Classifications

• • 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
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
  • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
  • C07D327/04—Five-membered rings
• • 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
  • C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
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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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
  • C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4825—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

Definitions

• the present invention relates to 1, 3-oxathiolane-2-thione derivatives, their preparation process, and their uses.
• the present invention also relates to the silylated polyurethanes obtained from said derivatives 1, 3-oxathiolane-2-thione, as well as the compositions comprising them.
• Silylated polymers are typically used as adhesives, sealants, coatings, for example in the aeronautics, automotive or construction industries.
• Such polymers generally comprise end groups of alkoxysilane type linked, directly or indirectly, to a main chain of polyether or polyurethane type.
• the silylated polyurethanes can be obtained from hydroxysilane derivatives comprising an alkoxysilane function.
• hydroxysilanes typically exhibit stability problems due in particular to the possible transalcoxylation between the hydroxyl function and the alkoxysilane function of the hydroxysilane.
• This secondary reaction can lead to secondary oligomeric products by intra and / or intermolecular reaction, which can affect the crosslinking properties of silylated polyurethanes leading to lower mechanical properties.
• silylated polyurethanes typically have a high viscosity which makes their handling and use more difficult.
• the hydroxyl number of an alcoholic compound represents the number of hydroxyl functions per gram of product, which is expressed in the form of the equivalent number of milligrams of potassium hydroxide (KOH) used in the determination of the hydroxyl functions, per gram of product;
• KOH potassium hydroxide
• the viscosity measurement at 23 ° C (or at 100 ° C) can be done using a Brookfield viscometer according to ISO 2555.
• the measurement carried out at 23 ° C can be done using a Brookfield RVT viscometer, a needle adapted to the viscosity range and a rotation speed of 20 revolutions per minute (rpm); the number-average molecular masses (Mn) of the polyols expressed in g / mole are calculated from their hydroxyl indices and their functionalities.
• the present invention relates to a compound of formula (I):
• R a represents R 1 or R 2 ;
• R b represents R 1 or R 2 ;
• R a represents R 2 then R b represents R 1 , and when R a represents R 1 then R b represents R 2 ;
• each of R 1 and R 2 represents, independently of one another, a radical chosen from the group consisting of:
• a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkyl radical comprising from 1 to 60 carbon atoms, preferably 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, and advantageously from 1 to 8 atoms of carbon ;
• o R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms
• o R 4 represents a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkyl radical, an alkylaryl radical, an arylalkyl radical or an aryl radical, said alkyl, alkylaryl, arylalkyl or aryl radicals each comprising from 1 to 60 carbon atoms, preferably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, and advantageously from 1 to 8 carbon atoms, where each of R j and R 'represents, independently of each other, a linear alkyl radical or branched, aliphatic or cyclic, saturated or unsaturated, comprising from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, preferably from 1 to 2 carbon atoms, and in particular methyl or ethyl;
• R k represents, independently of each other, a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkylene radical comprising from 2 to 4 carbon atoms, and in particular R k represents an ethylene or a butylene;
• each of x, y and z represents, independently of each other, an integer such that the number-average molecular mass (Mn) of the radical varies from 45 to 20,000 g / mol, preferably from 45 to 10,000 g / mol, preferably from 45 to 5000 g / mol, advantageously from 45 to 1000 g / mol, for example from 45 to 500 g / mol;
• R 7 represents a bond or a divalent linear or branched alkylene radical comprising from 1 to 20 carbon atoms
• R 8 represents a linear or branched, aliphatic alkyl or cyclic, saturated or unsaturated, comprising from 1 to 60 carbon atoms, preferably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, advantageously from 1 to 8 carbon atoms, or an arylalkyl comprising from 7 to 20 carbon atoms;
• R 9 represents a bond or a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms
• R 10 and R 11 independently represent one on the other, an atom hydrogen or linear or branched, aliphatic or cyclic alkyl, comprising from 1 to 60 carbon atoms, preferably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms;
• R 12 represents a hydrogen atom, an alkyl radical, linear or branched, cyclic or aliphatic, comprising from 1 to 60 carbon atoms, preferably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, and in particular from 1 to 8 carbon atoms, or a radical -R 13 -SiR 14 p (OR 15 ) 3- P ;
• R 13 represents an alkylene radical, linear or branched, cyclic or aliphatic, comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, and advantageously from 1 to 3 carbon atoms;
• R 14 represents an alkyl radical, linear or branched, cyclic or aliphatic, comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, and advantageously from 1 to 3 carbon atoms;
• p 0, 1, or 2.
• R 1 , R 12 , R 13 , R 14 , R 15 , and p are as defined above.
• the compounds of formula (I) are preferably compounds of formula (1A).
