Classifications

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  • 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
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
  • C08G18/0809—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups
  • C08G18/0814—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups containing ammonium groups or groups forming them
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
  • C08G18/0833—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups together with anionic or anionogenic groups
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  • 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
  • C08G18/088—Removal of water or carbon dioxide from the reaction mixture or reaction components
  • C08G18/0885—Removal of water or carbon dioxide from the reaction mixture or reaction components using additives, e.g. absorbing agents
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  • 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
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  • 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
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
  • C08G18/1825—Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino groups
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  • 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
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  • 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
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3271—Hydroxyamines
  • C08G18/3275—Hydroxyamines containing two hydroxy groups
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  • 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
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
  • C08L75/08—Polyurethanes from polyethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
  • C08L75/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
• • 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
  • 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
  • C09J175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
• • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
  • C08K2003/265—Calcium, strontium or barium carbonate
• • 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
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
  • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C09J201/10—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups

Definitions

• the present invention relates to an ionic silylated copolyurethane and its preparation process.
• the invention also relates to a composition comprising said ionic silylated copolyurethane and the use of said composition.
• Silylated polymers are typically used as adhesives, sealants and coatings, for example in the aeronautical, automotive or construction industries. Such polymers generally comprise terminal groups of the alkoxysilane type linked, directly or indirectly, to a main chain, in particular of the polyurethane type.
• silylated polymers available industrially we can cite silylated polyurethanes which can be obtained from the reaction of a prepolymer with isocyanate endings and a silylated compound comprising alkoxysilane functions.
• compositions based on polyurethane with alkoxysilane terminations also called silylated polyurethane
• silylated polyurethane have the advantage of being free of free isocyanates (once the silylated polyurethane is formed). These compositions therefore constitute an alternative, preferred from a toxicological point of view, to compositions based on polyurethane with isocyanate terminations.
• compositions based on silylated polyurethane occurs, in the presence of humidity, by hydrolysis of the alkoxysilane groups carried by the polymer, then their condensation to form a siloxane bond (-Si- O-Si-) which unites the polymer chains into a solid three-dimensional network.
• metal crosslinking catalysts can be organic crosslinking catalysts, in particular 1,8-5 diazabicyclo[5.4.0] undec-7-ene (DBU) or 1,5,7-triazabicyclo[4.4. 0]dec-5-ene (TBD).
• DBU 1,8-5 diazabicyclo[5.4.0] undec-7-ene
• TBD 1,5,7-triazabicyclo[4.4. 0]dec-5-ene
• the present invention aims to provide a self-catalyzed silylated polyurethane for an adhesive and/or sealant composition, in particular a putty, which leads to similar or improved mechanical properties compared to a silylated polyurethane composition ( non-self-catalyzed) comprising a crosslinking catalyst.
• the present invention relates to an ionic silylated copolyurethane of formula (I):
• the invention also relates to a process for preparing the ionic silylated copolyurethane of formula (I) according to the invention.
• the invention also relates to a composition comprising the ionic silylated copolyurethane of formula (I) according to the invention.
• the invention also relates to the use of the composition according to the invention, as an adhesive and/or putty, preferably as a putty.
• the invention also relates to an article comprising the composition according to the invention, in airtight packaging, protected from air.
• the subject of the invention is a process for assembling two substrates comprising: - coating the composition according to the invention, on at least one of the two substrates to be assembled; Then
• the cationic ammonium group pendant to the ionic silylated copolyurethane according to the invention makes it possible to catalyze the crosslinking reaction when the ionic silylated copolyurethane comes into contact with humidity, for example air, or any other source of humidity. or water.
• the ionic silylated copolyurethane according to the invention is therefore self-catalyzed.
• the invention relates to an ionic silylated copolyurethane of formula (I): in which :
• - R 1 represents a divalent hydrocarbon radical comprising from 5 to 45 carbon atoms, saturated or unsaturated, with a linear or branched open chain, or comprising one or more optionally aromatic rings, and optionally comprising at least one heteroatom chosen from O, S and NOT
• - R 2 represents a saturated or unsaturated, linear or branched divalent hydrocarbon radical possibly comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur, silicon,
• - A represents a nitrogen atom, or a carbon atom substituted by a hydrogen atom or a carbon atom substituted by an alkyl radical comprising from 1 to 10 carbon atoms,
• R represents a covalent bond and R’ represents a divalent hydrocarbon radical with a linear or branched open chain, optionally comprising at least one heteroatom chosen from O and S, or
• R' represents a covalent bond and R represents a divalent hydrocarbon radical with a linear or branched open chain, optionally comprising at least one heteroatom chosen from O and S; preferably -OR- corresponds to the formula: -O-CH(R 0 )-CH 2 -[O-CH(R 0 )-CH 2 ] x -, and/or -R'-O- corresponds to the formula : - [CH 2 -CH(R 0 )-O]y-CH 2 -CH(R 0 )-O-, in which R° is a hydrogen atom or an alkyl radical comprising one or two carbon atoms, and in which x and y, identical or different integers, are such that the molar mass or the number average molecular mass Mn of the radical -ORA(R”-NHR 7 R 8 )-R'-O- is 190 g/ mol to 20000 g/mol, preferably from 190 g/mol to
• - R represents a divalent linear or branched alkylene radical, preferably linear, comprising from 1 to 8 carbon atoms, preferably from 1 to 4 carbon atoms,
• R 7 and R 8 identical or different, each represent a linear or branched alkyl radical, preferably linear, comprising from 1 to 4 carbon atoms, or R 7 and R 8 form a 5 or 6-membered heterocycle with nitrogen atom to which they are attached, and R 7 and R 8 optionally comprise a heteroatom chosen from N, O and S,
• R 10 represents a saturated or unsaturated, linear or branched divalent hydrocarbon radical possibly comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur, silicon
• - G R 13 represents the conjugate base of an acid HR 13 , HR 13 which may be an organic or inorganic acid, preferably organic, which has a pKa at 25°C less than 6, preferably less than or equal to 5, more preferably between -15 and 5.5, even more preferably between -3.0 and 5.0,
• n identical or different, are each an integer greater than or equal to 1, such that the ratio n/m is included in a range going from 0.04 to 20, preferably from 0.06 to 13, more preferably from 0.08 to 5, and even more preferably from 0.10 to 1,
• - 1 is an integer equal to 0 or 1, preferably equal to 0,
• - u is an integer greater than or equal to 0, preferably equal to 0 or 1, more preferably equal to 0,
• the number average molecular mass Mn of the ionic silylated copolyurethane of formula (I) is included in a range going from 1500 to 50000 g/mol, preferably 3000 g/mol at 30,000 g/mol,
• R 4 represents a linear or branched alkyl radical comprising 1 to 4 carbon atoms, and when p is equal to 2, the R 4 radicals are identical or different,
• - X represents a divalent radical chosen from -NR S -, -NH- and -S-,
• the number average molecular mass Mn can be measured by methods well known to those skilled in the art, for example by NMR or by size exclusion chromatography using polystyrene type standards.
