DE102012202804A1 - Recycling partially crosslinked polyolefins, preferably partially crosslinked polyethylene, comprises selectively and partially dissolving uncrosslinked components of polyolefin, in solvent, and recovering uncrosslinked polyolefin - Google Patents

Recycling partially crosslinked polyolefins, preferably partially crosslinked polyethylene, comprises selectively and partially dissolving uncrosslinked components of polyolefin, in solvent, and recovering uncrosslinked polyolefin Download PDF

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Publication number
DE102012202804A1
DE102012202804A1 DE201210202804 DE102012202804A DE102012202804A1 DE 102012202804 A1 DE102012202804 A1 DE 102012202804A1 DE 201210202804 DE201210202804 DE 201210202804 DE 102012202804 A DE102012202804 A DE 102012202804A DE 102012202804 A1 DE102012202804 A1 DE 102012202804A1
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Prior art keywords
polyolefin
partially crosslinked
uncrosslinked
solvent
partially
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German (de)
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Fausto Rota
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Trocellen GmbH
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Trocellen GmbH
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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
    • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
    • C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

Recycling partially crosslinked polyolefins, preferably partially crosslinked polyethylene, comprises (a) selectively and at least partially dissolving uncrosslinked components of the partially crosslinked polyolefin, in a solvent, and (b) recovering the uncrosslinked polyolefin from the solution.

Description

Die Erfindung betrifft ein Verfahren zum Recyceln von teilvernetzten Polyolefinen, insbesondere von teilvernetztem Polyethylen.The invention relates to a process for recycling partially crosslinked polyolefins, in particular partially crosslinked polyethylene.

Technisches GebietTechnical area

Vernetzter Polyolefinschaum wird industriell in großem Umfang verwendet. Für die Herstellung von Polyolefinschäumen wird insbesondere Polyethylen mit einem Schäummittel, insbesondere Azodicarbonamid, versehen und als sogenannte Matrix extrudiert. Die Matrix kann dabei chemische Vernetzungsmittel, insbesondere Dicumylperoxid, enthalten und/oder nach Extrusion der Matrix durch Elektronenbeschuss (β-Strahlung) physikalisch vernetzt werden. Für die Herstellung eines Schaumstoffs wird das Polyolefin in aller Regel nur zu einem gewissen Anteil vernetzt, wobei der Vernetzungsgrad als sogenannter Gel-Gehalt bestimmt wird und in der Regel zwischen 30 und 80% beträgt.Crosslinked polyolefin foam is used industrially on a large scale. For the production of polyolefin foams in particular polyethylene is provided with a foaming agent, in particular azodicarbonamide, and extruded as a so-called matrix. The matrix may contain chemical crosslinking agents, in particular dicumyl peroxide, and / or be physically crosslinked after extrusion of the matrix by electron bombardment (β radiation). For the production of a foam, the polyolefin is usually crosslinked only to a certain extent, wherein the degree of crosslinking is determined as a so-called gel content and is usually between 30 and 80%.

Stand der TechnikState of the art

Aus der DIN EN 579 ist es bekannt, zur Bestimmung des Vernetzungsgrades teilvernetzte Polyolefine bei einer Temperatur von 120°C in Xylol zu behandeln. Durch Wiegen des unlöslichen Anteils wird der Gel-Gehalt, also der vernetzte Anteil des Polyolefins, bestimmt.From the DIN EN 579 It is known to treat partially crosslinked polyolefins at a temperature of 120 ° C in xylene to determine the degree of crosslinking. By weighing the insoluble fraction, the gel content, ie the cross-linked portion of the polyolefin, is determined.

Polyethylen-Schaumstoffe werden üblicherweise in Bahnenware, in geringerem Umfang auch in Form von großen Blöcken oder dünneren Folien hergestellt und häufig durch Ausstanzen von Formteilen und beispielsweise thermische Umformung weiter verarbeitet. Die anfallenden Stanzreste etc. können wegen ihrer Vernetzung nicht ohne weiteres in den Produktionsprozess zurückgeführt werden. Sie werden üblicherweise für geringwertige Produkte wie Polstermaterialien etc. verwendet (”Downcyclen”) oder energetisch durch Verbrennen genutzt.Polyethylene foams are usually produced in webs, to a lesser extent in the form of large blocks or thinner films and often further processed by punching moldings and, for example, thermal forming. Due to their cross-linking, the resulting stamping residues etc. can not be easily returned to the production process. They are usually used for low-value products such as upholstery materials, etc. ("downcycling") or energetically used by burning.

Aufgabetask

Aufgabe der vorliegenden Erfindung ist es, ein alternatives Verfahren zum Recyceln von teilvernetzten Polyolefinen, insbesondere teilvernetztem Polyethylen zur Verfügung zu stellen.The object of the present invention is to provide an alternative process for the recycling of partially crosslinked polyolefins, in particular partially crosslinked polyethylene.

