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    • 专利摘要:
    COMPOSITION OF CURABLE EPOXY RESIN AND METHODS FOR CURING AN EPOXY RESIN SYSTEM AND FOR MANUFACTURING A COMPOSITE STRUCTURE A method for using the exothermic energy generated by a low temperature cure reaction to access a reaction is disclosed here high temperature curing which is otherwise energetically inaccessible at a chosen tool temperature, thereby producing a cured resin matrix with properties that closely match those produced via high temperature curing reactions, but obtained via a short cure and low cure temperature. Also disclosed is a short curing resin composition containing: (a) at least one multifunctional epoxy resin having an epoxy functionality greater than 1; (b) a hardener composition containing: (i) at least one aliphatic or cycloaliphatic amine curing agent having one or more amino groups per molecule; (ii) at least one aromatic amine curing agent having one or more amino groups per molecule and, optionally, (ill) an imidazole as a curing accelerator. The improved properties of this resin composition include being curable at a temperature of (...).
    公开号:BR112014010528B1
    申请号:R112014010528-6
    申请日:2013-02-25
    公开日:2020-11-10
    发明作者:Jonathan E. Meegan
    申请人:Cytec Technology Corp；
    IPC主号:
    专利说明:

    BACKGROUND
    [0001] Thermosetting epoxy resins are widely used in the production of advanced composite materials, in which reinforcing fibers, such as glass or carbon fibers, are impregnated with a formulation composed of epoxy resins and a curing agent and then cured to form a composite material of fiber resin matrix. Reinforced epoxy resin composites having high strength to weight ratios find widespread use in the aerospace industry and in other applications where high strength, corrosion resistance and light weight are desirable. For example, fiber resin matrix materials have replaced aluminum and other metals in the primary and secondary structures of modern aircraft. Sports equipment like tennis rackets and golf clubs have also successfully adopted fiber resin materials. Since the advent of fiber resin matrix materials, much effort has been spent on improving its properties and characteristics, including the development of many different curing systems. SUMMARY
    [0002] A method for using the exothermic energy (ie, heat) generated by a low temperature cure reaction to activate a high temperature cure reaction, which is otherwise energetically inaccessible at the chosen cure temperature, is disclosed here . The application of the method results in a cured resin matrix obtained at a commensurable tool temperature with the lowest cure temperature reaction (<120 ° C). Tool temperature refers to the temperature of the tool or mold used to cure a resin system.
    [0003] Also disclosed is a resin composition containing: (a) at least one multifunctional epoxy resin having an epoxy functionality greater than 1; (b) at least one aliphatic or cycloaliphatic amine curing agent having one or more amino groups per molecule; (c) at least one aromatic amine curing agent having one or more amino groups per molecule; and optionally (d) an imidazole as a cure accelerator. The improved properties of this resin composition include being curable at or below 120 ° C for a period of time less than 10 minutes, or <5 minutes in some embodiments, to obtain more than 90%, preferably more 95% degree of cure. BRIEF DESCRIPTION OF THE DRAWINGS
    [0004] FIG. 1 is a schematic graph illustrating the energy transfer concept of the present disclosure.
    [0005] FIG. 2 is an exemplary embodiment of the concept described in FIG. 1.
    [0006] FIG. 3 shows selected mechanical test data for two composite laminates described in an example. DETAILED DESCRIPTION
    [0007] "Curing" or "curing" is a term that refers to the hardening of a polymer material by the chemical crosslinking of polymer chains. The term "curable" means that the composition is capable of being subjected to conditions that will make the composition into a cured or thermoset state or condition.
    [0008] The use of aromatic diamine dressings for polyepoxy resins allows the formation of cross-linked polymers (thermoset resins) with the high glass transition temperature (Tg) and generically superior properties when compared to aliphatic amine dressings. However, high curing temperatures, long curing times (typically 1 to 3 hours), and long post-curing heating are generally required to obtain these higher performance characteristics.
    [0009] For low temperature, rapid curing of epoxy / amine systems, aliphatic amines were used due to the positive inductive effect of the alkyl backbones on the electron pair alone located in the amine functionality and the increase in reactivity with epoxy groups that this effect brings in comparison with aromatic amine molecules. However, epoxy formulations containing aliphatic amines are generally unsuitable for curing large volumes of resin with temperatures close to or above the start of the reaction due to their increased reactivity and propensity associated with the exotherm.
