EP4077447A1 - Polymère pour augmenter de la résistance électrique d'une composition de polyuréthane - Google Patents

Polymère pour augmenter de la résistance électrique d'une composition de polyuréthane

Info

Publication number
EP4077447A1
EP4077447A1 EP20829896.8A EP20829896A EP4077447A1 EP 4077447 A1 EP4077447 A1 EP 4077447A1 EP 20829896 A EP20829896 A EP 20829896A EP 4077447 A1 EP4077447 A1 EP 4077447A1
Authority
EP
European Patent Office
Prior art keywords
weight
meth
poly
urethane polymer
moisture
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
EP20829896.8A
Other languages
German (de)
English (en)
Inventor
Marc Balmer
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.)
Sika Technology AG
Original Assignee
Sika Technology AG
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 Sika Technology AG filed Critical Sika Technology AG
Publication of EP4077447A1 publication Critical patent/EP4077447A1/fr
Pending legal-status Critical Current

Links

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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
    • C08G18/08—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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/285—Nitrogen containing compounds
    • C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
    • 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
    • C08G18/302—Water
    • C08G18/307—Atmospheric humidity
    • 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
    • C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
    • 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
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/4825—Polyethers containing two hydroxy 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
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy 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
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end 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
    • C08G18/48—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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • 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
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/715—Monoisocyanates or monoisothiocyanates containing sulfur in addition to isothiocyanate sulfur
    • 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
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from 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
    • C08G2170/00—Compositions for adhesives
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/14—Glass
    • C09J2400/143—Glass in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane

