JPH01117861A - Unsaturated bisimide compound and production thereof - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (X1 and X2 are -O-, -CO- or -COO- provided that both groups are not -O- at the same time; D1 and D2 are bivalent organic group having ethylenic unsaturated double bond group; R1-R4 are H, lower alkyl or perfluoroalkyl; R5 and R6 are H, lower alkyl or perfluoroalkyl). USE:A raw material for a polymer having excellent heat-resistance and flexibility. PREPARATION:The compound of formula I can be produced by contacting a diamine compound of formula II with an ethylenic unsaturated dicarboxylic acid anhydride of formula III and formula IV in a solvent such as DMF and subjecting the obtained aromatic unsaturated bisamidic acid to dehydrative cyclization in acetone with acetic anhydride in the presence of triethylamine and nickel acetate, etc., as a catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an unsaturated bisimide compound useful as a polymer intermediate and a method for producing the same.

[Prior art]

Conventionally, the raw materials for heat-resistant polymers are maleic anhydride and
N,N-substituted bismaleimides obtained from diamine compounds (JP-A-60-156669) and reaction products of maleic anhydride and aniline resins are known. However, although these conventional imide compounds have good heat resistance, they have the drawbacks that it is difficult to impart flexibility and that they have poor solubility in solvents such as acetone and toluene.

[Problem that the invention seeks to solve]

An object of the present invention is to provide an unsaturated bisimide compound useful as a raw material for a polymer having excellent heat resistance and flexibility.

[Means for Solving the Problems] (Margins below this page) The first invention of the present application is represented by the general formula (1), which may be the same or different from each other. However, both X and x2 will not be 10- at the same time. Further, D and D are divalent organic groups having an ethylenically unsaturated double bond group, and may be the same or different. R1-R represents hydrogen, a lower alkyl group, or a perfluoroalkyl group, and may be the same or different. R3 and R4 are hydrogen, a lower alkyl group or a perfluoroalkyl group, and may be the same or different. ) is an unsaturated bisimide compound represented by

Further, the second invention is represented by the general formula (II) (n), which may be the same or different from each other. However, both xl and x2 will not become 10- at the same time. R8-R4 represent hydrogen, a lower alkyl group, or a perfluoroalkyl group, and may be the same or different from each other. Ijs and R6 are hydrogen, a lower alkyl group, or a perfluoroalkyl group, and may be the same or different. ) and the general formula [■] and the general formula (IV) (wherein, D, D, are divalent organic groups having an ethylenically unsaturated double bond group, and The general formula (1) shown below is characterized by reacting ethylenically unsaturated dicarboxylic acid anhydrides represented by may also be different. However, both X and X2 cannot be -0- at the same time, and D, D, are divalent organic groups having an ethylenically unsaturated double bond group, and are the same as each other. may also be different. R1 to R4 represent hydrogen, a lower alkyl group, or a perfluoroalkyl group, and may be the same or different.

Rs and Rh represent hydrogen, a lower alkyl group, or a perfluoroalkyl group, and may be the same or different. ) is a method for producing an unsaturated bisimide compound represented by:

The present invention will be explained in detail below.

In the present invention, the general formula [I] [■] (X+, Xt= D+, Dz, R+=R4, Rs
, R6 is as described above, and the unsaturated bisimide compound represented by ) is, for example, (white space below) CI.

CFI CH.

CH3 C.O.

CH3 CH3 F2 CH3 H3 CR3 CHI C.F.

CR2 CF3 CR3 CF3 CR3 CF3 and so on.

Used in the method for producing an aromatic unsaturated bisimide compound represented by the general formula (1), -general formula (n) (II) (L, Examples of the diamine compound represented include t
ts C2H% 4H9 CF3 CaF* 4F9 CH3 CH3 F3 HI F3 CI.

h CH.

and so on.

Further, as the ethylenically unsaturated dicarboxylic acid anhydride represented by the general formula (I[[) and the general formula (IV) (D,, ox is as described above), for example, maleic anhydride, citraconic anhydride, Itaconic acid, pyrodinconic anhydride, dichloromaleic anhydride, etc., or Diels-Alde combinations of these compounds and dicyclodiene
At least one r adduct is used.

Regarding the reaction method for obtaining the general formula (1) of the present invention from the above general formulas (n) and (III) and general formula (IV),
Although not particularly limited, in order to produce the unsaturated bisimide compound of the general formula CI), in the first step, the formula (V) 1!しVノ(L, )h, R+-Ra, Rs, R&, Dl
, Dl is as described above). Known methods are used for this purpose.

