EP1442003A1 - Procede de production de polyolalkylethers - Google Patents

Procede de production de polyolalkylethers

Info

Publication number
EP1442003A1
EP1442003A1 EP02783048A EP02783048A EP1442003A1 EP 1442003 A1 EP1442003 A1 EP 1442003A1 EP 02783048 A EP02783048 A EP 02783048A EP 02783048 A EP02783048 A EP 02783048A EP 1442003 A1 EP1442003 A1 EP 1442003A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
ether
polyol
sulfate
sulfates
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Withdrawn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
EP02783048A
Other languages
German (de)
English (en)
Inventor
Thomas Albers
Karl Heinz Schmid
Ansgar Behler
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.)
Cognis IP Management GmbH
Original Assignee
Cognis Deutschland GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Cognis Deutschland GmbH and Co KG filed Critical Cognis Deutschland GmbH and Co KG
Publication of EP1442003A1 publication Critical patent/EP1442003A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
    • 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
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • 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
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur

Definitions

  • the invention relates to a new process for the preparation of polyolalkyl ethers.
  • polyolalkyl ethers especially alkylglycerol ethers
  • polyols with strong bases are usually deprotonated and then reacted with alkyl (ether) sulfate powders or pastes in the presence of organic solvents.
  • the aqueous phase obtained in the reaction by washing the reaction mixture contains, in addition to unreacted polyols, a high proportion of sulfate, which is troublesome during further processing. For this reason, the unreacted polyols contained in the aqueous phase cannot be returned to the process.
  • the disposal of the aqueous phase which contains large amounts of the polyol, places a heavy burden on the wastewater through sulfates.
  • foam problems arise on the one hand during dewatering and on the other hand the alkyl (ether) sulfates tend to the pastes for more hydrolysis.
  • the object of the present invention was to provide a process for the preparation of polyolalkyl ethers, in the production of which the unreacted polyols in the resulting aqueous phase can be worked up and thus further processed due to the reduced sulfate content.
  • the polyolalkyl ethers should be produced in a particularly environmentally and health-friendly manner and thus the use of organic solvents should be avoided, thus by-products with organically bound chlorine should be avoided and the foam problems and susceptibility to hydrolysis when metering the alkyl (ether) sulfates should be reduced.
  • polyol alkyl ethers with a high monoalkyl polyol ether content are to be obtained by this process. Description of the invention
  • the present invention relates to a process for the preparation of polyol alkyl ethers, in which a polyol is deprotonated with a base, preferably alkali metal or alkaline earth metal oxides, carbonates or hydroxides
  • the deprotonated polyol after addition of a base, preferably alkali metal or alkaline earth metal oxides, carbonates or hydroxides, mixed with alkyl sulfate and the water formed is removed continuously from the reaction mixture, after carrying out the reaction the sulfate salt contained in the reaction product by adding 10 to 20 moles, preferably 11 to 15 and in particular 12 to 13 moles of water, per mole of alkyl (ether) sulfate, alkenyl (ether) sulfate or alkyl sulfuric acid precipitates at a temperature of 50 to 100 and preferably 80 to 90 ° C. and the polyol alkyl ether obtained in a manner known per se from the aqueous and solid phase.
  • a base preferably alkali metal or alkaline earth metal oxides, carbonates or hydroxides
  • polyol alkyl ethers can be prepared by reacting polyols with bases and with alkyl (ether) sulfates, alkenyl (ether) sulfates or sulfuric acid alkyl esters, and when they are worked up, the sulfate salt contained in the reaction mixture can be precipitated and filtered off by adding a defined amount of water ,
  • the polyol alkyl ethers thus obtained have a high content of monoalkyl polyol ethers.
  • the unreacted polyols in the aqueous phase are worked up more easily owing to the reduced sulfate content and can thus be made accessible to other applications or can be recycled back into the process as a starting component.
  • the addition of solvents to isolate the polyol alkyl ethers is not necessary.
  • Polyols that come into consideration here have at least two hydroxyl groups. Typical examples are
  • Alkylene glycols such as, for example, ethylene glycol, diethylene glycol, polyethylene glycols with an average molecular weight of 100 to 1,000 daltons, propylene glycol and polypropylene glycol;
  • Methyl compounds such as in particular trimethylol propane
