WO2012065291A1 - Recyclage de polyuréthanes réticulés - Google Patents

Recyclage de polyuréthanes réticulés Download PDF

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Publication number
WO2012065291A1
WO2012065291A1 PCT/CN2010/078735 CN2010078735W WO2012065291A1 WO 2012065291 A1 WO2012065291 A1 WO 2012065291A1 CN 2010078735 W CN2010078735 W CN 2010078735W WO 2012065291 A1 WO2012065291 A1 WO 2012065291A1
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WIPO (PCT)
Prior art keywords
polyurethane
thermoplastic polyurethane
crosslinked
polyurethanes
thermoplastic
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PCT/CN2010/078735
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English (en)
Inventor
Andre Kamm
Joern Duwenhorst
Choon Nga Phua
Dong Liang
Original Assignee
Basf Se
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.)
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Publication date
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Priority to PCT/CN2010/078735 priority Critical patent/WO2012065291A1/fr
Priority to PCT/EP2011/069703 priority patent/WO2012065887A1/fr
Publication of WO2012065291A1 publication Critical patent/WO2012065291A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/0026—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting
    • B29B17/0042—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting for shaping parts, e.g. multilayered parts with at least one layer containing regenerated plastic
    • 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
    • C08G18/08—Processes
    • C08G18/089—Reaction retarding agents
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0058—≥50 and <150kg/m3
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • 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

  • the present invention relates to a process for producing composite materials made of thermoplastic polyurethane and of crosslinked polyurethane, where the crosslinked polyurethane and the thermoplastic polyurethane are mixed at temperatures above the melting point of the thermoplastic polyurethane, and the mixture is charged to a mold and is cooled to a temperature below the melting point of the thermoplastic polyurethane.
  • the invention further relates to shoe soles, damping elements, underlays, floor mats, gaskets, and grips obtainable by this type of process.
  • the production industry is interested in avoiding, or recycling, production wastes from the production of polyurethane products.
  • the recycling of wastes can save raw materials and reduce costs.
  • This approach is already used by producers that produce products made of thermoplastic polyurethane.
  • sprues from production can be ground and up to 30% of these can be mixed with virgin materials.
  • Crosslinked polyurethanes are generally incinerated in order to obtain energy.
  • Another possibility is the glycolysis of compounds of this type, where the polyurethane wastes are treated with appropriate glycols or alcohols at relatively high temperatures. The urethane group is cleaved here, the result being that polyols are liberated and reclaimed. These can then be used as raw material for virgin polyurethanes. Processes of this type are described by way of example in John Schiers "Polymer Recycling", John Wiley & Sons, 1998. A disadvantage of these processes is that energy consumption is high and that the polyols obtained are mostly of low quality.
  • US 2008/0132591 describes a process in which ground foam residues are heated with thermoplastic polyurethane and mixed in order to obtain a first thermoplastic polyurethane, preferably in the form of pellets.
  • This first thermoplastic polyurethane is mixed with a further thermoplastic polyurethane in a twin-screw extruder, and pelletized.
  • a disadvantage of said process is complicated conduct of the process due to the use of two separate extruders. The mechanical properties of the resultant material are also unsatisfactory.
  • EP 844724 discloses a process in which polyurethane wastes are first swollen with a plasticizer and are then processed with thermoplastic polyurethane in a twin-screw extruder to give pellets. However, items produced from said pellets have poor mechanical properties.
  • EP 844274 further discloses a process in which polyurethane wastes are first swollen with a plasticizer and are then mixed with diisocyanates, diols, and chain extenders in a twin-screw reactive extruder, and are processed to give a blend made of polyurethane and of thermoplastic polyurethane.
  • Thermoplastic polyurethanes of this type have markedly improved mechanical properties, but said process is very complicated since it requires a reactive extruder suitable for producing thermoplastic polyurethane.
  • the object of the invention was achieved via a process for producing composite materials made of thermoplastic polyurethane and of crosslinked polyurethane, where the crosslinked polyurethane and the thermoplastic polyurethane are mixed at temperatures above the melting point of the thermoplastic polyurethane, and the mixture is charged to a mold and is cooled to a temperature below the melting point of the thermoplastic polyurethane.
