EP3983419A1 - Silylierte addukte, silylierte polymere und diese enthaltende zusammensetzungen - Google Patents

Silylierte addukte, silylierte polymere und diese enthaltende zusammensetzungen

Info

Publication number
EP3983419A1
EP3983419A1 EP20743205.5A EP20743205A EP3983419A1 EP 3983419 A1 EP3983419 A1 EP 3983419A1 EP 20743205 A EP20743205 A EP 20743205A EP 3983419 A1 EP3983419 A1 EP 3983419A1
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
radical
linear
group
branched alkyl
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
EP20743205.5A
Other languages
English (en)
French (fr)
Inventor
Boris COLIN
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.)
Bostik SA
Original Assignee
Bostik SA
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 Bostik SA filed Critical Bostik SA
Publication of EP3983419A1 publication Critical patent/EP3983419A1/de
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
    • C08G18/83—Chemically modified polymers
    • C08G18/837—Chemically modified polymers by silicon containing compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0892—Compounds with a Si-O-N linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
    • 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
    • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
    • 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
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • 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
    • 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
    • C08G18/70—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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C09K3/1021—Polyurethanes or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
    • C09K2200/065—Polyurethanes

Definitions

  • the present invention relates to a silylated adduct, as well as its preparation process.
  • the present invention also relates to the silylated polymers obtained from said silylated adducts, as well as to the compositions comprising them.
  • Silylated polymers are typically used as adhesives, sealants, coatings, for example in the aircraft, automotive or construction industry.
  • Such polymers generally comprise terminal groups of alkoxysilane type linked, directly or indirectly, to a main chain of polyether or polyurethane type.
  • silylated polyethers obtained by hydrosilylation of the corresponding diallyl ethers
  • silylated polyethers obtained by reaction of a polyether polyol or of a polyurethane containing hydroxyl end groups with an isocyanatosilane (STPE / STPU)
  • silylated polyurethanes obtained by reaction of a prepolymer containing isocyanate endings and of an aminosilane comprising alkoxysilane functions (SPUR).
  • silylated polyurethanes typically have a high viscosity which makes their handling and uses more complex.
  • these silylated polyurethanes also present stability problems with respect to the change in viscosity over time, especially when they are synthesized using aminosilane comprising a primary amine.
  • the hydroxyl number of an alcoholic compound represents the quantity of hydroxyl functions per gram of product, which is expressed in the form of the equivalent number of milligrams of potash (KOH) used in the determination of hydroxyl functions, per gram of product;
  • the viscosity measurement at 23 ° C can be done using a Brookfield viscometer according to the ISO 2555 standard.
  • the measurement carried out at 23 ° C (or at 100 ° C) can be done using a Brookfield RVT viscometer, a needle adapted to the viscosity range and at a rotational speed of 20 revolutions per minute (rev / min);
  • the present invention relates to a compound of formula (I) below:
  • - R 2 is a radical chosen from the group consisting of -C (0) 0R ⁇ -C (0) NH 2 , -CONHR 1 , -C (0) N (R 1 ) 2 , -CN, -N0 2 , -PO (OR 1 ) 2 , -S0 2 R 1 and -S0 2 OR 1 ;
  • - R 3 is a radical chosen from the group consisting of a hydrogen atom, -CH3, -R 1 , -C (0) OR 1 and -CH 2 C (0) OR 1 ;
  • - R 4 is a radical chosen from the group consisting of a hydrogen atom, -R 1 , - C (0) OR 1 and -CN;
  • R 1 represents an organic radical comprising from 1 to 20 carbon atoms, optionally comprising at least one heteroatom such as, for example, O;
  • R 5 is a divalent linear or branched alkylene radical comprising from 1 to 12 carbon atoms
  • R 6 is a linear or branched alkyl group comprising from 1 to 8 carbon atoms, or an alkoxy group comprising from 1 to 8 carbon atoms;
  • - R ' is a radical chosen from a hydrogen atom, a linear or branched alkyl radical comprising from 1 to 10 carbon atoms, a linear or branched alkenyl radical comprising from 2 to 10 carbon atoms, a cyclic alkyl radical comprising from 3 to 10 carbon atoms, an aryl radical comprising from 6 to 12 carbon atoms, or a -CH2-N radical (G 1 G 2 ) where G 1 and G 2 represent, independently of one another a linear or branched alkyl radical comprising from 1 to 10 carbon atoms, or a linear or branched alkenyl radical comprising from 2 to 10 carbon atoms or a benzyl radical;
  • R j is a radical chosen from a linear or branched alkyl radical comprising
  • G 1 G 2 a cyclic alkyl radical comprising from 3 to 10 carbon atoms, an aryl radical comprising from 6 to 12 carbon atoms, or a -CH2-N radical (G 1 G 2 ) where G 1 and G 2 represent, independently of one another, a linear or branched alkyl radical comprising from 1 to 10 carbon atoms, or linear or branched alkenyl radical comprising from 2 to 10 carbon atoms or a benzyl radical;
  • R - or R 'and R j together form an aliphatic ring comprising from 3 to 14 carbon atoms, preferably from 4 to 8 carbon atoms, said aliphatic ring being optionally substituted by at least one alkyl group comprising from 1 to 4 carbon atoms. carbon, and said ring optionally comprising one or more heteroatoms chosen from an oxygen atom, a sulfur atom or a nitrogen atom, said nitrogen atom then not being bonded to a hydrogen atom;
  • - a is an integer equal to 0, 1 or 2, preferably equal to 0 or 1.
