Method for producing one or more polymers selected from group consisting of polyurethanes, polyurethane ureas, polyisocyanurate and mixtures of two or more thereof from solid material W

Abstract

The invention relates to a method for producing one or more polymers from a solid material W, selected from the group consisting of polyurethanes, polyurethane ureas, polyisocyanurate and mixtures of two or more thereof.

Description

[0001] The present invention relates to a method for producing one or more polymers from a solid material W, the one or more polymers being selected from the group consisting of polyurethanes, polyurethaneureas, polyisocyanurates and mixtures of two or more thereof.

[0002] Polyurethanes belong to the class of polycondensation polymers. They are usually produced from one or more polyols and one or more di- or polyisocyanates.

[0003] In terms of sustainability, polyurethanes should be recycled as much as possible. In general, polyurethanes can be recycled in a variety of ways. One of the most interesting ways is to re-monomerize polyurethanes or polyurethane waste by recovering polyol and isocyanate components or corresponding precursors. For this purpose, the prior art proposes to cleave polyurethanes by, for example, hydrolysis, glycolysis, alcoholysis and aminolysis to form isocyanate derivatives (amines, carbamates, ureas) and polyols.

[0004] For example, WO 2008 / 014988 A1 relates to the re-cleavage of polyurethanes. Specifically, a method for the cleavage of polyurethanes and polyurethane ureas is described, in which the polymers are first reacted with gaseous or liquid aliphatic or cycloaliphatic secondary amines, and the secondary ureas formed are cleaved into isocyanates after removal together with hydrogen chloride. In addition, the polyols or polyamines also formed in the reaction are processed and purified.

[0005] One of the biggest challenges of prior art recycling methods is the separation of polyols from isocyanate derivatives, which is mainly based on phase decay. However, this may only be applicable to selected polyurethanes and may be prone to failure due to possible contamination in polyurethane waste. Therefore, prior art recycling methods are typically severely limited in their applicability.

[0006] Therefore, there is a need for an improved process for producing polymers such as polyurethanes, polyurethaneureas and polyisocyanurates using recycling of waste materials.It is therefore an object of the present invention to provide an improved process for producing one or more polymers such as polyurethanes, polyurethaneureas and polyisocyanurates from solid waste.

[0007] Surprisingly, it has been found that the process of the present invention allows to circumvent the problems of the prior art. Thus, the present invention relates to a process for producing one or more polymers from a solid material W, the one or more polymers being selected from the group consisting of polyurethanes, polyurethaneureas, polyisocyanurates and mixtures of two or more thereof, the process comprising

[0008] (i) preparing a mixture M comprising one or more polyurea-containing compounds from a solid material W, the mixture M further comprising one or more polyols, including:

[0009] (i.1) providing the solid material W comprising one or more polymers selected from the group consisting of polyurethane, polyurethaneurea, polyisocyanurate and a mixture of two or more thereof;

[0010] (i.2) In the reactor unit R A introducing the solid material W provided in (i.1) and one or more primary amines to obtain a mixture;

[0011] (i.3) subjecting the mixture obtained according to (i.2) to R A subjecting the mixture to aminolysis reaction conditions to obtain a mixture M comprising one or more polyurea-containing compounds and further comprising one or more polyols;

[0012] (ii) separating the one or more polyurea-containing compounds of M obtained according to (i) from the one or more polyols of M obtained according to (i) to obtain a mixture U comprising the one or more polyurea-containing compounds and a mixture P comprising the one or more polyols;

[0013] (iii) subjecting the mixture U obtained according to (ii) to a reactor unit R C subjecting the mixture to cleavage reaction conditions to obtain one or more corresponding polyamines or one or more corresponding polyisocyanates;

[0014] (iv) subjecting the mixture P obtained according to (ii) to purification conditions to obtain a purified mixture comprising one or more polyols;

[0015] (v) preparing one or more polymers selected from the group consisting of polyurethanes, polyurethaneureas, polyisocyanurates, and mixtures of two or more thereof, comprising:

[0016] (v.1) introducing the one or more polyols obtained according to (iv) into unit N PU middle;

[0017] (v.2) converting the one or more polyamines obtained according to (iii) into one or more polyisocyanates in a reactor to obtain one or more polyisocyanates, and introducing the one or more polyisocyanates obtained into N PU or

[0018] The one or more polyisocyanates obtained according to (iii) are introduced into N PU middle;

[0019] (v.3) According to (v.2), N is introduced PU The one or more polyisocyanates in (v.1) are introduced into N PUThe one or more polyols in the mixture are contacted in the presence of a catalyst for polymerization to obtain one or more polymers selected from the group consisting of polyurethane, polyurethane urea, polyisocyanurate and a mixture of two or more thereof.

[0020] Preferably, the method further comprises, before (i), subjecting the solid material W to a pretreatment, more preferably a mechanical pretreatment, wherein the mechanical pretreatment more preferably comprises one or more of grinding, crushing, chopping and cutting, more preferably grinding or chopping the solid material W.

[0021] Preferably, the method further comprises, before (i), more preferably after subjecting the solid material W to a pretreatment as defined above, drying the solid material W, wherein the drying is more preferably carried out at a temperature in the range of 40°C to 100°C, more preferably in the range of 50°C to 85°C, and wherein the drying is more preferably carried out in a gas atmosphere comprising one or more of nitrogen and oxygen, more preferably in air.

[0022] Preferably, the water content of the solid material W, more preferably after drying as defined above, is below 1000 ppm-weight-%, more preferably below 100 ppm-weight-%, more preferably between 0 and 100 ppm-weight-%.

[0023] Preferably, the solid material W is waste solid material.

[0024] Preferably, the waste material is an end-of-life material, such as one or more of an end-of-life foam, an end-of-life flexible foam, an end-of-life rigid foam, an end-of-life dense elastomer and an end-of-life dense duromer. In the context of the present invention, an end-of-life material is a material at the end of its life cycle.

[0025] Preferably, in addition to one or more polymers, the solid material W further comprises impurities, which may be one or more of glass, sand, wood, metal, paper, inorganic solids and polymers other than polyurethane, polyurethane urea and polyisocyanurate. The polymers other than polyurethane, polyurethane urea and polyisocyanurate may be, for example, one or more of polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET) or polystyrene (PS).

[0026] Preferably, the solid material W is one or more of a powder, a foam block, a pellet, a granule and a flake.

[0027] Preferably, the average particle size of the solid material W provided in (i) is between 10 -6 Up to 10 -1 m, preferably within the range of 10 -6 Up to 10 -2The average particle size is determined by laser diffraction or optical microscopy in the range of 100 to 200 m. The skilled person adjusts these methods to the particle size range. Therefore, particle sieve analysis can also be used to determine the average particle size.

[0028] Preferably, the one or more polymers contained in the solid material W are one or more polyurethanes, more preferably the one or more polyurethanes are thermosetting materials or elastomers.

[0029] According to the present invention, there is no particular limitation on the polyurethane of W used in the method of the present invention. However, preferably, the polyurethane of W is prepared by a process in which a polyisocyanate is reacted with a polyol in the presence of one or more catalysts as known in the art.

[0030] Suitable polyisocyanate components for the production of polyurethanes of W include any polyisocyanate known for the production of polyurethanes. These include aliphatic, alicyclic and aromatic difunctional or polyfunctional isocyanates known from the prior art, as well as any desired mixtures thereof. Examples are diphenylmethane 2,2'-, 2,4'- and 4,4'-diisocyanates, mixtures of monomeric diphenylmethane diisocyanates with diphenylmethane diisocyanate homologues having a greater number of rings (polymeric MDI), isophorone diisocyanate (IPDI) and its oligomers, toluene 2,4- and 2,6-diisocyanates (TDI), and mixtures of these, tetramethylene diisocyanate and its oligomers, hexamethylene diisocyanate (HDI) and its oligomers, naphthylene diisocyanate (NDI) and mixtures thereof.

[0031] Preference is given to toluene 2,4- and / or 2,6-diisocyanate (TDI) or mixtures thereof, monomeric diphenylmethane diisocyanate, and / or diphenylmethane diisocyanate homologues with a greater number of rings (polymeric MDI), and mixtures of these. Other possible isocyanates are mentioned, for example, in "Kunststoffhandbuch [Plastics handbook] [Plastics Handbook], Volume 7, Polyurethane [Polyurethanes] Polyurethane [Polyurethane]", Carl Hanser Verlag, 3rd edition, 1993, Chapters 3.2 and 3.3.2.

[0032] Suitable polyols for producing the polyurethane of W are selected from the group consisting of polyether polyols, polyester polyols, polyetherester polyols and mixtures thereof.

[0033] The polyether alcohols are produced, for example, from epoxides, such as propylene oxide and / or ethylene oxide, or from tetrahydrofuran and starting compounds which exhibit hydrogen activity, such as fatty alcohols, phenols, amines, carboxylic acids, water, or compounds based on natural substances, such as sucrose, sorbitol or mannitol, using catalysts. Mention may be made here of basic catalysts and double metal cyanide catalysts, as described, for example, in WO 2006 / 034800, EP 0090444, or WO 2005 / 090440.

[0034] Polyesterols are produced, for example, from aliphatic or aromatic dicarboxylic acids and polyols, polythioether polyols, polyesteramides, hydroxylated polyacetals, and / or hydroxylated aliphatic polycarbonates, preferably in the presence of an esterification catalyst. Other possible polyols are mentioned, for example, in "Kunststoffhandbuch [Plastics handbook] [Plastics Handbook], Volume 7, Polyurethane [Polyurethanes] Polyurethane [Polyurethane]", Carl Hanser Verlag, 3rd edition, 1993, Chapter 3.1.

[0035] Alternatively, preferably, the one or more polymers contained in the solid material W are one or more polyurethane ureas. According to the present invention, there are no particular restrictions on the polyurethane ureas used in the method of the present invention. However, preferably, the polyurethane urea of ​​W is prepared by a process in which a polyisocyanate is reacted with a polyol in the presence of a catalyst as is well known in the art. Suitable polyisocyanates and suitable polyols, preferably polyether polyols, are as defined above and are known in the art.

[0036] Alternatively, preferably, the one or more polymers contained in the solid material W are one or more polyisocyanurates. According to the present invention, there are no particular restrictions on the polyisocyanurates used in the method of the present invention. However, preferably, the polyisocyanurates of W are prepared by a method in which polyisocyanates react with polyols in the presence of at least one catalyst as known in the art. Suitable polyisocyanates are those listed above. Other possible isocyanates are, for example, mentioned in "Kunststoffhandbuch [Plastics handbook] [Plastics Handbook], Vol. 7, Polyurethane [Polyurethanes] Polyurethane [Polyurethane]", Carl Hanser Verlag, 1993, 3rd edition, Chapters 3.2 and 3.3.2. Preferably, polyisocyanates are toluene 2,4- and / or 2,6-diisocyanate (TDI) or mixtures thereof, monomeric diphenylmethane diisocyanate, and / or diphenylmethane diisocyanate homologues (polymer MDI) with more rings, and mixtures of these. Suitable polyols for producing the polyisocyanurates of W are those known in the art, for example those listed in "Kunststoffhandbuch [Plastics handbook] [Plastics Handbook], Volume 7, Polyurethane [Polyurethanes] Polyurethane [Polyurethane]", Carl Hanser Verlag, 3rd edition 1993, Chapters 3.2 and 3.3.2. Preferably, the polyols for producing the polyisocyanurates of W are polyester polyols, such as branched polyester polyols based on terephthalic acid and having an OH number of 245 mg KOH / g.

