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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—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
  • C08G18/28—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
  • C08G18/2815—Monohydroxy compounds
  • C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/285—Nitrogen containing compounds
  • C08G18/2875—Monohydroxy compounds containing tertiary amino 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
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3203—Polyhydroxy compounds
  • C08G18/3218—Polyhydroxy compounds containing cyclic groups having at least one oxygen atom in the ring
• • 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
  • C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
  • C08G18/3844—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing one nitrogen atom in the ring
  • C08G18/3846—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing one nitrogen atom in the ring containing imide groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/7875—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
  • C08G18/7881—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring having one nitrogen atom in the ring
• • 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
  • 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

Definitions

• the present invention relates to a reactive organic product comprising one or more multifunctional organic compounds of formula (I), and its use as a cleavable crosslinking agent in a two-component reactive composition.
• the invention also relates to crosslinkable compositions, and more particularly to coating compositions comprising such a reactive organic product.
• the invention relates to the use of these coatings as self-healing coatings, as well as to a self-healing process.
• the self-healing materials are able to undergo, at the molecular level as well as at the macroscopic scale, a phenomenon of chemical or physical repair in response to an external stimulus, without it is necessary to involve an outside operator.
• the micro-encapsulation of healing agents which consists in enclosing in the material microcapsules or microfibers containing a healing agent, capable of breaking at the same time as the material.
• the healing agent present in the material is thus spread in the cracks of the material which it fills by polymerization, for example under the action of a catalyst dispersed in the matrix.
• the method of reversible covalent bonds consists in incorporating in the structure of macromolecules covalent bonds capable of breaking and reforming "on command", by simple displacement of the thermodynamic equilibrium. It is possible to control this balance by an external stimulus, such as temperature, pH, humidity, etc.
• This method has the advantage of allowing several self-scarring at the same point of the material, while being easily controllable.
• the reversible covalent bonds can easily integrate into a pre-existing material: it suffices for them to be incorporated in a crosslinking agent, which requires little variations in formulation and reconciles the self-healing properties sought with the usual mechanical properties of the materials in which they are integrated.
• the inventors have today developed a new self-healing reagent organic product comprising a reversible covalent bond capable, under the effect of external stimulation and without the addition of additional chemical species, of repairing cracks, and thus of increase the life of the coatings.
• This new self-healing product is a reversibly cleavable crosslinking agent capable of replacing conventional crosslinking agents.
• the crosslinking agent of the invention carries isocyanate functions, and may advantageously be used in coatings based on polyol resins. Once the crosslinking has been carried out, the branches formed by the crosslinking agent are capable of breaking and reforming in a reversible manner on command, without modifying the urethane functions obtained in place of the alcohol functions.
• the crosslinking agent of the invention is formed and cleaved in the final coating by reaction of Diels-Alder and retro-Diels-Alder.
• This reaction which won Otto Diels and Kurt Aider's Nobel Prize in Chemistry in 1950, is a cycloaddition reaction in which a conjugated diene reacts on a so-called "dienophile" alkene to form a six-atom unsaturated ring.
• the synthetic strategy of the crosslinking agent of the invention may, for example, use a diisocyanate and a hydroxyl derivative of furan, the resulting diene then reacting by Diels-Alder reaction with a bismaleimide.
• the resulting Diels-Alder adduct is likely to cleave by retro-Diels-Alder in response to an external stimulus.
• the synthesis strategy of the crosslinking agent of the invention can use a bismaleimide (a central chain terminated by two maleimide groups, structurally very close to maleic anhydride) and a furan derivative, and makes it possible to obtain a central chain terminated on each side by a Diels-Alder adduct capable of cleaving in response to an external stimulus, the other side of the adduct carrying an alcohol function.
• This alcohol is reacted on a diisocyanate to obtain a crosslinking agent terminated on each side by an isocyanate function, cleavable by retro-Diels-Alder.
