Novel bismaleimide compounds with improved solubility and their use in curable compositions

Abstract

The present invention relates to certain bismaleimide compounds, curable compositions comprising at least one of these bismaleimides and at least one specific polyimide. Furthermore, the present invention relates to a method for producing these curable compositions and to the crosslinked polymers obtained by this method. Finally, the present invention relates to a method for producing a composite material, comprising curing a mixture of a fibrous or particulate reinforcing material and the curable composition or crosslinked polymer of the present invention, and to the composite material obtained.

Description

[Technical field]

[0001] The present invention relates to certain bismaleimide compounds, curable compositions comprising at least one of these bismaleimides and at least one specific polyimide. Furthermore, the present invention relates to a method for producing these curable compositions and to the crosslinked polymers obtained by this method. Finally, the present invention relates to a method for producing a composite material, comprising curing a mixture of a fibrous or particulate reinforcing material and the curable composition or crosslinked polymer of the present invention, and to the composite material obtained.

[0002] Commercially known bismaleimide (BMI) monomers, including aliphatic monomers, are known to have low solubility. Therefore, to produce solvent-based formulations with high resin content used in the production of printed circuit boards, the use of prepolymerized or chain-extended BMI is necessary, which means additional production costs, toxic chain extenders, and increased solution viscosity (Evsyukov, et al., Curr. Trends Polym. Sci, 2020, 20, 1-28). Alternatively, amide-based solvents with high toxicity and high boiling points can be used to some extent (even in these powerful solvents, BMI has limited solubility).

[0003] To economically manufacture solution-processed prepregs and fiber-reinforced laminates therefrom, highly soluble aliphatic BMIs are required. To date, no alternative aliphatic BMIs are known that have high solubility and provide high heat resistance. 36Dimeric BMI, also known as X-BMI, based on dimeric diamines (DeFusco, et al., NWC Tech. Publ. 6543, Naval Weapons Center, China Lake, California, USA, 1984; Dershem et al., U.S. Pat. No. 7102015, 2006), is highly soluble in organic solvents but has low heat resistance in the cured form due to the long distance between the functional maleimide groups. As a result, cured resins based on X-BMI have been reported to exhibit Tg (glass transition temperature) in the range of 60-95°C, which is about 200°C lower than standard BMI resins (Gouzman, et al., Adv. Mater. Technol., 2019, 4, 1900368; Evsyukov, et al., Curr. Trends Polym. Sci, 2020, 20, 1-28).

[0004] Furthermore, it is desirable to improve the processability of solution-based BMI resins for the production of BMI and BMI / comonomer products. Due to the increasing limitations of the use of toxic amide-type solvents, which are typical BMI processing solvents according to the prior art, there is a need to develop resins that can be processed from traditional low boiling solvents, preferably below 120°C, and more preferably below 100°C.

[0005] In addition, improved solubility should allow for improved compatibility with other monomers and comonomers in hot melt formulations.

[0006] It was therefore an object of the present invention to provide a BMI having high solubility, preferably at least 30%, more preferably at least 34%, in preferably at least three low boiling point solvents.

[0007] Surprisingly, it has been found that the use of certain propane-1,3-diamines as starting materials in standard BMI synthesis (reaction with maleic anhydride followed by cyclodehydration) results in the formation of highly soluble bismaleimides of formula (I) that can be used, for example, in solution-based BMI formulations in conventional low boiling solvents and hot melt formulations without prepolymerization or chain extension. The high solubility in conventional low boiling solvents allows for highly concentrated solutions to be obtained without prepolymerization or chain extension.

[0008] In the present invention, 2-(3,3,5-trimethylcyclohexyl)propane-1,3-diamine is used as an example compound of a specific propane-1,3-diamine. It is described that 2-(3,3,5-trimethylcyclohexyl)propane-1,3-diamine is suitable for use as a curing agent for epoxy resin compositions by (i) the reaction of isophorone with malononitrile, and (ii) the hydrogenation of 2-(3,5,5-trimethylcyclohex-2-en-1-ylidene)malononitrile (II) using a cobalt alloy catalyst. Partial hydrogenation of II by reaction of II with H2 in THF in the presence of Pd / alumina at 75°C and 50 bar H2 for 5 hours, followed by completion of hydrogenation of the resulting product solution using a cobalt alloy containing 75.9 wt% cobalt, 20.0 wt% aluminum, 1.5 wt% chromium, and 2.6 wt% nickel at 100°C and 100 bar H2 for 5 hours, gives 2-(3,3,5-trimethylcyclohexyl)propane-1,3-diamine in 76% yield (EP 3255035).

[0009] Furthermore, 2-(3,3,5-trimethylcyclohexyl)propane-1,3-diamine is used as a curing agent in an epoxy resin composition comprising (a) an epoxy resin, (b) 0.1-100 wt. % of 2-(3,3,5-trimethylcyclohexyl)propane-1,3-diamine and 0-99.9 wt. % of a crosslinking agent consisting of other diamines and / or polyamines, (c) 0.1-10 wt. % of other crosslinking catalysts, (d) optionally one or more crosslinking precursors, and (e) optionally other additives (EP 3255079 A1).

[0010] definition Terms used collectively in this specification, including the appended claims, have the following meanings unless expressly stated otherwise.

[0011] The term "curable" as used herein means that the original compound or mixed material can be converted into a solid, substantially non-flowable material by, for example, chemical reaction, crosslinking, or crosslinking by radiation.

[0012] As used herein, the term "mixture" means a combination of two or more separate, chemically distinct compounds that are not physically or mechanically aggregated or chemically bonded.

[0013] The term "comonomer" as used herein means a compound capable of undergoing polymerization or copolymerization, thereby contributing a constitutional unit to the essential structure of a polymer.

[0014] As used herein, the term "comonomer component" means one comonomer or a mixture of two or more comonomers, preferably one comonomer or a mixture of two to four comonomers.

[0015] The term "alkenylphenol" as used herein means an organic compound containing at least one alkenyl-substituted phenol group. The term "alkenylphenol" includes alkylphenols in which two phenol groups are bridged through a difunctional group, such as alkenylbisphenols. An example is 2,2'-diallylbisphenol A.

[0016] The term "alkenyl phenyl ether" as used herein refers to an organic compound containing at least one alkenyloxyphenyl group, i.e. an organic compound containing an ether group in which an ether oxygen atom is bonded to an alkenyl residue on the one hand and to a phenyl residue on the other hand. The term "alkenyl phenyl ether" includes alkenyl phenyl ethers in which two phenyl groups are bridged by a difunctional group, such as alkenyl bisphenol ethers. An example is the diallyl ether of bisphenol A.

