EP3983467A1 - Mousses particulaires novatrices - Google Patents

Mousses particulaires novatrices

Info

Publication number
EP3983467A1
EP3983467A1 EP20731490.7A EP20731490A EP3983467A1 EP 3983467 A1 EP3983467 A1 EP 3983467A1 EP 20731490 A EP20731490 A EP 20731490A EP 3983467 A1 EP3983467 A1 EP 3983467A1
Authority
EP
European Patent Office
Prior art keywords
diisocyanate
foamed
isocyanate
granules
thermoplastic polyurethane
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.)
Pending
Application number
EP20731490.7A
Other languages
German (de)
English (en)
Inventor
Elmar Poeselt
Uwe Keppeler
Christina Tepper
Frank Prissok
Dirk Kempfert
Lisa Marie Schmidt
Wolfgang Guenter MICKLITZ
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.)
BASF SE
BASF Polyurethanes GmbH
Original Assignee
BASF SE
BASF Polyurethanes 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 BASF SE, BASF Polyurethanes GmbH filed Critical BASF SE
Publication of EP3983467A1 publication Critical patent/EP3983467A1/fr
Pending legal-status Critical Current

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    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/35—Composite foams, i.e. continuous macromolecular foams containing discontinuous cellular particles or fragments
    • 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
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • 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
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
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    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/48—Polyethers
    • C08G18/4858—Polyethers containing oxyalkylene groups having more than four carbon atoms in the alkylene group
    • 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
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    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7678—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing condensed aromatic rings
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C08J9/18—Making expandable particles by impregnating polymer particles with the 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C08J9/228—Forming foamed products
    • C08J9/232—Forming foamed products by sintering expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08J9/236—Forming foamed products using binding agents
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
    • E01C13/00—Pavings or foundations specially adapted for playgrounds or sports grounds; Drainage, irrigation or heating of sports grounds
    • E01C13/04—Pavings made of prefabricated single units
    • E01C13/045—Pavings made of prefabricated single units the prefabricated single units consisting of or including bitumen, rubber or plastics
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
    • E01C13/00—Pavings or foundations specially adapted for playgrounds or sports grounds; Drainage, irrigation or heating of sports grounds
    • E01C13/06—Pavings made in situ, e.g. for sand grounds, clay courts E01C13/003
    • E01C13/065—Pavings made in situ, e.g. for sand grounds, clay courts E01C13/003 at least one in situ layer consisting of or including bitumen, rubber or plastics
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F13/00—Coverings or linings, e.g. for walls or ceilings
    • E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
    • E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements
    • E04F13/18—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements of organic plastics with or without reinforcements or filling materials or with an outer layer of organic plastics with or without reinforcements or filling materials; plastic tiles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/36—Feeding the material to be shaped
    • B29C44/38—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length
    • B29C44/44—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length in solid form
    • B29C44/445—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length in solid form in the form of expandable granules, particles or beads
    • 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
    • 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/25—Solid
    • B29K2105/251—Particles, powder or granules
    • 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
    • C08G2101/00—Manufacture of cellular products
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • 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
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    • C08J2375/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate

Definitions

  • the present invention relates to a method for producing a thermoplastic polyurethane, at least comprising the reaction of at least one
  • Isocyanate composition (ZI) containing an isocyanate (11) selected from the group consisting of 1,5-naphthylene diisocyanate (NDI), 4,4'-diphenylmethane diisocyanate (MDI), p-phenyl diisocyanate (PPDI) and o-tolidine diisocyanate (TODI), ethylene diphenyl diisocyanate (EDI) or mixtures thereof and a polyol composition (ZP) containing a
  • the present invention further relates to a thermoplastic polyurethane obtained or obtainable by such a process and to foamed granules comprising such a thermoplastic polyurethane.
  • the present invention furthermore comprises the use of a foamed granulate according to the invention for producing a shaped body.
  • Thermoplastic polyurethanes are known per se. Depending on the desired
  • the isocyanates, polyols and chain extenders used can be varied according to their property profiles. Also foamed granules, which are also called particle foams (or
  • Particle foams, particle foam are designated, as well as those made from them
  • thermoplastic polyurethane or other elastomers are known per se (e.g. WO 94/20568, WO 2007/082838 A1, WO2017030835, WO 2013/153190 A1, WO2010010010) and can be used in many ways.
  • a foamed granulate or a particle foam or particle foam in the context of the present invention denotes a foam in the form of a particle, the mean diameter of the particles usually being between 0.2 to 20, preferably 0.5 to 15 and in particular between 1 to 12 mm .
  • diameter means the longest dimension.
  • thermoplastic polyurethanes in particular for
  • foamed granules or particle foams with improved processability to give the corresponding moldings at the lowest possible temperatures while maintaining advantageous mechanical properties.
  • This is particularly relevant in the currently common welding processes, in which the energy input for welding the foamed granules is brought in by an auxiliary medium such as water vapor, as better bonding is achieved here and damage to the material or the foam structure is reduced and at the same time adequate bonding or
  • Adequate bonding or welding of the foamed granules is essential in order to obtain advantageous mechanical properties of the molded part produced from the foamed granules. If the foam particles are not adhesively bonded or welded together, their properties cannot be used to the full extent, as a result of which the overall mechanical properties of the molded part obtained are negatively influenced. The same applies to a weakening of the shaped body. Here, the mechanical properties at the weakened points are unfavorable with the same result as mentioned above. The properties of the polymer used must therefore be easily adjustable.
  • the shoe sector where the foamed granules can be used for moldings for components of the shoe in which cushioning and / or cushioning is relevant, e.g. Midsoles and insoles.
  • thermoplastic polyurethanes and foamed granules based on thermoplastic polyurethanes which have sufficient rigidity but at the same time have good mechanical properties and are easy to process.
  • Another object of the present invention was to provide a process for producing the corresponding thermoplastic polyurethanes and foamed granules.
  • thermoplastic polyurethane at least comprising steps (i) and (ii):
  • Isocyanate (11) selected from the group consisting of 1,5-naphthylene diisocyanate (NDI), 4,4'-diphenylmethane diisocyanate (MDI), p-phenyl diisocyanate (PPDI) and o-tolidine diisocyanate (TODI), ethylene diphenyl diisocyanate (EDI) or mixtures thereof and a polyol composition (ZP) containing a polytetrahydrofuran or a derivative thereof to obtain an isocyanate group-containing prepolymer,
  • NDI 1,5-naphthylene diisocyanate
  • MDI 4,4'-diphenylmethane diisocyanate
  • PPDI p-phenyl diisocyanate
  • TODI o-tolidine diisocyanate
  • EDI ethylene diphenyl diisocyanate
  • ZP polyol composition
  • the invention also relates to a thermoplastic polyurethane obtainable or obtained by a process according to the invention.
  • thermoplastic polyurethanes and foamed granules produced therefrom can be obtained which have a high E modulus and at the same time a low softening point, so that the foamed granules can be easily processed to moldings and at the same time have a low Tg of the soft phase.
  • the foamed according to the invention are also distinguished
  • Granules have good mechanical properties, such as high elasticity and good rebound resilience.
  • the dynamic long-term use properties are also very good.
  • according to the invention it was possible to achieve very good phase separation with, at the same time, better meltability of the hard phase, so that a harder and at the same time easily processable foamed granulate was obtained.
  • the compressive strength has been significantly improved compared to conventional materials.
  • thermoplastic polyurethanes according to the invention and foamed granules produced therefrom have very good and good low-temperature properties
  • the rebound resilience is determined analogously to DIN 53512, April 2000; the deviation from the norm is the test body height, which should be 12 mm, but this test is carried out with 20 mm in order to prevent the sample from "penetrating" and measuring the substrate, unless otherwise specified.
  • thermoplastic polyurethanes according to the invention can be processed well to give foamed granules which, in turn, can be further processed well to give moldings which in particular have a high modulus of elasticity and very good rebound resilience.
  • the isocyanate composition (ZI) containing an isocyanate (11) is selected from the group consisting of 1,5-naphthylene diisocyanate (NDI), 4,4'-diphenylmethane diisocyanate (MDI), p-phenyl diisocyanate (PPDI) and o -Tolidine diisocyanate (TODI), ethylene diphenyl diisocyanate (EDI) or mixtures thereof with a polyol composition (ZP) containing a
  • step (ii) Polytetrahydrofuran or a derivative thereof reacted to obtain an isocyanate group-containing prepolymer.
  • step (ii) the prepolymer obtained according to step (i) is reacted with at least one chain extender (KV).
  • step (ii) can be carried out after step (i). However, it is also possible to carry out both steps in one stage of the process. I.
