Method for producing a polyol composition containing polyols liberated from polyurethane waste

Abstract

A method for producing a polyol composition containing polyol liberated from polyurethane waste is described, as well as the polyol composition produced by this method and its uses.

Description

Technical Field

[0001] The present invention relates to a method for producing a polyol composition containing a polyol released from polyurethane waste materials, as well as to a polyol composition produced by this method and its use.

[0002] German Patent Invention No. 19512778 proposes a method for producing an isocyanate-reactive polyol dispersion. In this method, polyurethane waste materials are subjected to a decomposition reaction with a cyclic dicarboxylic anhydride and / or a cyclic dicarboxylic acid-forming dicarboxylic acid and / or its derivatives at a temperature of about 140 to 250 °C in the presence of a polyether polyol having a molar mass of about 500 to 5000 g / mol and a hydroxyl value of 2 to 5. At this time, the polyether polyol is subjected to a radical grafting reaction with a carbon unsaturated monomer containing a carbonyl group before, during or after the decomposition reaction. The grafting reaction is typically carried out in the presence of a radical forming agent, and a peroxide, for example, is used as the radical forming agent.

[0003] International Publication No. 2018 / 091568 describes a method for producing a polyol dispersion from polyurethane waste generated in the post-consumer sector in the presence of a polyetherol, in which, in a first reaction step a), the polyurethane waste is first reacted at a temperature of 170°C to 210°C with a reaction mixture containing at least one dicarboxylic acid or dicarboxylic acid derivative and at least one polyetherol having an average molar mass of 400 to 6000 g / mol and a hydroxyl value of 2 to 4 to form a dispersion; in a second reaction step b), the dispersion obtained in a) is further reacted at a temperature of 180°C to 230°C with at least one short-chain diol and / or short-chain triol to form a polyol dispersion. Preferably, a radical-forming agent suitable for initiating radical polymerization is added to initiate or accelerate the chemical reaction between the polyurethane group and the aforementioned dicarboxylic acid or dicarboxylic acid derivative (e.g., dicarboxylic acid anhydride), i.e., to activate the reaction mixture. Suitable radical-forming agents are preferably peroxide compounds, for example, inorganic peroxides, preferably hydrogen peroxide and / or organic peroxides, preferably tert-butyl hydroperoxide, tert-amyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide and / or cumene hydroperoxide.

[0004] However, the use of radical-forming agents (radical initiators), such as peroxides, comes with several drawbacks. For example, radical-forming agents such as peroxides are dangerous substances that can induce explosions. Therefore, the plant for the method described in German Patent Invention No. 19512778 or International Publication No. 2018 / 091568 must be explosion-proof.

[0005] The method described in German Patent No. 19512778 or International Publication No. 2018 / 091568 is carried out in the presence of at least one polyetherol (polyether polyol). Commercially available polyether polyols typically contain one or more antioxidants. Polyurethane waste materials themselves also typically contain antioxidants. These antioxidants react with radical-forming agents, such as peroxides, to form products that cause the resulting polyol dispersion to have a dark color (brown, and in some cases even a deep dark brown). For this reason, this polyol dispersion cannot be used to produce polyurethane materials for high-value applications.

[0006] The reaction between antioxidants and radical-forming agents, such as peroxides, can proceed very violently under certain conditions, such as those involving strong foam formation. This complicates process control and requires careful monitoring of the process. Furthermore, certain polyether polyols (e.g., some polyether polyols produced by the KOH method, and some polyether polyols primarily containing primary OH groups) tend to exhibit undesirable side reactions in the presence of radical-forming agents, resulting in the formation of lumps (i.e., very large agglomerates), deposits on plant components, and severe quality loss of free polyols.

[0007] A further drawback of the above-mentioned prior art methods is that they are not suitable for recovering polyester polyols from polyurethane waste, or the quality of the free polyester polyols is very low.

[0008] The present invention is based on the objective of providing a method for producing a polyol composition containing polyols liberated from polyurethane waste, which overcomes the aforementioned drawbacks of the prior art.

[0009] According to the present invention, this problem is solved by a method for producing a polyol composition containing a polyol liberated from polyurethane waste, wherein in the reaction mixture, (a) Polyurethane waste and (b) Below: - Polyether polyols having an average molar mass of 200 g / mol to 8000 g / mol and a hydroxyl value of 2 to 4, - Polyester polyols with an average molar mass of 250 g / mol to 8000 g / mol and a hydroxyl value of 2 to 4. One or more compounds from the group consisting of, (c) One or more compounds from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, (d) Water and This problem is solved by reacting the materials to form a polyol composition containing polyols liberated from polyurethane waste.

[0010] Surprisingly, it was found that the release of polyols from polyurethane waste could be initiated by adding water, even without adding radical-forming agents such as peroxide compounds.

[0011] Preferably, desalted water, distilled water, or deionized water is used.

[0012] Water is preferably added in an amount of 0.2% to 10% by weight, preferably 1% to 6% by weight, and more preferably 2% to 5% by weight, based on 100% by weight of the total weight of the starting materials (a), (b), (c), (d) and optionally (e) (see below). Here, water already present in the polyurethane waste material is not included in the calculation. Advantageously, it is desirable that the polyurethane waste material is not wet.

[0013] If the reaction mixture contains more water than is necessary for the reaction, the excess water can be removed by distillation.

[0014] In certain cases, particularly when dealing with waste materials mainly containing flexible polyurethane foam, the water content of the reaction mixture is preferably 1.5% to 10% by weight relative to the total weight of the starting materials (a), (b), (c), (d) and optionally (e), where water already present in the polyurethane waste (e.g., water absorbed by the waste from ambient moisture or atmospheric moisture) is included in the calculation. Therefore, advantageously, pre-drying of the polyurethane waste is unnecessary.

[0015] The total amount of water (d) to be used can be measured and supplied in small increments. For example, preferably, the first portion of water (d) is charged together with the compounds (b) from the group consisting of polyether polyols and polyester polyols as defined above, and the compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids. Further water (d) is added in parallel with the addition of polyurethane waste material (a), either in one or more portions or continuously.

[0016] In the method according to the present invention, it is preferable that the peroxide is used in an amount of less than 0.1% by weight, based on 100% by weight of the total weight of the starting materials (a), (b), (c), (d), and optionally (e) (see below), and more preferably in an amount of 0.05% by weight or less, particularly preferably 0.01% by weight or less, based on 100% by weight of the total weight of the starting materials (a), (b), (c), (d), and optionally (e) (see below). Particularly preferably, no peroxide is used, and more preferably, no radical-forming agent is used at all. Therefore, advantageously, no peroxide is added in the method according to the present invention, and the polyol composition produced by the method according to the present invention does not contain any reaction products formed by the reaction of a peroxide or a reaction with a peroxide. Even more preferably, no radical-forming agent is added in the method according to the present invention, and the resulting polyol composition does not contain any reaction products formed by the reaction of a radical-forming agent or a reaction with a radical-forming agent.

[0017] The polyurethane waste that can be post-processed by the method according to the present invention includes both post-production waste and post-consumer waste, for example, in the form of discarded furniture, pads, cushions, mattresses, car seats, and shoe soles. The polyurethane waste may include, for example, fillers and / or additives. The polyurethane waste may be, for example, solid or foamed. There are no limitations in the method according to the present invention regarding the type and composition of the polyurethane waste. It is not necessary to provide a single type of polyurethane waste, and therefore, advantageously, time-consuming preliminary sorting of polyurethane waste can be avoided.

[0018] For process engineering reasons, it is often preferable to separate polyurethane waste from contaminating components such as textiles, steel, and wood, as well as further contaminants.

