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
  • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
  • C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
  • C08G18/6423—Polyalkylene polyamines; polyethylenimines; Derivatives 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
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
  • C08G18/3821—Carboxylic acids; Esters thereof with monohydroxyl compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—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
  • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
  • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
  • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/6858—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
• • 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
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/02—Polyamines
  • C08G73/0206—Polyalkylene(poly)amines
  • C08G73/0213—Preparatory process
• • 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
  • C09D175/02—Polyureas
• • 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
• • 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
  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
• • 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

Definitions

• the present invention relates to a process for preparing an aminosuccinic resin, as well as the aminosuccinic resin capable of being obtained following this process, which has an amine number of less than 190 mg KOH/g. It also relates to the use of this aminosuccinic resin for the manufacture of two-component binders containing at least one polyisocyanate.
• a crosslinking agent such as a polyisocyanate makes it possible to obtain extemporaneous formulations of two-component binder.
• These formulations are useful for the preparation of adhesive compositions, paints or coatings, in particular for protecting metal surfaces against corrosion, impact or abrasion. These compositions find applications in particular in the automobile, wind power and construction industries (floor coverings, sealing parts, etc.).
• Aspartic resins are marketed by the company COVESTRO under the commercial reference Pasquick®. These aspartic resins are prepared from primary diamines sold under the commercial reference Desmophen® and they are capable of reacting with an aliphatic polyisocyanate sold under the commercial reference Desmodur® to form polyureas. Their amine index is at least 190 mg KOH/g.
• Document EP 1 516 886 also describes aspartic resins which can be used in the manufacture of binders. These resins are obtained following a process comprising a first step of transesterification of an a,
• the aspartic resins thus obtained have an amine index which is at least 200 mg KOH/g.
• Document US-5,925,711 discloses a similar process for preparing aspartic resins, except that the oligoester obtained in the first step is formed either by reaction of an unsaturated diacid, such as maleic or fumaric acid, with a polyol and a mono-alcohol, for example 1,6-hexanediol combined with n-butanol, or by transesterification of a C1-Cs alkyl diester with a polyol such as 1,6-hexanediol.
• an unsaturated diacid such as maleic or fumaric acid
• a polyol and a mono-alcohol for example 1,6-hexanediol combined with n-butanol
• transesterification of a C1-Cs alkyl diester with a polyol such as 1,6-hexanediol.
• the inventors have developed a process making it possible to satisfy the aforementioned needs, which uses, in the first step of preparing the aminosuccinic resin, a light diester transesterified using one or more heavy mono-alcohols and optionally of one or more polyols. It was observed that the use of a heavy monoalcohol made it possible to increase the molar mass of the diester and thus reduce the amine number of the aminosuccinic resin prepared subsequently, without significantly increasing the polydispersity (and therefore the viscosity) of the diester thus obtained, and to maintain a pot life of the mixture of the resin with a polyisocyanate which is adapted to the intended use.
• the subject of the present invention is therefore a process for preparing an aminosuccinic resin comprising the following steps: a) the transesterification of at least one alkyl diester of formula (I) using at least one compound A chosen from a mono-alcohol of formula (II), a precursor thereof and their mixtures , and optionally at least one polyol of formula (III):
• the invention also relates to a binder formulation comprising the aforementioned aminosuccinic resin and a polyisocyanate component.
• the invention relates to a process for preparing an aminosuccinic resin essentially comprising two steps, namely a first step of transesterification and a second step of reaction of the product thus obtained with an amine.
• the hydrocarbon chain R' is preferably a (mono or poly)cyclic hydrocarbon chain, more preferably a non-aromatic monocyclic hydrocarbon chain.
• the hydrocarbon chain R' is preferably devoid of oxyethylene units, more preferably the hydrocarbon chain R' is devoid of ether function.
• R' is a (mono or poly)cyclic hydrocarbon chain, preferably R' is a non-aromatic monocyclic hydrocarbon chain, z is greater than 0, preferably z ranges from 1 to 20.
• compound A may in particular be a mono-alcohol resulting from the reaction between a mono-alcohol (in particular a heavy mono-alcohol as defined above) and a precursor of a mono-alcohol chosen from a lactone and a cyclic diester.
