Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • 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
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
  • C08G18/20—Heterocyclic amines; Salts thereof
• • 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
  • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
  • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4825—Polyethers containing two hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4866—Polyethers having a low unsaturation value
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/08—Polyurethanes from polyethers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/08—Polyurethanes from polyethers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
• • C—CHEMISTRY; METALLURGY
  • 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 present invention relates to a process for preparing a crosslinkable composition.
• the present invention also relates to the use of the composition as a sealant, coating or adhesive.
• Sealants are widely used in the field of construction, in particular for assembling - by expansion joints - substrates, for example concrete or steel, and through their mechanical properties, and in particular elastic, to obtain a joint stable to dimensional variations induced in particular by temperature changes.
• sealants are those obtained from compositions based on moisture-crosslinkable silyl polymers.
• the latter are commonly prepared by a process implementing a polyaddition step in the presence of a tin-based catalyst, such as dioctyltin dilaurate (DOTL), or dibutyltin dilaurate (DBTL).
• a tin-based catalyst such as dioctyltin dilaurate (DOTL), or dibutyltin dilaurate (DBTL).
• DNL dioctyltin dilaurate
• DBTL dibutyltin dilaurate
• compositions based on silylated polymers employ other catalysts.
• catalysts other than tin-based catalysts has not resulted in crosslinked compositions exhibiting mechanical and / or adhesive properties of the same order as those obtained with tin-based catalysts.
• the present invention relates to a process for preparing a crosslinkable composition comprising at least one silylated polymer P containing alkoxysilane endings, and at least one catalytic system B, said process comprising the following steps:
• step a-2) reacting the NCO terminated polymer obtained in step a-1) with an organosilane compound having at least one reactive function with the -NCO function of the NCO terminated polymer;
• step a) bringing the silylated polymer P obtained in step a) into contact with a catalytic crosslinking system B which is a mixture of carboxylate (s) based on zinc and cyclic amidine, said process being carried out by absence of tin catalyst.
• a catalytic crosslinking system B which is a mixture of carboxylate (s) based on zinc and cyclic amidine, said process being carried out by absence of tin catalyst.
• organosilane relates to compounds which on the one hand have at least one, preferably two or three, hydrolyzable groups, preferably alkoxy or acyloxy groups, directly linked to the Si atom by Si- bonds. O, and on the other hand at least one organic radical directly linked to the Si atom by an Si-C bond.
• the process according to the invention comprises a step a-1) which is a polyaddition reaction between a composition of polyol (s) and a composition of polyisocyanate (s), in the presence of a catalyst A chosen from bismuth carboxylates and / or zinc, to prepare a polymer with NCO terminations.
• a catalyst A chosen from bismuth carboxylates and / or zinc
• the aforementioned polyol composition (s) may consist of a polyol or a mixture of polyols.
• the polyol (s) which can be used can be chosen from among those having a number-average molecular mass ranging from 200 g / mol to 20,000 g / mol, preferably of 400 g / mol to 18,000 g / mol.
• the number-average molecular weight of the polyols can be calculated from the hydroxyl number (IOH) expressed in mg KOH / g and the functionality of the polyol or determined by methods well known to those skilled in the art, by example by steric exclusion chromatography (or SEC in English) with standard PEG (polyethylene glycol).
• the polyols can have a hydroxyl functionality ranging from 2 to 6, preferably 2 to 3. In the context of the invention, and unless otherwise stated, the hydroxyl functionality of a polyol is the average number of hydroxyl functions per mole of polyol. .
• the polyol (s) which can be used can be chosen from polyester polyols, polyether polyols, polydiene polyols, polycarbonate polyols, poly (ether-carbonate) polyols, pre -OH-terminated polymers, and mixtures thereof.
• the polyol (s) which can be used can be chosen from aromatic polyols, aliphatic polyols, carbonate polyols and mixtures of these compounds.
• the polyester polyol (s) may have a number average molecular weight ranging from 1000 g / mol to 10,000 g / mol, preferably from 2000 g / mol to 6000 g / mol. .
• polyester polyols mention may for example be made of:
• polyester polyols of natural origin such as castor oil
• aliphatic (linear, branched or cyclic) or aromatic polyols such as, for example, ethanediol, 1, 2-propanediol, 1, 3-propanediol, glycerol, trimethylolpropane, 1, 6- hexanediol, 1,2,6-hexanetriol, butenediol, sucrose, glucose, sorbitol, pentaerythritol, mannitol, triethanolamine, N-methyldiethanolamine, and mixtures thereof, with
• polycarboxylic acid or its ester or anhydride derivative such as 1, 6-hexanedioic acid, dodecanedioic acid, azelaic acid, sebacic acid, adipic acid, 1, 18- acid octadecanedioic acid, phthalic acid, succinic acid and mixtures of these acids, an unsaturated anhydride such as, for example, maleic or phthalic anhydride, or a lactone such as, for example, caprolactone.
• an unsaturated anhydride such as, for example, maleic or phthalic anhydride
• a lactone such as, for example, caprolactone.
• polyester polyols can be prepared in a conventional manner, and for the most part are commercially available.