  • the preferred polyols used are glycerol, alkylene glycols, technical oligoglycerol mixtures, methylol compounds, sugar alcohols and their addition products with ethylene oxide and / or propylene oxide, particularly preferably glycerol, diethylene glycol, diglycerol and other technical oligoglycerol mixtures, trimethylolpropane, xylitol and, in particular, glycerol.
  • Alkyl and / or alkenyl (ether) sulfates which are also frequently referred to as fatty alcohol (ether) sulfates, are to be understood as meaning the sulfation products of primary alcohols which follow the formula (I)
  • R 1 for a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 8 to 18 carbon atoms
  • A for a C2H 0 or CaH ⁇ O group
  • n for 0 or numbers from 1 to 10
  • X represents an alkali and / or alkaline earth metal or ammonium.
  • alkyl (ether) sulfates which can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, Cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol, as well as their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from the aniloxides and the synthesis products from the Roelens oxide to the synthesis products of the Roelens oxide ,
  • the sulfation products can preferably be in the form of their alkali salts and special of their sodium salts are used.
  • the alkyl and / or alkenyl (ether) sulfate preferably the sodium alkyl and / or alkenyl (ether) sulfate
  • Anhydrous in the sense of the invention means 0.01 to 5, preferably 0.1 to 3 and in particular 0.4 to 2% by weight of water.
  • the commercial products Lanette-E, Texapon-K-12-G, Texapon-K-12-P, Sulfopon-1218-G, Texapon-CPS and Texapon-EHS-P from Cognis are preferably used.
  • Sulfuric acid alkyl esters can be produced on an industrial scale by S0 3 - or chlorosulfonic acid (CSA) sulfation of fatty alcohol.
  • CSA chlorosulfonic acid
  • sulfuric acid alkyl esters which follow the formula (II)
  • R 2 is a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms
  • A is a C2H4O or CsHeO group and m is 0 or numbers from 1 to 10.
  • Typical examples are the sulfuric acid esters of capronic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, aryl alcohol alcohol, arylyl alcohol, petroyl alcohol, petroselyl alcohol, and aryl alcohol alcohol mixtures.
  • the sulfuric acid esters can have both a conventional and a narrow homolog distribution. Particularly preferred is the use of sulfuric acid alkyl esters based on adducts of technical C12 / 14 or G16 / 18 coconut fatty alcohol fractions as well as C ⁇ fatty alcohol, Ci2 fatty alcohol, Ci6 fatty alcohol and cis fatty alcohol.
  • acidic sulfuric acid alkyl esters in the process according to the invention has the advantage that the neutralization step with aqueous sodium hydroxide solution and subsequent dehydration to the alkyl (ether) sulfates does not have to be carried out in the run-up to the reaction with great technical effort, but rather the acidic sulfuric acid esters can be used directly.
  • the polyol alkyl ethers according to the invention in the production of which polyol / water mixtures, preferably glycerol / water mixtures, with a low sulfate salt content are obtained, are prepared by reacting polyol anions with alkyl and / or alkenyl (ether) sulfates or sulfuric urealkyl esters.
  • the polyol is initially introduced and slowly at a temperature of 110 to 130 ° C and preferably 120 ° C as the base alkali metal, alkaline earth metal oxides, carbonates or hydroxides and preferably alkali metal or alkaline earth metal hydroxides and in particular sodium hydroxide, preferably 25 to 50 wt. -%, added dropwise.
  • the water formed is continuously removed at 110 to 130.degree. C. and preferably 120.degree. C. during the dropping or after the dropping of the base.
  • the water formed during the reaction is removed at temperatures of 110 to 130 ° C. and preferably 120 ° C., if appropriate, by applying a vacuum of 150 to 10, preferably 130 to 20 and in particular 120 to 30 mbar.
  • a vacuum of 150 to 80 and in particular 120 to 100 mbar is preferably applied at the start of the water separation at the temperature listed above, and this is increased to 50 to 10 and in particular 30 to 15 mbar only at the end of the water separation.
  • the polyol (sum of polyol and deprotonated polyol) is then mixed with the alkyl and / or alkenyl (ether) sulfates.
  • the reaction with the alkyl and / or alkenyl (ether) sulfates takes place at a temperature of 150 to 220 and preferably 170 to 180 ° C.
  • the mixture is preferably stirred at this temperature for 7 to 10 and in particular 8 to 9 h.
  • the alkyl and / or alkenyl (ether) sulfate preferably the sodium alkyl and / or sodium alkenyl (ether) sulfate, preferably as granules or as a powder and in particular as granules, preferably in anhydrous form, can be added ,
