Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
  • C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D247/00—Heterocyclic compounds containing rings having two nitrogen atoms as the only ring hetero atoms, according to more than one of groups C07D229/00 - C07D245/00
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
  • C08G59/3263—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing sulfur
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
  • C08G59/5046—Amines heterocyclic
  • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
  • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
  • C08K5/3445—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/37—Thiols
  • C08K5/378—Thiols containing heterocyclic rings

Definitions

• the present invention relates to the field of thermosetting polymers or thermosets used mainly as materials, coatings or adhesives.
• the invention relates more particularly to the use of specific molecules as agents for modifying curing systems for thermosetting polymers.
• thermosetting polymers In contrast to thermoplastic polymers, which can be transformed and re-transformed using heat which, with or without a contribution of shearing mechanical energy, softens them and allows them to flow, thermosetting polymers constitute chemically crosslinked polymer networks, that is to say crosslinked by irreversible crosslinking bonds of covalent type, which, once obtained, can no longer be transformed by the action of heat.
• a thermosetting resin once the polymer network has been formed, becomes a thermoset polymer network which will not flow under the effect of heat, even with a contribution of shearing mechanical energy.
• thermoset polymer subjected to the effect of a constant increase in temperature, will end up by decomposing before being able to flow, as a result of the robustness of the crosslinking network formed by covalent bonds.
• thermoset crosslinked networks involving a great variety of possible chemistries, such as, for example epoxy, polyurethane, phenol/formaldehyde, melamine/formaldehyde, silicone, urea/formaldehyde, polyester or unsaturated polyester networks.
• thermoset polymer network is obtained by the mixing and consequent reaction of at least two components, with at least one of the two having a functionality greater than 2 with regard to the reaction involved. It is also customary for a person skilled in the art, in particular in the case of systems of epoxy or polyurethane type, to call the component carrying epoxy or isocyanate functional groups “the resin” and to call the component carrying amine or alcohol functional groups “the curing agent”. Another type of language which may be encountered in this field is that which assigns the name “resin” also to the polymer network being formed or to the final polymer network. Thus, it is not uncommon to hear talk of, for example, epoxy, polyurethane or polyester resins.
• the curing agent is thus a compound, often a polyfunctional compound, carrying reactive amine or alcohol units. It is possible to include, as a mixture with this curing agent, inter alia, compounds which are inert with regard to the reaction (such as solvents) or, on the contrary, reactive solvents or diluents which make it possible to control the reaction and to adjust certain mechanical properties of the final product, and also catalysts which make it possible to accelerate the crosslinking of the reactive components.
• a subject matter of the invention is thus the use of molecules of a specific type, such as amines or alcohols carrying associated units, as partial or complete replacement for normal amine or alcohol curing agents, with the aim of forming materials, coatings or adhesives having improved properties, such as, for example a better chemical resistance, a better adhesion to supports, a better flexibility, an optimum open time or an optimum setting time.
• a subject matter of the invention is thus the use, as curing agent for a thermosetting resin, of a molecule carrying an associative group and, preferably, of a molecule carrying an associative group of formula (I):
• R denotes a unit comprising at least one reactive functional group, preferably an alcohol, thiol or amine functional group
• R′ denotes a hydrogen atom
• A denotes an oxygen or sulfur atom, preferably an oxygen atom.
• Such a use exhibits considerable advantages in comparison with normal curing agents since it makes it possible to partially or completely dispense with the use of a setting accelerator and/or of a flexibilizing agent and/or of an adhesion promoter for the final resin.
• thermoset resin examples include but not limited to, but not limited to, butyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aditol)
• a thermoset resin examples include but not limited to, butyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoeth
• a catalyst for epoxy resins is often a tertiary amine incorporated in the curing agent. The majority of the catalysts, however, are not said to promote flexibility in the final resin.
• a flexibilizing agent can either be introduced with the base epoxy resin carrying oxirane functional groups or in the curing agent. It is a resin which is more flexible than the base epoxy resin or a crosslinking agent having a molecular structure which is more mobile than that of the curing agent and, in this case, it is then a cocuring agent.