Definitions

  • the invention relates to low-monomer polyurethane polymers and their use in moisture-curing polyurethane compositions, in particular for use as an adhesive for bonding the windows of vehicles.
  • Curable compositions based on polyurethanes are often used as adhesives for elastic bonds, for example in vehicle construction. Good properties are required for this, in particular with regard to storage stability, applicability, open time, curing speed, adhesion, strength, elasticity, weather resistance and classification of hazardous substances.
  • Polymers containing isocyanate groups such as are present as binders in one-component polyurethane adhesives and harden through reaction with moisture, are generally produced by reacting polyols with monomeric diisocyanates. As a result of chain extension reactions, such polymers contain a residual content of monomeric diisocyanates, typically in the range from 0.5 to 3% by weight.
  • Monomeric diisocyanates are potentially harmful to health. Preparations containing monomeric diisocyanates must be provided with hazard symbols and warning notices on the label and in the data sheets, especially from a concentration of 0.1% by weight, and in some countries they can only be sold and used under certain conditions.
  • Moisture-curing elastic one-component polyurethane adhesives for industrial applications in particular in the area of window bonding, usually contain a high proportion of carbon black, which is particularly important for the excellent mechanical properties, such as increased tensile strength, and the good application properties Thixotropy, is responsible.
  • Carbon black as a thixotropic, reinforcing filler however, has the disadvantage that, from a certain percentage onwards, the electrical conductivity of the polyurethane composition is significantly increased, or the electrical resistance (volume resistance) is significantly reduced.
  • WO 2002053671 A1 teaches that the use of a short MDI prepolymer made from a polycarbonate diol and diphenylmethane diisocyanate (MDI) has a positive influence on the antenna properties (lowering the impedance) and the volume resistance (increasing the volume resistance) of polyurethane adhesives .
  • MDI polycarbonate diol and diphenylmethane diisocyanate
  • the polycarbonate prepolymer taught in this patent application has the disadvantage that, due to the manufacturing process, it contains a residual MDI content of approx. 10-15%, which is a major regulatory factor Brings disadvantages.
  • the high isocyanate content can also lead to increased bubble formation during curing.
  • the strong influence on the mechanical properties of the adhesive is also disadvantageous in many cases and the electrical properties achieved can still be improved.
  • No. 5,508,372 discloses isocyanate group-containing polyacrylate urethane polymers based on aliphatic polyisocyanates, in particular HDI, and suitable for coatings. A use of these polymers in adhesives to increase the volume resistance or to reduce the impedance is not taught.
  • JP 5696397 discloses primer compositions containing an isocyanate group-containing polyacrylate urethane polymer based on aliphatic polyisocyanates, in particular IPDI. A use of these polymers in adhesives to increase the volume resistance or to reduce the impedance is not taught.
  • the object of the present invention is to provide an additive for moisture-curing elastic polyurethane adhesives which can be processed at room temperature, which additive increases the volume resistance of such adhesives and reduces the impedance without any loss of other relevant product properties, in particular applicability, curing speed, blistering, strength, Extensibility, elasticity and classification of hazardous substances to cause.
  • the polymer is based on a monomeric diisocyanate, in particular 4,4'-diphenylmethane diisocyanate, and a poly (meth) acrylate polyol with an OFI number in the range from 50 to 200 mg KOFI / g. It has an NCO content in the range from 2.5 to 8% by weight and a monomeric diisocyanate content of at most 0.5% by weight.
  • the polymer according to the invention can be processed at room temperature and is very suitable as an additive for polyurethane compositions.
  • Poly (meth) acrylate urethane polymer An even better effect on the electrical properties, as well as better application properties and better mechanical values of the adhesive, are obtained by blocking the isocyanate groups of the poly (meth) acrylate urethane polymer with an alcohol (e.g. methanol) or an amine (e.g. butylamine).
  • an alcohol e.g. methanol
  • an amine e.g. butylamine
  • Blocking the polyol by acetylation or by reaction with a monoisocyanate eg p-toluenesulfonyl isocyanate
  • a monoisocyanate eg p-toluenesulfonyl isocyanate
  • the invention relates to an isocyanate group-containing poly (meth) acrylate urethane polymer obtained from the reaction of at least one monomeric diisocyanate and a poly (meth) acrylate polyol with an OH number in the range from 50 to 200 mg KOH / g in an NCO / OH ratio of at least 3/1 and subsequent removal of a large part of the monomeric diisocyanate by means of a suitable separation process, characterized in that it has an NCO content in the range from 2.5 to 8% by weight based on the poly (meth) acrylate urethane polymer , and has a content of monomeric diisocyanates of at most 0.5% by weight.
  • a “monomeric diisocyanate” is an organic compound with two isocyanate groups that are separated from one another by a divalent hydrocarbon radical with 4 to 15 carbon atoms.
  • a polymer is referred to as “poly (meth) acrylate urethane polymer” which has (meth) acrylate groups as repeating units and additionally contains urethane groups.
  • a “poly (meth) acrylate polyol” is a poly (meth) acrylate polymer which has several hydroxyl groups.
  • the “NCO content” refers to the content of isocyanate groups in% by weight based on the entire polymer.
  • Molecular weight is the molar mass (in grams per mole) of a molecule or a remnant of a molecule.
  • Average molecular weight is the number average molecular weight (M n ) of a polydisperse mixture of oligomeric or polymeric molecules or molecular residues. It is determined by means of gel permeation chromatography (GPC) against polystyrene as the standard.
  • GPC gel permeation chromatography
  • a substance or a composition is referred to as “storage-stable” or “storable” if it can be stored at room temperature in a suitable container for a longer period of time, typically for at least 3 months, in particular up to 6 months and more, without it changes in its application or usage properties through storage to an extent relevant to its use.
  • room temperature A temperature of 23 ° C is referred to as “room temperature”.
  • Suitable poly (meth) acrylate polyols for the production of the poly (meth) acrylate urethane polymer are preferably exclusively poly (meth) acrylate polyols, although small amounts of other polyols can also be used.
  • the polyols used to produce the poly (meth) acrylate urethane polymer should preferably consist of at least 90% by weight, in particular at least 95% by weight, most preferably 100% by weight, of poly (meth) acrylate polyols.
  • Poly (meth) acrylate polyols can be polyacrylate polyols or polymethacrylate polyols.
  • the at least one poly (meth) acrylate polyol has an OH number of at least 50, preferably at least 75, in particular at least 100, most preferably at least 120. Furthermore, the poly (meth) acrylate polyol has an OH number of at most 200, in particular at most 175, most preferably at most 150.
  • OH number, OH functionality and equivalent weight of polyols are related.
  • Equivalent weight Mn / OH functionality (II) where the OH number (hydroxyl number) is defined as the amount of potassium hydroxide in milligrams, which is equivalent to the amount of acetic acid bound in the acetylation of one gram of polyol, and
  • M n is the number average molecular weight of the polyol. Both formulas (I) and (II) allow the calculation of the equivalent weight. The values required for the calculation are available experimentally (M n , OH number) or are made known by the manufacturer of the polyols (M n , OH functionality).
  • small amounts of low molecular weight di- or polyhydric alcohols such as 1,2-ethanediol, 1,2- and 1,3-propanediol can be used , Neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1, 3- and 1,4-cyclohexanediols, dimeric alcohols, bisimethanol, hydrogenated bisimethanol, hydrogen
