EP3883980A1 - Procédé de préparation de copolymères séquencés d'oxyde de polyalkylène de polyoxyméthylène - Google Patents

Procédé de préparation de copolymères séquencés d'oxyde de polyalkylène de polyoxyméthylène

Info

Publication number
EP3883980A1
EP3883980A1 EP19802180.0A EP19802180A EP3883980A1 EP 3883980 A1 EP3883980 A1 EP 3883980A1 EP 19802180 A EP19802180 A EP 19802180A EP 3883980 A1 EP3883980 A1 EP 3883980A1
Authority
EP
European Patent Office
Prior art keywords
polyoxymethylene
polymer
alkylene oxide
catalyst
oxide
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Withdrawn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
EP19802180.0A
Other languages
German (de)
English (en)
Inventor
Markus MEURESCH
Aurel Wolf
Christoph Gürtler
Annika STUTE
Mike SCHÜTZE
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 EP3883980A1 publication Critical patent/EP3883980A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy 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
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/18—Copolymerisation of aldehydes or ketones
    • C08G2/22—Copolymerisation of aldehydes or ketones with epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4866—Polyethers having a low unsaturation value
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/54—Polycondensates of aldehydes
    • C08G18/546—Oxyalkylated polycondensates of aldehydes
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/56—Polyacetals
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/38—Block or graft polymers prepared by polymerisation of aldehydes or ketones on to macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C08G64/183—Block or graft polymers containing polyether sequences
    • 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
    • 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