[0019] The method according to the present invention is also suitable for polyurethane waste in which polyurethane is integrated with thermoplastics such as polyolefins, ABS, or PVC, and is difficult to separate from them. Such thermoplastic resins are dispersed in the polyol composition produced by the present invention and can be removed from the polyol composition by solid-liquid separation, for example by filtration.

[0020] Preferably, the polyurethane waste material is used in a crushed form. The degree of crushing can be freely selected and is only affected by the reaction rate of the polyurethane waste material.

[0021] The method according to the present invention is suitable, for example, for the post-treatment of polyurethane foam waste, particularly for the post-treatment of flexible polyurethane foam materials, cellular and microcellular polyurethane materials, polyurethane elastomers, rigid PUR integrated foam, semi-rigid polyurethane, thermoplastic polyurethane (TPU), rigid polyurethane foam materials, and rigid PUR / PIR foam materials. Polyurethane waste can be post-treated by the method according to the present invention in either a separated or unseparated form. Polyurethane waste may originate from production and post-consumer sectors.

[0022] The method according to the present invention is suitable, for example, for post-treatment of polyurethane foam waste (rigid foam, semi-rigid foam, and flexible foam), and particularly for post-treatment of semi-rigid and flexible foam.

[0023] Flexible polyurethane (PU) foam materials, where unknown, have an open-cell structure or a partially open-cell structure. These are manufactured by free-foaming using a wide variety of techniques and methods, such as continuous block manufacturing or batch box manufacturing, or by foaming using molds, and are known to those skilled in the art by the following terms: PU block foam, cold foam, standard flexible polyurethane foam, HR-PU foam (high-rebound polyurethane foam), viscoelastic polyurethane foam (memory PU foam), PU molded foam, flexible POP foam, flexible SAN (styrene-acrylonitrile) filled foam, etc. The aforementioned flexible polyurethane foam materials are available in different density grades (typically 10 kg / m³). 3 For example, packing foam, up to 200 kg / m 3 It is manufactured (for example, for industrial use) and is mainly used in the manufacture of mattresses, the furniture industry, automotive applications, and also as industrial flexible PU foam and PU packaging material, for example.

[0024] The flexible polyurethane foam can have a closed-cell structure, a hardness of 300 N to 500 N at 40% load measured in accordance with SS-EN ISO 2439:2008(E), and an elastic modulus of 25% to 60% (measured in accordance with EN ISO 8307).

[0025] Cellular and microcellular polyurethane elastomers have a closed-cell or open-cell structure. The integral rigid foam as a variation of cellular and microcellular polyurethane elastomers has a porous core and a substantially solid edge zone, and is produced by the reaction injection molding method or the reaction injection molding (RIM) method in a mold. Cellular and microcellular polyurethane elastomers can be produced as flexible, semi-flexible, and rigid products. Typical applications include, for example, automotive seat pads and mold pads, headrests, armrests and footrests, bicycle saddles, handle covers, and shoe soles (including midsoles and insoles).

[0026] The method according to the invention is suitable, for example, for the post-treatment of elastic, thermoplastic, foamed or solid polyurethane waste materials with an elongation at break [Eb] of 20% to 600% (measured in accordance with DIN EN ISO 1798:2008).

[0027] The method according to the invention is suitable, for example, for the post-treatment of waste polyurethane materials in which at least 40 parts of a polyether or polyester-based polyol with a hydroxyl value of 28 mg KOH / g to 100 mg KOH / g (measured in accordance with DIN 53240) are used in the formulation during production.

[0028] Semi-rigid means that the foam material is much harder than soft foam, but does not have the hardness and dimensional stability of rigid foam. However, the transition is smooth and all desirable intermediate stages can be set. The semi-rigid foam material is, in the absence of information, of the open-cell type and does not form a skin (i.e., a significant amount of edge zone) worthy of mention during foaming. Semi-rigid polyurethane foam can, for example, have an open-cell structure with a compressive strength of at least 100 kPa (measured in accordance with EN ISO 844:2009).

[0029] Typical applications of semi-rigid PUR foam materials, which are characterized by good energy absorption capacity, are side impact protection elements for doors and energy absorbers for bumpers, and they are also used for sound wave attenuation in the pipeline industry, the marine industry, the automotive industry, and residential construction.

[0030] The method according to the present invention is suitable, for example, for the post-treatment of waste polyurethane materials in which at least 40 parts of a polyether or polyester-based polyol having a hydroxyl value of 60 mg KOH / g to 450 mg KOH / g (measured in accordance with DIN 532404) are used in the formulation during production.

[0031] Rigid PUR / PIR foam materials are cross-linked for strength and, in the absence of information, have a closed-cell structure with high compressive strength. The closed-cell ratio is usually >90%. Insulation materials made of rigid polyurethane foam can be used for multiple purposes due to their optimal insulation capacity, and can be used not only as insulation materials (e.g., for cooling equipment, refrigeration systems, building insulation, etc.) but also in combination with various cover layers as building materials.

[0032] Polyurethane rigid foam, in the absence of information, has a closed-cell structure with a compressive strength of at least 25 kPa (e.g., foam in a 1 k can) and, in some cases, at least 100 kPa (measured in accordance with EN ISO 844:2009).

[0033] The method according to the present invention is suitable, for example, for the post-treatment of waste polyurethane materials in which at least 40 parts of a polyether or polyester-based polyol having a hydroxyl value of 150 mg KOH / g to 600 mg KOH / g (measured in accordance with DIN 53240) was used in the formulation during manufacturing.

[0034] The polyurethane waste material (a) is preferably used in an amount of 30% to 60% by weight, preferably 35% to 45% by weight, with the total weight of the starting materials (a), (b), (c), and (d) defined above being 100% by weight.

[0035] Typically, compound (b) from the group consisting of polyether polyols and polyester polyols as defined above is a primary polyol (i.e., a polyol not obtained by cleavage of polyurethane), such as those typically used in the production of polyurethanes. In the method according to the present invention, either compound (b) from the group consisting of polyether polyols as defined above or compound (b) from the group consisting of polyester polyols as defined above is usually used, and advantageously, polyether polyols and polyester polyols are not used in the same reaction mixture.

[0036] Compound (b) from the group of polyether polyols preferably has an average molar mass in the range of 200 g / mol to 6000 g / mol, preferably 400 g / mol to 5000 g / mol. Compound (b) from the group of polyester polyols preferably has an average molar mass in the range of 350 g / mol to 6000 g / mol, preferably 400 g / mol to 5000 g / mol.

[0037] When a compound (b) from the group of polyether polyols is used, typically one or more antioxidants are miscible with it.

[0038] In particular, when polyester polyols are used, it is preferable that no peroxides are used in the method according to the present invention, and preferably no radical-forming agents are used at all.

[0039] Compound (b) from the group consisting of polyether polyols and polyester polyols as defined above is preferably used in a total amount of 20% to 60% by weight, preferably 20% to 55% by weight, with the total weight of the starting materials (a), (b), (c), and (d) defined above being 100% by weight. The addition of the total amount of compound (b) from the group consisting of polyether polyols and polyester polyols to be used can be carried out in multiple steps. For example, preferably, the first portion of compound (b) from the group consisting of polyether polyols and polyester polyols is charged together with compound (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, and water (d), and later in the method, when the polyurethane waste material (a) has already been sufficiently decomposed, a further portion of compound (b) is added. Surprisingly, it has been found that adding the total amount of compound (b) from the group consisting of polyether polyols and polyester polyols as defined above in small amounts in multiple steps during the reaction reduces the formation of agglomerates in the polyol composition.

[0040] If the total amount of compound(b) from the group consisting of polyether polyols and polyester polyols defined above is to be added in multiple steps, i.e., in multiple parts, it is possible to add the same compound(b) from the group consisting of polyether polyols and polyester polyols defined above in each step, or to add different compounds(b) from the group consisting of polyether polyols and polyester polyols defined above in each step.

