/86—Polyethers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
  • A61P19/00—Drugs for skeletal disorders
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/06—Phosphorus compounds without P—C bonds
  • C07F9/08—Esters of oxyacids of phosphorus
  • C07F9/09—Esters of phosphoric acids
  • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
  • C08G65/327—Polymers modified by chemical after-treatment with inorganic compounds containing phosphorus

Definitions

• the invention relates to phosphoric acid triesters derived from alkoxylated fatty alcohols having more than 50 alkoxy groups.
• Phosphoric acid esters are toxicologically and ecotoxicologically harmless, skin-friendly due to their neutral pH values and well suited for use in cosmetic formulations.
• Alkyl or Alkenylphosphosphorklarester are usually prepared by condensation of fatty alcohols with diphosphorus pentoxide or orthophosphoric acid, with mixtures of mono- / di- / triesters are obtained with a major proportion of mono- and diesters.
• JP 09-268193 describes a method for the preparation of phosphoric acid triesters wherein phosphorus oxychloride is reacted with a fatty alcohol or an alkoxylated fatty alcohol in the presence of a catalyst selected from TiCu, MgCl 2 or AICI 3 .
• Phosphoric acid triesters are obtained which can carry up to 50 -CH 2 CH 2 O units (EO).
• EO -CH 2 CH 2 O units
• These ethoxylated phosphoric acid esters can be used advantageously as thickeners.
• their disadvantage is their low water solubility and difficult processibility to aqueous formulations.
• phosphoric acid triesters are sought, which have no production-related chlorine-containing impurities.
• the present invention therefore provides phosphoric acid triesters of the formula (I)
• Ri, R 2 and R 3 may be the same or different and is a linear or branched, saturated alkyl group having 6 to 30, preferably 8 to 22 and particularly preferably 12 to 18 carbon atoms, for a linear or branched, mono- or polyunsaturated alkenyl group with 6 to 30, preferably 8 to 22 and particularly preferably 12 to 18 carbon atoms, or an aryl group, in particular a phenyl group substituted with 1 to 3 branched alkyl groups, each independently 3 to 18 and preferably 4 to 12 carbon atoms substituted each group (OAi) x , (A2 ⁇ ) y and (A 3 O) Z are each independently selected from units selected from CH 2 CH 2 O, C 3 H 6 O and C 4 HeO, and wherein Units CH 2 CH 2 O, C 3 H 6 O and C 4 HeO within the individual groups (OAi) x , (A 2 O) y and (A 3 O) 2 may be arranged block-wise or randomly distributed, and Each of x, y
• the units OA ⁇ OA 2 and OA 3 in the phosphoric acid esters of the formula (I) mean CH 2 CH 2 O.
• the radicals Rr (OAi) x , R 2 - (OA 2 ) y and R 3 - (OA 3 ) Z in the Phosphorklam of formula (I) derived from fatty alcohol ethoxylates selected from fatty alcohol ethoxylates having 51 to 200 EO units ( EO CH 2 CH 2 O), preferably with 55 to 150 EO units and particularly preferably with 60 to 100 EO units, where the respective fatty alcohol radical RiO-, R 2 O- and R 3 O- is derived from alcohols selected from Octanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, behenyl alcohol, fatty alcohols having C-chain sections between 8 and 22, preferably Ci 0 / Ci 2 fatty alcohol, C 12 / Ci 4 fatty alcohol, Ci 2 / Ci 5 Fatty alcohol and Ci 6 / Ci 8 fatty alcohol
• the groups (OAi) x , (OA 2 ) y and (OA 3 ) Z in the phosphoric acid triesters of the formula (I) are each composed of CH 2 CH 2 O and C 3 HeO units, where the CH 2 CH 2 O and C 3 H 6 O units within the individual groups (OAi) x , (OA 2 ) y and (OA 3 ) Z may be arranged block-wise or randomly distributed, and contain in each case 51 to 199, preferably 55 to 150 and particularly preferably 60 to 100 CH 2 CH 2 O units and 1 to 20, preferably 1 to 10 and particularly preferably 2 to 5 C 3 H 6 ⁇ units.
