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WO2017106596A1 - Compositions époxy durcissables et procédés d'accélération du durcissement de compositions époxy - Google Patents

Compositions époxy durcissables et procédés d'accélération du durcissement de compositions époxy Download PDF

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Publication number
WO2017106596A1
WO2017106596A1 PCT/US2016/067092 US2016067092W WO2017106596A1 WO 2017106596 A1 WO2017106596 A1 WO 2017106596A1 US 2016067092 W US2016067092 W US 2016067092W WO 2017106596 A1 WO2017106596 A1 WO 2017106596A1
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Prior art keywords
curable composition
accelerator
curable
aromatic
substrate
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Inventor
Mario A. Perez
Brett J. SITTER
Wayne S. Mahoney
Ryan B. Prince
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3M Innovative Properties Co
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3M Innovative Properties Co
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    • 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
    • C08G59/5006—Amines aliphatic
    • 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
    • C08G59/5026—Amines cycloaliphatic
    • 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
    • C08G59/68—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 catalysts 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
    • C08G59/68—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 catalysts used
    • C08G59/681—Metal alcoholates, phenolates or carboxylates
    • C08G59/685—Carboxylates
    • 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
    • C08G59/68—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 catalysts used
    • C08G59/686—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 catalysts used containing nitrogen

Definitions

  • the present disclosure relates to curable thermoset compositions, especially epoxy-based compositions, and methods for accelerating the curing of the thermoset compositions.
  • thermoset compositions have proven useful in a wide variety of applications.
  • Thermoset compositions are those materials that irreversibly cures to form hard or rigid materials. This is in contrast to a thermoplastic material that becomes pliable or nioldable above a specific temperature and solidifies upon cooling, and is able to repeat these processes, that is to say the material upon cooling is able to be reheated to become pliable or moldable and solidify upon cooling.
  • Thermoset compositions are used in a number of different applications including surface protection, bonding, and the like.
  • the one-part formulation may either have a relatively short shelf life or the composition might need to be stored at a reduced temperature (in a refrigerator or freezer for example).
  • Some one-part compositions are relatively stable at ambient temperatures, but may require high temperatures to fully cure, temperatures that may be too high for use in certain applications.
  • Epoxy resins are a commonly used class of thermoset materials.
  • the epoxy resins are often cured with a curing agent such as an alcohol or amine which ring opens the epoxy ring forming a rigid matrix.
  • Epoxy resins are supplied both in one-part and two- part compositions. Typically two-part compositions cure at a relatively low temperature, even room temperature and typically have the epoxy resin in one-part and an amine or other curing agent in the other part.
  • One-part epoxy resin compositions are available in a wide variety of forms such as films, pastes, and powders. Examples of one-part epoxy compositions include epoxy adhesive films used for example in aerospace applications, epoxy paste adhesives, and epoxy powders used as protective coatings for rebar, pipes and the like.
  • the curable composition comprises an aromatic epoxy resin, an aromatic amine curing agent, and an accelerator comprising an aromatic carboxylic acid compound, where the curable composition is essentially free of water, and the curing temperature of the curable composition is 50-100°C less than for the same composition in the absence of the accelerator.
  • Also disclosed herein are methods for controlling the cure time of curable epoxy compositions comprise providing a curable mixture that is essentially free of water comprising an aromatic epoxy resin, and an aliphatic or cycloaliphatic amine curing agent, and selecting an accelerator comprising an aromatic carboxylic acid, wherein the accelerator has an log P value in the range of from -0.5 to 4.0, wherein P is the partition coefficient, adding the accelerator to either the aromatic epoxy resin or the aliphatic or cycloaliphatic amine curing agent, and mixing the aromatic epoxy resin, aliphatic amine curing agent and accelerator to form a curable composition.
  • the mixed curable composition is permitted to cure at room temperature, where the curing time of the curable composition is less than 1 hour.
  • Figure 1 is a graph showing exotherm traces of various examples and comparative examples of this disclosure.
  • Figure 2 is a graph showing exotherm traces of various examples of this disclosure.
  • Figure 3 is a graph plotting the Time to Maximum Exotherm Temperature vs the Log of the Partition Coefficient of the accelerator.
  • Figure 4 is a graph plotting the Time to Maximum Exotherm Temperature vs the pKa of the accelerator.
  • Figure 5 is a graph showing exotherm traces of various examples of this disclosure.
  • Figure 6 is a graph showing exotherm traces of various examples of this disclosure.
  • Figure 7 is a graph showing exotherm traces of various examples of this disclosure.
  • Figure 8 is a graph showing exotherm traces of various examples of this disclosure.
  • Figure 9 is a graph showing exotherm traces of various examples and comparative examples of this disclosure.
  • thermoset coatings have proven useful in a wide variety of applications including surface protection, bonding, and the like.
  • Epoxy resin compositions are a particularly useful class of thermoset materials that have many desirable features including high internal strength and thus provide durable protective coatings and adhesives with high adhesion to a wide range of substrates.
  • cured epoxy coatings tend to be brittle and also in order to form a coating with high temperature stability, often the resins need to be cured at very high temperatures and for long times, making them unsuitable for many substrates that cannot sustain the curing conditions.
  • curable epoxy resin systems which can be cured at relatively lower temperatures and for shorter times and yet have high temperature stability are desirable and are still being sought.
  • curable epoxy resin systems are used either as "one-part compositions", meaning that the epoxy resin, curatives, and any property modifying additives are all present together, and "two-part compositions", meaning that the epoxy resin/change extension agents and curatives are kept separate and mixed immediately prior to use.
  • One part compositions have the advantages of convenience and ease of dispensing, but can have issues with premature curing upon storage. Also, because the curing of epoxy compositions is an exothermic process, if the mass of the one-part composition is relatively large, this premature curing can become self-accelerating and the heat produced can cause fires, or other damage. For this reason one-part compositions are often stored and shipped at reduced temperatures.
