EP2928948A1 - Procédé pour une extraction chimique sélective de l'acide lactique depuis un blend de polymères - Google Patents

Procédé pour une extraction chimique sélective de l'acide lactique depuis un blend de polymères

Info

Publication number
EP2928948A1
EP2928948A1 EP13799078.4A EP13799078A EP2928948A1 EP 2928948 A1 EP2928948 A1 EP 2928948A1 EP 13799078 A EP13799078 A EP 13799078A EP 2928948 A1 EP2928948 A1 EP 2928948A1
Authority
EP
European Patent Office
Prior art keywords
alcoholysis
lactic acid
carried out
blends
polymer blends
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13799078.4A
Other languages
German (de)
English (en)
Inventor
Wolfgang Tietz
Armin BÖRNER
Ivan SHUKLOV
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Uhde Inventa Fischer GmbH
ThyssenKrupp AG
Original Assignee
Uhde Inventa Fischer GmbH
ThyssenKrupp AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Uhde Inventa Fischer GmbH, ThyssenKrupp AG filed Critical Uhde Inventa Fischer GmbH
Publication of EP2928948A1 publication Critical patent/EP2928948A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • 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 the chemical extraction of lactic acid
  • Polymer blends comprising polylactic acid and one or more other polyesters, as well as blends comprising polylactic acid and one or more other plastic polymers, are selectively cross-esterified as a method of efficient and resource-efficient recycling of plastics.
  • Polylactic acid plays a prominent role as a polymer derived from renewable raw materials in a sustainable and ecological way
  • Plastic chemistry Re-use after its one-time use would further increase sustainability and enable a closed material cycle. Thus, it is important to find an effective method that only degrades polylactic acid from polymer blends.
  • plastic materials There are various known from the prior art with respect. The chemical recycling of plastic materials.
  • the degradation of polyesters is possible by hydrolysis to the monomeric building blocks, the hydroxycarboxylic acids. Alcoholysis leads to the corresponding hydroxycarboxylic acid esters.
  • PLAs or PLLAs pure polylactic acids
  • WO 2010/1 18955 describes the reaction of the extracted by means of lactic acid ethyl ester PLLA with alcohols in the presence of basic or acidic transesterification catalysts, wherein PLLA is decomposed in the course of the reaction in their monomers and the pure
  • Lactic acid esters are finally obtained by distillation.
  • the processes mentioned require large amounts of the solvent, lactic acid ethyl ester, which must first be prepared from the lactic acid obtained in the patents.
  • the direct production of lactic acid ester would therefore be advantageous, also in terms of reuse as a monomer for the polylactic acid synthesis.
  • the object is achieved by a recycling process for the selective chemical extraction of lactic acid ester from polymer blends, comprising
  • Polylactic acid and one or more other plastic polymers as well as from
  • Mixtures comprising polylactic acid and one or more others
  • Plastic polymers wherein an alcoholysis of the polymer blends in the presence of an alcohol for 6 to 30 h, at 80 to 160 ° C and a pressure of 0.05 to 10 bar is performed.
  • Preferred ranges for the procedure are that the alcoholysis is carried out for 10 to 25 hours, preferably for 12 to 20 and / or a temperature of 100 to 130 ° C, preferably from 1 10 to 125 ° is maintained and the pressure in the range of 4 up to 8 bar.
  • Extract reaction with alcohols in the form of their lactic acid esters can be applied directly to blends or mixtures without first having to extract the PLA portion by special techniques. Under the conditions according to the process, the PLA-foreign constituents of the blends or the mixtures are chemically attacked, or only slightly attacked. These remaining residual components can thus be used for a different purpose.
  • a polymer blend is understood to be a macroscopically homogeneous mixture which is prepared, for example, by melting the components together.
  • mixtures means a macroscopically heterogeneous mixture of several plastics.
  • the other plastic polymers of the mixed ester of terephthalic acid, 1, 4-butanediol and adipic acid is a mixed ester and is also known as Ecoflex ®.
  • the particular value of the invention lies in the application to blends and mixtures with other polyesters.
  • the polyester blend or the mixtures are comminuted before the alcoholysis.
  • advantage is the alcohol, which for the
  • Alcoholysis is used methanol.
  • the present invention is carried out without the addition of a catalyst.
  • the execution in the presence of a catalyst is carried out without the addition of a catalyst.
  • Catalyst is possible, however, wherein the catalyst is selected from the group of metals comprising ruthenium, rhodium, rhenium, palladium, platinum, nickel, cobalt, molybdenum, tungsten, titanium, zirconium, niobium, vanadium, chromium, manganese, osmium, iridium , Iron, copper, zinc, silver, gold, barium and mixtures thereof, and preferably copper oxide-chromium oxide catalysts and / or barium-doped copper oxide-chromium oxide catalysts are used.
  • Other possible catalysts are stannous octoate, paratoluene sulfonic acid, triazabicyclodecene and derivatives thereof.
  • the crude product from the alcoholysis is filtered and concentrated and / or distilled.
  • the invention also claims the use of the lactic acid ester, which is obtained by the process according to the invention, for the polymerization to polylactic acid.
  • Ecovio ® used, which consists of the two polyesters PLA and Ecoflex ® . Under the process conditions, the PLA fraction can be extracted from Ecovio ® without attacking the Ecoflex ® component.
  • the Ecoflex ® component can be represented as follows:
  • the blend Ecovio - F film A 2203 was used in the form of crushed and printed, so-called Aldi Ecotüten
  • the alcoholysis was carried out in all the following examples with MeOH at 120 ° C in the presence of a heterogeneous Cu / Cr / Ba catalyst or without catalyst in a closed pressure tube and provides after about 15 hours GC-pure methyl lactate.
  • the running in the reaction with Ecovio ® reaction can be represented as follows. Lactic acid methyl ester (LAMe) is the sought-after product and terephthalic acid dimethyl ester (TEMe 2 ), dimethyl adipate (ADMe 2 ) and 1,4-butanediol (BDO) are the predominant by-products which do not or only to a small extent result from the action according to the process.
  • Lactic acid methyl ester LAMe
  • TEMe 2 terephthalic acid dimethyl ester
  • ADMe 2 dimethyl adipate
  • BDO 1,4-butanediol
  • Experiment 1 was carried out in the absence of a catalyst. There are after 20 hours at 120 ' ⁇ at a pressure of about 6.5 bar in the pressure tube in addition to the main product of methyl lactate (LAMe) only small amounts of terephthalate (TEMe 2 ) and adipic acid dimethyl ester (ADMe 2 ) found. Detailed NMR and GC analysis also shows traces of
  • Example 2 Alkolyse a shopping bag on the basis of Ecovio ® F Film A 2203:
  • Example 2 Alkolyse a shopping bag on the basis of Ecovio ® F Film A 2203 in admixture with polypropylene (PP):
  • Example 3 Alkolyse a shopping bag on the basis of Ecovio ® F Film A 2203 in the presence of polyethylene terephthalate (PET):