• the phosphoric acid triesters of the formula (I) can preferably be prepared by reacting phosphoric acid or phosphoric acid derivatives with alkoxylated fatty alcohols, the alkoxylated fatty alcohols bearing at least 51 alkoxy groups.
• the preparation of the phosphoric acid esters of the formula (I) is particularly preferably carried out by reacting phosphoric acid or a phosphoric acid derivative selected from Orthophosphorklare, Tetraphosphordecaoxid, polyphosphoric acid, phosphorus oxychloride or phosphorus pentachloride with fatty alcohol alkoxylates at temperatures between 150 and 250 0 C, preferably between 180 and 240 0 C and in particular preferably between 200 and 230 ° C.
• the preparation of the phosphoric acid esters of the formula (I) is particularly preferably carried out by reaction of orthophosphoric acid, polyphosphoric acid or tetraphosphorodecoxide and, most preferably, by reaction of orthophosphoric acid with fatty alcohol alkoxylates.
• phosphoric acid triesters of the formula (I) which are chlorine-free are obtained. This means in particular that they contain no chlorine impurities.
• the phosphoric acid esters of the formula (I) are chlorine-free.
• the phosphoric acid triesters of the formula (I) may advantageously also be present together with other phosphoric acid esters in mixtures.
• a further subject of the present invention are therefore mixtures comprising one or more phosphoric triesters of the formula (I) and one or more phosphoric esters of the formula (II) (A 2 O) W R 5
• Ri is a linear or branched, saturated alkyl group having 6 to 30, preferably 8 to 22 and particularly preferably 12 to 18 carbon atoms, for a linear or branched, mono- or polyunsaturated alkenyl group having 6 to 30, preferably 8 to 22 and particularly preferably 12 to 18 carbon atoms, or an aryl group, in particular a phenyl group which may be substituted by 1 to 3 branched alkyl groups, each of which independently contains 3 to 18 and preferably 4 to 12 carbon atoms, is
• R 4 is H, Li + , Na + , K + , Mg ++ , Ca ++ , Al +++ , NH 4 + or quaternary
• R a, R b and R c are independently hydrogen, a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched, mono- or polyunsaturated alkenyl group having 2 to 22 Carbon atoms, a linear mono-hydroxyalkyl group having 2 to 10 carbon atoms, preferably a mono-
• Hydroxyethyl or mono-hydroxypropyl group or a linear or branched dihydroxyalkyl group having 3 to 10 carbon atoms,
• R 5 has the meaning of Ri or R 4
• the individual groups (OAi) x and (A 2 O) w each independently consist of units selected from CH 2 CH 2 O, C 3 H 6 O and C 4 H 8 O and wherein the units CH 2 CH 2 O, C 3 H 6 O and C 4 H 8 O within the individual groups (OAi) x and (A 2 O) w can be arranged block-wise or randomly distributed,
• x is a number from 51 to 200, preferably from 55 to 150 and particularly preferably from 60 to 100, and
• w is 0 or a number from 51 to 200, preferably from 55 to 150 and particularly preferably from 60 to 100.
• Preferred mixtures according to the invention consist of the compounds of the formula (I) and (II).
• the amount of phosphoric triesters according to formula (I) is preferably greater than 80.0% by weight, more preferably from 82.0 to 95.0% by weight and particularly preferably from 85.0 to 89.0 wt .-%, based on the total weight of the phosphoric acid ester according to formula (I) and formula (II).
• the degree of neutralization of the non-esterified phosphorus valencies (P-OH) in the phosphoric esters according to formula (II) can be between 0 and 100%.