An advantageous method is to contact the diamine compound of the general formula (II) and the ethylenically unsaturated dicarboxylic acid anhydride of the general formulas (III) and (IV) in an organic liquid that is a solvent for both. be. Solvents commonly used for -m include dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, N-methylcaprolactam, tetrahydrofuran, dioxane, acetone, and diethylketone. Next, in the second step, the unsaturated bisamidic acid is cyclized and dehydrated to generate an imide ring. This method includes U,S,P,3,018.290,U,S,P,3
．． No. 018.292 and 11, S, P, 3.127.
A known method described in No. 414 or the like may be used. That is, dehydration from the amic acid of formula (V) can be carried out by using acetic anhydride as the anhydride in an amount of 1.05 to 1.5 mol per 1 mol of the amic acid group, and removing a tertiary amine such as triethylamine from the amic acid group. Add 0.15 to 0.5 mol per 1 mol, and further add 0.15 to 0.5 mol per 1 mol of amic acid group as a catalyst.
．． This is preferably carried out in acetone in the presence of 5 to 0.05 moles of nickel acetate, sodium acetate, potassium acetate, or the like.

The unsaturated bisimide compound represented by the general formula (1) of the present invention is added with a monomer containing at least one polymerizable CH,·C group, which may be of vinyl, allyl, or acrylic type. It can be denatured by here,
Examples of monomers include styrene, vinyltoluene, α
- Methylstyrene, divinylbenzene, diallylphthalate, diallylphthalate prepolymer, chlorstyrene, dichlorostyrene, bromstyrene, dibromstyrene, diallylbenzene phosphonate, diallylaryl phosphylate, acrylic acid, methacrylate, triaryl Examples include lucyanurate, triallyl cyanurate prepolymer, tribromophenol allyl ether, and these can be used alone or in combination of two or more.

Further, the unsaturated bisimide compound represented by the general formula (1') of the present invention can be modified before curing by adding a known unsaturated polyester. Here, unsaturated polyester is composed of unsaturated dibasic acids, saturated dibasic acids and their anhydrides, or lower alkyl ester derivatives thereof, diols, alkylene monooxides, and derivatives thereof, etc., in the presence or absence of a catalyst. A polyester resin matrix containing an unsaturated group synthesized by condensation or addition polymerization using reactions such as esterification and transesterification, and an ethylene-based (e.g. vinyl group,
It consists of a mixture of a polymerizable compound (allyl group, etc.) and a peroxide catalyst. In addition, vinyl ester resins obtained by reacting bisphenol A type and novolac type epoxy compounds with methacrylic acid or acrylic acid are also useful. Here, typical unsaturated dibasic acids and saturated dibasic acids include maleic acid, maleic anhydride, fumaric acid, chloromaleic acid, dichloromaleic acid, citraconic acid, citraconic anhydride,
Mesaconic acid, itaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, phthalic anhydride,
Isophthalic acid, terephthalic acid, methylglutaric anhydride, pimelic acid, hexahydrophthalic acid and its anhydride, tetrahydrophthalic acid, carpic anhydride, Hett's acid and its anhydride, tetrahyphthalic acid and its anhydride, tetrahyphthalic acid Acids, their anhydrides, and their lower alkyl esters are used, and diol components include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, and hexamethylene glycol. , 2.2-diethylpropanediol,
1.3-neopentyl glycol, dibromneopentyl glycol, bisphenoldioxydiethyl ether, hydrogenated bisphenol A, 2.2-di(4-hydroxypropoxyphenyl)propane, ethylene oxide, propylene oxide, 3.3.3 -) Lichloropropylene oxide, 2-methyl-3,3,3-trichloropropylene oxide, phenylglycidyl ether, allylglycidyl ether, etc. are used. In addition, if necessary, 3
Polybasic acids and/or polyhydric alcohols with higher functionality may be used in combination. Examples of crosslinking agents include styrene, vinyltoluene, α-methylstyrene, divinylbenzene, diallyl phthalate, diallyl phthalate prepolymer, chlorstyrene, dichlorostyrene. , bromustyrene, dibromustyrene, diallylbenzene phosphonate, diallylaryl phosphylate, acrylic ester, methacrylic ester, triallyl cyanurate, triallyl cyanurate prepolymer, tribromophenol allyl ether, etc. are used. In the unsaturated polyester to be added, acid components, alcohol components,
The crosslinking agent is not limited to one type, and two or more types can be used in combination. It is also possible to add various modifications and modifiers. Further, the unsaturated polyester is not limited to one type, and a mixture of two or more types is also possible.

