Classifications

• • 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
  • 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
  • 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
  • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
  • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
  • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
• • 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
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/285—Nitrogen containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
  • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
  • C08G18/348—Hydroxycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4825—Polyethers containing two hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—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
  • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
  • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/08—Polyurethanes from polyethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2170/00—Compositions for adhesives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2190/00—Compositions for sealing or packing joints

Definitions

• the subject of the present invention is a novel silylated polyurethane, more precisely with terminal alkoxysilane groups, as well as its preparation process. It also relates to a crosslinkable composition, which can be used as an adhesive and / or mastic, comprising said polyurethane and a process for assembling 2 substrates using it.
• Sealants are widely used, in particular because of their mechanical properties and their affinity for various materials, both in the construction field and for certain industrial applications.
• the adhesive seal thus formed therefore exhibits great strength, marked by high resistance to deformation. It also has a flexibility (or elasticity) which allows it to adapt to the relative movements of the substrates that it brings together, for example under the effect of dimensional variations induced by changes in temperature or even under the effect of mechanical stresses. to which the assembly may be subjected during its lifetime.
• the resistance to deformation of a sealant is often quantified, in practice, by the tensile strength (expressed in Pa). The latter is simply defined, in a tensile test of a specimen made up of said mastic, as being the stress which must be applied to said specimen in order to obtain its rupture.
• the elasticity of a mastic is, for its part, generally represented by a measurement of the elongation at break (expressed in%), and which is defined, in the aforementioned tensile test, as the elongation measured for said test piece at the time of its rupture.
• the most common sealants on the market are in the form of compositions which comprise, generally in combination with a mineral filler, a moisture-crosslinkable prepolymer, the chemical structure of which is endowed with reactive groups, generally terminal, isocyanate or alkoxysilane. .
• the reaction of these reactive groups with the water which comes from the humidity of the air or of the substrates to be assembled, when the mastic is used, is called the crosslinking reaction.
• Moisture-crosslinkable mastic compositions based on prepolymers containing alkoxysilane endings have the advantage of being free of isocyanates, in particular of monomeric diisocyanates. These compositions therefore constitute an alternative, which is preferred from a toxicological point of view, to compositions based on polyurethane with isocyanate endings.
• silylated mastics takes place, in the presence of humidity, by hydrolysis of the alkoxysilane groups carried by the prepolymer, then their condensation to form a siloxane bond (-Si-O-Si-) which unites the prepolymer chains in a polymer forming a solid three-dimensional network.
• the prepolymers included in the silylated mastics can comprise, among different types of main chains, a polyurethane chain, thus forming a silylated prepolyurethane (also referred to simply as polyurethane).
• the most well-known silylated polyurethanes are generally prepared by a 2-step process.
• the 1st step consists in forming a polyurethane with isocyanate endings, by reacting a poly (propylene glycol) with a diisocyanate.
• the second step consists in reacting the prepolyurethane thus obtained with an aminosilane comprising an alkoxysilane group, so as to obtain a main polyurethane chain which comprises 2 terminal alkoxysilane groups, each linked to said chain via a urea function.
• SPUR polyurethanes
• the crosslinking time of these silylated polyurethanes, in particular of these SPURs, must be accelerated to meet the needs of the users, and for this purpose it is compulsory to incorporate a crosslinking catalyst in the mastic compositions comprising them.
• the crosslinking catalyst included in the mastics or adhesive compositions based on silylated polymers, in particular on SPUR is a metal catalyst, and more particularly a tin-based catalyst, such as dibutyltin dilaurate (or DBTDL), dibutyltin diacetate or dibutyltin or dioctyltin bis (acetylacetonate).
• DBTDL dibutyltin dilaurate
• these catalysts are the subject of criticism relating to their toxicity or their impact on the environment, which leads the manufacturers concerned to limit, or even avoid their use, especially since these metal catalysts remain in the adhesive seal. , once the composition has been crosslinked.
