Classifications

• • 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
  • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
  • C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
• • 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
  • C08G18/30—Low-molecular-weight compounds
• • 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
• • 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
  • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
  • C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
• • 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
  • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0008—Foam properties flexible
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2190/00—Compositions for sealing or packing joints
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/1376—Foam or porous material containing

Definitions

• the present invention relates to cellular materials, more particularly to flexible and flexible materials made of expanded polyurethane polymer, in particular those that can be used for producing sealing, insulating and / or damping elements.
• Such materials are applicable inter alia in the automotive industry and in the industries of manufacturing various electrical utensils. Examples of application of the automotive industry include foam seals that are intended to be adapted to models of doors, door cladding, headlights, air conditioners, etc.
• foamed polyurethane joints is carried out by extrusion removal on the part to be provided with the seal of a suitable viscosity material which develops in foam by crosslinking in the open air or in a controlled atmosphere, the application material that can be made in a groove, a shape or a smooth surface.
• Coated foams can also be produced, the material of suitable viscosity being deposited by web extrusion on a support such as paper or glass cloth impregnated with silicone, fluorinated product, etc., or a plastic film, and then, after adjustment of the layer in thickness, foaming and crosslinking of the product, the sheet is peeled and then cut to the desired joint dimensions.
• the foam is coated on a non-stick substrate, such as a polyester film, which is an integral part of the finished cell product.
• the material to be deposited can be prepared in advance and be in a stable form, storable under inert atmosphere until use. Such a system is called “monocomponent”. Or the material to deposit consists of components stored separately from each other and mixed in appropriate amounts just prior to application through dosing and mixing facilities. The system is called “two-component”. For a more detailed description of these techniques, reference may be made to European Patent 0 930 323 B1 in the name of the applicant company.
• foamed materials must meet numerous tests to verify that their mechanical properties, their temperature resistance and their resistance to aging, especially in a humid environment meet standards established by car manufacturers. These standards are becoming more severe.
• the present invention therefore firstly relates to the use of at least one polyol (P) chosen from polyesters and polyether polyols grafted with chains of at least one of polystyrene, polyacrylonitrile and copolymers of styrene and acrylonitrile, and polyesters and polyether polyols in which at least one of polystyrene, polyacrylonitrile and styrene copolymers and acrylonitrile, as part of the formulation of the polyol component or of the polyol-polyamine component of a polyurethane forming the polymer matrix of a flexible hydrolysis-resistant cellular material, said at least one polyol (P) representing at least a part of of said polyol component or at least a portion of the polyol moiety of said polyol-polyamine component.
• P polyol
• copolymer of styrene and acrylonitrile is meant both random copolymers and block copolymers and combinations thereof.
• the polyols (P) according to the invention are in particular polyether-and polyesters-polyols on the backbone of which are grafted segments derived from at least one of styrene and acrylonitrile.
• the backbones of polyethers and polyester polyols are, for example, poly (ethylene oxide), poly (propylene oxide) or poly (propylene oxide-ethylene oxide).
• the backbone is a copolymer incorporating ethylene oxide units and propylene oxide units, such copolymers being block copolymers in which an ethylene oxide oligomer is attached to a propylene oxide oligomer, random copolymers wherein the ethylene oxide subunits and the propylene oxide subunits are randomly dispersed, or polymers which are a combination of block polymers and random polymers.
• graft polyether polyols examples are found in US-A-4,670,477 in which they are described as modified polyether polyols. Also disclosed are poly (ethylene oxide / propylene oxide) ether polyols in which at least one of polystyrene and polyacrylonitrile is dispersed. Graft polyols can be found commercially in a number of companies. Polyols called “Polymer Polyol” by the Bayer Company, those called “Graft Polyol” by the BASF Company and those called “Co-polymer Polyol” by the Dow Company.
• the polyol (s) (s) advantageously represent at least 5% by weight, especially 10% by weight of the polyol component or of the polyol-polyamine component of the prepolymer polyurethane.
• the cellular material may be in the form of tape, plate, strand or seal tube, or seal, seal, insulation or cushioning part.
• the present invention also relates to a composition intended to form the polyurethane polymer matrix of a flexible cellular material resistant to hydrolysis, characterized in that it comprises:
• A a polyol component formed of at least one polyol having a functionality of at least 2 or a polyol-polyamine component consisting of at least one functional polyol of at least 2 and at least one functional polyamine of at least less than 2, at least a part of said polyol component or of the polyol fraction of said polyol-polyamine component being formed by at least one polyol (P) chosen from polyesters and polyether-polyols grafted with chains of at least l one of polystyrene, polyacrylonitrile and copolymers of styrene and acrylonitrile, and polyesters and polyether polyols in which at least one of polystyrene, polyacrylonitrile and copolymers of styrene and acrylonitrile is dispersed; ,; and
• (B) a polyisocyanate component, the amounts of constituents (A) and (B) being chosen in particular so that said constituents (A) and (B) are capable of reacting in a molar ratio of NCO / (OH + NH 2 ) at least 2, in particular of the order of 2 to 5, preferably 2 to 3.5.
• the one or more polyols other than the polyols (P) and the polyamines that may be included in the formulation of the constituent (A) may be chosen from polyols and polyamines having a backbone of the polyester, polycaprolactone, polyether or polyolefin type, for example.
• hydroxylated EVA copolymer saturated or unsaturated polybutadiene, polyisoprene, polydimethylsiloxane, for example of the type: aliphatic and / or aromatic polyester, preferably substantially aliphatic, in particular derived from aliphatic glycols, optionally diethylene glycol, and from aliphatic and / or aromatic acids ; or polyether, especially polyethylene oxide and / or propylene or polytetrahydrofuran.
• the polyol or polyol-polyamine component is advantageously an oligomer with a molecular mass of less than or equal to about 100 000 g / mol, preferably of the order of 500 to 4000 g / mol, in particular of 1500 to
• Its functionality is preferably of the order of 2 per higher value, in particular from 1500 to 3500 g / mol.
• Constituent (B) may be chosen from simple molecules, in particular aromatic, bearing at least two isocyanate functional groups, as well as oligomers (of molecular weight that may be chosen in particular from the ranges indicated above), the isocyanates above modified in the form of prepolymers, and the prepolymer isocyanates, these oligomers and prepolymers, of functionality at least 2, having isocyanate end groups.