Definitions

  • the present invention relates to a process for the preparation of polyoxymethylene-polyalkylene oxide block copolymers, comprising the step of polymerizing an alkylene oxide in the presence of an OH-terminated polyoxymethylene polymer and a catalyst. It further relates to copolymers obtainable by the process, a process for the production of polyurethane polymers using these copolymers and polyurethanes obtainable therefrom.
  • Block copolymers containing polyoxymethylene units in addition to other polymer and polycondensate units are described, for example, in JP 2007 211082 A, WO 2004/096746 A1, GB 807589, EP 1 418 190 A1, US 3,754,053, US 3,575,930, US 2002/0016395 and JP 04- 306215.
  • JP 2007 211082 A describes the reaction of polyoxyalkylene polyols with an equivalent weight of> 2500 with formaldehyde, formaldehyde oligomers or formaldehyde polymers to give polyoxymethylene-polyoxyalkylene block copolymers using anionic or cationic polymerization catalysts.
  • the high-molecular polyoxyalkylene-polyol starters with low polydispersity are produced using double metal cyanide (DMC) catalysis.
  • DMC double metal cyanide
  • the polyoxymethylene-polyoxyalkylene block copolymers obtained have a molecular weight of at least> 5000 g / mol and can therefore be used less widely than a polyurethane building block.
  • No. 3,754,053 describes polyoxymethylene-polyoxyalkylene block copolymers with a molecular weight> 10,000 g / mol.
  • trioxane is converted to a polyoxymethylene prepolymer in a first step and this is then reacted with alkylene oxides in the presence of, for example, NaOH as a polymerization catalyst.
  • the polymers described are less suitable for applications as a polyurethane building block because of their high molecular weight.
  • WO 2004/096746 A1 and US 2006/0205915 A1 disclose the reaction of formaldehyde oligomers with alkylene oxides and / or isocyanates.
  • these applications do not disclose any differentiated activation conditions, such as the activation temperature, of the alkoxylation catalysts used, which are also important from a safety and quality point of view for possible large-scale use due to undefined temperature peaks during the exothermic polymerization process (22.7 kcal / mol PO from M. Ionesco; Chemistry and Technology of Polyols for Polyurethanes, Rapra Techn. Ftd., 2005) are disadvantageous. Furthermore, only block copolymers with very short formaldehyde blocks are accessible via this method.
  • EP 1 870 425 A1 discloses a process for the preparation of polyols containing polyoxyalkylene by condensation of substituted or unsubstituted phenol structures with formaldehyde and / or other substituted alkanal structures.
  • the resulting phenol-formaldehyde condensates are used as polyol starters for the alkoxylation, no oxymethylene repeat units being formed within these starter compounds.
  • the resulting properties of the alkoxylated, aromatic-containing polyols differ fundamentally from aliphatic polyol structures due to the different chemical structure.
  • WO 2012/091968 A1 claims a process for the preparation of polyether materials by polymerizing alkylene oxides on starter compounds with the aid of DMC catalysts.
  • oligomeric phenol-formaldehyde condensates are disclosed as corresponding starters, which differ fundamentally in structure from the polyoxymethylene starter structure.
  • WO 2015/155094 A1 relates to a process for the production of polyoxymethylene block copolymers by catalytic addition of alkylene oxides and optionally further comonomers onto at least one polymeric formaldehyde starter compound which has at least one terminal hydroxyl group, in the presence of a double metal cyanide (DMC) catalyst, wherein (i) in a first step the DMC catalyst is activated in the presence of the polymeric formaldehyde starter compound, with a partial amount (based on the total amount of the amount of alkylene oxides used in the activation and polymerization) of one or more alkylene oxides is added, (ii) in a second step one or more alkylene oxides and optionally further comonomers are added to the mixture resulting from step (i), the Alkylene oxides used in step (ii) may be the same or different from the alkylene oxides used in step (i), characterized in that the activation of the DMC catalyst in the first step (i) at an activ
  • WO 2015/155094 A1 states that suitable polymeric formaldehyde starter compounds generally have molar masses from 62 to 30,000 g / mol, preferably from 62 to 12,000 g / mol, particularly preferably from 242 to 6000 g / mol and very particularly preferably from 242 have up to 3000 g / mol and comprise from 2 to 1000, preferably from 2 to 400, particularly preferably from 8 to 200 and very particularly preferably from 8 to 100, oxymethylene repeat units.
  • the preparation of the starter compounds is not described.
  • Commercially available paraformaldehyde is used in the exemplary embodiments.
  • the object of the present invention is to provide polyoxymethylene-polyalkylene oxide block copolymers which are easy to process and which have a higher proportion of formaldehyde than previous block copolymers. Another task is to reduce the activation time (clock) of the DMC catalyst.
  • the object is achieved by a process according to claim 1, a polyoxymethylene-polyalkylene oxide block copolymer according to claim 11, a process for producing a polyurethane polymer according to claim 14 and a polyurethane polymer according to claim 15.
  • Advantageous further developments are specified in the subclaims. They can be combined as required, unless the context clearly indicates the opposite.
  • the polyoxymethylene polymer has a number average molecular weight M n , determined after derivatization with propylene oxide and gel permeation chromatography with tetrahydrofuran as an eluent against polystyrene standards, from> 1100 g / mol to ⁇ 2300 g / mol (preferably> 1400 g / mol to ⁇ 2100 g / mol) and the ratio of alkylene oxide to polyoxymethylene polymer is> 0.05 mol / G. It has been found that block copolymer polyols are obtained by the process according to the invention can be obtained, which can be further processed in an advantageous manner to polyurethane polymers.
  • the block copolymers according to the invention are less expensive than the standard building blocks for polyols in PU applications. Furthermore, their so-called carbon footprint is smaller, so that more environmentally friendly building blocks can be provided for the PU market.
  • the catalyst is activated by adding an alkylene oxide before the actual polymerization, this amount of alkylene oxide is also taken into account in the mol / g ratio of alkylene oxide to polyoxymethylene polymer according to the invention.
  • the polymerization of the alkylene oxide in the presence of the OH-terminated polyoxymethylene polymer and the catalyst is preferably carried out at a temperature from> 60 ° C. to ⁇ 70 ° C.
  • alkylene oxides (epoxides) having 2-24 carbon atoms can be used for the process according to the invention.
  • the alkylene oxides having 2-24 carbon atoms are, for example, one or more compounds selected from the group consisting of ethylene oxide, propylene oxide, 1-butene oxide, 2,3-butene oxide, 2-methyl-l, 2-propene oxide (isobutene oxide), 1-pentene oxide, 2,3-pentene oxide, 2-methyl-1, 2-butene oxide, 3-methyl-1, 2-butene oxide, 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-octene oxide, 1-non-oxide, 1-decene oxide, 1-undecene oxide, 1-dodecene oxide, 4-methyl-l, 2-pentene oxide, butadiene mon
  • Glycidyloxypropyl-ethyl diethoxysilane 3-glycidyloxypropyltrisisopropoxysilane.
  • alkylene oxides are ethylene oxide and / or propylene oxide, in particular propylene oxide.
  • polyoxymethylene polymers to be used hereinafter also referred to as “formaldehyde starter compound” or “pFA”, can be described as polymers with a medium chain length, ie with a number of formaldehyde units in the polymer between that of paraformaldehyde and that of the material POM.
  • Such polymers can be obtained by a method described in the European one filed on November 22, 2018 Patent application with the application number EP18207740 is described.
  • the molecular weight of the polyoxymethylene polymers to be used cannot be determined directly since they are insoluble in the common eluents of gel permeation chromatography (GPC). Instead, an indirect method is chosen in which derivatization with propylene oxide takes place beforehand.
  • the number-average molecular weight M n, product of the derivatized polymer, which can also be a product of the process according to the invention, is determined by means of GPC against polystyrene standards and THF as the eluent.
  • the weight ratio of propylene oxide to polyoxymethylene polymer in the derivatization is preferably in a range from 2: 1 to 4: 1.
  • the polyoxymethylene block copolymers obtainable by the process according to the invention preferably contain less than 2% by weight, in particular less than 1% by weight, based on the total mass of the polyoxymethylene block copolymer obtained, formate and / or methoxy impurities.