• Organic crosslinking catalysts derived from nitrogenous heterocycles such as l, 8-diazabicyclo (5.4.0) undec-7-ene (also called DBU) or even 1,5,7-triazabicyclo [4.4.0] dec-5 -ene (also called TBD) have been used as an alternative to metal catalysts, especially tin-based catalysts.
• DBU 8-diazabicyclo
• TBD 1,5,7-triazabicyclo [4.4.0] dec-5 -ene
• the object of the present invention is to remedy the drawbacks of silylated polyurethanes known from the prior art, in particular the drawbacks of SPURs.
• Another object of the invention is to provide a silylated polyurethane the crosslinking of which does not require, or substantially does not require, a tin-based catalyst, or an organic catalyst derived from a nitrogenous heterocycle.
• Another aim of the invention is to provide a silylated polyurethane which can crosslink in the absence of a catalyst.
• Another aim of the invention is to provide a mastic composition based on silylated polyurethane which makes it possible, without addition, or without substantial addition, of catalyst, to reduce the crosslinking time.
• Another aim of the invention is to provide a mastic composition based on silylated polyurethane which has improved mechanical properties.
• Another aim of the invention is to provide a mastic composition based on silylated polyurethane which has better adhesion properties on various substrates, in particular on a metal substrate.
• the present invention relates firstly to an ionic silylated copolyurethane comprising 2 ureido-alkylene-alkoxysilane end groups and corresponding to formula (I): in which :
• R 1 represents a divalent hydrocarbon radical comprising from 5 to 45 carbon atoms which may be aromatic or aliphatic, linear, branched or cyclic and may include at least one heteroatom chosen from O, S and N;
• R 2 represents a divalent linear or branched alkylene radical comprising from 2 to 4 carbon atoms
• - n is an integer such that the number-average molecular mass Mn of the block of formula - [OR 2 ] n - ranges from 2500 to 20,000 g / mole;
• - R represents a hydrogen atom or an alkyl radical comprising from 1 to 18 carbon atoms
• R, R 'and R " identical or different, each represent a saturated, unsaturated or aromatic hydrocarbon radical, optionally comprising a heteroatom chosen from N, O and S; R, R' and R" further being such as tertiary amine of formula N (R) (R ') (R ”) is a linear, branched or cyclic amine or polyamine whose number-average molar mass Mn ranges from 59 to 6000 g / mol and which has a pKa greater than 8 ;
• - x and y are integers ranging from 1 to 8;
• - z is an integer ranging from 0 to 8.
• q / m and q are each an integer greater than or equal to 1, such that the q / m ratio is in a range ranging from 0.04 to 20, preferably from 0.10 to 13, more preferably from 0.10 to 5, and even more preferably from 0.15 to 1.
• F 1 represents a radical of formula (Ha) and F 2 represents a radical of formula
• R 3 represents a divalent linear or branched alkylene radical comprising from 1 to 6 carbon atoms
• R 4 represents a linear or branched alkyl radical comprising from 1 to
• R 5 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, an alkylcarbonyl radical comprising from 2 to 8 carbon atoms, or a dialkylimino radical comprising from 3 to 8 carbon atoms:
• R 6 represents a phenyl radical, a linear, branched or cyclic alkyl radical comprising from 1 to 6 carbon atoms, or a radical chosen from the radicals:
• R 7 is a linear or branched alkyl radical comprising from 1 to 6 carbon atoms;
• the ionic silylated copolyurethane of formula (I) advantageously leads to mastic and / or adhesive compositions which exhibit, in the absence of a catalyst, in particular in the absence of a tin-based catalyst, a reduced crosslinking time. compared to S PURs of the prior art.
• the adhesive joint which is formed by the crosslinking in the presence of moisture of an adhesive composition and / or mastic comprising said copolyurethane and at least one inorganic filler, also exhibits better mechanical properties, and in particular resistance to water. improved deformation and elasticity, marked respectively by increased stress and elongation at break.
• the adhesion of said adhesive seal to a support is reinforced, including in the presence of water and / or humidity, which is very advantageous in certain applications. Mention may be made, for example, of the durability of a windshield seal which is brought into contact with rainwater.