[0037] In the context of the present invention, it is also conceivable that as another alternative, the one or more polymers contained in the solid material W are preferably a mixture of one or more of polyurethanes, polyisocyanurates and polyurethaneureas.

[0038] Preferably, the reactor unit R according to (ii) A The method comprises, more preferably consists of: one or more reactors, more preferably at least two reactors, more preferably two reactors, wherein more preferably at least two reactors are arranged in parallel.

[0039] Preferably, each of the one or more reactors is a stirred reactor, more preferably a stirred tank reactor.

[0040] Preferably, each of the one or more reactors is a heated reactor, an adiabatic reactor or an autoclave.

[0041] Preferably, the one or more primary amines used in (i.2) do not contain hydroxyl groups.

[0042] Preferably, the one or more primary amines used in (i.2) contain no hydroxyl groups and no aldehyde groups. More preferably, the one or more primary amines used in (i.2) contain no hydroxyl groups, no aldehyde groups and no ketone groups.

[0043] In other words, preferably, the atoms forming the one or more primary amines used in (i.2) are C, H and N.

[0044] Preferably, the one or more primary amines are selected from the group consisting of aliphatic monoamines, aliphatic polyamines, aromatic monoamines, aromatic polyamines and mixtures of two or more thereof, more preferably selected from the group consisting of aliphatic monoamines, aliphatic polyamines, aromatic monoamines and mixtures of two or more thereof, more preferably selected from the group consisting of aliphatic monoamines, aromatic monoamines and mixtures of two of them.

[0045] Preferably, the one or more primary amines are of the formula H2NR 1 The aliphatic monoamines

[0046] Where R 1 Choose from (C3-C 25 ) alkyl, phenyl, (C7-C 25 )aralkyl and (C7-C 25 )alkylaryl group, preferably selected from (C3-C 20 ) alkyl, (C8-C 22 )aralkyl and (C8-C 22 )alkylaryl, more preferably selected from the group consisting of (C3-C 10 ) alkyl, phenyl, (C 10 -C 20 )aralkyl and (C 10 -C 20 ) alkylaryl. More preferably, the aliphatic monoamine is selected from the group consisting of n-butylamine, cyclohexylamine, n-octylamine, n-hexylamine, n-propylamine, n-dodecylamine, n-tridecylamine, n-octadecylamine and a mixture of two or more thereof, more preferably selected from the group consisting of n-butylamine, n-octylamine, n-hexylamine and n-propylamine. More preferably, the aliphatic monoamine is n-butylamine.

[0047] Alternatively, preferably, the one or more primary amines are aromatic monoamines, wherein the aromatic monoamine is selected from the group consisting of aniline, toluidine, naphthylamine and mixtures of two or more thereof, wherein the aromatic monoamine is preferably aniline.

[0048] Alternatively, preferably, the one or more primary amines are aliphatic polyamines, wherein the aliphatic polyamine is selected from the group consisting of hexamethylenediamine, ethylenediamine, propylenediamine (such as propane-1,3-diamine, propane-1,2-diamine), isophoronediamine, butanediamine (such as butane-1,4-diamine, butane-1,3-diamine), pentanediamine, pentane-1,5-diamine, diaminocyclohexane (such as 1,2-diaminocyclohexane) and a mixture of two or more thereof, more preferably selected from the group consisting of hexamethylenediamine, ethylenediamine, propylenediamine and butanediamine, more preferably selected from the group consisting of hexamethylenediamine, ethylenediamine and propylenediamine; wherein the aliphatic polyamine is more preferably selected from the group consisting of ethylenediamine and propylenediamine.

[0049] In the context of the present invention, all isomers of the above-mentioned aliphatic polyamines are envisaged. Preferably, the propylenediamine is propane-1,3-diamine or propane-1,2-diamine.

[0050] Alternatively, preferably, the one or more primary amines are of the formula H2N-R 2 -NH2 aromatic polyamines,

[0051] Where R 2 Choose from (C3-C 25 ) alkylene, (C6-C 25 )aralkylene and (C6-C 25 )alkylene aryl group, preferably selected from the group consisting of (C8-C 22 ) alkylene, (C8-C 22 )aralkylene and (C8-C 22 ) alkylene aryl group, more preferably selected from the group consisting of (C 10 -C 20 ) alkylene, (C 10 -C 20 ) aralkylene and (C 10 -C 20 ) a group consisting of alkylene aryl groups,

[0052] Among them, the aromatic polyamine is more preferably selected from the group consisting of diaminotoluene, phenylenediamine and diaminodiphenylmethane, more preferably selected from the group consisting of diaminotoluene, phenylenediamine and 4,4'-diaminodiphenylmethane, more preferably diaminotoluene, and more preferably 2,4-diaminotoluene.

[0053] More preferably, the one or more primary amines are aromatic monoamines or aliphatic monoamines. More preferably, the primary amine used in (i.2) is aniline or n-butylamine.

[0054] Preferably, the introduction of R A The weight of the solid material W introduced in R AThe weight ratio of the one or more primary amines in the composition is in the range of 1:100 to 1:1, more preferably in the range of 1:40 to 1:3, more preferably in the range of 1:10 to 1:5.

[0055] Preferably, the aminolysis reaction according to (i.3) is carried out at a temperature in the range of 50°C to 250°C, more preferably in the range of 80°C to 200°C, more preferably in the range of 100°C to 220°C, more preferably in the range of 140°C to 200°C.

[0056] Preferably, the aminolysis reaction according to (i.3) is carried out at a pressure in the range of 1.0 to 25.0 bar (absolute pressure), more preferably in the range of 1.0 to 20.0 bar (absolute pressure), more preferably in the range of 1.0 to 18.0 bar (absolute pressure).

[0057] Preferably, the aminolysis reaction according to (i.3) is carried out for a duration in the range of 1 to 600 min, more preferably in the range of 20 to 450 min, more preferably in the range of 60 to 300 min.

[0058] Preferably, at most 0.1 wt-%, more preferably 0 to 0.01 wt-%, more preferably 0 to 0.001 wt-% of the mixture M obtained according to (i) consists of polymers selected from the group consisting of polyurethanes, polyurethaneureas and polyisocyanurates.

[0059] In other words, it is preferred that the mixture M is substantially free, more preferably free of polymers selected from the group consisting of polyurethanes and polyisocyanurates, meaning substantially free, preferably free of polyurethanes and polyisocyanurates. This is determined by analyzing the mixture M by IR spectroscopy: the mixture M has a relative humidity of 200-2400 cm -1 No NCO-stretching vibrations were present, which means that the reaction (aminolysis) was complete.

[0060] Preferably, (i) further comprises

[0061] (i.4) From R A The mixture M obtained according to (i.3) is taken out.

[0062] Preferably, the method further comprises, after (i.4) and before (ii),

[0063] According to (i.4) from R A The mixture M taken out from the solid-liquid separation unit is sent to obtain a liquid mixture M containing the one or more polyurea-containing compounds and the one or more polyols. SLS And a solid mixture containing impurities is obtained.

[0064] Preferably, the impurities are one or more of glass, sand, wood, metal, paper, inorganic solids and polymers other than polyurethane, polyurethane urea and polyisocyanurate. The polymers other than polyurethane, polyurethane urea and polyisocyanurate may be, for example, one or more of polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET) or polystyrene (PS).

[0065] Preferably, the solid-liquid separation unit is a filtration unit or a centrifuge, more preferably a filtration unit, more preferably a filter, more preferably a bag filter, a bag filter, a membrane filter, a candle filter, an agitated pressure filter, a vacuum belt filter, a plate and frame filter, or a suction filter.

[0066] Preferably, according to (i.4) from R A The mixture M taken out is sent to a solid-liquid separation unit at a temperature in the range of 50°C to 250°C, more preferably in the range of 80°C to 200°C, more preferably in the range of 100°C to 220°C, more preferably in the range of 140°C to 200°C.

[0067] Preferably, the solid-liquid separation is performed at a pressure in the range of 1.0 to 20.0 bar (absolute), more preferably in the range of 1.0 to 18.0 bar (absolute).

[0068] Preferably, (ii) comprises

[0069] (ii.1) Preferably, a solvent and the mixture M obtained according to (i), more preferably a liquid mixture M as defined above, are added. SLS into an evaporation unit EU, from which a vapor mixture V comprising the solvent and at least a portion of the one or more primary amines, and a liquid mixture M comprising the one or more polyurea-containing compounds and the one or more polyols are obtained EU ;

[0070] (ii.2) adding a solvent to the mixture M obtained according to (i), more preferably a liquid mixture M as defined above SLS , more preferably the liquid mixture M obtained according to (ii.1) EU allowing the one or more polyurea-containing compounds to precipitate to obtain a mixture comprising the one or more precipitated polyurea-containing compounds;

[0071] (ii.3) passing the mixture comprising the one or more precipitated polyurea-containing compounds obtained according to (ii.2) through a solid-liquid separation unit SLU to obtain a liquid mixture P comprising the one or more polyols and a solid mixture U comprising the one or more polyurea-containing compounds.

[0072] Preferably, the present invention relates to a method for producing one or more polymers from a solid material W, the one or more polymers being selected from the group consisting of polyurethanes, polyurethaneureas, polyisocyanurates and mixtures of two or more thereof, the method comprising

[0073] (i) preparing a mixture M comprising one or more polyurea-containing compounds from a solid material W, the mixture M further comprising one or more polyols, including:

[0074] (i.1) providing the solid material W comprising one or more polymers selected from the group consisting of polyurethane, polyurethaneurea, polyisocyanurate and a mixture of two or more thereof;

[0075] (i.2) In the reactor unit R A Introducing the solid material W provided in (i.1) and one or more primary amines to obtain a mixture, wherein more preferably the atoms forming the one or more primary amines are C, H and N;

[0076] (i.3) subjecting the mixture obtained according to (i.2) to R A subjecting the mixture to aminolysis reaction conditions to obtain a mixture M comprising one or more polyurea-containing compounds and further comprising one or more polyols;

[0077] (ii) separating the one or more polyurea-containing compounds of M obtained according to (i) from the one or more polyols of M obtained according to (i), wherein (ii) comprises

[0078] (ii.2) adding a solvent (more preferably having a water content in the range of 0 to 1000 ppm) to the mixture M obtained according to (i), allowing the one or more polyurea-containing compounds to precipitate, obtaining a mixture comprising one or more precipitated polyurea-containing compounds;

[0079] (ii.3) passing the mixture comprising the one or more precipitated polyurea-containing compounds obtained according to (ii.2) through a solid-liquid separation unit SLU to obtain a liquid mixture P comprising the one or more polyols and a solid mixture U comprising the one or more polyurea-containing compounds;

[0080] (iii) subjecting the mixture U obtained according to (ii) to a reactor unit R C subjecting the mixture to cleavage reaction conditions to obtain one or more corresponding polyamines or one or more corresponding polyisocyanates;

[0081] (iv) subjecting the mixture P obtained according to (ii) to purification conditions to obtain a purified mixture comprising one or more polyols;

[0082] (v) preparing one or more polymers selected from the group consisting of polyurethanes, polyurethaneureas, polyisocyanurates, and mixtures of two or more thereof, comprising:

[0083] (v.1) introducing the one or more polyols obtained according to (iv) into unit N PU middle;

[0084] (v.2) converting the one or more polyamines obtained according to (iii) into one or more polyisocyanates in a reactor to obtain one or more polyisocyanates, and introducing the one or more polyisocyanates obtained into N PU or

[0085] The one or more polyisocyanates obtained according to (iii) are introduced into N PU middle;

[0086] (v.3) According to (v.2), N is introduced PU The one or more polyisocyanates in (v.1) are introduced into N PU The one or more polyols in the mixture are contacted in the presence of a catalyst for polymerization to obtain one or more polymers selected from the group consisting of polyurethane, polyurethane urea, polyisocyanurate and a mixture of two or more thereof.