• the subject of the invention is a reactive organic product comprising one or more multifunctional organic compounds corresponding to the following formula (I): ## STR3 ## 2-CONH) x -R 3 -NHCO-2-DA] n -R 1 -AD-2-CONH-R 3
• ⁇ RI is selected from aliphatic Ci-Qo / preferably Ci-C 3 S, the aromatic groups, C 6 -C 2 o, preferably C 6 -C 3, or alkylaryl groups in which the or aryl groups are C 6 -C 20 and the alkyl chain (s) are C 1 -C 10 , R 1 being advantageously a linear or branched C 1 -C 6 aliphatic group optionally comprising a saturated or unsaturated C 5 -C 6 cycloaliphatic group; , and preferably an unsaturated C 6 cycloaliphatic group, or R 1 is a C 6 -C 20 aromatic group, or R 1 is an alkylaryl group in which the aryl group (s) are (C 6 -C 20) and the alkyl chain (s) are in the form of C1-C40, and even more advantageously R1 is a C1-C40 alkoxylated chain, linear or branched, preferably comprising 1 to 20 alkoxy
• the polyether block is chosen from C1-C40 alkoxylated chains, preferably comprising 1 to 20 alkoxylated units, and even more preferably 1 to 15 alkoxylated units, such as ethoxy, propoxy or butoxy units, or a mixture of units ethoxy and propoxy, or the CrCo hydroxytelechelic polybutadiene or polyester chains,
• DA is a Diels-Alder adduct between a diene compound D carrying a chain R2 and a dienophile compound A carrying an RI group, the diene functions of the diene compound D being chemically blocked by reaction of Diels-Alder with the compound dienophile A,
• R 2 is a C 1 -C 4 , preferably C 1 -C 2 , alkyl chain bearing a hydroxy group reacted with an isocyanate functional group to form a urethane linkage
• ⁇ R 3 is selected from aliphatic C 5 -C 20 aromatic groups or C 6 -Ci2 and preferably R3 is a cycloaliphatic C 6 optionally substituted by one or more linear alkyl chains or branched -C C 6 .
• Aliphatic group a hydrocarbon group in Q-Qo / acyclic or cyclic, linear or branched, saturated or unsaturated, excluding aromatic groups, preferably C 1 -C 35 .
• branched means that at least one lower alkyl group such as methyl or ethyl is carried by a linear aliphatic chain.
• Alkyl group a linear or branched, preferably C 1 -C 35 , saturated Q-Qo hydrocarbon aliphatic group.
• branched means that at least one lower alkyl group such as methyl or ethyl is carried by a linear alkyl chain.
• Alkene group an unsaturated aliphatic hydrocarbon group comprising a covalent double bond between two carbon atoms, linear or branched, C 2 -C 2 o, preferably C 2 -Ci 2 , and even more preferably Q-Ce.
• branched means that at least one lower alkyl group such as methyl or ethyl is carried by a linear alkenyl chain.
• Cycloalkyl group any functional group or substituent derived from a non-aromatic ring comprising at least three carbon atoms, and preferably C 3 -C 12 , optionally containing one or more heteroatoms chosen from S, O and N.
• groups mention may be made especially of cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; the optionally substituted cyclohexyl group being preferred.
• Aromatic group any functional group or substituent derived from at least one aromatic ring; an aromatic ring corresponds to any planar mono- or polycyclic group comprising a delocalized ⁇ system in which each atom of the cycle comprises an orbital p, said orbital p overlapping each other; among such aromatic groups, there may be mentioned phenyl, biphenyl, naphthalene and anthracene groups.
• the aromatic groups of the invention are C 6 -C 20 , and preferably C 6 -C 3 .
• Alkoxylated chain any chain, linear or branched, comprising at least one polyether chain.
• Said polyether chain may comprise from 1 to 40, preferably from 1 to 20, and even more preferably from 1 to 15 alkoxylated units (or oxyalkylenated), such as ethoxy, propoxy, butoxy units, and preferably a mixture of ethoxy and propoxy units.