[0041] Compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids cause acid decomposition and cleavage of polyurethane contained in waste materials. In this process, polyols originally used in the manufacture of polyurethane are released, and further compounds from the group consisting of polyureas, oligoureas and acylureas, and possibly amines, amides and imides, as well as further isocyanate-reactive oligomers may be produced. At this time, polyurethane decomposition products that do not correspond to the liquid polyol originally used to form the polyurethane typically exist as dispersed particles in the liquid phase containing the polyol.

[0042] Preferably, compound (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids is selected from the group consisting of adipic acid and maleic acid anhydride, phthalic acid anhydride, hexahydrophthalic acid anhydride and succinic acid anhydride.

[0043] In certain cases, the reaction mixture includes one or more compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, as well as one or more monocarboxylic acids, such as acrylic acid.

[0044] 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% to 20% by weight, with the total weight of the starting materials (a), (b), (c), and (d) defined above being 100% by weight. The addition of the total amount of compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids to be used can be carried out in multiple steps, for example, preferably the first portion of compound (c) is charged together with compounds (b) from the group consisting of polyether polyols and polyester polyols defined above, and water (d), and later in the method, when the polyurethane waste material (a) has already been sufficiently decomposed, further portions of compound (c) are added. The addition of compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids in the later stages of the method is particularly useful for the deamination reaction of the polyol composition to be produced. If the total amount of compound(c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids to be used is added in multiple steps, i.e., in multiple parts, it is possible to add the same compound(c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids in each step, or to add different compounds(c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids in each step.

[0045] Typically, in the method according to the present invention, components (b) to (d) of the reaction mixture defined above are charged and heated to a temperature of 130°C to 230°C, preferably 140°C to 200°C. Subsequently, polyurethane waste material (a) is added to form the reaction mixture. During the addition of the polyurethane waste material, the temperature is maintained in the range of 130°C to 230°C, preferably 140°C to 210°C. In parallel with the addition of polyurethane waste material (a), additional water (d) may be added in one or more parts or continuously.

[0046] The reaction mixture is then held at a temperature preferably in the range of 190°C to 240°C, more preferably 200°C to 240°C, for several hours (1 to 5 hours, preferably 2 to 3.5 hours).

[0047] Subsequently, further portions of one or more compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids can be added. This is particularly useful for the deamination reaction of the polyol composition, and for this purpose, after the addition of further portions of compound (c), the reaction mixture is held at a temperature in the range of 170°C to 240°C, preferably 180°C to 230°C, for 0.5 to 3 hours, preferably 0.5 to 1.5 hours.

[0048] Next, the reaction mixture can be cooled. At this time, further portions of compound (b) from the group consisting of polyether polyols and polyester polyols as defined above can be added.

[0049] The following configuration is preferred: - below: (b) Below: - Polyether polyols having an average molar mass of 200 g / mol to 8000 g / mol and a hydroxyl value of 2 to 4, - Polyester polyols with an average molar mass of 250 g / mol to 8000 g / mol and a hydroxyl value of 2 to 4. One or more compounds from the group consisting of, (c) One or more compounds from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, and optionally one or more monocarboxylic acids, (d) Water and A mixture containing is charged and heated to a temperature of 130°C to 230°C, preferably 140°C to 200°C. - Add polyurethane waste material (a) to this mixture to form a reaction mixture, while maintaining the temperature in the range of 130°C to 230°C, preferably 140°C to 210°C. - In parallel with the addition of polyurethane waste material (a), further water (d) is added in one or more parts or continuously. - The reaction mixture is held at a temperature in the range of 150°C to 240°C, preferably 200°C to 230°C, for 1 to 5 hours, preferably 2 to 3.5 hours. - Add a further portion of one or more compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, - After adding one or more portions of compound (c), the reaction mixture is held at a temperature in the range of 170°C to 240°C, preferably 180°C to 230°C, for 0.5 to 3 hours, preferably 0.5 to 1.5 hours. - Afterwards, the reaction mixture is cooled.

[0050] In one preferred modification of the method according to the present invention, the total weight of the starting materials (a), (b), (c), and (d) defined above is set to 100% by weight, (a) 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% to 60% by weight, and / or (c) Compounds from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, and optionally monocarboxylic acids, in a total amount of 5% to 20% by weight, and / or (d) Water in an amount of 0.2% to 10% by weight, preferably 1% to 6% by weight, and more preferably 2% to 5% by weight It will be used.

[0051] In one particularly preferred modification of the method according to the present invention, the total weight of the starting materials (a), (b), (c), and (d) defined above is set to 100% by weight, (a) Polyurethane waste material in a total amount of 30% to 60% by weight, and (b) Compounds from the group consisting of polyether polyols and polyester polyols, in a total amount of 20% to 60% by weight, and (c) Compounds from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, and optionally monocarboxylic acids, in a total amount of 5% to 20% by weight, (d) Water in an amount of 0.2% to 10% by weight, preferably 1% to 6% by weight, and more preferably 2% to 5% by weight It will be used.

[0052] Regardless of whether the total amount of each starting material is added in one step or distributed over multiple steps at different points in the process (i.e., in the form of multiple parts), the data for the amounts of starting materials (a), (b), (c), and (d) are all relative to the total amount of the above-defined starting materials (a) to (d) used in the reaction batch.

[0053] In a particular embodiment of the method according to the present invention, in addition to the components (a) to (d) defined above, the reaction mixture is: (e) One or more compounds from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms. It is added.

[0054] Compound (e) is particularly used when it is desirable to produce a polyol composition suitable for the manufacture of rigid polyurethane foam.

[0055] Compound (e) of the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms causes glycolysis-induced cleavage of polyurethane contained in waste materials.

[0056] 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.

[0057] In a method configuration in which 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 used, it is preferable that the compounds (e) from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms are used in a total amount of 1% to 30% by weight, with the total weight of the starting materials (a), (b), (c), (d), and (e) defined above being 100% by weight.

[0058] The addition of the total amount of compound(e) from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms to be used can be carried out in multiple steps, for example, preferably, the first portion of compound(e) is added when at least one-third, preferably half or all, of the polyurethane waste material(a) has been added and dissolved, and then one or more further portions of compound(e) are added later in the method. The addition of compound(e) from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms, preferably dipropylene glycol or diethylene glycol, later in the method plays a role in reducing the acid value of the polyol composition, particularly by the bonding of acidic groups.

[0059] If the total amount of compound(e) from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms to be used is added in multiple steps, i.e., in multiple parts, it is possible to add the same compound(e) from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms in each step, or to add different compounds(e) from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms in each step.

[0060] Typically, in the method according to the present invention, components (b) to (d) of the reaction mixture defined above are charged and heated to a temperature of 130°C to 230°C, preferably 140°C to 200°C. Subsequently, polyurethane waste material (a) is added to form the reaction mixture. During the addition of the polyurethane waste material, the temperature is maintained in the range of 130°C to 230°C, preferably 140°C to 210°C. In parallel with the addition of polyurethane waste material (a), additional water (d) may be added in one or more parts or continuously.

[0061] At least one-third, preferably half, of the polyurethane waste material (a) is added and dissolved, at which point 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. Alternatively, the addition 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 carried out at the stage when the polyurethane waste material (a) is completely dissolved. The reaction mixture is then held at a temperature preferably in the range of 150°C to 240°C, preferably 200°C to 230°C for several hours (1 to 5 hours, preferably 2 to 3.5 hours). After that, further portions of one or more compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids can be added. After the addition of further portions of compound (c), the reaction mixture can be cooled, or it can be held at a temperature in the range of 150°C to 240°C, preferably 200°C to 230°C for 0.25 to 1.5 hours, preferably 0.5 to 1 hour, and then cooled. During the cooling of the reaction mixture, further portions of compound (b) from the group consisting of polyether polyols and polyester polyols as defined above can be added.