[0087] More preferably, the present invention relates to a method for producing one or more polymers from a solid material W, the one or more polymers being selected from the group consisting of polyurethanes, polyurethaneureas, polyisocyanurates and mixtures of two or more thereof, the method comprising

[0088] (i) preparing a mixture M comprising one or more polyurea-containing compounds from a solid material W, the mixture M further comprising one or more polyols, including:

[0089] (i.1) providing the solid material W comprising one or more polymers selected from the group consisting of polyurethane, polyurethaneurea, polyisocyanurate and a mixture of two or more thereof;

[0090] (i.2) In the reactor unit R A Introducing the solid material W provided in (i.1) and one or more primary amines to obtain a mixture, wherein more preferably the atoms forming the one or more primary amines are C, H and N;

[0091] (i.3) subjecting the mixture obtained according to (i.2) to R Asubjecting the mixture to aminolysis reaction conditions to obtain a mixture M comprising one or more polyurea-containing compounds and further comprising one or more polyols;

[0092] (ii) separating the one or more polyurea-containing compounds of M obtained according to (i) from the one or more polyols of M obtained according to (i), wherein (ii) comprises

[0093] (ii.1) a solvent (more preferably having a water content in the range of 0 to 1000 ppm) and the mixture M obtained according to (i), more preferably a liquid mixture M as defined above SLS into an evaporation unit EU, from which a vapor mixture V comprising the solvent and at least a portion of the one or more primary amines, and a liquid mixture M comprising the one or more polyurea-containing compounds and the one or more polyols are obtained EU ;

[0094] (ii.2) adding a solvent (more preferably having a water content in the range of 0 to 1000 ppm) to the liquid mixture M obtained according to (ii.1) EU allowing the one or more polyurea-containing compounds to precipitate to obtain a mixture comprising the one or more precipitated polyurea-containing compounds;

[0095] (ii.3) passing the mixture comprising the one or more precipitated polyurea-containing compounds obtained according to (ii.2) through a solid-liquid separation unit SLU to obtain a liquid mixture P comprising the one or more polyols and a solid mixture U comprising the one or more polyurea-containing compounds;

[0096] (iii) subjecting the mixture U obtained according to (ii) to a reactor unit R C subjecting the mixture to cleavage reaction conditions to obtain one or more corresponding polyamines or one or more corresponding polyisocyanates;

[0097] (iv) subjecting the mixture P obtained according to (ii) to purification conditions to obtain a purified mixture comprising one or more polyols;

[0098] (v) preparing one or more polymers selected from the group consisting of polyurethanes, polyurethaneureas, polyisocyanurates, and mixtures of two or more thereof, comprising:

[0099] (v.1) introducing the one or more polyols obtained according to (iv) into unit N PU middle;

[0100] (v.2) converting the one or more polyamines obtained according to (iii) into one or more polyisocyanates in a reactor to obtain one or more polyisocyanates, and introducing the one or more polyisocyanates obtained into N PU or

[0101] The one or more polyisocyanates obtained according to (iii) are introduced into N PU middle;

[0102] (v.3) According to (v.2), N is introduced PU The one or more polyisocyanates in (v.1) are introduced into N PU The one or more polyols in the mixture are contacted in the presence of a catalyst for polymerization to obtain one or more polymers selected from the group consisting of polyurethane, polyurethane urea, polyisocyanurate and a mixture of two or more thereof.

[0103] In the context of the present invention, preferably, the liquid mixture M EU Contains a liquid mixture based on M EU At most 10 wt-%, more preferably at most 8 wt-%, more preferably at most 5 wt-%, more preferably from 0 to 5 wt-% of the one or more primary amines by weight.

[0104] Preferably, the evaporation in the EU according to (ii.1) is carried out under a pressure difference, which is the difference between the pressure before the evaporation unit and the pressure at the evaporation unit, which is in the range of 0 to 30 bar (absolute pressure), preferably in the range of 0.1 to 25 bar (absolute pressure), more preferably in the range of 0.2 to 20 bar (absolute pressure).

[0105] Preferably, the solvent used in one or more of (ii.1) and (ii.2), more preferably in (ii.1) and (ii.2), has a water content in the range of 0 to 1000 ppm, more preferably in the range of 0 to 500 ppm, more preferably in the range of 0 to 100 ppm. In the context of the present invention, the solvent is therefore preferably an anhydrous solvent.

[0106] Preferably, in one or more of (ii.1) and (ii.2), more preferably the solvent used in (ii.1) and (ii.2) is selected from the group consisting of hydrocarbons, ketones and ethers, more preferably selected from the group consisting of xylene, toluene, n-heptane, methyl ethyl ketone (MEK), dioxane, benzene, hept-2-one and a mixture of two or more thereof, more preferably selected from the group consisting of xylene, toluene, n-heptane, benzene and a mixture of two or more thereof, more preferably xylene or toluene or benzene.

[0107] Preferably, the evaporation unit EU used in (ii.1) is one or more of a reactor equipped with a filter, a fractional distillation column and a flash drum, more preferably a reactor equipped with a filter, more preferably a stirred tank reactor equipped with a filter (such as a wire mesh).

[0108] Preferably, for (ii.1), the amount of solvent added is calculated based on the weight ratio of the solvent relative to the one or more polymers of W provided according to (i), which weight ratio is in the range of 0.1:1 to 50:1, more preferably in the range of 1:1 to 20:1, more preferably in the range of 1:1 to 15:1, and more preferably in the range of 1:1 to 10:1.

[0109] Preferably, for (ii.2), the amount of solvent added is calculated based on the weight ratio of the solvent relative to the one or more polymers of W provided according to (i), which weight ratio is in the range of 0.1:1 to 50:1, more preferably in the range of 1:1 to 20:1, more preferably in the range of 1:1 to 15:1, and more preferably in the range of 1:1 to 10:1.

[0110] Preferably, the solid-liquid separation unit SLU in (ii.3) is a filter.

[0111] Preferably, at most 0.1 wt.-%, more preferably 0 to 0.01 wt.-%, more preferably 0 to 0.001 wt.-% of the mixture U consists of polyols. In other words, it is preferred that the mixture U contains essentially no, more preferably no, polyols. This can be achieved, for example, by 13 C_NMR or HPLC.

[0112] Preferably, the process further comprises, after (ii) and before (iii), washing the mixture U obtained according to (ii) on the SLU with a solvent, wherein the solvent is selected from the group consisting of hydrocarbons, ketones and ethers, more preferably selected from the group consisting of benzene, xylene, toluene, n-heptane, methyl ethyl ketone (MEK), dioxane, hept-2-one and mixtures of two or more thereof, preferably selected from the group consisting of xylene, toluene, n-heptane, benzene and mixtures of two or more thereof, more preferably benzene, xylene or toluene.

[0113] Preferably, the solvent has a water content in the range of 0 to 1000 ppm, more preferably in the range of 0 to 500 ppm, more preferably in the range of 0 to 100 ppm. In the context of the present invention, the solvent is therefore preferably an anhydrous solvent.

[0114] Preferably, the solvent is the same as used in (ii.1) and (ii.2).

[0115] More preferably, the ratio of the weight of the solvent relative to the weight of the solid mixture U is in the range of 0.01:1 to 100:1, more preferably in the range of 0.1:1 to 10:1, more preferably in the range of 1:1 to 5:1.

[0116] Preferably, the reactor unit R C It comprises one or more reactors, more preferably at least two reactors, more preferably in the range of 2 to 5 reactors, more preferably two reactors, and at least two reactors are more preferably arranged in parallel.

[0117] Preferably, R C , EU and SLU are three unique units, among which EU is located upstream of SLU, which is located upstream of Rc.

[0118] Alternatively, preferably, R C For (v) as one or more of an evaporation unit EU and a solid-liquid separation unit SLU, preferably as an evaporation unit EU and a solid-liquid separation unit SLU. Therefore, more preferably (v) and (vi) are carried out in the same unit, which is more preferably a stirred tank reactor equipped with a filter.

[0119] Preferably, the cleavage reaction conditions according to (iii) are hydrolysis reaction conditions.

[0120] Preferably, (iii) comprises

[0121] water and the mixture U obtained according to (ii) comprising the one or more polyurea-containing compounds in R C The method comprises mixing a polyamine with water, wherein the weight ratio of water to the one or more polyurea-containing compounds is in the range of 1:1 to 50:1, more preferably in the range of 5:1 to 20:1, more preferably in the range of 10:1 to 18:1, to obtain a mixture containing one or more corresponding polyamines.

[0122] Preferably, the hydrolysis is carried out at a temperature in the range of 150°C to 350°C, more preferably in the range of 210°C to 290°C, more preferably in the range of 230°C to 270°C.

[0123] Preferably, the hydrolysis is carried out at a pressure in the range of 20 to 70 bar (absolute), more preferably in the range of 25 to 65 bar (absolute), more preferably in the range of 30 to 60 bar (absolute).

[0124] Preferably, the hydrolysis is carried out for a duration in the range of 0.1 to 15 h, more preferably in the range of 0.25 to 10 h, more preferably in the range of 0.5 to 8 h.

[0125] Alternatively, preferably, the cleavage reaction conditions according to (iii) are acidic cleavage conditions. More preferably, (iii) comprises

[0126] The Bronsted acid is mixed with a mixture U comprising one or more polyurea-containing compounds obtained according to (ii) in R C The Brønsted acid is preferably selected from the group consisting of hydrochloric acid, sulfonic acid and mixtures thereof, to obtain a mixture comprising one or more corresponding polyisocyanates.

[0127] Preferably, the sulfonic acid is one or more of methanesulfonic acid, toluenesulfonic acid and trifluoromethanesulfonic acid.

[0128] Alternatively, preferably, the cleavage reaction conditions according to (iii) are alkaline cleavage conditions. More preferably, (iii) comprises

[0129] The Brønsted base is mixed with a solid mixture U obtained according to (ii) comprising one or more polyurea-containing compounds in R C The Brønsted base is mixed with water, wherein the Brønsted base has a pH value in the range of 8 to 12 in water, to obtain a mixture comprising one or more corresponding polyisocyanates.

[0130] Examples of bases for the cleavage reaction are alkali metal hydroxides, alkaline earth metal hydroxides, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]octane (DABCO), triethylamine and primary amines as defined above for the aminolysis reaction.

[0131] Preferably, (iii) further comprises

[0132] The mixture comprising the one or more corresponding polyamines is fed to an evaporation unit from which a vapour mixture comprising water and at least a portion of the one or more primary amines, and a liquid mixture comprising the one or more polyamines are obtained. Preferably, the evaporation unit is one or more of a flash tank and a fractional distillation column.

[0133] In the context of the present invention it is noted that further extraction / purification known to those skilled in the art may be performed to further remove trace impurities.

