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
  • C08G18/28—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
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
  • C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
  • C08G18/4233—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups derived from polymerised higher fatty acids or alcohols
• • 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
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4202—Two or more polyesters of different physical or chemical nature
• • 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
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
  • C08G18/4269—Lactones
  • C08G18/4277—Caprolactone and/or substituted caprolactone
• • 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
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
  • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• • 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
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
  • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
  • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
  • C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
• • 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
  • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

• the present invention relates to a composition based on a methacrylate monomer.
• the invention also relates to the use of said composition for the repair and / or the semi-structural or structural bonding of materials in the field of transport, marine, assembly or construction.
• Acrylic compositions are known reactive systems crosslinking by radical polymerization. They are used as adhesives, sealants and coatings. Radical polymerization is typically initiated by a redox system which through an oxidation-reduction reaction results in the production of radicals.
• the majority of acrylic systems are two-component systems.
• the first component traditionally contains the reducing agent and reactive monomers, and the second component contains the oxidizing agent. Once the two components are mixed, the reducing agent induces the cleavage of the 0-0 bond of organic peroxide, for example, and initiates polymerization.
• the bonds can be subjected to high temperatures. This is the case, for example, for bondings close to the engine in cars, or even adhesives close to the windshield or windows and subjected to high temperatures due to solar radiation. It is therefore important that the bonds exhibit a high resistance to these high temperatures, and that they maintain a good level of cohesion.
• the hydroxyl number of an alcoholic compound represents the number of hydroxyl functions per gram of product, which is expressed in the form of the equivalent number of milligrams of potash (mg KOH / g) used in the determination of the hydroxyl functions, per gram of product;
• the viscosity measurement at 23 ° C can be done using a Brookfield viscometer according to the ISO 2555 standard.
• the measurement carried out at 23 ° C (or at 100 ° C) can be done using a Brookfield RVT viscometer, a needle adapted to the viscosity range and at a rotational speed of 20 revolutions per minute (rev / min);
• the present invention also relates to a two-component composition
• a two-component composition comprising:
• composition A comprising:
• composition A at least one polyurethane P comprising at least two terminal (meth) acrylate functions, the polyurethane P content being greater than or equal to 6% by weight relative to the total weight of composition A;
• composition B comprising:
• polyurethane P being obtained by a process comprising:
• step E2 the reaction of the product formed at the end of step E1) with at least one M (meth) acrylate monomer comprising at least one hydroxyl function.
• the usable polyisocyanate (s) can be added sequentially or reacted as a mixture.
• the polyisocyanate (s) can be chosen from diisocyanates or triisocyanates.
• the polyisocyanate (s) can be monomer (s), oligometic (s) or polymer (s).
• the polyisocyanate (s) are diisocyanate (s), preferably chosen from the group consisting of isophorone diisocyanate (I PDI), hexamethylene diisocyanate (HDI), heptane diisocyanate, octane diisocyanate, nonane diisocyanate, decane diisocyanate, undecane diisocyanate, dodecane diisocyanate, 2,4'-methylenebis (cyclohexylisocyanate) (2,4'-H6MDI), 4,4'- methylenebis (cyclohexylisocyanate) (4,4'-H6MDI), norbornane diisocyanate, norbornene diisocyanate, 1, 4-cyclohexane diisocyanate (CHDI), methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, ethylcycl
• R c represents a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 1 to 20 carbon atoms, preferably from 6 to 14 carbon atoms
• R d represents a divalent alkylene group, linear or branched, having from 2 to 4 carbon atoms, and preferably a divalent propylene group; and their mixtures.
• the allophanate of formula (Y) above is such that p, q, R c and R d are chosen such that the HDI allophanate derivative above comprises an isocyanate group NCO content ranging from 12 to 14 % by weight relative to the weight of said derivative.
• the polyisocyanate (s) which can be used are triisocyanate (s), preferably chosen from isocyanurates, biurets, and adducts of diisocyanates and triols.
• the isocyanurate (s) can be used (s) in the form of a technical mixture of (poly) isocyanurate (s) with a purity of greater than or equal to 70% by weight isocyanurate (s).
• the diisocyanate isocyanurate (s) which can be used according to the invention can (wind) correspond to the following general formula (W):
• R 5 represents an alkylene group, linear or branched, cyclic, aliphatic, arylaliphatic or aromatic, comprising from 4 to 9 carbon atoms, with the proviso that the NCO groups are not covalently bonded to a carbon atom forming part of an aromatic hydrocarbon ring such as a phenyl group.
• trimers of diisocyanates which can be used according to the invention, there may be mentioned:
• the polyisocyanate (s) is (are) chosen from diisocyanates, preferentially from toluene diisocyanate (in particular the 2,4 TDI isomer, the 2,6-TDI isomer or their mixtures. ), 4,4'-diphenylmethanediisocyanate, 2,4'-diphenylmethane diisocyanate, meta-xylylene diisocyanate (m-XDI), isophorone diisocyanate (IPDI), and mixtures thereof.
