EP1937408A2 - Procede de production de catalyseurs a base de complexes bimetalliques a pont cyanure - Google Patents
Procede de production de catalyseurs a base de complexes bimetalliques a pont cyanureInfo
- Publication number
- EP1937408A2 EP1937408A2 EP06754948A EP06754948A EP1937408A2 EP 1937408 A2 EP1937408 A2 EP 1937408A2 EP 06754948 A EP06754948 A EP 06754948A EP 06754948 A EP06754948 A EP 06754948A EP 1937408 A2 EP1937408 A2 EP 1937408A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- iii
- acid
- group
- metal
- metal compound
- 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- Withdrawn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
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
-
- 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
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/48—Ring-opening reactions
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/20—Carbonyls
Definitions
- the invention relates to a process for the preparation of Doppelmetallcyanidkomplex- catalysts (DMC catalysts), the DMC catalysts themselves and their use Phyg.
- DMC catalysts Doppelmetallcyanidkomplex- catalysts
- Tailored polyether polyols are required for the production of polyurethane foams having a wide range of properties.
- long-chain polyols are used for flexible foams and shorter-chain polyols for rigid foams.
- polyether polyols The preparation of polyether polyols is carried out from alkylene oxides in the presence of a starter using different catalysts, such as potassium hydroxide, hydrophobized double layer oxides, Lewis acid systems and DMC compounds.
- catalysts such as potassium hydroxide, hydrophobized double layer oxides, Lewis acid systems and DMC compounds.
- DMC compounds For increasing economic interest are long-chain polyether polyols having a low content of unsaturated constituents.
- DMC compounds For the preparation of such polyether polyols in particular DMC compounds have proven to be catalysts.
- DMC catalysts are prepared by combining zinc chloride and potassium or calcium hexacyanocobaltate in water.
- a catalyst with increased activity is obtained by using an organic solvent instead of water, e.g. Ethylene glycol or diethylene glycol.
- WO 99/16775 discloses the preparation of crystalline DMC catalysts by reaction of aqueous solutions of cyanometallic acid, for example hexacyanocobaltate (III) -hydrogenic acid, with aqueous solutions of metal carboxylates, preferably zinc formate, zinc acetate and zinc propionate. After combining the aqueous solutions, water-miscible, heteroatom-containing components can be added as ligands to the resulting aqueous suspension.
- cyanometallic acid for example hexacyanocobaltate (III) -hydrogenic acid
- the object of the invention is to provide improved DMC catalysts.
- the object of the invention is furthermore to provide an alternative process for the preparation of DMC catalysts.
- the object is achieved by a process for preparing double metal cyanide complex catalysts of the general formula (I)
- M 1 is a metal ion selected from the group consisting of Zn (II), Fe (II), Co (III), Ni (II), Mn (II),
- M 2 is a metal ion selected from the group consisting of Sr (I), Mg (II), Zn (II), Fe (II), Fe (III),
- X is a non-cyanide group which forms a coordinative bond to M 1 selected from the group consisting of carbonyl, cyanate, isocyanate, nitrile, thiocyanate and nitrosyl,
- a, b, r, t are integers chosen to satisfy the electroneutrality condition
- R is the anion of a very weak protic acid with a pKa of ⁇ 20, and
- Y is the anion of an inorganic mineral acid or a moderately strong to strong organic acid having a pK s of -10 to +10, w is the valence of M 2 , u + v is the valency of M 2 , where u and v each are at least 1,
- reaction is carried out in a nonaqueous, aprotic solvent.
- the process according to the invention is characterized in that it is carried out in a nonaqueous medium.
- the DMC catalysts prepared according to the invention can be obtained as pumpable gels and also be used as such. This eliminates filtration and drying steps as well as the handling of solids.
- Particularly preferred metal ions M 2 are Co (III) and Fe (III). Particularly preferred metal ion M 1 is Zn (II).
- Cyanometalate-hydrazoic acids are compounds which are very easy to handle in aqueous solution.
- cyanometalic acid For the preparation of cyanometalic acid, several methods are known. For example, starting from the alkali metal cyanometallate, they can be prepared via the silver cyanometalate as described in W. Klemm et al., Z. Anorg. AIIg. Chem. 308 (1961) 179. Further, alkali or Erdalkalicyanometallate can be converted by means of an acidic ion exchanger in the cyanometalic acid, see F. Hein, H. Lily, Z. Anorg. AIIg. Chem. 270 (1952) 45, A. Ludi et al., HeIv. Chim.
- cyanometalic acid are Hexacyanocobalt (lll) acid and Hexacyanoeisen (lll) acid.
