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WO2025016920A1 - Procédé de clivage hydroglycolytique ou hydrolytique autocatalytique de flux de déchets contenant du polyuréthane - Google Patents

Procédé de clivage hydroglycolytique ou hydrolytique autocatalytique de flux de déchets contenant du polyuréthane Download PDF

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Publication number
WO2025016920A1
WO2025016920A1 PCT/EP2024/069873 EP2024069873W WO2025016920A1 WO 2025016920 A1 WO2025016920 A1 WO 2025016920A1 EP 2024069873 W EP2024069873 W EP 2024069873W WO 2025016920 A1 WO2025016920 A1 WO 2025016920A1
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Prior art keywords
amine
isocyanate
polyurethane
polyol
depolymerization
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PCT/EP2024/069873
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English (en)
Inventor
Patrick SCHMATZ-ENGERT
Jens Ferbitz
Matthias Hinrichs
Matthias Maximilian NIEDERMAIER
Torsten Mattke
Marta KUBIAK
Michaela STUPPY
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BASF SE
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BASF SE
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Publication of WO2025016920A1 publication Critical patent/WO2025016920A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/14—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with steam or water
    • 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
    • C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
    • C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to isocyanurate 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • 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
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • 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
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two 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
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
    • 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
    • C08G18/4829—Polyethers containing at least three 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
    • C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/28—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic compounds containing nitrogen, sulfur or phosphorus
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention is directed to a process for cleavage recycling of polyurethane or polyiso- cyanurate foams containing waste comprising the steps of providing a composition comprising a comminuted polyurethane or polyisocyanurate foam which is obtained from isocyanate compo- sition (IC) comprising isocyanate (I1), and depolymerization of the comminuted polyurethane or polyisocyanurate, wherein the depolymerization is carried out in the presence of amine (A1) as catalytic active component and amine (A1) is the complementary amine to isocyanate (I1).
  • IC isocyanate compo- sition
  • I1 isocyanate
  • the present invention further relates to a polyol composition obtained or obtainable according to said process and the use thereof for the preparation of polyurethanes or polyisocyanurates.
  • the recycling of waste streams represents an essential building block for achieving greater sus- tainability of existing value chains.
  • remonomerizations as recycling techniques are those with the greatest circularity.
  • polyurethane plastics are a large-volume group.
  • Polyurethanes are formally prepared by polyaddition of at least one polyol with at least one polyisocyanate.
  • US20010027246 discloses a method of recovering a decomposition product from a polyurethane, the method comprising the steps of thermally decomposing a polyurethane into a liquid containing a polyol and a urea compound which is soluble in the polyol, and solids containing a urea com- pound which is insoluble in the liquid in the presence of a polyamine compound at a temperature of 120 to 250°C; removing the solids; hydrolyzing the residue with water retained at a high tem- perature of 200 to 320°C and a high pressure; and recovering the resulting polyamine and/or polyol.
  • EP 1142945 A2 relates to a method of chemically decomposing the cuttings made in molding or fabricating articles of polyurethane resins and waste of such resin articles for industrially advan- tageous recovery of a polyamine compound and a polyol compound useful as the raw materials of the polyurethane resin.
  • a polyurethane waste material is decomposed in aqueous solution, and the catalyst is separated in the water-phase so as to be used cyclically.
  • the decomposed product polyether and toluene diamine can be separated in water.
  • WO2022/063764 discloses a process for the recovery of raw materials (i.e.
  • polyols and option- ally additional amines) from polyurethane products comprising the reaction of the polyurethane product with an alcohol in the presence of a catalyst.
  • a product mixture containing alcohol, poly- ols and carbamates and optionally water is obtained.
  • the carbamates may be hydrolyzed with liberation of an amine corresponding to an isocyanate of the isocyanate component.
  • the problem is an irreversible reaction of the catalysts used with carbon di- oxide, especially in hydroglycolysis under pressure. On the one hand, this leads to a reduced yield of polyols and amine monomers.
  • insoluble solids are formed, which make downstream processing technically very difficult.
  • the circularity of the catalyst is also no longer given.
  • a process for recycling of polyure- thane or polyisocyanurate containing waste comprising the steps of a) providing a composition comprising a comminuted polyurethane or polyisocyanurate foam which is obtained from an isocyanate composition (IC) comprising isocyanate (I1); b) depolymerization of the comminuted polyurethane or polyisocyanurate provided in step a), wherein the depolymerization is carried out in the presence of amine (A1) as catalytic active component and amine (A1) is the complementary amine to isocyanate (I1).
  • a “comminuted polyurethane or polyisocyanurate foam” means the material is obtained from a foam and the comminuted polyurethane or polyisocyanu- rate is for example used in shredded form, in the form of granules, flakes, as an agglomerate, or as a powder.
  • the polyurethane or polyisocyanurate foams can be comminuted by conventional methods, for example by shredding, e.g. in a rotation mill or rotary mill at room temperature, to a particle size of ordinarily less than 500 mm, for example to a particle size in the range of from 10 to 500 mm, preferably to a particle size of less than 20 mm, or ground, e.g. by known cold grinding processes.
  • a particle size of less than 5 mm is selected, for example a particle size in the range of 0.01 mm to 5 mm, and preferably in the range of 0.01 mm to 1 mm.
  • polyurethane foams are used in the process of the present invention.
  • the present invention is also directed to the process as disclosed above, wherein the polyurethane foams are selected from the group consisting of polyisocyanate de- rived polyurethane foams.
