EP1866084A2 - Procede de fabrication de catalyseurs dmc - Google Patents

Procede de fabrication de catalyseurs dmc

Info

Publication number
EP1866084A2
EP1866084A2 EP06708667A EP06708667A EP1866084A2 EP 1866084 A2 EP1866084 A2 EP 1866084A2 EP 06708667 A EP06708667 A EP 06708667A EP 06708667 A EP06708667 A EP 06708667A EP 1866084 A2 EP1866084 A2 EP 1866084A2
Authority
EP
European Patent Office
Prior art keywords
acid
acids
catalysts
dmc catalysts
dmc
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Withdrawn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
EP06708667A
Other languages
German (de)
English (en)
Inventor
Edward Bohres
Michael Triller
Raimund Ruppel
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP1866084A2 publication Critical patent/EP1866084A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J27/26—Cyanides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • 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
    • C08G65/26—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 from cyclic ethers and other compounds
    • 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
    • C08G65/26—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 from cyclic ethers and other compounds
    • C08G65/2642—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 from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's

Definitions

  • the invention relates to a process for the preparation of multimetal cyanide compounds, also referred to as DMC catalysts.
  • DMC catalysts are used in the preparation of polyether alcohols by addition of alkylene oxides to H-functional starter substances, especially alcohols.
  • the space-time yield in the production can be increased.
  • the polyether alcohols produced by this process are characterized by a reduced content of unsaturated constituents.
  • the preparation of DMC catalysts is usually carried out by reacting a hexacyanometallate compound, preferably hexacyanocobaltate or hexacyanocobaltic acid, with a metal salt.
  • a hexacyanometallate compound preferably hexacyanocobaltate or hexacyanocobaltic acid
  • metal salt preferably hexacyanometallic acids
  • hexacyanometallic acids are usually prepared by means of ion exchangers, as described in EP 862 997.
  • a Hexacyanometallatsalz is dissolved in water and acidified with sulfuric acid.
  • an organic solvent for example methanol, is added, which leads to the precipitation of potassium sulfate.
  • This is filtered off and the thus obtained solution of Hexacyanometallatklare by combining with an aqueous solution of the metal salt component to the D MC catalyst reacted.
  • ligands and / or organic additives may be present or added.
  • This process represents an alternative to the recovery of hexacyanometallic acid by ion exchange.
  • Removal of potassium sulfate by filtration, like ion exchange, is an additional process step, in this case even involving the handling of a solid
  • an organic solvent must be used for precipitation, which leads to additional costs and it can not be ruled out that at least some of the salt formed remains in the catalyst.
  • WO 99/56874 describes a catalyst which is treated with a protic acid. The addition of the acid occurs during or after the catalyst synthesis, but in any case only after the precipitation of the metal salt DMC compound and cyanometalate component. Polyetherols having a reduced high molecular weight fraction can be prepared with these catalysts.
  • the processes described require an additional process step of treating the precipitated DMC compound with a mineral acid. If the acid remains in the DMC catalyst as described in US Pat. No. 4,477,589, corrosion problems may arise, for example with hydrochloric acid, which is described as being preferred in US Pat. No. 4,477,589. So you have to design the reactors for polyol production corrosion resistant, which leads to higher costs. Furthermore, it can not be ruled out that the acid which has only been adsorbed on the DMC catalyst and thus becomes more volatile passes into the product prepared by means of DMC catalyst. For chlorine-containing acids, this could be problematic due to the possible formation of organochlorine compounds. For example, it can not be ruled out that the hydrochloric acid catalyzes an ether cleavage and thus an undesired reaction, in which organochlorine compounds in turn could also be formed.
  • the object of the present invention was to find a simplified process for the preparation of DMC catalysts, which leads to DMC catalysts having a high catalytic activity.
  • DMC catalysts having a high catalytic activity can be obtained when the reaction of the cyanometallate compound with the metal salt takes place in the presence of a Bronsted acid.