• the compounds of formulas (I), (1A) or (1B) above are those for which R 2 represents H.
• the compounds of formula (I) mentioned above are chosen from the compounds of formulas (II) or (III) below:
• the compounds of formula (II) are chosen from the compounds of formulas (IV), (V), (VI), (VII) and (VIII) below:
• the compounds of formula (IV) are compounds of formula (II) in which R 1 represents a linear or branched, aliphatic or cyclic, saturated or unsaturated alkyl radical, comprising from 1 to 60 carbon atoms, preferably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, advantageously from 1 to 8 carbon atoms; R 12 , R 13 , R 14 , R 15 , and p being as defined above; the compounds of formula (V) below:
• R 3 , R 4 , R ', R j , R k , x, y, z, R 12 , R 13 , R 14 , R 15 , and p are as defined above;
• R 7 , R 8 , R 12 , R 13 , R 14 , R 15 , and p are as defined above;
• R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , and p are as defined above.
• the compounds of formulas (I), (II), (III), (IV), (V), (VI), (VII) and (VIII) mentioned above are those for which:
• R 15 methyl
• R 13 propylene
• - R 12 H, butyl, or -CH 2 -CH (CH2CH3) -CH2-CH2-CH2-CH 3 (ethyl-2-hexyl).
• the compounds of formulas (I), (II), (III), (IV), (V), (VI), (VII) and (VIII) mentioned above are those for which:
• R 15 methyl
• R 13 propylene
• - R 12 H, butyl, or -CH 2 -CH (CH2CH3) -CH2-CH2-CH2-CH 3 (ethyl-2-hexyl).
• the compounds of formulas (I), (1-A) and (1-B) mentioned above are those for which:
• R 1 represents:
• R 1 is a butyl or ethyl-2- radical hexyl: -CH2-CH (CH2CH3) -CH2-CH2-CH2-CH3; o a radical
• R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, preferably from 1 to 5 carbon atoms, for example methylene;
• R 4 represents a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkyl radical comprising from 1 to 12 carbon atoms
• R k represents, independently of each other, a linear or branched, aliphatic or cyclic, saturated or unsaturated alkylene radical, comprising from 2 to 4 carbon atoms, and in particular R k represents an ethylene or a butylene;
• each of x, y and z represents, independently of each other, an integer such that the number-average molecular mass (Mn) of the radical varies from 45 to 20,000 g / mol, preferably from 45 to 10,000 g / mol, preferably from 45 to 5000 g / mol, advantageously from 45 to 1000 g / mol, for example from 45 to 500 g / mol.
• Mn number-average molecular mass
• R 1 is a butyl or ethyl-2- radical hexyl: -CH2-CH (CH2CH3) -CH2-CH2-CH2-CH3; o a radical
• R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, preferably from 1 to 5 carbon atoms, for example methylene;
• R 4 represents a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkyl radical comprising from 1 to 12 carbon atoms
• R k represents, independently of each other, a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkylene radical comprising from 2 to 4 carbon atoms, and in particular R k represents an ethylene or a butylene; o each of x, y and z represents, independently of each other, an integer such that the number-average molecular mass (Mn) of the radical varies from 45 to 20,000 g / mol, preferably from 45 to 10,000 g / mol, preferably from 45 to 5000 g / mol, advantageously from 45 to 1000 g / mol, for example from 45 to 500 g / mol.
• Mn number-average molecular mass
• R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 5 carbon atoms, preferably methylene;
• R 4 represents a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkyl comprising from 1 to 8 carbon atoms, preferably from 4 to 8 carbon atoms;
• - y is 0 or 2;
• each of R j and R ' represents, independently of each other, a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkyl radical comprising from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, preferably from 1 to 2 carbon atoms, and in particular methyl or ethyl.