  • the polyurethane or polyisocyanurate foams used in the present invention are preferably ob- tained from items produced from polyurethane foams at a time after use for the purpose for which they were manufactured or polyurethane foam waste from production processes.
  • the items Before subjecting to the process of the present invention, the items may be subjected to sorting steps and/or to mechanical comminution. That is, further sorting and bringing the items into appropri- ate sizes, e.g., by shredding, sieving or separation by rates of density, i.e. by air, a liquid or magnetically.
  • these fragments may then undergo processes to eliminate impurities, e.g. paper labels.
  • steps to remove blowing agents may be included in the process. Suitable methods are in principle known to the person skilled in the art.
  • the term “polyurethane foam waste” includes end-of-life polyurethane foams and pro- duction rejects of PU foams or waste generated through further processing of PU foams.
  • polyurethane foam denotes an item produced from a polyurethane foam at a time when it has already been used for the purpose for which it was manufactured.
  • “Production rejects of polyurethane foams“ denotes polyurethane foam waste occurring in pro- duction processes of PU foams.
  • polyurethane foams are produced by a reaction between a polyisocyanate compo- nent and a polyol component.
  • methylenedi(phenylisocyanate) (MDI) or its polymeric forms or tolylene 2,4 and 2,6-diisocyanate (TDI) are used as polyisocya- nate components for the production of PU rigid foams and PU flexible foams.
  • MDI methylenedi(phenylisocyanate)
  • TDI 2,4 and 2,6-diisocyanate
  • organic polyisocyanates that can be used in the preparation of polyurethanes are any of the known organic polyisocyanates, preferably aromatic polyfunctional isocyanates.
  • polyisocyanate encompasses isocyanates with 2 or more iso- cyanate groups, i.e. also diisocyanates.
  • Suitable polyisocyanate components used for the production of the polyurethanes or polyisocy- anurates comprise any of the polyisocyanates known for the production of polyurethanes or pol- yisocyanurates. These comprise the aliphatic, cycloaliphatic, and aromatic difunctional or poly- functional isocyanates known from the prior art, and also any desired mixtures thereof.
  • Exam- ples are diphenylmethane 2, 2’-, 2,4’-, and 4,4’-diisocyanate, the mixtures of monomeric diphe- nylmethane diisocyanates with diphenylmethane diisocyanate homologs having a larger number of rings (polymer MDI), isophorone diisocyanate (IPDI) and its oligomers, tolylene 2,4- and 2,6- diisocyanate (TDI), and mixtures of these, tetramethylene diisocyanate and its oligomers, hexa- methylene diisocyanate (HDI) and its oligomers, naphthylene diisocyanate (NDI), and mixtures thereof.
  • polymer MDI polymer MDI
  • IPDI isophorone diisocyanate
  • TDI tolylene 2,4- and 2,6- diisocyanate
  • HDI hexa- methylene diisocyanate
  • tolylene 2,4- and/or 2,6-diisocynate or a mixture thereof, monomeric diphenyl- methane diisocyanates, and/or diphenylmethane diisocyanate homologs having a larger num- ber of rings (polymer MDI), and mixtures of these.
  • polymer MDI polymer
  • isocyanates are mentioned by way of example in "Kunststoffhandbuch [Plastics handbook], volume 7, Polyurethane [Polyure- thanes]", Carl Hanser Verlag, 3rd edition 1993, chapter 3.2 and 3.3.2.
  • the organic polyisocyanates may be used individually or in the form of mixtures.
  • Polyols used in huge quantities are, e.g., selected from the group consisting of poly- ether polyols, polyester polyols, polyetherester polyols and mixtures thereof.
  • Polyetherols are by way of example produced from epoxides, for example propylene oxide and/or ethylene oxide, or from tetrahydrofuran with starter compounds exhibiting hydrogen-ac- tivity, for example aliphatic alcohols, phenols, amines, carboxylic acids, water, or compounds based on natural substances, for example sucrose, sorbitol or mannitol, with use of a catalyst.
  • Polyesterols are by way of example produced from aliphatic or aromatic dicarboxylic acids and polyhydric alcohols, polythioether polyols, polyesteramides, hydroxylated polyacetals, and/or hydroxylated aliphatic polycarbonates, preferably in the presence of an esterification catalyst.
  • Other possible polyols are mentioned by way of example in "Kunststoffhandbuch [Plastics hand- book], volume 7, Polyurethane [Polyurethanes]", Carl Hanser Verlag, 3rd edition 1993, chapter 3.1.
  • Polyesterpolyols may for example be selected from polyester alcohols whose OH numbers are in the range from 25 to 800 mg KOH/g, in particular from 25 to 500 mgKOH/g, preferably from 25 to 350 mgKOH/g, particularly preferable from 30 to 70 mgKOH/g.
  • the polyester alcohols used are mostly prepared via condensation of polyhydric alcohols, preferably polyetherpolyols with a molecular weight up to 800 g/mol, preferably up to 650 g/mol, or diols, having from 2 to 12 carbon atoms, preferably from 2 to 6 carbon atoms, with polybasic carboxylic acids having from 2 to 12 carbon atoms, e.g.
  • succinic acid glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, or preferably phthalic acid, isophthalic acid, terephthalic acid, or the isomeric naphthalenedicarboxylic acids.
  • cy-root anhydrides may be used such as for example phthalic acid dianhydride.
