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WO2024156568A1 - Procédé de dépolymérisation de poly(téréphtalates d'alkylène) dans une extrudeuse - Google Patents

Procédé de dépolymérisation de poly(téréphtalates d'alkylène) dans une extrudeuse Download PDF

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Publication number
WO2024156568A1
WO2024156568A1 PCT/EP2024/051053 EP2024051053W WO2024156568A1 WO 2024156568 A1 WO2024156568 A1 WO 2024156568A1 EP 2024051053 W EP2024051053 W EP 2024051053W WO 2024156568 A1 WO2024156568 A1 WO 2024156568A1
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WO
WIPO (PCT)
Prior art keywords
barrel
integer
suspension
structural formula
polymer
Prior art date
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Ceased
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PCT/EP2024/051053
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English (en)
Inventor
Christian Zander
Thomas Richter
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Evonik Operations GmbH
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Evonik Operations GmbH
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Application filed by Evonik Operations GmbH filed Critical Evonik Operations GmbH
Priority to EP24701338.6A priority Critical patent/EP4655342A1/fr
Priority to KR1020257024496A priority patent/KR20250140523A/ko
Priority to CN202480008856.5A priority patent/CN120584149A/zh
Publication of WO2024156568A1 publication Critical patent/WO2024156568A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
    • C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
    • 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
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals
    • 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
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—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
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the invention relates to a process for depolymerization of at least one polymer Pi which is a polyalkylene terephthalate, i.e. a polymer comprising terephthalic acid units and alkylene glycol units, in particular polyethylene terephthalate PET or polybutylene terephthalate PBT.
  • the process is particularly suitable for depolymerization and for recycling of PET-containing wastes.
  • the process is performed in an extruder E having at least two barrels Gi, G2, wherein the at least one polymer Pi is provided in the barrel G1 in the form of a suspension Si in a polyolefin PO, for example polyethylene PE or polypropylene PP.
  • the suspension Si is then transported into the barrel G2.
  • At least one glycol compound G preferably ethylene glycol, and at least one alkali metal alkoxide are introduced into the barrel G2 and mixed with the suspension Si.
  • the at least one glycol compound G reacts in suspension Si with the at least one polymer Pi to afford a mixture MG2 comprising the corresponding cleavage products P2.
  • the resulting mixture MG2 is transported to the product outlet Ex of the extruder E and withdrawn there.
  • the process allows for a safer process mode since it avoids the uncontrolled increase in temperature and pressure during depolymerization of the polymer Pi.
  • PET Polyethylene terephthalate
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • the prior art proposes multiple processes for cleavage of PET.
  • GB 784,248 A describes the methanolysis of PET.
  • Ugduler et al. also discuss the problem of contamination of the PET starting material with additional polymers such as low-melting polyolefins (“polyolefin” is abbreviated as "PO" below).
  • WO 2020/053051 A1 describes in detail the saponification (page 8, line 1 of WO 2020/053051 A1), i.e. the hydrolysis, of PET using alkali metal or alkaline earth metal hydroxides, wherein ethylene glycol solvent is additionally supplied to the reaction mixture as a stream separate from the alkali metal/alkaline earth metal hydroxide stream (see figure 1 ; example 2, page 19, lines 25 to 28; example 4, page 20, lines 27 to 28 of WO 2020/053051 A1).
  • Biermann etal. also disclose the saponification of PET.
  • Mohsin et al describes the reaction of molten PET with ethylene glycol in an extruder. Mohsin et al. however does not describe the use of ethylene glycolate or the presence of additional polymers in the PET.
  • US 3,884,850 describes a system for depolymerization of PET in which PET is converted into BHET and low molecular weight oligomers of BHET. This process is not performed in an extruder.
  • glycolysis of polyesters for example PET
  • apparatuses typical for polymer processing for example extruders
  • glycolysis of polyalkylene terephthalates such as PET suffers from the problem that the melting temperature thereof is above the boiling temperature of ethylene glycol.
  • the resulting vapour pressure of the glycol compound results in pulsing and unstable operating states of the reactor. Accordingly only very small amounts of the glycol compound may be employed, which leads to the formation of oligomeric melts with relatively high viscosity, or the extruder must be operated with a pressure maintenance means to compensate the vapour pressure of the glycol compound, in particular of the ethylene glycol.
  • the depolymerization of polyalkylene terephthalates in extruders using glycol compounds may be performed without the above-described disadvantages (inhomogeneous process mode, build-up of pressure spikes) when the relevant polyester is employed in the form of a suspension.
  • the polyester is present as a solid phase, while a polyolefin PO is employed as a continuous, liquid phase.
  • Figure 1 shows one embodiment of the process according to the invention. This is performed in an extruder E ⁇ 3> having two barrels Gi ⁇ 31 > and G2 ⁇ 32> and a product outlet Ex ⁇ 33>.
  • Extruder E ⁇ 3> is a twin-screw extruder, wherein each barrel G1 ⁇ 31 > and G2 ⁇ 32> comprises a respective screw element ⁇ 91 >, ⁇ 92>.
  • the temperature in G1 ⁇ 31 > is adjusted such that PO ⁇ 2> is in the liquid state while PET ⁇ 1 > is in the solid state.
  • the mixing and kneading function of the screw element ⁇ 91 > ensures that PO ⁇ 2> forms a continuous phase PKon ⁇ 42> in which the PET particles Pp ar ⁇ 41 > are suspended.
  • PET ⁇ 1 > is introduced into the barrel G1 ⁇ 31 > in the form of particles Pp ar ⁇ 41 >.
  • Additional comminuting elements in the barrel G1 ⁇ 31 > may be used to further comminute the particles Pp ar ⁇ 41 > if the PET starting material is employed in uncomminuted form to ensure sufficient comminution in the barrel G1 ⁇ 31 >.
  • PET ⁇ 1 > can also be introduced in larger pieces which can then be comminuted into the desired PET particles ⁇ 41 > using optional suitable comminution elements in the barrel G1 ⁇ 31 >.
  • the resulting suspension Si ⁇ 4> is mixed by the screw element ⁇ 91 > so that a uniform distribution of the PET particles Pp a r ⁇ 41 > in PKon ⁇ 42> is achieved.
  • Simultaneously Si ⁇ 4> is transported (or "conveyed") by the screw element ⁇ 91 > in the direction of the barrel G2 ⁇ 32> and thus in the direction of the product outlet Ex ⁇ 33> ("downstream").
  • Si ⁇ 4> is mixed with a stream ⁇ 5> of ethylene glycol and a stream ⁇ 6> of a 30% by weight solution of sodium methoxide in methanol (solid sodium methoxide is alternatively employable) to afford a suspension Si ⁇ 7> comprising PET ⁇ 1 > in which the content of ethylene glycol, sodium methoxide and methanol is elevated relative to the suspension Si ⁇ 4> in the barrel Gi ⁇ 31 >.
  • Suspension ⁇ 7> is converted into the mixture MG2 ⁇ 8> upon passing through the extruder E ⁇ 3>.
  • PET ⁇ 1 > is reacted with ethylene glycol in a cleavage reaction under methoxide catalysis to afford the product BHET ⁇ 43> and oligomers of BHET ⁇ 44>.