  • the first type of curable compositions are room temperature curable compositions in which acceleration of the cure means that the curable compositions cure more rapidly at room temperature than the same composition without the accelerant.
  • the second type of curable compositions are ones that cure at elevated temperatures in which acceleration of the cure means that the temperature at which the compositions cure is reduced relative to the temperature of cure for the same composition without the accelerant.
  • thermoset refers to those materials that irreversibly cure to form a hard or rigid material.
  • essentially free of water refers to compositions to which no water is intentionally added and care is taken to ensure that all reactants and/or additives are free of water.
  • alkyl refers to a monovalent group that is a radical of an alkane, which is a saturated hydrocarbon.
  • the alkyl can be linear, branched, cyclic, or combinations thereof and typically has 1 to 20 carbon atoms. In some embodiments, the alkyl group contains 1 to 18, 1 to 12, 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms.
  • alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, and ethylhexyl.
  • alkylene refers to a divalent group that is a radical of an alkane.
  • the alkylene can be straight-chained, branched, cyclic, or combinations thereof.
  • the alkylene often has 1 to 20 carbon atoms.
  • the alkylene contains 1 to 18, 1 to 12, 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms.
  • the radical centers of the alkylene can be on the same carbon atom (i.e., an alkylidene) or on different carbon atoms.
  • aryl refers to a monovalent group that is aromatic and carbocyclic.
  • the aryl can have one to five rings that are connected to or fused to the aromatic ring.
  • the other ring structures can be aromatic, non-aromatic, or combinations thereof.
  • Examples of aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, anthryl, naphthyl, acenaphthyl, anthraquinonyl, phenanthryl, anthracenyl, pyrenyl, perylenyl, and fluorenyl.
  • arylene refers to a divalent group that is carbocyclic and aromatic.
  • the group has one to five rings that are connected, fused, or combinations thereof.
  • the other rings can be aromatic, non-aromatic, or combinations thereof.
  • the arylene group has up to 5 rings, up to 4 rings, up to 3 rings, up to 2 rings, or one aromatic ring.
  • the arylene group can be phenylene.
  • partition coefficient refers to the logarithm of "P” the partition coefficient.
  • partition coefficient is a well understood physical parameter.
  • a partition coefficient (P) is the ratio of concentrations of a compound in a mixture of two immiscible phases at equilibrium. These coefficients are a measure of the difference in solubility of the compound in these two phases.
  • the two phases are often restricted to mean two immiscible solvents.
  • a partition coefficient is the ratio of concentrations of a compound in the two phases of a mixture of two immiscible liquids at equilibrium.
  • the log P value is also known as a measure of lipophilicity.
  • the curable composition comprises at least one aromatic epoxy resin.
  • the aromatic epoxy resin is a liquid epoxy resin.
  • suitable liquid epoxy resins include the DGEBA-type (diglycidyl ether of bisphenol A) and DGEBF-type (diglycidyl ether of bisphenol F) epoxy resins such as those commercially available from HEXION under the trade name EPON and Dow Chemical under the trade name D.E.R..
  • Other suitable aromatic epoxy resins are the multifunctional epoxy novolacs such as epoxy phenol novolac resins (EPN) and epoxy cresol novolac resins (ECN).
  • Epoxy phenol novolac resins are made by epoxidation of the phenol-formaldehyde condensates (novolacs) obtained from acid catalyzed condensation of phenol and formaldehyde, which produces random ortho- and para-methylene bridges. Combinations of aromatic epoxy resins can also be used.
  • Reactive diluents and modifiers include mono- and di- functional glycidyl ethers which can be used to reduce the viscosity of typical epoxy resins without causing significant changes in final physical properties.
  • suitable reactive diluents include butyl glycidyl ether, C12-C14 aliphatic glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, and 2-ethylhexyl glycidyl ether.
  • Commercially available diluents and modifier include the EPODIL resins commercially available from Air Products and Chemicals.
  • the curable composition also comprises at least one aliphatic or cycloaliphatic amine curing agent.
  • suitable curing agents can be used. Often, particularly suitable curing agents also include aromatic groups.
  • a curing agent is considered to be an aliphatic amine curing agent as long as all of the bonds to the nitrogen atom of the amine group or groups are hydrogen atoms or aliphatic groups.
  • a wide range of aliphatic or cycloaliphatic amine curing agents are suitable.
  • the curing agent is a liquid curing agent.
  • Solid curing agents are typically insoluble or have limited solubility in the epoxy resins and therefore do not have sufficient reactivity at room temperature to be suitable for use in the curable compositions of this disclosure.
  • Suitable aliphatic or cycloaliphatic amine curing agents include: liquid polyetheramines such as the commercially available JEFF AMINE T-403 and JEFF AMINE D-230 from Huntsman Corp.; polyamidoamines such as VESAMID 125 and GENAMID 490 commercially available from BASF; ethyleneamines such as DETA (diethylene triamine), TETA (trethylenetetramine), TEPA (tetraethylenepentamine), and AEP (N-aminoethylpiperazine); cycloaliphatics such as PACM (bis-(p- aminocyclohexyl)methane), DACH (diaminocyclohexane), TCD-diamine (the diaminomethyl tricyclodecane 3(4), 8(9)-bis(aminomethyl)-tricyclo[5.2.1.0(2.6)]decane (commercially available from OXEA Corporation, Dallas, TX)), and DMCH (bis- (d
  • Particularly suitable aliphatic or cycloaliphatic amine curing agents are meta-xylene diamine (m-XDA), norbornene dimethylamine, and chain-extended compounds and derivatives thereof.
