WO2026022110A1 - Procédé de préparation d'un mélange de diamines ou d'une diamine à partir de déchets plastiques contenant un (co)polymère à base d'éthylène - Google Patents

Procédé de préparation d'un mélange de diamines ou d'une diamine à partir de déchets plastiques contenant un (co)polymère à base d'éthylène

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Publication number
WO2026022110A1
WO2026022110A1 PCT/EP2025/070909 EP2025070909W WO2026022110A1 WO 2026022110 A1 WO2026022110 A1 WO 2026022110A1 EP 2025070909 W EP2025070909 W EP 2025070909W WO 2026022110 A1 WO2026022110 A1 WO 2026022110A1
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Prior art keywords
aliphatic
proportion
mixture
diamine
composition
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PCT/EP2025/070909
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English (en)
Inventor
Raphael Johannes WISCHERT
Joel POLLINO
Stéphane JEOL
Matthieu CORBET
Thierry Senninger
Yann BERTHOLO
Philippe Marion
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Syensqo Specialty Polymers USA LLC
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Syensqo Specialty Polymers USA LLC
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Publication of WO2026022110A1 publication Critical patent/WO2026022110A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
    • C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/84—Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/22—Preparation of carboxylic acid nitriles by reaction of ammonia with carboxylic acids with replacement of carboxyl groups by cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/06—Oxidation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/50—Partial depolymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • 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
    • C08J11/16—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 inorganic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
    • C08J11/26—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing carboxylic acid groups, their anhydrides or esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene

Definitions

  • the present disclosure relates to a method for preparing a mixture of aliphatic diamines (method M1) or an aliphatic diamine (method M2) from plastic wastes containing an ethylene-based (co)polymer.
  • Plastic pollution is nowadays a global environmental threat as plastic pollution is now prevalent and ubiquitous. Yet, burning plastic wastes is not an environmentally friendly solution. Plastic pollution calls for new, sustainable and effective ways to recycle plastics and to preserve their material value.
  • Russ. J. Appl. Chem. 2010, 83, 97-101 discloses the chemical transformation of polyethylene into diacids.
  • Science 2022, 378, 207-211 discloses the chemical transformation of PE into diacids with the use of O 2 in the presence of at least one catalyst.
  • the invention relates to a method (M2) for preparing at least one aliphatic diamine of formula H2N-(CH2)x-NH2, x being an integer from 6 to 12, from a plastic product (P) comprising at least one ethylene-based (co)polymer (POL), the method comprising the following sequence of steps a), b), c) and d) or steps a), b), c*), d*) and e*):
  • MDI aliphatic dicarboxylic acids
  • MDA comprises the aliphatic diamines (DA X ) of formula H2N-(CH 2 ) X -NH2 where x is an integer from 4 to 12 where the total proportion of said diamines is at least 40 wt.%, preferably at least 50.0 wt.%, more preferably at least 60.0 wt.%, even more preferably at least 70.0 wt.%, even more preferably at least 80.0 wt.%, this proportion being relative to the total proportion of all aliphatic diamines present in MDA.
  • Plastic product (P) comprises at least one ethylene-based (co)polymer (POL).
  • An ethylene-based (co)polymer designates a polymer comprising at least 75.0 mol% of ethylene units, preferably at least 80.0 mol%, preferably at least 90.0 mol%, preferably at least 95.0 mol%, preferably at least 99.0 mol%.
  • the richer the proportion of ethylene units in POL the better the yield of the chemical transformation POL -> aliphatic dicarboxylic acids. Also, the richer the proportion of ethylene units in POL, the better for obtaining a mixture richer in diacids after the oxidation step a).
  • the ethylene-based (co)polymer (POL) is preferably a polyolefin.
  • alpha-olefin comonomers examples include propylene, 1-butene, 3-methyl-1-butene, 3,3- dimethyl-1 -butene, 1 -pentene, 1 -pentene with one or more methyl, ethyl, or propyl substituents, 1 -hexene, 1 -hexene with one or more methyl, ethyl, or propyl substituents, 1 -heptene, 1 -heptene with one or more methyl, ethyl, or propyl substituents, 1-octene, 1-octene with one or more methyl, ethyl, or propyl substituents, 1-nonene, 1-nonene with one or more methyl, ethyl, or propyl substituents, ethyl, methyl, or dimethyl-substituted 1-decene and 1-dodecene.
  • Butadiene is an example
  • the ethylene-based (co)polymer is more preferably selected in the group consisting of very low density polyethylene, low density polyethylene (LDPE), linear low density polyethylene, medium density polyethylene, cross-linked polyethylene, high density polyethylene (HDPE), high density cross-linked polyethylene, high molecular weight polyethylene, ultra-low molecular weight polyethylene, ultra-high molecular weight polyethylene and combinations thereof.