Darstellung der ErfindungPresentation of the invention

Die Erfindung löst diese Aufgabe durch ein Verfahren nach Anspruch 1, bevorzugt in Verbindung mit einem oder mehreren der Merkmale der Unteransprüche.The invention achieves this object by a method according to claim 1, preferably in conjunction with one or more of the features of the subclaims.

Kern der Erfindung ist es, den löslichen Anteil des teilvernetzten Polyolefin-Materials mit an sich bekannten Lösungsmitteln herauszulösen und aus diesen den unvernetzten Polyehtylen-Anteil wiederzugewinnen. Aus der unlöslichen Fraktion des Ausgangsmaterials können ggf. in einem weiteren Verarbeitungsschritt weitere nutzbare Rohstoffe zurückgewonnen werden, alternativ kann diese Fraktion jedoch auch – wie im Stand der Technik bislang für das gesamte Material üblich – beispielsweise durch Verbrennen thermisch genutzt werden.The essence of the invention is to dissolve the soluble portion of the partially crosslinked polyolefin material with known solvents and recover from these the uncrosslinked Polyehtylen share. From the insoluble fraction of the starting material further usable raw materials can possibly be recovered in a further processing step, alternatively, however, this fraction can also - as in the prior art for the entire material usual - be used thermally, for example by burning.

Das erfindungsgemäße Verfahren eignet sich in besonderem Maße für das Recyceln von teilvernetzten Polyolefinschaumstoffen, insbesondere von chemisch und/oder physikalisch vernetztem Polyethylen-Schaumstoff, insbesondere mit einem Vernetzungsgrad zwischen 30 und 80%.The inventive method is particularly suitable for the recycling of partially crosslinked polyolefin foams, in particular of chemically and / or physically crosslinked polyethylene foam, in particular with a degree of crosslinking between 30 and 80%.

Nach einer bevorzugten Ausführungsform der Erfindung wird Xylol als Lösungsmittel verwendet. Grundsätzlich ist es jedoch möglich, auch andere Lösungsmittel einzusetzen, in denen unvernetztes Polyolefin lösbar, vernetztes Polyolefin jedoch nicht lösbar ist.According to a preferred embodiment of the invention, xylene is used as the solvent. In principle, however, it is also possible to use other solvents in which uncrosslinked polyolefin is soluble, but crosslinked polyolefin is not soluble.

ZITATE ENTHALTEN IN DER BESCHREIBUNG QUOTES INCLUDE IN THE DESCRIPTION

Diese Liste der vom Anmelder aufgeführten Dokumente wurde automatisiert erzeugt und ist ausschließlich zur besseren Information des Lesers aufgenommen. Die Liste ist nicht Bestandteil der deutschen Patent- bzw. Gebrauchsmusteranmeldung. Das DPMA übernimmt keinerlei Haftung für etwaige Fehler oder Auslassungen.This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Zitierte Nicht-PatentliteraturCited non-patent literature

  • DIN EN 579 [0003] DIN EN 579 [0003]

Claims (6)

Verfahren zum Recyceln von teilvernetzten Polyolefinen, insbesondere teilvernetztem Polyehtylen, mit folgenden Verfahrensschritten: – die unvernetzten Bestandteile des teilvernetzten Polyolefins werden mit einem Lösungsmittel selektiv zumindest zum Teil gelöst; – aus der Lösung wird das unvernetzte Polyolefin zurückgewonnen.Process for the recycling of partially crosslinked polyolefins, in particular partially crosslinked polyethylene, with the following process steps: - The uncrosslinked constituents of the partially crosslinked polyolefin are selectively dissolved with a solvent, at least in part; - From the solution, the uncrosslinked polyolefin is recovered. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass als teilvernetztes Polyolefin ein chemisch oder physikalisch vernetzter Polyethylen-Schaumstoff mit einem Vernetzungsgrad zwischen 30 und 80% verwendet wird.A method according to claim 1, characterized in that a chemically or physically crosslinked polyethylene foam having a degree of crosslinking between 30 and 80% is used as the partially crosslinked polyolefin. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass als Lösungsmittel Xylol verwendet wird.A method according to claim 1 or 2, characterized in that xylene is used as the solvent. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der im ersten Verfahrensschritt nicht gelöste Anteil des teilvernetzten Polyolefins mit einer Säure behandelt wird.Method according to one of claims 1 to 3, characterized in that the non-dissolved in the first step portion of the partially crosslinked polyolefin is treated with an acid. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Lösen der unvernetzten Bestandteile des teilvernetzten Polyolefins mit dem Lösungsmittel bei einer Temperatur zwischen 100 und 150°C erfolgt.Method according to one of claims 1 to 4, characterized in that the dissolution of the uncrosslinked constituents of the partially crosslinked polyolefin with the solvent takes place at a temperature between 100 and 150 ° C. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das Zurückgewinnen des unvernetzten Polyolefins aus der Lösung durch Destillation der Lösung erfolgt und dass die Lösungsmittelfraktion aus der Destillation zur weiteren Lösung des unvernetzten Polyolefins im Verfahrensschritt 1 wiederverwendet wird.Method according to one of claims 1 to 5, characterized in that the recovery of the uncrosslinked polyolefin from the solution by distillation of the solution is carried out and that the solvent fraction from the distillation is reused for further solution of the uncrosslinked polyolefin in process step 1.
DE201210202804 2012-02-23 2012-02-23 Recycling partially crosslinked polyolefins, preferably partially crosslinked polyethylene, comprises selectively and partially dissolving uncrosslinked components of polyolefin, in solvent, and recovering uncrosslinked polyolefin Withdrawn DE102012202804A1 (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170102286A (en) * 2014-12-30 2017-09-08 도레이 플라스틱스 아메리카 인코오포레이티드 Multi-layer polyolefin foam structure co-extruded from recycled polyolefin material and method of making same
US10814590B2 (en) 2013-12-31 2020-10-27 Toray Plastics (America), Inc. Methods of producing foam structures from recycled metallized polyolefin material
US11007761B2 (en) 2017-03-31 2021-05-18 Toray Plastics (America), Inc. Method of making coextruded, cross-linked polyolefin foam with TPU cap layers
US11590677B2 (en) 2019-03-29 2023-02-28 Toray Plastics (America), Inc. Method of making coextruded, crosslinked polyolefin foam with KEE cap layers
US11590730B2 (en) 2019-03-29 2023-02-28 Toray Plastics (America), Inc. Coextruded, crosslinked polyolefin foam with KEE cap layers

