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WO2000039206A1 - Procede de recyclage de polyurethanne - Google Patents

Procede de recyclage de polyurethanne Download PDF

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Publication number
WO2000039206A1
WO2000039206A1 PCT/BR1999/000105 BR9900105W WO0039206A1 WO 2000039206 A1 WO2000039206 A1 WO 2000039206A1 BR 9900105 W BR9900105 W BR 9900105W WO 0039206 A1 WO0039206 A1 WO 0039206A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyurethane
process according
comminuting
shearing
organic solvent
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.)
Ceased
Application number
PCT/BR1999/000105
Other languages
English (en)
Inventor
Luiz Carlos Oliveira Da Cunha Lima
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to AU17630/00A priority Critical patent/AU1763000A/en
Publication of WO2000039206A1 publication Critical patent/WO2000039206A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/82—Post-polymerisation 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • 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

  • This invention relates to a process for polyurethane recycling based on the capacity of polyurethanes to lower their resistance to shearing and hydrolysis by absorption of solvents.
  • Description of the Related Art The first information available on polyurethane obtention dates back to 1848, when it was first synthetized by A. Wurtz. Only in the next century, namely, in 1937, Bayer started with polyurethane commercial production. Polyurethane has by far the widest range of applications when compared to existing synthetic polymers. It is used to produce following products:
  • Polyurethane scraps are processed by adding heated prepolymer to small piece-s of cru-shed polyurethane with subsequent cross-linking agent. The reaction is obtained under vacuum. The method Is simplified and accelerated by activation in the presence of dimethylketone or methylenechloride between 18 and 20° C.
  • the present invention relates to a polyurethane recycling process whereby the polyurethane is comminuted into very fine particles that are perfectly compatible with the original product.
  • Polyurethane comminuting is done by swelling the polyurethane with a solvent and further comminuting the resulting scraps by shearing, with or without processing in the presence of hydrolyzing agents.
  • the product obtained is polyurethane powder, an inert filler.
  • an active filler is obtained, that is, micro polyurethane containing OH radicals .
  • the present invention refers also to a process for polyurethane scrap regeneration, whereby a high-quality final product is obtained that can be incorporated into the original composition while maintaining compatible characteristics.
  • present invention relates to a process for polyurethane comminuting and/or regeneration, characterized by the fact hat the polyurethane is crushed in the presence-, or absence y of hydrolyzing agents. Particle size may vary from 1 milimeter to 0,01 micron, more specifically from 0,1 mm to 0,1 micron.
  • the material so regenerated can be further utilized to make either-, compact objects or foamed polyurethane.
  • foamed polyurethante production requires the material to be mixed with polyisocianates; more specifically, it is first mixed with polyol and further mixed with polyisocianates, although it can also be mixed with prepolymers.
  • Ketones dimethylketone, diethylketone, methylethylketone, m thylbutylketone.
  • -Alcohols methanol, ethanol, isopropanol, propanol, butanol, isobutanol, glycols.
  • -Aromatic hydrocarbons toluene, xylenes, cresols.
  • -Paraffin hydrocarbon _ hexane,, ⁇ Lepthane-, octane ⁇ - Naphthenic hydrocarbons: cyclopentane, cyclohexane, dipentene, turpentine.
  • Mentioned swelling agents may be used alone or in blends, the purpose always being to swell high molecular weight chains and/or to dissolve low molecular weight chains, thus weakening the mechanical properties imported by cross-li king.
  • a suitable * pure or blended solvent is applicable, that is, a solvent that can more efficiently swell the polyurethane and favour the size reductio process.
  • a suitable solvent or solvent mixture can be selected experimentally.
  • the swelling solvents must be present at approximately 1 to 20 parts of polyurethane, preferably * at about 4 to 8 parts by weight.
  • the time required for polyurethane swelling with a solvent depends on the solvent type used and on the state of the polyurethane particles or scraps, as well as on the polyurethane consistency - whether it is in compact or foamed state - and on polyurethane particle or scrap size.
  • the polyurethane particles are large and compact * and it will take longer to he absorbed, maybe-, hours or days; in this case, it is convenient to heat the solvent so as to reduce viscosity rates. Also, in this case, it is convenient to use, say, petroleum aromatic extract as a solvent.
  • hydrolysing agents When using a fluid solvent and foamed polyurethane, absorption takes place almost immediately; in this case a trichloroethylene at ambient temperature should be used on the foamed polyurethane.
  • hydrolysing agents When the hydrolysing agents are present as a solution to be mixed with the solvent-swollen polyurethane, they act simultaneously with the polymer carbon chain shearing process * reduces the molecular weight size, and the hydrolyzing process thus takes place.
  • hydroly-zing elements those acid solutions and alkalis which are employed in ester hydrolysing.
  • the process considers acids * such as, sulfuric acid, hydrochlroric acid and their derivatives.
  • the alkalis considered in the process are hidroxydes, such as, sodium hydroxyde, potassium hydroxyde and derivatives .
  • hydrolyzing agents of above mentioned products occurs at above 0.001%- by polyurethane, preferably, at about 0,01% by weight.
  • Equipment used are ball, bar, sphere and plate mills, indented plate comminutors, perforated cylinders, compression-driven gears and machines, such as extruding machines * pumps and injectors that may subject the swollen polyurethane to restrictions, such as, slots, grades, * holes, screens,, interized or sponged material.
  • extruding machines * pumps and injectors that may subject the swollen polyurethane to restrictions, such as, slots, grades, * holes, screens,, interized or sponged material.
  • pressure-driven pumps and injectors * comminuting may also occur by decompression (flash) after the swollen polyurethane release through mentioned -restrict] ons.
  • the time required for polyurethane regeneration by hydrolyzing agents depends- on the eguipment used in the regeneration process. For instance, it can take centesimal .of a second * when the swollen polyurethane is pressed through restriction means with simultaneous particle comminuting and hydrolysis, or else, it can take hours, when shearing and/or regeneration are processed at ball mills.
  • Table I shows the characteristics of each example, with the purpose of illustrating the practical aspects of the recycling process by both, polyurethane size reduction and regeneration, respectively * whereas said considerations should not be considered as limiting factors what concerns the definition of this invention. .As -evidenced in Table I, the size reduction process alone produces an inert filler only -compatible with the polyurethane * but downgrades prevailing characteristics, whereas the regeneration process maintains the guality of original polyurethane to some extent.
  • Weight measure units will apply to this invention whenever no measure unit is herein indicated.
  • Example 1 About 100 g of crushed polyurethane was swollen with 1 liter of acetone and crushed -a.t porcelain ball mills at ambient temperature during 24 hours. The crushed material was dried and resulting scattered powder was mixed with polyol at 10, 20 and 30% by weight. Completing the basic formulation * following results were obtained: Table 1.
  • crushed polyurethane was swollen with 1 liter of ethyl acetate * wherein lOg of a solution containing about 0.01 g of hydrochloric acid was added, and the mate-rial was next crushed at a .stainless steel bar mill at ambient temperature during 24 hours.
  • the crushed material 4 «*as dried and resulting -scattered powder was then mixed with polyol at 10, 20 30% by weight.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