    [0010] Imidazois have been used as curing agents / accelerators in amine-epoxy systems for fast curing (for example, less than 1 hour) at temperatures around 100 ° C or higher, however, the Tg of the resin The resulting cured surface is typically low, making these resin systems more applicable for adhesive applications. In addition, these resin systems are also prone to exothermic reaction in volume.
    [0011] It has been discovered that the exothermic energy generated by a curing reaction that occurs at low temperature can be used to activate a reaction that is otherwise energetically inaccessible (which exhibits a higher start temperature for curing), and that the properties of the resulting cured resin can be influenced by the high temperature curing system instead of being solely representative of the lower curing temperature reaction; this concept is represented in FIG. 1 the horizontal geometric axis represents the temperature of the tool in which curing occurs, and the vertical geometric axis represents the exothermic energy generated. FIG. 1 shows that the low temperature reaction has a lower reaction start than the higher temperature reaction, and that the start of the higher temperature reaction is not initiated by the tool temperature. Instead, the overlapping region is used to initiate the higher temperature reaction. The high temperature curing reaction, as used here, refers to the curing reaction (i.e., crosslinking) of thermoset resin and curing agent initiated by applying heat at a temperature equal to or greater than 130 ° C. Low temperature curing reaction refers to the curing reaction of thermoset resin and curing agent initiated by applying heat at a temperature within the range of 30 ° C to 100 ° C.
    [0012] A practical method for using the exothermic energy released from curing in an epoxy resin system was devised based on the aforementioned energy transfer concept to produce a cured resin matrix with properties influenced by those of temperature curing reactions high, but obtained through a short cure time (<30 minutes, in some cases, <10 minutes) at a lower cure temperature than the start of the high cure temperature reaction in isolation. This short curing method includes selecting a specific combination of epoxy resins and curing agents: at least one multifunctional epoxy resin, an aliphatic or cycloaliphatic amine, an aromatic amine, and optionally, an imidazole as a curing accelerator. The aliphatic or cycloaliphatic amine curing agent is capable of curing the multifunctional epoxy resin at a low curing temperature. The aromatic amine curing agent is capable of curing the multifunctional epoxy resin at a high curing temperature. The components are then mixed to form a curable resin composition, followed by applying heat to the resin composition in an amount or temperature sufficient to initiate the polymerization reaction of the low temperature cure reaction. During the polymerization phase, the low temperature curing reaction generates exothermic energy, the portion of which is sufficient to initiate the high temperature curing reaction polymerization reaction. In the present case, the reaction of epoxy resin, aliphatic or cycloaliphatic amine, and imidazole is the low temperature cure reaction that generates exothermic energy, and the reaction of epoxy resin, aromatic amine and imidazole is the temperature cure reaction elevated.
    [0013] According to a preferred embodiment, a short curing resin composition based on the aforementioned energy transfer concept is composed of (a) at least one multifunctional epoxy resin having an epoxy functionality greater than 1; and (b) a curing composition containing two different types of curing agents: (i) at least one aliphatic or cycloaliphatic amine curing agent having one or more amino groups per molecule; (ii) at least one aromatic amine curing agent having one or more amino groups per molecule; and optionally (iii) an imidazole as a cure accelerator.
    [0014] The short curing resin composition has a curing start temperature of less than 100 ° C, preferably less than 50 ° C (for example, 45 ° C) as measured by DSC at a rate of 5 ° C / minute, and is curable in a temperature range equal to or less than 120 ° C, for example, 110 ° C to 120 ° C, for a period of time less than 10 minutes (<5 minutes in some modes, <3 minutes in other modalities) to obtain a higher degree of cure than that derived from the same composition with only (i) aliphatic / cycloaliphatic amine or (ii) aromatic amine in isolation. When this short-cured resin composition is used to infuse resin into a mold to impregnate a fiber reinforcing material, for example, through a Resin Transfer Molding (RTM) process, greater than 95% degree of cure, or greater than 97% degree of cure, can be obtained after less than 5 minutes of cure (eg 3 minutes) at 120 ° C or less. The degree of cure as discussed in it is measured by DSC at the rate of 5 ° C / minute.