- Suitable metal compounds (IIIa) and (NIb) are, for example, dimethylzinc, diethylzinc, di-n-butylzinc, diisopropylzinc, diisobutylzinc, diethylaluminum cyanide, trimethylaluminum, triisobutylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-octylaluminum, tri-n -decylaluminum, tri-n-hexylaluminum, bis (tetramethylcyclopentadienyl) manganese, diethylmagnesium, di-n-butylmagnesium, n-butylethylmagnesium, strontium (2, 2,6,6-tetramethyl-3,5-heptanedionate), bis (pentamethylcyclopentadienyl) strontium, 1, 1'-dimethylferrocene, ferroc
- Bis (cyclopentadienyl) manganese bis (pentamethylcyclopentadienyl) manganese, bis (cyclopentadienyl) titanium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) dicarbonyltitanium (II) and bis (cyclopentadienyl) dimethyltitanium.
- Preferred metal compounds (IIIa) are dialkylzinc compounds such as dimethylzinc, diethylzinc, di-n-butylzinc, diisopropylzinc and diisobutylzinc, in particular diethylzinc.
- the reaction of the cyanometalic acid (II) with the metal compound (IIIa) or (IIIb) is generally carried out in a nonaqueous, dipolar or apolar aprotic solvent.
- Suitable aprotic solvents are, for example, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), sulfolane, carbon disulfide, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and N-methylpyrrolidone (NMP); preference is given to DMSO, DMF and NMP.
- the reaction can be carried out in the presence of one or more further organic components which act as surface-active components for controlling the catalyst morphology and / or as chemically bound ligands.
- This further organic component can just as well be added only after the reaction of the product solution or suspension containing the DMC compound (I).
- Preferred further organic components are selected from the group consisting of 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 ethers, polyvinyl ethyl ethers, polyvinyl acetate, polyvinyl alcohol, poly-N- vinylpyrrolidone, poly (N-vinylpyrrolidone-co-acrylic acid), polyvinylmethylketone, poly (4-vinylphenol), poly (acrylic acid-co-styrene), oxazoline polymers, polyalkyleneimines, maleic acid and maleic anhydride copolymer, hydroxyethylcellulose, polyacetates, ionic surface and surfact
- the reaction can be carried out batchwise, semicontinuously or continuously.
- the DMC catalysts (I) prepared according to the invention can be used as catalysts or for the preparation of supported catalysts.
- the DMC catalyst (I) can be isolated from the solution obtained in the reaction by conventional solid / liquid separation method and used as a moist precipitate as a catalyst, or even without prior separation of the solvent as a suspension or as a gel.
- the DMC catalysts are used for the alkoxylation of compounds which have active H atoms, with alkylene oxides, preferably with ethylene oxide, propylene oxide and / or butylene oxide. Active hydrogen atoms are present, for example, in hydroxyl groups or primary and secondary amino groups.
- the DMC catalysts prepared according to the invention are preferably used for the preparation of polyether polyols by reacting diols or polyols with ethylene oxide, propylene oxide, butylene oxide or mixtures thereof.
- the DMC catalysts prepared according to the invention are distinguished by a particularly good "start-up behavior", ie the alkoxylation reaction starts immediately upon addition of the alkylene oxide to the compound having active H atoms to be alkoxylated, which manifests itself in an extremely rapid pressure reduction according to US Pat Alkylene oxide addition, due to the immediate onset of consumption of the alkylene oxide by the reaction.
- the present invention also provides the DMC catalysts according to the invention itself and their use for the alkoxylation of compounds having active H atoms, preferably for the alkoxylation of diols or polyols with ethylene oxide, propylene oxide, butylene oxide or mixtures thereof.
- the DMC catalyst according to the invention based on the amount of the product obtained, in amounts of generally 5 to 5000 ppm, preferably 10 to 1000 ppm, more preferably 15 to 500 ppm used.
- the alkoxylation can be carried out by all methods known from the prior art as a batch, semibatch or continuous process.
- FIG. 5 shows the pressure and temperature profile.
