CN112888718B - Polymaleimide composition and process for producing the same - Google Patents
Polymaleimide composition and process for producing the same Download PDFInfo
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- CN112888718B CN112888718B CN201980067195.2A CN201980067195A CN112888718B CN 112888718 B CN112888718 B CN 112888718B CN 201980067195 A CN201980067195 A CN 201980067195A CN 112888718 B CN112888718 B CN 112888718B
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Abstract
The present invention addresses the problem of providing a polymaleimide composition which has good solubility in solvents and can be melted at a relatively low temperature. The polymaleimide composition is an amorphous solid containing at least 2 compounds selected from the group of compounds represented by the following general formula (1). In the general formula, each R is independently a hydrogen atom or an alkyl group having 1 to 9 carbon atoms and optionally having a branched structure, and each X and Y is independently a single bond, an alkylene group having 1 to 15 carbon atoms and optionally having a branched or cyclic structure in the structure, a sulfonyl group (-SO) 2 -), a sulfur atom, or an oxygen atom, m is an integer of 0 to 3, n is an integer of 0 to 3, j is an integer of 0 to 4, k is an integer of 0 to 4, p is an integer of 0 to 4, and q is an integer of 0 to 4.
Description
Technical Field
The present invention relates to a polymaleimide composition exhibiting an amorphous solid state, a method for producing the same, a curable composition using the same, and a method for producing a cured product.
Background
It is known that a polymaleimide compound having 2 or more maleimide groups can give a cured product having excellent heat resistance by homopolymerization of a double bond contained in a maleimide group, such as radical polymerization or ionic polymerization, addition reaction with hydrogen of an aromatic amine, or copolymerization with allylphenol. In particular, a cured product obtained by the reaction of a polymaleimide compound with an aromatic amine or allylphenol is excellent in toughness and is therefore used as a matrix resin for leading-edge composite materials, mainly carbon fiber composite materials in the aerospace field. In addition, polymaleimide compounds have been put to practical use in the fields of printed wiring boards, insulating powder coatings, resist inks, and the like, by using them in combination with epoxy resins as heat resistance improvers for epoxy resins that are widely used in the electronic field. Here, as a representative compound of the polymaleimide compounds, bismaleimide having 2 maleimide groups is exemplified, and in the present invention, a compound having a plurality of maleimide groups is referred to as a polymaleimide compound, as typified by such a bismaleimide compound. In addition, the term of the polyamine compound is also represented by a diamine compound having 2 amino groups in the present invention, and is used as a compound having 2 or more amino groups. As for a curable composition containing such a polymaleimide compound, various compositions have also been proposed, as represented by patent document 1, for example.
Polymaleimide compounds typified by diaminodiphenylmethane bismaleimide are synthesized by the reaction of maleic anhydride and a polyamine compound having 2 or more amino groups. The polyamine compound used in this case is not particularly limited, and various polyamine compounds such as aliphatic diamine, alicyclic diamine, and aromatic diamine can be used, and therefore, polymaleimide compounds having various skeletons can be selected as a raw material according to various purposes. As such an example, patent document 2 proposes a bismaleimide compound which improves solubility to a low-boiling organic solvent and improves removability of the solvent from the prepared curable composition.
Documents of the prior art
Patent literature
Patent document 1: japanese laid-open patent publication No. 2015-193628
Patent document 2: japanese patent laid-open publication No. 2018-12671
Disclosure of Invention
Problems to be solved by the invention
As disclosed in patent document 2, the polymaleimide compound has insufficient solubility in a low-boiling solvent, and has a high melting point of about 150 ℃ which is close to 170 to 180 ℃ which is a standard for initiating a spontaneous reaction, and therefore, it is difficult to prepare a material for molding a material by impregnating a varnish, impregnating the varnish and drying the varnish, or melt-mixing the varnish with an epoxy resin, a curing agent, a filler, or the like.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a polymaleimide composition which has good solubility in a solvent and can be melted at a relatively low temperature.
Means for solving the problems
The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that when a plurality of polyamine compounds are simultaneously subjected to a maleimide reaction in maleic anhydride, or a plurality of polymaleimide compounds are mixed and dissolved or melted to form an amorphous solid, the solid not only exhibits good solubility in a solvent, but also can be melted at about 90 to 100 ℃. The amorphous solid polymaleimide composition may be cured alone or in combination with a curing agent such as an aromatic amine, allylphenol, or cyanate ester, as in the case of conventional polymaleimides. Further, since the epoxy resin is also excellent in compatibility with the epoxy resin, an arbitrary amount of the epoxy resin can be dissolved therein to improve heat resistance. The present invention is based on the above findings, and provides the following embodiments.
(1) The present invention relates to a polymaleimide composition which contains 2 or more compounds selected from the group of compounds represented by the following general formula (1) and is an amorphous solid,
[ chemical formula 1]
In the general formula (1), each R is independently a hydrogen atom or an alkyl group having 1 to 9 carbon atoms and optionally having a branched structure, and each X is independently a single bond, an alkylene group having 1 to 15 carbon atoms and optionally having a branched or cyclic structure in the structure, or a sulfonyl group (-SO) 2 -), a sulfur atom, or an oxygen atom, each Y independently represents a single bond, and optionally has a branch or a ring in the structureAn alkylene group having 1 to 15 carbon atoms in the structure, a sulfonyl group (-SO) 2 -), a sulfur atom, or an oxygen atom, m is an integer of 0 to 3, n is an integer of 0 to 3, j is an integer of 0 to 4, k is an integer of 0 to 4, p is an integer of 0 to 4, and q is an integer of 0 to 4.
(2) The present invention also relates to the polymaleimide composition according to item (1), which contains 2 or more compounds selected from the following group of compounds as the 2 or more compounds,
[ chemical formula 2]
(3) The present invention also relates to a curable composition containing the polymaleimide composition described in the above (1) or (2).
(4) The present invention also relates to a method for producing a cured product, the method comprising: and (3) curing the curable composition.