  • a mixture MG2 ⁇ 8> comprising BHET, oligomers of BHET, PO and ethylene glycol is thus obtained at the product outlet Ex ⁇ 33>.
  • MG2 ⁇ 8> still comprises a proportion of PET ⁇ 1 >. Since the PET particles Pp ar ⁇ 41 > in G1 ⁇ 31 > are provided suspended in the inert phase PKon ⁇ 42> the glycolysis of the PET ⁇ 1 > can proceed in a controlled fashion and pressure and temperature spikes during the process are avoided.
  • FIG. 2 shows a further embodiment of the process according to the invention. This corresponds to the embodiment shown in Figure 1 with the following differences:
  • PET ⁇ 1 > and PO ⁇ 2> are passed into the barrel G1 ⁇ 31 > as mixed stream ⁇ 12>.
  • This embodiment is especially relevant when the process according to the invention is used for depolymerization and recycling of PET ⁇ 1 > coated with PO ⁇ 2>, in particular polyethylene PE or polypropylene PP.
  • a mixture of glycol and sodium methoxide is supplied to the barrel G2 ⁇ 32> as mixed stream ⁇ 56>.
  • Sodium methoxide is typically dissolved in glycol as powder and the resulting mixture used as stream ⁇ 56>.
  • FIG. 3 shows a further embodiment of the process according to the invention. This corresponds to the embodiment shown in Figure 2 with the following differences:
  • the extruder E ⁇ 3> comprises a further barrel G3 ⁇ 35> having an additional screw element ⁇ 95>.
  • the process according to the invention is a process for depolymerization of at least one polymer Pi.
  • MHET also encompasses the corresponding carboxylate of the structure shown.
  • TS also encompasses the corresponding mono- and dicarboxylate of the structure shown.
  • the m interlinked repeating units of structural formula (I) comprised by the polymer Pi are identical or different, in particular identical.
  • the m interlinked repeating units of structural formula (I) are interlinked within the polymer Pi in such a way that the bond of the one repeating unit of structural formula (I) labelled “(i)” is linked to the bond of the adjacent repeating unit of the structural formula (I) labelled “(ii)".
  • the process according to the invention is particularly suitable for depolymerization of polymers Pi which at least in part comprise segments of polyethylene terephthalate [“PET”; following option (p)] or segments of polybutylene terephthalate ["PBT”; following option (a)].
  • the end group of the first repeating unit of the m interlinked repeating units of the polymer Pi which is present for said units in the structural formula (I) at the bond defined by “(i)”, and the end group of the mth repeating unit of the m interlinked repeating units of the polymer Pi which is present for said units in the structural formula (I) at the bond defined by “(ii)” are not particularly limited and are a consequence of the method used in the production method of the polymer Pi.
  • end groups may be termination fragments of a repeating unit of structural formula (I) or may be one or more repeating units Wx, wherein Wx is distinct from the structural formula (I).
  • - optionally at least one group selected from aliphatic radical comprising -OH, -O- (which may in particular be a group, optionally at least one group, selected from alkyl group comprising -OH, -O-);
  • - optionally at least one group selected from alkyl group comprising -OH, -O-;
  • the end group connected to the bond labelled “(ii)” in the structural formula (I) is preferably selected from the group consisting of -H, -OH, a radical of structural formula (IV) or (VII), more preferably from the group consisting of -H, -OH, a radical of structural formula (IV), yet more preferably from the group consisting of -OH, a radical of structural formula (IV), wherein the structural formulae (IV) and (VII) are as follows:
  • the process according to the invention may thus also be used for depolymerization of polymers Pi which in addition to the m interlinked repeating units of structural formula (I) comprise further repeating units WY distinct therefrom.
  • polymers Pi which comprise comonomer units such as in particular repeating units of below-mentioned formula (VI) in which a, b, c have the above-mentioned definitions:
  • the polymer Pi thus comprises any polymer comprising at least one segment Ai which consists of m interlinked repeating units of structural formula (I) which are identical or different, preferably identical, within segment Ai and wherein the m interlinked repeating units of structural formula (I) are interlinked within segment Ai in such a way that the bond of the one repeating unit of structural formula (I) labelled "(i)” is linked to the bond of the adjacent repeating unit of the structural formula (I) labelled "(ii)".
  • the polymer Pi may comprise further, preferably organic, groups GF, which are not composed of repeating units of the structural formula (I), for example oligomer segments or polymer segments composed of repeating units Wz distinct from structural formula (I).
  • groups GF which are not composed of repeating units of the structural formula (I)
  • a segment Ai composed of the m interlinked repeating units of structural formula (I) may be linked with such organic groups GF within the polymer Pi via bond (i) of the first repeating unit of the m interlinked repeating units of structural formula (I) in segment Ai and/or via bond (ii) of the mth repeating unit of the m interlinked repeating units of structural formula (I) in segment Ai.
  • the polymer Pi may also comprise two or more segments Ai, A2 etc. which are each composed of m interlinked repeating units of structural formula (I) and are connected to one another via organic groups GF distinct from structural formula (I), for example oligomers or polymers composed of repeating units WA distinct from structural formula (I), wherein these organic groups GF bond to bond (ii) of the mth repeating unit of the first segment Ai and bond (i) of the first repeating unit of the following segment A2.
  • organic groups GF distinct from structural formula (I)
  • the polymer Pi has m interlinked repeating units of structural formula (I), wherein the proportion of repeating units of structural formula (I) in the polymer Pi is > 50% by weight, in particular > 60% by weight, preferably > 70% by weight, more preferably > 80% by weight, yet more preferably > 90% by weight, yet more preferably > 95% by weight, most preferably > 99% by weight, in each case based on the molar weight of the polymer Pi.
  • the suspension Si provided in step (a) preferably comprises different polymers Pi.
  • the individual polymers Pi in this embodiment typically have different degrees of polymerization, i.e. m is different for at least a portion of the polymers Pi comprised in the suspension Si provided in step (a).
  • the suspension Si provided in step (a) comprises different polymers Pi, wherein at least 10%, preferably at least 20%, more preferably at least 30%, yet more preferably at least 50%, yet more preferably at least 75%, most preferably at least 99% of all of the polymers Pi comprised in the suspension Si provided in step (a) comprise at least one segment Ai composed of m > 100 interlinked repeating units of structural formula (I).
  • a polymer Pi having structural formula (I’) can also be represented as follows:
  • W‘i thus conforms to the structure comprised in the parentheses indexed with “n‘i” in structural formula (l‘).
  • the unit W‘i thus has the following structure:
  • n‘i units W‘i interlinked within the polymer Pi according to structural formula (l‘) are identical or different to one another, in particular identical, within the polymer Pi.
  • R' is selected from -H, -(CH2)a*-[O-(CH2)b*]c*-OH.
  • R" is selected from the group consisting of -H, -OH, a radical of structural formula (IV) or (VII), more preferably from the group consisting of -H, -OH, a radical of structural formula (IV), more preferably from the group consisting of -OH, a radical of structural formula (IV), wherein the structural formulae (IV) and (VII) are as follows:
  • the process according to the invention is especially suitable for depolymerization of polyethylene terephthalate (“PET”) and polybutylene terephthalate (“PBT”).
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • the polymer Pi is selected from PET, PBT.
  • the polymer Pi is most preferably PET.
