EP2178945A2 - Method for producing alkoxylated phosphoric acid triesters - Google Patents

Method for producing alkoxylated phosphoric acid triesters

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Publication number
EP2178945A2
EP2178945A2 EP08785170A EP08785170A EP2178945A2 EP 2178945 A2 EP2178945 A2 EP 2178945A2 EP 08785170 A EP08785170 A EP 08785170A EP 08785170 A EP08785170 A EP 08785170A EP 2178945 A2 EP2178945 A2 EP 2178945A2
Authority
EP
European Patent Office
Prior art keywords
phosphoric acid
formula
fatty alcohol
ethylene oxide
oai
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08785170A
Other languages
German (de)
French (fr)
Inventor
Peter Klug
Franz-Xaver Scherl
Waltraud Simsch
Adelgunde Oberhauser
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Finance BVI Ltd
Original Assignee
Clariant Finance BVI Ltd
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Filing date
Publication date
Application filed by Clariant Finance BVI Ltd filed Critical Clariant Finance BVI Ltd
Publication of EP2178945A2 publication Critical patent/EP2178945A2/en
Withdrawn legal-status Critical Current

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    • 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
    • C07F9/113—Esters of phosphoric acids with unsaturated acyclic alcohols
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/55—Phosphorus compounds
    • A61K8/556—Derivatives containing from 2 to 10 oxyalkylene groups
    • 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
    • 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

Definitions

  • the invention relates to a process for the preparation of phosphoric acid triesters from phosphoric acid or chlorine-free phosphoric acid derivatives and alkoxylated fatty alcohols.
  • Phosphoric triesters are toxicologically and ecotoxicologically harmless, skin-friendly due to their neutral pH values and well suited as thickeners 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 a method for the preparation of Phosphor Text retriestern is described, wherein phosphorus oxychloride is reacted with a fatty alcohol or an alkoxylated fatty alcohol in the presence of a catalyst selected from TiCl 4 , MgCl 2 or AICI 3 .
  • a catalyst selected from TiCl 4 , MgCl 2 or AICI 3 .
  • HCl is formed, which can be removed only with great effort.
  • Phosphoric acid triesters containing chlorine-containing impurities are unsuitable for use in cosmetic formulations.
  • the present invention therefore provides a process for the preparation of phosphoric 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 for an aryl group, in particular a phenyl group, which are substituted by 1 to 3 branched alkyl groups, each independently 3 to 18 and preferably 4 to 12 carbon atoms each of the groups (OAi) x , (A 2 O y y and (A 3 O) 2 may be independently selected from the group consisting of CH 2 CH 2 O, C 3 H 6 O and C 4 HsO and wherein Units CH 2 CH 2 O, C 3 H 6 O and C 4 H 8 O within the individual groups (OAi) x , (A 2 O) y and (A 3 O) 2 may be arranged blockwise or randomly distributed, and each
  • aoxylated alcohols of the formulas (II), (III) and (IV) may be the same or different.
  • the orthophosphoric acid is used as the reactant.
  • Ci ⁇ / Ci 8 fatty alcohol branched fatty alcohols, preferably Guerbet alcohols and monounsaturated fatty alcohols, preferably delta-9-cis-hexadecanol, delta-9-cis-octadecanol, trans-9-octadecanol and cis-DeIta-11-octadecanol.
  • the alkoxylated alcohols of formulas (II), (III) and (IV) are identical or different and are selected from C 16 / i 8 fatty alcohol ethoxylates having 10 to 150 ethylene oxide units, preferably with 25 to 120 ethylene oxide units, especially preferably Ci 6 / i 8 fatty alcohol ethoxylate with 25 ethylene oxide units, Ci 6 / i ⁇ fatty alcohol ethoxylate with 50 ethylene oxide units or Ci6 / 1 8 fatty alcohol ethoxylate with 80 ethylene oxide units.
  • alkoxylated alcohols of the formulas (II), (III) and (IV), which may be identical or different are fatty alcohol ethoxypropoxylates, preferably fatty alcohol ethoxypropoxylates having 25 to 149 CH 2 CH 2 O units (EO) and 1 to 20 C 3 H 6 O units (PO), particularly preferably having 40 to 120 EO and 2 to 10 PO units and particularly preferably having 51 to 100 EO and 2 to 5 PO units, wherein the fatty alcohol radicals of Derive the above fatty alcohols.
  • the process according to the invention is carried out in such a way that the molar ratio of phosphoric acid or phosphoric acid derivative to alkoxylated alcohol is 1: 3.
  • the process according to the invention is carried out in the absence of a catalyst.
  • the phosphoric triesters of the formula (I) are of light color and have iodine color numbers of ⁇ 5, preferably ⁇ 2, on.