• polyester polyols mention may for example be made of the following products with a hydroxyl functionality equal to 2:
• - TONE ® 0240 (marketed by UNION CARBIDE) which is a polycaprolactone with a number-average molecular mass of around 2000 g / mol, and a melting point of around 50 ° C,
• - DYNACOLL ® 7360 (marketed by EVONIK) which results from the condensation of adipic acid with hexanediol, and has a number-average molecular mass of approximately 3500 g / mol, and a melting point of 55 ° C approximately
• - DYNACOLL ® 7330 (marketed by EVONIK) with a number-average molecular mass of approximately 3500 g / mol, and having a melting point of approximately 85 ° C
• polyester polyol having a viscosity of 180 Pa.s at 23 ° C, a number-average molecular mass Mn equal to 5500 g / mol, and a T g equal to -50 ° VS,
• polyester polyol having a viscosity of 68 Pa.s at 23 ° C, a number average molecular mass equal to 6000 g / mol, and a T g equal to -64 ° C,
• KURARAY® P-10010 polyester polyol having a viscosity of 687 Pa.s at 23 ° C, and a number-average molecular mass equal to 10,000 g / mol.
• the polyester polyol is chosen from: a polycaprolactone; Castor oil ; a polyester polyol resulting from the condensation of ethylene glycol, propylene glycol, 1, 3-propanediol and / or 1, 6-hexanediol with adipic acid and / or the various isomers of phthalic acid; and their mixtures.
• the polyether polyol (s) may have a number average molecular weight ranging from 200 to 20,000 g / mol, preferably from 400 to 18,000 g / mol.
• the polyether polyol (s) has (have) a hydroxyl functionality ranging from
• the polyether polyol (s) which can be used according to the invention is (are) preferably chosen from polyoxyalkylene polyols, in which the alkylene part, linear or branched, comprises from 1 to 4 carbon atoms , preferably 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, and better still polyoxyalkylene diols, including the alkylene part, linear or branched, comprises from 1 to 4 carbon atoms, preferably from 2 to 3 carbon atoms.
• polyoxyalkylene diols or triols which can be used according to the invention, there may be mentioned for example:
• polyoxypropylene diol or triol also referred to as polypropylene glycols (PPG) diol or triol
• PPG polypropylene glycols
• polyoxybutylene glycols also referred to as polybutylene glycols (PBG) diol or triol
• PBG polybutylene glycols
• PolyTHF polytetrahydrofuran diol or triol having a number average molecular mass ranging from 250 g / mol to 12,000 g / mol,
• PTMG polytetramethylene glycols
• the polyether polyol (s) which can be used is (are) chosen from polyoxypropylene diols or triols.
• the polyether polyols mentioned above can be prepared in a conventional manner, and are widely available commercially. They can for example be obtained by polymerization of the corresponding alkylene oxide in the presence of a catalyst based on a double metal-cyanide complex.
• polyether diols examples include marketed under the name "Acclaim®” by Covestro society, such as G “ACCLAIM ® 12200” of average molecular neighbor number of 11,335 g / mol, “ACCLAIM® 8200” with a number-average molecular mass close to 8,057 g / mol, and “ACCLAIM® 4200” with a number-average molecular mass close to 4,020 g / mol, or else the polyoxypropylene diol marketed under the name “VORANOL P2000” by the company DOW with a number-average molecular weight close to 2 004 g / mol.
• polyether triols examples include the polyoxypropylene triol sold under the name “VORANOL CP3355” by the company DOW, with a number-average molecular mass of around 3,554 g / mol.
• the polydiene polyol (s) which can be used according to the invention can be preferably chosen from polydienes comprising terminal hydroxyl groups, and their corresponding hydrogenated or epoxidized derivatives.
• the polydiene polyol (s) which can be used according to the invention is (are) chosen from polybutadienes comprising terminal hydroxyl groups, optionally hydrogenated or epoxidized.
• the polydiene polyol (s) which can be used according to the invention is (are) chosen from the homopolymers and copolymers of butadiene comprising terminal hydroxyl groups, optionally hydrogenated or epoxidized.
• terminal hydroxyl groups” of a polydiene polyol is understood to mean the hydroxyl groups located at the ends of the main chain of the polydiene polyol.
• the hydrogenated derivatives mentioned above can be obtained by total or partial hydrogenation of the double bonds of a polydiene comprising terminal hydroxyl groups, and are therefore saturated or unsaturated.
• the epoxy derivatives mentioned above can be obtained by chemoselective epoxidation of the double bonds of the main chain of a polydiene comprising terminal hydroxyl groups, and therefore contain at least one epoxy group in its main chain.
• polybutadiene polyols mention may be made of the homopolymers of butadiene, saturated or unsaturated, comprising terminal hydroxyl groups, optionally epoxidized, such as, for example, those sold under the name POLY BD® or KRASOL® by the company CRAY VALLEY. .
• CONVERGE POLYOL 212-10 and CONVERGE POLYOL 212-20 marketed by the company NOVOMER respectively with a molecular mass in number (Mn) equal to 1000 and 2000 g / mol whose hydroxyl numbers are 112 and 56 mg KOH / g, respectively
• DESMOPHEN® C XP 2716 marketed by COVESTRO with a number molecular mass (Mn) equal to 326 g / mol whose hydroxyl number is 344 mg KOH / g
• the POLYOL C -590, C1090, C-2090 and C-3090 sold by KURARAY having a number molecular mass (Mn) ranging from 500 to 3000 g / mol and a hydroxyl number ranging from 224 to 37 mg KOH / g.
