JPH07228546A - Allylated polyphenol, its production, curing agent for epoxyresin and for maleimideresin - Google Patents

Abstract

PURPOSE:To obtain an allylated polyphenol having a specific chemical structure and easy handling property, useful as an intermediate, curing agent, etc., for an epoxyresin useful for IC containment material, capable of giving a superior forming processability, flexibility, impact resistance and water proof property to a cured material. CONSTITUTION:An allylated phenol of formula I [Ar is a 6-15C benzene ring (derivative); R<1> is an alkylene with a carbon number of 5, 10 or 15; R<2> is a group of formula II ((q) is 1 or 2), formula III or formula IV, and a group having a mixed chain of these with a total chain length of 10 or less; at least one of R<1> and R<2> is -C5H10-; P is 1 or 2; (n) is 0 or 1]. This allylated polyphenol is obtained by reaction a compound of the formula HO-Ar-(R<3>)n-R<1>-Ar-OH [R<3> is a group of the formula C5mH10m-Ar(OH) (m is 1-3) or a group having a mixed chain of these, but the total number of these chains in the mixed chain is 10 or less] with an alkali compound and an allyl halide, and then conducting a Claisen rearrangement.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to novel allylated polyphenols useful as curing agents for epoxy resin intermediates and epoxy resins and maleimide resins, a method for producing the same, and an epoxy resin containing the allylated polyphenols. The present invention relates to a curing agent and a curing agent for maleimide resin.

[0002]

2. Description of the Related Art Conventionally, as allylated phenols,
Allylphenol produced from phenol and allyl halide, diallylphenol produced from bisphenols (US Pat. No. 2,910,455) and the like are known. Further, a curable resin composition comprising these allylated phenols and a maleimide compound (JP-A-55-39242), a curable resin composition comprising an allylated phenol, a maleimide compound and an epoxy resin (JP JP-A-53-134099) is also known.

However, these allylated phenols are
When used as a curing agent for maleimide resin or epoxy resin, a cured product with excellent mechanical properties can be provided even at a high temperature of 200 ° C, but the cured product is brittle and easily absorbs a relatively large amount of water. However, there is a drawback that mechanical properties deteriorate under high temperature and high humidity conditions.

As resins for improving these disadvantages, polyaddition products of dicyclopentadiene and phenol, and allylated products of polyaddition product of limonene and phenol (US Pat. No. 4,546,129, JP-A-4-139142). Gazette) has been proposed. Although these resins have improved the above-mentioned drawbacks of the resins, they have high viscosity and therefore have a problem such as lack of workability when used as a curing agent for maleimide resin compositions and the like.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel allylated polyphenol which is easy to handle and is useful as an epoxy resin intermediate and a curing agent for epoxy resin and maleimide resin. It is in.

Another object of the present invention is to provide an epoxy resin composition which can be used especially for laminates, etc., by imparting excellent solvent solubility and the like to a cured product and having excellent moldability, flexibility and resistance. It is an object of the present invention to provide a curing agent for an epoxy resin which can give impact resistance and moisture resistance.

Another object of the present invention is to provide a maleimide resin composition which can be used as CFRP matrix resin, multilayer printed circuit board, IC encapsulant, powder coating material, electrical insulating material, precision molding material, adhesive agent, etc. Another object of the present invention is to provide a curing agent for a maleimide resin, which is capable of imparting excellent solvent solubility and the like to a cured product and imparting excellent moldability, flexibility, impact resistance, moisture resistance and the like.

[0008]

According to the present invention, an allylated polyphenol represented by the following general formula (5) (hereinafter referred to as allylated polyphenol A) is provided.

[0009]

[Chemical 5]

According to the present invention, the compound represented by the following general formula 6 is obtained by reacting an isoprene-containing substance with a phenol having a benzene ring or a naphthalene ring having 6 to 15 carbon atoms in the presence of an acid catalyst. There is provided a method for producing the allylated polyphenol A, which comprises reacting a polyphenol (hereinafter referred to as polyphenol B) with an alkali compound and an allyl halide and then performing Claisen rearrangement.

[0011]

[Chemical 6]

Further according to the present invention, there is provided an allylated polyphenol represented by the following general formula 7 (hereinafter referred to as allylated polyphenol C).

[0013]

[Chemical 7]

Furthermore, according to the present invention, there is provided a curing agent for an epoxy resin containing the above allylated polyphenol A or C.

Further, according to the present invention, there is provided a curing agent for a maleimide resin, which contains the above allylated polyphenols A or C.