  • the poly (meth) acrylate polyol preferably has an average OH functionality of 3.5 to 4.5.
  • Suitable poly (meth) acrylate polyols are commercially available, for example under the name of Joncryl ® from BASF.
  • the poly (meth) acrylate urethane polymer according to the invention preferably has a monomeric diisocyanate content of at most 0.3% by weight, in particular at most 0.2% by weight.
  • Such a polymer is particularly suitable for use in polyurethane compositions with less than 0.1% by weight of monomeric diisocyanates; these are safe to use even without special protective measures and can be sold in many countries without a hazardous substance classification.
  • aromatic, aliphatic or cycloaliphatic diisocyanates in particular 4,4'-diphenylmethane diisocyanate, optionally with proportions of 2,4'- and / or 2,2'-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate or mixtures, are suitable as monomeric diisocyanates of which with 2,6-tolylene diisocyanate (TDI), 1,4-phenylene diisocyanate (PDI), naphthalene-1,5-diisocyanate (NDI), 1,6-hexane diisocyanate (HDI), 2, 2 (4), 4-trimethyl 1,6-hexamethylene diisocyanate (TMDI), cyclohexane-1,3 or 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPD
  • the monomeric diisocyanate used for the reaction is preferably 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4-tolylene diisocyanate or mixtures thereof with 2,6-tolylene diisocyanate (TDI), 1-isocyanato-3,3, 5- trimethyl-5-isocyanatomethylcyclohexane (IPDI) or 1,6-hexane diisocyanate (HDI).
  • 4,4'-MDI 4,4'-diphenylmethane diisocyanate
  • TDI 2,4-tolylene diisocyanate
  • IPDI 1-isocyanato-3,3, 5- trimethyl-5-isocyanatomethylcyclohexane
  • HDI 1,6-hexane diisocyanate
  • IPDI is particularly preferred.
  • a polymer is particularly suitable in moisture-curing polyurethane compositions with particularly high light stability.
  • the most preferred monomeric diisocyanate is 4,4'-MDI.
  • the 4,4'-MDI is in particular of a quality which contains only small proportions of 2,4'- and / or 2,2'-diphenylmethane diisocyanate and is solid at room temperature.
  • Such a polymer hardens particularly quickly and enables particularly high strengths.
  • the polymer according to the invention is obtained from the reaction of at least one monomeric diisocyanate and the poly (meth) acrylate polyol in an NCO / OH ratio of at least 3/1.
  • the NCO / OH ratio is preferably in the range from 3/1 to 10/1, particularly preferably 3/1 to 8/1, in particular 4/1 to 7/1, most preferably 4/1 to 6/1.
  • the reaction is preferably carried out with exclusion of moisture at a temperature in the range from 20 to 160 ° C., in particular from 40 to 140 ° C., if appropriate in the presence of suitable catalysts.
  • the monomeric diisocyanate remaining in the reaction mixture is removed by means of a suitable separation process, except for the residual content described.
  • a preferred separation process is a distillative process, in particular thin-film distillation or short-path distillation, preferably with the application of a vacuum.
  • a multi-stage process in which the monomeric diisocyanate is removed in a short-path evaporator at a jacket temperature in the range from 120 to 200 ° C. and a pressure of 0.001 to 0.5 mbar is particularly preferred.
  • the preferred monomeric diisocyanate removal by distillation is particularly difficult. For example, it must be ensured that the condensate does not solidify and clog the system.
  • a jacket temperature in the range from 160 to 200 ° C. is preferred 0.001 to 0.5 mbar and the removed monomer is condensed at a temperature in the range from 40 to 60 ° C.
  • reaction of the monomeric diisocyanate with the poly (meth) acrylate polyol and the subsequent removal of most of the monomeric diisocyanate remaining in the reaction mixture preferably take place without the use of solvents or entrainers.
  • the monomeric diisocyanate removed after the reaction is then preferably reused, i.e. reused for the production of isocyanate group-containing polymer.
  • the polymer according to the invention is typically liquid at room temperature. It preferably has a viscosity at 20 ° C. of not more than 1 ⁇ 00 Pa s, in particular not more than 500 Pa s.
  • the viscosity is determined using a cone-plate viscometer with a cone diameter 25 mm, cone angle 1 °, cone tip-plate distance 0.05 mm at a shear rate of 50 s- 1 .
  • the OH groups of the poly (meth) acrylate polyol react with the isocyanate groups of the monomeric diisocyanate.
  • chain lengthening reactions in which OH groups and / or isocyanate groups of reaction products between polyol and monomeric diisocyanate react.
  • a measure of the chain extension reaction is the average molecular weight of the polymer or the width and distribution of the peaks in the GPC analysis. Another measure is the effective NCO content of the monomer-free polymer in relation to the theoretical NCO content calculated from the reaction of each OH group with a monomeric diisocyanate.
  • the NCO content in the poly (meth) acrylate urethane polymer according to the invention is preferably at least 75%, in particular at least 80% of the theoretical NCO content, which is calculated from the addition of one mole of monomeric diisocyanate per mole of OH groups of the poly (meth) acrylate polyol.
  • Such a polymer has a low viscosity and enables good application properties.
  • the poly (meth) acrylate urethane polymer according to the invention is initially isocyanate-functional after the production described above, that is to say has free isocyanate groups.
  • the content of NCO groups is in the range from 2.5 to 8% by weight, based on the poly (meth) acrylate urethane polymer.
  • the poly (meth) acrylate urethane polymer according to the invention can be used directly as an additive in moisture-curing polyurethane compositions.
  • these free NCO groups of the poly (meth) acrylate urethane polymer according to the invention are blocked in an additional reaction step with a monoalcohol or a monoamine with the formation of urethane or urea bonds.
  • the monoalcohol or the monoamine is preferably used in a stoichiometric excess with respect to the NCO groups of the poly (meth) acrylate urethane polymer and is preferably reacted at an elevated temperature and / or optionally using a known catalyst.
  • the excess monoalcohol or the excess monoamine is removed, preferably by distillation or under vacuum.
  • the NCO groups originally present are at least partially, preferably completely, converted to urethane or urea bonds.
  • This reaction does not adversely affect the inventive effect on the electrical properties of a polyurethane adhesive mixed therewith, but rather even improves it in comparison with a poly (meth) acrylate urethane polymer containing NCO groups, while the mechanical properties of the polyurethane adhesive can also be improved.
  • the poly (meth) acrylate urethane polymers partially or completely blocked in this way have the advantage over the unblocked polymers according to the invention that they enable even better electrical properties in the adhesive and, moreover, improve the mechanical properties and application properties of the adhesive even more than they do not blocked polymers according to the invention.
  • the poly (meth) acrylate urethane polymer according to the invention is preferably liquid at room temperature and is therefore easy to handle and, due to the low monomer content, has no or only a mild hazard classification and is suitable as an additive in moisture-curing elastic polyurethane adhesives, where it also has the electrical properties the adhesives improved.
  • Another object of the invention is a moisture-curing polyurethane composition which is suitable as an elastic adhesive and / or sealant containing - at least one isocyanate-containing polyether urethane polymer, and
  • the moisture-curing polyurethane composition preferably contains 0.5 to 15.0% by weight, preferably 1.0 to 10.0% by weight, in particular
  • Suitable polyether urethane polymers containing isocyanate groups are all polyoxyalkylene-based polyurethane polymers with NCO groups, for example those based on polypropylene glycol, polyethylene glycol and polytetramethylene ether glycols as polyols.
  • a polyether urethane polymer with a majority of polyoxypropylene structural units is particularly suitable.
  • Such a polymer is particularly suitable as the main binder for elastic adhesives and / or sealants with high extensibility.
  • the polyether segments in the polyether urethane polymer preferably consist of at least 80% 1,2-propyleneoxy units and optionally additionally 1,2-ethyleneoxy units.