  • Another object of the present invention are also phosphoric acid esters of the formula (I) obtainable by the process according to the invention.
  • the phosphoric acid esters of the formula (I) obtainable by the process according to the invention are chlorine-free. This means, in particular, that these phosphoric esters of the formula (I) obtainable by the process according to the invention contain no chlorine impurities.
  • the degree of conversion of the esterification is> 80.0%, d. H. More than 80.0% of all esterifiable functions of phosphoric acid or phosphoric acid derivatives are esterified. Particularly preferred is a degree of conversion> 90.0%, particularly preferably> 95.0%.
  • reaction products obtained by the process according to the invention thus represent, in particular, mixtures of phosphoric esters, the proportion of phosphoric triester preferably being more than 80.0% by weight and more preferably> 85.0% by weight, based on the phosphoric acid ester mixture.
  • the phosphoric esters of the formula (I) obtainable by the process according to the invention are present in a preferred embodiment of the invention in admixture with one or more phosphoric acid esters of the formula (V)
  • 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 ammonium ions [HNR 3 R 0 R 0 ] "1" , where R a , R b and R c are independently hydrogen, a linear or branched alkyl group having 1 to
  • 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 HeO and C 4 H 8 O within the individual groups (OAi) x and (A 2 O) W can be arranged block-wise or statistically distributed,
  • x is a number from 10 to 150, preferably from 25 to 120, particularly preferably from 40 to 120 and particularly preferably from 51 to 100
  • w is 0 or a number from 10 to 150, preferably from 25 to 120, particularly preferably from 40 to 120 and particularly preferably from 51 to 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 3 R 0 R 0 J + , 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 degree of neutralization of the unsubstituted phosphorus valencies (P-OH) can be between 0 and 100%.
  • the phosphoric esters according to the formula (V) are neutralized with a degree of neutralization of 0-20.0%.
  • the phosphoric acid esters according to the formula (V) are neutralized with a degree of neutralization of 20.1-100%.
  • Phosphor yarn retriestern of the formula (I) one or more phosphoric acid esters of
  • R 4 and R 5 may be the same or different.
  • phosphoric acid esters of the formula (V) in which R 5 has the meaning of R 1 and w is from 10 to 150, preferably from 25 to 120, particularly preferably 40 to 120, and more preferably from 51 to 100, stands.
  • These compounds are di-phosphoric acid esters, preferably in amounts of 5.0 to 19.0 wt .-%, particularly preferably from 10.0 to 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 (V), are present.
  • R 5 has the meaning of R 1 and w is from 10 to 150, preferably from 25 to 120, particularly preferably 40 to 120, and more preferably from 51 to 100, stands.
  • di-phosphoric acid esters preferably in amounts of 5.0 to 19.0 wt .-%, particularly preferably from 10.0 to 17.0 wt .-% and particularly preferably from 11, 0 to 15.0 wt .-%
  • Di-phosphoric acid esters the radicals R 1 and R 5 may be the same or different.
  • 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 0 C and esterified (water discharge).
  • the Reaction times are 24 to 42 hours (calculated from 230 ° C.
  • esterification temperature in particular 40 hours.
  • the residual acid number is then ⁇ 3 mg KOH / g. This corresponds to about 93 to 96% conversion (based on starting acid number).
  • the product is cooled to 80 0 C, poured into a dish and crushed the solidified melt.
  • Esters of 17.3g of phosphoric acid and 666.0g Ceteareth-25 (C 6 / i 8 fatty alcohol + 25 moles ethylene oxide) in a molar ratio 1: 3, residual acid number of 1.7 mg KOH / g (95% conversion), 31 P-NMR: Diester / Triester 11/89 mol%
  • esters of 12.7g of phosphoric acid and 701.3g Ceteareth-50 (C- ⁇ 6 / i 8 fatty alcohol + 50 moles ethylene oxide) in a molar ratio 1: 3, residual acid number: 0.8 mg KOH / g (97% conversion), 31 P-NMR : Diester 13/87 mol%

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Abstract

The invention relates to a method for producing phosphoric acid triesters of formula (I). According to said method, phosphoric acid or a phosphoric acid derivative selected from orthophosphoric acid, tetraphosphoric decaoxide and polyphosphoric acid is reacted with alkoxylated alcohols of formulae (II) R1-(OA1)x-OH, (III) R2-(OA2)y-OH, and (IV) R3-(OA3)Z-OH, in the molar ratio phosphoric acid or phosphoric acid derivative to alkoxylated alcohol of 1 : 2.5 to 1 : 3.3, at between 200 and 240°C.