[0017] The term "alkenylphenol ether" as used herein refers to an organic compound containing at least one alkenylphenoxy group, e.g., an ether group in which the ether oxygen atom is bonded to an alkenylphenyl group on the one hand and to an alkyl or aryl group on the other hand. The term "alkenylphenol ether" includes organic compounds in which two alkenylphenoxy groups are bridged by a difunctional group, e.g., an aromatic group such as a benzophenone group. Examples include bis-(o-propenylphenoxy)benzophenone.

[0018] The term "polyamine" as used herein means an organic compound having two or more primary amino groups -NH2. Examples include, but are not limited to, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, diaminodiphenylindane, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, m-xylylenediamine, and aliphatic diamines such as ethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, 1,12-diaminododecane.

[0019] The term "aminophenol" as used herein means an amino-substituted phenol. Examples include m-aminophenol and p-aminophenol.

[0020] The term "amino acid hydrazide" as used herein means any hydrazide of an amino acid. Examples include m-aminobenzhydrazide and p-aminobenzhydrazide.

[0021] The term "cyanate ester" as used herein refers to bisphenols or polyphenols, e.g., novolaks, derivatives in which the hydrogen atom of a phenolic OH group has been replaced with a cyano group resulting in an --OCN group. Examples include bisphenol A dicyanate esters, commercially available, for example, as Primaset BADCy from Lonza or AroCy B-10 from Huntsman, as well as other Primaset or AroCy types, such as bis(3,5-dimethyl-4-cyanatophenyl)methane (AroCy M-10), 1,1-bis(4-cyanatophenyl)ethane (AroCy L-10), 2,2-bis(4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropane (AroCy F-10), 1,3-bis(1-(4-cyanatophenyl)-1-methylethylidene)benzene (AroCy XU-366), di(4-cyanatophenyl)thioether (AroCy RDX-80371; AroCy T-10), bis(4-cyanatophenyl)dichloromethylidenemethane (AroCy RD98-228), bis(4-cyanatophenyl)octahydro-4,7-methanoindene (AroCy XU-71787.02L), as well as bis(4-cyanatophenyl)methane, bis(3-methyl-4-cyanatophenyl)methane, bis(3-ethyl-4-cyanatophenyl)methane, di(4-cyanatophenyl)ether, 4,4-dicyanatobiphenyl, 1,4-bis(1-(4-cyanatophenyl)-1-methylethylidene)benzene, resorcinol dicyanate. A preferred example is bisphenol A dicyanate ester.

[0022] A bond in brackets represents a bond connecting the moiety within the brackets to another moiety in the same compound. For example, the group shown below [ka] in the above, the two bonds in the bracketed ethenyl group on the right side link this moiety to another moiety in the compound that contains this ethenyl group.

[0023] As used herein, the term "halogen" means a fluorine, chlorine, bromine, or iodine atom, preferably a fluorine or chlorine atom, more preferably a fluorine atom.

[0024] As used herein, "alkyl" refers to a linear or branched alkyl group. The term "alkyl having n to m carbon atoms" refers to an alkyl group having n to m carbon atoms. Unless otherwise specified, "alkyl" refers to an alkyl group having 1 to 6 carbon atoms. In the context of the present invention, preferred alkyl groups are linear or branched alkyl groups having up to 4 carbon atoms. Examples of linear and branched alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, isomeric pentyls, isomeric hexyls, preferably methyl and ethyl, most preferably methyl.

[0025] As used herein, "alkylene" refers to a difunctional alkyl group. The term "alkylene having n to m carbon atoms" refers to an alkylene group having n to m carbon atoms. Unless otherwise specified, "alkylene" refers to an alkylene group having 1 to 12 carbon atoms. In the context of the present invention, preferred alkylene groups are those having 1 to 9 carbon atoms, more preferably 1 to 6 carbon atoms. Examples include, but are not limited to, methylene, ethylene, propylene, butylene, hexamethylene, and 2,2,4-trimethylhexamethylene. Particularly preferred is 2,2,4-trimethylhexamethylene.

[0026] As used herein, "alkenylene" refers to a difunctional alkenyl group. The term "alkenylene having n to m carbon atoms" refers to an alkenylene group having n to m carbon atoms. Unless otherwise specified, "alkenylene" refers to an alkenylene group having 2 to 12 carbon atoms. In the context of the present invention, preferred alkenylene groups are those having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms. Examples include, but are not limited to, ethenylene, propenylene, and butenylene. Particularly preferred is ethenylene.

[0027] As used herein, "alkoxy" refers to a straight or branched alkyl group attached to a compound via an oxygen atom (-O-). The term "alkoxy having n to m carbon atoms" refers to an alkoxy having n to m carbon atoms. Unless otherwise stated, "alkoxy" refers to a straight or branched alkoxy group having up to 6 carbon atoms. In the context of the present invention, preferred alkoxy groups are straight or branched alkoxy groups having up to 4 carbon atoms.

[0028] As used herein, "alkenyl" refers to a straight or branched hydrocarbon group containing a carbon-carbon double bond. The term "alkenyl having n to m carbon atoms" refers to an alkenyl having n to m carbon atoms. Unless otherwise specified, "alkenyl" refers to a straight or branched hydrocarbon group containing a carbon-carbon double bond in any desired position and containing 2 to 10 carbon atoms. In the context of the present invention, preferred alkenyl groups contain a carbon-carbon double bond in any desired position and contain 2 to 6, more preferably 2 to 4, carbon atoms. Examples of alkenyl groups include, but are not limited to, ethenyl, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, and isobutenyl. Preferred examples are 1-propenyl and 2-propenyl.

[0029] As used herein, the term "monocyclic carbocyclic group" means a "monocyclic carbocyclic aliphatic group" or a "monocyclic carbocyclic aromatic group."

[0030] The term "bicyclic carbocyclic group" as used herein means a "bicyclic carbocyclic aliphatic group" or a "bicyclic carbocyclic aromatic group".

[0031] As used herein, the term "monocyclic carbocyclic aliphatic group" means a "cycloalkylene group."

[0032] In this specification, "cycloalkyl" refers to a monofunctional saturated carbocyclic ring system. The term "cycloalkyl having n to m carbon atoms" refers to a cycloalkyl having n to m carbon atoms. Preferably, cycloalkyl refers to a cycloalkyl group having 5 to 6 carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropanyl, cyclobutanyl, cyclopentanyl, cyclohexanyl, cycloheptanyl, or cyclooctanyl, preferably cyclopentanyl and cyclohexanyl.

