EP4638545A1 - Polyols recyclés - Google Patents

Polyols recyclés

Info

Publication number
EP4638545A1
EP4638545A1 EP23820945.6A EP23820945A EP4638545A1 EP 4638545 A1 EP4638545 A1 EP 4638545A1 EP 23820945 A EP23820945 A EP 23820945A EP 4638545 A1 EP4638545 A1 EP 4638545A1
Authority
EP
European Patent Office
Prior art keywords
diaminotoluene
anhydride
polyols
tda
reaction
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.)
Pending
Application number
EP23820945.6A
Other languages
German (de)
English (en)
Inventor
Roland Hubel
Annegret Terheiden
Olga FIEDEL
Emily Clare SCHWEISSINGER
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.)
Evonik Operations GmbH
Original Assignee
Evonik Operations GmbH
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 Evonik Operations GmbH filed Critical Evonik Operations GmbH
Publication of EP4638545A1 publication Critical patent/EP4638545A1/fr
Pending 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
    • C08G18/4829—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
    • C08G18/08—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
    • C08G18/165—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 covered by C08G18/18 and C08G18/24
    • 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
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1825—Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino 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
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic 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
    • C08G18/70—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
    • 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
    • C08G65/2618—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 nitrogen
    • C08G65/2621—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 nitrogen containing amine groups
    • C08G65/2624—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 nitrogen containing amine groups containing aliphatic amine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
    • 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
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the invention relates to a process for reducing the content of 2,6-diaminotoluene and/or 2,4- diaminotoluene in polyols containing 2,6-diaminotoluene and/or 2, 4-diaminotoluene by reaction with suitable compounds as specified in Claim 1.
  • Polyols containing 2,6-diaminotoluene and/or 2, 4-diaminotoluene are obtained, for example, when polyurethane and/or polyurethanepolyurea wastes are chemically recycled or depolymerized by chemolysis.
  • the abbreviation “PU” is also used for polyurethane in the context of this invention.
  • the most commonly used method is glycolysis, in which the polyurethane is cleaved with a glycol or glycol mixture to give a shorter-chain urethane (see, for example, EP 0835901 A2, EP 0899292 A1 , EP 0546415 A1 , EP 0 771 644 A2).
  • the reaction mixture is reacted with the shorter-chain urethane, which is reactive because of the free hydroxyl group, and the polyurethane component cleaved off, generally without further workup, is then reacted with an isocyanate component to give a polyurethane compound again.
  • Glycolytic cleavage can be used, for example, when the individual components such as aromatic amines and polyether polyol of the polyurethane to be cleaved are not to be recovered.
  • a further method of cleaving polyurethanes that takes account of this aspect is hydrolysis.
  • Cleavage products formed in the reaction of the polyurethane with water, as well as carbon dioxide, are amine and polyether polyol components.
  • the advantage of this method is that the amine and the polyether polyol component can be returned to the polyurethane production and hence, if desired, the same isocyanate or a uniform polyurethane can be produced again.
  • the hydrolysis of polyurethanes is known from the literature (see, for example, US 4,035,314, US 4,316,992, US 3,441 ,616, W02022042909A1 , WO2022042910A1).
  • the cleavage components can typically be separated and worked up. It is preferably possible, in a vacuum distillation, to fractionate the water, solvent and the amine formed directly from the reaction mixture. Water and solvent can generally be used again for the recycling process without further workup steps.
  • the amine can be subjected to a fine purification if desired depending on the requirement.