  • step (i) the isocyanate composition (ZI) is reacted with the polyol composition (ZP) comprising a polytetrahydrofuran or a derivative thereof.
  • polyol composition contains at least one polytetrahydrofuran or a derivative thereof and can contain further components, in particular further substances which are reactive toward isocyanates, for example further polyols.
  • the polyol composition can also contain mixtures of different polytetrahydrofurans with different average molecular weights or mixtures of one
  • the polytetrahydrofuran has a number average molecular weight Mn in the range from 500 g / mol to 5000 g / mol, more preferably in the range from 550 to 2500 g / mol, particularly preferably in the range from 650 to 2000 g / mol.
  • the number average molecular weight Mn of the polytetrahydrofuran is in the range from 500 to 1400 g / mol.
  • polytetrahydrofurans can also be used according to the invention, i. Mixtures of polytetrahydrofurans with different molecular weights.
  • the polyol composition it is also possible for the polyol composition to contain further polyols. Suitable polyols are known per se to the person skilled in the art. For example, polyethers, polyesters or polycarbonates are suitable.
  • polytetrahydrofurans are also referred to as ⁇ -hydro-w-hydroxypoly (oxytetramethylene) diols.
  • the polyol composition contains a polytetrahydrofuran or a derivative thereof.
  • a derivative is also understood to mean, for example, a reaction product of polytetrahydrofuran.
  • Suitable derivatives are, for example, those obtained by reacting the free hydroxyl groups
  • Polytetrahydrofurans are obtained.
  • Suitable derivatives are, for example, poly-e-caprolactone polyols, i.e. Polyols made by reacting e-caprolactone and a
  • Polytetrahydrofuran can be obtained as a starter molecule.
  • the present invention also relates to a method as described above, wherein the poly-s-caprolactone polyol used is obtainable or is obtained by reacting e-caprolactone and a starter molecule which is selected from the group consisting of a-hydro -m-hydroxypoly (oxytetramethylene) diols.
  • the polyol composition can also contain further poly-s-caprolactone polyols, in particular those with a number average molecular weight in the range from 500 to 5000 g / mol, preferably in the range from 1000 to 5000 g / mol, more preferably in the range from 1500 to 2500 g / mol mol.
  • Preference is given to using poly-s-caprolactone diols, ie those poly-s-caprolactone polyols which are obtained using a difunctional starter I.
  • Suitable starters for the purposes of the present invention are
  • diols with a number average molecular weight in the range from 80 to 1500 g / mol
  • polyether polyols or polyester polyols for example
  • Polyether polyols are suitable.
  • the present invention therefore also relates to a method as described above, wherein the poly-s-caprolactone polyol used is obtainable or is obtained by reacting e-caprolactone and a starter molecule which is selected from the group consisting of diols with a number average
  • BDO 1,4-butanediol
  • HDO 1,6-hexanediol
  • the number average molecular weights are obtained by determining the OH number, unless stated otherwise.
  • the present invention also relates to a method as described above, wherein the poly-s-caprolactone polyol used is obtainable or is obtained by reacting e-caprolactone and a starter molecule which is selected from the group consisting of a-hydro -m-hydroxypoly (oxytetramethylene) diols,
  • Polyethylene glycols and polypropylene glycols preferably from the group consisting of ⁇ -Hydro-ü) -hydroxypoly (oxytetramethylene) diols with a number average molecular weight in the range from 150 to 1500 g / mol, polyethylene glycols with a number average
  • the polyol composition (ZP) can also be reactive towards isocyanates
  • the present invention accordingly also relates to a method as described above, the derivative of polytetrahydrofuran being a poly-e-caprolactone polyol.
  • composition of the polyol composition (ZP) can vary within wide ranges.
  • the present invention also relates to a method as described above, the polyol composition containing the ⁇ -hydro-w-hydroxypoly (oxytetramethylene) polyol in an amount of 0.1 to 50% by weight, based on the polyol composition .
  • the present invention also relates to a method as described above, the poly-s-caprolactone polyol and / or the a-hydro-w-hydroxypoly (oxytetramethylene) polyol having a number average molecular weight in the range from 1500 to 2500 g / mol .
  • the number-average molecular weights of the two polyols in the mixture of poly-s-caprolactone polyols and ⁇ -hydro-m-hydroxypoly (oxytetramethylene) polyols are around 2000 g / mol.
  • the number average molecular weights Mn are determined in the context of the present invention by means of GPC.
  • the process according to the invention can also be carried out in such a way that, in the reaction according to step (i), the polyol component (ZP) contains further polyols in addition to the polytetrahydrofuran and derivatives thereof.
  • Suitable polyols are known in principle to the person skilled in the art and are described, for example, in "Kunststoffhandbuch, Volume 7, Polyurethane", Carl Hanser Verlag, 3rd Edition 1993, Chapter 3.1.
  • Polyesteroie or polyetheroie are particularly preferably used as polyols as polyol (P1).
  • Polycarbonates can also be used.
  • Copolymers can also be used in the context of the present invention.
  • Polyetheroie are suitable according to the invention, but also polyesteroie, block copolymers and hybrid polyols such as poly (ester / amide).
  • preferred polyetherols are polyethylene glycols, polypropylene glycols, polyadipates, polycarbonate (diols) and polycaprolactone.
  • the polyols or the polyol composition used preferably have an average functionality between 1.8 and 2.3, preferably between 1.9 and 2.2, in particular 2.
  • the polyols used according to the invention preferably have only primary hydroxyl groups.
  • the reaction in step (i) can be carried out, for example, at a temperature in the range from 110 to 180 ° C., preferably in the range from 130 to 170 ° C. and particularly preferably from 140 to 155 ° C., to give a prepolymer containing isocyanate groups.
  • the isocyanate-terminated prepolymer obtained in this way has according to the invention
  • the prepolymer obtained generally has a viscosity between 800-5000 mPas at 80 ° C., measured with a rotary viscometer.
  • At least 50% by weight, particularly preferably at least 80% by weight, even more preferably at least 90% by weight and in particular 100% by weight of the polyol component are used to produce the isocyanate-terminated prepolymer.
  • further polyols it is also possible for further polyols to be used in the reaction according to step (ii).
  • composition of the polyol composition can vary within wide ranges within the scope of the present invention.
  • the polyol composition can also contain a solvent. Suitable solvents are known per se to the person skilled in the art.
  • the present invention accordingly also relates to a process as described above, with further processes in the implementation according to step (ii)
  • Chain extenders are used.
  • the isocyanate composition (ZI) is also used in step (i).
  • the isocyanate composition (ZI) contains an isocyanate (11) selected from the group consisting of 1,5-naphthylene diisocyanate (NDI), 4,4'-diphenylmethane diisocyanate (MDI), p-phenyl diisocyanate (PPDI) and o-tolidine diisocyanate (TODI) , Ethylene diphenyl diisocyanate (EDI), or mixtures thereof.
  • the isocyanate composition (ZI) can also contain other isocyanates.
  • the isocyanate composition (ZI) preferably contains an isocyanate (11) selected from the group consisting of 1,5-naphthylene diisocyanate (NDI), p-phenyl diisocyanate (PPDI) and o-tolidine diisocyanate (TODI), ethylene diphenyl diisocyanate (EDI) or mixtures thereof.
  • the isocyanate composition (ZI) further preferably contains 1,5-naphthylene diisocyanate (NDI) as the isocyanate (11).
  • thermoplastic polyurethanes with advantageous properties are obtained.
  • mixtures containing 1,5-naphthylene diisocyanate (NDI) and 4,4′-diphenylmethane diisocyanate (MDI) can also be used.
  • Suitable mixtures can contain naphthylene diisocyanate (NDI) and 4,4'-diphenylmethane diisocyanate (MDI), for example in a ratio in the range from 50:50 to 30:70.
  • Diisocyanates in particular aliphatic or aromatic diisocyanates, more preferably aromatic diisocyanates.
  • prereacted products can be used as
  • Isocyanate components are used in which some of the OH components are reacted with an isocyanate in an upstream reaction step. In a subsequent step, the actual polymer reaction, the products obtained are reacted with the remaining OH components and then form the
  • thermoplastic polyurethane thermoplastic polyurethane
  • isocyanates are preferably in the isocyanate composition (ZI) in an amount in the range from 0.1 to 20% by weight, more preferably in the range from 0.1 to 10% by weight and particularly preferably in one Amount in the range from 0.5 to 5% by weight.
  • the polyisocyanate composition can furthermore also contain one or more solvents.
  • Suitable solvents are known to the person skilled in the art.
  • non-reactive solvents such as ethyl acetate, methyl ethyl ketone and hydrocarbons are suitable.