  • the polyether urethane polymer containing isocyanate groups preferably has an average molecular weight in the range from 200 to 2000 g / mol, preferably from 300 to 1500 g / mol.
  • It is preferably liquid at room temperature.
  • the polyether urethane polymer containing isocyanate groups preferably has an NCO content in the range from 1 to 5% by weight, in particular from 1 to 3% by weight.
  • a suitable polyether urethane polymer containing isocyanate groups is obtained in particular from the reaction of at least one polyether polyol with a more than stoichiometric amount of at least one monomeric diisocyanate.
  • the reaction is preferably carried out with exclusion of moisture at a temperature in the range from 20 to 160 ° C., in particular from 40 to 140 ° C., if appropriate in the presence of suitable catalysts.
  • the NCO / OH ratio is preferably in the range from 1.3 / 1 to 10/1.
  • the monomers diisocyanate remaining in the reaction mixture after the conversion of the OH groups can be removed, in particular by means of distillation.
  • the NCO / OFI ratio in the reaction is preferably in the range from 3/1 to 10/1, in particular 4/1 to 7/1, and the isocyanate group-containing one obtained After the distillation, polymer contains preferably at most 0.5% by weight, particularly preferably at most 0.3% by weight, of monomeric diisocyanate.
  • monomeric diisocyanate is removed in particular by means of short-path distillation in vacuo.
  • the NCO / OFI ratio in the reaction is preferably in the range from 1.3 / 1 to 2.5 / 1.
  • polymer contains at most 3% by weight, preferably at most 2% by weight, of monomeric diisocyanate.
  • Preferred as monomeric diisocyanate are the aromatic, aliphatic or cycloaliphatic diisocyanates already mentioned, in particular MDI, TDI, HDI or IPDI, or mixtures thereof.
  • Suitable polyether polyols are commercially available polyols or mixtures thereof, in particular polymerization products of ethylene oxide or 1,2-propylene oxide or 1,2 or 2,3-butylene oxide or oxetane or tetrahydrofuran or mixtures thereof, these using a starter molecule with two or three active hydrogen atoms can be polymerized, in particular a starter molecule such as water, ammonia or a compound with several OFI or NFI groups such as 1,2-ethanediol, 1,2- or 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols or tripropylene glycols, the isomeric butanediols, pentanediols, flexanediols, fleptan
  • Preferred polyether polyols are polyoxypropylene diols or polyoxypropylene triols, or so-called ethylene oxide-terminated (EO-capped or EO-tipped) polyoxypropylene diols or triols. The latter are
  • Polyoxyethylene-polyoxypropylene mixed polyols which are obtained in particular by further alkoxylating polyoxypropylene diols or triols with ethylene oxide after the polypropoxylation reaction has ended and thereby have primary hydroxyl groups.
  • polyether polyols having an average molecular weight in the range from 400 to 20-00 g / mol, in particular from 100 to 15-00 g / mol.
  • Polyether polyols with an average OH functionality in the range from 1.6 to 3 are preferred.
  • the polyether urethane polymer containing isocyanate groups contains only a small amount of monomeric diisocyanates. It preferably contains at most 0.5% by weight, particularly preferably at most 0.3% by weight, in particular at most 0.2% by weight, of monomeric diisocyanates. Such a polymer enables polyurethane compositions with a particularly attractive hazard classification.
  • a preferred monomeric diisocyanate is IPDI or 4,4'-MDI, in particular 4,4'-MDI.
  • a preferred monomeric diisocyanate is IPDI or 4,4'-MDI, in particular 4,4'-MDI.
  • a mixture of these two particularly preferred polyether urethane polymers is also particularly preferred.
  • the moisture-curing polyurethane composition preferably also contains at least one further component selected from
  • Melt components Melt components, blocked amines, fillers, plasticizers, diisocyanate oligomers, catalysts and stabilizers.
  • the moisture-curing polyurethane composition preferably additionally contains at least one blocked amine.
  • a suitable blocked amine preferably has at least one aldimino group or oxazolidino group. When it comes into contact with moisture, it reacts with hydrolysis and liberation of the amino group with isocyanate groups present and can promote rapid, bubble-free curing, a particularly non-sticky surface and / or particularly good mechanical properties.
  • Preferred oxazolidines are mono-oxazolidines or bis-oxazolidines, in particular those derived from isobutyraldehyde, benzaldehyde or substituted benzaldehyde, especially benzaldehyde, which is substituted in the para position with an optionally branched alkyl group having 10 to 14 carbon atoms.
  • Suitable aldimines are in particular di- or trialdimines from the reaction of commercially available primary di- or triamines with aldehydes which cannot be enolized. These are aldehydes which have no hydrogen atom in the alpha position to the carbon atom of the aldehyde group.
  • Preferred blocked amines are selected from aldimines of the formula (III) and (IV), where n is 2 or 3, A represents an n-valent, optionally ether-oxygen-containing Koh lenwasserstoffrest with a molecular weight in the range from 28 to 600 g / mol,
  • R 1 and R 2 independently of one another, each represent a monovalent hydrocarbon radical with 1 to 12 carbon atoms or together for a divalent hydrocarbon radical with 4 to 12 carbon atoms, the part of an optionally substituted, carbocyclic ring with 5 to 8, preferably 6 , Carbon atoms, stand,
  • R 3 stands for a hydrogen radical or a linear or branched alkyl, arylalkyl or alkoxycarbonyl radical with 1 to 12 carbon atoms,
  • R 4 represents a hydrogen radical or a monovalent hydrocarbon radical having 1 to 20 carbon atoms
  • R 5 represents an alkyl or alkoxy radical having 6 to 20 carbon atoms.
  • A preferably stands for an aliphatic, cycloaliphatic or arylaliphatic radical, in particular with a molecular weight in the range from 28 to 500 g / mol, in particular for a radical selected from the group consisting of 1,6-hexylene, (1, 5.5- Trimethylcyclohexan-1-yl) methane-1,3,4 (2) -methyl-1,3-cyclohexylene, 1,3-cyclohexylenebis (methylene), 1,4-cyclohexylenebis (methylene), 1,3 -Phenylene-bis (methylene), 1,2-cyclohexylene,
  • R 1 and R 2 are preferably each methyl.
  • R 3 preferably represents a hydrogen radical.
  • R 4 preferably represents methyl or undecyl.
  • R 5 preferably stands for an optionally branched alkyl radical having 10 to 14 carbon atoms in the para position.
  • Particularly preferred blocked amines are selected from the group consisting of N, N'-bis (2,2-dimethyl-3-lauroyloxypropylidene) hexylene-1,6-diamine, N, N'-bis (2,2-dimethyl- 3-acetoxypropylidene) -3-aminomethyl-3,5,5-trimethylcyclohexylamine, N, N'-bis (2,2-dimethyl-3-lauroyloxypropylidene) -3-aminomethyl-3,5,5-trimethylcyclohexylamine, N, N '-Bis (4-Cio-14-alkylbenzylidene) -3-aminomethyl-3,5,5-trimethylcyclohexylamine, N, N'-bis (2,2-dimethyl-3-acetoxy
  • Suitable fillers are in particular ground or precipitated calcium carbonates, which are optionally coated with fatty acids, especially stearates, barytes (heavy spar), quartz flours, quartz sands, dolomites, wollastonites, calcined kaolins, sheet silicates such as mica or talc, zeolites, aluminum hydroxides, magnesium hydroxides, silicic acids including highly dispersed silicas from pyrolysis processes, cements, plaster, fly ash, graphite, metal powder, for example from aluminum, copper, iron, silver or steel, PVC powder or lightweight fillers such as hollow glass spheres or gas-filled hollow plastic spheres (microspheres), in particular those under the trade name Expancel ® (from Akzo Nobel).
  • fatty acids especially stearates, barytes (heavy spar)
  • quartz flours quartz sands, dolomites, wollastonites, calcined kaolins
  • sheet silicates such as mica or talc
  • Suitable plasticizers are in particular carboxylic acid esters such as phthalates, especially diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) or di (2-propylheptyl) phthalate (DPHP), hydrogenated phthalates or 1,2-cyclohexanedicarboxylic acid esters, especially hydrogenated diisononyl phthalate or diisononyl-1 , 2-cyclohexanedicarboxylate (DINCH), terephthalates, especially bis (2-ethylhexyl) terephthalate (DOTP) or diisononyl terephthalate (DINT), hydrogenated terephthalates or 1,4-cyclohexanedicarboxylic acid esters, especially hydrogenated bis (2-ethylhexy