  • the compounds of formula (I) are preferably those for which R 1 represents a linear or branched alkyl group comprising from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, and even more preferably from 1 to 5 atoms of carbon.
  • - R 2 is a -C (0) OR 1 radical
  • - R 3 is a radical chosen from the group consisting of a hydrogen atom, -C (0) OR 1 and -CH 2 C (0) OR 1 ; and or
  • R 4 is a hydrogen atom or -C (0) OR 1 ;
  • R 1 preferably representing a linear or branched alkyl group comprising from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, and even more preferably from 1 to 5 carbon atoms.
  • - R 2 is a radical-C (0) OR 1 ;
  • R 3 is a radical chosen from the group consisting of a hydrogen atom, C (0) OR 1 and -CH 2 C (0) OR 1 ;
  • - R 4 is a hydrogen atom or -C (0) OR 1 ; - R 1 representing a linear or branched alkyl group comprising from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, and even more preferably from 1 to 5 carbon atoms.
  • alkyl In the context of the invention, the "alkyl”, “aryalkyl” and “aryl” groups may or may not be substituted.
  • the compounds of formula (I) above preferably have one of the following formulas (1-1), (I-2) or (I-3):
  • R 1 , R 5 , R 6 , and R 7 are as defined above, and R 4 represents H;
  • R 1 , R 5 , R 6 , R 7 are as defined above and R 4 represents H;
  • each R 1 represents, independently of one another, a linear or branched alkyl group comprising from 1 to 12 carbon atoms, preferably from 1 to 8 carbon atoms, and even more preferably from 1 to 5 carbon atoms;
  • R 4 represents a hydrogen atom
  • R 5 represents a divalent linear or branched alkylene radical comprising from 1 to 6 carbon atoms, preferably 3 carbon atoms.
  • R - R ' represents a hydrogen atom, or a linear or branched alkyl radical comprising from 1 to 10 carbon atoms such as, for example, a methyl;
  • R j represents a linear or branched alkyl radical comprising from 1 to 8 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably from 1 to 5 carbon atoms, or a phenyl radical, or a -CH2 radical -N (G 1 G 2 ) where G 1 and G 2 represent, independently of one another, preferably a methyl, ethyl, propyl, butyl, pentyl or benzyl radical (-CH2-C 6 H 5 ), more preferably a methyl, ethyl, propyl or benzyl radical.
  • R 'and R j together form an aliphatic ring comprising from 5 to 12 carbon atoms, preferably 6 carbon atoms, said aliphatic ring being optionally substituted by at least one alkyl radical comprising from 1 to 4 carbon atoms, and said ring optionally comprising one or more heteroatoms chosen from an oxygen atom, a sulfur atom or a nitrogen atom, said nitrogen atom then not being bonded to a hydrogen atom.
  • the ring is neither substituted nor comprises a heteroatom.
  • R - R ' is a linear or branched alkyl radical comprising from 1 to 4 carbon atoms
  • R j represents a linear or branched alkyl radical comprising from 1 to 8 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably from 1 to 5 carbon atoms, or a phenyl radical.
  • the compounds of formula (I) are preferably compounds of formula (1-1) as defined above.
  • the compounds of formula (I) are chosen from the following compounds:
  • the present invention also relates to a process for preparing a compound of formula (I) as defined above, comprising the reaction between a compound of following formula (II):
  • R 2 , R 3 , R 4 , R 5 , R 6 and a are as defined above in formulas (I), (1-1),
  • R 8 represents an alkyl radical or an acyl radical comprising from 1 to 8 carbon atoms, preferably from 1 to 3 carbon atoms;
  • R 'and R j are as defined above.
  • the reaction can be carried out at a temperature ranging from 0 ° C to 100 ° C, preferably 23 ° C to 80 ° C.
  • the molar ratio of compound of formula (II): compound of formula (III) (r3) can vary from 1: 0.1 to 1: 3, and preferably from 1: 1 to 1: 3, even more preferably it is equal to 1: 1.
  • the reaction can take place in the presence or absence of solvent, preferably in the absence of solvent.
  • the reaction can take place in the presence or absence of a plasticizer, preferably in the absence of a plasticizer.
  • R - R ' is a linear or branched alkyl radical comprising from 1 to 4 carbon atoms
  • R j represents a linear or branched alkyl radical comprising from 1 to 8 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably from 1 to 5 carbon atoms;
  • R - R ' is a linear or branched alkyl radical comprising from 1 to 4 carbon atoms
  • R j represents a phenyl radical, or a -CH2-N (G 1 G 2 ) radical where G 1 and G 2 represent, independently of one another, preferably a methyl, ethyl, propyl or butyl radical, pentyl or benzyl (-CH2-C6H5), more preferably a methyl, ethyl, propyl or benzyl group;
  • R j and R together form an aliphatic ring comprising from 5 to 12 carbon atoms, preferably 6 carbon atoms, said aliphatic ring being optionally substituted by at least one alkyl radical comprising from 1 to 4 carbon atoms, and said ring optionally comprising one or more heteroatoms chosen from an oxygen atom, a sulfur atom or a nitrogen atom, said nitrogen atom then not being bonded to an atom of hydrogen.
  • cyclohexanone oxime or cyclododecanone oxime.
  • These 2 compounds are widely available commercially.
  • cyclohexanone oxime can be obtained from the company OMG Borchers sour the trade name Borchi ® NOX C3.
  • the compounds of formula (II) are preferably chosen from the compounds of formulas (11-1), (II-2) and (II-3) below:
  • R 1 , R 5 , R 6 and R 8 are as defined above, and R 4 represents H;
  • R 1 , R 5 , R 6 and R 8 are as defined above.
  • R 8 represents an alkyl radical comprising 1 or 2 carbon atoms.
  • each R 1 identical or different, represents, independently of one another, a linear alkyl group or branched comprising from 1 to 12 carbon atoms, preferably from 1 to 8 carbon atoms, and even more preferably from 1 to 5 carbon atoms.
  • the compounds of formula (II) can be obtained by a process comprising the reaction between a compound of the following formula (IV):
  • the reaction can be carried out at a temperature ranging from 0 ° C to 100 ° C, preferably 23 ° C to 80 ° C.
  • the molar ratio of compound of formula (IV): compound of formula (V) is preferably equal to 1: 1.