  • Plastic product (P) may be pretreated prior to step a).
  • the pretreatment step may include a mechanical or physical modification of plastic product (P), such as cutting, crushing or grinding.
  • plastic product (P) Prior to step a), plastic product (P) is advantageously transformed into particles of plastic product (P) with a size lower than 10.0 mm, preferably lower than 5.0 mm, even preferably lower than 3.0 mm. This makes it possible to decrease the reaction time of the oxidation step a).
  • plastic product (P) is subjected to a controlled oxidation of the ethylenebased (co)polymer (POL) effective to obtain a stream (Sa) comprising a mixture of aliphatic diacids (MDI) of formula HOOC-Alk-COOH where Aik designates a linear alkylene group.
  • POL ethylenebased polymer
  • MDI aliphatic diacids
  • Aik is typically a C2-C25 linear alkylene group.
  • the controlled oxidation of step a) consists in bringing into contact the ethylenebased (co)polymer (POL) present in plastic product (P) with at least one oxidizing agent.
  • the function of the oxidizing agent is to break down the macromolecules containing the ethylene recurring units and to create carboxylic acid groups.
  • the oxidizing agent is generally selected in the group consisting of oxygen (O 2 ), nitric oxide (NO), nitrous oxide (N 2 O), nitrogen dioxide (NO 2 ), nitric acid (HNO 3 ) and combinations thereof. It is advantageously nitric acid.
  • the temperature at which the oxidation of step a) is performed is generally at least 100°C.
  • the reaction medium (RM) comprising the plastic product (P) and the oxidizing agent in which the controlled oxidation takes place typically comprises water.
  • a catalyst is typically present in the reaction medium (RM) comprising the plastic product (P) and the oxidizing agent.
  • the controlled oxidation is typically performed in a closed reactor under an autogenous pressure P higher than 1 bar.
  • the oxidizing agent is O 2 or NO+O 2 .
  • the temperature at which the oxidation of step a) is performed is generally at least 120°C.
  • Conditions disclosed in D4 and in the supplementary materials of D4 may be followed to convert the ethylene-based (co) polymer (POL) into dicarboxylic acids using O 2 as an oxidizing agent in the presence of a catalyst.
  • the oxidation reaction may be performed according to the following conditions: catalyst: Ru/TiO 2 + air; temperature between 150 and 200°C; pressure of air > 1 MPa; duration between 5 and 24 hours.
  • Conditions disclosed in D2 or in D8 may be followed to convert the ethylene-based (co)polymer (POL) into dicarboxylic acids using NO+O 2 as an oxidizing agent.
  • the conditions of D8 lead to a MDI comprising essentially succinic, glutaric, adipic and pimelic acids.
  • Example D provides specific conditions according to D8.
  • Conditions disclosed in D9 may be followed to convert the ethylene-based (co)polymer (POL) into dicarboxylic acids using O 2 in the presence of a catalyst.
  • Conditions disclosed in D10 and in the supplementary materials of D10 may be followed to convert the ethylene-based (co) polymer (POL) into dicarboxylic acids using O 2 in the presence of at least one catalyst.
  • Typical conditions are the following: O 2 and H 2 under pressure; temperature between 130 and 180°C; catalysts: Co(OAc) 2 +Mn(OAc) 2 ; N-hydroxyphthalimide.
  • the supplementary materials of D10 disclose the conditions to optimize the proportions of Dl 6 ⁇ i 2 in the MDI.
  • Example A provides specific conditions according to D10.
  • Conditions disclosed in D12 may be followed to convert the ethylene-based (co)polymer (POL) into dicarboxylic acids using O 2 in the presence of a catalyst based on Mn and Co.
  • Example C provides specific conditions according to D12.
  • Embodiment (E2) [0083] Conditions disclosed in the above-referenced documents of the background art can be followed for performing step a) under embodiment (E2).
  • the oxidizing agent is HNO 3 .
  • the temperature at which the ethylene-based (co)polymer (POL) of plastic product (P) reacts with HNO 3 is at least 100°C, preferably between 100 and 200°C.
  • the weight ratio HNO 3 / ethylene-based (co)polymer (POL) is generally between 1.0 and 30.0.
  • the temperature and duration of the oxidation have an influence on the relative proportions of the dicarboxylic acids as is visible in table 3 of D5. The higher the temperature and the duration of the oxidation, the lower the proportion of Dl> 6 .
  • D1 and D7 Conditions disclosed in D1 and D7 may be followed to convert the ethylene-based (co)polymer (POL) into dicarboxylic acids using HNO 3 .