L'invention se rapporte à un procédé de recyclage de polyuréthanne, fondé sur la capacité des polyuréthannes à réduire leur résistance au cisaillement et à l'hydrolyse par absorption de solvants. Les dispositifs de cisaillement considérés comme adaptés à ce procédé sont en particulier des dispositifs du type broyeur à boulets, broyeur à galets, laminoir à tôles fortes, marteau et tout dispositif permettant l'écoulement d'un matériau dans des fentes, des trous, des tamis, des plaques microporeuses de matriçage avec préforme, du type injecteurs, pompes et extrudeuses, sous pression. L'agent d'hydrolyse ajouté lors du processus de cisaillement ou de fragmentation du polyuréthanne comprend des solutions acides et des solutions alcalines. Le procédé de cette invention permet de produire de la poudre de polyuréthanne ou du polyuréthanne régénéré dans des conditions modérées qui permettent une nouvelle intégration à la formulation de base tout en assurant une perte minimale des caractéristiques d'origine du produit.
PCT/BR1999/000105 1998-12-23 1999-12-21 Procede de recyclage de polyurethanne Ceased WO2000039206A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU17630/00A AU1763000A (en) 1998-12-23 1999-12-21 Process for polyurethane recycling

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BRPI9805620-4 1998-12-23
BR9805620A BR9805620A (pt) 1998-12-23 1998-12-23 Processo para reciclagem de poliuretanos

Publications (1)

Publication Number Publication Date
WO2000039206A1 true WO2000039206A1 (fr) 2000-07-06