Description

Beschreibung description
Verfahren zur Herstellung alkoxylierter PhosphorsäuretriesterProcess for the preparation of alkoxylated phosphoric triesters
Die Erfindung betrifft ein Verfahren zur Herstellung von Phosphorsäuretriestern aus Phosphorsäure oder chlorfreien Phosphorsäurederivaten und alkoxylierten Fettalkoholen.The invention relates to a process for the preparation of phosphoric acid triesters from phosphoric acid or chlorine-free phosphoric acid derivatives and alkoxylated fatty alcohols.
Phosphorsäuretriester sind toxikologisch und ökotoxikologisch unbedenklich, aufgrund ihrer neutralen pH-Werte hautfreundlich und für die Verwendung in kosmetischen Formulierungen als Verdicker gut geeignet.Phosphoric triesters are toxicologically and ecotoxicologically harmless, skin-friendly due to their neutral pH values and well suited as thickeners 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 Phosphorsäu retriestern beschrieben, wobei Phosphoroxychlorid mit einem Fettalkohol oder einem alkoxylierten Fettalkohol in Gegenwart eines Katalysators ausgewählt aus TiCI4, MgCI2 oder AICI3 umgesetzt wird. Der Nachteil dieses Herstellverfahrens ist, dass HCl gebildet wird, das nur mit hohem Aufwand entfernt werden kann. Phosphorsäuretriester mit chlorhaltigen Verunreinigungen sind für den Einsatz in kosmetischen Formulierungen jedoch ungeeignet.In JP 09-268193 a method for the preparation of Phosphorsäu retriestern is described, wherein phosphorus oxychloride is reacted with a fatty alcohol or an alkoxylated fatty alcohol in the presence of a catalyst selected from TiCl 4 , MgCl 2 or AICI 3 . The disadvantage of this manufacturing process is that HCl is formed, which can be removed only with great effort. Phosphoric acid triesters containing chlorine-containing impurities, however, are unsuitable for use in cosmetic formulations.
Es bestand daher die Aufgabe, ein Verfahren zur Herstellung von Phosphorsäu retriestern zur Verfügung zu stellen, mit dem chlorfreie Phosphorsäuretriester, vorzugsweise mit einem Triesteranteil größer 80 Gew.-%, zugänglich sind.It was therefore an object to provide a process for the preparation of Phosphorsäu retriestern available with the chlorine-free Phosphorsäuretriester, preferably with a triester content greater than 80 wt .-%, are accessible.
Es wurde überraschend gefunden, dass diese Aufgabe gelöst wird durch ein Verfahren zur Herstellung von Phosphorsäuretriestern, gekennzeichnet durch die Umsetzung von Phosphorsäure oder chlorfreien Phosphorsäurederivaten, insbesondere ausgenommen Phosphoroxychloriden, mit alkoxylierten Fettalkoholen bei Temperaturen im Bereich von 200 bis 240 0C.It has surprisingly been found that this object is achieved by a process for the preparation of phosphoric triesters, characterized by the reaction of phosphoric acid or chlorine-free phosphoric acid derivatives, in particular excluding phosphorus oxychlorides, with alkoxylated fatty alcohols at temperatures ranging from 200 to 240 ° C.
Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zur Herstellung von Phosphorsäuretriestern der Formel (I)The present invention therefore provides a process for the preparation of phosphoric triesters of the formula (I)
(A2O)xR2 (A 2 O) x R 2
OO
R1-(OA1Jx-O-P=O (0 R 1 - (OA 1 J x -OP = O (0
OO
(A3O)2R3 (A 3 O) 2 R 3
worinwherein
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, 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, (A2OJy und (A3O)2 jeweils unabhängig voneinander aus Einheiten ausgewählt aus CH2CH2O, C3H6O und C4HsO bestehen und wobei die Einheiten CH2CH2O, C3H6O und C4H8O 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 10 bis 150, bevorzugt von 25 bis 120, besonders bevorzugt von 40 bis 120 und insbesondere bevorzugt von 51 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 for an aryl group, in particular a phenyl group, which are substituted by 1 to 3 branched alkyl groups, each independently 3 to 18 and preferably 4 to 12 carbon atoms each of the groups (OAi) x , (A 2 O y y and (A 3 O) 2 may be independently selected from the group consisting of CH 2 CH 2 O, C 3 H 6 O and C 4 HsO and wherein Units CH 2 CH 2 O, C 3 H 6 O and C 4 H 8 O within the individual groups (OAi) x , (A 2 O) y and (A 3 O) 2 may be arranged blockwise or randomly distributed, and each of x, y and z independently represents a number from 10 to 150, preferably from 25 to 120, more preferably from 40 to 120, and most preferably from 51 to 100,