  • the amines may be adducted to a multifunctional epoxy resin by pre-reacting excess amine with some of the epoxy resin, as described by Clive H. Hare in Protective Coatings: Fundamentals of Chemistry and Composition Technology Publishing Company, Pittsburgh, PA (ISBN 0-938477-90-0) Chapter 15-Epoxy Systems, pp 187-237.
  • the resulting adducts are essentially high molecular weight amines with epoxy backbones.
  • the aliphatic or cycloaliphatic amine curing agent comprises 10-35 parts by weight of aliphatic or cycloaliphatic amine curing agent per 100 parts total weight of reactive components. In some embodiments the aliphatic or cycloaliphatic amine curing agent comprises 10-20 parts by weight or 12-18 parts by weight of aliphatic or cycloaliphatic amine curing agent per 100 parts total weight of reactive components.
  • the curable composition also comprises at least one accelerator comprising an aromatic carboxylic acid compound.
  • aromatic carboxylic acid compounds are suitable.
  • the effectiveness of the aromatic carboxylic acid compound as an accelerator for the aromatic epoxy resin/ aliphatic or cycloaliphatic amine curing agent curing system has been found to correlate to the value of "log P" for the aromatic carboxylic acid compound. This value is the logarithm of P, where P is the partition coefficient. Details of log P are explained above. It has also found that the effectiveness of the aromatic carboxylic acid compound as an accelerator for the aromatic epoxy resin/ aliphatic or cycloaliphatic amine curing agent curing system did not correlate to standard acid parameters such as pKa.
  • the accelerator has a log P value in the range of from -0.5 to 4.0.
  • the log P value is in the range of from 0.5 to 4.0, in the range of from 1.0 to 4.0, or even in the range of from 3.0 to 4.0.
  • the accelerator speeds up the reaction time at room temperature for the curing of the curable composition.
  • the curing time of the curable compositions of this disclosure are less than 1 hour at room temperature.
  • the curing time can be measured in a variety of different ways. In the present Examples, curing time is determined by using DSC (Differential Scanning Calorimetry), where curing time is the time necessary to reach the maximum exotherm temperature.
  • the correlation of curing time to log P of the aromatic carboxylic acid accelerator has been observed to be: when the accelerator has a log P value in the range of from -0.5 to 4.0 the curing time of the curable composition is less than 1.0 hour; when the accelerator has a log P value in the range of from 0.5 to 4.0 the curing time of the curable composition is less than 0.5 hour; when the accelerator has a log P value in the range of from 1.0 to 4.0 the curing time of the curable composition is less than 20 minutes; and when the accelerator has a log P value in the range of from 3.0 to 4.0 the curing time of the curable composition is less than 10 minutes.
  • aromatic carboxylic acid accelerators examples include 3- methyl salicylic acid, salicylic acid, anthranilic acid, 2-hydroxynicotinic acid, and combinations thereof.
  • the aromatic carboxylic acid accelerators are present in small quantities in the curable compositions. Generally, the aromatic carboxylic acid accelerators are present in amounts of from 0.01-5.0 parts by weight per 100 parts total weight of reactive components in the curable composition. In some embodiments, the aromatic carboxylic acid accelerators are present in amounts of from 0.02-2.0 parts by weight per 100 parts total weight of reactive components in the curable composition, amounts of from 0.02-1.0 parts by weight per 100 parts total weight of reactive components in the curable composition, or 0.02-0.5 parts by weight per 100 parts total weight of reactive components in the curable composition, or even 0.02-0.15 parts by weight per 100 parts total weight of reactive components in the curable composition.
  • the curable composition may contain additional optional additives.
  • These optional additives can be either solids or liquids, and reactive or unreactive.
  • suitable additives include thermally conductive fillers, flame retardants (such as ATH (aluminum trihydrate) or phosphate flame retardants), colorants such as pigments or dyes, nanoparticles or functionalized nanoparticles, chain extenders, toughening agents, or combinations thereof.
  • these components are typically solids, but some of the additive components can be liquids, and these liquid components may be suitable.
  • non-reactive additives include fillers, flame retardants, nanoparticles, and toughening agents.
  • Particularly suitable non-reactive additives are fillers such as metal oxides (silica, titania, magnesium oxide, and the like) and thermal conductivity enhancers such as boron nitride.
  • Suitable chain extension agents include aromatic hydroxyl-functional materials such as di-hydroxyl phenolic compounds such as catechol and other di-hydroxyphenols, as well as compounds such as bisphenol A and bisphenol F. Examples of additional suitable chain extension agents are included in US Patent Publication Nos. 2014/0069583 and 2014/0296447 (Kincaid et al.).
  • the aromatic epoxy resin comprises: a diglycidyl ether of bis-phenol A, a diglycidyl ether of bis-phenol F, or a combination thereof;
  • the aliphatic or cycloaliphatic amine curing agent comprises meta- xylene diamine, norbornene dimethylamine or a chain-extended compound or derivative thereof;
  • the accelerator comprises salicylic acid, 3-methyl salicylic acid, anthranilic acid, 2-hydroxynicotinic acid, or combinations thereof.
  • the above described curable composition can be supplied as a two-part curable epoxy composition comprising a first part comprising an aromatic epoxy resin, and a second part comprising an aliphatic or cycloaliphatic amine curing agent. Additionally, one of the two parts additionally comprises an accelerator comprising an aromatic carboxylic acid compound. In other words, the accelerator can be placed in either of the two parts.
  • a two-part curable epoxy composition of this disclosure comprises a first part comprising an aromatic epoxy resin, and an accelerator comprising an aromatic carboxylic acid compound, and a second part comprising an aliphatic or cycloaliphatic amine curing agent.
  • the first part and the second part are essentially free from water, and the two parts when mixed form a curable composition with a curing time that is less than 1 hour at room temperature.
