EP3535316A1 - Mousses particulaires à base d'élastomères thermoplastiques expansés - Google Patents

Mousses particulaires à base d'élastomères thermoplastiques expansés

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Publication number
EP3535316A1
EP3535316A1 EP17787204.1A EP17787204A EP3535316A1 EP 3535316 A1 EP3535316 A1 EP 3535316A1 EP 17787204 A EP17787204 A EP 17787204A EP 3535316 A1 EP3535316 A1 EP 3535316A1
Authority
EP
European Patent Office
Prior art keywords
particles according
blowing agent
foam particles
thermoplastic
thermoplastic elastomer
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.)
Withdrawn
Application number
EP17787204.1A
Other languages
German (de)
English (en)
Inventor
Frank Prissok
Gnuni Karapetyan
Dirk Kempfert
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
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP3535316A1 publication Critical patent/EP3535316A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0042—Use of organic additives containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • 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
    • B29C44/3461—Making or treating expandable particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D35/00—Producing footwear
    • B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
    • B29D35/122—Soles
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • 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
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • 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
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • 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
    • 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
    • C08J9/236—Forming foamed products using binding agents
    • 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
    • C08J9/34—Chemical features in the manufacture of articles consisting of a foamed macromolecular core and a macromolecular surface layer having a higher density than the core
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
    • 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
    • B29C44/3415—Heating or cooling
    • B29C44/3426—Heating by introducing steam in the mould
    • 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
    • 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
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
    • B29C67/205—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored comprising surface fusion, and bonding of particles to form voids, e.g. sintering
    • 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
    • B29K2101/00—Use of unspecified macromolecular compounds as moulding material
    • B29K2101/12—Thermoplastic materials
    • 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
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • 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
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0063—Density
    • 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
    • C08J2203/06—CO2, N2 or noble gases
    • 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
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/06—Flexible foams
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/26—Elastomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • 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
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • 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
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
    • 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
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08J2483/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences

Definitions

  • the invention relates to foam particles based on thermoplastic elastomers which contain a siloxane, and to processes for producing the foam particles and particle foams, obtainable by welding foam particles by water vapor or irradiation of high-frequency radiation or by bonding with reactive adhesives, solvent-containing adhesives or dispersion adhesives.
  • Expanded thermoplastic polymers are used, for example, for the production of any foam solid bodies, for example for gymnastic mats, body protectors, lining elements in the automotive industry, sound and vibration absorbers, packaging or shoe soles. It is preferred to fill a mold with foam particles of an expanded polymer and to melt the individual foam particles by the action of heat on their surface and in this way to bond together to form a particle foam. Thus, in addition to simple and complex semi-finished or molded parts can be produced with undercuts. From WO-A 2007/082838 a process for the production of expanded, propellant-containing thermoplastic polyurethane is known. Therein, in a first step, a thermoplastic polyurethane is extruded into a granulate.
  • the granules are impregnated in aqueous suspension under pressure with a blowing agent and expanded in a third step.
  • the thermoplastic polyurethane is melted together with a blowing agent in an extruder and the melt granulated without a device that prevents foaming
  • WO 2015/05581 1 describes a process for the preparation of expanded thermoplastic polymer, comprising the following steps: (a) adding monomers and / or oligomers used for the preparation of the thermoplastic polymer and / or oligomers and optionally further starting materials to a first stage of a polymer processing machine, (b ) Mixing the monomers and / or oligomers as well as the optionally added further starting materials and reaction of the monomers and / or oligomers to a polymer melt in the first stage of the polymer processing machine, (c) introducing the polymer melt into a second stage of the polymer processing machine and adding a blowing agent and optionally other starting materials to obtain a blowing agent-containing polymer melt, (d) forming the blowing agent-containing polymer melt into an expanded thermoplastic polymer.
  • thermoplastic molding compositions may include, inter alia, organosiloxanes, such as dimethylpolysiloxane.
  • the object of the present invention is to provide foam particles based on thermoplastic elastomers which can be processed into particle foams having high dimensional stability and improved mechanical properties, in particular high compression hardness, rebound resilience and high tear propagation resistance at a low density, which is normal.
  • Preferred siloxanes used are oligomeric or polymeric organosiloxanes.
  • the siloxanes preferably have isocyanate-reactive organic groups, in particular non-reactive aromatic groups.
  • Particularly preferred are organosilane-modified polysilioxanes having organosilane groups bonded via carbon atoms.
  • Preferred polysiloxanes are polydiorganosiloxanes having the repeating unit - [0-SiR 2 R 3 ] -, especially those of the general formula R 1 3Si- [0-SiR 2 R 3 ] -O-SiR 1 3, where R 1 , R 2 and R 3 can independently be hydrogen, alkyl or aryl groups.
  • R 1 and R 2 are particularly preferably methyl and R 3 is phenylethyl.
  • siloxanes terminated with aromatic groups Preference is given to using siloxanes terminated with aromatic groups. Particular preference is given to using aryl-modified siloxanes, for example phenylethylmethylpolysiloxane such as Tegomer® M-Si 2650 from Evonik.
  • aryl-modified siloxanes for example phenylethylmethylpolysiloxane such as Tegomer® M-Si 2650 from Evonik.
  • Suitable siloxanes are also siloxane block polymers having at least one organosiloxane block and a polyether block, as described, for example, in DE 10 2014 218 635.
  • Preferred polyether blocks consist of EO, PO or PESOL.
  • Particular preference is given to polyester siloxanes or polyether siloxanes, such as trimethylsiloxy-terminated dimethylmethyl (propyl (propylene oxide)) siloxane, for example DOW CORNING 1248 FLUID.
  • the siloxanes are preferably used in amounts ranging from 0.1 to 5% by weight, more preferably in the range from 0.1 to 2% by weight, based on the thermoplastic elastomer. Preference is given to using a siloxane, in particular an aryl-modified siloxane. But it can also be used more siloxanes. For several siloxanes, the amounts given refer to the total amount of all siloxanes.
  • the siloxanes used according to the invention act as cell regulators, cell stabilizers and surface modifiers. They produce a smooth, closed-cell and shiny surface, and a gradient in the cell size distribution of larger cell diameters in the core of the foam particles to smaller cell diameters in the edge regions.
  • the gradient in cell size distribution and the compact surface result in better weldability and associated improved mechanical properties. Due to the smooth surface, the frictional resistance is reduced and the abrasion resistance of the particle foams is improved.
  • the foam particles in the interior preferably have an average cell diameter in the range of 200-1000 microns, preferably 200-600 microns, and in the edge region in the range of 0.1-200 microns, preferably 0.1-100 microns. By the edge region is meant the outer 20% of the radius of the particle.
  • the core is the inner 50% around the center of the particle.
  • thermoplastic elastomers are, for example, thermoplastic polyurethanes (TPU), thermoplastic polyester elastomers (for example polyether esters and polyester esters), thermoplastic copolyamides (for example polyethercopolyamides) or thermoplastic styrene-butadiene block copolymers. Particular preference is given to foam particles based on thermoplastic polyurethane (TPU).
  • the bulk density of the foam particles is preferably in the range of 30 to 250 kg / m 3 .
  • the foam particles may be obtained by impregnation of thermoplastic elastomer granules containing at least one siloxane with a blowing agent in suspension or by melt impregnation of molten thermoplastic elastomer with a blowing agent and subsequent granulation. Suitable processes for producing the foam particles based on thermoplastic elastomers are described, for example, in WO 2005/023920, WO 2007/082838, WO 2013/153190 and WO 2014/198779
  • thermoplastic elastomer containing a siloxane is melted, admixed with a blowing agent, and the blowing agent-containing melt is granulated with foaming.
  • Another, preferred process variant for the production of foam particles comprises the following steps:
  • thermoplastic elastomer (a) addition of monomers and / or oligomers used for the preparation of the thermoplastic elastomer, of at least one siloxane and optionally further starting materials into a first stage of a polymer processing machine,
  • blowing agent-containing polymer melt into an expanded thermoplastic elastomer.
  • screw-type piston machines or melt pumps can be used as polymer processing machines.
  • extruders are preferably used as screw piston machines for carrying out the method according to the invention.
  • steps (b) and (c) are performed in one machine.
  • the first stage is a first section of the screw machine, in which the reaction of the monomers and / or oligomers, in the presence of a siloxane and optionally further reactants, to the polymer and the second stage, a second section of the screw machine, which is directly on connects the first section, in which the propellant is added