dadurch gekennzeichnet, dasscharacterized in that
a) Phosphorsäure oder ein Phosphorsäurederivat ausgewählt ausa) phosphoric acid or a phosphoric acid derivative selected from
Orthophosphorsäure, Tetraphosphordecaoxid und Polyphosphorsäure mit alkoxylierten Alkoholen der Formel (II), (III) und (IV)Orthophosphoric acid, tetraphosphorodecoxide and polyphosphoric acid with alkoxylated alcohols of the formula (II), (III) and (IV)
Rr(OAi)x-OH Formel (II)Rr (OAi) x -OH formula (II)
R2-(OA2)y-OH Formel (III)R 2 - (OA 2 ) y-OH formula (III)
R3-(OA3)z-OH Formel (IV)R 3 - (OA 3 ) z -OH formula (IV)
wobei Ri, R2, R3, (OA1)X, (A2O )y und (A3O)2 die in Formel (I) genannten Bedeutungen besitzen,where R 1, R 2 , R 3 , (OA 1 ) X , (A 2 O) y and (A 3 O) 2 have the meanings given in formula (I),
b) im Molverhältnis Phosphorsäure bzw. Phosphorsäurederivat zu alkoxyliertem Alkohol von 1 : 2,5 bis 1 : 3,3,b) in the molar ratio phosphoric acid or phosphoric acid derivative to alkoxylated alcohol of 1: 2.5 to 1: 3.3,
c) bei 200 bis 240 0C, bevorzugt bei 220 bis 230 0C, umgesetzt wird.c) at 200 to 240 0 C, preferably at 220 to 230 0 C, is reacted.
Die aikoxylierten Alkohole der Formeln (II), (III) und (IV) können gleich oder verschieden sein.The aoxylated alcohols of the formulas (II), (III) and (IV) may be the same or different.
Vorzugsweise wird als Reaktand die Orthophosphorsäure eingesetzt.Preferably, the orthophosphoric acid is used as the reactant.
Weiterhin bevorzugt werden als alkoxylierte Alkohole der Formeln (II), (III) und (IV), die gleich oder verschieden sein können, Fettalkoholethoxylate, bevorzugt Fettalkoholethoxylate mit 25 bis 150 EO-Einheiten (EO = CH2CH2O), besonders bevorzugt mit 40 bis 120 EO-Einheiten und insbesondere bevorzugt mit 51 bis 100 EO-Einheiten eingesetzt, wobei der jeweilige Fettalkoholrest R-iO-, 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 C10/Ci2-Fettalkohol, C12/C14-Fettalkohol, Ci2/C15- Fettalkohol undFurther preferred alkoxylated alcohols of the formulas (II), (III) and (IV) which may be identical or different are fatty alcohol ethoxylates, preferably fatty alcohol ethoxylates having 25 to 150 EO units (EO = CH 2 CH 2 O) with 40 to 120 EO units and more preferably with 51 to 100 EO units are used, the respective fatty alcohol radical R-iO-, R 2 O- and R 3 O- being derived from alcohols selected from octanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, behenyl alcohol, fatty alcohols with C chain sections 8-22, preferably C 10 / C 2 fatty alcohol, C 12 / C 14 fatty alcohol, C 2 / C 15 - fatty alcohol and
Ciδ/Ci8-Fettalkohol, verzweigten Fettalkoholen, vorzugsweise Guerbetalkoholen und einfach ungesättigten Fettalkoholen, vorzugsweise Delta-9-cis-Hexadecanol, Delta-9-cis-Octadecanol, trans-9-Octadecanol und cis-DeIta-11 -Octadecanol.Ci δ / Ci 8 fatty alcohol, branched fatty alcohols, preferably Guerbet alcohols and monounsaturated fatty alcohols, preferably delta-9-cis-hexadecanol, delta-9-cis-octadecanol, trans-9-octadecanol and cis-DeIta-11-octadecanol.
Besonders bevorzugt sind die alkoxylierten Alkohole der Formeln (II), (III) und (IV) gleich oder verschieden und ausgewählt aus C16/i8-Fettalkoholethoxylaten mit 10 bis 150 Ethylenoxid-Einheiten, bevorzugt mit 25 bis 120 Ethylenoxid-Einheiten, besonders bevorzugt Ci6/i8-Fettalkoholethoxylat mit 25 Ethylenoxid-Einheiten, Ci6/iβ-Fettalkoholethoxylat mit 50 Ethylenoxid-Einheiten oder Ci6/18-Fettalkoholethoxylat mit 80 Ethylenoxid-Einheiten.Especially preferred are the alkoxylated alcohols of formulas (II), (III) and (IV) are identical or different and are selected from C 16 / i 8 fatty alcohol ethoxylates having 10 to 150 ethylene oxide units, preferably with 25 to 120 ethylene oxide units, especially preferably Ci 6 / i 8 fatty alcohol ethoxylate with 25 ethylene oxide units, Ci 6 / iβ fatty alcohol ethoxylate with 50 ethylene oxide units or Ci6 / 1 8 fatty alcohol ethoxylate with 80 ethylene oxide units.
