WO2023209022A1 - Recyclage de polyuréthanes par aminolyse avec des réactifs comprenant des groupes amino primaires et/ou secondaires et tertiaires dans la structure - Google Patents

Recyclage de polyuréthanes par aminolyse avec des réactifs comprenant des groupes amino primaires et/ou secondaires et tertiaires dans la structure Download PDF

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WO2023209022A1
WO2023209022A1 PCT/EP2023/060983 EP2023060983W WO2023209022A1 WO 2023209022 A1 WO2023209022 A1 WO 2023209022A1 EP 2023060983 W EP2023060983 W EP 2023060983W WO 2023209022 A1 WO2023209022 A1 WO 2023209022A1
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reagent
primary
amine
reaction mixture
polyurethane
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PCT/EP2023/060983
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English (en)
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Ema ŽAGAR
David PAHOVNIK
Maja GRDADOLNIK
Blaž ZDOVC
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Kemijski Institut
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/28—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic compounds containing nitrogen, sulfur or phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic

Definitions

  • the present invention relates to recycling of polyurethanes, in particular polyurethane foams by aminolysis with reagents comprising both primary and/or secondary and tertiary amino groups in the structure to recover, depending on reaction conditions, either fully hydroxyl-functionalized polyols of comparable quality to the virgin ones, or partially aromatic amino functionalized polyols.
  • PU foams are an important class of materials.
  • Flexible PUFs are used for upholstered furniture, mattresses, and automotive seats, while rigid PUFs are used mainly for building insulation. Since PUFs account for a large portion of the total production and consumption of PUs, they generate an increasing amount of waste, which requires efficient waste management. Due to stringent environmental regulations and the need for a circular economy, sustainable approaches to the production of PUFs, such as recycling and the use of bio-derived feedstock, are emerging as the most suitable solutions. 1
  • PUFs have a thermostable, cross-linked structure. Therefore, decomposition of the PUF network by chemical degradation is the best option for their sustainable recycling. In this way, recycled polyols (RPs) are obtained, which can be reused for variety of applications. Currently, RPs can also be used to synthesize flexible PUFs of the same quality, but only part of the virgin polyol in the PUF formulation is replaced by the recycled one. Over the years, many chemical methods have been developed and applied for PUF recycling, such as glycolysis, 2 ' 15 hydrolysis, 16,17 acidolysis, 18-22 and aminolysis. 23-31
  • PUF hard segments consisting of oligourea sequences can also be degraded to some extent thermally or by other side reactions, leading to the excessive formation of unwanted toxic aromatic amines.
  • the degree of degradation of urethane bonds and urea bonds of hard segments in PUF structure depends on the experimental conditions used.
  • Aminolysis is a reaction in which the amine reagent displaces the polyol at the urethane bond, forming free RP and a urea bond between the reagent and the end group of the oligourea segments (Fig. 1).
  • Amine reagents already used for PUF degradation include various alkanolamines and amines containing primary and secondary groups in the structure, as well as ammonia in the so-called ammonolysis reaction (US patent No. 4, 162, 995).
  • 32 US patent No. 3, 117,940 33 describes a method for improved liquefaction of PU-based plastics.
  • PU plastics including PU cellular plastics known as PUFs
  • PUFs PU cellular plastics
  • a few patents describe the use of alkanolamines for the chemical degradation of PUF waste, mostly for rigid PUFs (US 4, 162, 995, 32 US 3, 708, 440, 34 US 3, 738, 946, 35 and US 4,014, 809).
  • 36 All describe chemical degradation of PUFs at elevated temperatures (up to 250 °C) in the presence of alkanolamines via alcoholysis/glycolysis pathway rather than aminolysis mechanism.
  • Reported alkanolamine reagents which are used in amounts up to 20 wt.% per PUF, include diethanolamine, triethanolamine, dipropanolamine, diisopropanolamine, N-(2- hydroxypropyl)ethanolamine, 3,3'-iminobis(2-hydroxybutane), where some of the aforementioned amines include the tertiary amino group in the structure, such as triethanolamine.
  • Tertiary amines such as triethylenediamine, dimethylpiperazine, triethanolamine or dimethylaniline, used in catalytic amounts, are proposed as suitable catalysts that allow lowering the reaction temperature in the glycolysis of PU resins (US patent No. 3, 632, 530).