[0033] In this specification, "cycloalkylene" means a bifunctional saturated carbocyclic ring system. The term "cycloalkylene having n to m carbon atoms" means a cycloalkylene having n to m carbon atoms. Unless otherwise specified, "cycloalkylene" means a cycloalkylene group having 3 to 8 carbon atoms. In the context of the present invention, preferred cycloalkylene groups are cycloalkylene groups having 5 to 7, more preferably 5 or 6 carbon atoms. Examples include, but are not limited to, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, or cyclooctylene, preferably cyclopentylene and cyclohexylene.

[0034] As used herein, a "bicyclic carbocyclic aliphatic group" refers to a bifunctional condensed, bridged or fused bicyclic saturated ring system. Unless otherwise specified, a "bicyclic carbocyclic aliphatic group" refers to a bifunctional condensed, bridged or fused bicyclic saturated ring system having from 9 to 20 carbon atoms. Examples include, but are not limited to, decalinyl, hydrindanyl, and norbornyl.

[0035] The term "monocyclic or bicyclic aromatic group" as used herein means a bifunctional monocyclic or bicyclic aromatic system, preferably having 6 to 12 carbon atoms, preferably a monocyclic aromatic system. Examples include, but are not limited to, toluene, phenylene, naphthylene, tetrahydronaphthylene, indenylene, indanylene, pentanylene, fluorenylene, etc., preferably toluene, phenylene, or indanylene.

[0036] The term "aryl" as used herein means a monofunctional monocyclic or bicyclic aromatic system, preferably having 6 to 12 carbon atoms, preferably a monocyclic aromatic system. Examples include, but are not limited to, toluyl, phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl, fluorenyl, etc., preferably toluyl, phenyl, or indanyl.

[0037] As used herein, the term "heterocyclic group" means a "heterocycloaliphatic group" or a "heterocyclic aromatic group."

[0038] As used herein, the term "heterocyclic aliphatic group" refers to a difunctional saturated ring system containing carbon atoms and one, two, or three atoms selected from nitrogen, oxygen, and / or sulfur. Preferred heterocyclic aliphatic groups are those containing 3 to 5 carbon atoms and one nitrogen, oxygen, or sulfur atom.

[0039] The term "heterocyclic aromatic group" as used herein refers to a monocyclic aromatic 5- or 6-membered ring containing 1, 2, or 3 atoms selected from nitrogen, oxygen, and / or sulfur, or a bicyclic aromatic group containing two 5- or 6-membered rings, where one or both rings can contain 1, 2, or 3 atoms selected from nitrogen, oxygen, or sulfur. Examples include, but are not limited to, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxydiazolyl, isoxazolyl, thiadiazolyl, tetrazolyl, pyrazolyl, imidazolyl, thiazolyl, thienyl, quinolinyl, isoquinolinyl, cinnolinyl, pyrazolo[1,5-a]pyridyl, imidazo[1,2-a]pyridyl, quinoxalinyl, benzothiazolyl, benzotriazolyl, indolyl, and indazolyl.

[0040] As used herein, the term "bridged polycyclic group" means a group consisting of at least two groups selected from a monocyclic carbocyclic aromatic group, a bicyclic carbocyclic aromatic group, and a cycloalkylene group, which groups are linked together by a direct carbon-carbon bond or a divalent group.

[0041] Preferred divalent groups are oxy, thio, alkylene groups having 1 to 3 carbon atoms, sulfone, methanone, and the following groups: [ka] [In the formula, R 23 ~R 28 are independently selected from alkyl groups having 1 to 6 carbon atoms; R 29 and R 30 are independently selected from alkylene groups having 1 to 6 carbon atoms. It is.

[0042] In one embodiment, the term "bridged polycyclic group" refers to a group that is linked by a direct carbon-carbon bond or by an oxy group, a thio group, an alkylene group having 1 to 3 carbon atoms, a sulfone group, a methanone group, or the following groups: [ka] [In the formula, R 23 ~R 28 are independently selected from alkyl groups having 1 to 6 carbon atoms; R 29 and R 30 are independently selected from alkylene groups having 1 to 6 carbon atoms. "R" refers to a group consisting of two monocyclic carbocyclic aliphatic groups linked together by a divalent group such as one of:

[0043] In one embodiment, the term "bridged polycyclic group" refers to a group that is linked by a direct carbon-carbon bond or by an oxy group, a thio group, an alkylene group having 1 to 3 carbon atoms, a sulfone group, a methanone group, or the following groups: [ka] [In the formula, R 23 ~R 28 are independently selected from alkyl groups having 1 to 6 carbon atoms; R 29 and R 30 are independently selected from alkylene groups having 1 to 6 carbon atoms. "Cyclohexylene" means a group consisting of two cyclohexylene groups linked together by a divalent group such as one of

[0044] In one embodiment, the term "bridged polycyclic group" refers to a group consisting of two phenylene groups linked to each other by a direct carbon-carbon bond or by a divalent group, such as an oxy group, a thio group, an alkylene group having 1 to 3 carbon atoms, a sulfone group, or a methanone group.

[0045] As used herein, the addition of the term "unsubstituted" or "substituted" means that the respective group is unsubstituted or has 1 to 4 substituents selected from alkyl, alkoxy, and halogen. Preferred substituents are methyl or ethyl.

[0046] As used herein, the terms "x functional group", "y functional group", "y' functional group", and "y" functional group" refer to a group that is attached to the remainder of a compound via an x, y, y', or y" bond, respectively. Preferably, the "x functional group", "y functional group", "y' functional group", and "y" functional group" are difunctional groups, i.e., x, y, y', and y" are preferably 2.

[0047] As used herein, the term "difunctional group" refers to a group that is attached to the remainder of a compound through two bonds. Difunctional groups include, but are not limited to, difunctional aliphatic groups and difunctional aromatic groups. Difunctional aliphatic groups include, but are not limited to, the following groups: [ka] Examples include:

[0048] Difunctional aromatic groups include, but are not limited to, the following groups: [ka] Examples include:

[0049] Further bifunctional groups include, but are not limited to, the following groups: [ka] Examples include:

[0050] The term "glass transition temperature" or "Tg" as used herein means the temperature of a reversible transition of an amorphous solid, e.g., a polymer, between a highly elastic state and a vitreous (glassy) state, when the polymer becomes brittle on cooling and softens on heating. More specifically, it defines a pseudo-second-order phase transition that, when a supercooled melt is cooled, produces a glassy structure and properties similar to those of a crystalline material, e.g., an isotropic solid material.