  • the recovered polyols cannot normally be freed entirely of 2,6-diaminotoluene and/or 2,4- diaminotoluene by distillation. According to the distillation conditions, polyols are obtained, especially polyether polyols, with a different content of 2,6-diaminotoluene and/or 2,4-diaminotoluene.
  • TDA content means the sum total of 2,6-diaminotoluene and 2,4-diaminotoluene present.
  • TDA means the totality of 2,6-diaminotoluene and 2,4- diaminotoluene.
  • TDA content means the sum total of 2,6- diaminotoluene and 2,4-diaminotoluene present.
  • a synonym for 2,6-diaminotoluene (CAS No. 823- 40-5) is toluene-2,6-diamine.
  • a synonym for 2,4-diaminotoluene (CAS No. 95-80-7) is toluene-2,4- diamine.
  • the “TDA polyol” of a polyol is ⁇ 0.03% by weight, for example, what this means in the context of this invention is that ⁇ 0.03% by weight in total of 2,6-diaminotoluene and 2,4-diaminotoluene, meaning the sum total of 2,6-diaminotoluene and 2,4-diaminotoluene present, may be present in the polyol in question; the percentages by weight relate here to the total amount of the polyol in question plus 2,6-diaminotoluene and 2,4-diaminotoluene present therein.
  • the polyol contains 2,4- diaminotoluene only, but no 2,6-diaminotoluene, or that the polyol contains 2,6-diaminotoluene only, but no 2,4-diaminotoluene; preferably, 2,6-diaminotoluene and 2,4-diaminotoluene are present.
  • the specific problem addressed by the invention was that of providing a means of reducing the level of 2,6-diaminotoluene and/or 2,4-diaminotoluene in polyols containing 2,6-diaminotoluene and/or 2,4-diaminotoluene, for example in recycled polyols, especially recycled polyether polyols.
  • the “polyol” is especially a polyether having two or more, preferably three or more, isocyanate-reactive groups, especially OH groups, preferably a polyether polyol (i.e., a polyether having at least two hydroxyl groups reactive toward isocyanate groups), preferably obtained by depolymerization, especially hydrolysis, of a polyurethane.
  • recycled polyols and “recycled polyether polyols” in the context of this invention are polyols and polyether polyols that have been obtained from the depolymerization, especially hydrolysis, of polyurethane, especially PU foam. Most preferably, recycled polyols are, for example, those as obtainable according to the teaching of document W02022042909A1 or of document W02022042910A1.
  • Document WO 2023/275033 A1 discloses a method of producing PU foams by reacting (a) at least one polyol component that contains recycled polyol with (b) at least one isocyanate component in the presence of (c) one or more catalysts that catalyse the reactions of isocyanate-polyol and/or isocyanate-water and/or the isocyanate trimerization reaction, (d) at least one foam stabilizer and € optionally one or more chemical or physical blowing agents, and the recycled polyol contains 2,4- toluenediamine, 2,6-toluenediamine, 2,2’-diaminodiphenylmethane, 2,4’-diaminodiphenylmethane and 4,4’-diaminodiphenylmethane.
  • a foam is prepared from a recycled polyol having a diaminotoluene content of 0.00389 wt.-%.
  • Document DE 4215014 A1 document discloses a method for reducing the amount of amine byproducts in the production of polyols by alcoholysis of polyurethanes and/or polyureas using a reagent that reacts with the by-products.
  • the amine by-product includes toluenediamine and the reagent is an epoxy.
  • Document EP 1229071 A1 discloses a method for removing amines from amine-containing polyols resulting from the decomposition of polyurethanes.
  • the process involves a step in which a polyol containing toluene diamine is reacted with maleic anhydride at 120°C, where the maleic anhydride is present in an amine/anhydride ratio of 1 .
  • reaction with a number of suitable compounds as defined specifically in Claim 1 enables reduction in the TDA content of polyols containing 2,6-diaminotoluene and/or 2,4-diaminotoluene as desired, preferably even to a TDA content ⁇ 0.03% by weight, where TDA content means the sum total of 2,6-diaminotoluene and 2,4- diaminotoluene present.
  • TDA content means the sum total of 2,6-diaminotoluene and 2,4- diaminotoluene present.