  • a method for recycling PU materials (including PUFs) using different glycols in combination with aliphatic amines or polyamines, where preferred amines contain at least two primary and at least one tertiary amino group e. g. A/,A/-bis-(3-aminopropyl)-A/-methylamine, A/,A/-bis(2-aminopropyl)-A/-methylamine, N,N- bis(2-aminoethyl)-/V-methylamine
  • patent EP 2 270 083 39 describes a method for producing polyol components from PUF waste using glycols and aliphatic amines, such as A/,A/-bis-(3-aminopropyl)-A/- methylamine, and finally specific mixture of fatty acids is added.
  • glycols and aliphatic amines such as A/,A/-bis-(3-aminopropyl)-A/- methylamine
  • specific mixture of fatty acids is added.
  • U patent No. 6,750,260 B2 40 various chemolysis processes are proposed.
  • aminolysis with preferably low molecular weight diamines is described to be carried out at atmospheric pressure and lower temperatures compared to PUF glycolysis, but the type of amine reagents is not precisely defined.
  • patent FR 1 429 011 41 aminolysis of PU materials (including PUFs) using aliphatic, cycloaliphatic and aromatic amines, which act both as solvent and reagent, is described. Reagents containing primary and/or secondary and tertiary amino groups in the molecule are not mentioned.
  • European patent application No. EP 1 142 945 A2 42 describes a method of aminolysis using polyamine compounds as a solubilizer for polyurethane resins (including PUFs), typically toluenediamine, but also diaminodiphenylmethane, polymethyl polyphenyl polyamine, and mixtures thereof.
  • Patent WO 2015/027319 A1 43 aims to improve the efficiency of various chemolysis methods, highlighting glycolysis as the most promising by using low molecular weight glycols, while bases (including amines and alkanolamines) are used as catalysts. Aminolysis of PUFs is also mentioned as a possible chemical degradation pathway, but no further details are given.
  • Patent EP 1 149 862 A1 44 deals with recycling of rigid PUFs either by glycolysis or aminolysis. Amine reagents such as ethanolamine and tolylenediamine in a PUF/amine reagent ratio of 1/0.4 to 1/5 (wt%) are proposed.
  • Patent EP 3 098 257 B1 45 describes glycerolysis using eco-reagent (crude glycerol) at temperatures between 150-290 °C, preferably from 220 to 240 °C, using catalysts that include alkanolamines such as ethanolamine, diethanolamine and triethanolamine (tertiary amine).
  • Patent CN 10,3012, 838A 46 describes the recycling of PUF waste with aminolysis using aromatic amine or alkanolamine, such as diethanolamine and triethanolamine (tertiary amine) at temperatures from 150 to 250 °C in the presence of a catalyst, such as acetate, titanic acid ester of a metal base or alkaline earth metal.
  • DE 4 217 524 A1 48 describes an improved method for recovering isocyanate-reacted components using a combination of different reagents selected from water, amino compounds having a molecular weight of 177 to 399 Da, and optionally mono-, di-, or polyfunctional alcohols having a molecular weight of 32 to 250 Da.
  • Amine reagents include ammonia, primary or secondary amines (alkylamines such as butylamine or (cyclo)hexylamine) and alkanolamines such as aminoethanol or N- methylaminoethanol, also hexamethylenediamine, diaminodiphenylmethane or, optionally alkyl-substituted, toluenediamine.
  • the patents mentioned so far use conventional heating of reaction mixtures.
  • the patent EP 2 480 584B1 49 describes the recycling of rigid PUFs using bioreagents from renewable sources with active hydroxyl functional groups at elevated temperatures (from 150 to 300 °C).
  • microwave heating has also been proposed as a way to reduce energy costs.
  • 30,50,51 Alkanolamines such as ethanolamine, diethanolamine, and triethanolamine (tertiary amine) are reported to be used only as catalysts in PU recycling, with PUF/amine ratios ranging from 500/1 to 10/1.
  • Patent application US 2008/0047824 A, 50 similar to DE 4 217 524 A1 48 describes the chemical degradation of PU using one or more reactive reagents such as water, amino compounds with molecular weight of 177 to 399 Da, and mono-, di-, or polyfunctional alcohols with a molecular weight of 32 to 2500 Da, but using microwaves as the heat source instead of conventional heating.