    [0015] After curing for less than 10 minutes (<5 minutes in some embodiments) at a curing temperature of 120 ° C or less, the short curing resin composition provides a cured resin matrix with a glass transition temperature ( Tg) within the range of 110 ° C to 150 ° C, or 115 ° C to 120 ° C, as measured by DSC. The cured resin matrix is a chemically homogeneous network phase.
    [0016] The resin composition discussed above allows for a short cure time in combination with a relatively low curing start temperature. These desirable properties in this short cure resin composition refer to the use of the second higher temperature cure reaction to absorb exothermic energy from the first lower temperature cure reaction as illustrated in FIG. 1.
    [0017] An exemplary embodiment of the energy transfer concept described above is shown in FIG. 2. FIG. 2 shows the DSC traces for the reactivity of bisphenol F epoxy resin and isophorone diamine (a low temperature reaction) and the reactivity of bisphenol F epoxy resin and 3,3'-aminodiphenyl sulfone (an elevated temperature reaction) . Isophorone diamine is a cycloaliphatic amine, and 3,3'-aminodiphenyl sulfone is an aromatic amine. The traits for low temperature reaction and high temperature reaction closely match the concept described in FIG. 1. The third dash shows an equimolar combination of isophorone diamine and 3,3'-aminodiphenyl sulfone in a stoichiometric balance with bisphenol F epoxy resin and illustrates that the two curing agents in combination have a surprising and desired effect. Epoxy Resins
    [0018] As used herein, the term "multifunctional epoxy resin" refers to a compound having an epoxy functionality greater than one, and capable of being cured to a polymeric state. Epoxy resins suitable for use in the present disclosure are composed of polyepoxide having more than one group of epoxide per molecule available for reaction with amine curing agents. In general, multifunctional resins can be saturated, unsaturated, cyclic or acyclic, aliphatic, alicyclic, aromatic or heterocyclic molecules with epoxy functionality. Suitable multifunctional epoxy resins, as an example, include those based on cresol and phenol epoxy novolacs, glycidyl ethers of aldehyde adducts; glycidyl ethers of dialytic diols; diglycidyl ether; diglycidyl ether of diethylene glycol; aromatic epoxy resins; dialytic triglycidyl ethers, polyglycidyl aphphatic ethers; epoxidized olefins; brominated resins; aromatic glycidyl amines; heterocyclic imidines and glycidyl amides; glycidyl ethers; fluorinated epoxy resins.
    [0019] Examples of suitable epoxides include polyglycidyl ethers, which are prepared by reacting epichlorohydrin or epibromohydrin with a polyphenol in the presence of alkali. Suitable polyphenols, therefore, are, for example, resorcinol, pyrocatechol, hydroquinone, bisphenol A (bis (4-hydroxyphenyl) -2,2-propane), bisphenol F (bis (4-hydroxyphenyl) methane), bisphenol S, bis (4 -hydroxyphenyl) -1, l-isobutane, fluorene 4,4'-dihydroxy benzophenone, bis (4-hydroxyphenyl) -1, 1-ethane, bisphenol Z (4,4'-Cyclohexylidene bisphenol), and 1,5-hydroxy -naphthalene. Polyglycidyl ethers of polyalcohols, aminophenols or aromatic diamines are also suitable.
    Additional examples include: polyglycidyl ethers of polyvalent phenols, for example, pyrocatechol; resorcinol; hydroquinone; 4,4'-dihydroxidiphenyl methane; 4,4'-di-idroxy-3,3'-dimethyl diphenyl methane; 4,4'-dihydroxidiphenyl dimethyl methane; 4,4'-dihydroxy diphenyl methyl methane; 4,4'-dihydroxidiphenyl cyclohexane; 4,4'-di-idroxy-3,3'-dimethyl diphenyl propane; 4,4'-dihydroxydiphenyl sulfone; or tris (4-hydroxyphenyl) methane; polyglycidyl ethers of chlorination and bromination products of the aforementioned diphenols; polyglycidyl ethers of novolacs (ie, reaction products of monohydric or polyhydric phenols with aldehydes, formaldehyde in particular, in the presence of an acid catalyst).