[0134] Preferably, (iv) comprises

[0135] The mixture P obtained according to (ii) is sent to a purification unit PU(1) to separate the one or more polyols from the liquid mixture P, obtaining a mixture comprising the one or more polyols, reduced by at least a portion of compounds other than polyols.

[0136] Preferably, purification unit PU(1) comprises a distillation column, more preferably is a distillation column.

[0137] Preferably, (iv) comprises

[0138] The liquid mixture P obtained according to (ii) is fed to a purification unit PU (1) to obtain a liquid mixture comprising one or more polyols, reduced by at least a portion of the solvent, and a vapor mixture V comprising at least a portion of the solvent. S .

[0139] Preferably, (iv) further comprises

[0140] The vapor mixture V comprising at least a portion of the solvent S feeding into a purification unit PU (2) to obtain a liquid mixture containing the solvent;

[0141] The liquid mixture obtained is introduced into a storage tank, more preferably before being used as solvent in (ii.1) and / or (ii.2).

[0142] Preferably, (v.2) includes

[0143] (v.2.1) mixing a solvent into the one or more polyamines obtained according to (iii) and stirring, more preferably at a temperature in the range of 50°C to 180°C, more preferably in the range of 70°C to 140°C, more preferably in the range of 80°C to 120°C, to obtain a polyamine mixture;

[0144] (v.2.2) contacting the polyamine mixture obtained according to (v.2.1) with phosgene in a reactor and heating the obtained mixture to a temperature in the range of 90° C. to 140° C., more preferably in the range of 110° C. to 130° C., to obtain a mixture comprising one or more polyisocyanates;

[0145] (v.2.3) introducing the one or more polyisocyanates obtained according to (v.2.2) into N PU middle.

[0146] Preferably, (v.2.2) further comprises

[0147] The mixture comprising the one or more polyisocyanates is purified to obtain a mixture comprising the one or more polyisocyanates and reduced in at least a portion of compounds other than polyisocyanates.

[0148] More preferably, (v.2.2) further comprises

[0149] Removing at least a portion of the solvent from the mixture comprising the one or more polyisocyanates and reducing at least a portion of the compounds other than polyisocyanates, a mixture comprising the one or more polyisocyanates is obtained, wherein 80 to 100 weight-%, preferably 85 to 99 weight-%, more preferably 90 to 98 weight-% of the mixture consists of the one or more polyisocyanates.

[0150] Preferably, the solvent is selected from the group consisting of monochlorobenzene, toluene, o- or p-dichlorobenzene, trichlorobenzene, chlorotoluene, chloroxylene, chloroethylbenzene, chloronaphthalene, chlorinated biphenyls, xylene, decalin, benzene and a mixture of two or more thereof, preferably selected from the group consisting of monochlorobenzene, toluene and o-dichlorobenzene. More preferably, the solvent is monochlorobenzene.

[0151] Alternatively, preferably, (v.2) is gas phase phosgenation, gas-liquid phosgenation, phosgenation via salt or phosgene-free conversion. These reactions are known to those skilled in the art. Examples of gas-liquid phosgenation methods are disclosed in WO 2022 / 106716, examples of gas phase phosgenation methods are disclosed in EP 1761483 B1, EP 2079684 B1, EP 2188247 B1, EP2408738 B1 and EP 2539314 B1, and examples of phosgene-free conversion are disclosed in WO 2018 / 185168 and EP 3250 622 B1.

[0152] Preferably, (v.2) comprises introducing the one or more polyisocyanates obtained according to (iii) into N PU middle.

[0153] Preferably, unit N PU It is a mixing nozzle.

[0154] Preferably, the catalyst used in (v.3) is one or more of 1,4-diazabicyclo[2.2.2]octane (DABCO), stannous octoate, stannous ricinoleate, bis(2-dimethylaminoethyl)ether and potassium acetate.

[0155] The present invention is further illustrated by the following groups of embodiments and the combination of embodiments obtained by the dependencies and back-references as shown. In particular, it should be noted that in each case where a series of embodiments is mentioned, for example, in the context of a term such as "a method as described in any one of embodiments 1 to 4", each embodiment in this series is intended to be clearly disclosed to the technician, that is, the wording of this term should be understood by the technician as synonymous with "a method as described in any one of embodiments 1, 2, 3 and 4". In addition, it should be clearly pointed out that the following group of embodiments represents a suitable structural part of the general description of the preferred aspects of the present invention, and therefore appropriately supports but does not represent the claims of the present invention.

[0156] 1. A method for producing one or more polymers from a solid material W, the one or more polymers being selected from the group consisting of polyurethanes, polyurethane ureas, polyisocyanurates and mixtures of two or more thereof, the method comprising

[0157] (i) preparing a mixture M comprising one or more polyurea-containing compounds from a solid material W, the mixture M further comprising one or more polyols, including:

[0158] (i.1) providing the solid material W comprising one or more polymers selected from the group consisting of polyurethane, polyurethaneurea, polyisocyanurate and a mixture of two or more thereof;

[0159] (i.2) In the reactor unit R A introducing the solid material W provided in (i.1) and one or more primary amines to obtain a mixture;

[0160] (i.3) subjecting the mixture obtained according to (i.2) to R A subjecting the mixture to aminolysis reaction conditions to obtain a mixture M comprising one or more polyurea-containing compounds and further comprising one or more polyols;

[0161] (ii) separating the one or more polyurea-containing compounds of M obtained according to (i) from the one or more polyols of M obtained according to (i) to obtain a mixture U comprising the one or more polyurea-containing compounds and a mixture P comprising the one or more polyols;

[0162] (iii) subjecting the mixture U obtained according to (ii) to a reactor unit R C subjecting the mixture to cleavage reaction conditions to obtain one or more corresponding polyamines or one or more corresponding polyisocyanates;

[0163] (iv) subjecting the mixture P obtained according to (ii) to purification conditions to obtain a purified mixture comprising one or more polyols;

[0164] (v) preparing one or more polymers selected from the group consisting of polyurethanes, polyurethaneureas, polyisocyanurates, and mixtures of two or more thereof, comprising:

[0165] (v.1) introducing the one or more polyols obtained according to (iv) into unit N PU middle;

[0166] (v.2) converting the one or more polyamines obtained according to (iii) into one or more polyisocyanates in a reactor to obtain one or more polyisocyanates, and introducing the one or more polyisocyanates obtained into N PU or

[0167] The one or more polyisocyanates obtained according to (iii) are introduced into N PU middle;

[0168] (v.3) According to (v.2), N is introduced PU The one or more polyisocyanates in (v.1) are introduced into N PU The one or more polyols in the mixture are contacted in the presence of a catalyst for polymerization to obtain one or more polymers selected from the group consisting of polyurethane, polyurethane urea, polyisocyanurate and a mixture of two or more thereof.

[0169] 2. The method as described in Example 1 further comprises, before (i), subjecting the solid material W to pretreatment, preferably mechanical pretreatment, wherein the mechanical pretreatment comprises grinding, crushing, chopping and cutting, preferably grinding or chopping the solid material W. One or more.

[0170] 3. The method as described in Example 1 or 2 further comprises, before (i), preferably after subjecting the solid material W to the pretreatment as defined in Example 2, drying the solid material W, wherein the drying is preferably carried out at a temperature in the range of 40°C to 100°C, more preferably in the range of 50°C to 85°C, and wherein the drying is more preferably carried out in a gas atmosphere comprising one or more of nitrogen and oxygen, more preferably in air.

[0171] 4. The method of any one of embodiments 1 to 3, wherein the solid material W is waste solid material.

[0172] 5. The method of any one of embodiments 1 to 4, wherein the one or more polymers contained in the solid material W are one or more polyurethanes; wherein the one or more polyurethanes are thermosetting materials or elastomers.

[0173] 6. The method of any one of embodiments 1 to 4, wherein the one or more polymers contained in the solid material W are one or more polyurethane ureas.

[0174] 7. The method of any one of embodiments 1 to 4, wherein the one or more polymers contained in the solid material W are one or more polyisocyanurates.

[0175] 8. The method according to any one of embodiments 1 to 7, wherein the reactor unit R according to (ii) A It comprises, preferably consists of: one or more reactors, preferably at least two reactors, more preferably two reactors, wherein preferably the at least two reactors are arranged in parallel.

[0176] 9. The method of embodiment 8, wherein each of the one or more reactors is a stirred reactor, more preferably a stirred tank reactor.

[0177] 10. The method of embodiment 8 or 9, wherein each of the one or more reactors is a heated reactor, an adiabatic reactor, or an autoclave.

[0178] 11. The method of any one of embodiments 1 to 10, wherein the one or more primary amines used in (i.2) do not contain hydroxyl groups, preferably wherein the atoms forming the one or more primary amines used in (i.2) are C, H and N.

[0179] 12. The method of any one of embodiments 1 to 11, wherein the one or more primary amines are selected from the group consisting of aliphatic monoamines, aliphatic polyamines, aromatic monoamines, aromatic polyamines, and mixtures of two or more thereof, preferably selected from the group consisting of aliphatic monoamines, aliphatic polyamines, aromatic monoamines, and mixtures of two or more thereof, more preferably selected from the group consisting of aliphatic monoamines, aromatic monoamines, and mixtures of two or more thereof.

[0180] 13. The method of embodiment 12, wherein the one or more primary amines are of the formula H2NR 1 The aliphatic monoamines

[0181] Where R 1 Choose from (C3-C 25 ) alkyl, phenyl, (C7-C 25 )aralkyl and (C7-C 25 )alkylaryl group, preferably selected from (C3-C 20 ) alkyl, (C8-C 22 )aralkyl and (C8-C 22 )alkylaryl, more preferably selected from the group consisting of (C3-C 10 ) alkyl, phenyl, (C 10 -C 20 )aralkyl and (C 10 -C 20 ) a group consisting of an alkylaryl group,

[0182] Wherein more preferably the aliphatic monoamine is selected from the group consisting of n-butylamine, cyclohexylamine, n-octylamine, n-hexylamine, n-propylamine, n-dodecylamine, n-tridecylamine, n-octadecylamine and a mixture of two or more thereof, more preferably selected from the group consisting of n-butylamine, n-octylamine, n-hexylamine and n-propylamine, wherein more preferably the aliphatic monoamine is n-butylamine.

[0183] 14. The method of embodiment 12, wherein the one or more primary amines are aromatic monoamines, wherein the aromatic monoamines are selected from the group consisting of aniline, toluidine, naphthylamine, and mixtures of two or more thereof, wherein the aromatic monoamine is preferably aniline.

[0184] 15. A method as described in Example 12, wherein the one or more primary amines are aliphatic polyamines, wherein the aliphatic polyamine is selected from the group consisting of hexamethylenediamine, ethylenediamine, propylenediamine, isophoronediamine, butanediamine, pentamethylenediamine, diaminocyclohexane and a mixture of two or more thereof, more preferably selected from the group consisting of hexamethylenediamine, ethylenediamine, propylenediamine and butanediamine, more preferably selected from the group consisting of hexamethylenediamine, ethylenediamine and propylenediamine; wherein the aliphatic polyamine is more preferably selected from the group consisting of ethylenediamine and propylenediamine.