  • the invention thus provides a process for preparing DMC catalysts by reacting cyanometalate compounds, preferably cyanometalate salts, in particular alkali metal or alkaline earth metal salts, with metal salts, characterized in that the reaction is carried out in the presence of a Bronsted acid.
  • cyanometalate compounds preferably cyanometalate salts, in particular alkali metal or alkaline earth metal salts
  • the invention furthermore relates to the DMC catalysts prepared by the process according to the invention.
  • the metal salt and the cyanometallate compound are reacted with each other in the form of their solutions, in particular as aqueous solutions.
  • the invention furthermore relates to a process for preparing polyether alcohols by adding alkylene oxides to H-functional starter substances using the DMC catalysts prepared by the novel process.
  • all water-soluble and room temperature stable mineral and carboxylic acids can be used as Bronsted acids.
  • carboxylic acids which may contain one or more carboxyl groups and up to 20 carbon atoms are carboxylic acids substituted with electronegative elements, for example chloroacetic acids, fluoroacetic acids or halogenated benzoic acids.
  • mineral acids are used.
  • These are preferably selected from the group containing sulfuric acid, hydrochloric acid, sulfurous acid , alkyl, aryl and halosulfonic acids HSO 3 X, where X is halogen, alkyl having an alkyl group of 1 to 20 carbon atoms, aryl, preferably phenyl or naphthyl , di Sulfuric acid, hydrochloric acid, chloric acid, perchloric acid, hydrobromic acid, hydrazoic acid, hydrofluoric acid, hydrosilicic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, tetrafluoroboric acid, hexafluorophosphoric acid, nitric acid, nitrous acid.
  • X is halogen, alkyl having an alkyl group of 1 to 20 carbon atoms, aryl, preferably phenyl or naphthyl , di Sulfuric acid, hydrochloric acid, chloric acid, perchloric acid, hydrobromic acid,
  • sulfuric acid alkyl, aryl and halosulfonic, hydrochloric, perchloric, hydrobromic, hydroiodic, hydrofluoric, phosphoric, nitric, most preferably sulfuric and hydrochloric.
  • the acid is preferably added in an amount such that the pH after DMC precipitation is between 3 and 6, preferably between 4 and 6.
  • the acid can be added to at least one of the starting compounds or both or fed to the reaction vessel as a separate stream.
  • the acid is added to the hexacyanometallate compound. It is essential that the acid must already be present at the beginning of the reaction, that is to say when the solution of the metal salt is combined with the solution of the cyanometalate compound.
  • the preparation of the multimetal according to the invention takes place in the usual manner, wherein, as stated, the reaction takes place in the presence of a Brönsted acid.
  • an aqueous solution of a Cyanometallatharm, in particular a Cyanometallat salt, combined with the aqueous solution of a metal salt. in this connection is usually worked with a stoichiometric excess of the metal salt.
  • the molar ratio of the metal ion to the cyanometalate component is from 1.1 to 7.0, preferably from 1.2 to 5.0 and particularly preferably from 1.3 to 3.0. It is advantageous to provide the Cyanometallatains together with the Brönsted acid and add the metal salt solution, but it can also be reversed procedure. During and after the combination of the educt solutions, thorough mixing, for example by stirring, is necessary.
  • the content of the cyanometallate compound in the aqueous solution is from 0.1 to 30% by weight, preferably from 0.1 to 20% by weight, in particular from 0.2 to 10% by weight.
  • the content of the metal salt component in the metal salt solution, based on the mass of metal salt solution is 0.1 to 50 wt .-%, preferably 0.2 to 40 wt .-%, in particular 0.5 to 30 wt .-%.
  • At least one of the aqueous solutions of the starting materials contains a ligand containing heteroatoms, as denoted and explained as L in the general formula (I).
  • the ligands containing heteroatoms can also be added to the resulting suspension only after the two starting materials have been combined, and good mixing must also be ensured here.
  • the content of the ligands containing heteroatoms, if such compounds are used, in the suspension formed after the precipitation should be 1 to
  • the surface-active substances are generally already introduced into at least one of the two solutions or preferably added during and / or directly after the precipitation.
  • the content of surface-active substances in the precipitation solution is preferably between 0.01 and 40% by weight, in particular between 0.05 and 30% by weight.