(5) The present invention also relates to a method for producing a polymaleimide composition, which comprises:
a reaction step of simultaneously reacting 2 or more compounds selected from polyamine compounds having 2 or more amino groups and maleic anhydride in the presence of a solvent; and
and a step of removing the solvent from the reaction mixture after the reaction step by distillation to obtain an amorphous solid containing a mixture of 2 or more species of polymaleimide compounds.
(6) The present invention also relates to (5) the method for producing a polymaleimide composition, wherein the polyamine compound is represented by the following general formula (1 a),
[ chemical formula 3]
In the above general formula (1 a), each R is independently a hydrogen atom or a branched structureAn alkyl group having 1 to 9 carbon atoms, each X independently represents a single bond, an alkylene group having 1 to 15 carbon atoms optionally having a branched or cyclic structure in the structure, or a sulfonyl group (-SO) 2 -), a sulfur atom, or an oxygen atom, and each Y is independently a single bond, an alkylene group having 1 to 15 carbon atoms which may have a branched or cyclic structure in the structure, or a sulfonyl group (-SO) 2 -), a sulfur atom, or an oxygen atom, m is an integer of 0 to 3, n is an integer of 0 to 3, j is an integer of 0 to 4, k is an integer of 0 to 4, p is an integer of 0 to 4, and q is an integer of 0 to 4.
(7) The present invention also relates to the method for producing a polymaleimide composition as described in the item (5) or (6), wherein the 2 or more compounds selected from the polyamine compounds are 2 or more compounds selected from the following group of compounds,
[ chemical formula 4]
(8) The present invention also relates to a method for producing a polymaleimide composition, which comprises:
melting a mixture of 2 or more compounds selected from the group of compounds represented by the following general formula (1) to prepare a melt, and then cooling the melt to prepare an amorphous solid containing the mixture,
[ chemical formula 5]
In the general formula (1), each R is independently a hydrogen atom or an alkyl group having 1 to 9 carbon atoms and optionally having a branched structure, and each X is independently a single bond, an alkylene group having 1 to 15 carbon atoms and optionally having a branched or cyclic structure in the structure, or a sulfonyl group (-SO) 2 -), a sulfur atom, or an oxygen atom, and each Y is independently a single bond, an alkylene group having 1 to 15 carbon atoms which may have a branched or cyclic structure in the structure, or a sulfonyl group (-SO) 2 -), a sulfur atom, or an oxygen atom, m is0 to 3, n is an integer from 0 to 3, j is an integer from 0 to 4, k is an integer from 0 to 4, p is an integer from 0 to 4, and q is an integer from 0 to 4.
(9) The present invention also relates to a method for producing a polymaleimide composition, which comprises:
a mixture of 2 or more compounds selected from the group of compounds represented by the following general formula (1) is dissolved in a solvent to prepare a solution, and then the solvent is distilled off from the solution to prepare an amorphous solid containing the mixture,
[ chemical formula 6]
In the general formula (1), each R is independently a hydrogen atom or an alkyl group having 1 to 9 carbon atoms and optionally having a branched structure, and each X is independently a single bond, an alkylene group having 1 to 15 carbon atoms and optionally having a branched or cyclic structure in the structure, or a sulfonyl group (-SO) 2 -), a sulfur atom, or an oxygen atom, and each Y is independently a single bond, an alkylene group having 1 to 15 carbon atoms which may have a branched or cyclic structure in the structure, or a sulfonyl group (-SO) 2 -), a sulfur atom, or an oxygen atom, m is an integer of 0 to 3, n is an integer of 0 to 3, j is an integer of 0 to 4, k is an integer of 0 to 4, p is an integer of 0 to 4, and q is an integer of 0 to 4.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a polymaleimide composition which has good solubility in a solvent and can be melted at a relatively low temperature can be provided.
Drawings
FIG. 1 is a DSC chart of the polymaleimide compositions of examples 1 to 6 relating to the present invention.
FIG. 2 is a DSC chart showing crystals of the polymaleimide compositions of examples 1 and 2 of the present invention and the bismaleimide compounds of comparative examples 1 to 3.
Detailed Description
Three embodiments of one embodiment of the polymaleimide composition, one embodiment of the curable composition, one embodiment of the method for producing a cured product, and the method for producing the polymaleimide composition of the present invention will be described below. The present invention is not limited to the following embodiments and embodiments, but can be implemented with appropriate modifications within the scope of the present invention.
< polymaleimide composition >
First, an embodiment of the polymaleimide composition of the present invention will be described. The polymaleimide composition of the present invention contains 2 or more polymaleimide compounds selected from the group of compounds represented by the following general formula (1), and is an amorphous solid. A polymaleimide compound having a plurality of maleimide groups, as represented by a bismaleimide compound having 2 maleimide groups, has high crystallinity, and is generally marketed as a chemical raw material in a crystalline state. The polymaleimide compound thus sold is important as a raw material for a curable composition because it is a cured product having high heat resistance by reacting with a curing agent such as a polyamine compound as described above. However, the crystal of the polymaleimide compound has a problem that it is difficult to melt or dissolve the polymaleimide compound in order to ensure moldability when the polymaleimide compound is used as a curable composition because of its high melting point and low solubility in organic solvents.
The amorphous solid containing a mixture containing 2 or more species of polymaleimide compounds of the polymaleimide composition of the present invention has a lower melting point and significantly improved solubility in a solvent than the polymaleimide compounds in a crystalline state because of its amorphous state, and on the other hand, is easily melt-kneaded with a curing agent, a filler, and the like because of its large difference between the melting temperature and the polymerization temperature, and can solve various problems occurring when the crystals of the polymaleimide compounds are used in the preparation of the curable composition as described above. In the present invention, the term "polymaleimide composition" is used to indicate a mixture of 2 or more polymaleimide compounds, and the polymaleimide composition of the present invention may contain compounds other than polymaleimide compounds such as polymerizable compounds such as epoxy resins and compounds having an ethylenically unsaturated bond, curing agents such as polyamine compounds and allylphenol compounds, and the like.
