EP2185629A2 - Alkoxylated phosphoric acid triesters with a high degree of alkoxylation - Google Patents
Alkoxylated phosphoric acid triesters with a high degree of alkoxylationInfo
- Publication number
- EP2185629A2 EP2185629A2 EP08785169A EP08785169A EP2185629A2 EP 2185629 A2 EP2185629 A2 EP 2185629A2 EP 08785169 A EP08785169 A EP 08785169A EP 08785169 A EP08785169 A EP 08785169A EP 2185629 A2 EP2185629 A2 EP 2185629A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- units
- carbon atoms
- formula
- branched
- phosphoric acid
- 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- Withdrawn
Links
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 36
- -1 phosphoric acid triesters Chemical class 0.000 title claims abstract description 25
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 21
- 150000002191 fatty alcohols Chemical class 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 150000005691 triesters Chemical class 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 4
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 claims description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 claims description 2
- BTFJIXJJCSYFAL-UHFFFAOYSA-N arachidyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 claims description 2
- 125000004990 dihydroxyalkyl group Chemical group 0.000 claims description 2
- 229960000735 docosanol Drugs 0.000 claims description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 2
- 230000008719 thickening Effects 0.000 abstract description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 150000005690 diesters Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AFINAILKDBCXMX-PBHICJAKSA-N (2s,3r)-2-amino-3-hydroxy-n-(4-octylphenyl)butanamide Chemical compound CCCCCCCCC1=CC=C(NC(=O)[C@@H](N)[C@@H](C)O)C=C1 AFINAILKDBCXMX-PBHICJAKSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000013011 aqueous formulation Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910010165 TiCu Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000008406 cosmetic ingredient Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229940045860 white wax Drugs 0.000 description 1
Classifications
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- 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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- Polyethers (AREA)
Abstract
The invention relates to alkoxylated phosphoric acid triesters of formula (I) wherein x, y and z respectively stand for a number between 51 and 200. The alkoxylated phosphoric acid triesters of formula (I) are characterised especially by advantageous thickening properties.
Description
Beschreibung description
Alkoxylierte Phosphorsäuretriester mit hohem AlkoxylierungsgradAlkoxylated phosphoric acid triesters with a high degree of alkoxylation
Die Erfindung betrifft Phosphorsäuretriester, die sich von alkoxylierten Fettalkoholen mit mehr als 50 Alkoxygruppen ableiten.The invention relates to phosphoric acid triesters derived from alkoxylated fatty alcohols having more than 50 alkoxy groups.
Phosphorsäureester sind toxikologisch und ökotoxikologisch unbedenklich, aufgrund ihrer neutralen pH-Werte hautfreundlich und für die Verwendung in kosmetischen Formulierungen gut geeignet.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- bzw. Alkenylphosphosphorsäureester werden üblicherweise durch Kondensation von Fettalkoholen mit Diphosphorpentoxid oder Orthophosphorsäure hergestellt, wobei Gemische aus Mono-/Di-/Triester erhalten werden mit einem Hauptanteil an Mono- und Diester.Alkyl or Alkenylphosphosphorsäureester 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.
In JP 09-268193 wird eine Methode zur Herstellung von Phosphorsäuretriestern beschrieben, wobei Phosphoroxychlorid mit einem Fettalkohol oder einem alkoxylierten Fettalkohol in Gegenwart eines Katalysators ausgewählt aus TiCU, MgCI2 oder AICI3 umgesetzt wird. Es werden Phosphorsäuretriester erhalten, die bis zu 50 -CH2CH2O-Einheiten (EO) tragen können. Diese ethoxylierten Phosphorsäureester können vorteilhaft als Verdicker eingesetzt werden. Nachteilig ist jedoch deren geringe Wasserlöslichkeit und schwere Verarbeitbarkeit zu wässrigen Formulierungen. Zudem werden Phosphorsäuretriester gesucht, die keinerlei herstellungsbedingte Chlor-haltige Verunreinigungen aufweisen.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). These ethoxylated phosphoric acid esters can be used advantageously as thickeners. However, their disadvantage is their low water solubility and difficult processibility to aqueous formulations. In addition, phosphoric acid triesters are sought, which have no production-related chlorine-containing impurities.
Es bestand daher die Aufgabe, Phosphorsäuretriester bereitzustellen, die sowohl gute verdickende Eigenschaften zeigen und zugleich leicht in Zusammensetzungen auf wässriger Basis eingearbeitet werden können und gute Kompatibilitäten mit kosmetischen Inhaltsstoffen haben.
Es wurde überraschend gefunden, dass diese Aufgabe gelöst wird durch Phosphorsäuretriester mit einem Alkoxylierungsgrad > 50. Diese zeichnen sich durch eine gute verdickende Wirkung in wässrigen Zusammensetzungen aus, sind gut wasserlöslich und können in einfacher Weise zu wässrigen Formulierungen verarbeitet werden.It is an object of the present invention to provide phosphoric acid triesters which exhibit both good thickening properties and at the same time can be easily incorporated into aqueous-based compositions and have good compatibility with cosmetic ingredients. It has surprisingly been found that this object is achieved by phosphoric triesters having a degree of alkoxylation> 50. These are characterized by a good thickening effect in aqueous compositions, are readily soluble in water and can be processed in a simple manner into aqueous formulations.