• the compounds of formula (I) are chosen from the following compounds:
• the present invention also relates to a process for the preparation of a compound of the above-mentioned formula (I) comprising the reaction between a compound of formula (IX):
• R 12 , R 13 , R 14 , R 15 and p are as defined above;
• each of R 1 and R 2 represents, independently of one another, a radical chosen from the group consisting of:
• a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkyl radical comprising from 1 to 60 carbon atoms, preferably 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, and advantageously from 1 to 8 atoms of carbon ;
• o R 3 represents a bond or a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms
• o R 4 represents a linear or branched, aliphatic or cyclic, saturated or unsaturated alkyl radical, an alkylaryl radical, an arylalkyl radical or an aryl radical, said alkyl, alkylaryl, arylalkyl or aryl radicals each comprising from 1 to 60 carbon atoms, preferably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, and advantageously from 1 to 8 atoms of carbon, where each of R j and R 'represents, independently of each other, a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkyl radical comprising from 1 to 10 carbon atoms, preferably from 1 to 6 atoms carbon, preferably from 1 to 2 carbon atoms, and in particular methyl or ethyl;
• R k represents, independently of each other, a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkylene radical comprising from 2 to 4 carbon atoms, and in particular R k represents an ethylene or a butylene;
• each of x, y and z represents, independently of each other, an integer such that the number-average molecular mass (Mn) of the radical varies from 45 to 20,000 g / mol, preferably from 45 to 10,000 g / mol, preferably from 45 to 5000 g / mol, advantageously from 45 to 1000 g / mol, for example from 45 to 500 g / mol;
• R 5 represents a bond or a divalent linear or branched alkylene radical comprising from 1 to 20 carbon atoms
• R 6 represents a linear or branched, aliphatic alkyl or cyclic, saturated or unsaturated, comprising from 1 to 60 carbon atoms, preferably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms; an aryl comprising from 6 to 20 carbon atoms; or an arylalkyl comprising from 7 to 20 carbon atoms
• a radical -R 7 -C (0) -0-R 8 in which R 7 represents a bond or a divalent linear or branched alkylene radical comprising from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, and particular from 1 to 8 carbon atoms
• R 8 represents a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkyl comprising from 1 to 20
• R 9 represents a bond or a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms
• R 10 and R 11 independently represent one on the other, a hydrogen atom or a linear or branched, aliphatic or cyclic alkyl group, comprising from 1 to 60 carbon atoms, preferably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms.
• the compounds of formula (IX) are N- (n-butyl) -3-aminopropyltrimethoxysilane and 3-aminopropyltrimethoxysilane.
• the compounds of above-mentioned formula (X) have the following formula (XI):
• R 1 is as defined above.
• R 1 represents:
• a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkyl radical comprising from 1 to 60 carbon atoms, preferably 1 to 20 carbon atoms, preferably from 1 to 18 carbon atoms, advantageously from 1 to 12 carbon atoms , and in particular from 1 to 8 carbon atoms;
• R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, preferably from 1 to 5 carbon atoms, for example methylene;
• R 4 represents a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkyl radical comprising from 1 to 12 carbon atoms
• R k represents, independently of each other, a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkylene radical comprising from 2 to 4 carbon atoms, and in particular R k represents an ethylene or a butylene;
• each of x, y and z represents, independently of each other, an integer such that the number-average molecular mass (Mn) of the radical varies from 45 to 20,000 g / mol, preferably from 45 to 10,000 g / mol, preferably from 45 to 5000 g / mol, advantageously from 45 to 1000 g / mol, for example from 45 to 500 g / mol.
• Mn number-average molecular mass
• the compounds of formula (X) are preferably chosen from the following compounds:
• the reaction can be carried out under anhydrous conditions.
• the reaction can be carried out at a temperature ranging from 10 ° C to 100 ° C, preferably from 10 ° C to 80 ° C.
• the reaction can be carried out in the presence of a solvent, such as, for example, toluene, ethyl acetate, dichloromethane, methyl ethyl ketone, tetrahydrofuran, acetone, butanone, or their mixtures.
• a solvent such as, for example, toluene, ethyl acetate, dichloromethane, methyl ethyl ketone, tetrahydrofuran, acetone, butanone, or their mixtures.
• a solvent such as, for example, toluene, ethyl acetate, dichloromethane, methyl ethyl ketone, tetrahydrofuran, acetone, butanone, or their mixtures.
• the reaction is carried out in tetrahydrofuran.
• the reaction is carried out in a compound (X) / compound (IX) molar ratio ranging from 1.2 to 0.8, preferably 1.1 to 0.9, preferably the ratio is 1.
• the reaction time can vary in particular according to the nature of the reagents used, their concentrations, the temperature of the reaction.
• the compound of formula (I) can be recovered, in particular by evaporation of the reaction solvent, and can optionally be subjected to a purification step.
• R 1 and R 2 are as defined above;
• the alkali metal halides can be chlorides, iodides or bromides of sodium, potassium or lithium. Mention may for example be made of LiBr, LiCI, LU, NaCI, NaBr, Nal, KCI, KBr or Kl.
• the reaction is carried out in the presence of LiBr.
• the reaction can be carried out in the presence of at least one solvent, for example chosen from the group consisting of ketones, amides, ethers, alcohols, nitriles, and mixtures thereof. It can for example be acetone, DMF, methanol, ethanol, propan-2-ol, acetonitrile, proprionitrile, THF, or mixtures thereof.
• at least one solvent for example chosen from the group consisting of ketones, amides, ethers, alcohols, nitriles, and mixtures thereof. It can for example be acetone, DMF, methanol, ethanol, propan-2-ol, acetonitrile, proprionitrile, THF, or mixtures thereof.