The unsaturated bisimide compound represented by the general formula ['I] of the present invention reacts with polyamines, particularly diamines, and becomes a heat-resistant material with excellent flexibility. Here, as the amine compound, for example, p-phenylenediamine, p-phenylenediamine, benzidine, 3,3-dimethyl-4,
4-diaminobiphenyl, 3.3-dichlorobenzidine, 3.3-dimethoxybenzidine, 4.4-diaminodiphenylmethane, 1.1-bis(4-aminophenyl)
Ethane, 2.2-bis(4-aminophenyl)propane, 2゜2-bis(4-aminophenyl)hexafluoropropane, 2.2-bis(4-aminophenyl)-1,
3-dichloro-1,1,3,3-tetrafluoropropane, 4,4-diaminodiphenyl ether, 4°4'-
Diaminodiphenylsulfide, 3,3-diaminophenyl sulfide, 4,4-diaminodiphenylsulfoxide, 4,4-diaminodiphenylsulfone, 3
．． 3-diaminodiphenylsulfone, 3,3-diaminodibenzophenone, 4,4'-diaminobenzophenone, 3,4-diaminobenzophenone, N,N-bis(4
-aminophenyl)methylamine, N,N-bis(4-
aminophenyl)-n-butylamine, N,N-bis(
4-aminophenyl)amine, -monoaminobenzoyl p-aminoanilide, 4-aminophenyl-3-aminobenzoate, 4,4-diaminoazobenzene, 3.3
'-Diaminoazobenzene, bis(3-aminophenyl)diethylsilane, bis(4-aminophenyl)phenylphosphine oxyto, bis(4-aminophenyl)ethylphosphine oxyto, 1.5-diaminonaphthalene, 2.6- Diamitupyridine, 2,5-diamino-1,
1,4-oxadiazole, trans-xylylenediamine,
p-xylylenediamine, 2.4 (p-β-amino-t
-butylphenyl)ether, p-bis-2-(2-methyl-4-aminopentyl)benzene, p-bis(1,
1-dimethyl-5-aminopentyl)benzene, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, 2.11-diaminododecane, i, 12-
Diaminoctadecane, 2,2-dimethylpropylenediamine, 2,5-dimethylenehexamethylenediamine,
3-methylhbutamethylenediamine, 2.5-dimethylhbutamethylenediamine, 4.4-dimethylhbutamethylenediamine, 5-methylnonamethylenediamine, 1.
4-diaminocyclohexane, bis(p-aminocyclohexyl)methane, 3-methoxyhexamethylenediamine, 1,2-bis(3-aminopropoxy)ethane, bis(3-aminopropyl)sulfide, N,N-bis( Examples include 3-aminopropyl) methylamine. Also, 2,4-diaminodiphenylamine, 2,4-
Diamino-5-methyldiphenylamine, 2,4-diamino-4-methyldiphenylamine, 1-anilino-2
, 4-diaminonaphthalene, and 3,3-diamino-4-anilinobenzophenone.

Furthermore, polyamines represented by the general formula (wherein, X is an alkylidene group containing a methylene group, and the number represents an average number of 0.1 or more) are also useful. Particularly effective in imparting flexibility are 2, 2
-bis(4-(4-aminophenoxy)phenylpropane, 2,2-bis[3-methyl-4-(4-aminophenoxy)phenylpropane, or 2,4-bis(4-aminophenoxy)phenylpropane,
-(4-aminophenoxy)phenylgo 2-methylpentane, 2,4-bis(4-(4-aminophenoxy)
phenyl]-2-(fluoro)-methylpentane, 1-
(4-(3-aminophenoxy)phenyl)-1,3,
3-trimethyl-6-(3-aminophenoxy)indane, 6,6-bis(3-aminophenoxy)-3,3i
3', 3-tetramethyl-1,1-spirobiindane,
6.6-bis(4-aminophenoxy)-3,3°3'
, 3-tetramethyl-1,1-spirobiindane, and the like. Of course, in the present invention, the general formula (II
) can also be used.

Further, the aromatic unsaturated bisimide compound represented by the general formula (1) of the present invention can be used in a wider range of applications by being used in combination with conventionally known N,N'-substituted bismaleimide compounds. . An N,N'-substituted bismaleimide compound is a compound represented by the formula: [wherein A represents an alkylene group, an arylene group, or a divalent organic group substituted therewith], for example, N,N'-substituted bismaleimide compounds. -ethylene bismaleimide, N, N-hexamethylene bismaleimide, N
.

