EP4225838A1 - Procédé de production d'une composition de polyols contenant des polyols libérés par des déchets de polyuréthane - Google Patents

Procédé de production d'une composition de polyols contenant des polyols libérés par des déchets de polyuréthane

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Publication number
EP4225838A1
EP4225838A1 EP21789728.9A EP21789728A EP4225838A1 EP 4225838 A1 EP4225838 A1 EP 4225838A1 EP 21789728 A EP21789728 A EP 21789728A EP 4225838 A1 EP4225838 A1 EP 4225838A1
Authority
EP
European Patent Office
Prior art keywords
compounds
group
mol
added
weight
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
EP21789728.9A
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German (de)
English (en)
Inventor
Valentin Stoychev
Tsvetomir Tsonev
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.)
H&s Anlagentechnik GmbH
Original Assignee
H&s Anlagentechnik 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 H&s Anlagentechnik GmbH filed Critical H&s Anlagentechnik GmbH
Publication of EP4225838A1 publication Critical patent/EP4225838A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • C08J11/26—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 carboxylic acid groups, their anhydrides or esters
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • 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 relates to a process for producing a polyol composition containing polyols released from polyurethane waste and a polyol composition produced using this process and the use thereof.
  • DE 195 12 778 C1 proposes a process for producing isocyanate-reactive polyol dispersions, in which polyurethane waste is treated with cyclic dicarboxylic anhydrides and/or cyclic dicarboxylic anhydride-forming dicarboxylic acids and/or derivatives thereof in the presence of polyether oils with a molecular weight of about 500 to 5000 g / mol and a hydroxyl functionality of 2 to 5 at a temperature of about 140 to 250° C. are subjected to a degradation reaction, the polyether oils being subjected to a radical grafting reaction with carbon-unsaturated, carbonyl-containing monomers before, during or after the degradation reaction.
  • the grafting reaction is typically carried out in the presence of free-radical generators, with peroxides, for example, being used as free-radical generators.
  • WO 2018/091568 A1 describes a process for the production of polyol dispersions from polyurethane waste from the post-consumer sector in the presence of polyether oils, wherein in a first reaction step a) the polyurethane waste is first a reaction mixture containing at least one dicarboxylic acid or a dicarboxylic acid derivative and at least one polyetherol having an average molar mass of 400 to 6000 g/mol and a hydroxyl functionality of 2 to 4 at temperatures of 170°C to 210°C to form a dispersion; and in a second reaction step b) the dispersion obtained under a) is reacted with at least one short-chain diol and/or a short-chain triol at temperatures of 180° C.
  • a free-radical agent suitable for initiating a free-radical polymerization is preferably added.
  • Peroxide compounds for example an inorganic peroxide, preferably hydrogen peroxide, and/or an organic peroxide, preferably tert-butyl hydroperoxide, tert-amyl hydroperoxide, 1,1,3,3-tetramethylbutyl- hydroperoxide and/or cumene hydroperoxide.
  • radical formers such as peroxides
  • peroxides are hazardous substances that can cause explosions. Therefore, systems for the processes described in DE 195 12 778 C1 and WO 2018/091568 A1 must be designed to be explosion-proof.
  • the processes described in DE 195 12 778 C1 and WO 2018/091568 A1 are carried out in the presence of at least one polyetherol (polyether-polyol).
  • One or more antioxidants are usually added to commercially available polyether polyols.
  • Antioxidants are also typically contained in the polyurethane waste itself. Antioxidants react with radical formers such as peroxides to form products that cause the polyol dispersion produced to turn dark (brown, in some cases even deep dark brown). This stands in the way of using the polyol dispersion to produce polyurethane materials for high-quality applications.
  • antioxidants with radical formers such as peroxides
  • radical formers such as peroxides
  • certain polyether polyols eg, some polyether polyols that were prepared with the KOH process, and some polyether polyols with predominantly primary OH groups
  • Radical generators tend to form lumps (ie very large agglomerates), deposits on parts of the plant and severe quality losses in the released polyols due to undesirable side reactions.
  • a further disadvantage of the above-mentioned processes from the prior art is that they are not suitable for the recovery of polyester polyols from polyurethane waste, or the quality of the polyester polyols released is very poor.
  • the object of the present invention is to provide a process for the production of a polyol composition containing polyols released from polyurethane waste which overcomes the stated disadvantages of the prior art.
  • this object is achieved by a process for producing a polyol composition containing polyols released from polyurethane waste, in a reaction mixture
  • Demineralized, distilled or deionized water is preferably used. Water is preferably added in an amount of 0.2% to 10% by weight, preferably 1% to 6% by weight, in some cases particularly preferably 2% to 5% by weight, based on the total mass of the Educts (a), (b), (c), (d) and optionally (e) (see below) as 100% by weight. This does not include any water already contained in the polyurethane waste. Preferably, the scrap polyurethane should not be soaked.