• the average molecular mass Mn is measured by size exclusion chromatography (or SEC, acronym for "Size Exclusion Chromatography” in English) which is also designated by the terms of gel permeation chromatography (or by the acronym English correspondent GPC).
• the calibration used is usually a PEG (PolyEthylene Glycol) or PS (PolyStyrene) calibration, preferably PS.
• R 3 represents the methylene or n-propylene radical, preferably n-propylene
• R 4 and R 5 identical or different, each represent the methyl or ethyl radical, preferably methyl;
• R 6 represents a linear alkyl radical comprising from 1 to 4 carbon atoms, preferably an n-butyl, or a radical of formula (Ile) in which R 7 is an alkyl radical comprising from 1 to 3 carbon atoms, R 7 preferably being an ethyl radical.
• the main chain of the ionic silylated copolyurethane of formula (I) therefore consists of a repeating unit repeated m times and a repeating unit repeated q times. It is understood that the distribution of these 2 units on said main chain is statistical, and that the copolyurethane of formula (I) is therefore a random copolymer.
• the following variants of the main chain are also more particularly preferred, taken individually or in combination with one another or else in combination with the variants described above for the end groups F 1 and F 2 .
• R 1 radical which is included in the 2 repeating units is chosen from one of the following divalent radicals, the formulas of which below reveal the 2 free valences:
• IPDI isophorone diisocyanate
• - i is an integer ranging from 2 to 5;
• - j is an integer ranging from 1 to 2;
• R 11 represents a hydrocarbon radical, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 6 to 14 carbon atoms;
• R 12 represents a divalent propylene group
• hexamethylene diisocyanate allophanate corresponding to formula (IVb) comprises an NCO isocyanate group content ranging from 12 to 14% by weight relative to the weight of said allophanate.
• the radical R 1 is the divalent radical derived from isophorone diisocyanate.
• the unit repeated m times comprises the polyether block of formula: - [OR 2 ] n -. According to other embodiments of said pattern:
• the R 2 radical advantageously represents a divalent alkylene radical comprising from 2 to 3 carbon atoms, even more preferably the isopropylene radical; and or
• the integer n is such that the number-average molecular mass Mn of the block of formula - [OR 2 ] n - ranges from 3,500 to 12,000 g / mole.
• - R represents an alkyl radical comprising from 1 to 4 carbon atoms, preferably a methyl, ethyl or n-propyl radical, even more preferably a methyl radical;
• the unit repeated q times thus comprises a pendant anionic carboxylate group, the counterion of which is an ammonium of formula: HN + (R) (R ′) (R ′′).
• the pKa of the corresponding amine is greater than or equal to 10.
• the ionic silylated copolyurethane of formula (I) is generally in the form of a viscous liquid, and is characterized by a Brookfield viscosity at 23 ° C ranging from 10 to 300 Pa.s, preferably from 30 to 200 Pa.s . It is then advantageously easy to use and can be combined with an additional component such as a filler, to form an adhesive and / or mastic composition.
• a subject of the invention is also a process for preparing ionic silylated copolyurethane comprising 2 ureido-alkylene-alkoxysilane end groups and corresponding to formula (I), according to the invention, said process comprising the sequential steps:
• R 1 represents a divalent hydrocarbon radical comprising from 5 to 45 carbon atoms which may be aromatic or aliphatic, linear, branched or cyclic and may include at least one heteroatom chosen from O, S and NOT ; .
• the polyisocyanate (A) of formula (IVa) is such that the radical R 1 is chosen from one of the following divalent radicals, the formulas of which below reveal the 2 free valences:
• IPDI isophorone diisocyanate
• HMDI 4,4'- and 2,4'-dicyclohexylmethane diisocyanate
• polyisocyanates whose radical R 1 corresponds to the radicals a) to f) above are well known to those skilled in the art and widely available commercially.
• a polyisocyanate in which the radical R 1 is the divalent group g) above is also sold under the name "Tolonate ®" by the company Vencorex, for example under the name "Tolonate ® X FLO 100".
• the polyisocyanate (A) is isophorone diisocyanate (IPDI).
