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

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

Applications Claiming Priority (3)

Publications (1)

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• 1991
  • 1991-08-28 DE DE19914128588 patent/DE4128588A1/de not_active Withdrawn
• 1992
  • 1992-08-21 JP JP5501164A patent/JPH06510068A/ja active Pending
  • 1992-08-21 EP EP92918011A patent/EP0600994A1/de not_active Withdrawn
  • 1992-08-21 WO PCT/DE1992/000702 patent/WO1993005106A1/de not_active Application Discontinuation
  • 1992-08-21 CA CA002116434A patent/CA2116434A1/en not_active Abandoned

Non-Patent Citations (1)

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