• diisocyanates preferentially from toluene diisocyanate (in particular the 2,4 TDI isomer, the 2,6-TDI isomer or their mixtures. ), 4,4'-diphenylmethanediisocyanate, 2,4'-diphenylmethane diisocyanate, meta-xylylene diisocyanate (m-XDI), isophorone diisocyanate (IPDI), and
• the polyisocyanate is chosen from polyisocyanates based on diphenylmethane diisocyanate (MDI), and in particular from monomeric and polymeric polyisocyanates.
• MDI diphenylmethane diisocyanate
• Diphenylmethane diisocyanate may be in the form of a single isomer, for example chosen from 2,4'-MDI and 4,4'-MDI, or in the form of a mixture of isomers by example 2,4'-MDI and 4,4'-MDI.
• the diphenylmethane diisocyanate is in the form of a mixture of isomers comprising more than 50% by weight of the 4,4′-MDI isomer, and less than 50% by weight of isomer 2, 4'-MDI, the percentages being relative to the total weight of diphenylmethane diisocyanate.
• the polyisocyanate (s) which can be used is (are) typically 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
• the “DESMODUR® I” marketed by the company COVESTRO
• corresponding to an isocyanurate of HDI the “TAKENATE TM 500” marketed by MITSUI CHEMICALS corresponding to an m-XDI
• TAKENATE TM 600 marketed by MITSUI CHEMICALS corresponding to an m-H6XDI
• the “VESTANAT® H12MDI” marketed by EVONIK
• the polyisocyanate is chosen from:
• Monomeric diphenylmethane diisocyanate such as, for example, a mixture of approximately 70% by weight of 4,4′-MDI monomer and 30% by weight of 2,4′-MDI monomer, or 4,4′-MDI;
• the polyol (s) can be chosen from polyester polyols, polyether polyols, polyene polyols, polycarbonate polyols, poly (ether-carbonate) polyols, and mixtures thereof.
• the polyol (s) which can be used can be chosen from aromatic polyols, aliphatic polyols, arylaliphatic polyols and mixtures of these compounds.
• the polyol (s) which can be used can be chosen from among those having a number-average molecular weight (Mn) ranging from 200 g / mol to 20,000 g / mol, preferably from 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 have a hydroxyl functionality ranging from 2 to 6.
• the hydroxyl functionality of a polyol is the average number of hydroxyl functions per mole of polyol.
• 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 monoethylene glycol, diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, butenediol, 1,6-hexanediol, cyclohexane dimethanol, tricyclodecane dimethanol, neopentyl glycol, cyclohexane dimethanol, a polyether polyol, glycerol, trimethylolpropane, 1, 2,6-hexanetriol, sucrose, glucose , sorbitol, pentaerythritol, mannitol, N-methyldiethanolamine, triethanolamine, a dimeric fatty alcohol, a trimeric fatty alcohol and mixtures thereof, with
• polycarboxylic acid or its ester or anhydride derivative such as 1, 6-hexanedioic acid (adipic acid), dodecanedioic acid, azelaic acid, sebacic acid, adipic acid, acid 1, 18-octadecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, a dimeric fatty acid, a trimeric fatty acid and mixtures of these acids, an unsaturated anhydride such as for example l maleic or phthalic anhydride, or a lactone such as, for example, caprolactone;
• an unsaturated anhydride such as for example l 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 approximately 2000 g / mol, and a melting point of approximately 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 Approx. ° 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 ° C,
• KURARAY® P-6010 polyester polyol having a viscosity of 68 Pa.s at 23 ° C, a number-average molecular mass Mn equal to 6000 g / mol, and a T g equal at -64 ° C,
• KURARAY® P-10010 polyester polyol having a viscosity of 687 Pa.s at 23 ° C, and a number-average molecular mass Mn equal to 10,000 g / mol
• polyester polyol having a number-average molecular mass Mn close to 1000 g / mol and whose hydroxyl number ranges from 108 to 116 mg KOH / g. It is a product resulting from the condensation of adipic acid, diethylene glycol and monoethylene glycol,
• DEKATOL® 3008 (marketed by the company BOSTIK) with a number-average molar mass Mn close to 1060 g / mol and whose hydroxyl number ranges from 102 to 112 mg KOH / g. It is a product resulting from the condensation of adipic acid, diethylene glycol and monoethylene glycol; - “PRIPLAST® 3186” (marketed by CRODA): bio-based polyester polyol having an IHO equal to 66 mg KOH / g;
• the polyether polyol (s) can have a number-average molecular mass ranging from 200 to 20,000 g / mol, preferably from 300 to 12,000 g / mol, and preferably from 400 at 4000 g / mol.