  • reaction mixture contains more water than is required for the reaction, the excess amount of water can be distilled off.
  • the water content of the reaction mixture is 1.5% by weight to 10% by weight, based on the total mass of the starting materials (a), (b) , (c), (d) and optionally (e), whereby water already contained in the polyurethane waste (e.g. water absorbed by the waste from the humidity of the environment or air humidity) is included.
  • water already contained in the polyurethane waste e.g. water absorbed by the waste from the humidity of the environment or air humidity
  • the total amount of water (d) to be used can be metered in portions, e.g. a first portion of water (d) together with the above-defined compounds (b) from the group consisting of polyether polyols and polyester polyols and compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, and further water (d) is added in parallel with metering in the polyurethane waste (a) in one or more portions or continuously.
  • portions e.g. a first portion of water (d) together with the above-defined compounds (b) from the group consisting of polyether polyols and polyester polyols and compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, and further water (d) is added in parallel with metering in the polyurethane waste (a) in one or more portions or continuously.
  • peroxides are used in an amount of less than 0.1% by weight, based on the total mass of the starting materials (a), (b), (c), (d) and optionally (e) (see below) than 100% by weight, preferably 0.05% by weight or less, particularly preferably 0.01% by weight, of peroxides or less, based in each case on the total mass of the starting materials (a), (b), (c) , (d) and optionally (e) (see below) as 100% by weight.
  • Particular preference is given to not using any peroxides, more preferably not using any radical formers at all.
  • the polyol composition produced with the process according to the invention contains no reaction products formed by reactions of or with peroxides.
  • no free-radical generators are added to the process according to the invention, and the polyol composition formed contains no reaction products formed by reactions of or with free-radical generators.
  • Polyurethane waste that can be processed using the method according to the invention includes both production waste (“post production waste”) and usage waste (“post consumer waste”), e.g. in the form of discarded furniture, upholstery, pillows, mattresses, car seats and shoe soles.
  • the polyurethane waste can contain fillers and/or additives, for example.
  • the polyurethane scraps can be solid or foamed, for example.
  • the type and composition of the polyurethane waste there are no restrictions in the process according to the invention. It is not necessary to provide sorted polyurethane waste, and thus a complex pre-sorting of the polyurethane waste can advantageously be omitted.
  • the method according to the invention is also suitable for polyurethane waste in which polyurethane is associated with thermoplastics such as polyolefins, ABS or PVC and is difficult to separate from them.
  • thermoplastics such as polyolefins, ABS or PVC and is difficult to separate from them.
  • Such thermoplastics are present in the polyol composition produced according to the invention in dispersed form and can be removed from the polyol composition by means of solid/liquid separation, e.g. by filtration.
  • the polyurethane waste is preferably used in comminuted form.
  • the degree of shredding can be freely selected and only influences the speed at which the polyurethane waste is converted.
  • the process according to the invention is suitable, for example, for the processing of polyurethane foam waste, in particular for the processing of flexible polyurethane foams, cellular and microcellular polyurethane materials, polyurethane elastomers, PUR integral rigid foam, semi-rigid polyurethanes, thermoplastic polyurethanes (TPU), rigid polyurethane foams and PUR/PIR rigid foams.
  • the polyurethane waste can be processed in sorted or unsorted form using the process according to the invention.
  • the polyurethane waste can come from the production as well as from the post-consumer area.
  • the process according to the invention is suitable, for example, for the processing of polyurethane foam waste (both rigid and semi-rigid as well as flexible foam), particularly for processing semi-rigid and flexible foam).
  • flexible polyurethane (PU) foams have an open cell structure or a partially open cell structure. They are manufactured using a wide variety of technologies and processes, such as continuous block or discontinuous box manufacturing processes, as well as free foaming or foaming in the mold and are known to those skilled in the following terms: PU block foam, cold foam, standard flexible polyurethane foam , HR PU foam (High Resilience Polyurethane Foam), viscoelastic polyurethane foam (Memory PU foam), PU molded foam, POP flexible foams, SAN (styrene-acrylonitrile)-filled flexible foams, etc.
  • the mentioned flexible polyurethane foams are used in different degrees of density (typically from 10 kg/m 3 , e.g. packing foam, to over 200 kg/m 3 , e.g. for technical applications) and are mainly used in the manufacture of mattresses, in the furniture industry, automotive applications, as well as e.g technical PU flexible foams and PU packaging.
  • Flexible polyurethane foams can have an open cell structure, a hardness of 300 N to 500 N at 40% load measured according to SS-EN ISO 2439:2008(E) and an elasticity of 25 to 60% (measured according to EN ISO 8307).