  • Some conditions of D7 lead to a MDI where the relative proportions of diacids are the following: Dl 4 (49 wt.%); Dis (39 wt.%) and Die (12 wt.%).
  • Example H provides specific conditions according to D1.
  • HNO 3 ethylene-based (co)polymer
  • temperature between 100 and 150°C
  • weight ratio HNOs/ethylene-based (co)polymer (POL) between 1.5 and 25.0
  • duration between 1 and 10 hours.
  • Example E, F and G provide specific conditions according to D6.
  • Mixture MDI comprises aliphatic diacids of formula HOOC-Alk-COOH where Aik designates a linear alkylene group.
  • stream (Sa) and the mixture of aliphatic diacids (MDI) typically comprise diacids selected in the group consisting of oxalic acid (Dl 2 ); malonic acid (Dl 3 ); succinic acid (DU); glutaric acid (Dl 5 ); adipic acid (Die); pimelic acid (DI?); suberic acid (Dl 8 ); azelaic acid (Dl 9 ); sebacic acid (DU); undecanedioic acid (Din); dodecanedioic acid (DU) and aliphatic diacids having 13 or more carbon atoms (DI>1 3 ).
  • the conditions of the controlled oxidation are preferably such that in the mixture MDI obtained at the end of step a) or at the end of step b),
  • the proportion of Dl 2 is lower than or equal to 12.0 wt.% ( ⁇ 12.0 wt.%), preferably lower than or equal to 10.0 wt.% ( ⁇ 10.0 wt.%), preferably lower than or equal to 5.0 wt.% ( ⁇ 5.0 wt.%); and/or
  • the proportion of Dl 3 is lower than or equal to 12.0 wt.% ( ⁇ 12.0 wt.%), preferably lower than or equal to 10.0 wt.% ( ⁇ 10.0 wt.%), preferably lower than or equal to 5.0 wt.% ( ⁇ 5.0 wt.%); and/or
  • the proportion of Dl 4 is lower than or equal to 20.0 wt.% ( ⁇ 20.0 wt.%), preferably lower than 15.0 wt.% ( ⁇ 15.0 wt.%), preferably lower than 5.0 wt.% ( ⁇ 5.0 wt.%); these proportions being given in wt.% relative to the total proportions of all aliphatic dicarboxylic acids in MDI.
  • the conditions of the controlled oxidation are preferably such that in the mixture MDI obtained at the end of step a) or at the end of step b),
  • the proportion of D 11 2 is lower than or equal to 10.0 wt.% ( ⁇ 10.0 wt.%), preferably lower than 5.0 wt.% ( ⁇ 5.0 wt.%); and/or
  • the proportion of D11 3 is lower than or equal to 5.0 wt.% ( ⁇ 5.0 wt.%), preferably lower than 2.0 wt.% ( ⁇ 2.0 wt.%); and/or
  • each DUi 2 is greater than or equal to 2.0 wt.% (> 2.0 wt.%), preferably greater than or equal to 1 .0 wt.% (> 1 .0 wt.%); these proportions being given in wt.% relative to the total proportions of all aliphatic dicarboxylic acids in MDI.
  • the conditions of the controlled oxidation are preferably such that in the mixture MDI obtained at the end of step a) or at the end of step b), the total proportion of Dl 6 ⁇ i 2 is greater than or equal to 40.0 wt.% (> 40.0 wt.%), preferably greater than or equal to 50.0 wt.% (> 50.0 wt.%), this proportion being given in wt.% relative to the total proportions of all aliphatic dicarboxylic acids in MDI.
  • the conditions of the controlled oxidation are preferably such that in the mixture MDI obtained at the end of step a) or at the end of step b), the total proportion of DI 2 ⁇ 13 is greater than or equal to 60.0 wt.% (> 60.0 wt.%), preferably greater than or equal to 70.0 wt.% (> 70.0 wt.%), preferably greater than or equal to 80.0 wt.% (> 80.0 wt.%), this proportion being given in wt.% relative to the total proportions of all aliphatic dicarboxylic acids in MDI.
  • the conditions of the controlled oxidation are preferably such that in the mixture MDI obtained at the end of step a) or at the end of step b), the total proportion of the aliphatic dicarboxylic acids having > 20 carbon atoms (DI>2O) is lower than or equal to 10.0 wt.% ( ⁇ 10.0 wt.%), preferably lower than or equal to 5.0 wt.% ( ⁇ 5.0 wt.%), this proportion being given in wt.% relative to the total proportions of all aliphatic dicarboxylic acids in MDI.
  • Optional step b) may be performed according to step b1) and/or step b2) and makes it possible to improve the chemical efficiency of steps c) and d) or steps c*) and d*).