  • Retiary amine such as 1 ,1 ,1-diazabycyclooctane (DABCO) was used as catalyst.
  • Patent EP 2 183 311 B1 51 describes glycolysis of PUF waste using microwave heating of reaction mixtures up to 300 °C in the presence of alkanolamines such as ethanolamine, diethanolamine and triethanolamine tertiary amine as catalysts.
  • the final product is a mixture of alkoxylated RP, alkoxylated aromatic amines, and alkoxylated short-chain carbamates or/and ureas, and these recycled products were used as partial replacement (20 and 40 wt. %) of virgin polyol in formulation for flexible PUF synthesis.
  • Kanaya and Takahashi 25 provided insight into the reaction mechanism of PUFs with alkanolamines by investigating the type of the functional group of (mono)ethanolamine (MEA) and diethanolamine amine (DEA) involved in the degradation of urethane bonds in flexible PUFs prepared from methylene diphenyl isocyanate (MDI).
  • the obtained products were used as curing agents for epoxy resin.
  • Aminolysis of rigid PUFs was also performed by Chuayjuljit and co-workers 29 using diethylenetriamine (DETA) with or without the presence of a catalyst (NaOH). They confirmed that metal hydroxides play a role in the degradation of urethane and urea groups.
  • Modification of PUF recycling by aminolysis with ethylene diamine (EDA) was published by Rane et al. 30 To minimize the extent of side reactions in aminolysis, which were not specified, they performed aminolysis with microwaves under varying reaction time and temperature. The main advantage of microwave heating was a reduction in reaction time from 3.0 to 0.5 hours and also the extent of side reactions involved was lower.
  • the successful PUF degradation was confirmed by the determination of hydroxyl and amine values of the obtained products.
  • the recycled product was further used in polyurethane urea-based coatings.
  • amine reagents are capable of acting simultaneously as reagent and catalyst.
  • These reagents are amines containing both primary and/or secondary and tertiary amino groups in the structure of the same reagent.
  • the primary and/or secondary amino group actively participates as a reagent in the degradation of urethane groups, while the tertiary amino group catalyzes the aminolysis reaction, allowing efficient degradation of PU urethane groups.
  • the present invention provides a method of recycling polyurethane to polyols, comprising:
  • the polyurethanes (PU) used as a starting material can be any waste PUs, in particular PUFs with either flexible or rigid structure, which are used for example as mattresses, in upholstered furniture, automotive seats, and for building insulation, respectively.
  • the reagent comprising at least one primary and/or secondary amino group and at least one tertiary amino group is not particularly limited, provided that both the primary and/or secondary amino group as well as the tertiary amino group are part of a single compound, for example bound to the same framework structure.
  • Particularly preferred amine degradation reagents according to the invention for use in step (i) include tris(2- aminoethyl)amine (TREN, Fig. 2), and highly branched polyethylenimine (PEI: hyperbranched or dendrimer; Fig. 2) with various molecular weights.
  • TREN contains three primary amino groups and one tertiary amino group in its structure.
  • PEI dendrimers consist of multiple primary and tertiary amino groups due to their fully branched structure, while hyperbranched PEIs contain secondary amino groups in addition to primary and tertiary amino groups.
  • amine reagents tris(3-aminopropyl)amine, 2-(4- methyl-piperazin-1 -yl)-ethylamine, 1 ,4-bis(3-aminopropyl)piperazine, 1 -(2- aminoethyl)piperazine, 3,3’-diamino-/V-methyldipropylamine, 3-(dimethylamino)-1 - propylamine, A/,/V-dimethylethylenediamine, A/./V-dimethyldipropylenetriamine, polypropylenimine tetramine dendrimers of different generation (reagents shown in Fig. 3), and the like, as well as combinations of two or more amine reagents comprising, among which one of the reagent used contains both primary and/or secondary as well as tertiary amino groups in the structure.
  • the above-defined reagent comprising at least one primary and/or secondary amino group as well as at least one tertiary amino group in its structure is used either as the sole reagent for PU degradation or it is used in the second step of one pot-degradation of PU or it is used to completely degrade urethane groups of partially aromatic amino functionalized recycled polyols recovered from PU in the first degradation step. That means that the proposed aminolysis reaction is carried out in the absence of any additional reagents such as diols, glycols, diacids, water, etc.