• 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, more preferably from 2 to 3 carbon atoms.
• the polyether polyol (s) which can be used according to the invention is (are) preferably chosen from polyoxyalkylene diols or polyoxyalkylene triols, of which the alkylene part, linear or branched, comprises 1 with 4 carbon atoms, more preferably from 2 to 3 carbon atoms.
• Polyoxypropylene diols or triols also referred to as polypropylene glycol (PPG) diols or triols
• PPG polypropylene glycol
• Mn number average molecular mass
• polyoxyethylene diols or triols also designated by polyethylene glycol (PEG) diols or triols
• Mn number-average molecular mass
• polyether polyols can be prepared in a conventional manner, and are widely available commercially. They can be obtained by polymerization of the corresponding alkylene oxide in the presence of a basic catalyst (for example potassium hydroxide) or of a catalyst based on a double metal-cyanide complex.
• a basic catalyst for example potassium hydroxide
• a catalyst based on a double metal-cyanide complex for example sodium bicarbonate
• VORANOL® P1010 sold by the company DOW with a number-average molecular mass (Mn) of around 1020 g / mol and whose hydroxyl number is around 110 mg KOH / g;
• VORANOL® P2000 sold by the company DOW, a difunctional PPG with a number-average molecular mass of approximately 2000 g / mol
• - VORANOL® EP 1900 sold by the company DOW, a difunctional PPG with a number-average molecular mass of approximately 4,008 g / mol, and of hydroxyl number lo H equal to 28 mg KOH / g;
• - ACCLAIM ® 4200 difunctional PPG with a number-average molecular mass of approximately 4000 g / mol, and a hydroxyl number lo H equal to 28 mg KOH / g;
• - ACCLAIM ® 8200 difunctional PPG with a number-average molecular mass of 8,016 g / mol, and a hydroxyl number lo H equal to 14 mg KOH / g;
• - ACCLAIM ® 12200 difunctional PPG with a number-average molecular mass of 11222 g / mol, and a hydroxyl number lo H equal to 10 mg KOH / g;
• - ACCLAIM ® 18200 difunctional PPG with a number-average molecular mass of 17,265 g / mol, and a hydroxyl number lo H equal to 6.5 mg KOH / g.
• polyether triol By way of example of polyether triol, mention may be made of the polyoxypropylene triol marketed under the name “VORANOL® CP 450” by the company DOW, with a number-average molecular mass (Mn) close to 450 g / mol and whose index hydroxyl ranges from 370 to 396 mg KOH / g, or the polyoxypropylene triol marketed under the name “VORANOL® CP3355” by the company DOW, with a number-average molecular mass close to 3,554 g / mol, or “ACCLAIM® 6300 Which is a trifunctional PPG with a number-average molecular mass of approximately 5,948 g / mol, and of hydroxyl number lo H equal to 28.3 mg KOH / g.
• Mn number-average molecular mass
• ACCLAIM® 6300 which is a trifunctional PPG with a number-average molecular mass of approximately 5,948 g / mol
• the polyene polyol (s) which can be used according to the invention can be preferably chosen from polyenes comprising terminal hydroxyl groups, and their corresponding hydrogenated or epoxidized derivatives.
• the polyene polyol (s) which can be used according to the invention is (are) chosen from polybutadienes comprising terminal hydroxyl groups, optionally hydrogenated or epoxidized.
• the polyene polyol (s) which can be used according to the invention is (are) chosen from homopolymers and copolymers of butadiene comprising terminal hydroxyl groups, optionally hydrogenated or epoxidized.
• terminal hydroxyl groups of a polyene polyol is understood to mean the hydroxyl groups located at the ends of the main chain of the polyene 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 epoxidized derivatives mentioned above can be obtained by chemioselective epoxidation of the double bonds of the main chain of a polyene comprising terminal hydroxyl groups, and therefore comprise at least one epoxy group in its main chain.
• polyene 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 as well as isoprene homopolymers, saturated or unsaturated, comprising terminal hydroxyl groups, such as, for example, those sold under the name “POLY IP TM or EPOL TM” by the company IDEMITSU KOSAN.
• the polycarbonate polyols can be chosen from polycarbonate diols or triols, having in particular a number-average molecular weight (M n ) ranging from 300 to 12,000 g / mol.
• CONVERGE® POLYOL 212-10 and “CONVERGE® POLYOL 212-20” marketed by the company NOVOMER respectively of molecular mass in number (M n ) equal to 1000 and 2000 g / mol, the hydroxyl numbers of which are respectively from 1 12 and 56 mg KOH / g,
• POLYOL C-590, C1090, C-2090 and C-3090 marketed by KURARAY having a number molecular mass (M n ) ranging from 500 to 3,000 g / mol and a hydroxyl number ranging from 224 to 37 mg KOH / g.