• the reaction can be carried out at a temperature ranging from 0 ° C to 100 ° C, preferably from 10 ° C to 60 ° C.
• the present invention also relates to compounds of the following formula (A):
• R 4 represents a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkyl radical, an alkylaryl radical, an arylalkyl radical or an aryl radical, said alkyl, alkylaryl, arylalkyl or aryl radicals each comprising from 1 to 60 carbon atoms, preferably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, and advantageously from 1 to 8 carbon atoms;
• each of R j and R ' represents, independently of each other, a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkyl radical comprising from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, preferably from 1 to 2 carbon atoms, and in particular methyl or ethyl;
• R k represents, independently of each other, a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkylene radical comprising from 2 to 4 carbon atoms, and in particular R k represents an ethylene or a butylene;
• each of x, y and z represents, independently of each other, an integer such that the number-average molecular mass (Mn) of the radical varies from 45 to 20,000 g / mol, preferably from 45 to 10,000 g / mol , preferably from 45 to 5000 g / mol, advantageously from 45 to 1000 g / mol, for example from 45 to 500 g / mol;
• the compounds of formula (A) are compounds of formulas (A-1), (A-2) or (A-3) following:
• R k represents butylene
• R ' represents H
• R j represents a methyl radical
• R k represents butylene
• R ' represents H
• R j represents a methyl radical
• R 4 represents a butyl radical.
• each R j can be the same or different for each value of y.
• each R k can be identical or different for each value of x.
• the present invention also relates to a composition C comprising two different compounds of formula (I), the formula (I) being as defined above.
• composition C comprises:
• R 1 , R 2 , R 12 , R 13 , R 14 , R 15 and p are as defined above.
• composition C Preferably, in the above-mentioned composition C:
• the radical R 1 of the formula (1A) is identical to the radical R 1 of the formula (1B);
• radical R 2 of the formula (1A) is identical to the radical R 2 of the formula (1B);
• radical R 12 of the formula (lA) is identical to the radical R 12 of the formula (lB) - the radical R 13 of the formula (lA) is identical to the radical R 13 of the formula (lB)
• the radical R 14 of the formula (lA) is identical to the radical R 14 of the formula (lB)
• the radical R 15 of the formula (lA) is identical to the radical R 15 of the formula (lB)
• p of the formula (lA ) is identical to the p of formula (Ib).
• composition C comprises:
• R 1 , R 12 , R 13 , R 14 , R 15 and p are as defined above.
• composition C Preferably, in the above-mentioned composition C:
• radical R 12 of formula (II) is identical to the radical R 12 of formula (III);
• radical R 1 of the formula (II) is identical to the radical R 1 of the formula (III);
• radical R 13 of formula (II) is identical to the radical R 13 of formula (III);
• radical R 14 of formula (II) is identical to the radical R 14 of formula (III);
• radical R 15 of formula (II) is identical to the radical R 15 of formula (III);
• p of formula (II) is identical to p of formula (III).
• the present invention also relates to the use of a compound of formula (I) as defined above or of the above-mentioned composition C for preparing a polymer.
• the present invention also relates to a polyurethane P obtained by a process comprising a reaction step between:
• a prepolymer preferably polyurethane prepolymer, of formula (XII) below:
• the polyurethane P according to the invention is obtained by a process comprising a reaction step between:
• the prepolymer of formula (XII) can be obtained by any method known to a person skilled in the art for the preparation of prepolymer terminated with -NCO groups.
• the prepolymer of formula (XII) mentioned above is a polyurethane obtained by polyaddition reaction: a) 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 molar ratio (r1) in quantities such that the NCO / OH molar ratio (r1) is strictly greater than 1, preferably ranges from 1.2 to 2.
• 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
• NCO / SH (r2) molar ratio is preferably between 1, 3 and 5.
• (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 / SH molar ratio corresponding to the molar ratio of the number of isocyanate groups to the number of mercapto groups carried respectively by all of the isocyanate (s) (especially with regard to the polyurethane prepolymer with NCO endings 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).
• step E1 When the polyurethane with NCO endings is obtained during step E1) from a mixture of polyisocyanates or from several polyisocyanates added successively, the calculation of the ratio (r1) takes account on the one hand of the NCO groups carried by the all of the polyisocyanates present in the reaction medium of step E1), and on the other hand 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 for preparing the prepolymer of formula (XII) mentioned above used according to the invention can be chosen from those whose number average molecular mass (Mn) goes from 300 to 20,000 g / mol, preferably from 400 to 15,000 g / mol, and preferably from 500 to 12,000 g / mol.
• 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 may (wind) have a hydroxyl number (IOH) (average) ranging from 9 to 570 milligrams of KOH per gram of polyol (mg KOH / g), preferably 35 to 430 mg KOH / g, more preferably 55 to 340 mg KOH / g.