• the polyol composition (s) consists of one or more polyols chosen from those mentioned above and their mixtures.
• the polyol composition (s) may consist of one or more polyols, including at least one polyether polyol. More particularly, the polyol (s) composition can consist of one or more polyether polyols.
• polyisocyanate is understood to mean a compound comprising at least two isocyanate (NCO) groups.
• the aforementioned polyisocyanate composition (s) may consist of a polyisocyanate or a mixture of polyisocyanates.
• the polyisocyanate (s) which can be used can be chosen from those typically used in the synthesis of a polyurethane with NCO terminations.
• the polyisocyanate (s) which can be used can be aliphatic (linear (s) or branched (s)) or aromatic (s), and optionally substituted (s).
• the polyisocyanate (s) is (are) chosen from diisocyanates, triisocyanates, and mixtures thereof.
• the polyisocyanate (s) is (are) chosen from the group consisting of pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), heptane diisocyanate, octane diisocyanate, nonane diisocyanate, decane diisocyanate, undecane diisocyanate, dodecane diisocyanate, isophorone diisocyanate (I PDI), norbornan diisocyanate, norbornene diisocyanate, 1, 4-diisocyanate (CHDIane) ), methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, 1, 5-diisocyanane (1-
• MDI can be presented as an isomer or as a mixture of isomers, such as 4,4'-MDI and / or 2,4'-MDI.
• TDI can be presented as an isomer or as a mixture of isomers, such as 2,4-TDI and / or 2,6-TDI.
• the polyisocyanate is MDI, and in particular 4,4'-MDI.
• the polyisocyanate (s) which can be used for preparing the polyurethane used according to the invention are typically widely available commercially.
• SCURANATE® TX marketed by the company VENCOREX, corresponding to a 2,4-TDI with a purity of the order of 95%
• SCURANATE® T100 marketed by the company VENCOREX
• DESMODUR® I marketed by the company COVESTRO
• ISONATE® M125 marketed by DOW, corresponding to an MDI containing at least 97 % by weight of the 4,4'-MDI isomer.
• the polyisocyanate composition comprises IPDI.
• polyaddition reaction and “polyaddition” are understood in an equivalent manner.
• the polyaddition step can be carried out at a temperature below 95 ° C, preferably ranging from 60 ° C to 90 ° C, more preferably ranging from 65 ° C to 80 ° C.
• the polyaddition step can be carried out under anhydrous conditions, for example under a nitrogen atmosphere.
• the polyaddition step can be carried out in amounts of polyisocyanate (s) and of polyol (s) such that the NCO / OH molar ratio is strictly greater than 1, for example between 1, 1 and 2.5, preferably between 1, 1 and 2.2, preferably between 1, 2 and 2.0, for example between 1, 20 and 1, 80, advantageously between 1, 20 and 1, 50, in particular between 1, 30 and 1, 40 , so as to advantageously obtain a polyurethane with NCO terminations.
• the NCO / OH molar ratio corresponds to the molar ratio of the number of isocyanate groups (NCO) to the number of hydroxyl groups (OH) carried respectively by the polyisocyanates and polyols used.
• Catalyst A is chosen from carboxylates based on bismuth and / or zinc.
• bismuth-based catalyst means a catalyst comprising bismuth.
• Such a catalyst can therefore comprise other metal atoms in addition to bismuth, such as, for example, zinc.
• the carboxylates can be those in which the carboxylic acid contains 2 to 20 carbon atoms, preferably 4 to 14 carbon atoms.
• carboxylic acids mention may be made, for example, of: butyric acid, isobutyric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, l 'myristic acid, palmitic acid, stearic acid, iso-stearic acid, abietic acid, neodecanoic acid, 2,2,3,5-tetramethylhexanoic acid, 2,4 -dimethyl-2-isopropylpentanoic acid, 2,5-dimethyl-2-ethylhexanoic acid, 2,2-dimethyloctanoic acid, 2,2-diethylhexanoic acid, and arachidic acid.
• the carboxylates can be mono-carboxylates, dicarboxylates, tricarboxylates, or mixtures thereof.
• Catalyst A can be selected from the group consisting of zinc-based carboxylates, bismuth-based carboxylates, bismuth and zinc-based carboxylates, and mixtures thereof.
• catalyst A is chosen from bismuth 2-ethyl hexanoate, zinc 2-ethyl hexanoate, bismuth neodecanoate, zinc neodecanoate, bismuth zinc neodecanoate, zinc 2-ethyl hexanoate and bismuth, and mixtures thereof.
• catalyst A is chosen from carboxylates based on bismuth, and in particular those comprising only bismuth as metal.
• bismuth carboxylates can be mentioned for example the Borchi KAT ® 320 (CAS Number: 67874-71-9, 2-ethyl hexanoate bismuth), the Borchi KAT ® 315 (CAS Number: 34364-26-6, neodecanoate bismuth) available from BORCHERS, K-KAT XK- 651 (bismuth carboxylate) available from KING INDUSTRIES, K-KAT XC-B221 available from KING INDUSTRIES (bismuth tris (carboxylate), carboxylic acid), and COSCAT 83 (bismuth tris (neodecanoate), neodecanoic acid) available from VERTELLUS.