  • a further preferred embodiment provides that the surface-active substances are distributed proportionally to the two educt solutions.
  • the reaction of the metal salt with the cyanometalate compound takes place in two stages.
  • a catalytically inactive, in particular cubic, phase of the multimetal cyanide compound is first prepared and subsequently converted by recrystallization into a catalytically active phase of the multimetal cyanide compound.
  • the recrystallization can be carried out by various measures. This makes it possible to reduce the post-implementation pension add further educt solutions, in particular the solution of the metal salt. Another possibility is to change the temperature of Desitlsuspension after completion of precipitation, in particular to heat the suspension. Another possibility is to add further heteroatoms-containing ligands and / or surface-active substances to the precipitation suspension after completion of the precipitation.
  • a particularly crystalline multimetal cyanide compound is first prepared, as described, for example, in WO 99/16775. This can then be converted into the multimetal cyanide compound according to the invention in a further step, for example by a temperature treatment, preferably in the presence of an inert gas.
  • the multimetal cyanide compound can be separated from the precipitation suspension and dried.
  • the multimetal cyanide compound may also be subjected to the temperature treatment in the precipitation suspension.
  • the multimetal cyanide compound prepared by conventional methods can be added to the starting substance used for the preparation of the polyether alcohols and the mixture subjected to a temperature treatment, optionally under vacuum and / or by passing an inert gas, the temperature treatment.
  • the temperature treatment is preferably carried out at a temperature in the range between 90 and 200 ° C., in particular between 100 and 160 ° C.
  • the precipitated multimetal cyanide compound is separated from the precipitation suspension. This can be done by centrifugation or preferably by filtration. The separated precipitate is washed once or several times, preferably with water. It is also possible to add organic ligand and / or a surface-active compound to the wash water.
  • the multimetal cyanide catalysts prepared by the process according to the invention have the general formula:
  • M 1 is a metal ion selected from the group consisting of Zn 2+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Ni 2+ , Mn 2+ , Sn 2+ , Sn 4+ , Pb 2+ , Mo 4+ , Mo 6+ , Al 3+ , V 4+ , V 5+ , Sr 2+ , W 4+ , W 6+ , Cr 2+ , Cr 3+ , Cd 2+ , Cu 2+ , La 3+ , Ce 3+ , Ce 4+ , Eu 3+ , Mg 2+ , Ti 3+ , Ti 4+ , Ag + , Rh 2+ , Ru 2+ , Ru 3+ , Pd 2+ , preferably Zn 2+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , M 2 is a metal ion selected from the group consisting of Fe 2+ , Fe 3+ , Co 2+ , Co
  • A is an anion selected from the group comprising halide, hydroxide, sulfate, hydrogensulfate, carbonate, bicarbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate, nitrosyl, phosphate, hydrogen phosphate or dihydrogen phosphate
  • X is an anion selected from the group comprising halide, hydroxide, sulfate, hydrogensulfate, carbonate, bicarbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate or nitrite (NO 2 ' ),
  • L is a water-miscible ligand selected from the group comprising alcohols, aldehydes, ketones, ethers, polyethers, esters, polyesters, polycarbonate, ureas, amides, nitriles, sulfides or mixtures thereof,
  • P is an organic additive selected from the group comprising polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylamide-co-maleic acid), polyacrylonitrile, polyalkyl acrylates, polyalkyl methacrylates , Polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyCN-vinylpyrrolidone-co-acrylic acid), polyvinyl methyl ketone, poly (4-vinylphenol), poly (acrylic acid-co-styrene), oxazoline polymers, polyalkyleneimines, Maleic acid and maleic anhydride copolymer, hydroxyethyl cellulose, polyacetates, ionic surfaces and surface-
  • a, b, d, g and n are integers or fractions greater than zero
  • c, f, e, h and k are integers or fractions greater than or equal to zero
  • a, b, c and d, and g and n are selected so that the electroneutrality is ensured.
  • the DMC catalysts are, as described, preferably by reaction of metal salts of the general formula M 1 a X n with Cyanometallattagen the general my formula M 3 a [M 2 (CN) b (A) c ] d , wherein M 3 is alkali or alkaline earth metals and the other symbols have the meaning described above, prepared.