• Step (i) uses the polyether diol (B) of formula (IVb):
• R 2 represents a divalent linear or branched alkylene radical comprising from 2 to 4 carbon atoms
• - n is an integer such that the number-average molecular mass Mn of the block of formula - [OR 2 ] n - ranges from 2,500 to 20,000 g / mole.
• the polyether diol (B) is such that:
• the R 2 radical represents a divalent alkylene radical comprising from 2 to 3 carbon atoms, and / or
• n is such that the number-average molecular mass of the block of formula - [OR 2 ] n - ranges from 3,500 to 12,000 g / mole.
• the polyether diol (B) is a polypropylene glycol diol, for which R 2 is an isopropylene radical.
• R 2 is an isopropylene radical.
• Such polypropylene glycols are commercially available under the ACCLAIM ® brand with the COVESTRO society. We can cite as examples:
• the hydroxyl number IOH is the number of hydroxyl functions per gram of diol, expressed as the equivalent number of milligrams of KOH used in the determination of hydroxyl functions.
• Step (i) uses the carboxylic diol (C) of formula (IVc): in which :
• - R represents a hydrogen atom or an alkyl radical comprising from 1 to 18 carbon atoms
• - x and y are integers ranging from 1 to 8.
• - z is an integer ranging from 0 to 8.
• - R represents an alkyl radical comprising from 1 to 4 carbon atoms, preferably a methyl, ethyl or n-propyl radical, even more preferably a methyl radical;
• carboxylic diols (C) As specific examples of carboxylic diols (C), the following ⁇ , ⁇ -dimethylolalkanoic acids may be mentioned:
• the carboxylic diol (C) used in step (i) is 2,2-di (hydroxymethyl) propionic acid, also called ⁇ , ⁇ -dimethylolpropionic acid (conveniently designated under the English acronym DMPA) of formula:
• the carboxylic diols (C) of formula (IVc) are prepared according to conventional organic synthesis methods, as described for example in US Pat. No. 3,412054 to UNION CARBIDE, and many are those, such as DMPA, available commercially.
• step (i) of the process according to the invention the polyisocyanate (A), the polyether diol (B) and the carboxylic diol (C) are reacted in amounts corresponding to an excess of the equivalent number of groups - NCO of the polyisocyanate (A) relative to the equivalent number of -OH groups provided by the diols (B) and (C).
• these amounts correspond to an -NCO / -OH equivalent ratio of between 1.1 and 4.2, preferably between 1.3 and 3.8, more preferably between 1.5 and 2.
• Said ratio is defined as being equal to the equivalent number of -NCO groups of the polyisocyanate (A), divided by the sum of the equivalent numbers of -OH groups provided by the polyether diol (B) and by the carboxylic diol (C).
• the weight quantities of the reactants to be loaded into the reactor are determined on the basis of this equivalent ratio -NCO / -OH and from the hydroxyl number I OH of (B) and the molecular masses of (A) and ( VS).
• the relative amounts of the polyether diol (B) and of the carboxylic diol (C) to be introduced into the reactor for reaction in step (i) generally correspond to a molar ratio: number of moles of (C) / number of moles of ( B) which can vary over a wide range, possibly ranging from 0.04 to 20, preferably from 0.10 to 13, more preferably from 0.10 to 5, and even more preferably from 0.15 to 1.
• the amount of the carboxylic diol (C) to be loaded is advantageously such that the molar ratio: [molar equivalent number of (C)] / [equivalent number of -NCO function of the copolyurethane of formula (IV) formed] is included in a range ranging from from 0.1 to 1.
• the polyaddition reaction of 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 minus one polyol.
• a catalyst is, for example, chosen from bismuth and / or zinc carboxylates. Examples commercially available include the Borchi KAT ® 315 of the company Borchers GmbH is a bismuth neodecanoate; or the Borchi KAT ® 15 of the same company which is a zinc neodecanoate.
• the polyaddition reaction is carried out, under anhydrous conditions, at a temperature between 60 and 120 ° C.