  • the present invention accordingly also relates to a process as described above, wherein the polyisocyanate composition is an isocyanate selected from the group consisting of 1,5-naphthylene diisocyanate (NDI), 4,4'-diphenylmethane diisocyanate (MDI), p-phenyl diisocyanate ( PPDI) and o-tolidine diisocyanate (TODI), ethylene diphenyl diisocyanate (EDI) or mixtures thereof in an amount in the range from 90 to 100% by weight, based on the total polyisocyanate composition.
  • NDI 1,5-naphthylene diisocyanate
  • MDI 4,4'-diphenylmethane diisocyanate
  • PPDI p-phenyl diisocyanate
  • TODI o-tolidine diisocyanate
  • EDI ethylene diphenyl diisocyanate
  • the present invention accordingly also relates to a process as described above, the polyisocyanate composition containing 1,5-naphthylene diisocyanate (NDI) in an amount in the range from 90 to 100% by weight, based on the total polyisocyanate composition.
  • NDI 1,5-naphthylene diisocyanate
  • the prepolymer obtained according to step (i) is reacted with at least one chain extender (KV).
  • the prepolymer obtained is preferably reacted with the chain extender (KV) according to step (ii), with optionally further polyols or further chain extenders and optionally catalyst, optionally blowing agents and / or crosslinkers and optionally auxiliaries and / or additives, provided they are not or only partially were added in the first step, can be added.
  • the chain extender used contains less than 100 ppm of water.
  • the prepolymer obtained in step (i) is preferably reacted in step (ii) in amounts such that the equivalence ratio of NCO groups to the sum of the reactive hydrogen atoms, 0.8: 1 to 1.5: 1, preferably 0.85: 1 to 1.3: 1 and in particular 1.02: 1 to 1.15: 1.
  • a ratio of 1: 1 corresponds to an isocyanate index of 100.
  • the isocyanate index is understood to mean the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups, multiplied by 100.
  • Chain extenders are known per se to the person skilled in the art. Chain extenders are, for example, compounds with two groups which are reactive toward isocyanate groups, in particular those with a molecular weight of less than 500 g / mol. Suitable
  • Chain extenders are, for example, diamines or diols. According to the invention, diols are further preferred. Mixtures of two or more chain extenders can also be used in the context of the present invention.
  • the present invention accordingly also relates to a method as described above, the chain extender (KV) being selected from the group consisting of diols with a molecular weight in the range from 50 to 500 g / mol and diamines with a molecular weight in the range of 50 to 500 g / mol.
  • the chain extender (KV) being selected from the group consisting of diols with a molecular weight in the range from 50 to 500 g / mol and diamines with a molecular weight in the range of 50 to 500 g / mol.
  • aliphatic, araliphatic, aromatic and / or cycloaliphatic diols with a molecular weight of 50 g / mol to 220 g / mol can be used as chain extenders.
  • Alkanediols having 2 to 10 carbon atoms in the alkylene radical in particular di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycols, are preferred.
  • MEG, 1,4-butanediol, 1,3-propanediol and 1,6-flexanediol are particularly preferred for the present invention. I.
  • branched compounds such as 1,4-cyclohexyldimethanol, 2-butyl-2-ethylpopanediol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, pinacol, 2-ethyl-1,3-hexanediol or 1,4 Cyclohexanediols are suitable as chain extenders (KV) in the context of the present invention.
  • KV chain extenders
  • the present invention accordingly also relates to a method as described above, wherein the chain extender (KV) is selected from the group consisting of MEG, 1,4-butanediol, 1,3-propanediol, 1,6-hexanediol, 2 -Ethyl-1,3-hexanediol or 2-butyl-2-ethylpropanediol.
  • KV chain extender
  • Chain extenders selected from the group consisting of MEG, 1,4-butanediol, 1,3-propanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol or 2-butyl-2-ethylpropanediol are used will.
  • the proportions of the components used are preferably chosen in accordance with step (ii) so that a hard segment proportion in the range from 10 to 40% is obtained.
  • step (i) and (ii) it is possible for the reactions according to step (i) and (ii) to be carried out in two separate steps. According to the invention, however, it is also possible for the process to be carried out in one stage. According to the invention, the method can be carried out in a multi-stage or even one-stage process, for example on one
  • Reaction extruder in which the prepolymer is produced continuously in the first zones. It is also possible, for example, to first continuously produce a prepolymer in accordance with step (i) in a tubular reactor or vessel and then to carry out step (ii), for example in the form of a reaction in the belt or reaction extruder process.
  • the NCO / OH ratio is preferably between 0.85 and 1.30.
  • a one-stage process procedure has proven advantageous when using MDI, for example.
  • the present invention also relates to a thermoplastic polyurethane, obtainable or obtained by a process at least comprising steps (i) and (ii): I.
  • Ethylene diphenyl diisocyanate or mixtures thereof and one
  • step (ii) Reaction of the prepolymer obtained in step (i) with at least one chain extender (KV).
  • thermoplastic polyurethanes according to the invention are particularly suitable for producing foamed granules.
  • the foamed granules obtained have good mechanical properties and, in particular, very good rebound resilience.
  • the present invention also relates to a foamed granulate comprising a thermoplastic polyurethane obtainable or obtained by a process according to the invention or a thermoplastic polyurethane according to the invention.
  • the foamed granules according to the invention can easily be processed into molded articles.
  • the foamed granules can be welded well.
  • the present invention also relates to a molded body made from a foamed granulate as described above.
  • the present invention also relates to the use of a thermoplastic
  • Polyurethane obtainable or obtained by a process according to the invention or a thermoplastic polyurethane according to the invention for producing a molded body or a foamed granulate.
  • thermoplastic polyurethane In addition to the properties of the thermoplastic polyurethane, the process for producing a foamed granulate often has a decisive influence on it
  • the present invention also relates to a method for producing a foamed granulate.
  • the present invention relates to a
  • a method for producing a foamed granulate comprising the steps I.
  • thermoplastic polyurethane a thermoplastic polyurethane, the thermoplastic polyurethane being obtainable or obtained by a process at least comprising steps (a) and (b):
  • ZI isocyanate composition
  • NDI 1,5-naphthylene diisocyanate
  • MDI 4,4'-diphenylmethane diisocyanate
  • PPDI p-phenyl diisocyanate
  • TODI o -Tolidine diisocyanate
  • Ethylene diphenyl diisocyanate or mixtures thereof and one
  • step (b) reaction of the prepolymer obtained in step (a) with at least one chain extender (KV);
  • composition (Z1) can be used in the form of a melt or in the form of granules.
  • the method according to the invention can comprise further steps, for example
  • Polymer mixture of the composition (Z1) is made in a known manner from the
  • Processing aids are, for example, customary mixing processes with the aid of a kneader, continuous or discontinuous, or an extruder such as, for example
  • compatibilizers or auxiliaries such as stabilizers
  • these can also be incorporated into the components when they are made.
  • the components are all dosed into the intake and conveyed together into the extruder or individual components are added via a side metering.
  • Processing takes place at a temperature at which the components are in a plasticized state.
  • the temperature depends on the softening resp.
  • Additives such as pigments or fillers or other of the abovementioned customary auxiliaries, such as flame retardants or antistatic auxiliaries, are not melted at the same time, but are incorporated in the solid state.
  • the foamed granules according to the invention generally have a bulk density of 50 g / l to 200 g / l, preferably 60 g / l to 180 g / l, particularly preferably 80 g / l to 150 g / l.
  • the diameter of the foamed granules is between 0.5 and 30; preferably 1 to 15 and in particular between 3 to 12 mm.
  • diameter means the longest dimension.
  • the amount of propellant is preferably 0.1 to 50, in particular 0.5 to 35 and particularly preferably 1 to 30 parts by weight, based on 100 parts by weight of the amount of the composition (Z1) used.
  • One embodiment of the above method includes I.
  • composition (Z1) according to the invention in the form of granules
  • composition (Z1) according to the invention in the form of a
  • the unexpanded granulate preferably has an average minimum diameter of 0.2-10 mm (determined via 3D evaluation of the granulate, e.g. via dynamic image analysis with the use of an optical measuring apparatus called PartAn 3D from Microtrac).
  • the present invention also relates to a process for the production of foamed granules as described above, the polyurethane being impregnated with the blowing agent in an extruder, the impregnated polyurethane being cut into granules and the granules immediately after cutting into expanded thermoplastic Polyurethane particles relaxed.