  • any additional amine reagents are used with the aim to reduce the cost of the PU degradation process, then they are used in the first step of the two-step process, while the second step is always performed with the amine reagents containing both primary and/or secondary as well as tertiary amino group in the structure, which is a prerequisite to completely degrade the urethane groups.
  • the reaction mixtures can be heated by conventional heating method or by microwaves as an energetically favorable, time- and cost-effective method, which shortens the reaction time, improves the degree of degradation and reaction yield, and reduces the extent of side reactions.
  • Aminolysis reactions of PU e.g. flexible PUF can be carried out at 150 - 230 °C, preferably 220 °C or lower, for about 20 to 50 min, in particular for up to 30-40 min, preferably 30 min, with various amounts of the amine reagent containing primary and/or secondary as well as tertiary amino groups in the structure.
  • the amine reagent is preferably used in an amount equal to or greater than 2 primary amino groups per PU urethane group, more preferably in an amount equal to or greater than 3 primary amino groups per PU urethane group and in particular in an amount equal to or greater than 4 primary amino groups per PU urethane group.
  • the method of the invention further comprises a step of preheating the reaction mixture of (i) to a temperature in a range of about 120-180 °C, preferably about 175 °C, in a span of about 2-5 min, preferably about 3 min, before subjecting the mixture to a main heating in step (ii).
  • Preheating is favorable to ensure partial liquefaction of the PU and better stirring of the reaction mixture.
  • Aminolysis can be performed as one-step or two-step reaction using conventional or microwave heating of the reaction mixtures.
  • the degree of degradation of urethane groups increases with increasing amount of degradation reagent used.
  • the entire amount of amine reagent is added to the reaction mixture at once, whereas in a two-step as well as two-step, one-pot process amine reagent(s) is added in two steps as described below.
  • Fully hydroxyl-functionalized RP is a consequence of the complete degradation of the PU urethane groups.
  • amine reagent is used in molar amounts less than 4/1 (primary amino/urethane group)
  • incomplete degradation of urethane groups of PU is observed, however the amount of aromatic diamine formed during reaction is lower.
  • the incomplete degradation of urethane groups leads to RPs partially functionalized with aromatic amino end groups (in addition to hydroxyl end groups).
  • the content of aromatic amino functionalized end groups is in direct correlation with the degree of degradation of urethane groups and depends on the amount of reagent used and the reaction temperature and time applied.
  • a sufficiently large amount of the amine reagent is also necessary to prevent the formation of double bonds at the polyol chain ends that can be formed at insufficient amounts of amine degradation reagent under basic conditions by one of the possible thermal degradation mechanisms.
  • 53 ' 55 Double bonds at the polyol chain ends are inactive for polymerization with the diisocyanate and reduce the degree of PU cross-linking. This problem becomes apparent only when the amine reagent is used in molar amounts of less than 2/1 (primary amino groups of the amine reagents per urethane group in the PU structure).
  • Complete degradation of the urethane groups can also be achieved by a two-step aminolysis process at a reduced amount of the necessary amine degradation reagent containing primary and/or secondary as well as tertiary amino groups in the structure, wherein amine reagent is added in two steps, the first portion to the PU to be recycled and the second portion to the product of the crude RP obtained in the first step of reaction, after being separated from the reaction mixture.
  • Amine reagent in the first aminolysis step could be any amine reagent containing primary and/or secondary amino group (HMDA, TREN, DETA, etc.).
  • the amine reagent with primary and/or secondary as well as tertiary amino groups in the same structure, such as TREN or any of the above mentioned amine reagents must be used to run the reaction to completion.
  • the method of the invention comprises:
  • a first amine reagent which can be any amine reagent containing primary and/or secondary amino group(s) in the structure
  • step (111.2) recovering the RP, wherein in step (i.1 ), the first amine reagent is added in an amount of equal to or more than 2 primary and/or secondary amino groups per PU urethane group and less than 4 primary and/or secondaryamino groups per PU urethane group, and in step (i.2), the reagent is added in at least 1 .5 or higher amount (to 4-fold excess) of primary amino and/or secondary groups relative to the remaining urethane groups in the crude RP.