Weiterhin bevorzugte alkoxylierte Alkohole der Formeln (II), (III) und (IV), die gleich oder verschieden sein können, sind Fettalkoholethoxy-propoxylate, bevorzugt Fettalkoholethoxy-propoxylate mit 25 bis 149 CH2CH2O-Einheiten (EO) und 1 bis 20 C3H6O-Einheiten (PO), besonders bevorzugt mit 40 bis 120 EO- und 2 bis 10 PO-Einheiten und insbesondere bevorzugt mit 51 bis 100 EO- und 2 bis 5 PO-Einheiten, wobei sich die Fettalkoholreste von den oben genannten Fettalkoholen ableiten.Further preferred alkoxylated alcohols of the formulas (II), (III) and (IV), which may be identical or different, are fatty alcohol ethoxypropoxylates, preferably fatty alcohol ethoxypropoxylates having 25 to 149 CH 2 CH 2 O units (EO) and 1 to 20 C 3 H 6 O units (PO), particularly preferably having 40 to 120 EO and 2 to 10 PO units and particularly preferably having 51 to 100 EO and 2 to 5 PO units, wherein the fatty alcohol radicals of Derive the above fatty alcohols.
Weiterhin bevorzugt wird das erfindungsgemäße Verfahren derart ausgeführt, dass das Molverhältnis von Phosphorsäure bzw. Phosphorsäurederivat zu alkoxyliertem Alkohol 1 : 3 ist.With further preference the process according to the invention is carried out in such a way that the molar ratio of phosphoric acid or phosphoric acid derivative to alkoxylated alcohol is 1: 3.
Weiterhin bevorzugt wird das erfindungsgemäße Verfahren ohne Verwendung eines Lösungsmittels durchgeführt.With further preference the process according to the invention is carried out without using a solvent.
Weiterhin bevorzugt wird das erfindungsgemäße Verfahren in Abwesenheit eines Katalysators durchgeführt. Die Phosphorsäuretriester der Formel (I) sind von heller Farbe und weisen lod- Farbzahlen von < 5, bevorzugt < 2, auf.With further preference the process according to the invention is carried out in the absence of a catalyst. The phosphoric triesters of the formula (I) are of light color and have iodine color numbers of <5, preferably <2, on.
Weiterer Gegenstand der vorliegenden Erfindung sind auch Phosphorsäureester der Formel (I) erhältlich nach dem erfindungsgemäßen Verfahren.Another object of the present invention are also phosphoric acid esters of the formula (I) obtainable by the process according to the invention.
In einer bevorzugten Ausführungsform der Erfindung sind die nach dem erfindungsgemäßen Verfahren erhältlichen Phosphorsäureester der Formel (I) chlorfrei. Dies bedeutet insbesondere, dass diese nach dem erfindungsgemäßen Verfahren erhältlichen Phosphorsäureester der Formel (I) keine Chlorverunreinigungen enthalten.In a preferred embodiment of the invention, the phosphoric acid esters of the formula (I) obtainable by the process according to the invention are chlorine-free. This means, in particular, that these phosphoric esters of the formula (I) obtainable by the process according to the invention contain no chlorine impurities.
Vorzugsweise ist der Umsetzungsgrad der Veresterung > 80,0 %, d. h. mehr als 80,0 % aller veresterbaren Funktionen der Phosphorsäure oder der Phosphorsäurederivate sind verestert. Besonders bevorzugt ist ein Umsetzungsgrad > 90,0 %, insbesondere bevorzugt > 95,0 %.Preferably, the degree of conversion of the esterification is> 80.0%, d. H. More than 80.0% of all esterifiable functions of phosphoric acid or phosphoric acid derivatives are esterified. Particularly preferred is a degree of conversion> 90.0%, particularly preferably> 95.0%.
Die nach dem erfindungsgemäßen Verfahren erhaltenen Umsetzungsprodukte stellen somit insbesondere Mischungen von Phosphorsäureestern dar, wobei der Anteil an Phosphorsäuretriester vorzugsweise mehr als 80,0 Gew.-% und besonders bevorzugt > 85,0 Gew.-%, bezogen auf die Phosphorsäureestermischung, beträgt.The reaction products obtained by the process according to the invention thus represent, in particular, mixtures of phosphoric esters, the proportion of phosphoric triester preferably being more than 80.0% by weight and more preferably> 85.0% by weight, based on the phosphoric acid ester mixture.
