Classifications

• • 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
• • 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
  • C08G65/266—Metallic elements not covered by group C08G65/2648 - C08G65/2645, or compounds thereof

Definitions

• the present invention relates to a process for the preparation of a polyetherol, comprising the reaction of at least one alkylene oxide with at least one starter compound in the presence of a multimetal oxide catalyst, and the polyetherols, in particular polypropylene glycol or polyethylene glycol, prepared by such a process, and their use for polyurethane synthesis , as a fuel additive or as a surfactant.
• polyetherols can be used for different applications. Especially for polyurethane syntheses, polyfunctional or polyfunctional polyetherols play an important role as starting material.
• EP-A 1 002 821 describes metal antimonates and processes for the preparation of polyether polyols using such catalysts.
• the catalysts disclosed in EP-A 1 002 821 are in particular antimonates of alkaline earth metals, metals from groups LTA, ULA, VA of the periodic table of the elements or transition metals from groups DB, TTTB, VB or VIIIB.
• the reaction of water or polyfunctional alcohols with an alkylene oxide to polyether polyols in the presence of these antimonates is described as a catalyst.
• the metal antimony oxide hydroxides described there as catalysts are characterized by a comparatively high proportion of hydroxide. This can lead to instability at elevated temperatures in polyetherol synthesis.
• the catalysts described there have a comparatively low specific BET surface area, which leads to a lower catalytic activity.
• this object is achieved by a process for the preparation of a polyetherol comprising the reaction of at least one alkylene oxide with at least one starter compound in the presence of a catalyst, characterized in that a multimetal oxide compound of the general formula I is used as the catalyst:
• M 1 at least one element from groups IA, HA, IHA, IV A, VA,
• M 2 is at least one element from Groups IV A, VA and / or VIA of the Periodic Table of the Elements,
• n is a fractional or whole number from 2 to 3, in particular from greater than 2 to 3,
• - p is 0 or a fractional or whole number greater than 0,
• q is a fractional or whole number greater than 0
• the metal M 1 is at least one element from one of the groups IA, DA, ⁇ IA, ⁇ VA, VA, Iß, ÜB, Hrß, ⁇ VB, VB, Vro, V ⁇ B and / or VUrB of the periodic table of the elements.
• the metal M 1 is selected from the group consisting of aluminum, tin, magnesium, titanium, zircon, cadmium, lanthanum and zinc, particularly preferably zinc and aluminum.
• the metal M 2 is at least one element from groups IV A, VA and / or VIA of the periodic table of the elements.
• M 2 is preferably selected from the group consisting of arsenic, antimony, bismuth, tin, germanium, selenium and tellurium, particularly preferably arsenic, antimony or arsenic and antimony, in particular antimony.
• the catalysts used according to the invention thus have an OH / O ratio of 0 to 1, in particular 0 to less than 1. Because of the comparatively small proportion of OH groups, the multimetal oxide compounds used as catalysts are distinguished by improved thermal stability ,
• Such multimetal oxide compounds can be produced inexpensively, for example, from simple starting compounds of the metals M 1 and M 2 , for example from salts, oxide hydroxides or oxides of the metals M 1 and M 2 .
• salts known to the person skilled in the art are suitable, in particular water-soluble salts such as chlorides, acetates, nitrates or acetylacetonates.
• the multimetal oxide compounds used according to the invention as a catalyst are preferably prepared from a salt of the metal M 1 and an oxide, oxide hydroxide or hydroxide of the metal M 2 .
• These simple starting compounds of the metals M 1 and M 2 can in particular be reacted as mixtures either by a solid-state reaction, for example by means of calcination, or in a solvent in solution or suspension, in particular in water. It may also be advantageous to first use the metal M 2 in a lower oxidation state and to oxidize it to the desired oxidation state before or during the reaction with the salt of the metal M 1 .
• the reaction of the starting compounds in the preparation of the catalyst in the presence of a solvent is preferably carried out at elevated temperatures, generally above 40 ° C., for example at least 60 ° C., preferably at least 70 ° C., in particular at least 80 ° C. or at at least 90 ° C.