  • the invention provides a process for reducing the content of 2,6-diaminotoluene and/or 2,4-diaminotoluene, preferably of 2,6- diaminotoluene and 2,4-diaminotoluene, in polyols containing 2,6-diaminotoluene and/or 2,4- diaminotoluene, preferably 2,6-diaminotoluene and 2,4-diaminotoluene, wherein these polyols containing 2,6-diaminotoluene and/or 2,4-diaminotoluene, preferably 2,6-diaminotoluene and 2,4- diaminotoluene, are reacted with at least one compound selected from the group consisting of a), b) and c), where a), b) and c) are defined as follows: a) one or more
  • the process according to the invention makes it possible to reduce the content of 2,6-diaminotoluene and/or 2,4-diaminotoluene in polyols containing 2,6-diaminotoluene and/or 2,4-diaminotoluene, preferably to a TDA content ⁇ 0.03% by weight, where TDA content means the sum total of 2,6- diaminotoluene and 2,4-diaminotoluene present.
  • TDA content means the sum total of 2,6- diaminotoluene and 2,4-diaminotoluene present.
  • the polyol containing 2,6-diaminotoluene and/or 2,4-diaminotoluene, prior to employment of the process according to the invention that has higher TDA contents, for example in the region of not less than, preferably greater than, 0.1 % by weight up to, for example, 5% by weight or up to, for example, 7% by weight or up to, for example, 3% by weight.
  • the employment of the process according to the invention then leads to a reduction in the previously higher TDA content, especially to values of ⁇ 0.03% by weight.
  • a possible lower limit for the TDA content after employment of the process according to the invention may preferably, for example, be 0.0001 % by weight, where TDA content in each case means the sum total of 2,6-diaminotoluene and 2,4-diaminotoluene.
  • TDA content in each case means the sum total of 2,6-diaminotoluene and 2,4-diaminotoluene.
  • the process according to the invention has excellent applicability to the purification of what are called recycled polyols since these generally have higher TDA contents.
  • the process according to the invention enables simple reduction in relatively high TDA contents of recycled polyols, where TDA content means the sum total of 2,6-diaminotoluene and 2,4-diaminotoluene present.
  • the polyols containing 2,6-diaminotoluene and/or 2,4- diaminotoluene are polyether polyols.
  • the polyols containing 2,6-diaminotoluene and/or 2,4-diaminotoluene are those polyols, preferably polyether polyols, that have been obtained from the depolymerization of polyurethanes, preferably PU foam, especially depolymerization by hydrolysis.
  • the reaction according to the invention is conducted until the polyols have a TDA content ⁇ 0.03% by weight, where TDA content means the sum total of 2,6-diaminotoluene and 2,4-diaminotoluene present.
  • TDA content means the sum total of 2,6-diaminotoluene and 2,4-diaminotoluene present.
  • the percentages by weight are based here on the total amount of the polyol in question plus 2,6-diaminotoluene and 2,4- diaminotoluene present therein.
  • the TDA content in the polyol containing 2,6-diaminotoluene and/or 2,4- diaminotoluene can be reduced as desired by reaction with one or more epoxy-functional compounds as defined in Claim 1 under a).
  • the reaction is preferably effected at temperatures of 80°C to 150°C, preferably of 120°C to 140°C.
  • the use amounts are preferably calculated such that the molar ratio of the epoxy-functional compounds as defined under a) to the sum total of 2,6-diaminotoluene and 2,4-diaminotoluene present is 5:1 to 2:1 , preferably 4:1 .
  • solvents for example propylene glycol and/or ethylene glycol and the like, for dilution; preference is given to using no solvents.
  • Optional catalysts used may preferably be Lewis acids, such as, in particular, zinc chloride, tin dichloride and/or iron trichloride, most preferably zinc chloride. They may preferably be used in total amounts of 1 mol% to 20 mol%, preferably 8 mol% to 15 mol%, based on total TDA, where total TDA means the sum total of 2,6-diaminotoluene and 2,4-diaminotoluene present.
  • Lewis acids such as, in particular, zinc chloride, tin dichloride and/or iron trichloride, most preferably zinc chloride. They may preferably be used in total amounts of 1 mol% to 20 mol%, preferably 8 mol% to 15 mol%, based on total TDA, where total TDA means the sum total of 2,6-diaminotoluene and 2,4-diaminotoluene present.
  • the reaction with the epoxy-functional compound(s) is ended preferably after two to eight hours, more preferably after three to seven hours, especially preferably after three to six hours.