• the (meth) acrylate monomer M can be chosen from those having the following formula (I): [Chem 9]
• R 6 represents a methyl or a hydrogen, preferably R 6 being a methyl
• R a representing a linear or branched alkyl radical compris
• the monomer M has one of the following formulas:
• R 7 represents a divalent linear or branched alkylene radical, aliphatic or cyclic, saturated or unsaturated, comprising from 2 to 22 carbon atoms, preferably from 2 to 18, preferably from 2 to 14, even more preferably from 2 to 10, and advantageously from 2 to 6 carbon atoms;
• - w is an integer ranging from 1 to 10, preferably from 1 to 5, and preferably w is equal to 5;
• - s is an integer ranging from 1 to 10, s preferably being equal to 2;
• R 8 represents a divalent linear or branched alkylene radical, aliphatic or cyclic, saturated or unsaturated, comprising from 2 to 22 carbon atoms, preferably from 2 to 18, preferably from 2 to 14, even more preferably from 2 to 10, and advantageously from 2 to 6 carbon atoms;
• R 9 represents a divalent linear or branched alkylene radical, aliphatic or cyclic, saturated or unsaturated, comprising from 2 to 4 carbon atoms, t is an integer ranging from 2 to 120, preferably from 1 to 10, t being from preferably equal to 2 or 3.
• HEMA 2-hydroxyethyl methacrylate
• HPA 2-hydroxypropyl methacrylate
• 4-hydroxybutyl acrylate 2-hydroxybutyl methacrylate
• HPA 2-hydroxypropyl acrylate
• SARTOMER COGNIS or BASF
• the monomer M is 2-hydroxyethyl methacrylate (HEMA):
• the polyaddition reaction E1) can be carried out at a temperature preferably below 95 ° C. and / or under conditions which are preferably anhydrous.
• the polyaddition reaction can be carried out in the presence or absence of at least one catalyst.
• the reaction catalyst (s) which can be used during the polyaddition reaction can be any catalyst known to those skilled in the art for catalyzing the formation of polyurethane by reaction of at least one polyisocyanate with at least one polyol.
• An amount of up to 0.3% by weight of catalyst (s) relative to the weight of the reaction medium of the polyaddition step can be used.
• the polyaddition reaction E1) can be carried out in the presence or absence of at least one solvent.
• the solvent can be chosen from solvents which do not react with the reactive functions of the ingredients used in step E1). It can, for example, be methyl methacrylate, toluene, ethyl acetate, xylene, and mixtures thereof.
• Step E1) is preferably carried out in amounts of reagents such that the NCO / OH (r1) molar ratio ranges from 1.5 to 5, preferably from 1.5 to 2.5.
• (r1) is the NCO / OH molar ratio corresponding to the molar ratio of the number of isocyanate groups (NCO) to the number of hydroxyl groups (OH) carried by respectively by the all of the polyisocyanate (s) and all of the alcohol (s) present in the reaction medium of step E1) (polyol (s)).
• the polyurethane obtained in step E1) advantageously comprises two NCO end groups, said groups being present at the endings of the main chain.
• Step E2) can be carried out at a temperature preferably below 80 ° C, preferably below or equal to 60 ° C, and / or under preferably anhydrous conditions.
• Step E2) can be carried out in the presence or absence of at least one catalyst. It can be the same catalyst as that used in step E1).
• Step E2) can be carried out in the presence or absence of at least one solvent.
• the solvent can be chosen from solvents which do not react with the reactive functions of the ingredients used in step E2). It can, for example, be methyl methacrylate, toluene, ethyl acetate, xylene, and mixtures thereof.
• step E2) is carried out by adding the monomer (s) M in the reaction medium of step E1), without isolation of the product formed in step E1).
• Step E2) is preferably carried out in quantities of reagents such that the OH / NCO (r2) molar ratio is less than or equal to 1, preferably ranges from 0.90 to 1.00, and even more preferably ranges from 0.95 to 1.00.
• (r2) is the OH / NCO molar ratio corresponding to the molar ratio of the number of hydroxyl groups (OH) to the number of isocyanate groups (NCO) carried respectively by the assembly alcohol (s), and isocyanate (s) (especially polyurethane with NCO terminations and optionally unreacted polyisocyanate (s) at the end of step E1) ) present in the reaction medium of step E2).
• the polyurethane P may be in solution in a solvent such as, for example, methyl methacrylate.
• the polyurethane content in the solution can range from 40% to 80% by weight, preferably from 50% to 70% by weight.
• Polyurethane P preferably has a number-average molecular mass (Mn) greater than or equal to 2,000, preferably greater than or equal to 5,000 g / mol, preferably greater than or equal to 7,000 g / mol, better still greater than or equal to at 10,000 g / mol.
• Mn number-average molecular mass
• Polyurethane P preferably comprises at least two (meth) acrylate functions in the terminal position of the main chain.