  • the individual granules generally have an average mass in the range from 0.1 to 100 mg, for example in the range from 1 to 50 mg, preferably in the range from 4 to 40 mg and particularly preferably in the range from 7 to 32 mg. This mean mass of the granules
  • a suitable, closed reaction vessel e.g. autoclave
  • step (I) can be carried out in the presence of water and optionally
  • Suspending or suspending aids take place or only in the presence of the propellant and the absence of water.
  • Suitable suspension aids are e.g. water-insoluble inorganic solids such as tricalcium phosphate, magnesium pyrophosphate, metal carbonates; also polyvinyl alcohol and ionic surfactants, e.g. Sodium dodecyl aryl sulfonate or nonionic surfactants. They are usually used individually or in combination in amounts of 0.05 to 10% by weight, based on the composition according to the invention.
  • the impregnation temperatures are, depending on the pressure selected, in the range from 90 ° C. to 200 ° C., preferably 100 ° C.-200 ° C., more preferably 100 ° C. to 180 ° C., the pressure in the reaction vessel between 2 and 250 bar , preferably between 5 and 100 bar, particularly preferably between 20 and 60 bar, the impregnation time is generally 0.5 to 10 hours.
  • the present invention also relates to a method for producing a foamed granulate as described above, the granulate in step (i) with 0.1 to 50% by weight of a blowing agent at a temperature in the range from 90 to 180 ° C and a pressure in the range of 0.5 to 10 MPa is impregnated.
  • Suitable propellants for carrying out the process in a suitable closed reaction vessel are e.g. organic liquids and gases used in the
  • Processing conditions exist in a gaseous state, such as hydrocarbons or inorganic gases or mixtures of organic liquids or gases and inorganic gases, and these can also be combined.
  • Suitable hydrocarbons are, for example, halogenated or non-halogenated, saturated or unsaturated aliphatic hydrocarbons, preferably non-halogenated, saturated or unsaturated aliphatic hydrocarbons.
  • Preferred organic blowing agents are saturated, aliphatic hydrocarbons, especially those with 3 to 8 carbon atoms such as butane or pentane.
  • Suitable inorganic gases are nitrogen, air, ammonia or carbon dioxide, preferably nitrogen or carbon dioxide or mixtures of the gases mentioned above.
  • the impregnation of the granulate with a propellant under pressure comprises a process and subsequent expansion of the granulate in steps (a) and ( ⁇ ):
  • Suitable blowing agents in this process variant are volatile organic compounds with a boiling point of -25 ° C to 150 ° C, in particular -10 ° C to 125 ° C at normal pressure 1013 mbar.
  • Hydrocarbons preferably halogen-free
  • C4-10 alkanes for example the isomers of butane, pentane, hexane, heptane and octane, particularly preferably isobutane
  • Further possible blowing agents are sterically more demanding compounds such as alcohols, ketones, esters, ethers and organic carbonates.
  • composition in step (a) is mixed in an extruder with melting with the blowing agent under pressure, which is fed to the extruder.
  • Propellant-containing mixture is under pressure, preferably with moderately controlled
  • the polyurethane in one embodiment, it is possible here, for example, for the polyurethane to be impregnated with the blowing agent in an extruder, for the impregnated polyurethane to be cut into granules and the granules to be expanded after cutting
  • thermoplastic polyurethane particles relaxed.
  • the thermoplastic polyurethane is mixed with a blowing agent in the extruder with melting, which is fed to the extruder.
  • the blowing agent-containing mixture is then pressed and granulated under such pressure and temperature conditions that expanded foam particles are obtained.
  • the pressure and temperature depend on the polyurethane used and the amount of blowing agent.
  • the pressure is usually in the range from 1 to 20 bar, preferably in the range from 2 to 15 bar, and the temperature between 20 ° C and 60 ° C, preferably between 20 ° C and 40 ° C. I.
  • thermoplastic polyurethane and the addition of the blowing agent for the production of the expanded thermoplastic polyurethane can take place in two different extruders. Alternatively, however, it is also possible to use only one extruder.
  • the front part of the extruder, into which the isocyanate, the compound reactive with the isocyanate, the chain extender and any other additives are added serves as a reactive extruder and at a later point in the extruder where the conversion to the polyurethane is complete. the propellant is added.
  • the production of a foamed granulate from a thermoplastic polyurethane according to the invention comprises steps (a) to (c):
  • thermoplastic polyurethane as particles in a suitable geometrical granulate form
  • thermoplastic PU are converted into the desired form of granules either during their production or in a separate step (a). Cylindrical, ellipsoidal or spherical granules with a middle are preferred
  • Diameters of 0.2 to 10 mm, in particular 0.5 to 5 mm, are used. In the case of cylindrical or ellipsoidal granules, the diameter means the longest dimension.
  • the individual granules generally have an average mass in the range from 1 to 100 mg, preferably in the range from 2 to 60 mg, more preferably in the range from 3 to 50 mg and particularly preferably in the range from 4 to 35 mg. This mean mass of the granules
  • Granulate particles determined are preferably cylindrical or round granules. These preferably cylindrical or round granules can be produced by all compounding processes known to the person skilled in the art with subsequent granulation as cold or hot cut
  • step (b) this is usually impregnated in aqueous suspension with 0.1 to 50% by weight of a blowing agent at a temperature in the range from 90 to 180 ° C. and a pressure in the range from 0.5 to 10 MPa.
  • a blowing agent at a temperature in the range from 90 to 180 ° C. and a pressure in the range from 0.5 to 10 MPa.
  • the hot aqueous suspension containing the granulate is then suddenly expanded without cooling (explosion expansion process), the softened particles containing propellant foaming immediately to form the expanded particles.
  • the expanded thermoplastic polyurethane can in principle be produced as described in WO-A 2007/082838. I.
  • the blowing agent used to produce the expanded thermoplastic polyurethane particles can vary depending on the production process.
  • volatile organic compounds with a boiling point at normal pressure of 1013 mbar in the range from -25 to 160 ° C., in particular from -10 to 125 ° C., are preferably used as blowing agents.
  • halogen-substituted hydrocarbons are very suitable, halogen-free hydrocarbons being preferred.
  • C -Cio-alkanes are particularly preferred, for example the isomers of butane, pentane, cyclopentane, hexane, heptane, and octane, particularly preferably s-pentane.
  • Suitable blowing agents are also sterically more demanding compounds, such as alcohols, ketones, esters, ethers and organic carbonates. Mixtures of the blowing agents mentioned can also be used according to the invention.
  • Suitable inorganic gases are, for example, nitrogen, air, ammonia or carbon dioxide or combinations of these or combinations with the further blowing agents mentioned above.
  • halogenated hydrocarbons can also be used, but the propellant is preferably halogen-free. However, small proportions of halogen-containing propellants in the propellant mixture should not be excluded.
  • the propellants can be used either as a pure substance or in any mixture.
  • the amount of blowing agent is preferably in the range from 0.1 to 50 parts by weight, in particular 0.5 to 40 and particularly preferably 1 to 30 parts by weight, based on 100 parts by weight of thermoplastic polyurethane used.
  • Nitrogen can also be added as a co-driving agent at an onset temperature below the first melt peak in the DSC of the thermoplastic elastomer, for example in the range from 30 to 75 ° C, by forcing in and increasing the internal pressure in the impregnation reactor by 200 to 3000 kPa.
  • the impregnation in step (b) is preferably carried out at an impregnation temperature IMT in the range from 90 to 190.degree.
  • the suspension is generally heated to the impregnation temperature (IMT) at a heating rate of preferably 2 ° C./min or higher
  • step (b) The blowing agent-containing granules obtained in step (b) are foamed into foam particles in a subsequent step (c) by releasing the pressure.
  • step (c) is usually carried out by emptying the pressure vessel into an expansion vessel via an open shut-off valve
  • the foamed granules obtained by the process according to the invention and made from a thermoplastic polyurethane according to the invention preferably have a bulk density in the range from 20 to 250 kg / m 3 , particularly preferably in the range from 35 to 150 kg / m 3 .
  • the foamed granules are generally at least approximately spherical.
  • the exact geometric shape or the diameter depends on the selected geometry and the particle weight of the starting granulate and on the bulk density produced.
  • the present invention accordingly also relates to foamed granules obtained by a method as described above, the mean diameter of the particles preferably being in the range from 0.5 to 20 mm.
  • the particles usually have a maximum length extension in the range from 1 to 25 mm, preferably from 2 to 15 mm and particularly preferably a maximum
  • the expanded foam particles produced according to the invention are usually predominantly closed-cell, with the determination of the volume fraction of closed cells based on DIN EN ISO 4590 of 08/01/2003, and generally have a cell density (number of cells / area) of 1 to 750 cells / mm 2 , preferably 2 to 500 cells / mm 2 , in particular 5 to 200 cells / mm 2 and particularly preferably 10 to 100 cells / mm 2 .