  • optionally remove optional catalyst particles from the polyol it is possible to use any known processes for filtration or sedimentation.
  • the optional removal can preferably be conducted at temperatures of 10°C to 100°C, preferably at 20°C to 80°C.
  • the optionally applied pressure differentials may preferably be 0.001 bar to 200 bar, more preferably 0.1 bar to 100 bar, especially preferably 0.1 bar to 25 bar, where the pressure differential used is dependent on the apparatus used.
  • the content of 2,6-diaminotoluene and/or 2,4-diaminotoluene can if desired be reduced to such an extent that it is possible to obtain polyols, preferably polyether polyols having a TDA content of ⁇ 0.03% by weight, where TDA content means the sum total of 2,6- diaminotoluene and 2,4-diaminotoluene present. It is possible without difficulty to reuse the resulting polyols as polyol component for production of a polyurethane, preferably PU foam, in particular flexible PU foam.
  • a polyol containing 2,6-diaminotoluene and/or 2,4-diaminotoluene, preferably polyether polyol is reacted with one or more acid anhydrides as defined in Claim 1 under b), especially phthalic anhydride, by means of which it is possible to obtain a polyol, preferably polyether polyol, having a reduced total TDA content such as preferably of ⁇ 0.03% by weight, where TDA content means the sum total of 2,6-diaminotoluene and 2,4-diaminotoluene present.
  • Acid anhydrides used may preferably be acetic anhydride, propionic anhydride, butyric anhydride, pentanoic anhydride, hexanoic anhydride, heptanoic anhydride, octanoic anhydride, adipic anhydride, fumaric anhydride, dodecenylsuccinic anhydride, trimellitic anhydride, pivalic anhydride, citraconic anhydride, itaconic anhydride, benzoic anhydride, glutaric anhydride, phthalic anhydride, isophthalic anhydride and/or terephthalic anhydride, cyclohexylalkanoic anhydrides, malonic anhydride, succinic anhydride, polymaleic anhydride, anhydrides based on adducts of maleic acid with styrene, dodecenylsuccinic anhydride and/or anhydrides of maleic acid and any alkene
  • the reaction is preferably effected at temperatures of 80°C to 150°C, preferably of 100°C to 140°C.
  • the use amounts are preferably calculated such that the molar ratio of total TDA to total acid anhydride is from 1 :1 to 1 :4, preferably 1 :1 .2 to 1 :2.5, where total TDA means the sum total of 2,6- diaminotoluene and 2,4-diaminotoluene present.
  • solvents capable of dissolving the acid anhydride in solid form are optionally possible to use; more preferably, no solvent is used.
  • reaction with one or more acid anhydride(s) according to the invention is ended preferably after two to eight hours, more preferably after two to seven hours, especially preferably after two to five hours.
  • any precipitated reaction products or solid reactants from the polyol it is possible if desired to use any of the known methods of filtration or sedimentation.
  • the optional separation can preferably be conducted at temperatures of 10°C to 100°C, further preferably at 20°C to 80°C.
  • the optionally applied pressure differentials may preferably be 0.001 bar to 200 bar, more preferably 0.1 bar to 100 bar, especially preferably 0.1 bar to 25 bar, where the pressure differential used is dependent on the apparatus used.
  • the TDA content can if desired be reduced to such an extent that it is possible to obtain polyols, preferably polyether polyols having a TDA content of preferably ⁇ 0.03% by weight, where TDA content means the sum total of 2,6-diaminotoluene and 2,4-diaminotoluene present. It is possible without difficulty to reuse the resulting polyols as polyol component for production of a PU foam, in particular flexible PU foam.
  • the TDA content of the polyols can likewise be reduced as desired by the reaction with aldehydes as defined in Claim 1 under c), where TDA content means the sum total of 2,6-diaminotoluene and 2,4-diaminotoluene present.
  • the reaction is preferably effected at temperatures of 40°C to 130°C, preferably of 50°C to 120°C, especially preferably at 50°C to 100°C.
  • the use amounts are preferably calculated such that the molar ratio of aldehyde to total TDA is 5:1 to 1 :1 , preferably 4:1 to 2:1 , where total TDA means the sum total of 2,6-diaminotoluene and 2,4- diaminotoluene present.