    [0021] Additional examples of epoxy resins include diglycidyl ethers of diene-modified phenolic novolacs, reaction products of polyfunctional cycloaliphatic carboxylic acids with epichlorohydrin, cycloaliphatic epoxies, cycloaliphatic epoxy ethers and similar cycloaliphatic epoxy esters.
    [0022] Appropriate multifunctional epoxy resins can include difunctional, tri-functional and tetrafunctional epoxies, in any combination. Examples of difunctional epoxy resins include diglycidyl ethers of bisphenol A (e.g. Epon ™ 828 (liquid epoxy resin), DER 331, DER 661 (solid epoxy resin) from Dow Chemical Co., EJ-190 from Dyne Chemical Co., Tactix 123 of Huntsman Advanced Materials), diglycidyl ethers of bisphenol F (DGEBF), (for example, PY306 from Huntsman Advanced Materials, Epikote ™ 158 (from Momentive). Examples of functional epoxy resins include aminofeol ether triglycidyl ether , for example, Araldite® MY 0510, MY 0500, MY 0600, MY 0610 supplied by Huntsman Advanced Materials. Examples of tetrafunctional epoxy resins include methylene dianiline tetraglycidyl ether (for example Araldite® MY 9655 from Huntsman Advanced Materials), tetraglycidyl diamino diphenyl methane (for example, Araldite® MY 721, MY 720, MY 725, MY 9663, MY 9634, MY 9655 provided by Huntsman Advanced Materials).
    [0023] Multifunctional epoxy resins having functionality based on glycidyl amine or glycidyl ether, or both, are particularly suitable. Multifunctional epoxy resins having both glycidyl amine and glycidyl ether functional groups are more preferable. In certain embodiments, the multifunctional epoxy resins for the short cure resin composition disclosed here can be selected from a group of epoxies represented by the following structures:
    Methylene bis (N, N-diglycidyl aniline)
    Bisphenol F diglycidyl ether
    Triphenylol methane triglycidyl ether
    4-glycidyloxy-N, N-diglycidyl aniline
    3-ulycidyloxy-N, N-diglycidyl aniline
    [0024] Note that structure (I) contains functional groups of glycidyl amine, structures (II) and (III) contain functional group of glycidyl ether, and structures (IV) and (V) contain functional groups of both glycidyl amine and glycidyl ether. Curing agents and accelerators
    [0025] Suitable aliphatic or cycloaliphatic amine curing agents are those having hydrogen-amine functionality greater than 1 and are capable of curing the multifunctional epoxy resin at a temperature within the range of 30 ° C to 100 ° C. Exemplary aliphatic amines include, but are not limited to: triethyl amine, diethyl amine, triethylene tetramine (TETA), diethyl toluene diamine (DETDA), polyether amines (for example, those commercially available from Huntsman Corp, under the trademark Jeffamine). Exemplary cycloaliphatic amines include, but are not limited to: isophorone diamine, menthane diamine, 1,2-diamino cyclohexane, 1,3-diamino cyclohexane, 1,4-diamino cyclohexane, 1,3-di (amino methyl) cyclohexane, 4 , 4'-methylene dicyclohexyl amine, 4,4'-diamino dicyclohexyl methane, 3,3'-dimethyl-4,4'-diaminodicyclohexyl methane, and combinations thereof.
    [0026] Suitable aromatic amine curing agents are those having an amine-hydrogen functionality greater than 1 and are capable of curing the multifunctional epoxy resin at a temperature of 120 ° C or greater, more preferably 130 ° C or greater. Exemplary aromatic amines include, but are not limited to: 3,3’-diamino diphenyl sulfone (3,3’DDS), 4,4’-diamino diphenyl sulfone (4,4’DDS); 4,4'-methylene-bis (3-chloro-2,6-diethylaniline) (MCDEA); 4,4'-methylene-bis (2,6-diethyl aniline) (MDEA); 2,6-diethyl aniline (DEA); dianiline as methylene dianiline (MDA), 9,9-Bis (3-chloro-4-amino phenyl) -9H-fluorene (CAF).