  • the components of the two-part curable composition have all been described above.
  • the two-part curable epoxy composition can also include a variety of additional additives, as described above. These additives can be added either to the first part or to the second part or to both as desired, as long addition of the additive to a particular part does not interfere with the curing reaction upon mixing.
  • suitable additives include fillers, thermally conductive fillers, flame retardants, nanoparticles or functionalized nanoparticles, chain extenders, toughening agents, and combinations thereof.
  • a two-part curable epoxy composition of this disclosure comprises a first part comprising an aromatic epoxy resin, and a second part comprising an aliphatic or cycloaliphatic amine curing agent, and an accelerator comprising an aromatic carboxylic acid compound.
  • the first part and the second part are essentially free from water, and the two parts when mixed form a curable composition with a curing time that is less than 1 hour at room temperature.
  • the components of the two-part curable composition have all been described above.
  • the two parts of the curable epoxy composition are kept separate until mixed to form the curable composition of this disclosure.
  • the two parts can be kept separate in a wide variety of ways, depending upon the desired use.
  • the two parts can be stored and shipped in separate sealed containers, or the two parts can be incorporated into a single container with two separate compartments. A wide variety of such containers are known in the art.
  • curable compositions comprising an aromatic epoxy resin, an aromatic amine curing agent, and an accelerator comprising an aromatic carboxylic acid compound.
  • aromatic epoxy resins and the accelerators have been described in detail above.
  • aromatic amine curing agents are suitable. Among the most suitable are m-PDA (w-phenylene diamine), MDA (methylene dianiline), and DDS (diaminodiphenyl sulfone).
  • curable compositions that use of aromatic amine curing agents typically are not room temperature curable and thus the application of heat is used to cure these compositions.
  • acceleration relates to a decrease in the cure temperature. For example, in an unaccelerated composition typically cures at a temperature of 150°C, an example of acceleration would be for the composition to cure at a temperature of 100°C.
  • the acceleration of curing can be modeled by the use of a DSC instrument.
  • the sample is heated at a specific rate, typically 10°C per minute, and the thermal profile is studied to determine where the onset of an exothermic reaction occurs.
  • the acceleration of compositions of aromatic epoxy resins and aromatic amine curing agents results in the onset of curing at a temperature that is 50-100°C less for the accelerated compositions than for the unaccelerated compositions. Examples of cure profiles are presented in the Examples section and the Figures.
  • the aromatic amine curing agent comprises 10-35 parts by weight of aromatic amine curing agent per 100 parts total weight of reactive components. In some embodiments the aromatic amine curing agent comprises 10-20 parts by weight or 12-18 parts by weight of aromatic amine curing agent per 100 parts total weight of reactive components.
  • the method of controlling the cure time of curable epoxy composition comprises providing a curable mixture that is essentially free of water, where the curable mixture comprises an aromatic epoxy resin, and an aliphatic or cycloaliphatic amine curing agent, and selecting an accelerator comprising an aromatic carboxylic acid, adding the accelerator to either the aromatic epoxy resin or the aliphatic or cycloaliphatic amine curing agent, mixing the aromatic epoxy resin, aliphatic amine curing agent and accelerator to form a curable composition, and permitting the curable composition to cure at room temperature.
  • the aromatic carboxylic acid accelerator has a log P value in the range of from -0.5 to 4.0, where P is the partition coefficient, as described above.
  • the curing time of the curable composition is less than 1 hour, at room temperature.
  • the curable composition can be applied to a substrate to form a curable layer using a variety of techniques, including dip coating, forward and reverse roll coating, wire wound rod coating, and die coating.
  • Die coaters include knife coaters, slot coaters, slide coaters, fluid bearing coaters, slide curtain coaters, and drop die curtain coaters.
  • the curable composition is permitted to cure at ambient temperature to form a cured coating.
  • the thickness of the coating varies depending upon the desired use for the coating. Typically the coatings range from 25 micrometers (1 mil) to 1 millimeter in thickness. In some embodiments, particularly for the pipe coatings described below, the thickness can be considerably greater.
  • coatings of from 25 micrometers (1 mil) to 1 millimeter in thickness are typically sufficient. In other instances, when the coating is relied upon to assist in providing structural integrity to the pipe, coatings with a thickness of 5 millimeters or greater are typical. In yet other embodiments in which the curable composition is utilized to impregnate a woven or nonwoven web of material such as a sock or other reinforcement (sometimes referred to as a CIPP, or cure in place pipe), the coating thickness can be up to 50 millimeters in thickness.
  • the curable composition is a pipe coating.
  • the substrate comprises a metal substrate which is a pipe
  • the second major surface of the substrate comprises an external surface of the pipe.
  • One advantage of the curable compositions of the present disclosure for use as pipe coatings is that they cure rapidly at ambient temperature, and thus can be readily used in the field to coat or repair coatings without the need for specialized curing equipment.
  • the pipe coating can be applied to the inside surface of the pipe, i.e. the second major surface of the substrate comprises an internal surface of the pipe. Such coatings can be much more difficult to apply and may require specialized equipment.
  • the curable compositions can be used as coatings for pipeline joints. The pipeline joint coatings can be applied either internally or externally.
  • Embodiment 4 is the curable composition of embodiment 1, wherein the curing time of the curable composition is less than 10 minutes at room temperature.
  • Embodiment 5 is the curable composition of any of embodiments 1-4, wherein the accelerator has a log P value of from -0.5 to 4.0 where P is the partition coefficient.
  • Embodiment 6 is the curable composition of any of embodiments 1-4, wherein the accelerator has a log P value of from 0.5 to 4.0 where P is the partition coefficient.
  • Embodiment 9 is the curable composition of any of embodiments 1-8, wherein the accelerator comprises 3-methyl salicylic acid, salicylic acid, anthranilic acid, 2- hydroxynicotinic acid, or combinations thereof.