• the diene compound D is a cyclic diene, preferably C 5 -C 6 , and even more preferably a C 5 -C 6 cyclic diene comprising a heteroatom, said diene compound.
• D is carrying an alkyl chain R2 in C1-C4, preferably in C x C 2 , carrying a hydroxyl group.
• the diene compound D preferably corresponds to the following formula:
• Ra, Rb, Rc and Rd are selected from H or alkyl chains of C 1 -C 12, at least one of the radicals Ra or Rd is an alkyl chain R2 -C-Q, preferably Ci-C 2 , carrying a hydroxy group.
• the diene compound D carrying an alkyl chain R 2 C 1 -C 4, preferably Ci-C 2, bearing a hydroxy group is furfuryl alcohol of the formula:
• the dienophile compound is dienophile compound
• A is an alkene, preferably an optionally substituted Q-Cs cyclic alkene, bearing an RI group and comprising at least one imide group.
• Said imide group may be an ⁇ , ⁇ -ethylenically unsaturated imide, preferably selected from the group consisting of maleimide, tetrahydrophthalimide, imide derivative of anhydride or itaconic acid.
• the dienophile compound A is a bismaleimide compound corresponding to the following formula:
• - RI is an aliphatic C 1 -C40 linear or branched, optionally comprising a cycloaliphatic C 5 -C 6 saturated or unsaturated, and preferably a cycloaliphatic C 6 unsaturated, or RI is an aromatic group of C 6 -C 20, or RI is an alkoxylated chain CRCW, preferably comprising 1 to 20 alkoxy units, and even more preferably 1 to 15 alkoxy units, such as ethoxy units, propoxy, butoxy, or a mixture of ethoxy units and propoxy, or RI is an alkoxyaryl group in which the aryl group (s) are C 6 -C 2 O and the alkoxylated chain (s) are in CrQo, said alkoxyaryl group preferably having the following formula (excluding from this
• the polyether block is selected from alkoxylated chain Ci-Qo / preferably comprising 1 to 20 alkoxy units, and even more preferably 1 to 15 alkoxy units, such as ethoxy units, propoxy, butoxy, or a mixture of units ethoxy and propoxy, or the CrCo hydroxytelechelic polybutadiene or polyester chains, - Re, Rf, Rg and Rh, identical or different, are chosen from H, the linear or branched alkyl chains in C 1 - 12 , or Re and Rf on the one hand and Rg and Rh on the other hand are interconnected to form a C 6 aliphatic ring.
• the dienophile compound A is a bismaleimide compound corresponding to the following formula:
• R1 is a C1-C10 alkoxylated chain, preferably comprising 1 to 20 alkoxylated units, and even more preferably 1 to 15 alkoxylated units, such as ethoxy, propoxy or butoxy units, or a mixture of ethoxy and propoxy units, or RI is an alkoxyaryl group in which the aryl group (s) are C 6 -C 2 O and the alkoxylated chain (s) are in Q-Qo, said alkoxyaryl group preferably having the following formula (excluding from this formula both
• polyether block is selected from C 1 -C 10 alkoxylated chains, preferably comprising 1 to 20 alkoxylated units, and even more preferably 1 to 15 alkoxylated units, such as ethoxy, propoxy, butoxy units, or a mixture of ethoxy and propoxy units, or polybutadiene chains or hydroxytelechelic polyesters in CrGw /
• the molecular weight of the bismaleimide of the invention advantageously varies between 600 and 1400 g. mol "1 , still more preferably between 700 and 1000 g mol -1 .
• IPDI isophorone diisocyanate
• the retro-Diels-Alder cleavage of the organic reactive product of the invention can be achieved by increasing the temperature, and is attainable from 60 ° C.
• the cleavage may optionally require temperatures up to 140 ° C. depending on the stereochemistry of the Diels-Alder adducts obtained: it is indeed easier to cleave the endo adduct than the exo adduct.