  • the catalysts prepared by the process according to the invention may be crystalline or amorphous. In the case where k is zero, crystalline double metal cyanide compounds are preferred. In the case where k is greater than zero, both crystalline, partially crystalline, and substantially amorphous catalysts are preferred.
  • DMC catalysts produced by the process according to the invention there are various preferred embodiments.
  • a preferred embodiment is catalysts of the formula (I) in which k is greater than zero.
  • the preferred catalyst then contains: a) at least one multimetal cyanide compound b) at least one organic ligand c) at least one organic additive P.
  • k is zero, optionally e is also zero, and X is exclusively carboxylate, preferably formate, acetate and propionate.
  • DMC catalysts are described, for example, in WO 99/16775. In this embodiment, crystalline double metal cyanide catalysts are preferred.
  • f, e and k are equal to zero.
  • DMC catalysts containing a water-miscible organic ligand usually in amounts of from 0.5 to 30% by weight, and an organic additive usually in amounts of from 5 to 80% by weight, as in WO 98/06312 described.
  • the catalysts can be prepared with stirring, as described in US Pat. No. 5,158,922, preferably with vigorous stirring, for example 24,000 rpm with a Turrax.
  • DMC catalysts are prepared with organic sulfones of the general form RS (O) 2 -R or sulfoxides of the general form RS (O) -R as an organic complexing agent. Advantages of the catalyst include short induction times and moderate exothermicity in the addition of the alkylene oxides.
  • RS (O) 2 -R organic sulfones of the general form RS (O) 2 -R or sulfoxides of the general form RS (O) -R as an organic complexing agent.
  • Advantages of the catalyst include short induction times and moderate exothermicity in the addition of the alkylene oxides.
  • DMC catalysts are synthesized by an "Incipient Wetness Method.” These catalysts can likewise be prepared by the process according to the invention.
  • the preparation of polyether alcohols using the DMC catalysts prepared by the process according to the invention is carried out, as stated, by adding alkylene oxides using the catalysts described to H-functional starter substances.
  • alkylene oxides it is possible to use all known alkylene oxides, for example ethylene oxide, propylene oxide, butylene oxide, styrene oxide.
  • the alkylene oxides used are ethylene oxide, propylene oxide and mixtures of the compounds mentioned.
  • H-functional compounds are used.
  • alcohols having a functionality of 1 to 8, preferably 2 to 8, are used.
  • Alcohols having a functionality of 2 to 6, in particular 2 and 3 are used as starting substances for the preparation of polyether alcohols which are used for flexible polyurethane foams. Examples are ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol.
  • alkylene oxides by means of DMC catalysts, it is advantageous to use together with or in place of the alcohols mentioned their reaction products with alkylene oxides, in particular propylene oxide.
  • Such compounds preferably have a molecular weight of up to 1000 g / mol.
  • the addition of the alkylene oxides in the preparation of these reaction products can be carried out with any catalysts, for example with basic catalysts.
  • the polyether alcohols for the production of flexible polyurethane foams usually have a hydroxyl number in the range between 20 and 100 mg KOH / g.
  • the entire starting substance is initially charged and after activation the alkylene oxide is added.
  • difunctional alcohols are used as starter substances.
  • carrier oils are used as starting substances monofunctional alcohols having 5 to 20 carbon atoms in the main chain.
  • the addition of the alkylene oxides in the preparation of the polyether used for the process according to the invention can be carried out according to the known methods. It is thus possible that the polyether alcohols contain only one alkylene oxide. When using a plurality of alkylene oxides, a so-called block-wise addition in which the alkylene oxides are added one after the other in succession, or a so-called statistical addition, in which the alkylene oxides are added together, possible. It is also possible to incorporate blockwise as well as random sections into the polyether chain in the preparation of the polyether alcohols. For the preparation of surface-active compounds and carrier oils, the addition of the alkylene oxides takes place mostly in blocks.
  • these polyether alcohols Preferably, these polyether alcohols have a propylene oxide block at the chain end.