Die nach dem erfindungsgemäßen Verfahren erhältlichen Phosphorsäureester der Formel (I) liegen in einer bevorzugten Ausführungsform der Erfindung in Mischung mit einem oder mehreren Phosphorsäureestern der Formel (V) vorThe phosphoric esters of the formula (I) obtainable by the process according to the invention are present in a preferred embodiment of the invention in admixture with one or more phosphoric acid esters of the formula (V)
(A 2θ)wR5 30( A 2 θ) w R 5 30
I OI O
R1-(OA1Jx-O-P=O (v)R 1 - (OA 1 J x -OP = O ( v)
OO
R4 worinR 4 wherein
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 [HNR3R0R0]"1" steht, worin Ra, Rb und Rc unabhängig voneinander Wasserstoff, eine lineare oder verzweigte Alkylgruppe mit 1 bisR 4 is H, Li + , Na + , K + , Mg ++ , Ca ++ , Al +++ , NH 4 + or quaternary ammonium ions [HNR 3 R 0 R 0 ] "1" , where R a , R b and R c are independently hydrogen, a linear or branched alkyl group having 1 to
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,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 di-hydroxyalkyl group with 3 to 10 carbon atoms, mean
R5 die Bedeutung von Ri oder R4 besitzt,R 5 has the meaning of Ri or R 4 ,
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, C3HeO und C4H8O innerhalb der einzelnen Gruppen (OAi)x und (A2O)W blockartig oder statistisch verteilt angeordnet sein können,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 HeO and C 4 H 8 O within the individual groups (OAi) x and (A 2 O) W can be arranged block-wise or statistically distributed,
x für eine Zahl von 10 bis 150, bevorzugt von 25 bis 120, besonders bevorzugt von 40 bis 120 und insbesondere bevorzugt von 51 bis 100, steht, w für 0 oder für eine Zahl von 10 bis 150, bevorzugt von 25 bis 120, besonders bevorzugt von 40 bis 120 und insbesondere bevorzugt von 51 bis 100, steht, undx is a number from 10 to 150, preferably from 25 to 120, particularly preferably from 40 to 120 and particularly preferably from 51 to 100, w is 0 or a number from 10 to 150, preferably from 25 to 120, particularly preferably from 40 to 120 and particularly preferably from 51 to 100, and
wobei die Menge der Phosphorsäuretriester der Formel (I) größer 80,0 Gew.-% und bevorzugt > 85,0 Gew.-%, bezogen auf das Gesamtgewicht der Phosphorsäureester gemäß Formel (I) und Formel (V), ist, und der Neutralisationsgrad der nicht veresterten Phosphorvalenzen (P-OH) in den Phosphorsäureestern gemäß Formel (V) zwischen 0 und 100 % betragen kann.wherein the amount of Phosphorsäuretriester of formula (I) greater than 80.0 wt .-%, and preferably> 85.0 wt .-%, based on the total weight of the phosphoric acid ester according to formula (I) and formula (V), and, Neutralization degree of non-esterified Phosphorvalences (P-OH) in the phosphoric acid esters according to formula (V) 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 +, quatemären Ammoniumionen [HNR3R0R0J+, 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.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 3 R 0 R 0 J + , 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.
Der Neutralisationsgrad der unsubstituierten Phosphorvalenzen (P-OH) kann zwischen 0 und 100 % betragen.The degree of neutralization of the unsubstituted phosphorus valencies (P-OH) can be between 0 and 100%.
In einer bevorzugten Ausführungsform sind die Phosphorsäureester gemäß der Formel (V) mit einem Neutralisationsgrad von 0 - 20,0 % neutralisiert.In a preferred embodiment, the phosphoric esters according to the formula (V) are neutralized with a degree of neutralization of 0-20.0%.
In einer anderen bevorzugten Ausführungsform der Erfindung sind die Phosphorsäureester gemäß der Formel (V) mit einem Neutralisationsgrad von 20,1 - 100 % neutralisiert.In another preferred embodiment of the invention, the phosphoric acid esters according to the formula (V) are neutralized with a degree of neutralization of 20.1-100%.
Nach dem erfindungsgemäßen Verfahren können neben denAccording to the inventive method, in addition to the
Phosphorsäu retriestern der Formel (I) ein oder mehrere Phosphorsäureester derPhosphorsäu retriestern of the formula (I) one or more phosphoric acid esters of
Formel (V) erhalten werden, worin R5 die Bedeutung von R4 besitzt, und w für oFormula (V) wherein R 5 has the meaning of R 4 , and w for O
0 steht. Bei diesen Verbindungen handelt es sich um Mono-Phosphorsäureester, die vorzugsweise in Mengen < 3,0 Gew.-%, besonders bevorzugt < 1 ,0 Gew.-% und insbesondere bevorzugt < 0,1 Gew.-%, bezogen auf das Gesamtgewicht der Phosphorsäureester gemäß Formel (I) und (V), vorliegen. In den Mono- Phosphorsäureestern können R4 und R5 gleich oder verschieden sein.0 stands. These compounds are mono-phosphoric acid esters which are preferably in amounts of <3.0% by weight, more preferably <1.0% by weight and particularly preferably <0.1% by weight, based on the total weight the phosphoric acid ester according to formula (I) and (V). In the mono-phosphoric acid esters, R 4 and R 5 may be the same or different.
