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WO1993005106A1 - Procede de fabrication de liquides disperses renfermant des composes a fonctions hydroxy et/ou amino, et leur utilisation - Google Patents

Procede de fabrication de liquides disperses renfermant des composes a fonctions hydroxy et/ou amino, et leur utilisation Download PDF

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Publication number
WO1993005106A1
WO1993005106A1 PCT/DE1992/000702 DE9200702W WO9305106A1 WO 1993005106 A1 WO1993005106 A1 WO 1993005106A1 DE 9200702 W DE9200702 W DE 9200702W WO 9305106 A1 WO9305106 A1 WO 9305106A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyurethane
diamine
polyurea
polyether polyol
rrim
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/DE1992/000702
Other languages
German (de)
English (en)
Inventor
Hannelore Baumgarten
Alfred Mayer
Uwe Frank
Manfred Schmiedel
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.)
Pebra GmbH
Original Assignee
Pebra GmbH
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 Pebra GmbH filed Critical Pebra GmbH
Priority to EP92918011A priority Critical patent/EP0600994A1/fr
Priority to JP5501164A priority patent/JPH06510068A/ja
Publication of WO1993005106A1 publication Critical patent/WO1993005106A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08J11/28—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 compounds containing nitrogen, sulfur or phosphorus
    • 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
    • C08G18/83—Chemically modified polymers
    • C08G18/833—Chemically modified polymers by nitrogen containing 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • 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 the production of disperse liquids which contain hydroxy- and / or amino-functional compounds from polyurethane, polyurethane / polyurea or polyurea wastes which are used in PUR-RIM and / or - RRIM- Process (Polyurethane (Reinforced) Reaction Injection Molding process) were produced.
  • reaction product In almost all of the processes described, chemical degradation is carried out using diols, with hydroxy-functional compounds being formed as the reaction product.
  • the reaction conditions for the cleavages are usually drastic. At temperatures around 200 ° C the reaction times are 1-2 hours. In this case, side reactions occur which are undesirable for toxicological, qualitative and economic reasons.
  • the isocyanates used for example methylene diphenyl diisocyanate (MDI) and tolylene diisocyanate (TDI), corresponding amines, methylenediphenyldiamine (MDA) and toluenediamine (TDA) r which are classified as carcinogenic.
  • MDI methylene diphenyl diisocyanate
  • TDI tolylene diisocyanate
  • corresponding amines methylenediphenyldiamine
  • MDA methylenediphenyldiamine
  • TDA toluenediamine
  • the so-called PUR-RRIM parts are a special application of the polyurethanes, predominantly in the motor vehicle sector.
  • These polyurethane / polyurea RRIM systems consist of a Polyether polyol, an aromatic isocyanate and a diamine crosslinker.
  • the isocyanate and the diamine crosslinker react with one another to form urea structures.
  • Several successive sequences of isocyanate-amine units result in a so-called hard segment chain.
  • the hard segment chains are connected to one another via hydrogen bonds and, as hard segment domains that separate in the soft segment phase (polyether polyol), represent the crosslinking points of the material.
  • the invention is therefore based on the object of a process for the degradation of polyurethane, polyurethane / polyurea, poly to provide urea waste that avoids the disadvantages of the alcoholysis process.
  • This object is achieved according to the invention by a process for the production of disperse liquids which contain hydroxy- and / or amino-functional compounds, by reaction of polyurethane, polyurethane / polyurea, polyurea wastes which are in the PUR-RIM and / or -RRIM -Procedures were made with at least one diamine compound.
  • a process is preferred in which aromatic diamines as amine compounds in a weight ratio of polymer wastes to diamine of 1: 0.1 to 1: 2, in particular of 1: 0.15 to 1: 0 . 4 at a temperature of 140 to 180 ° C, in particular 160 to 180 ° C, and a reaction time of 30 to 120 minutes, in particular 45 to 120 minutes, optionally in the presence of at least one catalyst.
  • the polyether polyol which is the basis of the polyurethane / polyurea waste or which is used to blend the recycling product for use in the RRTM process is advantageously chosen as the reaction medium.
