EP3898765A1 - Procédé de production d'un copolymère bloc polyester-polyetherpolyol - Google Patents

Procédé de production d'un copolymère bloc polyester-polyetherpolyol

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Publication number
EP3898765A1
EP3898765A1 EP19817744.6A EP19817744A EP3898765A1 EP 3898765 A1 EP3898765 A1 EP 3898765A1 EP 19817744 A EP19817744 A EP 19817744A EP 3898765 A1 EP3898765 A1 EP 3898765A1
Authority
EP
European Patent Office
Prior art keywords
acid
catalyst
polyester
dmc
functional starter
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Withdrawn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
EP19817744.6A
Other languages
German (de)
English (en)
Inventor
Markus MEURESCH
Christoph Gürtler
Aurel Wolf
Martin MACHAT
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.)
Covestro Intellectual Property GmbH and Co KG
Original Assignee
Covestro Intellectual Property 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 Covestro Intellectual Property GmbH and Co KG filed Critical Covestro Intellectual Property GmbH and Co KG
Publication of EP3898765A1 publication Critical patent/EP3898765A1/fr
Withdrawn legal-status Critical Current

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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
    • C08G65/2603—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 the other compounds containing oxygen
    • C08G65/2615—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 the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used

Definitions

  • the invention relates to a process for the production of a polyester-polyether polyol block copolymer by reacting an H-functional starter substance with lactone in the presence of a catalyst to give a polyester, followed by reacting the polyester from step i) with alkylene oxides in the presence of a catalyst (B) , the lactone being a 4-membered lactone.
  • a catalyst B
  • Another subject is the polyester-polyether polyol block copolymer obtainable by the present process.
  • WO 2011/000560 A1 discloses a process for the preparation of polyetherester polyols having primary hydroxyl end groups, comprising the steps of reacting a starter compound having active hydrogen atoms with an epoxide with double metal cyanide catalysis, reacting the product obtained with a cyclic carboxylic acid anhydride and reacting the product obtained Product with ethylene oxide in the presence of a catalyst which comprises at least one nitrogen atom per molecule, with the exception of non-cyclic, identically substituted tertiary amines.
  • the resulting polyetherester polyols of this multi-stage process have a primary hydroxyl group content of a maximum of 76%.
  • WO2008 / 104723 A1 discloses a process for producing a polylactone or polylactam, in which the lactone or lactam is reacted with an H-functional starter substance in the presence of a non-chlorinated aromatic solvent and a sulfonic acid on a microliter scale.
  • an H-functional starter substance low molecular weight monofunctional or polyfunctional alcohols or thiols are used as the H-functional starter substance, with (monofunctional) n-pentanol, with e-caprolactone or d-valerolactone in the presence of high amounts of trifluoromethanesulfonic acid of 2.5 mol% or more being disclosed in the exemplary embodiments is.
  • GB 1201909 also describes a process for the production of polyester by reacting a lactone with an H-functional starter compound in the presence of an organic carbon or sulfonic acid whose PKs value at 25 ° C. is less than 2.0.
  • all reaction components such as short-chain alcohols and epsilon-caprolactone or mixtures were made Isomeric methyl-epsilon-caprolactone in large amounts of trichloro- or trifluoroacetic acid catalyst and reacted in the batch process for at least 20 hours, resulting in solids or liquid products with a broad molar mass distribution.
  • US5032671 discloses a process for the preparation of polymeric lactones by reacting an H-functional starter substance and lactones in the presence of a double metal cyanide (DMC) catalyst.
  • DMC double metal cyanide
  • the reaction of polyether polyols with e-caprolactone, d-valerolactone or ⁇ -propiolactone to give polyether-polyester polyol block copolymers is disclosed, these reactions being carried out in the presence of high amounts of 980 ppm to 1000 ppm of the cobalt-containing DMC catalyst and in Is carried out in the presence of organic solvents, the resulting products having a broad molecular weight distribution from 1.32 to 1.72.
  • polyester-polyether-polyol block copolymer under the polyester-polyether-polyol block copolymer according to the invention, is a block copolymer consisting of an inner block (A), preferably polyester block (A), which is formed in the first process step and an outer block (B ) preferably polyether polyol block (B).
  • an inner polyester block (A) with two terminal carboxy groups the reaction of both takes place in step ii) Carboxy groups with alkylene oxides to form two outer terminal polyether polyol blocks (B), so that a (B) - (A) - (B) structure is formed.
  • the inner block (A) can also have a block copolymer structure per se, for example polyesters, polycarbonates, polyether carbonates, polyether ester carbonate polyols and polyethers (block A ') terminated by reaction of hydroxyl and or carboxy groups with lactones (polyester A “) to form an (A “) - (A ') - (A“) structure.
  • block copolymer structure for example polyesters, polycarbonates, polyether carbonates, polyether ester carbonate polyols and polyethers (block A ') terminated by reaction of hydroxyl and or carboxy groups with lactones (polyester A “) to form an (A “) - (A ') - (A“) structure.
  • the H-functional starter substance comprises an H-functional starter compound with one or more free carboxy group (s) and / or functional starter compound with one or more free hydroxyl group (s), preferably an H-functional starter compound with one or more free carboxy group (s).
  • an H-functional compound is used, the H-functional compound having one or more hydroxyl group (s), preferably 1 to 8 and particularly preferably 2 to 6.
  • H-functional compound with a hydroxyl group can be CI to C20 alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 3-buten-1-ol, 3-butyn l-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, propargyl alcohol, 2-methyl-2-propanol, l-tert-butoxy-2-propanol, 1- Pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, Phenol, 2-hydroxybiphenyl, 3-hydroxybiphenyl, 4-hydroxybiphen
  • Suitable H-functional compounds with several hydroxyl groups are polyvalent CI to C20 alcohols such as, for example, dihydric alcohols (such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-butenediol, 1,1 4-butynediol, neopentylglycol, 1,5-pentanediol, methylpentanediols (such as 3-methyl-1,5-pentanediol), 1,6-hexanediol; 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol , Bis (hydroxymethyl) cyclohexanes (such as 1,4-bis (hydroxymethyl) cyclohexane), Triethylene glycol, tetraethylene glycol, polyethylene glycols, di
  • the H-functional starter substances with several hydroxyl groups can also be selected from the class of polyether polyols, in particular those with a molecular weight Mn in the range from 100 to 4000 g / mol.