  • the reaction can take place in the presence or absence of solvent, preferably in the absence of solvent.
  • the reaction can take place in the presence or absence of a plasticizer, preferably in the absence of a plasticizer.
  • the compounds of formula (IV) can be chosen from methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isodecyl acrylate, lauryl acrylate, lauryl ethoxylate (40E) acrylate, propoxylated lauryl (40P) acrylate, isotridecyl acrylate, stearyl acrylate, behenyl acrylate, 2 (2-ethoxyethoxy) ethyl acrylate, tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate, 3,3,5- trimethyl cyclohexyl acrylate, methyl acrylamide, dibutyl acrylamide, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, isooctyl me
  • the compounds of above-mentioned formula (V) are preferably chosen from 3-aminopropyltriethoxysilane, 2-aminoethyl-dimethylmethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3- aminopropyltrimethropy-methylinethoxysilane, 3-aminopropyltrimoxy-methylinethoxysilane, 3-aminopropyltrimethoxy-3-methoxysilane amino-2-methylpropyltrimethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyldimethoxy-methylsilane, 4-amino-3-methylbutyltrimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, 4-aminobutyldimethoxy-methylsilane, 4-amino-3-methylbutyltri
  • the present invention also relates to the use of the compounds of formula (I) for the preparation of silylated polymers, and more particularly of silylated polyurethanes.
  • the present invention relates to a silylated polyurethane P comprising at least one terminal function of formula (VI) below:
  • - R 2 is a radical selected from the group consisting of -C (0) 0R ⁇ -C (0) NH 2 , CONHR 1 , -C (0) N (R 1 ) 2 , -CN, -N0 2 , - PO (OR 1 ) 2 , -S0 2 R 1 and -S0 2 OR 1 ;
  • - R 3 is a radical chosen from the group consisting of a hydrogen atom, -CH3, -R 1 , -C (0) OR 1 and -CH 2 C (0) OR 1 ;
  • - R 4 is a radical chosen from the group consisting of a hydrogen atom, -R 1 , - C (0) OR 1 and -CN;
  • R 1 represents an organic radical comprising from 1 to 20 carbon atoms, optionally comprising at least one heteroatom such as, for example, O;
  • R 5 is a divalent linear or branched alkylene radical comprising from 1 to 12 carbon atoms
  • R 6 is a linear or branched alkyl group comprising from 1 to 8 carbon atoms, or an alkoxy group comprising from 1 to 8 carbon atoms;
  • - R ' is a radical chosen from a hydrogen atom, a linear or branched alkyl radical comprising from 1 to 10 carbon atoms, a linear or branched alkenyl radical comprising from 2 to 10 carbon atoms, a cyclic alkyl radical comprising from 3 to 10 carbon atoms, an aryl radical comprising from 6 to 12 carbon atoms, or a -CH 2 -N (G 1 G 2 ) radical where G 1 and G 2 represent, independently of one another, a linear or branched alkyl radical comprising from 1 to 10 carbon atoms, or a linear or branched alkenyl radical comprising from 2 to 10 carbon atoms or a benzyl radical;
  • R j is a radical chosen from a linear or branched alkyl radical comprising
  • G 1 G 2 represent, independently of one another, a linear or branched alkyl radical comprising from 1 to 10 carbon atoms, or linear or branched alkenyl radical comprising from 2 to 10 carbon atoms or a benzyl radical;
  • R - or R 'and R j together form an aliphatic ring comprising from 3 to 14 carbon atoms, preferably from 4 to 8 carbon atoms, said aliphatic ring being optionally substituted by at least one alkyl group comprising from 1 to 4 carbon atoms. carbon, and said ring optionally comprising one or more heteroatoms chosen from an oxygen atom, a sulfur atom or a nitrogen atom, said nitrogen atom then not being bonded to a hydrogen atom; - a is an integer equal to 0, 1 or 2, preferably equal to 0 or 1.
  • the polyurethane is that for which in the above-mentioned formula (VI), R 1 represents a linear or branched alkyl group comprising from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, and even more preferably from 1 to 5 carbon atoms.
  • R 2 is a radical-C (0) OR 1 ;
  • R 3 is a radical chosen from the group consisting of a hydrogen atom, C (0) OR 1 and -CH 2 C (0) OR 1 ; and or
  • R 4 is a hydrogen atom or -C (0) OR 1 ;
  • R 1 preferably representing a linear or branched alkyl group comprising from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, and even more preferably from 1 to 5 carbon atoms.
  • - R 2 is a radical-C (0) OR 1 ;
  • R 3 is a radical chosen from the group consisting of a hydrogen atom, C (0) OR 1 and -CH 2 C (0) OR 1 ; and R 4 is a hydrogen atom or -C (0) OR 1 ;
  • R 1 representing a linear or branched alkyl group comprising from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, and even more preferably from 1 to 5 carbon atoms.
  • polyurethanes P preferably have at least one terminal function of formula (VI-1), (VI-2) or (VI-3) below:
  • R 1 , R 6 , R 7 and R 5 are as defined above, and R 4 represents H;
  • R 1 , R 5 , R 6 and R 7 are as defined above, and R 4 represents H;
  • each R 1 represents, independently of one another, a linear or branched alkyl group comprising from 1 to 12 carbon atoms, preferably from 1 to 8 carbon atoms, and even more preferably from 1 to 5 carbon atoms;
  • R 4 represents a hydrogen atom
  • R 5 represents a divalent linear or branched alkylene radical comprising from 1 to 6 carbon atoms, preferably 3 carbon atoms. According to one embodiment, in formulas (VI), (VI-1), (VI-2) and (VI-3):
  • R - R ' represents a hydrogen atom, or a linear or branched alkyl radical comprising from 1 to 10 carbon atoms such as, for example, a methyl;
  • R j represents a linear or branched alkyl radical comprising from 1 to 8 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably from 1 to 5 carbon atoms, or a phenyl radical, or a -CH2 radical -N (G 1 G 2 ) where G 1 and G 2 represent, independently of one another, preferably a methyl, ethyl, propyl, butyl, pentyl or benzyl radical (-CH2-C 6 H 5 ), more preferably a methyl, ethyl, propyl or benzyl radical.