[0051] The solubility of the compounds according to the invention is determined as follows: 10 g of sample is weighed into a 100 ml Erlenmeyer flask. 50 ml of solvent is added to the flask and the mixture is stirred with a magnetic stir bar for 1 h at 25 °C to ensure the formation of a saturated solution. If the entire sample is dissolved, an additional portion of sample should be added and the mixture stirred for another hour. Eventually, some of the undissolved material should be clearly visible at the bottom of the flask. The supernatant is then filtered through a folded filter. Approximately 15 g of the filtrate is weighed into a tared round-bottom flask and the solvent is evaporated to dryness in a rotary evaporator at 90 °C under reduced pressure. Finally, the flask is dried in a vacuum drying cabinet at 120 °C under reduced pressure for 2 h, cooled to room temperature in a desiccator and weighed.

[0052] The solubility value is then calculated as follows: Solubility [%] = ([output weight] x 100) / [original sample weight]

[0053] Bismaleimides according to the invention In a first aspect, the present invention provides a compound of formula (I) [ka] [In the formula, R is a substituted or unsubstituted C 3~7 Alicyclic ring, preferably C 5~6 an alicyclic ring, or Formula (II) [ka] [In the formula, R 1 and R 2 may be the same or different, C 1~12 , preferably C 3~6 and an alkyl group or an alkenyl group. is the basis of In a preferred embodiment, the bismaleimide is 3~7 Alicyclic rings contain 1 to 5 C 1~4 It is substituted with an alkyl group.

[0054] In a preferred embodiment, R of the bismaleimide of formula (I) is a bismaleimide of formula (III) [ka] [In the formula, R 3 ~R 6 may be the same or different, H or C 1~3 alkyl groups] is a cyclohexyl group.

[0055] In a preferred embodiment, the bismaleimide has the formula (IV): [ka] and 2-(3,3,5-trimethylcyclohexyl)propane-1,3-bismaleimide having the formula:

[0056] Curable compositions according to the present invention In a second aspect, the present invention provides a method for producing a pharmaceutical composition comprising the steps of: (i) at least one bismaleimide according to the present invention; (ii) General formula (V) [ka] [In the formula, B is a difunctional group containing a carbon-carbon double bond; A is the y functional group, y is an integer equal to or greater than 2] and at least one polyimide selected from the group consisting of (iii) at least one comonomer or a combination of at least two comonomers, (a) Formula (VI) [ka] [In the formula, R 7 is a difunctional group, R 8 and R 9 may be the same or different and are independently selected from alkenyl groups having 2 to 6 carbon atoms. Compounds of (b) Formula (VII) [ka] [In the formula, R 10 is a difunctional group, R 11 and R 12 may be the same or different and are independently selected from alkenyl groups having 2 to 6 carbon atoms. Compounds of (c) Formula (VIII) [ka] [In the formula, R 13 is a difunctional group, R 14 and R 15 may be the same or different and are independently selected from alkenyl groups having 2 to 6 carbon atoms. Compounds of (d) Formula (IX) [ka] [In the formula, R 16 is a difunctional group, R 17 and R 18may be the same or different and are independently selected from alkenyl groups having 2 to 6 carbon atoms. Compounds of (e) Formula (X) [ka] [In the formula, R 19 is the y' functional group, R 20 is an alkenyl group having 2 to 6 carbon atoms, y' is an integer equal to or greater than 2. Compounds of (f) Formula (XI) [ka] [In the formula, R 21 is the y'' functional group, R 22 is an alkenyl group having 2 to 6 carbon atoms, y'' is an integer equal to or greater than 2. Compound and at least one comonomer or a combination of at least two comonomers selected from The present invention relates to a curable composition comprising:

[0057] In a preferred embodiment, B in the polyimide of formula (V) is a difunctional group: [ka] is selected from.

[0058] In a preferred embodiment, A in the polyimide of formula (V) is a difunctional group: a) an alkylene group having 2 to 12 carbon atoms, b) a cycloalkylene group having 5 to 6 carbon atoms, c) a heterocyclic group having 4 to 5 carbon atoms and at least one nitrogen, oxygen or sulfur atom in the ring; d) a monocyclic or bicyclic carbocyclic group, e) a bridged polycyclic group consisting of at least two groups selected from a monocyclic carbocyclic aromatic group, a bicyclic carbocyclic aromatic group, a cycloalkylene group, which is connected by a direct carbon-carbon bond or by a divalent group, preferably an oxy group, a thio group, an alkylene group having 1 to 3 carbon atoms, a sulfone group, a methanone group, or the following groups: [ka] [In the formula, R 23 ~R 28 are independently selected from alkyl groups having 1 to 6 carbon atoms; R 29 and R 30 are independently selected from alkylene groups having 1 to 6 carbon atoms. bridged polycyclic groups linked together by a divalent group selected from one of f) Formula (XII) [ka] [In the formula, R 31 is based on the following [ka] is one of the The group defined by is selected from.

[0059] In a preferred embodiment, the polyimide of formula (V) is represented by the formula (Va): [ka] [In the formula, R 32 is based on the following [ka] and B is as defined in formula (V). It is a bisimide of the formula:

[0060] In a preferred embodiment, the at least one polyimide of formula (V) is selected from the group consisting of 4,4'-bismaleimidodiphenylmethane, bis(3-methyl-5-ethyl-4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, 4,4'-bismaleimidodiphenyl ether, 4,4'-bismaleimidodiphenyl sulfone, 3,3'-bismaleimidodiphenyl sulfone, bismaleimidodiphenylindane, 2,4-bismaleimidotoluene, 2,6-bismaleimidotoluene, 1,3-bismaleimidobenzene, 1,2-bismaleimidodiphenylmethane ... and wherein the bismaleimide is selected from 1,4-bismaleimidobenzene, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 1,6-bismaleimido-(2,2,4-trimethyl)hexane, 1,6-bismaleimido-(2,4,4-trimethyl)hexane, 1,4-bis(maleimidomethyl)cyclohexane, 1,3-bis(maleimidomethyl)cyclohexane, 1,4-bismaleimidodicyclohexylmethane, 1,3-bis(maleimidomethyl)benzene, 1,4-bis(maleimidomethyl)benzene, or mixtures thereof.