Family

ID=4071239

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/BR1999/000105 Ceased WO2000039206A1 (fr) 1998-12-23 1999-12-21 Procede de recyclage de polyurethanne

Country Status (3)

Country Link
AU (1) AU1763000A (fr)
BR (1) BR9805620A (fr)
WO (1) WO2000039206A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1027975A3 (fr) * 1999-02-10 2002-02-06 R & D Technology, Inc. Procédé pour convertir des élastomères et utilisation des particules élastomères moulues
US6680110B1 (en) 1998-02-10 2004-01-20 R & D Technology, Inc. Particle size reduction using supercritical materials
US6743836B2 (en) 2000-01-26 2004-06-01 R&D Technology, Inc. Method for predispersing compounding ingredients
US6815510B2 (en) 2001-11-19 2004-11-09 Michael W. Rouse Elastomer reclaiming composition and method
GB2459639A (en) * 2008-02-15 2009-11-04 Screenex Mfg Recycled polyurethane screen panel & method of manufacture
EP3287475A1 (fr) 2016-08-25 2018-02-28 Covestro Deutschland AG Procede de fabrication de polymeres de polyurethane resorbables et procede de preparation associe
CN108178842A (zh) * 2017-12-20 2018-06-19 广州冠志新材料科技有限公司 一种利用废弃水性聚氨酯及分散体回收制备水性聚氨酯树脂的方法
WO2021236385A1 (fr) * 2020-05-19 2021-11-25 Huntsman International Llc Procédé de recyclage d'un matériau de polyuréthane
CN113773549A (zh) * 2021-09-23 2021-12-10 青岛科技大学 一种聚氨酯泡沫废料活化微粉及其制备方法、聚氨酯软泡及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4339358A (en) * 1979-12-21 1982-07-13 Schuetz Wilhelm Process and apparatus for reclaiming polyurethanes
US5648431A (en) * 1990-09-27 1997-07-15 Michael Demuth Process for the utilization of plastics

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4339358A (en) * 1979-12-21 1982-07-13 Schuetz Wilhelm Process and apparatus for reclaiming polyurethanes
US5648431A (en) * 1990-09-27 1997-07-15 Michael Demuth Process for the utilization of plastics

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6680110B1 (en) 1998-02-10 2004-01-20 R & D Technology, Inc. Particle size reduction using supercritical materials
EP1027975A3 (fr) * 1999-02-10 2002-02-06 R & D Technology, Inc. Procédé pour convertir des élastomères et utilisation des particules élastomères moulues
US6743836B2 (en) 2000-01-26 2004-06-01 R&D Technology, Inc. Method for predispersing compounding ingredients
US6815510B2 (en) 2001-11-19 2004-11-09 Michael W. Rouse Elastomer reclaiming composition and method
US8047380B2 (en) 2008-02-15 2011-11-01 Screenex Manufacturing (Pty) Ltd. Screen panels
GB2459639B (en) * 2008-02-15 2010-09-08 Screenex Mfg Screen panels with recycled polyurethane
GB2459639A (en) * 2008-02-15 2009-11-04 Screenex Mfg Recycled polyurethane screen panel & method of manufacture
EP3287475A1 (fr) 2016-08-25 2018-02-28 Covestro Deutschland AG Procede de fabrication de polymeres de polyurethane resorbables et procede de preparation associe
CN108178842A (zh) * 2017-12-20 2018-06-19 广州冠志新材料科技有限公司 一种利用废弃水性聚氨酯及分散体回收制备水性聚氨酯树脂的方法
WO2021236385A1 (fr) * 2020-05-19 2021-11-25 Huntsman International Llc Procédé de recyclage d'un matériau de polyuréthane
CN115702181A (zh) * 2020-05-19 2023-02-14 亨斯迈国际有限责任公司 回收聚氨酯材料的方法
CN115702181B (zh) * 2020-05-19 2025-08-19 亨斯迈国际有限责任公司 回收聚氨酯材料的方法
US12503567B2 (en) 2020-05-19 2025-12-23 Huntsman International Llc Process for recycling a polyurethane material
CN113773549A (zh) * 2021-09-23 2021-12-10 青岛科技大学 一种聚氨酯泡沫废料活化微粉及其制备方法、聚氨酯软泡及其制备方法和应用

Also Published As

Publication number Publication date
AU1763000A (en) 2000-07-31
BR9805620A (pt) 2000-09-26

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