  • the use of the word “on” in connection with countable quantities is to be understood here and in the following only as a number word if this is clear from the context (for example by the phrase "exactly one"). Otherwise, expressions such as “an alkylene oxide” include , "A polyoxymethylene polymer” etc. always include those embodiments in which two or more alkylene oxides, two or more polyoxymethylene polymer, etc. are used.
  • the catalyst is a double metal cyanide catalyst.
  • DMC catalysts suitable for the process according to the invention 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 US Pat. A 5 158 922).
  • DMC catalysts which are described for example 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 a very high activity in the polymerization of alkylene oxides and possibly the copolymerization of alkylene oxides with suitable comonomers and enable the production of polyoxymethylene copolymers at very low catalyst concentrations, so that the catalyst is separated from the finished product is generally no longer required.
  • a typical example are 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 tert-butanol), also a polyether with a number average molecular weight greater than 500 g / mol included.
  • a double metal cyanide compound eg zinc hexacyanocobaltate (III)
  • an organic complex ligand eg tert-butanol
  • the concentration of DMC catalyst used is usually 10 to 10,000 ppm, preferably 20 to 5000 ppm and more preferably 50 to 2000 ppm, based on the mass of the polyoxymethylene block copolymer to be produced.
  • the DMC catalyst can be left in the product or (partially) separated.
  • the (partial) separation of the DMC catalyst can take place, for example, by treatment with adsorbents and / or filtration.
  • the ratio of alkylene oxide to polyoxymethylene polymer is still ⁇ 0.1125 mol / g.
  • the ratio is preferably in a range from> 0.054 mol alkylene oxide / g polyoxymethylene polymer to ⁇ 0.1 mol alkylene oxide / g polyoxymethylene polymer.
  • the polyoxymethylene polymer has an average OH functionality of> 1.9.
  • the average OH functionality is preferably> 2 to ⁇ 3.
  • a comonomer which is not an alkylene oxide is used in the reaction.
  • all oxygen-containing cyclic compounds in particular cyclic ethers, such as e.g. Oxetane, THF, dioxane or cyclic acetals such as e.g. 1,3-dioxolane or 1,3-dioxepane, cyclic esters such as e.g. g-butyrolactone, g-valerolactone, e-caprolactone, or cyclic acid anhydrides such as e.g. Maleic anhydride, glutaric anhydride or phthalic anhydride and carbon dioxide are used. Carbon dioxide is preferably used as the comonomer.
  • polyoxymethylene-polyether carbonate block copolymers can be obtained from cyclic ethers, such as e.g. Oxetane, THF, dioxane or cyclic acetals such as e.g. 1,
  • CO2 is, among other things, a waste product of energy generation from fossil raw materials and is re-used here for chemical recycling, the incorporation of CO2 into the polymer structures results in economic as well as ecological advantages (favorable CCE balance of the product polymers, etc.).
  • Polyoxymethylene-polyoxyalkylene carbonate block copolymers for the purposes of the invention refer to polymeric compounds which contain at least one polyoxymethylene block and at least one polyoxyalkylene carbonate block.
  • Polyoxymethylene-polyoxyalkylene carbonate block copolymers are particularly interesting as feedstocks in the polyurethane sector and for applications in the polyoxymethylene (POM) sector.
  • POM polyoxymethylene
  • the physical properties can be adapted to the respective application, which opens up new areas of application for these block copolymers.
  • polyoxymethylene-polyoxyalkylene carbonate copolymers can be provided by the process according to the invention, a high content of built-in CO2 being achieved, the products having a comparatively low polydispersity and containing very few by-products and decomposition products of the polymeric formaldehyde.
  • an excess of carbon dioxide based on the expected or estimated amount of carbon dioxide incorporated in the polyoxyalkylene carbonate block is preferably used, since an excess of carbon dioxide is advantageous due to the inertia of carbon dioxide is.
  • the amount of carbon dioxide can be determined via the total pressure under the respective reaction conditions.
  • the total pressure (absolute) has proven to be advantageous in the range from 0.01 to 120 bar, preferably 0.1 to 110 bar, particularly preferably from 1 to 100 bar for the copolymerization for the preparation of the polyoxyalkylene carbonate block.
  • the copolymerization for the production of the polyoxyalkylene carbonate block is advantageously at 50 to 150 ° C., preferably at 60 to 145 ° C., particularly preferably at 70 to 140 ° C. and very particularly preferably at 90 to 130 ° C. is carried out. If temperatures are set below 50 ° C, the reaction proceeds disproportionately slowly. At temperatures above 150 ° C, the amount of unwanted by-products increases sharply.
  • CO2 changes from the gaseous state to the liquid and / or supercritical liquid state when selecting pressure and temperature.
  • CO2 can also be added to the reactor as a solid and then change to the liquid and / or supercritical liquid state under the chosen reaction conditions.
  • Carbon dioxide can be used in the gaseous, solid, liquid or supercritical state, preferably in the gaseous or solid state, particularly preferably in the gaseous state.
  • a carbon dioxide partial pressure of 1 to 73.8 bar, preferably 1 to 60 bar, particularly preferably 5 to 50 bar is selected.
  • the combination of pressure and temperature is when using gaseous carbon dioxide chosen such that carbon dioxide is in the gaseous state as a pure substance under the selected reaction conditions.
  • the corresponding conditions can be derived from the phase diagram. After introducing gaseous carbon dioxide into the reactor, it partially or completely dissolves in the reaction mixture.
  • the catalyst is a double metal cyanide catalyst (DMC catalyst) and:
  • the DMC catalyst is activated in the presence of the polyoxymethylene polymer, a portion (based on the total amount of the amount of alkylene oxide used in the activation and polymerization) of an alkylene oxide being added to activate the DMC catalyst ,
  • step (ii) in a second step, an alkylene oxide is added to the mixture resulting from step (i), it being possible for the alkylene oxide used in step (ii) to be the same or different from the alkylene oxide used in step (i) and the activation of the DMC Catalyst in the first step (i) at an activation temperature of> 20 ° C to ⁇ 120 ° C.
  • the step of activating the DMC catalyst with the conditioning of the polymeric formaldehyde starter can be carried out at mild temperatures. Conditioning the formaldehyde starter compound in the presence of the DMC catalyst enables the starter in the subsequent polymerization step to be reacted with alkylene oxides and, if appropriate, further comonomers even at higher reaction temperatures, without further defragmentation and / or the formation of secondary substances - and decomposition products is coming.
  • the conditioned formaldehyde starter compound usually has a significantly higher solubility after conditioning, so that only small amounts or no further solvents and / or suspending agents are required. Furthermore, it can be ensured that an active DMC catalyst system is available for the polymerization and that a continuously progressing polymerization with continuous addition of the comonomers ensures a safe process and high product quality.
  • the DMC catalyst is therefore activated in the presence of the polymeric formaldehyde starter compound.
  • the starter compound and the DMC catalyst can optionally be suspended in a suspending agent. It is also possible to use a further liquid starter compound (“costarter”) in a mixture, the DMC catalyst and the polymeric formaldehyde starter compound being suspended therein.
  • the DMC catalyst is activated at an activation temperature in the range from 20 to 120 ° C, preferably at 30 to 120 ° C, particularly preferably at 40 to 100 ° C and very particularly preferably at 60 to 100 ° C.
  • the process is preferably carried out in such a way that the activation of the catalyst and the conditioning of the polymeric formaldehyde starter compound in step ( ⁇ ) is followed by a polymerization step (g) with metering in of one or more alkylene oxides.
  • the process can also be ended after step ( ⁇ ), so that the conditioned polymeric formaldehyde starter compound then represents the end product of the process. Due to the conditioning according to the invention, this generally has a high stability and can, if desired, be used analogously to the polyoxymethylene block copolymer obtained from step (g) as an OH-functional building block for various subsequent reactions.