• BORCHI® KAT 0761 (CAS number: 27253-29-8, zinc neodecanoate) available from BORCHERS
• TIB KAT® 616 (zinc neodecanoate) available from TIB CHEMICALS
• K-KAT XK-664 (zinc carboxylate) available from KING INDUSTRIES.
• KAT 244 bismuth and zinc 2-ethyl hexanoate
• KAT 244 DS bismuth and zinc neodecanoate
• the total content of catalyst (s) A used in the polyaddition reaction can range from 0.001% to 1% by weight, preferably from 0.01% to 0.8% by weight, preferably from 0.015% to 0.5% by weight relative to the total weight of the reactants used in the polyaddition reaction.
• the NCO terminated polyurethane may have a number average molecular weight ranging from 1,000 g / mol to 50,000 g / mol, preferably from 1,000 g / mol to 30,000 g / mol, preferably from 5,000 g / mol to 20,000 g / mol, advantageously from 15,000 g / mol to 25,000 g / mol.
• the number average molecular weight of NCO terminated polyurethanes can be measured by methods well known to those skilled in the art, for example by size exclusion chromatography (or SEC) using standards of the polyethylene glycol type.
• the NCO terminated polyurethane may have a polymolecularity index ranging from 1.5 to 3.5, preferably from 2.0 to 3.3.
• the polymolecularity index is defined as the ratio M w (average molecular mass by weight) / M n (average molecular mass by number) of the polyurethane.
• the polyurethane with NCO terminations can have a mass content of NCO groups ranging from 0.1% to 5% by weight, preferably from 0.1% to 1% by weight relative to the total weight of the polyurethane.
• Step a-2) of the process according to the invention corresponds to the reaction of the NCO terminated polymer obtained in step a-1) with an organosilane compound having at least one reactive function with the -NCO function of the terminated polymer. NCO.
• the organosilane compound can be chosen from mercaptosilanes and aminosilanes, preferably aminosilanes.
• Aminosilanes contain as an amine function as reactive function with the -NCO function of the polymer with NCO terminations.
• the aminosilane preferably has the following formula (I);
• R 4 identical or different, each represents a linear or branched monovalent hydrocarbon radical comprising from 1 to 10 carbon atoms;
• R 5 identical or different, each represents an acyl radical, or a linear or branched monovalent hydrocarbon radical comprising from 1 to 10 carbon atoms,
• - p is an integer equal to 0, 1 or 2;
• R 3 represents a divalent linear or branched alkylene radical comprising from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms, R 3 preferably representing methylene or n-propylene, and
• R 6 represents H, a linear or branched alkyl radical, an arylalkyl radical, a cyclic radical comprising from 1 to 20 carbon atoms, or a radical having the following formula (II):
• R 7 and R 8 are, independently of one another, hydrogen or a radical chosen from the group consisting of -R 9 , -COOR 9 and -CN;
• the R 10 radical is hydrogen, or a radical chosen from the group consisting of - CH2-COOR 9 , -COOR 9 , -CONHR 9 , -CON (R 9 ) 2 , -CN;
• radical R 9 being a hydrocarbon radical having from 1 to 20 carbon atoms optionally comprising at least one heteroatom.
• radical of formula (II) can be chosen from one of the following radicals: [Chem 2]
• aminosilane of formula (I) is that in which:
• R 4 identical or different, each represents a linear or branched alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms;
• R 5 identical or different, each represents a linear or branched alkyl comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms,
• - p is an integer equal to 0, 1 or 2, preferably p is 0;
• R 3 represents a divalent linear or branched alkylene radical comprising from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms, R 3 preferably representing methylene or n-propylene, and
• R 6 represents a linear or branched alkyl radical comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms.
• aminosilanes of formula (I) above are preferably primary aminosilanes such as, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyldimethoxymethylsilane; secondary aminosilanes such as for example N- butyl-3-aminopropyltrimethoxysilane, N-butyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane; the products of the reaction of the Michael addition of primary aminosilanes such as, for example, 3-aminopropyltrimethoxysilane or 3-aminopropyldimethoxymethylsilane with Michael's acceptors such as for example acrylonitrile, acrylic esters,
• the raminosilane is N-butyl-3-aminopropyltrimethoxysilane.
• Aminosilanes may be commercially available such as, for example, Dynasylan® 1189 sold by Evonik.
• Step a-2 can be performed under anhydrous conditions.
• Step a-2 can be carried out at a temperature less than or equal to 95 ° C, preferably at a temperature ranging from 50 ° C to 80 ° C.
• Step a-22) can be performed in a time ranging from 5 to 30 min, preferably 10 to 20 min.
• step a-2) is carried out in amounts of polymer with NCO terminations and of aminosilanes such that the NH / NCO molar ratio is between 0.90 and 1.00, preferably between 0 , 95 and 1, 00.
• the NH / NCO molar ratio corresponds to the molar ratio of the number of NH groups carried by the aminosilane to the number of isocyanate (NCO) groups carried by the polymer with NCO terminations.