• the modifying agent has relatively high molecular weights which have the effect of increasing the distance between the crosslinking nodes by the incorporation thereof in the final polymer network, with a significant decline in the mechanical properties of the final resin.
• An alternative form of this method of modifying one of the main components of an epoxy resin which is targeted at giving flexibility to the finished resin is prior hybridization.
• modified base epoxy resins such as epoxy/polyamide, epoxy/vinyl or epoxy/polysulfide resins.
• Some of these hybrid modifying agents improve the adhesion (case of the epoxy resins obtained between a base epoxy resin, such as a liquid resin of bisphenol A diglycidyl ether or “BADGE” type, and a polyamide), but at the expense of the thermomechanical properties.
• oligomeric or polymeric flexibilizing agents can be used, in a base resin or else in the curing agent, with, for example, alkyl diisocyanate prepolymers reacted with the alcohol functional groups of a base epoxy resin, or else with a silicone polymer comprising amine ends which is then employed as coreactant of the polyamine curing agent.
• alkyl diisocyanate prepolymers reacted with the alcohol functional groups of a base epoxy resin
• silicone polymer comprising amine ends which is then employed as coreactant of the polyamine curing agent.
• Other polymeric coreactants or other additives have been developed in order to make possible greater flexibility of the final resin, such as liquid polybutadiene derivatives making possible the introduction of an elastic phase into the thermoset.
• polysulfides can be used either as flexibilizing agents or as curing agents in a standard ratio 1:1 with the base epoxy resin but, in this case, they absolutely have to be catalyzed by a tertiary amine, such as DMP-30, for example. Furthermore, their odor may require the addition of specific additives.
• thermoset In addition to their high cost, all these polymers or prepolymers, modified for the purpose of being able to make possible greater flexibility of the final resin, have in common a need to profoundly modify the processing of the thermoset with respect to its original formulation when a need for flexibility is required in application.
• a new type of additive into the epoxy formulation, such as a compatibilizing agent or coupling agent which makes it possible to limit the problems of phase separation and heterogeneity inside the flexibilized resin, or else it is necessary to introduce an additive which reduces the additional viscosity caused by resorting to a thermoplastic polymer component (case of epoxy-nylon resins, for example).
• Nonreactive diluents are formally plasticizers and not flexibilizing agents, they bring about a deterioration in the mechanical properties of epoxy resins and sometimes bring about a phenomenon of exudation, which is particularly undesirable for adhesives.
• the reactive diluents are non-migrating as they participate in the formation of the polymer network. They are often long-chain molecules comprising a monoglycidyl functionality but reactive diluents comprising a diglycidyl functionality can contribute to the density of the final thermoset network without, however, improving the adhesion. They are conventionally combined with the base epoxy component of the resin due to their compatibility.
• organosilanes constitute a widely used family which are good promoters of adhesion between the crosslinked epoxy resin and an inorganic support carrying surface hydroxyl functional groups, for example, an inorganic filler (such as a clay or alumina), a composite reinforcing glass fiber or a ceramic.
• Organosilanes are also used to increase the adhesion of the epoxy resin to a metal support. They can be employed as primer coating directly on the support or else can be incorporated in the formulating of the thermoset.
• organosilanes exhibit a sensitivity to moisture which can make their use problematic and their effectiveness uncertain.
• the use thereof on a polymer support requires the latter to have, at its surface, free reactive groups capable of reacting with the silanes, typically OH groups, with the result that applications involving organosilanes relate in particular to the preparation of composites for which it is desired to increase the mechanical strength properties and the durability by a coupling between the thermoset organic binder and the inorganic or metal reinforcement.
• organometallic complexes titanium oxide or zirconate for example
• these complexes are problematic to apply due to the high risk of overdosage, their optimum effectiveness being obtained for the amount which provides for the formation of a single layer at the surface of the support.
• the use thereof is thus instead reserved for the surface treatment of inorganic fillers, in order to facilitate the dispersion thereof in the organic matrix.