  • polyether polyols which are composed of repeating ethylene oxide and propylene oxide units, preferably in a proportion of 35 to 100% propylene oxide units, particularly preferably in a proportion of 50 to 100% propylene oxide units.
  • These can be statistical copolymers, gradient copolymers, alternating or block copolymers of ethylene oxide and propylene oxide.
  • Suitable polyether polyols composed of repeating propylene oxide and / or ethylene oxide units are, for example, the Desmophen®, Acclaim®, Arcol®, Baycoll®, Bayfill®, Bayflex®, Baygal®, PET® and polyether polyols from Covestro AG (such as Desmophen® 3600Z, Desmophen® 1900U, Acclaim® Polyol 2200, Acclaim® Polyol 40001, Arcol® Polyol 1004, Arcol® Polyol 1010, Arcol® Polyol 1030, Arcol® Polyol 1070, Baycoll® BD 1110, Bayfill® VPPU 0789, Baygal® K55, PET® 1004, Polyether® S180).
  • Covestro AG such as Desmophen® 3600Z, Desmophen® 1900U, Acclaim® Polyol 2200, Acclaim® Polyol 40001, Arcol® Polyol 1004, Arcol® Polyol 1010, Arcol® Polyol 1030, Arcol®
  • suitable homo-polyethylene oxides are, for example, the Pluriol® E brands from BASF SE
  • suitable homo-polypropylene oxides are, for example, the Pluriol® P brands from BASF SE
  • suitable mixed copolymers of ethylene oxide and propylene oxide are, for example, the Pluronic® PE or Pluriol® RPE Brands of BASF SE.
  • the H-functional starter substances with several hydroxyl groups can also be selected from the substance class of the polyester polyols, in particular those with a molecular weight Mn in the range from 200 to 4500 g / mol.
  • At least difunctional polyesters can be used as polyester polyols.
  • Polyester polyols preferably consist of alternating acid and alcohol units. Examples of acid components which can be used are succinic acid, maleic acid, maleic anhydride, adipic acid, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or mixtures or the anhydrides and / or the acids mentioned and.
  • alcohol components are ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis (hydroxymethyl) cyclohexane, Diethylene glycol, dipropylene glycol, trimethylolpropane, glycerol, pentaerythritol or mixtures of the alcohols mentioned are used.
  • divalent or as alcohol component When polyvalent polyether polyols are used, polyester ether polyols are obtained which can also serve as starter substances for the production of the polyether carbonate polyols.
  • polycarbonate diols can be used as H-functional starter substances with several hydroxyl groups, in particular those with a molecular weight Mn in the range from 150 to 4500 g / mol, preferably 500 to 2500 g / mol, which can be obtained, for example, by reacting phosgene, dimethyl carbonate, diethyl carbonate or Diphenyl carbonate and difunctional alcohols or polyester polyols or polyether polyols can be produced.
  • polycarbonates can be found e.g. in EP-A 1359177.
  • the Desmophen® C types from Covestro AG can be used as polycarbonate diols, e.g. Desmophen® C 1100 or Desmophen® C 2200.
  • polyether carbonate polyols and / or polyether ester carbonate polyols can be used as H-functional starter substances with several hydroxyl groups.
  • polyether ester carbonate polyols can be used.
  • These polyetherester carbonate polyols used as H-functional starter substances can be prepared beforehand in a separate reaction step.
  • an H-functional compound is used, the H-functional compound having one or more carboxy group (s), preferably 1 to 8 and particularly preferably 2 to 6.
  • the H-functional compound having one or more carboxy group (s) has no free primary and / or secondary hydroxyl groups.
  • the H-functional starter substance with one or more free carboxy group (s) is one or more compound (s) and is selected from the group consisting of monovalent carboxylic acids, polyvalent carboxylic acids, carboxy group (s) terminated polyesters, Carboxy group (s) terminated polycarbonates, carboxy group (s) terminated polyether carbonates, carboxy group (s) terminated polyether ester carbonate polyols and carboxy group (s) terminated polyethers.
  • Suitable monovalent carboxylic acids are monovalent CI to C20 carboxylic acids such as, for example, methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, lactic acid, fluoroacetic acid, chloroacetic acid, bromoacetic acid, bromoacetic acid, bromoacetic acid, bromoacetic acid, bromoacetic acid and bromoacetic acid, bromoacetic acid, bromoacetic acid, bromoacetic acid, bromoacetic acid, bromoacetic acid and bromoacetic acid , Trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, o
  • Suitable polyvalent carboxylic acids are polyvalent C 1 to C 20 carboxylic acids such as, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, citric acid, trimesic acid, fumaric acid, maleic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanoic acid , Phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and trimellitic acid.
  • carboxylic acids such as, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, citric acid, trimesic acid, fumaric acid, maleic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanoic acid
  • the H-functional starter substances can also be selected from the substance class of the carboxy group (s) terminated polyester, in particular those with a molecular weight Mn in the range from 50 to 4500 g / mol.
  • At least difunctional polyesters can be used as the polyester.
  • Polyesters preferably consist of alternating acid and alcohol units.
  • acid components e.g. Succinic acid, maleic acid, maleic anhydride, adipic acid, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or mixtures of the acids and / or anhydrides mentioned.
  • alcohol components e.g.
  • the resulting polyesters have terminal carboxy groups.
  • Carboxy group (s) terminated polycarbonates are preferably obtained, for example, by reacting polycarbonate polyols, preferably polycarbonate diols with a stoichiometric addition or stoichiometric excess, preferably a stoichiometric excess of polyvalent carboxylic acids and / or cyclic anhydrides.
  • the polycarbonate diols in particular have a molecular weight Mn in the range from 1000 to 4500 g / mol, preferably 1500 to 2500 g / mol, the polycarbonate diols being prepared, for example, by reacting phosgene, dimethyl carbonate, diethyl carbonate or diphenyl carbonate and difunctional alcohols or polyester polyols or polyether polyols.
  • polycarbonates can be found, for example, in EP-A 1359177.
  • the Desmophen® C types from Covestro AG can be used as polycarbonate diols, such as Desmophen® C 1100 or Desmophen® C 2200.