  • Preferred plasticizers are phthalates or plasticizers with a polyether structure.
  • Suitable diisocyanate oligomers are in particular HDI biurets such as Desmo dur ® N 100 or N 3200 (from Covestro), Tolonate ® HDB or HDB-LV (from Vencorex) or Duranate ® 24A-100 (from Asahi Kasei); HDI isocyanurates such as Desmodur ® N 3300, N 3600 or N 3790 BA (all from Covestro), Tolonate ® HDT, HDT-LV or HDT-LV2 (from Vencorex), Duranate ® TPA-100 or THA-100 (from Asahi Kasei ) or Coronate HX ® (vonTosoh Corp.); HDI uretdiones as Desmodur ® N 3400 (from Covestro); HDI Iminooxadiazindiones as Desmodur ® XP 2410 (of Covestro);
  • Suitable catalysts are catalysts for accelerating the reaction of isocyanate groups, in particular organotin (IV) compounds such as, in particular, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, di-butyltin diacetylacetonate, dimethyltin dilaurate, dioctyltin diacetone, or dioctyltin diacetone (IV), or dioctyltin diacetone (IV) or dioctyltin diacetone (IV) butyltin diacetate, dioctyltin diacetate (IV) or ), in particular with ligands selected from alcoholates, carboxylates, 1,3-diketonates, oxinate, 1,3-ketoesterates and 1,3-ketoamidates, or compounds containing tertiary amino groups such as in particular 2,2'-dimorpholinodiethylether
  • suitable catalysts are also catalysts for the hydrolysis of the blocked amino groups, in particular organic acids, in particular carboxylic acids such as 2-ethylhexanoic acid, lauric acid, stearic acid, isostearic acid, oleic acid, neodecanoic acid, benzoic acid, salicylic acid or 2-nitrobenzoic acid, organic carboxylic acid anhydrides such as phthalic anhydride, hexahydrophthalic anhydride or hexahydromethylphthalic anhydride, silyl esters of carboxylic acids, organic sulphonic acids such as methanesulphonic acid, p-toluenesulphonic acid or 4-dodecylbenzenesulphonic acid, or mixtures of the above-mentioned inorganic acids and organic acid esters, sulphonic acid esters.
  • Carboxylic acids are particularly preferred, in particular aromatic carboxylic acids
  • Suitable stabilizers are, in particular stabilizers against oxidation, heat, light or UV radiation, in particular titanium dioxide, iron oxides, zinc oxides, benzophenones, benzotriazoles, compounds having 2,6-di-tert-butylphenol groups, such as for example, under the trade name Irganox ® ( from BASF) are known, compounds with 2, 2,6,6-tetramethylpiperidine groups, so-called HALS (hindered amine light stabilizers), as they are, for example, under the trade name Tinuvin ® (from BASF) are known, or phosphorus-containing compounds, such as are known, for example, under the trade name Irgafos ® (from BASF).
  • Irganox ® from BASF
  • HALS hinderetramethylpiperidine groups
  • Tinuvin ® from BASF
  • phosphorus-containing compounds such as are known, for example, under the trade name Irgafos ® (from BASF).
  • the moisture-curing polyurethane composition can contain further additives, in particular
  • Inorganic or organic pigments in particular titanium dioxide, chromium oxides or iron oxides;
  • Fibers in particular glass fibers, carbon fibers, metal fibers, ceramic fibers, plastic fibers such as polyamide fibers or polyethylene fibers, or natural fibers such as wool, cellulose, hemp or sisal;
  • Nanofillers such as graphene or carbon nanotubes
  • - drying means particularly molecular sieve, calcium oxide, highly reactive isocyanates such as p-tosyl isocyanate, mono-oxazolidines such as lncozol ® 2 (of Incorez) or OrthoameisenTexreester;
  • Adhesion promoters in particular organoalkoxysilanes, in particular epoxysilanes such as in particular 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane, (meth) acrylosilanes, anhydridosilanes, carbamatosilanes, alkyl silanes or iminosilanes, or oligomeric forms of these silanes, or titanates; - Other catalysts which accelerate the reaction of the isocyanate groups;
  • Rheology modifiers in particular thickeners, in particular sheet silicates such as bentonites, derivatives of castor oil, hydrogenated castor oil, polyamides, polyamide waxes, polyurethanes, urea compounds, pyrogenic silicas, cellulose ethers or hydrophobically modified polyoxyethylene;
  • thickeners in particular sheet silicates such as bentonites, derivatives of castor oil, hydrogenated castor oil, polyamides, polyamide waxes, polyurethanes, urea compounds, pyrogenic silicas, cellulose ethers or hydrophobically modified polyoxyethylene;
  • Non-reactive polymers in particular homopolymers or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl (meth) acrylates, in particular polyethylenes (PE), polypropylenes (PP), polyisobutylenes , Ethylene vinyl acetate copolymers (EVA) or atactic poly- ⁇ -olefins (APAO);
  • PE polyethylenes
  • PP polypropylenes
  • EVA Ethylene vinyl acetate copolymers
  • APAO atactic poly- ⁇ -olefins
  • Flame-retardant substances in particular the already mentioned fillers aluminum hydroxide or magnesium hydroxide, and in particular organic phosphoric acid esters such as, in particular, triethyl phosphate, tricresyl phosphate, triphenyl phosphate, diphenyl cresyl phosphate, isodecyl diphenyl phosphate, tris (1,3-dichloro-2-phosphate, 2- chloro-propyl) phosphate, tris (1,3-dichloro-2-phosphate , Tris (2-ethylhexyl) phosphate, tris (chloroisopropyl) phosphate, tris (chloropropyl) phosphate, isopropylated triphenyl phosphate, mono-, bis- or tris (isopropylphenyl) phosphates with different degrees of isopropylation, resorcinol bis (diphenyl phosphate), bisphenol A- bis (dipheny
  • Additives in particular wetting agents, leveling agents, defoamers, deaerators or biocides; or other substances commonly used in moisture-curing polyurethane compositions.
  • the polyurethane composition according to the invention preferably contains little solvent. In particular, it contains less than 5% by weight, preferably less than 2.5% by weight, of solvent. Most preferred is that Polyurethane composition according to the invention essentially free from solvents.
  • the moisture-curing polyurethane composition preferably contains 15 to 60% by weight of polyether urethane containing isocyanate groups
  • soot especially highly structured and / or non-oxidized soot
  • plasticizers - 0 to 35% by weight plasticizers, and optionally other components, in particular blocked amines, diisocyanate oligomers, organosilanes, catalysts or stabilizers.
  • the moisture-curing polyurethane composition preferably contains a total of less than 0.1% by weight of monomeric diisocyanates. Such a composition can be transported and sold in many countries without a hazardous substance classification.
  • the moisture-curing polyurethane composition is produced in particular with the exclusion of moisture and stored in moisture-tight containers at ambient temperature.
  • a suitable moisture-proof container consists in particular of an optionally coated metal and / or plastic and represents in particular a barrel, a container, a hobbock, a bucket, a canister, a can, a bag, a tubular bag, a cartridge or a tube.
  • the moisture-curing polyurethane composition can be in the form of a one-component or in the form of a multi-component, in particular two-component, composition.
  • “One-component” is a composition in which all components of the composition are in the same container and which as such is storage-stable.
  • a composition is referred to as “two-component” in which the constituents of the composition are present in two different components, which are stored in separate containers and are only mixed with one another shortly before or during the application of the composition.
  • the moisture-curing polyurethane composition is preferably one-component. With suitable packaging and storage, it is stable in storage, typically for several months, preferably up to a year or longer.
  • the curing process begins when the moisture-curing polyurethane composition is applied. As a result, the cured composition is formed.
  • the composition can be mixed with an accelerator component which contains water and possibly a catalyst and / or a hardener during application, or the composition can be brought into contact with such an accelerator component after its application.
  • an accelerator component which contains water and possibly a catalyst and / or a hardener during application, or the composition can be brought into contact with such an accelerator component after its application.
  • the isocyanate groups react with one another under the influence of moisture.
  • the moisture-curing polyurethane composition contains a blocked amine