• composition A and in composition B can be the same or different.
• the (meth) acrylate monomers can comprise one (monofunctional) or more (meth) acrylate (polyfunctional) functions.
• the (meth) acrylate monomer (s) can be chosen from the group consisting of:
• R 10 represents a hydrogen atom or an alkyl group comprising from 1 to 4 carbon atoms
• R 11 is chosen from the group consisting of alkyls, cycloalkyls, alkenyls, cycloalkenyls, alkylaryl, arylalkyl or aryl, said alkyls, cycloalkyl, alkenyl, cycloalkenyl, alkylaryl, arylalkyl or aryl which may be optionally substituted and / or interrupted by at least one silane, a silicone, an oxygen, a halogen, a carbonyl, a hydroxyl, an ester, a urea, a urethane, a carbonate, an amine, an amide, a sulfur, a sulfonate, or a sulfone; - polyethylene glycol di (meth) acrylates;
• the (meth) acrylate monomer is chosen from methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate , 2-tert-butylheptyl (meth) acrylate, octyl (meth) acrylate, 3-isopropylheptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, 5-methylundecyl (meth) acrylate, dodecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate, tridecyl (meth) acrylate, (meth) acrylate 5-methyltridecyl, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate
• the (meth) acrylate monomer is a methacrylate.
• the (meth) acrylate monomer is methyl methacrylate.
• Composition A may comprise a (meth) acrylate monomer content ranging from 20% to 80%, preferably from 40% to 70%, advantageously from 50% to 65% by weight relative to the total weight of part A.
• the polyurethane content P in composition A is preferably between 6% and 20% by weight, preferably between 6% and 15% by weight.
• the polyurethane content P in composition A is 6% to 10% by weight, preferably 6% to 9% by weight, preferably 6% to 8% by weight, and again preferably from 6% to 7% by weight relative to the total weight of composition A.
• These proportions are particularly preferred in that they allow the production of compositions A having improved thermal resistance, while having good properties of membership.
• the reducing agent can be chosen from tertiary amines, sodium metabisulfite, sodium bisulfite, transition metals, azo compounds, alpha-aminosulfones, and mixtures thereof.
• azo compounds there may be mentioned, for example, azoisobutyric acid.
• alpha-sulfones mention may for example be made of bis (tolylsulfonmethyl) benzylamine.
• diisopropanol-p-toluidine DIIPT
• dimethyl-p-toluidine dipropoxy-p-toluidine
• dimethylaniline N, N-dimethylaminomethylphenol
• N, N-diisopropanol-p-chloroaniline N, N-diisopropanol-p- bromoaniline
• N N-dimethyl-p-chloroaniline
• N-dimethyl-p-bromoaniline N, N-diethyl-p-chloroaniline
• N, N-diethyl-p-bromoaniline N, N-diethyl-p-bromoaniline; and their mixtures.
• composition A comprises at least one tertiary amine.
• Composition A may comprise a reducing agent content ranging from 0.5% to 5%, preferably from 1% to 3%, by weight relative to the total weight of composition A.
• the oxidizing agent can be chosen from peroxides, organic salts of transition metals, compounds containing labile chlorine, and mixtures thereof.
• the peroxide can be chosen from organic peroxides, inorganic peroxides, and mixtures thereof.
• peroxydisulfuric acid and their salts such as ammonium peroxodisulfate, sodium peroxodisulfate and potassium peroxodisulfate.
• organic peroxides mention may be made of cumene hydroperoxide, para-menthane hydroperoxide, tert-butyl peroxyisobutyrate, tert-butyl peroxybenzoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, acetyl peroxide, benzoyl peroxide, dibenzoyl peroxide, 1,3-bis- (t-butylperoxyisopropyl) benzene, diacetyl peroxide, t-butylcumyl peroxide, tert-butyl peroxyacetate, cumyl, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butyl-peroxyhex-3-yne, 4-methyl-2,2 -di-t-butylperoxypentane, and mixture
• composition B comprises benzoyl peroxide
• Composition B can comprise a reducing agent content ranging from 1% to 20
• composition B preferably from 1% to 10%, by weight relative to the total weight of composition B.
• composition according to the invention can typically comprise a redox system, a reducing agent being included in part A and an oxidizing agent being included in part B.
• a redox system a reducing agent being included in part A
• an oxidizing agent being included in part B.
• the two-component composition according to the invention can comprise at least one additive chosen from the group consisting of catalysts, fillers, antioxidants, light stabilizers / UV absorbers, metal deactivators, antistatic agents, anti-fog agents, foaming agents, biocides, plasticizers, lubricants, emulsifiers, colorants, pigments, rheological agents, impact modifiers, adhesion promoters, optical brighteners, flame retardants, anti-seepage agents , nucleating agents, solvents, and mixtures thereof.