  • R 'and R j together form an aliphatic ring comprising from 5 to 12 carbon atoms, preferably 6 carbon atoms, said aliphatic ring being optionally substituted by at least one alkyl radical comprising from 1 to 4 carbon atoms, and said ring optionally comprising one or more heteroatoms chosen from an oxygen atom, a sulfur atom or a nitrogen atom, said nitrogen atom then not being bonded to a hydrogen atom.
  • the ring is neither substituted nor comprises a heteroatom.
  • R - R ' is a linear or branched alkyl radical comprising from 1 to 4 carbon atoms
  • R j represents a linear or branched alkyl radical comprising from 1 to 8 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably from 1 to 5 carbon atoms, or a phenyl radical.
  • the polyurethanes P are preferably polymers having at least one terminal function of formula (VI-1) mentioned above.
  • Polyurethane P can be obtained by a process comprising a reaction step between:
  • Polyurethane P can also be obtained by a process comprising a reaction step between:
  • r an integer or non-integer which may range from 2 to 4
  • B representing a multivalent organic radical
  • the prepolymer of formula (VII) can be obtained by any method known to those skilled in the art for the preparation of a prepolymer comprising -NCO terminations.
  • the prepolymer of above-mentioned formula (VII) is a polyurethane obtained by polyaddition reaction:
  • At least one polyisocyanate preferably chosen from diisocyanates, triisocyanates, and mixtures thereof;
  • polyether polyols preferably chosen from polyether polyols, polycarbonate polyols, polyester polyols, and mixtures thereof;
  • NCO / OH (r1) molar ratio is strictly greater than 1, preferably ranges from 1.2 to 2.0.
  • the polyurethane P according to the invention is prepared by a process comprising the following steps:
  • At least one polyisocyanate preferably chosen from diisocyanates, triisocyanates, and mixtures thereof;
  • polyether polyols preferably chosen from polyether polyols, polycarbonate polyols, polyester polyols, and mixtures thereof;
  • step E2 the reaction of the product formed at the end of step E1) with at least one compound of formula (I) as defined above, in particular in amounts such that the NCO / NH (r2) molar ratio is preferably between 0.8 and 1, 2, preferably between 0.9 and 1, 1, and preferably close to 1;
  • step E1 reaction of the product formed at the end of step E1) with at least one compound of formula (II) and at least one compound of formula (III) as defined above, in particular in amounts such than :
  • the NCO / NH (r2) molar ratio is preferably between 0.8 and 1, 2, preferably between 0.9 and 1, 1, and preferably close to 1;
  • the molar ratio compound of formula (II): compound of formula (III) (r3) ranges from 1: 0.1 to 1: 3, and preferably from 1: 1 to 1: 3, and even more preferably equal to 1: 1.
  • (r1) is the NCO / OH molar ratio corresponding to the molar ratio of the number of isocyanate groups (NCO) to the number of hydroxyl groups (OH) carried by all of the polyisocyanate (s) and polyol (s) present in the reaction medium of step E1).
  • (r2) is the NCO / NH molar ratio corresponding to the molar ratio of the number of isocyanate groups to the number of -NH- groups carried respectively by all the isocyanate (s ) (with regard in particular to the polyurethane prepolymer with NCO terminations and optionally the polyisocyanate (s) unreacted at the end of step E1)), and compound (s) of formula (I) present in the reaction medium of step E2).
  • (r3) is the molar ratio corresponding to the molar ratio of compound of formula (II): compound of formula (III).
  • step E1 When the polyurethane of formula (VII) is obtained during step E1) from a mixture of polyisocyanates or of several polyisocyanates added successively, the calculation of the ratio (r1) takes into account, on the one hand, the NCO groups carried by all the polyisocyanates present in the reaction medium of step E1), and on the other hand of the OH groups carried by the polyol (s) present in the reaction medium of step E1).
  • step E1 the polyaddition reaction is carried out at a temperature preferably below 95 ° C, and under preferably anhydrous conditions.
  • the polyol (s) which can be used to prepare the prepolymer of above-mentioned formula (VII) used according to the invention can be chosen from among those whose number-average molecular mass (Mn) is from 300 to 30,000 g / mol, preferably from 400 to 20,000 g / mol, and preferably from 500 to 12,000 g / mol. Preferably, their hydroxyl functionality ranges from 2 to 3. The hydroxyl functionality is the average number of hydroxyl functions per mole of polyol.
  • the polyol (s) which can be used according to the invention can have a hydroxyl number (IOH) (average) ranging from 3 to 570 milligrams of KOH per gram of polyol (mg KOH / g), of preferably from 5 to 430 mg KOH / g, more preferably from 9 to 340 mg KOH / g.
  • IOH hydroxyl number
  • the polyol (s) can be chosen from polyether polyols, polyester polyols, polycarbonate polyols and mixtures thereof.
  • step E1) is carried out with a polyether polyol.
  • the polyether polyol (s) which can be used according to the invention is (are) preferably chosen from polyoxyalkylene polyols, in which the alkylene part, linear or branched, comprises from 2 to 4 carbon atoms , more preferably from 2 to 3 carbon atoms.
  • the polyether polyol (s) which can be used according to the invention is (are) preferably chosen from polyoxyalkylene diols or polyoxyalkylene triols, of which the alkylene part, linear or branched, comprises of 1 to 4 carbon atoms, more preferably 2 to 3 carbon atoms.
  • Polyoxypropylene diols or triols also referred to as polypropylene glycol (PPG) diols or triols
  • PPG polypropylene glycol
  • Mn number-average molecular mass
  • polyoxyethylene diols or triols also referred to as polyethylene glycol (PEG) diols or triols
  • Mn number average molecular mass
  • polyoxybuylene diols or triols also designated by (PBG) diols or triols having a number molecular mass ranging from 300 to 20,000 g / mol;
  • polytetramethylene diols or triols also designated by PolyTHF or PTMEG having a number average molecular mass (Mn) ranging from 300 to 4000 g / mol;