  • the isocyanate groups also react with the hydrolyzing blocked amino groups.
  • the entirety of these reactions of the isocyanate groups leading to the curing of the composition is also referred to as crosslinking.
  • the moisture required for curing the moisture-curing polyurethane composition preferably comes from the air (humidity) by diffusion into the composition.
  • a solid layer of hardened composition (“skin”) forms on the surfaces of the composition that are in contact with air. The hardening continues along the diffusion direction from the outside to the inside, the skin becoming increasingly thick and finally encompassing the entire applied composition.
  • the moisture can additionally or completely also get into the composition from one or more substrate (s) to which the composition has been applied and / or come from an accelerator component that is added to the composition during application or after Application is brought into contact with this, for example by brushing or spraying.
  • the moisture-curing polyurethane composition is preferably applied at ambient temperature, in particular in the range from about -10 to 50.degree. C., preferably in the range from -5 to 45.degree. C., in particular from 0 to 40.degree.
  • the moisture-curing polyurethane composition can also be applied in the heated state, for example at a temperature of about 60.degree.
  • the curing of the moisture-curing polyurethane composition is preferably carried out at ambient temperature.
  • the moisture-curing polyurethane composition has a long processing time (open time) and fast curing.
  • the “open time” is the period of time during which the composition can be processed or reworked after application without any loss of functionality.
  • the open time also denotes, in particular, the period of time within which an adhesive bond must be made after its application in order to build up sufficient adhesion.
  • the open time is at the latest exceeded if a skin has formed or if there is no longer a sufficient build-up of adhesion to the substrates.
  • the moisture-curing polyurethane composition is preferably used as an elastic adhesive and / or sealant, in particular for adhesive or sealing applications in the construction and manufacturing industry or in vehicle construction, in particular for parquet gluing, assembly, attachment gluing, module gluing, window gluing, joint sealing, checks serial sealing, seam sealing or cavity sealing.
  • Elastic bonds in vehicle construction are, for example, the gluing of parts such as plastic covers, decorative strips, flanges, bumpers, driver's cabs or other add-on parts to the painted body of a vehicle, or the gluing of windows into the body, with the vehicles in particular automobiles, trucks, buses, rail vehicles or depict ships.
  • Use as an adhesive for bonding the windows of vehicles is particularly preferred.
  • the moisture-curing polyurethane composition is preferably formulated in such a way that it has a pasty consistency with structurally viscous properties.
  • a composition is applied by means of a suitable device, for example from commercially available cartridges or barrels or hobbocks, in particular in the form of a bead, which can have an essentially round or triangular cross-sectional area.
  • Suitable substrates which can be glued and / or sealed with the moisture-curing polyurethane composition are in particular
  • - Glass, glass ceramic or glass coated with screen printing ceramic or polycarbonate - Metals or alloys such as aluminum, copper, iron, steel, non-ferrous metals, including surface-refined metals or alloys such as galvanized or chrome-plated metals; - Coated or lacquered substrates, in particular powder-coated metals or alloys or lacquered sheets;
  • Plastics such as hard or soft PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resins, phenolic resins, PUR, POM, TPO, PE, PP, EPM or EPDM, each untreated or surface-treated, for example by means of plasma , Corona or flames;
  • Fiber-reinforced plastics such as carbon-fiber-reinforced plastics (CFRP), glass-fiber-reinforced plastics (GFRP) and sheet molding compounds (SMC);
  • CFRP carbon-fiber-reinforced plastics
  • GFRP glass-fiber-reinforced plastics
  • SMC sheet molding compounds
  • PCC polymer-modified cement mortar
  • ECC epoxy resin-modified cement mortar
  • - Insulating foams in particular made of EPS, XPS, PUR, PIR, rock wool, glass wool or foamed glass (foam glass);
  • the substrates can be pretreated before application, in particular by physical and / or chemical cleaning processes or the application of an activator or a primer.
  • Another object of the invention is a method for gluing or sealing, comprising the steps
  • At least one of the substrates is preferably selected from the group consisting of glass, glass ceramics, glass or polycarbonate coated with screen printing ceramics, metals, alloys, powder-coated metals or alloys, paints and lacquers and cured adhesive, in particular sheet metal coated with automotive top lacquers.
  • This article can be a building or a part thereof, in particular a building of civil engineering, a bridge, a roof, a stairwell or a facade, or it can be an industrial good or a consumer good, in particular a window, a pipe , a rotor blade of a wind turbine, a household machine or a means of transport such as in particular an automobile, a bus, a truck, a rail vehicle, a ship, an airplane or a helicopter, or an attachment thereof.
  • Another object of the invention is thus an article obtained from the described method for gluing or sealing.
  • the gluing method is particularly preferably used for the elastic gluing of panes on vehicles, in particular for replacement glazing or the gluing of panes in the manufacture of the vehicle.
  • the moisture-curing polyurethane composition has advantageous properties. It has particularly good electrical properties, in particular particularly high volume resistance and particularly low impedance. In addition, it has particularly good application properties, in particular a particularly good squeezability with high stability and short thread tension, a matt surface after curing and particularly good weather resistance, with unchanged good curing, strength, elasticity, elasticity and classification of hazardous substances.
  • the composition is therefore particularly suitable as an elastic adhesive in vehicle construction, in particular for bonding windshields to automobiles.
  • Another object of the invention is the use of the poly (meth) acrylate urethane polymer according to the preceding description as an additive for increasing the volume resistance and / or for lowering the impedance in a moisture-curing polyurethane composition.
  • inventive poly (meth) acrylate urethane polymer in an amount in the range from 0.5 to 15.0% by weight, preferably 1.0 to 10.0% by weight, in particular 1.5 to 7.5% by weight, based on the total polyurethane Composition used.
  • the viscosity was measured with a thermostated cone-plate viscometer Rheotec RC30 (cone diameter 25 mm, cone angle 1 °, cone tip-plate distance 0.05 mm, shear rate 50 s -1 ).
  • the content of monomeric diisocyanate was determined by means of HPLC (detection via photodiode array; 0.04 M sodium acetate / acetonitrile as mobile phase) after prior derivatization using N-propyl-4-nitrobenzylamine.
  • Polymer PE-1 polyether urethane polymer.
  • the volatile constituents in particular a large part of the monomeric 4,4'-diphenylmethane diisocyanate, were then removed by distillation in a short-path evaporator (jacket temperature 180 ° C., pressure 0.1 to 0.005 mbar, condensation temperature 47 ° C.).
  • the resulting polyether urethane polymer had an NCO content of 1.8% by weight, a viscosity of 15.2 Pa s at 20 ° C. and a monomeric 4,4′-diphenylmethane diisocyanate content of 0.08% by weight.
  • Polymer PE-2 polyether urethane polymer.
  • the volatile constituents in particular a large part of the monomeric 4,4'-diphenylmethane diisocyanate, were then removed by distillation in a short-path evaporator (jacket temperature 180 ° C., pressure 0.1 to 0.005 mbar, condensation temperature 47 ° C.).
  • the polyether urethane polymer obtained in this way had an NCO content of 6.0% by weight, a viscosity of 7.5 Pa s at 60 ° C. and a monomeric 4,4′-diphenylmethane diisocyanate content of 0.08% by weight.
  • Polymer PE-3 polyether urethane polymer.
  • Desmophen ® 5031 BT glycerine-started ethylene oxide-terminated polyoxypropylene triol, OH number 28.0 mg KOH / g, OH functionality approx. 2.3; from Covestro