• the role is then that of a coupling agent between inorganic filler and resin, which does not contribute to improving the adhesion between thermoset resin and an inorganic or metal support.
• organometallic complexes based on chromium or on cobalt have been studied but are of limited use due to their toxicity.
• thermosetting resin of a molecule carrying an associative group as defined above thus makes it possible to accelerate the setting of a two-component thermoset resin and to contribute flexibility without, however, seriously damaging the mechanical properties of the final resin.
• the use according to the invention also makes it possible to reinforce the adhesion of the resin on not only inorganic or metal supports but also polymers not carrying hydroxyl functional groups, such as PMMA, for example.
• the latter situation of adhesion between thermoset resin and polymer is illustrated by the possibility of obtaining, according to the invention, adhesion between polymers of different natures, as in the case, for example, of the deposition of a layer of thermoset of polyurethane type on an epoxy thermoset underlayer.
• the molecule carrying an associative group comprising a nitrogenous heterocycle is used as curing agent for at least two thermosetting resins which are preferably different.
• This embodiment is particularly advantageous since it makes it possible to increase the adhesion between two resins while dispensing with the use of an adhesive which exhibits the possible disadvantage of evaporation of solvent.
• thermosetting resin partially modified by a reactant, which resin is subsequently reacted with another resin. This is because this second processing stage can be difficult if it requires activation by heating, or else presents problems for the environment if the reaction has to be carried out at ambient temperature but while employing the chemistry of highly reactive groups, such as isocyanates, which can be harmful to the health, on the processing site.
• thermosetting resins comprising epoxy functional groups
• the endemic defects of these epoxy resins which are the excessive stiffness and their lack of adhesion, are for the first time improved by the same modifying agent, in the form of a molecule carrying an associative group.
• modifying the flexibility of the finished epoxy resin was obtained either by modifying the base pre-resin or resin carrying epoxy functional groups or by addition of reactive solvent, such as a fatty monoepoxide.
• adhesion of the finished epoxy resin was improved by the addition of adhesion-promoting agents of silylated type, for example, with the result that the two properties, stiffness and adhesion, involve significant modifications to the polymer network and complicated the processing thereof in terms of formulating.
• curing agent is understood to mean, within the meaning of the present invention, a compound capable of bringing about chemical crosslinking of a polymer network via irreversible crosslinking bonds of covalent type which, once they have been obtained, can no longer be transformed by the action of heat.
• the associated units according to the invention are units comprising nitrogenous heterocycles which are capable of creating, between units of at least two different molecules, complementary physical bonds of hydrogen bond type.
• sociative groups is understood to mean groups capable of associating with one another via hydrogen, ionic and/or hydrophobic bonds. They are, according to a preferred form of the invention, groups capable of associating via hydrogen bonds, comprising a nitrogenous heterocycle, preferably a dinitrogenous heterocycle, generally having 5 or 6 ring members, and preferably comprising a carbonyl group. Examples of associative groups which can be used according to this preferred form of the invention are imidazolidinyl, bis-ureyl, ureido-pyrimidyl groups. The imidazolidinyl group is preferred.
• these molecules carrying associative groups are used in combination with normal curing agents of amine or alcohol type, which makes it possible to adjust the properties of the thermoset resins obtained, such as the adhesion to supports and the flexibility.
• a molecule carrying an associative group comprising a nitrogenous heterocycle takes place in combination with a cocuring agent, that is to say a normal curing agent, in order to increase the adhesion of said resin to a support.
• R is chosen from H 2 N—(CH 2 ) n —, HS—(CH 2 ) n — or HO—(CH 2 ) n —, where n represents an integer between 1 and 18.
• the molecules carrying associative groups comprising, in addition to a nitrogenous heterocycle, at least one amine or alcohol functional group are particularly preferred.
• these molecules exhibit a water-soluble nature, which is the case in particular when, in the above formulae, n is equal to 1 or 2, in the H 2 N—(CH 2 ) n —, HS—(CH 2 ) n — or HO—(CH 2 ) n — units, this makes it possible to use them as curing agent for thermosetting resins in water or in an aqueous emulsion.