  • Embodiment 11 is the curable composition of embodiment 10, wherein the aliphatic or cycloaliphatic amine curing agent comprises meta xylene diamine, norbornene dimethylamine, or a chain-extended compound thereof.
  • Embodiment 18 is the two-part curable epoxy composition of embodiment 17, wherein the first part comprises: an aromatic epoxy resin; and an accelerator comprising an aromatic carboxylic acid compound; and the second part comprises: an aliphatic or cycloaliphatic amine curing agent.
  • Embodiment 19 is the two-part curable epoxy composition of embodiment 17, wherein the first part comprises: an aromatic epoxy resin; and the second part comprises: an aliphatic or cycloaliphatic amine curing agent; and an accelerator comprising an aromatic carboxylic acid compound.
  • Embodiment 20 is the two-part curable epoxy composition of any of embodiments
  • Embodiment 23 is the two-part curable epoxy composition of any of embodiments 17-20, wherein the curing time of the formed curable composition is less than 10 minutes at room temperature.
  • Embodiment 25 is the two-part curable epoxy composition of any of embodiments 17-20, wherein the accelerator has a log P value of from 0.5 to 4.0 where P is the partition coefficient.
  • Embodiment 30 is the two-part curable epoxy composition of embodiment 29, wherein the aliphatic or cycloaliphatic amine curing agent comprises meta xylene diamine, norbornene dimethylamine, or a chain-extended compound thereof.
  • Embodiment 31 is the two-part curable epoxy composition of any of embodiments 17-30, wherein the aromatic epoxy resin comprises a diglycidyl ether of bis-phenol A, a diglycidyl ether of bis-phenol F, or a combination thereof.
  • Embodiment 33 is the two-part curable epoxy composition of any of embodiments
  • Embodiment 34 is the two-part curable epoxy composition of any of embodiments 17-33, wherein the formed curable composition comprises 10-35 parts by weight of aliphatic or cycloaliphatic amine curing agent per 100 parts total weight of reactive components.
  • Embodiment 35 is the two-part curable epoxy composition of any of embodiments 17-34, wherein the formed curable composition comprises 0.01-5.0 parts by weight of aromatic carboxylic acid accelerator per 100 parts total weight of reactive components in the curable composition.
  • Embodiment 36 includes a method of controlling the cure time of a curable epoxy composition comprising: providing a curable mixture that is essentially free of water comprising: an aromatic epoxy resin; and an aliphatic or cycloaliphatic amine curing agent; and selecting an accelerator comprising an aromatic carboxylic acid, wherein the accelerator has an log P value in the range of from -0.5 to 4.0, wherein P is the partition coefficient; adding the accelerator to either the aromatic epoxy resin or the aliphatic or cycloaliphatic amine curing agent; mixing the aromatic epoxy resin, aliphatic amine curing agent and accelerator to form a curable composition; permitting the curable composition to cure at room temperature, wherein the curing time of the curable composition is less than 1 hour.
  • Embodiment 37 is the method of embodiment 36, wherein the curing time of the curable composition is determined using DSC (Differential Scanning Calorimetry).
  • Embodiment 38 is the method of embodiment 35 or 36, wherein the curing time of the curable composition is less than 0.5 hour at room temperature.
  • Embodiment 39 is the method of embodiment 35 or 36, wherein the curing time of the curable composition is less than 20 minutes at room temperature.
  • Embodiment 40 is the method of embodiment 35 or 36, wherein the curing time of the curable composition is less than 10 minutes at room temperature.
  • Embodiment 41 is the method of embodiment 35 or 36, wherein the accelerator has a log P value of from -0.5 to 4.0 where P is the partition coefficient.
  • Embodiment 42 is the method of embodiment 35 or 36, wherein the accelerator has a log P value of from 0.5 to 4.0 where P is the partition coefficient.
  • Embodiment 43 is the method of embodiment 35 or 36, wherein the accelerator has a log P value of from 1.0 to 4.0 where P is the partition coefficient.
  • Embodiment 44 is the method of embodiment 35 or 36, wherein the accelerator has a log P value of from 3.0 to 4.0 where P is the partition coefficient.
  • Embodiment 45 is the method of any of embodiments 35-44, wherein the accelerator comprises 3-methyl salicylic acid, salicylic acid, anthranilic acid, 2- hydroxynicotinic acid, or combinations thereof.
  • Embodiment 46 is the method of any of embodiments 35-45, wherein the aliphatic or cycloaliphatic amine curing agent comprises a xylene diamine, a TCD-diamine, a norbornene dimethylamine, or a chain-extended compound thereof.
  • Embodiment 47 is the method of embodiment 46, wherein the aliphatic or cycloaliphatic amine curing agent comprises meta xylene diamine, norbornene dimethylamine, or a chain-extended compound thereof.
  • Embodiment 48 is the method of any of embodiments 35-47, wherein the aromatic epoxy resin comprises a diglycidyl ether of bis-phenol A, a diglycidyl ether of bis-phenol F, or a combination thereof.
  • Embodiment 49 is the method of any of embodiments 35-48, wherein the aromatic epoxy resin comprises a diglycidyl ether of bis-phenol A, a diglycidyl ether of bis-phenol F, or a combination thereof; the aliphatic or cycloaliphatic amine curing agent comprises meta xylene diamine, norbornene dimethylamine or a chain-extended compound thereof; and the accelerator comprises salicylic acid, 3-methyl salicylic acid, anthranilic acid, 2- hydroxynicotinic acid, or combinations thereof.
  • Embodiment 50 is the method of any of embodiments 35-49, wherein the curable composition comprises 60-90 parts by weight of aromatic epoxy resin per 100 parts total weight of reactive components.