  • a suspending agent or the polyoxymethylene polymer is introduced and any water and / or other volatile compounds present are removed by drying (elevated temperature and / or reduced pressure), the DMC catalyst preceding or after the polyoxymethylene polymer or the suspending agent is added to the drying,
  • step ( ⁇ ) for activating the DMC catalyst in the presence of the polyoxymethylene polymer a portion (based on the total amount of the amount of alkylene oxides used in the activation and polymerization) of alkylene oxide is added to the mixture resulting from step (a), and then the resulting the following exothermic chemical reaction occurring temperature peak ("hotspot") and / or a pressure drop in the reactor is respectively waited for, and the step ( ⁇ ) for activation can also take place several times, and in the second step (ii)
  • step (g) an alkylene oxide is added to the mixture resulting from step ( ⁇ ), it being possible for the alkylene oxide used in step (g) to be identical or different from the alkylene oxide used in step ( ⁇ ) and for at least one of steps (a) and ( ⁇ ) ) at least one polyoxymethylene polymer is added.
  • step (g) is carried out at a temperature of> 60 ° C. to ⁇ 70 ° C.
  • At least one compound is selected from 4-methyl-2-oxo-1,3-dioxolane, 1,3-dioxolan-2-one, acetone, methyl ethyl ketone, acetonitrile, nitromethane, dimethyl sulfoxide in step (a) as a suspending agent , Sulfolane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dioxane, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, ethyl acetate, butyl acetate, pentane, n-hexane, benzene, toluene, xylene, ethylbenzene, chloroform, chlorobenzene, dichloro-benzene, dichloro-benzene, dichloro-tolene, dichloro-tolene, dichloro-toluene
  • step (a) in step (a)
  • a suspension medium and the DMC catalyst are initially introduced and water and / or other volatile compounds are removed by at least once at a temperature of> 90 ° C. to ⁇ 150 ° C. at> 1 bar to ⁇ 100 bar (absolute) of an inert gas and the excess pressure is then reduced to> 1 bar to ⁇ 20 bar (absolute) and in a subsequent step
  • the polymeric formaldehyde starter compound can be introduced together with the DMC catalyst and the suspending agent in step (a), or preferably after drying, at the latest in step ( ⁇ ).
  • the suspending agents optionally used generally do not contain any H-functional groups. All polar-aprotic, weakly polar-aprotic and non-polar-aprotic solvents which each contain no H-functional groups are suitable as suspending agents. A mixture of two or more of these suspending agents can also be used as the suspending agent.
  • step (a) (drying):
  • step (a) can be added simultaneously or in succession in any order.
  • a suspension medium which does not contain any H-functional groups is preferably placed in the reactor.
  • the amount of DMC catalyst required for the polymerization, which is preferably not activated, is then added to the reactor.
  • the order of addition is not critical. It is also possible first to fill the DMC catalyst and then the suspension medium into the reactor. Alternatively, the DMC catalyst can first be suspended in the suspension medium and then the suspension can be filled into the reactor.
  • the suspension medium provides a sufficient heat exchange surface with the reactor wall or cooling elements installed in the reactor, so that the heat of reaction released can be dissipated very well.
  • the suspension medium provides heat capacity in the event of a cooling failure, so that the temperature in this case can be kept below the decomposition temperature of the reaction mixture.
  • a suspending agent which does not contain any H-functional groups and additionally a partial amount of the polymeric formaldehyde starter compound and, if appropriate, a DMC catalyst can also be introduced into step (a) in the reactor, or a partial amount of the polymeric formaldehyde starter compound and optionally DMC catalyst are placed in the reactor. Furthermore, the total amount of the polymeric formaldehyde starter compound and, if appropriate, DMC catalyst can also be introduced into the reactor in step (a).
  • the polymeric formaldehyde starter compound can in principle be presented as a mixture with other polymeric formaldehyde starter compounds or other H-functional starter compounds.
  • the process can be carried out in such a way that a suspending agent, the polymeric formaldehyde starter compound and the DMC catalyst are introduced in step (a) and, if appropriate, water and / or other volatile compounds are removed by elevated temperature and / or reduced pressure (" Drying ") or, in an alternative embodiment, step (a) is carried out in such a way that a suspending agent and the DMC catalyst are introduced in step (a1) and, if appropriate, water and / or other volatile compounds by elevated temperature and / or reduced pressure are removed (“drying”) and in a subsequent step (a2) the formaldehyde starter compound is added to the mixture from step (a1).
  • the polymeric formaldehyde starter compound can be added after the reaction mixture from step (a1) has cooled, in particular at room temperature, or the reaction mixture can already be brought to the temperature prevailing in the subsequent step ( ⁇ ) and the addition can be carried out at this temperature.
  • the formaldehyde starter compound is generally added under inert conditions.
  • the DMC catalyst is preferably used in an amount such that the DMC catalyst content in the resulting reaction product is 10 to 10,000 ppm, particularly preferably 20 to 5000 ppm and most preferably 50 to 2000 ppm.
  • an inert gas for example argon or nitrogen
  • an inert gas / carbon dioxide mixture or carbon dioxide is introduced into the resulting mixture of suspending agent and DMC catalyst and / or the polymeric formaldehyde starter compound and at the same time a reduced pressure (absolute) of 10 mbar to 800 mbar, particularly preferably from 50 mbar to 200 mbar.
  • the resulting mixture of DMC catalyst with suspending agent and / or the polymeric formaldehyde starter compound is at least once, preferably three times with 1 bar to 100 bar (absolute), particularly preferably 3 bar to 50 bar (absolute) of an inert gas (for example argon or nitrogen), an inert gas / carbon dioxide mixture or carbon dioxide and then the overpressure is then reduced to about 1 bar to 20 bar (absolute).
  • an inert gas for example argon or nitrogen
  • the DMC catalyst can be added, for example, in solid form or as a suspension in one or more suspension medium (s) or - if the polymeric formaldehyde starter compound is in a liquid state of aggregation - as a suspension in a polymeric formaldehyde starter compound.
  • Step (ß) is used to activate the DMC catalyst.
  • This step can optionally be carried out under an inert gas atmosphere, under an atmosphere of an inert gas / carbon dioxide mixture or under a carbon dioxide atmosphere.
  • Activation in the sense of this invention refers to a step in which a portion of alkylene oxide is added to the DMC catalyst suspension at temperatures of 20 to 120 ° C. (“activation temperature”) and then the addition of the alkylene oxide is interrupted, due to a following exothermic chemical reaction a heat development, which can lead to a temperature spike (“hotspot”), and due to the reaction of alkylene oxide and possibly CO2, a pressure drop is observed in the reactor.
  • activation temperature a portion of alkylene oxide is added to the DMC catalyst suspension at temperatures of 20 to 120 ° C.
  • the alkylene oxide can be added in one step or stepwise in several portions. After adding a portion of alkylene oxide, the addition of the alkylene oxide is preferably interrupted until the development of heat occurs and only then is the next portion of alkylene oxide added.
  • the activation (step ( ⁇ )) in the presence of the polymeric formaldehyde starter compound for the preparation of the polyoxymethylene block copolymers advantageously at an activation temperature of 20 to 120 ° C., preferably at 30 to 120 ° C. is particularly preferably carried out at 40 to 100 ° C. and very particularly preferably at 60 to 100 ° C.
  • the heat development due to the chemical reaction during activation of the DMC catalyst preferably does not lead to a temperature of 120 ° C. being exceeded Reaction vessel.
  • the reaction proceeds very slowly below 20 ° C. and activation of the DMC catalyst takes a disproportionately long time or may not take place to the desired extent.
  • temperatures of 130 ° C and higher the amount of undesirable by-products / decomposition products of polymeric formaldehyde starter compounds increases sharply. For example, the formation of formate and methoxy traces is observed. It has also been shown to be an advantage of this embodiment that the properties of the polyoxymethylene block copolymer obtained, in particular the length of the polyoxymethylene block, can also be influenced by precisely coordinating the parameters in this area.