  • Polyurethane alcohols having a high content of primary hydroxyl groups and an ethylene oxide end block in an amount of ⁇ 20% by weight, based on the weight of the polyether alcohol are used in particular for the production of flexible polyurethane foams.
  • polyetherols for flexible foams produced exclusively by means of DMC catalysis it is also possible to use the preparation processes for alkoxylation described in WO 01/44347 and the polyetherols resulting therefrom.
  • the addition of the alkylene oxides is carried out under the usual conditions, at temperatures in the range of 60 to 180 0 C, preferably between 90 to 140 0 C, in particular between 100 to 130 ° C and pressures in the range of 0 to 20 bar, preferably in the range of 0 to 10 bar and in particular in the range of 0 to 5 bar.
  • the mixture of starting substance and DMC catalyst can be pretreated by stripping before starting the alkoxylation according to the teaching of WO 98/52689.
  • alkylene oxides of the polyether alcohol After completion of the addition of the alkylene oxides of the polyether alcohol is worked up by conventional methods by the unreacted alkylene oxides and volatile constituents are removed, usually by distillation, steam or gas stripping and other methods of deodorization. If necessary, filtration can also be carried out.
  • polyether alcohols thus prepared can be used, for example, for the preparation of polyurethanes, as surfactants or as carrier oils.
  • polyether alcohols can be prepared which have very good properties.
  • the narrow molecular weight distribution results in a low product viscosity and a low content of high molecular weight components.
  • the induction time at the start of the reaction of the alkoxylation is significantly reduced, and the reaction on runs at lower total pressures and lower concentrations of free alkylene oxide.
  • DMC catalysts Compared with the process described in the prior art for the preparation of DMC catalysts, in which a hexacyanometallic acid is first prepared in a separate step, a process step is thus saved.
  • the catalytic activity is comparable to or better than DMC catalysts, hereinafter called conventional DMC catalysts, obtained from the reaction of H 3 [Co (CN) 6 ] prepared by ion exchange or salt metathesis with metal salt.
  • the DMC catalysts prepared by the process according to the invention lead in the reaction of starter alcohols with alkylene oxides polyether alcohols of excellent quality, such as low viscosity, narrow molecular weight distribution, and a low content of high molecular weight fractions that are comparable or better than polyols ole, with conventional DMC Catalysts were synthesized.
  • the new, improved DMC catalysts do not contain any acid as an ingredient.
  • Example 3 The procedure was as in Example 1, except that instead of 100g Pluronic ® PE 6200 were 40 g Lutensol ® AP20 BASF AG used.
  • 100g Pluronic ® PE 6200 were 40 g Lutensol ® AP20 BASF AG used
  • Example 4
  • Example 2 The procedure was as in Example 1, except that instead of 100g Pluronic ® PE 6200 were 40 g Lutensol ® AP ⁇ BASF AG used
  • a glycerol propoxylate molecular weight about 900 g / mol (hereinafter called VP900) with the appropriate amount of DMC catalyst by means of an Ultraturrax device for 5 minutes finely dispersed.
  • the reactor was sealed and evacuated at a temperature of 100 0 C for two hours at 3 mbar.
  • 36 g of propylene oxide were metered in within 2 minutes and the course of the pressure and temperature was recorded.
  • the reaction product was discharged from the autoclave at 100 ° C. after inerting with nitrogen and degassing at 10 mbar, and the yield was determined. From the recorded curves, the time to the occurrence of the maximum determined was taken as a measure of the activity.
  • the colorless, clear liquid obtained had the following characteristics: OHN 49.0 mg KOH / g, acid number 0.034 mg KOH / g, viscosity (25 ° C.) 577 mPas, iodine value 0.04 g 12/100 g.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Toxicology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Polyethers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé de fabrication de catalyseurs DMC par réaction de composés de cyanométallates, de préférence de sels de cyanométallates, notamment de sels d'alcalins ou d'alcalino-terreux, avec des sels de métaux, caractérisé en ce que la réaction est réalisée en présence d'un acide de Brönstedt.
EP06708667A 2005-03-10 2006-03-07 Procede de fabrication de catalyseurs dmc Withdrawn EP1866084A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005011581A DE102005011581A1 (de) 2005-03-10 2005-03-10 Verfahren zur Herstellung von DMC-Katalysatoren
PCT/EP2006/060517 WO2006094979A2 (fr) 2005-03-10 2006-03-07 Procede de fabrication de catalyseurs dmc