  • a preheating step is carried out before the main heating in step (ii.1).
  • the reaction mixture of (i.1 ) is preferably preheated to a temperature in a range of about 120-180 °C, more preferably about 175°C, in a span of about 2-5 min, preferably about 3 min, before subjecting the mixture to heating in step (ii.1).
  • the molar amount of amine reagent should be greater than 2/1 and less than 4/1 (primary and/or secondary amino groups of amine reagents per urethane group in the PU structure) to achieve a degree of degradation of urethane groups (other groups are amino functionalized) of around 85-90% or more without formation of double bonds at the polyol chain-ends.
  • the resulting crude RP comprises partially aromatic amino functionalized recycled polyol. It is recovered in step (iii.1 ), for example by decanting, and subjected to a second degradation step.
  • amine reagent which must contain primary and/or secondary as well as tertiary amino groups in the same structure, is added in at least 1 .5 or higher amount, at least 4-fold excess or preferably 6-fold excess of primary amino groups relative to the remaining urethane groups (Example 3).
  • the first amine reagent added in step (i.1 ) can be the same as or different from the reagent used in step (i.2). In particular embodiments, a different amine reagent can be used for the first aminolysis cycle (Example 4).
  • the first amine reagent and the reagent comprising at least one primary and/or secondary amino group and at least one tertiary amino group in its structure, respectively are the only reagents used. That is, the reaction is preferably carried out in the absence of any additional reagents such as diols, glycols, diacids, water, etc., so that the reaction mechanism of PU degradation is only aminolysis in the absence of any glycolysis, hydrolysis, alcoholysis or acidolysis. This reduces the occurrence of by-products.
  • Complete degradation of urethane groups can also be achieved by two-step, one- pot aminolysis, where amine reagents in first and second step are added consecutively into the same reaction mixture. Performing aminolysis in two-steps in one-pot was introduced to reduce the amount of reagent containing both primary and/or secondary and tertiary amino groups in the same structure.
  • Amine reagent in the first aminolysis step could be any amine reagent containing primary and/or secondary amino group (HMDA, TREN, DETA, etc.).
  • the amine reagent with primary and/or secondary as well as tertiary amino groups in the same structure, such as TREN or any of the above mentioned amine reagents must be used to run the reaction to completion.
  • the method of the invention comprises:
  • step (111.2) recovering the RP, wherein in step (i.1 ), the first amine reagent is added in an amount of equal to or more than 2 primary and/or secondary amino groups per PU urethane group and less than 4 primary and/or secondary amino groups per PU urethane group, and in step (i.2), the reagent is added in at least 1 .5 or higher amount and preferably in 6-fold excess of primary amino and/or secondary groups relative to the remaining urethane groups in the crude RP.
  • a preheating step is carried out before the main heating in step (ii.1).
  • the reaction mixture of (i.1) is preferably preheated to a temperature in a range of about 120-180 °C, more preferably about 175 °C, in a span of about 2-5 min, preferably about 3 min, before subjecting the mixture to heating in step (ii.1).
  • the molar amount of the first amine reagent should be greater than 2/1 and less than 4/1 (primary and/or secondary amino groups of amine reagents per urethane group in the PU structure) to achieve a degree of degradation of urethane groups (other groups are amino functionalized) of around 85-90% or more without formation of double bonds at the polyol chain-ends.
  • the first amine reagent added in step (i.1) of two- step, one-pot aminolysis is different from the reagent used in step (i.2).
  • the resulting reaction mixture contains partially aromatic amino functionalized crude recycled polyol (RP).
  • the reagent which must contain both primary and/or secondary and tertiary amino groups in the same structure, is added to the reaction mixture in at least 1.5 or higher amount (preferably in 6-fold excess per remaining urethane groups) (Examples 5).
  • the first amine reagent contains either primary and/or secondary amino groups
  • a reagent comprising at least one primary and/or secondary amino group as well as at least one tertiary amino group in its structure has to be used
  • the reaction is preferably carried out with a combination of amine reagents in the absence of any additional reagents such as diols, alcohols, glycols, water, diacids, etc., so aminolysis of PU is the only degradation mechanism. This reduces the occurrence of by-products.
  • the one-step aminolysis requires less time than the two-step aminolysis.