    [0027] It has been found that imidazole in combination with at least one of the aliphatic and aromatic amine curing agents discussed above causes a more premature curing start temperature and increases reactivity. Suitable imidazole accelerators include, but are not limited to, imidazole, methyl imidazole, ethyl methyl imidazole, ethyl methyl imidazole proprionitrile, cyanoethyl phenyl bismethyl imidazole. Preparation of resin composition
    [0028] In general, the curable resin composition based on the energy transfer concept of the present disclosure is prepared by mixing one or more epoxy resins with a hardener composition containing amines and optionally imidazole. The preparation of the hardener composition may include the application of heat to dissolve the aromatic amine in the aliphatic amine followed by cooling before adding the imidazole. The epoxy resin (s) can be preheated as needed to decrease its viscosity before mixing it with the amines. The stoichiometry of the epoxy-amine mixture is based on an equivalent ratio of amine groups to epoxy groups of 0.1: 2, preferably 1: 1. The weight ratio of aromatic amine to aliphatic amine can vary, depending on the selected amines, to obtain the desired stoichiometric ratio. Imidazole can be present in less than 2.0% by weight based on the total weight of the resin composition.
    [0029] In one embodiment, the short cure resin contains 100 parts of multifunctional epoxy resin (s), 10 to 90 parts of curing agent mixture, and 0 to 10 parts of imidazole. Application
    [0030] The curable resin composition, as described above, is suitable for impregnating (or infusing) fiber reinforcements using conventional resin infusion techniques to form composite materials and structures. The resin composition disclosed is particularly suitable, but not limited to, 2-part resin transfer molding (RTM), in which a low viscosity resin system is important. RTM is a process by which a low viscosity resin composition is introduced into a closed mold that contains a dry fiber preform. The fiber preform is made up of reinforcement fibers, which can take the form of continuous fiber layers or woven cloth. The fiber preform can be molded into a desired three-dimensional configuration suitable for making a composite part. The resin composition can be prepared by combining part A (epoxy resin composition) and part B (hardener composition). The pre-mixed and formulated resin composition is then injected into the mold which is kept under low pressure or under vacuum. Low resin viscosity at the injection temperature is desirable to obtain optimum mold filling and fiber wetting. After the mold is filled, it is heated according to the appropriate curing program. The resulting molded part can then be removed from the mold and post-cured as needed. To obtain good fiber infusion and low void content during RTM processing, resin viscosity below approximately 1 Poise at the injection temperature of approximately 50 to 100 ° C is highly desirable. In addition, the resin system must keep this viscosity low for a period of time sufficient to fully fill the mold and infuse the fiber preform. For RTM processing, this time is often measured in terms of the life of the resin, which can be defined as the time required for the resin to reach 5 Poise.
    [0031] Reinforcement fibers for making composite structures can take the form of continuous fibers, cut fibers, or woven cloth. The fiber material can be selected from, but is not limited to, carbon, graphite, aromatic polyamide (Kevlar), poly (benzothiazole) and poly (benzimidazole), poly (benzoxazole) (PBO), alumina, titania, quartz, glass , aramid, polyethylene, polyester, silicon carbide and combinations thereof. The selection of the type of fiber reinforcement is determined by the performance requirements for the composite structure. For many aircraft applications where high strength and low weight are critical, graphite or carbon fibers with high modulus are the preferred reinforcements.
    [0032] The relative proportions of fiber reinforcement and resin matrix in the composite material can be varied, as determined by the intended application. In an embodiment for advanced composite applications, the weight fraction of the fiber reinforcement present in the composite can vary between approximately 50% and 70% by weight, preferably 69%, based on the total weight of the composite.