Gegenstand der vorliegenden Erfindung sind daher Phosphorsäuretriester der Formel (I)The present invention therefore provides phosphoric acid triesters of the formula (I)
(A2O)yR2 (A 2 O) y R 2
OO
R1-(OAOx-O-P=O (l)R 1 - (OAO x -OP = O ( l)
OO
(A3O)2R3 (A 3 O) 2 R 3
worinwherein
Ri, R2 und R3 gleich oder verschieden sein können und für eine lineare oder verzweigte, gesättigte Alkylgruppe mit 6 bis 30, vorzugsweise 8 bis 22 und besonders bevorzugt 12 bis 18 Kohlenstoffatomen, für eine lineare oder verzweigte, ein- oder mehrfach ungesättigte Alkenylgruppe mit 6 bis 30, vorzugsweise 8 bis 22 und besonders bevorzugt 12 bis 18 Kohlenstoffatomen, oder für eine Arylgruppe, insbesondere eine Phenylgruppe, die mit 1 bis 3 verzweigten Alkylgruppen, die jeweils unabhängig voneinander 3 bis 18 und vorzugsweise 4 bis 12 Kohlenstoffatome enthalten, substituiert sein kann, steht, die einzelnen Gruppen (OAi)x, (A2θ)y und (A3O)Z jeweils unabhängig voneinander aus Einheiten ausgewählt aus CH2CH2O, C3H6O und C4HeO bestehen und wobei die Einheiten CH2CH2O, C3H6O und C4HeO innerhalb der einzelnen Gruppen (OAi)x, (A2O )y und (A3O)2 blockartig oder statistisch verteilt angeordnet sein können, und
x, y und z jeweils unabhängig voneinander eine Zahl von 51 bis 200, bevorzugt von 55 bis 150 und besonders bevorzugt von 60 bis 100, bedeuten.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 , (A2θ) 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 and z independently represents a number from 51 to 200, preferably from 55 to 150 and more preferably from 60 to 100.
Vorzugsweise stehen die Reste R1, R2 und R3 der Phosphorsäureester der Formel (I), welche gleich oder verschieden sein können, für eine lineare oder verzweigte, gesättigte Alkylgruppe mit 6 bis 30, vorzugsweise 8 bis 22 und besonders bevorzugt 12 bis 18 Kohlenstoffatomen, oder für eine lineare oder verzweigte, ein- oder mehrfach ungesättigte Alkenylgruppe mit 6 bis 30, vorzugsweise 8 bis 22 und besonders bevorzugt 12 bis 18 Kohlenstoffatomen.The radicals R 1 , R 2 and R 3 of the phosphoric acid esters of the formula (I), which may be identical or different, preferably represent a linear or branched, saturated alkyl group having 6 to 30, preferably 8 to 22 and particularly preferably 12 to 18 Carbon atoms, or 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.
Weiterhin bevorzugt bedeuten die EinheitenOA^ OA2 und OA3 in den Phosphorsäureestern der Formel (I) CH2CH2O.Further preferably, the units OA ^ OA 2 and OA 3 in the phosphoric acid esters of the formula (I) mean CH 2 CH 2 O.
Besonders bevorzugt sind die Reste Rr(OAi)x, R2-(OA2)y und R3-(OA3)Z in den Phosphorsäureestem der Formel (I) abgeleitet von Fettalkoholethoxylaten ausgewählt aus Fettalkoholethoxylaten mit 51 bis 200 EO-Einheiten (EO = CH2CH2O), bevorzugt mit 55 bis 150 EO-Einheiten und besonders bevorzugt mit 60 bis 100 EO-Einheiten, wobei der jeweilige Fettalkoholrest RiO-, R2O- und R3O- abgeleitet ist von Alkoholen ausgewählt aus Octanol, Decanol, Dodecanol, Tetradecanol, Hexadecanol, Octadecanol, Eicosanol, Behenylalkohol, Fettalkoholen mit C-Ketten-Schnitten zwischen 8 und 22, vorzugsweise Ci0/Ci2-Fettalkohol, C12/Ci4-Fettalkohol, Ci2/Ci5-Fettalkohol und Ci6/C-i8-Fettalkohol, besonders bevorzugt Ci6/18-Fettalkoholethoxylat mit 80 Ethylenoxid-Einheiten (z.B. Genapol® T 800), verzweigten Fettalkoholen, vorzugsweise Guerbetalkoholen und einfach ungesättigten Fettalkoholen, vorzugsweise Delta-9-cis-Hexadecanol, Delta-9-cis-Octadecanol, trans-9- Octadecanol und cis-Delta-11 -Octadecanol.Particularly preferably, the radicals Rr (OAi) x , R 2 - (OA 2 ) y and R 3 - (OA 3 ) Z in the Phosphorsäureestem 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, more preferably Ci 6/18 fatty alcohol ethoxylate with 80 ethylene oxide units (eg Genapol ® T 800), branched fatty alcohols, preferably Guerbet alcohols and monounsaturated fatty alcohols, preferably delta-9-cis-hexadecanol , Delta-9-cis-octadecanol, trans-9-octadecanol and cis delta-11 octadecanol.
Weiterhin bevorzugt sind die Gruppen (OAi)x, (OA2)y und (OA3)Z in den Phosphorsäuretriestern der Formel (I) jeweils aus CH2CH2O- und C3HeO-Einheiten aufgebaut, wobei die CH2CH2O- und C3H6O-Einheiten innerhalb der einzelnen Gruppen (OAi)x, (OA2)y und (OA3)Z blockartig oder statistisch verteilt angeordnet sein können, und enthalten jeweils 51 bis 199, bevorzugt 55 bis 150 und
besonders bevorzugt 60 bis 100 CH2CH2O-Einheiten und 1 bis 20, bevorzugt 1 bis 10 und besonders bevorzugt 2 bis 5 C3H6θ-Einheiten.Further preferably, 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 θ units.