• the suspension obtained can be freed from the solvent. Drying can be carried out, for example, by spray drying. However, it is also possible to dry the catalyst by means of freeze-drying or conventional drying, that is to say, for example, by filling or centrifuging, washing and subsequent drying, for example at elevated temperature.
• the product obtained can then preferably be calcined.
• the calcination step is preferably carried out at temperatures from 100 ° C.
• calcination is carried out for a period of 10 minutes to several hours.
• the calcination can generally be carried out under inert gas, but also under a mixture of inert gas and oxygen such as. B. air or under pure oxygen. Calculation under a reducing atmosphere is also possible.
• the required calcination time decreases with increasing calcining temperature.
• Multimetal oxide compounds with M 2 antimony which are suitable as catalysts for the process according to the invention are described, for example, in WO 99/51341 and DE-A 24 07 677, the contents of which are referred to in their entirety.
• Antimonates of the general formula I have proven to be particularly suitable for the process according to the invention, where M 2 is antimony.
• the multimetal oxide compounds are e.g. B. available according to the manufacturing methods described in detail in DE-A 24 076 _77.
• IM 2 stands for antimony
• a procedure is preferred in which antimony trioxide and / or Sb 2 O 4 in an aqueous medium by means of hydrogen peroxide in an amount which is equal to or exceeds the stoichiometric at temperatures between 40 and Oxidized 100 ° C to antimony (V) - oxide hydroxide hydrate, before this oxidation, during this oxidation and / or after this oxidation aqueous solutions and / or suspensions of suitable starting compounds of the other elemental constituents of the multimetal oxide compounds, optionally NH 3 admits, then optionally at a temperature between 40 and 100 ° C for a defi- niert time, then the resulting aqueous mixture dries, preferably spray-dried at an inlet temperature of 200 to 600 ° C and an outlet temperature of 80 to 150 ° C, and then calcined the intimate dry mixture as described.
• the pH of the reaction mixture can be changed by adding NH 3 . In many cases it may
• the multimetal oxide compounds can be comminuted again, for example by wet or dry grinding, for. B. in a ball mill or by jet milling.
• a preferred way of producing the multimetal oxide compounds consists in antimony trioxide and / or Sb 2 O in an aqueous medium using hydrogen peroxide first in a, preferably finely divided, Sb (V) compound, for. B. Sb (V) - oxide hydroxide hydrate, to transfer the resulting aqueous mixture with an ammoniacal aqueous solution of a water-soluble salt, for example an acetate, of the metal M 1, to stir and dry the resulting aqueous mixture, e.g. B. spray-drying as described, and calcining the powder obtained, optionally after subsequent kneading with water and subsequent extrusion and drying, as described. Therefore, in a preferred embodiment, the present invention relates to a process for producing a polyetherol, Sb 2 O or Sb 2 O being used to produce the corresponding multimetal oxide compound.
• the multimetal oxide compounds of the general formula I have particularly advantageous catalytic properties with regard to the preparation of polyetherols.
• a multimetal oxide compound of the general formula I is used as catalyst for the process for producing a polyetherol, which fulfills at least one of the following properties:
• p is an integer or fractional number from 0 to 3, preferably from 0.5 to 2, in particular from 0.9 to 1.1, for example 1;
• (2) q is an integer or fractional number greater than 0.5 to 3, preferably 0.7 to 2, in particular 0.9 to 1.1, for example 1;
• x is an integer or fraction from 1.2 to 14, preferably from 1.4 to 7, in particular from 1.6 to 5, for example from 1.8 to 3.2;
• the metal M 2 is antimony and / or arsenic
• the metal M 1 is selected from the group consisting of aluminum, tin, magnesium, titanium, zircon, cadmium, lanthanum and zinc; and (6) n is an integer or fraction from 2 to 3, preferably from greater than 2 to 3.