  • Suitable devices for carrying out the process according to the invention for producing foamed granules are known per se to the person skilled in the art.
  • Single-screw and twin-screw extruders e.g. type ZSK from Werner & Pfleiderer
  • co-kneaders e.g. type ZSK from Werner & Pfleiderer
  • Kombiplast machines e.g. MPC kneading mixers, FCM mixers, KEX kneading screw extruders and shear roll extruders, as e.g. in Saechtling (ed.), Kunststoff-Taschenbuch, 27.
  • the extruder is usually operated at a temperature at which the composition (Z1) is present as a melt, for example at 120 ° C to 250 ° C, in particular 150 to 210 ° C and a pressure after the addition of the blowing agent of 40 to 200 bar, preferably 60 to 150 bar, particularly preferably 80 to 120 bar, in order to ensure that the blowing agent is homogenized with the melt.
  • a temperature at which the composition (Z1) is present as a melt for example at 120 ° C to 250 ° C, in particular 150 to 210 ° C and a pressure after the addition of the blowing agent of 40 to 200 bar, preferably 60 to 150 bar, particularly preferably 80 to 120 bar, in order to ensure that the blowing agent is homogenized with the melt.
  • This can be carried out in an extruder or in an arrangement of one or more extruders.
  • the first extruder the
  • Components are melted and blended and a propellant is injected.
  • the impregnated melt is homogenized and the temperature and / or the pressure is set. If, for example, three extruders are combined with one another, the mixing of the components and the injection of the blowing agent can also be divided between two different process parts. If, as preferred, only one extruder is used, then all process steps, melting, mixing, injection of the
  • the corresponding, possibly even already colored, foamed granules can be produced directly from the granules in that the corresponding granules are coated with a
  • Suitable supercritical fluids are e.g. those described in WO2014150122 or, e.g. Carbon dioxide, nitrogen dioxide, ethane, ethylene, oxygen or nitrogen, preferably carbon dioxide or nitrogen.
  • the supercritical fluid can also contain a polar fluid with a Hildebrand solubility parameter equal to or greater than 9 MPa 1/2 .
  • the supercritical fluid or the heated fluid may also contain a dye, whereby a colored, foamed article is obtained.
  • the expanded thermoplastic polyurethane particles i.
  • the foamed granules are used in particular for the production of moldings from particle foams.
  • the present invention also relates to a molded body made from a foamed granulate as described above. Processes for producing moldings of this type are known per se.
  • the present invention also relates to the use of a foamed granulate according to the invention or a foamed granulate, obtained or obtainable by a process according to the invention for producing moldings. According to a further embodiment, the present invention also relates to the use I.
  • the present invention also relates to the use of a foamed granulate according to the invention for producing a shaped body.
  • Another object of the present invention is a molded body made from
  • a method that is suitable according to the invention for producing a molded body from foamed granules comprises, for example, the following steps:
  • step (B) Fusion of the foamed granules according to the invention from step (i).
  • the fusing in step (B) is preferably carried out in a closed form, it being possible for the fusing to take place by means of steam, hot air (as described e.g. in EP1979401 B1) or energetic radiation (microwaves or radio waves).
  • the temperature when the foamed granules are fused is preferably below or close to the melting temperature of the polymer from which the particle foam was produced.
  • the temperature for fusing the foamed granulate is accordingly between 100 ° C and 180 ° C, preferably between 120 and 150 ° C.
  • Temperature profiles / residence times can be determined individually, e.g. in analogy to the method described in US20150337102 or EP2872309B1.
  • Welding using energetic radiation generally takes place in the frequency range of microwaves or radio waves, possibly in the presence of water or other polar liquids, such as polar groups, microwave absorbing
  • Hydrocarbons such as esters of carboxylic acids and diols or triols or glycols and liquid polyethylene glycols
  • Hydrocarbons such as esters of carboxylic acids and diols or triols or glycols and liquid polyethylene glycols
  • Foam particles includes the following steps:
  • the heating of the surface of the particles of the foamed granulate required for welding, so that they melt, is achieved individually or in any combination by exposure to steam, hot air or high-energy radiation.
  • Suitable high-energy radiation is, for example, microwave radiation, radio radiation or infrared radiation.
  • microwave radiation for example, microwave radiation, radio radiation or infrared radiation.
  • radio radiation for example, radio radiation or infrared radiation.
  • steam or hot air is preferred,
  • the present invention accordingly also relates to the use as described above, the production of the molded body by means of
  • the temperature of the water vapor which is introduced into the mold can be adjusted by the pressure.
  • the use of superheated water vapor or unsaturated water vapor is also possible.
  • Suitable pressures with which the steam is introduced into the mold are, for example, 0.1 bar to 6 bar, preferably 0.3 to 3 bar.
  • the foamed granules can also contain colorants.
  • the addition of dyes can take place in various ways.
  • the foamed granules produced can be colored after production.
  • the corresponding foamed granules are contacted with a carrier liquid containing a dye, the carrier liquid (TF) having a polarity which is suitable for sorption of the carrier liquid into the foamed granules.
  • TF carrier liquid
  • Suitable dyes are, for example, inorganic or organic pigments.
  • Suitable natural or synthetic inorganic pigments are, for example, carbon black, graphite,
  • Suitable organic pigments are, for example, azo pigments and polycyclic pigments.
  • the color can be added during the production of the foamed granulate.
  • the dye can be added to the extruder via extrusion during the production of the foamed granules.
  • already colored material can be used as starting material for the production of the foamed granulate, which is extruded or expanded in a closed vessel according to the above-mentioned process.
  • the supercritical liquid or the heated liquid can contain a dye.
  • the molded parts according to the invention have advantageous properties for the above-mentioned applications in the shoe or sports shoe sector.
  • the tensile and compression properties of the molded bodies produced from the foamed granules are characterized in that the tensile strength is above 600 kPa (ASTM D 5035), the elongation at break is above 100% (ASTM D 503) and the
  • Compressive stress is above 15 kPa at 10% compression (analogous to DIN EN ISO 844, November 2014; the deviation from the standard is the height of the specimen with 20 mm instead of 50 mm and thus the adjustment of the test speed to 2 mm / min).
  • the rebound resilience of the molded bodies produced from the foamed granules is preferably above 55% (analogous to DIN 53512, April 2000; the deviation from the standard is the test body height, which should be 12 mm, but in this test it is carried out with 20 mm in order to "strike through" of the sample and measuring the subsurface).
  • the density of the molded parts produced is advantageously between 75 and 375 kg / m 3 , preferably between 100 and 300 kg / m 3 , particularly preferably between 150 and 200 kg / m 3 (DIN EN ISO 845, October 2009).
  • foamed granules (degree of compaction VG) is generally between 1.5 and 3.5, preferably 1.8 to 2.5.
  • foamed granules according to the invention can be used particularly well for shoe soles, part of a shoe sole, mattresses, pads, handles, protective films, components in the
  • the present invention accordingly also relates to the use as described above, the shaped body being a shoe sole, part of a shoe sole, a mattress, pad, handle, protective film, a component in the interior and exterior of automobiles, an exercise mat, a body protector , a lining element in the
  • a muffler a vibration damper, a padding, a bicycle saddle, a toy, a tire or a tire part or a surface for an athletics track, a sports hall or a sidewalk, a damping layer or a damping core in a sandwich element or packaging.
  • the present invention also relates to the use of a foamed granulate as described above in balls and sports equipment or as floor covering and wall cladding, in particular for sports surfaces, athletics running tracks, sports halls, children's playgrounds and sidewalks.
  • the moldings obtained according to the invention are suitable, for example, for the production of shoe soles, parts of a shoe sole, bicycle saddles, upholstery, mattresses, pads, handles, protective films, components in the automotive interior and exterior, in balls and
  • Sports equipment or as flooring and wall cladding in particular for sports surfaces, athletics running tracks, sports halls, children's playgrounds and sidewalks.
  • the present invention also relates to the use of a foamed granulate according to the invention or a foamed granulate, obtained or obtainable by a method according to the invention for the production of moldings, the moldings being a shoe sole, part of a shoe sole, a bicycle saddle, a padding, A mattress, pad, handle, protective film is a component in the interior and exterior of an automobile.
  • the present invention also relates to the use of the foamed granules or foamed particles according to the invention in balls and
  • Sports equipment or as flooring and wall cladding in particular for sports surfaces, athletics running tracks, sports halls, children's playgrounds and sidewalks.
  • the present invention also relates to a hybrid material containing a matrix made of a polymer (PM) and a foamed granulate according to the present invention.