N-dodecamethylene bismaleimide, N,N'-ta-
Phenylene bismaleimide, N,N-di4,4-phenyl ether bismaleimide, N,N'-4,4-diphenylmethane bismaleimide, N,N'-4,4-dicyclohexylmethane bismaleimide, N,N'- 4,4'
- metaxylene bismaleimide, N, N'4+4'';
Phenylcyclohexane bismaleimide or general formula (IV) [■] (wherein R2-R6 represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different from each other. R6 and R1 are hydrogen, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, and D is a divalent organic group having 2 to 24 carbon atoms. 2,2-bis[4-(4-maleimidophenoxy)
phenyl]propane, 2,2-bis[3-methyl-4-
(4-maleimidophenoxy)phenyl]propane, 2
．． 2-bis[3-'F Rolow 4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3-bromo 4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3- Ethyl-4-(maleimidophenoxy)phenyl]propane, 2,2-bis[3-propyl-4-(4-maleimidophenoxy)phenyl]
Propane, 2,2-bis[3-isopropyl-4-(4
-maleimidophenoxy)phenyl]propane, 2,2
-bis[3-butyl-4-(4-maleimidophenoxy)phenyl]propane, 2.2-bis(3-sec-butyl-4-(4-maleimidophenoxy)phenyl)propane, 2.2-bis[3 -Methoxy-4-(4-maleimidophenoxy)phenyl]propane, 1.1-bis(4-(4-maleimidophenoxy)phenyl)ethane, 1.1-bis[3-methyl-4-(4-maleimidophenoxy) ) phenyl]ethane, 1.1-bis[3-chloro-4-(4-maleimidophenoxy)phenyl]ethane, 1.1-bis[3-bromo4-(4-maleimidophenoxy)phenyl]ethane, bis( 4-(4-maleimidophenoxy)phenylcomethane, bis[3-methyl-4-(4-maleimidophenoxy)phenylcomethane, bis[3-chloro-4-(4-maleimidophenoxy)phenylcomethane, bis[ 3-bromo-4-(4-
maleimidophenoxy)phenylcomethane, 1.1.1
．． 3,3.3-hexafluoro-2,2-bis(4-(
4-Maleimidophenoxy)phenyl]propane, 1,
1.1.3.3.3-hexachloro-2,2-bisC4
-C4-maleimidophenoxy)phenyl]propane,
3.3-bis(4-(4-maleimidophenoxy)phenyl]pentane, 1.1-bis(4-(4-maleimidophenoxy)phenyl)propane, 1.1.1.3.3
．． 3-hexafluoro-2,2-bis[3,5-dibromo-4(4-maleimidophenoxy)phenyl]propane, 1.1.1.3.3.3-hexafluoro-2,2
-bis[3-methyl-4(4-maleimidophenoxy)
Examples include phenyl]propane, 2゜4-bis(4-(4-maleimidophenoxy)phenyl)-2-methylpentane, and the like.Also, two or more of these may be used as a mixture. Further, mixtures with mono-substituted maleimide, tri-substituted maleimide, and tetra-substituted maleimide can also be used as appropriate.

Muff', =, 2.4-His(4-(4-endomethylenetetrahydrophthalimide, phenoxy)phenyl)-
2-Methylpentane, 2,4-bis(4-(4-maleimidophenoxy)phenyl)-2-(fluoro)-methylpentane, 1-(4-(3-maleimidophenoxy)
phenyl) -1,3,3-trimethyl-6-(3-maleimidophenoxy)indan, 1-(4-(3-endomethylenetetrahydrophthalimidophenoxy)phenyl) -1,3,3-1-limethyl-6- (3-endomethylenetetrahydrophthalimidophenoxy)indan, 1-(4-(3-maleimidophenoxy)phenyl)-1,3,3-trimethyl-6-(3-endomethylenetetrahydrophthalimidophenoxy)indan,
6.6-bis(3-maleimidophenoxy) -3,3
, 3', 3-tetramethyl-1,1'-spirobiindane and the like can also be used.

In addition, by adding epoxy compounds, heat resistance,
It also becomes a cured product with excellent moldability.