  • the suspension Si provided in step (a) preferably comprises different polymers Pi according to structural formula (l‘).
  • the individual polymers Pi in this embodiment typically have different degrees of polymerization, i.e. n‘i is different for at least a portion of the polymers Pi according to structural formula (l‘) comprised in the suspension Si provided in step (a).
  • the suspension Si provided in step (a) comprises different polymers Pi of structural formula (l‘), wherein in at least 10%, preferably at least 20%, more preferably at least 30%, yet more preferably at least 50%, yet more preferably at least 75%, most preferably at least 99% of all of the polymer molecules Pi according to structural formula (l‘) comprised in the suspension Si provided in step (a) n‘i > 99, yet more preferably n‘i > 100.
  • the process according to the invention is performed in an extruder E.
  • Extruders are familiar to the skilled person and described for various chemical reactions and processes, for example in WO 2020/053051 A1 and EP 2 455 424 A1 .
  • An extruder is generally understood as being a machine which accommodates solid to liquid moulding materials, typically in an interior of the extruder, and presses these as extrudate out of a product outlet (or “opening”) which is in particular a die, predominantly continuously (according to DIN 24450: 1987-02); see Somborn R, Extruder, RD-05-02432 (2004) in Bockler F., Dill B., Eisenbrand G., Faupel F., Fugmann B., Gamse T., Matissek R., Pohnert G., Ruhling A., Schmidt S., Sprenger G., ROMPP [Online], Stuttgart, Georg Thieme Verlag, [December 2022]; retrievable online at https://roempp.thieme.de/lexicon/RD-05-02432, last retrieved 14 January 2023
  • the extruder E comprises two barrels Gi, G2 and optionally a further barrel G3.
  • barrel is to be understood as meaning sections in the interior of the extruder in which the reaction conditions (in particular temperature) may be adjusted independently of the remaining sections of the extruder.
  • Extruders additionally comprise transporting means with which the contents of the extruder may be transported from one barrel into the next and finally to the product outlet. In single- or multi-screw extruders this task is assumed for example by the screw elements.
  • the extruder E is selected from the group consisting of piston extruders and multi-screw extruders, wherein multi-screw extruders are particularly preferable.
  • Preferred multi-screw extruders are planetary roller extruders or multi-screw extruders, in particular multi-screw extruders, more preferably twin-screw extruders.
  • an inert gas for example nitrogen, is passed through the extruder E during the process according to the invention.
  • a suspension Si comprising a continuous phase PKon of at least one liquid polyolefin PO and particles Pp ar of the at least one polymer Pi suspended in PKon is provided in barrel Gi and transported from the barrel Gi into the barrel G2.
  • suspension is to be understood as meaning a composition comprising insoluble solids particles ("Pp a r” in the present invention) in a liquid continuous phase (“PKon” in the present invention); see also: RD-19- 05060 (2002) in Bockler F., Dill B., Eisenbrand G., Faupel F., Fugmann B., Gamse T., Matissek R., Pohnert G., Ruhling A., Schmidt S., Sprenger G., ROMPP [Online], Stuttgart, Georg Thieme Verlag, [December 2022]; retrievable at https://roempp.thieme.de/lexicon/RD-19-05060, last retrieved 14 January 2023).
  • step (a) of the process according to the invention the at least one polymer Pi is employed as a solid, namely in the form of particles Pp ar , i.e. in the suspension Si according to the invention the at least one polymer Pi is suspended in the form of the particles Pp ar .
  • step (a) and preferably also step (b) are performed at a temperature that is below the melting temperature of the at least one polymer Pi.
  • At least 50%, in particular at least 90%, of the particles Pp ar of the at least one polymer Pi employed in step (a) have, in a preferred embodiment, a size of at most 20 mm (“D90”), more preferably a value between 1 mm to 10 mm.
  • the particle size distribution is determined by sieve analysis according to the standard DIN 66165-2:2016-08.
  • the process according to the invention is particularly suitable for processing wastes comprising the at least one polymer Pi and the polyolefin PO.
  • the wastes to be worked up in the process according to the invention may be comminuted before step (a) to allow particles Pp ar of suitable size to be employed in step (a). This comminution is achieved by grinding for example.
  • the suspension Si provided in step (a) comprises as the continuous phase PKon in which the particles Ppar of the at least one polymer Pi are suspended at least one polyolefin PO which is liquid, i.e. in the form of a melt.
  • the polyolefin PO has a melting temperature ("TRO") lower than the melting temperature (“TRI”) of the at least one polymer Pi.
  • the ratio of the weight of all polymers Pi comprised by the suspension Si provided in step (a) to the weight of all polyolefins PO comprised by the suspension Si provided in step (a) is thus not limited further and is in particular in the range 99 : 1 to 1 : 99, preferably 98 : 2 to 10 : 90, more preferably 97 : 3 to 25 : 75, yet more preferably 96 : 4 to 50 : 50, yet more preferably 95 : 5 to 60 : 40, most preferably 80 : 20.
  • the “temperature T a ” is the temperature at which step (a) is performed.
  • the suspension Si comprises a melt of the at least one polyolefin PO.
  • the temperature T a at which the suspension Si is provided in step (a) of the process according to the invention is above the melting temperature of the polyolefin PO, in particular at least 1 °C, preferably at least 5°C, more preferably at least 10°C.
  • step (a) of the process according to the invention is performed at a temperature T a which is below the melting temperature TRI of the at least one polymer Pi.
  • the temperature T a is preferably in a range from 165°C to 220°C, more preferably in the range from 170°C to 220°C, yet more preferably in the range from 180°C to 220°C, yet more preferably in the range from 190°C to 210°C, most preferably in the range from 195°C to 202°C.
  • the temperature T a in another embodiment is preferably in a range from 130°C to 255°C, more preferably in a range from 165°C to 240°C, even more preferably in a range from 165°C to 220°C, yet more preferably in the range from 170°C to 220°C, yet more preferably in the range from 180°C to 220°C, yet more preferably in the range from 190°C to 210°C, most preferably in the range from 195°C to 202°C.
  • the proportion of the weight of all polyolefins PO in the suspension Si provided in step (a) is in the range from 1% to 99% by weight, preferably in the range from 3% to 75% by weight, preferably in the range from 5% to 50% by weight, more preferably in the range from 10% to 40% by weight, more preferably in the range from 15% to 30% by weight, wherein the remainder of the suspension Si provided in step (a) is polymer Pi.
  • the suspension Si is transported from the barrel Gi into the barrel G2. This may be done using the transport apparatuses known to those skilled in the art and customary in extruders, in particular screw elements, pistons, preferably screw elements.
  • step (b) of the process according to the invention at least one glycol compound G is introduced into the barrel G2 via at least one feed ZG.
  • At least one catalyst K mixed with or separate from, preferably mixed with, the at least one glycol compound G is introduced into the barrel G2.
  • the at least one glycol compound G and the at least one catalyst K are mixed with the suspension Si and the at least one glycol compound G is at least partially reacted with the at least one polymer Pi in the suspension Si to afford a mixture MG2 comprising at least one cleavage product P2. This reaction is thus carried out in the presence of the catalyst K.
  • the glycol compound G added in step (b) has the structural formula (V): HO-(CH 2 )d-[O-(CH 2 )e]f-OH.