  • a is used as the solvent Hydroxyl-containing polyether polyol with a molecular weight of 200 to 12000 in a weight ratio of polymer waste to polyether polyol of 1: 1 to 1:10, in particular from 1: 1 to 1: 5, is used.
  • R can be an aromatic ring optionally substituted with one or more different or the same alkyl radicals.
  • the aminolysis reagent consists of the chain extender on which the polyurethane, polyurethane / polyurea, polyurea formation reaction is based.
  • Detda diethyltoluenediamine
  • the excess of the diamine therefore has no adverse effect on the recycling of the aminolysis product as the starting polyol for a polyurethane / polyurea product.
  • Organometallic compounds can be used as catalysts. Dibutyltin dilaurate is preferred.
  • the products produced by the process according to the invention only have carcinogenic methylene diphenyldiairtine or toluenediamine in minimal or undetectable amounts compared to the product pn produced by alkyolysis.
  • the process according to the invention requires shorter reaction times and lower temperatures, which is to be regarded as an essential economic advantage.
  • the present process leads to fewer side reactions, which is reflected in a higher yield and in a better quality product.
  • the diamine used does not interfere with the reprocessing of the aminolysis products, since it is an ingredient already present in the polymer.
  • the diol used in the alcoholysis leads to reaction groups which are new polymer and can therefore have a disadvantageous effect on the product properties.
  • polymer wastes which are composed of polyether polyol, aromatic isocyanates and diethyltoluenediamine.
  • RIM and / or RRIM production wastes are generally suitable, even if they are mixed with glass fibers or still contain paint components.
  • the polymer wastes can either be mixed in the cold with the polyether / slide in / optionally a catalyst mixture and brought to the appropriate reaction temperature, or can be metered directly into the previously heated polyether / diamine / catalyst mixture. In any case, thorough mixing must be ensured, and the reaction can be carried out in a continuous or discontinuous manner.
  • the polyurethane / polyurea systems usually already liquefy when the urethane bonds are cleaved.
  • the urea resin segments remain in the system as a reactive solid and there an OH-terminated polyether is formed.
  • the disperse liquids produced according to the invention are particularly well suited for the production of polyurethanes, polyurethaneureas or ureas, in particular by the RIM and / or RRIM process.
  • the following examples illustrate the invention.
  • a reaction vessel equipped with a reflux condenser, N-w feed and with a stirrer was mixed with a mixture of 91 g of polyether polyol (MW 4800)
  • detda diethyltoluenediamine
  • 25g finely divided polyurethane / polyurea waste 80mg DBTDL (dibutyltin dilaurate)
  • the insoluble content in DMSO was about 20% of the PTJ / PH material used (corresponds to about 20% glass fiber)
  • Example 2 The procedure was as in Example 1, but with 6 g of ethylene glycol (EG) instead of the diamine and 97 g of polyether. 3 phases formed at room temperature, the product settling out, which is to be regarded as disadvantageous.
  • EG ethylene glycol
  • the insoluble fraction in DMSO was approximately 33% of the PU / PH material used (corresponds to approximately 20% glass fiber and approximately 13% unreacted material).
  • Example 2 The procedure was as in Example 1, but with 50 g of polyurethane / polyurea waste and 160 mg of DBTDL. The highly viscous mass became a practically homogeneous brown mass during the reaction. At room temperature, a practically homogeneous, viscous, disperse liquid resulted. No sedimentation of solid particles was observed. No MDA formation occurred after the GC spectrum.
  • the insoluble content in DMSO was about 20% of the PU / PH material used (corresponds to about 20% glass fiber).
  • a viscous, disperse liquid was obtained.
  • the solid particles tended to settle after a few hours.
  • Example 1 The procedure was as in Example 1.
  • the reaction temperature was 150 ° C. with a reaction time of 45 minutes. It became a highly viscous, disperse liquid with little residual PUR fabrics received.
  • the viscosity at 25 ° C. was 12 • 10 Pas and one
  • the reaction vessel was made with a mixture of
  • the result was a homogeneous, viscous, disperse liquid.
  • the result was a viscosity at 25 ° C. of 11 ⁇ 10 'as, NH j number of 130 and an MDA content of 0.2%.
  • the reaction vessel was made with a mixture of
  • the result was a viscosity at 25 ° C. of 10.5 ⁇ 10 ⁇ mPas, an NH j number of 64 and an MDA content of 0.25%.
  • the reaction vessel was made with a mixture of