  • Both steps b1) and b2) are based on at least one separation process conducted by any suitable known methods such as, for example distillation, filtration, extraction, adsorption, crystallization, chromatography and combination of these methods.
  • stream (Sb) is obtained.
  • step c) the mixture of aliphatic diacids (MDI) present in stream (Sa) or (Sb) is chemically converted into a mixture of aliphatic diamines (MDA).
  • MDI mixture of aliphatic diacids
  • ROOC-Alk-COOR N C-Alk-CHN H 2 N-Alk-NH 2 being understood that Aik designates a linear alkylene group and that in those reactions, the number of carbon atoms for each reaction is preserved.
  • the MDI is brought into contact with ZnO and p-TsOH*H 2 O and the mixture is brought into contact with gaseous NH 3 .
  • the temperature at which the mixture is heated is higher than 200°C, preferably higher than 250°C.
  • the conditions disclosed in the experimental section may more particularly be followed.
  • the MDI is brought into contact with phosphoric acid and ammonia at a temperature of at least 200°C.
  • the MDN is generally put into contact with hydrogen in the presence of a catalyst, such as a hydrogenation catalyst based on Ni typically Raney® nickel.
  • a catalyst such as a hydrogenation catalyst based on Ni typically Raney® nickel.
  • the conditions disclosed below may more particularly be followed:
  • MDN is put into contact with a hydrogenation catalyst, ammonia and hydrogen at a temperature between 100°C and 200°C.
  • the hydrogenation catalyst may be a hydrogenation catalyst based on Ni typically Raney® nickel; or
  • the MDN is brought into contact with a hydrogenation catalyst based on Ni typically Raney® nickel, ammonia, isopropanol and hydrogen.
  • a hydrogenation catalyst based on Ni typically Raney® nickel, ammonia, isopropanol and hydrogen.
  • the temperature at which the mixture is heated is higher than 100°C.
  • R is typically selected in the group consisting of methyl, ethyl, n-propyl, /so-propyl, n-butyl, /so-butyl and pentyl.
  • This reaction of esterification is known as an equilibrated reaction.
  • An acid catalyst is normally used such as sulfuric acid, methanesulfonic acid or an acidic resin such as AmberlystTM. Removal of water to shift the reaction towards the diesters is typically used to improve the yield of conversion into the diesters.
  • the mixture of aliphatic diesters comprises diesters of formula ROOC-(CH 2 )x-2 _ COOR where x is an integer from 4 to 12 where the total proportion of said diesters is at least 40.0 wt%, preferably at least 50.0 wt.%, more preferably at least 60.0 wt.%, even more preferably at least 70.0 wt.%, even more preferably at least 80.0 wt.%, this proportion being relative to the total proportion of all aliphatic diesters present in MDE; and/or comprises the diesters of formula ROOC-(CH 2 )x-2 _ COOR where x is an integer from 6 to 12 where the total proportion of said diesters is at least 40.0 wt.%, preferably at least 50.0 wt.%, more preferably at least 60.0 wt.%, even more preferably at least 70.0 wt.%, this proportion being relative to the total proportion of all aliphatic die
  • This conversion is performed in conditions similar to those disclosed above for conversion MDI MDN.
  • a typical reaction involves bringing MDE in contact with ammonia at a temperature higher than 150°C optionally in the presence of a catalyst.
  • step c) of the method of the invention may be implemented following the two chemical routes below: route 1 : MDI MDN MDA route 2: MDI MDE MDN MDA
  • the total proportion in MDE of the aliphatic diesters (DE X ) that are derived from dicarboxylic acids having >6 carbon atoms is at least 80.0 wt.%, this proportion being relative to the total weight of MDE.
  • Such MDE enriched in the aliphatic diesters derived from dicarboxylic acids having >6 carbon atoms can be prepared by one or more distillation steps. The conditions distillation are adapted to cut off the aliphatic diesters derived from dicarboxylic acids having ⁇ 5 carbon atoms.
  • step c At the end of step c), one recovers a mixture of aliphatic diamines (MDA).
  • MDA aliphatic diamines
  • step d) at least one aliphatic diamine DA X of formula H 2 N-(CH 2 ) X -NH 2 is separated from MDA and recovered by at least one separation process.
  • the separation process may be selected in the group consisting of distillation, extraction, adsorption, crystallization, chromatography and any combination thereof.
  • Step d) of method (M2) may be performed with only one separation process notably from the list of separation processes above or with more than one separation processes notably from the list of separation processes above.
  • Fig. 4/4 illustrates the case where several separation processes (noted SP) leading to recovery of three distinct diamines DA X , DA y and DA Z are performed. These separation processes are performed either in parallel (see separation processes SP2 and SP2*; in SP1 , the mixture of diamines MDA leads to two streams S1 and S1*) or in succession (see separation processes SP2 leading to stream S2 and SP3).