• a mono-alcohol in particular a heavy mono-alcohol as defined above
• a precursor of a mono-alcohol chosen from a lactone and a cyclic diester.
• a polyol may optionally be present in the reaction mixture to adjust the rate of increase in viscosity of the varnish obtained from the aminosuccinic resin according to the invention.
• This polyol corresponds to formula (III):
• R 4 designates a saturated, linear, branched or (mono or poly)cyclic hydrocarbon chain containing at least 2 carbon atoms, preferably at least 4 carbon atoms and more preferably at least 5 carbon atoms, and generally less than 36 atoms carbon, and
• n is equal to 2.
• the hydrocarbon chain R 4 can in particular be interrupted by one or more functions chosen from ether, ester, carbonate, urea and urethane.
• the hydrocarbon chain R 4 contains only carbon and hydrogen atoms and is optionally interrupted and/or substituted by one or more atoms. of oxygen.
• polyols include: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl - 1,5-pentanediol, 1,10-decanediol, 1,12-dodecanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyalkylene glycols such as polyethylene glycol or polypropylene glycol (preferably of number average molecular weight Mn, calculated from the OH index, ranging from 250 to 3000 g/mol), 1,4-cyclohexanedimethanol, 1,6-cyclohexane
• the molar ratio of compound A to the diester ranges from 0.01 to 1.99, preferably from 0.1 to 1.5 and more preferably from 0.2 to 1.0.
• the molar ratio of the polyol to the diester is generally less than 0.6/n, preferably less than 0.4/n and more preferably less than 0.2/n.
• This reaction is generally carried out at a temperature of 50 to 300°C, preferably 80 to 250°C and more preferably 150 to 200°C.
• the reaction is generally controlled by measuring the hydroxyl number of the reaction product, so that the temperature is maintained for a period allowing a hydroxyl number of less than 10 mg KOH/g to be achieved, preferably less than 5 mg KOH/g, as measured as described in the examples below.
• the transesterification reaction is generally carried out in the presence of a catalyst.
• the catalyst can for example be chosen from oxides and organic salts of metals such as titanium, tin, zinc, antimony or iron, for example from: titanium (IV) butoxide, titanium titanate tetrakis(2-ethylhexyl), tin(IV) oxide, dibutyltin oxide, butyltin hydroxide, dibutyltin bis(2-ethylhexyl mercaptoacetate), dibutyltin bis(2-ethylhexanoate) , butyl stannoic acid, dibutyltin dichloride, octyltin hydroxide, zinc(IV) oxide and zinc(ll) oxide.
• titanium (IV) butoxide titanium titanate tetrakis(2-ethylhexyl)
• tin(IV) oxide dibutyltin oxide
• butyltin hydroxide dibutyltin bis(2-ethylhexyl mercaptoa
• transesterification reaction be carried out under an inert atmosphere, for example under nitrogen bubbling.
• a so-called “heavy” polyester is obtained which is reacted, in the second step of the process according to the invention, with at least one primary polyamine and optionally at least a primary monoamine, together hereinafter referred to as "the amine", unless otherwise indicated.
• the molar ratio between the amine functions and the double bonds of the diester ranges from 0.8 to 1.2, preferably from 0.9 to 1.1 and more preferably from 0.95 to 1.05.
• the mono- and polyamines used according to the invention can be chosen from amines comprising a linear, cyclic or branched, saturated or unsaturated (optionally aromatic) hydrocarbon chain, to which one or more amino groups are linked.
• the polyamine can be chosen from diamines, triamines and tetramines. It is preferably a diamine.
• the primary polyamine may in particular correspond to formula (IV):
• Rs is a linear, cyclic or branched, saturated or unsaturated (optionally aromatic) chain comprising at least 2 carbon atoms, preferably at least 4 carbon atoms and more preferably at least 5 carbon atoms, and generally less than 100 carbon atoms. carbon, preferably less than 40 carbon atoms, and 2 ⁇ m ⁇ 4, preferably 2 ⁇ m ⁇ 3 and more preferably m is equal to 2.
• the Rs chain is a hydrocarbon chain optionally interrupted by one or more heteroatoms independently chosen from oxygen and nitrogen.