• the silylated polymer P with alkoxysilane terminations is a polymer comprising at least two groups of formula (III):
• R 4 identical or different, each represents a linear or branched monovalent hydrocarbon radical comprising from 1 to 10 carbon atoms;
• R 5 identical or different, each represents an acyl radical, or a linear or branched monovalent hydrocarbon radical comprising from 1 to 10 carbon atoms,
• the silylated polymer P comprises at least one group of formula (III) above in which each occurrence of R 5 represents a linear or branched alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 with 5 carbon atoms.
• the silylated polymer P comprises groups of formula (III) above chosen from trimethoxysilyl groups, triethoxysilyl groups, methyldimethoxysilyl groups, methyldiethoxysilyl groups, dimethylmethoxysilyl groups, and dimethylethoxysilyl groups.
• the silylated polymer P comprises trimethoxysilyl groups.
• the silylated polymer P is a polyurethane.
• the silylated polymer P can have a number-average molecular mass ranging from 500 to 100,000 g / mol, more preferably ranging from 700 to 50,000 g / mol, and preferably from 1,000 to 30,000 g / mol.
• the number-average molecular weight of the polymers can be measured by methods well known to those skilled in the art, for example by size exclusion chromatography using standards of the polyethylene glycol type.
• the silylated polymer P may have a viscosity at 23 ° C., less than or equal to 350,000 mPa.s, preferably less than or equal to 300,000 mPa.s, more preferably ranging from 10,000 mPa.s to 300,000 mPa.s , in particular from 20,000 mPa.s to 250,000 mPa.s, advantageously from 20,000 to 120,000 mPa.s.
• Viscosity can be measured using a Brookfield viscometer according to ISO 2555 (1999). Typically, the measurement carried out at 23 ° C can be done using a Brookfield RVT viscometer, a needle suitable for the viscosity range and at a speed of 20 revolutions per minute.
• the silylated polymer P preferably has the formula (IV) below
• R 1 represents a divalent hydrocarbon radical comprising from 5 to 15 carbon atoms which may be aromatic, aliphatic or cyclic
• - R 3 represents a divalent linear or branched alkylene radical comprising from 1 to 6 carbon atoms, preferably R 3 representing methylene or n-propylene,
• R 2 represents a divalent linear or branched alkylene radical comprising from 2 to 4 carbon atoms
• R 4 and R 5 are as defined above, preferably R 4 and R 5 , identical or different, each represent a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, even more preferably R 4 and R 5 representing methyl,
• R 6 represents a linear or branched alkyl radical comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms;
• - n and m are such that the number-average molecular mass of the polymer of formula (III) ranges from 500 g / mol to 50,000 g / mol, preferably from 700 g / mol to 22,000 g / mol,
• - p is an integer equal to 0, 1 or 2, p preferably being 0 or 1.
• the radical R 1 is chosen from one of the following divalent radicals, the formulas of which below reveal the 2 free valences:
• the radical R 1 is the divalent radical derived from isophorone diisocyanate.
• the process according to the invention comprises bringing the silylated polymer P obtained in step a) into contact with a catalytic crosslinking system B which is a mixture of carboxylate (s) based on zinc and cyclic amidine.
• Catalytic system B is a crosslinking catalyst.
• the crosslinking of the silylated polymer P allows in particular to catalyze the crosslinking of the silylated polymer P in the presence of water or humidity.
• the water or moisture can be provided by the surface of the support or the surrounding environment, naturally (atmospheric humidity) or controlled in contact with the crosslinkable composition according to the invention.
• This crosslinking results in particular in the creation of a three-dimensional network formed by the polymer chains linked together by siloxane type bonds.
• cyclic aminidines can be chosen from those having the following formula (V): [Chem 14]
• each A represents, independently of one another, a radical containing a nucleophilic non-protic group
• - s represents an integer equal to or different from 0;
• - R represents an integer equal to or different from 0;
• - t is a number equal to 0 or different from 0, preferably t is 1, 2, or 3, even more preferably 3.
• s + r is 0, 1 or 2, preferably
• Group A can be selected from the group consisting of tertiary phosphines, tertiary amino groups.
• the nitrogen atom of amino groups or the phosphorus atom of phosphines can be directly attached to a carbon atom of the ring structure.
• group A has one of the following formulas: - (CH2) X N (R) 2 or - (CH2) X P (R) 2 in which x is from 0 to 6, preferably 0, 1 or 2, and R is an alkyl group or a phenyl group, preferably an alkyl group containing from 2 to 4 carbon atoms.
• the cyclic amidines are chosen from 1, 8-diazabicyclo [5.4.0] -undéc-7-ene (DBU) and 6- (dibutylamino) -1, 8-diazabicyclo [5.4.0 ] undec-7-ene, and mixtures thereof.
• the metal carboxylates can be those in which the carboxylic acid contains 2 to 20 carbon atoms, preferably 4 to 14 carbon atoms.
• carboxylic acids mention may be made, for example, of butyric acid, isobutyric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, l 'myristic acid, palmitic acid, stearic acid, iso-stearic acid, abietic acid, neodecanoic acid, 2,2,3,5-tetramethylhexanoic acid, 2,4 -dimethyl-2-isopropylpentanoic acid, 2,5-dimethyl-2-ethylhexanoic acid, 2,2-dimethyloctanoic acid, 2,2-diethylhexanoic acid, and arachidic acid.