• Step (ii) consists of the reaction of the copolyurethane of formula (IV) obtained in step (i) with an amine (D) of formula (IVd):
• R, R 'and R " identical or different, each represent a saturated, unsaturated or aromatic hydrocarbon radical, optionally comprising a heteroatom chosen from N,
• tertiary amine (D) of formula N (R) (R') (R") is a linear, branched or cyclic amine or polyamine whose average molar mass in Mn number ranges from 59 to 6000 g / mol and which has a pKa greater than 8.
• the tertiary amine (D) is chosen from:
• DBN 5-diazabicyclo [4.3.0] non-5-ene
• the pKa of the corresponding amine is greater than or equal to 10.
• the amine (D) is triethylamine
• the amine (D) is chosen from DBU and DABCO.
• Such an amine is often incorporated as a crosslinking catalyst in a mastic and / or adhesive composition comprising a SPUR. It then has the drawback of leading, after crosslinking of said composition, to yellowing of the adhesive seal, probably linked to its migration to the surface of said seal.
• the incorporation in step (ii) of the process according to the invention of such an amine, as an agent for neutralizing the pendant carboxylate group has the advantageous effect of the absence of yellowing of the adhesive joint which results from the crosslinking of the mastic and / or adhesive composition which comprises the ionic silylated copolyurethane according to the invention prepared by said process. Such an effect is probably linked to the chemical integration of the corresponding quaternary ammonium in the main chain of the copolyurethane according to the invention.
• the amine (D) is advantageously introduced in step (ii) in an amount corresponding to a molar equivalent ratio: [number of moles of (D)] / [number of moles of the carboxylic diol (C) introduced into the step (i)] which is within a range ranging from 0.8 to 2.5, preferably from 1 to 2.
• the neutralization reaction is carried out at a temperature within a range of 20 to 80 ° C, preferably 20 to 40 ° C.
• Step (iii) uses an aminosilane (E) derived from a secondary amine, of formula (VI): in which :
• R 3 represents a divalent linear or branched alkylene radical comprising from 1 to 6 carbon atoms
• R 4 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms
• R 5 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, an alkylcarbonyl radical comprising from 2 to 8 carbon atoms, or a dialkylimino radical comprising from 3 to 8 carbon atoms:
• - p is equal to 0 or 1;
• R 6 represents a phenyl radical, a linear, branched or cyclic alkyl radical comprising from 1 to 6 carbon atoms, or a radical chosen from the radicals:
• R 7 is a linear or branched alkyl radical comprising from 1 to 6 carbon atoms;
• Aminosilanes of formula (VI) are widely available commercially. We can cite by way of example: - N - (3 (trimethoxysilyl) propyl) butylamine) available under the name
• aminosilanes of formula (VI) are easily obtained by synthesis from commercial products. This is the case with the compound referred to below as “aminotriethoxysilane DEM + Al 100”, which corresponds to the formula: and which is obtained by reacting diethyl maleate with g-aminopropyltriethoxysilane.
• the latter compound is available under the name SILQUEST ® Al 100 from MOMENTIVE and corresponds to the formula:
• aminosilanes of formula (VI) in which R 6 represents a radical of formula (Ilf) or (Ilg) can be obtained by neutralization, using the amine (D) of formula (IVd), of the silyl compounds substituted with a amino acid which are described in US Patent 9567354 in the name of SHIN-ETSU CHEMICAL CO LTD.
• R 3 represents the methylene or n-propylene radical, preferably n-propylene
• R 4 and R 5 identical or different, each represent the methyl or ethyl radical, preferably methyl;
• R 6 represents a linear alkyl radical comprising from 1 to 4 carbon atoms, preferably an n-butyl, or a radical of formula (Ile) in which R 7 is an alkyl radical comprising from 1 to 3 carbon atoms, R 7 preferably being an ethyl radical.
• the copolyurethane with -NCO end groups of formula (V) is reacted, in accordance with step (iii) , with a substantially stoichiometric amount of the aminosilane (E).
• the molar amounts of these reagents advantageously correspond to an equivalent -NCO / -NH ratio which is between 0.90 and 1.1, and is preferably equal to approximately 1.
• the reaction of the —NH group of the aminosilane (E) on each of the 2 end groups —NCO of the copolyurethane of formula (V) leads to the formation of a urea function.