• unsaturated we mean one or more unsaturations.
• the unsaturations can be bond (for example double or triple bond) and/or cycle.
• the pKa of an acid is equal to - log (Ka), Ka being the acidity constant of the acid in water.
• Ka being the acidity constant of the acid in water.
• between x and y or “ranging from x to y”, we mean an interval in which the terminals x and y are included.
• the range “between 1 and 5” includes in particular the values 1 and 5.
• f represents a radical of formula (II) in which:
• R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 3 carbon atoms, preferably n-propylene;
• - R 5 represents a methyl or ethyl radical, preferably methyl;
• - X represents a divalent radical -NR 6 -,
• R 6 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, preferably n-butyl, and
• the radical R 1 is chosen from the following radicals whose formulas show the free valences:
• IPDI isophorone diisocyanate
• RDI hexamethylene diisocyanate
• m-XDI m-xylylene diisocyanate
• R 11 represents a hydrocarbon radical, saturated or unsaturated, cyclic, linear or branched, comprising from 6 to 14 carbon atoms;
• R 12 represents a divalent propylene group
• hexamethylene diisocyanate allophanate corresponding to formula (III) comprises an NCO isocyanate group content ranging from 12 to 14% by weight relative to the weight of said allophanate.
• the radical R 2 or the radical R 10 comprises one or more heteroatoms
• said heteroatom(s) are not present at the end of the chain.
• the free valences of the divalent radical R 2 and the divalent radical R 10 linked to the neighboring oxygen atoms of the silylated polymer each come from a carbon atom.
• the main chain of the radical R 2 and the divalent radical R 10 is terminated by a carbon atom at each of the two ends, said carbon atom then having a free valence.
• the ionic silylated copolyurethane of formula (I) is obtained from polyols chosen from polyether polyols, polyester polyols, polycarbonate polyols, polyacrylate polyols, polysiloxanes polyols, polyolefin polyols and their mixtures, preferably from diols chosen from polyether diols, polyester diols, polycarbonate diols, polyacrylate diols, polysiloxane diols, polyolefin diols and their mixtures, more preferably from polyether diols .
• diols can be represented by the formula HO-R 2 -OH or HO-R 10 -OH, where R 2 and R 10 have the same meaning as in formula (I).
• the radical R 2 and/or R 10 can be chosen from the following divalent radicals whose formulas below show the two free valences:
• - q represents an integer such that the number average molar mass of the radical R 2 and/or R 10 ranges from 500 g/mol to 20000 g/mol, preferably from 3000 g/mol to 14000 g/mol,
• - r and s represent zero or a non-zero integer such that the number average molar mass of the radical R 2 and/or R 10 ranges from 500 g/mol to 20000 g/mol, preferably from 3000 g/mol to 14000 g /mol, it being understood that the sum r+s is different from zero,
• Q 1 represents a linear or branched, saturated or unsaturated divalent aromatic or aliphatic alkylene radical, preferably having from 1 to 18 carbon atoms, more preferably from 1 to 8 carbon atoms,
• Q 2 represents a linear or branched divalent alkylene radical preferably having from 2 to 36 carbon atoms, more preferably from 1 to 8 carbon atoms,
• the ionic silylated copolyurethane is of formula (I) in which:
• - q represents an integer such that the number average molar mass of the radical R 2 ranges from 500 g/mol to 20000 g/mol, preferably from 3000 g/mol to 14000 g/mol.
• R 7 and R 8 are identical and represent an ethyl radical
• the ionic silylated copolyurethane is of formula (I) in which:
• - A represents a carbon atom substituted by a hydrogen atom
• - R' represents the divalent radical -CH 2 -
• R 7 and R 8 are identical and represent an ethyl radical
• R 10 represents a radical derived from a polypropylene glycol as described above.