  • SP separation processes
  • Step d) conveniently comprises one or more distillation steps. Each distillation step is based on the use of [or performed with] a distillation column. Distillation is a convenient technique for step d2), all the more so that it is observed that the differences between the boiling points of the dinitriles are not as pronounced for the dinitriles as for the diamines.
  • distillation steps are preferably performed under vacuum, preferably at a pressure below 100 mbar absolute head pressure.
  • distillation column(s) that can be used (number of theoretical stages, reflux ratio, feed point, pressure) are adapted according to the composition of the stream entering into a column and according to the component(s) to be recovered.
  • step d one recovers at least one aliphatic diamine of formula H 2 N-(CH 2 ) X -NH 2 with a purity (p) of at least 99.0 wt.%, preferably at least 99.5 wt.%.
  • Step c* [00146]
  • the mixture of aliphatic diacids (MDI) present in stream (Sa) or (Sb) is chemically converted into a mixture of aliphatic diesters (MDE). Details and embodiments about the conversion of a diacid into a diester, notably embodiment (e), provided above apply here.
  • the esterification reaction is the following:
  • the mixture of aliphatic diesters comprises diesters of formula ROOC-(CH 2 ) X.2 -COOR where x is an integer from 4 to 12 where the total proportion of said diesters is at least 40.0 wt%, preferably at least 50.0 wt.%, more preferably at least 60.0 wt.%, even more preferably at least 70.0 wt.%, even more preferably at least 80.0 wt.%, this proportion being relative to the total proportion of all aliphatic diesters present in MDE; and/or comprises the diesters of formula ROOC-(CH 2 ) X.2 -COOR where x is an integer from 6 to 12 where the total proportion of said diesters is at least 40.0 wt.%, preferably at least 50.0 wt.%, more preferably at least 60.0 wt.%, even more preferably at least 70.0 wt.%, this proportion being relative to the total proportion of all aliphatic diesters present in MDE; and
  • step d* one or more aliphatic diesters DE X of formula ROOC-(CH 2 ) X.2 -COOR is/are separated from MDE and recovered by at least one separation process.
  • the separation process may be selected in the group consisting of distillation, extraction, adsorption, crystallization, chromatography and any combination thereof.
  • Step d*) of method (M2) may be performed with only one separation process notably from the list of separation processes above or with more than one separation processes notably from the list of separation processes above.
  • Step d* conveniently comprises one or more distillation steps. Each distillation step is based on the use of [or performed with] a distillation column. Distillation is a convenient technique for step d*), all the more so that it is observed that the differences between the boiling points of the dinitriles are not as pronounced for the dinitriles as for the diesters. Therefore, the distillation is a convenient technique to purify a diester prior to its being converted into the corresponding diamine.
  • distillation column(s) that can be used (number of theoretical stages, reflux ratio, feed point, pressure) are adapted according to the composition of the stream entering into a column and according to the component(s) to be recovered.
  • R is more particularly methyl or ethyl to have light diesters to be separated by distillation.
  • step e* diester DE X is then converted into the corresponding diamine DA X , the chemical conversion being notably based on the conversion of the diester into a dinitrile which is converted into the diamine.
  • the chemical conversion can be the following:
  • diamine DA X may be purified through one or more distillation steps to obtain the targeted purity (p).
  • the methods of the invention make it possible to obtain one or more aliphatic diamines with a high purity (p) suitable to be used in a polycondensation process to prepare a polyamide.
  • p purity
  • the proportion of monoamines needs to be low.
  • the total proportion of monoamine(s) in the recovered aliphatic diamine is at most 0.5 wt.%, this proportion being based on the total weight of the aliphatic diamine.
  • the total proportion of C1-C18 monoamine(s) in the recovered aliphatic diamine is at most 0.5 wt.%, this proportion being based on the total weight of the aliphatic diamine.
  • the purity (p) of the diamines and the quantification of the other molecules present can be determined by any suitable analytical technique.
  • a convenient analytical technique for determining the purity (p) is gas chromatography (GC) or liquid chromatography (HPLC).
  • step c At the end of step c), one obtains a mixture MDA. After step d) or step d*), one obtains a diamine DA X .
  • the recovered diamine DA X typically contains trace quantities of the other diamines DA x+i and DA x -i where x is any one of the integers present in the range ⁇ 6-12 ⁇ .
  • the recovered diamine DA X is typically part of a composition (C) comprising diamine DA X where x is any one of the integers present in the range ⁇ 6-12 ⁇ and the diamines DA x+i and DA x ⁇ i with the following proportions:
  • - diamine DA X at least 99.0 wt.%, preferably at least 99.5 wt.%;
  • each diamine DA x+i and DA x -i at most 0.5 wt.%, preferably at most 0.1 wt.%; these proportions being based on the total weight of composition (C).