Die Phosphorsäuretriester der Formel (I) können vorzugsweise hergestellt werden durch Umsetzung von Phosphorsäure oder Phosphorsäurederivaten mit alkoxylierten Fettalkoholen, wobei die alkoxylierten Fettalkohole mindestens 51 Alkoxygruppen tragen.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.
Die Darstellung der Phosphorsäureester der Formel (I) erfolgt besonders bevorzugt durch Umsetzung von Phosphorsäure oder einem Phosphorsäurederivat ausgewählt aus Orthophosphorsäure, Tetraphosphordecaoxid, Polyphosphorsäure, Phosphoroxychlorid oder Phosphorpentachlorid mit Fettalkoholalkoxylaten bei Temperaturen zwischen 150 und 250 0C, bevorzugt zwischen 180 und 240 0C und insbesondere bevorzugt zwischen 200 und 230 0C.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 Orthophosphorsäure, 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.
Die Darstellung der Phosphorsäureester der Formel (I) erfolgt insbesondere bevorzugt durch Umsetzung von Orthophosphorsäure, Polyphosphorsäure oder Tetraphosphordecaoxid und außerordentlich bevorzugt durch Umsetzung von Orthophosphorsäure mit Fettalkoholalkoxylaten. Gemäß dieser Ausführungsform des Verfahrens werden Phosphorsäuretriester der Formel (I) erhalten, die chlorfrei sind. Dies bedeutet insbesondere, dass sie keine Chlorverunreinigungen enthalten.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. According to this embodiment of the process, phosphoric acid triesters of the formula (I) which are chlorine-free are obtained. This means in particular that they contain no chlorine impurities.
In einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung sind die Phosphorsäureester der Formel (I) chlorfrei.In a further preferred embodiment of the present invention, the phosphoric acid esters of the formula (I) are chlorine-free.
Die Phosphorsäuretriester der Formel (I) können vorteilhafter weise auch zusammen mit anderen Phosphorsäureestern in Mischungen vorliegen.The phosphoric acid triesters of the formula (I) may advantageously also be present together with other phosphoric acid esters in mixtures.
Weiterer Gegenstand der vorliegenden Erfindung sind daher Mischungen enthaltend einen oder mehrere Phosphorsäuretriester der Formel (I) und einen oder mehrere Phosphorsäureester der Formel (II)
(A2O)WR5 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
OO
R1-(OA1Jx-O-P=O (H)R 1 - (OA 1 J x -OP = O (H)
OO
I R.I R.
worinwherein
Ri für eine lineare oder verzweigte, gesättigte Alkylgruppe mit 6 bis 30, vorzugsweise 8 bis 22 und besonders bevorzugt 12 bis 18 Kohlenstoffatomen, für eine lineare oder verzweigte, ein- oder mehrfach ungesättigte Alkenylgruppe mit 6 bis 30, vorzugsweise 8 bis 22 und besonders bevorzugt 12 bis 18 Kohlenstoffatomen, oder für eine Arylgruppe, insbesondere eine Phenylgruppe, die mit 1 bis 3 verzweigten Alkylgruppen, die jeweils unabhängig voneinander 3 bis 18 und vorzugsweise 4 bis 12 Kohlenstoffatome enthalten, substituiert sein kann, steht,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
R4 für H, Li+, Na+, K+, Mg++, Ca++, Al+++, NH4 + oder quaternäreR 4 is H, Li + , Na + , K + , Mg ++ , Ca ++ , Al +++ , NH 4 + or quaternary
Ammoniumionen [HNRaRbRc]+ steht, worin Ra, Rb und Rc unabhängig voneinander Wasserstoff, eine lineare oder verzweigte Alkylgruppe mit 1 bis 22 Kohlenstoffatomen, eine lineare oder verzweigte, einfach oder mehrfach ungesättigte Alkenylgruppe mit 2 bis 22 Kohlenstoffatomen, eine lineare Mono- Hydroxyalkylgruppe mit 2 bis 10 Kohlenstoffatomen, bevorzugt eine Mono-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 having 2 to 10 carbon atoms, preferably a mono-
Hydroxyethyl- oder Mono-Hydroxypropylgruppe, oder eine lineare oder verzweigte Di-Hydroxyalkylgruppe mit 3 bis 10 Kohlenstoffatomen, bedeuten,Hydroxyethyl or mono-hydroxypropyl group, or a linear or branched dihydroxyalkyl group having 3 to 10 carbon atoms,
R5 die Bedeutung von Ri oder R4 besitzt,
die einzelnen Gruppen (OAi)x und (A2O)w jeweils unabhängig voneinander aus Einheiten ausgewählt aus CH2CH2O, C3H6O und C4H8O bestehen und wobei die Einheiten CH2CH2O, C3H6O und C4H8O innerhalb der einzelnen Gruppen (OAi)x und (A2O )w blockartig oder statistisch verteilt angeordnet sein können,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 für eine Zahl von 51 bis 200, bevorzugt von 55 bis 150 und besonders bevorzugt von 60 bis 100, steht, undx is a number from 51 to 200, preferably from 55 to 150 and particularly preferably from 60 to 100, and
w für O oder für eine Zahl von 51 bis 200, bevorzugt von 55 bis 150 und besonders bevorzugt von 60 bis 100, steht.w is 0 or a number from 51 to 200, preferably from 55 to 150 and particularly preferably from 60 to 100.