• IOH hydroxyl number
• the polyol (s) can be chosen from polyether polyols, polyester polyols, polycarbonate polyols and their mixtures.
• 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 polyol, the alkylene part of which, 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, the alkylene part of which, linear or branched, comprises 1 to 4 carbon atoms, more preferably 2 to 3 carbon atoms.
• polyoxypropylene diols or triols also known as polypropylene glycol (PPG) diols or triols
• PPG polypropylene glycol
• Mn number average molecular weight
• polyoxyethylene diols or triols also known as polyethylene glycol (PEG) diols or triols
• Mn number average molecular weight
• 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 250 to 4000 g / mol;
• the polyether polyols raised 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 potash) or a catalyst based on a double metal-cyanide complex.
• a basic catalyst for example potash
• a catalyst based on a double metal-cyanide complex for example
• VORANOL® EP 1900 difunctional PPG of number average molecular mass of approximately 4,008 g / mol, and of hydroxyl index I O H equal to 28 mg KOH / g
• ACCLAIM ® 8200 difunctional PPG of number average molecular mass of 8,016 g / mol, and of hydroxyl index lo H equal to 14 mg KOH / g;
• ACCLAIM® 12200 difunctional PPG of number average molecular mass of 1122 g / mol, and of hydroxyl index lo H equal to 10 mg KOH / g; ACCLAIM ® 18200: difunctional PPG of number average molecular mass of 17,265 g / mol, and of hydroxyl index lo H equal to 6.5 mg KOH / g.
• VORANOL® CP 755 trifunctional PPG of number average molecular mass of approximately 710 g / mol, and of hydroxyl index lo H equal to 237 mg KOH / g; VORANOL® CP 3355: trifunctional PPG of number average molecular weight of approximately 3544 g / mol, and of hydroxyl index lo H equal to 47.5 mg KOH / g; ACCLAIM ® 6300: trifunctional PPG of number average molecular weight of approximately 5,948 g / mol, and of hydroxyl index lo H equal to 28.3 mg KOH / g.
• TERATHANE ® PTMEG 250 Difunctional polyTHF of number average molecular weight of approximately 4,008 g / mol, and of hydroxyl index I O H ranging from 230 to 270 mg KOH / g;
• TERATHANE ® PTMEG 2900 Difunctional polyTHF of average molecular mass in number of approximately 4,008 g / mol, and of hydroxyl index I O H ranging from 37.7 to 39.7 mg KOH / g.
• hydroxyl functionality of a polyether polyol means 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 By way of example of polyester diol or triol, there may be mentioned: "REALKYD® XTR 10410" sold by the company CRAY VALLEY with a number average molecular mass (Mn) close to 1000 g / mol and whose hydroxyl index ranges from 108 to 1116 mg KOH / g. It is a product resulting from the condensation of adipic acid, diethylene glycol and monoethylene glycol;
• the polycarbonate polyols can be chosen from polycarbonate diols or triols, in particular having 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 whose hydroxyl indices are respectively 1 12 and 56 mg KOH / g,
• DESMOPHEN® C XP 2716 marketed by COVESTRO with a molecular mass in number (M n ) equal to 326 g / mol and whose hydroxyl index is 344 mg KOH / g
• POLYOL C-590, C1090, C-2090 and C-3090 marketed by 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 for preparing the prepolymer of formula (XII) mentioned above can be added sequentially or reacted in the form of 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 diisocyanate, 1,4-cyclohexane diisocyanate (CHDI), methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diiso
• the polyisocyanate (s) is (are) chosen from toluene diisocyanate (in particular the 2,4 TDI isomer, the 2,6-TDI isomer or mixtures thereof), the meta- xylylene, IPDI, and mixtures thereof.
• the polyisocyanate is isophorone diisocyanate (IPDI).
• the polyisocyanate (s) which can be used are typically widely available commercially.
• SCURANATE® TX sold by the company VENCOREX, corresponding to a 2,4-TDI of purity of the order of 95%
• SCURANATE® T100 sold by the company VENCOREX, corresponding to a 2,4-TDI of purity greater than 99% by weight
• 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 not of at least one reaction catalyst.
• reaction catalyst (s) which can be used during the polyaddition reaction of step E1) can be any catalyst known to a person skilled in the art for catalyzing the formation of polyurethane by reaction 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 of step E1) can be used. In particular, it is preferable to use from 0.02 to 0.2% by weight of catalyst (s) relative to the total weight of the reaction medium of step E1).
• Step E2) can be carried out under anhydrous conditions.
• Step E2) can be carried out at a temperature ranging from 40 ° C to 100 ° C, preferably from 60 ° C to 100 ° C.
• the polyaddition reaction of step E2) can be carried out in the presence or not of at least one reaction catalyst.