The polymaleimide composition of the present invention contains 2 or more polymaleimide compounds selected from the group of compounds represented by the following general formula (1) as described above, and more preferably contains 2 compounds selected from the group of compounds represented by the following general formula (1). The method for preparing the amorphous solid polymaleimide composition of the present invention by mixing these compounds will be described later.
[ chemical formula 7]
In the general formula (1), each R is independently a hydrogen atom or an alkyl group having 1 to 9 carbon atoms optionally having a branched structure. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, and a 2-ethylhexyl group. In the present specification, "independently" means that, when a plurality of the subject substituents (R in this case) are present, each substituent is arbitrarily selected from the group shown, and in this case, the substituents may be the same or different from each other. Depending on the values of m, n, j, p, q, and k, the number of the substituents to be targeted may be only 1, and in this case, the description of "independently" is omitted, and the term "each" attached to the substituent to be targeted is also omitted.
In the general formula (1), each X is independently a single bond, an alkylene group having 1 to 15 carbon atoms optionally having a branched or cyclic structure in the structure, or a sulfonyl group (-SO) 2 -), a sulfur atom, or an oxygen atom. Examples of such alkylene groups include methylene, 1,1-ethylene, 1,2-ethylene, 1,1-propylene, 1,2-propylene, 1,3-propylene, 2,2-propylenePropyl, 1,1-butylene, 1,2-butylene, 1,3-butylene, 1,4-butylene, 2,2-butylene, 2,3-butylene, 1,1-pentylene, 1,2-pentylene, 1,3-pentylene, 1,4-pentylene, 1,5-pentylene, 1,1-hexylene, 3567-hexylene, 1,3-hexylene, 1,4-hexylene, 4235 zxft 624235-hexylene, 1,6-hexylene, 1,7-heptylene, 58 zxft 58-octylene, 6258-nonylene, 6258 zxft 62626262626258, 626258 zxft 6258-cyclohexylene, methylene-cyclohexylene, 58 zxft 6258-cyclohexylene, 1,8-butylene, and the like. The "ring structure" contained in X may contain an alicyclic ring or an aromatic ring. In the case where X contains an aromatic ring, X is not generally referred to as alkylene, but in this case, X is also treated as alkylene in the present invention. That is, X as a substituent having a valence of 2 may have an alkylene group (methylene group) at a position bonded to another structure. This also applies to Y described later.
In the general formula (1), each Y is independently a single bond, an alkylene group having 1 to 15 carbon atoms optionally having a branched or cyclic structure in the structure, or a sulfonyl group (-SO) 2 -), a sulfur atom, or an oxygen atom. Examples of such alkylene groups include the same alkylene groups as those listed for X.
In the general formula (1), m is an integer of 0 to 3, n is an integer of 0 to 3, j is an integer of 0 to 4, k is an integer of 0 to 4, p is an integer of 0 to 4, and q is an integer of 0 to 4.
More specifically, the group of compounds represented by the following general formula (2) can be preferably used as the group of polymaleimide compounds represented by the general formula (1).
[ chemical formula 8]
In the general formula (2), R, X, Y, m and n are the same as in the general formula (1). In the above general formula (2), R 1 、R 2 、R 3 And R 4 Each independently represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms and optionally having a branched structure. As such an alkyl group, there may be mentioned,examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl and 2-ethylhexyl.
More specifically, a mixture of 2 or more polymaleimide compounds selected from the group of polymaleimide compounds represented by the following formula (1) can be mentioned.
[ chemical formula 9]
These polymaleimide compounds are commercially available, and the symbol marked under the chemical formula is the product number of the compound commercially available from KI chemical company. When the polymaleimide compounds are mixed to prepare the polymaleimide composition of the present invention, the mixing ratio thereof is, for example, BMI: BMI-70. Further, 2 or 3 kinds of BMI, BMI-70, BMI-80 and BMI-50P may be mixed in any ratio.
The polymaleimide composition of the present invention is an amorphous solid, and therefore, has both a low melting point and high solubility. Therefore, melt molding can be performed without using a polar solvent, and in applications such as CFRP and printed wiring boards, generation of voids due to residual solvent can be suppressed, and recovery of solvent is not required, whereby improvement in reliability and cost reduction can be achieved. In addition, in the field of sealing semiconductors, the field of sealing insulating powders, and the like, in which it is necessary to melt-knead a curing agent, a filler, a catalyst, various auxiliary materials, and the like before molding, since melt-kneading at a low temperature is also possible, a molding compound having stable quality can be produced. The polymaleimide composition of the present invention may be added with a curing agent, an epoxy resin, or the like to prepare an amorphous solid, and such an amorphous solid is also an embodiment of the polymaleimide composition of the present invention. The curing agent, epoxy resin and the like are explained in the first curable composition of the present invention. The polymaleimide composition of the present invention can be confirmed as an amorphous solid by analyzing the solid by DSC (differential scanning calorimeter) or XRD (X-ray diffraction). When this solid is analyzed by DSC, a small endothermic peak at around 60 to 80 ℃ and a DSC shift (base shift) are observed based on the glass transition, and it can be confirmed as an amorphous state. Further, when the solid was analyzed by XRD, it was found to have a wide pattern and to be in an amorphous state.
< curable composition >
Next, one embodiment of the curable composition of the present invention will be described. The curable composition of the present invention contains the above-mentioned polymaleimide composition, and the polymaleimide compound is polymerized and cured by heating. The curable composition may contain a curing agent, an epoxy resin, and the like in addition to the above-mentioned polymaleimide composition. In this case, the curable composition of the present invention may be a solid mixture obtained by adding a component such as a solid curing agent to the solid polymaleimide composition of the present invention, or may be a mixture prepared by adding a component of a curing agent to the polymaleimide composition of the present invention, temporarily liquefying the mixture, and then making the mixture solid again, or may be a mixture kept in a liquid state.