  • one-step aminolysis requires a larger amount of reagent to run the reaction to completion, and the amount of aromatic diamine released is higher.
  • Aminolysis is suitable for chemical recycling of PUFs synthesized from homo- or copolyether polyols.
  • the virgin or recycled polyol can be used as the medium, or no medium is required if effective stirring of the reaction mixtures is ensured (e.g. by mechanical stirring).
  • the polyols are simply poured off the reaction mixtures or extracted from reaction mixture by using a good solvent for the polyol (ethyl acetate, chloroform, dichloromethane, etc).
  • the obtained recycled polyols contain only a very small amount of side products; the main one is aromatic diamine, which is soluble to some extent in the polyol, and a trace amount of urea.
  • Crude recycled polyols contain soluble aromatic diamines to some extent and trace amounts of urea as remnants of oligourea hard segments. These side products can be easily removed from the RPs by purification with acidic solution (HCI/water). Next, thus obtained RP is washed with water (Milli-Q H 2 O), and finally dried.
  • the present invention further provides a recycled polyols (RPs), obtained by the method described herein.
  • RPs recycled polyols
  • the quality of the obtained RPs is comparable to that of their commercial analogues.
  • a further aspect of the present invention concerns the use of a recycled polyol obtained by the method described herein as a reagent, in particular for the synthesis of polyurethane foams.
  • Purified RPs can be used as substitutes for commercial polyols in the formulations for the synthesis of PU, in particular new flexible PUFs without affecting the properties of PUFs even if they are exclusively prepared from RPs thus obtained.
  • Purified RPs can successfully be used in various amounts, including 100%, in the formulation for the synthesis of PU, in particular new flexible PUFs without adjustment of the formulation.
  • the PUFs made even from 100% RP are of the same quality as the foams made from 100% virgin polyols.
  • Crude or purified RPs can also be used in a variety of other applications, as its structural and molecular weight properties match those of the commercial polyols.
  • Fig. 1 Reaction scheme of aminolysis of PUF with primary amine reagent, leading to the RP and the residues of PUF hard segments terminated via urea bonds with the amine reagent.
  • Fig. 2 Structure of tris(2-aminoethyl)amine (TREN) and branched polyethylenimine (PEI) reagents containing primary and/or secondary and tertiary amino groups in the structure.
  • TREN tris(2-aminoethyl)amine
  • PEI branched polyethylenimine
  • Fig. 3 Proposed amine reagents containing primary and/or secondary and tertiary amino groups in the structure.
  • Fig. 4 1 H NMR spectra of commercial polyether polyol (1), purified RP (2), and crude RP (3) obtained by PUF aminolysis and recorded in DMSO-c/e. Complete degradation of the urethane groups in RP ((2) and (3)) is confirmed in the magnified spectra recorded in DMSO-c/e with added TFA (to shift the signal of the amino groups toward a lower magnetic field) by the absence of the peak at 4.88 ppm belonging to the methyne group of the polyol adjacent to the urethane group. The presence of TDA in DMSO- /e is indicated by asterisks (*).
  • Fig. 5 SEC/MALS-RI chromatograms of commercial polyether polyol (1), purified RP (2), and crude RP obtained by PUF aminolysis (3).
  • Fig. 6 MALDI-TOF mass spectra of commercial PPO-based polyether polyol (1) and purified recycled analogue obtained by PUF aminolysis (2), where complete degradation of urethane groups was achieved.
  • the measured monoisotopic signals are denoted in the magnified regions of the mass spectra and are in good agreement with the calculated exact masses (M) ionized with the sodium ion for the proposed structures.
  • Fig. 7 FTIR spectra of commercial polyether polyol (1) and purified recycled analogue obtained by PUF aminolysis (2), where complete degradation of urethane groups was achieved.
  • Fig. 8 (A) MALDI-TOF mass spectra, (B) magnified 1 H NMR spectra, (C) SEC/UV-RI chromatograms, and (D) FTIR spectra of VP5611 (1) and the corresponding RPs obtained with 13.2 wt% TREN (4.00 Eqs of TREN amino per PUF urethane group) with RP as medium (2) and without the use of medium (bulk) (3) at 220 °C for 30 min.
  • the 1 H NMR spectra were normalized to the methyl group of the PO repeating units.