  • a hybrid material containing a matrix made of a polymer (PM) and a foamed granulate according to the present invention.
  • Materials which comprise a foamed granulate and a matrix material are referred to as hybrid materials in the context of this invention.
  • the matrix material can consist of a compact material or also of a foam.
  • Polymers (PM) suitable as matrix material are known per se to the person skilled in the art.
  • ethylene-vinyl acetate copolymers, epoxy-based binders or even polyurethanes are suitable.
  • polyurethane foams or compact polyurethanes such as, for example, are suitable
  • thermoplastic polyurethanes are thermoplastic polyurethanes.
  • the polymer (PM) is selected such that there is sufficient adhesion between the foamed granulate and the matrix in order to obtain a mechanically stable hybrid material.
  • the matrix can completely or partially surround the foamed granulate.
  • the hybrid material can contain further components, for example further fillers or granulates.
  • the hybrid material can also contain mixtures of different polymers (PM).
  • the hybrid material can also contain mixtures of different polymers (PM).
  • Foamed granules which can be used in addition to the foamed granules according to the present invention are known per se to the person skilled in the art. Foamed granules made from thermoplastic polyurethanes are particularly suitable for the purposes of the present invention.
  • the present invention accordingly also relates to a
  • Hybrid material containing a matrix made of a polymer (PM), a foamed granulate according to the present invention and a further foamed granulate made of a thermoplastic polyurethane.
  • the matrix consists of a polymer (PM).
  • suitable matrix material are, for example, elastomers or foams, in particular foams based on polyurethanes, for example elastomers such as ethylene-vinyl acetate copolymers or also thermoplastic polyurethanes.
  • the present invention also relates to a hybrid material as described above, the polymer (PM) being an elastomer.
  • the present invention also relates to a hybrid material as described above, the polymer (PM) being selected from the group consisting of ethylene-vinyl acetate copolymers and thermoplastic polyurethanes.
  • the present invention also relates to a hybrid material containing a matrix made from an ethylene-vinyl acetate copolymer and a foamed granulate according to the present invention.
  • the present invention relates to a hybrid material containing a matrix made from an ethylene-vinyl acetate copolymer, a foamed granulate I.
  • a further foamed granulate for example made of a thermoplastic polyurethane.
  • the present invention relates to a hybrid material containing a matrix made of a thermoplastic polyurethane and a foamed granulate according to the present invention.
  • the present invention relates to a hybrid material containing a matrix composed of a thermoplastic polyurethane, a foamed granulate according to the present invention and a further foamed granulate, for example composed of a thermoplastic polyurethane.
  • thermoplastic polyurethanes are known per se to the person skilled in the art. Suitable thermoplastic polyurethanes are described, for example, in "Kunststoffhandbuch, Volume 7, Polyurethane", Carl Hanser Verlag, 3rd Edition 1993, Chapter 3.
  • the polymer (PM) is preferably a polyurethane.
  • Polyurethane in the context of the invention includes all known elastic polyisocyanate polyadducts. These include in particular massive polyisocyanate
  • Polyaddition products such as viscoelastic gels or thermoplastic polyurethanes, and elastic foams based on polyisocyanate polyaddition products, such as
  • polyurethanes are to be understood as meaning elastic polymer blends containing polyurethanes and other polymers, and also foams made from these polymer blends.
  • the matrix is preferably a hardened, compact polyurethane binder, an elastic polyurethane foam or a viscoelastic gel.
  • a polyurethane binder is understood to mean a mixture which comprises at least 50% by weight, preferably at least 80% by weight and in particular at least 95% by weight of a prepolymer containing isocyanate groups, hereinafter referred to as isocyanate prepolymer called, exists.
  • the viscosity of the polyurethane binder according to the invention is preferably in a range from 500 to 4000 mPa.s, particularly preferably from 1000 to 3000 mPa.s, measured at 25 ° C. in accordance with DIN 53 018.
  • polyurethane foams are understood to mean foams according to DIN 7726.
  • the density of the matrix material is preferably in the range from 1.2 to 0.01 g / cm3.
  • the matrix material is particularly preferably an elastic foam or an integral I.
  • Hybrid materials that contain a matrix material made of a polyurethane foam preferably have good adhesion between the matrix material and the foamed granulate.
  • the present invention also relates to a hybrid material containing a matrix made of a polyurethane foam and a foamed granulate according to the present invention.
  • the present invention relates to a hybrid material containing a matrix composed of a polyurethane foam, a foamed granulate according to the present invention and a further foamed granulate, for example composed of a thermoplastic polyurethane.
  • the present invention relates to a hybrid material containing a matrix made of a polyurethane integral foam and a foamed granulate according to the present invention.
  • the present invention relates to a hybrid material containing a matrix made of a polyurethane integral foam, a foamed granulate according to the present invention and a further foamed granulate, for example made of a thermoplastic polyurethane.
  • a hybrid material according to the invention containing a polymer (PM) as a matrix and a foamed granulate according to the invention can be produced, for example, by mixing the components used to produce the polymer (PM) and the foamed granulate, if appropriate with further components, and converting them to the hybrid material, the The reaction is preferably carried out under conditions under which the foamed granulate is essentially stable.
  • Suitable processes and reaction conditions for producing the polymer (PM), in particular an ethylene-vinyl acetate copolymer or a polyurethane, are the following processes and reaction conditions:
  • the hybrid materials according to the invention are integral skin foams, in particular integral skin foams based on polyurethanes.
  • Suitable processes for producing integral skin foams are known per se to the person skilled in the art.
  • the integral skin foams are preferably produced by the one-shot process with the aid of low-pressure or high-pressure technology in closed, expediently temperature-controlled molds.
  • the molding tools usually consist of I.
  • Metal e.g. Aluminum or steel. These procedures are described, for example, by Piechota and Rschreib in "Integralschaumstoff, Carl-Hanser-Verlag, Kunststoff, Vienna, 1975, or in Kunststoff-Handbuch, Volume 7, Polyurethane, 3rd Edition, 1993, Chapter 7.
  • the amount of the reaction mixture introduced into the molding tool is such that the molded bodies obtained from integral skin foams have a density of 0.08 to 0.70 g / cm 3 , in particular 0.12 to 0.60 g / cm 3 .
  • the degrees of compaction for producing the shaped bodies with a compacted edge zone and a cellular core are in the range from 1.1 to 8.5, preferably from 2.1 to 7.0.
  • hybrid materials with a matrix of a polymer (PM) and the foamed granulate according to the invention contained therein, in which there is a homogeneous distribution of the foamed particles.
  • the foamed granulate according to the invention can easily be used in a method for producing a hybrid material, since the individual particles are free-flowing due to their small size and do not make any special demands on processing. Techniques for homogeneous distribution of the foamed granulate, such as slow rotation of the mold, can be used.
  • Auxiliaries and / or additives can optionally also be added to the reaction mixture for producing the hybrid materials according to the invention.
  • Examples include surface-active substances, foam stabilizers, cell regulators, release agents, fillers, dyes, pigments, hydrolysis inhibitors, odor-absorbing substances and fungistatic and bacteriostatic substances.
  • emulsifiers such as the sodium salts of castor oil sulfates or of fatty acids, as well as salts of fatty acids with amines, e.g. oleic acid diethylamine, stearic acid diethanolamine, ricinoleic acid diethanolamine, salts of sulfonic acids, e.g. Alkali or ammonium salts of dodecylbenzene or
  • Foam stabilizers such as siloxane-oxalkylene copolymers and other organopolysiloxanes, ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil or. Ricinoleic acid esters, turkey red oil and peanut oil, and cell regulators such as paraffins, fatty alcohols and dimethylpolysiloxanes.
  • Oligomeric acrylates with polyoxyalkylene and fluoroalkane residues are also suitable for improving the emulsifying effect, the cell structure and / or stabilizing the foam
  • Suitable release agents are: reaction products of fatty acid esters with polyisocyanates, salts of polysiloxanes containing amino groups and fatty acids, I.
  • Fillers are the customary organic and inorganic fillers, reinforcing agents, weighting agents, agents for improving the abrasion behavior in paints, coating agents, etc., which are known per se.
  • inorganic fillers such as silicate minerals, for example sheet silicates such as antigorite, bentonite, serpentine, tinsel, amphiboles, chrysotile, talc;
  • Metal oxides such as kaolin, aluminum oxides, titanium oxides, zinc oxide and iron oxides, metal salts such as chalk, barite and inorganic pigments such as
  • Kaolin china clay
  • aluminum silicate and coprecipitates of barium sulfate and aluminum silicate as well as natural and synthetic fibrous minerals such as wollastonite, metal and in particular glass fibers of various lengths, which can optionally be sized, are preferably used.