  • the deprotonated polyol is mixed with alkali metal, alkaline earth metal oxides, carbonates or hydroxides and preferably alkali metal or alkaline earth metal hydroxides and in particular sodium hydroxide (50% strength aqueous solution) and with sulfuric acid alkyl esters and then in the deprotonation or neutralization water formed continuously at 110 to 130 and preferably 120 ° C, optionally removed by applying a vacuum as described above from the reaction mixture.
  • the reaction of the deprotonated polyol with the sulfuric alkyl esters is carried out at from 150 to 220 and preferably from 170 to 180.degree. For this purpose, it is preferably stirred at this temperature for 7 to 10 and in particular 8 to 9 h.
  • the reaction is controlled by determining the anionic surfactant content, which should be significantly below 5, preferably 3 and in particular 1% by weight, based on the active substance content.
  • the alkyl (ether) sulfates, alkylene (ether) sulfates or sulfuric acid alkyl esters and the polyol are preferably in a molar ratio of 1: 1 to 1:10, preferably 1: 2 to 1: 8 and in particular 1: 3 to 1: 6 used.
  • the base and the alkyl (ether) sulfates, alkylene (ether) sulfates or sulfuric acid alkyl esters are in a molar ratio of 0.9: 1 to 1.5: 1, preferably from 1.1: 1 to 1.4: 1 and in particular 1, 2: 1 to 1.3: 1. If the aqueous phase obtained in the reaction, which contains unreacted polyols, preferably glycerol, is used again in the process as starting polyols, a molar ratio of base to alkyl (ether) sulfates, alkylene (ether) is chosen. sulfates or sulfuric acid alkyl esters of from 0.9: 1 to 1.3: 1.
  • the reaction mixture is mixed with 10 to 20, preferably 11 to 15, mol of water and in particular 12 to 13 mol of water per mol of alkyl (ether) sulfate , Alkenyl (ether) sulfate or sulfuric acid alkyl esters and optionally additionally with 1 to 20 and preferably 5 to 10 ml of 10 to 70% and preferably 50% base (see above), preferably alkali metal hydroxide per mole of alkyl (ether) sulfate, alkenyl ( ether) sulfate or alkyl sulfuric acid ester mixed at a temperature of 50 to 100 and preferably 70 to 90 ° C.
  • the phases are then waited for and the resulting phases are separated.
  • the sulfate salt is first filtered off and then the polyol alkyl ether obtained is separated from the aqueous phase, or the polyol alkyl ether obtained is separated from the aqueous phase and the sulfate salt is then filtered off from the aqueous phase.
  • the aqueous phase obtained after working up which contains unreacted polyols, can be filtered in a manner known per se (removal of the precipitated sulfate) and dried and then added to the process according to the invention as the starting polyol.
  • the upper organic phase (polyol ether phase) is washed with 100 to 500, preferably 200 to 300 and in particular 250 ml of water per mol of alkyl (ether) sulfate, alkenyl (ether) sulfate or sulfuric acid alkyl esters at a temperature of 70 to 95 ° C. and again separate the phases.
  • a preferred reaction product contains - based on the total concentration - about 80 to 95 and preferably 90% by weight of polyol mono- and 20 to 5 and preferably 10% by weight of polyol dialkyl ether.
  • the sulfate contents of the polyol alkyl ethers are preferably in the range from 0 to 5 and in particular 0.1 to 2% by weight, based on the active substance content.
  • polyolalkyl ethers according to the invention can be used in all surface-active preparations known to the person skilled in the art, such as preferably in detergents and dishwashing detergents, household cleaners and cosmetic and / or pharmaceutical preparations and in particular in cosmetic preparations for hair and body care and in cleaning agents.
  • These surface-active preparations can be used as further auxiliaries and additives pearlescent waxes, consistency agents, thickeners, superfatting agents, stabilizers, silicone compounds, fats, waxes, lecithins, phospholipids, antioxidants, deodorants, antiperspirants, antidandruff agents, swelling agents, tyrosine inhibitors, preservatives, hydrotropes, solubilizers, hydrotropes Perfume oils, dyes, other surfactants and the like contain.
  • Cosmetic and / or pharmaceutical preparations include, for example, oral and dental care products, hair shampoos, hair lotions, bubble baths, shower baths, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions and emulsions.
  • the reaction mixture is mixed with 225 ml of water and 5 ml of 50% sodium hydroxide solution at a temperature of 90 ° C. and the phases are then waited for. The resulting phases are then separated.
  • the lower phase is filtered to remove the precipitated sodium sulfate and the upper organic phase (glycerol ether phase) is washed with 250 ml of water at a temperature of 90 ° C. and the phases are separated again.
  • the organic phase is freed from water by distillation by means of vacuum distillation.
  • the C12 glycerol ether remains as a distillation residue.
  • the product contains approx. 90% monolaurylglycerol ether and 10% dilaurylglycerol ether.