- the temperature in 0 C upper curve, left axis
- the pressure in bar lower curve, right axis
- a rapid pressure drop can be seen after the start of ethylene oxide addition.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
L'invention concerne un procédé de production de catalyseurs à complexes bimétalliques à pont cyanure de formule générale (I) M<SUP>2</SUP> <SUB>a</SUB>[
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102005020347A DE102005020347A1 (de) | 2005-05-02 | 2005-05-02 | Verfahren zur Herstellung von Doppelmetallcyanidkomplex-Katalysatoren |
PCT/EP2006/061962 WO2006117364A2 (fr) | 2005-05-02 | 2006-05-02 | Procede de production de catalyseurs a base de complexes bimetalliques a pont cyanure |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1937408A2 true EP1937408A2 (fr) | 2008-07-02 |
Family
ID=37101366
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06754948A Withdrawn EP1937408A2 (fr) | 2005-05-02 | 2006-05-02 | Procede de production de catalyseurs a base de complexes bimetalliques a pont cyanure |
Country Status (6)
Country | Link |
---|---|
US (1) | US20080292526A1 (fr) |
EP (1) | EP1937408A2 (fr) |
JP (1) | JP2008540080A (fr) |
CN (1) | CN101213017A (fr) |
DE (1) | DE102005020347A1 (fr) |
WO (1) | WO2006117364A2 (fr) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101646492B (zh) * | 2007-02-05 | 2013-06-05 | 巴斯夫欧洲公司 | Dmc催化剂、其制备方法及其用途 |
WO2010072769A1 (fr) | 2008-12-23 | 2010-07-01 | Basf Se | Procédé de production de copolymères à blocs polyéther |
PT2408841E (pt) | 2009-03-17 | 2014-12-11 | Basf Se | Corpo moldado de poliuretano com resistência ao rasgamento melhorada e comportamento de fadiga a flexões repetidas melhorado |
CN107200837B (zh) | 2016-03-18 | 2019-10-18 | 淮安巴德聚氨酯科技有限公司 | 一种利用dmc催化剂循环制备聚醚多元醇的方法 |
JP7316221B2 (ja) * | 2017-05-10 | 2023-07-27 | ダウ グローバル テクノロジーズ エルエルシー | ポリエーテル重合プロセス |
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 |
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 |
CN114133416A (zh) * | 2020-09-03 | 2022-03-04 | 万华化学集团股份有限公司 | 一种dmc催化剂的制备方法及由其制备的dmc催化剂 |
CN112194178B (zh) * | 2020-10-20 | 2021-06-01 | 福州大学 | 一种二氧化钛和普鲁士蓝有序组装态介晶纳米材料及其制备方法 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3365282A (en) * | 1968-01-23 | Du Pont | Process for preparing amino derivatives of polyhedral boron compounds | |
JPS62294636A (ja) * | 1986-05-21 | 1987-12-22 | Eisai Co Ltd | 2−メチル−1,4−ナフトキノンの製造法 |
US6642423B2 (en) * | 1999-07-09 | 2003-11-04 | Dow Global Technologies, Inc. | Polymerization of ethylene oxide using metal cyanide catalysts |
WO2001004178A1 (fr) * | 1999-07-09 | 2001-01-18 | The Dow Chemical Company | Polymerisation d'oxydes d'alkylene faisant appel a des catalyseurs au cyanure metallique et a des composes d'amorce insatures |
JP2003525328A (ja) * | 2000-02-29 | 2003-08-26 | ビーエーエスエフ アクチェンゲゼルシャフト | 多金属シアニド化合物の製造方法 |
BR0308674A (pt) * | 2002-03-19 | 2005-02-01 | Dow Global Technologies Inc | Métodos para preparar catalisador de cianeto metálico usando sais metálicos insolúveis |
ATE352373T1 (de) * | 2003-05-22 | 2007-02-15 | Dow Global Technologies Inc | Nanoskalige dmc-katalysatorpartikel |
WO2006049214A1 (fr) * | 2004-11-05 | 2006-05-11 | Nippon Shokubai Co., Ltd. | Poudre de polymere de vinylpyrrolidone et procede pour la produire |
JP5151480B2 (ja) * | 2005-08-17 | 2013-02-27 | 旭硝子株式会社 | ポリエステルエーテルポリ(モノ)オールの製造方法およびポリウレタンの製造方法 |
DE102007002555A1 (de) * | 2007-01-17 | 2008-07-24 | Bayer Materialscience Ag | Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen |
-
2005
- 2005-05-02 DE DE102005020347A patent/DE102005020347A1/de not_active Withdrawn
-
2006
- 2006-05-02 CN CNA2006800242038A patent/CN101213017A/zh active Pending
- 2006-05-02 WO PCT/EP2006/061962 patent/WO2006117364A2/fr active Application Filing
- 2006-05-02 US US11/913,484 patent/US20080292526A1/en not_active Abandoned
- 2006-05-02 EP EP06754948A patent/EP1937408A2/fr not_active Withdrawn
- 2006-05-02 JP JP2008509432A patent/JP2008540080A/ja not_active Withdrawn
Non-Patent Citations (1)
Title |
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See references of WO2006117364A2 * |
Also Published As
Publication number | Publication date |
---|---|
US20080292526A1 (en) | 2008-11-27 |
WO2006117364A3 (fr) | 2007-01-11 |
JP2008540080A (ja) | 2008-11-20 |
WO2006117364A2 (fr) | 2006-11-09 |
DE102005020347A1 (de) | 2006-11-09 |
CN101213017A (zh) | 2008-07-02 |
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