  • Cyclic anhydrides are, for example, succinic anhydride, methyl succinic anhydride, maleic anhydride, Phthalic anhydride, tetrahydrophthalic anhydride and hexahydro-phthalic anhydride.
  • Carboxy group (s) terminated polyether carbonates and / or polyether ester carbonates are preferably obtained, for example, by reacting polyether carbonate polyols and / or polyether ester carbonate polyols with a stoichiometric addition or stoichiometric excess, preferably a stoichiometric excess of polyvalent carboxylic acids and / or cyclic anhydrides.
  • the polyether carbonate polyols e.g.
  • polyether carbonate polyols, polycarbonate polyols and / or polyether ester carbonate polyols can be obtained by reacting alkylene oxides, preferably ethylene oxide, propylene oxide or mixtures thereof, optionally further co-monomers with CO 2 in the presence of a further H-functional starter compound and using catalysts.
  • These catalysts include double metal cyanide catalysts (DMC catalysts) and / or metal complex catalysts, for example based on the metals zinc and / or cobalt, such as zinc glutarate catalysts (described, for example, in MH Chisholm et al., Macromolecules 2002, 35, 6494) , so-called zinc diiminate catalysts (described for example in SD Allen, J. Am. Chem. Soc. 2002, 124, 14284) and so-called cobalt salen catalysts (described for example in US Pat. No. 7,304,172 B2, US 2012/0165549 Al) and / or manganese-salen complexes.
  • DMC catalysts double metal cyanide catalysts
  • metal complex catalysts for example based on the metals zinc and / or cobalt, such as zinc glutarate catalysts (described, for example, in MH Chisholm et al., Macromolecules 2002, 35, 6494) , so-called zinc di
  • Cyclic anhydrides are, for example, succinic anhydride, methyl succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride and hexahydrophthalic anhydride.
  • Carboxy group (s) terminated polyethers are preferably obtained, for example, by reacting polyether polyols with stoichiometric addition or a stoichiometric excess, preferably a stoichiometric excess of polyvalent carboxylic acids and / or cyclic anhydrides.
  • the polyether polyols which are composed of repeating ethylene oxide and propylene oxide units, preferably with a proportion of 50 to 100% propylene oxide units, particularly preferably with a proportion of 80 to 100% propylene oxide units. These can be statistical copolymers, gradient copolymers, alternating or block copolymers of ethylene oxide and propylene oxide.
  • Suitable polyether polyols composed of repeating propylene oxide and / or ethylene oxide units are, for example, the Desmophen®, Acclaim®, Arcol®, Baycoll®, Bayfill®, Bayflex® Baygal®, PET® and polyether polyols from Covestro AG (such as Desmophen® 3600Z, Desmophen® 1900U, Acclaim® Polyol 2200, Acclaim® Polyol 40001, Arcol® Polyol 1004, Arcol® Polyol 1010, Arcol® Polyol 1030, Arcol® Polyol 1070, Baycoll® BD 1110, Bayfill® VPPU 0789, Baygal® K55, PET® 1004, Polyether® S180).
  • Covestro AG such as Desmophen® 3600Z, Desmophen® 1900U, Acclaim® Polyol 2200, Acclaim® Polyol 40001, Arcol® Polyol 1004, Arcol® Polyol 1010, Arcol® Polyol 1030, Arcol® Poly
  • suitable homo-polyethylene oxides are, for example, the Pluriol® E brands from BASF SE
  • suitable homo-polypropylene oxides are, for example, the Pluriol® P brands from BASF SE
  • suitable mixed copolymers of ethylene oxide and propylene oxide are, for example, the Pluronic® PE or Pluriol® RPE Brands of BASF SE.
  • Cyclic anhydrides include maleic anhydride, succinic anhydride, methyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride and hexahydrophthalic anhydride.
  • the H-functional starter substance with one or more free carboxy group (s) is one or more compounds and is selected from the group consisting of methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, lactic acid, fluoroacetic acid, chloroacetic acid, bromoacetic acid, iodoacetic acid, difluoroacetic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, oleic acid, salicylic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
  • lactones are to be understood as heterocyclic compounds, lactones by intramolecular esterification, i.e. the reaction of a hydroxy functionality with a carboxy functionality of a hydroxycarboxylic acid. It is therefore cyclic esters with a ring oxygen.
  • the 4-membered ring lactone is one or more compounds which are selected from the group consisting of propiolactone, ⁇ -butyrolactone, diketene, preferably propiolactone and ⁇ -butyrolactone.
  • step i) is carried out in the presence of the catalyst (A).
  • the catalyst (A) used in step i) is an amine (A), a double metal cyanide (DMC) catalyst (A) or a Bronsted acid catalyst (A), preferably a double metal cyanide (DMC). Catalyst (A).
  • the catalyst (A) is an amine (A), the tertiary amine (A) being at least one compound selected from at least one group consisting of:
  • R2 and R3 are independently hydrogen, alkyl or aryl
  • R2 and R3 together with the N atom carrying them form an aliphatic, unsaturated or aromatic heterocycle
  • n is an integer from 1 to 10;
  • R4 is hydrogen, alkyl or aryl
  • R4 stands for - (CH2) x-N (R41) (R42), where:
  • R41 and R42 are independently hydrogen, alkyl or aryl
  • R41 and R42 together with the N atom carrying them form an aliphatic, unsaturated or aromatic heterocycle
  • x is an integer from 1 to 10;
  • R5 is hydrogen, alkyl or aryl
  • R6 and R7 are independently hydrogen, alkyl or aryl
  • n and o are independently an integer from 1 to 10;
  • the catalyst (A) is a double metal cyanide (DMC) catalyst (A).
  • DMC double metal cyanide
  • the DMC catalysts which can preferably be used in the process according to the invention contain double metal cyanide compounds which are the reaction products of water-soluble metal salts and water-soluble metal cyanide salts.
  • Double metal cyanide (DMC) catalysts for use in the homopolymerization of alkylene oxides are known in principle from the prior art (see, for example, US Pat. Nos. 3,440,109, 3,829,505, 3,941,849 and 5) 158 922).
  • DMC catalysts e.g. in US-A 5 470 813, EP-A 700 949, EP-A 743 093, EP-A 761 708, WO 97/40086, WO 98/16310 and WO 00/47649 have a very high activity and enable the production of polyoxyalkylene polyols at very low catalyst concentrations.