• the conditions for preparing the reactive organic product of the invention are preferably adjusted to promote the production of the endo stereochemical form.
• the reactive organic product comprising one or more polyfunctional organic compounds of formula (I) according to the invention can be characterized by its index ⁇ ⁇ # which is advantageously between 50 and 90 mgKOH.g "1.
• the index I N co can be determined by back-titration with excess n-dibutylamine.
• Another object of the invention is a first process for preparing a reactive organic product comprising one or more multifunctional organic compounds of formula (I) according to the invention comprising the following steps:
• Steps (i) and (ii) are preferably carried out at a temperature between 20 and 40 ° C to promote the production of the endo stereochemical form. They are also preferably carried out under an inert atmosphere, for example under nitrogen, and optionally in the presence of a desiccant such as tosyl isocyanate, to avoid the presence of water and to avoid side reactions involving the isocyanate functions.
• a desiccant such as tosyl isocyanate
• the steps (i) and (ii) may also be carried out in a polar solvent, in particular chosen from acetic acid esters such as ethyl acetate and butyl acetate, or ketones such as acetone, butan-2-one, heptan-2-one, methyl isobutyl ketone and cyclohexanone.
• a polar solvent in particular chosen from acetic acid esters such as ethyl acetate and butyl acetate, or ketones such as acetone, butan-2-one, heptan-2-one, methyl isobutyl ketone and cyclohexanone.
• the reactive organic product comprising one or more multifunctional organic compounds of formula (I) of the invention may also be prepared according to a second process comprising the following steps:
• the steps (i 7 ) and (ii 1 ) are preferably carried out at a temperature between 20 and 40 ° C to promote the production of the endo stereochemical form. They are also preferably carried out under an inert atmosphere, for example under nitrogen, and optionally in the presence of a desiccant such as tosylsocyanate, to avoid the presence of water and to avoid side reactions involving the isocyanate functions.
• a desiccant such as tosylsocyanate
• the steps (0 and ( ⁇ ') can be carried out in a polar solvent, in particular chosen from acetic acid esters such as ethyl acetate and butyl acetate, or ketones such as acetone. butan-2-one, heptan-2-one, methyl isobutyl ketone and cyclohexanone.
• a polar solvent in particular chosen from acetic acid esters such as ethyl acetate and butyl acetate, or ketones such as acetone. butan-2-one, heptan-2-one, methyl isobutyl ketone and cyclohexanone.
• the diene D compound carrying an alkyl chain R2 C1-C4, preferably C1-C2, bearing a hydroxy group used during steps (i) and r) of the methods of the invention is preferably alcohol furfuryl.
• the dienophile compound of formula R 1 - (A) n + 1 used during steps (ii) and ( ⁇ of the processes of the invention is advantageously a bismaleimide compound corresponding to the following formula:
• R1, Re, Rf, Rg and Rh are as previously defined.
• the bismaleimide ED-600 BM marketed by the company Specifies Polymers.
• the asymmetric aliphatic diisocyanate is isophoronediisocyanate (IPDI).
• the steps (i) and (N 1 ) of the processes of the invention can be carried out in the presence of a catalyst which influences the reactivity of the isocyanate, and makes it possible to increase the reactivity of the secondary isocyanate function.
• Said catalyst is preferably based on tin, bismuth, titanium, zinc, or zirconium.
• the catalyst is based on tin: it is an organotin compound, and more particularly dibutyltin dilaurate. (DBSnDL).
• the catalyst may be added at a molar level ranging from 0.1 to 1 mol%, and preferably from 0.2 to 0.5 mol%, relative to the total mol% of diisocyanate.
• the present invention also relates to the use of an organic reagent product according to the invention, or obtained by a process according to the invention, as a cleavable crosslinking agent in a two-component reactive composition, preferably in a two-component reactive composition.
• a cleavable crosslinking agent in a two-component reactive composition, preferably in a two-component reactive composition.