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4164484A (en) * 1978-01-13 1979-08-14 Director-General, Masao Kubota of the Agency of Industrial Science and Technology Process for recovering polyolefin and polystyrene materials by dissolving, vacuum-evaporating and precipitating
DE19732673A1 (en) * 1997-07-29 1999-02-04 Fraunhofer Ges Forschung Process for the recovery of soluble polymers or polymer mixtures from plastic-containing materials
WO2000077082A1 (en) * 1999-06-16 2000-12-21 Der Grüne Punkt-Duales System Deutschland Ag Method of separating polyolefinic synthetic mixtures
JP2001192495A (en) * 2000-01-06 2001-07-17 Chubu Electric Power Co Inc Method for reprocessing cross-linked polyolefin
EP1170326A1 (en) * 2000-07-06 2002-01-09 Siemens Axiva GmbH & Co. KG Process for Analysing the content of HDPE and LDPE in Polyolefin Mixtures

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4164484A (en) * 1978-01-13 1979-08-14 Director-General, Masao Kubota of the Agency of Industrial Science and Technology Process for recovering polyolefin and polystyrene materials by dissolving, vacuum-evaporating and precipitating
DE19732673A1 (en) * 1997-07-29 1999-02-04 Fraunhofer Ges Forschung Process for the recovery of soluble polymers or polymer mixtures from plastic-containing materials
WO2000077082A1 (en) * 1999-06-16 2000-12-21 Der Grüne Punkt-Duales System Deutschland Ag Method of separating polyolefinic synthetic mixtures
JP2001192495A (en) * 2000-01-06 2001-07-17 Chubu Electric Power Co Inc Method for reprocessing cross-linked polyolefin
EP1170326A1 (en) * 2000-07-06 2002-01-09 Siemens Axiva GmbH & Co. KG Process for Analysing the content of HDPE and LDPE in Polyolefin Mixtures

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DIN EN 579

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10814590B2 (en) 2013-12-31 2020-10-27 Toray Plastics (America), Inc. Methods of producing foam structures from recycled metallized polyolefin material
KR20170102286A (en) * 2014-12-30 2017-09-08 도레이 플라스틱스 아메리카 인코오포레이티드 Multi-layer polyolefin foam structure co-extruded from recycled polyolefin material and method of making same
JP2018502746A (en) * 2014-12-30 2018-02-01 トーレ プラスティックス （アメリカ） インコーポレイテッド Co-extrusion cross-linked multilayer polyolefin foam structure from recycled polyolefin material and method for producing the same
KR102478432B1 (en) 2014-12-30 2022-12-15 도레이 플라스틱스 아메리카 인코오포레이티드 Co-extrusion crosslinked multi-layer polyolefin foam structure from recycled polyolefin material and method for producing the same
US11007761B2 (en) 2017-03-31 2021-05-18 Toray Plastics (America), Inc. Method of making coextruded, cross-linked polyolefin foam with TPU cap layers
US11628657B2 (en) 2017-03-31 2023-04-18 Toray Plastics (America), Inc. Method of making coextruded, cross-linked polyolefin foam with TPU cap layers
US11590677B2 (en) 2019-03-29 2023-02-28 Toray Plastics (America), Inc. Method of making coextruded, crosslinked polyolefin foam with KEE cap layers
US11590730B2 (en) 2019-03-29 2023-02-28 Toray Plastics (America), Inc. Coextruded, crosslinked polyolefin foam with KEE cap layers

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