  • x is any one of the integers present in the range ⁇ 6-12 ⁇ , for example x is 6, 7, 8, 9, 10, 11 or 12.
  • composition (C) comprises diamine DA 6 (of formula H 2 N- (CH 2 )6-NH 2 )
  • - diamine DA 6 at least 99.0 wt.%, preferably at least 99.5 wt.%;
  • - diamine DA? at most 0.5 wt.%, preferably at most 0.1 wt.%;
  • composition (C) at most 0.5 wt.%, preferably at most 0.1 wt.%; these proportions being based on the total weight of composition (C).
  • composition (C) comprises diamine DAg (of formula H 2 N-(CH 2 ) 9 -NH 2 ):
  • - diamine DA 9 at least 99.0 wt.%, preferably at least 99.5 wt.%;
  • - diamine DA 8 at most 0.5 wt.%, preferably at most 0.1 wt.%;
  • composition (C) at most 0.5 wt.%, preferably at most 0.1 wt.%; these proportions being based on the total weight of composition (C).
  • composition (C) is preferably the following:
  • the total proportion of the aliphatic diamines DA y in composition (C) where y is an integer different from x, x+1 and x-1 , is at most 0.5 wt.%.
  • composition (C) of the invention is preferably at most 0.5 wt.%, preferably at most 0.25 wt.%, this proportion being based on the total weight of composition (C).
  • the total proportion of Ci-Cis monoamine(s) in composition (C) of the invention is preferably at most 0.5 wt.%, preferably at most 0.25 wt.%, this proportion being based on the total weight of composition (C).
  • Composition (C) may be used for the preparation of a polyamide comprising in polymerized form a diamine DA X .
  • Composition (C) can be prepared by the method disclosed herein, notably in the method disclosed in any one of the claims.
  • Examples A-H illustrate the chemical conversion of polyethylene into a mixture of dicarboxylic acids.
  • the other examples 1-12 illustrate the preparation of one of more diamines.
  • the conditions of transformation of the mixtures disclosed in examples 1-12 are applicable to mixture of dicarboxylic acids (MDI) obtained in examples A-H.
  • Example A illustrates oxidation of PE under embodiment (E1)
  • Conditions used 54 kDa HDPE bead or 99 kDa milk bottle (350 mg, 1250 mM repeating ethylene unit), Co(OAc) 2 (9.7 wt.%, 9.6 mM), Mn(OAc) 2 (9.5 wt.%, 9.6 mM), NHPI (22.4 wt.%, 24.0 mM), 8 bar O 2 /72 bar N 2 , 2.5 hr, 160°C.
  • Example B illustrates oxidation of PE under embodiment (E1)
  • Preparation of catalyst the preparation of the photocatalyst included two steps. Firstly, polyvinylpyrrolidone (PVP; 1.0 g), Bi(NO 3 )3*5H 2 O (0.8 mmol) were mixed with ethylene glycol (40 mL) (mixture A). 0.8 mmol of NH 4 VO 3 was dissolved into 40 mL of deionized water (solution B). Mixture A and solution B were then mixed and stirred for 0.5 h, followed by keeping at 180°C for 10 h. Finally, the solid was filtered out and washed three times with ethanol.
  • PVP polyvinylpyrrolidone
  • Bi(NO 3 )3*5H 2 O 0.8 mmol
  • the BiVO 4 nanoparticles obtained were dried in an oven overnight.
  • 20 mL of sodium iodide (Nal) solution (20 mM) was dripped into the above suspension. After stirring for 2 h, the mixture was centrifuged at 10,000 rpm for 10 min at room temperature. The solid obtained was washed 3 times with distilled water and dried at 60°C overnight.
  • LED lightemitting diode
  • Example C illustrates oxidation of PE under embodiment (E1)
  • a milk bottle (HOPE) was converted into dicarboxylic acids with a 41% yield, including 75% of C 4 -C 9 dicarboxylic acids, alongside the detection of acetic acid and formic acid.
  • Example D illustrates oxidation of PE under embodiment (E1)
  • Example E illustrates oxidation of PE under embodiment (E2)
  • the feedstock for this example was 10 g polyethylene and 100 g of a 70 wt.% aqueous nitric acid.
  • the oxidation reaction was conducted in a vessel for 9 hours at 120°C and atmospheric pressure.
  • the products were dicarboxylic acids (50-65 wt.%) and a separate fraction (35-50 wt.%) containing other components including nitro-substituted dicarboxylic acids.