  • the glycol compound G added in step (b) is at least one of the products of the depolymerization of the polymer Pi according to the invention.
  • glycol compound G added in step (b) is preferably ethylene glycol when the polymer Pi at least in part comprises segments of polyethylene terephthalate PET and yet more preferably when the polymer Pi is PET.
  • PBT polybutylene terephthalate
  • the feed ZG by means of which the at least one glycol compound G is introduced into the barrel may be selected by a person skilled in the art according to their knowledge and may be in the form of a valve for example.
  • step (b) of the process according to the invention of the at least one portion of the polymers Pi in suspension Si with the at least one glycol compound G in step (b) is carried out in the presence of at least one catalyst K.
  • the catalyst K is selected from the group consisting of MA ethylene glycolate, ROMA, wherein MA is an alkali metal and R is an alkyl radical having 1 to 6 carbon atoms.
  • MA ethylene glycolate and ROMA are thus "alkali metal alkoxides".
  • the catalyst K is introduced into the barrel G2 in step (b) mixed with, i.e. together with, the at least one glycol compound G.
  • the catalyst K may be introduced into the barrel G2 separately from the at least one glycol compound G in step (b).
  • MA ethylene glycolate is to be understood as meaning the corresponding salt of ethylene glycol with MA.
  • the term “MA ethylene glycolate” comprises at least one of MAO-CH2-CH2-OH and MAO-CH2-CH2-OMA, preferably at least MAO-CH2-CH2-OH, most preferably MAO-CH2-CH2-OH and MAO-CH2-CH2-OMA.
  • MA is in particular selected from the group consisting of lithium, potassium, sodium.
  • MA is preferably selected from the group consisting of potassium, sodium. It is very particularly preferable when MA is sodium.
  • R is an alkyl radical having 1 to 6 carbon atoms.
  • R is in particular selected from the group consisting of methyl; ethyl; propyl, wherein n-propyl or /so-propyl is concerned; butyl, in particular n-butyl; pentyl, in particular n-pentyl; hexyl, in particular n-hexyl.
  • the alkali metal alkoxide employable in the process according to the invention as catalyst K may be produced according to the knowledge of a person skilled in the art, for example by reactive distillation from the corresponding alcohol and the corresponding alkali metal hydroxide, as described in EP 1 997 794 A1 , WO 01/42178 A1 , WO 2021/148174 A1 , WO 2021/148175 A1 , WO 2022/117803 A1 , WO 2022/167311 A1 , WO 2022/263032 A1 , EP 4 074 684 A1 , EP 4 074 685 A1 .
  • the alkali metal alkoxide employable in the process according to the invention as catalyst K may alternatively also be produced by transalcoholization from the corresponding alcohol and another alkoxide.
  • a corresponding preparation of alkali metal alkoxides is described, for example, by CS 213 119 B1 , GB 490,388 A, DE 689 03 186 T2 and EP 0 776 995 A1 .
  • Transalcoholizations by reactive distillation which likewise provide alkoxides, in particular alkali metal alkoxides, employable in the process according to the invention as catalyst K, are described in WO 2021/122702 A1 , DE 27 26 491 A1 , DE 1 254 612 B.
  • alkoxides employable as catalyst K according to the invention may also be produced electrochemically as described for example in EP 3 885 470 A1 , EP 3 885 471 A1 , EP 4 043 616 A1 , EP 4 112 778 A1 , WO 2023/274796 A1 , WO 2023/274794 A1 .
  • the amount of the catalyst K used in step (b) may be selected by a person skilled in the art according to their knowledge in the art.
  • the molar amount of all catalysts K employed in step (b) based on the molar amount of all glycol compounds G employed in step (b) is in particular in the range from 0.01 % to 10%, preferably in the range from 0.1 % to 5%, more preferably in the range from 1 % to 4%, yet more preferably in the range from 2.5% to 3.5%.
  • the catalyst K is preferably employed in the form of a solid, for example in the form of a powder or granulate.
  • step (b) of the process according to the invention is performed in particular until the weight of all polymers Pi in the mixture MG2 withdrawn at the product outlet Ex in step (c) has fallen by at least 10% by weight, preferably by at least 20% by weight, more preferably by at least 30% by weight, more preferably by at least 40% by weight, more preferably by at least 50% by weight, yet more preferably by at least 60% by weight, yet more preferably by at least 70% by weight, yet more preferably by at least 80% by weight, yet more preferably by at least 90% by weight, most preferably by at least 98% by weight, in each case based on the weight of all polymers Pi in the suspension Si provided in step (a).
  • step (b) water content in the mixture Si during the reaction according to step (b) and in the mixture MG2 obtained after termination of step (b) is as low as possible so that in the reaction according to step (b) of the glycol compound G with the polymer Pi the proportion of solvolytic transesterification is as high as possible and the proportion of hydrolytic ester cleavage is as low as possible.
  • the water content in the suspension Si during the reaction according to step (b) is therefore ⁇ 10% by weight, more preferably ⁇ 5% by weight, yet more preferably ⁇ 1% by weight, yet more preferably ⁇ 0.1% by weight, most preferably ⁇ 0.01% by weight, in each case based on the total weight of the suspension Si.
  • the proportion of the at least one glycol compound G added to the suspension Si in the barrel G2 in step (b) is not limited further. It is advantageous when in step (b) the polymer Pi is cleaved into the highest possible proportion of cleavage products P2. This is advantageously controlled via the amount of at least one glycol compound G added to the suspension Si in step (b).
  • the molar amount of all glycol compounds G introduced into the barrel G2 in step (b) is > 0.01 molar equivalents and is more preferably in the range from 0.1 to 50 molar equivalents, more preferably in the range from 0.3 to 40 molar equivalents, more preferably in the range from 0.5 to 20 molar equivalents, yet more preferably in the range from 1 .0 to 15 molar equivalents, yet more preferably in the range from 2.0 to 10 molar equivalents, yet more preferably in the range from 3.0 to 5.0 molar equivalents, in each case based on the molar amount of all repeating units of structural formula (I) comprised by the polymers Pi in the suspension Si provided in step (a).
  • the process according to the invention is preferably performed solvolytically to minimize the proportion of undesired products (such as TS or MHET in the case of hydrolysis of PET) in the reaction product as far as possible and to maximize the proportion of desired products (such as BHET in the case of solvolysis of PET with ethylene glycol) in the reaction product. It is therefore preferable when the water content in the glycol compounds G added in step (b) based on the total weight of all glycol compounds G added in step (b) is ⁇ 10% by weight, more preferably ⁇ 5% by weight, yet more preferably ⁇ 1% by weight, yet more preferably ⁇ 0.1% by weight, most preferably ⁇ 0.01% by weight.
  • the polyolefin PO is inert with respect to the reaction conditions according to step (b) in the suspension Si, i.e. it substantially does not undergo reaction with the glycol compound G.
  • Tb is to be understood as meaning the temperature during the reaction according to step (b).
  • step (b) of the process according to the invention is in particular performed at a temperature Tb above the melting temperature TRO of the polyolefin PO.
  • the polyolefin PO is thus present as a melt in step (b), and already in step (a), and the reaction according to step (b) may advantageously be performed in said melt.
  • the temperature Tb may also be selected so that it is below or above the melting temperature TRI of the at least one polymer Pi during step (b). It is preferable when in step (b) the temperature Tb is below the melting temperature TRI of the at least one polymer Pi.