Nach dem erfindungsgemäßen Verfahren können neben den Phosphorsäuretriestern der Formel (I) Phosphorsäureester der Formel (V) erhalten werden, worin R5 die Bedeutung von Ri besitzt und w für eine Zahl von 10 bis 150, bevorzugt von 25 bis 120, besonders bevorzugt von 40 bis 120 und insbesondere bevorzugt von 51 bis 100, steht. Bei diesen Verbindungen handelt es sich um Di-Phosphorsäureester, die vorzugsweise in Mengen von 5,0 bis 19,0 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 (V), vorliegen. In denIn addition to the phosphoric acid triesters of the formula (I), it is possible by the process according to the invention to obtain phosphoric acid esters of the formula (V) in which R 5 has the meaning of R 1 and w is from 10 to 150, preferably from 25 to 120, particularly preferably 40 to 120, and more preferably from 51 to 100, stands. These compounds are di-phosphoric acid esters, preferably in amounts of 5.0 to 19.0 wt .-%, particularly preferably from 10.0 to 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 (V), are present. In the
Di-Phosphorsäureestern können die Reste R1 und R5 gleich oder verschieden sein.Di-phosphoric acid esters, the radicals R 1 and R 5 may be the same or different.
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 100 0C 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 0C aufgeheizt und verestert (Wasseraustrag). Die Reaktionszeiten betragen 24 bis 42 Stunden (ab 230 0C Veresterungstemperatur gerechnet), insbesondere 40 Stunden. Die Rest-Säurezahl liegt dann bei < 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.In 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 0 C and esterified (water discharge). The Reaction times are 24 to 42 hours (calculated from 230 ° C. esterification temperature), in particular 40 hours. The residual acid number is then <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.
Beispiel 1example 1
Ester aus 17.3g Phosphorsäure und 666.0g Ceteareth-25 (Ci6/i8 Fettalkohol + 25 Mol Ethylenoxid) im Molverhältnis 1 : 3, Rest-Säurezahl: 1.7 mg KOH/g (95 % Umsatz), 31P-NMR: Diester/Triester = 11/89 mol-%Esters of 17.3g of phosphoric acid and 666.0g Ceteareth-25 (C 6 / i 8 fatty alcohol + 25 moles ethylene oxide) in a molar ratio 1: 3, residual acid number of 1.7 mg KOH / g (95% conversion), 31 P-NMR: Diester / Triester = 11/89 mol%
Beispiel 2Example 2
Ester aus 12.7g Phosphorsäure und 701.3g Ceteareth-50 (C-ι6/i8 Fettalkohol + 50 Mol Ethylenoxid) im Molverhältnis 1 : 3, Rest-Säurezahl: 0.8 mg KOH/g (97 % Umsatz), 31P-NMR: DiestetfTriester = 13/87 mol-%Esters of 12.7g of phosphoric acid and 701.3g Ceteareth-50 (C-ι 6 / i 8 fatty alcohol + 50 moles ethylene oxide) in a molar ratio 1: 3, residual acid number: 0.8 mg KOH / g (97% conversion), 31 P-NMR : Diester = 13/87 mol%
Beispiel 3Example 3
Ester aus 11.4 g Phosphorsäure und 935.1 g Ceteareth-80 (C16/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-% Ester from 11.4 g phosphoric acid and 935.1 g ceteareth-80 (C 16 / iβ fatty alcohol + 80 mol ethylene oxide) in molar ratio 1: 3, residual acid number: 0.8 mg KOH / g (96% conversion), 31 P-NMR: diester / Triester = 15/85 mol%

Claims

Patentansprüche: claims:
1. Verfahren zur Herstellung von Phosphorsäuretriestern der Formel (I)1. Process for the preparation of phosphoric acid triesters of the formula (I)
(A2O)yR2 (A 2 O) y R 2
II
OO
R1-(OA1Jx-O-P=O (l)R 1 - (OA 1 J x -OP = O ( l)
OO
(A3O)2R3 (A 3 O) 2 R 3
worinwherein
R1, 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,R 1 , R 2 and R 3 may be the same or different and represent 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 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, (A2O)y und (A3O)2 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, (A2O )y und (A3O )z blockartig oder statistisch verteilt angeordnet sein können, undthe individual groups (OAi) x , (A 2 O) y and (A 3 O) 2 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 , (A 2 O) y and (A 3 O) z may be arranged block-wise or randomly distributed, and