  • Cellular and micro-cellular polyurethane elastomers have an open-cell or closed-cell structure. Integral rigid foams as a variation of cellular and microcellular polyurethane elastomers have a porous core and an almost solid edge zone and are produced by reaction injection molding in a mold, or by the reaction injection molding (RIM) process. Cellular and microcellular polyurethane elastomers can be manufactured as flexible, semi-flexible, and rigid products. Typical applications include seat and molded cushions, head, arm and footrests for cars, bicycle saddles, steering wheel covers and shoe soles (including midsole and inner sole).
  • the process according to the invention is suitable, for example, for processing elastic, thermoplastic, foamed or solid polyurethane waste which has an elongation at break [Eb] of 20% to 600% (measured according to DIN EN ISO 1798:2008).
  • the process according to the invention is suitable, for example, for the processing of waste polyurethane materials containing at least 40 parts of polyether or polyester base polyol with a hydroxyl number of 28 mgKOH/g to 100 mgKOH/g (measured according to DIN 53240).
  • Semi-rigid means that these foams are significantly harder than flexible foams but lack the hardness or dimensional stability of rigid foams. However, the transition is fluid and all desired intermediate levels can be set. In case of doubt, semi-rigid foams are open-celled and do not form any appreciable skin during foaming (i.e. no solid edge zone). Semi-rigid polyurethane foams, for example, can have an open cell structure with a compressive strength of at least 100 kPa (measured according to EN ISO 844:2009).
  • a typical application for semi-rigid PUR foams which are characterized by good energy absorption capacity, are side impact protection elements in doors and energy absorbers in bumpers. They are also used in the pipeline and offshore industry, the automotive industry and in noise reduction in house construction.
  • the process according to the invention is suitable, for example, for the processing of waste from such polyurethane materials in whose production formulation at least 40 parts of polyether or polyester base polyol with a hydroxyl number of 60 mgKOH/g to 450 mgKOH/g (measured according to DIN 532404) are used.
  • PUR/PIR rigid foams are heavily cross-linked and, in case of doubt, have a closed cell structure with higher compressive strength.
  • the closed-cell density is usually >90%.
  • Insulating materials made of rigid polyurethane foam can be used in many different ways because of their optimal insulating properties - both as insulating material (e.g. for refrigerators and cooling systems, building insulation, etc.) and as construction material in combination with various top layers.
  • rigid polyurethane foams have a closed cell structure with a compressive strength of at least 25 kPa (e.g. 1 k can foam), in some cases at least 100 kPa (measured according to EN ISO 844:2009).
  • the process according to the invention is suitable, for example, for the processing of waste from such polyurethane materials, in the production formulation of which at least 40 parts of polyether or polyester base polyol with a hydroxyl number of 150 mgKOH/g to 600 mgKOH/g (measured according to DIN 53240) can be used.
  • the polyurethane waste (a) is preferably used in a total amount of 30% by weight to 60% by weight, preferably 35% by weight to 45% by weight, based on the total mass of the starting materials (a), (b) defined above. , (c) and (d) as 100% by weight.
  • the compounds (b) from the group consisting of polyether polyols and polyester polyols as defined above are primary polyols (i.e. polyols not obtained by cleavage of polyurethane) as are typically used for the production of polyurethanes.
  • primary polyols i.e. polyols not obtained by cleavage of polyurethane
  • compounds (b) from the group consisting of polyether polyols as defined above or compounds (b) from the group consisting of polyester polyols as defined above are usually used, but preferably not polyether polyols and polyester polyols in one and the same reaction mixture.
  • Compounds (b) from the group of polyether polyols preferably have an average molar mass in the range from 200 g/mol to 6000 g/mol, preferably 400 g/mol to 5000 g/mol.
  • Compounds (b) from the group of polyester polyols preferably have an average molar mass in the range from 350 g/mol to 6000 g/mol, preferably 400 g/mol to 5000 g/mol.
  • antioxidants are typically added to them.
  • polyester polyols In particular when using polyester polyols, it is preferred that no peroxides are used in the process according to the invention, and preferably no radical formers at all.
  • Compounds (b) from the group consisting of polyether polyols and polyester polyols as defined above are preferably used in a total amount of 20% by weight to 60% by weight, preferably 20% by weight to 55% by weight, based on the total mass of the starting materials defined above (a), (b), (c) and (d) as 100% by weight.
  • the total amount of compounds (b) from the group consisting of polyether polyols and polyester polyols can be added in several steps, for example a first portion of the compounds (b) from the group consisting of polyether polyols and polyester polyols together with compounds (c) is preferably added the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids and water (d), and another A portion of the compounds (b) is added at a later stage of the process when the polyurethane waste (a) has already largely decomposed.
  • the same compounds (b) or different compounds (b) in each step can be added in each step added to the group consisting of polyether polyols and polyester polyols as defined above.
  • the polyols originally used to produce the polyurethanes are released, and poly-, oligo- and acyl ureas and possibly compounds from the group of amines, amides and imides and other isocyanate-reactive oligomers can also be formed.