Bevorzugte erfindungsgemäße Mischungen bestehen aus den Verbindungen der Formel (I) und (II).Preferred mixtures according to the invention consist of the compounds of the formula (I) and (II).
In den erfindungsgemäßen Mischungen enthaltend Phosphorsäureester der Formel (I) und (II) ist die Menge der Phosphorsäuretriester gemäß Formel (I) vorzugsweise größer 80,0 Gew.-%, besonders bevorzugt von 82,0 bis 95,0 Gew.-% und insbesondere bevorzugt von 85,0 bis 89,0 Gew.-%, bezogen auf das Gesamtgewicht der Phosphorsäureester gemäß Formel (I) und Formel (II).In the mixtures according to the invention comprising phosphoric acid esters 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).
Der Neutralisationsgrad der nicht veresterten Phosphorvalenzen (P-OH) in den Phosphorsäureestern gemäß Formel (II) kann zwischen 0 und 100 % betragen.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%.
Die übrigen freien Valenzen am Phosphoratom können Säuregruppen sein, aber auch Gegenionen, gewählt aus Li+, Na+, K+, Mg++, Ca++, Al+++, NH4 +, quaternären Ammoniumionen [HNRaRbRc]+, worin Ra, Rb und Rc unabhängig voneinander Wasserstoff, eine lineare oder verzweigte Alkylgruppe mit 1 bis 22 Kohlenstoffatomen, eine lineare oder verzweigte, einfach oder mehrfach ungesättigte Alkenylgruppe mit 2 bis 22 Kohlenstoffatomen, eine lineare Mono- Hydroxyalkylgruppe mit 2 bis 10 Kohlenstoffatomen, bevorzugt eine Mono- Hydroxyethyl- oder Mono-Hydroxypropylgruppe, sowie eine lineare oder verzweigte Di-Hydroxyalkylgruppe mit 3 bis 10 Kohlenstoffatomen, sein können.
In einer weiteren bevorzugten Ausführungsform der Erfindung sind die Phosphorsäureester gemäß der Formel (II) mit einem Neutralisationsgrad von 0 - 20,0 % neutralisiert.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. In a further preferred embodiment of the invention, the phosphoric esters according to the formula (II) are neutralized with a degree of neutralization of 0-20.0%.
In einer anderen bevorzugten Ausführungsform der Erfindung sind dieIn another preferred embodiment of the invention are the
Phosphorsäureester gemäß der Formel (II) mit einem Neutralisationsgrad von 20,1 - 100 % neutralisiert.Phosphoric acid ester according to the formula (II) with a degree of neutralization of 20.1 - 100% neutralized.
Die erfindungsgemäßen Mischungen können einen oder mehrere Phosphorsäureester der Formel (II) enthalten, worin R5 die Bedeutung von R4 besitzt, und w für 0 steht. Bei diesen Verbindungen handelt es sich um Mono- Phosphorsäureester. Diese liegen in den erfindungsgemäßen Mischungen vorzugsweise in einer Menge < 3,0 Gew.-%, besonders bevorzugt < 1 ,0 Gew.-% und insbesondere bevorzugt < 0,1 Gew.-%, bezogen auf das Gesamtgewicht der Phosphorsäureester gemäß Formel (I) und (II), vor. In den Mono-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
Phosphorsäureestem der Formel (II) können R4 und R5 gleich oder verschieden sein.Phosphoric acid esters of the formula (II) R 4 and R 5 may be the same or different.
In einer weiteren bevorzugten Ausführungsform der Erfindung enthalten die erfindungsgemäßen Mischungen einen oder mehrere Phosphorsäureester der Formel (II), worin R5 die Bedeutung von R-i besitzt und w für eine Zahl von 51 bis 200, bevorzugt von 55 bis 150 und besonders bevorzugt von 60 bis 100, steht. Bei diesen Verbindungen handelt es sich um Di-Phosphorsäureester. Diese liegen in den erfindungsgemäßen Mischungen vorzugsweise in einer Menge von 5,0 bis 18,0 Gew.-%, besonders bevorzugt von 10,0 bis 17,0 Gew.-% und insbesondere bevorzugt von 11 ,0 bis 15,0 Gew.-%, bezogen auf das Gesamtgewicht der Phosphorsäureester gemäß Formel (I) und (II), vor. In den Di-Phosphorsäureestern der Formel (II) können die Reste R1 und R5 gleich oder verschieden sein.In a further preferred embodiment of the invention, 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. In the di-phosphoric acid esters of the formula (II), the radicals R 1 and R 5 may be identical or different.
Die Darstellung von Mischungen der Phosphorsäureester der Formeln (I) und (II) erfolgt vorzugsweise durch Umsetzung von Phosphorsäure oder einem Phosphorsäurederivat ausgewählt aus Orthophosphorsäure,
Tetraphosphordecaoxid und Polyphosphorsäure und besonders bevorzugt durch Umsetzung von Orthophosphorsäure, mit Fettalkoholalkoxylaten bei Temperaturen zwischen 150 und 250 0C, bevorzugt zwischen 180 und 240 0C und insbesondere bevorzugt zwischen 200 und 230 0C.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.