• (B) can thus be chosen from para-phenylene diisocyanate, trans-1,4-cyclohexane diisocyanate, 3-isocyanate-methyl-3, 5-trimethylcyclohexyl isocyanate, naphthalene-1,5-diisocyanate, methylene-bis-4-phenylisocyanate (pure MDI), crude MDI, 2,4-toluene diisocyanate (TDI 2,4), 2,6-toluene diisocyanate (TDI 2,6) and mixtures thereof, such as TDI 80/20 comprising 80% isomer 2, 4 or TDI 65/35, as well as crude TDI (TDI 80/20 unpurified).
• the functionality is preferably of the order of 2 per larger value, in particular of the order of 2 to 2.8.
• composition according to the invention may furthermore comprise at least one usual additive chosen from particulate or pulverulent, organic or inorganic fillers, such as calcium carbonate and carbon black; plasticizers, dyes, stabilizers, surfactants, cell regulators and catalysts, said additive or additives being generally combined with component (A).
• particulate or pulverulent, organic or inorganic fillers such as calcium carbonate and carbon black
• plasticizers, dyes, stabilizers, surfactants, cell regulators and catalysts said additive or additives being generally combined with component (A).
• charge here generally means a product neither soluble nor miscible in the polymer matrix, dispersible in the latter, which makes it possible to improve one or more properties or characteristics.
• composition according to the invention is in the form of a viscous paste (one-component product) consisting of the isocyanate-terminated polyurethane prepolymer resulting from the reaction of the constituents (A). and (B) optionally incorporating at least one additive.
• a viscous paste one-component product
• Such a reaction is well known to those skilled in the art, the temperatures and reaction times being variable depending on the constituents used.
• the isocyanate-terminated polyurethane prepolymer may alternatively be subjected to a trialkoxysilylation reaction to give a trialkoxysilyl terminated prepolymer polyurethane.
• a trialkoxysilane capable of reacting with an NCO group may be a trialkoxyaminosilane, for example an aminopropyl trialkoxysilane, such as aminopropyl trimethoxysilane or a trialkoxymercaptosilane.
• (B) are intended to be mixed just before use (two-component system) in the presence of water as a foaming agent, said mixture being then extruded at the time of application on the part or the support to give the cellular material .
• the present invention also relates to a process for producing a cellular material by extrusion of a composition as defined above, characterized in that it comprises the steps consisting of:
• the gas under pressure may preferably be nitrogen, but also any other gas known for this purpose: air, carbon dioxide, n-pentane, etc.
• the wet crosslinking treatment can be carried out under conditions known to those skilled in the art, for example in a temperature range from room temperature to 80 ° C., in an atmosphere having a relative humidity of the order of 40 to 80.degree. 100%.
• the present invention also relates to a process for producing a cellular material by extrusion of a composition as defined above, characterized in that it comprises the steps of:
• the extrudable material may be deposited on a part intended to receive it, in particular it may be deposited material following a band or strand or ring to form a seal, insulation or damping on said piece.
• step (d) of the first process mentioned above or in step (b) of the second process mentioned above it is also possible to deposit the extrudable material in a strip, a sheet or a wafer on a support such as paper or a fabric of glass impregnated with silicone, fluorinated product, etc., or a plastic film, possibly passing the support-extruded material assembly between two rollers to adjust the thickness thereof, and then detach the foamed extruded material possibly cut to forms and desired dimensions for the seal, insulation or damping.
• a support such as paper or a fabric of glass impregnated with silicone, fluorinated product, etc., or a plastic film
• extrusion is meant here in a broad sense a technique in which a material is conveyed in the fluid or viscous state to an application orifice or nozzle.
• This term does not limit the invention to a conformation technique of the material, the latter being free to adopt at the outlet of the orifice dimensions substantially different from those of the outlet of the nozzle.
• the present invention finally relates to a hydrolysis resistant cellular material obtained by extrusion of an isocyanate-terminated polyurethane prepolymer, the foaming having been carried out by injection of gas under pressure and / or by chemical reaction between the water and said isocyanate end groups, at least one polyol
• polystyrene selected from polyesters and polyether polyols grafted with chains of at least one of polystyrene, polyacrylonitrile and copolymers of styrene and acrylonitrile, and polyesters and polyether polyols in which is dispersed at least one of polystyrene, polyacrylonitrile and copolymers of styrene and acrylonitrile, having entered into the formulation of the polyol component or polyol-polyamine component of a polyurethane forming the polymeric matrix of said cellular material, said or said polyols (P) representing at least a portion of said polyol component or at least a portion of the polyol moiety of said polyol-polyamine component.
• the cellular material is advantageously in the form of a ribbon, a plate, a strand or tube for sealing, insulating and / or damping.
• a polyurethane prepolymer is prepared by reacting a polyether grafted with a styrene-acrylonitrile copolymer with methylene-bis-4-phenylisocyanate (MDI).
• MDI methylene-bis-4-phenylisocyanate
• This grafted polyether is the one marketed in the Lupranol range by BASF; it is characterized by an OH number of approximately 19.8 (expressed in mg of KOH per gram of product).
• the MDI used is a mixture of pure MDI having a functionality of 2.0 and an NCO isocyanate group content of 33.5% (in% by weight of NCO equivalents per gram of product) and crude MDI having a functionality of 2.7 and an NCO isocyanate group content of 31.5% (in% by weight of NCO equivalents per gram of product).
• the crude MDI represents 24% by weight of the total weight of the isocyanates.
• an amine catalyst is added at a rate of 0.275% of the product, 0.4% of carbon black and 0.25% of a silicone surfactant. After homogenization, the product is conditioned rapidly in a dry atmosphere.
• the single-component product prepared above was extruded in the presence of nitrogen under pressure in a foaming machine of the type described in EP-A-0 654 297, comprising: a stock of product and means for heating said product to its temperature of extrusion; a mixing device provided with a viscous product supply duct and a pressurized nitrogen supply duct; and
• the nitrogen dissolves in the single-component product.
• the material is exposed to atmospheric pressure, causing the release of the nitrogen by expansion with the formation of gas bubbles that expand the polymer.
• the extrusion conditions are adapted to form an extruded strand about 6 mm in diameter.
• the nozzle is heated to 35 ° C. so as to maintain the viscosity of the material at the desired value at the outlet of the extrusion channel.
• the extrusion operation is followed by a wet crosslinking step of the extruded strand in two types of conditions: at room temperature and relative humidity of the order of 50 to 60%, or in a hot atmosphere, for example at a temperature of 55 ° C. to 60 ° C. and at a relative humidity of 85% to 95% in a suitable enclosure.
• the elongation was measured on rods 6 mm in diameter according to DIN 53571 with a stretching speed of 300 mm / minute, the spacing between the clamps being 100 mm.
• Example 2 The procedure was as in Example 1 (same NCO / OH molar ratio), except that, in place of the grafted polyol, this same graft polyol was used mixed with a polyether based on an ethylene oxide / propylene mixture. oxide.
• the polyether based on an ethylene oxide / propylene oxide mixture is that sold under the trade name Lupranol by the company BASF; it is characterized by an OH number of approximately 28 (expressed in mg of KOH per gram of product).