[0062] Here, the following method configuration is preferred: - below: (b) Below: - Polyether polyols having an average molar mass of 200 g / mol to 8000 g / mol and a hydroxyl value of 2 to 4, - Polyester polyols with an average molar mass of 250 g / mol to 8000 g / mol and a hydroxyl value of 2 to 4. One or more compounds from the group consisting of, (c) One or more compounds from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, and optionally one or more monocarboxylic acids, (d) Water and A mixture containing is charged and heated to a temperature of 130°C to 230°C, preferably 140°C to 200°C. - Add polyurethane waste material (a) to this mixture to form a reaction mixture, while maintaining the temperature in the range of 130°C to 230°C, preferably 140°C to 210°C. - In parallel with the addition of polyurethane waste material (a), further water (d) is added in one or more parts or continuously. - At least one-third, preferably half, of the polyurethane waste material (a) is added and dissolved, then 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; or, at the stage when the polyurethane waste material (a) is completely dissolved, 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, - The reaction mixture is held at a temperature in the range of 150°C to 240°C, preferably 200°C to 230°C, for 1 to 5 hours, preferably 2 to 3.5 hours. - Add a further portion of one or more compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, - The reaction mixture is cooled after the addition of one or more further portions of compound (c), or after being held at a temperature in the range of 150°C to 240°C, preferably 200°C to 230°C, for 0.25 to 1.5 hours, preferably 0.5 to 1 hour, and then cooled.

[0063] Alternatively, after adding polyurethane waste material (a) (optionally while simultaneously adding further water (d) as described above), the reaction mixture may be held at a temperature in the range of 150°C to 240°C, preferably 200°C to 230°C for 1 to 5 hours, preferably 2 to 3.5 hours, and then further portions of one or more compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids may be added. After holding the reaction mixture at a temperature in the range of 170°C to 240°C, preferably 180°C to 230°C for 0.25 to 1.5 hours, preferably 0.5 to 1 hour, 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 may be added. After adding compound (e), the reaction mixture can be held at a temperature in the range of 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 then be cooled. During the cooling of the reaction mixture, further portions of compound (b) from the group consisting of polyether polyols and polyester polyols as defined above can be added.

[0064] Here, the following method configuration is preferred: - below: (b) Below: - Polyether polyols having an average molar mass of 200 g / mol to 8000 g / mol and a hydroxyl value of 2 to 4, - Polyester polyols with an average molar mass of 250 g / mol to 8000 g / mol and a hydroxyl value of 2 to 4. One or more compounds from the group consisting of, (c) One or more compounds from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, and optionally one or more monocarboxylic acids, (d) Water and A mixture containing is charged and heated to a temperature of 130°C to 230°C, preferably 140°C to 200°C. - Add polyurethane waste material (a) to this mixture to form a reaction mixture, while maintaining the temperature in the range of 130°C to 230°C, preferably 140°C to 210°C. - In parallel with the addition of polyurethane waste material (a), further water (d) is added in one or more parts or continuously. - The reaction mixture is held at a temperature in the range of 150°C to 240°C, preferably 200°C to 230°C, for 1 to 5 hours, preferably 2 to 3.5 hours. - Add a further portion of one or more compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, - After adding one or more portions of compound (c), the reaction mixture is held at a temperature in the range of 170°C to 240°C, preferably 180°C to 230°C, for 0.25 to 1.5 hours, preferably 0.5 to 1 hour. - Add 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, - After adding one or more compounds (e), the reaction mixture is kept at a temperature in the range of 170°C to 240°C, preferably 180°C to 230°C, for 0.25 to 1.5 hours, preferably 0.5 to 1 hour. - Afterwards, the reaction mixture is cooled.

[0065] Furthermore, the total amount of compound (e) from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms can also be added in small amounts in multiple steps during the reaction process. Here, the 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 material (a) has been added and dissolved, or when the polyurethane waste material (a) has been completely dissolved. The reaction mixture is then held at a temperature preferably in the range of 150°C to 240°C, preferably 200°C to 230°C for several hours (1 to 5 hours, preferably 2 to 3.5 hours). After that, further portions of one or more compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids can be added. After the addition of further portions of one or more compounds (c), the reaction mixture can be held at a temperature preferably in the range of 170°C to 240°C, preferably 180°C to 230°C for 0.25 to 1.5 hours, preferably 0.5 to 1 hour. Subsequently, 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. The addition of further portions of compound (e) plays a role in binding excess acid groups, thereby yielding a polyol composition with a low acid value. After the addition of further portions of compound (e), the reaction mixture can be held at a temperature in the range of 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 then be cooled. During the cooling of the reaction mixture, further portions of compound (b) from the group consisting of polyether polyols and polyester polyols as defined above can be added.

[0066] Here, the following method configuration is preferred: - below: (b) Below: - Polyether polyols having an average molar mass of 200 g / mol to 8000 g / mol and a hydroxyl value of 2 to 4, - Polyester polyols with an average molar mass of 250 g / mol to 8000 g / mol and a hydroxyl value of 2 to 4. One or more compounds from the group consisting of, (c) One or more compounds from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, and optionally one or more monocarboxylic acids, (d) Water and A mixture containing is charged and heated to a temperature of 130°C to 230°C, preferably 140°C to 200°C. - Add polyurethane waste material (a) to this mixture to form a reaction mixture, while maintaining the temperature in the range of 130°C to 230°C, preferably 140°C to 210°C. - In parallel with the addition of polyurethane waste material (a), further water (d) is added in one or more parts or continuously. - At least one-third, preferably half, of the polyurethane waste material (a) is added and dissolved, then 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; or, at the stage when the polyurethane waste material (a) is completely dissolved, 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, - The reaction mixture is held at a temperature in the range of 150°C to 240°C, preferably 200°C to 230°C, for 1 to 5 hours, preferably 2 to 3.5 hours. - Add a further portion of one or more compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, - After adding one or more portions of compound (c), the reaction mixture is held at a temperature in the range of 170°C to 240°C, preferably 180°C to 230°C, for 0.25 to 1.5 hours, preferably 0.5 to 1 hour. - Add a further 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, - After adding further portions of one or more compounds (e), the reaction mixture is held at a temperature in the range of 170°C to 240°C, preferably 180°C to 230°C, for 0.25 to 1.5 hours, preferably 0.5 to 1 hour. - Afterwards, the reaction mixture is cooled.

[0067] In a preferred modification of the above method configuration, in which 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, the total weight of the above-defined starting materials (a), (b), (c), (d), and (e) is 100% by weight, and each of them is: (a) 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% to 60% by weight, and / or (c) Compounds from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, and optionally monocarboxylic acids, in a total amount of 5% to 20% by weight, and / or (d) Water in an amount of 0.2% to 10% by weight, preferably 1% to 6% by weight, and / or more preferably 2% to 5% by weight. (e) Compounds from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms, in a total amount of 1% to 30% by weight It will be used.

[0068] In a preferred modification of the above method configuration, in which 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, the total weight of the above-defined starting materials (a), (b), (c), (d), and (e) is 100% by weight, and each of them is: (a) Polyurethane waste material in a total amount of 30% to 60% by weight, and (b) Compounds from the group consisting of polyether polyols and polyester polyols, in a total amount of 20% to 60% by weight, and (c) Compounds from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, and optionally monocarboxylic acids, in a total amount of 5% to 20% by weight, (d) Water in an amount of 0.2% to 10% by weight, preferably 1% to 6% by weight, and more preferably 2% to 5% by weight, (e) Compounds from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms, in a total amount of 1% to 30% by weight It will be used.