• Step (iii) is carried out, also under anhydrous conditions, at a temperature within a range of 20 to 80 ° C, preferably 20 to 40 ° C.
• the present invention also relates to a composition, which can be used as a mastic and / or adhesive, comprising:
• said composition comprises:
• the filler (s) that can be used in the composition according to the invention can be chosen from mineral fillers and mixtures of organic fillers and mineral fillers.
• mineral filler (s) which can be used, it is possible to use any mineral filler (s) usually used in the field of adhesive and / or adhesive compositions. or putty. These charges are in the form of particles of various geometry. They can be for example spherical, fibrous, or have an irregular shape.
• clay, quartz, carbonate fillers are used.
• carbonate fillers are used, such as carbonates of alkali or alkaline earth metals, and more preferably calcium carbonate.
• These fillers can be natural or treated, for example using an organic acid such as stearic acid, or a mixture of organic acids consisting mainly of stearic acid.
• hollow mineral microspheres such as hollow glass microspheres, and more particularly those made of sodium and calcium borosilicate or of aluminosilicate.
• organic filler (s) which can be used, it is possible to use any organic filler (s) and in particular polymeric filler (s) usually used in field of adhesive and / or mastic compositions.
• PVC polyvinyl chloride
• EVA ethylene vinyl acetate
• Kevlar® polyvinyl chloride
• PVC polyvinyl chloride
• EVA ethylene vinyl acetate
• Kevlar® aramid fibers
• hollow microspheres of expandable or non-expandable thermoplastic polymer Mention may in particular be made of hollow vinylidene chloride / acrylonitrile microspheres.
• PVC is used.
• the average particle size of the usable filler (s) is preferably less than or equal to 10 microns, more preferably less than or equal to 3 microns, in order to avoid their sedimentation in the adhesive composition and / or of mastic according to the invention during its storage.
• the average particle size is measured for a particle size distribution by volume and corresponding to 50% by volume of the sample of particles analyzed.
• the average particle size corresponds to the median diameter (D50 or Dv50) which corresponds to the diameter such that 50% of the particles by volume have a size smaller than said diameter.
• D50 or Dv50 the median diameter
• this value is expressed in micrometers and determined according to Standard NL ISO 13320-1 (1999) by laser diffraction on a device of the MALVERN type.
• the composition according to the invention can also comprise at least one moisture-absorbing agent, an adhesion promoter, a plasticizer and / or a rheology agent.
• Suitable moisture absorbing agents include alkoxysilanes such as trialkoxysilanes (particularly trimethoxysilanes) and alkoxysilanes containing an amino, mercapto or epoxy group. Examples of this are vinyltrimethoxysilane (or VTMO), gamma-glycidyloxypropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, aminopropyltrimethoxysilane, trimethoxymethylsilane.
• alkoxysilanes such as trialkoxysilanes (particularly trimethoxysilanes) and alkoxysilanes containing an amino, mercapto or epoxy group. Examples of this are vinyltrimethoxysilane (or VTMO), gamma-glycidyloxypropyltrimethoxysilane, N-beta- (aminoethy
• Some of these compounds can also act as an adhesion promoter, particularly trialkoxysilanes containing an amino, mercapto or epoxy group.
• an adhesion promoter particularly trialkoxysilanes containing an amino, mercapto or epoxy group.
• any plasticizer commonly used in the field of mastic and / or adhesive compositions can be used.
• any plasticizer commonly used in the field of mastic and / or adhesive compositions can be used.
• DIDP diisodecyl phthalate
• the plasticizer is generally included in the composition according to the invention in an amount of 5 to 20% by weight, preferably 10 to 15% by weight, based on the weight of said composition.
• the rheological agents which can be used are any rheological agent usually used in the field of adhesive and / or mastic compositions.
• one or more rheology agents chosen from thixotropic agents, and more preferably from:
• rheology agent (s) which can be included in the composition according to the invention can vary from 1 to 40% by weight, preferably from 5 to 30% by weight, more preferably from 10 to 25% by weight, based on the weight of said composition.