The present invention will be described in more detail below. The allylated polyphenols of the present invention are the allylated polyphenols A represented by the general formula 5 and the allylated polyphenols C represented by the general formula 7. The average molecular weight of the allylated polyphenols A and C is
It is preferably 336 to 2000, especially 350 to 1000, and the viscosity at 70 ° C. is preferably 1 to 500 poises, particularly 1 to 100 poises. The hydroxyl equivalent is 168 to 350 g / eq, especially 170 to 250 g.
It is preferably / eq. If it is less than 168 g / eq, the moisture resistance is not sufficient, and if it exceeds 350 g / eq, the curability is insufficient, which is not preferable.

In the allylated polyphenols A, Ar is a group consisting of a benzene ring, a benzene ring derivative, a naphthalene ring or a naphthalene ring derivative, and the group consisting of the benzene ring derivative is represented by the following formula (8). A structure etc. can be mentioned.

[0018]

[Chemical 8]

Further, examples of the group consisting of a naphthalene ring derivative include a structure represented by the following chemical formula 9.

[0020]

[Chemical 9]

In the above-mentioned allylated polyphenols A, R ¹ is a group derived from an isoprene-containing material described later, and specifically, for example, -C ₅ H ₁₀ -CH ₂ CH (CH ₃ ). CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH (CH ₃ )-, -C (CH ₃ ) ₂ C
H ₂ CH _2- , -C (CH ₃ ) ₂ CH (CH ₃ )-, -CH ₂ CH ₂ CH ₂ CH (CH ₃ )-, -CH ₂
CH ₂ CH (C ₂ H ₅ )-, -CH (CH ₃ ) CH (C ₂ H ₅ )-, -CH (CH ₃ ) CH ₂ CH (C
H ₃₎ - group is derived from isoprene monomers such as; -C ₁₀ H ₂₀ -
-(CH ₂ CH (CH ₃ ) CH ₂ CH ₂ ) ₂ -,-(CH ₂ CH (CH ₃ ) CH (CH
₃ )) ₂ -,-(C (CH ₃ ) ₂ CH ₂ CH ₂ ) ₂ -,-(C (CH ₃ ) ₂ CH (CH ₃ )) ₂ -,-
(CH ₂ CH ₂ CH ₂ CH (CH ₃ )) ₂ -,-(CH ₂ CH ₂ CH (C ₂ H ₅ )) ₂ -,-(CH (CH
₃ ) CH (C ₂ H ₅ )) ₂ -,-(CH (CH ₃ ) CH ₂ CH (CH ₃ )) _2-, etc. isoprene dimer-derived groups; represented by -C ₁₅ H _30- -(CH ₂ C
H (CH ₃ ) CH ₂ CH ₂ ) ₃ -,-(CH ₂ CH (CH ₃ ) CH (CH ₃ )) ₃ -,-(C (CH ₃ ) ₂
CH ₂ CH ₂ ) ₃ -,-(C (CH ₃ ) ₂ CH (CH ₃ )) ₃ -,-(CH ₂ CH ₂ CH ₂ CH (C
H ₃ )) ₃ -,-(CH ₂ CH ₂ CH (C ₂ H ₅ )) ₃ -,-(CH (CH ₃ ) CH (C ₂ H ₅ ))
_{3 -, - (CH (CH} 3) CH 2 CH (CH 3)) 3 - , or the like can be isoprene trimer preferably exemplified group derived from body.

In R ² of the allylated polyphenols A, the mixed chain means that two or three kinds of the respective constituent chains represented by the following formula 10 shown in the formula 5 are bonded randomly or in a block or the like. In this case, it means a binding chain.

[0023]

[Chemical 10]

The total of the constituent chains is 10 or less. 1
When it exceeds 0, an epoxy resin composition using this,
The fluidity of the maleimide resin composition at the time of molding becomes poor. Also -C ₅ H ₁₀ in the formula -, - C ₁₀ H ₂₀ - or -C ₁₅ H ₃₀ - Examples of can be mentioned those similar to the groups specifically enumerated in the R ^1.

In the allylated polyphenols A, the -C ₅ H _10- , -C ₁₀ H ₂₀ -,-in R ¹ and R ² is
C ₁₅ H ₃₀ -may be the same or different, but at least-
It is preferable that C ₅ H _10- becomes closer to 20 to 100 mol%, particularly 30 to 100 mol%, and more preferably 100 mol% with respect to the total amount of R ¹ and R ² . If it is less than 20 mol%, the curability is deteriorated, which is not preferable.