  • the partial amount of the alkylene oxide can be added to the reaction mixture in several individual steps, optionally in the presence of CO 2, and the addition of the alkylene oxide can then be interrupted in each case.
  • the process step of activation comprises the period of time from the addition of the first partial amount of alkylene oxide, optionally in the presence of CO 2, to the reaction mixture until the occurrence of heat after the addition of the last partial amount of alkylene oxide.
  • the activation step can be preceded by a step for drying the DMC catalyst and, if appropriate, the polymeric formaldehyde starter compound at elevated temperature and / or reduced pressure, if appropriate by passing an inert gas through the reaction mixture, this step of drying not being part of the Activation step in the sense of the present invention.
  • one or more alkylene oxides and, if appropriate, the further comonomers, in particular carbon dioxide
  • Dosing can be started from the suppressor or at a previously selected form.
  • the admission pressure is preferably set by introducing an inert gas (such as nitrogen or argon) or carbon dioxide, the pressure (absolute) being 5 mbar to 100 bar, preferably 10 mbar to 50 bar and preferably 20 mbar to 50 bar.
  • an inert gas such as nitrogen or argon
  • carbon dioxide the pressure (absolute) being 5 mbar to 100 bar, preferably 10 mbar to 50 bar and preferably 20 mbar to 50 bar.
  • An alternative embodiment is also a two-stage activation (step ⁇ ), wherein
  • step (g) (polymerization):
  • One or more alkylene oxides can be dosed simultaneously or sequentially via separate doses (additions) or via one or more doses. If several alkylene oxides are used for the synthesis of the polyoxymethylene block copolymers, the alkylene oxides can be metered in individually or as a mixture.
  • the three steps (a), ( ⁇ ) and (g) can be carried out in the same reactor or in each case separately in different reactors.
  • Particularly preferred reactor types for the process according to the invention are stirred tanks, tubular reactors and loop reactors. Furthermore, extruders, kneaders, etc. can also be used as preferred reactors for the process according to the invention.
  • reaction steps a, ⁇ and g are carried out in different reactors, a different type of reactor can be used for each step.
  • the individual steps or steps (a) and ( ⁇ ) of (g) should preferably be spatially separated from one another, so that separate temperature control and a suitable gas supply and application of a suppressor, addition of polymeric formaldehyde and metering of monomers in the individual steps is possible according to the invention.
  • the polyoxymethylene block copolymers according to the invention can be worked up in particular by distillation.
  • Thin-film evaporators, strand evaporators and stripping columns and combinations of these are preferably used to remove solvents or suspending agents, volatile constituents and unreacted monomers and / or oligomers.
  • all other apparatuses are also suitable here for thermal distillation workup. This type of workup can be carried out continuously or discontinuously, in parallel or after the reaction.
  • the invention also relates to a polyoxymethylene-polyalkylene oxide block copolymer obtainable by a process according to the invention. They can be used for the production of polyurethanes, detergent and cleaning agent formulations, drilling fluids, fuel additives, ionic and nonionic surfactants, lubricants, process chemicals for paper or textile production or cosmetic formulations.
  • the polyoxymethylene-polyalkylene oxide block copolymer has a viscosity at 20 ° C., determined by DIN 51562, from> 22000 mPas to ⁇ 26000 mPas, preferably> 23000 mPas to ⁇ 25000 mPas. At 25 ° C the viscosity is preferably> 14000 mPas to ⁇ 18000 mPas and more preferably> 15000 mPas to ⁇ 17000 mPas.
  • the polymer is a polyoxymethylene-polyoxyalkylene carbonate block copolymer and comprises an inner polyoxymethylene block (“starter”) and at least one outer polyoxyalkylene carbonate block according to the formula: where R independently of one another represents an organic radical, a, b and c stand for an integer, R can differ in different repeating units, the structural unit “starter” represents a polyoxymethylene block resulting from the polyoxymethylene polymer, and a, b and c are selected such that the proportion of the “starter” ⁇ 35% by weight, the proportion of structural units originating from CO2 ⁇ 25% by weight and the proportion of structural units originating from alkylene oxides, the difference from 100% by weight, in each case based on the total weight of the polymer.
  • starter an inner polyoxymethylene block
  • R independently of one another represents an organic radical
  • a, b and c stand for an integer
  • R can differ in different repeating units
  • the structural unit “starter” represents a polyoxy
  • R can represent, for example, an organic radical such as alkyl, alkylaryl, arylalkyl or aryl, which in each case can also contain heteroatoms such as O, S, Si, etc.
  • blocks with the structure shown can in principle be found in the polyoxymethylene-polyoxyalkylene carbonate block copolymer obtained, but the order, number and length of the blocks and the OH functionality of the “starter” can vary and is not based on the polyoxymethylene shown -Polyoxyalkylene carbonate block copolymer limited.
  • Another aspect of the invention is a method for producing a polyurethane polymer, comprising the step of reacting a polyisocyanate component with a polyol component, the polyol component comprising a polyoxymethylene-polyalkylene oxide block copolymer according to the invention.
  • Suitable polyisocyanates are, for example, TDI, MDI, polymeric MDI, H12-MDI, HDI, HDI isocyanurate (HDI trimer) and IPDI.
  • Other polyols such as polyether polyols, polyester polyols or polyether ester polyols and additives such as blowing agents or fillers can also be used.
  • the invention also relates to a polyurethane polymer obtainable by a process according to the invention.
  • polyurethane thermoplastics polyurethane coatings, fibers, elastomers, adhesives and in particular also polyurethane foams, including flexible foams (such as flexible polyurethane foams and flexible polyurethane foams) and rigid foams.
  • flexible foams such as flexible polyurethane foams and flexible polyurethane foams
  • FIG. 1 shows a gel permeation chromatogram of a sample from example 1
  • FIG. 2 shows a gel permeation chromatogram of a sample from example 2
  • FIG. 3 shows a gel permeation chromatogram of a sample from example 3
  • FIG. 4 shows a gel permeation chromatogram of a sample from counterexample 2
  • the composition of the polymer was determined by means of I-NMR (Bruker, DPX 400, 400 MHz; pulse program zg30, waiting time DI: 10s, 64 scans). The sample was dissolved in deuterated chloroform.
  • PPO Polypropylene oxide
  • Methoxy (MeO) trace by-product, with resonance at 3.4 ppm.
  • composition of the reaction mixture determined in this way is then converted into parts by weight and normalized to 100.
  • the polymer composition is calculated and standardized using the proportions PPO and pFA, so that here too It is stated in parts by weight of 100 (% by weight).
  • the molecular weight of the pFA block in the product polymer was carried out by means of gravimetric and NMR analytical methods according to the formulas below:
  • Example 1 (according to the invention): Preparation of a polyoxymethylene-polyoxyalkylene block copolymer using the polyoxymethylene polymer as a starter material
  • Example 2 (according to the invention): Preparation of a polyoxymethylene-polyoxyalkylene block copolymer using the polyoxymethylene polymer as a starter material
  • a polyoxymethylene-polyoxyalkylene block copolymer was produced in accordance with Example 1, only 100 g of propylene oxide being conveyed during the semibatch phase.
  • the Molar mass distribution is shown in the GPC diagram of FIG. 2 to see.
  • Example 3 (according to the invention): Preparation of a polyoxymethylene-polyoxyalkylene block copolymer using the polyoxymethylene polymer as a starter material
  • a smaller amount of catalyst and a larger amount of propylene oxide were used for catalyst activation compared to example 2.
  • the propylene oxide dosage also differed.
  • a polyoxymethylene-polyoxyalkylene block copolymer was produced in accordance with Example 1, only 50 g of propylene oxide being conveyed during the semibatch phase. After the addition of propylene oxide, there was a lot of solid in the reaction solution and on the reactor wall, so that the reaction mixture could not be analyzed.
  • This example is a comparative example since the molar mass of the paraformaldehyde is not in the range provided according to the invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Toxicology (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