• This embodiment is of great industrial and commercial interest for the preparation, in particular, of aqueous-based coatings and adhesives.
• thermosetting resin is present in water or in an aqueous emulsion.
• said molecule carrying an associative group is preferably chosen from: 1-(2-aminoethyl)imidazolidone, also known as 1-(2-aminoethyl)imidazolidin-2-one (UDETA), 1-(2-hydroxyethyl)imidazolidone (HEIO), 1-(2-[(2-aminoethyl)amino]ethyl)imidazolidone (UTETA), 1-(2-[(2- ⁇ 2-aminoethylamino ⁇ ethylamino]ethyl)imidazolidone (UTEPA) or N-(6-aminohexyl)-N′-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)urea (UPy).
• 1-(2-aminoethyl)imidazolidone also known as 1-(2-aminoethyl)imidazolidin-2-one (UDETA), 1-(2-hydroxyethyl)imidazolidone
• the compounds UDETA, UTETA and UTEPA can be obtained by reaction of urea with a polyamine.
• UDETA, UTETA and UTEPA can be respectively prepared by reacting urea with diethylenetriamine (DETA), triethylenetetramine (TETA) and tetraethylenepentamine (TEPA).
• DETA diethylenetriamine
• TETA triethylenetetramine
• TEPA tetraethylenepentamine
• the compound HEIO can be obtained by reaction of urea with the corresponding diaminoalcohol, namely 2-[(2-aminoethyl)amino]ethanol.
• the molecules carrying associative groups can be used alone as curing agents for thermosetting resin, these molecules are preferably used as a mixture with other curing agents.
• these molecules carrying associative groups are used in combination with normal curing agents, they are used at a content of 0.1 to 50% by weight, with respect to the total weight of the combination.
• the molecule carrying an associative group according to the invention can be used in combination with a setting-accelerating agent and/or a flexibilizing agent and/or an adhesion promoting agent or even in combination with another molecule carrying an associative group. It is thus possible to envisage, for example, the use of UDETA and HEIO as curing agent or cocuring agent for a polyurethane/polyurea resin.
• the epoxy or polyurethane setting accelerator can be a tertiary amine, such as the Jeffcat® catalyst for polyurethanes from Huntsman, a phenol, such as Epikure® 3253 from Huntsman, Lewis acids for catalyzing the reaction with the epoxy oxiranes or 2-ethyl-4-methylimidazole (EMI).
• a tertiary amine such as the Jeffcat® catalyst for polyurethanes from Huntsman
• a phenol such as Epikure® 3253 from Huntsman
• Lewis acids for catalyzing the reaction with the epoxy oxiranes or 2-ethyl-4-methylimidazole (EMI).
• EMI 2-ethyl-4-methylimidazole
• the flexibilizing agent can be a difunctional resin which is more flexible than the base resin and can then be employed alone or in co-crosslinking with the normal curing agent or else the flexibilizing agent can be found among long-chain molecules comprising a monoglycidyl functionality or sometimes a diglycidyl functionality (in the case of epoxy resins).
• the adhesion-promoting agent can be chosen from an organosilane, an organometallic complex of titanate or zirconate type and more generally from the abovementioned compounds.
• additives can be used in combination with the molecules according to the invention. They are, for example, solvents or diluents, which are or are not reactive, catalysts for the crosslinking reaction and monofunctional compounds other than the molecules carrying associative groups according to the invention.
• tertiary amines such as Epikure® 3253 from Huntsman, or all the tertiary amines of the Jeffcat® range from Huntsman, mention may be made among the fillers particularly valued in the context of the invention, of talc, calcined silica, alumina, silicates, clays, calcium carbonate, aluminum trioxide as flame retardant, metal powders or carbon nanotubes as thermally or electrically conducting agent.
• thermosetting resin is understood to mean, within the meaning of the present invention, a polymer which can be crosslinked chemically by a curing agent to give a thermoset resin which, once obtained, can no longer be transformed by the action of heat.