    [0033] One or more functional additives can be added to the curable resin composition prior to resin infusion to impart certain properties to the uncured composition or the cured composite structure. Functional additives can be added to influence one or more of the mechanical, rheological, electrical, optical, chemical, flame resistant and / or thermal properties of the cured or uncured epoxy composition. Examples of additives may include, but are not limited to, flame retardants, ultraviolet (UV) stabilizers, inorganic fillers, conductive particles or flakes. EXAMPLES
    [0034] The following non-limiting examples are illustrative of the short curing method and resin composition based on the aforementioned energy transfer concept and should not be construed as limiting its scope in any way. Example 1
    [0035] Five formulations were prepared as revealed in table 1 and analyzed using differential scanning calorimetry. Formulation 5 covers the concept of energy transfer discussed above. In Table 1, PY306 is bisphenol F diglycidyl ether, CN or Curamid CN is 2-ethyl-4-methyl-177-imidazole-1-propanitrile (a curing accelerator), 3,3'DDS is 3,3 'diaminodiphenyl sulfone (an aromatic amine), IDA is isophorone diamine (an aliphatic amine). All quantities are expressed in grams. TABLE 1

    [0036] The formulations were analyzed using DSC (TA Instruments Q2000) and the results are shown in table 2. TABLE 2

    [0037] As can be seen from Table 2, formulation 5 has the lowest curing initiation temperature and produced significantly less exothermic energy during a 5 minute cure compared to the other formulations. Example 2
    [0038] A short curing resin composition was prepared based on the formulation disclosed in TABLE 3. TABLE 3

    [0039] The formulation was divided into two parts, part A contained the components of epoxy and part B contained the components of amine and imidazole. Part A was prepared by heating DGEBF (70 ° C) until a clear fluid was obtained. Triglycidyl m-aminophenol (room temperature) was added to this fluid and the components mixed until homogeneous using an air line. Part B was prepared by dissolving 3,3'DDS in isophorone diamine (80 ° C) with stirring, the mixture was allowed to cool to room temperature before adding imidazole.
    [0040] Part A and part B were degassed separately (30 ° C, -1 atm) for 15 minutes before being combined together in a mass ratio of 2.2: 1 (A: B) using line agitation of air to obtain homogeneity. The mixture was then quickly degassed again to remove air introduced during the degassing phase (30 ° C, -1 atm). 10 g of the combined parts A and B were transferred to an aluminum dish and heating was carried out for 5 minutes in an oil bath (110 ° C), after which the dish was removed and allowed to cool to room temperature.
    [0041] For comparison, cured resin samples were prepared using commercially available RTM epoxy resins: CYCOM 890, CYCOM 823, PRISM EP2400. The cured resin samples were then characterized using the following test methods / instruments:
    The results are shown in Table 4. TABLE 4

    [0042] These results show that the short-curing resin can achieve mechanical properties comparable to other commercial resin systems in a much shorter curing time of 5 minutes. Example 3
    [0043] A short cure formulation was prepared as detailed in Table 5. TABLE 5
    TABLE 6 shows courses of experiment in which more than 95% degree of cure was obtained in 2-3 minutes of cure time. TABLE 6

    [0044] For each pass, part A and part B were prepared based on the resin formulation shown in table 5. Part A was prepared by mixing pre-heated (70 ° C) PY306 with MY0610 at room temperature using a line of air until a visually homogeneous mixture was obtained. Part B was prepared by dissolving 3,3'DDS in isophorone diamine (IDA) (80 ° C) for 10 minutes until dissolved. The mixture was then cooled to 50 ° C before 0.2 g of imidazole was added with stirring to distribute.
    [0045] Part A and part B were degassed at room temperature before being combined based on the mixing ratio and temperature revealed in Table 6. 10 g of the combined parts A and B were transferred to an aluminum plate, and heating it was performed in an oil bath according to the cure temperature shown in Table 6, and then the cure time was recorded. Example 4
    [0046] The resin of example 3 was taken and introduced in a carbon fiber preform made of IMS65 12k unidirectional fibers and having an area weight of 196 gsm, through High Pressure RTM processing, using a curing cycle 3 minutes at 120 ° C to provide a laminate with a volume fraction of 49%.
    [0047] For comparison, the same laminate was prepared using epoxy based resin CYCOM 977-2 (available from Cytec Engineered Materials Inc.) and a curing cycle of 180 ° C for 3 h. The characteristics of the two laminates, normalized to 50%, are summarized in FIG. 3.
    [0048] These results show that the mechanical performance of the carbon fiber laminate derived from the short-cured resin is comparable to that of the resin system known to be used in high-performance aerospace applications and typically cured using significantly longer curing times longer and higher curing temperature.