The polymaleimide composition is as already described in the above-mentioned one of the polymaleimide compositions of the present invention, and therefore, the details are omitted. The polymaleimide compound is a cured product having high heat resistance by radical polymerization or ionic polymerization alone, but a known curing agent may be used in combination with the polymaleimide compound. Specific examples of such curing agents include: amine compounds having active hydrogen which may undergo addition reaction with polymaleimide compounds, and allylphenol, cyanate ester, acrylate ester, and the like which are unsaturated compounds copolymerizable with the double bond of maleimide. In addition, a curing catalyst may be used in order to accelerate the curing reaction. Further, in order to form a strong structure by combining with another curable resin which forms a network structure alone or a network interpenetrating structure (IPN structure) without directly reacting with the polymaleimide composition, an epoxy resin, an acrylic resin, a phenol resin, or the like may be used in combination. When a curing agent is used in addition to the polymaleimide compound to form the curable composition, the curing agent is usually added in an amount equivalent to the maleimide group, but when the amount of the curing agent added is less than this equivalent, the heat resistance is improved, but the resulting cured product becomes brittle, and the amount of the curing agent added is preferably 1.5 to 0.5 equivalents, more preferably 1.2 to 0.7 equivalents, relative to the maleimide group. Further, a catalyst may be used for the purpose of improving the curability of the curable composition.
Examples of the amine compound usable as the curing agent include compounds having primary amino group (-NH) 2 ) The compound of (1). The amine compound preferably has 2 or more primary amino groups from the viewpoint of being able to serve as a crosslinking agent. As amines, there may be mentioned o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3-methyl-1,4-diaminobenzene, 2,5-dimethyl-1,4-diaminobenzene, 4,4' -diaminodiphenylmethane, 4,4' -diamino-3,3 ' -dimethyldiphenylmethane, 4,4' -diamino-3,3 ' -diethyldiphenylmethane, 4,4' -diaminodiphenyl ether, 4,4' -diaminodiphenyl sulfone, 3,3' -diaminodiphenyl sulfone, 4,4' -diaminodiphenyl ketone, benzidine, 3,3' -dimethyl-4,4 ' -diaminobiphenyl, 2,2 '-dimethyl-4,4' -diaminobiphenyl, 3,3 '-dihydroxybenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3-dimethyl 5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4' -bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (3524 zxft 354-aminophenyl) fluorene, and the like. These amines may be used alone, or two or more kinds thereof may be used in combination. The amount of the amine compound to be added is preferably about 1.5 to 0.5 equivalent, more preferably about 1.2 to 0.7 equivalent, of active hydrogen to 1 equivalent of maleimide groupAnd (4) about equivalent weight.
Examples of the allylphenol include o, o ' -diallylbisphenol A, o, o ' -diallylbisphenol F, o, o ' -diallylbisphenol S, 2,2' -diallyl-4,4 ' -biphenol, 3,3' -diallyl-4,4 ' -dihydroxydiphenyl ether, 3,3' -diallyl-4,4 ' -dihydroxydiphenyl sulfide, o ' -dimethylacrylic acid bisphenol A, o, o ' -dimethylacrylic acid bisphenol F, and the like. These allylphenols may be used alone, or two or more of them may be used in combination. The amount of allylphenol to be incorporated in the curable composition is preferably about 1.5 to 0.5 equivalents of allyl group, more preferably about 1.2 to 0.7 equivalents of allyl group, based on 1 equivalent of maleimide group. Further, an allylphenol obtained by isomerizing the double bond of these allylphenols can be used in the same manner as allylphenol. When allylphenol is used instead of or together with allylphenol, the whole amount is the same as in the case of allylphenol.
As a catalyst for promoting the reaction between the maleimide compound and the curing agent, an imidazole, a tertiary amine, a salt of a tertiary amine, a phosphorus compound, a peroxide, or the like can be added. The amount of these additives is preferably about 0.01 to 10 parts by mass, more preferably about 0.1 to 5 parts by mass, based on 100 parts by mass of the curable composition.
Imidazoles are compounds having an imidazole skeleton. As the imidazoles, imidazole, 1-methylimidazole, 1-ethylimidazole, 1-vinylimidazole, carbonyldiimidazole, 1-methyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, TBZ (2,3-dihydro-1H-pyrrolo [1,2-a)]Benzimidazole), trimellitic acid 1-cyanoethyl-2-undecylimidazole
Salt, trimellitic acid 1-cyanoethyl-2-phenylimidazole
Salt, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, chlorinated 1-dodecyl-2-methyl-3-benzylimidazole
Salts and the like.
Examples of tertiary amines include 1,8-diazabicyclo (5,4,0) -7-undecene (DBU), 1,5-diazabicyclo (4,3,0) -5-nonene (DBN), and the like. Examples of the salt of a tertiary amine include DBU-phenolate, DBU-octylate, DBU-p-toluenesulfonate, tris (dimethylaminomethyl) phenol (DMP-30), and the like. Examples of the phosphorus-containing compound include triphenylphosphine and tetraphenyl
Tetraphenylborate, and the like.
The peroxide decomposes by heating to generate free radicals. The radical polymerizes the polymaleimide compound and the compound having an ethylenically unsaturated bond contained in the curable composition. Examples of peroxides include methyl ethyl ketone peroxide, cyclohexane peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylhexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, 4,4-bis (t-butylperoxy) pentanoic acid n-butyl ester, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, dicumyl hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, alpha, α' -bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, benzoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic peroxide, 2,4-dichlorobenzoyl peroxide, m-toluyl peroxide, diisopropyl peroxide, di-2-ethylhexyl peroxide dicarbonate, di-n-propyl peroxide dicarbonate, bis (4-t-butylcyclohexyl) peroxide dicarbonate, dimyristyl peroxide dicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, bis (3-methyl-3-methoxybutyl) peroxydicarbonate, diallyl peroxydicarbonate, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxyneodecanoate, cumyl peroxyneodecanoate, t-butyl peroxy2-ethylhexanoate, t-butyl peroxy 3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butyl peroxymaleate, t-butyl isopropyl peroxycarbonate, cumyl peroxyoctoate, t-hexyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxyneohexanoate, acetyl peroxycyclohexyl sulfonyl, t-butyl allyl peroxycarbonate, and the like.