Publications (1)

Publication Number Publication Date
EP1866084A2 true EP1866084A2 (fr) 2007-12-19

Family

ID=36477234

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06708667A Withdrawn EP1866084A2 (fr) 2005-03-10 2006-03-07 Procede de fabrication de catalyseurs dmc

Country Status (7)

Country Link
US (1) US7811958B2 (fr)
EP (1) EP1866084A2 (fr)
JP (1) JP5329217B2 (fr)
KR (1) KR20070116249A (fr)
CN (1) CN101300074B (fr)
DE (1) DE102005011581A1 (fr)
WO (1) WO2006094979A2 (fr)

Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005057895A1 (de) * 2005-12-02 2007-06-06 Basf Ag Verfahren zur Herstellung von Multimetallcyanidverbindungen
WO2010072769A1 (fr) 2008-12-23 2010-07-01 Basf Se Procédé de production de copolymères à blocs polyéther
WO2011047780A1 (fr) * 2009-10-19 2011-04-28 Basf Se Conditionnement de catalyseurs cyanures métalliques doubles
WO2011160296A1 (fr) * 2010-06-23 2011-12-29 Basf Se Catalyseur de type cyanure métallique double modifié
ES2525022T3 (es) 2010-12-20 2014-12-16 Bayer Intellectual Property Gmbh Procedimiento para la preparación de polioléteres
KR101404702B1 (ko) 2011-03-08 2014-06-17 에스케이이노베이션 주식회사 에테르 결합 단위체를 함유한 이산화탄소/에폭사이드 공중합체의 제조 방법
BR112014009157B1 (pt) 2011-10-28 2020-11-10 Dow Global Technologies Llc composição lubrificante e método para preparar uma composição lubrificante
US9562134B2 (en) 2013-03-12 2017-02-07 Covestro Llc Catalyst for the production of polyols having lower amounts of high molecular weight tail
GB201515350D0 (en) 2015-08-28 2015-10-14 Econic Technologies Ltd Method for preparing polyols
GB201703324D0 (en) 2017-03-01 2017-04-12 Econic Tech Ltd Method for preparing polyether carbonates
GB201717441D0 (en) 2017-10-24 2017-12-06 Econic Tech Ltd A polymerisation process
GB201717459D0 (en) 2017-10-24 2017-12-06 Econic Tech Limited Methods for forming polycarbonate ether polyols and high molecular weight polyether carbonates
EP3784718B1 (fr) 2018-04-25 2024-06-26 Henkel AG & Co. KGaA Procédé de préparation de copolymères séquencés de polyéthers et de polysiloxanes fonctionnalisés par hydroxyles
KR20210020916A (ko) 2018-06-19 2021-02-24 헨켈 아게 운트 코. 카게아아 고 활성 이중 금속 시아나이드 화합물