• the ionic silylated copolyurethane is of formula (I) in which:
• - -OR- corresponds to the formula: -O-CH(CH 3 )-CH 2 -[O-CH(CH 3 )-CH 2 ] X -
• -R'- O- corresponds to the formula: -[ CH 2 -CH(CH 3 )-O] y -CH 2 -CH(CH 3 )-O-, in which x and y are preferably equal to 0,
• - R represents a divalent linear alkylene radical comprising from 2 to 4 carbon atoms, preferably 3 carbon atoms,
• R 7 and R 8 are identical and represent a methyl, ethyl, propyl or butyl radical, preferably methyl or ethyl, more preferably methyl, and
• R 7 and R 8 are identical and represent a methyl radical
• the unit repeated n times includes a pendant cationic ammonium group, the counterion of which is anionic and of formula: ®R 13 .
• the anionic counterion ®R 13 comes from an acid of formula HR 13 , after reaction with the pendant amine(s) of the unit repeated n times.
• organic acid is meant an acid of formula HR 13 in which R 13 is a radical comprising at least one carbon atom.
• organic acid is meant an acid of formula HR 13 in which R 13 is a radical comprising no carbon atom.
• the acid of formula HR 13 is an organic acid.
• R 13 represents an OR 9 radical, in which R 9 represents an unsaturated hydrocarbon radical, with a linear or branched open chain, or comprising one or more optionally aromatic rings, R 9 comprising at least one oxygen atom and optionally an or several heteroatoms chosen from N, F and S.
• the ionic silylated copolyurethane is of formula (I) in which R 13 is such that the acid of formula HR 13 is a carboxylic or sulfonic acid which has a pKa at 25°C of between -15 and 5.5, preferably between -3.0 and 5.0.
• carboxylic acid is meant an organic acid comprising at least one -C(O)OH group.
• sulfonic acid is meant an organic acid comprising at least one -S(O)2OH group.
• the ionic silylated copolyurethane is of formula (I) in which R 13 is such that the acid of formula HR 13 is chosen from hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acid, sulfuric acid, perchloric acid, formic acid, acetic acid, trifluoroacetic acid, hydroxyacetic acid, oxalic acid, propanoic acid, 3-hydroxypropionic acid, malonic acid, methylmalonic acid, butanoic acid, iso-butyric acid, succinic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, pentanoic acid, hexanoic acid , citric acid, sorbic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, acrylic acid, propiolic acid, crotonic acid, isocrotonic acid , methacrylic acid, benzoic acid, methanesulf
• the viscosity at 23°C of the ionic silylated copolyurethane according to the invention can vary from 10 to 300 Pa.s, preferably from 20 to 100 Pa.s.
• the viscosity of the ionic silylated copolyurethane according to the invention can for example be measured using a Brookfield type method at 23°C and 50% relative humidity (S28 needle).
• the ionic silylated copolyurethane is of formula (I) in which:
• R 1 represents the divalent radical derived from isophorone diisocyanate
• - R 2 represents a radical derived from a polyethylene glycol or a polypropylene glycol as described above, preferably from a polypropylene glycol
• - q is an integer such that the number average molecular mass of the radical R 2 ranges from 3000 to 14000 g/mol, - A represents a nitrogen atom,
• OR- corresponds to the formula: -O-CH(CH 3 )-CH 2 -
• -R'-O- corresponds to the formula: -CH 2 -CH(CH 3 )-O-
• - R represents a divalent linear alkylene radical comprising 3 carbon atoms, and - R 7 and R 8 are identical and represent a methyl radical,
• R 13 is such that the acid of formula HR 13 is chosen from acetic acid, acrylic acid and methanesulfonic acid,
• - m and n are such that the n/m ratio is included in a range ranging from 0.10 to 1, - f represents a radical of formula (II) in which:
• R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 3 carbon atoms, preferably n-propylene;
• R 5 represents a methyl or ethyl radical, preferably methyl
• the invention also relates to a process for preparing the ionic silylated copolyurethane of formula (I) according to the invention, comprising the following steps:
• step (ii) reacting the copolyurethane from step (i) with an acid of formula HR 13 to form an ionic copolyurethane and
• R 1 , R 2 , m, n, t, u, R, R', R”, A, R 7 , R 8 , R 10 , R 13 , X, R 3 , R 4 , R 5 and p are such as described above, including the embodiments.
• copolyurethane from step (i) is meant the copolyurethane of formula (IV) or one of its derivatives (in particular an ionic derivative with -NCO endings obtained during step (ii) or a silylated derivative obtained during step (iii)).
• step (ii) can be implemented on the copolyurethane of formula (IV) and followed by step (iii), or step (iii) can be implemented implemented on the copolyurethane of formula (IV) and followed by step (ii).
• the method according to the invention comprises sequential steps 5:
• polymer polyol preferably a polymer diol, of formula (IVb): H- OR 2 -OH, and
• the polymer polyol of formula (IVb) is a polyether diol, preferably a polypropylene glycol diol.
• polypropylene glycols are available commercially, in particular under the brand ACCLAIM® from the company COVESTRO. We can cite as examples:
• the IOH hydroxyl number is the number of hydroxyl functions per gram of polyol, expressed as the equivalent number of milligrams of KOH used in the determination of hydroxyl functions. It can be determined by titrimetry according to the ISO 14900:2017 standard.
• step (i) is advantageously implemented with a molar ratio (branched polyol of formula (IVc) / polyol of formula (IVb)) corresponding to the n/m ratio as defined previously.
• the molar ratio (branched polyol of formula (IVc)/polyol of formula (IVb)) is even more preferably between 0.10 and 1.
• step (i) is advantageously carried out with an excess of the equivalent number of -NCO groups of the polyisocyanate of formula (IVa) relative to the equivalent number of -OH groups provided by the polyols of formulas (IVb) and (IVc).