The curable composition of the present invention contains the above-mentioned polymaleimide composition of the present invention, and has both a low melting point and high solubility. Therefore, the resin composition can be easily liquefied at the time of molding, and is preferably used. Examples of such applications include production of heat-resistant resins, sealing materials for electronic components, impregnating varnishes, and laminated sheets.
< method for producing cured product >
Next, an embodiment of the method for producing a cured product of the present invention will be described. The method for producing a cured product of the present invention comprises: and curing the curable composition of the present invention.
In carrying out the method for producing a cured product of the present invention, the curable composition of the present invention is dissolved in a solvent, or melted and liquefied by heating to about 100 to 150 ℃. Next, the liquefied curable composition is molded into a desired shape, or impregnated into a substrate such as carbon fiber or glass fiber and molded into a desired shape.
Then, the curable composition molded into a desired shape is heated to cure the curable composition. The heating temperature is, for example, about 180 to 250 ℃. This operation corresponds to the step of "curing the curable composition" in the present invention.
The cured product obtained by the method for producing a cured product of the present invention has high heat resistance and also has excellent properties as an electronic material in view of low dielectric loss tangent.
< first embodiment of the method for producing a polymaleimide composition >
Next, a first embodiment of the method for producing the polymaleimide composition of the present invention will be described. In the present embodiment, 2 or more species of polymaleimide compounds are synthesized in a solvent, and then the solvent is distilled off to obtain a polymaleimide composition as an amorphous solid.
That is, the method for producing the polymaleimide composition of the present embodiment includes: a reaction step of simultaneously reacting 2 or more compounds selected from polyamine compounds having 2 or more amino groups with maleic anhydride in the presence of a solvent; and a step of solidifying an amorphous solid in which the solvent is distilled off from the reaction mixture after the reaction step to obtain a mixture containing 2 or more species of polymaleimide compounds. Hereinafter, each step will be described.
[ reaction Process ]
First, the reaction step will be explained. The step is a step of simultaneously reacting 2 or more compounds selected from polyamine compounds having 2 or more amino groups and maleic anhydride in the presence of a solvent.
In this step, 2 or more kinds of polyamine compounds are used as one of the raw materials. That is, a mixture of 2 or more polyamine compounds different in structure is used. The amino group contained in the polyamine compound is reacted with maleic anhydride as another raw material, thereby being converted into a maleimide group. Therefore, the skeleton portion of the polyamine compound becomes the skeleton portion of the future polymaleimide compound, and therefore, the polyamine compound is selected according to the desired structure of the polymaleimide compound.
The polyamine compound includes 2 or more compounds selected from the group of compounds represented by the following general formula (1 a). The following general formula (1 a) is a polymaleimide compound represented by the following general formula (1) obtained by changing the maleimide group of the polymaleimide compound of the above general formula (1) to an amino group and allowing maleic anhydride to act on the compound represented by the following general formula (1 a).
[ chemical formula 10]
In the general formula (1 a), each R is independently a hydrogen atom or an alkyl group having 1 to 9 carbon atoms optionally having a branched structure. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, and a 2-ethylhexyl group.
In the general formula (1 a), each X is independently a single bond, an alkylene group having 1 to 15 carbon atoms which may have a branched or cyclic structure, or a sulfonyl group (-SO) 2 -), a sulfur atom, or an oxygen atom. <xnotran> , , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- . </xnotran> X may be contained inThe "ring structure" includes an alicyclic ring and an aromatic ring. In the case where X contains an aromatic ring, X is not generally referred to as alkylene, but in this case, X is also treated as alkylene in the present invention. That is, X as a substituent having a valence of 2 may have an alkylene group (methylene group) at a position bonded to another structure. This also applies to Y described later.
In the general formula (1 a), each Y is independently a single bond, an alkylene group having 1 to 15 carbon atoms optionally having a branched or cyclic structure in the structure, or a sulfonyl group (-SO) 2 -), a sulfur atom, or an oxygen atom. Examples of such alkylene groups include the same alkylene groups as those listed for X.
In the general formula (1 a), m is an integer of 0 to 3, n is an integer of 0 to 3, j is an integer of 0 to 4, k is an integer of 0 to 4, p is an integer of 0 to 4, and q is an integer of 0 to 4.
More specifically, the polyamine compound represented by the general formula (1 a) preferably includes a compound represented by the following general formula (2 a).
[ chemical formula 11]
In the general formula (2 a), R, X, Y, m and n are the same as in the general formula (1 a). In the above general formula (2 a), R 1 、R 2 、R 3 And R 4 Each independently represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms and optionally having a branched structure. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, and a 2-ethylhexyl group.
More specifically, a mixture of 2 or more polyamine compounds selected from the group of polyamine compounds represented by the general formula (1 a) is exemplified.
[ chemical formula 12]
The amount of the maleic anhydride used in the present embodiment is not particularly limited, and is preferably about 1 to 5 equivalents, more preferably about 1 to 2 equivalents, and still more preferably 1 to 1.5 equivalents, based on the amino group contained in the polyamine compound.
As the solvent in the present embodiment, a solvent which does not inhibit the reaction, is insoluble in water, and can be azeotroped with water is preferably used. In this reaction, maleic anhydride is reacted with an amino group of a polyamine compound to form a maleimide compound, and then the maleimide compound is imidized by dehydration condensation, and therefore, in order to remove condensation water generated in the reaction system to the outside of the system, a solvent azeotropic with water is preferably used as the solvent. Preferred examples of such a solvent include aromatic hydrocarbon solvents such as toluene and xylene; halogen-containing solvents such as chlorobenzene and dichloromethane; aliphatic hydrocarbon solvents such as n-hexane, cyclohexane and n-decane are more preferably aromatic hydrocarbon solvents such as toluene and xylene, from the viewpoint that the reaction system is easily made uniform.