    权利要求:
    Claims (15)
    [0001]
    1. Curable epoxy resin composition, characterized by the fact that it comprises: (a) at least one multifunctional epoxy resin having an epoxy functionality greater than 1 and that functionality is based on glycidyl amine, or glycidyl ether or both; (b) a hardener composition comprising: (i) at least one aliphatic or cycloaliphatic amine curing agent having one or more amino groups per molecule and capable of curing said at least one multifunctional epoxy resin at a temperature within range of 30 ° C to 100 ° C, wherein said aliphatic or cycloaliphatic amine curing agent is selected from a group consisting of: isophorone diamine, triethyl amine, diethyl amine, triethylene tetramine (TETA), polyether amines; (ii) at least one aromatic amine curing agent having one or more amino groups per molecule and capable of curing said at least one multifunctional epoxy resin at a temperature of 120 ° C or greater, wherein said curing agent aromatic amine cure is selected from a group consisting of: 3.3 'diamino diphenyl sulfone, 4.4' diamino diphenyl sulfone; 4,4'-methylene-bis (3-chloro-2,6-diethyl aniline) (MCDEA), 4,4'-methylene-bis- (2,6-diethyl aniline) (MDEA), 2,6-diethyl aniline (DEA), dianiline; wherein said epoxy resin composition has a curing start temperature of <50 ° C as measured by Differential Scanning Calorimetry (DSC) at a rate of 5 ° C / minute and is curable at a temperature of 120 ° C or less for a period of time less than 10 minutes to obtain a higher degree of cure than that derived from the same composition with only (i) aliphatic or cycloaliphatic amine or (ii) aromatic amine in isolation.
    [0002]
    2. Curable epoxy resin composition according to claim 1, characterized by the fact that the hardener composition further comprises an imidazole as a curing accelerator.
    [0003]
    3. Curable epoxy resin composition according to claim 1 or 2, characterized by the fact that the hardener composition comprises isophorone diamine and 3,3'-diamine diphenyl sulfone.
    [0004]
    4. Curable epoxy resin composition according to any one of claims 1 to 3, characterized by the fact that the at least one multifunctional epoxy resin comprises a combination of a difunctional epoxy resin and a trifunctional or tetrafunctional epoxy resin.
    [0005]
    5. Curable epoxy resin composition according to any one of claims 1 to 4, characterized by the fact that it is curable for a period of time of 5 minutes or less.
    [0006]
    6. Curable epoxy resin composition according to any one of claims 1 to 5, characterized by the fact that the equivalent ratio of amine groups to epoxy groups in the epoxy resin composition is 0.1: 2.
    [0007]
    7. Curable epoxy resin composition according to any one of claims 1 to 6, characterized by the fact that the equivalent ratio of amine groups to epoxy groups is 1: 1.
    [0008]
    8. Curable epoxy resin composition according to any one of claims 1 to 7, characterized by the fact that the multifunctional epoxy resin is selected from a group consisting of:
    [0009]
    9. Method for curing an epoxy resin system, said method characterized by the fact that it comprises: (a) selecting the following components: (i) at least one multifunctional epoxy resin having an epoxy functionality greater than 1, this functionality is based on at least one glycidyl amine and glycidyl ether; (ii) an aliphatic or cycloaliphatic amine curing agent capable of curing said multifunctional epoxy resin at a temperature within the range of 30 ° C to 100 ° C, said aliphatic or cycloaliphatic amine curing agent being selected from a group consisting of: isophorone diamine, triethyl amine, diethyl amine, triethylene tetramine (TETA), polyether amines; (iii) an aromatic amine curing agent capable of curing said multifunctional epoxy resin at a temperature of 120 ° C or higher, said aromatic amine curing agent being selected from a group consisting of: 3,3 'diamino diphenyl sulfone, 4.4 'diamino diphenyl sulfone; 4,4'-methylene-bis (3-chloro-2,6-diethyl aniline) (MCDEA), 4,4'-methylene-bis- (2,6-diethyl aniline) (MDEA), 2,6-diethyl aniline (DEA), dianiline; and (iv) an imidazole as a cure accelerator; (b) mixing said components to form a curable resin composition; and (c) applying heat to the resin composition in an amount sufficient to initiate the polymerization reaction of components (i) + (ii) + (iv), in which the reaction of components (i) + (ii) + (iv ) generates exothermic energy, and a portion of said exothermic energy is sufficient to initiate the polymerization reaction of the components (i) + (iii) + (iv).