• crosslinkable and even more preferably an acrylic resin functionalized with hydroxy groups.
• the reactive organic product of the invention is a crosslinkable agent heat-cleavable reversibly in a two-component reactive composition.
• Another subject of the invention relates to a crosslinkable composition
• a crosslinkable composition comprising an organic reagent product according to the invention, or obtained by a process according to the invention, and a component comprising at least one reactive functional group capable of reacting with said reactive organic product such as an acrylic resin functionalized with hydroxy groups.
• the crosslinkable composition of the invention is preferably a coating composition selected from paints, varnishes, inks and adhesives, a molding composition, a composite composition, or a sealant composition.
• the invention also relates to the use of a crosslinkable composition according to the invention for the self-healing of the surface of coatings or articles based on such a composition, or for the recycling of thermoplastic or thermosetting polymers, in particular composite moldings.
• a last object of the invention is a self-healing process comprising a step of applying a crosslinkable composition according to the invention to a substrate, followed by a step of de-protection (cleavage) by retro -Diels-Alder functions dienes chemically blocked from the crosslinking agent contained in said composition, under the effect of an external energy, and especially by conduction, convection, or radiation.
• the step of deprotecting back-Diels-Alder is preferably a thermo-cleavage step performed by heating at a temperature ranging from 60 to 120 ° C, and preferably from 70 to 100 ° C. This heating step can be carried out for a period ranging from 5 minutes to 2 hours, and preferably between 15 minutes and 1 hour.
• the self-healing process of the invention may further comprise, after the step of deprotection by retro-Diels-Alder, a step of healing by cooling, preferably at a temperature ranging from 20 to 30 ° C. and even more preferably at room temperature (25 ° C).
• the invention also comprises other arrangements which will become apparent from the additional description which follows, which relates to examples of synthesis of reactive organic products comprising one or more multifunctional organic compounds of formula (I) according to US Pat. invention, and their evaluation in self-healing coating formulations, as well as the photographs of Figures 1 and 2 which show coatings according to the invention before and after heating.
• the urethane is synthesized at room temperature in a batch of 1 L, inerted with nitrogen and provided with a circulating agitation module (marine propeller) agitated at 100 revolutions.min * 1 , from 46.73 g of furfuryl alcohol (Sigma-Aldrich) and 105.88 g of isophoronediisocyanate (IPDI) (Sigma-Aldrich), in the presence of 0.98 g of dibutyltin dilaurate (DBSnDL) (Sigma-Aldrich) .
• the reaction is conducted by adding the furfuryl alcohol dropwise to the PDI, each of which is diluted in butyl acetate (Sigma-Aldrich) (153.59 g).
• the progress of the reaction is monitored by HH NMR.
• the conversion rate reaches a plateau of 99.0 to 99.8% after 35 minutes of reaction.
• the index I NC o of the crosslinking agent 1 obtained at the end of this process is determined by back-titration with excess n-dibutylamine. According to this method, the crosslinking agent 1 has an N- index of 66 mgKOH.g -1
• Example 2 Preparation of a crosslinking agent 2 according to the invention by reaction of Diels-Alder, then reaction with a diisocyanate lere stage: synthesis of the diol
• the synthesis of a crosslinking agent according to the invention is this time carried out starting with a Diels-Alder reaction between 395.7 g of ED-600 BM and 92.35 g of furfuryl alcohol. This reaction is performed at room temperature, adding the furfuryl alcohol on the ED-600 BM drip.
• the 2 nd step corresponds to the addition of 223.90 g dlPDI the diol obtained at the end of the st step, in the presence 1.91 g of dibutyltin dilaurate (DBSnDL).
• DBSnDL dibutyltin dilaurate
• the progress of the 2nd step is also followed by 1H NMR in deuterated acetone. A strong rise in viscosity is also observed, indicating the progress of the reaction.