  • Thermoplastic polyurethanes are polyurethanes which exhibit thermoplastic properties.
  • Thermoplastic properties here mean that the thermoplastic polyurethane is capable of repeated melting when heated, and that it exhibits plastic flow during that process.
  • the TPUs of the invention have an at least semicrystalline soft phase.
  • TPUs are inter alia good strength values, abrasion values, tear-propagation-resistance values, and chemicals resistance value, and that they can be produced with almost any desired hardness by using a suitable composition of raw materials.
  • TPUs are usually produced via reaction of (a) diisocyanates with (b) compounds reactive toward isocyanates and having a molar mass of from 500 g/mol to preferably 8000 g/mol, and with (c) chain extenders having a molar mass of from 60 g/mol to 499 g/mol, also, if appropriate, in the presence of (d) catalysts, and/or of (e) conventional auxiliaries.
  • the process usually takes place continuously, using belt technology or reactive-extruder technology, or batchwise by the casting process. Further details concerning thermoplastic polyurethanes of the invention are found in "Kunststoffhandbuch, Band 7, Polyurethane” [Plastics Handbook, volume 7, Polyurethanes], Carl Hanser Verlag, 3rd edition 1993, chapter 8.2.
  • the molar ratios of structural components (b) and (c) can be varied relatively widely. Success has been obtained by using molar ratios of component (b) to the entirety of chain extenders (c) to be used which are from 1:0.5 to 1:8, in particular from 1:1 to 1:4, where the hardness of the TPUs rises as content of (c) increases.
  • the reaction to produce the TPUs can take place with an index of from 0.8 to 1.2:1, preferably at an index of from 0.9 to 1:1.
  • the index is defined via the ratio of the total number of isocyanate groups used during the reaction in component (a) to the number of groups reactive toward isocyanates, i.e. to the active hydrogen atoms, in component (b) and, if appropriate, (c) and, if appropriate, in monofunctional components which act as chain terminators and which are reactive toward isocyanates, e.g., monoalcohols.
  • thermoplastic polyurethanes are usually produced by the one-shot process or prepolymer process, on a belt system or in a reactive extruder.
  • the components to be reacted here: (a), (b), and (c), and also, if appropriate, chain terminators, and also (d) and/or (e) are combined together or in a particular sequence, and are reacted.
  • structural components (a) to (c), and also, if appropriate, chain terminators, (d), and/or (e) are introduced individually or in the form of a mixture into the extruder, and are reacted by way of example at temperatures from 100 to 250°C, preferably from 140 to 220°C, and the resultant TPU is extruded, cooled, and pelletized.
  • the isocyanates used usually diisocyanates, can be aliphatic, cycloaliphatic, araliphatic and/or aromatic diisocyanates.
  • aromatic isocyanates tolylene 2,4-diisocyanate, mixtures of tolylene 2,4- and 2,6-diisocyanate, diphenylmethane 4,4'-, 2,4'-, and/or 2,2'-diisocyanate, mixtures of diphenylmethane 2,4'- and 4,4'-diisocyanate, urethane-modified liquid diphenylmethane 4,4'- and/or 2,4-diisocyanates, 4,4'-diisocyanato-l,2-diphenylethane, and naphthylene 1,5-diisocyanate.
  • the aliphatic diisocyanates (a) used comprise conventional aliphatic and/or cycloaliphatic diisocyanates, examples being tri-, tetra-, penta-, hexa-, hepta- and/or octamethylene diisocyanate, 2-methyl- pentamethylene 1,5-diisocyanate, 2-ethylbutylene 1,4-diisocyanate, l-isocyanato-3,3,5- trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and/or l,3-bis(isocyanatomethyl)cyclohexane (HXDI), 1,4-cyclohexane diisocyanate,
  • 1-methylcyclohexane 2,4- and/or 2,6-diisocyanate, dicyclohexylmethane 4,4'-, 2,4'-, and/or 2,2' -diisocyanate Preference is given to use of hexamethylene 1,6-diisocyanate (hexamethylene diisocyanate, HDI) and/or diphenylmethane 4,4'-, 2,4'-, and/or 2,2' -diisocyanate (MDI) as isocyanate (a).