  • Embodiment 51 is the method of embodiment 50, wherein the curable composition comprises 10-35 parts by weight of aliphatic or cycloaliphatic amine curing agent per 100 parts total weight of reactive components.
  • Embodiment 52 is the method of embodiment 49 or 50, wherein the curable composition comprises 0.01-5.0 parts by weight of aromatic carboxylic acid accelerator per 100 parts total weight of reactive components in the curable composition.
  • Embodiment 53 is the method of any of embodiments 35-52, wherein the accelerator has a log P value in the range of from 0.5 to 4.0; and the curing time of the curable composition is less than 0.5 hours.
  • Embodiment 54 is the method of any of embodiments 35-52, wherein the accelerator has a log P value in the range of from 1.0 to 4.0; and the curing time of the curable composition is less than 20 minutes.
  • Embodiment 55 is the method of any of embodiments 35-52, wherein the accelerator has a log P value in the range of from 3.0 to 4.0; and the curing time of the curable composition is less than 10 minutes.
  • Embodiment 56 includes an article comprising: a substrate comprising a first major surface and a second major surface; and a coating on at least a portion of the second major surface of the substrate, wherein the coating comprises a cured layer of a curable composition, wherein the curable composition comprises: an aromatic epoxy resin; an aliphatic or cycloaliphatic amine curing agent; and an accelerator comprising an aromatic carboxylic acid compound, wherein the curable composition is essentially free of water, and wherein the curing time of the curable composition is less than 1 hour at room temperature.
  • Embodiment 57 is the article of embodiment 56, wherein the curing time of the curable composition is less than 0.5 hour at room temperature.
  • Embodiment 58 is the article of embodiment 56, wherein the curing time of the curable composition is less than 20 minutes at room temperature.
  • Embodiment 59 is the article of embodiment 56, wherein the curing time of the curable composition is less than 10 minutes at room temperature.
  • Embodiment 60 is the article of any of embodiments 56-59, wherein the accelerator has a log P value of from -0.5 to 4.0 where P is the partition coefficient.
  • Embodiment 61 is the article of any of embodiments 56-59, wherein the accelerator has a log P value of from 0.5 to 4.0 where P is the partition coefficient.
  • Embodiment 62 is the article of any of embodiments 56-59, wherein the accelerator has a log P value of from 1.0 to 4.0 where P is the partition coefficient.
  • Embodiment 63 is the article of any of embodiments 56-59, wherein the accelerator has a log P value of from 3.0 to 4.0 where P is the partition coefficient.
  • Embodiment 64 is the article of any of embodiments 56-63, wherein the accelerator comprises 3-methyl salicylic acid, salicylic acid, anthranilic acid, 2- hydroxynicotinic acid, or combinations thereof.
  • Embodiment 65 is the article of any of embodiments 56-64, wherein the aliphatic or cycloaliphatic amine curing agent comprises a xylene diamine, a norbornene dimethylamine, or a chain-extended compound thereof.
  • Embodiment 66 is the article of embodiment 65, wherein the aliphatic or cycloaliphatic amine curing agent comprises meta xylene diamine, norbornene dimethylamine, or a chain-extended compound thereof.
  • Embodiment 67 is the article of any of embodiments 56-66, wherein the aromatic epoxy resin comprises a diglycidyl ether of bis-phenol A, a diglycidyl ether of bis-phenol F, or a combination thereof.
  • Embodiment 68 is the article of any of embodiments 56-67, wherein the aromatic epoxy resin comprises a diglycidyl ether of bis-phenol A, a diglycidyl ether of bis-phenol F, or a combination thereof; the aliphatic or cycloaliphatic amine curing agent comprises meta xylene diamine, norbornene dimethylamine or a chain-extended compound thereof; and the accelerator comprises salicylic acid, 3-methyl salicylic acid, anthranilic acid, 2- hydroxynicotinic acid, or combinations thereof.
  • Embodiment 69 is the article of any of embodiments 56-68, wherein the curable composition comprises 60-90 parts by weight of aromatic epoxy resin per 100 parts total weight of reactive components.
  • Embodiment 70 is the article of embodiment 69, wherein the curable composition comprises 10-35 parts by weight of aliphatic or cycloaliphatic amine curing agent per 100 parts total weight of reactive components.
  • Embodiment 71 is the article of embodiment 69 or 70, wherein the curable composition comprises 0.01-5.0 parts by weight of aromatic carboxylic acid accelerator per 100 parts total weight of reactive components in the curable composition.
  • Embodiment 72 is the article of any of embodiments 56-71, wherein the substrate comprises a metal substrate, a ceramic substrate, a glass substrate, a polymeric substrate, or a wooden substrate.
  • Embodiment 73 is the article of embodiments 72, wherein the substrate comprises a metal substrate comprising a pipe, and wherein the second major surface of the substrate comprises an external surface of the pipe.
  • Embodiment 74 is the article of embodiment 72, wherein the substrate comprises a metal substrate comprising a pipe, and wherein the second major surface of the substrate comprises an internal surface of the pipe.
  • Embodiment 75 is the article of any of embodiments 56-74, wherein the coating has a thickness of from 25 micrometers to 5 millimeters.
  • Embodiment 76 is the article of any of embodiments 56-74, wherein the coating has a thickness of from 25 micrometers to 1 millimeter.
  • Embodiment 77 is the article of any of embodiments 56-74, wherein the coating has a thickness of up to 50 millimeters.
  • Embodiment 78 includes a curable composition comprising: an aromatic epoxy resin; an aromatic amine curing agent; and an accelerator comprising an aromatic carboxylic acid compound, wherein the curable composition is essentially free of water, and wherein the curing temperature of the curable composition is 50-100°C less than for the same composition in the absence of the accelerator.