[0061] In a preferred embodiment, the bismaleimide of formula (I) is 2-(3,3,5-trimethylcyclohexyl)propane-1,3-bismaleimide and the polyimide according to formula (V) is 4,4'-bismaleimidodiphenylmethane, bis(3-methyl-5-ethyl-4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, 4,4'-bismaleimidodiphenylether, 4,4'-bismaleimidodiphenylsulfone, 3,3'-bismaleimidodiphenylsulfone, bismaleimidodiphenylindane, 2,4-bismaleimidotoluene, 2,6-bismaleimidodiphenylmethane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidodi ... bismaleimidotoluene, 1,3-bismaleimidobenzene, 1,2-bismaleimidobenzene, 1,4-bismaleimidobenzene, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 1,6-bismaleimido-(2,2,4-trimethyl)hexane, 1,6-bismaleimido-(2,4,4-trimethyl)hexane, 1,4-bis(maleimidomethyl)cyclohexane, 1,3-bis(maleimidomethyl)cyclohexane, 1,4-bismaleimidodicyclohexylmethane, 1,3-bis(maleimidomethyl)benzene and 1,4-bis(maleimidomethyl)benzene.

[0062] In one embodiment, the curable composition further comprises one or more cure inhibitors. Cure inhibitors retard the polymerization reaction, thus modifying the processability and storage stability of the composition and intermediate products, such as prepregs, molding compounds, and resin solutions. Suitable cure inhibitors are hydroquinone, 1,4-naphthoquinone, ionol, and phenothiazine, which are used in concentrations of 0.1% to 2.0% by weight, based on the total weight of the composition. It is advantageous to dissolve the inhibitor in one of the components before preparing the mixture.

[0063] In one embodiment, the curable composition further comprises one or more curing accelerators. The curing accelerators accelerate the curing process. Typically, the curing accelerators are added in an amount of 0.01% to 5% by weight, preferably 0.1% to 2% by weight, based on the total weight of the curable composition. Suitable curing accelerators include ionic polymerization catalysts and free radical polymerization catalysts. Examples of free radical polymerization catalysts include (a) organic peroxides such as di-tert-butyl peroxide, diamyl peroxide, and t-butyl perbenzoate, and (b) azo compounds such as azobisisobutyronitrile. Examples of ionic catalysts are alkali metal compounds, tertiary amines such as triethylamine, dimethylbenzylamine, dimethylaniline, azabicyclooctane, heterocyclic amines such as quinoline, N-methylmorpholine, methylimidazole, and phenylimidazole, and phosphorus compounds such as triphenylphosphine, and quaternary phosphonium halides. The cure accelerator can be mixed with the components of the curable composition by either a powder blending process or a solvent blending process.

[0064] The curable composition may further comprise at least one comonomer. In one embodiment, the at least one comonomer is selected from 2,2'-diallyl bisphenol-A, bisphenol-A diallyl ether, bis(o-propenylphenoxy)benzophenone, m-aminobenzhydrazide, bisphenol-A dicyanate ester, diallyl phthalate, triallyl isocyanurate, triallyl cyanurate, styrene, divinylbenzene, or a mixture thereof.

[0065] In one embodiment, the at least one comonomer is selected from an alkenylphenol, an alkenylphenyl ether, an alkenylphenol ether, a polyamine, an aminophenol, an amino acid hydrazide, a cyanate ester, a diallyl phthalate, a triallyl isocyanurate, a triallyl cyanurate, a styrene, a divinylbenzene, and the comonomer is preferably present at 1% to 30% by weight, based on the total weight of the composition.

[0066] In one embodiment, the molar ratio between the unsaturated imide groups and the reactive alkenyl groups in the curable composition is in the range of 1.0 to 0.1, such as 1.0 to 0.2, 1.0 to 0.3, 1.0 to 0.4, 1.0 to 0.5, 1.0 to 0.6, 1.0 to 0.7, or 1.0 to 0.8, which provides a desirable cure rate.

[0067] In one embodiment, the curable composition further comprises at least one reaction inhibitor. The reaction inhibitor improves processability and storage stability before use. Suitable reaction inhibitors are hydroquinone, 1,4-naphthoquinone, and phenothiazine, which can be used at a concentration of 0.1% to 2.0% by weight based on the total weight of the composition. It is advantageous to dissolve the inhibitor in one of the components before preparing the composition.

[0068] In one embodiment, the curable composition further comprises at least one reaction modifier selected from alkenylphenols, alkenylphenyl ethers, alkenylphenol ethers, polyamines, aminophenols, amino acid hydrazides, cyanate esters, diallyl phthalates, triallyl isocyanurates, triallyl cyanurates, styrene, divinylbenzene, or mixtures thereof. The reaction modifier can be present at 1% to 30% by weight based on the total weight of the composition. Among these, allyl-type components such as diallyl bisphenol A, bisphenol A diallyl ether, diallyl phthalate, triallyl isocyanurates, and triallyl cyanurates are preferred. These can slow down the polymerization rate, thus widening the processing window. Reaction modifiers such as styrene and divinylbenzene are very effective at concentrations of 10% to 20% by weight, but they accelerate the polymerization rate, speed up the curing of the resin, and reduce the polymerization temperature. Thus, reaction modifiers are an additional means to modify the cure rate of the curable composition of the present invention. When such a reaction modifier is used, it is advantageous to first blend the bismaleimide according to the invention with the reaction modifier in the required proportions and then, in a second step, dissolve the polyimide portion of the mixture in this blend, if necessary at elevated temperatures.

[0069] In one embodiment, the curable composition of the present invention may further comprise 0.01% to about 30% by weight, based on the total weight of the composition, of at least one thermoplastic polymer, such as polyarylethers, polyarylsulfones, polyarylates, polyamides, polyarylketones, polyimides different from formula (V), polyimideethers, polyolefins, ABS resins, polydiene or diene copolymers, or mixtures thereof. Thermoplastic resins such as polysulfones and phenoxy resins are particularly miscible with the curable composition of the present invention and can be used to adjust the viscosity of the resin and to control flow during curing. Thermoplastic polymers can also be added to improve fracture toughness. The thermoplastic polymer can be added to the curable composition as a fine powder or dissolved in either the bismaleimide according to formula (I) or the reaction modifier.

[0070] In one embodiment, the curable composition may include at least one catalyst. The catalyst may be present in an amount of 0.01% to 5% by weight, preferably 0.1% to 2% by weight, based on the total weight of the curable composition. Suitable catalysts include ionic and free radical polymerization catalysts. Examples of free radical polymerization catalysts include (a) organic peroxides, such as di-tert-butyl peroxide, diamyl peroxide, and t-butyl perbenzoate, and (b) azo compounds, such as azobisisobutyronitrile. Examples of ionic catalysts are alkali metal compounds, tertiary amines, such as triethylamine, dimethylbenzylamine, dimethylaniline, azabicyclooctane, heterocyclic amines, such as quinoline, N-methylmorpholine, methylimidazole, and phenylimidazole, and phosphorus compounds, such as triphenylphosphine, and quaternary phosphonium halides. The catalyst may be mixed with the components of the curable composition or may be added during processing, either by powder blending or solvent blending processes, as described below.