• the carboxylates can be mono-carboxylates, dicarboxylates, tricarboxylate
• the zinc-based carboxylate is chosen from zinc 2-ethyl hexanoate, zinc neodecanoate, and mixtures thereof.
• Step b) can be carried out at a temperature ranging from 5 ° C to 80 ° C.
• the process according to the invention can include additional steps to steps a) and b).
• the method may comprise a step (s) of adding additional compounds, such as for example at least one additive.
• additional compounds can be added before step b) and / or simultaneously with step b), and / or after step b).
• the method may include a step c) of mixing the composition resulting from step b) or resulting from a possible step subsequent to step b).
• the process according to the invention is advantageously less toxic to humans and the environment since it is carried out in the absence of a tin-based catalyst, and in particular in the absence of an organotin catalyst.
• the present invention also relates to a crosslinkable composition
• a crosslinkable composition comprising:
• At least one catalytic crosslinking system B which is a mixture of carboxylate (s) based on zinc and cyclic amidine,
• the present invention also relates to a crosslinkable composition obtained according to the process detailed above, the composition comprising:
• At least one catalytic crosslinking system B which is a mixture of carboxylate (s) based on zinc and cyclic amidine, said composition not comprising a tin-based catalyst.
• catalyst A of the reticular system B, of silylated polymer P, and in particular the preferred characteristics, are in particular those defined above in the process according to the invention.
• the polymer P is advantageously the polymer of formula (IV) as defined above.
• the composition according to the invention comprises from 3% to 80% by weight, preferably from 5% to 60% by weight, preferably from 5% to 50% by weight, advantageously from 10% to 50% , for example from 10% to 40% by weight, of at least one silylated polymer containing alkoxysilane endings, preferably chosen from the polymers of formulas (IV) mentioned above.
• the composition according to the invention comprises from 0.001% to 0.5% by weight, preferably from 0.005% to 0.20% by weight of catalyst A relative to the total weight of the composition.
• the composition according to the invention comprises from 0.01% to 2% by weight, preferably from 0.1% to 1% by weight, preferably from 0.2% to 0.5% by weight of the catalytic system B relative to the total weight of the composition.
• the composition further comprises at least one additive chosen from plasticizers, solvents, pigments, adhesion promoters, moisture absorbers, UV stabilizers (or antioxidants), molecular sieves, flakes, fluorescent materials, rheological additives, fillers, and mixtures thereof.
• the filler can be chosen from organic fillers, inorganic fillers and mixtures thereof.
• organic filler (s) it is possible to use any organic filler (s) and in particular polymeric filler (s) typically used in the field of mastic compositions.
• polyvinyl chloride PVC
• polyolefins rubber
• aramid fibers such as KEVLAR ®
• hollow microspheres of expandable or non-expandable thermoplastic polymer Mention may in particular be made of hollow vinylidene chloride / acrylonitrile microspheres.
• 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 composition 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. In the present application, this value is expressed in micrometers and determined according to Standard NF ISO 13320-1 (1999) by laser diffraction on an apparatus of the MALVERN type.
• the filler is an inorganic filler.
• mineral filler As examples of mineral filler (s), it is possible to use any mineral filler (s) typically used in the field of surface coating compositions, glue or putty.
• Inorganic fillers can be in the form of particles of various geometry. They can be for example spherical, fibrous, or have an irregular shape.
• the filler is chosen from sand, glass beads, glass, quartz, barite, alumina, mica, talc, carbonate fillers, and mixtures thereof.
• the sand which can be used in the present invention preferably has a particle size ranging from 0.1 to 400 ⁇ m, preferably from 1 to 400 ⁇ m, more preferably from 10 to 350 ⁇ m, more preferably from 50 to 300 ⁇ m.
• the glass beads which can be used in the present invention preferably have a particle size ranging from 0.1 to 400 ⁇ m, preferably from 1 to 400 ⁇ m, more preferably from 10 to 350 ⁇ m, more preferably from 50 to 300 ⁇ m. .
• the filler is a carbonate filler chosen from alkali metal or alkaline earth metal carbonates, such as, for example, calcium carbonate.
• the 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.
• the total amount of filler can vary from 0.01% to 70% by weight, preferably from 20% to 65%, preferably from 20% to 50%, advantageously from 25% to 40% by weight relative to the total weight of the composition.
• the aforementioned composition can comprise at least one plasticizer in an amount of 5% to 30% by weight, preferably from 10% to 30% by weight, preferably from 15% to 25% by weight relative to the total weight of said composition.
• plasticizer As an example of a plasticizer that can be used, there may be mentioned any plasticizer usually used in the field of adhesives, sealants and / or surface coatings, such as for example phthalates, benzoates, esters. trimethylolpropane, trimethylolethane esters, trimethylolmethane esters, glycerol esters, pentaerythritol esters, naphthenic mineral oils, adipates, cyclohexyldicarboxylates, paraffinic oils, natural oils (optionally epoxidized), polypropylenes, polybutylenes, hydrogenated polyisoprenes, and mixtures thereof.
• phthalates benzoates
• esters trimethylolpropane, trimethylolethane esters, trimethylolmethane esters, glycerol esters, pentaerythritol esters, naphthenic mineral oils, adipates, cyclohexyldicarboxylates
• phthalates mention may for example be made of diisononyl phthalate, di-isobutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, diisooctyl phthalate, diisododecyl phthalate, dibenzyl phthalate, diisodecy phthalate (for example sold by BASF name PALATINOL TM DIDP), or butylbenzyl phthalate.