  • hexamethylene 1,6-diisocyanate hexamethylene diisocyanate, HDI
  • MDI diphenylmethane 4,4'-, 2,4'-, and/or 2,2' -diisocyanate
  • Compounds (b) used that are reactive toward isocyanates can be well-known polyhydroxy compounds having molar masses from 500 g/mol to 8000 g/mol, preferably from 800 g/mol to 6000 g/mol, in particular from 2000 g/mol to 4000 g/mol, and preferably having an average functionality of from 1.8 to 2.6, preferably from 1.9 to 2.2, in particular 2, examples being well- known polyesterols, polyetherols, and/or polycarbonate diols.
  • Preferred compounds (b) used are ⁇ -caprolactone, polytetrahydrofuran and/or polyesterdiol based on adipic acid and ethane- 1,2-diol, butane- 1,4-diol and/or hexane-l,6-diol as diol component, where the ratio of the diols can be freely selected as a function of the desired properties of the thermoplastic polyurethane.
  • polymerdiols derived from polyethers are equally used, and in specific instances these may derive from polyalkylene or from polyolefins. Polymerdiols of this type are well-known and commercially available.
  • Polymerdiols here are polymer polyols in which the substrate polyol is a diol.
  • Polymerdiols are produced via free-radical polymerization of the monomers, preferably acryloniltrile and styrene and also, if appropriate, further monomers, and of a macromer and, if appropriate, of a moderator, with use of a free-radical initiator, mostly azo compounds or peroxide compounds, in a polyetherdiol or polyesterdiol as continuous phase.
  • the polyetherdiol or the polyesterdiol representing the continuous phase is termed substrate polyol.
  • Chain extenders (c) used can be well-known compounds, examples being diamines and/or alkanediols having 2 to 10 carbon atoms in the alkylene radical, in particular ethylene glycol and/or 1,4-butanediol, and/or hexanediol and/or di- and/or trioxyalkylene glycols having from 3 to 8 carbon atoms in the oxyalkylene radical, preferably corresponding oligo-polyoxypropylene glycols, and it is also possible here to use a mixture of the chain extenders.
  • Another chain extender that can be used is l,4-bis(hydroxymethyl)benzene (1,4-BHMB), 1,4-bis- (hydroxyethyl)benzene (1,4-BHEB), or l,4-bis(2-hydroxyethoxy)benzene (1,4-HQEE).
  • a preferred chain extender used is ethylene glycol, butanediol and/or hexanediol.
  • Suitable catalysts which in particular accelerate the reaction between the NCO groups of the diisocyanates (a) and the hydroxy groups of structural components (b) and (c) are the conventional tertiary amines that are known from the prior art, examples being triethylamine, dimethylcyclohexylamine, N-methylmorpholine, ⁇ , ⁇ '-dimethylpiperazine, 2-(dimethylamino- ethoxy)ethanol, diazabicyclo[2.2.2]octane, and the like, and also in particular organometallic compounds, such as titanic esters, iron compounds, e.g. iron(III) acetylacetonate, tin compounds, e.g.
  • tin diacetate, tin dioctoate, tin dilaurate, or the dialkyltin salts of aliphatic carboxylic acids e.g. dibutyltin diacetate, dibutyltin dilaurate, or the like.
  • the amounts usually used of the catalysts are from 0.0001 to 0.1 part by weight per 100 parts by weight of polyhydroxy compound (b).
  • auxiliaries include surfactant substances, flame retardants, nucleating agents, lubricants and mold-release aids, dyes, and pigments, inhibitors, antioxidants, stabilizers to counter hydrolysis, light, or UV light, heat, oxidation, or discoloration, preservatives to counter microbial degradation, inorganic and/or organic fillers, reinforcing agents, and plasticizers.
  • antioxidants and stabilizers to counter heat, light, or UV radiation are stabilizers from the group of the sterically hindered phenols, phosphites, HALS stabilizers (hindered amine light stabilizer), triazines, benzophenones, and the benzotriazoles.