• additives chosen from the group consisting of catalysts, fillers, antioxidants, light stabilizers / UV absorbers, metal deactivators, antistatic agents, anti-fog agents, foaming agents, biocides, plasticizers, lubricants, emulsifiers, colorants, pigments, rheological agents, impact modifiers, adhesion promoters, optical brighteners, flame retardants, anti-seepage agents , nucleating agents, solvents, and mixtures
• composition A and / or composition B of the composition according to the invention can be present in composition A and / or composition B of the composition according to the invention.
• plasticizer As an example of a plasticizer that can be used, there may be mentioned any plasticizer usually used in the field of adhesives, such as, for example, epoxy resins, phthalates, benzoates, trimethylolpropane esters, trimethylolethane esters. , trimethylolmethane esters, glycerol esters, pentaerythritol esters, naphthenic mineral oils, adipates, cyclohexyldicarboxylates, paraffinic oils, natural oils (optionally epoxidized), polypropylenes, polybutylenes, hydrogenated polyisoprenes and hydrogenated polyisoprenes their mixtures.
• epoxy resins phthalates, benzoates
• trimethylolpropane esters trimethylolethane esters.
• trimethylolmethane esters trimethylolmethane esters
• glycerol esters pentaerythritol esters
• naphthenic mineral oils
• soybean oil such as, for example, sold under the name VIKOFLEX® 7170 by the company ARKEMA.
• rheological agent (s) which can be used, there may be mentioned any rheological agent usually used in the field of adhesive compositions.
• the thixotropic agents are chosen from:
• - PVC plastisols corresponding to a suspension of PVC in a plasticizer miscible with PVC, obtained in situ by heating at temperatures ranging from 60 ° C to 80 ° C.
• These plastisols can be those described in particular in the work “Polyurethane Sealants”, Robert M. Evans, ISBN 087762-998-6,
• composition according to the invention can further comprise at least one organic and / or mineral filler.
• the usable mineral filler (s) is (are) advantageously chosen so as to improve the mechanical performance of the composition according to the invention in the crosslinked state.
• mineral filler As an example of usable mineral filler (s), it is possible to use any mineral filler (s) usually used in the field of adhesive compositions. These fillers are typically in the form of particles of various geometry. They may for example be spherical, fibrous, or have an irregular shape.
• the filler (s) is (are) chosen from the group consisting of clay, quartz, carbonate fillers, kaolin, gypsum, clays, and their mixtures, preferably the filler (s) is (are) chosen from carbonate fillers, such as carbonates of alkali or alkaline earth metals, and more preferably calcium carbonate or chalk.
• These fillers can be untreated 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.
• composition according to the invention can also comprise at least one adhesion promoter, preferably chosen from silanes, such as aminosilanes, epoxysilanes or acryloylsilanes, or adhesion promoters based on phosphate ester.
• adhesion promoter preferably chosen from silanes, such as aminosilanes, epoxysilanes or acryloylsilanes, or adhesion promoters based on phosphate ester.
• 2-hydroxyethyl methacrylate phosphate ester 2-methacryloyloxyethyl phosphate, bis- (2-methacryloyloxyethyl phosphate), 2-acryloyloxyethyl phosphate, bis- (2-acryloyloxyethyl phosphate), methyl- (2-methacryloyloxyethyl phosphate), ethyl- (2-methacryloyloxyethyl phosphate), a mixture of mono and di-phosphate esters of 2-hydroxyethyl methacrylate.
• 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.
• a pigment When a pigment 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 pigment may for example represent from 0.1% to 3% by weight or from 0.4% to 2% by weight of the total weight of the composition.
• the pigments can be organic or inorganic pigments.
• the pigment is PO2, in particular KRONOS® 2059 sold by the company KRONOS.
• the composition may comprise an amount of 0.1% to 3%, preferably 1% to 3% 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 primary antioxidants which scavenge 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 A comprises at least one acrylic block copolymer, preferably in a content ranging from 2% to 40% by weight, even more preferably from 5% to 20% by weight relative to the total weight.
• Acrylic block copolymers are typically impact modifiers.
• the acrylic block copolymers can be copolymers comprising:
• At least one rigid block (A) whose glass transition temperature is above ambient temperature by at least 20 ° C; - from 1 to 99% by weight of at least one flexible block (B), the glass transition temperature of which is at least 10 ° C below ambient temperature.
• the copolymers are rigid block / flexible block / rigid block triblocks, in which:
• the flexible block (B) advantageously contains:
• the rigid block (A) preferably comprises monomer units derived from methyl methacrylate monomers.
• the rigid block (A) can also comprise at least one dialkylacrylamide monomer whose alkyl groups, linear or branched, comprise from 1 to 10 carbon atoms, such as N, N-dimethylacrylamide.
• the flexible block (B) preferably comprises monomer units derived from at least one monomer chosen from butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, 2-ethylhexyl methacrylate, l n-octyl acrylate and mixtures thereof.