  • the at least one polymer Pi is then present in particle form during step (b).
  • step (b) of the process according to the invention is thus preferably performed at a temperature Tb above the melting temperature TRO of the polyolefin PO and below the melting temperature TRI of the at least one polymer Pi.
  • the temperature Tb is preferably in a range from 165°C to 220°C, more preferably in the range from 170°C to 215°C, yet more preferably in the range from 180°C to 210°C, most preferably in the range from 190°C to 200°C.
  • polyolefin PO is selected from polyethylene ("PE”; T P0 : 135°C), polypropylene (“PP”; T P0 : 160°C), polyisobutylene ("PIB”; TRO: 54 - 56°C), polybutylene (“PB”; TRO: 135°C), more preferably when the polyolefin PO is selected from PE, PP.
  • PE polyethylene
  • PP polypropylene
  • PIB polyisobutylene
  • PB polybutylene
  • the temperature Tb is preferably in a range from 165°C to 255°C, more preferably in the range from 170°C to 240°C, yet more preferably in the range from 180°C to 210°C, most preferably in the range from 190°C to 200°C. This is advantageous especially when the polyolefin PO is selected from PE, PP, PIB, PB, more preferably when the polyolefin PO is selected from PE, PP.
  • the temperature Tb is preferably in a range from 140°C to 255°C, more preferably in the range from 150°C to 240°C, yet more preferably in the range from 165°C to 230°C, yet more preferably in the range from 180°C to 210°C, most preferably in the range from 190°C to 200°C.
  • 4.4 Cleavage product P2 is preferably in a range from 140°C to 255°C, more preferably in the range from 150°C to 240°C, yet more preferably in the range from 165°C to 230°C, yet more preferably in the range from 180°C to 210°C, most preferably in the range from 190°C to 200°C.
  • step (b) of the process according to the invention at least a portion of the polymers Pi comprised by the suspension Si are reacted with the at least one glycol compound G and the at least one catalyst K to afford at least one cleavage product P2 in the barrel G2.
  • Step (b) accordingly affords a mixture MG2 comprising at least one cleavage product P2.
  • Structural formula (II) may also be expressed as “R ll1 -(W2)n2-R 112 ”. W2 thus conforms to the structure comprised in the parentheses indexed with “n2” in structural formula (II): w 2
  • the repeating units W2 interlinked within the cleavage product P2 for 2 ⁇ n2 s 48 may be identical or different within the cleavage product P2. This has the result for example that a molecule P2 may comprise groups W2 that are identical or different (i.e. have different values of a", b" and/or c" for example).
  • R 111 is selected from the group consisting of -H, -(CH2)a»-[O-(CH2)b»]c»-OH .
  • R" 2 is selected from the group consisting of -H, -OH, a radical of structural formula (IV), preferably from the group consisting of -OH, a radical of structural formula (IV), wherein structural formula (IV) is as follows:
  • the amount of cleavage product P2 and of polymer Pi in a particular mixture, in particular in the suspension Si or the mixture MG2, is determinable by methods of measurement known to those skilled in the art.
  • the molecular weight distributions of the polymers Pi and the cleavage products P2 are determined by gel permeation chromatography ("GPC") according to method 1 (see examples section).
  • the content of compounds (III) in a particular mixture, in particular in the suspension Si orthe mixture MG2, can be determined via methods of measurement known to those skilled in the art, preferably via nuclear magnetic resonance ("NMR”) or chromatography.
  • NMR nuclear magnetic resonance
  • a mixture MG2 comprising at least one cleavage product P2 is obtained after termination of step (b).
  • the proportion of the molar amount of all cleavage products P2 which are comprised by the mixture MG2 at the product outlet Ex and comprise not more than 20 repeating units of structural formula W2 based on the molar amount of all cleavage products P2 comprised by the mixture MG2 is at least 25%, preferably at least 40%, more preferably at least 50%, yet more preferably at least 70%, yet more preferably at least 85%.
  • the proportion of the molar amount of all compounds of structural formula (III) comprised by the mixture MG2 at the product outlet Ex based on the molar amount of all cleavage products P2 comprised by the mixture MG2 at the product outlet Ex is at least 10%, more preferably at least 25%, yet more preferably at least 30%, yet more preferably at least 50%, wherein structural formula (III) is as follows:
  • R 1 and R 2 are independently of one another selected from the group consisting of -H, -(CH2)p-[O-(CH2)q]r-OH, wherein preferably at least one, yet more preferably both, of the radicals R 1 and R 2 are independently of one another a radical of structural formula -(CH2)p- [O-(CH 2 )q]r-OH.
  • radicals R 1 and R 2 are each the same radical of structural formula -(CH2) P -[O(CH 2 )q]r-OH.
  • step (b) affords a mixture MG2 comprising at least one cleavage product P2.
  • This mixture MG2 is transported to product outlet Ex in step (c).
  • the mixture MG2 is withdrawn at the product outlet Ex.
  • Suitable product outlets Ex include any opening in the extruder E from which the mixture MG2 may be withdrawn. This product outlet Ex is typically located at the end of the extruder E. In the embodiments where the extruder E comprises only the two barrels G1 and G2 the product outlet Ex typically follows the barrel G2 so that the mixture is obtained directly after passing through the barrel G2. In the embodiments where the extruder E comprises a further barrel G3 in addition to the two barrels G1 and G2 the mixture MG2 is typically withdrawn after passing through the barrel G3.
  • step (b) in the process according to the invention is advantageously performed until the cleavage products P2 make up the majority of the mixture MG2 withdrawn at the product outlet Ex.
  • the proportion of all cleavage products P2 in the mixture MG2 withdrawn at the product outlet Ex is at least 50% by weight, more preferably at least 60% by weight, yet more preferably at least 70% by weight, yet more preferably at least 80% by weight, yet more preferably at least 90% by weight, in each case based on the total weight of the mixture MG2 withdrawn at the product outlet Ex.
  • the constituents of the mixture MG2 withdrawn at the product outlet Ex that are distinct from the cleavage products P2 are in particular selected from glycol compounds G, unconverted polymers Pi, preferably glycol compounds G.
  • the ratio of the weight (in grams) of all cleavage products P2 in the mixture MG2 withdrawn at the product outlet Ex to the weight (in grams) of all polymers Pi in the mixture MG2 withdrawn at the product outlet Ex is > 1 : 1 , more preferably > 2 : 1 , yet more preferably > 3: 1 , yet more preferably > 4: 1 , yet more preferably > 10: 1 , yet more preferably > 30: 1 , yet more preferably > 100: 1 , yet more preferably > 1000: 1 .
  • the extruder E comprises another further barrel G3 through which the mixture MG2 passes during transport from the barrel G2 to the product outlet Ex.
  • This embodiment is advantageous if the reaction is not sufficiently advanced in barrel G2 and is completed before the product outlet Ex.
  • a postreaction may then be carried out in barrel G3, optionally at a temperature elevated or reduced relative to the temperature in G2, or the mixture MG2 may be allowed to cool in barrel G3.
  • the process according to the invention is characterized in that the PET to be subjected to the depolymerization is employed as a suspension Si in step (a) with polyolefins as the continuous phase P Ko n.