  • the dicarboxylic acids were separated by distillation of the reaction filtrate followed by evaporation to remove the majority of aqueous nitric acid.
  • the table below provides the ranges of various dicarboxylic acids that were found in that fraction.
  • a 250 mL round bottom flask equipped with a magnetic stir bar was loaded with 10 g polyethylene and 100 g of a 67 wt.% HNOs.
  • the reaction flask was equipped with a glass thermometer, placed onto a temperature-controlled IKA heating plate and attached to a water condenser.
  • the reaction flask was stirred at maximum stir rate (2000 rpm) and heated to a desired reaction temperature. The beginning of the reaction time was marked once the desired temperature has been reached (15—20 min). After reaction time, the heater was turned off, the reaction flask lifted from the heater, and quickly cooled while stirring (15-20 min). The final mixture
  • Tr.decatiedioic acid (CI G i i.S- l i"
  • C14 rctradecanedioic acid
  • Example G illustrates oxidation of PE under embodiment (E2)
  • the feedstock was contaminated plastic film from a material recovery facility.
  • the composition of these films includes LDPE, HDPE, as well as a miscellaneous materials that were not identified.
  • the surface contamination included dirt, debris, food residue and greases. These films were shredded into non-uniform pieces with average size 20 cmx20cm.
  • Example H illustrates oxidation of PE under embodiment (E2)
  • a FlexiWave microwave system from Milestone (Sorisole, Italy) with a maximum power of 1900 W was utilized.
  • a 0.5-g portion of LDPE powder (/W w ⁇ 35000 g/mol, thickness 70 pm, length 200-300 pm) was placed in a FlexiWave Teflon vial together with 20 mL of aqueous nitric acid solution with the nitric acid (0.50 g/mL).
  • the run times were set to be from 0.5 to 2 h.
  • a 20 min ramp time was needed; thereafter, the temperature was held constant at 180°C and the effect was 1200 W for the duration of the reaction.
  • Ammonia was directly fed from a gas cylinder (Air Liquide + ref: NH 3 -N36+ 1 L + 100%, H 2 O ⁇ 100ppm). Nitrogen and hydrogen were directly fed from gas lines.
  • Nitrilation reactions were carried out in a quartz reactor with a volume of 200 mL, equipped with a mechanical stirrer (IKA Eurostar 60 control with a Rushton turbine), a heating mantle (Elit + type + 73W) and a reflux condenser, the latter connected to an ammonia abatement column.
  • Ammonia was fed from a gas cylinder directly into the molten acid mixture via a gas dispersion tube (diameter, frit pore size, 2 cm above bottom of the reactor) while nitrogen was fed on top of the mixture via one of the necks of the reactor.
  • Gas flows were controlled via individual pressure reducing valves and calibrated flow meters (Bronkhorst EL- FLOW Prestige FG-201CV).
  • the temperature of the reaction was controlled by a thermocouple inserted into the reaction media (2 cm above bottom of the reactor). To follow the progress of the reaction, several aliquots of the reaction mixture were taken by inserting a glass rod.
  • a mixture composed of dicarboxylic acids as indicated in Table 1 was loaded into the nitrilation reactor together with 0.45 g of ZnO and 123 mg of p-TsOH»H2O, and was heated to a temperature of 220°C within 1 h under a nitrogen gas flow (2.5 L/h), and kept at this temperature for another 3 h under a mixed gas flow of nitrogen (5 L/h) and ammonia (10 L/h).
  • the acid mixture melted and the stirring speed was gradually increased to 300 rpm.
  • the stirring speed was adjusted to 600 rpm.
  • the mixture of the dicarboxylic acids (MDI) representative of a mixture obtained from the degradation of polyethylene yields a mixture of dinitriles (MDN). It can be seen that the yields of C4-C6 dinitriles are low.
  • a mixture composed of dicarboxylic acids as indicated in Table 2 was loaded into the nitrilation reactor together with 0.36 g (0.7 wt.%) of ZnO and 84 mg (0.17 wt.%) of p-TsOH «H 2 O, and heated to a temperature of 190°C within 1 h under a nitrogen gas flow (2.5 L/h), and kept at this temperature for another 3 h under a mixed gas flow of nitrogen (5 L/h) and ammonia (10 L/h).
  • the acid mixture melted, and the stirring speed was gradually increased to 300 rpm.
  • the stirring speed was adjusted to 600 rpm.
  • Example 3 preparation of a mixture of dinitriles (MDN) from a mixture of dicarboxylic acids (MDI) (conversion MDI MDN)
  • a mixture composed of dicarboxylic acids as indicated in Table 3 was loaded into the nitrilation reactor together with 0.5 g (1 wt.%) of phosphoric acid and heated to a temperature of 190°C within 1 h under a nitrogen gas flow (2.5 L/h) , and kept at this temperature for another 3 h under a mixed gas flow of nitrogen (5 L/h) and ammonia (10 L/h).