  • Degradation products of the polyurethane, which do not correspond to the liquid polyols originally used to form the polyurethanes, are typically present as dispersed particles in a liquid phase containing polyols.
  • the compounds (c) are preferably selected from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids from the group consisting of adipic acid and the anhydrides of maleic acid, phthalic acid, hexahydrophthalic acid and succinic acid.
  • the reaction mixture also contains one or more monocarboxylic acids, for example acrylic acid, in addition to one or more compounds (c) from the group consisting of dicarboxylic anhydrides and dicarboxylic acids.
  • monocarboxylic acids for example acrylic acid
  • Compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids and optionally monocarboxylic acids are preferably used in a total amount of 5% by weight to 20% by weight, based on the total mass of the starting materials (a), (b), () defined above. c) and (d) as 100% by weight.
  • the addition of the total amount of compounds (c) to be used from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids can be carried out in several steps, for example a first portion of the compounds (c) together with the compounds (b) defined above from the group consisting of polyether polyols and polyester polyols and water (d) is preferably initially introduced, and a further portion of the compounds ( c) is added at a later stage of the process when the polyurethane waste (a) has already largely decomposed.
  • the addition of compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids at a late stage of the process is used in particular for deamination of the polyol composition to be produced.
  • the same or different compounds (c) from the group can be used in each step in each step be added from dicarboxylic acid anhydrides and dicarboxylic acids.
  • the components (b)-(d) defined above of the reaction mixture are usually initially taken and heated to a temperature of 130.degree. C. to 230.degree. C., preferably 140.degree. C. to 200.degree. Then the polyurethane waste (a) is metered in so that a reaction mixture is formed.
  • the temperature is kept in the range from 130.degree. C. to 230.degree. C., preferably from 140.degree. C. to 210.degree.
  • further water (d) can be added in one or more portions or continuously.
  • the reaction mixture is then preferably kept for several hours (1 to 5 hours, preferably 2 to 3.5 hours) at a temperature in the range from 190°C to 240°C, preferably 200°C to 240°C.
  • a further portion of one or more compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids can then be added. This is used in particular for deamination of the polyol composition, for which purpose the reaction mixture, after addition of the further portion of compounds (c), is heated for 0.5 to 3 hours, preferably 0.5 to 1.5 hours, at a temperature in the range from 170° C. to 240 °C, preferably 180 °C to 230 °C.
  • reaction mixture can then be cooled.
  • a further portion of compounds (b) from the group consisting of polyether polyols and polyester polyols as defined above can be added here. Preference is given to process configurations comprising a mixture
  • polyurethane waste in a total amount of 30% to 60% by weight and/or (b) compounds from the group consisting of polyether polyols and polyester polyols in a total amount of 20% by weight to 60% by weight, and/or
  • water is used in an amount of 0.2% by weight to 10% by weight, preferably 1% by weight to 6% by weight, in some cases particularly preferably 2% by weight to 5% by weight, in each case based on the total mass of the starting materials (a), (b), (c) and (d) defined above as 100% by weight.
  • water is used in an amount of 0.2% by weight to 10% by weight, preferably 1% by weight to 6% by weight, in some cases particularly preferably 2% by weight to 5% by weight, in each case based on the total mass of the starting materials (a), (b), (c) and (d) defined above as 100% by weight.
  • All quantities for the starting materials (a), (b), (c) and (d) relate to the total amounts used in a reaction mixture of the starting materials (a)-(d) defined above, regardless of whether the total amount of respective reactants was added completely in one step, or distributed over several steps (i.e. in the form of several portions) at different points in time in the course of the process.
  • the compounds (e) from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms cause the polyurethanes contained in the waste to be split by glycolysis.
  • Preferred compounds (e) from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms are diols and triols from the group consisting of ethylene glycol, diethylene glycol, dipropylene glycol, 1,3-propane glycol, 1,2-butanediol, 1 ,4-butane glycol and glycerin.
  • the total amount of compounds (e) to be used from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms can be added in several steps, e.g. a first portion of the compounds (e) is preferably added if the polyurethane waste (a) are metered in and dissolved at least to a third, preferably a half, or completely, and a further portion of one or more compounds (e) is added at a later stage of the process.
  • the total amount of compounds (e) to be used is added from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms in several steps, ie in the form of several portions, the same can be used in each step, or in each Step other compounds (e) from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms are added.
  • the components (b)-(d) defined above of the reaction mixture are usually initially taken and heated to a temperature of from 130.degree. C. to 230.degree. C., preferably from 140.degree. C. to 200.degree. Then the polyurethane waste
  • one or more compounds (e) from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms are added.
  • one or more compounds (e) from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms are added when the polyurethane wastes (a) are completely dissolved.