Examples of the epoxy compound used in the present invention include diglycidyl ether of bisphenol A, butadiene dieboxide, 3,4-epoxycyclohexylmethyl-(3
, 4-epoxy) cyclohexane carboxylate, vinyl cyclohexane dioxide, 4,4-di(1,2
-Epoxyethyl) diphenyl ether, 2,2-bis(3,4-epoxycyclohexyl)propane, glycidyl ether of resorcinol, diglycidyl ether of phloroglucin, diglycidyl ether of methylphloroglucin, bis(2,3-epoxycyclopentyl) Ether, 2-(3,4-epoxy)cyclohexane-5,
5-spiro (3,4-epoxy)cyclohexane-dioxane, bis(3,4-epoxy-6-methylcyclohexyl)adipate, N,N'-m-phenylenebis(4,5-epoxy-1,2 - Difunctional epoxy compounds such as cyclohexanedicarboximide, triglycidyl ether of para-aminophenol, polyallyl glycidyl ether, 1.3.5- ) li (l, 2-
Tri- or higher functional epoxy compounds such as epoxyethyl)benzene, 2,2',4,4-tetraglycidoxybenzophenone, polyglycidyl ether of phenol formaldehyde novolac resin, triglycidyl ether of glycerin, trimethylolpropane and triglycidyl ether , halogenated epoxy compounds such as brominated epoxy, or hydantoin epoxy compounds are also used.

Furthermore, by combining it with a phenol-formaldehyde condensate or adding an epoxy compound or the like to the combination, molding processability is increased and it becomes easier to dissolve in a solvent, making it possible to use it for casting purposes.

Further, it is effective to use a known curing agent for epoxy compounds in order to improve the curability.

For example, Hiroshi Kakiuchi; Epoxy Resins (published September 1970) pages 109-149; Lee, Neville; BpoxyResins (Me Graw-Hi)
ll Book Company Inc, NewY
ork, published in 1957) pages 63-141, P.
, written by E. Brunis; εpoxy Re5ins T
technology (IntersciencePu
blishese, New York+, published in 1968), pages 45 to 111,
For example, aliphatic polyamines, aromatic polyamines, amines including secondary and tertiary amines, carboxylic acids, carboxylic acid anhydrides, aliphatic and aromatic polyamide oligomers and polymers, boron trifluoride-amine complexes, phenols. resin, melamine resin, urea resin,
In addition to synthetic resin initial condensates such as urethane resins, there are also dicyandiamide, carboxylic acid hydrazide, polyaminomaleimide, poly-p-hydroxystyrene, and the like.

One or more of the above curing agents can be used depending on the use and purpose.

In addition, in the present invention, by combining ortho-diallyl bisphenol compounds having the general formula (%), it is possible to obtain a highly compatible face that can provide a cured product with excellent heat resistance and flexibility. . Examples of such compounds include CH.

C.F.

CH3 etc., and one or more types can be used in combination.

Furthermore, when the unsaturated bisimide compound of the present invention is used in combination with a polycarboxylic acid or a cyanuric acid allyl ester, a fast-curing resin composition with excellent high-temperature strength can be obtained. is particularly useful as a composite material. Examples of allyl ester compounds of polyhydric carboxylic acid or cyanuric acid include triallyl trimellitate, diallyl phthalate, I) + p-
Diaryloxycarbonyl diphenyl ether, 1111
)-diaryloxyluponyl diphenyl ether, triallyl cyanurate, triallyl cyanurate prepolymer, and the like. Two or more of the above compounds can also be used in combination.

Moreover, it can also be used in combination with an N-vinyl-pyrrolidone compound.

Examples of N-vinyl-pyrrolidora compounds include N-
Vinyl-2-pyrrolidone, N-vinyl-2-piperidone, N-vinyl-ε-caprolactam, N-vinyl-5-
Methyl-2-pyrrolidone, N-vinyl-3,3,5-)
Dimethyl-2-pyrrolidone, 3-methyl-2-pyrrolidone, or a dimer of N-vinyl-2-pyrrolidone,
In addition, N-vinyl-pyrrolidone, acrylonitrile,
Copolymers with allyl alcohol, allyl acetate, ethylene, maleic anhydride, methyl methacrylate, styrene, vinyl acetate, vinyl chloride, vinylene, carbonate, vinyl cyclohexyl ether, vinyl phenyl ether, etc., or polyvinylpyrrolidone, etc. , at least one of them can be used.

Furthermore, by using it in combination with a butadiene compound, a cured product with excellent heat resistance and flexibility can be obtained. As a butadiene compound, in particular, molecular weight 3
00-10.000 1,2-polybutadiene, 1.3
-polybutadiene, 1,4-polybutadiene, butadiene-styrene copolymer and butadiene-acrylonitrile copolymer, and also reactive groups at the terminals of each of the above polymers, such as carboxyl group, hydroxyl group, amine salt, aldehyde group, nitro At least one of those having an isocyanate group, an isocyanate group, and a vinyl group is used.

Further, the unsaturated bisimide compound of the present invention can be used in combination with a carboxylic acid compound. For example, pyromellitic acid, 2.3,6.7-naphthalenetetracarboxylic acid,
3.4,9.10-perylenetetracarboxylic acid, 3.3
', 4.4'-diphenyltetracarboxylic acid, 3,
3', 4.4-diphenylmethanetetracarboxylic acid, ethylenetetracarboxylic acid, 2.2-diphenyl-3
, 3', 4.4-propanetetracarboxylic acid, 3.3
'.