  • the process of the invention typically yields a polyamine comprising an amino group attached to the carbon atom to which in the initial polyisocyanate an isocyanate group was bound, e.g., methylene diphenyl diamines (MDA), oligomeric and polymeric meth- ylene phenylene amine and toluenediamines (TDA), in particular 2,4 toluenediamine or 2,6-tolu- enediamine, hexamethylene diamine (HDA), or naphthylene diamines (NDA).
  • MDA methylene diphenyl diamines
  • TDA oligomeric and polymeric meth- ylene phenylene amine and toluenediamines
  • HDA hexamethylene diamine
  • NDA naphthylene diamines
  • the commonly used polyols as described above preferably also can be re-isolated.
  • the process prefera- bly further yields, e.g., polyester polyols, fragments of polyesterpolyols, low molecular weight polyols such as ethylene glycol or propylene glycol, or high molecular weight polyether polyols based on glycerol, sorbitol, ethylene glycol, polypropylene glycol and polytetramethylene glycol.
  • the process of the present invention comprises steps a) and b) and may comprise further steps.
  • a composition comprising a comminuted polyurethane or polyisocy- anurate foam which is obtained from an isocyanate composition (IC) comprising isocyanate (I1) is provided.
  • the composition might contain further components, for example solvents.
  • the comminuted polyurethane or polyisocyanurate provided in step a) is depoly- merized, wherein the depolymerization is carried out in the presence of amine (A1) as catalytic active component and amine (A1) is the complementary amine to isocyanate (I1).
  • amine (A1) as catalytic active component
  • amine (A1) is the complementary amine to isocyanate (I1).
  • the depolymerization results in polyol components and amine components.
  • the polyol-containing phase may be used at least proportionally in new PU formu- lations.
  • the polyamine preferably can be converted back to the corresponding isocyanate, for example by means of phosgenation, and as such can then be used at least pro- portionally as an isocyanate component in PU production.
  • amine monomers obtainable in the depol- ymerization process as catalyst in the depolymerization step, in particular in a hydroglycolysis step.
  • the complementary amine to isocyanate (I1) is used as catalyst in the hydroglycol- ysis, said amines react with CO2 to unstable carbamic acids under pressure and by their de- composition free amine is generated in turn which acts as catalyst and accelerates the reaction autocatalytically.
  • the complementary amine has not to be separated off in the process.
  • at least one of the amine-containing streams formed during the reaction or work-up is completely or in parts recycled in the reaction stage to introduce the amine as a catalyst.
  • the catalyst is recovered in the course of the reaction.
  • the present invention is also directed to the process as dis- closed above, wherein the amine (A1) is prepared in the process itself, in particular wherein the amine (A1) is prepared in the process itself and is supplied by at least proportional recycling of at least one of the amine-containing components occurring in the process.
  • the present invention is also directed to the process as dis- closed above, wherein at least one of the amine-containing streams formed during the reaction or work-up is completely or in parts recycled in the reaction stage to introduce the amine as a catalyst.
  • Amine-containing components may be present in the process according to the present invention for example during the removal of particulate solids from the reaction mixture obtained in step b) or during phase separation in a polyol-containing phase and an amine-containing phase or dur- ing the distillative work-up of the amine phase, comprising alcohol, water and corresponding amine or during the purification of polyol-containing phase under recovery of a purified polyol. Suitable methods for depolymerization are in principle known to the person skilled in the art.
  • the depolymerization is achieved by hydrolysis, hydroglycolysis, or by aminolysis ac- cording to the present invention.
  • depolymerization is achieved by hydroglycolysis or hydrolysis according to the present invention.
  • the alcoholysis and glycolysis are suitable methods for the depolymerization.
  • the depolymerization leads primarily to carba- mates, a polyaddition product of the utilized glycol or alcohol with the isocyanate component and not the respective amine of the isocyanate component. The autocatalytic behavior of the reaction cannot be achieved.
  • urea groups which are formed during the foaming process by adding water can be depolymerized to isocyanate derived amines.
  • isocyanate derived amines because of the equilibrium reaction for the glycolysis/alcoholysis only small amounts of amines are formed which typically will accelerate the reaction rate more likely for the carbamate formation as the amine formation.
  • different products are obtained. Prefera- bly, it is possible to recover both starting material components from the polyurethane.
  • a component comprising an isocyanate precursor like an amine, carbamate or urea is obtained and can be separated but also the polyol component or monomer fragments of the polyol com- ponent is separated,
  • the amine component is to be un- derstood as a component obtained in the depolymerization process comprising an isocyanate precursor like an amine, carbamate or urea.
  • the depolymerization results in a mixture of components which might be separated us- ing suitable separation techniques.
  • the process of the present invention may also comprise fur- ther separation steps.
  • the present invention is also directed to the process as dis- closed above, wherein the depolymerization according to step b) is carried out by a method se- lected from hydrolysis or hydroalcoholysis, in particular hydroglycolysis. Suitable conditions for the depolymerization are in principle known to the person skilled in the art. According to the present invention, further additives including solvents or further catalytically active component may be added in step b). Preferably, the depolymerization is carried out with- out the addition of further catalyst. The resulting products of the depolymerization may be sepa- rated using suitable separation techniques which are in principle known to the person skilled in the art.