  • the reaction mixture is preferably kept for several hours (1 to 5 hours, preferably 2 to 3.5 hours) at a temperature in the range of 150°C to 240°C, preferably 200°C to 230°C.
  • a further portion of one or more compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids can then be added.
  • the reaction mixture can be cooled, or at a temperature in the range from 150° C. to 240° C., preferably for 0.25 to 1.5 hours, preferably 0.5 to 1 hour 200°C to 230°C and then cooled.
  • a further portion of compounds (b) from the group consisting of polyether polyols and polyester polyols as defined above may be added.
  • polyurethane waste (a) is metered into this mixture, so that a reaction mixture is formed, the Temperature in the range of 130 ° C to 230 ° C, preferably 140 ° C to 210 ° C, is maintained, parallel to metering in the polyurethane waste (a) in one or more portions or continuously further water (d) is added, a or several compounds (e) from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms are added when at least one third, preferably half, of the polyurethane waste (a) has been metered in and dissolved; or one or more compounds (e) from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms is added when the polyurethane wastes (a) are completely dissolved, the reaction mixture for 1 to 5 hours, preferably 2 to 3.5 hours, at a temperature in the range from 150°C to 240°C, preferably
  • the reaction mixture for 1 to 5 hours, preferably 2 to 3.5 hours, at a temperature in the range of 150° C. to 240° C., preferably 200° C. to 230° C., and then a further portion of one or more compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids are added.
  • the reaction mixture has been kept at a temperature in the range from 170° C. to 240° C., preferably 180° C.
  • the addition takes place one or more compounds (e) from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms.
  • the reaction mixture is kept at a temperature in the range from 170° C. to 240° C., preferably 180° C. to 230° C., for 0.25 to 1.5 hours, preferably 0.5 to 1 hour.
  • the reaction mixture can be cooled. As the reaction mixture cools, a further portion of compounds (b) from the group consisting of polyether polyols and polyester polyols as defined above may be added.
  • the total amount of the compounds (e) from the group consisting of the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms can be added portionwise in several steps during the course of the reaction.
  • a first portion of one or more compounds (e) from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms is added when at least one third, preferably half, of the polyurethane waste (a) has been metered in and dissolved or when the polyurethane wastes (a) are completely dissolved.
  • reaction mixture is preferably kept for several hours (1 to 5 hours, preferably 2 to 3.5 hours) at a temperature in the range of 150°C to 240°C, preferably 200°C to 230°C.
  • a further portion of one or more compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids can then be added.
  • the reaction mixture can be heated for 0.25 to 1.5 hours, preferably 0.5 to 1 hour, at a temperature in the range from 170° C. to 240° C., preferably 180° C to 230°C.
  • One or more compounds (e) from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms are then added.
  • This addition of a further portion of compounds (e) serves in particular to bind excess acid groups in order to obtain a polyol composition with a low acid number.
  • the reaction mixture can be stirred for 0.25 to 1.5 hours, preferably 0.5 to 1 hour, at a temperature in the range from 170° C. to 240° C., preferably 180° C. to 230°C are maintained. Then the reaction mixture can be cooled. As the reaction mixture cools, a further portion of compounds (b) from the group consisting of polyether polyols and polyester polyols as defined above may be added.
  • All amounts given for the starting materials (a), (b), (c), (d) and (e) relate to the total amounts of starting materials (a)-(e) defined above used in a reaction mixture, regardless of whether the total amount of the respective starting materials was added completely in one step or distributed over several steps (i.e. in the form of several portions) at different times in the process.
  • reaction device for the process according to the invention, it must be taken into account that the process takes place at high temperatures in the presence of corrosive substances (acid anhydrides and/or acids). Therefore, it is preferred that the reaction is carried out in a vessel made of stainless steel.
  • the entire reaction device and periphery is particularly preferably made of corrosion-resistant and acid-resistant stainless steel.
  • the device contains a fractionation or distillation device, e.g. in the form of a column, and suitable metering devices
  • a polyol composition according to the invention comprises a liquid phase which contains the polyols released from the polyurethane waste and one or more compounds (b) from the group consisting of polyether polyols and polyester polyols as defined above (as used as starting material).
  • a polyol composition according to the invention also contains reaction products formed during the acidolytic and - in the case of process configurations with the addition of a compound (e) as defined above - glycolytic cleavage of the polyurethane waste, which are dispersed in the liquid phase in the form of particles, e.g. oligourethanes (after partial degradation shorter urethane chains remaining from the original polyurethanes), oligo- and polyureas and acylureas. Amines, amides and imides may be present as further degradation products of the polyurethane waste.
  • a compound (e) as defined above - glycolytic cleavage of the polyurethane waste which are dispersed in the liquid phase in the form of particles, e.g. oligourethanes (after partial degradation shorter urethane chains remaining from the original polyurethanes), oligo- and polyureas and acylureas.