Gemäß diesem Verfahren werden Mischungen der Phosphorsäureester der Formeln (I) und (II) erhalten, die chlorfrei sind. Dies bedeutet insbesondere, dass diese Phosphorsäureester der Formeln (I) und (II) keine Chlorverunreinigungeπ enthalten.According to this method, mixtures of the phosphoric acid esters of the formulas (I) and (II) are obtained, which are chlorine-free. This means in particular that these phosphoric acid esters of the formulas (I) and (II) contain no Chlorverunreinigungeπ.
Weiterhin bevorzugte erfindungsgemäße Mischungen enthaltend Phosphorsäureester gemäß Formel (I) und Formel (II) sind chlorfrei.Further preferred mixtures according to the invention comprising phosphoric acid esters of the formula (I) and formula (II) are chlorine-free.
Die nachfolgenden Beispiele und Anwendungen sollen die Erfindung näher erläutern, ohne sie jedoch darauf zu beschränken. Bei allen Prozentangaben handelt es sich um Gewichts-% (Gew.-%).The following examples and applications are intended to illustrate the invention without, however, limiting it thereto. All percentages are by weight (% by weight).
Herstellbeispiele, Allgemeine Arbeitsvorschrift:Production examples, general working instructions:
Bei der Herstellung der erfindungsgemäßen Phosphorsäureester werden Phosphorsäure (85 %ig), und Fettalkoholethoxylat in einem bestimmten Molverhältnis eingesetzt. Hierzu werden alle Edukte in einer Rührapparatur mit Heizpilz, Auskreiser mit Kühler und Vakuumanschluss vorgelegt. Die Mischung wird auf 1000C aufgeheizt, dreimal bis 100 mbar evakuiert und anschließend mit Stickstoff wieder belüftet. Nach weiteren 4 Stunden Inertisierung (Stickstoffeinleitung von 20 Liter/Stunde) bei 100 0C wird der Ansatz unter Stickstoffeinleitung auf 230 °C aufgeheizt und verestert (Wasseraustrag). Die Reaktionszeiten betragen 24 bis 42 Stunden (ab 230 0C Veresterungstemperatur gerechnet), insbesondere 40 Stunden. Die Rest-Säurezahl liegt dann beiIn the preparation of the phosphoric acid esters according to the invention, phosphoric acid (85% strength) and fatty alcohol ethoxylate are used in a certain molar ratio. For this purpose, 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. After a further 4 hours of inerting (nitrogen inlet of 20 liters / hour) at 100 0 C, 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
< 3 mg KOH/g. Dies entspricht etwa 93 bis 96 % Umsatz (bezogen auf Start- Säurezahl). Nach beendeter Umsetzung wird das Produkt auf 80 0C gekühlt, in eine Schale ausgegossen und die erstarrte Schmelze zerkleinert.
Beispiel 1<3 mg KOH / g. This corresponds to about 93 to 96% conversion (based on starting acid number). After completion of the reaction, the product is cooled to 80 0 C, poured into a dish and crushed the solidified melt. example 1
Ester aus 11.4 g Phosphorsäure und 935.1 g Ceteareth-80 (Ci6/iβ Fettalkohol + 80 Mol Ethylenoxid) im Molverhältnis 1 : 3, Rest-Säurezahl: 0.8 mg KOH/g (96 % Umsatz), 31P-NMR: Diester/Triester = 15/85 mol-%. Es handelt sich um ein weißes Wachs mit einem Schmelzpunkt von ca. 40 0C.
Esters from 11.4 g of phosphoric acid and 935.1 g Ceteareth-80 (C 6 / iβ 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.
Claims
1. Phosphorsäuretriester der Formel (I)1. Phosphoric acid triesters of the formula (I)
(A2O)yR2 (A 2 O) y R 2
OO
R1-(OA1Jx-O-P-OR 1 - (OA 1 J x -OPO
(I) O(I) O
(A3O)2R3 (A 3 O) 2 R 3
worinwherein
Ri, R2 und R3 gleich oder verschieden sein können und für eine lineare oder verzweigte, gesättigte Alkylgruppe mit 6 bis 30, vorzugsweise 8 bis 22 und besonders bevorzugt 12 bis 18 Kohlenstoffatomen, für eine lineare oder verzweigte, ein- oder mehrfach ungesättigte Alkenylgruppe mit 6 bis 30, vorzugsweise 8 bis 22 und besonders bevorzugt 12 bis 18 Kohlenstoffatomen, oder für eine Arylgruppe, insbesondere eine Phenylgruppe, die mit 1 bis 3 verzweigten Alkylgruppen, die jeweils unabhängig voneinander 3 bis 18 und vorzugsweise 4 bis 12 Kohlenstoffatome enthalten, substituiert sein kann, steht,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 can be, stands,
die einzelnen Gruppen (OAi)x, (A2OJy und (A3O)2 jeweils unabhängig voneinander aus Einheiten ausgewählt aus CH2CH2O, C3HeO und C4H8O bestehen und wobei die Einheiten CH2CH2O, C3HOO und C4H8O innerhalb der einzelnen Gruppen (OAi)x, (A2O)y und (A3O)2 blockartig oder statistisch verteilt angeordnet sein können, undeach group (OAi) x , (A 2 O y y and (A 3 O) 2 each independently consist of units selected from CH 2 CH 2 O, C 3 HeO and C 4 H 8 O and wherein the units CH 2 CH 2 O, C 3 HOO and C 4 H 8 O within the individual groups (OAi) x , (A 2 O) y and (A 3 O) 2 may be arranged block-wise or randomly distributed, and
x, y und z jeweils unabhängig voneinander eine Zahl von 51 bis 200, bevorzugt von 55 bis 150 und besonders bevorzugt von 60 bis 100, bedeuten. Each of x, y and z independently represents a number from 51 to 200, preferably from 55 to 150 and more preferably from 60 to 100.