  • Embodiment 79 is the curable composition of embodiment 78, wherein the accelerator comprises 3-methyl salicylic acid, salicylic acid, anthranilic acid, 2- hydroxynicotinic acid, or combinations thereof.
  • Embodiment 80 is the curable composition of embodiments 78 or 79, wherein the aromatic amine curing agent comprises m-PDA (w-phenylene diamine), MDA (methylene dianiline), DDS (diaminodiphenyl sulfone), or combinations thereof.
  • m-PDA w-phenylene diamine
  • MDA methylene dianiline
  • DDS diaminodiphenyl sulfone
  • Embodiment 81 is the curable composition of any of embodiments 78-80, wherein the aromatic epoxy resin comprises a diglycidyl ether of bis-phenol A, a diglycidyl ether of bis-phenol F, or a combination thereof.
  • Embodiment 82 is the curable composition of any of embodiments 78-81, wherein the aromatic epoxy resin comprises a diglycidyl ether of bis-phenol A, a diglycidyl ether of bis-phenol F, or a combination thereof; the aromatic amine curing agent comprises m- PDA (w-phenylene diamine), MDA (methylene dianiline), DDS (diaminodiphenyl sulfone), or combinations thereof; and the accelerator comprises salicylic acid, 3-methyl salicylic acid, anthranilic acid, 2-hydroxynicotinic acid, or combinations thereof.
  • the aromatic epoxy resin comprises a diglycidyl ether of bis-phenol A, a diglycidyl ether of bis-phenol F, or a combination thereof
  • the aromatic amine curing agent comprises m- PDA (w-phenylene diamine), MDA (methylene dianiline), DDS (diaminodiphenyl sulfone), or combinations thereof
  • Embodiment 83 is the curable composition of any of embodiments 78-82, wherein the curable composition comprises 60-90 parts by weight of aromatic epoxy resin per 100 parts total weight of reactive components.
  • Embodiment 84 is the curable composition of embodiment 83, wherein the curable composition comprises 10-35 parts by weight of aromatic amine curing agent per 100 parts total weight of reactive components.
  • Embodiment 85 is the curable composition of embodiment 83 or 84, wherein the curable composition comprises 0.01-5.0 parts by weight of aromatic carboxylic acid accelerator per 100 parts total weight of reactive components in the curable composition.
  • Embodiment 86 is a structural adhesive comprising the curable composition of any of embodiments 1-16.
  • Embodiment 87 is the structural adhesive of embodiment 86, wherein the structural adhesive comprises a two-part curable epoxy composition of any of embodiments 17-35.
  • Embodiment 88 is the structural adhesive of embodiment 86 or 87, wherein the cure time of the structural adhesive is controlled by any of the methods of embodiments 36-55.
  • Embodiment 89 is an article comprising a first substrate comprising a first major surface and a second major surface; and a coating on at least a portion of the second major surface of the first substrate, wherein the coating comprises a cured layer of a curable composition, wherein the curable composition comprises: an aromatic epoxy resin; an aliphatic or cycloaliphatic amine curing agent; and an accelerator comprising an aromatic carboxylic acid compound, wherein the curable composition is essentially free of water, and wherein the curing time of the curable composition is less than 1 hour at room temperature, and a second substrate comprising a first major surface and a second major surface, wherein the first major surface of the second substrate is in contact with the cured layer of the curable composition, such that the cured layer of the curable composition forms a structural adhesive bond between the first substrate and the second substrate.
  • the curable composition comprises: an aromatic epoxy resin; an aliphatic or cycloaliphatic amine curing agent; and an accelerator comprising an aromatic carboxylic
  • Embodiment 90 is the article of embodiment 89, wherein the curing time of the curable composition is less than 0.5 hour at room temperature.
  • Embodiment 91 is the article of embodiment 89, wherein the curing time of the curable composition is less than 20 minutes at room temperature.
  • Embodiment 92 is the article of embodiment 89, wherein the curing time of the curable composition is less than 10 minutes at room temperature.
  • Embodiment 93 is the article of any of embodiments 89-92, wherein the accelerator has a log P value of from -0.5 to 4.0 where P is the partition coefficient.
  • Embodiment 94 is the article of any of embodiments 89-92, wherein the accelerator has a log P value of from 0.5 to 4.0 where P is the partition coefficient.
  • Embodiment 95 is the article of any of embodiments 89-92, wherein the accelerator has a log P value of from 1.0 to 4.0 where P is the partition coefficient.
  • Embodiment 96 is the article of any of embodiments 89-92, wherein the accelerator has a log P value of from 3.0 to 4.0 where P is the partition coefficient.
  • Embodiment 97 is the article of any of embodiments 89-96, wherein the accelerator comprises 3-methyl salicylic acid, salicylic acid, anthranilic acid, 2- hydroxynicotinic acid, or combinations thereof.
  • Embodiment 98 is the article of any of embodiments 89-97, wherein the aliphatic or cycloaliphatic amine curing agent comprises a xylene diamine, a norbornene dimethylamine, or a chain-extended compound thereof.
  • Embodiment 99 is the article of embodiment 98, wherein the aliphatic or cycloaliphatic amine curing agent comprises meta xylene diamine, norbornene dimethylamine, or a chain-extended compound thereof.
  • Embodiment 100 is the article of any of embodiments 89-98, wherein the aromatic epoxy resin comprises a diglycidyl ether of bis-phenol A, a diglycidyl ether of bis-phenol F, or a combination thereof.
  • Embodiment 101 is the article of any of embodiments 89-100, wherein the aromatic epoxy resin comprises a diglycidyl ether of bis-phenol A, a diglycidyl ether of bis-phenol F, or a combination thereof; the aliphatic or cycloaliphatic amine curing agent comprises meta xylene diamine, norbornene dimethylamine or a chain-extended compound thereof; and the accelerator comprises salicylic acid, 3-methyl salicylic acid, anthranilic acid, 2-hydroxynicotinic acid, or combinations thereof.