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Polyurethanes Or Polyureas (AREA)
• Sealing Material Composition (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2005
  • 2005-08-17 FR FR0552529A patent/FR2889848B1/fr active Active
• 2006
  • 2006-08-03 JP JP2008526576A patent/JP2009504870A/ja not_active Withdrawn
  • 2006-08-03 WO PCT/IB2006/052674 patent/WO2007020552A1/fr active Application Filing
  • 2006-08-03 US US12/063,823 patent/US20100260956A1/en not_active Abandoned
  • 2006-08-03 CN CN2013100332854A patent/CN103130975A/zh active Pending
  • 2006-08-03 BR BRPI0614313-0A patent/BRPI0614313A2/pt not_active IP Right Cessation
  • 2006-08-03 MX MX2008002131A patent/MX2008002131A/es active IP Right Grant
  • 2006-08-03 KR KR1020087006376A patent/KR101351658B1/ko not_active IP Right Cessation
  • 2006-08-03 CN CNA2006800297191A patent/CN101283013A/zh active Pending
  • 2006-08-03 EP EP06780300A patent/EP1917284A1/fr not_active Withdrawn
• 2014
  • 2014-01-17 JP JP2014006728A patent/JP2014088577A/ja not_active Withdrawn
• 2016
  • 2016-03-16 JP JP2016052627A patent/JP6243460B2/ja not_active Expired - Fee Related

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