[0185] 16. The method of embodiment 12, wherein the one or more primary amines are of the formula H2N-R 2 -NH2 aromatic polyamines,

[0186] Where R 2 Choose from (C3-C 25 ) alkylene, (C6-C 25 )aralkylene and (C6-C 25 )alkylene aryl group, preferably selected from the group consisting of (C8-C 22 ) alkylene, (C8-C 22 )aralkylene and (C8-C 22 ) alkylene aryl group, more preferably selected from the group consisting of (C 10 -C 20 ) alkylene, (C 10 -C 20 ) aralkylene and (C 10 -C 20 ) a group consisting of alkylene aryl groups,

[0187] Among them, the aromatic polyamine is more preferably selected from the group consisting of diaminotoluene, phenylenediamine and diaminodiphenylmethane, more preferably selected from the group consisting of diaminotoluene, phenylenediamine and 4,4'-diaminodiphenylmethane, more preferably diaminotoluene, and more preferably 2,4-diaminotoluene.

[0188] 17. The method of any one of embodiments 1 to 16, wherein RA The weight of the solid material W in R A The ratio by weight of the one or more primary amines in the formula (I) is in the range of 1:100 to 1:1, preferably in the range of 1:40 to 1:3, more preferably in the range of 1:10 to 1:5.

[0189] 18. A method as described in any one of Examples 1 to 17, wherein the aminolysis reaction according to (i.3) is carried out at a temperature in the range of 50°C to 250°C, preferably in the range of 80°C to 200°C, more preferably in the range of 100°C to 220°C, more preferably in the range of 140°C to 200°C.

[0190] 19. A method as described in any one of embodiments 1 to 18, wherein the aminolysis reaction according to (i.3) is carried out at a pressure in the range of 1.0 to 25.0 bar (absolute pressure), preferably in the range of 1.0 to 20.0 bar (absolute pressure), and more preferably in the range of 1.0 to 18.0 bar (absolute pressure).

[0191] 20. The method of any one of embodiments 1 to 19, wherein the aminolysis reaction according to (i.3) is carried out for a duration in the range of 1 to 600 min, preferably in the range of 20 to 450 min, more preferably in the range of 60 to 300 min.

[0192] 21. The process of any one of embodiments 1 to 20, wherein at most 0.1 wt.-%, preferably 0 to 0.01 wt.-%, more preferably 0 to 0.001 wt.-% of the mixture M obtained according to (i) consists of a polymer selected from the group consisting of polyurethanes, polyurethane ureas and polyisocyanurates.

[0193] 22. The method of any one of embodiments 1 to 21, wherein (i) further comprises (i.4) A The mixture M obtained according to (i.3) is taken out.

[0194] 23. The method of embodiment 22 further comprises, after (i.4) and before (ii), converting the product obtained from R according to (i.4) to A The mixture M taken out from the solid-liquid separation unit is sent to obtain a liquid mixture M containing the one or more polyurea-containing compounds and the one or more polyols. SLS And a solid mixture containing impurities is obtained.

[0195] 24. The method of embodiment 23, wherein the AThe mixture M taken out is sent to a solid-liquid separation unit at a temperature in the range of 50°C to 250°C, preferably in the range of 80°C to 200°C, more preferably in the range of 100°C to 220°C, and more preferably in the range of 140°C to 200°C.

[0196] 25. The method of any one of embodiments 1 to 24, wherein (ii) comprises

[0197] (ii.1) Preferably, the solvent and the mixture M, preferably a liquid mixture M as defined in Example 23, are mixed. SLS into an evaporation unit EU, from which a vapor mixture V comprising the solvent and at least a portion of the one or more primary amines, and a liquid mixture M comprising the one or more polyurea-containing compounds and the one or more polyols are obtained EU ;

[0198] (ii.2) adding a solvent to the mixture M, preferably a liquid mixture M as defined in Example 23 SLS , more preferably the liquid mixture M obtained according to (ii.1) EU allowing the one or more polyurea-containing compounds to precipitate to obtain a mixture comprising the one or more precipitated polyurea-containing compounds;

[0199] (ii.3) passing the mixture comprising the one or more precipitated polyurea-containing compounds obtained according to (ii.2) through a solid-liquid separation unit SLU to obtain a liquid mixture P comprising the one or more polyols and a solid mixture U comprising the one or more polyurea-containing compounds.

[0200] 26. A method as described in Example 25, wherein in one or more of (ii.1) and (ii.2), preferably the solvent used in (ii.1) and (ii.2) is selected from the group consisting of hydrocarbons, ketones and ethers, more preferably selected from the group consisting of xylene, toluene, n-heptane, methyl ethyl ketone (MEK), dioxane, benzene, hept-2-one and mixtures of two or more thereof, preferably selected from the group consisting of xylene, toluene, n-heptane, benzene and mixtures of two or more thereof, more preferably xylene or toluene or benzene; and / or wherein in one or more of (ii.1) and (ii.2), preferably the solvent used in (ii.1) and (ii.2) has a water content in the range of 0 to 1000 ppm, preferably in the range of 0 to 500 ppm, more preferably in the range of 0 to 100 ppm.

[0201] 27. A method as described in Example 25 or 26, wherein for (ii.1), the amount of the solvent added is calculated based on the weight ratio of the solvent relative to the one or more polymers W provided according to (i), and the weight ratio is in the range of 0.1:1 to 50:1, preferably in the range of 1:1 to 20:1, more preferably in the range of 1:1 to 15:1, and more preferably in the range of 1:1 to 10:1.

[0202] 28. A method as described in any of embodiments 25 to 27, wherein for (ii.2), the amount of the solvent added is calculated based on the weight ratio of the solvent relative to the one or more polymers of W provided according to (i), and the weight ratio is in the range of 0.1:1 to 50:1, preferably in the range of 1:1 to 20:1, more preferably in the range of 1:1 to 15:1, and more preferably in the range of 1:1 to 10:1.

[0203] 29. The process of any one of embodiments 1 to 28, wherein at most 0.1 wt-%, preferably 0 to 0.01 wt-%, more preferably 0 to 0.001 wt-% of the mixture U consists of polyols.

[0204] 30. The method of any one of embodiments 1 to 29, wherein the cleavage reaction conditions according to (iii) are hydrolysis reaction conditions.

[0205] 31. The method of embodiment 30, wherein (iii) comprises

[0206] water and the mixture U obtained according to (ii) comprising the one or more polyurea-containing compounds in R C wherein the weight ratio of water to the one or more polyurea-containing compounds is in the range of 1:1 to 50:1, preferably in the range of 5:1 to 20:1, more preferably in the range of 10:1 to 18:1, to obtain a mixture comprising one or more corresponding polyamines;

[0207] wherein preferably the hydrolysis is carried out at a temperature in the range of 150°C to 350°C, more preferably in the range of 210°C to 290°C, more preferably in the range of 230°C to 270°C;

[0208] wherein more preferably the hydrolysis is carried out at a pressure in the range of 20 to 70 bar (absolute pressure), more preferably in the range of 25 to 65 bar (absolute pressure), more preferably in the range of 30 to 60 bar (absolute pressure);

[0209] Therein more preferably the hydrolysis is carried out for a duration in the range of 0.1 to 15 h, more preferably in the range of 0.25 to 10 h, more preferably in the range of 0.5 to 8 h.

[0210] 32. The method of any one of embodiments 1 to 29, wherein the cleavage reaction conditions according to (iii) are acidic cleavage conditions.

[0211] 33. The method of embodiment 32, wherein (iii) comprises

[0212] The Bronsted acid is reacted with the mixture U obtained according to (ii) comprising the one or more polyurea-containing compounds in R C The Brønsted acid is preferably selected from the group consisting of hydrochloric acid, sulfonic acid and mixtures thereof to obtain a mixture comprising one or more corresponding polyisocyanates.

[0213] 34. The method of any one of embodiments 1 to 33, wherein (iv) comprises

[0214] The mixture P obtained according to (ii) is sent to a purification unit PU(1) to separate the one or more polyols from the liquid mixture P, obtaining a mixture comprising the one or more polyols, reduced by at least a portion of compounds other than polyols.

[0215] 35. The process according to embodiment 34, wherein the purification unit PU (1) comprises a distillation column, more preferably a distillation column.

[0216] 36. The method of embodiment 34 or 35, insofar as embodiment 34 or 35 is dependent upon embodiment 24, wherein (iv) comprises

[0217] The liquid mixture P obtained according to (ii) is fed to a purification unit PU (1) to obtain a liquid mixture comprising one or more polyols, reduced by at least a portion of the solvent, and a vapor mixture V comprising at least a portion of the solvent. S .

[0218] 37. The method of embodiment 36, wherein (iv) further comprises

[0219] The vapor mixture V comprising at least a portion of the solvent S feeding into a purification unit PU (2) to obtain a liquid mixture containing the solvent;

[0220] The liquid mixture obtained is introduced into a storage tank, preferably before being used as solvent in (ii.1) and / or (ii.2).

[0221] 36. The method of any one of embodiments 1 to 35, wherein (v.2) comprises

[0222] (v.2.1) mixing a solvent into the one or more polyamines obtained according to (iii) and stirring, preferably at a temperature in the range of 50°C to 180°C, more preferably in the range of 70°C to 140°C, more preferably in the range of 80°C to 120°C, to obtain a polyamine mixture;

[0223] (v.2.2) contacting the polyamine mixture obtained according to (v.2.1) with phosgene in a reactor and heating the obtained mixture to a temperature in the range of 90° C. to 140° C., preferably in the range of 110° C. to 130° C., to obtain a mixture comprising one or more polyisocyanates;

[0224] (v.2.3) introducing the one or more polyisocyanates obtained according to (v.2.2) into N PU middle.

[0225] 37. The method of embodiment 36, wherein (v.2.2) further comprises

[0226] The mixture comprising the one or more polyisocyanates is purified to obtain a mixture comprising the one or more polyisocyanates and reduced in at least a portion of compounds other than polyisocyanates.

[0227] 38. The method of embodiment 37, wherein (v.2.2) further comprises

[0228] Removing at least a portion of the solvent from the mixture comprising the one or more polyisocyanates and reducing at least a portion of the compounds other than the polyisocyanates to obtain a mixture comprising the one or more polyisocyanates, wherein 80 to 100 wt-%, preferably 85 to 99 wt-%, more preferably 90 to 98 wt-% of the mixture

[0229] The weight-% consists of the one or more polyisocyanates.

[0230] 39. The method of any one of embodiments 36 to 38, wherein the solvent is selected from the group consisting of monochlorobenzene, toluene, o- or p-dichlorobenzene, trichlorobenzene, chlorotoluene, chloroxylene, chloroethylbenzene, chloronaphthalene, chlorinated biphenyls, xylene, decalin, benzene, and a mixture of two or more thereof, preferably selected from the group consisting of monochlorobenzene, toluene, and o-dichlorobenzene.

[0231] 40. The method of embodiment 39, wherein the solvent is monochlorobenzene.

[0232] 41. The method of any one of embodiments 1 to 35, wherein (v.2) comprises introducing the one or more polyisocyanates obtained according to (iii) into N PU middle.

[0233] 42. The method of any one of embodiments 1 to 41, wherein the unit N PU It is a mixing nozzle.

[0234] 43. The method of any one of embodiments 1 to 42, wherein the catalyst used in (v.3) is one or more of 1,4-diazabicyclo[2.2.2]octane (DABCO), stannous octoate, stannous ricinoleate, bis(2-dimethylaminoethyl)ether, and potassium acetate.