  • reaction is ended preferably after one to eight hours, more preferably after two to seven hours, especially preferably after two to five hours.
  • Aldehydes used may be one or more aldehydes, preferably selected from the group consisting of pentanal, n-hexanal, octylaldehyde, nonanal, decanal, citral, salicylaldehyde, benzaldehyde, cinnamaldehyde and anisaldehyde, particular preference being given to benzaldehyde.
  • the TDA content can if desired be reduced to such an extent that it is possible to obtain polyols, preferably polyether polyols having a TDA content of preferably ⁇ 0.03% by weight, where TDA content means the sum total of 2,6-diaminotoluene and 2,4-diaminotoluene present. It is possible without difficulty to reuse the resulting polyols as polyol component for production of a PU foam, in particular flexible PU foam.
  • the invention further provides polyols, preferably polyether polyols, obtained by the process according to the invention, especially as specified in any of Claims 1 to 8, having a TDA content of preferably ⁇ 0.03% by weight, where TDA content means the sum total of 2,6-diaminotoluene and 2,4-diaminotoluene present.
  • TDA content means the sum total of 2,6-diaminotoluene and 2,4-diaminotoluene present.
  • the percentages by weight are based here on the total amount of the polyol in question plus 2,6-diaminotoluene and 2,4-diaminotoluene present therein.
  • a preferred lower limit in the TDA content may, for example, be 0.0001 % by weight.
  • the invention further provides a process for preparing polyurethanes, preferably PU foam, by reacting polyisocyanates with polyols, using polyols obtained in accordance with the invention, especially those according to Claim 9.
  • polyols obtained in accordance with the invention in amounts of at least 25% by weight, preferably at least 50% by weight, further preferably at least 75% by weight, in particular even 100% by weight, based on the total amount of polyol used.
  • polyurethanes can typically be prepared by the reaction, known to the person skilled in the art, of polyisocyanates, preferably diisocyanates, for example 4,4'- methylenebis(phenyl isocyanate), or tolylene 2,4-diisocyanate, with polyols, such as preferably polyether polyols and/or polyester polyols.
  • polyether polyols can be prepared, for example, by alkoxylation of polyhydroxy-functional starters. Commonly used starters are, for example, glycols, glycerol, trimethylolpropane, pentaerythritol, sorbitol or sucrose.
  • Polyether polyols can also be obtained, as already mentioned, by depolymerization of polyurethanes.
  • Optional blowing agents may be used in the production of polyurethane foams, examples being pentane, methylene chloride, acetone or carbon dioxide.
  • a chemical blowing agent used if desired may optionally be water. All this is known to those skilled in the art.
  • stabilization can optionally also be accomplished using surface-active substances, especially silicone surfactants.
  • catalysts examples include particular amines or organic tin compounds.
  • polyurethane foams because of their excellent mechanical and physical properties, find use in a wide variety of different areas.
  • PU foam polyurethane foams
  • a wide variety of different types of PU foam is known, for example by means including flexible PU foams, rigid PU foams, integral PU foams, and other PU foams having properties between the classifications.
  • the invention further provides polyurethane, preferably PU foam, obtainable by the aforementioned process.
  • the invention further provides for the use of at least one compound selected from the group consisting of a), b) and c), each as defined in Claim 1 , for reducing the TDA content in polyols containing 2,6-diaminotoluene and/or 2,4-diaminotoluene, preferably polyether polyols containing 2,6-diaminotoluene and/or 2,4-diaminotoluene, especially those that have been obtained from the depolymerization of polyurethanes, especially PU foams, where the TDA content means the sum total of 2,6-diaminotoluene and 2,4-diaminotoluene present.
  • the TDA content means the sum total of 2,6-diaminotoluene and 2,4-diaminotoluene present.