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)
  • General Chemical & Material Sciences (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne un procédé de fabrication de liquides dispersés renfermant des composés à fonctions hydroxy et/ou amino, caractérisé en ce qu'on fait réagir des déchets de polyuréthanne, de polyuréthanne/polyurée et de polyurée, obtenus dans les procédés PUR-RIM et/ou RRIM (procédés par moulage par injection et réaction renforcée du polyuréthanne) avec au moins un composé diaminé. Les liquides dispersés ainsi obtenus conviennent pour la fabrication de polyuréthannes, de polyuréthanne-urées ou de polyurées.
PCT/DE1992/000702 1991-08-28 1992-08-21 Procede de fabrication de liquides disperses renfermant des composes a fonctions hydroxy et/ou amino, et leur utilisation Ceased WO1993005106A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP92918011A EP0600994A1 (fr) 1991-08-28 1992-08-21 Procede de fabrication de liquides disperses renfermant des composes a fonctions hydroxy et/ou amino, et leur utilisation
JP5501164A JPH06510068A (ja) 1991-08-28 1992-08-21 ヒドロキシ官能性および／またはアミノ官能性化合物を含有する分散液の製造法並びに該分散液の使用

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4128588.3 1991-08-28
DE19914128588 DE4128588A1 (de) 1991-08-28 1991-08-28 Verfahren zur herstellung disperser fluessigkeiten, die hydroxy- und/oder aminofunktionelle verbindungen enthalten sowie deren verwendung

Publications (1)

Publication Number Publication Date
WO1993005106A1 true WO1993005106A1 (fr) 1993-03-18

Family

ID=6439343

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1992/000702 Ceased WO1993005106A1 (fr) 1991-08-28 1992-08-21 Procede de fabrication de liquides disperses renfermant des composes a fonctions hydroxy et/ou amino, et leur utilisation

Country Status (5)

Country Link
EP (1) EP0600994A1 (fr)
JP (1) JPH06510068A (fr)
CA (1) CA2116434A1 (fr)
DE (1) DE4128588A1 (fr)
WO (1) WO1993005106A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000159925A (ja) * 1998-11-30 2000-06-13 Takeda Chem Ind Ltd ポリウレタン樹脂の分解回収設備
JP2001348457A (ja) * 2000-04-04 2001-12-18 Mitsui Takeda Chemicals Inc ポリウレタンの分解方法
CA2342464A1 (fr) 2000-04-04 2001-10-04 Takashi Kumaki Methode de dissociation du polyurethane
DE102022106913A1 (de) 2022-03-23 2023-09-28 Performance Chemicals Handels Gmbh Verfahren zur Verflüssigung von Polyurethanen

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3404103A (en) * 1965-06-10 1968-10-01 Bridgestone Tire Co Ltd Method of decomposing urethane polymer
EP0130741A1 (fr) * 1983-07-05 1985-01-09 Texaco Development Corporation Agents de durcissement à terminaison amine et résines époxydes durcies par ces agents de durcissement
GB2181736A (en) * 1985-10-22 1987-04-29 Basf Corp Reaction injection molded microcellular polyurethane elastomers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3404103A (en) * 1965-06-10 1968-10-01 Bridgestone Tire Co Ltd Method of decomposing urethane polymer
EP0130741A1 (fr) * 1983-07-05 1985-01-09 Texaco Development Corporation Agents de durcissement à terminaison amine et résines époxydes durcies par ces agents de durcissement
GB2181736A (en) * 1985-10-22 1987-04-29 Basf Corp Reaction injection molded microcellular polyurethane elastomers

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPIL Section Ch, Week 8618, Derwent Publications Ltd., London, GB; Class A25, AN 86-115530 & JP,A,61 055 129 (HUMAN IND CORP KK) 19. März 1986 *
DATABASE WPIL Section Ch, Week 9229, Derwent Publications Ltd., London, GB; Class A25, AN 92-240356 & SU,A,1 669 934 (TYRE IND RES INST) 15. August 1991 *

Also Published As

Publication number Publication date
DE4128588A1 (de) 1993-03-04
JPH06510068A (ja) 1994-11-10
CA2116434A1 (fr) 1993-03-18
EP0600994A1 (fr) 1994-06-15

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