• benzoates there may be mentioned, for example: neopentylglycol dibenzoate (for example available under the name UNIPLEX ® 512 from LANXESS), dipropylene glycol dibenzoate (for example available under the name BENZOFLEX ® 9-88SG from EASTMAN), a mixture of diethylene glycol dibenzoate and of dipropylene glycol dibenzoate (for example available under the name K-FLEX ® 850 S from KALAMA CHEMICAL), or a mixture of diethylene glycol dibenzoate, of dipropylene glycol dibenzoate and of triethylene glycol dibenzoate (for example available under the name BENZOFLEX ® 2088 from EASTMAN).
• neopentylglycol dibenzoate for example available under the name UNIPLEX ® 512 from LANXESS
• dipropylene glycol dibenzoate for example available under the name BENZOFLEX ® 9-88
• pentaerythritol esters mention may be made, for example, of pentaerythritol tetravalerate (for example available under the name PEVALEN TM from the company PERSTORP).
• cyclohexanedicarboxylates mention may be made, for example, of diisononyl 1, 2-cyclohexanedicarboxylate (for example available under the name HEXAMOLL DINCH® from BASF).
• one or more rheology agents chosen from thixotropic agents, and more preferably from:
• rheology agent (s) which can be used can vary from 1% to 40% by weight, preferably from 5% to 30% by weight, more preferably from 10% to 25% by weight relative to to the total weight of the composition.
• the solvent is preferably a volatile solvent at temperature to 23 ° C.
• the volatile solvent can, for example, be chosen from alcohols volatile at 23 ° C, such as ethanol or isopropanol.
• the volatile solvent makes it possible, for example, to reduce the viscosity of the composition and to make the composition easier to apply.
• the volatile nature of the solvent allows in particular the seal, obtained after hardening of the composition, to no longer contain solvent. Thus, for example, the solvent has no negative influence on the hardness of the seal.
• a solvent in particular a volatile solvent
• its content is preferably less than or equal to 5% by weight, more preferably less than or equal to 3% by weight, relative to the total weight of the mixture. composition.
• the content of solvent (s) in the composition is between 0% and 5% by weight.
• the pigments can be organic or inorganic pigments.
• the pigment is PO2, in particular KRONOS® 2059 sold by the company KRONOS.
• the moisture absorber may for example be chosen from hydrolyzable, non-polymeric alkoxysilane derivatives with a molecular mass of less than 500 g / mol, preferably chosen from trimethoxysilane and triethoxysilane derivatives. Such an agent can typically extend the shelf life of the composition during storage and transportation prior to use.
• gamma-metacryloxypropyltrimethoxysilane for example available under the trade name SILQUEST® A-174 from the company MOMENTIVE
• methacryloxymethyltrimethoxysilane for example available under the name GENIOSIL® XL33 from WACKER
• vinyltrimethoxysilane isooctyltrimethoxysilane or phenyltrimethoxysilane.
• a moisture absorber When a moisture absorber is present in the composition, its content is preferably less than or equal to 3% by weight, more preferably less than or equal to 2% by weight relative to the total weight of the composition. When it is present, the moisture absorber may for example represent from 0.5% to 3% by weight or from 1% to 2% by weight relative to the total weight of the composition.
• the composition may comprise an amount from 0.1% to 3%, preferably from 0.1% to 3%, even more preferably from 0.1% to 1% by weight, of at least one UV stabilizer or antioxidant.
• UV stabilizer or antioxidant typically introduced to protect the composition from degradation resulting from a reaction with oxygen which may be formed by the action of heat or light.
• These compounds can include antioxidants primers that trap free radicals.
• Primary antioxidants can be used alone or in combination with other secondary antioxidants or UV stabilizers.
• IRGANOX® 1010 Mention may be made, for example, of IRGANOX® 1010, IRGANOX® B561, IRGANOX® 245, IRGAFOS® 168, TINUVIN® 328 or TINUVIN TM 770 sold by BASF.
• composition according to the invention comprises:
• compositions from 0% to 50% by weight, in particular from 0.1% to 40% by weight relative to the total weight of the composition of at least one additive chosen from plasticizers, solvents, pigments, promoters of adhesion, moisture absorbers, UV stabilizers (or antioxidants), molecular sieves, flakes, fluorescent materials, rheological additives, fillers, and mixtures thereof.
• additives chosen from plasticizers, solvents, pigments, promoters of adhesion, moisture absorbers, UV stabilizers (or antioxidants), molecular sieves, flakes, fluorescent materials, rheological additives, fillers, and mixtures thereof.
• composition according to the invention can be in single-component form, that is to say that all the components are packaged in the same compartment.
• composition is preferably ready to use, that is to say that the user (private or professional) can directly apply the composition to achieve the joint, without having to perform any prior mixing.
• an elastic recovery greater than or equal to 70%, preferably greater than or equal to 75%, and even more preferably greater than or equal to 80%.
• the composition according to the invention is advantageously a low modulus mastic composition, in particular classified 25LM according to standard EN 15651-1 (2012-11) and EN 15651-4 (2017-04).