L'invention concerne un procédé de préparation de copolymères séquencés d'oxyde de polyalkylène de polyoxyméthylène, comprenant l'étape de polymérisation d'un oxyde d'alkylène en présence d'un polymère de polyoxyméthylène à terminaison OH et d'un catalyseur. Le polymère de polyoxyméthylène présente une masse moléculaire moyenne en nombre Mn, déterminée selon la dérivation avec de l'oxyde de propylène et une chromatographie par perméation de gel avec du tétrahydrofuranne en tant qu'éluant par rapport aux normes de polystyrol, supérieur ou égal à 1100 g/mol et inférieur ou égal à 2300 g/mol, et le rapport d'oxyde d'alkylène au polymère de polyoxyméthylène étant supérieur ou égal à 0,05 mol/g. L'invention concerne en outre des copolymères pouvant être obtenus selon le procédé, un procédé de préparation de polymères de polyuréthane à l'aide desdits copolymères ainsi que des polyuréthanes pouvant être obtenus à partir de ce dernier.
EP19802180.0A 2018-11-22 2019-11-14 Procédé de préparation de copolymères séquencés d'oxyde de polyalkylène de polyoxyméthylène Withdrawn EP3883980A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP18207807.1A EP3656797A1 (fr) 2018-11-22 2018-11-22 Procédé de production de copolymères séquencés de polyalkylène-oxyde-polyoxyméthylène
PCT/EP2019/081407 WO2020114751A1 (fr) 2018-11-22 2019-11-14 Procédé de préparation de copolymères séquencés d'oxyde de polyalkylène de polyoxyméthylène