• step (i) is implemented with an -NCO/-OH molar equivalent ratio of between 1.1 and 4.2, preferably between 1.3 and 3.8, more preferably between 1.5 and 2.
• the -NCO/-OH molar equivalent ratio is defined as being equal to the molar equivalent number of -NCO groups of the polyisocyanate of formula (IVa), divided by the sum of the molar equivalent numbers of -OH groups provided by the polyols of formulas (IVb ) and (IVc).
• the molar equivalent number of -NCO groups of the polyisocyanate of formula (IVa) is equal to: f(-NCO)*(m ( iva)/M(i V a)), where f(-NCO) is the number of groups -NCO of the polyisocyanate of formula (IVa), m ⁇ iva) is the mass introduced in g of polyisocyanate of formula (IVa) and M ⁇ iva) is the molar mass in g/mol of the polyisocyanate of formula (IVa).
• the polyisocyanate of formula (IVa) is a diisocyanate and f(-NCO) is therefore equal to 2.
• the polyols of formulas (IVb) and (IVc) are diols, and f(— OH) ( ivb) and f(— OH)(ivo are therefore each equal to 2.
• Step (i) is generally carried out in the presence of a catalyst which can be any catalyst known to those skilled in the art to catalyze the formation of polyurethane by reaction of a polyisocyanate and at least one polyol.
• a catalyst is for example chosen from carboxylates, in particular neodecanoate, of bismuth and/or zinc.
• Step (i) is advantageously carried out under anhydrous conditions.
• Step (i) is advantageously carried out at a temperature between 60°C and 120°C.
• Step (i) is advantageously carried out at atmospheric pressure.
• Step (ii) corresponds to the reaction of the -NR 7 R 8 pendant group which is included in the unit repeated n times of the copolyurethane of formula (IV) with the acid of formula HR 13 .
• the molar ratio (acid of formula HR 13 / branched polyol of formula (IVc) introduced in step (i)) can vary from 0.8 to 2.5 , preferably from 1 to 2, more preferably equal to 1.
• Step (ii) is advantageously carried out under anhydrous conditions.
• Step (ii) is advantageously carried out at a temperature between 20°C and 80°C, preferably between 20°C and 453.
• Step (ii) is advantageously carried out at atmospheric pressure.
• step (iii) the terminal -NCO groups of the copolyurethane (in particular of formula (V)) react with the -XH group of the silylated compound of formula (IIa).
• Silylated compounds of formula (IIa) are widely available commercially. We can cite for example N-(3(trimethoxysilyl)propyl)butylamine available under the name Dynasylan® 1189 from Evonik.
• step (iii) can be implemented with a molar equivalent ratio -XH/-NCO equal to 1, preferably between 0.90 and 1.15.
• the molar equivalent ratio -XH/-NCO is defined as being equal to the molar equivalent number of -XH groups of the silylated compound of formula (IIa) divided by the molar equivalent number of -NCO groups of the copolyurethane (in particular of formula (V)).
• the molar equivalent number of -XH groups of the silylated compound of formula (lia) is equal to: f(- XH)*(m(iia)/M(na)), where f(-XH) is the number of - groups XH of the Sillylé Formula (HA) compound, M ( IIA) is the mass introduced in G of Sillylé Formula (LIA) and M ( N A ) is the molar mass in G/MOL of the SILYLÉ Formula (HA) compound (ha) compound (ha) compound (ha) compound .
• the molar equivalent number of -NCO groups of the copolyurethane corresponds to the molar equivalent number of -NCO groups of the polyisocyanate of formula (IVa) introduced in excess compared to the molar equivalent number of -OH groups provided by the polyols of formulas (IVb) and (IVc).
• Step (iii) is advantageously carried out under anhydrous conditions.
• Step (iii) is advantageously carried out at a temperature within a range ranging from 20°C to 80°C, preferably from 20°C to 40°C.
• Step (iii) is advantageously carried out at atmospheric pressure.
• the process according to the invention is carried out in the absence of water as solvent.
• the process according to the invention is implemented without adding free water, that is to say other than that included inherently in the ingredients used.
• the water content introduced into the process according to the invention is less than 5% by weight relative to the total weight of the ingredients used, preferably less than 3% by weight, in particular less than 1% by weight.
• composition comprising an ionic silylated copolyurethane according to the invention
• the invention also relates to a composition comprising the ionic silylated copolyurethane of formula (I) according to the invention.
• the content of ionic silylated copolyurethane is advantageously between 10% and 50% by weight relative to the total weight of the composition, preferably from 20% to 48% by weight, more preferably from 35% to 45% by weight.
• the composition according to the invention further comprises a filler.
• the filler content is advantageously between 20% and 60% by weight relative to the total weight of the composition, preferably from 30% to 58% by weight, more preferably still from 40% to 55% by weight.
• the filler usable in the composition according to the invention can be chosen from mineral fillers and mixtures of organic fillers and mineral fillers.
• any mineral filler usually used in the field of adhesive and/or putty compositions we can cite any mineral filler usually used in the field of adhesive and/or putty compositions. These charges are in the form of particles of various geometry. They can be, for example, spherical, fibrous, or have an irregular shape.
• the mineral fillers are formed by the group consisting of clay, quartz, hollow mineral microspheres and carbonate fillers.
• hollow mineral microspheres mention may be made of hollow glass microspheres, and more particularly those of sodium and calcium borosilicate or aluminosilicate.
• the mineral fillers are formed by the group consisting of carbonate fillers.
• the carbonate filler is chosen from alkali or alkaline earth metal carbonates and their mixtures.
• the carbonated filler comprises calcium carbonate, more preferably the carbonated filler is chalk or calcium carbonate coated with fatty acids, even more preferably precipitated calcium carbonate coated with fatty acids.