2. Phosphorsäuretriester nach Anspruch 1 , dadurch gekennzeichnet, dass die Reste R-i, R2 und R3 gleich oder verschieden sein können und für eine lineare oder verzweigte, gesättigte Alkylgruppe mit 6 bis 30, vorzugsweise 8 bis 22 und besonders bevorzugt 12 bis 18 Kohlenstoffatomen, oder für eine lineare oder verzweigte, ein- oder mehrfach ungesättigte Alkenylgruppe mit 6 bis 30, vorzugsweise 8 bis 22 und besonders bevorzugt 12 bis 18 Kohlenstoffatomen stehen.2. phosphoric acid triester according to claim 1, characterized in that the radicals Ri, R 2 and R3 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, or 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.
3. Phosphorsäuretriester nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Einheiten OAi, OA2 und OA3 CH2CH2O bedeuten.3. phosphoric triester according to claim 1 or 2, characterized in that the units OAi, OA 2 and OA 3 CH 2 CH 2 O mean.
4. Phosphorsäuretriester nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Reste Ri-(OAi)x, R2-(OA2)y und R3-(OA3)Z abgeleitet sind von Fettalkoholethoxylaten ausgewählt aus Fettalkoholethoxylaten mit 51 bis 200 EO-Einheiten (EO = CH2CH2O), vorzugsweise mit 55 bis4. phosphoric triester according to one or more of claims 1 to 3, characterized in that the radicals Ri- (OAi) x , R 2 - (OA 2 ) y and R 3 - (OA 3 ) Z are derived from fatty alcohol ethoxylates selected from fatty alcohol ethoxylates with 51 to 200 EO units (EO = CH 2 CH 2 O), preferably with 55 to
150 EO-Einheiten und besonders bevorzugt mit 60 bis 100 EO-Einheiten, wobei der jeweilige Fettalkoholrest R1O-, R2O- und R3O- abgeleitet ist von Alkoholen ausgewählt aus Octanol, Decanol, Dodecanol, Tetradecanol, Hexadecanol, Octadecanol, Eicosanol, Behenylalkohol, Fettalkoholen mit C-Ketten-Schnitten zwischen 8 und 22, vorzugsweise Ci0/Ci2-Fettalkohol, Ci2/Cu-Fettalkohol, Ci2/Ci5-Fettalkohol und Ciβ/Cis-Fettalkohol, besonders bevorzugt Ci6/18-Fetta!koholethoxylat mit 80 Ethylenoxid-Einheiten, verzweigten Fettalkoholen, vorzugsweise Guerbetalkoholen und einfach ungesättigten Fettalkoholen, vorzugsweise Delta-9-cis-Hexadecanol, Delta-9-cis-Octadecanol, trans-9-Octadecanol und cis-Delta-11 -Octadecanol.150 EO units and particularly preferably with 60 to 100 EO units, wherein the respective fatty alcohol radical R 1 O-, R 2 O- and R 3 O- is derived from alcohols selected from octanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol , Eicosanol, behenyl alcohol, fatty alcohols with C chain cuts between 8 and 22, preferably Ci 0 / Ci 2 fatty alcohol, Ci 2 / Cu fatty alcohol, Ci 2 / Ci 5 fatty alcohol and Ciβ / cis fatty alcohol, particularly preferably Ci6 / 18-fatty alcohol ethoxylate with 80 ethylene oxide units, branched fatty alcohols, preferably Guerbet alcohols and monounsaturated fatty alcohols, preferably delta-9-cis-hexadecanol, delta-9-cis-octadecanol, trans-9-octadecanol and cis-delta-11 -Octadecanol.
5. Phosphorsäuretriester nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Gruppen (OAi)x, (OA2)y und (OA3)Z jeweils aus CH2CH2O- und C3H6O-Einheiten aufgebaut sind, wobei die CH2CH2O- und C3H6O-Einheiten innerhalb der einzelnen Gruppen (OAi)x, (OA2)y und (OA3)Z blockartig oder statistisch verteilt angeordnet sein können, und jeweils 51 bis 199, bevorzugt 55 bis 150 und besonders bevorzugt 60 bis 100 CH2CH2O-Einheiten und 1 bis 20, bevorzugt 1 bis 10 und besonders bevorzugt 2 bis 5 C3H6O-Einheiten enthalten. 5. phosphoric triester according to claim 1 or 2, characterized in that the groups (OAi) x , (OA 2 ) y and (OA 3 ) Z are each composed of CH 2 CH 2 O and C 3 H 6 O units, wherein 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 in each case 51 to 199, preferably 55 to 150 and more 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 O units.
6. Phosphorsäuretriester nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass er chlorfrei ist.6. phosphoric triester according to one or more of claims 1 to 5, characterized in that it is chlorine-free.