  • a polyurethane material is alco- holised by contacting the polyurethane material with an alcoholising substance, wherein water is added in an amount so that a water content of a resulting mixture is from about 0.2 eq. to about 30 eq. water, in particular about 1 eq. to about 20 eq. water, in particular about 1.15 eq. to about 10 eq., for example about 1.3 eq. to about 5 eq., for example about 1.4 eq. to about 2 eq., based on the amount of cleavable bonds in the polyurethane material.
  • Eq. refers to equivalents per cleavable bond of the polyurethane material.
  • Cleavable bonds are defined as urethane bonds,urea bonds and isocyanurate bonds within the polyurethane material and include segments in the polyurethane material in which segments are linked via allophanate units as well as linkages via biuret groups.
  • the amount of cleav- able bonds is equivalent to the amount of the isocyanate group content in the original polyure- thane material.
  • the present invention is also directed to the process as disclosed above, wherein the process comprises further purification steps.
  • Suitable treatment steps are in principle known to the person skilled in the art. Suitable treatment and/or purification steps may be carried out between steps a) and b), or between steps b) and c).
  • step b) is carried out directly after step a).
  • step c) is carried out directly after step b).
  • steps a) and b) might also be combined and carried out in the same apparatus.
  • the composition provided in step a) might also comprise solvents, for example solvents which might be used in step b) of the process according to the present invention.
  • the work-up of the depolymerization product in particular the isolation of the polyamine and the polyol can be realized case dependent, for example by extractive work-up, precipitation of the amine component as a hydrochloride, as a urea (in case of an aminolysis), chromatography or distillation under reduced pressure.
  • the work up comprises several steps.
  • solids may be removed from the mixture before or af- ter the mixture is allowed to settle, preferably by one or more of the following: filtration, centrifu- gation, decantation.
  • the present invention is also directed to the process as dis- closed above, wherein the process further comprises a step c) c) removal of particulate solids from the reaction mixture.
  • Suitable methods for removal of particulate solids are in principle known to the person skilled in the art.
  • filtration units or a centrifuge may be used.
  • a filtration step is carried out according to the present invention using a filtration unit, more preferably a filter, more preferably a pocket filter, a bag filter, a membrane filter, a candle filter, an agitated pres- sure filter, a vacuum belt filter, a frame & plate filter, or a nutsche filter.
  • filter membranes having an average mesh size of about 30 ⁇ m or less may be used. It can be beneficial to use a cascade of filters.
  • a first filter mem- brane of the cascade of filters has an average mesh size of about 250 ⁇ m to about 290 ⁇ m.
  • a second filter membrane of the cascade of filters preferably has an average mesh size of about 50 ⁇ m to about 90 ⁇ m and, in particular, a third filter membrane of the cascade of filters has an average mesh size of 20 ⁇ m or less.
  • centrifugation is a preferred solid-liquid-separation method.
  • the process comprises allowing the mixture to settle.
  • one or more phases are formed and the components of the mixture may be separated by suitable separation steps.
  • an excess of water is removed from the mixture, before allowing the mixture to settle, preferably by evaporation of the excess of water.
  • the mixture is heated and/or a vacuum is applied.
  • an excess of water is removed by using flash evaporation or applying vacuum to the already heated mixture.
  • a water removal step may be performed for about 120 minutes or less, in particular about 90 minutes or less, for example about 75 minutes or less, for example about 60 minutes or less.
  • the water removal step is performed for about 10 minutes or more, in particular for about 30 minutes or more, for example for about 40 minutes or more.
  • the present invention is also directed to the process as dis- closed above, wherein the process further comprise a step d) d) separation of the amine component and the polyol components.
  • the process further comprise a step d) d) separation of the amine component and the polyol components.
  • compounds are separated according to their volatility, with more vola- tile compounds being separated first.
  • Additives, water or solvents used in the depolymerization can also be removed via distillation prior further work-up of the polyol-polyamine mixtures.
  • the “volatility” of a liquid may be described using its vapor pressure, wherein a high vapor pressure indicates a high volatility, and vice versa.
  • the polyamine is more volatile than the polyol as it is for example the case for TDA, monomeric MDA and NDA
  • the polyamine is recovered from the depolymerization product via distillation, preferably via distillation at reduced pressure. After distilling-off the polyamine, a distillation bottoms remains which contains the polyol.
  • Suitable conditions for the distillation are in principle known to the person skilled in the art and are for example disclosed in EP22178796.3 or EP22178797.1.
  • the polyol may be recovered by extraction from the depolymerization mixture us- ing a suitable extractant or a pair of extractants. It is also possible to precipitate the polyamine component in the form of it ⁇ s hydrochloride by adding HCl and extracting the polyol component with a suitable solvent for example as described in DE2854940A1, which is preferably dissolv- ing the polyol component but not the hydrochlorides of the polyamine component.
  • the hydro- chloride of the polyamine component can after separation then either be transferred to the free polyamine by adding a base but also directly used in the phosgenation to generate new polyiso- cyanates for the polyurethane synthesize.
  • the hydrochloride can be directly fed to an MDA synthesis plant at a position prior to the neutralization step.
  • the process comprises preferably a work-up of the phase, which is polyol substance rich by purification of the polyol substance.
  • the purification may for example comprise one or more of the following but may also comprise fur- ther purification steps: - filtration; - centrifugation; - decantation; - distillation; - full or partial evaporation of the phase in one or more evaporators; - contacting the phase with an ion exchange material; - contacting the phase with one or more adsorbents; -extracting the phase via one or more extraction agents.
  • the phase which is polyol substance rich, preferably an acid number of 0.1 mg KOH/g or less.