  • the invention further provides a process for preparing one or more polyols, preferably polyether polyols, by depolymerization of polyurethanes, preferably by hydrolysis, wherein the depolymerization is followed by one or more steps of workup of the reaction mixture from the depolymerization in order to separate the one or more polyol(s) from the reaction mixture, preferably comprising at least one distillation step and/or extraction step, wherein the polyol(s) separated off are reacted with at least one compound selected from the group consisting of a), b) and c), each as defined in Claim 1 , wherein the reaction is preferably conducted until the polyols have a TDA content ⁇ 0.03% by weight, where TDA content means the sum total of 2,6-diaminotoluene and 2,4- diaminotoluene present.
  • TDA content means the sum total of 2,6-diaminotoluene and 2,4- diaminotoluene present
  • the percentages by weight are based here on the total amount of the polyol in question plus 2,6-diaminotoluene and 2,4-diaminotoluene present therein.
  • a preferred lower limit in the TDA content may, for example, be 0.0001 % by weight.
  • 2,6-Diaminotoluene > 97%), zinc chloride (> 98%, anhydrous), phthalic anhydride (> 99%) and benzaldehyde (> 99%) were sourced from Sigma-Aldrich.
  • Dodecyl/tetradecyl glycidyl ether ipox® RD 24
  • Arcol® Polyol 1104 was sourced from the company Covestro.
  • 2,4- and 2,6-diaminotoluene were determined by reverse-phase HPLC/DAD.
  • a suitable amount of the sample was weighed out and made up to the mark in a standard flask with a solution of 50 mM aqueous (NH4)CIO4 (pH 9.25) and acetonitrile (8:2 vol/vol).
  • 2,4- and 2,6-diaminotoluene are weighed out as reference and admixed with a water/acetonitrile mixture (1 :1 vol/vol), such that the concentration of diaminotoluene is 0.013 mg/ml.
  • This stock solution is used for production of the calibration solutions.
  • the appropriate amount of the stock solution is transferred into a standard flask and made up to the mark with a solution of 50 mM aqueous (NH4)CIO4 (pH 9.25) and acetonitrile (8:2 vol/vol).
  • the concentration of the calibration solutions is in the range from 0.004 pg/ml to 13.0 pg/ml.
  • DAD diode array detector
  • Example A1 Preparation of a polyol containing 2,6-diaminotoluene
  • Example A2 Preparation of a polyol containing 2,6-diaminotoluene
  • Example B1 Preparation of a low-2, 6-diaminotoluene polyol by reaction with dodecyl/tetradecyl glycidyl ether (inventive)
  • Example B2 Preparation of a low-2, 6-diaminotoluene polyol by reaction with phthalic anhydride (inventive)
  • Example B3 Preparation of a low-2, 6-diaminotoluene polyol by reaction with benzaldehyde (inventive)
  • 1.0 part (1.0 pphp) of a component here means 1 g of this substance per 100 g of polyol.
  • Polyol Standard Arcol® 1104 polyether polyol obtainable from Covestro. This is a glycerol-based polyether polyol having an OH number of 56 mg KOH/g and an average molar mass of 3000 g/mol, or polyols obtained from Example A2, B1 or B3.
  • KOSMOS® T9 available from Evonik Industries, the tin(l I) salt of 2-ethylhexanoic acid.
  • Dabco® DMEA dimethylethanolamine, available from Evonik Industries. Amine catalyst for production of polyurethane foams.
  • KOSMOS® EF emission-free metal catalyst available from Evonik Industries.
  • TEGOAMIN® ZE1 amine catalyst (with low emission values) available from Evonik Industries.
  • the polyurethane foams were produced in the laboratory as handmade foams. The foams were produced at 22°C and an air pressure of 762 mmHg.
  • the polyurethane foams according to formulations 1 and 2 were respectively produced using 150 g and 300 g of polyol. The other formulation constituents were adjusted accordingly. For example, 1 .0 part (1 .0 pphp) of a component meant 1 g of said substance per 100 g of polyol.
  • a paper cup was initially charged with the tin catalyst (tin(ll) 2-ethylhexanoate or tin(ll) ricinoleate), polyol, water, the amine catalysts and the respective foam stabilizer, and the contents were mixed with a disc stirrer at 1000 rpm for 60 s.
  • the isocyanate was added and incorporated with the same stirrer at 2500 rpm for 7 s and the reaction was then immediately transferred to a paper-lined box (for foams made from 300 g of polyol: base area 30 cm x 30 cm and height 30 cm, for foams made from 150 g of polyol: base area 18 cm x 18 cm and height 18 cm).
  • the foam had been poured in, it rose up in the foaming box. In the ideal case, the foam blew off on reaching the maximum rise height and then settled slightly. This opened the cell membranes of the foam bubbles, and an open-pore cell structure of the foam was obtained.