• the remaining free valencies on the phosphorus atom may be acid groups, but also counterions selected from Li + , Na + , K + , Mg ++ , Ca ++ , Al +++ , NH 4 + , quaternary ammonium ions [HNR a R b R c ] + , wherein R a , R b and R c are independently hydrogen, a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched, mono- or polyunsaturated alkenyl group having 2 to 22 carbon atoms, a linear mono-hydroxyalkyl group with May be 2 to 10 carbon atoms, preferably a mono-hydroxyethyl or mono-hydroxypropyl group, as well as a linear or branched di-hydroxyalkyl group having 3 to 10 carbon atoms.
• the phosphoric esters according to the formula (II) are neutralized with a degree of neutralization of 0
• the mixtures according to the invention may contain one or more phosphoric acid esters of the formula (II) in which R 5 has the meaning of R 4 , and w is 0. These compounds are mono-phosphoric acid esters. These are preferably present in the mixtures according to the invention in an amount of ⁇ 3.0% by weight, more preferably ⁇ 1.0% by weight and particularly preferably ⁇ 0.1% by weight, based on the total weight of the phosphoric acid esters of the formula ( I) and (II). In the mono
• Phosphoric acid esters of the formula (II) R 4 and R 5 may be the same or different.
• the mixtures according to the invention contain one or more phosphoric acid esters of the formula (II) in which R 5 has the meaning of Ri and w is a number from 51 to 200, preferably from 55 to 150 and particularly preferably from 60 to 100, stands.
• These compounds are di-phosphoric acid esters. These are preferably present in the mixtures according to the invention in an amount of from 5.0 to 18.0% by weight, more preferably from 10.0 to 17.0% by weight and particularly preferably from 11.0 to 15.0% by weight. -%, Based on the total weight of the phosphoric acid esters according to formula (I) and (II) before.
• the radicals R 1 and R 5 may be identical or different.
• the preparation of mixtures of the phosphoric acid esters of the formulas (I) and (II) is preferably carried out by reacting phosphoric acid or a phosphoric acid derivative selected from orthophosphoric acid, Tetraphosphordecaoxid and polyphosphoric acid and particularly preferably by reaction of orthophosphoric acid, with fatty alcohol alkoxylates at temperatures between 150 and 250 0 C, preferably between 180 and 240 0 C and particularly preferably between 200 and 230 0 C.
• mixtures of the phosphoric acid esters of the formulas (I) and (II) are obtained, which are chlorine-free.
• these phosphoric acid esters of the formulas (I) and (II) contain no Chlorverungraphye ⁇ .
• phosphoric acid (85% strength) and fatty alcohol ethoxylate are used in a certain molar ratio.
• all starting materials are initially charged in a stirred apparatus with a heating mushroom, a descaling unit with a condenser and a vacuum connection.
• the mixture is heated to 100 0 C, evacuated three times to 100 mbar and then re-aerated with nitrogen.
• the mixture is heated under nitrogen inlet to 230 ° C and esterified (water discharge).
• the reaction times are from 24 to 42 hours (calculated from 230 ° C. esterification temperature), in particular 40 hours.
• the residual acid number is then included
• Esters from 11.4 g of phosphoric acid and 935.1 g Ceteareth-80 (C 6 / i ⁇ fatty alcohol + 80 moles ethylene oxide) in a molar ratio 1: 3, residual acid number: 0.8 mg KOH / g (96% conversion), 31 P-NMR: diester / Triester 15/85 mol%. It is a white wax with a melting point of about 40 0 C.

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• 2007
  • 2007-08-02 DE DE102007036187A patent/DE102007036187A1/de not_active Withdrawn
• 2008
  • 2008-07-29 US US12/671,802 patent/US20110230449A1/en not_active Abandoned
  • 2008-07-29 EP EP08785169A patent/EP2185629A2/de not_active Withdrawn
  • 2008-07-29 CN CN200880101583A patent/CN101790554A/zh active Pending
  • 2008-07-29 JP JP2010518555A patent/JP2010535255A/ja active Pending
  • 2008-07-29 WO PCT/EP2008/006221 patent/WO2009015859A2/de not_active Ceased

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