• the primary diamine corresponds to the formula (IVa): H2N-R5-NH2 (IVa) in which R5 is as defined above.
• monoamines examples include: sec-butylamine, isobutylamine, tert-butylamine, cyclohexylamine, 1,1,3,3-tetramethyl butylamine (or tert-octylamine) and mixtures thereof.
• triamines examples include guanidine and N-(2-aminoethyl)-1,3-propane diamine.
• guanidine examples include N,N'-di-(2-aminoethyl)piperazine.
• the primary polyamine may also be a polyetheramine.
• a polyetheramine is a polyamine comprising ether bonds (-O-), more particularly ethylene oxide (-O-CH2-CH2) and/or propylene oxide (-O-CH2-CHCH3-) units.
• Examples of polyetheramines are the compounds marketed by Hunstmann under the reference Jeffamine®, in particular the Jeffamine® D, ED and EDR series. These series include in particular the following references Jeffamine® D-230, Jeffamine® D-400, Jeffamine® D-2000, Jeffamine® D-4000, Jeffamine® ED-6OO, Jeffamine® ED-900, Jeffamine® ED-2OO3, Jeffamine ® EDR-148, Jeffamine® EDR-176.
• the order of introduction of the above reagents is not critical, provided that the monoamines, if used, are introduced before the diamines. Typically, the product of the transesterification step is added slowly to the amine.
• the reaction between the amine(s) and the product of the first step is a Michael reaction, which is generally carried out at a temperature of 0 to 160°C, preferably 20 to 140°C and more preferably 30 to 80°C. C, for a period of 1 to 4 hours. It is preferred that this reaction be carried out under an inert atmosphere, for example under nitrogen bubbling.
• the product obtained is generally then maintained at room temperature for a period of 15 to 90 days, for example 30 to 60 days, always under an inert atmosphere.
• the two steps described above can be carried out in the presence or absence of a solvent.
• a solvent examples include polar organic solvents such as: ketones, in particular acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as n-butyl acetate and methoxypropyl acetate; N-methylpyrrolidone; and their mixtures.
• non-polar organic solvents such as toluene and xylene can be used.
• the amine number of the aminosuccinic resin obtained at the end of the second step described below is less than 190 mg KOH/g, preferably less than 180 mg KOH/g or even less than 150 mg KOH/g, as measured as described in the examples below.
• the process according to the invention makes it possible to obtain an aminosuccinic resin.
• the invention also relates to an aminosuccinic resin comprising at least one unit according to formula (VI): in which :
• Ri is a saturated, linear or branched hydrocarbon chain that contains less than 5 carbon atoms
• R 3 is a saturated or unsaturated, linear, branched or (mono or poly)cyclic hydrocarbon chain containing more than 4 carbon atoms;
• Rs is a linear, cyclic or branched, saturated or unsaturated (possibly aromatic) hydrocarbon chain comprising at least 2 carbon atoms.
• the aminosuccinic resin comprises at least one unit according to formula (VII): in which Ri, R 3 and R 5 are as defined above;
• R4 is a hydrocarbon chain containing at least 2 carbon atoms as described in the process according to the invention.
• the aminosuccinic resin can in particular be obtained by the process described above.
• Ri may in particular correspond to the group Ri which is present on the alkyl diester of formula (I) before the transesterification reaction;
• R 3 may in particular correspond to the residue of compound A of formula (II) or (llb) (without the OH group) used in the transesterification reaction;
• Rs can in particular correspond to the primary polyamine residue of formula (IV) (without the NH2 groups).
• aminosuccinic resins prepared according to the invention can be used in binder formulations, in combination with a crosslinking agent such as a polyisocyanate.
• the present invention also relates to a binder formulation comprising: a) a polyisocyanate component, and b) an isocyanate-reactive component.
• This type of formulation is a two-component formulation (also called 2K formulation). Such a formulation is extemporaneous, that is to say it is prepared shortly before its application by the end user.
• Component b) above comprises the aminosuccinic resin according to the invention and optionally another compound reactive with isocyanates.