• the present invention relates to a process for the preparation of a polyetherol, wherein a multimetal oxide compound of the general formula I is used as the catalyst which fulfills at least one of the following properties:
• the metal M 2 is antimony;
• the metal M 1 is selected from the group consisting of zinc and aluminum; and
• (6 ') n is an integer or fractional number greater than 2 to 3.
• the multimetal oxide compound used as catalyst fulfills two or more of the properties (1 ') to (6').
• a multimetal oxide compound used as a catalyst in the process according to the invention can fulfill all of the properties (! ') To (6').
• the present invention relates to a process in which the catalyst used has the general formula Zn [SbO n (OH) 2 ( 3-n )] 2 or Al [SbO n (OH) 2 ( 3-n )] 3 , where n is an integer or fraction from 2 to 3, preferably from greater than 2 to 3.
• the present invention relates to a process for producing a polyetherol, the metal M 1 being zinc or aluminum.
• the multimetal oxide compound used as a catalyst in a process according to the invention is essentially in crystalline form.
• the multimetal oxide compound generally consists essentially of small crystallites, the largest dimension of which is typically 0.05 to 100 ⁇ m.
• the multimetal oxide compound can also be amorphous and / or crystalline.
• Suitable multimetal oxide compounds have, for example, a crystal structure that is isotypic to the structure of the mineral Parzite, ie Cu 2 Sb 2 (O, OH) 7 .
• the present invention therefore also relates to a process for the preparation of a polyetherol, the multimetal oxide compound of the general formula I having a crystal structure which is isotypic to the structure of the mineral partzite.
• the catalytic activity of the multimetal oxide compounds used is, for example, also dependent on the specific BET surface area of the compounds.
• the specific BET surface area determined according to Brunner-Emmet-Teller is influenced, for example, by the lamination temperature.
• the for The multimetal oxide compounds used in the process of the invention have, for example, a specific BET surface area of 15 to 500 m 2 / g, preferably 20 to 200 m Ig, in particular 20 to 150 m Ig, particularly preferably 40 to 150 m 2 / g ,
• the present invention relates to a process for producing a polyetherol, the multimetal oxide compound of the general formula I having a specific BET surface area of 15 to 500 m 2 / g.
• the catalyst concentration used in the process according to the invention, based on the product, is less than 5.0% by weight, preferably less than 2.0% by weight, in particular less than 1.5% by weight, particularly preferably less than 1.0 wt%.
• the catalyst can be used, for example, as a suspension or as a fixed bed catalyst.
• OH-functional compounds for example OH-monofunctional or polyfunctional compounds, are preferred as starter compounds.
• the present invention therefore relates to a process for producing a polyetherol, the starter compound being an OH-mono- or polyfunctional compound.
• Suitable starter compounds according to the invention are, for example, the following compounds: water, organic dicarboxylic acids, such as succinic acid, adipic acid, phthalic acid and terephthalic acid, aliphatic and aromatic, optionally N-mono-, N, N- and N, N'- dialkyl-substituted diamines with 1 to 4 carbon atoms in the alkyl radical, such as optionally mono- and dialkyl-substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5- and 1,6-hexamethylenediamine, phenylenediamines, 2,3-, 2,4- and 2,6-toluenediamine and 4,4'-, 2,4'- and 2, 2'-diamino-di-phenylmethane.
• organic dicarboxylic acids such
• alkanolamines such as, for. B. ethanolamine, N-methyl and N-ethylethanolamine, dial kanolamines, e.g. B. diethanolamine, N-methyl and N-ethyl-diethanolamine, and trialkanolamines, such as. B. triethanolamine, and ammonia and mono- or polyhydric alcohols, such as monoethylene glycol, 1,2-propanediol and 1,3, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, trimethylolpropane , Pentaerythritol, sorbitol and sucrose.