  • Peak assignment refers to polyol methyl (a), methylene, and methyne protons (b,c) of the repeating PO unit (-CH 3 ; 1.04 ppm and -CH 2 , -CH ⁇ ; 3.15-3.70 ppm).
  • the residual DMSO solvent peak in the 1 H NMR spectra is indicated with an asterisk.
  • the solid and dashed curves in the SEC/UV-RI chromatograms represent the Rl and UV detector responses, respectively.
  • Fig. 9 HPLC-ELS chromatograms obtained on a mixed-mode column (A) with magnified area (B) for commercial polyether polyol (1) and purified RPs with a degree of degradation of urethane groups of > 99% (2) and 68% (3).
  • the low intensity peaks at elution volumes of 4.65 mL and 8.32 mL represent the polyol chains functionalized with the aromatic amino group at one chain end and a dimer in which two polyol chains are linked with a hard segment, respectively (both types of polyols are the result of incomplete urethane group degradation).
  • FIG. 10 Comparison of (A) MALDI-TOF MS, (B) 1 H NMR, (C) SEC/RI-UV and (D) HPLC characterization results for purified RP (2) recovered from PPO-based PUF by a two-step aminolysis procedure with TREN and the corresponding VP5611 (1).
  • the measured monoisotopic signals of the fully hydroxyl-functionalized polyol in MALDI-TOF mass spectra are shown in the magnified regions of (A).
  • the 1 H NMR spectra were normalized to the methyl group of the PO repeating units.
  • Peak assignment refers to polyol methyl (a), methylene, and methyne protons (b,c) of the repeating PO unit (-CH 3 ; 1.04 ppm and -CH 2 , -CH ⁇ ; 3.15-3.70 ppm).
  • the residual DMSO solvent peak in the 1 H NMR spectra is indicated with an asterisk.
  • the solid and dashed curves in (C) represent the Rl and UV detector responses, respectively.
  • FIG. 11 (A) MALDI-TOF mass spectra, (B) magnified 1 H NMR spectra, (C) SEC/UV-RI chromatograms, (D) FTIR spectra and (E) HPLC chromatograms of VP5611 (1) and the corresponding fully hydroxyl-functionalized RP (2) obtained by two-step aminolysis, where the first aminolysis step was performed with HMDA (4.00 Eqs of HMDA amino per PUF urethane group) at 220 °C for 30 min and the second aminolysis step with TREN (6.00 Eqs of TREN amino per PUF urethane group) at 220 °C for 20 min.
  • the 1 H NMR spectra were normalized to the methyl group of the PO repeating units.
  • Peak assignment refers to polyol methyl (a), methylene, and methyne protons (b,c) of the repeating PO unit (-CH 3 ; 1.04 ppm and -CH 2 , - CH ⁇ ; 3.15-3.70 ppm).
  • the residual DMSO solvent peak in the 1 H NMR spectra is indicated with an asterisk.
  • the solid and dashed curves in the SEC/UV-RI chromatograms represent the Rl and UV detector responses, respectively.
  • Fig. 12 (A) MALDI-TOF mass spectra, (B) magnified 1 H NMR spectra, (C) SEC/UV-RI chromatograms and (D) FTIR spectra of VP5611 (1) and the corresponding fully hydroxyl-functionalized RP (2) obtained by two-step aminolysis carried out at 220 °C in one-pot manner by successively adding HMDA (4.00 Eqs of HMDA amino per PUF urethane group, for 30 min) and TREN (6.00 Eqs of TREN amino per PUF urethane group, for 20 min) to the same reaction mixture.
  • HMDA (4.00 Eqs of HMDA amino per PUF urethane group, for 30 min
  • TREN (6.00 Eqs of TREN amino per PUF urethane group, for 20 min)
  • Peak assignment refers to polyol methyl (a), methylene, and methyne protons (b,c) of the repeating PO unit (-CH 3 ; 1.04 ppm and -CH 2 , -CH ⁇ ; 3.15-3.70 ppm).
  • the residual DMSO solvent peak in the 1 H NMR spectra is indicated with an asterisk.
  • the solid and dashed curves in the SEC/UV-RI chromatograms represent the Rl and UV detector responses, respectively.