[0235] In the context of the present invention, polyurethane may be abbreviated as PUR or PU and refers to a class of polymers containing urethane (urethane) bonds. In addition, polyisocyanurate may be abbreviated as PIR and refers to polymers containing isocyanurate groups.

[0236] In the context of the present invention, urea is an organic compound of formula (RR'N)2CO, wherein R and R' are independently hydrogen or an organic residue, such as an alkyl residue or an aryl residue. Thus, this definition includes the specific compound ((H2N)2CO).

[0237] In addition, in the context of the present invention, PMDI refers to polymeric diphenylmethane diisocyanate, also referred to as industrial MDI, which is a mixture of methylene diphenyl diisocyanate and homologous aromatic polyisocyanates. Therefore, it is a mixture of compounds with several (usually up to 6) phenylene groups, each of which has an isocyanate group.

[0238] Furthermore, in the context of the present invention, the term "polyurea-containing compound" refers to a compound, preferably a polymer, comprising at least two urea groups. In particular, in the context of the present invention, a polyurea-containing compound, preferably a polyurea-containing polymer, is preferably a compound derived from a polyurethane subjected to aminolysis.

[0239] In the context of the present invention, the term "primary amine" includes "primary monoamine" and "primary polyamine". As is well known in the art, primary amine refers to a compound having one or more amino groups, wherein the nitrogen atom is directly bonded to only one C atom.

[0240] In the context of the present invention, an alkyl group consists of carbon atoms and hydrogen atoms.

[0241] Furthermore, in the context of the present invention, the term "X is (or comprises) one or more of A, B and C", where X is a given feature and each of A, B and C represents a specific implementation of the feature, should be understood as disclosing that X is (or comprises) A, or B, or C, or A and B, or A and C, or B and C, or A and B and C. In this regard, it should be noted that a skilled person is able to convert the above abstract terms into specific examples, for example, where X is a chemical element and A, B and C are specific elements such as Li, Na and K, or X is a temperature and A, B and C are specific temperatures such as 10°C, 20°C and 30°C. In this regard, it is further noted that the skilled person is able to expand the above terms to less specific implementations of the features, such as “X is (or includes) one or more of A and B”, which discloses that X is (or includes) A, or B, or A and B, or to more specific implementations of the features, such as “X is (or includes) one or more of A, B, C, and D”, which discloses that X is A, or B, or C, or D, or A and B, or A and C, or A and D, or B and C, or B and D, or C and D, or A and B and C, or A and B and D, or B and C and D.

[0242] The present invention is further illustrated by the following examples.

[0243] Examples

[0244] Reference Example 1: Determination of FTIR spectrum

[0245] IR spectroscopy was performed to determine the conversion of the amination and aminolysis reactions.

[0246] For urea synthesis, at 2200-2400cm -1 The absence of NCO stretching vibrations indicates complete conversion of the corresponding isocyanate component (eg M20S).

[0247] For aminolysis, the urethane vibration (1700-1750 cm -1 ) is related to the conversion rate.

[0248] For the solubility test, the solubility of polyurea is characterized by the presence of characteristic carbonyl vibrations (1600-1700 cm -1 ). The area of ​​this vibration is related to the mass fraction of urea. In order to determine that the carbonyl vibration is characteristic of the solubility of urea, the IR device was calibrated with 1 wt-% solutions of dibutylamine and n-butylamine.

[0249] Reference Example 2: 13 Determination of C-NMR spectrum

[0250] In order to evaluate the purity of the synthesized urea, 13C-NMR spectroscopy. The absence of peaks in the 50 to 80 ppm chemical shift range indicates the absence of polyols. The sample was dissolved in DMSO. As a reference standard, tetramethylsilane was used.

[0251] Reference Example 3: Appliance and structural foam and its composition

[0252] a) PUR appliance foam: Model foams were prepared by mixing 56 wt.% Lupranat M20S (Lupranat M20S is a commercial product of BASF, having a typical NCO content of 31.5 g / 100 g and a viscosity of about 200 mPas at 25° C.) and 35% by weight of polyol (a mixture of polyols 1, 2 and 3), and additionally contains additives required for foaming, such as catalysts, surfactants, blowing agents

[0253] b) PIR-structural foam: A model foam was prepared by mixing 71.4 wt.-% Lupranat M50S (Lupranat M50S is a commercial product of BASF, having a typical NCO content of 31.5 g / 100 g and a viscosity of about 550 mPas at 25° C.) and 18.4 wt-% of polyol (polyol 4 is the main polyol), and additionally includes additives required for foaming, such as catalysts, surfactants, blowing agents;

[0254] c) Polyols (see Figure 2 ):

[0255] Polyol 1 is a polyether-polyol synthesized from ortho-TDA (toluenediamine) as an initiator and PEO and PPO side chains, with an OH value of 160 mg KOH / g

[0256] Polyol 2 is a polyether-polyol synthesized from ortho-TDA (toluenediamine) as an initiator and PPO side chains; its OH-value is 400 mg KOH / g

[0257] Polyol 3 is a mixture of two polyether-polyols, one of which is synthesized from sorbitol as a starter and PPO side chains, and the other polyether-polyol is synthesized from glycerol as a starter and PPO side chains, and its OH-value is 430 mg KOH /

[0258] Polyol 4 is a slightly branched polyester polyol based on terephthalic acid with an OH value of 245 mg KOH / g

[0259] d) Surfactant: silicone oil;

[0260] e) Blowing agent: water, cyclopentane;

[0261] f) Catalyst: Lupragen N100, Lupragen N206, Lupragen N600 (all commercially available from BASF); These catalysts are generally tertiary amines of the general formula R1R2R3N. The fragments R1R2R3 are alkyl side chains with a chain length of 3 to 10 carbon atoms.

[0262] Reference Example 4: End-of-Life Foam

[0263] a) PUR - End of Life (EoL) foam: Foam powder obtained from refrigerator disassembly company (MDI based)

[0264] b) PU-flexible conventional foam from a mattress disassembly company, TDI based);

[0265] c) Polyols:

[0266] Polyol Type type composition Polyether-polyol sugar Sorbitol-PPO Polyether-polyol TDA TDA-PPO, TDA-PPO-PEO Polyether-polyol amine Ethylenediamine-PPO Polyether-polyol Soft Glycerin-PPO Polyester-polyol ester Phthalic acid / diethylene glycol (DEG) Polyether- / Polyester-Polyols Hybridization Biodiesel / Sugar Polyether-polyol MDA MDA-PPO

[0267] Reference Example 5: Solubility Test

[0268] Four different model systems were prepared for solubility testing of the corresponding resulting ureas in the presence of polyether / polyester-polyols.

[0269] 5.1. Synthesis of model systems

[0270] 5.1.a Polyurea derived from PMDI (using secondary amines)

[0271] In a 2L round flask, 50g of anhydrous dibutylamine (DBA) and 300g of monochlorobenzene (MCB) were mixed and stirred continuously. 17g of polymeric isocyanate (Lupranat) was added through a dropping funnel. A solution consisting of M20S (M20S, with a typical NCO content of 31.5 g / 100 g and a viscosity of about 200 mPas at 25° C.; BASF) and 281 g of monochlorobenzene was added dropwise over a period of 1 h. During the reaction, the reaction temperature was increased from 22.7° C. to 30.1° C. Afterwards, the reaction mixture was stirred overnight. The product obtained was analyzed using FTIR spectroscopy. At 2200-2400 cm -1 The absence of NCO stretching vibrations in the range indicated complete conversion of the isocyanate groups. Monochlorobenzene and excess dibutylamine were evaporated under vacuum and a highly viscous residue was obtained. The yield was 33.9 g, corresponding to 98%.

[0272] 5.1.b Polyurea derived from PMDI (using primary amines)

[0273] In a 2L round flask, 50g of anhydrous n-octylamine (aliphatic monoamine) and 450g of monochlorobenzene were mixed and stirred continuously. 16g of polymeric isocyanate (Lupranat) was added through a dropping funnel. A solution consisting of M20S (M20S, with a typical NCO content of 31.5 g / 100 g and a viscosity of about 200 mPas at 25° C.; BASF) and 307 g of monochlorobenzene was added dropwise over a period of 1 h. During the reaction, the reaction temperature was increased from 22.7° C. to 50.8° C. Afterwards, the reaction mixture was stirred overnight. The product obtained was analyzed using FTIR spectroscopy. At 2200-2400 cm -1 The absence of NCO stretching vibrations in the range indicated complete conversion of the isocyanate groups. Monochlorobenzene and excess n-octylamine were evaporated under vacuum and a crystalline solid was obtained. The yield was 32.0 g, corresponding to 98%.

[0274] 5.1.c Polyurea derived from PMDI (using primary amines)

[0275] In a 2L round flask, 41g of anhydrous n-butylamine (aliphatic monoamine) and 364g of monochlorobenzene were mixed and stirred continuously. 22g of polymeric isocyanate (Lupranat) was added through a dropping funnel. A solution consisting of M20S (M20S, with a typical NCO content of 31.5 g / 100 g and a viscosity of about 200 mPas at 25° C.; BASF) and 406 g of monochlorobenzene was added dropwise over a period of 1 h. During the reaction, the reaction temperature was increased from 21.7° C. to 31.4° C. Afterwards, the reaction mixture was stirred overnight. The product obtained was analyzed using FTIR spectroscopy. At 2200-2400 cm -1 The absence of NCO stretching vibrations in the range indicated complete conversion of the isocyanate groups. Monochlorobenzene and excess n-butylamine were evaporated under vacuum and a crystalline solid was obtained. The yield was 34.1 g, corresponding to 98%.

[0276] 5.1.d Polyureas derived from PMDI (using primary amines)

[0277] In a 2L round flask, 84g of anhydrous aniline (aromatic monoamine) and 762g of monochlorobenzene were mixed and stirred continuously. 36g of polymeric isocyanate (Lupranat) was added through a dropping funnel. A solution of 1,2-dimethoxy- ... -1 The absence of NCO stretching vibrations in the range indicated complete conversion of the isocyanate groups. Monochlorobenzene and excess aniline were evaporated under vacuum and a crystalline solid was obtained. The yield was 61.2 g, corresponding to 98%.

[0278] 5.1.e Polyureas derived from PMDI (using primary amines)

[0279] In a 2L round flask, 33.1g of anhydrous toluenediamine (TDA - aromatic polyamine) and 1100g of monochlorobenzene were mixed and stirred continuously. 3.6g of polymeric isocyanate (Lupranat) was added through a dropping funnel. A solution of 1,2-dichloro-1-(2-nitro-2-yl)-1-nitro-2-ol (1,2-dichloro ... -1 The absence of NCO stretching vibrations indicated complete conversion of the isocyanate groups. Monochlorobenzene and excess TDA were evaporated under vacuum and a crystalline solid (6.9 g) was obtained. The yield was 99%.

[0280] 5.1.f Polyurea derived from PMDI (using primary amines)

[0281] In a 2L round flask, 33g of anhydrous ethylenediamine (aliphatic polyamine) and 300g of monochlorobenzene were mixed and stirred continuously. 22g of polymeric isocyanate (Lupranat) was added through a dropping funnel. A solution of 1,4-dichlorobenzene (340 g) and 1,4-dichlorobenzene (3,4-dichlorobenzene) was added dropwise over 1 h. The reaction mixture was then stirred overnight. The product obtained was analyzed using FTIR spectroscopy. The FTIR spectrum was 2200-2400 cm -1 The absence of NCO stretching vibrations indicated complete conversion of the isocyanate groups. Monochlorobenzene and excess ethylenediamine were evaporated under vacuum and a crystalline solid (29.8 g) was obtained. The yield was 93%.