  • polyether polyols can be prepared in a conventional manner, and are widely available commercially. They can be obtained by polymerization of the corresponding alkylene oxide in the presence of a basic catalyst (for example potassium hydroxide) or of a catalyst based on a double metal-cyanide complex.
  • a basic catalyst for example potassium hydroxide
  • a catalyst based on a double metal-cyanide complex for example sodium bicarbonate
  • - VORANOL® EP 1900 difunctional PPG with a number-average molecular mass of approximately 4,008 g / mol, and a hydroxyl index I OH equal to 28 mg KOH / g;
  • - ACCLAIM ® 8200 difunctional PPG with a number-average molecular mass of 8,016 g / mol, and a hydroxyl number Icm equal to 14 mg KOH / g;
  • - ACCLAIM ® 12200 difunctional PPG with a number-average molecular mass of 11222 g / mol, and a hydroxyl number Icm equal to 10 mg KOH / g;
  • - ACCLAIM ® 18200 difunctional PPG with a number-average molecular mass of 17,265 g / mol, and a hydroxyl index Icm equal to 6.5 mg KOH / g.
  • - VORANOL® CP 755 trifunctional PPG with a number-average molecular mass of approximately 710 g / mol, and a hydroxyl number Icm equal to 237 mg KOH / g;
  • - VORANOL® CP 3355 trifunctional PPG with a number-average molecular mass of approximately 3544 g / mol, and a hydroxyl number Icm equal to 47.5 mg KOH / g;
  • - ACCLAIM ® 6300 trifunctional PPG with a number-average molecular mass of approximately 5,948 g / mol, and a hydroxyl number Icm equal to 28.3 mg KOH / g.
  • PTMEG 250 difunctional polyTHF with a number average molecular mass of approximately 4,008 g / mol, and an IOH hydroxyl number ranging from 230 to 270 mg KOH / g;
  • PTMEG 2900 difunctional polyTHF with a number-average molecular weight of approximately 4,008 g / mol, and an IOH hydroxyl number ranging from 37.7 to 39.7 mg KOH / g.
  • hydroxyl functionality of a polyether polyol is understood to mean the average number of hydroxyl functions per mole of polyether polyol.
  • the polyester polyols can be chosen from polyester diols and polyester triols, and preferably from polyester diols.
  • polyester diol or triol there may be mentioned:
  • polycaprolactone diols or triols marketed by the company PERSTORP under the reference CAPA Polyols with a number-average molecular mass (Mn) ranging from 240 to 8,000 g / mol.
  • the polycarbonate polyols can be chosen from polycarbonate diols or triols, having in particular a number-average molecular mass (M n ) ranging from 300 g / mol to 12,000 g / mol.
  • CONVERGE POLYOL 212-10 and CONVERGE POLYOL 212-20 marketed by the company NOVOMER respectively of molecular mass in number (M n ) equal to 1000 and 2000 g / mol, the hydroxyl numbers of which are respectively 1 12 and 56 mg KOH / g,
  • KURARAY having a number molecular mass (M n ) ranging from 500 to 3,000 g / mol and a hydroxyl number ranging from 224 to 37 mg KOH / g.
  • the polyisocyanate (s) which can be used to prepare the prepolymer of formula (VII) above can be added sequentially or reacted as a mixture.
  • the polyisocyanate (s) which can be used are diisocyanate (s), preferably chosen from the group consisting of isophorone diisocyanate (I PDI), hexamethylene diisocyanate (HDI) , heptane diisocyanate, octane diisocyanate, nonane diisocyanate, decane diisocyanate, undecane diisocyanate, dodecane diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate) (4,4'-HMDI), norbornane diisocyanate, norbornene, 1, 4-cyclohexane diisocyanate (CHDI), methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, diisocyanate formulationthyldiéthylcyclohexane
  • the polyisocyanate (s) is (are) chosen from toluene diisocyanate (in particular the 2,4 TDI isomer, the 2,6-TDI isomer or their mixtures), the meta- xylylene, IPDI, and mixtures thereof.
  • the polyisocyanate is isophorone diisocyanate (IPDI).
  • Usable polyisocyanate are typically widely available commercially.
  • SCURANATE® TX marketed by the company VENCOREX, corresponding to a 2,4-TDI with a purity of the order of 95%
  • SCURANATE® T100 marketed by the company VENCOREX
  • DESMODUR® I "marketed by the company COVESTRO, corresponding to an IPDI or else DESMODUR® N3300" marketed by the company COVESTRO
  • corresponding to an isocyanurate of HDI the “TAKENATE TM 500” marketed by MITSUI CHEMICALS corresponding to an m-XDI
  • TAKENATE TM 600 marketed by MITSUI CHEMICALS corresponding to an m-H6XDI
  • VESTANAT® H12MDI marketed by EVONIK corresponding to an H12MDI.
  • the polyisocyanate is isophorone diisocyanate (IPDI).
  • the polyaddition reaction of step E1) can be carried out in the presence or absence of at least one reaction catalyst.
  • the reaction catalyst (s) which can be used during the polyaddition reaction of step E1) can be any catalyst known to those skilled in the art for catalyzing the formation of polyurethane by reaction of at least one polyisocyanate with at least one polyol.
  • An amount ranging up to 0.3% by weight of catalyst (s) relative to the weight of the reaction medium from step E1) can be used.
  • Steps E2) and E’2) can be carried out under anhydrous conditions.
  • Steps E2) and E’2) can be carried out at a temperature ranging from 40 ° C to 100 ° C, preferably from 60 ° C to 100 ° C.
  • Steps E2) and E’2 can be) can be carried out in the presence or absence of at least one reaction catalyst.
  • reaction catalyst (s) which can be used during the polyaddition reaction of step E2) (or E'2)) can be any catalyst known to those skilled in the art for catalyze this type of reaction.
  • An amount ranging up to 0.3% by weight of catalyst (s) relative to the weight of the reaction medium of step E2) (or E’2)) can be used. In particular, it is preferred to use from 0.02 to 0.2% by weight of catalyst (s) relative to the total weight of the reaction medium of step E2) (or E’2)).
  • the prepolymer of formula (Vil) can comprise a content by mass of NCO groups ranging from 0.1 to 15%, preferably from 0.2 to 10%, preferably from 0.5 to 8%, advantageously from 0.6 to 3 % relative to the total mass of said prepolymer.