  • 275 g 4,4'-diphenylmethane diisocyanate (Desmodur ® 44 MC L, from Covestro) were by a known method at 80 ° C to a poly ether urethane polymer with an NCO content of 7.6% by weight, a viscosity of 6.5 Pa s at 20 ° C and a content of monomeric 4,4'- Diphenylmethane diisocyanate converted by about 20% by weight.
  • the volatile constituents in particular most of the monomeric 4,4'-diphenylmethane diisocyanate, were then removed by distillation in a short-path evaporator (jacket temperature 180 ° C., pressure 0.1 to 0.005 mbar, condensation temperature 47 ° C.).
  • the polyether urethane polymer thus obtained had an NCO content of 1.7% by weight, a viscosity of 19 Pa s at 20 ° C. and a monomeric 4,4′-diphenylmethane diisocyanate content of 0.04% by weight.
  • Polymer PP-1 polyester urethane polymer.
  • Priplast ® 1838 (dimer fatty acid-based polyester polyol, Croda)
  • Polymer PA-1 Poly (meth) acrylate urethane polymer according to the invention.
  • Joncryl ® 963 polyacrylate polyol from BASF, OH-number 130 mg KOH / g, equivalent weight 432 g
  • 540 g of 4,4'-diphenylmethane diisocyanate (Desmodur ® 44 MC L, of Covestro) were according to a known method at 80 ° C converted to a poly (meth) acrylate urethane polymer with an NCO content of 14.0% by weight, a viscosity of 14.7 Pa s at 20 ° C. and a content of monomeric 4,4′-diphenylmethane diisocyanate of about 33% by weight.
  • the volatile constituents in particular most of the monomeric 4,4'-diphenylmethane diisocyanate, were then removed by distillation in a short-path evaporator (jacket temperature 180 ° C., pressure 0.1 to 0.005 mbar, condensation temperature 47 ° C.).
  • the poly (meth) acrylate urethane polymer thus obtained had an NCO content of 4.8% by weight, a viscosity of 50.7 Pa s at 60 ° C. and a content of monomeric 4,4′-diphenylmethane diisocyanate of 0.12% by weight .
  • Polymer PA-1b Polymer PA-1 (NCO groups blocked with monoalcohol). 473.4 g of the poly (meth) acrylate urethane polymer PA-1 were dissolved in 493.6 g of diisodecyl phthalate (DIDP) at 23 ° C. (RT). Then 32.9 g of methanol with 0.2 g of tin catalyst solution were added to the mixture. The amount of methanol corresponded to twice the amount which is required to react off all isocyanate groups of the polymer PA-1. The mixture was stirred at rt for 3 hours. After this time there was an NCO content measured from 0.07%. The reaction mixture was then heated to 110 ° C. and the excess methanol was removed under a vacuum of 50 mbar.
  • DIDP diisodecyl phthalate
  • Polymer PA-1a Polymer PA-1 (NCO groups blocked with monoamine). 471.3 g of the poly (meth) acrylate urethane polymer PA-1 were dissolved in 491.4 g of DIDP at 60.degree. 37.4 g of butylamine were then added. This is the stoichiometric amount to react off all isocyanate groups. Due to evaporation losses, however, an additional 20 g of butylamine had to be added in order to achieve a final NCO content of 0.12%.
  • Polymer PA-2 Non-functional poly (meth) acrylate polymer.
  • Arufon ® UP1020 (Toagosei, Japan).
  • Polymer PA-3 Blocked poly (meth) acrylate polymer.
  • Polymer PA-4 Blocked poly (meth) acrylate polymer.
  • Polymer PC-2 polycarbonate polyol.
  • Eternacoll ® PH200D (UBE Chemical, Spain).
  • Commercially available liquid copolycarbonate polyol (OH number approx. 56 mg KOH / g) with molecular weight 2000 g / mol, viscosity 2500 mPa.s at 75 ° C.
  • Polymer PC-3 polycarbonate polyol.
  • Eternacoll ® UT-200 (UBE Chemical, Spain).
  • Commercially available liquid, linear polycarbonate / polyether diol (OH number approx. 56 mg KOH / g) with molecular weight 2000 g / mol, viscosity 8500 mPa.s at 25 ° C.
  • Polymer PC-4 Blocked polycarbonate urethane polymer.
  • Eternacoll ® PH-50 (OH number about 220 mg KOH / g, about 3.92 mol OH), and 440.21 g (4.31 mol) of acetic anhydride were weighed into a 200 ml round bottom flask, who was equipped with Vigreux Kollonne, T - piece and receiving flask. The mixture was stirred for 3 hours at 130 ° C. under a gentle stream of nitrogen, after which no OH bands were visible in the IR. The volatile components were removed on a rotary evaporator at 80 ° C. and 5 mbar for 30 minutes, followed by aftertreatment in a high vacuum for 30 minutes. The product had a viscosity of 0.60 Pa s at 20 ° C.
  • Moisture-curing polyurethane compositions are:
  • compositions Z1 to Z16 are Compositions Z1 to Z16:
  • composition was prepared using the ingredients specified in Tables 1 to 4 in the specified amounts (in parts by weight) well mixed by means of a planetary mixer under vacuum and with exclusion of moisture, the composition is filled into an airtight aluminum cartridge and stored at room temperature.
  • DIDP diisodecyl phthalate, a plasticizer.
  • the Russ Monarch ® 570 (from Cabot) used is a highly structured, non-oxidized soot with very good reinforcing properties.
  • the tin catalyst is a bibutyl tin dilaurate (10% by weight in DIDP).
  • Desmodur ® N3300 (from Covestro) is a hexamethylene diisocyanate trimer. Each composition was tested as follows:
  • each composition was pressed between two silicone-coated release papers to form a film 2 mm thick and stored in a standard climate for 14 days. After removing the release paper, some test specimens were punched out and tested as follows:
  • flanges with a length of 75 mm with a web length of 30 mm and a web width of 4 mm were punched out of the film and these were punched out according to DIN EN 53504 tested at a pulling speed of 200 mm / min.
  • the impedance was determined via the dielectric constant (product of resistance and capacitance) at radio frequencies of 1 MHz, 6 MHz and 100 MHz using an Agilent / Hewlett Packard HP 4291A impedance meter. For this, samples were prepared by the to be examined
  • Adhesive was applied between two copper plates (Rocholl, Germany) and compressed to a thickness (adhesive) of 2 mm. After the adhesive had hardened (7 days at 23 ° C, 50% rh), the hardened adhesive part oozing out between the plates was cut off with a sharp knife and a sandwich-like test specimen was obtained in which 2mm of the hardened adhesive was wedged between the copper plates. This test specimen was measured with respect to impedance on the above-mentioned measuring device at the frequencies mentioned. The electrical resistance was measured at 1 V, 10 V and 100 V voltages.
  • Chroma Insulation Tester 11200 Chroma 11200 Capacitor Leakage Current / IR Meter, Chroma USA
  • compositions labeled “(Ref.)” are comparative examples.
  • Table 1 Composition (in parts by weight) and properties from Z1 to
  • Table 2 Composition (in parts by weight) and properties from Z7 to
  • Table 3 Composition (in parts by weight) and properties from Z13 to Z16.
  • Table 4 Composition (in parts by weight) and properties from Z17 to Z22. “N / m” means that the value was not measured.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un polymère de poly (méth)acrylateuréthane qui est obtenu par réaction d'au moins un diisocyanate monomère et d'un poly(méth)acrylate polyol ayant un indice d'OH dans la plage de 50 à 200 mg KOH/g en un rapport NCO/OH d'au moins 3/1 et par l'élimination ultérieure d'une majorité du diisocyanate monomère au moyen d'un procédé de séparation approprié, caractérisé en ce que ledit polymère présente une teneur en NCO de 2,5 à 8 % en poids, par rapport au polymère de poly(méth)acrylateuréthane, et une teneur résiduelle en diisocyanates monomères n'ayant pas réagi d'au plus 0,5 % en poids. L'invention concerne également son utilisation comme additif et des compositions de polyuréthane durcissant à l'humidité le contenant. Le polymère selon l'invention est facile à manipuler. Il permet la production de compositions de polyuréthane durcissant à l'humidité destinées à être utilisées à des températures ambiantes, ayant des propriétés améliorées en termes de résistance électrique et d'impédance, d'adhérence, d'applicabilité et de résistance aux intempéries, avec de bonnes propriétés inchangées de stabilité au stockage, de vitesse de durcissement, de résistance, de ductilité, d'élasticité et de classification de matières dangereuses. Ces compositions sont particulièrement appropriées pour être utilisées comme adhésifs élastiques pour le collage du verre de véhicules.
EP20829896.8A 2019-12-17 2020-12-16 Polymère pour augmenter de la résistance électrique d'une composition de polyuréthane Pending EP4077447A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19216869 2019-12-17
PCT/EP2020/086483 WO2021122788A1 (fr) 2019-12-17 2020-12-16 Polymère pour augmenter de la résistance électrique d'une composition de polyuréthane