The allylated polyphenols A of the present invention are
Allylated polyphenol C represented by the above formula 7
And R in the formula of the allylated polyphenol C
¹ is the same as R ¹ in the formula of 5, also R ⁴ is a group in R ² of the formula of 5 Ar is benzene ring, and the total of mixed chain of 2 or less, p is 1 It is the same as the expression 5 except for the case of. As other specific examples of the allylated polyphenols A, there may be mentioned compounds in which Ar and R ₁ listed above are specifically combined, preferably, for example, the compounds represented by the following formula 11 and the like. .

[0027]

[Chemical 11]

In order to produce the allylated polyphenol A containing the allylated polyphenol C, first, an isoprene-containing material and a phenol having a benzene ring or a naphthalene ring having 6 to 15 carbon atoms are prepared in the presence of an acid catalyst. By reacting, the polyphenol B represented by the general formula 6 is prepared. Ar in polyphenols B
Is the same as Ar in the above formula 5, and R ³ is the same as the above formula 5.
R ² is the same except that it does not have an allyl group.

The isoprene-containing material includes diolefins having 4 to 15 carbon atoms, such as butadiene, piperylene, cyclopentadiene, cyclohexadiene, norbornadiene, dicyclopentadiene, tetrahydroindene, in addition to the use of isoprene alone. It may contain vinyl norbornene, tricyclopentadiene, pinene, limonene, etc., and the content thereof is preferably 0 to 3
It is 0% by weight.

Specific examples of the phenol having a benzene ring or a naphthalene ring having 6 to 15 carbon atoms include phenol, o-cresol, m-cresol and p.
-Cresol, diethylphenol, hydroquinone, catechol, resorcin, pyrogallol, α-naphthol, β-naphthol, dihydroxynaphthalene, bisphenol A, dihydroxybiphenyl and the like can be mentioned, and phenol and cresol are particularly preferable.

The amount of phenol having a benzene ring or a naphthalene ring having 6 to 15 carbon atoms is 0.8 to 2 with respect to 1 equivalent of isoprene in the isoprene-containing material.
0 equivalent is preferable, and 1 to 12 equivalent is particularly desirable.

Examples of the acid catalyst include inorganic acids such as sulfuric acid; alkanesulfonic acids having 1 to 10 carbon atoms such as p-toluenesulfonic acid and methanesulfonic acid; trifluoromethanesulfonic acid; trifluoroacetic acid; anion exchange resins. ;
Heteropoly acid; AlCl ₃ ; BF _{3 and the} like can be mentioned. From the viewpoint of activity and ease of post-treatment, a BF ₃ -based catalyst,
Specifically, BF ₃ -phenol complex, BF ₃ -ether complex, BF ₃ -amine complex and the like are particularly preferable.

The amount of the acid catalyst charged varies depending on the kind of the acid catalyst used and the purpose. For example, in the case of BF ₃ -phenol complex, it is 0.1 with respect to 100 parts by weight of isoprene in the isoprene-containing material. -15 parts by weight, especially 1-
8 parts by weight is desirable.

In the reaction of the isoprene-containing material with the phenol having a benzene ring or a naphthalene ring having 6 to 15 carbon atoms (hereinafter referred to as "alkylation"), it is preferable to use a solvent within the range that does not affect the reaction. it can. Specific examples of the solvent include benzene, toluene, xylene, chlorobenzene, dichloroethane and the like.

The reaction temperature for carrying out the above-mentioned alkylation varies depending on the kind of the acid catalyst used, but is, for example, B
In the case of an F ₃ -phenol complex, the temperature is preferably 10 to 170 ° C, and particularly preferably 50 to 150 ° C. After completion of the alkylation, the catalyst is deactivated with sodium hydroxide, potassium hydroxide, magnesium hydroxide, magnesium oxide, hydrotalcites, etc., and further washed with water or filtered to remove and concentrate the polyphenol. Class B
Can be obtained. At this time, it is particularly preferable to use hydrotalcites which can be easily removed only by filtering the deactivating agent after deactivating the acid catalyst.

In the above alkylation, R ¹ and R ³ in the obtained polyphenols B are —C ₅ H ₁₀ —.
In order to improve the selectivity of (alkylene chain consisting of 1 unit of isoprene), an excess equivalent amount to the isoprene-containing substance,
Specifically, homopolymerization of isoprene is carried out by a method of sequentially adding an isoprene-containing material to a system composed of a phenol having a benzene ring or a naphthalene ring having 6 to 15 carbon atoms in an amount of 5 to 15 times equivalent and an acid catalyst. A method of advancing an alkylation reaction while suppressing is preferable.