• the 25LM classification requires in particular: - a modulus at 100% elongation at 23 ° C less than or equal to 0.40 MPa;
• the modulus at 100% elongation at 23 ° C is measured according to the test described in ISO 8339 (2005-06), on an aluminum or mortar support, with method A of ISO 8339 ( 2005-06) as a preconditioning method.
• the elastic recovery is measured at 100% elongation and 23 ° C according to ISO 7389 (2004-04), on an aluminum or mortar support, according to pre-conditioning method A of ISO 7389 (2004-05).
• composition according to the invention is advantageously a mastic composition, in particular an elastic mastic composition.
• composition according to the invention is advantageously a low modulus mastic composition.
• composition according to the invention advantageously presents a good compromise between mechanical properties and adhesion properties, while being more respectful of man and the environment.
• the composition according to the invention is advantageously useful in the field of construction.
• the present invention also relates to the use of a composition as defined above, as an adhesive, mastic or coating, preferably as a mastic, for example as a construction mastic.
• composition can be used for applications on concrete, mortar, brick, glass, metal, wood, plastic.
• the composition is preferably applied at a temperature ranging from 5 ° C to 50 ° C, and can crosslink under these conditions.
• the composition can in particular be used for sealing and expansion joints in buildings, especially between concrete / concrete substrates.
• 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 1% and 3%” notably includes the values 1% and 3%.
• EXPERIMENTAL PART - ACCLAIM ® 12200 polyether polyol of average molecular weight in neighboring of 1 1335 g / mol, marketed by COVESTRO;
• - PALATINOL N (marketed by BASF): diisononylphthalate (plasticizer);
• IRGANOX 1076 marketed by BASF (antioxidant);
• - TINUVIN 765 marketed by BASF (HALS type UV stabilizer);
• - DYNASYLAN® 1 146 sold by Evonik, oligomeric amino silane (adhesion promoter);
• TIB KAT 244 DS bismuth and zinc neodecanoate sold by NITROCHEMIE (catalyst);
• Acclaim 12200 (having an IOH of 9 to 11 mg KOH / g, and a number average molecular mass of about 12000) is introduced, then the Ti additive and the medium is heated to 60-65 ° C. . Then the IPDI is introduced, mixed for 10 min and then the catalyst is introduced. The mixture is then heated to 70 ° C. for one hour with stirring. The NCO index is then checked, if the theoretical NCO index is not reached, the reaction time is extended by as many periods of 15 minutes as necessary. When the theoretical NCO index is reached, Dynasilane 1189 is added, the mixture is stirred for 10 minutes.
• the reactor is then placed in cooling mode and the VTMO as well as the Exxsol D 100 and the DINP are added, the mixture is then kept under stirring for 20 minutes.
• the amounts indicated in the following table are expressed as percentages by mass relative to the total weight of the polyurethane composition.
• Example 2 preparation of the mastic composition C1
• Composition C1 was prepared according to the following procedure: mixing the silylated polymer, DINP, Tinuvin 765 and half of Dynasilane VTMO for 5 minutes at low speed. Then the powder components were added: Irganox 1076, Ti02, Crayvallac Super and Omyacarb 2T AV. The reaction mixture was stirred at high speed under vacuum until reaching 75 ° C. After 15 minutes at 75 ° C, the medium was cooled. Then the following compounds were added: Exxsol D100, second half of Dynasilane VTMO, Dynasilane 1146 and KKAT 670. The medium was stirred under vacuum at low speed for 15 minutes.
• the measurement of the skin formation time was carried out in a controlled atmosphere at a temperature of 20 ° C. and a relative humidity of about 50%.
• the composition was applied using a wooden spatula and in the form of a thin film approximately 0.5 mm thick, on a glass slide 76 mm long and 26 mm wide.
• a stopwatch was started and it was examined every minute using a light touch of the finger if the film is dry or if a residue of composition is transferred to the finger .
• the skin formation time is the time after which the film of composition is dry and for which there is no longer any transfer of adhesive residue to the finger. The result is expressed in minutes.
• the measurement of the resistance and the elongation at break (or "elongation at break” in English) by tensile test was carried out according to the protocol described below: the principle of the measurement consists in stretching in a machine. traction, the movable jaw of which moves at a constant speed equal to 5.5 mm / minute, a standard test piece made of the crosslinked composition and to be recorded applied to a standardized support such as anodized aluminum or cement mortar, and to measure the stress at 100% elongation (in MPa) as well as the maximum stress (in MPa) as well as the elongation of the test piece (in%) at the moment when the test piece breaks.
• the standard test piece is called "H test piece", it consists of 2 supports with an area of 75 X 12.5 mm and a central gasket applied to these 2 supports and made of the material to be tested, the dimensions of which are 50 X 12.5 X 12.5 mm.
• the modulus at 100% elongation at 23 ° C was determined according to standard ISO 8339 (2005-06), on an aluminum or mortar support, with a preconditioning carried out according to method A of ISO 8339 (2005-06) ).
• the elastic recovery at 100% elongation at 23 ° C was determined according to standard ISO 7389 (2004-04), on an aluminum or mortar support, with a preconditioning carried out according to method A of ISO 7389 (2004- 04).
• the elastic recovery at 23 ° C is greater than or equal to 70%.

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