  • the propellant is then added.
  • the second stage of the screw-type piston machine has, for example, suitable mixing units on the screw. It is also possible to use a static mixer in addition.
  • melt pump In addition to an extruder, a melt pump can alternatively be used. In order to obtain a uniform distribution of the blowing agent in the polymer, the melt pump is preferably followed by a static mixer before it enters a granulating system.
  • the polymer melt is usually extruded into strands, which are then cut into foam particles.
  • the blowing agent By the addition of the blowing agent, the polymer melt expands on leaving the extruder due to the pressure drop and there is a foamed product, in the granulation in this way an expanded foam particles.
  • step (d) it is preferable to press the polymer melt through a tempered perforated plate into a granulating chamber, cut it into individual expanding foam particles with a cutting device and to discharge the foam particles from the granulating chamber with a liquid stream.
  • the temperature of the tempered perforated plate is preferably between 150 and 280 ° C.
  • the pressure in the tempering liquid flowing through the granulation chamber is preferably between 0.7 bar and 20 bar.
  • the pressure in the liquid is between 5 and 15 bar, more preferably a pressure between 10 and 15 bar is preferred.
  • the propellant in a preferred embodiment contains carbon dioxide, nitrogen or a mixture of carbon dioxide and nitrogen. Any mixture of nitrogen and carbon dioxide can be used here.
  • the blowing agent may also contain an organic blowing agent, for example alkanes, halogenated hydrocarbons or a mixture of these substances.
  • alkanes for example, ethane, propane, butane or pentane are suitable here.
  • the sole use of CO2 and / or N2 and their combination as a propellant is particularly advantageous because it is inert gases that are incombustible, so that during production no explosive atmospheres can arise. As a result, cost-intensive safety precautions become unnecessary and the potential danger in the production is greatly reduced. It is also advantageous that no removal time of the products due to the evaporation of volatile combustible materials is required.
  • the siloxanes used are preferably oligomeric or polymeric organosiloxanes.
  • the siloxanes preferably have isocyanate-reactive organic groups, in particular non-reactive aromatic groups.
  • Particularly preferred are organosilane-modified polysilioxanes having organosilane groups bonded via carbon atoms.
  • Preferred polysiloxanes are polydiorganosiloxanes having the repeating unit - [0-SiR 2 R 3 ] -, especially those of the general formula R 1 3Si- [0-SiR 2 R 3 ] -O-SiR 1 3, where R 1 , R 2 and R 3 can independently be hydrogen, alkyl or aryl groups.
  • R 1 and R 2 are particularly preferably methyl and R 3 is phenylethyl.
  • siloxanes terminated with aromatic groups Preference is given to using siloxanes terminated with aromatic groups. Particular preference is given to using aryl-modified siloxanes, for example phenylethylmethylpolysiloxane such as Tegomer® M-Si 2650 from Evonik.
  • aryl-modified siloxanes for example phenylethylmethylpolysiloxane such as Tegomer® M-Si 2650 from Evonik.
  • Suitable siloxanes are also siloxane block polymers having at least one organosiloxane block and a polyether block, as described, for example, in DE 10 2014 218 635.
  • Preferred polyether blocks consist of EO, PO or PESOL.
  • Particular preference is given to polyester siloxanes or polyether siloxanes, such as trimethylsiloxy-terminated dimethylmethyl (propyl (propylene oxide)) siloxane, for example DOW CORNING 1248 FLUID.
  • the siloxanes are preferably added in amounts ranging from 0.1 to 5 wt .-%, particularly preferably in the range of 0.1 to 2 wt .-%, based on the monomers and oligomers, in step (a) and in step (b) mixed.
  • the amounts given refer to the total amount of all siloxanes. Further advantages result if the blowing agent-containing polymer melt additionally an o- or more nucleating agents are added as additional reactants.
  • nucleating agents are talc, calcium fluoride, sodium phenylphosphinate, aluminum oxide, carbon black, graphite, pigments and finely divided polytetrafluoroethylene, individually or else in any desired mixtures.
  • a nucleating agent is talc.
  • the proportion of nucleating agent based on the total mass of the thermoplastic molding composition or the polymer melt is preferably from 0 to 4 wt .-%, in particular 0.1 to 2% by weight.
  • the nucleating agent can be added either in the first stage or in the second stage.
  • thermoplastic polyurethane can be any thermoplastic polyurethane known to those skilled in the art. Thermoplastic polyurethanes and processes for their preparation have already been described many times, for example in Gerhard W. Becker and Dietrich Braun, Kunststoffhandbuch, Volume 7, "Polyurethane", Carl Hanser Verlag, Kunststoff, Vienna, 1993.
  • the thermoplastic polyurethane is prepared by reaction of a mixture of isocyanates with isocyanate-reactive compounds, preferably having a molecular weight of from 0.5 kg / mol to 10 kg / mol as monomers or oligomers and optionally chain extenders, preferably with a molecule. large weight of 0.05 kg / mol to 0.5 kg / mol.
  • at least one chain regulator, a catalyst and optionally at least one filler, auxiliary and / or additive are added to the mixture for the preparation of the thermoplastic polyurethane.
  • a mixture of isocyanates and isocyanate-reactive compounds is required for the production of thermoplastic polyurethane.
  • the invention therefore provides a process for producing particle foams by thermal bonding of the above-described foam particles according to the invention by steam or irradiation of high-frequency electromagnetic radiation.
  • foam particles and particle foams based on thermoplastic elastomers in particular thermoplastic polyurethanes (TPU), having a smooth and glossy surface can be obtained.
  • TPU thermoplastic polyurethanes
  • the reaction of the educts is driven so far by the reaction that are injected with a distance of 14 D before the end of the main extruder as blowing agent 0.49 g / min of nitrogen and 2.1 g / min of carbon dioxide by Gasdosierstationen in the melt.
  • the melt is thawed after the tenth zone by means of a recirculating screw element.
  • the blowing agent-containing melt is forced through the perforated plate of an underwater pelletizer.
  • the diameter of the holes is 2.5 mm.
  • the perforated plate is heated to 190 ° C.
  • a rotating knife in the granulation chamber generates foam particles with a particle weight of 25 mg.
  • the particles are discharged from the granulation chamber with a granulating liquid having a pressure of 4 bar and a temperature of 30 ° C and conveyed to a centrifugal dryer, where they are separated from the water and dried.
  • the bulk density of the expanded foam particles is 130 g / l.
  • Measuring methods To determine the bulk density, a 2000 ml vessel was filled with the expanded particles and the weight was determined by means of a balance. It can be assumed that an accuracy of ⁇ 5 g / l.
  • test specimens The density of the test specimens (foam boards) was determined according to DIN EN ISO 1 183-1, A.
  • the compression hardness of the foam panels was measured in accordance with DIN EN ISO 3386 at 10%, 25%, 50% and 75% compression.
  • Table 1 Composition and cell morphology of the expanded TPU foam particles of Examples 1-4 and the comparative experiment