  • Embodiment 102 is the article of any of embodiments 89-101, wherein the curable composition comprises 60-90 parts by weight of aromatic epoxy resin per 100 parts total weight of reactive components.
  • Embodiment 103 is the article of embodiment 102, wherein the curable composition comprises 10-35 parts by weight of aliphatic or cycloaliphatic amine curing agent per 100 parts total weight of reactive components.
  • Embodiment 104 is the article of embodiment 102 or 103, wherein the curable composition comprises 0.01-5.0 parts by weight of aromatic carboxylic acid accelerator per 100 parts total weight of reactive components in the curable composition.
  • Embodiment 105 is the article of any of embodiments 89-104, wherein the first substrate comprises a metal substrate, a ceramic substrate, a glass substrate, a polymeric substrate, or a wooden substrate.
  • Embodiment 106 is the article of any of embodiments 89-105, wherein the second substrate comprises a metal substrate, a ceramic substrate, a glass substrate, a polymeric substrate, or a wooden substrate.
  • Embodiment 107 is the article of any of embodiments 89-106, wherein the coating has a thickness of from 25 micrometers to 1 millimeter.
  • Embodiment 108 is a structural adhesive comprising the curable composition of any of embodiments 78-81. Examples
  • Acid accelerated epoxy formulations were prepared and cured.
  • the accelerant was premixed into the epoxy prior to contacting with the amine curing agent.
  • the exotherm was monitored by immersion of a K-type thermocouple into 10 grams of the mixture.
  • a hand held Omega HH506RA temperature logger was utilized to acquire and store the data. A data point was collected every 15 seconds. The data are presented in Figure 1.
  • Comparative Example 1 was a mixture of 7 grams of EP1 epoxy cured with 3 grams of amine CA1. The exotherm was monitored by immersion of a K-type thermocouple into 10 grams of the mixture. A hand held Omega HH506RA temperature logger was utilized to acquire and store the data. A data point was collected every 15 seconds. The data are presented in Figure 1.
  • Examples 2A-2D were mixtures of 10 grams of EP2 epoxy cured with 2 grams of amine CA1 with 0.5 grams of various acid accelerants as shown in Table 1. The method described above was used to mix and record temperature data. The results are shown in Figure 2.
  • Figure 3 shows the fit of time to maximum exotherm temperature vs. log of the 0 partition coefficient.
  • Figure 4 shows the data for the time to maximum exotherm temperature vs pKa, demonstrating that there is not a straight line fit correlation.
  • Examples 3A-3C were mixtures of 10 grams of EP2 epoxy cured with stoichiometric proportions of various amines (E3A 1.6 grams CA2, E3B 2.0 grams CA1, E3C 1.5 grams CA3) with 0.5 grams of A4 acid. The method described above was used to mix and record temperature data. The results are shown in Figure 5.
  • Example 4- Effect of acid amount on working time of amines and epoxy.
  • Examples 4A-4C were mixtures of 10 grams of EP2 epoxy cured with 2 grams of amine CA1 with various amounts of acid Al (E4A 0.3 grams, E4B 1.0 grams, E4C 2.0 grams). The method described above was used to mix and record temperature data. The results are shown in Figure 6.
  • Example 5- Effect of mixtures of acid on working time of amines and epoxy.
  • Examples 5A-5D were mixtures of 10 grams of EP2 epoxy cured with 2 grams of amine CA1 with various mixtures of acid Al and A2 as shown in Table 2. The method described above was used to mix and record temperature data. The results are shown in Figure 7.
  • Example 6- Effect of acid addition to epoxy or amine side.
  • Examples 6A-6D were mixtures of 10 grams of EP2 epoxy cured with 2 grams of amine CA3 or CA1 with 0.5 grams of acid Al as shown in Table 3. The method described above was used to mix and record temperature data. In one instance, salicylic acid (Al) was added to the epoxy side (EP2), dispersed well and then amine was added to this mixture. Alternatively, salicylic acid (Al) was added to the amine side and then mixed with epoxy (EP2). In either case a reaction exotherm took place followed by hardening of the mixture. The results are shown in Figure 8.
  • Examples 7A-7B were mixtures of 3 parts EP2 epoxy cured with 0.72 parts aromatic amine CA4 with 0.12 parts of acid Al for E7A and 0.12 parts of acid A2 for E7B. The method described above was used to mix. The effectiveness of the acceleration for the acids was observed by DSC (Differential Scanning Calorimetry) scan as shown in Figure 9.
  • Comparative Example 2 was mixture of 3 parts EP2 epoxy cured with 0.72 parts aromatic amine CA4. The method described above was used to mix. The exotherm was observed by DSC (Differential Scanning Calorimetry) scan as shown in Figure 9.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne des procédés de régulation du temps de durcissement de compositions époxy durcissables comprenant la sélection d'un accélérateur d'acide carboxylique aromatique qui présente une valeur log P s'inscrivant dans la plage de -0,5 à 4,0, où P est le coefficient de partition. Les compositions époxy durcissables sont essentiellement exemptes d'eau et comprennent une résine époxy aromatique, un agent de durcissement amine et l'accélérateur. Lorsque l'agent de durcissement amine est une amine aliphatique ou cycloaliphatique, la composition durcissable durcit en moins d'une heure à la température ambiante. Lorsque l'agent de durcissement amine est une amine aromatique, de la chaleur est appliquée pour effectuer le durcissement.
PCT/US2016/067092 2015-12-18 2016-12-16 Compositions époxy durcissables et procédés d'accélération du durcissement de compositions époxy Ceased WO2017106596A1 (fr)

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