  • a temperature ramp-up the acid mixture melted, and the stirring speed was gradually increased to 300 rpm.
  • the stirring speed was adjusted to 600 rpm.
  • Example 4 preparation of a mixture of dinitriles from a mixture of diacids (conversion MDI MDN)
  • a mixture composed of diacids as indicated in Table 4 was loaded into the nitrilation reactor together with 0.5 g of phosphoric acid, and was heated to a temperature of 160°C within 30 min under a nitrogen gas flow (2.5 L/h) while increasing steadily the stirring speed as the mixture melted. Then, the stirring speed was increased to 600 rpm and a mixed feed of nitrogen (5 L/h) and ammonia (10 L/h) was introduced via a frit plunged into the reaction medium. The temperature was increased to 180°C and kept for 1 h after which it was increased to 240°C. The feed was kept at 5 L/h for nitrogen and reduced to 5 L/h for ammonia.
  • Example 5 preparation of a mixture of dinitriles from a mixture of dicarboxylic acids (conversion MDI MDN)
  • a mixture composed of dicarboxylic acids as indicated in Table 5 was loaded into the nitrilation reactor together with 0.5 g of phosphoric acid, and was heated to a temperature of 160°C within 30 min under a nitrogen gas flow (2.5 L/h) while increasing steadily the stirring speed as the mixture melted. Then, the stirring speed was increased to 600 rpm and a pure feed of ammonia (10 L/h) was introduced via a frit plunged into the reaction medium. The temperature was increased to 180°C and kept for 2 h after which it was increased to 240°C. The ammonia feed was reduced to 5 L/h. After another 1 h under these conditions, the ammonia feed was reduced to 2.5 L/h and the temperature was increased to 300°C. After 3 h under these conditions the reaction was stopped. The yields of the dinitriles corresponding to the different starting acids are reported in Table 5.
  • Example 6 preparation of a mixture of diamines (MDA) from a mixture of dinitriles (MDN) (conversion MDN MDA)
  • a mixture composed of dinitriles as indicated in Table 6 was loaded into the hydrogenation reactor, together with Raney® Ni (0.17 g), aqueous ammonia (8.08 g) and isopropanol (6 ml_).
  • the reactor was closed and purged three times with nitrogen (10 bar), and filled with hydrogen (20 bar).
  • the mixture was brought to a temperature of 110°C and stirred (1400 rpm) for 4 h.
  • the consumption of hydrogen was monitored by measuring the pressure of hydrogen.
  • the reaction mixture was filtered (Millipore 0.45 pm hydrophilic) and separated from the solvent in a rotary evaporator. The yields of aliphatic diamines corresponding to the different starting compounds are also reported.
  • Example 7 preparation of a stream (Sb) under step b1)
  • a mixture composed of dicarboxylic acids (10.5 g) as indicated in Table 7 was mixed with 15 mL of water and stirred (40 rpm) for 15 min at a temperature of 10°C.
  • the residual solid was filtered off (pore size 3) and mixed again with 15 mL of fresh water and treated as described. After performing this process three times, the solid residue was dried for 30 min at 40°C, affording 4.8 g of a mixture of acids (46% of the initial) with the composition indicated in Table 7.
  • the three filtrates were combined and dried in a rotary evaporator and then for 30 min at 40°C, affording 6.1 g of a mixture of acids with the composition indicated in Table 7. It is immediately apparent that succinic and glutaric acid were quantitatively washed out from the initial mixture.
  • Example 8 preparation of stream (Sb) under step b1)
  • Example 10 preparation of a mixture of diesters from a mixture of diacids
  • Example 11 preparation of a mixture of dinitriles from a mixture of diesters through gas phase process
  • reaction mixture in the storage tank was washed by adding 2 times the mass of dichloromethane in two parts and the organic phase (methanol + dichloromethane) was evaporated to dryness to give the product MDN in a molar yield close to 90%.
  • Example 12 preparation of dinitriles by liquid phase nitrilation of diesters

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Abstract

L'invention concerne un procédé (M1) de préparation d'un mélange de diamines aliphatiques (MDA) à partir d'un produit plastique (P) comprenant au moins un (co)polymère à base d'éthylène (POL), les diamines aliphatiques étant de formule H2N−(CH2)x−NH2 où x est un nombre entier de 6 à 12.
PCT/EP2025/070909 2024-07-22 2025-07-21 Procédé de préparation d'un mélange de diamines ou d'une diamine à partir de déchets plastiques contenant un (co)polymère à base d'éthylène Pending WO2026022110A1 (fr)

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