[0282] 5.2. Evaluation of polyurea solubility

[0283] 5.2.a Solubility screening

[0284] About 5 g of polyurea according to the corresponding model system, 2.5 g of a polyether-polyol mixture containing TDA, glycerol and sucrose-derived polyether-polyol and 25 g of the corresponding solvent were mixed at room temperature. After stirring for 90 min, the polyether-polyol was added and an IR sample was taken, diluted with chloroform and analyzed. At 1600-1700 cm -1 The carbonyl vibration area in the range is correlated with the amount of urea dissolved. Detection limit <1.0 wt-%. The results of the solubility tests of the model system prepared according to 1.ad are shown in Table 1 below.

[0285] Table 1

[0286] Solubility test results of the model system prepared according to 5.1.af.

[0287]

[0288] Solubility test result (table 1) shows, the polyurea derived from the reaction of secondary amine (particularly dibutylamine) and PMDI is soluble in the solvent of test, and the polyurea derived from the reaction of primary amine and PMDI is actually insoluble.Especially, find that 9.1 weight-% of the polyurea derived from the reaction of dibutylamine and PMDI can be dissolved in toluene.Therefore, can expect that in dimethylbenzene, comparable solubility will be realized.In contrast, be less than 1.0 weight-% derived from primary amine, particularly the polyurea of ​​the reaction of n-octylamine, n-butylamine and aniline used in reference example 1.b-1.d can be dissolved in dimethylbenzene.Therefore, think that the polyurea of ​​these examples is insoluble in the solvent of test.

[0289] Example 1: Ammonolysis of PUR appliance foam with n-butylamine

[0290] 30 g of PUR-appliance foam according to reference example 3a) were ground using a coffee grinder and dried overnight at 100° C. in a nitrogen-purged atmosphere at atmospheric pressure. The dried foam and 150 g of n-butylamine were then charged into a stirred autoclave. The aminolysis reaction was carried out at 140° C. and about 5 bar (depending on the vapor pressure of n-butylamine) for 75 min. After the reaction, the mixture was cooled to room temperature and about 120 mL of n-butylamine was evaporated. 150 g of xylene were added to the resulting residue and the precipitation of the polyurea began. To complete the precipitation, the remaining n-butylamine was evaporated. Subsequently, the precipitated polyurea was filtered out and washed several times with xylene. With the help of 13 C-NMR- and IR-spectroscopy were used to record the conversion and purity of the precipitate. Figure 2 As can be seen from the IR spectrum shown, no characteristic urethane vibrations of polyurea were detected. The conversion rate was about 95% and only a small amount of ether groups were detected, such as from Figure 3 shown 13The C-NMR spectrum showed that the purity was higher than 90%, and 16.1 g of the corresponding polyurea-containing compound was obtained (yield: 61%).

[0291] Example 2: Aniline hydrolysis of PUR appliance foam

[0292] 10 g of PUR-appliance foam according to reference example 3a) was ground using a coffee grinder and dried overnight at 100 ° C in a nitrogen-purged atmosphere at atmospheric pressure. Afterwards, the dried foam and 110 g of aniline were loaded into a 0.5 L round flask. The aminolysis reaction was carried out at 180 ° C under reflux for 1 h. During the aminolysis reaction, all compounds were completely dissolved in the aniline. After the reaction, the mixture was cooled to room temperature and the formed polyurea began to precipitate. After 12 h, the precipitate was filtered out. The solid was washed several times with xylene and dried overnight to obtain 3.5 g of polyurea, equivalent to 40%. Excess aniline was evaporated from the filtrate, and 250 g of xylene was added to the residue. The solution was stirred overnight. The newly formed precipitate was filtered, washed and dried to obtain 2.1 g of polyurea, equivalent to 24%. With the aid of 13C-NMR- and IR-spectroscopy, the aminolysis conversion and purity of the precipitate were recorded. The conversion rate was about 98% and no ether groups were detected. The purity was higher than 95%. 5.6 g of the corresponding polyurea-containing compound were obtained (yield: 64%).

[0293] Example 3: Ammonolysis of PUR-End-of-Life (EoL) Foam with n-Butylamine

[0294] 24 g of PUR-appliance end-of-life (EoL) foam according to reference example 4a) and 120 g of n-butylamine were charged into a stirred autoclave. The aminolysis reaction was carried out at 140° C. and about 5 bar (depending on the vapor pressure of n-butylamine) for 75 min. After the reaction, the mixture was cooled to room temperature. After the pressure was relaxed, the mixture was heated to 60° C. and filtered through a nylon filter to remove insoluble inorganic and organic impurities (m 杂质 =2.0 g). Then, about 120 mL of n-butylamine were evaporated. 150 g of xylene were added to the resulting residue and after a while the precipitation of the polyurea began. To complete the precipitation, the remaining n-butylamine was evaporated. Subsequently, the precipitated polyurea was filtered off and washed several times with xylene. 13 The precipitate was analyzed for conversion and purity of the aminolysis by C-NMR and IR spectroscopy. The conversion was about 98% and no ether groups were detected. The purity was above 95%. 8.6 g of the corresponding polyurea-containing compound were obtained.

[0295] Example 4: Ammonialysis of PUR-End-of-Life (EoL) Foam with Aniline

[0296] 25 g of PUR-appliance end-of-life (EoL) foam according to reference example 4a) and 250 g of aniline were added to a 0.5 L round flask. The aminolysis reaction was carried out at 180° C. under reflux for 1 h. During the aminolysis reaction, inorganic impurities precipitated. After the reaction, the mixture was filtered using a nylon filter and the filtrate was cooled to room temperature (m 杂质 =2.1 g). Then, the formed polyurea began to precipitate. After 12 h, the precipitate was filtered off. The solid was washed several times with xylene and dried overnight (m 聚脲，1 =10.3 g). Excess aniline was evaporated from the filtrate, and 250 g of xylene was added to the residue. The solution was stirred overnight. The resulting precipitate was filtered off, washed, and dried. (m 聚脲，2 =1.8 g, yield = 24%). 13 The precipitate was analyzed for conversion and purity by C-NMR- and IR-spectroscopy. The conversion was about 90% and no ether groups were detected. The purity was above 95%. 12.1 g of the corresponding polyurea-containing compound were obtained.

[0297] Example 5: Ammonolysis of PU soft foam with n-butylamine

[0298] 15 g of PU flexible foam according to reference example 4b) was mixed with liquid nitrogen, then ground using a coffee grinder and dried overnight at 100° C. in a nitrogen-purged atmosphere at atmospheric pressure. The dried foam and 150 g of n-butylamine were then added to a stirred autoclave. The aminolysis reaction was carried out at 140° C. and about 5 bar (depending on the vapor pressure of n-butylamine) for 75 min. After the reaction, the mixture was filtered under pressure at 140° C. to remove solid impurities. Then, the n-butylamine was evaporated under vacuum and the remaining residue was washed several times with n-heptane. Use 13 The conversion and purity of the precipitated polyurea were analyzed by C-NMR- and IR-spectroscopy. The conversion was about 90% and no ether groups were detected. The purity was above 80%. 6.1 g of the corresponding polyurea-containing compound were obtained.

[0299] Example 6: Decomposition of polyisocyanurate (PIR) structural foam using aniline

[0300] 15 g of dried and chopped PIR-structural foam according to reference example 3b) polyisocyanurate structural foam and 400 g of aniline were charged into a round flask equipped with a reflux condenser. The aminolysis reaction was carried out at 180°C for 60 min until the foam components were completely dissolved in the aniline. The mixture was cooled to room temperature and polyurea began to precipitate. The precipitated polyurea was filtered and the filtrate was concentrated by evaporation to remove the aniline. The remaining solid was also filtered out and washed several times with acetone. Use 13The precipitate was analyzed for conversion and purity by C-NMR- and IR-spectroscopy. The conversion was about 90% and no ether groups were detected. The purity was above 95%. 12.2 g of the corresponding polyurea-containing compound were obtained (yield: 60%).

[0301] Example 7: Hydrolysis of polyurea-containing compounds (polymers) with water

[0302] 5.1 g of the polyurea obtained from Example 3 and 75 g of water were charged into a pressure autoclave. The mixture was heated to 250° C. and the temperature was maintained for 5 h, whereby the pressure was about 40 bar (absolute). After cooling, the mixture was analyzed using GC to assess the amount of PMDA. The purity was determined based on the area ratio of the GC peaks, and was therefore 85% (m 残余物 =4.3g). BRIEF DESCRIPTION OF THE DRAWINGS

[0303] Figure 1 is a schematic diagram of a method according to an embodiment of the present invention.

[0304] As from Figure 1It can be seen that the method according to a preferred embodiment of the present invention includes ammonolysis of a solid material W with one or more primary amines, the solid material comprising one or more polymers, such as polyurethane, polyurethane urea and polyisocyanurate. This allows a mixture M comprising one or more polyurea-containing compounds and further comprising one or more polyols to be obtained. For example, the ammonolysis reaction can occur at 140 ° C and between about 4.5-5 bar (absolute pressure). The reaction time can be about 75min. In order to remove solid impurities, such as glass, sand, wood, metal, paper, other organic solids like polymers (e.g., PE, PP, PS, PET) or other inorganic solids, the method further includes passing the mixture M through a solid-liquid separation unit. Preferably, the mixture M is filtered under pressure via, for example, a bag filter. The method further includes mixing the obtained liquid mixture comprising a polyurea-containing compound and one or more primary amines (unreacted) with a solvent (preferably an anhydrous solvent, more preferably xylene), which is preferably stored in a tank T. The method further includes flashing the obtained mixture into a reactor, preferably a stirred tank reactor equipped with a filter inlet or a suction filter, to evaporate the primary amine / solvent mixture. The method further comprises precipitating one or more polyurea-containing compounds with an anhydrous solvent. The precipitate is retained by the filter inlet. The method further comprises transferring the filtrate containing one or more polyols to a storage tank (not shown). The precipitate containing one or more polyurea-containing compounds can be further washed with an anhydrous solvent, and the washing solution can also be transferred to the polyol storage tank. After the washing step, the method further comprises hydrolyzing one or more polyurea-containing compounds to obtain corresponding one or more polyamines. The hydrolysis comprises adding water vapor (e.g., 50 bar (absolute pressure) / 250°C for 1h) to a reactor already containing polyurea-containing compounds. Preferably, the obtained mixture containing one or more corresponding polyamines is further flashed in a tank to evaporate primary amine / water to obtain a vapor mixture containing primary amine and water and a liquid mixture containing one or more polyamines.

[0305] The method further comprises withdrawing the filtrate from the storage tank and introducing the filtrate into a purification unit, preferably a distillation column, to obtain a liquid mixture comprising the polyol and a vapor mixture comprising the solvent. The method further comprises passing the vapor mixture through a second purification unit to recover the solvent and introduce it into T before being used in the evaporation and / or separation steps discussed above.