Publications (1)

Publication Number Publication Date
EP4077447A1 true EP4077447A1 (fr) 2022-10-26

Family

ID=68944149

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20829896.8A Pending EP4077447A1 (fr) 2019-12-17 2020-12-16 Polymère pour augmenter de la résistance électrique d'une composition de polyuréthane

Country Status (4)

Country Link
US (1) US12503545B2 (fr)
EP (1) EP4077447A1 (fr)
CN (1) CN114829437B (fr)
WO (1) WO2021122788A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4549480A1 (fr) * 2023-10-31 2025-05-07 Sika Technology AG Mousse de polyuréthane à haute résilience et à faible teneur en monomère
GB202317086D0 (en) * 2023-11-07 2023-12-20 Sylmasta Ltd Bandages
WO2025147907A1 (fr) * 2024-01-10 2025-07-17 Huntsman International Llc Système à base de polyuréthane

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5696397A (en) 1979-12-28 1981-08-04 Ricoh Kk Gas alarm
SU1759844A1 (ru) * 1990-09-28 1992-09-07 Государственный научно-исследовательский и проектный институт лакокрасочной промышленности Акрилуретанова композици дл окраски пластмасс
DE4213361A1 (de) 1992-04-23 1993-10-28 Bayer Ag Verfahren zur Herstellung von Isocyanatpräpolymeren und ihre Verwendung zur Herstellung von Beschichtungsmitteln
JP4010609B2 (ja) 1996-10-08 2007-11-21 旭化成ケミカルズ株式会社 アクリル系ポリイソシアネート組成物
JP4029563B2 (ja) * 1999-12-09 2008-01-09 大日本インキ化学工業株式会社 光ファイバー被覆用樹脂組成物及び光ファイバー若しくはユニット
DE60117097T2 (de) 2000-12-30 2006-09-28 Sika Schweiz Ag Gefüllte polyurethan klebstoffe auf basis polycarbonat polyole und ihre verwendung in antennenbau
JP4565777B2 (ja) * 2001-07-25 2010-10-20 旭化成ケミカルズ株式会社 アクリル系ポリイソシアネート組成物及びそれを含むシーリング材
JP2003119446A (ja) * 2001-10-15 2003-04-23 Nippon Carbide Ind Co Inc アクリル系感圧接着剤組成物
JP5145354B2 (ja) * 2006-12-21 2013-02-13 ダウ グローバル テクノロジーズ エルエルシー 乗り物の窓を取り付けるための接着剤として有用な組成物
JP5696397B2 (ja) * 2010-08-17 2015-04-08 オート化学工業株式会社 建築用シーリング材または塗膜防水材の下地処理用１液湿気硬化型プライマー
JP6095297B2 (ja) * 2012-08-24 2017-03-15 ヘンケルジャパン株式会社 積層シート用接着剤
CN104974655B (zh) * 2015-06-26 2017-10-03 中科院广州化学有限公司南雄材料生产基地 潮湿固化聚丙烯酸酯/聚氨酯复合防水涂料及其制备方法

Also Published As

Publication number Publication date
US12503545B2 (en) 2025-12-23
CN114829437A (zh) 2022-07-29
US20220396657A1 (en) 2022-12-15
CN114829437B (zh) 2023-10-10
WO2021122788A1 (fr) 2021-06-24

Similar Documents

Publication Publication Date Title
EP3833702A1 (fr) Polymère contenant des groupes isocyanate ayant une faible teneur en diisocyanates monomères
EP4499721B1 (fr) Adhésif durcissant à l'humidité à base de polyuréthane pour vitres
EP3947509B1 (fr) Composition durcissant à l'humidité présentant de bonnes propriétés adhésives
EP3833700A1 (fr) Composition de polyuréthane comprenant un plastifiant polymère et ayant une faible teneur en diisocyanates monomères
EP3947507B1 (fr) Polymère contenant des groupes isocyanate basé sur un polyesterdiol et des acides gras dimères
EP3833701A1 (fr) Composition de polyuréthane ayant une faible teneur en diisocyanates monomères
EP3880728B1 (fr) Raccordement adhésif entre une matière thermoplastique et une composition d'élastomère
WO2021122788A1 (fr) Polymère pour augmenter de la résistance électrique d'une composition de polyuréthane
EP4100451B1 (fr) Composition de polyuréthane à bonne adhérence à des matières plastiques
EP3880729B1 (fr) Agent thixotrope pour compositions durcissables
EP4100455B1 (fr) Polymère linéaire contenant des groupes isocyanate
EP4165099B1 (fr) Composition de polyuréthane à adhérence améliorée aux surfaces peintes
EP3880730B1 (fr) Solvant pour acides carboxyliques ou sulfoniques aromatiques
EP4671293A1 (fr) Stabilisateur pour compositions contenant des groupes isocyanate
EP4574867A1 (fr) Compositions polymères durcissables contenant des isocyanates, aldimines et composés comprenant des groupes méthylène activés
BR112021012810B1 (pt) Polímero de poliéster uretano, uso do mesmo como promotor de adesão, composição de poliuretano de cura por umidade, método de ligação ou vedação, e artigo obtido pelo mesmo

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20220718

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20260205