  • the acid number (corresponding to the acid value) is determined according to DIN EN ISO 4629-2, with minor changes.
  • a mixture of iso-propanol/water 1:1 was used as solvent mixture, instead of toluene/ethanol 2:1.
  • NaOH/KOH was dissolved in methanol instead of ethanol.
  • the OH numbers are in the range from 25 to 800 mg KOH/g, in particular from 25 to 500 mgKOH/g, preferably from 25 to 350 mgKOH/g, in particular from 30 to 70 mgKOH/g.
  • a polyol component having a func- tionality of from 1 to 6, preferably between 1 to 4.5 is used, in particular in the range of from 1 to 4.1, more preferable in the range of from 1 to 3.9, most preferable in the range of from 1.1 to 3.5.
  • the polyol com- ponent may comprise polyol fragments such as for example fragments of polyesterpolyols.
  • the polyol components or polyol fragments may be treated to form a polyol.
  • the phase may comprise polyol components such as glycols and may also comprise mono- or-diacids in case polyesterpolyols are present in the polyurethane or pol- yisocyanurate. Diacids may also be present in the form of diammonium salts.
  • the treatment may comprise further treatments such as for example thermal treatments and/or vapor stripping to obtain the free acid prior to re-ester- fication of the polyol fragments. Suitable conditions for example for re-esterfication are known to the person skilled in the art.
  • the ratio of acids and polyalcohols is typically adjusted to obtain a mixture which is then suitable as a starting material for esterification of the acids and polyalco- hols.
  • the ratio of acids is adjusted to a molar ratio of acid groups to hydroxy groups in the range of from 1:1.03 to 1:2.5, in particular to 1:1.05 to 1:2.0.
  • the process may for example comprise steps such as adding diacids to the mixture; adding pol- yalcohols to the mixture; adding esterification catalysts, for example titan tetrabutanolate; re- moval of diols by evaporation /distillation; or removal of solvent from the mixture.
  • the process may furthermore comprise suitable treatment steps to achieve condensation of polyalcohols and acids in the mixture.
  • suitable to achieve re-condensation of polyols and acids Suit- able conditions for example for re-esterfication are known to the person skilled in the art and may for example include condensation of alcohols and acids by heating under vacuum and re- moval of condensation product, online analytics to follow reaction progress and optionally adjust monomer composition.
  • the process further comprises work-up of the mixture by purification of the amine substance, for example including distillation, extraction, adsorption, precipitation or crystalliza- tion in order to purify the amine substance.
  • the separation process described above can be combined with any of the various embodiments of the inventive process described herein.
  • the yield of the polyol substances or monomer fragments of those which are released is about 90 % or more, preferably of 97 wt.-% or more, in particular of 99 wt.-% or more.
  • the present invention is also directed to the polyol composition obtained or obtainable according to the process of the present invention.
  • the polyol composition for flexible foams comprises or consists of one or more poly- ols having a molecular weight of about 2500 to about 3500 g/mole, a nominal OH functionality of about 3 and having an OH number of about 48 mg KOH/g to about 56 mg KOH/g.
  • the polyol composition for rigid foams comprises or consists of one or more polyols having a molecular weight of about 400 to about 800 g/mole, a nominal OH functionality of about 2-3 and having an OH number of about 200 mg KOH/g to about 300 mg KOH/g.
  • the polyol composition may comprise or con- sist of one or more polyols having a molecular weight of about 3000 to about 6500 g/mole, a nominal OH functionality of about 3 and having an OH number of about 20 mg KOH/g to about 50 mg KOH/g.
  • the present invention is also directed to the use of the polyol com- position according to the present invention or a polyol composition obtained or obtainable ac- cording to the process of the present invention for the preparation of polyurethanes or polyiso- cyanurates.
  • the amine substance resulting from the recovery process is fed into a purification sec- tion of an amine producing plant, an amine storage tank or an isocyanate producing plant, for example in the phosgenation section of an isocyanate production plant.
  • the amine substance needs to be essentially free of polyol substance, residual metals and silicon compounds.
  • the amine substance is phosgenated so that an isocyanate substance is formed.
  • TDA may be phosgenated to prepare TDI or MDA may be phosgenated to prepare MDI.
  • pMDA may be phosgenated to prepare pMDI and NDA may be phosgenated to prepare NDI.
  • Suitable conditions for the phosgenation are in principle known to the person skilled in the art.
  • the present invention therefore is also directed to the pro- cess as disclosed above, wherein the process further comprises step e) e) conversion of the amine component to obtain an isocyanate composition.
  • isocyanate composition encompasses all iso- cyanates known to the person skilled in the art in connection with polyurethane chemistry, such as, in particular, toluene diisocyanate (TDI; prepared from toluene diamine, TDA) or the di- and polyisocyanates of the diphenylmethane series (MDI; prepared from the di- and polyamines of the diphenylmethane series, MDA).
  • TDI toluene diisocyanate
  • MDI di- and polyisocyanates of the diphenylmethane series
  • MDA diphenylmethane series
  • isocyanate composition also encompasses embodiments in which two or more different isocyanates (e.g. mixtures of MDI and TDI) have been used in the preparation of the polyurethane material.
  • Suitable processes are for example liquid phosgenation, gasphase phosgenation or gas-liquid phosgenation or a phosgenation via salt or a phosgene-free conver- sion for example carbamate cleavage.