• the hydrophobic coating of calcium carbonate may represent from 0.1% to 3.5% by weight, based on the total weight of calcium carbonate.
• the fatty acids coating the calcium carbonate comprise or consist of more than 50% by weight of stearic acid relative to the total weight of the fatty acids.
• an organic filler mention may be made of any organic filler, in particular polymeric, usually used in the field of adhesive and/or mastic compositions.
• the organic fillers are formed by the group consisting of polyvinyl chloride (PVC), polyolefins, rubber, ethylene vinyl acetate (EVA), hollow microspheres of expandable or non-expandable thermoplastic polymer (such as microspheres hollow vinylidene chloride/acrylonitrile) and aramid fibers (such as Kevlar®), preferably PVC.
• PVC polyvinyl chloride
• EVA ethylene vinyl acetate
• hollow microspheres of expandable or non-expandable thermoplastic polymer such as microspheres hollow vinylidene chloride/acrylonitrile
• aramid fibers such as Kevlar®
• the average particle size of the filler is between 10 nm and 400 pm, preferably between 20 nm and 100 pm, more preferably between 30 nm and 1 pm, even more preferably between 40 nm and 300 nm.
• the average particle size advantageously corresponds to the particle size d50, that is to say the maximum size of 50% of the smallest particles by volume, and can be measured with a particle size analyzer, in particular by laser diffraction on a MALVERN type device. (for example according to the NF ISO 13320 standard).
• the composition according to the invention has an ionic silylated copolyurethane content of between 10% and 50% by weight and a filler content of between 20% and 60% by weight, the percentages by weight being by relative to the total weight of the composition.
• composition according to the invention may further comprise at least one additive chosen from moisture absorbers, adhesion promoters, plasticizers, rheology agents, UV stabilizers and mixtures thereof.
• composition according to the invention comprises a mixture of additives chosen from moisture absorbers and adhesion promoters.
• Suitable moisture absorbers include alkoxysilanes such as trialkoxysilanes (particularly trimethoxysilanes). Such an agent advantageously extends the shelf life of the composition according to the invention during storage and transport, before its use.
• the moisture absorber is chosen from vinyltrimethoxysilane, trimethoxymethylsilane, propyltrimethoxysilane, vinyltriethoxysilane, alkoxyarylsilanes (for example GENIOSIL® XL 70 marketed by WACKER) and their mixtures.
• the moisture absorber is chosen from vinyltrimethoxysilane, vinyltriethoxysilane and their mixture, more preferably vinyltrimethoxysilane.
• the moisture absorber content can be between 0.5% and 5% by weight relative to the total weight of the composition according to the invention, preferably between 1% and 3.5% by weight.
• the adhesion promoter can be chosen from amino-, mercapto- and epoxy-alkoxysilanes, and mixtures thereof.
• the adhesion promoter is chosen from aminoalkoxysilanes, more preferably from aminotrialkoxysilanes, even more preferably from aminotrimethoxysilanes, for example N-(3-
• epoxy-alkoxysilane As an example of an epoxy-alkoxysilane, mention may be made of (3-glycidyloxypropyl)trimethoxysilane (also called GLYMO).
• the aminotrimethoxysilanes are formed by the group consisting of 4-amino-3,3-dimethylbutyltrimethoxysilane (for example SILQUEST A-LINK 600 marketed by MOMENTIVE), (3-aminopropyl)trimethoxysilane (for example DYNASYLAN® AMMO marketed by EVONIK) and N-(3-(trimethoxysilyl)propyl)ethylenediamine (for example GENIOSIL® GF9 marketed by the company WACKER).
• the aminotrimethoxysilanes are N-(3-(trimethoxysilyl)propyl)ethylenediamine.
• the content of adhesion promoter can be between 0.1% and 5% by weight relative to the total weight of the composition according to the invention, preferably between 0.5% and 3% by weight, more preferably between 1 .0% and 2.0% by weight.
• the plasticizer can be any plasticizer usually used in the field of adhesive and/or putty compositions.
• the plasticizer is chosen from:
• DINP diisononyl phthalate
• PALATINOL® N marketed by BASF
• - an ester of alkylsulphonic acid and phenol for example MESAMOLL® marketed by LANXESS
• PEVALENTM marketed by PERSTORP
• the plasticizer content can vary from 5% to 20% by weight relative to the total weight of the composition according to the invention, preferably from 10% to 15% by weight.
• the rheology agent can be any rheology agent usually used in the field of adhesive and/or putty compositions.
• the rheology agent is chosen from:
• - PVC plastisols corresponding to a suspension of PVC in a plasticizing agent miscible with PVC, obtained in situ by heating at temperatures ranging from 60°C to 80°C.
• These plastisols may be those described in particular in the work “Polyurethane Sealants”, Robert M. Evans, ISBN 087762-998-6,
• CRAYVALLAC® SLX CRAYVALLAC® SLW or CRAYVALLAC® SUPER marketed by Arkema
• THIXATROL® AS8053 or THIXATROL® MAX (EC number: 432-430 - 3) which are available from ELEMENTIS, or the RHEOBYK 7503 marketed by BYK.
• amide waxes is meant waxes comprising one or more compounds having at least one amide group.
• amide waxes can be obtained from fatty acid(s) (for example ricinoleic acid) and (di)amine(s).
• micronized is meant an average particle size of less than 1 mm, advantageously less than 500 pm, preferably less than 100 pm, more preferably less than 10 pm.