  • the present invention relates in particular to a polyurethane P ’having the following formula (VIII):
  • - R represents an integer or non-integer ranging from 2 to 4;
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are as defined above.
  • Polyurethane P ′ can be a particular example of the aforementioned polymer P.
  • the polyurethane P ’ preferably has the following formula (IX):
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are as defined above.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 may be the same or different.
  • each occurrence of each of a, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 which may be identical or different is meant for example that each occurrence of R 1 in the formula (IX) may be the same or different, or alternatively that each occurrence of a may be the same or different in formula (IX). The same goes for all the radicals cited.
  • each occurrence of each of a, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 is identical.
  • the polyurethane P ’ according to the invention preferably has one of the following formulas (X), (XI) or (XII):
  • R 1 , R 5 , R 6 , and R 7 are as defined above and R 4 represents H;
  • R 1 , R 5 , R 6 , and R 7 are as defined above, and R 4 represents H;
  • R 1 , R 5 , R 6 , and R 7 are as defined above.
  • polyurethanes P ’of formulas (VIII), (IX), (X), (XI), and (XII), mentioned above are those for which:
  • each R 1 represents, independently of one another, a linear or branched alkyl group comprising from 1 to 12 carbon atoms, preferably from 1 to 8 carbon atoms, and even more preferably from 1 to 5 carbon atoms;
  • R 4 represents a hydrogen atom
  • R 5 represents a divalent linear or branched alkylene radical comprising from 1 to 6 carbon atoms, preferably 3 carbon atoms.
  • R - R ' represents a hydrogen atom, or a linear or branched alkyl radical comprising from 1 to 10 carbon atoms such as, for example, a methyl;
  • R j represents a linear or branched alkyl radical comprising from 1 to 8 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably from 1 to 5 carbon atoms, or a phenyl radical, or a -CH2 radical -N (G 1 G 2 ) where G 1 and G 2 represent, independently of one another, preferably a methyl, ethyl, propyl, butyl, pentyl or benzyl radical (-CH2-C 6 H 5 ), more preferably a methyl, ethyl, propyl or benzyl radical.
  • R 'and R j together form an aliphatic ring comprising from 5 to 12 carbon atoms, of preferably 6 carbon atoms, said aliphatic ring being optionally substituted by at least one alkyl radical comprising from 1 to 4 carbon atoms, and said ring optionally comprising one or more heteroatoms chosen from an oxygen atom, a sulfur atom or a nitrogen atom, said nitrogen atom then not being bonded to a hydrogen atom.
  • the ring is neither substituted nor comprises a heteroatom.
  • R - R ' is a linear or branched alkyl radical comprising from 1 to 4 carbon atoms
  • R j represents a linear or branched alkyl radical comprising from 1 to 8 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably from 1 to 5 carbon atoms, or a phenyl radical.
  • the present invention also relates to the use of the above-mentioned polyurethanes (P and P ’) for the preparation of adhesives, sealants or coatings.
  • silylated polyurethanes according to the invention advantageously have a lower viscosity than the existing silylated polyurethanes, which makes their handling and their use easier. This also advantageously makes it possible not to have recourse to plasticizers and / or solvents during their synthesis or during the preparation of formulations.
  • silylated polyurethanes according to the invention advantageously have a lower viscosity than the existing silylated polyurethanes while retaining good bonding properties.
  • silylated polyurethanes according to the invention advantageously exhibit a high elongation at break, which makes them useful for applications in construction, for example.
  • silylated polyurethanes according to the invention advantageously make it possible to reduce or even avoid the release of methanol.
  • the present invention relates to a formulation comprising at least one polyurethane P or P 'according to the invention, and at least one additive chosen from the group consisting of catalysts, fillers, antioxidants, light stabilizers / UV absorbers, metal deactivators, antistats, foaming agents, biocides, plasticizers, lubricants, emulsifiers, colorants, pigments, rheological agents, impact modifiers, adhesion promoters, optical brighteners, flame retardants, anti-seepage agents, nucleating agents, solvents, reactive diluents and mixtures thereof.
  • the fillers usually used are, for example, inorganic or organic powders, for example calcium carbonates and silicates, inorganic fibrous materials, for example glass fibers.
  • organic fillers such as carbon fibers, mixtures of organic and inorganic fillers, for example mixtures of glass and carbon fibers or, mixtures of carbon fibers and inorganic fillers.
  • the fillers can be added in an amount ranging from 1 to 75% by weight, relative to the total weight of the formulation.
  • the UV stabilizers, the antioxidants and the metal deactivators used in the formulations according to the invention advantageously exhibit good resistance to migration and high thermal stability. They are chosen, for example, from the following groups a) to t).
  • the compounds of groups a) to g) and i) are light stabilizers / UV absorbers, while compounds j) to t) act as stabilizers:
  • crosslinking catalysts are optionally used in proportions ranging from 0.01% to approximately 10% by weight, relative to the total weight of the formulation.
  • the crosslinking catalyst can be chosen from:
  • titanium acetyl acetonate commercially available under the name TYZOR ® AA75 from the company DuPont
  • Ti (OnBu) 4 commercially available under the name TYZOR® TnBT from DoRF Ketal
  • aluminum chelate commercially available under the name K-KAT ® 5218 from the company King Industries