[0071] Method for Producing a Curable Composition According to the Invention In a third aspect, the present invention relates to a method for producing a curable composition according to the present invention, comprising blending at least one polyimide and at least one bismaleimide using a powder blending process, a melt blending process, or a solvent assisted blending process to obtain a curable composition. The curable composition may be a solid, low melting, sticky, or liquid curable composition.

[0072] Solvent Blending Process In one embodiment, the method of making the curable composition of the present invention is a solvent blending process that includes dissolving the components of the curable composition in a solvent or diluent to obtain a stable solution that can be further processed into a prepreg. Alternatively, the solvent or diluent can be subsequently removed to obtain the curable composition as a solvent-free mass (resin), which can be further used in various hot melt processing techniques.

[0073] In one embodiment, the dissolving step is carried out at a temperature above 30°C.

[0074] Suitable solvents and diluents are all conventional inert organic solvents. These include, but are not limited to, ketones such as acetone, methyl ethyl ketone, cyclohexanone, glycol ethers such as methyl glycol, methyl glycol acetate, propylene glycol monomethyl ether (methyl proxitol), methyl proxitol acetate, diethylene glycol, and diethylene glycol monomethyl ether, toluene and xylene, preferably in combination with 1,3-dioxolane as co-solvent.

[0075] In one embodiment, the solvent mixture comprises up to 50% by weight, preferably up to 40% by weight, based on the total weight of the solvent mixture, of a ketone, such as acetone, methyl ethyl ketone, cyclohexanone, or a glycol ether, such as ethylene glycol ether, propylene glycol ether, butylene glycol ether, and acetates thereof.

[0076] In one embodiment, the solution of the curable composition of the present invention comprises 30% to 70% by weight, preferably 40% to 60% by weight, of a solvent, such as a solvent for 1,3-dioxolane, or a solvent mixture comprising 1,3-dioxolane and said solvent, such concentrations being typically used in industrial dip coating processes.

[0077] Melt Blending Process In one embodiment, the method for producing the curable composition of the present invention is a melt blending process. In one embodiment, the melt blending is carried out at a temperature between 70° C. and 250° C. In a preferred embodiment, the method is carried out at a temperature between 90° C. and 170° C., more preferably between 100° C. and 150° C. The curable composition is obtained as a low melting mass (resin).

[0078] Crosslinked polymers of the curable compositions according to the present invention In a further aspect, the present invention relates to a crosslinked polymer obtainable from the curable composition according to the invention by heating the curable composition to a temperature in the range of from 70°C to 280°C.

[0079] The curable compositions of the present invention have been found to be useful in the preparation of crosslinked polymers.

[0080] In one embodiment, the heating is carried out at a temperature between 90°C and 260°C, preferably between 100°C and 250°C.

[0081] Composite material according to the present invention and method for producing same The curable compositions of the present invention have been found to be useful in the preparation of composite materials.

[0082] In a further aspect, the present invention relates to a method for producing a composite material, comprising the steps of mixing the curable composition according to the invention or the crosslinked polymer according to the invention with a fibrous or particulate reinforcing material and curing the mixture.

[0083] In a final aspect, the present invention relates to a composite material obtainable by the method according to the invention.

[0084] In one embodiment, the curing process can be performed by co-molding under pressure to obtain molded articles, laminates, adhesives, and foams.

[0085] In one embodiment, the cured composition or the crosslinked polymer containing fibrous or particulate reinforcing material can be processed by known methods of the powder molding industry to produce molded articles, with curing occurring with simultaneous molding under pressure. For these applications, the curable composition is mixed with fibrous or particulate reinforcing material (hereinafter also called filler), and optionally with colorants and flame retardants. Ideal fillers are, for example, short glass fibers, short carbon fibers, or short aramid fibers, particulate fillers such as quartz, silica, ceramic, metal powder, and carbon powder. Depending on the technical application of the molded article, two or more different fillers can be used simultaneously.

[0086] Purpose In one embodiment, the composite material is a fiber composite material. For this application, a filler, in particular a fiber such as glass, carbon or aramid in the form of a roving, fabric, short fiber mat or felt, is impregnated with the curable composition using a solution of the curable composition to impregnate the reinforcement. After the solvent is dried off, a prepreg remains, which can be cured in a second stage, optionally under pressure, at a temperature between 180°C and 350°C.

[0087] Melted prepreg In one embodiment, the composite material is a fiber-reinforced composite material obtained by a hot melt process. To obtain such a fiber-reinforced composite material, the curable composition is processed as a hot melt into a resin film on a carrier foil, and then a filler, for example a fiber in the form of a roving or fabric, is pressed into the molten resin film to form a prepreg. In this process, a low temperature and low viscosity curable composition is advantageous in order to fully impregnate the fiber roving or fabric.

[0088] Laminate In one embodiment, the composite material is a fiber laminate. Prepregs made from glass, carbon, or aramid fibers in the form of fabrics or rovings, either by solvent / solution or hot melt processes, are stacked into a prepreg laminate and subsequently cured under pressure or in a vacuum bag at temperatures between 150°C and 280°C, preferably between 170°C and 260°C.

[0089] In one embodiment, the curable composition defined above is mixed with, e.g., spread onto or blended with, fibrous or particulate reinforcing materials (fillers) using standard processing techniques, e.g., hot melt or solution-based prepregging, resin transfer molding (RTM), resin injection molding (RIM), filament winding (FW), or kneading techniques.

[0090] Curing can be carried out at a temperature in the range of 70°C to 280°C, preferably in the range of 80°C to 270°C, more preferably in the range of 90°C to 260°C, and most preferably in the range of 100°C to 250°C, preferably for a time sufficient to achieve complete curing.

[0091] In one embodiment, the composite material is a fiber-reinforced composite material.In one embodiment, the composite material is a particle-filled composite material.

[0092] In one embodiment, the present invention provides a method for preparing a composite material, comprising the steps of: (a) preparing a curable composition as defined above, (b) applying the curable composition defined above onto a fibrous reinforcement material or blending it with a particulate filler; (c) curing the above defined curable composition at a temperature in the range of 70° C. to 280° C., preferably for a time sufficient to completely cure; and (d) simultaneously applying pressure to obtain a composite material; The present invention relates to a method comprising the steps of:

[0093] Treatment step c) may be carried out at a temperature in the range of 70°C to 280°C, preferably at a temperature in the range of 80°C to 270°C, more preferably at a temperature in the range of 90°C to 260°C, and most preferably at a temperature in the range of 100°C to 250°C, preferably for a time sufficient to achieve complete curing.