In addition to the above-mentioned solvents, a solvent that is soluble in water and does not azeotrope with water may be added as necessary as long as the reaction is not inhibited. Examples of such a solvent include aprotic polar solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone.
In addition to the polyamine compound, maleic anhydride and solvent, an acid catalyst may be added to the reaction system. Examples of such an acid catalyst include aliphatic sulfonic acids such as methanesulfonic acid, and sulfonic acids containing aromatic sulfonic acids such as p-toluenesulfonic acid, benzenesulfonic acid, and xylenesulfonic acid; inorganic acids such as sulfuric acid, fuming sulfuric acid, and phosphoric acid; carboxylic acids such as formic acid, acetic acid, propionic acid, and trifluoroacetic acid; lewis acids such as boron trifluoride-Tetrahydrofuran (THF) complex, aluminum chloride, and zinc chloride; among them, sulfonic acids (organic sulfonic acids) such as p-toluenesulfonic acid and sulfuric acid are more preferable from the viewpoint of availability and ease of handling.
The amount of the acid catalyst to be used is not particularly limited, and is preferably about 0.01 to 1 equivalent, more preferably about 0.1 to 0.9 equivalent, and still more preferably about 0.2 to 0.8 equivalent to the amino group contained in the polyamine compound.
In order to react these compounds to produce a polymaleimide compound, maleic anhydride and a solvent are added to a reaction vessel, and a polyamine compound dissolved in the solvent and an acid catalyst used as needed are added dropwise to the reaction vessel while heating the reaction solution to about 80 to 100 ℃. Then, azeotropic water is removed to the outside of the reaction system, and the reaction mixture is heated under reflux.
After the completion of the reaction, the acid catalyst, the water-soluble solvent, and unreacted maleic anhydride were removed by repeating water washing. The reaction mixture thus obtained is subjected to a solidification step.
[ solidification Process ]
The solidification step is a step of distilling off the solvent from the reaction mixture after the reaction step to obtain an amorphous solid containing a mixture of 2 or more polymaleimide compounds.
The method for distilling off the solvent includes known methods, and is not particularly limited. As an example of such a method, a method of heating the reaction mixture under reduced pressure to evaporate the solvent may be mentioned. In this step, 2 or more kinds of polymaleimide compounds present in the reaction mixture are impurities, and depending on the case, solvent molecules are introduced into or between the molecules of the polymaleimide compounds, thereby forming a solid in an amorphous state without crystallization. The amorphous solid thus obtained corresponds to the polymaleimide composition of the present invention.
< second embodiment of the method for producing a polymaleimide composition >
Next, a second embodiment of the method for producing the polymaleimide composition of the present invention will be described. In the present embodiment, a mixture of 2 or more compounds selected from the group of compounds represented by the following general formula (1) is melted to prepare a melt, and the melt is cooled to obtain an amorphous solid containing the mixture, that is, a polymaleimide composition.
[ chemical formula 13]
(in the general formula (1), each R is independently a hydrogen atom or an alkyl group having 1 to 9 carbon atoms and optionally having a branched structure, and each X is independently a single bond, an alkylene group having 1 to 15 carbon atoms and optionally having a branched or cyclic structure in the structure, or a sulfonyl group (-SO) 2 -), a sulfur atom, or an oxygen atom, and each Y is independently a single bond, an alkylene group having 1 to 15 carbon atoms which may have a branched or cyclic structure in the structure, or a sulfonyl group (-SO) 2 -), a sulfur atom, or an oxygen atom, m is an integer of 0 to 3, n is an integer of 0 to 3, j is an integer of 0 to 4, k is an integer of 0 to 4, p is an integer of 0 to 4, and q is an integer of 0 to 4. )
The compound group represented by the above general formula (1) is the same as that described in the above polymaleimide composition of the present invention, and the description thereof is omitted here.
When melting a group of 2 or more compounds represented by the above general formula (1), first, only 1 compound is melted at around the melting point of the compound, and then the remaining compounds may be added and melted in order while stirring. Then, if the obtained molten mixture is quenched, an amorphous solid can be obtained. The amorphous solid thus obtained corresponds to the polymaleimide composition of the present invention.
< third embodiment of the method for producing a polymaleimide composition >
Next, a third embodiment of the method for producing a polymaleimide composition of the present invention will be described. In this embodiment, a mixture of 2 or more compounds selected from the group of compounds represented by the following general formula (1) is dissolved in a solvent to prepare a solution, and the solvent is distilled off from the solution to obtain an amorphous solid containing the mixture, that is, a polymaleimide composition.
[ chemical formula 14]
(in the general formula (1), each R is independently a hydrogen atom or an alkyl group having 1 to 9 carbon atoms and optionally having a branched structure, and each X is independently a single bond, an alkylene group having 1 to 15 carbon atoms and optionally having a branched or cyclic structure in the structure, or a sulfonyl group (-SO) 2 -), a sulfur atom, or an oxygen atom, and each Y is independently a single bond, an alkylene group having 1 to 15 carbon atoms which may have a branched or cyclic structure in the structure, or a sulfonyl group (-SO) 2 -), a sulfur atom, or an oxygen atom, m is an integer of 0 to 3, n is an integer of 0 to 3, j is an integer of 0 to 4, k is an integer of 0 to 4, p is an integer of 0 to 4, and q is an integer of 0 to 4. )
The compound group represented by the above general formula (1) is the same as that described in the above polymaleimide composition of the present invention, and therefore, the description thereof is omitted here.
The solvent for dissolving the group of 2 or more compounds represented by the above general formula (1) is not particularly limited as long as the group of compounds can be dissolved. Examples of such a solvent include polar solvents such as dimethylformamide and N-methylpyrrolidone.