• the average particle size advantageously corresponds to the particle size d50, that is to say the maximum size of 50% of the smallest particles by volume, and can be measured with a particle size analyzer, in particular by laser diffraction on a MALVERN type device. (for example according to the NF ISO 13320 standard).
• the content of rheology agent can vary from 1% to 40% by weight relative to the total weight of the composition according to the invention, preferably from 5% to 30% by weight, more preferably from 10% to 25% by weight. .
• composition according to the invention may comprise up to 1% by weight of one or more UV stabilizers (or antioxidants) relative to the total weight of the composition.
• UV stabilizers are typically introduced to protect the composition from degradation resulting from a reaction with oxygen which is likely to be formed by the action of heat or light.
• antioxidants may include antioxidants that can scavenge free radicals.
• the UV stabilizer(s) are chosen from benzotriazoles, benzophenones, so-called hindered amines such as bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate (CAS No.: 41556-26-7), methyl 1,2,2,6,6-pentametiyl-4-piperidyl sebacate (CAS number: 82919-37-7), 3-(3,5-di-ter ⁇ -butyl-4-hydroxyphenyl)propionate octadecyl, 4,4'-bis(a,a-dimethylbenzyl)diphenylamine, and mixtures thereof.
• hindered amines such as bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl
• composition according to the invention comprises:
• the composition according to the invention consists essentially of the ingredients mentioned above.
• composition according to the invention does not comprise a crosslinking catalyst.
• crosslinking catalyst is meant a catalyst known to those skilled in the art for the condensation of silanol.
• Such catalysts include:
• titanium acetyl acetonate titanium tetrapylate, titanium tetrabutylate
• zirconium acetyl acetonate zirconium tetrapropylate
• zirconium tetrabutylate zirconium tetrabutylate
• DBU 1,8-diazabicyclo[5.4.0]undec-7-ene
• DBN 1,5-diazabicyclo[4.3.0]non-5-ene
• DBDEE diethyl-2 ether ,2'-morpholine
• DABCO 1,4-diazabicylo[2.2.2]octane
• - tin-based catalysts such as compounds derived from dioctyltin or dibutyltin.
• the composition according to the invention does not comprise water as a solvent.
• the water content in the composition according to the invention is advantageously less than 5% by weight relative to the total weight of said composition, preferably less than 3% by weight, in particular less than 1% by weight.
• composition according to the invention is preferably stored in an anhydrous environment, for example in hermetic packaging, where said composition is protected from humidity and preferably protected from light.
• composition according to the invention can be prepared by simply mixing its ingredients.
• the composition according to the invention is prepared at atmospheric pressure and at a temperature between 10°C and 55°C, more preferably between 18°C and 40°C.
• Example 8 An example of preparation of the composition according to the invention is described in Example 8.
• the invention also relates to the use of the composition according to the invention, as an adhesive and/or putty, preferably as a putty.
• the invention also relates to an article comprising the composition according to the invention, in airtight packaging, protected from air.
• the airtight packaging is a polyethylene bag or a polyethylene cartridge fitted with a cover.
• the subject of the invention is a process for assembling two substrates comprising:
• the assembly process according to the invention is carried out at room temperature (approximately 23°C).
• Suitable substrates are, for example, inorganic substrates such as glass, ceramics, concrete, metals or alloys (such as aluminum, steel, non-ferrous metals, galvanized metals), or organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins, or even paint-coated metal and composite substrates (for example, in the field of automobiles).
• inorganic substrates such as glass, ceramics, concrete, metals or alloys (such as aluminum, steel, non-ferrous metals, galvanized metals)
• organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins, or even paint-coated metal and composite substrates (for example, in the field of automobiles).
• - ACCLAIM® 4200 marketed by Covestro: poly(propylene oxide) with a number average molar mass of approximately 4000 g/mol, having two -OH endings and an IOH hydroxyl number equal to 28.0 mg KOH/g;
• IPDI isophorone diisocyanate
• TIBKAT® 223 marketed by TIB Chemicals: dioctyltin bis(acetylacetonate) with a molar mass equal to 543.15 g/mol, crosslinking catalyst;
• the %NCO is determined automatically using a T5 Excellence titrator (marketed by Mettler Toledo). A sample of the reaction medium is taken and introduced into the titrator, then a solution of dicyclohexylamine in DMF (N,N-dimethylformamide) is added automatically. The excess amine is also titrated automatically with hydrochloric acid.
• the crosslinking time is measured by determining the skin formation time.
• a bead of putty (approximately 10 cm in length and approximately 1 cm in diameter) is first placed on a cardboard support. Then, using a low density polyethylene (LDPE) pipette tip, the surface of the putty is touched every minute for up to 2 hours, to determine the exact time at which surface skin forms. This test is carried out under controlled conditions of humidity and temperature (23°C and 50% relative humidity).
• LDPE low density polyethylene
• the tensile strength and elongation at break were measured in accordance with standard ISO 37 (2012), at a constant speed equal to 100 mm/min.
• dumbbell-shaped specimen H2
• type 2 as illustrated in the international standard ISO 37 (2012) is used.
• the narrow part of the dumbbell used is 20 mm long, 4 mm wide and 3 mm thick.
• the composition to be tested (previously packaged in a cartridge) is extruded into a Teflon mold, and is left to crosslink for 14 days under standard conditions (23°C and 50% relative humidity).
• the principle of measurement consists of stretching a standard test piece in a traction machine (for example Zwick Roell 2.5KN), whose movable jaw moves at a constant speed equal to 100 mm/min, and recording:
• the measurement is repeated for 5 test pieces, and the corresponding average of the results obtained is calculated.