4.4-Diphenylsulfonetetracarboxylic acid, 3゜4
．． 3',4-benzophenonetetracarboxylic acid, 3゜3
', 4.4-azoxybenzenetetracarboxylic acid,
There are dianhydrides such as 3,3', 4,4-azobenzenetetracarboxylic acid and 3,3', 4,4-diphenyloxytetracarboxylic acid.

In order to impart flexibility to the cured product obtained by heating the resin composition detailed above, known compounds that cause plastic hardening to the resin composition, such as triphenyl phosphate and tricresyl phosphate, are added to the resin composition. , trioctyl phosphate, dioctyl phthalate, dioctyl hexahydrophthalate, dilauryl succinate, higher aliphatic amides, silicone polymers, and diglycidyl ester of dimic acid.゛It is desirable to add a polymerization initiator to the above-mentioned resin composition in order to complete its curing by heating for a short time. Such polymerization initiators include benzoyl peroxide, p-chlorobenzoyl peroxide, 2.4
-dichlorobenzoyl peroxide, cabrylyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, bis(1-hydroxycyclohexyl peroxide), hydroxyhebutyl peroxide, t
-butyl hydroperoxide, p-menthane hydroperoxide, t-butyl perbenzoate, t-butyl peracetate, 1-butyl peroctoate, t
Organic peroxides such as -butylperoxyisobutyrate and di-t-butylshiba-phthalate are useful, and one or more of them can be used. ′
In the present invention, the above-mentioned polymerization catalysts include, for example, lauryl mercaptan, N-butyl sulfide, diphenyl sulfide, p-toluenesulfonic acid, quaternary ammonium salts, β-diketones, peracetic acid type epoxy compounds, sulfonium salts, and naphthenes. These include manganese acid, vanadyl octoate, copper naphthenate, calcium naphthenate, other metal salts of naphthenic acid, metal chelate compounds, amines, phosphorus-containing compounds, and sulfur-containing compounds. In addition, polymerization inhibitors such as the following may be used, such as p-benzoquinone, naphthoquinone, phenanthraquinone, parakydylonquinone, 2,5-diphenyl-p-benzoquinone, 2,5-diacetoxy-p - Quinones such as benzoquinone, hydroquinone, pt-butylcatechol,
2. Hydroquinones such as monobutylhydroquinone, mono-t-butylhydroquinone, di-t-
Phenols such as butyl, para-cresol, hydroquinone monomethyl ether, alpha-naphthol, organic and inorganic copper salts such as copper naphthenate, amidines such as acetamidine acetate and acetamidine sulfate, phenylhydrazine hydrochloride, hydrazine hydrochloride, etc. Hydrazine salts, other quaternary ammonium salts, amines, nitro compounds, oximes, sulfur, polyhydric phenols, and amine hydrochloric acids can be used.

〔Example〕

Example 1 19.6 parts by weight of maleic anhydride was mixed with 200 parts by weight of acetone.
46.6 parts by weight of 2.2-bis(4-(4-aminobenzcarboxylate)phenyl)propane was dissolved in 500% of acetone while stirring at 5°C or lower in a nitrogen gas atmosphere. The solution was gradually added dropwise.

After the reaction was stirred at room temperature for 4 hours, 200 m of acetic anhydride and 1.0 parts by weight of potassium acetate were added, and the mixture was reacted for about 2 hours under refluxing acetone. Thereafter, the reactant was mixed with about 3000
If the mixture was poured into pure water to form a precipitate, it was filtered, washed and dried to obtain the aromatic unsaturated bisimide compound [A] of the present invention.

Infrared absorption (I) of the aromatic unsaturated bisimide compound
R) As a result of measuring the spectrum, 1712 cm-' and 1
A characteristic absorption derived from an imide bond was observed at 777 cm-'.

Example 2 The present invention was carried out in the same manner as in Example 1, except that 19.6 parts by weight of maleic anhydride in Example 1 was changed to 10 parts by weight, and 15.2 parts by weight of endomethylenetetrahydrophthalic anhydride was added. Aromatic unsaturated bisimide compounds for the purpose of the invention [
B] was obtained.

As a result of measuring the IR spectrum of the aromatic unsaturated bisimide compound, characteristic absorptions originating from imide bonds were observed at 1714 cm and 1781 cm.