GB201814526D0 (en) 2018-09-06 2018-10-24 Econic Tech Ltd Methods for forming polycarbonate ether polyols and high molecular weight polyether carbonates
CN110964191B (zh) * 2018-09-29 2021-02-02 杭州普力材料科技有限公司 一种混合酸改性的锌钴双金属氰化物催化剂及其制备方法
CN110964192B (zh) * 2018-09-29 2022-05-17 杭州普力材料科技有限公司 一种用于制备二氧化碳基聚碳酸酯的混合酸改性双金属氰化物催化剂及其制备方法
WO2020084033A1 (fr) 2018-10-26 2020-04-30 Basf Se Copolymères s'associant de manière hydrophobe pour le transport tertiaire de pétrole comprenant des monomères dotés d'unités propylènoxy
WO2020084046A1 (fr) 2018-10-26 2020-04-30 Basf Se Procédé pour la préparation de monomères s'associant de manière hydrophobe contenant propylènoxy à l'aide de catalyse dmc
EP3663371B1 (fr) 2018-12-06 2024-03-13 Henkel AG & Co. KGaA Préparation de copolymères de brosse de polysiloxane polyalkylèneglycol
EP3663372B1 (fr) 2018-12-06 2024-03-13 Henkel AG & Co. KGaA Composition durcissable comprenant des copolymères de polysiloxane polyalkylèneglycol en brosse
GB201906214D0 (en) 2019-05-02 2019-06-19 Econic Tech Ltd A polyol block copolymer, compositions and processes therefor
GB201906210D0 (en) 2019-05-02 2019-06-19 Econic Tech Limited A polyol block copolymer, compositions and processes therefor
GB202003003D0 (en) 2020-03-02 2020-04-15 Econic Tech Ltd A polyol block copolymer
GB202003002D0 (en) 2020-03-02 2020-04-15 Crane Ltd Method of preparation of a polyol block copolymer
CN111349224B (zh) * 2020-03-30 2021-06-01 杭州普力材料科技有限公司 一种液相法管道化连续化生产聚碳酸酯-聚醚多元醇的方法
CN111393629B (zh) * 2020-03-30 2021-06-01 杭州普力材料科技有限公司 一种预加热液相法管道化连续化生产聚碳酸丙烯酯的方法
CN111484610B (zh) * 2020-03-30 2021-11-09 杭州普力材料科技有限公司 一种聚碳酸酯-聚醚二元醇的制备方法
CN111378106B (zh) * 2020-03-30 2021-06-01 杭州普力材料科技有限公司 一种预加热液相法管道化连续化生产聚碳酸酯-聚醚多元醇的方法
EP3932973A1 (fr) 2020-07-01 2022-01-05 Henkel AG & Co. KGaA Copolymères de brosse de polysiloxane bifonctionnalisés
GB202017531D0 (en) 2020-11-05 2020-12-23 Econic Tech Limited (poly)ol block copolymer
WO2023017276A1 (fr) 2021-08-11 2023-02-16 Econic Technologies Ltd Procédé de préparation de tensioactifs par copolymérisation d'epoxydes et de co2 à l'aide d'un mélange composé d'un catalyseur bimétallique macrocyclique et d'un catalyseur à base de cyanure bimétallique
GB202115335D0 (en) 2021-10-25 2021-12-08 Econic Tech Ltd Surface-active agent