7. Mischung enthaltend einen oder mehrere Phosphorsäuretriester der Formel (I) nach einem oder mehreren der Ansprüche 1 bis 6 und einen oder mehrere Phosphorsäureester der Formel (II)7. Mixture comprising one or more phosphoric triesters of the formula (I) according to one or more of claims 1 to 6 and one or more phosphoric acid esters of the formula (II)
(A2O)WR5 (A 2 O) W R 5
OO
R1-(OA1Jx-O-P=O (M) R 1 - (OA 1 J x -OP = O (M)
OO
worinwherein
Ri für eine lineare oder verzweigte, gesättigte Alkylgruppe mit 6 bis 30, vorzugsweise 8 bis 22 und besonders bevorzugt 12 bis 18 Kohlenstoffatomen, für eine lineare oder verzweigte, ein- oder mehrfach ungesättigte Alkenylgruppe mit 6 bis 30, vorzugsweise 8 bis 22 und besonders bevorzugt 12 bis 18 Kohlenstoffatomen, oder für eine Arylgruppe, insbesondere eine Phenylgruppe, die mit 1 bis 3 verzweigten Alkylgruppen, die jeweils unabhängig voneinander 3 bis 18 und vorzugsweise 4 bis 12 Kohlenstoffatome enthalten, substituiert sein kann, steht,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
R4 für H, Li+, Na+, K+, Mg++, Ca++, Al+++, NH4 + oder quaternäre Ammoniumionen [HNRaRbRc]+ steht, worin Ra, Rb und Rc unabhängig voneinander Wasserstoff, eine lineare oder verzweigte Alkylgruppe mit 1 bis 22 Kohlenstoffatomen, eine lineare oder verzweigte, einfach oder mehrfach ungesättigte Alkenylgruppe mit 2 bis 22 Kohlenstoffatomen, eine lineare Mono- Hydroxyalkylgruppe mit 2 bis 10 Kohlenstoffatomen, bevorzugt eine Mono- Hydroxyethyl- oder Mono-Hydroxypropylgruppe, oder eine lineare oder verzweigte Di-Hydroxyalkylgruppe mit 3 bis 10 Kohlenstoffatomen, bedeuten,R 4 is H, Li + , Na + , K + , Mg ++ , Ca ++ , Al +++ , NH 4 + or quaternary ammonium ions [HNR a R b R c ] + , where R a , R b and R c independently of one another are 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 monohydroxyalkyl 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,
R5 die Bedeutung von Ri oder R4 besitzt,R 5 has the meaning of Ri or R 4 ,
die einzelnen Gruppen (OA1Jx und (A2O)W jeweils unabhängig voneinander aus Einheiten ausgewählt aus CH2CH2O, C3H6O und C4H8O bestehen und wobei die Einheiten CH2CH2O, C3H6O und C4H8O innerhalb der einzelnen Gruppen (OAi)x und (A2O )w blockartig oder statistisch verteilt angeordnet sein können,the individual groups (OA 1 J x and (A 2 O) W each independently of one another consist of units selected from CH 2 CH 2 O, C 3 H 6 O and C 4 H 8 O and where the units CH 2 CH 2 O, C 3 H 6 O and C 4 H 8 O may be arranged block-wise or randomly distributed within the individual groups (OAi) x and (A 2 O) w ,
x für eine Zahl von 51 bis 200, bevorzugt von 55 bis 150 und besonders bevorzugt von 60 bis 100, steht, undx is a number from 51 to 200, preferably from 55 to 150 and particularly preferably from 60 to 100, and
w für 0 oder für eine Zahl von 51 bis 200, bevorzugt von 55 bis 150 und besonders bevorzugt von 60 bis 100, steht.w is 0 or a number from 51 to 200, preferably from 55 to 150 and more preferably from 60 to 100, stands.
8. Mischung nach Anspruch 7, dadurch gekennzeichnet, dass sie aus den Verbindungen der Formel (I) und (II) besteht.8. Mixture according to claim 7, characterized in that it consists of the compounds of formula (I) and (II).
9. Mischung nach Anspruch 7 oder 8, dadurch gekennzeichnet, dass die Menge der Phosphorsäuretriester gemäß Formel (I) größer 80,0 Gew.-%, bevorzugt von 82,0 bis 95,0 Gew.-% und besonders bevorzugt von 85,0 bis 89,0 Gew.-% ist, bezogen auf das Gesamtgewicht der Phosphorsäureester gemäß Formel (I) und Formel (II).9. Mixture according to claim 7 or 8, characterized in that the amount of Phosphorsäuretriester according to formula (I) greater than 80.0 wt .-%, preferably from 82.0 to 95.0 wt .-% 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).
10. Mischung nach einem oder mehreren der Ansprüche 7 bis 9, dadurch gekennzeichnet, dass sie einen oder mehrere Phosphorsäureester der Formel (II), worin R5 die Bedeutung von Ri besitzt und w für eine Zahl von 51 bis 200, bevorzugt von 55 bis 150 und besonders bevorzugt von 60 bis 100, steht, enthält und diese in einer Menge von 5,0 bis 18,0 Gew.-%, bevorzugt von 10,0 bis10. Mixture according to one or more of claims 7 to 9, characterized in that it comprises one or more phosphoric acid esters of the formula (II), wherein R 5 has the meaning of Ri and w is a number from 51 to 200, preferably from 55 to 150 and more preferably from 60 to 100, contains, and in an amount of 5.0 to 18.0 wt .-%, preferably from 10.0 to
17,0 Gew.-% und besonders bevorzugt von 11 ,0 bis 15,0 Gew.-%, bezogen auf das Gesamtgewicht der Phosphorsäureester gemäß Formel (I) und (II), vorliegen. 17.0 wt .-% and particularly preferably from 11, 0 to 15.0 wt .-%, based on the total weight of the phosphoric acid esters according to formula (I) and (II), are present.