  • - organic tin derivatives such as for example dibutyltin dilaurate (or DBTL), dibutyltin dilaurate (DOTDL), dioctyltin bisacetylacetonate, (available under the name TIBKAT ® 223) or TibKat® 425 (which is a mixture of dioctyl tin oxide and vinyltrimethoxysilane),
  • amidines for example 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) and 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN), 1, 5,7- Triazabicyclo [4.4.0] dec-5-ene (TBD), di-o-tolylguanidine (DOTG), and mono-, di- and trialkylamines C1 to C6, in particularly triethylamine and fe / f-butylamine.
  • DBU 8-diazabicyclo [5.4.0] undec-7-ene
  • DBN 5-diazabicyclo [4.3.0] non-5-ene
  • TCD 1, 5,7- Triazabicyclo [4.4.0] dec-5-ene
  • TGD di-o-tolylguanidine
  • the formulation does not include a tin catalyst, and even more preferably, it does not contain a crosslinking catalyst.
  • a tin catalyst and even more preferably, it does not contain a crosslinking catalyst.
  • the choice of additives used is advantageously a function of the end use which is made of the formulation according to the invention, which can be adjusted according to the application specifications by those skilled in the art.
  • the formulation preferably comprises more than 20% by weight, advantageously more than 30% by weight of polyurethane P or P ’according to the invention relative to the total weight of said formulation.
  • the present invention also relates to the use of the above formulation for the preparation of adhesives, sealants or coatings.
  • between x and y or “ranging from x to y” is meant an interval in which the limits x and y are included.
  • the range “between 0% and 25%” notably includes the values 0% and 25%.
  • BORCHIKAT 315 bismuth neodecanoate available from OMG BORCHERS;
  • TIBKAT 223 dioctyltin bis (acetylacetonate) sold by TIB CHEMICALS;
  • SILQUEST A-11 10 3-aminopropyltrimethoxysilane available from MOMENTIVE;
  • SILQUEST A-1100 3-aminopropyltriethoxysilane available from MOMENTIVE;
  • DYNASYLAN 1122 bis (3-triethoxysilyl) propyl) amine sold by EVONIK;
  • DYNASYLAN 1124 bis (3-trimethoxysilyl) propyl) amine sold by EVONIK;
  • DYNASYLAN 1189 N- (3 (trimethoxysilyl) propyl) butylamine) sold by EVONIK;
  • GF9 N- (3 (trimethoxysilyl) propyl) ethylenediamine) marketed by WACKER;
  • BORCHINOX C3 cyclohexanone oxime marketed by OMG BORCHERS;
  • BORCHINOX M2 2-butanone oxime marketed by OMG BORCHERS;
  • MIBKO methylisobutyl ketoxime marketed by TCI CHEMICALS
  • APO acetophenone oxime marketed by SIGMA ALDRICH;
  • MESAMOLL akulsulfonate marketed by LANXESS
  • VTMO vinyltrimethoxysilane sold by SIGMA ALDRICH;
  • CALOFORT SV precipitated calcium carbonate (average size 0.07 microns, stearate coated) marketed by SPECIALITY MINERAL.
  • Example 12 Preparation of silylated polymer P5
  • the mixture is heated to 70 ° C. and mixed until the characteristic band of the -NCO functions is no longer detectable by infrared spectroscopy.
  • 125.2 g of silylated polyurethane (P5) is obtained which is packaged in aluminum cartridges protected from humidity.
  • Example 15 measurement of the viscosities of polymers P1 to P7
  • the viscosity of the silylated polymers P1 to P7 was measured using a Brookfield DV-1-Prime viscometer at 23 ° C.
  • the silylated polymers P2 to P7 according to the invention advantageously have a lower viscosity than that of the silylated polymer P1 (comparative) (at 23 ° C), which in particular allows easier handling and use.
  • a lower viscosity advantageously avoids the additional use of plasticizer / solvent in the formulations.
  • Sealants M1 to M7 were prepared by mixing the ingredients mentioned in the following table in a speed mixer at room temperature: [Table 2]
  • the percentages are percentages by weight relative to the total weight of each mastic composition.
  • Measurement of stress at break by tensile test The measurement of the tensile stress at break was carried out according to the protocol described below.
  • the principle of the measurement consists in stretching in a traction machine, whose movable jaw moves at a constant speed equal to 100 mm / minute, a standard test piece (H2) made up of the crosslinked composition and to record, at the moment when produces the fracture of the test piece, the applied tensile stress (in MPa) as well as the elongation of the test piece (in%).
  • the standard test piece is in the shape of a dumbbell, as illustrated in international standard ISO 37 of 201 1.
  • the narrow part of the dumbbell used has a length of 20 mm, a width of 4 mm and a thickness of 500 mp ⁇ . Samples were stored under standard conditions (23 ° C ⁇ 1 ° C, 50% ⁇ 5% R.H.) for 14 days. After 14 days, when the compositions have fully crosslinked, the tests were carried out on a ZWICK ROELL 2.5KN dynanometer.
  • the measurement of the skinning time was carried out in a controlled atmosphere at a temperature of 23 ° C. and a relative humidity of about 50%.
  • the composition was applied with a wooden spatula and as a thin film on a slide on cardboard about 7 cm long.
  • a stopwatch was started and it was examined every 15 minutes using a light pressure from an LDPE (low density polyethylene LDPE) pipette if the film is dry or if a composition residue is transferred to the pipette.
  • LDPE low density polyethylene LDPE
  • the skin formation time is the time at the end of which the film of composition is dry and for which there is no longer any transfer of adhesive residue onto the pipette. The result is expressed in minutes.
  • the M2 to M7 sealants according to the invention advantageously have a significantly higher elongation at break than for the comparative M1 sealant.
  • M3, M4 and M5 sealants were observed to crosslink faster than the comparative M1 sealant.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP20743205.5A 2019-06-13 2020-06-11 Silylierte addukte, silylierte polymere und diese enthaltende zusammensetzungen Pending EP3983419A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1906297A FR3097223B1 (fr) 2019-06-13 2019-06-13 Adduits silylés, polymères silylés et compositions les comprenant
PCT/FR2020/050990 WO2020249901A1 (fr) 2019-06-13 2020-06-11 Adduits silyles, polymeres silyles et compositions les comprenant