Publications (1)

Publication Number Publication Date
EP3883980A1 true EP3883980A1 (fr) 2021-09-29

Family

ID=64453376

Family Applications (2)

Application Number Title Priority Date Filing Date
EP18207807.1A Ceased EP3656797A1 (fr) 2018-11-22 2018-11-22 Procédé de production de copolymères séquencés de polyalkylène-oxyde-polyoxyméthylène
EP19802180.0A Withdrawn EP3883980A1 (fr) 2018-11-22 2019-11-14 Procédé de préparation de copolymères séquencés d'oxyde de polyalkylène de polyoxyméthylène

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP18207807.1A Ceased EP3656797A1 (fr) 2018-11-22 2018-11-22 Procédé de production de copolymères séquencés de polyalkylène-oxyde-polyoxyméthylène

Country Status (4)

Country Link
US (1) US20220119579A1 (fr)
EP (2) EP3656797A1 (fr)
CN (1) CN113195575A (fr)
WO (1) WO2020114751A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3931230A1 (fr) * 2019-02-28 2022-01-05 Covestro Intellectual Property GmbH & Co. KG Prépolymères à terminaison isocyanate destinés à la production de mousses intégrées de polyuréthane
WO2022258570A1 (fr) 2021-06-10 2022-12-15 Covestro Deutschland Ag Procédé pour la production de copolymères polyoxyméthylène-polyoxyalkylène