Example 3 The aromatic compound for the purpose of the present invention was prepared in the same manner as in Example 1, except that 19.6 parts by weight of maleic anhydride in Example 1 was replaced with 30.4 parts by weight of endomethylenetetrahydrophthalic anhydride. An unsaturated bisimide compound (C) was obtained.

As a result of measuring the IR spectrum of the aromatic unsaturated bisimide compound, 1713C111-' and 1780cm-
Characteristic absorption derived from imide bonds was observed in '.

Application Examples 1 to 8 Aromatic unsaturated bisimide compounds (A), CB), (C) obtained in Examples 1 to 3, unsaturated polyester (manufactured by Hitachi Chemical Co., Ltd., PS-518), N, N '-4゜4-bis(diphenylmethane)maleimide, 4,4'-diaminobiphenylmethane, and an epoxy compound (ortho-cresol novolac type; epoxy equivalent: 195) were separately mixed in the prescribed blending amounts (parts by weight) shown in Table 1. Combined with
Eight different formulations were created. For these, the first
The curing accelerators shown in the table (dicyandiamide and dicumyl peroxide), 40 weight percent of fused silica glass powder as fillers, and spherical Al2O with an average particle size of 1 μ-
3 powder by weight, 3 parts by weight of an acylate-type alkoxy titanate compound as a coupling agent, 403.1 parts by weight of an epoxysilane compound KBM (manufactured by Shin-Etsu Chemical Co., Ltd.), and carnauba wax 2 as a mold release agent.
After adding 1 part by weight of carbon black as a coloring agent, the mixture was uniformly mixed using a kneader.

The above composition was then heated at 150-180°C 170kg/
c4. Various cured products (test specimens for measuring characteristics) were created by heating and press molding under conditions of 3 to 5 minutes.

Table 1 shows the characteristics of various cured products.

(Margin below this page) Example 4 19.6 parts by weight of maleic anhydride was dissolved in 300 tri of N-methyl-2-pyrrolidone (NMP), and while stirring in a nitrogen gas atmosphere, 2,2 -Bis(4-
57.8 parts by weight of (4-aminobenzcarboxylate)phenyl]hexafluoropropane was added to NMP 500
A solution dissolved in mf was gradually added dropwise. After reacting with stirring at room temperature for 4 hours, 300 rnl of acetic anhydride, 1 part by weight of potassium acetate, and 0.5 ml of triethylamine were added.
The reaction was stirred at 0"C to 100"C for about 2 hours. Thereafter, the reaction product was poured into cooled pure water of about 300 On/O to form a precipitate.Then, the precipitate was filtered, washed, and dried to obtain the aromatic unsaturated bisimide compound of the present invention. CD) was obtained. As a result of measuring the IR spectrum of the aromatic unsaturated bisimide compound, 1710cn+-
Characteristic absorptions derived from imide bonds were observed at ' and 1782 cm-'.

Example 5 The same method as in Example 4 was used except that 19.6 parts by weight of maleic anhydride in Example 4 was replaced with 32 parts by weight of methylendomethylenetetrahydrophthalic anhydride. An unsaturated bisimide compound (E) was obtained.

As a result of measuring the IR spectrum of the aromatic unsaturated bisimide compound, characteristic absorptions derived from imide bonds were observed at 1710 cm-' and 1778 cm-'.

Application Examples 9 to 14 Aromatic unsaturated bisimide compounds CD) and (E) obtained in Example 4 and Example 5, and epoxy compound EOC
N-1028 (manufactured by Hitachi Chemical Co., Ltd.), novolak type phenolic resin IP-607N (manufactured by Hitachi Chemical Co., Ltd.), N, N'
-Bismaleimide-diphenylmethane, 2,2-bis(
4-(4-maleimidophenoxy)phenyl]hexafluoropropane and poly p-hydroxystyrene resin (manufactured by Maruzen Sekiyu Co., Ltd.) in the proportions shown in Table 2, (
(parts by weight) were mixed to prepare different formulations. In addition, 5 parts by weight of dicyandiamide, 2 parts by weight of triphenylphosphine as a curing accelerator, 4 parts by weight of an acylate type alkoxy titanate compound S-181 (manufactured by Nippon Soda Co., Ltd.) and epoxy silane KBH303 as a coupling agent. (Manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part by weight, 2 parts by weight of calcium stearate as a mold release agent, 81 parts by weight of Bexto wax, and an average particle size of 1 μm as a filler.
60% by weight of spherical alumina powder and an average particle size of 5~
25% by weight of 44 μm spherical fused silica glass powder;
After adding 2 parts by weight of carbon black as a coloring agent, the mixture was uniformly mixed using a kneader.