  • Amines, amides and imides may be present as further degradation products
  • polyurethane waste which contains polyurethane associated with thermoplastics such as polyolefins, ABS or PVC
  • the polyol composition produced by the process according to the invention contains these thermoplastics in dispersed form Filtration are removed from the polyol composition.
  • a polyol composition according to the invention can contain unreacted residual polyurethane in the form of dispersed particles.
  • the unfiltered polyol composition according to the invention contains predominantly or almost exclusively particles with a size in the range from 8 nanometers to 300 micrometers (average particle size in the range from 150 to 200 micrometers), and at most a small proportion of agglomerates with a size in the range from> 300 micrometers to 5 millimeters (2% by weight or less based on the weight of the unfiltered polyol composition).
  • the particle size distribution is determined using a combination of dynamic light scattering (detects particle sizes from 1 nm to 1 pm), microscopy (detects particle sizes from 1 pm to 250 pm) and grindometry (detects particle sizes from 250 pm) in order to determine the entire range of possible particle sizes to capture.
  • the polyol composition that can be produced by the process according to the invention is isocyanate-reactive, ie the polyol contained in the dispersion and released from the polyurethane waste can be reacted with polyisocyanate to form a new polyurethane material.
  • a polyol composition according to the invention is characterized in that it has a lighter color and/or a smaller average particle size and/or a narrower particle size distribution than a polyol composition not according to the invention which was produced from an identical starting material (polyurethane waste) under identical process conditions with the The only exception is that no water, but a free radical generator, e.g. a peroxide, in particular hydrogen peroxide, was added.
  • a free radical generator e.g. a peroxide, in particular hydrogen peroxide
  • produced under identical process conditions means in particular that for the production of the polyol composition according to the invention and the polyol composition not according to the invention, identical starting material in the form of polyurethane waste (a) and the same compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids and optionally monocarboxylic acids, and the same compounds (b) from the group consisting of polyether polyols and polyester polyols as defined above are each used in identical amounts and the reaction takes place at identical temperature control, and optionally the same compounds (e) from the group consisting from diols and triols as defined above are each used in identical amounts, and the reaction takes place at the same temperature and for the same duration.
  • the lighter color of the polyol composition according to the invention results in particular from the fact that fewer or even no radical formers such as peroxides are used in the process according to the invention, which cause undesirable reactions with the polyurethane waste or in the used Compounds from the group consisting of polyether polyols contained antioxidants can enter.
  • Lighter color means in this context that a color difference of at least 1 dE (AE), preferably at least 2 dE (AE), particularly preferably at least 5 dE (AE) (according to Lambert-Beer's law) is measurable between the Polyol composition according to the invention and a polyol composition not according to the invention, which was produced from an identical starting material (polyurethane waste) under identical process conditions with the only exception that no water but a free radical generator, eg a peroxide, in particular hydrogen peroxide, was added.
  • a free radical generator eg a peroxide, in particular hydrogen peroxide
  • An unfiltered polyol composition according to the invention contains predominantly or almost exclusively particles with a size in the range from 8 nanometers to 300 micrometers (average particle size from 150 to 200 micrometers), and at most a small proportion of agglomerates with a size in the range from> 300 micrometers to 5 millimeters (2% by weight or less based on the weight of the unfiltered polyol composition).
  • the particle size distribution is determined using a combination of dynamic light scattering (detects particle sizes from 1 nm to 1 pm), microscopy (detects particle sizes from 1 pm to 250 pm) and grindometry (detects particle sizes from 250 pm) in order to determine the entire range of possible particle sizes to capture.
  • a polyol composition not according to the invention which was produced from identical starting material (polyurethane waste) under identical process conditions with the only exception that no water but a free-radical generator, e.g. a peroxide, in particular hydrogen peroxide, was added, always at least 10%, often at least 20%, or even at least 50% higher proportion of agglomerates with a size in the range of 250 micrometers to 3 millimeters.
  • a free-radical generator e.g. a peroxide, in particular hydrogen peroxide
  • a narrower particle size distribution results for a polyol composition according to the invention compared to a polyol composition not according to the invention, which was produced from identical starting material (polyurethane waste) under identical process conditions with the only exception that no water, but a radical former, for example a peroxide, in particular hydrogen peroxide, was added.
  • a polyol composition according to the invention appears regularly more homogeneous and of finer dispersity than a polyol composition not according to the invention, which was produced from identical starting material (polyurethane waste) under identical process conditions with the only exception that no water, but a free radical generator, e.g. a peroxide, in particular hydrogen peroxide, was added.
  • the polyols released from polyurethane waste and contained in a polyol composition according to the invention can have an average molar mass (Mn) in the range from 200 to 10,000 g/mol.