11. Mischung nach einem oder mehreren der Ansprüche 7 bis 10, dadurch gekennzeichnet, dass sie chlorfrei ist. 11. Mixture according to one or more of claims 7 to 10, characterized in that it is chlorine-free.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102007036187A DE102007036187A1 (en) | 2007-08-02 | 2007-08-02 | New alkoxylated phosphoric acid triester derivatives exhibiting high alkoxylating degree useful in cosmetic formulations |
| PCT/EP2008/006221 WO2009015859A2 (en) | 2007-08-02 | 2008-07-29 | Alkoxylated phosphoric acid triesters with a high degree of alkoxylation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2185629A2 true EP2185629A2 (en) | 2010-05-19 |
Family
ID=39399886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP08785169A Withdrawn EP2185629A2 (en) | 2007-08-02 | 2008-07-29 | Alkoxylated phosphoric acid triesters with a high degree of alkoxylation |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20110230449A1 (en) |
| EP (1) | EP2185629A2 (en) |
| JP (1) | JP2010535255A (en) |
| CN (1) | CN101790554A (en) |
| DE (1) | DE102007036187A1 (en) |
| WO (1) | WO2009015859A2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007036186A1 (en) * | 2007-08-02 | 2008-06-19 | Clariant International Limited | New phosphoric acid ester comprising structural units of orthophosphoric acid, alkoxylate compound and polyols having more than two hydroxyl-groups, useful in cosmetic/pharmaceutical/dermatological composition as e.g. thickeners |
| DE102007036188A1 (en) | 2007-08-02 | 2008-06-19 | Clariant International Limited | Preparing phosphoric acid ester compounds, useful as thickener in cosmetic formulation, comprises reacting phosphoric acid comprising orthophosphoric acid, tetraphosphorus decaoxide or polyphosphoric acid with alkoxyalcohol compounds |
| JP2010535254A (en) * | 2007-08-02 | 2010-11-18 | クラリアント・ファイナンス・（ビーブイアイ）・リミテッド | Phosphate esters containing phosphorus atoms bridged through diol units |
| DE102008006857A1 (en) * | 2008-01-31 | 2009-01-29 | Clariant International Ltd. | Composition, useful as cosmetic-, pharmaceutical- or dermatological-composition, comprises anionic, cross-linked, hydrophobically modified polymers and phosphoric acid ester comprising structural units e.g. orthophosphoric acid and polyol |
| WO2012019688A2 (en) | 2010-07-27 | 2012-02-16 | Clariant International Ltd | Compositions comprising hydrogen peroxide or hydrogen peroxide donor substances |
| DE102010054918A1 (en) | 2010-12-17 | 2011-06-30 | Clariant International Ltd. | Composition, useful e.g. for bleaching and/or dyeing of hair, comprises substances comprising hydrogen peroxide or hydrogen peroxide releasing substances, water, polymers with thickening properties and substances comprising hydroxypyridone |
| DE102013204605A1 (en) * | 2013-03-15 | 2014-09-18 | Evonik Industries Ag | Phosphoric acid esters, their preparation and use |
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| DE102007036186A1 (en) * | 2007-08-02 | 2008-06-19 | Clariant International Limited | New phosphoric acid ester comprising structural units of orthophosphoric acid, alkoxylate compound and polyols having more than two hydroxyl-groups, useful in cosmetic/pharmaceutical/dermatological composition as e.g. thickeners |
| US20100260696A1 (en) * | 2007-08-02 | 2010-10-14 | Clariant Finance (Bvi) Limited | Aqueous Compositions Containing Alkoxylated Phosphoric Acid Triesters |
| JP2010535254A (en) * | 2007-08-02 | 2010-11-18 | クラリアント・ファイナンス・（ビーブイアイ）・リミテッド | Phosphate esters containing phosphorus atoms bridged through diol units |
| DE102007036188A1 (en) * | 2007-08-02 | 2008-06-19 | Clariant International Limited | Preparing phosphoric acid ester compounds, useful as thickener in cosmetic formulation, comprises reacting phosphoric acid comprising orthophosphoric acid, tetraphosphorus decaoxide or polyphosphoric acid with alkoxyalcohol compounds |
| DE102008006857A1 (en) * | 2008-01-31 | 2009-01-29 | Clariant International Ltd. | Composition, useful as cosmetic-, pharmaceutical- or dermatological-composition, comprises anionic, cross-linked, hydrophobically modified polymers and phosphoric acid ester comprising structural units e.g. orthophosphoric acid and polyol |
-
2007
- 2007-08-02 DE DE102007036187A patent/DE102007036187A1/en not_active Withdrawn
-
2008
- 2008-07-29 EP EP08785169A patent/EP2185629A2/en not_active Withdrawn
- 2008-07-29 WO PCT/EP2008/006221 patent/WO2009015859A2/en active Application Filing
- 2008-07-29 US US12/671,802 patent/US20110230449A1/en not_active Abandoned
- 2008-07-29 CN CN200880101583A patent/CN101790554A/en active Pending
- 2008-07-29 JP JP2010518555A patent/JP2010535255A/en active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2009015859A2 (en) | 2009-02-05 |
| CN101790554A (en) | 2010-07-28 |
| WO2009015859A3 (en) | 2009-09-03 |
| US20110230449A1 (en) | 2011-09-22 |
| DE102007036187A1 (en) | 2008-06-19 |
| JP2010535255A (en) | 2010-11-18 |
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