• the reaction catalyst (s) which can be used during the polyaddition reaction of step E2) can be any catalyst known to a person skilled in the art for catalyzing this type of reaction between a mercapto compound and an NCO finished prepolymer.
• An amount of up to 0.3% by weight of catalyst (s) relative to the weight of the reaction medium of step E2) can be used.
• the prepolymer of formula (XII) can comprise a mass content 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 (XIII):
• B represents a multivalent organic radical
• t represents an integer or a non-integer ranging from 2 to 4;
• R a represents R 1 or R 2 ;
• R b represents R 1 or R 2 ;
• R a represents R 2 then R b represents R 1 , and when R a represents R 1 then R b represents R 2 ;
• each of R 1 and R 2 represents, independently of one another, a radical chosen from the group consisting of:
• a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkyl radical comprising from 1 to 60 carbon atoms, preferably 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, and advantageously from 1 to 8 atoms of carbon ;
• R 3 represents a bond or a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms
• R 4 represents a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkyl radical, an alkylaryl radical, an arylalkyl radical or an aryl radical, said alkyl, alkylaryl, arylalkyl or aryl radicals each comprising from 1 to 60 carbon atoms, preferably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, and advantageously from 1 to 8 carbon atoms, where each of R j and R 'represents, independently of each other, a linear alkyl radical or branched, aliphatic or cyclic, saturated or unsaturated, comprising from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, preferably from 1 to 2 carbon atoms, and in particular methyl or ethyl;
• R k represents, independently of each other, a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkylene radical comprising from 2 to 4 carbon atoms, and in particular R k represents an ethylene or a butylene;
• each of x, y and z represents, independently of each other, an integer such that the number-average molecular mass (Mn) of the radical varies from 45 to 20,000 g / mol, preferably from 45 to 10,000 g / mol, preferably from 45 to 5000 g / mol, advantageously from 45 to 1000 g / mol, for example from 45 to 500 g / mol;
• R 5 represents a bond or a divalent linear or branched alkylene radical comprising from 1 to 20 carbon atoms
• R 6 represents a linear or branched, aliphatic alkyl or cyclic, saturated or unsaturated, comprising from 1 to 60 carbon atoms, preferably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms; an aryl comprising from 6 to 20 carbon atoms; or an arylalkyl comprising from 7 to 20 carbon atoms;
• R 7 represents a bond or a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms
• R 8 represents a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkyl comprising from 1 to 60 carbon atoms, preferably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, advantageously from 1 to 8 carbon atoms, or an arylalkyl comprising from 7 to 20 carbon atoms;
• R 9 represents a bond or a divalent linear or branched alkylene radical comprising from 1 to 20 carbon atoms
• R 10 and R 11 independently represent the one of the other, a hydrogen atom or a linear or branched, aliphatic or cyclic alkyl group, comprising from 1 to 60 carbon atoms, preferably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms ;
• R 12 represents a hydrogen atom, an alkyl radical, linear or branched, cyclic or aliphatic, comprising from 1 to 60 carbon atoms, preferably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, and in particular from 1 to 8 carbon atoms, or a radical -R 13 -SiR 14 p (OR 15 ) 3- P ;
• R 13 represents an alkylene radical, linear or branched, cyclic or aliphatic, comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, and advantageously from 1 to 3 carbon atoms;
• R 14 represents an alkyl radical, linear or branched, cyclic or aliphatic, comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, and advantageously from 1 to 3 carbon atoms;
• Polyurethane P ' can be a particular example of the polyurethane P mentioned above.