[0069] Regardless of whether the total amount of each starting material is added in one step or distributed over multiple steps at different points in the process (i.e., in the form of multiple parts), the data for the amounts of starting materials (a), (b), (c), (d), and (e) are all relative to the total amount of the above-defined starting materials (a) to (e) used in the reaction batch.

[0070] In designing the reactor for the method according to the present invention, it must be considered that the method is carried out at high temperatures in the presence of corrosive substances (acid anhydrides and / or acids). Therefore, it is preferable that the reaction be carried out in a stainless steel vessel. Particularly preferable, the reactor and the surrounding area are finished with corrosion-resistant and acid-resistant stainless steel. In certain embodiments, the apparatus comprises, for example, a fractional or distillation unit in the form of a column and a suitable metering and feeding unit.

[0071] For example, in the absence of radical-forming agents such as peroxides, the reaction does not proceed very vigorously, and therefore reactor cooling is not essential. This is a further advantage over the method described in German Patent No. 19512778 or International Publication No. 2018 / 091568.

[0072] The subject of the present invention is further a polyol composition that can be produced by the method according to the present invention described above, preferably by a method having one or more of the above preferred features, or by one of the above preferred modifications.

[0073] The polyol composition according to the present invention comprises a liquid phase containing a polyol liberated from polyurethane waste material and one or more compounds (b) from the group consisting of polyether polyols and polyester polyols as defined above (used as a starting material).

[0074] The polyol composition according to the present invention further comprises reaction products formed by acid decomposition of polyurethane waste and, in a method configuration in which compound (e) defined above is added, by glycolysis, the reaction products dispersed in the liquid phase in the form of particles, and are, for example, oligourethanes (urethane short chains remaining after the partial decomposition of the original polyurethane), oligoureas, polyureas, and acylureas. Further decomposition products of polyurethane waste may include amines, amides, and imides.

[0075] When polyurethane waste materials containing polyurethane integrated with thermoplastics such as polyolefins, ABS, or PVC are used, the polyol composition produced by the method according to the present invention contains these thermoplastic resins in a dispersed form, which can be removed from the polyol composition by solid-liquid separation, for example by filtration, as needed.

[0076] The polyol composition according to the present invention may contain unreacted residual polyurethane in the form of dispersed particles.

[0077] The unfiltered polyol composition according to the present invention mainly or almost exclusively contains particles with a size in the range of 8 nanometers to 300 micrometers (average particle size in the range of 150 to 200 micrometers), with only a small proportion of agglomerates with a size in the range of >300 micrometers to 5 millimeters (less than 2% by weight relative to the weight of the unfiltered polyol composition). To detect all conceivable particle size ranges, the particle size distribution is determined by combining dynamic light scattering (detecting particle sizes from 1 nm to 1 μm), microscopy (detecting particle sizes from 1 μm to 250 μm), and grinding (detecting particle sizes of 250 μm or larger).

[0078] Filtration can effectively remove agglomerates with a size in the range of >300 micrometers from the polyol composition.

[0079] The polyol composition that can be produced by the method according to the present invention is isocyanate reactive; that is, a polyol contained in a dispersion and liberated from polyurethane waste material can be reacted with polyisocyanate to form a new polyurethane material.

[0080] The polyol composition according to the present invention is characterized by having a lighter color and / or a smaller average particle size and / or a narrower particle size distribution compared to a polyol composition not according to the present invention, which is produced from the same starting material (polyurethane waste) under the same method and conditions, with the sole exception that a radical-forming agent, such as a peroxide, particularly hydrogen peroxide, is added instead of water.

[0081] In this context, "produced under the same method and conditions" means, in particular, that the production of the polyol composition according to the present invention and the polyol composition not according to the present invention uses the same starting materials in the form of polyurethane waste (a) as defined above, 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, each in the same amount, the reaction is carried out under the same temperature control, and, if necessary, the same compounds (e) from the group consisting of diols and triols as defined above are each used, and the reaction is carried out at the same temperature for the same period of time. Furthermore, it will be obvious to those skilled in the art that, in order to enable comparison in the production of the polyol composition according to the present invention and the polyol composition not according to the present invention, all other parameters (e.g., step duration and unified order of starting materials (a) to (e)) are also the same, and the same (same structure) apparatus is used.

[0082] While not bound by any particular theory, it is presumed that the lighter color of the polyol compositions according to the present invention is particularly due to the use of less or no radical-forming agents, such as peroxides, which can react undesirably with antioxidants contained in or in compounds of the group consisting of polyether polyols used in polyurethane waste materials, in the method according to the present invention.

[0083] In this context, "lighter color" means that a color difference of at least 1 dE(ΔE), preferably at least 2 dE(ΔE), and particularly preferably at least 5 dE(ΔE) (according to the Lambert-Beer law) can be measured between a polyol composition according to the present invention and a polyol composition not according to the present invention, both produced from the same starting material (polyurethane waste) under the same method and conditions, with the sole exception that a radical-forming agent, such as a peroxide, particularly hydrogen peroxide, is added instead of water.

[0084] While not bound by any particular theory, it is presumed that the smaller average particle size of the polyol composition according to the present invention results from the sufficient avoidance of agglomerate formation in the size range of 1 to 10 millimeters by the method according to the present invention. The unfiltered polyol composition according to the present invention mainly or almost exclusively contains particles in the size range of 8 nanometers to 300 micrometers (average particle size of 150 to 200 micrometers), with only a small proportion of agglomerates in the size range of >300 micrometers to 5 millimeters (less than 2% by weight relative to the weight of the unfiltered polyol composition). To detect all conceivable particle size ranges, the particle size distribution is determined by combining dynamic light scattering (detecting particle sizes of 1 nm to 1 μm), microscopy (detecting particle sizes of 1 μm to 250 μm), and grinding (detecting particle sizes of 250 μm or larger).

[0085] Compared to the polyol compositions according to the present invention, non-Polyol compositions produced from the same starting material (polyurethane waste) under the same method and conditions, with the sole exception that a radical-forming agent, such as a peroxide, particularly hydrogen peroxide, is added instead of water, always have at least 10%, often at least 20%, or even at least 50% higher proportion of agglomerates in the size range of 250 micrometers to 3 millimeters.

[0086] In the polyol composition according to the present invention, there are virtually no agglomerates larger than 250 micrometers in size. Therefore, compared to polyol compositions not according to the present invention, produced from the same starting material (polyurethane waste) under the same method and conditions, with the sole exception that a radical-forming agent, such as a peroxide, particularly hydrogen peroxide, is added instead of water, the particle size distribution is narrower.

[0087] The polyol composition according to the present invention appears to be more uniform, more homogeneous, and exhibits higher levels of fine dispersion than a polyol composition not according to the present invention, produced from the same starting material (polyurethane waste) under the same method and conditions, with the sole exception that a radical-forming agent, such as a peroxide, particularly hydrogen peroxide, is added instead of water.

[0088] The polyol liberated from polyurethane waste material contained in the polyol composition according to the present invention may have an average molar mass (Mn) in the range of 200 to 10,000 g / mol.

[0089] The polyol composition according to the present invention is typically as follows: - Hydroxyl value of 30-650 mg KOH / g (measured according to DIN 53240) and / or - Amine value of 1-40 mg KOH / g (measured according to DIN 53176) and / or - Acid value of 0.1 to 10 mg KOH / g (measured according to DIN 53402) and / or - Viscosity of 1,000 to 50,000 mPa·s (measured according to DIN 53019) It holds.

[0090] Preferably, the polyol composition according to the present invention, as follows: - Hydroxyl value of 30-400 mg KOH / g (measured according to DIN 53240) and - Amine value of 1-20 mg KOH / g (measured according to DIN 53176) and - Acid value of 0.1~5 mg KOH / g (measured in accordance with DIN 53402) and - Viscosity of 2000 to 12000 mPa·s, particularly preferably 3000 to 8000 mPa·s (measured in accordance with DIN 53019) It holds.