  • TBA aromatic amine
  • Example 6 To test whether the efficiency of a combination of an amine degradation reagent containing only primary amino groups (reactant) and a catalyst containing only a tertiary amino group in the structure, is as effective as our amine reagents, which contain both types of amino groups in the same molecule, the degradation of PUFs was carried out using the reagent hexamethylenediamine (HMDA) and the commercial catalyst B11 catalyst (mixture of dimethylaminoethoxyethanol and bis(2-dimethylaminoethyl)ether).
  • HMDA reagent hexamethylenediamine
  • B11 catalyst mixture of dimethylaminoethoxyethanol and bis(2-dimethylaminoethyl)ether
  • the amine reagent which structure consists of primary and/or secondary as well as tertiary functional amino groups, is much more effective and guarantees complete degradation of the urethane groups in the PUF structure and thus the synthesis of high-quality recycled polyols, while the PUF degradation with the reagent containing only primary amino groups in the presence of a catalyst containing only tertially amino group in the structure is less effective and leads to partially aromatic aminofunctionalized recycled polyol.
  • the polyol methyne signal (-NHCOO-CH ⁇ ) adjacent to the remaining urethane groups is at the chemical shift of 4.88 ppm in the 1 H NMR spectra of RPs recorded in DMSO-c/e with the addition of TFA.
  • the 2,6-TDA and 2,4-TDA isomers soluble in polyol show methyl proton signals at 1 .79 and 1 .88 ppm (H 2 N-(CH 3 (CeH 6 ))-NH 2 ), respectively, aromatic proton signals (H 2 N-(CH 3 (CeH 6 ))-NH 2 ; 5.75, 5.88, 5.92 and 6.54 ppm), and amino protons (-NH 2 ; from 4.43 to 4.46 ppm).
  • the hydroxyl groups of RPs are at 4.40 ppm.
  • the urea can be found in trace amounts, with methyl proton signals (-CH 3 ) of the terminal units at 2.05, 2.07, 2.08 ppm, aromatic signals between 6-7 ppm and amino protons (-NH 2 ) at the chemical shifts from 4.68 to 4.71 ppm.
  • methyl proton signals -CH 3
  • aromatic signals between 6-7 ppm
  • amino protons -NH 2
  • the SEC/UV-MALS-RI chromatogram (Fig. 5) of the obtained purified recycled polyol (chromatogram (2) in Fig. 5) shows the presence of polyol at 9.4 minutes.
  • the high degree of degradation of the PUF network is confirmed by the absence of any high molecular weight species.
  • the chromatogram of the crude RP (chromatogram (3) in Fig. 5) also shows the presence of low molecular weight residues of hard segments, such as isomers of TDA detected at longer elution times (22-37 minutes). Low molecular weight side products are completely removed by purification of RP (chromatogram (2) in Fig. 5).
  • the FTIR spectra (Fig. 7) of commercial polyether polyol ((1), black) and its recycled analogue ((2), blue) obtained by PUF aminolysis process are in perfect agreement.
  • the broad band at 3474 cm' 1 in the FTIR spectra is due to the stretching vibration of the polyol hydroxyl end groups.
  • the bands between 3060 and 2750 cm' 1 correspond to the C-H stretching vibrations and the bands at 1454 cm' 1 and 1373 cm' 1 correspond to the C-H bending vibrations of the methyl, methylene and methyne groups of the polyol.
  • the intense band at 1094 cm' 1 is due to the C-O-C stretching vibration of the polyol ether groups.
  • Removing polyurethane coatings of metal insert components comprises subjecting the polyurethane coating to a solvolysis treatment in a liquid or vapor state and in the presence of a solvolyzing agent containing diol and aliphatic amine. DE 10 2007 020 541 A1 , 2008.

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Abstract

La présente invention concerne le recyclage de polyuréthane, en particulier de mousses de polyuréthane par aminolyse avec des réactifs comprenant à la fois des groupes amino primaires et/ou secondaires et tertiaires dans la structure pour récupérer des polyols de qualité comparable aux polyols commerciaux.
PCT/EP2023/060983 2022-04-29 2023-04-26 Recyclage de polyuréthanes par aminolyse avec des réactifs comprenant des groupes amino primaires et/ou secondaires et tertiaires dans la structure WO2023209022A1 (fr)

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