After dissolving a group of 2 or more compounds represented by the above general formula (1) in a solvent, the solvent is distilled off. The method for distilling off the solvent includes known methods, and is not particularly limited. An example of such a method is a method in which the solution is heated under reduced pressure to evaporate the solvent. In this step, 2 or more kinds of polymaleimide compounds present in the solution are impurities, and depending on the case, solvent molecules are introduced into the molecule or between the molecules to become a solid in an amorphous state without crystallization. The amorphous solid thus obtained corresponds to the polymaleimide composition of the present invention.
Examples
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples.
[ example 1]
A500 mL glass four-necked flask equipped with a stirrer, a condenser, a thermometer, a nitrogen inlet and a dropping funnel was charged with 50.0g of maleic anhydride and 250.0g of chlorobenzene. Then, while maintaining the temperature in the reaction system at 85 to 95 ℃, a solution obtained by dissolving 4,4' -diaminodiphenylmethane (manufactured by Fuji film Wako pure chemical industries, ltd.), 14.7g of methylenebis (2-ethyl-6-methylaniline) (manufactured by Fuji film Wako pure chemical industries, ltd., the same below), 17.0g of 2,2-bis [4- (4-aminophenoxy) phenyl ] propane (manufactured by Nippon pure chemical industries, same below) 18.9g and 5.2g of N-methyl-2-pyrrolidone in 120.0g of chlorobenzene was added dropwise to the reaction system over 2 hours. After completion of the dropwise addition, the reaction was carried out at the same temperature for 2 hours, 2.4g of p-toluenesulfonic acid was added to the reaction system, condensed water azeotropic under reflux conditions and chlorobenzene were cooled and separated, and only chlorobenzene as an organic layer was added back to the system and dehydrated, and the reaction was carried out for 2 hours. After the reaction, water washing was repeated to remove p-toluenesulfonic acid, N-methyl-2-pyrrolidone and excess maleic anhydride. Subsequently, the reaction solution was concentrated to obtain 77.5g of an amorphous solid bismaleimide composition. The polymaleimide composition contained 3 kinds of bismaleimide compounds (BMI, BMI-70, and BMI-80 described above).
[ example 2]
A500 mL glass four-necked flask equipped with a stirrer, a condenser, a thermometer, a nitrogen inlet and a dropping funnel was charged with 50.0g of maleic anhydride and 200.0g of toluene. Then, while maintaining the temperature in the reaction system at 85 to 95 ℃, a solution obtained by dissolving 29.7g of methylenebis (2-ethyl-6-methylaniline), 33.4g of 2,2-bis [4- (4-aminophenoxy) phenyl ] propane and 5.0g of N-methyl-2-pyrrolidone in 100.0g of toluene was added dropwise to the reaction system over 2 hours. After completion of the dropwise addition, the reaction was carried out at the same temperature for 2 hours, 2.4g of p-toluenesulfonic acid was added to the reaction system, condensed water azeotropic under reflux conditions and chlorobenzene were cooled and separated, and only toluene as an organic layer was added back to the system and dehydrated, and the reaction was carried out for 2 hours. After the reaction, water washing was repeated to remove p-toluenesulfonic acid, N-methyl-2-pyrrolidone and excess maleic anhydride. Subsequently, the reaction solution was concentrated to obtain 91.1g of an amorphous solid bismaleimide composition. The polymaleimide composition contained 2 kinds of bismaleimide compounds (BMI-70 and BMI-80 described above).
[ example 3]
50.0g of BMI-80 (manufactured by KI chemical Co., ltd., the same shall apply hereinafter) was put into a 500mL separable glass flask equipped with a stirrer, a cooling condenser, a thermometer, a nitrogen inlet and a dropping funnel, and heated at 180 ℃. After confirming that the charged BMI-80 was melted, 50.0g of the BMI-70 (manufactured by KI Kabushiki Kaisha, the same shall apply hereinafter) was gradually added thereto, and mixed and melted. Then, 50.0g of BMI (KI chemical Co., ltd., the same shall apply hereinafter) was gradually added thereto and mixed and melted. The melt was placed in a stainless steel bucket in a water bath and quenched. After cooling to 50 ℃ and taking out the cured product from the pail, 140.3g of an amorphous solid polymaleimide composition was obtained.
[ example 4]
Into a 500mL separable glass flask equipped with a stirrer, a cooling condenser, a thermometer, a nitrogen inlet and a dropping funnel was charged 75.0g of the BMI-80, and the flask was heated at 180 ℃. After confirming that the BMI-80 charged was melted, 75.0g of the BMI was slowly added and mixed and melted. The melt was placed in a stainless steel bucket in a water bath and quenched. After cooling to 50 ℃ and taking out the cured product from the pot, 143.0g of an amorphous solid polymaleimide composition was obtained.
[ example 5]
Into a 500mL separable glass flask equipped with a stirrer, a cooling condenser, a thermometer, a nitrogen inlet and a dropping funnel was charged 75.0g of the BMI-80, and the flask was heated at 180 ℃. After confirming that the input BMI-80 was melted, the above-mentioned BMI-70.0 g was slowly added thereto, and mixed and melted. The melt was placed in a stainless steel bucket in a water bath and quenched. After cooling to 50 ℃ and taking out the cured product from the pail, 141.4g of an amorphous solid polymaleimide composition was obtained.
[ example 6]
In a 500mL glass separable flask equipped with a stirrer, a cooling condenser, a thermometer, a nitrogen inlet and a dropping funnel, 50.0g of the BMI-80 was charged and heated at 180 ℃. The BMI-70.0 g was slowly added thereto, and the mixture was melted by mixing. Next, 50.0g of BMI-50P was gradually added thereto, and the mixture was mixed and melted. The melt was placed in a stainless steel bucket in a water bath and quenched. After cooling to 50 ℃ and taking out the cured product from the pail, 139.4g of an amorphous solid polymaleimide composition was obtained.