  • a typical example is the highly active DMC catalysts described in EP-A 700 949, which, in addition to a double metal cyanide compound (eg zinc hexacyanocobaltate (III)) and an organic complex ligand (eg ferf-butanol), also a polyether with a number average molecular weight greater than 500 contain g / mol.
  • a double metal cyanide compound eg zinc hexacyanocobaltate (III)
  • an organic complex ligand eg ferf-butanol
  • the DMC catalysts which can be used according to the invention are preferably obtained by (1.) in the first step an aqueous solution of a metal salt with the aqueous solution of a metal cyanide salt in the presence of one or more organic complex ligands, e.g. an ether or alcohol,
  • the solid obtained is dried at temperatures of generally 20-120 ° C. and at pressures of generally 0.1 mbar to normal pressure (1013 mbar),
  • the double metal cyanide compounds contained in the DMC catalysts which can be used according to the invention are the reaction products of water-soluble metal salts and water-soluble metal cyanide salts.
  • an aqueous zinc chloride solution preferably in excess based on the metal cyanide salt
  • potassium hexacyanocobaltate are mixed and then dimethoxyethane (Glyme) or r-butanol (preferably in excess, based on zinc hexacyanocobaltate) added to the suspension formed.
  • Metal salts suitable for the preparation of the double metal cyanide compounds preferably have a composition of the general formula (I)
  • M is selected from the metal cations Zn 2+ , Fe 2+ , Ni 2+ , Mn 2+ , Co 2+ , Sr 2+ , Sn 2+ , Pb 2+ and, Cu 2+ , M Zn 2+ is preferred, Fe 2+ , Co 2+ or Ni 2+ ,
  • X are one or more (ie different) anions, preferably an anion selected from the group consisting of the halides (ie fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate and nitrate ;
  • M is selected from the metal cations Fe 3+ , Al 3+ , Co 3+ and Cr 3+ ,
  • X comprises one or more (i.e. different) anions, preferably an anion selected from the group of the halides (i.e. fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate isocyanate, isothiocyanate, carboxylate, oxalate and nitrate;
  • halides i.e. fluoride, chloride, bromide, iodide
  • M is selected from the metal cations Mo 4+ , V 4+ and W 4+ ,
  • X comprises one or more (ie different) anions, preferably an anion selected from the group consisting of the halides (ie fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate and nitrate ;
  • M is selected from the metal cations Mo 6+ and W 6+ ,
  • X comprises one or more (i.e. different) anions, preferably anions selected from the group of halides (i.e. fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate and nitrate;
  • halides i.e. fluoride, chloride, bromide, iodide
  • hydroxide sulfate
  • carbonate cyanate
  • thiocyanate thiocyanate
  • isocyanate isothiocyanate
  • carboxylate oxalate and nitrate
  • suitable metal salts are zinc chloride, zinc bromide, zinc iodide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, iron (II) sulfate, iron (II) bromide, iron (II) chloride, iron (III) chloride, cobalt (II) chloride, Cobalt (II) thiocyanate, nickel (II) chloride and nickel (II) nitrate. Mixtures of different metal salts can also be used.
  • Metal cyanide salts suitable for the preparation of the double metal cyanide compounds preferably have a composition according to the general formula (V)
  • M ' is selected from one or more metal cations from the group consisting of Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II), Mn ( III), Ir (III), Ni (II), Rh (III), Ru (II), V (IV) and V (V), M 'is preferably one or more metal cations from the group consisting of Co (II), Co (III), Fe (II), Fe (III), Cr (III), Ir (III) and Ni (II),
  • Y is selected from one or more metal cations from the group consisting of alkali metal (ie Li + , Na + , K + , Rb + ) and alkaline earth metal (ie Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ ),
  • A is selected from one or more anions from the group consisting of halides (i.e. fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, azide, oxalate or nitrate and
  • a, b and c are integer numbers, the values for a, b and c being chosen so that the electroneutrality of the metal cyanide salt is given; a is preferably 1, 2, 3 or 4; b is preferably 4, 5 or 6; c preferably has the value 0.
  • Suitable metal cyanide salts are sodium hexacyanocobaltate (III), potassium hexacyano cobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), calcium hexacyano cobaltate (III) and lithium hexacyanocobaltate (III).
  • Preferred double metal cyanide compounds which are contained in the DMC catalysts which can be used according to the invention are compounds having compositions of the general formula (VI)
  • M Zn (II), Fe (II), Co (II) or Ni (II) and
  • M ’ Co (III), Fe (III), Cr (III) or Ir (III).
  • Suitable double metal cyanide compounds are zinc hexacyanocobaltate (III), zinc hexacyanoiridate (III), zinc hexacyanoferrate (III) and cobalt (II) hexacyanocobaltate (III).
  • suitable double metal cyanide compounds are e.g. US 5 158 922 (column 8, lines 29-66).
  • Zinc hexacyanocobaltate (III) can be used particularly preferably.
  • the organic complex ligands which can be added in the preparation of the DMC catalysts are described, for example, in US Pat. No. 5,158,922 (see in particular column 6, lines 9 to 65), US Pat. No. 3,404,109, US Pat. No.
  • organic complex ligands water-soluble organic compounds with heteroatoms, such as oxygen, nitrogen, phosphorus or sulfur, which can form complexes with the double metal cyanide compound, are used as organic complex ligands.
  • organic complex ligands are alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides and mixtures thereof.
  • Particularly preferred organic complex ligands are aliphatic ethers (such as dimethoxyethane), water-soluble aliphatic alcohols (such as ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, 2-methyl-3-buten-2-ol and 2-methyl-3-butyn-2-ol), compounds which contain both aliphatic or cycloaliphatic ether groups and aliphatic hydroxyl groups (such as, for example, ethylene glycol mono-tert-butyl ether, diethylene glycol mono-tert-butyl ether, tripropylene glycol mono-methyl ether and 3-methyl-3-oxetane-methanol).
  • aliphatic ethers such as dimethoxyethane
  • water-soluble aliphatic alcohols such as ethanol, isopropanol, n-butanol, isobutanol, sec-butan
  • Most preferred organic complex ligands are selected from one or more compounds from the group consisting of dimethoxyethane, tert-butanol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, ethylene glycol mono- tert-butyl ether and 3-methyl-3-oxetane-methanol.