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  • Chemical Kinetics & Catalysis (AREA)
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  • Mechanical Engineering (AREA)
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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne des particules de mousse à base d'élastomères thermoplastiques contenant au moins un siloxane modifié par aryle, ainsi que des procédés de fabrication de ces particules de mousse et des mousses particulaires pouvant être obtenues par soudage des particules de mousse à la vapeur d'eau ou exposition à un rayonnement électromagnétique à haute fréquence, ou par collage au moyen d'adhésifs réactifs, d'adhésifs contenant des solvants ou d'adhésifs en dispersion.
EP17787204.1A 2016-11-04 2017-10-25 Mousses particulaires à base d'élastomères thermoplastiques expansés Withdrawn EP3535316A1 (fr)

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PCT/EP2017/077297 WO2018082984A1 (fr) 2016-11-04 2017-10-25 Mousses particulaires à base d'élastomères thermoplastiques expansés

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CN110204769B (zh) * 2019-05-16 2021-10-29 美瑞新材料股份有限公司 一种发泡热塑性聚硅氧烷-聚氨酯嵌段共聚物及其制备方法和应用
CN117157349A (zh) 2021-04-22 2023-12-01 巴斯夫欧洲公司 用于制备涂覆成型体的方法和涂覆成型体的用途
WO2024083787A1 (fr) 2022-10-18 2024-04-25 Basf Se Particules enrobées stables au stockage et leur préparation

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