• the polyurethane P ' preferably has the following formula (XIV): in which :
• B represents a multivalent organic radical
• R a represents R 1 or R 2 ;
• R b represents R 1 or R 2 ;
• R a represents R 2 then R b represents R 1 , and when R a represents R 1 then R b represents R 2 ;
• each of R 1 and R 2 represents, independently of one another, a radical chosen from the group consisting of:
• a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkyl radical comprising from 1 to 60 carbon atoms, preferably 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, and advantageously from 1 to 8 atoms of carbon ;
• ⁇ R 3 is a bond or a divalent linear or branched alkylene radical comprising 1 to 20 carbon atoms,
• R 4 represents a linear or branched alkyl radical, aliphatic or cyclic, saturated or unsaturated, an alkylaryl radical, an arylalkyl radical or an aryl radical, said alkyl, alkylaryl, arylalkyl or aryl each having from 1 to 60 carbon atoms, preferably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, and advantageously from 1 to 8 carbon atoms,
• each of R j and R ' represents, independently of each other, a linear or branched, aliphatic or cyclic, saturated or unsaturated, comprising from 1 to 10 carbon atoms, preferably 1 with 6 carbon atoms, preferably from 1 to 2 carbon atoms, and in particular methyl or ethyl;
• R k represents, independently of each other, a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkylene radical comprising from 2 to 4 carbon atoms, and in particular R k represents an ethylene or a butylene;
• ⁇ each of x, y and z represent, independently of each other, an integer such that the molecular weight (Mn) of the group varies from 45 to 20 000 g / mol, preferably from 45 to 10 000 g / mol, preferably from 45 to 5000 g / mol, advantageously from 45 to 1000 g / mol, for example from 45 to 500 g / mol;
• R 5 represents a bond or a divalent linear or branched alkylene radical comprising from 1 to 20 carbon atoms
• R 6 represents a linear or branched, aliphatic alkyl or cyclic, saturated or unsaturated, comprising from 1 to 60 carbon atoms, preferably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms; an aryl comprising from 6 to 20 carbon atoms; or an arylalkyl comprising from 7 to 20 carbon atoms;
• R 7 represents a bond or a divalent linear or branched alkylene radical comprising from 1 to 20 carbon atoms
• R 8 represents a linear or branched, aliphatic alkyl or cyclic, saturated or unsaturated, comprising from 1 to 60 carbon atoms, preferably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, advantageously from 1 to 8 carbon atoms, or an arylalkyl comprising from 7 to 20 carbon atoms;
• R 9 represents a bond or a linear or branched divalent alkylene radical comprising from 1 to 20 carbon atoms
• R 10 and R 11 independently represent one on the other, a hydrogen atom or a linear or branched, aliphatic or cyclic alkyl group, comprising from 1 to 60 carbon atoms, preferably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms
• R 12 represents a hydrogen atom, an alkyl radical, linear or branched, cyclic or aliphatic, comprising from 1 to 60 carbon atoms, preferably from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, and in particular from 1 to 8 carbon atoms, or a radical -R 13 -SiR 14 p (OR 15 ) 3-P
• R 13 represents an alkylene radical, linear or branched, cyclic or aliphatic, comprising from 1 to 10 carbon
• R 14 represents an alkyl radical, linear or branched, cyclic or aliphatic, comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, and advantageously from 1 to 3 carbon atoms;
• Each occurrence of each of R a , R b , R 1 , R 2 , R 12 , R 13 , R 14 , R 15 and p can be the same or different.
• each occurrence of each of R a , R b , R 1 , R 2 , R 12 , R 13 , R 14 , R 15 and p which may be identical or different
• each occurrence of R a in formula (XIV) can be the same or different, or that each occurrence of p can be the same or different in formula (XIV).
• R a of the formula (XIV) can represent H
• the other R a can represent a radical -CHR 1 .
• each occurrence of each of R a , R b , R 1 , R 2 , R 12 , R 13 , R 14 , R 15 and p is identical.
• the polyurethane P ’ according to the invention preferably has one of the following formulas (XV), (XVI) or (XVII):
• R 1 , R 12 , R 13 , R 14 , R 15 and p are as defined above.
• the polyurethanes P ’of the formulas (XIII), (XIV), (XV), (XVI), (XVII) mentioned above are those for which:
• R 15 methyl
• R 13 propylene
• - R 12 H, butyl, or -CH 2 -CH (CH2CH3) -CH2-CH2-CH2-CH 3 (ethyl-2-hexyl).
• polyurethanes P ’of the formulas (XIX), (XX), (XXI), (XXII), (XXIII) mentioned above are those for which:
• R 15 methyl
• R 13 propylene
• - R 12 H, butyl, or -CH 2 -CH (CH2CH3) -CH2-CH2-CH2-CH 3 (ethyl-2-hexyl).
• the group R 1 represents:
• a saturated aliphatic linear or branched alkyl radical comprising from 1 to 8 carbon atoms, preferably 4 carbon atoms or -CH2-CH (CH2CH 3 ) -CH2-CH2- CH 2 -CH 3 (ethyl-2-hexyl);
• R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 5 carbon atoms, preferably methylene;
• R 4 represents a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkyl comprising from 1 to 8 carbon atoms, preferably from 4 to 8 carbon atoms;
• each of R j and R ' represents, independently of each other, a linear or branched, aliphatic or cyclic, saturated or unsaturated, alkyl radical comprising from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, preferably from 1 to 2 carbon atoms, and in particular methyl or ethyl;
• the present invention also relates to the use of the aforementioned polyurethanes (P and P ’) for the preparation of adhesives, sealants or coatings.
• silylated polyurethanes according to the invention advantageously have a lower viscosity than existing silylated polyurethanes, which makes their handling and their use easier.
• the present invention relates to a composition V comprising at least one, preferably at least three, polyurethane (s) P (or P ’) according to the invention.