  • the settling, or the further rise, is calculated as the difference in the foam height immediately after blow-off and after 3 minutes after the foam blow-off.
  • the foam height is measured at the maximum in the centre of the foam crest by means of a needle secured to a centimetre scale.
  • a positive value here describes the settling of the foam after blow-off; a negative value correspondingly describes the further rise of the foam.
  • the air permeability of the foam was determined based on DIN EN ISO 4638:1993-07 by a dynamic pressure measurement on the foam.
  • the measured dynamic pressure was reported in mm water column, lower dynamic pressure values being characteristic of a more open foam. The values were measured within a range from 0 to 300 mm water column.
  • the dynamic pressure was measured by means of an apparatus comprising a nitrogen source, reducing valve with pressure gauge, flow-regulating screw, wash bottle, flowmeter, T-piece, applicator nozzle and a graduated glass tube filled with water.
  • the applicator nozzle has an edge length of 100 x 100 mm, a weight of 800 g, an internal diameter at the outlet opening of 5 mm, an internal diameter at the lower applicator ring of 20 mm and an external diameter at the lower applicator ring of 30 mm.
  • the measurement is carried out by setting the nitrogen inlet pressure to 1 bar by adjusting the reducing valve and setting the flow rate to 480 l/h.
  • the amount of water in the graduated glass tube is set so that no pressure difference builds up and none can be read off.
  • the applicator nozzle is applied to the corners of the test specimen, flush with the edges, and also once to the (estimated) centre of the test specimen (in each case on the side having the greatest surface area). The result is read off when a constant dynamic pressure has been established.
  • the evaluation is based on the calculated average of the five measurements obtained. e) Cell count
  • Table 2 Foaming results for the flexible PU foams produced according to formulation 1 , Table 1 , with 150 g of polyol using the inventive polyol from Example B1 and the non-inventive polyol from Example A2, and the conventional polyol Arcol® 1 104
  • Table 2 compares the properties of the foams that were produced using the inventive polyol from Example B1 and the non-inventive polyol from example A2 with Arcol® 1104.
  • the inventive polyol from Example B1 contained 0.0004% by weight of 2,6-diaminotoluene, and the non-inventive polyol from Example A2 0.2% by weight of 2,6-diaminotoluene.
  • the PU foam that was produced exclusively with Arcol® 1104 was the reference. Comparison of the properties of foams #1 , #2 and #3 shows that comparable foams were obtained with the inventive polyol from Example B1 (#2) and reference foam #1 made from Arcol® 1 104.
  • Table 3 compares the properties of the foams that were produced using the inventive polyol from Example B3 and the non-inventive polyol from example A2 with Arcol® 1104.
  • the inventive polyol from Example B3 contained 0.028% by weight of 2,6-diaminotoluene, and the non-inventive polyol from Example A2 0.2% by weight of 2,6-diaminotoluene.
  • the PU foam that was produced exclusively with Arcol® 1104 was the reference.
  • Comparison of the properties of foams #1 , #2 and #3 shows that comparable foams with similar properties were obtained with the inventive polyol from Example B3 (#2) and reference foam #1 made from Arcol® 1104.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne un procédé de réduction de la teneur en 2,6-diaminotoluène et/ou 2,4-diaminotoluène dans des polyols contenant du 2,6-diaminotoluène et/ou du 2,4-diaminotoluène, qui sont notamment des polyols recyclés, le polyol contenant du 2,6-diaminotoluène et/ou du 2,4-diaminotoluène étant mis à réagir avec au moins un composé choisi dans le groupe constitué par a), b) et c) : a) un ou plusieurs composés à fonction époxy, de préférence dodécyl/tétradécyl glycidyl éther, b) un ou plusieurs anhydrides d'acide, en particulier l'anhydride phtalique, et c) un ou plusieurs aldéhydes, de préférence du benzaldéhyde.
EP23820945.6A 2022-12-21 2023-12-11 Polyols recyclés Pending EP4638545A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP22215298 2022-12-21
PCT/EP2023/085036 WO2024132619A1 (fr) 2022-12-21 2023-12-11 Polyols recyclés