  • a polyol composition according to the invention generally has a hydroxyl number of 30 to 650 mg KOH/g (determined according to DIN 53240) and/or an amine number of 1 to 40 mg KOH/g (determined according to DIN 53176) and/or an acid number of 0, 1 to 10 mg KOH/g (determined according to DIN 53402) and/or a viscosity of 1000 to 50000 mPa*s (determined according to DIN 53019).
  • a polyol composition according to the invention preferably has a hydroxyl number of 30 to 400 mg KOH/g (determined according to DIN 53240) and an amine number of 1 to 20 mg KOH/g (determined according to DIN 53176) and an acid number of 0.1 to 5 mg KOH/g. g (determined according to DIN 53402) and a viscosity of 2000 to 12000 mPa*s, particularly preferably 3000 to 8000 mPa*s (determined according to DIN 53019).
  • Polyol compositions according to the invention thus have a hydroxyl number which is in the range of the polyols which are customarily used for the production of polyurethanes.
  • polyol with a hydroxyl number in the range from 150 to 600 mg KOH/g is preferably used for the production of rigid foams
  • polyol with a hydroxyl number in the range from 28 to 100 mg KOH/g is preferred for the production of flexible foams of prepolymers
  • adhesives and/or elastomers are preferred
  • the hydroxyl numbers are determined according to DIN 53240.
  • the concentration of primary aromatic amines in the polyol composition according to the invention is preferably less than 0.1%, based on the total mass of the polyol composition.
  • the present invention also relates to the use of a polyol composition obtainable by a process according to the invention for the production of polyurethanes.
  • Corresponding processes for the production of polyurethanes are known to those skilled in the art.
  • a mixture of polyol recovered from polyurethane waste by the process according to the invention and primary polyol i.e. polyol not obtained by splitting polyurethane
  • primary polyol i.e. polyol not obtained by splitting polyurethane
  • polyurethane waste 40% by weight polyurethane waste (post-consumer mattresses, unsorted, shredded to approx. 2 cm x 2 cm x 2 cm in size) was added, maintaining the temperature in the range of 150°C to 210°C, until the polyurethane scraps (a) were dissolved. During the addition of the polyurethane waste (a).
  • the polyol composition obtained was then pumped off, filtered using a self-cleaning filter (150 ⁇ m) and cooled to room temperature.
  • the polyol composition After filtering, the polyol composition has the following properties
  • Viscosity 5,600 m Pa*s at 25°C determined according to DIN 53019
  • Amine number 18 mg KOH/g determined according to DIN 53176.
  • This polyol composition is suitable for producing rigid polyurethane foam. Thanks to the low acid number, a negative influence on the catalysis in the subsequent production of rigid polyurethane foam is avoided.
  • diethylene glycol 9 wt% diethylene glycol added while maintaining the temperature in the range 200°C to 220°C.
  • the diethylene glycol can be added when at least half, preferably at least two thirds, of the polyurethane waste (a) has been metered into the reactor. The mixture was stirred at a temperature in the range from 210° C. to 225° C. for 1.5 hours. Then, with stirring
  • the polyol composition obtained was then pumped off, filtered using a self-cleaning filter (150 ⁇ m) and cooled to room temperature.
  • a polyol composition with an acid number below 1.5 mg KOH/g and a content of primary aromatic amines below 0.05% by weight was obtained. After filtering, the polyol composition has the following properties:
  • Viscosity 4,800 m Pa*s at 25°C determined according to DIN 53019
  • Amine number 14 mg KOH/g determined according to DIN 53176.
  • This polyol composition is suitable for the production of rigid polyurethane foams (PUR and/or PUR/PIR).
  • PUR/PIR foam panels polyol recovered from polyurethane waste and primary polyol (i.e. polyol not obtained by splitting polyurethane) were used in a weight ratio of 10/90 to 50/50 according to the inventive method according to example 1 or 2 .
  • PUR/PIR panels were obtained whose properties were not adversely altered compared to corresponding original PUR products (without the addition of polyol recovered from polyurethane waste). In particular, the compressive strength, dimensional stability and thermal conductivity of the products were comparable or equivalent.
  • the polyol composition obtained was filtered at 100° C. using a 250 ⁇ m filter and cooled to room temperature.
  • the polyol composition After filtering, the polyol composition has the following properties
  • Hydroxyl number 53 mg KOH/g determined according to DIN 53240.
  • Viscosity 8,700 m Pa*s at 25°C determined according to DIN 53019
  • Amine number 9 mg KOH/g determined according to DIN 53176.
  • This polyol composition is suitable for the production of flexible polyurethane foams.
  • polyurethane waste polyurethane waste (polyester-based shoe soles, unsorted) added, maintaining the temperature in the range of 150°C to 210°C. Parallel to the addition of the polyurethane waste (a), further
  • the polycomposition obtained was filtered at 100° C. using a 200 ⁇ m filter and cooled to room temperature.