[ example 7]
Into a 500mL separable glass flask equipped with a stirrer, a cooling condenser, a thermometer, a nitrogen inlet and a dropping funnel was charged 75.0g of the BMI-70, and the flask was heated at 180 ℃. After confirming that the charged BMI-70 had melted, 75.0g of BMI-50P was gradually added thereto and mixed and melted. The melt was placed in a stainless steel bucket in a water bath and quenched. After cooling to 50 ℃ and taking out the cured product from the pail, 140.5g of an amorphous solid polymaleimide composition was obtained.
[ example 8]
Into a 500mL separable glass flask equipped with a stirrer, a cooling condenser, a thermometer, a nitrogen inlet and a dropping funnel was charged 75.0g of the BMI-80, and the flask was heated at 180 ℃. After confirming that the charged BMI-80 was molten, 75.0g of BMI-50P was gradually added thereto and mixed and molten. The melt was placed in a stainless steel bucket in a water bath and quenched. After cooling to 50 ℃ and taking out the cured product from the pail, 139.8g of an amorphous solid polymaleimide composition was obtained.
[ DSC analysis ]
The polymaleimide compositions obtained in examples 1 to 8, the BMI crystals (comparative example 1), BMI-70 crystals (comparative example 2) and BMI-80 crystals (comparative example 3) were analyzed by DSC (differential scanning calorimeter), respectively. The results are shown in fig. 1 and 2. FIG. 1 is a DSC chart of the polymaleimide compositions of examples 1 to 6 relating to the present invention. FIG. 2 is a DSC chart showing crystals of the polymaleimide compositions of examples 1 and 2 of the present invention and the bismaleimide compounds of comparative examples 1 to 3.
As shown in FIGS. 1 and 2, in the polymaleimide compositions of examples 1 to 8, small endothermic peaks and DSC shifts were observed at around 60 to 80 ℃. As a result, it was confirmed that the polymaleimide compositions of examples 1 to 8 exhibited a glass transition in this temperature range and were amorphous solids. On the other hand, as shown in FIG. 2, in the bismaleimide crystals of comparative examples 1 to 3, a large endothermic peak indicating a melting point was observed at around 160 ℃.
[ melting Point measurement ]
With respect to the polymaleimide compositions obtained in examples 1 to 8, BMI crystals (comparative example 1), BMI-70 crystals (comparative example 2) and BMI-80 crystals (comparative example 3), a small amount of solid was placed in a capillary for melting point measurement, and the melting point (or melting point) was measured using a melting point measuring machine. When the melting point was measured, the temperature at which melting started and the temperature at which melting ended were recorded, and the range was evaluated as the melting point. The results are shown in table 1.
[ Table 1]
As can be understood from Table 1, the melting points of the polymaleimide compositions of the present invention were all lower than those of the individual components contained therein, i.e., the crystals of bismaleimide compounds (comparative examples 1 to 3). In addition, the polymaleimide composition of the present invention has higher solubility in solvents with low boiling points (methyl ethyl ketone, toluene, etc.) than crystals of the bis (or poly) maleimide compound, which is a single component contained therein. From the above, it was confirmed that the polymaleimide composition of the present invention has the characteristics required for the preparation of a curable composition such as low melting point and high solubility.
Claims (6)
1. A composition which is an amorphous solid and contains 2 or more compounds selected from the following compound groups,
2. a curable composition comprising the composition according to claim 1.
3. A method for producing a cured product, comprising:
a step of curing the curable composition according to claim 2.
4. A method of making a composition, the method comprising:
a reaction step of simultaneously reacting 2 or more compounds selected from polyamine compounds having 2 or more amino groups and maleic anhydride in the presence of a solvent; and
a step of removing the solvent from the reaction mixture after the reaction step by distillation to obtain an amorphous solid containing a mixture of 2 or more species of polymaleimide compounds,
the polyamine compound is 2 or more compounds selected from the following group of compounds,
5. a method of making a composition, the method comprising:
a mixture of 2 or more compounds selected from the following compound group is melted to prepare a melt, and the melt is cooled to prepare an amorphous solid containing the mixture,
6. a method of making a composition, the method comprising:
a mixture of 2 or more compounds selected from the following group of compounds is dissolved in a solvent to prepare a solution, and then the solvent is distilled off from the solution to prepare an amorphous solid containing the mixture,
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02269716A (en) * | 1989-02-28 | 1990-11-05 | Ciba Geigy Ag | Curable composition based on aromatic bismaleimide |
| JPH06128225A (en) * | 1992-10-19 | 1994-05-10 | Mitsubishi Petrochem Co Ltd | Production of amorphous bismaleimide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5086139A (en) * | 1990-06-29 | 1992-02-04 | Shell Oil Company | Composition comprising bisimide and triene |
| JP3237200B2 (en) * | 1992-06-18 | 2001-12-10 | 三菱化学株式会社 | Amorphous bismaleimide resin |
| US7592072B2 (en) * | 2005-12-14 | 2009-09-22 | Hexcel Corporation | Bismaleimide prepreg systems |
| US8686162B2 (en) * | 2010-08-25 | 2014-04-01 | Designer Molecules Inc, Inc. | Maleimide-functional monomers in amorphous form |
| JP6509009B2 (en) * | 2014-03-28 | 2019-05-08 | 日鉄ケミカル＆マテリアル株式会社 | Bismaleimide compound, composition containing the same, and cured product |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02269716A (en) * | 1989-02-28 | 1990-11-05 | Ciba Geigy Ag | Curable composition based on aromatic bismaleimide |
| JPH06128225A (en) * | 1992-10-19 | 1994-05-10 | Mitsubishi Petrochem Co Ltd | Production of amorphous bismaleimide |
Non-Patent Citations (1)
| Title |
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| "DSC Analysis of Thermosetting Polyimides Based on Three Bismaleimide Resin Eutectic Mixtures";Afsoon Fallahi等;《Iranian Polymer Journal》;20110228;第20卷(第2期);第161-171页 * |
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