• isocyanate-reactive compounds other than aminosuccinic resin are compounds having one or more functions chosen from alcohol, amine and thiol, preferably diols or diamines or amino alcohols.
• Component a) above comprises a polyisocyanate.
• Component a) may comprise a mixture of polyisocyanates.
• a polyisocyanate is a compound having at least 2 -NCO functions.
• Component a) may in particular comprise an aliphatic or aromatic polyisocyanate, preferably an aliphatic polyisocyanate.
• Component a) may in particular comprise a diisocyanate, a dimeric or trimeric form of a diisocyanate (in particular biuret, allophanate, uretdione, isocyanurate) a polymer form of a diisocyanate, an elongated form of a diisocyanate (in particular a diisocyanate elongated by reaction with a polyol or a diisocyanate having a carbodiimide group obtained by decarboxylation reaction between 2 diisocyanate molecules) or a mixture thereof.
• a diisocyanate in particular biuret, allophanate, uretdione, isocyanurate
• a polymer form of a diisocyanate in particular a diisocyanate elongated by reaction with a polyol or a diisocyanate having a carbodiimide group obtained by decarboxylation reaction between 2 diisocyanate molecules
• polyisocyanates examples include: 1,4-diisocyanatobutane or tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), 1,6-diisocyanatohexane or hexamethylene diisocyanate (HDI), 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- or 1,4-diiso-cyanatocyclohexane, l-isocyanato- 5- isocyanatomethyl-3,3,5-trimethyl-cyclohexane or isophorone diisocyanate (IPDI), 2,3-, 2,4- or 2,6-diisocyanato-l-methylcyclohexane, 4,4'- or 2,4'-diisocyanatodicyclohe
• polyisocyanates examples include HDI trimers, as well as polyisocyanates prepared from 1,6-diisocyanato-hexane, which contain isocyanurate groups and optionally uretdione groups. These polyisocyanates generally have an NCO content of 19 to 24% by weight, relative to the weight of the polyisocyanate.
• polyisocyanates can optionally be used in combination with polyether-modified polyisocyanates, which can be obtained by reaction of aforementioned polyisocyanates with an ether of alcohol or polyol and polyoxyalkylene, in particular polyoxyethylene, such as polyethylene glycol monomethyl ether.
• the aminosuccinic resin and the polyisocyanate are mixed in a molar ratio of isocyanate groups to primary amine groups ranging from 0.5:1 to 8:1, preferably from 0.75:1 to 6 :1 and more preferably from 1:1 to 4:1.
• formulations may also include other compounds capable of reacting with polyisocyanates, including hydroxyl-functional polyacrylates and polyester polyols.
• additives such as fillers, colorants, thickeners, dispersants, surfactants, anti-sedimentation agents, catalysts, UV stabilizers, anti-foaming agents, leveling agents. , adhesion promoters, mattifying agents, opacifying agents, waxes and mixtures thereof. They may also comprise one or more solvents, chosen for example from the esters, ketones and aromatic hydrocarbons listed above.
• the formulation comprises a colorant.
• a colorant may be selected from a dye, a pigment, and mixtures thereof.
• the term “dye”, as used herein, means a dye having a solubility of 10 mg/L or more in the medium into which it is introduced at 25°C.
• the term “pigment” is defined in standard DIN 55943, as a dye which is practically insoluble in the application medium under the ambient conditions which characterize it, and whose solubility is therefore less than 10 mg/l in this medium at 25°C.
• the dye may in particular be a pigment.
• Organic and/or inorganic pigments can be used. If the dye is not a self-dispersible pigment, the formulations may additionally contain a dispersant, more preferably a polymeric dispersant, as described below.
• the pigment may be selected from black, cyan, magenta, yellow, red, orange, purple, blue, green, brown or a mixture thereof. Pigment can be chosen among those disclosed by HERBST, Willy, et al. Industrial Organic Pigments, Production, Properties, Applications. 3rd edition. Wiley - VCH, 2004. ISBN 3527305769.
• the formulation may in particular have a Pigment Volume Concentration (PVC) ranging from 3 to 60%, preferably from 5% to 50%, more preferably from 10 to 40%.