• thermosetting resin once the polymer network has been formed, becomes a thermoset polymer network which will not flow under the effect of heat, even with a contribution of shearing mechanical energy.
• thermosetting resins Preference is given, among thermosetting resins to those comprising epoxy, isocyanate or acid units, such as those which result in the production of thermoset networks of epoxy, polyurethane or polyester type by reaction with the molecule carrying associative groups carrying, in addition to a nitrogenous heterocycle, an amine or alcohol functional group.
• epoxy resins to be crosslinked using the curing agent according to the invention mention may be made, by way of example, of epoxidized resins exhibiting a functionality, defined as the number of epoxide functional groups per molecule, at least equal to 2, such as bisphenol A diglycidyl ether, butadiene diepoxide, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, 4,4′-di(1,2-epoxyethyl)diphenyl ether, 4,4′-di(1,2-epoxyethyl)biphenyl, 2,2-bis(3,4-epoxycyclohexyl)propane, resorcinol diglycidyl ether, phloroglucinol diglycidyl ether, bis(2,3-epoxycyclopentyl)ether, 2-(3,4-epoxy)cyclohexyl
• R3 is a group of formula —CH 2 —O—R4-O—CH 2 — in which R4 is a divalent group chosen from alkylene groups having from 2 to 12 carbon atoms and also comprising at least one substituted or unsubstituted aliphatic or aromatic ring.
• polyepoxidized resins comprising three or more epoxide groups per molecule, such as, for example, p-aminophenol triglycidyl ether, polyaryl glycidyl ethers, 1,3,5-tri(1,2-epoxy)benzene, 2,2′,4,4′-tetraglycidoxybenzophenone, tetraglycidoxytetraphenyle-thane, the polyglycidyl ether of the phenol/formaldehyde resin of novolac type, glycerol triglycidyl ether, trimethyloipropane triglycidyl ether and tetraglycidyl-4,4′-diaminodiphenylmethane.
• polyepoxidized resins comprising three or more epoxide groups per molecule, such as, for example, p-aminophenol triglycidyl ether, polyaryl glycidyl ethers
• HMDI hexamethylene diisocyanate
• TMDIs trimethylhexamethylene diisocyanates
• UNTIs 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate
• UNTIs undecane triisocyanates
• NBDI norbornane diisocyanate
• H12MDI 2,4- or 2,6-toluene diisocyanate
• MDIs diphenylmethane diisocyanates
• NDI p-phenylene diisocyanate
• polyisocyanates of modified polyisocyanates, such as those comprising carbodiimide groups, urethane groups, isocyanurate groups, urea groups or biurea groups.
• polys which make it possible to crosslink the polyisocyanates in order to obtain polyurethanes and in which the molecule carrying an associative functional group according to the invention, such as HEIO, can be directly incorporated
• polyether polyols obtained by addition of alkylene oxides, in particular ethylene oxide and/or propylene oxide, to aromatic amines, in particular the mixture of 2,4- and 2,6-toluenediamine, are also suitable.
• polystyrene resin Mention may be made, as other types of polyols, of in particular polythioethers comprising hydroxyl ends, polyamides, polyesteramides, polycarbonates, polyacetals, polyolefins and polysiloxanes.
• polyester and unsaturated polyester resins obtained by reaction of a polyacid with a polyol mention may be made, for the acid component, of succinic acid, pentanedioic acid, adipic acid, maleic acid, fumaric acid, itaconic acid and anhydrides of these acids, heptanedioic acid, octanedioic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, octadecenedioic acid, eicosanedioic acid, docosanedioic acid and fatty acid dimers comprising 36 carbons.
• succinic acid pentanedioic acid, adipic acid, maleic acid, fumaric acid, it
• the abovementioned fatty acid dimers are dimerized fatty acids obtained by oligomerization or polymerization of unsaturated monobasic fatty acids comprising a long hydrocarbon chain (such as linoleic acid and oleic acid), as described in particular in the document EP 0 471 566.