[0091] Therefore, the polyol compositions according to the present invention have hydroxyl values ​​within the range of polyols commonly used in the production of polyurethanes. For example, polyols with a hydroxyl value in the range of 150 to 600 mgKOH / g are preferably used in the production of rigid foams, polyols with a hydroxyl value in the range of 28 to 100 mgKOH / g are preferably used in the production of flexible foams, and polyols with a hydroxyl value in the range of 35 to 160 mgKOH / g are preferably used in the production of prepolymers, adhesives and / or elastomers. The hydroxyl values ​​are measured in accordance with DIN 53240.

[0092] Advantageously, the concentration of the primary aromatic amine in the polyol composition according to the present invention is less than 0.1% of the total weight of the polyol composition.

[0093] The use of polyol compositions obtainable by the method according to the present invention in the production of polyurethane is also a subject of the present invention. Corresponding methods for the production of polyurethane are known to those skilled in the art. Herein, a mixture of polyol recovered from polyurethane waste by the method according to the present invention and primary polyol (i.e., polyol not obtained by cleavage of polyurethane) is used as the polyol component for polyurethane formation, and this is reacted with a polyisocyanate component in the usual manner, preferably in a weight ratio of 10:90 to 60:40.

[0094] The following examples are for further illustration of the present invention, but are not limiting.

[0095] The experiments in the examples were conducted under a protective gas atmosphere.

[0096] Example 1: In a heated stainless steel stirred reactor equipped with a fractionation column, under stirring (b) 37% by weight of a long-chain polyethertriol (Lupranol® 3300, BASF) with an average molar mass of 420 g / mol, (c) 8% by weight of phthalic anhydride, (d) Desalinated water 2% by weight and The mixture was added and heated to 150°C within 90 minutes. At this temperature, under stirring... (a) Polyurethane waste (post-consumer mattress, unsorted, shredded into approximately 2cm x 2cm x 2cm pieces) 40% by weight The polyurethane waste material (a) was added, and the temperature was maintained in the range of 150°C to 210°C until it dissolved. During the addition of the polyurethane waste material (a), (d) Desalinated water, further 2% by weight It was added gradually. Then, it was stirred for 1 hour, and then (e) Short-chain glycol (diethylene glycol) 7% by weight The mixture was added, and the temperature was maintained in the range of 220°C to 235°C. Then, the mixture was stirred at 220°C for 1 hour, and then under stirring... (c) Anhydrous maleic acid 2% by weight And after 10 minutes, under stirring (e) Dipropylene glycol 2% by weight [The substance] was added. This mixture was held at 220°C for a further 30 minutes, and then cooled to 80°C under stirring.

[0097] The resulting polyol composition was then pumped out, filtered through a self-cleaning filter (150 μm), and cooled to room temperature.

[0098] The polyol composition has the following properties after filtration: Hydroxyl value: 268 mg KOH / g, measured according to DIN 53240. Acid value: 0.7 mg KOH / g, measured according to DIN 53402. Viscosity: 5,600 mPa·s measured at 25°C in accordance with DIN 53019. Amine value: 18 mg KOH / g, measured according to DIN 53176.

[0099] This polyol composition is suitable for the production of rigid polyurethane foam. Its low acid value avoids adverse effects on catalytic activity during subsequent rigid polyurethane foam production.

[0100] Example 2: In a heated stainless steel stirred reactor equipped with a fractionation column, under stirring (b) 38% by weight of polyethertriol (Dow Chemical Company, VORANOL CP 450) with an average molar mass of 440 g / mol, (c) 7% by weight of phthalic anhydride and 2% by weight of succinic anhydride, (d) Desalinated water 1.5% by weight and The mixture was added and heated to 165°C within 100 minutes. At this temperature, under stirring... (a) Polyurethane waste (post-consumer mattress, unsorted, shredded into approximately 2cm x 2cm x 2cm pieces) 40% by weight The polyurethane waste material was added, and the temperature was maintained in the range of 165°C to 200°C until the polyurethane waste material dissolved. In parallel with the addition of polyurethane waste material (a), (d) Desalinated water, plus 2.5% by weight The polyurethane waste material (a) was gradually added. After the polyurethane waste material (a) was completely metered and supplied to the reactor, under stirring (e) Diethylene glycol 9% by weight The diethylene glycol was added, while maintaining the temperature in the range of 200°C to 220°C. Alternatively, the diethylene glycol could be added when at least half, preferably at least two-thirds, of the polyurethane waste material (a) had been metered and supplied to the reactor. This mixture was stirred for 1.5 hours at a temperature in the range of 210°C to 225°C. Then, under stirring... (c) Anhydrous maleic acid 2% by weight The mixture was then added and immediately cooled to 120°C under stirring.

[0101] The resulting polyol composition was then pumped out, filtered through a self-cleaning filter (150 μm), and cooled to room temperature.

[0102] A polyol composition was obtained having an acid value of less than 1.5 mg KOH / g and a primary aromatic amine content of less than 0.05% by weight. After filtration, the polyol composition has the following properties: Hydroxyl value: 270 mg KOH / g, measured according to DIN 53240. Acid value: 1.2 mg KOH / g, measured according to DIN 53402. Viscosity: 4,800 mPa·s measured at 25°C in accordance with DIN 53019. Amine value: 14 mg KOH / g, measured according to DIN 53176.

[0103] This polyol composition is suitable for the production of rigid polyurethane foam (PUR and / or PUR / PIR). In tests relating to the production of PUR / PIR foam panels, polyol recovered from polyurethane waste by the method according to the present invention as described in Example 1 or Example 2 and primary polyol (i.e., polyol not obtained by polyurethane cleavage) were used in a weight ratio of 10 / 90 to 50 / 50. PUR / PIR panels were obtained, and their properties were not unfavorably altered compared to the corresponding original PUR product (without the addition of polyol recovered from polyurethane waste). In particular, the compressive strength, dimensional stability, and thermal conductivity of the product were comparable or equivalent.

[0104] Example 3: In a heated stainless steel stirred reactor equipped with a fractionation column, under stirring (b) 38% by weight of a long-chain polyether polyol (Arcol® Polyol 1108, Covestro) with a hydroxyl value of 48 mgKOH / g, (c) 6% by weight of phthalic anhydride and 4% by weight of acrylic acid, (d) Desalinated water 1% by weight and The mixture was added and heated to 160°C within 90 minutes. At this temperature, under stirring... (a) Soft polyurethane foam waste (unsorted) 41% by weight The following was added, and the temperature was maintained in the range of 160°C to 210°C. In parallel with the addition of polyurethane waste, (d) Desalinated water, further 4% by weight The mixture was gradually added. Then, it was stirred at 210°C for 1 hour until the polyurethane waste material was completely dissolved. Next, the temperature was maintained in the range of 220°C to 225°C for 2 hours under stirring. The mixture was then stirred at 225°C for a further 30 minutes. After that, under stirring... (c) Anhydrous maleic acid 2% by weight And after 10 minutes, under stirring (e) Dipropylene glycol 1% by weight The mixture was then stirred at 220°C for a further 30 minutes, and then cooled to 130°C while stirring. (b)Arcol(R) Polyol 1108 3% by weight Added.

[0105] The obtained polyol composition was filtered at 100°C using a 250 μm filter and cooled to room temperature.

[0106] The polyol composition has the following properties after filtration: Hydroxyl value: 53 mg KOH / g, measured according to DIN 53240. Acid value: 0.7 mg KOH / g, measured according to DIN 53402. Viscosity: 8,700 mPa·s measured at 25°C in accordance with DIN 53019. Amine value: 9 mg KOH / g, measured according to DIN 53176.