  • HALS stabilizers hindered amine light stabilizer
  • triazines benzophenones
  • benzotriazoles can be added to the TPU directly during synthesis or only once thermoplastic processing has begun, in bulk or after incorporation into a carrier, e.g. TPU, in the form of what are known as masterbatches.
  • chain terminators with a molecular weight of from 46 to 499.
  • These chain terminators are compounds which have just one functional group reactive toward isocyanates, examples being monoalcohols. Flow behavior can be adjusted as desired by using these chain terminators. Further details concerning the abvoementioned auxiliaries and additives can be found in the technical literature. All of the molar masses mentioned in this specification have the unit [g/mol] and represent the number- average molar mass, unless explicitly otherwise stated.
  • the melting point of the thermoplastic polyurethane can be determined by conventional methods.
  • the temperature at which the crosslinked polyurethane and the thermoplastic polyurethane are mixed is higher than the melting point of the thermoplastic polyurethane, preferably higher by at least 5°C, particularly preferably at least by 10°C, and at most by 100°C, than the melting point of the thermoplastic polyurethane.
  • the crosslinked polyurethane used can comprise any polyurethane which is not repeatedly meltable, or which comprises at least one component of functionality > 2.0. Temperature increase here causes decomposition of the polyurethane.
  • Crosslinked polyurethanes are well-known.
  • This type of crosslinked polyurethane preferably has a network structure formed by way of example via use of relatively high-functionality isocyanates, such as polymer-MDI, and compounds that are reactive toward isocyanates and have a molar mass of from 500 g/mol to preferably 8000 g/mol and that have at least 3 hydrogen atoms reactive toward isocyanates, and/or use of crosslinking agents having molar masses smaller than 500 g/mol and having at least 3 hydrogen atoms reactive toward isocyanates.
  • relatively high-functionality isocyanates such as polymer-MDI
  • compounds that are reactive toward isocyanates and have a molar mass of from 500 g/mol to preferably 8000 g/mol and that have at least 3 hydrogen atoms reactive toward isocyanates and/or use of crosslinking agents having molar masses smaller than 500 g/mol and having at least 3 hydrogen atoms reactive toward isocyanates.
  • crosslinked polyurethanes examples are wastes from production, for example for foams, examples being cushioning elements or insulation foams, or integral foams, e.g. shoe soles or damping elements. It is also possible to use wastes from production of compact polyurethanes, examples being polyurethane elastomers.
  • the materials that can be used as crosslinked polyurethanes are naturally not only production wastes but also the abovementioned materials themselves, when they are no longer needed or when they have been used.
  • the crosslinked polyurethanes are used in comminuted form with average grain sizes or particle sizes that are preferably from 0.1 to 25 mm, with particular preference from 0.5 to 15 mm, and in particular from 1 to 8 mm.
  • Any known comminution process can be used here for comminuting the crosslinked polyurethanes, examples being grinding or shredding, for example in a rotating or rotary mill, at room temperature, to give a grain size that is usually smaller than 10 mm, or known low-temperature-grinding processes, for example using liquid- nitrogen cooling, in a roller mill or hammer mill, giving a grain size smaller than 1 mm.
  • plasticizers for example in EP 844274.
  • the proportion of crosslinked polyurethane, based on the total weight of crosslinked polyurethane and of thermoplastic polyurethane, is preferably from 0.1 to 40% by weight, particularly preferably from 0.5 to 30% by weight, and in particular from 1 to 20% by weight.
  • thermoplastic polyurethane which usually takes the form of pellets or of powder.
  • the TPU is mixed with the comminuted polyurethanes for example at temperatures of from 10 to 100°C, particularly preferably at ambient temperature.
  • a temperature in the range from 150 to 250°C, preferably from 160 to 230°C, and in particular from 180 to 220°C, can then be used for homogenization of the mixture in the flowable, softened or molten state, preferably with degassing, e.g.
  • the comminuted cellular polyurethanes and the TPU are introduced in mixtures or individually into an extruder, and to some extent melted, and that the mixture is extruded, e.g. in a single- or twin-screw machine, preferably with degassing, and then directly charged to a mold. The molten TPU is then recooled in the mold, to temperatures below the melting point.