  • Suitable conditions for the phosgenation are in principle known to the person skilled in the art and are for example disclosed in Ullmann’s Encyclopedia of Industrial Chemistry, 7 th ed. Vol.20, 2012, p.63-82, WO 99/54289 A, WO 2004/056756 A (liquid phosgenation); Ullmann’s Encyclopedia of Industrial Chemistry, 4 th ed. Vol.13, 2012, p.
  • the phosgenation comprises admixing a solvent to the amine component and stir- ring, more preferably at a temperature in the range of from 50 to 180 °C, more preferably in the range of from 70 to 140 °C, more preferably in the range of from 80 to 120 °C, obtaining a poly- amine mixture; and bringing the polyamine mixture in contact with phosgene in a reactor and heating the obtained mixture to a temperature in the range of from 90 to 140 °C, more prefera- bly in the range of from 110 to 130 °C, obtaining a mixture comprising one or more polyisocya- nates.
  • the present invention is also directed to the isocyanate composition obtained or obtainable ac- cording to the process as disclosed above. Furthermore, the present invention is directed to the use of the isocyanate composition according to the present invention or the isocyanate compo- sition obtained or obtainable according to the process according to the present invention for the preparation of polyurethanes or polyisocyanurates.
  • TDI or MDI produced accord- ing to the present invention can be used as isocyanate substance to produce polyurethane foam by reacting it with a polyol obtained according to the present invention or any other suited polyol component.
  • a process for recycling of polyurethane or polyisocyanurate containing waste comprising the steps of a) providing a composition comprising a comminuted polyurethane or polyisocyanurate foam which is obtained from isocyanate composition (IC) comprising isocyanate (I1) b) depolymerization of the comminuted polyurethane or polyisocyanurate provided in step a), wherein the depolymerization is carried out in the presence of amine (A1) as catalytic active component and amine (A1) is the complementary amine to isocyanate (I1). 2.
  • a process for recycling of polyurethane or polyisocyanurate containing waste comprising the steps of a) providing a composition comprising a comminuted polyurethane or polyisocyanurate foam which is obtained from isocyanate composition (IC) comprising isocyanate (I1) b) depolymerization of the comminuted polyurethane or polyisocyanurate provided in step a), wherein the depolymerization is carried out in the presence of amine (A1) as catalytic active component and amine (A1) is the complementary amine to isocyanate (I1) and wherein the amine (A1) is prepared in the process itself and supplied by at least pro- portional recycling of at least one of the amine-containing components occurring in the process.
  • a process for recycling of polyurethane or polyisocyanurate containing waste comprising the steps of a) providing a composition comprising a comminuted polyurethane or polyisocyanurate foam which is obtained from isocyanate composition (IC) comprising isocyanate (I1) b) depolymerization of the comminuted polyurethane or polyisocyanurate provided in step a) by a method selected from hydrolysis or hydroglycolysis, wherein the depolymerization is carried out in the presence of amine (A1) as catalytic active component and amine (A1) is the complementary amine to isocyanate (I1).
  • Polyol composition obtained or obtainable according to the process of any one of embodi- ments 1 to 8.
  • Polyol composition obtained or obtainable according to the process for recycling of polyu- rethane or polyisocyanurate containing waste comprising the steps of a) providing a composition comprising a comminuted polyurethane or polyisocyanurate foam which is obtained from isocyanate composition (IC) comprising isocyanate (I1) b) depolymerization of the comminuted polyurethane or polyisocyanurate provided in step a), wherein the depolymerization is carried out in the presence of amine (A1) as catalytic active component and amine (A1) is the complementary amine to isocyanate (I1).
  • Polyol composition obtained or obtainable according to the process for recycling of polyu- rethane or polyisocyanurate containing waste comprising the steps of a) providing a composition comprising a comminuted polyurethane or polyisocyanurate foam which is obtained from isocyanate composition (IC) comprising isocyanate (I1) b) depolymerization of the comminuted polyurethane or polyisocyanurate provided in step a) by a method selected from hydrolysis or hydroglycolysis, wherein the depolymerization is carried out in the presence of amine (A1) as catalytic active component and amine (A1) is the complementary amine to isocyanate (I1).
  • polyol composition according to any one of embodiments 9 to 12 or a polyol composition obtained or obtainable according to the process of any one of embodiments 1 to 8 for the preparation of polyurethanes or polyisocyanurates.
  • a process for recycling of polyurethane or polyisocyanurate containing waste comprising the steps of a) providing a composition comprising a comminuted polyurethane or polyisocyanurate foam which is obtained from isocyanate composition (IC) comprising isocyanate (I1), b) depolymerization of the comminuted polyurethane or polyisocyanurate provided in step a) by a method selected from hydrolysis or hydroglycolysis, wherein the depolymerization is carried out in the presence of amine (A1) as catalytic active component and amine (A1) is the complementary amine to isocyanate (I1), c) removal of particulate solids from the reaction mixture, d) separation of the amine component and the polyol components, e) conversion of the amine component to obtain an isocyanate component.
  • IC isocyanate composition
  • I1 isocyanate composition
  • depolymerization of the comminuted polyurethane or polyisocyan
  • Isocyanate composition obtained or obtainable according to the process for recycling of polyurethane or polyisocyanurate containing waste comprising the steps of a) providing a composition comprising a comminuted polyurethane or polyisocyanurate foam which is obtained from isocyanate composition (IC) comprising isocyanate (I1), b) depolymerization of the comminuted polyurethane or polyisocyanurate provided in step a) by a method selected from hydrolysis or hydroglycolysis, wherein the depolymerization is carried out in the presence of amine (A1) as catalytic active component and amine (A1) is the complementary amine to isocyanate (I1), c) removal of particulate solids from the reaction mixture, d) separation of the amine component and the polyol components, e) conversion of the amine component to obtain an isocyanate component.