[0094] In carrying out process step c), the conversion of the curable composition of the invention into a crosslinked (cured) polymer can be carried out in the presence of a curing catalyst as defined above.

[0095] The implementation of process step d) involves shaping under pressure in order to obtain the composite material of the invention. Process steps c) and d) are preferably carried out simultaneously.

[0096] The preferred application of the curable composition of the present invention is resin for fiber reinforced composites.To obtain such fiber composites, the curable composition of the present invention is processed as a hot melt into a resin film on a carrier foil, which is then used to prepare a prepolymer by pressing fibers in the form of roving or fabric into the resin film.In this process, a curable composition with low viscosity at low temperature is advantageous in order to fully impregnate the fiber roving or fabric.

[0097] In one embodiment, the composite material of the present invention is a fiber reinforced laminate or a copper clad laminate for use in printed circuit boards.

[0098] Working Example The following examples are intended to illustrate, but not limit, the present invention.

[0099] Working Example: A. Preparation of 2-(3,3,5-trimethylcyclohexyl)propane-1,3-bismaleimide Example 1 2-(3,3,5-trimethylcyclohexyl)propane-1,3-bismaleimide was prepared according to the following reaction scheme: [ka]

[0100] A glass reactor equipped with a mechanical stirrer, a thermometer, and a dropping funnel was charged with 120 ml of N,N-dimethylacetamide under nitrogen. 100 g of maleic anhydride was added and the mixture was stirred until dissolution was complete. Then, 99.2 g of 2-(3,3,5-trimethylcyclohexyl)propane-1,3-diamine was added dropwise so that the temperature did not exceed 60°C. After addition, the mixture was stirred at 50-55°C for 1 hour. Then, 128 g of acetic anhydride was added, followed by 200 g of triethylamine. The reaction mixture was heated to 90°C, stirred for 1 hour, and cooled to 60°C. The mixture was then stirred at 60°C for 20 minutes and poured into 2 liters of water with vigorous stirring. The precipitate was filtered off and washed by slurrying in distilled water. Finally, the product was filtered off and dried at 60°C under reduced pressure. For analytical purposes, the product was purified by column chromatography using silica gel as the solid phase and methyl ethyl ketone as the eluent, melting point 119° C. (DSC, 10° C. / min). [ka]

[0101] The resulting 2-(3,3,5-trimethylcyclohexyl)propane-1,3-bismaleimide has high solubility in various organic solvents compared to other aliphatic bismaleimides.

[0102] [Table 1]

[0103] The solubility of the Examples and Comparative Examples was determined as follows: 10 g of sample was weighed into a 100 ml Erlenmeyer flask. 50 ml of solvent was added to the flask and the mixture was stirred with a magnetic stir bar at 25 °C for 1 h to ensure the formation of a saturated solution. If the entire sample was dissolved, an additional portion of sample should be added and the mixture stirred for another hour. Eventually, some of the undissolved material should be clearly visible at the bottom of the flask. The supernatant was then filtered through a folded filter. Approximately 15 g of the filtrate was weighed into a tared round-bottom flask and the solvent was evaporated to dryness in a rotary evaporator at 90 °C under reduced pressure. Finally, the flask was dried in a vacuum drying cabinet at 120 °C for 2 h under reduced pressure, cooled to room temperature in a desiccator and weighed.

[0104] The solubility value is then calculated as follows: Solubility [%] = ([output weight] x 100) / [original sample weight]

[0105] B. Preparation of a curable mixture according to the invention based on a bismaleimide of formula (I), a polymaleimide of formula (V) and a comonomer.

[0106] The curable mixture according to the invention can be obtained according to the following general process: (a) Solvent-assisted process At least one polymaleimide of formula (V), at least one bismaleimide of formula (I), and, if necessary, at least one additional comonomer component, and an organic solvent, preferably toluene or methylene chloride, are heated at 90-100°C in a solid to solvent weight ratio of 1:1 until a clear solution is obtained. The solvent is then distilled off under reduced pressure while the temperature is increased to 100-120°C. Finally, the mixture is degassed for 2-10 minutes under a reduced pressure of 20 hPa [15 mmHg] to obtain a curable mixture. The resin / solvent ratio may vary depending on the solubility of the components. Other solvents or diluents described in this patent may also be used.

[0107] (b) Melting process At least one polymaleimide of formula (V), at least one bismaleimide of formula (I), and, if necessary, at least one additional comonomer component are melt blended at a temperature range of 100-120°C until a homogeneous mixture is obtained. The melt thus obtained is then further heated at the same temperature range for a time sufficient to obtain a stable melt. Finally, the melt is degassed under a reduced pressure of 20 hPa [15 mmHg] for 2-10 minutes to obtain a curable mixture.

[0108] (c) Reactivity measurement (c.1) Differential scanning calorimetry (DSC) To characterize the cure kinetics of the curable compositions of the present invention, differential scanning calorimetry (DSC) traces obtained at a defined heating rate (10°C / min) in the temperature range of 20-380°C are used. MAX represents the maximum heat release temperature due to polymerization at a specified heating rate. The onset of the heat release peak is the polymerization onset temperature T ONSET Represents T ONSET and T MAX The higher the temperature, the slower the resin will harden.

[0109] (c.2) Hot plate gel time Gel time, a standard measure of resin reactivity, is measured as described in the ISO 8987:2005-12 and ASTM D4217-07(2017) standards by placing 1 g of resin on an electrically heated metal block with a polished surface that can be maintained at a temperature between 130 °C and 230 °C, stirring continuously with a wooden stick and examining the molten sample.

[0110] C. Curable Polymaleimide / Asymmetrically Substituted Bisalkenyl Diphenyl Ether Blends Example 2 A curable mixture comprising 60% by weight of a bismaleimide of formula (IV) and 40% by weight of 2,2'-bis(3-allyl-4-hydroxyphenyl)propane prepared by a solvent-assisted process (a) using toluene as the solvent. Gel time: 54 minutes Dynamic viscosity at 90℃: 487mPa·s; 110℃: 122mPa·s DSC polymerization initiation (T ONSET ): 150℃ DSC polymerization highest (T MAX ): 279℃

[0111] Example 3 A curable mixture comprising 35% by weight of a bismaleimide of formula (IV), 35% by weight of meta-xylylene bismaleimide, and 30% by weight of 4,4'-bis(ortho-propenylphenoxy)benzophenone, prepared by a solvent-assisted process (a) using toluene as the solvent. Gel time: 48 minutes Dynamic viscosity at 90℃: 867mPa·s; 110℃: 194mPa·s DSC polymerization initiation (T ONSET ): 136℃ DSC polymerization highest (T MAX ): 253℃