x, y und z jeweils unabhängig voneinander eine Zahl von 10 bis 150, bevorzugt von 25 bis 120, besonders bevorzugt von 40 bis 120 und insbesondere bevorzugt von 51 bis 100, bedeuten, dadurch gekennzeichnet, dasseach of x, y and z independently represents a number from 10 to 150, preferably from 25 to 120, more preferably from 40 to 120, and most preferably from 51 to 100, characterized in that
a) Phosphorsäure oder ein Phosphorsäurederivat ausgewählt aus Orthophosphorsäure, Tetraphosphordecaoxid und Polyphosphorsäure mit alkoxylierten Alkoholen der Formel (II), (III) und (IV)a) phosphoric acid or a phosphoric acid derivative selected from orthophosphoric acid, tetraphosphorodecoxide and polyphosphoric acid with alkoxylated alcohols of the formula (II), (III) and (IV)
Rr(OAi)x-OH Formel (II)Rr (OAi) x -OH formula (II)
R2-(OA2)y-OH Formel (III)R 2 - (OA 2 ) y -OH formula (III)
R3-(OAa)2-OH Formel (IV)R 3 - (OAa) 2 -OH formula (IV)
wobei Ri, R2, R3, (OAi)x, (A2O)y und (A3O)2 die in Formel (I) genannten Bedeutungen besitzen,where R 1, R 2, R 3 , (OAi) x, (A 2 O) y and (A 3 O) 2 have the meanings given in formula (I),
b) im Molverhältnis Phosphorsäure bzw. Phosphorsäurederivat zu alkoxyliertem Alkohol von 1 : 2,5 bis 1 : 3,3,b) in the molar ratio phosphoric acid or phosphoric acid derivative to alkoxylated alcohol of 1: 2.5 to 1: 3.3,
c) bei 200 bis 240 0C, bevorzugt bei 220 bis 230 0C, umgesetzt wird.c) at 200 to 240 0 C, preferably at 220 to 230 0 C, is reacted.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass als Reaktand die Orthophosphorsäure eingesetzt wird.2. The method according to claim 1, characterized in that the orthophosphoric acid is used as the reactant.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die alkoxylierten Alkohole der Formeln (II), (III) und (IV) gleich oder verschieden sind und ausgewählt sind aus Ci6/iβ-Fettalkoholethoxylaten mit 10 bis 150 Ethylenoxid- Einheiten, bevorzugt mit 25 bis 120 Ethylenoxid-Einheiten, besonders bevorzugt Ci6/18-Fettalkoholethoxylat mit 25 Ethylenoxid-Einheiten, Ci6/iβ-Fettalkoholethoxylat mit 50 Ethylenoxid-Einheiten oder Ci6/18-Fettalkoholethoxylat mit 80 Ethylenoxid-Einheiten. 3. The method according to claim 1 or 2, characterized in that the alkoxylated alcohols of the formulas (II), (III) and (IV) are the same or different and are selected from Ci 6 / iβ fatty alcohol ethoxylates having 10 to 150 ethylene oxide units , preferably with 25 to 120 ethylene oxide units, more preferably Ci 6/18 fatty alcohol ethoxylate with 25 ethylene oxide units, Ci 6 / iβ fatty alcohol ethoxylate with 50 ethylene oxide units or Ci 6/18 fatty alcohol ethoxylate with 80 ethylene oxide units.
4. Verfahren nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass es ohne Verwendung eines Lösungsmittels durchgeführt wird.4. The method according to one or more of claims 1 to 3, characterized in that it is carried out without the use of a solvent.
5. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass es in Abwesenheit eines Katalysators durchgeführt wird.5. The method according to one or more of claims 1 to 4, characterized in that it is carried out in the absence of a catalyst.
6. Phosphorsäureester erhältlich nach einem Verfahren gemäß einem oder mehreren der Ansprüche 1 bis 5.6. Phosphoric acid esters obtainable by a process according to one or more of claims 1 to 5.
7. Phosphorsäureester nach Anspruch 6, dadurch gekennzeichnet, dass er chlorfrei ist. 7. Phosphoric acid ester according to claim 6, characterized in that it is chlorine-free.
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DE102007036188A1 (en) 2008-06-19
US8389756B2 (en) 2013-03-05
US8841475B2 (en) 2014-09-23
CN101918472B (en) 2012-08-29
WO2009015860A3 (en) 2009-08-20
WO2009015860A2 (en) 2009-02-05
JP2010535163A (en) 2010-11-18
US20110040116A1 (en) 2011-02-17
US20130158284A1 (en) 2013-06-20

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