[0107] This polyol composition is suitable for the manufacture of flexible polyurethane foam materials.

[0108] Example 4: In a heated stainless steel stirred reactor equipped with a fractionation column, under stirring (b) 36% by weight of polyester polyol (Lupraphen 5608 / 1, BASF) with an average molar mass of 2000 g / mol, (c) 7% by weight of phthalic anhydride and 3% by weight of adipic acid, (d) Desalinated water 2% by weight and The mixture was added and heated to 150°C within 90 minutes. At this temperature, under stirring... (a) Polyurethane waste (polyester-based shoe soles, unsorted) 41% by weight The following was added, and the temperature was maintained in the range of 150°C to 210°C. In parallel with the addition of polyurethane waste material (a), further (d) Desalinated water 1% by weight The mixture was gradually added. Then, it was stirred at 210°C for 1 hour until the polyurethane waste material (a) was completely dissolved. Next, the temperature was maintained in the range of 220°C to 225°C for 2 hours under stirring. The mixture was then stirred at a temperature of 225°C for a further 30 minutes. Afterward, under stirring... (c) Hexahydrophthalic anhydride 1.5% by weight And after 10 minutes, under stirring (e) Dipropylene glycol 1.5% by weight The mixture was then added. This mixture was held at 220°C for a further 30 minutes under stirring, and then cooled to 130°C under stirring. (b) Polyester polyol 7% by weight Added.

[0109] The obtained polyol composition was filtered at 100°C using a 200 μm filter and cooled to room temperature.

[0110] The polyol composition has the following properties after filtration: Hydroxyl value: 54 mg KOH / g, measured according to DIN 53240. Acid value: 1.5 mg KOH / g, measured according to DIN 53402. Viscosity: 4,700 mPa·s measured at 25°C in accordance with DIN 53019. Amine value: 5 mg KOH / g, measured according to DIN 53176.

[0111] This polyol composition is suitable for the manufacture of polyester-based polyurethane shoe soles.

[0112] Example 5: In a heated stainless steel stirred reactor equipped with a fractionation column, under stirring (b) 32% by weight of polyester polyol (STEPANPOL® PS-3152) with an average molar mass of 350 g / mol, (c) 7% by weight of phthalic anhydride and 2% by weight of maleic anhydride, (d) Desalinated water 2% by weight and The mixture was added and heated to 150°C within 90 minutes. At this temperature, under stirring... (a) Soft polyurethane foam waste (unsorted) 40% by weight The following was added, and the temperature was maintained in the range of 150°C to 210°C. In parallel with the addition of polyurethane waste material (a), (d) Desalinated water, further 1.5% by weight gradually (e) Diethylene glycol 14% by weight and The mixture was added, and the temperature was maintained in the range of 180°C to 210°C. Then, it was stirred at 210°C for 1 hour until the polyurethane waste material was completely dissolved. Next, the temperature was maintained in the range of 220°C to 235°C for 2 hours under stirring. This mixture was then stirred at a temperature of 225°C for a further 30 minutes. After that, under stirring... (c) Anhydride maleic acid 1.5% by weight The mixture was added, stirred at 220°C for a further 30 minutes, and then cooled to 100°C while stirring.

[0113] The obtained polyol composition was filtered at 100°C using a 150 μm filter and cooled to room temperature.

[0114] The polyol composition has the following properties after filtration: Hydroxyl value: 264 mg KOH / g, measured according to DIN 53240. Acid value: 1.8 mg KOH / g, measured according to DIN 53402. Viscosity: 7,500 mPa·s measured at 25°C in accordance with DIN 53019. Amine value: 16 mg KOH / g, measured according to DIN 53176.

[0115] This polyol composition is suitable for the manufacture of rigid polyurethane foam materials (PUR and / or PUR / PIR).

[0116] Example 6: In a heated stainless steel stirred reactor equipped with a fractionation column, under stirring (b) 38% by weight of a long-chain polyether polyol (VORANOL® 8136, DOW Chemicals) with an average molar mass of 3100 g / mol and a hydroxyl value of 55 mg KOH / g, (c) 7% by weight of phthalic anhydride and 3% by weight of acrylic acid, (d) Desalinated water 1% by weight and The mixture was added and heated to 160°C within 90 minutes. At this temperature, under stirring... (a) Soft polyurethane foam waste (unsorted) 41% by weight The following was added, and the temperature was maintained in the range of 160°C to 210°C. In parallel with the addition of polyurethane waste material (a), (d) Desalinated water, further 3.5% by weight The mixture was gradually added. Then, it was stirred at 210°C for 1 hour until the polyurethane waste material (a) was completely dissolved. Next, the temperature was maintained in the range of 220°C to 225°C for 2 hours under stirring. The mixture was then stirred at a temperature of 225°C for a further 30 minutes. Afterward, under stirring... (c) Maleic anhydride 1.75% by weight And after 10 minutes, under stirring (e) Dipropylene glycol 1.75% by weight Add the mixture and stir it at 220°C for a further 30 minutes, then cool it to 130°C while stirring. (b) (VORANOL(TM) 8136, DOW Chemicals) 3% by weight Added.

[0117] The obtained polyol composition was filtered at 100°C using a 250 μm filter and cooled to room temperature.

[0118] The polyol composition has the following properties after filtration: Hydroxyl value: 53 mg KOH / g, measured according to DIN 53240. Acid value: 0.7 mg KOH / g, measured according to DIN 53402. Viscosity: 8,700 mPa·s measured at 25°C in accordance with DIN 53019. Amine value: 9 mg KOH / g, measured according to DIN 53176.

[0119] This polyol composition is suitable for the manufacture of flexible polyurethane foam materials.

[0120] Example 7: In a heated stainless steel stirred reactor equipped with a fractionation column, the following applies: (b) 33% by weight of a long-chain polyether polyol (VORANOL® 3322, DOW Chemicals) having a hydroxyl value of 48 mgKOH / g and an average molar mass of 3400 g / mol, (c) 9.5% by weight of phthalic anhydride and 1% by weight of acrylic acid, (d) Desalinated water 1.8% by weight and The mixture was loaded and heated to 160°C within 90 minutes. At this temperature, (a) Soft polyurethane foam waste (unsorted) 42% by weight The following was added, and the temperature was maintained in the range of 160°C to 210°C. In parallel with the addition of polyurethane waste material (a), (d) Desalinated water, further 1.5% by weight The polyurethane material was gradually added. The mixture was then stirred for 1 hour at 210°C until the polyurethane material was completely dissolved. Next, the temperature was maintained in the range of 220°C to 225°C for 2 hours under stirring. The mixture was then stirred for a further 30 minutes at 225°C. After that, (c) Anhydrous maleic acid 1% by weight The mixture was then stirred at 220°C for a further 30 minutes, and then cooled to 130°C while stirring. (b) VORANOL(TM) 3322 10.2% by weight Added.

[0121] The obtained polyol composition was filtered at 100°C using a 250 μm filter and cooled to room temperature.

[0122] The polyol composition has the following properties after filtration: Hydroxyl value: 54 mg KOH / g, measured according to DIN 53240. Acid value: 1.8 mg KOH / g, measured according to DIN 53402. Viscosity: 8,900 mPa·s measured at 25°C in accordance with DIN 53019. Amine value: 10 mg KOH / g, measured according to DIN 53176.

[0123] This polyol composition is suitable for the manufacture of flexible polyurethane foam materials.