• alkanolamines such as, for. B. ethanolamine, N-methyl and N-ethylethanolamine
• dial kanolamines e.g. B. diethanolamine, N-methyl and N-ethyl-diethanolamine
• ethylene oxide and / or propylene oxide onto water monoethylene glycol, diethylene glycol, 1,2-propanediol, diproplyene glycol, glycerol, trimethylolpropane, ethylenediamine, triethanolamine, pentaerythritol, sorbitol and / or sucrose are preferably used individually or in mixtures as polyether-polyalcohols.
• the starter compounds can also be used in the form of alkoxylates, in particular those having a molecular weight M w in the range from 62 to 15000 g / mol.
• macromolecules with functional groups which have active hydrogen atoms for example hydroxyl groups, in particular those which are mentioned in WO 01/16209, are also suitable.
• starter compounds are monofunctional or polyfunctional alcohols having 1 to 24 carbon atoms; starter compounds having 8 to 15 carbon atoms, in particular 10 to 15 carbon atoms, such as, for example, tridecanol, are particularly preferred according to the invention.
• Alcohols suitable according to the invention are, in particular, octanol, nonanol, decanol, undecanol, dodekanol, tridekanol, tetradecanol, pentadekanol, ethylhexanol, propylheptanol, fatty alcohols with 10 to 18 carbon atoms, oxoalcohols, isoctanol, iso-nonanol, iso-decanol , iso-undekanol, iso-dodekanol, iso-tridekanol, iso-tetradekanol, iso-pentadecanol, preferably iso-decanol, 2-propylheptanol, tridekanol, iso-tridekanol or mixtures of C 13 to C 15 alcohols.
• the present invention relates to a process for the preparation of a polyetherol, the starter compound being a monofunctional or polyfunctional alcohol having 1 to 24 carbon atoms.
• epoxides can be used for the process according to the invention.
• C 2 -C o-alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, pentene oxide, hexene oxide, cyclohexene oxide, styrene oxide, dodecene epoxide, ocate decene epoxide, and mixtures of these epoxies.
• Ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide and pentene oxide are particularly suitable, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide and isobutylene oxide being particularly preferred.
• the present invention relates to a process for producing a polyetherol, the alkylene oxide being ethylene oxide, propylene oxide or butylene oxide or a mixture of two or more thereof.
• the alkylene oxide can also be used in the form of a mixture.
• a mixture can advantageously be, for example, a raffinate ( ⁇ ) oxide mixture.
• a raffinate (I) oxide mixture is understood to be a mixture which has been obtained by oxidation of a raffinate I stream.
• the composition of the raffinate ( ⁇ ) oxide mixture depends on the raffinate current used for the production.
• the raffinate ( ⁇ ) mixture obtained from a steam cracker contains isobutene, 1-butene and 2-butene. This mixture can be oxidized directly.
• the corresponding oxiranes are obtained as a raffinate (I) oxide mixture.
• the use of a raffinate (I) oxide mixture for the process according to the invention has the advantage that the alkylene oxide mixture used can be reacted essentially without prior purification and separation of the individual components. This enables the process to be operated in a particularly cost-effective manner by using cheap starting materials.
• the present invention therefore relates to a process for producing a polyetherol, in which a raffinate (I) oxide mixture is reacted.
• the raffinate (I) oxide mixture can be used essentially without cleaning or after a previous cleaning.
• the process for the preparation of the polyetherols is carried out at a temperature of 100 ° C. to 180 ° C., preferably 110 ° C. to 150 ° C.
• the process is preferably carried out at pressures from 0 bar to 50 bar.
• the present invention also relates to the use of a multimetal oxide compound of the general formula I as a catalyst for producing a polyetherol from at least one alkylene oxide and at least one starter compound:
• M 1 is at least one element from groups IA, DA, DIA, IV A, VA, D3, DB, DTß, rVB, VB, VIB, VDB and / or VDIB of the periodic table of the elements,
• M 2 is at least one element from Groups IV A, VA and / or VIA of the Periodic Table of the Elements,
• n is a fractional or whole number from 2 to 3, in particular from greater than 2 to 3,
• p is 0 or a fractional or whole number greater than 0,
• q is a fractional or whole number greater than 0
• x is a fractional or whole number from 1 to 20.