Landscapes

  • 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

L'invention concerne l'extraction chimique de l'acide lactique depuis des blends de polymères qui comprennent de l'acide polylactique et un ou plusieurs autres polyesters, ainsi qu'à partir de mélanges qui comprennent de l'acide polylactique et un ou plusieurs autres polymères plastiques, par une alcoolyse des blends de polymères en présence d'un alcool pendant 6 à 30 heures, à une température de 80 à 160 °C et sous une pression de 0,05 à 10 bar.
EP13799078.4A 2012-12-04 2013-12-04 Procédé pour une extraction chimique sélective de l'acide lactique depuis un blend de polymères Withdrawn EP2928948A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012023609 2012-12-04
PCT/EP2013/075508 WO2014086840A1 (fr) 2012-12-04 2013-12-04 Procédé pour une extraction chimique sélective de l'acide lactique depuis un blend de polymères

Publications (1)

Publication Number Publication Date
EP2928948A1 true EP2928948A1 (fr) 2015-10-14

Family

ID=49683760

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13799078.4A Withdrawn EP2928948A1 (fr) 2012-12-04 2013-12-04 Procédé pour une extraction chimique sélective de l'acide lactique depuis un blend de polymères

Country Status (2)

Country Link
EP (1) EP2928948A1 (fr)
WO (1) WO2014086840A1 (fr)

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5264626A (en) 1991-11-22 1993-11-23 E. I. Du Pont De Nemours And Company Rapid depolymerization of polyhydroxy acids
US5264614A (en) * 1991-11-22 1993-11-23 E. I. Du Pont De Nemours And Company Recovery of polyhydroxy acids
US5264617A (en) 1991-11-22 1993-11-23 E. I. Du Pont De Nemours And Company Preparation of alkyl esters by depolymerization
US5268597A (en) 1992-08-19 1993-12-07 Hyundai Electronics America Output buffer circuit with noise reduction circuit
JP3503127B2 (ja) 1995-09-14 2004-03-02 トヨタ自動車株式会社 高分子量ポリ乳酸からのラクチド回収方法
JPH11106554A (ja) 1997-10-01 1999-04-20 Kobe Steel Ltd ポリ乳酸の製造系又は分解系からラクチドを連続的に回収する方法
US6706843B1 (en) * 1999-10-22 2004-03-16 Teijin Limited Method for separating and recovering dimethyl terephthalate and ethylene glycol from polyester waste
AU2003231482A1 (en) 2002-04-25 2003-11-10 Yujiang Fan Process for producing lactide
EP1741707A4 (fr) 2004-04-30 2009-02-25 Kyushu Inst Technology Methode de recuperation de lactide à partir d'acide polylactique ou son derive
BE1018716A3 (fr) 2009-04-14 2011-07-05 Galactic Sa Recyclage chimique du pla par hydrolyse.
BE1019608A3 (fr) 2009-04-14 2012-09-04 Galactic Sa Recyclage chimique du pla par alcoolyse.
BE1018882A3 (fr) 2009-09-10 2011-10-04 Galactic Sa Procede de recyclage stereospecifique d'un melange de polymeres a base de pla.

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ANDERS SÖDERGARD ET AL: "3 INDUSTRIAL PRODUCTION OF HIGH MOLECULAR WEIGHT POLY(LACTIC ACID)", POLY(LACTIC ACID): SYNTHESIS, PROPERTIES, PROCESSING, AND APPLICATIONS, 1 January 2010 (2010-01-01), pages 27 - 41, XP055143073, Retrieved from the Internet <URL:http://onlinelibrary.wiley.com/store/10.1002/9780470649848.ch3/asset/ch3.pdf?v=1&t=i0jotxyn&s=557af384ef95d1528eb8a5138745393ef67b8bd4> [retrieved on 20140926] *
ARNAU CARN SNCHEZ ET AL: "The selective recycling of mixed plastic waste of polylactic acid and polyethylene terephthalate by control of process conditions", EUROPEAN POLYMER JOURNAL, PERGAMON PRESS LTD. OXFORD, GB, vol. 47, no. 10, 14 July 2011 (2011-07-14), pages 1970 - 1976, XP028294714, ISSN: 0014-3057, [retrieved on 20110726], DOI: 10.1016/J.EURPOLYMJ.2011.07.013 *
See also references of WO2014086840A1 *

Also Published As

Publication number Publication date
WO2014086840A1 (fr) 2014-06-12

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