  • step (a) the suspension Si is provided in barrel G1 and the glycol compound G is introduced only in barrel G2.
  • the ratio of the volume of the suspension Si in the extruder E upstream of the at least one feed ZG of the at least one glycol compound G into the barrel G2 to the sum of the volumes of the suspension Si and the mixture MG2 from the at least one feed ZG of the at least one glycol compound G into the barrel G2 to the product outlet Ex is in the range from 1 : 99 to 99 : 1 , more preferably in the range from 1 : 9 to 9 : 1 , yet more preferably in the range from 1 : 4 to 4 : 1 , yet more preferably in the range from 2 : 3 to 3 : 2, yet more preferably 1 : 1.
  • the extruder E is oriented such that the product outlet Ex occupies the lowest position. 2.
  • the product outlet Ex and all feeds and outputs of the extruder E between the product outlet Ex and the uppermost feed, used in the process according to the invention as feed ZG, are watertightly blocked.
  • the extruder E is filled with water until it overflows at the unblocked feed ZG. The volume of water in the extruder E is then determined. This volume is Udown.
  • Pi is added to Gi via at least one feed ZRI and the polyolefin PO is added to Gi separately therefrom via at least one feed ZRK, ZO is the uppermost feed of all feeds ZRI , ZRK.
  • the extruder E is filled with water until it overflows at the unblocked feed Zo.
  • the volume of water in the extruder E is then determined. This volume is u U p + Udown. The difference between this value and Udown gives u U p.
  • Comminuted PET flakes are metered gravimetrically and at 70°C drawn into a barrel Go (process space) of an extruder having a plurality of barrels (i.e. sections whose wall temperature can be separately adjusted).
  • the PET flakes are transported from the barrel Go into a barrel Gi in which the temperature has been raised to 265°C, thus melting the metered PET flakes.
  • the PET melt is transported into a barrel G2 where a 4% by weight solution of sodium ethylene glycolate in ethylene glycol is injected.
  • the mass flow ratio of sodium ethylene glycolate solution to PET is 0.5.
  • the barrel temperature directly downstream of the injection point is likewise 265°C and is reduced to 130°C towards the extruder outlet.
  • a pulsing discharge of ethylene glycol vapour is observed at irregular intervals. Comparative example 2
  • polyethylene granulate (PE) is metered gravimetrically at the extruder inlet in addition to PET flakes.
  • the proportion of PE based on the total polymer stream is 20% by weight.
  • the temperature profile and the metered addition of sodium ethylene glycolate solution in ethylene glycol are realized as in comparative example 1 .
  • the mass flow ratio of sodium ethylene glycolate solution to PET is 0.5.
  • a mixture comprising the main components BHET, BHET oligomers, PE agglomerates and ethylene glycol is discharged at the outlet of the extruder.
  • a pulsing discharge of ethylene glycol vapour is observed at irregular intervals.
  • Comminuted PET flakes are metered gravimetrically and at 70°C drawn into the barrel Go (process space) of the extruder used in comparative example 1.
  • the PET flakes are transported from the barrel Go into a barrel Gi in which the temperature has been raised to 195°C. From there, the PET flakes are transported to the extruder outlet at a barrel temperature of 195°C without addition of ethylene glycol or sodium ethylene glycolate.
  • the barrel temperature of the extruder does not exceed 195°C and is thus below the melting temperature of PET the PET flakes are heated and melted by friction, with the result that they are discharged from the extruder as agglomerates.
  • Comparative example 4 is performed in the same way as comparative example 3 but polyethylene granulate (PE) is metered gravimetrically in addition to PET flakes.
  • the proportion of PE based on the total polymer stream is 20% by weight.
  • a suspension of unmelted PET flakes in a PE melt is discharged at the extruder outlet.
  • the inventive example is performed according to the arrangement in comparative example 2.
  • the barrel temperature in barrel Gi is not set to 265°C, but rather to 195°C, i.e. below the melting temperature of the PET and above the melting temperature of the PE.
  • This forms a suspension of PET flakes in the PE melt.
  • This suspension is transported into the barrel G2 and a 4% by weight solution of sodium ethylene glycolate in ethylene glycol is injected.
  • the mass flow ratio of sodium ethylene glycolate solution to PET is 0.5.
  • the barrel temperature directly downstream of the injection site is likewise 195°C, and is lowered to 130°C toward the extruder exit.
  • a mixture comprising the main components BHET, BHET oligomers, PE agglomerates and ethylene glycol is discharged at the outlet of the extruder. A pulsing discharge of ethylene glycol vapour is not observed.
  • the molecular weight distributions of the polymers Pi and the cleavage products P2 are determined by gel permeation chromatography ("GPC") as per the following method 1.
  • GPC gel permeation chromatography
  • a sample of the mixture to be tested is diluted in a weight ratio of 1 : 333 in 1 ,1 ,1 ,3,3,3-hexafluoro- 2-propanol ("HFIP") and dissolved at room temperature for 24 hours.
  • HFIP hexafluoro- 2-propanol
  • the solution is filtered through a 1 pm disposable polytetrafluoroethylene filter and injected with an autosampler for analysis.
  • PMMA polymethylmethacrylate
  • the molar mass averages and the distribution thereof, which give the average degree of polymerization p in a given mixture, are calculated with computer assistance and are based on PMMA calibration by the strip method.

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Abstract

L'invention concerne un procédé de dépolymérisation d'au moins un polymère (P1) qui est un poly(téréphtalate d'alkylène), c'est-à-dire un polymère comprenant des motifs d'acide téréphtalique et des motifs d'alkylène glycol, en particulier le poly(téréphtalate d'éthylène) (PET) ou le poly(téréphtalate de butylène) (PBT). Le procédé est particulièrement adapté pour la dépolymérisation et pour le recyclage de déchets contenant du PET. Le procédé est réalisé dans une extrudeuse (E) comportant au moins deux cylindres (G1, G2), ledit polymère (P1) étant disposé dans le cylindre (G1) sous la forme d'une suspension (S1) dans une polyoléfine (PO), par exemple le polyéthylène (PE) ou le polypropylène (PP). La suspension (S1) est ensuite transportée dans le cylindre (G2). Au moins un composé de glycol (G), de préférence l'éthylène glycol, et au moins un alcoxyde de métal alcalin sont introduits dans le cylindre (G2) et mélangés avec la suspension (S1). Ledit composé de glycol (G) réagit en suspension (S1) avec ledit polymère (P1) pour obtenir un mélange (MG2) comprenant les produits de clivage correspondants (P2). Le mélange résultant (MG2) est transporté vers la sortie de produit (EX) de l'extrudeuse (E) et retiré à cet emplacement. Le procédé permet un mode de traitement plus sûr étant donné qu'il évite l'augmentation incontrôlée de température et de pression pendant la dépolymérisation du polymère (P1.S).