Publications (1)

Publication Number Publication Date
EP4638545A1 true EP4638545A1 (fr) 2025-10-29

Family

ID=84547302

Family Applications (1)

Application Number Title Priority Date Filing Date
EP23820945.6A Pending EP4638545A1 (fr) 2022-12-21 2023-12-11 Polyols recyclés

Country Status (4)

Country Link
EP (1) EP4638545A1 (fr)
CN (1) CN120390760A (fr)
MX (1) MX2025006845A (fr)
WO (1) WO2024132619A1 (fr)

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3441616A (en) 1966-11-07 1969-04-29 Wyandotte Chemicals Corp Process for recovery of polyether polyols from polyurethane reaction products
US4035314A (en) 1975-06-02 1977-07-12 The Firestone Tire & Rubber Company Recovery of polyurethane prepolymer and amine salt
US4316992A (en) 1981-02-23 1982-02-23 Ford Motor Company Process for polyol recovery from polyurethane foam comprising alcohol and steam hydrolysis
DE4215014C2 (de) 1991-05-10 1996-09-12 Braun Pebra Gmbh Verfahren zur Aufbereitung von Alkoholyse-Polyol
DE4140967A1 (de) 1991-12-12 1993-06-17 Bayer Ag Verfahren zur herstellung von hydroxylgruppen aufweisenden verbindungen und ihre verwendung
DE19540949A1 (de) 1995-11-03 1997-05-07 Bayer Ag Unter Einsatz von Recycling-Polyolen hergestellte Polyurethan-Verbundkörper (Sandwichelemente), ein Verfahren zu deren Herstellung sowie deren Verwendung
AU704932B2 (en) 1996-10-08 1999-05-06 Jong Han Jeon A method for preparation of recycled polyols and a method for manufacturing polyurethane foams with improved thermal insulation property
US5763692A (en) * 1996-10-28 1998-06-09 Basf Corporation Process for the preparation of recyclate polyols having a low amine content
DE19737184A1 (de) 1997-08-26 1999-03-04 Basf Ag Verfahren zur Verringerung des Amingehalts von Recyclatpolyolen
EP1229071A4 (fr) 1999-09-16 2004-05-26 Mitsui Takeda Chemicals Inc Procede de traitement du polyol recupere par decomposition et polyol ainsi recupere
AU2021332957A1 (en) 2020-08-24 2023-05-04 Evonik Operations Gmbh Depolymerization of polyurethanes under mild conditions
CA3188070A1 (fr) 2020-08-24 2022-03-03 Jens Hildebrand Nouveau procede de depolymerisation pour polyurethanes
MX2024000124A (es) 2021-07-02 2024-01-22 Evonik Operations Gmbh Produccion de espumas de pu que utilizan polioles reciclados.

Also Published As

Publication number Publication date
WO2024132619A1 (fr) 2024-06-27
CN120390760A (zh) 2025-07-29
MX2025006845A (es) 2025-07-01

Similar Documents

Publication Publication Date Title
US10189965B2 (en) Production of viscoelastic polyurethane systems using block polymers having bonded siloxane blocks as cell openers
KR100223377B1 (ko) 가요성 폴리우레탄 포옴의 제조방법
CN105814113B (zh) 后处理碱性聚醚多元醇的方法
US8912277B2 (en) Siloxane compositions
JP2003503516A (ja) ポリエーテルポリオールから製造された軟質ポリウレタンフォーム
CN1090987C (zh) 硅氧烷聚醚表面活性剂
MX2012009742A (es) Preparacion de poliuretanos.
KR101246496B1 (ko) 히드록시알킬화 폴리알킬렌폴리아민 조성물, 그의 제조방법 및 이것을 사용한 폴리우레탄 수지의 제조 방법
EP0213697A2 (fr) Polyétherpolyols, leur préparation et utilisation dans la préparation de polyuréthanes
MXPA04006158A (es) Productos de poliuretano producidos a partir de polieteroles catalizados con fosfonato de aluminio.
CN101039983A (zh) 新泡沫调节剂，由其制备的泡沫材料和制备泡沫材料的方法
WO2014037558A1 (fr) Procédé pour la préparation d'une composition de polyol
EP4638545A1 (fr) Polyols recyclés
JP5349806B2 (ja) ウレタン樹脂組成物
JP3113228B2 (ja) 難燃性ポリウレタンフォーム組成物
KR20190112103A (ko) 폴리올 중의 산화 규소 입자 분산물
CA2483983C (fr) Melange reactif ameliore a base d'isocyanate et procede de preparation connexe
US3264231A (en) Hydroxy (polyalkylenoxy) alkyl hydrazine based polyurethanes
JP2013067715A (ja) ポリオール組成物及びこれを用いたポリウレタンフォームの製造方法
CN1069326C (zh) 制备柔性聚氨酯泡沫体的方法
EP4559948A1 (fr) Composition de polyol et son procédé de préparation, composition pour préparation de polyuréthane comprenant une composition de polyol, et module de batterie
US4033990A (en) Hydroxybicyclosiloxane rigid urethane foam stabilizers
JP2013227490A (ja) 軟質ポリウレタンフォームの製造方法
EP3880734A1 (fr) Procédés aqueux pour la production de polyols de polyéther à partir de composés polyhydroxyliques solides
WO2025093350A1 (fr) Catalyseur thermolatent pour la préparation de polyuréthane

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: 20250707

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 ME 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)