• the mastic and / or adhesive composition according to the invention is preferably stored in an anhydrous environment, for example in an airtight packaging, where said composition is protected from humidity and preferably protected light.
• the present invention also relates to a process for preparing a mastic and / or adhesive composition according to the invention, said preparation process comprising a step in which the ingredient (s) optionally present in said composition is (are) mixed with a nonionic copolyurethane according to the invention, at a temperature less than or equal to 50 ° C, preferably ranging from 5 to 45 ° C, and better still ranging from 20 to 30 ° C.
• a subject of the present invention is also an article comprising the adhesive and / or mastic composition according to the invention in hermetic packaging, protected from air.
• the hermetic package is a polyethylene bag or a polyethylene cartridge provided with a seal.
• the invention relates to a process for assembling 2 substrates comprising:
• the coating of the composition according to the invention at room temperature in the form of a layer with a thickness of between 0.2 and 5 mm, preferably between 1 and 3 mm, on at least one of the 2 substrates to assemble; then
• 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; paint coated metal and composite substrates (such as in the automotive industry).
• 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; paint coated metal and composite substrates (such as in the automotive industry).
• Vacuum is left for 2 hours at 110 ° C for dehydration.
• the reactor is then cooled to 90 ° C in order to introduce under nitrogen:
• IPDI isophorone diisocyanate
• the quantities of reactants introduced correspond to a molar equivalent ratio -NCO / -OH equal to 1.94.
• the mixture is kept under stirring until an NCO% by weight of 1.7% is reached, corresponding to a number of -NCO functions equal to 184.6 mmol.
• the molar equivalent ratio -NCO / -NH- is equal to 1.
• the whole is heated to 70 ° C and kept under stirring until complete reaction, ie until the characteristic band of the -NCO functions is no longer detectable by infrared spectroscopy.
• SPUR A silylated polyurethane
• Brookfield viscosity at 23 ° C of SPUR A is 52 Pa.s.
• Mastic A the composition of which is indicated below on a weight basis, is prepared by simple mixing in a rapid mixer:
• VTMO vinyltrimethoxysilane
• a 2 nd variant of this sealant composition or A ' is prepared without the crosslinking catalyst, and by minimal adjustment of the proportions of other ingredients.
• the mastic composition obtained is left under stirring and under reduced pressure of 20 mbar for 15 minutes before being packaged in a polyethylene cartridge, to avoid the presence of moisture.
• composition is then subjected to the following tests.
• the crosslinking time is measured by determining the skin formation time.
• a bead of mastic (about 10 cm long and about 1 cm in diameter) is first placed on a cardboard support. Then, using a low density polyethylene (LDPE) pipette tip, the sealant surface is touched every minute for up to 2 hours to determine the exact time at which the surface skin forms. This test is performed under controlled conditions of humidity and temperature (23 ° C and 50% relative humidity).
• LDPE low density polyethylene
• the principle of the measurement consists in stretching in a tensile machine, whose movable jaw moves at a constant speed equal to 100 mm / minute, a standard test piece consisting of the crosslinked mastic composition and recording, at the moment when produces the fracture of the test piece, the applied tensile stress (in MPa) as well as the elongation of the test piece (in%).
• the standard test piece is in the shape of a dumbbell, as illustrated in the international standard ISO 37.
• the narrow part of the dumbbell used has a length of 20 mm, a width of 4 mm and a thickness of 3 mm.
• the composition packaged as described above is extracted at room temperature in a suitable mold and left to crosslink for 14 days under standard conditions (23 ° C and 50% relative humidity).
• Two rectangular aluminum specimens of dimensions: 100 x 25 x 1.25 mm are used.
• the mastic composition is applied to one of the 2 test pieces over an area of 25 x 10 mm and in the form of a layer approximately 250 ⁇ m thick. Then the second specimen is displayed so as to cover the 1st specimen thus coated.
• the assembly of the 2 specimens is maintained by clips for 14 days under standard conditions (23 ° C and 50% relative humidity) for complete crosslinking of the mastic.