• Composition V can have a Brookfield viscosity measured at 100 ° C., ranging from 100 to 3000 mPa.s.
• composition V comprises:
• each occurrence of each of R 1 , R 12 , R 13 , R 14 , R 15 , and p being preferably identical.
• the present invention relates to a formulation comprising at least one polyurethane P or polyurethane 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, antistatic agents, foaming agents, biocides, plasticizers, lubricants, emulsifiers, dyes, pigments, rheological agents, impact modifiers, adhesion promoters, optical brighteners , flame retardants, anti-seepage agents, nucleating agents, solvents, reactive diluents and their mixtures.
• at least one additive chosen from the group consisting of catalysts, fillers, antioxidants, light stabilizers / UV absorbers , metal deactivators, antistatic agents, foaming agents, biocides, plasticizers, lubricants, emulsifiers, dyes, pigments, rheological agents, impact modifiers, adhesion promoters, optical brighteners , flame retard
• the above-mentioned formulation advantageously comprises a polymer P ′ of formula (XV) as defined above.
• the fillers usually used are, for example, inorganic or organic powders, for example calcium carbonates and silicates, inorganic fibrous materials, for example glass fibers. It is also possible to use loads organic such as carbon fibers, mixtures of organic and inorganic fillers, for example mixtures of glass fibers and carbon 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 have good resistance to migration and great 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 the compounds j) to t) act as stabilizers:
• the catalysts are optionally used in proportions ranging from 0.01% to approximately 10% by weight, relative to the total weight of the formulation.
• the catalyst can be chosen from:
• titanium acetyl acetonate commercially available under the name TYZOR ® AA75 from DuPont
• Ti (OnBu) 4 commercially available under the name TYZOR® TNBT in Dorf Ketal
• - organic aluminum compounds such as aluminum chelate (commercially available under the name K-KAT ® 5218 from King Industries)
• - organic tin compounds such as dibutyltin dilaurate (DBTL or), dibutyltin dilaurate (DOTDL), the bisacetylacetonate dioctyltin (available under the tradename TIBKAT ® 223) or TibKat® 425 (which is a mixture of dioctyl tin oxide and vinyltrimethoxysilane),
• DBTL dibutyltin dilaurate
• DOTDL dibutyltin dilaurate
• 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, particularly triethylamine and fe / f-butylamine.
• DBU 8-diazabicyclo [5.4.0] undec-7-ene
• DBN 5-diazabicyclo [4.3.0] non-5-ene
• TGD 1,5,7- Triazabicyclo [4.4.0] dec-5-ene
• TGD di-o-tolylguanidine
• the solvents can be organic solvents, for example chosen from aprotic solvents, protic solvents and their mixtures.
• the present invention also relates to the use of the above-mentioned 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%” includes in particular the values 0% and 25%.
• E1 2-butyl oxirane available from SIGMA-ALDRICH;
• E2 2- (butoxymethyl) oxirane available from SIGMA-ALDRICH and COVESTRO;
• E3 2 - [[(2-ethylhexyl) oxy] methyl] oxirane available from SIGMA-ALDRICH;
• E4 polypropylene glycol mono glycidyl ether monobutyl ether (CAS number: 62412-80-0) synthesized according to the procedure described in WO 2015,148,192 from DOW GLOBAL TECHNOLOGIES;
• SILQUEST A- 1 1 10 3-aminopropyltrimethoxysilane available from MOMENTIVE;
• DYNASYLAN 1,189 N- (n-butyl) -3-aminopropyltrimethoxysilane marketed by EVONIK;
• BORCHIKAT 315 bismuth neodecanoate available from OMG BORCHERS;
• TIBKAT 223 Dioctyltinbis (acetylacetonate) available from TIB CHEMICALS.
• Example 1 is reproduced by substituting compound S1 with compound S2 obtained in example 1 (412.3 g) to quantitatively obtain the product of the following formula:
• Example 1 is reproduced by substituting compound S1 with compound S4 obtained in example 1 (644.3 g) to quantitatively obtain the product of the following formula:
• the reactor is then cooled to 70 ° C. in order to introduce 46.6 g of isophorone diisocyanate (IPDI) and 0.4 g of BORCHIKAT 315 (bismuth neodecanoate available from OMG BORCHERS) under a nitrogen blanket.
• the mixture is kept stirring until reaching a% NCO by weight of 1.7%, ie 0.40 meq NCO / g. 730.1 g of terminated polyurethane prepolymer -NCO (PO) are obtained.
• the viscosity of the silylated polymers P2, P3 and P4 advantageously have a viscosity lower than that of the silylated polymer P1 (comparison) (at 100 ° C), which allows in particular easier handling and use.
• a lower viscosity advantageously makes it possible to avoid the additional use of plasticizer in the formulations.

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