  • a process for recycling of polyurethane or polyisocyanurate containing waste comprising the steps of a) providing a composition comprising a comminuted polyurethane or polyisocyanurate foam which is obtained from isocyanate composition (IC) comprising isocyanate (I1), b) depolymerization of the comminuted polyurethane or polyisocyanurate provided in step a), wherein the depolymerization is carried out in the presence of amine (A1) as catalytic ac- tive component and amine (A1) is the complementary amine to isocyanate (I1), wherein amine (A1) is supplied by at least proportional recycling of at least one of the amine-containing components occurring in the process.
  • polyol composition according to embodiment 27 Use of the polyol composition according to embodiment 27 or a polyol composition ob- tained or obtainable according to the process of any one of embodiments 19 to 26 for the preparation of polyurethanes or polyisocyanurates. 29. The process according to embodiment 26, wherein the process further comprises step e) e) conversion of the amine component to obtain an isocyanate component. 30. Isocyanate composition obtained or obtainable according to the process according to em- bodiment 29. 31. Use of the isocyanate composition according to embodiment 30 or an isocyanate compo- sition ob-tained or obtainable according to the process according to embodiment 29 for the preparation of polyurethanes or polyisocyanurates.
  • Figure 1a shows the IR analyses after phase separation for example 1.
  • Figure 1b shows the ATR analyses of the amine phase of example 1. No urea vibration could be detected.
  • the symmetric and asymmetric N-C-N stretching vibration at 1553 cm ⁇ -1 could not be detected after the hydroglycolysis process (red curve).
  • Figure 6a shows the process scheme of batch column as used for example 5. This setup was used to distill DEG and TDA of the bottom phase.
  • Figure 6b shows the pressure/temperature curve in dependence to distillation time for example 5.
  • Figure 7 shows a general process scheme for the hydrolysis of a PU-rigid foam. Examples I.
  • PU flexible foam consists of TDI (Toluenediisocyanate, isomers: 2,4 TDI and 2,6 TDI) and long chain Polyether polyols (Polyol 1).
  • the foam contains foaming catalysts, a blowing agent and stabilizers as well.
  • End of life (EoL foam) flexible PU foam was sorted by a spectroscopic method to minimize the content of high resilience (HR) polyols and Styrene acrylonitrile resin (SAN) polymer particles.
  • PU rigid foam consists of polymeric isocyanate (pMDI) and polyether and/or polyester pol- yols. The foam contains foaming catalysts, blowing agents and stabilizers as well. II.
  • Isocyanate 1 TDI (Toluenediisocyanate, isomers: 2,4 TDI and 2,6 TDI)
  • Isocyanate 2 pMDI-1 is polymeric isocyanate with a typical NCO content of 31.5 g/100g and a viscosity at 25°C of about 550 mPas. It is available as a commercial product from BASF. III. Analytical methods: 1. IR-spectroscopy: IR spectroscopy was carried out to determine the conversion of the remonomerization reaction.
  • ATR-analysis ATR spectroscopy was carried out to check the absence of the urea vibra- tion after hydroglycolysis or hydrolysis process 3.
  • High performance liquid-chromatography HPLC analyses was carried out to de- termine 2,4-, 2,6-TDA and 2,2-, 2,4-, 4,4-MDA.
  • HPLC-setup Agilent Technologies “1200 Series” Column: Fluofix (5 ⁇ m, 250 x 4.6 mm) Detection: 205 nm Temperature: 25°C Injection volume: 10 ⁇ L
  • Mobile phase (A)1000 mL water + 1 ml H 3 PO 4 , (B) 950 mL Acetonitrile + 50 mL water + 1 mL H 3 PO 4 4.
  • GC-analysis Quantification of 2,2-, 2,4-, 4,4-MDA, 3-ring MDA, 4-ring MDA, and 5-ring MDA.
  • the detailed description of the GC method is listed below: GC-setup: Agilent 7890A Column: DB-5HT (30m x 0,32mm x 0,1 ⁇ m) Temperature program: 80°C-5min-6°C/min-370°C-30min Injection temperature: 340°C Injection volume: 1 ⁇ L Detector temperature: 340°C Carrier gas : Hydrogen (Constant Pressure 10psi) Split ratio: 15:1 5.
  • Model foam 1.1 Soft/flexible foam (MF1) Flexible foam: Hydroglycolysis of foam synthesized from isocyanate 1 (2,4 TDI and 2,6 TDI), polyols and additives like catalysts, surfactants, blowing agents required for foaming (30.9 wt.-% TDI and 61.9 wt.-% polyol 1).
  • Silicone oils Blowing agents Water, CO 2 Catalysts: Usually tertiary amines) 1.2 Rigid foams (MF2)
  • PIR-construction foam Hydrolysis of a foam synthesized from isocyanate 2, polyols and different additives like e. g.
  • catalysts, surfactants, blowing agents required for foaming (71.4 wt.-% M50S; 18.4 wt.-% polyols primarily polyol 2 and 3 containing predominately aromatic dicarboxylic acids, like phthalic acid and terephthalic acid and glycols as well as short-chain polyether polyols)
  • Surfactants Silicone oils Blowing agents: Water, Cyclopentane Catalysts: Usually tertiary amines) and potassium salts 2.