  • One or more complex-forming component (s) from the compound classes of polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylic acid) are optionally used in the production of the DMC catalysts which can be used according to the invention.
  • polyacrylonitrile polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinyl pyrrolidone, poly (N-vinyl pyrrolidone-co-acrylic acid), polyvinyl methyl ketone, poly (4-vinylphenol), poly (acrylic acid -co-styrene), oxazoline polymers, polyalkyleneimines, maleic and maleic anhydride copolymers, hydroxyethyl cellulose and polyacetals, or the glycidyl ethers, glycosides, carboxylic acid esters of polyhydric alcohols, bile acids or their salts, esters or amides, cyclodextrins, Phosphorus compounds, a, b-unsaturated carboxylic acid esters or ionic surface or
  • the aqueous solutions of the metal salt are preferably used in a stoichiometric excess (at least 50 mol%), based on the metal cyanide salt, in the preparation of the DMC catalysts which can be used according to the invention. This corresponds to at least a molar ratio of metal salt to metal cyanide salt of 2.25 to 1.00.
  • the metal cyanide salt e.g. potassium hexacyanocobaltate
  • the organic complex ligand e.g. tert-butanol
  • the organic complex ligand can be present in the aqueous solution of the metal salt and / or the metal cyanide salt, or it is added directly to the suspension obtained after precipitation of the double metal cyanide compound. It has proven advantageous to mix the aqueous solutions of the metal salt and the metal cyanide salt, and the organic complex ligand with vigorous stirring.
  • the suspension formed in the first step is then treated with a further complex-forming component.
  • the complex-forming component is preferably used in a mixture with water and organic complex ligands.
  • a preferred method for carrying out the first step i.e. the preparation of the suspension
  • the solid i.e. the catalyst precursor
  • the solid can be isolated from the suspension by known techniques such as centrifugation or filtration.
  • the isolated solid is then washed in a third process step with an aqueous solution of the organic complex ligand (e.g. by resuspending and then isolating again by filtration or centrifugation).
  • an aqueous solution of the organic complex ligand e.g. by resuspending and then isolating again by filtration or centrifugation.
  • water-soluble by-products such as potassium chloride
  • the amount of the organic complex ligand in the aqueous washing solution is preferably between 40 and 80% by weight, based on the total solution.
  • a further complex-forming component preferably in the range between 0.5 and 5% by weight, based on the total solution, is added to the aqueous washing solution in the third step.
  • washing is preferably carried out with an aqueous solution of the organic complex ligand (for example by resuspending and then isolating again by filtration or centrifugation), in order in this way to remove, for example, water-soluble by-products, such as potassium chloride, from the catalyst which can be used according to the invention.
  • an aqueous solution of the organic complex ligand for example by resuspending and then isolating again by filtration or centrifugation
  • the amount of the organic complex ligand in the aqueous washing solution is preferably between 40 and 80% by weight, based on the total solution of the first washing step.
  • either the first washing step is repeated one or more times, preferably once to three times, or preferably a non-aqueous solution, such as, for example, a mixture or solution of organic complex ligands and further complex-forming component (preferably in the range between 0.5 and 5% by weight, based on the total amount of the washing solution of the step, is used as the washing solution and the reading material is thus washed once or more times, preferably once to three times.
  • a non-aqueous solution such as, for example, a mixture or solution of organic complex ligands and further complex-forming component (preferably in the range between 0.5 and 5% by weight, based on the total amount of the washing solution of the step, is used as the washing solution and the reading material is thus washed once or more times, preferably once to three times.
  • the isolated and optionally washed solvent can then be dried, if appropriate after pulverization, at temperatures of 20-100 ° C. and at pressures from 0.1 mbar to normal pressure (1013 mbar).
  • the double metal cyanide catalyst (A) comprises an organic complex ligand, the organic complex ligand being one or more compound (s) and being selected from the group consisting of tert-butanol 2-methyl-3-buten-2 -ol, 2-methyl-3-butyn-2-ol, ethylene glycol mono-tert-butyl ether and 3-methyl-3-oxetane-methanol
  • the double metal cyanide (DMC) catalyst is used in an amount of 20 ppm to 5000 ppm, preferably 50 ppm to 4000 ppm, based on the polyester formed.
  • the catalyst (A) is a Bronsted acid (Bronsted acidic catalyst (A)).
  • Brönsted acids are substances that can transfer protons to a second reaction partner, the so-called Brönsted base, typically in an aqueous medium at 25 ° C.
  • the term of the Bronsted acid catalyst denotes a non-polymeric compound, the term of the Bronsted acid catalyst having a calculated molar mass of ⁇ 1200 g / mol, preferably of ⁇ 1000 g / mol and particularly preferably of ⁇ 850 g / mol.
  • the Bronsted acid catalyst (A) has a pKa value of less than or equal to 1, preferably less than or equal to 0.
  • the Bronsted acid catalyst is one or more compounds and is selected from the group consisting of aliphatic fluorinated sulfonic acids, aromatic fluorinated sulfonic acids, trifluoromethanesulfonic acid, perchloric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, fluorosulfonic acid, bis (trifluoromethane) sulfonimide, Hexafluoroantimonic acid,
  • Pentacyanocyclopentadiene picric acid, sulfuric acid, nitric acid, trifluoroacetic acid, methanesulfonic acid, paratoluenesulfonic acid, aromatic sulfonic acids and aliphatic sulfonic acids, preferably from trifluoromethanesulfonic acid, perchloric acid, hydrochloric acid, hydrobromic acid, hydrogen iodide, trisulfonic acid, fluorosulfonic acid, fluorosulfonic acid Nitric acid, trifluoro-acetic acid, methanesulfonic acid, paratoluenesulfonic acid, methanesulfonic acid and paratoluenesulfonic acid, particularly preferably from trifluoromethanesulfonic acid, perchloric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, bis (trifluoromethane) sulfonimide, pentacyanocyclophenic
  • the Bronsted acid catalyst is obtained in an amount of from 0.001 mol% to 0.5 mol%, preferably from 0.003 to 0.4 mol% and particularly preferably from 0.005 to 0.3 mol% used on the amount of lactone.
  • the catalyst (B) is a tertiary amine (B), a double metal cyanide (DMC) catalyst (B) or a Bronsted acid catalyst (B), preferably a double metal cyanide (DMC) catalyst (B).