• the present application also relates to polyetherols, in particular polypropylene glycol or polyethylene glycol, obtainable according to a process comprising the reaction of at least one alkylene oxide with at least one starter compound in the presence of a catalyst, characterized in that a multimetal oxide compound of the general formula I is used as a catalyst: M , p [M 2 q O "(OH) 2 (3-n) ] x (I),
• M 1 at least one element from groups IA, DA, DIA, IV A, VA,
• M 2 is at least one element from Groups IV A, VA and / or VIA of the Periodic Table of the Elements,
• n is a fractional or whole number from 2 to 3, in particular from greater than 2 to 3,
• - p is 0 or a fractional or whole number greater than 0,
• q is a fractional or whole number greater than 0
• x is a fractional or whole number from 1 to 20.
• the polyetherols obtained according to the invention are distinguished, for example, by a narrow molecular weight distribution and low proportions of high molecular weight impurities.
• the polyetherols according to the invention are suitable for various applications, depending on the type of starter compound used and the alkylene oxide.
• Polyetherols which are obtained by reacting monofunctional starter compounds with one or more alkylene oxides are suitable, for example, as fuel additives or surfactants. If starter compounds with two or more active functional groups are used, the polyetherols obtained are particularly suitable for use in polyurethane synthesis.
• the present invention therefore also relates to the use of a polyetherol obtainable by a process according to the invention or a polyetherol which can be obtained using a multimetal oxide compound according to the invention, for polyurethane synthesis, as a fuel additive or as a surfactant.
• the polyetherols obtained by a process according to the invention can also be used in paints, as plasticizers, as emulsifiers or as dispersants.
• a portion of the spray powder (product A) was heated to 150 ° C. in a rotary tube oven (1 l internal volume) while passing through 10 Nl / h of air at a heating rate of 1 min and held at this temperature for 2 hours (product B).
• product A Another part of the spray powder (product A) was heated in an analogous manner to a calcination temperature of 200 ° C. and held at this temperature for 2 hours (product C). Parts of product C were each heated at a rate of 3 ° / min to a calcination temperature of 300 ° C (product D), 400 ° C (product E), 500 ° C (product F), 600 ° C (product G) and 700 ° C (product H) heated and held there for 2 hours each.
• the products A to H obtained were characterized by different methods (Table 1). In X-ray diffraction studies, all products (A - H) were clearly crystalline.
• the XRD diagram of the partzite shows a sequence of reflexes similar to that of the XRD diagram of the cubic Sb 6 O 13 (JCPCS file No. 33-0111).
• a measurement of the X-ray reflexes for the products A - F obtained at calcination temperatures of ⁇ 500 ° C led to the following values:
• the calcination products G and H which were obtained at temperatures of> 600 ° C, showed the XRD diagram 38-0453 and thus the tetragonal crystal structure of the anhydrous ZnSb 2 O 6 (Ordonezite). Furthermore, the specific BET surface area of the calcination products was determined (according to DIN 66 131 by gas adsorption (N 2 ) according to Brunner-Emmet-Teller). The products tempered at 150 to 400 ° C had the same BET surface area as the uncalcined spray powder (62 m 2 / g). As the calcination temperature increases, the specific BET surfaces decrease (see Table 1).
• the calcination products A to H were heated in a DTG-TG apparatus (Netzsch STA 429) with a heating rate of 5 ° C / min in air (flow rate 70 cm 3 air / min) from room temperature (25 ° C) to 1000 ° C , the sample lost weight with increasing temperature.
• Table 1 shows the "weight loss (DTG)" for the weight loss, which results from the difference between the initial weights of the samples in the DTG-TG apparatus and the weights of the samples at 1000 ° C. in the DTG TG apparatus result.
• the product obtained was pressure-filtered through depth filters.
• Table 1 Zinc antimony oxides made from Sb 2 O 3

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