  • the Re ⁇ control action is performed on the definition of Anionentensidgehaltes which is after 8 hours of reac tion time ⁇ well below 1%.
  • the reaction mixture is mixed with 225 ml of water and 5 ml of 50% sodium hydroxide solution at a temperature of 90 ° C. and the phases are then waited for. The resulting phases are then separated.
  • the lower phase is filtered to remove the precipitated sodium sulfate and the upper organic phase (glycerol ether) was washed with 250 ml of water having a temperature of 90 ° C and times ⁇ but the phases separated.
  • Vacuum distillation removes water from the organic phase by distillation.
  • Ci6 / 18 glycerol ether remains in the distillation residue.
  • the product contains approx. 70% Mono-Ci6 / i8-glycerin ether and approx. 16% Di-Cie / i ⁇ -glycerin ether. 3.
  • the reaction mixture is mixed with 225 ml of water and 5 ml of 50% sodium hydroxide solution at a temperature of 90 ° C. and the phases are then waited for. The resulting phases are then separated.
  • the lower phase is filtered to separate the precipitated sodium sulfate and the upper organic phase (glycerol ether phase) is washed with 250 ml of water at a temperature of 90 ° C. and the phases are separated again.
  • the organic phase is freed from water by distillation by means of vacuum distillation.
  • the Ci2 glycerol ether remains as a distillation residue.
  • the product contains approx. 90% monolaurylglycerol ether and 10% dilaurylglycerol ether.
  • Ci2 sulfuric acid ester made from C12 fatty alcohol by sulfation with SO3 are mixed in a mixture of 400 g (4.37 mol) of Na glycerinate (made from 4 37 mol of glycerol and 0.87 mol of 50% sodium hydroxide solution) and 64 g (0.8 mol) of 50% sodium hydroxide solution were added dropwise.
  • the water contained is removed under vacuum.
  • the reaction mixture is then stirred at 180 ° C. for 8 h.
  • the reaction is controlled by determining the anionic surfactant content. This is below 3% after 8 hours.
  • the reaction mixture is mixed with 225 ml of water and 5 ml of 50% sodium hydroxide solution at a temperature of 90 ° C. and the phases are then waited for. The resulting phases are then separated.
  • the lower phase is filtered to separate the precipitated sodium sulfate and the upper organic phase (glycerol ether phase) is washed with 250 ml of water at a temperature of 90 ° C. and the phases are separated again.
  • the organic phase is freed from water by distillation by means of vacuum distillation.
  • the Ci2 glycerol ether remains as a distillation residue.
  • the product contains approx. 80% monolaurylglycerol ether and 8% dilaurylglycerol ether.
  • the vacuum is reduced to 10 mbar.
  • the Na glycerinate thus formed is mixed with 300 g (1 mol) of Texapon® K12G (sodium lauryl sulfate granules), suspended, heated to 180 ° C. and stirred at this temperature for 8 hours.
  • the reaction is controlled by determining the anionic surfactant content. After 8 hours, this is clearly below 1%.
  • the reaction mixture is mixed with 225 ml of water and 5 ml of 50% sodium hydroxide solution at a temperature of 90 ° C. and the phases are then waited for. The resulting phases are then separated.
  • the lower phase is filtered to separate the precipitated sodium sulfate and the upper organic phase (glycerol ether phase) is washed with 250 ml of water at a temperature of 90 ° C. and the phases are separated again.
  • the organic phase is freed from water by distillation by means of vacuum distillation.
  • the Ci2 glycerol ether remains as a distillation residue.
  • the product contains approx. 80% monolaurylglycerol ether and approx. 10% dilaurylglycerol ether.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Dermatology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production de polyolalkyléthers, consistant à déprotoner un polyol à l'aide d'une base et (a) à éliminer en continu l'eau, ainsi produite, contenue dans le mélange réactionnel puis à faire réagir le polyol déprotoné avec des sulfates d'alkyl- et/ou d'alcényl(éther) ou (b) à mélanger le polyol déprotoné, après l'ajout d'une base, avec des alkylesters d'acide sulfurique et à éliminer en continu l'eau produite dudit mélange réactionnel. Ce procédé consiste, après la mise en réaction, à précipiter le sel de sulfate, obtenu dans le produit de cette réaction, en ajoutant 10 à 20 moles d'eau par mole de sulfate d'alkyl(éther), de sulfate d'alcényl(éther) ou d'alkylester d'acide sulfurique à une température de 50 à 100 DEG C, puis à séparer le polyolalkyléther obtenu de la phase aqueuse et solide, de manière connue en soi.
EP02783048A 2001-11-09 2002-10-31 Procede de production de polyolalkylethers Withdrawn EP1442003A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10155058A DE10155058B4 (de) 2001-11-09 2001-11-09 Verfahren zur Herstellung von Polyolalkylethern
DE10155058 2001-11-09
PCT/EP2002/012145 WO2003040072A1 (fr) 2001-11-09 2002-10-31 Procede de production de polyolalkylethers