  • the catalyst (B) is a tertiary amine (B), the tertiary amine (B) having the definition according to the invention identical to the tertiary amine (A) from step i).
  • the catalyst (B) is a double metal cyanide (DMC) catalyst (B), the double metal cyanide (DMC) catalyst (B) having the definition according to the invention identical to the double metal cyanide (DMC) catalyst (A ) having.
  • DMC double metal cyanide
  • DMC double metal cyanide
  • the double metal cyanide (DMC) catalyst (B) comprises an organic complex ligand, the organic complex ligand being one or more compound (s) and being selected from the group consisting of tert-butanol 2-methyl-3- buten-2-ol, 2-methyl-3-butyn-2-ol, ethylene glycol mono-tert-butyl ether and 3-methyl-3-oxetane-methanol.
  • the catalyst (B) is a Bronsted acid catalyst (B), the Bronsted acid catalyst (B) having the definition according to the invention identical to the Bronsted acid catalyst (A).
  • the catalyst (A), preferably the double metal cyanide (DMC) catalyst (A), is identical to the catalyst (B), preferably the double metal cyanide (DMC) catalyst (B), and is added in step i).
  • the catalyst can also, but not preferably, be the amine or the Bronsted acid catalyst.
  • a solvent can be used in step i) and / or step ii) according to the method according to the invention.
  • a solvent is to be understood as meaning one or more compounds which dissolve the lactone, the polyester or the H-functional starter compound and / or the catalyst without, however, themselves with the lactone, the bi-functional starter compound and / or the catalyst to react.
  • Suitable solvents are aprotic solvents such as toluene, benzene, tetrahydrofuran, dimethyl ether and diethyl ether.
  • the process according to the invention is carried out without the addition of a solvent, so that it does not have to be removed in an additional process step after the polyester has been prepared.
  • step ii) the polyester from step i) is reacted in step ii) with alkylene oxides in the presence of a catalyst (B).
  • Alkylene oxides having 2-4 carbon atoms can be used as alkylene oxides in the process according to the invention.
  • the alkylene oxides having 2 to 45 carbon atoms are, for example, one or more compounds selected from the group comprising ethylene oxide, propylene oxide, 1-butene oxide, 2,3-butene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1 Pentene oxide, 2,3-pentene oxide, 2-methyl-l, 2-butene oxide, 3-methyl-l, 2-butene oxide, alkylene oxides of C6-C22 a-olefins, such as 1-hexene oxide, 2, 3 -hexene oxide, 3 , 4-hexene oxide, 2-methyl-1,2-pentene oxide, 4-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 1-heptene oxide, 1- Octenoxide, 1-nonoxide, 1-decene oxide, 1-undecene oxide, 1-d
  • Examples of derivatives of glycidol are phenyl glycidyl ether, cresyl glycidyl ether, methyl glycidyl ether, ethyl glycidyl ether and 2-ethylhexyl glycidyl ether.
  • alkylene oxides are ethylene oxide and / or propylene oxide, in particular propylene oxide. If ethylene oxide and propylene oxide are used in a mixture, the molar ratio EO / PO is 1:99 to 99: 1, preferably 5:95 to 50:50. If ethylene oxide and / or propylene oxide are used in a mixture with other unsaturated alkylene oxides, their proportion is 1 to 40 mol%, preferably 2 to 20 mol%.
  • the polyester from step i) is reacted in step ii) with alkylene oxides and a co-monomer in the presence of the catalyst (B), the co-monomer being, for example, carbon dioxide and the catalyst (B) the Double metal cyanide (DMC) catalyst (B) to form a polyester-polyether carbonate-polyol block copolymer.
  • the catalyst (B) the co-monomer being, for example, carbon dioxide and the catalyst (B) the Double metal cyanide (DMC) catalyst (B) to form a polyester-polyether carbonate-polyol block copolymer.
  • the reaction of the bi-functional starter substance with the lactone is carried out in the presence of the catalyst (A), preferably the Bronsted acid catalyst (A) in step i) at temperatures from 20 to 150 ° C., preferably from 20 to 100 ° C. Below 20 ° C there is no or only insignificant conversion to the product according to the invention and above 150 ° C the decomposition of the polyester formed and / or unwanted side or subsequent reactions take place.
  • the catalyst (A) preferably the Bronsted acid catalyst (A) in step i) at temperatures from 20 to 150 ° C., preferably from 20 to 100 ° C. Below 20 ° C there is no or only insignificant conversion to the product according to the invention and above 150 ° C the decomposition of the polyester formed and / or unwanted side or subsequent reactions take place.
  • the reaction of the H-functional starter substance with the lactone in the presence of the double metal cyanide (DMC) catalyst (A) in step i) at temperatures from 70 to 150 ° C., preferably from 90 to 130 ° C. . Below 70 ° C there is no or only insignificant conversion to the product according to the invention and above 150 ° C the decomposition of the polyester formed and / or unwanted parallel or subsequent reactions take place.
  • DMC double metal cyanide
  • the method according to the invention comprises the following steps for step i): i-1) introducing the H-functional starter substance and optionally the catalyst to form a mixture i)
  • the lactone is added continuously or stepwise to the H-functional starter substance in step i-2) and converted to the polyester (semi-batch mode).
  • continuous addition of the lactone is understood to mean a volume flow of the lactone of> 0 mL / min, the volume flow being constant or varying during this step (continuous lactone addition).
  • the lactone is added stepwise to mixture i) in step i-2) and then converted to the polyester (stepwise addition of lactone).
  • a gradual addition of the lactone is understood to mean at least the addition of the total amount of lactone in two or more discrete portions of the lactone, the volume flow of the lactone between the or more discrete portions being 0 ml / min and the volume flow of the lactone during of a discrete portion can be constant or varies but is> 0 mL / min.
  • step i) of the method according to the invention comprises the following steps:
  • step i) of the method according to the invention comprises the following steps:
  • the lactone and the H-functional starter substance can be premixed or the lactone and the H-functional starter substance can be added to the reactor by separate feeds.
  • step i) in step i) the H-functional starter substance, the lactone and the catalyst are continuously mixed and reacted with one another while the polyester product is continuously removed, the reaction being carried out, for example, in a tubular reactor or a continuous stirred tank reactor (English stirred tank reactor) is carried out which corresponds to a fully continuous production process for step i) of the process according to the invention of the polyester.