The above composition is then applied to 175-180″C170kg/
Various cured products (test specimens for measuring characteristics) were prepared by pressurizing and heating molding under the conditions of cd for 2 minutes.

Table 2 shows the characteristics of various cured products.

Table 2 shows the characteristics when 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane (old DAPP-B) was used as a comparative example of aromatic unsaturated bisimide compounds. .

(Space below this page) Application example 15 Sumiepoxy ESA-110 (bisphenol A type epoxy resin manufactured by Sumitomo Chemical, epoxy equivalent: 480) 60 parts by weight, 40 parts by weight of aromatic unsaturated bisimide (A), 40 parts by weight of methyl ethyl ketone, N- Methylpyrrolidone 40
Dissolved in dicyandiamide 1.6 parts by weight, 1
．． 2.0 parts by weight of 2.3-benzotriazole (B7^) was added and uniformly dissolved to obtain an epoxy resin composition.

The composition was coated with glass cloth (Kanebo Glass Fiber Co., Ltd. KS-
1600 plain weave), air-dried, and then heated at 130°C for 25 minutes in a constant temperature bath to obtain a prepreg.

6 layers of prepreg 160″C, 100kg/c4.20
The laminate was press-molded under conditions of 10 minutes, and then post-cured in a constant temperature bath at 180° C. for 60 minutes to obtain a laminate. Further, a copper-clad laminate was obtained using copper foil (32 μm manufactured by Furukawa Electric Co., Ltd.) and prepreg 6N under the same conditions as above. These obtained laminates are J
Table 3 shows the properties measured according to IS-C-6481.

(Margins below this page) Table 3 As shown in Table 3, the laminate of this application example has greater peel strength and lower water absorption after boiling than the conventional laminate.

Furthermore, it has excellent soldering heat resistance after boiling and a high glass transition point.

Comparative Example 2 A copper-clad laminate was produced in the same manner as in Application Example 15, except that 40 parts by weight of 4,4-bismaleimide-diphenylmethane was used instead of 40 parts by weight of aromatic unsaturated bisimide (A) in Application Example 15. was prepared and its characteristics were measured according to JIS-C-6481. The results are shown in Table 4.

Table 4 [Effects of the Invention] As explained above, according to the present invention, a novel unsaturated bisimide compound useful as a polymer raw material is provided, and by using the compound or this and other polymer raw materials, A polymer with excellent heat resistance, flexibility, moldability, and adhesiveness can be obtained.

Claims (1)

[Claims] 1. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, X_1 and X_2 are -O-, ▲mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, and may be the same or different. However, both X_1 and X_2 are −
It never becomes O-. Moreover, D_1 and D_2 are divalent organic groups having an ethylenically unsaturated double bond group, and may be the same or different from each other. R_1 to R_4 represent hydrogen, a lower alkyl group, or a perfluoroalkyl group, and may be the same or different from each other. R_5 and R
_6 represents hydrogen, a lower alkyl group, or a perfluoroalkyl group, and may be the same or different. ) is an unsaturated bisimide compound represented by 2. Claims characterized in that X_1, The unsaturated bisimide compound according to item 1. 3. General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (In the formula, X_1, X_2 are -O-, ▲ Numerical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, and may be the same or different. However, both X_1 and X_2 are −
It never becomes O-. R_1 to R_4 represent hydrogen, a lower alkyl group, or a perfluoroalkyl group, and may be the same or different from each other. R_5 and R_6 are hydrogen, a lower alkyl group, or a perfluoroalkyl group, and may be the same or different. ) and general formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] and general formula [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [IV] (In the formula, D_1 and D_2 are divalent organic groups having an ethylenically unsaturated double bond group, and may be the same or different from each other.) React the ethylenically unsaturated dicarboxylic acid anhydride represented by The following general formula [I] ▲ includes mathematical formulas, chemical formulas, tables, etc.▼ [I] (In the formula, X_1 and X_2 are -O-, ▲mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, and may be the same or different. However, both X_1 and X_2 are −
It never becomes O-. Further, D_1 and D_2 are divalent organic groups having an ethylenically unsaturated double bond group, and may be the same or different from each other. R_1~R_4
represents hydrogen, a lower alkyl group, or a perfluoroalkyl group, and may be the same or different from each other. R_5 and R_6 are hydrogen, a lower alkyl group, or a perfluoroalkyl group, and may be the same or different from each other. ) A method for producing an unsaturated bisimide compound represented by 4.X_1,
4. The method for producing an unsaturated bisimide compound according to claim 3, wherein is a methyl group, and D_1 and D_2 are -CH=CH-.