PCT/EP2024/051053 2023-01-23 2024-01-17 Procédé de dépolymérisation de poly(téréphtalates d'alkylène) dans une extrudeuse Ceased WO2024156568A1 (fr)

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EP24701338.6A EP4655342A1 (fr) 2023-01-23 2024-01-17 Procédé de dépolymérisation de poly(téréphtalates d'alkylène) dans une extrudeuse
KR1020257024496A KR20250140523A (ko) 2023-01-23 2024-01-17 압출기에서 폴리알킬렌 테레프탈레이트의 해중합을 위한 공정
CN202480008856.5A CN120584149A (zh) 2023-01-23 2024-01-17 用于在挤出机中解聚聚对苯二甲酸亚烷基酯的方法

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Citations (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB490388A (en) 1936-08-26 1938-08-15 Mathieson Alkali Works Improvements in production of alcoholates of higher alcohols
GB784248A (en) 1954-04-30 1957-10-09 Du Pont Improvements in the preparation of high quality dimethyl terephthalate
US3222299A (en) 1961-10-16 1965-12-07 Du Pont Process of reclaiming linear terephthalate polyester
DE1254612B (de) 1965-11-10 1967-11-23 Dynamit Nobel Ag Verfahren zur kontinuierlichen Herstellung von Alkalialkoholaten
US3884850A (en) 1970-02-13 1975-05-20 Fiber Industries Inc Continuous atmospheric depolymerization of polyester
DE2726491A1 (de) 1977-06-11 1978-12-14 Dynamit Nobel Ag Verfahren zur kontinuierlichen herstellung von alkalialkoholaten
CS213119B1 (cs) 1980-10-07 1982-03-26 Jan Vacek Způsob výroby alkoholátů alkalických kovů
US4355175A (en) 1981-04-06 1982-10-19 Pusztaszeri Stephen F Method for recovery of terephthalic acid from polyester scrap
DE68903186T2 (de) 1988-03-29 1993-04-22 Atochem Elf Sa Verfahren zur herstellung von natrium-fluoralkoholaten.
EP0723951A1 (fr) 1995-01-24 1996-07-31 ARS ING S.r.L. Procédé de préparation du téréphtalate de bis (2-hydroxyéthyle)
US5545746A (en) 1993-11-09 1996-08-13 Institut Francais Du Petrole Method for recovery of alkali metal or alkaline-earth metal terephthalate and of alkylene glycol from polyethylene terephthalates
EP0776995A1 (fr) 1995-11-29 1997-06-04 Hüls Aktiengesellschaft Procédé de préparation d'alcoolates
JP2000309663A (ja) 1999-04-27 2000-11-07 Asahi Chem Ind Co Ltd 熱可塑性ポリエステルの分解処理装置及び分解処理方法
WO2001042178A1 (fr) 1999-12-08 2001-06-14 Basf Aktiengesellschaft Procede de production de methylates alcalins
EP1997794A1 (fr) 2007-06-01 2008-12-03 Evonik Degussa GmbH Procédé de fabrication d'alcoolates de métaux alcalins
EP2455424A1 (fr) 2010-11-17 2012-05-23 Evonik Degussa GmbH Procédé de fabrication continue d'un prépolymère à base de résines phénoliques, d'oxazolines et d'époxydes
WO2020002999A2 (fr) 2018-06-25 2020-01-02 9449710 Canada Inc. Formation d'esters d'acide téréphtalique
CA3112586A1 (fr) * 2018-09-12 2020-03-19 Rittec Umwelttechnik Gmbh Retraitement continu du polyalkyleneterephtalate a partir de dechets
WO2021122702A1 (fr) 2019-12-18 2021-06-24 Basf Se Procédé de production d'alcoolates métalliques
WO2021148175A1 (fr) 2020-01-23 2021-07-29 Evonik Functional Solutions Gmbh Procédé de production écoénergétique d'alcoolats de sodium et de potassium
WO2021148174A1 (fr) 2020-01-23 2021-07-29 Evonik Functional Solutions Gmbh Procédé de production simultanée d'alcoolates de sodium et de potassium
DE102020106457A1 (de) * 2020-03-10 2021-09-16 Rittec Umwelttechnik Gmbh Verfahren und Vorrichtung zur Wiederaufarbeitung Polykondensat-haltiger Abfälle
EP3885470A1 (fr) 2020-03-24 2021-09-29 Evonik Functional Solutions GmbH Procédé de fabrication d'alcooliques métalliques alcalins dans une cellule d'électrolyse à trois chambres
EP3885471A1 (fr) 2020-03-24 2021-09-29 Evonik Functional Solutions GmbH Procédé amélioré de fabrication d'alcools de sodium
IT202000008935A1 (it) * 2020-04-24 2021-10-24 Garbo S R L Processo per depolimerizzare polietilene tereftalato (pet) tramite glicolisi, e relativo impianto per la sua realizzazione.
WO2022117803A1 (fr) 2020-12-04 2022-06-09 Basf Se Procédé intégré pour la production en parallèle de méthoxydes de métaux alcalins
WO2022167311A1 (fr) 2021-02-05 2022-08-11 Evonik Functional Solutions Gmbh Procédé de préparation écoénergétique d'alcoolates de métal alcalin
EP4043616A1 (fr) 2021-02-11 2022-08-17 Evonik Functional Solutions GmbH Procédé de production d'alcooliques métalliques alcalins dans une cellule d'électrolyse à trois chambres
EP4074685A1 (fr) 2021-04-16 2022-10-19 Evonik Functional Solutions GmbH Procédé de production économique en énergie d'alcoolates alcalimétales
EP4074684A1 (fr) 2021-04-16 2022-10-19 Evonik Functional Solutions GmbH Procédé de production économique en énergie d'alcoolates alcalimétales
WO2022263032A1 (fr) 2021-06-16 2022-12-22 Evonik Functional Solutions Gmbh Procédé de traitement d'un mélange méthanol/eau dans la production de méthoxydes de métaux alcalins dans une colonne de réaction
EP4112778A1 (fr) 2021-06-29 2023-01-04 Evonik Functional Solutions GmbH Cellule d'électrolyse à trois chambre destinée à la production d'alcoolates alcalimétaux
WO2023274796A1 (fr) 2021-06-29 2023-01-05 Evonik Functional Solutions Gmbh Cellule d'électrolyse à trois chambres pour la production d'alcoolates de métaux alcalins
WO2023274794A1 (fr) 2021-06-29 2023-01-05 Evonik Functional Solutions Gmbh Cellule d'électrolyse à trois chambres pour la production d'alcoolates de métaux alcalins

Patent Citations (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB490388A (en) 1936-08-26 1938-08-15 Mathieson Alkali Works Improvements in production of alcoholates of higher alcohols
GB784248A (en) 1954-04-30 1957-10-09 Du Pont Improvements in the preparation of high quality dimethyl terephthalate
US3222299A (en) 1961-10-16 1965-12-07 Du Pont Process of reclaiming linear terephthalate polyester
DE1254612B (de) 1965-11-10 1967-11-23 Dynamit Nobel Ag Verfahren zur kontinuierlichen Herstellung von Alkalialkoholaten
US3884850A (en) 1970-02-13 1975-05-20 Fiber Industries Inc Continuous atmospheric depolymerization of polyester
DE2726491A1 (de) 1977-06-11 1978-12-14 Dynamit Nobel Ag Verfahren zur kontinuierlichen herstellung von alkalialkoholaten
CS213119B1 (cs) 1980-10-07 1982-03-26 Jan Vacek Způsob výroby alkoholátů alkalických kovů
US4355175A (en) 1981-04-06 1982-10-19 Pusztaszeri Stephen F Method for recovery of terephthalic acid from polyester scrap
DE68903186T2 (de) 1988-03-29 1993-04-22 Atochem Elf Sa Verfahren zur herstellung von natrium-fluoralkoholaten.