  • a tubular reactor or a continuous stirred tank reactor (English stirred tank reactor) is carried out which corresponds to a fully continuous production process for step i) of the process according to the invention of the polyester.
  • the method according to the invention comprises the following steps for step ii):
  • step i) Submitting the polyester from step i) optionally containing the catalyst (A) and / or (B) ii-2) adding the alkylene oxide and optionally a co-monomer.
  • the alkylene oxide is added to the polyester continuously or stepwise in step ii-2) and converted to the polyester-polyether-polyol block copolymer (semi-batch mode).
  • a continuous addition of the alkylene oxide in step ii-2) is understood to mean a volume flow of the alkylene oxide of> 0 ml / min, the volume flow being able to be constant or varying during this step (continuous addition of alkylene).
  • the alkylene oxide is added stepwise to mixture i) in step ii-2) and then converted to the polyester-polyetherpolyol block copolymer (stepwise addition of alkylene oxide).
  • a gradual addition of the alkylene oxide is understood to mean at least the addition of the total amount of alkylene oxide in two or more discrete portions of the alkylene oxide, the volume flow of the alkylene oxide between the or more discrete portions being 0 ml / min and the volume flow of the alkylene oxide during of a discrete portion can be constant or varies but is> 0 mL / min.
  • step ii) of the method according to the invention comprises the following steps:
  • step ii-b converting the mixture (ii-a) to the polyester-polyether-polyol block copolymer, which corresponds to a batch-wise procedure of step ii).
  • step ii) of the method according to the invention comprises the following steps:
  • the alkylene oxide and the polyester can be premixed or the alkylene oxide and the polyester are added to the reactor by separate feeds. This corresponds to a CAOS (Continuous Addition of Starter) procedure of step ii).
  • step ii) the polyester optionally comprising the catalyst (A), the alkylene oxide and the optionally the catalyst (B) is continuously mixed and reacted with one another, while the polyester-polyether polyol block copolymer product is continuously removed , the reaction being carried out, for example, in a tubular reactor or in a continuous stirred tank reactor, which corresponds to a fully continuous production process for step ii) of the process according to the invention for the polyester.
  • step ii) is carried out in an inert gas atmosphere, such as, for example, or nitrogen, argon) or in a carbon dioxide atmosphere, polyester-polyether carbonate-polyol block copolymers being formed in the carbon dioxide atmosphere by incorporating the CO 2.
  • an inert gas atmosphere such as, for example, or nitrogen, argon
  • a carbon dioxide atmosphere polyester-polyether carbonate-polyol block copolymers being formed in the carbon dioxide atmosphere by incorporating the CO 2.
  • steps i) and ii) are carried out in the same reactor or in different reactors, preferably in the same reactor.
  • Another object of the present invention are polyesters obtainable by the process according to the invention.
  • polyester-polyether polyol block copolymers obtainable by the process according to the invention.
  • the polyester-polyether polyol block copolymer according to the invention has a number average molecular weight from 70 g / mol to 15,000 g / mol, preferably from 100 g / mol to 10,000 g / mol and particularly preferably from 100 g / mol to 5,000 g / mol, where the number average molecular weight is determined by means of the gel permeation chromatography (GPC) disclosed in the experimental part.
  • GPC gel permeation chromatography
  • Another object of the present invention are polyurethane polymers obtainable from the reaction of a polyisocyanate with a polyester-polyether polyol block copolymer obtainable by the process according to the invention and a process for the production of polyurethane polymers.
  • the polyisocyanate can be an aliphatic or aromatic polyisocyanate.
  • Examples are 1,4-butylene diisocyanate, 1,5-pentane diisocyanate, 1,6-hexamethylene diisocyanate (HDI) or their dimers, trimers, pentamers, heptamers or nonamers or mixtures thereof, isophorone diisocyanate (IPDI), 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis (4,4'-isocyanatocyclohexyl) methanes or their mixtures of any isomer content, 1,4-cyclohexylene diisocyanate, 1,4-phenylene diisocyanate, 2,4- and / or 2,6 Tolylene diisocyanate (TDI), 1,5-naphthylene diisocyanate, 2,2'- and / or 2,4'- and / or 4,4'-diphenyl
  • the invention relates to a method for producing a polyester-polyether-polyol block copolymer, comprising the following steps:
  • step ii) reacting the polyester from step i) with alkylene oxides in the presence of a catalyst (B); the lactone being a 4-membered lactone.
  • the invention relates to a process according to the first embodiment, step i) being carried out in the presence of the catalyst (A).
  • the invention relates to a process according to the second embodiment, the catalyst (A) being an amine (A), a double metal cyanide (DMC) catalyst (A) or a Bronsted acid catalyst (A), preferably a double metal cyanide (DMC) ) Catalyst (A).
  • the catalyst (A) being an amine (A), a double metal cyanide (DMC) catalyst (A) or a Bronsted acid catalyst (A), preferably a double metal cyanide (DMC) ) Catalyst (A).
  • the invention relates to a method of the third embodiment, wherein the catalyst (A) is a double metal cyanide (DMC) catalyst (A) and the double metal cyanide (DMC) catalyst (A) comprises an organic complex ligand, the organic complex ligand is one or more compound (s) and is selected from the group consisting of tert-butanol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, ethylene glycol mono-tert-butyl ether and 3-methyl-3-oxetane-methanol.
  • DMC double metal cyanide
  • DMC double metal cyanide
  • the invention relates to a method according to one of the first to fourth embodiments, the H-functional starter substance being an H-functional starter compound with one or more free carboxy group (s) and / or functional starter compound with one or more free hydroxyl group (s ) preferably comprises a bi-functional starter compound with one or more free carboxy group (s).
  • the invention relates to a method according to the fifth embodiment, wherein the H-functional starter substance is an H-functional starter compound with one or more free carboxy group (s) and the H-functional starter compound with one or more free carboxy group (s) is one or more compound (s) and is selected from the group consisting of the H-functional starter substance with one or more free carboxy group (s) one or more compound (s) and is selected from the group consisting of monovalent carboxylic acids, polyvalent carboxylic acids , Carboxy group (s) terminated polyesters, carboxy group (s) terminated polycarbonates, carboxy group (s) terminated polyether carbonates, carboxy group (s) terminated polyetherester carbonate polyols and carboxy group (s) terminated polyethers.