  • an injection-molding machine or a single-screw extruder is used for processing the mixture.
  • the mold material used here can comprise any of the mold materials usually used for the processing of thermoplastic polyurethanes. Examples of products produced in the mold are then a shoe sole, a damping element, an underlay, a floor mat, a gasket, and/or a grip.
  • the present invention therefore also provides shoe soles, damping elements, underlays, floor mats, gaskets and/or grips comprising composite materials of the invention.
  • the process of the invention is a simple process which by way of example can be used directly by a producer of crosslinked polyurethanes, for example a mattress producer or a producer of shoe soles. All that is required for this is that the production wastes are ground and are processed with the thermoplastic polyurethane. This process is very robust, and there is no need here for difficult process adjustments, or the use of complicated reactive extruders, these being by way of example a requirement for producing thermoplastic polyurethane.
  • the resultant composite materials of the invention nevertheless have very good mechanical properties, for example low abrasion, high tensile strength, and high tear-propagation resistance.
  • TPU Elastollan® S80 from BASF Polyurethanes GmbH
  • Polyol 1 Polyesterol based on adipic acid, monoethylene glycol, and butanediol with an OH number of 56 mg KOH/g
  • Polyol 2 Polyesterol based on adipic acid, monoethylene glycol, and butanediol with an OH number of 56 mg KOH/g
  • Stabi 1 Silicone stabilizer from Goldschmidt
  • the various polyol components were mixed with the prepolymers described in the table and charged to a 20*20*1 cm mold, thus giving moldings with appropriate density. After 24 hours, hardness was determined, and the sheets were comminuted in a Dreher mill to give small pieces. The ground product was dried at 110°C for 3 hours and then mixed with dried Elastolan® S80 and further processed as in the table below.
  • Examples comp 1 and comp 2 were first processed in a MP 19 twin-screw extruder from APV Chemischer Maschinenbau to give a homogeneous blend. The blend was then ground in a Dreher mill to give granules. The aperture size of the mill sieve was 8 mm here.
  • examples comp 1 and comp 2 were processed in an ES 330/80 HL injection-molding machine from Engel to give test sheets.
  • the mixture made of foam and TPU pellets was processed directly in the ES 330/80 HL injection-molding machine from Engel, to give test sheets. The results of the examples are shown in the table below:

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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)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un procédé de fabrication de matières composites faites de polyuréthane thermoplastique et de polyuréthane réticulé, le polyuréthane réticulé et le polyuréthane thermoplastique étant mélangés à des températures au-dessus du point de fusion du polyuréthane thermoplastique, et le mélange étant chargé dans un moule et étant refroidi à une température se situant au-dessous du point de fusion du polyuréthane thermoplastique. L'invention concerne en outre des semelles de chaussures, des éléments d'amortissement, des thibaudes, des tapis de plancher, des joints d'étanchéité et des poignées obtenus par ce type de procédé.
PCT/CN2010/078735 2010-11-15 2010-11-15 Recyclage de polyuréthanes réticulés WO2012065291A1 (fr)

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PCT/CN2010/078735 WO2012065291A1 (fr) 2010-11-15 2010-11-15 Recyclage de polyuréthanes réticulés
PCT/EP2011/069703 WO2012065887A1 (fr) 2010-11-15 2011-11-09 Recyclage de polyuréthanes réticulés

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106009616A (zh) * 2016-07-28 2016-10-12 东莞市隆鑫鞋业有限公司 一种pu爆米花鞋底的制备工艺
WO2019122122A1 (fr) 2017-12-20 2019-06-27 Basf Se Nouvelles mousses polyuréthanes souples
CN113243610A (zh) * 2021-05-20 2021-08-13 温州市巨伦鞋业有限公司 一种鞋底耐酸碱的安全鞋及其制备方法

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CN113243610B (zh) * 2021-05-20 2022-07-29 温州市巨伦鞋业有限公司 一种鞋底耐酸碱的安全鞋及其制备方法

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