• the copolymer is a polymethyl methacrylate / n-butyl polyacrylate / polymethyl methacrylate block copolymer.
• Nanostrength® marketed by Arkema (M52 comprising 52% by weight of n-butyl polyacrylate, or M75 comprising approximately 75% by weight of n-butyl polyacrylate or M65 comprising about 65% by weight of n-butyl polyacrylate).
• composition B comprises at least one epoxy resin.
• the epoxy resin can be aliphatic, cycloaliphatic, heterocyclic or aromatic.
• the epoxy resin can be monomeric or polymeric.
• the epoxy resins can be chosen from polyglycidyl ethers of polyphenolic compounds, preferably comprising from 2 to 6 glycidyl ether functions per mole of resin.
• a phenolic compound is a compound having at least two aromatic hydroxyl groups.
• the phenolic compounds can be selected from the group consisting of resorcinol, catechol, hydroquinone, bisphenol A (2,2-bis- (4-hydroxyphenyl) propane), bisphenol AP (1, 1-bis- (4 -hydroxyphenyl) -1-phenylethane), bisphenol AF (2,2-bis- (4-hydroxyphenyl) - hexafluoropropane), bisphenol B ((2,2-bis- (4-hydroxyphenyl) butane), bisphenol BP (bis- (4- hydroxyphenyl) -diphenylmethane), bisphenol C (2,2-bis- (3-methyl-4-hydroxyphenyl) propane), bisphenol Cil (bis (4-hydroxyphenyl) -2,2-dichloroethylene), bisphenol E ( 1, 1 -bis- (4- hydroxyphenyl) ethane), bisphenol F (bis (4-hydroxyphenyl) -2,2-dichloroethylene), bisphenol FL (4,4 '- (9H-fluoren-9-yliden
• the epoxy resin can have an epoxy functional content ranging from 0.3 to 10.8 meq per gram of resin.
• epoxy resins are typically available commercially. Mention may be made, for example, of the DER TM 331 and DER TM 383 resins marketed by the company DOW CHEMICALS, the EPON 862 resin marketed by HEXION SPECIALITY CHEMICALS, the EPOSIR® resins based on bisphenol A marketed by SIR INDUSTRIAL (for example EPOSIR® 7120, EPOSIR® resins based on bisphenol A / bisphenol F (for example EPOSIR® F556).
• the volume ratio of composition A / composition B in the composition of the invention ranges from 100/5 to 1/1, preferably from 20/1 to 1/1, preferably from 10/1 to 1 / 1.
• composition A comprising:
• composition A ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
• composition B comprising:
• the composition according to the invention is an adhesive composition.
• the present invention also relates to a ready-to-use kit, comprising composition A as defined above on the one hand and composition B as defined above on the other hand, packaged in two separate compartments. It may for example be a two-component cartridge.
• composition according to the invention can be in a two-component form, for example in a ready-to-use kit, comprising composition A on the one hand in a first compartment or drum and composition B d. 'on the other hand in a second compartment or barrel, in proportions suitable for direct mixing of the two components, for example using a metering pump.
• the kit further comprises one or more means allowing the mixing of compositions A and B.
• the mixing means are chosen from metering pumps, static mixers of diameter adapted to the quantities. used.
• the present invention also relates to the use of a composition as defined above, as an adhesive, mastic or coating, preferably as an adhesive.
• the invention also relates to the use of said composition for the repair and / or the structural or semi-structural bonding of materials in the field of transport, automobile (car, bus or truck), assembly, marine, etc. or construction.
• the present invention also relates to a method of assembling two substrates by bonding, comprising:
• compositions A and B as defined above
• the crosslinking step can be carried out at a temperature between 0 ° C and 200 ° C, preferably between 10 ° C and 150 ° C, preferably between 23 and 80 ° C and in particular between 20 ° C and 25 ° C.
• Crosslinking can also be induced using microwaves.
• Suitable substrates are, for example, inorganic substrates such as concrete, metals or alloys (such as aluminum alloys, steel, non-ferrous metals and galvanized metals); or organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins; metal substrates and painted composites.
• inorganic substrates such as concrete, metals or alloys (such as aluminum alloys, steel, non-ferrous metals and galvanized metals); or organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins; metal substrates and painted composites.
• compositions according to the invention once crosslinked, advantageously exhibit high resistance at high temperature.
• compositions according to the invention advantageously exhibit, after crosslinking, good adhesive properties.
• between x and y or “ranging from x to y”, is meant an interval in which the limits x and y are included.
• the range “between 0% and 25%” notably includes the values 0% and 25%.