Publications (1)

Publication Number Publication Date
EP3983419A1 true EP3983419A1 (de) 2022-04-20

Family

ID=67742820

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20743205.5A Pending EP3983419A1 (de) 2019-06-13 2020-06-11 Silylierte addukte, silylierte polymere und diese enthaltende zusammensetzungen

Country Status (6)

Country Link
US (1) US20220235172A1 (de)
EP (1) EP3983419A1 (de)
JP (1) JP2022536151A (de)
CN (1) CN113939523A (de)
FR (1) FR3097223B1 (de)
WO (1) WO2020249901A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114621284B (zh) * 2021-11-26 2024-03-01 浙江衢州硅宝化工有限公司 一种甲基二酮肟基烷氧基硅烷的制备方法
CN114591358B (zh) * 2021-11-26 2024-03-08 浙江衢州硅宝化工有限公司 一种甲基丙烯酰氧丙基三酮肟基硅烷的制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6057415A (en) * 1998-04-09 2000-05-02 Bayer Corporation Water dispersible polyisocyanates containing alkoxysilane groups
US8207252B2 (en) * 2007-03-07 2012-06-26 Momentive Performance Materials Inc. Moisture-curable silylated polymer resin composition
WO2016083309A1 (de) * 2014-11-24 2016-06-02 Sika Technology Ag Silangruppen-haltige zusammensetzung mit schneller aushärtung
US11613682B2 (en) * 2016-07-21 2023-03-28 Sika Technology Ag Flame-retardant adhesive and sealant with improved mechanical properties

Also Published As

Publication number Publication date
FR3097223A1 (fr) 2020-12-18
WO2020249901A1 (fr) 2020-12-17
JP2022536151A (ja) 2022-08-12
US20220235172A1 (en) 2022-07-28
CN113939523A (zh) 2022-01-14
FR3097223B1 (fr) 2022-04-29

Similar Documents

Publication Publication Date Title
JP5491391B2 (ja) 塗料接着付与剤を含有する硬化性シリル含有ポリマー組成物
EP3774972B1 (de) Polyurethanbasierte zusammensetzung
EP3983419A1 (de) Silylierte addukte, silylierte polymere und diese enthaltende zusammensetzungen
EP3898871A1 (de) Zusammensetzung aus epoxidharz und polyurethan
WO2021079063A1 (fr) Copolyurethane silyle ionique et composition de mastic le comprenant
EP3774971A1 (de) Polyurethanbasierte zusammensetzung
EP3877393B1 (de) Funktionalisierte hydroxysilane, silylierte polyurethane und zusammensetzungen damit
WO2020094974A1 (fr) Dérivés 1,3-oxathiolane-2-thione et leurs utilisations
EP3728386A1 (de) Verfahren zur herstellung einer zusammensetzung mit einem polyurethan mit nco-endgruppen
EP3830202A1 (de) Verfahren zur herstellung von verbindungen mit einer alkoxysilylgruppe
JP2018523000A (ja) 低色および色安定性を有するシリル化ポリマーの製造方法
WO2023237830A1 (fr) Copolyuréthane silylé ionique
WO2020115430A1 (fr) Polyurethane a terminaisons (2-oxo-1,3-dioxolane-4-carboxylate)
WO2020079370A1 (fr) Copolymeres hydrocarbones a blocs alternes et groupements terminaux alcoxysilanes
JPWO2020094974A5 (de)

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: 20211129

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)