• the water content of the ingredients in particular ACCLAIM® 4200 and Jeffcat® DPA, is measured according to a coulometric Karl Fischer method using HYDRANALTM as titrating agent, the equivalence point being detected electrometrically.
• the viscosity of the silylated polymers prepared in the examples below is measured using a Brookfield type method at 23°C and 50% relative humidity (S28 needle).
• ACCLAIM® 4200 In a 500 mL reactor, 304.81 g of ACCLAIM® 4200 are introduced (i.e. a molar equivalent number of -OH groups equal to 0.152 mol), then the reactor is left under vacuum (from 0.1 kPa to 0. 5 kPa) for 2 hours at 110°C to dehydrate the ACCLAIM® 4200. The water content of the ACCLAIM® 4200 is then less than or equal to 0.02% by weight relative to the total weight of the ACCLAIM® 4200.
• the reactor is then cooled to 90°C in order to introduce under nitrogen and at atmospheric pressure 32.6 g of IPDI (i.e. a molar equivalent number of -NCO groups equal to 0.293 mol) and 0.15 g of Borchi®Kat 315.
• the mixture is kept stirring until it reaches a % NCO by weight of 1.7% relative to the total weight of the compounds introduced into the reactor, which corresponds to the excess of -NCO groups introduced relative to the - groups.
• silylated polyurethane Approximately 375 g of silylated polyurethane are obtained and the silylated polyurethane is packaged in aluminum cartridges protected from humidity.
• the viscosity of this silylated polyurethane is 35,500 mPa.s at 23°C.
• Ionic silylated copolyurethane No. 1 is prepared in a similar manner to the reference silylated polyurethane, except that 0.6% by weight of Jeffcat® DPA relative to the weight of ACCLAIM® 4200 is introduced into the reactor before the addition of IPDI, and acetic acid is added, in an acetic acid/Jeffcat® DPA molar ratio equal to 1, after the reaction with IPDI.
• ACCLAIM® 4200 i.e. a molar equivalent number of -OH groups equal to 0.141 mol
• Jeffcat® DPA i.e. a molar equivalent number of -OH groups equal to 0.016 mol
• the reactor is left under vacuum (from 0.1 kPa to 0.5 kPa) for 2 hours at 110 °C to dehydrate ACCLAIM® 4200 and Jeffcat® DPA.
• the water content of the mixture of ACCLAIM® 4200 and Jeffcat® DPA is then less than or equal to 0.02% by weight relative to the total weight of said mixture.
• the reactor is then cooled to 90°C in order to introduce under nitrogen and at atmospheric pressure 32.09 g of IPDI (i.e. a molar equivalent number of -NCO groups equal to 0.288 mol) and 0.15 g of Borchi®Kat 315.
• the mixture is kept stirring until it reaches a % NCO by weight of 1.7% relative to the total weight of the compounds introduced into the reactor, which corresponds to the excess of -NCO groups introduced relative to the - groups.
• ionic silylated copolyurethane Approximately 350 g of ionic silylated copolyurethane are obtained and the ionic silylated copolyurethane is packaged in aluminum cartridges protected from humidity.
• the viscosity of this ionic silylated copolyurethane is 36,000 mPa.s at 23°C.
• Ionic silylated copolyurethane No. 2 is prepared in a similar manner to the reference silylated polyurethane, except that 1.3% by weight of Jeffcat® DPA relative to the weight of ACCLAIM® 4200 is introduced into the reactor before adding the IPDI, and that acetic acid is added, in an acetic acid/Jeffcat® DPA molar ratio equal to 1, after the reaction with IPDI.
• the reactor is then cooled to 90°C in order to introduce under nitrogen and at atmospheric pressure 33.53 g of IPDI and 0.15 g of Borchi®Kat 315.
• the mixture is kept stirring until it reaches a % NCO by weight of 1.7% relative to the total weight of the compounds introduced into the reactor, which corresponds to the excess of -NCO groups introduced relative to the -OH groups.
• ionic silylated copolyurethane Approximately 350 g of ionic silylated copolyurethane are obtained and the ionic silylated copolyurethane is packaged in aluminum cartridges protected from humidity.
• the viscosity of this ionic silylated copolyurethane is 40,500 mPa.s at 23°C.
• Ionic silylated copolyurethane No. 3 is prepared in a similar manner to the reference silylated polyurethane, except that 2.6% by weight of Jeffcat® DPA relative to the weight of ACCLAIM® 4200 is introduced into the reactor before adding the IPDI, and that acetic acid is added, in an acetic acid/Jeffcat® DPA molar ratio equal to 1, after the reaction with IPDI.
• the reactor is then cooled to 90°C in order to introduce under nitrogen and at atmospheric pressure 36.41 g of IPDI and 0.15 g of Borchi®Kat 315.
• the mixture is kept stirring until it reaches a % NCO by weight of 1.7% relative to the total weight of the compounds introduced into the reactor, which corresponds to the excess of -NCO groups introduced relative to the -OH groups.
• 1.93 g of acetic acid are then added at 40°C and stirring is left for 1 hour.
• ionic silylated copolyurethane Approximately 350 g of ionic silylated copolyurethane are obtained and the ionic silylated copolyurethane is packaged in aluminum cartridges protected from humidity.
• the viscosity of this ionic silylated copolyurethane is 59,000 mPa.s at 23°C.
• Ionic silylated copolyurethane No. 4 is prepared in a similar manner to the reference silylated polyurethane, except that 2.6% by weight of Jeffcat® DPA relative to the weight of ACCLAIM® 4200 is introduced into the reactor before adding the IPDI, and that acrylic acid is added, in an acrylic acid/Jeffcat® DPA molar ratio equal to 1, after the reaction with IPDI.