Publications (1)

Publication Number Publication Date
EP1442003A1 true EP1442003A1 (fr) 2004-08-04

Family

ID=7705174

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02783048A Withdrawn EP1442003A1 (fr) 2001-11-09 2002-10-31 Procede de production de polyolalkylethers

Country Status (5)

Country Link
US (1) US20040254404A1 (fr)
EP (1) EP1442003A1 (fr)
JP (1) JP2005507951A (fr)
DE (1) DE10155058B4 (fr)
WO (1) WO2003040072A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004022252A1 (de) * 2004-05-04 2005-12-01 Cognis Ip Management Gmbh Glycerinethergemisch, dieses enthaltende kosmetische Zusammensetzung sowie Verfahren zu dessen Herstellung
TWI565692B (zh) * 2010-10-06 2017-01-11 大同大學 高度甲基化甘油（含氧燃料）的製程與純化技術

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE615171C (de) * 1932-03-27 1935-06-28 Henkel & Cie Gmbh Verfahren zur Herstellung von hoeheren AEthern
US2339047A (en) * 1941-08-30 1944-01-11 Kay Fries Chemicals Inc Recovery of excess glycerin in residues from the preparation of mono- and di-methyl ethers of glycerol
DE4118568A1 (de) * 1991-06-06 1992-12-10 Henkel Kgaa Verfahren zur herstellung von glycerinethern
JPH06293688A (ja) * 1993-04-09 1994-10-21 Kao Corp ポリヒドロキシモノアルキルエーテルの製造法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03040072A1 *

Also Published As

Publication number Publication date
JP2005507951A (ja) 2005-03-24
DE10155058B4 (de) 2005-02-24
DE10155058A1 (de) 2003-05-22
US20040254404A1 (en) 2004-12-16
WO2003040072A1 (fr) 2003-05-15

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