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1008319A (en) 1962-07-03 1965-10-27 Kali Chemie Veb Process for the production of directly precipitated milori blue
AU552988B2 (en) * 1982-03-31 1986-06-26 Shell Internationale Research Maatschappij B.V. Polymerizing epoxides and catalyst suspensions for this
AU551979B2 (en) * 1982-03-31 1986-05-15 Shell Internationale Research Maatschappij B.V. Epoxy polymerisation catalysts
US5792513A (en) 1997-03-07 1998-08-11 Koslow Technologies Corporation Continuous solid state web coating process
US6063897A (en) 1998-05-05 2000-05-16 Arco Chemical Technology, L.P. Acid-treated double metal cyanide complex catalysts
US6613714B2 (en) * 1999-06-02 2003-09-02 Basf Aktiengesellschaft Multimetal cyanide compounds, their preparation and their use
US6423662B1 (en) 1999-07-09 2002-07-23 Dow Global Technologies Inc. Incipient wetness method for making metal-containing cyanide catalysts
JP2003504465A (ja) * 1999-07-09 2003-02-04 ザ ダウ ケミカル カンパニー ポリカルボン酸を用いた金属シアン化物触媒の製造方法
BR0308674A (pt) 2002-03-19 2005-02-01 Dow Global Technologies Inc Métodos para preparar catalisador de cianeto metálico usando sais metálicos insolúveis
WO2003080241A1 (fr) 2002-03-21 2003-10-02 Dow Global Technologies, Inc. Procedes de preparation de complexes catalyseurs au cyanure pour metaux au moyen d'agents complexants partiellement miscibles
KR20040108674A (ko) 2002-03-21 2004-12-24 다우 글로벌 테크놀로지스 인크. 0가 금속을 사용하는 금속 시아나이드 촉매의 제조 방법
WO2003091192A1 (fr) * 2002-04-26 2003-11-06 Basf Aktiengesellschaft Melanges de c10-alcanolalcoxylates et leur utilisation
DE10228254A1 (de) * 2002-06-24 2004-01-22 Basf Ag Verfahren zur Herstellung von Polyetheralkoholen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006094979A2 *

Also Published As

Publication number Publication date
CN101300074A (zh) 2008-11-05
WO2006094979A3 (fr) 2007-07-12
DE102005011581A1 (de) 2006-09-14
WO2006094979A2 (fr) 2006-09-14
US20080167502A1 (en) 2008-07-10
JP2008533227A (ja) 2008-08-21
KR20070116249A (ko) 2007-12-07
CN101300074B (zh) 2010-11-10
JP5329217B2 (ja) 2013-10-30
US7811958B2 (en) 2010-10-12

Similar Documents

Publication Publication Date Title
EP1866084A2 (fr) Procede de fabrication de catalyseurs dmc
EP1071509B1 (fr) Catalyseurs cyanures dimetalliques perfectionnes pour la preparation de polyols de polyether
EP0862947B2 (fr) Procédé pour la préparation de catalyseurs du type DMC et procédé pour la préparation de polyétheralcools
DE69433826T2 (de) Doppelmetallkatalysatoren zur Herstellung von Polyolen
DE19937114C2 (de) Verfahren zur Herstellung von Polyetherpolyolen
EP1259561B1 (fr) Procede de production de composes du type des cyanures polymetalliques
EP1239957B1 (fr) Catalyseurs a cyanure metallique double pour la production de polyols de polyether
EP1115490B1 (fr) Catalyseurs a base de cyanure bimetallique pour la preparation de polyols de polyether
EP1034035A1 (fr) Catalyseurs cristallins de cyanure de metaux composites pour preparer des polyols de polyether
WO2007082596A1 (fr) Procédé de fabrication de composes de cyanures multimétalliques
EP1542954B2 (fr) Production d'alcoxylats a partir d'oxyde d'ethylene et de 2-propylheptanol en presence d'un gaz inerte
EP1100617B1 (fr) Catalyseurs de cyanure bimetallique utilises pour preparer des polyols de polyether
WO2006117364A2 (fr) Procede de production de catalyseurs a base de complexes bimetalliques a pont cyanure
EP1534426A1 (fr) Composes de cyanure polymetallique
EP1448664B1 (fr) Procede de production d'alcools de polyether
EP1517940B1 (fr) Procede de production de catalyseurs dmc
WO2001053381A1 (fr) Procede pour la production d'alcools de polyether
EP1115489B1 (fr) Catalyseurs a base de cyanure bimetallique pour la preparation de polyols de polyether
EP1516007B1 (fr) Procede de production de polyether-alcools
EP1230289A1 (fr) Procede de preparation de polyols a mousse souple en bloc
DE19917897A1 (de) Verfahren zur Herstellung von Polyurethanen
DE10057891A1 (de) Verfahren zur Aufarbeitung von Polyetherpolyolen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

17P Request for examination filed

Effective date: 20080114

RBV Designated contracting states (corrected)

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BASF SE

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20110317

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20141001