• ACCLAIM® 4200 and 7.82 g of Jeffcat® DPA are introduced, then the reactor is left under vacuum (from 0.1 kPa to 0.5 kPa) for 2 hours at 110 °C to dehydrate ACCLAIMS) 4200 and Jeffcat® DPA.
• the water content of the mixture of ACCLAIM® 4200 and Jeffcat® DPA is then less than or equal to 0.02% by weight relative to the total weight of said mixture.
• the reactor is then cooled to 90°C in order to introduce under nitrogen and at atmospheric pressure 44.62 g of IPDI and 0.15 g of Borchi®Kat 315.
• the mixture is kept stirring until it reaches a % NCO by weight of 1.7% relative to the total weight of the compounds introduced into the reactor, which corresponds to the excess of -NCO groups introduced relative to the -OH groups.
• ionic silylated copolyurethane Approximately 390 g of ionic silylated copolyurethane are obtained and the ionic silylated copolyurethane is packaged in aluminum cartridges protected from humidity. The viscosity of this ionic silylated copolyurethane is 36,000 mPa.s at 23°C.
• Ionic silylated copolyurethane No. 5 is prepared in a similar manner to the reference silylated polyurethane, except that 2.6% by weight of Jeffcat® DPA relative to the weight of ACCLAIM® 4200 is introduced into the reactor before adding the IPDI, and that methanesulfonic acid is added, in a methanesulfonic acid/Jeffcat® DPA molar ratio equal to 1, after the reaction with IPDI.
• the reactor is then cooled to 90°C in order to introduce under nitrogen and at atmospheric pressure 44.53 g of IPDI and 0.15 g of Borchi®Kat 315.
• the mixture is kept stirring until it reaches a % NCO by weight of 1.7% relative to the total weight of the compounds introduced into the reactor, which corresponds to the excess of -NCO groups introduced relative to the -OH groups.
• ionic silylated copolyurethane Approximately 390 g of ionic silylated copolyurethane are obtained and the ionic silylated copolyurethane is packaged in aluminum cartridges protected from humidity.
• the viscosity of this ionic silylated copolyurethane is 61500 mPa.s at 23°C.
• Ionic Silylated Copolyurethane No. 6 is prepared similarly to Ionic Silylated Copolyurethane No. 1, except that N-methyldiethanolamine is used instead of Jeffcat® DPA (i.e. 0.6% by weight of N-methyldiethanolamine relative to weight of ACCLAIM® 4200, and an acetic acid/N-methyldiethanolamine molar ratio equal to 1).
• the polymers prepared in Examples 2 to 8 are used to prepare sealants, the composition of which is indicated in Table 1 below, the percentages being percentages by weight on the total weight of the sealant.
• step 1 the ingredients from step 1 are added at room temperature (approximately 23 °C) and at atmospheric pressure in a rapid blender and then mixed for 2 min.
• step 2 The ingredients from step 2 are then added and everything is mixed for 2 min.
• the stirring speed is approximately 2000 rpm (rotations per minute).
• the sealants obtained are packaged in polyethylene cartridges.
• sealants 1 to 8 The properties of sealants 1 to 8 (measured in accordance with Example 1) are summarized in Table 2 below.
• Comparative putty 1 prepared from the reference silylated polyurethane and without crosslinking catalyst, has a crosslinking time of 70 min.
• This crosslinking time decreases by more than half when the sealant is prepared from an ionic silylated copolyurethane according to the invention (sealants 3 to 7).
• the crosslinking time can be reduced by increasing the quantity of Jeffcat® DPA tertiary amine used during the preparation of the ionic silylated copolyurethane. In fact, when 2.6% instead of 0.6% by weight of Jeffcat® DPA relative to the weight of ACCLAIM® 4200 are used, the crosslinking time goes from 30 min to 22 min (comparison of sealants 3 and 5).
• the crosslinking time varies depending on the acid used during the preparation of the ionic silylated copolyurethane. Indeed, replacing acetic acid with acrylic (mastic 6) or methanesulfonic acid (mastic 7) makes it possible to obtain a crosslinking time equal to, or even less than, that observed for a mastic obtained using using a crosslinking catalyst and the reference silylated polyurethane (putty 2).
• the mastic based on the comparative ionic silylated copolyurethane No. 6 has a significantly greater crosslinking time than the ionic silylated copolyurethane according to the invention.
• the comparative copolyurethane No. 6 does not have a pendant tertiary amine, unlike the ionic silylated copolyurethane according to the invention.
• putty 8 has a sticky appearance after 24 hours, which is not suitable for use as a putty.
• sealants 3 to 7 according to the invention have good tensile strength, generally greater than that of comparative sealant 1, as well as a Young's modulus higher than that of comparative sealant 1.
• the sealants according to the invention are therefore particularly suitable for rigid bonding (after crosslinking), preventing the bonded substrates from moving relative to each other.
• the ionic silylated copolyurethane according to the invention is self-catalyzed, and can be used in a putty without the need to add a metallic or organic crosslinking catalyst.
• the ionic silylated copolyurethane according to the invention makes it possible to obtain sealants particularly suitable for rigid bonding.

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

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• 2022
  • 2022-06-08 FR FR2205493A patent/FR3136467B1/fr active Active
• 2023
  • 2023-06-05 WO PCT/FR2023/050790 patent/WO2023237830A1/fr not_active Ceased
  • 2023-06-05 EP EP23733391.9A patent/EP4536722A1/de active Pending

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