• PVC Pigment Volume Concentration
• the CPV can be defined as an arithmetic quantity corresponding to the percentage of the volume occupied by the pigments relative to the volume of the entire dry film obtained after application and drying of the formulation.
• the CPV can in particular be measured according to the ISO 4618-1:2006 standard.
• the formulation may further include a dispersant.
• the dispersant can be used to disperse insoluble material such as pigment or filler in the formulation.
• the dispersant may in particular be a polymer dispersant.
• Typical polymer dispersants are copolymers of two, three, four, five or even more monomers.
• the properties of polymer dispersants depend both on the nature of the monomers and their distribution in the polymer.
• the copolymer dispersants preferably have the following polymer compositions:
• polymer dispersants include:
• Fascat 4100 butyl stanoic acid
• NT Normality of the titrant (0.5 N)
• the dry thickness is measured on a dry film of varnish 24 hours after application (according to the NF EN ISO 2808 standard) with a filmograph of a varnish composition with a thickness of 150 pm wet (50 pm dry) on a plate of varnish.
• QD46 steel in an air-conditioned room at 23°C, and 50% relative humidity).
• MBCHA (36.55 g) is introduced into a reactor equipped with a reflux column, a nitrogen bubbling rod, a thermometer, a dropping funnel and a stirrer with inclined blades. A nitrogen bubbling of 30 ml/minute is imposed throughout the synthesis.
• 75.95 g of the product obtained in Example 5 is introduced into the dropping funnel then added over a period of 2 hours while maintaining the temperature below 50°C. The temperature is maintained at 50°C for another 1 hour then the contents of the reactor are transferred to an inert flask and kept closed at room temperature for 30 days.
• the reduction in the area under the peaks corresponding to the ethylenic protons (between 6.8 and 6.9 ppm) is followed by 1 H NMR.
• the theoretical dry extract of the finished product is 100%.
• the amine number measured after storage is 174 mg KOH/g.
• Example 5 76.09 g of the product obtained in Example 5 is introduced into a reactor equipped with a reflux column, a nitrogen bubbling rod, a thermometer, a dropping funnel and a stirrer. inclined blades. A nitrogen bubbling of 30 ml/minute is imposed throughout the synthesis. 3.45 g of CHA is added. The temperature is raised then maintained at 50°C for
• the temperature is maintained until a hydroxyl number of less than 5 mg KOH/g is obtained.
• Comparative Example 5 - DESMOPHEN N H 1420 Aminosuccinic resin having an amine number of 201 mg KOH/g relative to the mass resin with a viscosity of 1000 mPa.s at 25°C and a dry extract of 100%.
• the two-component varnish formulations are produced with a stoichiometric Amine/NCO ratio for aminosuccinic resins and a stoichiometric OH/NCO ratio for polyacrylics, adjusted to 75% dry extract by volume, containing a VOC value of 220g/L .
• the two-component varnish is stirred continuously for 30 seconds with a spatula, then it is left to rest for one minute to debubble before measuring its viscosity and applying it.
• Tables 1 and 2 above show that the varnishes obtained from the resins according to the invention have acceptable hardnesses at 14 days, viscosities and pot lives, with a lower consumption of polyisocyanate compared to the comparative tests.
• Comparative example 1 shows that the direct use of a heavy diester without a transesterification phase gives a film that is sticky at 24 hours and insufficiently hardened at 14 days.
• Comparative examples 2 and 3 show the impact of increasing the quantity of polyol on the initial viscosity of the formulation.
• This table also shows that, for an identical OH/maleic ester ratio, the resin according to the invention (Example 12) has a lower INH than the resin of Comparative Example 3.
• the varnish obtained also has a lower viscosity (implying the possibility of using a lower quantity of solvent), a longer pot life and a hardness at 1 week practically equivalent to those of the comparative varnish.
• Example 13 shows that excellent compromises between INH (low) and hardness (rather high) can be obtained with primary alcohol precursors (caprolactone).

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• 2022
  • 2022-09-12 FR FR2209142A patent/FR3139568B1/fr active Active
• 2023
  • 2023-09-12 WO PCT/EP2023/075060 patent/WO2024056688A1/fr not_active Ceased
  • 2023-09-12 US US19/109,181 patent/US20260078213A1/en active Pending
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