• HUNTSMAN is a diphenylmethane diisocyanate (MDI) comprising approximately 70% by weight of 4,4′-MDI monomer and approximately 30% by weight of 2,4′-MDI monomer, of functionality 2 and having a viscosity of 15 mPa / s at 25 ° C and an NCO percentage of 32.8%;
• MDI diphenylmethane diisocyanate
• HEMA 2-hydroxyethyl methacrylate
• PPG Polypropylene Glycol
• MMA - methyl methacrylate
• - Struktol 3622 Polyol modified from Bisphenol-A-diglycidylether (DGEBA) from the company Schill + Seilacher;
• DGEBA Bisphenol-A-diglycidylether
• - DER 331 liquid epoxy resin produced from the reaction of bisphenol A with epichloridrine from the company DOW; - Luperox ANS50: 50% benzoyl peroxide in a plasticizer produced by the company Arkema;
• - M65A triblock copolymer of type (polymethyl methacrylate-n-butyl polyacrylate-polymethyl methacrylate) comprising approximately 65% by weight of n-butyl polyacrylate, marketed by ARKEMA.
• Priplast 3186 and CAPA 2210 polyols were introduced and heated to 90 ° C under vacuum to dehydrate the polyols for about 1 hour.
• Desmodur VK 10 was introduced into the reactor and heated to 70 ° C for about 2h. Then, the reactor was fitted with a refrigerant. After a few minutes, methyl methacrylate was introduced. Then, 2-hydroxyethyl methacrylate was introduced, and the reaction medium was mixed at 70 ° C for 1 hour.
• Voranol TM P2000 polyol was introduced and heated to 90 ° C under vacuum to dehydrate the polyol for about 1 hour.
• Desmodur 44 MC was introduced into the reactor and heated at 70 ° C for about 2 h. After a few minutes, the catalyst and 2-hydroxyethyl methacrylate were introduced, and the reaction medium was mixed at 60 ° C for 1 h.
• composition n ° 1 was prepared with the following ingredients:
• Component A and component B above were mixed, in a volume ratio of 10: 1.
• the mixing is carried out at a temperature of approximately 23 ° C., according to the volume ratio given with a static mixer.
• Comparative composition No. 2 was prepared in the same way with the following ingredients: [Table 4]
• Component A and component B above were mixed, in a volume ratio of 10: 1.
• the mixing is carried out at a temperature of approximately 23 ° C., according to the volume ratio given with a static mixer.
• Measurement of tensile strength by tensile test The resistance (breaking stress) by tensile test was measured according to the protocol described below.
• the principle of the measurement consists in stretching in a tensile machine, the movable jaw of which moves at a constant speed equal to 100 mm / minute, a standard specimen consisting of the crosslinked composition and recording, at the moment when the rupture occurs. 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 form of a dumbbell, as illustrated in international standard ISO 37 of 201 1.
• the narrow part of the dumbbell used has a length of 20 mm, a width of 4 mm and a thickness of 500 ⁇ m.
• the bondings are made on aluminum sterigmas from the Rocholl company. On a sterigma, an area of 25 * 12.5mm was delimited using Teflon wedges 250pm thick in an area of 25 * 12.5mm. This zone was filled with the composition to be tested, then a second sterigma of the same material was laminated. The whole was held in place by forceps and placed in an air-conditioned room at 23 ° C or 100 ° C and 50% RH (relative humidity) for one week before traction on a dynamometer. The purpose of traction on a dynamometer is to assess the maximum force (in MPa) to be exerted on the assembly to separate it.
• a tensile machine makes it possible to subject a single lap joint placed between two rigid supports to a shear stress until failure by exerting a tension on the supports parallel to the surface of the assembly and to the principal axis of the test piece.
• the result to be recorded is the force or stress at break.
• the shear stress is applied via the movable jaw of the tensile machine with a displacement at the speed of 5 mm / min. This traction method is performed as defined by standard EN 1465 of 2009.
• Fmax maximum force at the moment of bond failure Composition No. 1 advantageously results in bonding to aluminum leading to a cohesive rupture (RC), which denotes in particular good adhesion in the automotive field with respect to obtaining an adhesive rupture RA.
• the maximum force (Fmax) at the time of rupture is advantageously higher at 23 ° C and at high temperature (100 ° C), than that obtained with comparative composition No. 2 having a polyurethane content P1 less than 6% by weight in component A.
• composition No. 1 advantageously results in an adhesive joint having, after crosslinking, a tensile strength greater than that obtained with composition No. 2 (comparative).

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• Chemical Kinetics & Catalysis (AREA)
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• Polymers & Plastics (AREA)
• Polyurethanes Or Polyureas (AREA)
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• 2019
  • 2019-03-28 FR FR1903223A patent/FR3094374B1/fr not_active Expired - Fee Related
• 2020
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  • 2020-03-25 US US17/441,360 patent/US20220153913A1/en not_active Abandoned
  • 2020-03-25 EP EP20712376.1A patent/EP3947502A1/fr active Pending
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