US5545746A (en) 1993-11-09 1996-08-13 Institut Francais Du Petrole Method for recovery of alkali metal or alkaline-earth metal terephthalate and of alkylene glycol from polyethylene terephthalates
EP0723951A1 (fr) 1995-01-24 1996-07-31 ARS ING S.r.L. Procédé de préparation du téréphtalate de bis (2-hydroxyéthyle)
EP0776995A1 (fr) 1995-11-29 1997-06-04 Hüls Aktiengesellschaft Procédé de préparation d'alcoolates
JP2000309663A (ja) 1999-04-27 2000-11-07 Asahi Chem Ind Co Ltd 熱可塑性ポリエステルの分解処理装置及び分解処理方法
WO2001042178A1 (fr) 1999-12-08 2001-06-14 Basf Aktiengesellschaft Procede de production de methylates alcalins
EP1997794A1 (fr) 2007-06-01 2008-12-03 Evonik Degussa GmbH Procédé de fabrication d'alcoolates de métaux alcalins
EP2455424A1 (fr) 2010-11-17 2012-05-23 Evonik Degussa GmbH Procédé de fabrication continue d'un prépolymère à base de résines phénoliques, d'oxazolines et d'époxydes
WO2020002999A2 (fr) 2018-06-25 2020-01-02 9449710 Canada Inc. Formation d'esters d'acide téréphtalique
CA3112586A1 (fr) * 2018-09-12 2020-03-19 Rittec Umwelttechnik Gmbh Retraitement continu du polyalkyleneterephtalate a partir de dechets
WO2020053051A1 (fr) 2018-09-12 2020-03-19 Rittec Umwelttechnik Gmbh Procédé, dispositif et utilisation essentiellement de polyalkylènetéréphthalate à des fins de retraitement
WO2021122702A1 (fr) 2019-12-18 2021-06-24 Basf Se Procédé de production d'alcoolates métalliques
WO2021148175A1 (fr) 2020-01-23 2021-07-29 Evonik Functional Solutions Gmbh Procédé de production écoénergétique d'alcoolats de sodium et de potassium
WO2021148174A1 (fr) 2020-01-23 2021-07-29 Evonik Functional Solutions Gmbh Procédé de production simultanée d'alcoolates de sodium et de potassium
DE102020106457A1 (de) * 2020-03-10 2021-09-16 Rittec Umwelttechnik Gmbh Verfahren und Vorrichtung zur Wiederaufarbeitung Polykondensat-haltiger Abfälle
EP3885470A1 (fr) 2020-03-24 2021-09-29 Evonik Functional Solutions GmbH Procédé de fabrication d'alcooliques métalliques alcalins dans une cellule d'électrolyse à trois chambres
EP3885471A1 (fr) 2020-03-24 2021-09-29 Evonik Functional Solutions GmbH Procédé amélioré de fabrication d'alcools de sodium
IT202000008935A1 (it) * 2020-04-24 2021-10-24 Garbo S R L Processo per depolimerizzare polietilene tereftalato (pet) tramite glicolisi, e relativo impianto per la sua realizzazione.
WO2022117803A1 (fr) 2020-12-04 2022-06-09 Basf Se Procédé intégré pour la production en parallèle de méthoxydes de métaux alcalins
WO2022167311A1 (fr) 2021-02-05 2022-08-11 Evonik Functional Solutions Gmbh Procédé de préparation écoénergétique d'alcoolates de métal alcalin
EP4043616A1 (fr) 2021-02-11 2022-08-17 Evonik Functional Solutions GmbH Procédé de production d'alcooliques métalliques alcalins dans une cellule d'électrolyse à trois chambres
EP4074685A1 (fr) 2021-04-16 2022-10-19 Evonik Functional Solutions GmbH Procédé de production économique en énergie d'alcoolates alcalimétales
EP4074684A1 (fr) 2021-04-16 2022-10-19 Evonik Functional Solutions GmbH Procédé de production économique en énergie d'alcoolates alcalimétales
WO2022263032A1 (fr) 2021-06-16 2022-12-22 Evonik Functional Solutions Gmbh Procédé de traitement d'un mélange méthanol/eau dans la production de méthoxydes de métaux alcalins dans une colonne de réaction
EP4112778A1 (fr) 2021-06-29 2023-01-04 Evonik Functional Solutions GmbH Cellule d'électrolyse à trois chambre destinée à la production d'alcoolates alcalimétaux
WO2023274796A1 (fr) 2021-06-29 2023-01-05 Evonik Functional Solutions Gmbh Cellule d'électrolyse à trois chambres pour la production d'alcoolates de métaux alcalins
WO2023274794A1 (fr) 2021-06-29 2023-01-05 Evonik Functional Solutions Gmbh Cellule d'électrolyse à trois chambres pour la production d'alcoolates de métaux alcalins

Non-Patent Citations (12)

* Cited by examiner, † Cited by third party
Title
B. BERGMANNW. BECKERJ. DIEMERTP. ELSNER, MACROMOL. SYMP., vol. 333, 2013, pages 138 - 141
BOCKLER F.DILL B.EISENBRAND G.FAUPEL F.FUGMANN B.GAMSE T.MATISSEK R.POHNERT G.RUHLING A.SCHMIDT S.: "ROMPP", 2002, GEORG THIEME VERLAG, article "Polyethylenterephthalate, RD-16-03258"
G. COLOMINESF. RIVASM.-L. LACOSTEJ.-J. ROBIN, MACROMOLECULAR MATERIALS AND ENGINEERING, vol. 290, 2005, pages 710 - 720
J.D. PATTERSON: "Continuous Depolymerization of Poly(ethylene terephthalate) via Reactive Extrusion", 28 March 2007, NORTH CAROLINA STATE UNIVERSITY, pages: 60
L. BIERMANNE. BREPOHLC. EICHERTM. PASCHETAGM. WATTSS. SCHOLL, GREEN PROCESS. SYNTH., vol. 10, 2021, pages 361 - 373
M. DANNOUXP. CASSAGNAUA. MICHEL, CAN J CHEM ENG, vol. 80, 2002, pages 1075 - 1082
M.A. MOHSINT. ABDULREHMANY. HAIK, INT. J. CHEM. ENG., 2017, pages 5361251
M.R. MILANAM. DENAROL. ARRIVABENEA. MAGGIOL. GRAMICCIONI, FOOD ADDITIVES AND CONTAMINANTS, vol. 15, 1998, pages 355 - 361
N.D. PINGALES.R. SHUKLA, EUROPEAN POLYMER JOURNAL, vol. 44, 2008, pages 4151 - 4156
S. UGDULERK.M. VAN GEEMR. DENOLFM. ROOSENN. MYSK. RAGAERTS. DE MEESTER, GREEN CHEM., vol. 22, 2020, pages 5376 - 5394
S.R. SHUKLAA.M. HARAD, JOURNAL OF APPLIED POLYMER SCIENCE, vol. 97, 2005, pages 513 - 517
T. YOSHIOKAN. OKAYAMAA. OKUWAKI, IND. ENG. CHEM. RES., vol. 37, 1998, pages 336 - 340

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