• the diacid when it is cycloaliphatic, it can comprise the following carbon-based backbones: norbornylmethane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di(methylcyclohexyl) or di(methylcyclohexyl) propane.
• the diacid is aromatic, it is chosen from phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic acid, trimellitic acid and naphthalenic diacids and anhydrides of these acids.
• polystyrene resin a compound having a molecule comprising at least two hydroxyl groups which make it possible to crosslink the polyacids in order to obtain polyesters
• polyether diols such as
• polyesteramides when a ternary mixture of HEIO, UDETA and polyol is employed with one of the diacids mentioned.
• TMPDA catalyst tetramethylpropylenediamine
• Formulation G Formulation G of example 1
• Formulation I Formulation G of example 1 with in addition 4% by weight of TMPDA
• Formulation J Formulation G of example 1 with in addition 4% by weight of 1-(2-aminoethyl)imidazolidin-2-one
• Formulation K Formulation D of example 1
• Formulation L Formulation D of example 1 with in addition 4% by weight of TMPDA
• Formulation M Formulation D of example 1 with in addition 4% by weight of 1-(2-aminoethyl)imidazolidin-2-one, that is to say like formulation E of example 1.
• the flexibility of a crosslinked resin can be measured in several ways. Its Shore hardness was measured according to the standard NF T 51109.
• the Shore hardness measurements were obtained with a needle durometer having the trademark symbol Andilog®.
• the device is calibrated in order to obtain a hardness of 100 for a hardened steel comprising 0.9% of carbon and of 35 for mild steels.
• each resin was maintained at 50° C. for several days and its Shore hardness was regularly measured (standard NF T 51109). According to this test, maintaining at 50° C. for 10 days corresponds approximately to aging for 6 months at ambient temperature.
• Formulation A Formulation A of example 1
• Formulation B Formulation B of example 1
• Formulation C Formulation C of example 1
• Time zero corresponds to the hardness measurement after reaction between the base resin and the curing agent comprising 1-(2-aminoethyl)imidazolidin-2-one (formulations B and C) or not comprising 1-(2-aminoethyl)imidazolidin-2-one (formulation A), that is to say after complete development of the exotherm caused by the crosslinking and return of the resin to ambient temperature.
• the measurements given in table 3 are the means of 5 hardness measurements.
• the principle consists in producing a criss-cross pattern on a resin, the crosslinking of which has taken place on different supports, by making parallel and perpendicular incisions in the resin.
• the criss-cross pattern is composed of 25 squares with dimension of 1 mm by 1 mm and with a thickness of 100 ⁇ m. The incisions have to penetrate as far as the support of the paint film.
• a strip of adhesive tape is placed on the criss-cross pattern produced, which strip is quickly torn off after 5 minutes. The adhesion is then characterized by the number of small squares torn off by the tape. The fewer squares torn off, the better the adhesion is judged to be.
• Formulations O and P exhibit a much lower tearing-Off than the reference N; the incorporation in the initial formulation of a few percent by weight of 1-(2-aminoethyl)imidazolidin-2-one very markedly improves the adhesion of the finished epoxy resin to ceramic, steel and polymer exhibiting carbonyl groups, such as PMMA.

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• General Chemical & Material Sciences (AREA)
• Epoxy Resins (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2009
  • 2009-06-04 FR FR0953680A patent/FR2946350B1/fr not_active Expired - Fee Related
• 2010
  • 2010-06-04 EP EP10737600.6A patent/EP2438114B1/fr not_active Not-in-force
  • 2010-06-04 US US13/375,533 patent/US20120074353A1/en not_active Abandoned
  • 2010-06-04 WO PCT/FR2010/051095 patent/WO2010139906A1/fr active Application Filing
  • 2010-06-04 KR KR1020127000280A patent/KR20120014942A/ko not_active Application Discontinuation
  • 2010-06-04 CN CN2010800348151A patent/CN102803367A/zh active Pending
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• 2011
  • 2011-12-01 IL IL216721A patent/IL216721A0/en unknown
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