• crosslinking agent 1 synthesized in Example 1 are evaluated in a polyol resin, e. Synocure® 854 BA 80 sold by Arkema. It is a resin highly functionalized with hydroxy groups, crosslinkable at room temperature by adding a prepolymer carrying isocyanate groups.
• the formulations are made by ensuring that there is the same number of hydroxy functions from the resin as isocyanate functions from the crosslinking agent:
• the resin and the crosslinking agent are placed in a metal pot, mixed with stirring 1000 tours.min "1 for two minutes using a module shearing. Their dynamic viscosity ⁇ is measured using a Brookfield viscometer tray The manipulations are started at ⁇ s 300 mPa.s at 25 ° C. If the viscosity is too high at the time of mixing, butyl acetate is added.
• Pot life also called pot-life, is the time during which it is possible to apply a formulation to a surface before it becomes too viscous.
• the formulations are then applied to QD 36 (Q-panel) type steel plates for their physicochemical analyzes.
• the formulations are applied by means of an apparatus for passing a metal bar at a height of 100 ⁇ m above the surface of the plate, allowing a viscous liquid of 100 ⁇ m to be uniformly spread therein. of wet thickness.
• the surface drying time (noted hereinafter tss) is measured according to the ISO 9117-3 standard, by depositing for 10 seconds on the surface of the plate a controlled quantity of glass beads having a particle size of between 125 and 250 ⁇ m. , which are then wiped with a brush; as long as the glass beads remain attached to the coating, the surface is not dry.
• the test is carried out at a temperature of 25 ° C ⁇ 3 ° C and 50% ⁇ 5% relative humidity.
• the drying time tss measured is 25 min.
• the thickness of the coating after drying (noted hereinafter es) is measured by magnetic induction according to ISO 2808: 2007. The measurements are carried out after one week of drying at a temperature of 25 ° C. ⁇ 3 ° C. and 50% ⁇ 5% relative humidity. The thickness measured is 40 ⁇ 6 ⁇ m.
• the adhesion of the coating is evaluated according to the ISO 2409: 2013 standard by streaking the surface of the QD 36 steel plate (Q-panel) with a comb with blades 1 mm apart, then removing and removing on the streaks an adhesive whose adhesion strength on steel is 750 Nm "1.
• an adhesion index of the coating on its support (noted hereinafter Iadh ) ranging from 0 (excellent adhesion) to 5 (almost zero adhesion) is attributed to coatings:
• the self-healing properties are evaluated hot by placing the metal plates previously used for physicochemical tests and having the streaks of the adhesion tests, in an oven at 90 ° C for 20 minutes.
• Self-healing coatings of the invention are compared with a conventional coating, a control formulation using the same resin (® Synocure 854 BA 80) and a crosslinkable non-cleavable, e. Tolonate TM HDT-LV2 sold by Vencorex Chemicals.
• the thickness of the applied reference formulation is also 100 ⁇ m wet thickness to have the same dry thickness as before, ie 40 ⁇ m ⁇ 6 ⁇ m. Streaks are made on the reference plate in the same way for the plates of 1'nvention, streaking the surface of the plate with a comb whose blades are spaced 1 mm.
• Photographs of the plates are made before and after heating, and are shown in Figure 1 (photograph from the top: before baking - photograph of the bottom lb: after steaming).
• the plates made with the crosslinking agent 1 of the invention are compared to the reference plate (T) comprising the Tolonate TM HDT-LV2.
• T the reference plate comprising the Tolonate TM HDT-LV2.
• a second self-healing test is performed on the same plates having already undergone the first self-healing test: new striations are made, and the plates are subjected to a second passage in the oven for 20 minutes at a temperature of 90 ° C.
• Photographs of the plates are made before and after heating, and are shown in Figure 2 (top 2a photographs: before baking - bottom 2b photographs: after steaming).
• the coating of the invention still has self-healing properties and several successive hot scars seem possible, which is not the case of the reference coating.

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• 2017
  • 2017-04-13 FR FR1753264A patent/FR3065219B1/fr active Active
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