Claims

1. A method for producing a polyol composition containing polyols liberated from polyurethane waste, wherein in the reaction mixture, (a) Polyurethane waste material and (b) Below: - Polyether polyols having an average molar mass of 200 g / mol to 8000 g / mol and a hydroxyl value of 2 to 4, - Polyester polyols with an average molar mass of 250 g / mol to 8000 g / mol and a hydroxyl value of 2 to 4 One or more compounds from the group consisting of, (c) One or more compounds from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, (d) Water and By reacting them, a polyol composition containing polyols liberated from polyurethane waste is formed. To the above reaction mixture, (e) One or more compounds from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms. Add, A method in which the peroxide is used in an amount of less than 0.1% by weight, where the total weight of the starting materials (a), (b), (c), (d), and (e) is 100% by weight.

2. - Compound (b) of the group of polyether polyols has an average molar mass in the range of 200 g / mol to 6000 g / mol, - The method for producing the polyol composition according to claim 1, wherein compound (b) of the group of polyester polyols has an average molar mass in the range of 350 g / mol to 6000 g / mol.

3. - Compound (c) of the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids is selected from the group consisting of adipic acid and maleic acid anhydride, phthalic acid anhydride, hexahydrophthalic acid anhydride and succinic acid anhydride. and / or - The method for producing a polyol composition according to claim 1 or 2, wherein the reaction mixture also comprises one or more monocarboxylic acids in addition to one or more compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids.

4. - below: (b) Below: - Polyether polyols having an average molar mass of 200 g / mol to 8000 g / mol and a hydroxyl value of 2 to 4, - Polyester polyols with an average molar mass of 250 g / mol to 8000 g / mol and a hydroxyl value of 2 to 4 One or more compounds from the group consisting of, (c) One or more compounds from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, (d) Water and A mixture containing [the substance] is charged in and heated to a temperature of 130°C to 230°C. - A reaction mixture is formed by adding polyurethane waste material (a) to the mixture, and the temperature is maintained in the range of 130°C to 230°C. - In parallel with the addition of the polyurethane waste material (a), further water (d) is added in one or more parts or continuously. - The reaction mixture is maintained at a temperature in the range of 150°C to 240°C for 1 to 5 hours. - Add a further portion of one or more compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, - After adding further portions of one or more of the compound (c), the reaction mixture is held at a temperature in the range of 170°C to 240°C for 0.5 to 3 hours. - The method according to any one of claims 1 to 3, wherein the reaction mixture is then cooled.

5. The compound (e) from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms is selected from the group consisting of ethylene glycol, diethylene glycol, dipropylene glycol, 1,3-propane glycol, 1,2-butanediol, 1,4-butane glycol, and glycerin, a method for producing a polyol composition according to any one of claims 1 to 4.

6. - below: (b) Below: - Polyether polyols having an average molar mass of 200 g / mol to 8000 g / mol and a hydroxyl value of 2 to 4, - Polyester polyols with an average molar mass of 250 g / mol to 8000 g / mol and a hydroxyl value of 2 to 4 One or more compounds from the group consisting of, (c) One or more compounds from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, (d) Water and A mixture containing [the substance] is charged in and heated to a temperature of 130°C to 230°C. - A reaction mixture is formed by adding polyurethane waste material (a) to the mixture, and the temperature is maintained in the range of 130°C to 230°C. - In parallel with the addition of the polyurethane waste material (a), further water (d) is added in one or more parts or continuously. - At the stage when at least one-third of the polyurethane waste material (a) has been added and dissolved, add 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; or, at the stage when the polyurethane waste material (a) has been completely dissolved, add 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 maintained at a temperature in the range of 150°C to 240°C for 1 to 5 hours. - Add a further portion of one or more compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, - The method according to any one of claims 1 to 5, wherein the reaction mixture is cooled after the addition of further portions of the one or more compounds (c); or cooled after being held at a temperature in the range of 150°C to 240°C for 0.25 to 1.5 hours.

7. - below: (b) Below: - Polyether polyols having an average molar mass of 200 g / mol to 8000 g / mol and a hydroxyl value of 2 to 4, - Polyester polyols with an average molar mass of 250 g / mol to 8000 g / mol and a hydroxyl value of 2 to 4 One or more compounds from the group consisting of, (c) One or more compounds from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, (d) Water and A mixture containing [the substance] is charged in and heated to a temperature of 130°C to 230°C. - A reaction mixture is formed by adding polyurethane waste material (a) to the mixture, and the temperature is maintained in the range of 130°C to 230°C. - In parallel with the addition of the polyurethane waste material (a), further water (d) is added in one or more parts or continuously. - The reaction mixture is maintained at a temperature in the range of 150°C to 240°C for 1 to 5 hours. - Add a further portion of one or more compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, - After adding further portions of one or more of the compound (c), the reaction mixture is held at a temperature in the range of 170°C to 240°C for 0.25 to 1.5 hours. - Add 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, - After adding one or more of the compounds (e), the reaction mixture is held at a temperature in the range of 170°C to 240°C for 0.25 to 1.5 hours. - The method according to any one of claims 1 to 5, wherein the reaction mixture is then cooled.

8. - below: (b) Below: - Polyether polyols having an average molar mass of 200 g / mol to 8000 g / mol and a hydroxyl value of 2 to 4, - Polyester polyols with an average molar mass of 250 g / mol to 8000 g / mol and a hydroxyl value of 2 to 4 One or more compounds from the group consisting of, (c) One or more compounds from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, (d) Water and A mixture containing [the substance] is charged in and heated to a temperature of 130°C to 230°C. - A reaction mixture is formed by adding polyurethane waste material (a) to the mixture, and the temperature is maintained in the range of 130°C to 230°C. - In parallel with the addition of the polyurethane waste material (a), further water (d) is added in one or more parts or continuously. - At the stage when at least one-third of the polyurethane waste material (a) has been added and dissolved, add 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; or, at the stage when the polyurethane waste material (a) has been completely dissolved, add 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 maintained at a temperature in the range of 150°C to 240°C for 1 to 5 hours. - Add a further portion of one or more compounds (c) from the group consisting of dicarboxylic acid anhydrides and dicarboxylic acids, - After adding further portions of one or more of the compound (c), the reaction mixture is held at a temperature in the range of 170°C to 240°C for 0.25 to 1.5 hours. - Add a further 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, - After adding further portions of one or more of the compound (e), the reaction mixture is held at a temperature in the range of 170°C to 240°C for 0.25 to 1.5 hours. - The method according to any one of claims 1 to 5, wherein the reaction mixture is then cooled.

9. When the reaction mixture is cooled, (b) Below: - Polyether polyols having an average molar mass of 200 to 8000 g / mol and a hydroxyl value of 2 to 4, - Polyester polyols having an average molar mass of 250 to 8000 g / mol and a hydroxyl value of 2 to 4 Compounds from the group consisting of The method according to any one of claims 4, 6, 7, or 8, further comprising adding a portion thereof.

10. The total weight of the starting materials (a), (b), (c), (d), and (e) is set to 100% by weight, and each of them is as follows: (a) Polyurethane waste material in a total amount of 30% to 60% by weight, and / or (b) Compounds from the group consisting of polyether polyols and polyester polyols, and acrylic acid, in a total amount of 20% to 60% by weight, and / or (c) Dicarboxylic acid anhydrides and compounds from the group consisting of dicarboxylic acids and monocarboxylic acids in a total amount of 5% to 20% by weight, and / or (d) Add water in an amount of 0.2% to 10% by weight, (e) Compounds from the group consisting of diols having 2 to 8 carbon atoms and triols having 3 to 8 carbon atoms, in a total amount of 1% to 30% by weight A method for producing the polyol composition according to any one of claims 1 to 9, which is to be added.

11. - Without adding radical-forming agents, and / or - Compound (b) of the group of polyether polyols is provided with one or more antioxidants. A method for producing a polyol composition according to any one of claims 1 to 10.

12. A polyol composition produced by the method described in any one of claims 1 to 11.

13. Use of a polyol composition obtained by the method described in any one of claims 1 to 11 for the production of polyurethane.