  • organic fillers are: carbon black, melamine, rosin,
  • Cyclopentadienyl resins and graft polymers as well as cellulose fibers, polyamide, polyacrylonitrile, polyurethane, polyester fibers based on aromatic and / or aliphatic dicarboxylic acid esters and especially carbon fibers.
  • the inorganic and organic fillers can be used individually or as mixtures.
  • the proportion by volume of the foamed granulate is preferably 20 percent by volume and more, particularly preferably 50
  • volume percent and more preferably 80 volume percent and more and in particular 90 volume percent and more, each based on the volume of the invention
  • hybrid materials according to the invention in particular hybrid materials with a matrix of cellular polyurethane, are distinguished by very good adhesion of the matrix material to the foamed granulate according to the invention.
  • an inventive tear breaks
  • Hybrid material preferably not at the interface between matrix material and foamed granulate. This makes it possible to produce hybrid materials that are opposite
  • conventional polymer materials especially conventional polyurethane materials I.
  • the elasticity of hybrid materials according to the invention in the form of integral skin foams is preferably greater than 40% and particularly preferably greater than 50% according to DIN 53512.
  • hybrid materials according to the invention in particular those based on integral foams, show high rebound elasticities at low density.
  • Integral foams based on hybrid materials according to the invention are therefore outstandingly suitable as materials for shoe soles. This results in light and comfortable soles with good durability properties.
  • Such materials are particularly as
  • hybrid materials according to the invention with a cellular matrix are suitable, for example, for upholstery, for example for furniture, and mattresses.
  • Hybrid materials with a matrix made of a viscoelastic gel are particularly characterized by increased viscoelasticity and improved elastic properties. These materials are therefore also suitable as upholstery materials, for example for seats, especially saddles such as bicycle saddles or motorcycle saddles.
  • Hybrid materials with a compact matrix are, for example, as floor coverings,
  • the properties of the hybrid materials according to the invention can depend on
  • polymer (PM) used vary within wide ranges and can be varied within wide limits, in particular by varying the size, shape and nature of the expanded granules, or by adding further additives, for example also other non-foamed granules such as plastic granules, for example rubber granules .
  • hybrid materials according to the invention have a high level of durability and resilience, which is particularly noticeable through a high tensile strength and elongation at break.
  • hybrid materials according to the invention have a low density.
  • thermoplastic polyurethane at least comprising steps (i) and (ii):
  • Ethylene diphenyl diisocyanate or mixtures thereof and one
  • step (ii) Reaction of the prepolymer obtained in step (i) with at least one chain extender (KV).
  • step (ii) further components selected from the group consisting of polyols, chain extenders, catalysts, cell nucleating agents, other auxiliary agents and additives are used.
  • poly-s-caprolactone polyol is obtainable or is obtained by reacting e-caprolactone and a starter molecule which is selected from the group consisting of a-Flydro-w-hydroxypoly (oxytetramethylene ) diols.
  • Polyol composition containing the ⁇ -hydro-m-hydroxypoly (oxytetramethylene) polyol in an amount in the range from 0.1 to 50% by weight, based on the polyol composition.
  • chain extender (KV) is selected from the group consisting of MEG, 1,4-butanediol, 1,3-propanediol, 1,6-hexanediol, 2-ethyl-1, 3-hexanediol or 2-butyl-2-ethyl propanediol.
  • Thermoplastic polyurethane obtainable or obtained by a process at least comprising steps (i) and (ii):
  • Ethylene diphenyl diisocyanate or mixtures thereof and one
  • step (ii) Reaction of the prepolymer obtained in step (i) with at least one chain extender (KV).
  • Polytetrahydrofuran is a poly-s-caprolactone polyol.
  • Thermoplastic polyurethane according to one of embodiments 10 to 13 wherein the poly-s-caprolactone polyol is obtainable or is obtained by reacting e-caprolactone and a starter molecule which is selected from the group consisting of ⁇ -hydro- ⁇ ) -hydroxypoly (oxytetramethylene ) diols.
  • Thermoplastic polyurethane according to one of embodiments 10 to 15 the polyisocyanate composition 1, 5-naphthylene diisocyanate (NDI) in an amount in the range from 90 to 100% by weight, based on the total
  • Thermoplastic polyurethane according to one of embodiments 10 to 16 the chain extender (KV) being selected from the group consisting of diols with a molecular weight in the range from 50 to 500 g / mol and diamines with a
  • Thermoplastic polyurethane according to one of embodiments 10 to 17 the chain extender (KV) being selected from the group consisting of MEG, 1,4-butanediol, 1,3-propanediol, 1,6-hexanediol, 2-ethyl-1,3 -hexanediol or 2-butyl-2-ethylpropanediol.
  • Foamed granules comprising a thermoplastic polyurethane obtainable or obtained according to a method according to one of embodiments 1 to 9 or a thermoplastic polyurethane according to one of embodiments 10 to 18.
  • a method for producing a foamed granulate comprising a
  • thermoplastic polyurethane according to embodiment 10 to 18, wherein the I.
  • Polyurethane is impregnated with the blowing agent in an extruder, the impregnated polyurethane is cut into granules and the granules are relaxed immediately after cutting to form expanded thermoplastic polyurethane particles.
  • a method for producing a foamed granulate comprising a
  • thermoplastic polyurethane according to any one of embodiments 10 to 18, comprising steps (a) to (c):
  • thermoplastic polyurethane as particles in a suitable geometrical granulate form
  • step (b) in with 0.1 to 50 wt .-% of a blowing agent at a temperature in the range from 90 to 180 ° C and a pressure in the range from 0.5 to 10 MPa is impregnated.
  • thermoplastic polyurethane particles with water vapor, hot air or high-energy radiation, so that the expanded thermoplastic
  • Foamed granules according to embodiment 19 the mean diameter of the particles being in the range from 0.5 to 20 mm.
  • Shoe sole part of a shoe sole, a mattress, pad, handle, protective film, a component in the automotive interior and exterior, an exercise mat
  • Body protector a lining element in automobile construction, a muffler, a vibration damper, a padding, a bicycle saddle, a toy, a tire or a tire part or a surface for an athletics track, a sports hall or a sidewalk, a damping layer or a damping core in a sandwich element or packaging.
  • Hybrid material containing a matrix made of a polymer (PM) and a foamed granulate according to one of the embodiments 19 or 28.
  • thermoplastic polyurethane at least comprising steps (i) and (ii):
  • Starter molecule which is selected from the group consisting of ⁇ -Hydro-w-hydroxypoly (oxytetramethylene) diols.
  • thermoplastic polyurethane obtainable or obtained according to a method according to any one of claims 35 to 41 or a thermoplastic polyurethane according to claim 42.
  • Foamed granules according to claim 43 wherein the mean diameter of the particles is in the range from 0.5 to 20 mm.
  • Shaped body made from a foamed granulate according to one of claims 43 or 44.
  • the particles are welded or glued together.
  • the molded body is a shoe sole, part of a shoe sole, a mattress, pad, handle, protective film, a component in the
  • an exercise mat a body protector, a lining element in automobile construction, a silencer, a vibration damper, upholstery, a bicycle saddle, a toy, a tire or a tire part or a surface for an athletics track, a sports hall or a sidewalk, is a cushioning layer or a cushioning core in a sandwich element or a packaging.
  • thermoplastic polyurethane at least comprising steps (i) and (ii):
  • step (ii) Reaction of the prepolymer obtained in step (i) with at least one chain extender (KV).
  • the method of claim 51 wherein the derivative of polytetrahydrofuran is a poly-e-caprolactone polyol.
  • Process according to one of claims 51 or 52, wherein further components selected from the group consisting of polyols, chain extenders, catalysts, cell nucleating agents, other auxiliaries and additives are used in the reaction according to step (ii).
  • Starter molecule which is selected from the group consisting of ⁇ -Hydro-w-hydroxypoly (oxytetramethylene) diols.
  • step (ii) Reaction of the prepolymer obtained in step (i) with at least one chain extender (KV).
  • V chain extender
  • Foamed granules comprising a thermoplastic polyurethane obtainable or obtained according to a process according to any one of claims 51 to 57 or a thermoplastic polyurethane according to claim 58.
  • Shaped body made from a foamed granulate according to one of claims 59 or 60.
  • the particles are welded or glued together.
  • the molded body is a shoe sole, part of a shoe sole, a mattress, pad, handle, protective film, a component in the
  • an exercise mat a body protector, a lining element in automobile construction, a silencer, a vibration damper, upholstery, a bicycle saddle, a toy, a tire or a tire part or a surface for an athletics track, a sports hall or a sidewalk, is a cushioning layer or a cushioning core in a sandwich element or a packaging.