Family Cites Families (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL216498A (fr) 1955-11-30
GB1063525A (en) 1963-02-14 1967-03-30 Gen Tire & Rubber Co Organic cyclic oxide polymers, their preparation and tires prepared therefrom
US3754053A (en) 1964-05-15 1973-08-21 Celanese Corp Polyoxymethylene-oxyalkylene block polymers
US3575930A (en) 1968-12-12 1971-04-20 Goodrich Co B F Polyoxymethylene glycol polymers
US3829505A (en) 1970-02-24 1974-08-13 Gen Tire & Rubber Co Polyethers and method for making the same
US3941849A (en) 1972-07-07 1976-03-02 The General Tire & Rubber Company Polyethers and method for making the same
CA1155871A (fr) 1980-10-16 1983-10-25 Gencorp Inc. Methode de traitement de poly(oxypropylene) et de poly(oxy-1,2-butylene)
US4721818A (en) 1987-03-20 1988-01-26 Atlantic Richfield Company Purification of polyols prepared using double metal cyanide complex catalysts
US4877906A (en) 1988-11-25 1989-10-31 Arco Chemical Technology, Inc. Purification of polyols prepared using double metal cyanide complex catalysts
WO1990007537A1 (fr) 1989-01-06 1990-07-12 Asahi Glass Company Ltd. Production de polyether
US4987271A (en) 1989-02-17 1991-01-22 Asahi Glass Company, Ltd. Method for purifying a polyoxyalkylene alcohol
US5010047A (en) 1989-02-27 1991-04-23 Arco Chemical Technology, Inc. Recovery of double metal cyanide complex catalyst from a polymer
US5391722A (en) 1990-03-30 1995-02-21 Olin Corporation Acid-catalyzed fabrication of precursors for use in making polyols using double metal cyanide catalysts
US5099075A (en) 1990-11-02 1992-03-24 Olin Corporation Process for removing double metal cyanide catalyst residues from a polyol
JP3110788B2 (ja) 1991-04-03 2000-11-20 旭化成工業株式会社 潤滑特性に優れたポリアセタールブロック共重合体及びその製法
US5158922A (en) 1992-02-04 1992-10-27 Arco Chemical Technology, L.P. Process for preparing metal cyanide complex catalyst
US5712216A (en) 1995-05-15 1998-01-27 Arco Chemical Technology, L.P. Highly active double metal cyanide complex catalysts
US5470813A (en) 1993-11-23 1995-11-28 Arco Chemical Technology, L.P. Double metal cyanide complex catalysts
US5482908A (en) 1994-09-08 1996-01-09 Arco Chemical Technology, L.P. Highly active double metal cyanide catalysts
US5545601A (en) 1995-08-22 1996-08-13 Arco Chemical Technology, L.P. Polyether-containing double metal cyanide catalysts
US5627120A (en) 1996-04-19 1997-05-06 Arco Chemical Technology, L.P. Highly active double metal cyanide catalysts
US5714428A (en) 1996-10-16 1998-02-03 Arco Chemical Technology, L.P. Double metal cyanide catalysts containing functionalized polymers
DE19905611A1 (de) 1999-02-11 2000-08-17 Bayer Ag Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen
JP4560261B2 (ja) 1999-07-30 2010-10-13 旭化成ケミカルズ株式会社 ポリアセタールブロックコポリマー
DE10251332B4 (de) 2002-11-05 2006-07-27 Ticona Gmbh Polyoxymethylen-Copolymere, deren Herstellung und Verwendung
DE10319242A1 (de) 2003-04-28 2004-11-18 Basf Ag Ausgangsverbindungen für die Herstellung von Polyurethanen
US7705106B2 (en) 2003-04-28 2010-04-27 Basf Aktiengesellschaft Initial compounds for producing polyurethanes
JP2007211082A (ja) 2006-02-08 2007-08-23 Asahi Glass Co Ltd ポリオキシメチレン−ポリオキシアルキレンブロック共重合体の製造方法
US7538162B2 (en) 2006-06-23 2009-05-26 Bayer Materialscience Llc Process for the production of polyoxyalkylene containing polyols from phenol condensation products
JP6060092B2 (ja) 2010-12-27 2017-01-11 ダウ グローバル テクノロジーズ エルエルシー 複合金属シアン化物触媒錯体およびマグネシウム、第３族〜第１５族金属またはランタニド系列金属化合物を用いるアルキレンオキシド重合
KR102159100B1 (ko) * 2012-05-24 2020-09-23 사우디 아람코 테크놀로지스 컴퍼니 폴리카보네이트 폴리올 조성물 및 방법
SG11201504408QA (en) * 2012-12-21 2015-07-30 Bayer Materialscience Ag Functionalized polyoxymethylene block copolymers
JP2016521788A (ja) * 2013-06-13 2016-07-25 コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ ポリエーテルカーボネイト−ポリオキシメチレンブロック共重合体
ES2702327T3 (es) * 2014-04-07 2019-02-28 Covestro Deutschland Ag Procedimiento para la producción de copolímeros de bloques de polioximetileno

Also Published As

Publication number Publication date
CN113195575A (zh) 2021-07-30
US20220119579A1 (en) 2022-04-21
WO2020114751A1 (fr) 2020-06-11
EP3656797A1 (fr) 2020-05-27

Similar Documents

Publication Publication Date Title
EP3129419B1 (fr) Procédé de fabrication de copolymères séquencés de polyoxyméthylène
EP3008100B1 (fr) Copolymères en bloc de polyoxyméthylène de polyéthercarbonate
WO2013017360A1 (fr) Procédé de production de polyéthercarbonates ramifiés et utilisation de ceux-ci
WO2012084762A1 (fr) Procédé de production de poly-éther polyols
EP3883980A1 (fr) Procédé de préparation de copolymères séquencés d'oxyde de polyalkylène de polyoxyméthylène
WO2019121205A1 (fr) Procédé de préparation de polyétheresterpolyols
EP3759150A1 (fr) Mousses souples de polyuréthane à base de copolymères séquencés de polyoxyméthylène-polyoxyalkylène
WO2020083814A1 (fr) Procédé de préparation de copolymères séquencés polyoxyméthylène-polyoxyalkylène
WO2017194709A1 (fr) Procédé pour la préparation de polyoxyalkylène polyols
WO2020249433A1 (fr) Procédé pour la préparation de polyéthercarbonatepolyols
EP3649166B1 (fr) Procédé de fabrication de polyoxyalkylène-polyols fonctionnalisés
EP4077435B1 (fr) Procédé de fabrication de copolymères polyoxyméthylène-polyoxyalkylène
WO2021004814A1 (fr) Procédé de production de polyols de carbonate d'ester de polyéther
WO2022258570A1 (fr) Procédé pour la production de copolymères polyoxyméthylène-polyoxyalkylène
EP3980480B1 (fr) Procédé de fabrication continue de polyols polyoxyalkylènes
EP4165104A1 (fr) Procédé de production de copolymères de polyoxyméthylène-polyoxyalkylène
EP4004083A1 (fr) Procédé de production de polyols de polyéthercarbonate
EP3750940A1 (fr) Procédé de production de polyéthercarbonate polyols
EP3455277A1 (fr) Procédé pour la préparation de polyoxyalkylène polyols

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

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

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

Free format text: ORIGINAL CODE: 0009012

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20210622

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

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

18D Application deemed to be withdrawn

Effective date: 20230601