  • the polyol composition After filtering, the polyol composition has the following properties:
  • Viscosity 4,700 m Pa*s at 25°C determined according to DIN 53019
  • Amine number 5 mg KOH/g determined according to DIN 53176.
  • This polyol composition is suitable for the manufacture of polyester-based polyurethane shoe soles.
  • the polyol composition obtained was filtered at 100° C. using a 150 ⁇ m filter and cooled to room temperature.
  • the polyol composition After filtering, the polyol composition has the following properties:
  • Viscosity 7,500 m Pa*s at 25°C determined according to DIN 53019
  • Amine number 16 mg KOH/g determined according to DIN 53176.
  • This polyol composition is suitable for the production of rigid polyurethane foams (PUR and/or PUR/PIR).
  • PUR rigid polyurethane foams
  • the polyol composition obtained was filtered at 100° C. using a 250 ⁇ m filter and cooled to room temperature.
  • the polyol composition After filtering, the polyol composition has the following properties Hydroxyl number: 53 mg KOH/g determined according to DIN 53240
  • Viscosity 8,700 m Pa*s at 25°C determined according to DIN 53019
  • Amine number 9 mg KOH/g determined according to DIN 53176.
  • This polyol composition is suitable for the production of flexible polyurethane foams.
  • the polyol composition After filtering, the polyol composition has the following properties
  • Viscosity 8,900 m Pa*s at 25°C determined according to DIN 53019
  • Amine number 10 mg KOH/g determined according to DIN 53176.
  • This polyol composition is suitable for the production of flexible polyurethane foams.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un procédé de production d'une composition de polyols contenant des polyols libérés par des déchets de polyuréthane, ainsi qu'une composition de polyols produite au moyen dudit procédé et son utilisation.
EP21789728.9A 2020-10-08 2021-10-08 Procédé de production d'une composition de polyols contenant des polyols libérés par des déchets de polyuréthane Pending EP4225838A1 (fr)

Applications Claiming Priority (2)

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DE102020126425.9A DE102020126425A1 (de) 2020-10-08 2020-10-08 Verfahren zur Herstellung einer Polyolkomposition enthaltend aus Polyurethan-Abfällen freigesetzte Polyole
PCT/EP2021/077837 WO2022074184A1 (fr) 2020-10-08 2021-10-08 Procédé de production d'une composition de polyols contenant des polyols libérés par des déchets de polyuréthane

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DE (1) DE102020126425A1 (fr)
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DE102020126425A1 (de) 2020-10-08 2022-04-14 H & S Anlagentechnik Gmbh Verfahren zur Herstellung einer Polyolkomposition enthaltend aus Polyurethan-Abfällen freigesetzte Polyole
DE102022113374A1 (de) * 2022-05-26 2023-11-30 Neveon Germany Gmbh Umsetzung von Polyurethan in einem sich verjüngenden Reaktor
WO2024081090A1 (fr) * 2022-10-11 2024-04-18 Stepan Company Procédé de chimiolyse de mousses de polyisocyanurate

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DE19512778C1 (de) 1995-04-05 1996-12-05 Gunter Prof Dr Bauer Verfahren zur Herstellung von isocyanatreaktiven Polyoldispersionen und deren Verwendung
CN102585286B (zh) 2012-03-08 2014-06-04 广州聚天化工科技有限公司 一种利用废旧聚氨酯再生多元醇的方法
DE102013106364B4 (de) 2013-06-18 2015-04-09 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Herstellung eines Polyurethan-Blockschaumstoffes
DE102016122275B4 (de) 2016-11-18 2020-04-02 H & S Anlagentechnik Gmbh Verfahren zur Herstellung von Polyoldispersionen aus Polyurethanabfällen und deren Verwendung
DE102016122276A1 (de) 2016-11-18 2018-05-24 H & S Anlagentechnik Gmbh Recyclingpolyol
CN107286369A (zh) 2017-08-02 2017-10-24 江苏世丰新材料有限公司 一种酸解聚氨酯软泡废弃物生成多元醇的方法
AU2021331097A1 (en) 2020-08-24 2023-05-04 Evonik Operations Gmbh New depolymerization method for polyurethanes
BR112023003200A2 (pt) 2020-08-24 2023-03-28 Evonik Operations Gmbh Método para hidrolisar um poliuretano e uso de poliéter que contém hidrogênio ativo
DE102020126425A1 (de) 2020-10-08 2022-04-14 H & S Anlagentechnik Gmbh Verfahren zur Herstellung einer Polyolkomposition enthaltend aus Polyurethan-Abfällen freigesetzte Polyole

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WO2022074184A1 (fr) 2022-04-14
US20230399486A1 (en) 2023-12-14
JP2023544656A (ja) 2023-10-24
MX2023003970A (es) 2023-08-03
DE102020126425A1 (de) 2022-04-14

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