  • the invention relates to a method according to the sixth embodiment, wherein the H-functional starter compound with one or more free carboxy group (s) is one or more compound (s) and is selected from the group consisting of methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, lactic acid, fluoroacetic acid, chloroacetic acid, bromoacetic acid, iodoacetic acid, difluoroacetic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, oleic acid, salicylic acid, benzoic acid, oxalic acid, malonic acid, Succinic acid, gluta
  • the invention relates to a process according to one of the first to seventh embodiments, the 4-membered lactone being one or more compounds selected from the group consisting of propiolactone, ⁇ -butyrolactone, ⁇ -isovalerolactone, ⁇ -caprolactone, ⁇ - Isocaprolactone, ß-methyl-ß-valerolactone, diketene preferred propiolactone and ß-butyrolactone.
  • the invention relates to a process according to one of the first to eighth embodiments, the catalyst (B) preferably a tertiary amine (B), a double metal cyanide (DMC) catalyst (B) or a Bronsted acid catalyst (B) is a double metal cyanide (DMC) catalyst (B).
  • the catalyst (B) preferably a tertiary amine (B), a double metal cyanide (DMC) catalyst (B) or a Bronsted acid catalyst (B) is a double metal cyanide (DMC) catalyst (B).
  • the invention relates to a method according to one of the first to ninth embodiments, the alkylene oxide being ethylene oxide and / or propylene oxide.
  • the invention relates to a method according to a third to seventh embodiment, wherein the double metal cyanide (DMC) catalyst (A) is identical to the double metal cyanide (DMC) catalyst (B) and is added in step i).
  • DMC double metal cyanide
  • the invention relates to a method according to one of the first to eleventh embodiments, the method being carried out without the addition of a solvent.
  • the invention relates to a polyester obtainable by a process according to one of the first to ninth embodiments.
  • the invention relates to a polyester-polyether polyol block copolymer obtainable by a process according to one of the first to twelfth embodiments.
  • the invention relates to a polyurethane polymer obtainable from the reaction of a polyisocyanate with a polyester-polyether polyol block copolymer according to the fourteenth embodiment.
  • PPG-1000 propylene oxide-based polyether with average molecular weight of 1000 g / mol
  • adipic acid Sigma-Aldrich, BioXtra, 99.5% (HPFQ)
  • a DMC catalyst was used, which was prepared according to Example 6 in WO 01/80994 A1.
  • the conversion of the respective monomer is determined as the integral of a suitable polymer signal divided by the sum of a suitable polymer signal and monomer signal. All signals are referenced to 1H.
  • the analysis of the samples was carried out in accordance with DIN EN ISO / IEC 17025 using a device of the type Mettler-Toledo GmbH TGA / SDTA851e. The measurement was carried out between 30 ° C and 600 ° C with a heating rate of 10 ° C / min in air (50.0 mL / min).
  • Example 1 Production of a Polvester-Polvetherpolvol block copolymer (with a PET-PES-PET block copolymer structure) by block copolymerization of propiolactone and propylene oxide by means of DMC catalysis
  • THF trifluorofuran
  • DMC catalyst 3000 ppm based on the total mass of starter and ⁇ -lactone
  • adipic acid 1.46 g, 10.0 mmol, 1.00 eq.
  • the reactor is flushed with N2.
  • ⁇ -propiolactone (18.5 g, 257 mmol, 25.7 eq.) Is then continuously fed into the reactor over 120 min.
  • the mixture is stirred at 130 ° C for 120 min.
  • Propylene oxide (10.0 g, 172 mmol, 17.2 eq.) Is then continuously fed into the reactor over 60 min.
  • the mixture is stirred at 130 ° C for 180 min.
  • Example 2 Preparation of a Polvester-Polvetherpolvol block copolymer (with a PET-PES-PET block copolymer structure) by block copolymerization of propiolactone and propylene oxide by means of DMC catalysis
  • THF trifluoride
  • DMC catalyst 3000 ppm based on the total mass of starter and ⁇ -lactone
  • adipic acid 2.92 g, 20.0 mmol, 1.00 eq.
  • the reactor is flushed with N.
  • ⁇ -propiolactone (17.1 g, 237 mmol, 11.9 eq.) Is then fed continuously into the reactor over 120 min.
  • the mixture is stirred at 130 ° C for 120 min.
  • Propylene oxide (40.0 g, 689 mmol, 34.5 eq.) Is then continuously fed into the reactor over 90 min.
  • the mixture is stirred at 130 ° C for 180 min.
  • the sales are determined by means of H NMR analysis of the reaction solution. Volatile components are then removed in vacuo.
  • the copolymer is examined for its thermal stability by means of TGA analysis.
  • Example 3 Preparation of a Polvester-Polvetherpolvol block copolymer (with a PES-PET-PES blockconol polymer structure) by polymerizing propiolactone onto a polymeric propylene oxide-based polyether using DMC catalysis
  • Table 2 Decomposition temperatures T d of the polyetherester block copolymers from ⁇ -lactones and propylene oxide by means of DMC catalysis

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Abstract

L'invention concerne un procédé de préparation d'un copolymère bloc polyester-polyetherpolyol par mise en réaction d'une substance d'amorce à fonction H avec une lactone en présence d'un catalyseur pour former un polyester i), suivie par la mise en réaction du polyester de l'étape i) avec des oxydes d'alkylène en présence d'un catalyseur (B), la lactone étant une lactone cyclique à 4 chaînons. Un autre objet de l'invention concerne le copolymère bloc polyester-polyetherpolyol pouvant être obtenu par le procédé selon l'invention.
EP19817744.6A 2018-12-21 2019-12-16 Procédé de production d'un copolymère bloc polyester-polyetherpolyol Withdrawn EP3898765A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP18215182.9A EP3670571A1 (fr) 2018-12-21 2018-12-21 Procédé de production d'un copolymère séquencé de polyester-polyétherpolyol
PCT/EP2019/085305 WO2020127016A1 (fr) 2018-12-21 2019-12-16 Procédé de production d'un copolymère bloc polyester-polyetherpolyol

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EP3898765A1 true EP3898765A1 (fr) 2021-10-27

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CN112851918B (zh) * 2021-02-05 2021-12-07 吉林大学 一种高性能脂肪族聚酯弹性体及其制备方法
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