[0306] The method further comprises preparing one or more polymers, i.e. polyurethanes and / or polyisocyanates, using polyols obtained from W and polyamines obtained from W. The method further comprises phosgenation of polyamines to obtain polyisocyanates. Then, the method further comprises reacting the polyols and polyisocyanates obtained from hydrolysis (or directly from HCl-cleavage) in the presence of a catalyst, such as one or more of DABCO, stannous octoate, stannous ricinoleate, bis(2-dimethylaminoethyl)ether, potassium acetate, and optionally one or more additives to obtain one or more polyurethanes (PU) and / or one or more polyisocyanurates (PIR).

[0307] Figure 2 Shown are spectra of an IR analysis of a model foam and of a polyurea derived from PMDI (pMDI-urea) according to Example 1. On the abscissa, the wavenumber is in cm -1 , and on the ordinate, the absorbance is given in arbitrary units.

[0308] Figure 3 The polyurea derived from PMDI according to Example 1 is shown. 13 C-NMR spectra. On the abscissa, the chemical shifts are given in ppm and on the ordinate, the absorbance is given in arbitrary units.

[0309] References

[0310] - WO 2008 / 014988 A1

[0311] - Kunststoffhandbuch [Plastics handbook] [Plastics handbook], Volume 7, Polyurethane [Polyurethanes] Polyurethane [Polyurethane]", Carl Hanser Verlag, 3rd edition, 1993, Chapters 3.4.4 and 3.4.6 to 3.4.11

[0312] - WO 2006 / 034800

[0313] -EP 0090444

[0314] - WO 2005 / 090440

[0315] -WO 2022 / 106716

[0316] -EP 1761483 B1

[0317] -EP 2079684 B1

[0318] -EP 2188247 B1

[0319] -EP 2408738 B1

[0320] -EP 2539314 B1

[0321] -WO 2018 / 185168

[0322] -EP 3 250 622 B1

Claims

1. A method for producing one or more polymers from a solid material W, the one or more polymers being selected from the group consisting of polyurethanes, polyurethane ureas, polyisocyanurates and mixtures of two or more thereof, the method comprising (i) preparing a mixture M comprising one or more polyurea-containing compounds from W, said mixture M further comprising one or more polyols, comprising: (i.1) providing the solid material W comprising one or more polymers selected from the group consisting of polyurethane, polyurethaneurea, polyisocyanurate and a mixture of two or more thereof; (i.2) In the reactor unit R A introducing the solid material W provided in (i.1) and one or more primary amines to obtain a mixture; (i.3) subjecting the mixture obtained according to (i.2) to R A subjecting the mixture to aminolysis reaction conditions to obtain a mixture M comprising one or more polyurea-containing compounds and further comprising one or more polyols; (ii) separating the one or more polyurea-containing compounds of M obtained according to (i) from the one or more polyols of M obtained according to (i) to obtain a mixture U comprising the one or more polyurea-containing compounds and a mixture P comprising the one or more polyols; (iii) subjecting the mixture U obtained according to (ii) to a reactor unit R C subjecting the mixture to cleavage reaction conditions to obtain one or more corresponding polyamines or one or more corresponding polyisocyanates; (iv) subjecting the mixture P obtained according to (ii) to purification conditions to obtain a purified mixture comprising one or more polyols; (v) preparing one or more polymers selected from the group consisting of polyurethanes, polyurethaneureas, polyisocyanurates, and mixtures of two or more thereof, comprising: (v.1) introducing the one or more polyols obtained according to (iv) into unit N PU middle; (v.2) converting the one or more polyamines obtained according to (iii) into one or more polyisocyanates in a reactor to obtain one or more polyisocyanates, and introducing the one or more polyisocyanates obtained into N PU or The one or more polyisocyanates obtained according to (iii) are introduced into N PU middle; (v.3) According to (v.2), N is introduced PU The one or more polyisocyanates in (v.1) are introduced into N PU The one or more polyols in the mixture are contacted in the presence of a catalyst for polymerization to obtain one or more polymers selected from the group consisting of polyurethane, polyurethane urea, polyisocyanurate and a mixture of two or more thereof.

2. The method of claim 1 , further comprising, before (i), subjecting the solid material W to a pretreatment, preferably a mechanical pretreatment, wherein the mechanical pretreatment comprises one or more of grinding, crushing, chopping and cutting, preferably grinding or chopping the solid material W.

3. The method according to claim 1 or 2, wherein: The one or more polymers contained in the solid material W are one or more polyurethanes; wherein the one or more polyurethanes are preferably thermosetting materials or elastomers; or wherein the one or more polymers contained in the solid material W are one or more polyisocyanurates.

4. The method according to any one of claims 1 to 3, wherein: The one or more primary amines are selected from the group consisting of aliphatic monoamines, aliphatic polyamines, aromatic monoamines and mixtures of two or more thereof, preferably selected from the group consisting of aliphatic monoamines, aromatic monoamines and mixtures of two thereof.

5. The method of claim 4, wherein: The one or more primary amines are of the formula H2NR 1 The aliphatic monoamines Where R 1 Choose from (C3-C 25 ) alkyl, phenyl, (C7-C 25 )aralkyl and (C7-C 25 )alkylaryl group, preferably selected from (C3-C 20 ) alkyl, (C8-C 22 )aralkyl and (C8-C 22 )alkylaryl, more preferably selected from the group consisting of (C3-C 10 ) alkyl, phenyl, (C 10 -C 20 )aralkyl and (C 10 -C 20 ) a group consisting of an alkylaryl group, Wherein more preferably the aliphatic monoamine is selected from the group consisting of n-butylamine, cyclohexylamine, n-octylamine, n-hexylamine, n-propylamine, n-dodecylamine, n-tridecylamine, n-octadecylamine and a mixture of two or more thereof, more preferably selected from the group consisting of n-butylamine, n-octylamine, n-hexylamine and n-propylamine; or Wherein the one or more primary amines are aromatic monoamines, wherein the aromatic monoamine is selected from the group consisting of aniline, toluidine, naphthylamine, and mixtures of two or more thereof.

6. The method of claim 5, wherein: The one or more primary amines are n-butylamine or aniline.

7. The method according to any one of claims 1 to 6, wherein: Introducing R A The weight of the solid material W in R A The ratio by weight of the one or more primary amines in the formula (I) is in the range of 1:100 to 1:1, preferably in the range of 1:40 to 1:3, more preferably in the range of 1:10 to 1:

5.

8. The method according to any one of claims 1 to 7, wherein: The aminolysis reaction according to (i.3) is carried out at a temperature in the range of 50°C to 250°C, preferably in the range of 80°C to 200°C, more preferably in the range of 100°C to 220°C, more preferably in the range of 140°C to 200°C; Wherein preferably the aminolysis reaction according to (i.3) is carried out at a pressure in the range of 1.0 to 25.0 bar (absolute pressure), more preferably in the range of 1.0 to 20.0 bar (absolute pressure), more preferably in the range of 1.0 to 18.0 bar (absolute pressure).

9. The method according to any one of claims 1 to 8, wherein: At most 0.1 wt-%, preferably 0 to 0.01 wt-%, more preferably 0 to 0.001 wt-% of the mixture M obtained according to (i) consists of polymers selected from the group consisting of polyurethanes, polyurethaneureas and polyisocyanurates.

10. The method according to any one of claims 1 to 9, wherein: (i) further includes (i.4) From R A The mixture M obtained according to (i.3) is taken out.

11. The method of claim 10, further comprising, after (i.4) and before (ii), converting the R A The mixture M taken out from the solid-liquid separation unit is sent to obtain a liquid mixture M containing the one or more polyurea-containing compounds and the one or more polyols. SLS And a solid mixture containing impurities is obtained.

12. The method according to any one of claims 1 to 11, wherein: (ii) including (ii.1) preferably a solvent and the mixture M, preferably a liquid mixture M as defined in claim 11 SLS into an evaporation unit EU from which a vapor mixture V is obtained, which comprises the solvent and at least a portion of the one or more primary amines, and a liquid mixture M comprising the one or more polyurea-containing compounds and the one or more polyols EU ; (ii.2) adding a solvent to the mixture M, preferably a liquid mixture M as defined in claim 11 SLS , more preferably the liquid mixture M obtained according to (ii.1) EU allowing the one or more polyurea-containing compounds to precipitate to obtain a mixture comprising the one or more precipitated polyurea-containing compounds; (ii.3) passing the mixture comprising the one or more precipitated polyurea-containing compounds obtained according to (ii.2) through a solid-liquid separation unit SLU to obtain a liquid mixture P comprising the one or more polyols and a solid mixture U comprising the one or more polyurea-containing compounds.

13. The method of claim 12, wherein: In one or more of (ii.1) and (ii.2), the solvent used in (ii.1) and (ii.2) is preferably selected from the group consisting of hydrocarbons, ketones and ethers, more preferably selected from the group consisting of xylene, toluene, n-heptane, methyl ethyl ketone (MEK), dioxane, benzene, hept-2-one and mixtures of two or more thereof, preferably selected from the group consisting of xylene, toluene, n-heptane, benzene and mixtures of two or more thereof, more preferably xylene or toluene or benzene; and / or wherein in one or more of (ii.1) and (ii.2), the solvent used in (ii.1) and (ii.2) has a water content in the range of 0 to 1000 ppm, preferably in the range of 0 to 500 ppm, more preferably in the range of 0 to 100 ppm.

14. The method according to any one of claims 1 to 13, wherein: The cleavage reaction conditions according to (iii) are hydrolysis reaction conditions; wherein (iii) preferably comprises water and the mixture U obtained according to (ii) comprising the one or more polyurea-containing compounds in R C wherein the weight ratio of water to the one or more polyurea-containing compounds is in the range of 1:1 to 50:1, more preferably in the range of 5:1 to 20:1, more preferably in the range of 10:1 to 18:1, to obtain a mixture comprising one or more corresponding polyamines; wherein more preferably the hydrolysis is carried out at a temperature in the range of 150°C to 350°C, more preferably in the range of 210°C to 290°C, more preferably in the range of 230°C to 270°C; wherein more preferably the hydrolysis is carried out at a pressure in the range of 20 to 70 bar (absolute pressure), more preferably in the range of 25 to 65 bar (absolute pressure), more preferably in the range of 30 to 60 bar (absolute pressure); Therein more preferably the hydrolysis is carried out for a duration in the range of 0.1 to 15 h, more preferably in the range of 0.25 to 10 h, more preferably in the range of 0.5 to 8 h.

15. The method according to any one of claims 1 to 14, wherein: (iv) including The mixture P obtained according to (ii) is sent to a purification unit PU(1) to separate the one or more polyols from the liquid mixture P, obtaining a mixture comprising the one or more polyols, reduced by at least a portion of compounds other than polyols.

16. The method according to any one of claims 1 to 15, wherein: (v.2) includes (v.2.1) mixing a solvent into the one or more polyamines obtained according to (iii) and stirring, preferably at a temperature in the range of 50°C to 180°C, more preferably in the range of 70°C to 140°C, more preferably in the range of 80°C to 120°C, to obtain a polyamine mixture; (v.2.2) contacting the polyamine mixture obtained according to (v.2.1) with phosgene in a reactor and heating the obtained mixture to a temperature in the range of 90° C. to 140° C., preferably in the range of 110° C. to 130° C., to obtain a mixture comprising one or more polyisocyanates; (v.2.3) introducing the one or more polyisocyanates obtained according to (v.2.2) into N PU middle.

17. The method according to any one of claims 1 to 15, wherein: (v.2) comprising introducing the one or more polyisocyanates obtained according to (iii) into N PU middle.

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