EP2178945A2 - Verfahren zur herstellung alkoxylierter phosphorsäuretriester - Google Patents
Verfahren zur herstellung alkoxylierter phosphorsäuretriesterInfo
- 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- Withdrawn
Links
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 20
- -1 phosphoric acid triesters Chemical class 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 150000001298 alcohols Chemical class 0.000 claims abstract description 10
- 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 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 150000005691 triesters Chemical class 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000005690 diesters Chemical class 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 description 1
- BTFJIXJJCSYFAL-UHFFFAOYSA-N arachidyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229960000735 docosanol Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000047 product Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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%
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Medicinal Chemistry (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Public Health (AREA)
- Polymers & Plastics (AREA)
- Birds (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Cosmetics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102007036188A DE102007036188A1 (de) | 2007-08-02 | 2007-08-02 | Verfahren zur Herstellung alkoxylierter Phosphorsäuretriester |
| PCT/EP2008/006222 WO2009015860A2 (de) | 2007-08-02 | 2008-07-29 | Verfahren zur herstellung alkoxylierter phosphorsäuretriester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2178945A2 true EP2178945A2 (de) | 2010-04-28 |
Family
ID=39399887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP08785170A Withdrawn EP2178945A2 (de) | 2007-08-02 | 2008-07-29 | Verfahren zur herstellung alkoxylierter phosphorsäuretriester |
Country Status (6)
| Country | Link |
|---|---|
| US (2) | US8389756B2 (enrdf_load_stackoverflow) |
| EP (1) | EP2178945A2 (enrdf_load_stackoverflow) |
| JP (1) | JP2010535163A (enrdf_load_stackoverflow) |
| CN (1) | CN101918472B (enrdf_load_stackoverflow) |
| DE (1) | DE102007036188A1 (enrdf_load_stackoverflow) |
| WO (1) | WO2009015860A2 (enrdf_load_stackoverflow) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007036187A1 (de) * | 2007-08-02 | 2008-06-19 | Clariant International Limited | Alkoxylierte Phosphorsäuretriester mit hohem Alkoxylierungsgrad |
| DE102007036186A1 (de) * | 2007-08-02 | 2008-06-19 | Clariant International Limited | Phosphorsäureester enthaltend über Polyol-Einheiten verbrückte Phosporatome |
| EP2176349A2 (de) * | 2007-08-02 | 2010-04-21 | Clariant Finance (BVI) Limited | Phosphorsäureester enthaltend über diol-einheiten verbrückte phosphoratome |
| DE102008006857A1 (de) * | 2008-01-31 | 2009-01-29 | Clariant International Ltd. | Zusammensetzungen enthaltend Phosphorsäureester und hydrophob modifizierte vernetzte, anionische Polymere |
| WO2012019688A2 (de) | 2010-07-27 | 2012-02-16 | Clariant International Ltd | Zusammensetzungen enthaltend wasserstoffperoxid oder wasserstoffperoxid freisetzende substanzen |
| DE102010054918A1 (de) | 2010-12-17 | 2011-06-30 | Clariant International Ltd. | Zusammensetzungen enthaltend Wasserstoffperoxid oder Wasserstoffperoxid freisetzende Substanzen |
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| US2895787A (en) * | 1954-12-30 | 1959-07-21 | American Viscose Corp | Process of producing all skin rayon |
| NL248754A (enrdf_load_stackoverflow) * | 1959-02-24 | |||
| CA1114394A (en) | 1978-06-05 | 1981-12-15 | Paritosh M. Chakrabarti | Phosphoric acid esters of poly (2-10) ethyleneoxy n-butane 1,4 diols in synthetic aquous based metal working fluid compositions |
| US4180532A (en) * | 1978-06-05 | 1979-12-25 | Gaf Corporation | Phosphoric acid esters of poly(2-10)ethyleneoxy n butane 1,4-diols |
| US4220611A (en) * | 1978-06-29 | 1980-09-02 | Sandoz, Inc. | Polyoxyalkylene bridged phosphate esters |
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| CN1930177A (zh) | 2004-03-17 | 2007-03-14 | 克莱里安特财务(Bvi)有限公司 | 液体纺织品预处理剂 |
| DE102004046356A1 (de) * | 2004-09-24 | 2006-03-30 | Clariant Gmbh | Verfahren zur Herstellung von Alk(en)ylphosphorsäureestersalzen |
| DE102004047092A1 (de) | 2004-09-29 | 2006-03-30 | Clariant Gmbh | Agrochemische Zusammensetzung enthaltend Phosphorsäureester |
| DE102007036187A1 (de) * | 2007-08-02 | 2008-06-19 | Clariant International Limited | Alkoxylierte Phosphorsäuretriester mit hohem Alkoxylierungsgrad |
| EP2176349A2 (de) * | 2007-08-02 | 2010-04-21 | Clariant Finance (BVI) Limited | Phosphorsäureester enthaltend über diol-einheiten verbrückte phosphoratome |
| DE102007036186A1 (de) * | 2007-08-02 | 2008-06-19 | Clariant International Limited | Phosphorsäureester enthaltend über Polyol-Einheiten verbrückte Phosporatome |
| JP2010535162A (ja) * | 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 | アルコキシル化されたリン酸トリエステルを含む水性組成物 |
| DE102008006857A1 (de) * | 2008-01-31 | 2009-01-29 | Clariant International Ltd. | Zusammensetzungen enthaltend Phosphorsäureester und hydrophob modifizierte vernetzte, anionische Polymere |
-
2007
- 2007-08-02 DE DE102007036188A patent/DE102007036188A1/de not_active Withdrawn
-
2008
- 2008-07-29 WO PCT/EP2008/006222 patent/WO2009015860A2/de active Application Filing
- 2008-07-29 CN CN2008801015825A patent/CN101918472B/zh not_active Expired - Fee Related
- 2008-07-29 JP JP2010518556A patent/JP2010535163A/ja active Pending
- 2008-07-29 EP EP08785170A patent/EP2178945A2/de not_active Withdrawn
- 2008-07-29 US US12/671,809 patent/US8389756B2/en not_active Expired - Fee Related
-
2013
- 2013-02-05 US US13/759,827 patent/US8841475B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2009015860A3 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009015860A3 (de) | 2009-08-20 |
| CN101918472B (zh) | 2012-08-29 |
| JP2010535163A (ja) | 2010-11-18 |
| WO2009015860A2 (de) | 2009-02-05 |
| US8389756B2 (en) | 2013-03-05 |
| CN101918472A (zh) | 2010-12-15 |
| DE102007036188A1 (de) | 2008-06-19 |
| US8841475B2 (en) | 2014-09-23 |
| US20110040116A1 (en) | 2011-02-17 |
| US20130158284A1 (en) | 2013-06-20 |
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