  • Example 1 Autocatalytical hydroglycolysis of flexible foam – model foam (MF1) 15 g of the model foam was cooled with liquid nitrogen and milled using a coffee grinder.
  • Example 2 Autocatalytical hydroglycolysis of flexible foam with higher mass load (EF1)
  • EF1 mass load 1
  • a model foam 177.05 g
  • DEG DEG
  • Water 180.23 g
  • both of TDA isomers (2,6-TDA, 11.053 g, purity of 97% and 2,4-TDA, 44.08 g, purity of 98%) were put into the pressure reactor.
  • the upper phase can be defined as amine poor phase whereas the bottom phase has a higher TDA content.
  • Upper phase wt.-% Lower phase TDA 14 16 DEG 9 42 Water 7 40 Polyol 69.4 Not detectable via GPC Comparing the ATR spectra no band at ca.1725 cm -1 (C O vibration) and at ca.1550 cm- 1 (N-H vibration) could be detected.
  • Example 5 Batch distillation of bottom phase- Recovery of DEG and TDA The bottom phase was distilled in a lab scale batch distillation column to recover DEG and TDA. The schematic setup of the distillation column is shown in figure 6a: The operating data during distillation in a lab distillation column are presented in fig.6b.
  • Example 7 Neutralization and phase separation after autocatalytic hydrolysis – model system
  • the model system is a mixture of pMDA, Terephthalic acid (TA), Phthalic acid (PA), DEG, MEG, glycerol.
  • the composition of the model system is similar to a representative composition of polyol 2 and 3.
  • the water content of the MCB phase was analyzed via Karl- Fischer-Titration.0.2 wt.-% water could be detected in the lower phase.
  • the chloro- benzene of the lower phase was totally evaporated.
  • An elementary analysis of the residue was carried out to check the absence of sodium salts and glycols in the lower phase.
  • the sodium content was lower than 30 ppm and the oxygen content was lower than 0.5 wt.-%.
  • Table 5 Results from the elementary analysis of the lower phase after MCB removal. Element Mass fraction / wt.-% Carbon (C) 78.8 Oxygen (O)_balanced ⁇ 0.5 Nitrogen (N) 14.4 Hydrogen (H) 7.0 Sodium(Na) ⁇ 0.003 3.8.
  • the solid-liquid separation unit is a filtration unit or a centrifuge, more preferably a filtration unit, more preferably a filter, more preferably a pocket filter, a bag filter, a membrane filter, a candle filter, an agitated pressure filter, a vacuum belt filter, a frame & plate filter, or a nutsche filter (Source: 220263 EP01) 3.9
  • Process scheme – PU-rigid foam- Hydrolysis A general process scheme is shown in figure 7.
  • the solid-liquid separation unit is a filtration unit or a centrifuge, more preferably a filtration unit, more preferably a filter, more preferably a pocket filter, a bag filter, a membrane filter, a candle filter, an agitated pressure filter, a vacuum belt filter, a frame & plate filter, or a nutsche filter
  • Extraction aid can be any organic solvent which has a mixing gap with water
  • Neutralization step As neutralization agent any base which has a higher basicity as ani- line can be applicated.
  • the neutralization is usually carried out in a stirred tank reactor at 80°C.
  • the neutralization unit is a stirred tank reactor.
  • Polyester-fragments-work up Re-polymerization of Polyester-fragments by polyconde- sation under vacuum, distillative removal of water in presence of a Bronsted or Lewis acid and if necessary in presence of further added glycols or acids to guarantee a equimolar ratio between OH- and COOH-groups.
  • pMDA- work up pMDA-work up and phosgenation

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un procédé de recyclage par clivage de mousses de polyuréthane ou de polyisocyanurate contenant des déchets comprenant les étapes consistant à fournir une composition comprenant une mousse de polyuréthane ou de polyisocyanurate broyée qui est obtenue à partir d'isocyanate (I1), et de dépolymérisation du polyuréthane ou du polyisocyanurate broyé, la dépolymérisation étant effectuée en présence d'amine (A1) en tant que composant actif catalytique et l'amine (A1) étant l'amine complémentaire de l'isocyanate (I1). La présente invention concerne en outre une composition de polyol obtenue ou pouvant être obtenue selon ledit procédé et son utilisation pour la préparation de polyuréthanes ou de polyisocyanurates.
PCT/EP2024/069873 2023-07-14 2024-07-12 Procédé de clivage hydroglycolytique ou hydrolytique autocatalytique de flux de déchets contenant du polyuréthane Pending WO2025016920A1 (fr)

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EP23185635 2023-07-14

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WO2018185168A1 (fr) 2017-04-05 2018-10-11 Basf Se Catalyseurs hétérogènes pour la carbonylation directe de composés nitro-aromatiques en isocyanates
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WO2022063764A1 (fr) 2020-09-23 2022-03-31 Covestro Deutschland Ag Procédé de récupération de matières premières à partir de produits de polyuréthane
WO2022106716A1 (fr) 2020-11-23 2022-05-27 Basf Se Procédé de production d'isocyanates
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WO2022063764A1 (fr) 2020-09-23 2022-03-31 Covestro Deutschland Ag Procédé de récupération de matières premières à partir de produits de polyuréthane
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