  • thermoplastic polyurethanes 1.
  • PCL capped PTHF PCL500-PTHF1000-PCL500
  • PTHF2000 4: 1) are heated to a temperature between 130-160 ° C and 200 parts by weight of NDI are added as a solid and reacted. After a reaction time of 30-50 minutes in a temperature range of 150-90 ° C., a prepolymer with an NCO content of 3.2% and a viscosity of 2500 mPas at 90 ° C. is obtained. I.
  • the material was tempered at a temperature of 110 ° C. for 14 hours, and the material obtained can be processed further by injection molding.
  • the TPU 1 obtained was granulated by means of a mill and processed by extrusion with a ZSK40 twin-screw extruder with a maximum zone temperature of 220 ° C. and a perforated plate temperature of 230 ° C. via underwater granulation to give lens granules.
  • the TPU was then dried at 80 ° C. for 15 h.
  • PCL capped PTHF, PTHF2000 4: 1 1000 parts by weight of polyol (PCL capped PTHF, PTHF2000 4: 1) are added to a PCL capped PTHF, PTHF2000 4: 1)
  • the material was tempered at a temperature of 110 ° C. for 14 hours, and the material obtained can be processed further by injection molding.
  • Di-n-hexylamine solution 166.8 g of di-n-hexylamine are made up to 1.0 L with xylene (in a 1 L volumetric flask) and homogenized.
  • 1% bromophenol blue solution 0.5 g bromophenol blue are dissolved in 49.5 g ethanol and transferred to a pipette bottle.
  • V p robe consumption of HCl (1.0 mol / L) for sample in L
  • NDI and, if necessary, solid additives are metered into the first housing of a twin-screw extruder, ZSK32 MC from Coperion with a process length of 56D.
  • the polyols, heated to 160 ° C, as well as the catalyst and, if necessary, liquid additives are fed to the molten NDI in the second housing. After mixing and I.
  • the (partial) reaction of the components takes place downstream, in the fifth zone, where the chain extender is added. At housing temperatures of 190-220 ° C, the reaction components are converted up to a degree of conversion of> 95%. Following the synthesis, the polymer melt obtained is granulated underwater and the granules obtained are dried.
  • Foam particles or molded parts were among others the following test methods or characteristic values are used: a. Melting point determination by means of DSC
  • thermoplastic elastomers according to the invention in granulate form 3-5 mg are heated in a 1st run between 20 ° C and 200 ° C at a heating rate of 20 ° C / min, then at 10 ° C / min to 20 ° C cooled, followed by a further heating cycle (2nd run) with a heating rate of 10 ° C / min.
  • the temperature of the peak maximum in the 2nd run was given as the melting point.
  • the foam particles are filled with the aid of a funnel with a defined geometry (completely filled with bulk material) into a measuring cylinder with a known volume, the
  • the funnel used is 40 cm high, had an opening angle of 35 ° and an outlet with a 50 mm diameter.
  • the measuring cylinder had an internal diameter of 188 mm and a volume of 10 I.
  • the bulk density (SD) was calculated from the mass of the bed [kg] / 0.01 [m 3 ].
  • the foam structure was assessed by optical image analysis with a PORE! SCAN Advanced Plus from Goldlücke Ingenieurdienst treated. For this purpose, 10 foam particles are halved and one cut surface is measured. With non-spherical, z. B. elongated, cylindrical or ellipsoidal foam particles, the division takes place in the direction of the longest dimension.
  • the mean cell density is the ratio of the number of cells on the cut surface to the cut surface and is given in 1 / mm 2 .
  • the value is assigned to a classification:
  • the degree of compaction VG is the ratio of molded part density (FT density) to
  • TPU materials were used for the E-TPU examples 1 to 7 (as well as the comparative examples):
  • TPU 1 in the form of lentil granules 1150 kg / m 3
  • TPU2 in the form of lentil granules 1150 kg / m 3
  • the tests were carried out with a boiler filling level of 80% and a phase ratio of 0.38.
  • the phase ratio is defined as the ratio of the masses of granulate to suspension medium, in the examples water.
  • the holding time is defined as the time during which the temperature of the liquid phase is in a temperature range of 5 ° C below the impregnation temperature and 2 ° C above the impregnation temperature.
  • the bulk density (SD) of the resulting foam particles is measured.
  • Table 1a Test parameters for Examples 1 to 7
  • Table 1 b Test parameters for Examples 1 to 7
  • the cell structure of the foamed granulate contains voids and cracks
  • the foam particles were then on an automatic molding machine from Kurtz Ersa GmbHFI (Energy Foamer K68) to form square plates with a side length of 200 mm and a thickness of 10 mm and 20 mm or on an automatic molding machine from Erlenbach (EFIV- C870 / 670) rectangular plates with a side length of 300x200 mm and a thickness of 10 mm, through
  • the molded parts can be produced by the pressure filling process or by the crack filling process.
  • the crack filling process was used for the examples according to the invention (see Table 2)
  • Molded parts were made from the particles produced above using a PU system or binder.
  • the liquid formulations were first prepared and then intensively mixed with the particles in a plastic container made of polyethylene before they were discharged into the molds.
  • a Teflon-coated wooden mold with internal dimensions of 4.5 x 4.5 x 4.5 cm served as the mold.
  • An insert measuring 4.5 x 4.5 x 2.5 cm made it possible to produce both cubes and 2 cm thick plates from the preparations. 5.2 Input materials
  • component A preheated to 40 ° C.
  • component B preheated to 25 ° C., with the composition listed in Table 4, were at a pressure of 16 bar time-controlled according to the information from Table 4 given to the corresponding amount of E-TPU, which was present in a 2.7 L plastic cup.
  • the dosage parameters are derived from the fact that a loss of approx. 10% of the total mass of the foam system remains when E-TPU and foam are mixed and transferred. This is checked by weighing the finished test panels, which are set to a density of 300 (PU foam 1) or 260 kg / m 3 (PU foam 2).
  • the system reacts for 30 minutes.
  • the ventilation of the tool is regulated by ventilation channels, while the mold temperature is kept constant at 45 ° C.
  • PU foam 3 was processed in the same way as foam 1 and 2 and a proportion of 70% particle mass was introduced. Due to the faster reaction time, PU foam 4 was put directly into a mold filled with E-TPU and then foamed around it. The completely filled form allows a proportion of approx. 50% of the particle mass. Due to the faster reacting system, a demoulding time of approx. 5 minutes is achieved. All further

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Composite Materials (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un procédé de production d'un polyuréthane thermoplastique, comprenant au moins la mise en réaction d'au moins une composition d'isocyanate (ZI) contenant un isocyanate (I1) choisi dans le groupe constitué par le 1,5-naphthylène diisocyanate (NDI), le 4,4'-diphényle méthane diisocyanate (MDI), le p-diphényle diisocyanate (PPDI) et le diisocyanate d'o-tolidine (TODI), le diisocyanate d'éthylènediphényle (EDI) ou des mélanges de ces derniers, et d'une composition de polyol (ZP) contenant un polytétrahydrofurane ou un dérivé de ce dernier, pour obtenir un prépolymère comportant des groupes isocyanate, et la mise en réaction du prépolymère obtenu avec au moins un allongeur de chaîne (KV). La présente invention concerne en outre un polyuréthane thermoplastique obtenu ou pouvant être obtenu selon un procédé de ce type ainsi qu'un granulé expansé comprenant un polyuréthane thermoplastique de ce type. La présente invention comprend en outre l'utilisation d'un granulé expansé selon l'invention pour la production d'un corps moulé.
EP20731490.7A 2019-06-14 2020-06-12 Mousses particulaires novatrices Pending EP3983467A1 (fr)

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EP1752481A1 (fr) * 2004-05-31 2007-02-14 Asahi Glass Company, Limited Elastomere polyurethane et methode de fabrication de semblable
CN105601980A (zh) 2006-01-18 2016-05-25 巴斯夫欧洲公司 基于热塑性聚氨酯的泡沫
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EP2836543B1 (fr) 2012-04-13 2020-03-04 Basf Se Procédé de production de granulés expansés
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JP6907133B2 (ja) 2015-03-13 2021-07-21 ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ 熱可塑性エラストマーに基づく粒子フォームをマイクロ波を使用した熱的結合により製造するための方法
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WO2020249727A1 (fr) 2020-12-17
TW202112863A (zh) 2021-04-01
JP2022536759A (ja) 2022-08-18
KR20220024554A (ko) 2022-03-03
US20220267553A1 (en) 2022-08-25
CN113950497A (zh) 2022-01-18

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