[0112] Example 4 A curable mixture comprising 30% by weight of a bismaleimide of formula (IV) prepared by a solvent-assisted process (a) using toluene as the solvent, 30% by weight of 4,4'-bismaleimidodiphenylmethane, 26.7% by weight of 4,4'-bis(ortho-propenylphenoxy)benzophenone, and 13.3% by weight of 2,2'-bis(3-allyl-4-hydroxyphenyl)propane. Gel time: 27 minutes Dynamic viscosity at 90℃: 2043mPa·s; 110℃: 3302mPa·s DSC polymerization initiation (T ONSET ): 135℃ DSC polymerization highest (T MAX ): 260℃

[0113] Example 5 A mixture containing 21 g of bismaleimide of formula (IV), 9 g of 2,2'-bis(3-allyl-4-hydroxyphenyl)propane, and 30 g of methyl ethyl ketone was stirred at 60°C for 10 minutes, filtered, and cooled to room temperature to obtain a resin solution containing 50 wt% solids. No crystallization was observed even after 6 weeks at room temperature. Gel time: 62 minutes Kinematic viscosity: 17mPa·s

Claims

1. Formula (I) 【Chemical 1】 [wherein,[ R is a substituted or unsubstituted C ３～７ alicyclic ring, or Formula (II) 【Chemical 2】 [wherein, R １ and R ２ may be the same or different and are each independently selected from a C １～１２ alkyl group or an alkenyl group] is a group of] Bismaleimide according to.

2. R is a cyclohexyl group of formula (III) [Chemical 3] [wherein, R ３ to R ６ may be the same or different and are each independently selected from H or a C １～３ alkyl group] The bismaleimide according to Claim 1, which is.

3. The bismaleimide is 2-(3,3,5-trimethylcyclohexyl)propane-1,3-bismaleimide having formula (IV) 【Chemical Formula 4】 The bismaleimide according to Claim 1, which is.

4. (i) At least one bismaleimide according to Claim 1 or 2, and (ii) General formula (V) 【Chemical Formula 5】 [wherein,[ B is a difunctional group containing a carbon-carbon double bond,[ A is a y-functional group,[ y is an integer of 2 or more] At least one polyimide of, and (iii) At least one comonomer or a combination of at least two comonomers, (a) Formula (VI) [Chemical Formula 6] [wherein,[ R ７ is a bifunctional group, R ８ and R ９ may be the same or different and are each independently selected from alkenyl groups having 2 to 6 carbon atoms] A compound of,[ (b) Formula (VII) [Chemical Formula 7] [wherein,[ R １０ is a bifunctional group, R １１ and R １２ may be the same or different and are independently selected from alkenyl groups having 2 to 6 carbon atoms] A compound of,[ (c) Formula (VIII) 【Chemical 8】 [wherein,[ R １３ is a bifunctional group, R １４ and R １５ may be the same or different and are independently selected from alkenyl groups having 2 to 6 carbon atoms] A compound of,[ (d) Formula (IX) 【Chemical Formula 9】 [wherein,[ R １６ is a bifunctional group, R １７ and R １８ may be the same or different and are independently selected from alkenyl groups having 2 to 6 carbon atoms] A compound of,[ (e) Formula (X) 【Chemical Formula 10】 [wherein,[ R １９ is a y' functional group, R ２０ is an alkenyl group having 2 to 6 carbon atoms, y' is an integer of 2 or more] A compound of,[ (f) Formula (XI) 【Chemical 11】 [wherein,[ R ２１ is a y'' functional group, R ２２ is an alkenyl group having 2 to 6 carbon atoms, y'' is an integer of 2 or more] A compound of At least one comonomer or a combination of at least two comonomers selected from and A curable composition containing.

5. B in the polyimide of formula (V) is the following difunctional group:[ 【Chemical Formula 12】 The curable composition according to Claim 4, which is selected from.

6. A in the polyimide of formula (V) is the following difunctional group:[ a) An alkylene group having 2 to 12 carbon atoms,[ b) A cycloalkylene group having 5 to 6 carbon atoms,[ c) A heterocyclic group having 4 to 5 carbon atoms and at least one nitrogen, oxygen or sulfur atom in the ring,[ d) A monocyclic carbocyclic group or a bicyclic carbocyclic group,[ e) A crosslinked polycyclic group composed of at least two groups selected from a monocyclic carbocyclic aromatic group, a bicyclic carbocyclic aromatic group, and a cycloalkylene group, which are linked to each other by a direct carbon-carbon bond or a divalent group,[ f) Formula (XII) 【Chemical 13】 [wherein, R ３１ is the following group 【Chemical Formula 14】 One of] A group defined by The curable composition according to Claim 4, which is selected from.

7. The polyimide of formula (V) is a bisimide of formula (Va) 【Chemical Formula 15】 [wherein, R ３２ is the following group 【Chemical Formula 16】 One of] The curable composition according to Claim 4, which is.

8. The at least one polyimide of formula (V) is 4,4'-bismaleimidodiphenylmethane, bis(3-methyl-5-ethyl-4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, 4,4'-bismaleimidodiphenylether, 4,4'-bismaleimidodiphenylsulfone, 3,3'-bismaleimidodiphenylsulfone, bismaleimidodiphenylindane, 2,4-bismaleimidotoluene, 2,6-bismaleimidotoluene, 1,3-bismaleimidobenzene, 1,2-bismaleimidobenzene, 1,4-bismaleimidobenzene, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 1,6-bismaleimido-(2,2,4-trimethyl)hexane, 1,6-bismaleimido-(2,4,4-trimethyl)hexane, 1,4-bis(maleimidomethyl)cyclohexane, 1,3-bis(maleimidomethyl)cyclohexane, 1,4-bismaleimidodicyclohexylmethane, 1,3-bis(maleimidomethyl)benzene, 1,4-bis(maleimidomethyl)benzene, or a bismaleimide selected from a mixture thereof. The curable composition according to claim 4.

9. A method for producing the curable composition according to claim 4, comprising the step of blending the at least one polyimide and the at least one bismaleimide using a powder blending process, a melt blending process, or a solvent-assisted blending process to obtain the curable composition.

10. A crosslinked polymer obtained from the curable composition by heating the curable composition according to claim 4 to a temperature in the range of 70°C to 280°C.

11. A method for producing a composite material, comprising the steps of mixing the curable composition according to claim 4 with a fibrous or particulate reinforcing material, and curing the mixture.

12. A composite material obtained by the method according to claim 11.

Images