    [0010]
    10. Method according to claim 9, characterized by the fact that step (c) is carried out for <5 minutes at a temperature of 120 ° C or less to produce a cured resin having a glass transition temperature (Tg) within the range of 110 ° C to 150 ° C, preferably 115 ° Cal20 ° C.
    [0011]
    11. Method according to claim 9 or 10, characterized by the fact that the cured resin composition comprises isophorone diamine and 3,3'-diamino diphenyl sulfone.
    [0012]
    12. Method of making a composite structure, characterized by the fact that it comprises: preparing a curable resin composition comprising: i. at least one multifunctional epoxy resin having an epoxy functionality greater than 1; ii. an aliphatic or cycloaliphatic amine curing agent capable of curing said multifunctional epoxy resin at a temperature within the range of 30 ° C to 100 ° C, said aliphatic or cycloaliphatic amine curing agent being selected from a group consisting of : isophorone diamine, triethyl amine, diethyl amine, triethylene tetramine (TETA), polyether amines; iii. an aromatic amine curing agent capable of curing said multifunctional epoxy resin at a temperature of 120 ° C or higher, said aromatic amine curing agent being selected from a group consisting of: 3,3 'diamino diphenyl sulfone, 4.4 'diamino diphenyl sulfone; 4,4'-methylene-bis (3-chloro-2,6-diethyl aniline) (MCDEA), 4,4'-methylene-bis- (2,6-diethyl aniline) (MDEA), 2,6-diethyl aniline (DEA), dianiline; and iv. an imidazole as a cure accelerator; infusing a fiber reinforcing material with said curable resin composition; and curing the infused fiber reinforcement material for 5 minutes or less at a temperature of 120 ° C or less to produce a cured composite structure having a glass transition temperature (Tg) within the range of 110 ° Cal50 ° C.
    [0013]
    13. Method according to claim 12, characterized in that the curable resin composition comprises isophorone diamine and 3,3'-diaminodiphenylsulfone.
    [0014]
    14. Method, according to claim 12 or 13, characterized by the fact that the infusion of the fiber reinforcing material is carried out in a mold via a Resin Transfer Molding (RTM) process.
    [0015]
    Method according to any one of claims 12 to 14, characterized in that said fiber reinforcing material comprises dry fibers made from materials selected from a group consisting of: carbon, graphite, aromatic polyamide, poly ( benzothiazole) and poly (benzimidazole), poly (benzoxazole) (PBO), alumina, titania, quartz, glass, aramid, polyethylene, polyester, silicon carbide and combinations thereof.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112014010528B1|2020-11-10|curable epoxy resin composition, and methods for curing an epoxy resin system and for making a composite structure
    BRPI1102649A2|2012-11-20|makeup and composite
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    同族专利:
    公开号 | 公开日
    KR102054360B1|2019-12-10|
    MX2014005919A|2014-06-05|
    MX341414B|2016-08-19|
    TW201343708A|2013-11-01|
    TWI557150B|2016-11-11|
    CA2865512C|2018-12-04|
    EP2782946A1|2014-10-01|
    MY166877A|2018-07-24|
    ES2625027T3|2017-07-18|
    US9039951B2|2015-05-26|
    KR20140138110A|2014-12-03|
    KR20190012267A|2019-02-08|
    BR112014010528A2|2017-05-02|
    JP6147770B2|2017-06-14|
    US20150218345A1|2015-08-06|
    JP2015508125A|2015-03-16|
    US20130225788A1|2013-08-29|
    AU2013226337A1|2014-05-15|
    CA2865512A1|2013-09-06|
    GB201203341D0|2012-04-11|
    AU2013226337B2|2015-02-12|
    WO2013130378A1|2013-09-06|
    EP2782946B1|2017-02-08|
    CN103946264A|2014-07-23|
    US9249282B2|2016-02-02|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-08-11| B09A| Decision: intention to grant|
    2020-11-10| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 25/02/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    GB1203341.1|2012-02-27|
    GBGB1203341.1A|GB201203341D0|2012-02-27|2012-02-27|Curable resin composition and short-cure method|
    PCT/US2013/027573|WO2013130378A1|2012-02-27|2013-02-25|Curable epoxy composition and short -cure method|
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