• the assembly is subjected to a shear test using a dynamometer operating at a speed of 10 mm / minute until the two specimens separate and the assembly breaks.
• RA adhesive rupture
• RC cohesive rupture
• An assembly of 2 test specimens held by the mastic composition is made by proceeding as previously. Said assembly is also maintained by clips for 14 days under standard conditions (23 ° C and 50% relative humidity) for complete crosslinking of the mastic.
• the assembly of the 2 test pieces obtained after complete crosslinking is deposited on a cotton strip and surrounded by it. Then, the assembly is introduced into a first polyethylene bag, in which is added a mass of deionized water equal to 10 times that of the cotton, taking care to wet the cotton uniformly by pressing.
• the polyethylene bag is sealed by welding with a welding clamp. To ensure a perfect seal, the assembly is placed in a second bag which is also welded like the first.
• the assembly of the 2 test pieces is removed from the bag and cotton, then placed for 2 h in an enclosure at -20 ° C.
• the assembly is finally placed for 2 to 4 h at room temperature, in order to carry out the shear test under conditions identical to those described for the shear test of the preceding test.
• Example 1 (according to the invention):
• Vacuum is left for 2 hours at 110 ° C for dehydration.
• the reactor is then cooled to 90 ° C in order to introduce under nitrogen:
• IPDI isophorone diisocyanate
• the quantities of reactants introduced correspond to a molar equivalent ratio -NCO / -OH equal to 1.80.
• the mixture is kept under stirring until an NCO% by weight of 1.7% is reached, corresponding to a number of -NCO functions equal to 183.3 mmol.
• the molar equivalent ratio -NCO / -NH- is equal to 1.
• the whole is heated to 40 ° C and kept under stirring until complete reaction, ie until the characteristic band of the -NCO functions is no longer detectable by infrared spectroscopy.
• ionic silylated copolyurethane About 500 g of ionic silylated copolyurethane are obtained, which are packaged in aluminum cartridges in a dry place.
• the Brookfield viscosity at 23 ° C of the ionic silylated copolyurethane is 80.35 Pa.s.
• This composition is prepared by repeating Example A 2), except that in the mastic composition A ′, the SPUR A is replaced by the ionic silylated copolyurethane with trimethoxysilane end groups prepared according to 1).
• Example A The procedure is as indicated in Example A for the measurement of the crosslinking time, for the measurement of the stress and the elongation at break by tensile test, for the fracture test on an aluminum support by shear test (without and after wet poultice).
• Example 1 is repeated with the amounts of ingredients indicated in Table 1.
• Example 1 With regard to the mastic of Example 1, it also appears a greater tensile strength in the shear test relative to mastic A, reflecting a marked improvement in the adhesion to aluminum, which is also observed in the presence of 'water.
• Example A 1) is repeated except that was replaced in the 2 nd step the introduction of 43.5 g of Dynasylan ® 1189 by 72.7 g of aminopropyltriethoxysilane DEM + Al 100 as defined above, with a molar mass of 393.58 g / mole.
• the corresponding molar equivalent ratio -NCO / -NH- is equal to 1.
• SPUR B silylated polyurethane
• the Brookfield viscosity at 23 ° C of SPUR B is 60 Pa.s.
• Example A 2 Preparation of 2 mastic compositions B and B 'comprising the SPUR B: Example A 2) is repeated, replacing the SPUR A and A' by, respectively, the
• Example 3 Repeating Example 1, except that replaces in step (iii) the aminosilane DYNASYLAN ® 1189 by aminotriethoxysilane DEM + 100 Al of Example B, and which is used the amounts of ingredients shown in Table 3.
• Examples 4-6 exhibit, in the tensile test and with respect to the composition of SPUR B, a stress and / or a Significantly improved elongation at break.
• Examples 5 and 6 also show a greatly reduced crosslinking time, which, with regard to polyurethanes containing ethoxysilane endings known for their difficult crosslinking, is particularly advantageous from the point of view of regulatory constraints.

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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)
• Polyurethanes Or Polyureas (AREA)
• Adhesives Or Adhesive Processes (AREA)
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• 2019
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• 2020
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