After completion of the alkylation, for example, by precision distillation or the like, the target raw material polyphenol B is obtained.
Can be prepared.

Then, in the production method of the present invention, the obtained polyphenol B is subjected to an allyl etherification reaction with an alkali compound and an allyl halide such as allyl chloride or allyl bromide. In this case, the alkali compound preferably includes, for example, inorganic bases such as sodium hydroxide and potassium hydroxide; alkali metal alkoxides such as sodium methoxide and sodium ethoxide.

The allyl etherification reaction can be carried out, for example, in the range of room temperature to 120 ° C., and specifically, a solution prepared by dissolving polyphenol B in a solvent such as n-propanol, n-butanol or acetone is used. It can be carried out by a method of dropping allyl halide to a system composed of an alkali compound and then reacting it for 0.1 to 10 hours. After the allyl etherification reaction, an allyl ether compound can be obtained by a method such as filtration of salts, washing with water, and distillation of the organic layer. The amount of the alkali compound charged is preferably 1 to 10 times, and more preferably 1 to 1.5 equivalents, relative to 1 equivalent of polyphenol B. Further, the charged amount of allyl halide is preferably 1 to 20 times equivalent, particularly 1 to 8 times equivalent to the polyphenol B.

Next, in the production method of the present invention, the allyl ether compound is subjected to Claisen rearrangement to produce an allylated polyphenol A containing the desired allylated polyphenol C. When the Claisen rearrangement is carried out without a catalyst, it can be promoted by a method of heating the allyl ether compound at preferably 120 to 230 ° C. for 0.1 to 10 hours. Also acid,
When the reaction is carried out in the presence of a catalyst such as an alkali or transition metal catalyst, the reaction proceeds under milder conditions as compared with the non-catalyst, but it is preferable to manufacture the catalyst without considering the complexity of removing the catalyst. Further, in the case of causing Claisen rearrangement in a solvent, it is preferable to carry out the reaction in a high boiling point solvent such as N, N′-dimethylaniline, tetralin, paraffin oil, carbitol or the like.

The curing agent for epoxy resin of the present invention contains the allylated polyphenol A or C. The content is preferably 30 to 100% by weight, particularly preferably 50 to 100% by weight. If the amount is less than 30% by weight, the curability of the cured epoxy resin will be decreased, and the desired cured product will not have desired moldability, flexibility, impact resistance and water resistance. There is a fear that it is not preferable.

In the epoxy resin curing agent of the present invention, in addition to the above-mentioned essential components, a known phenol resin may be used in combination as long as low hygroscopicity and curability are not impaired. Examples of the known phenol resin include bisphenol A, brominated bisphenol A, novolac phenol resin, novolac orthocresol resin, bisphenol A novolac type phenol resin, bisphenol F novolac type phenol resin, brominated novolac phenol resin, naphthol novolac type phenol. Preferable examples include resins and their allylated products. The blending ratio of the phenol resin is preferably in the range of 0 to 70% by weight based on the total amount of the curing agent for epoxy resin.

In order to prepare an epoxy resin cured product using the epoxy resin curing agent of the present invention, the epoxy resin curing agent, the epoxy resin and, if necessary, a curing accelerator are mixed, Preferably, it can be obtained by a method such as a curing reaction at a reaction temperature of 110 to 250 ° C. for 0.5 to 8 hours. In this case, the compounding ratio of the curing agent for epoxy resin is such that the hydroxyl group in the allylated polyphenol A or C in the curing agent for epoxy resin is 0.5 to 2 with respect to 1 equivalent of the epoxy group in the obtained epoxy resin. It is preferable to mix them in an amount of 0.0 equivalent, particularly 0.8 to 1.2 equivalent.

Specific examples of the epoxy resin include bisphenol A diglycidyl ether type epoxy resin,
Phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, brominated phenol novolac type epoxy resin, brominated bisphenol A glycidyl ether, naphthol novolac type epoxy resin, biphenyl di Examples thereof include trifunctional epoxy resins such as glycidyl ether resin and triglycidyl ether of trihydroxyphenylmethane, and tetrafunctional epoxy resins.

As the above-mentioned curing accelerator, any known and commonly used one can be used. For example, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complexes, phosphorus compounds such as triphenylphosphine, etc. They can be used, and when used, they can be used alone or as a mixture. The mixing ratio is preferably 0.01 to 5% by weight with respect to the total amount of the raw materials.

The epoxy resin curing agent of the present invention can be used as a curing agent for an epoxy resin composition which is useful for, for example, printed wiring boards, IC sealing materials, conductive pastes, powder coatings, solder resists, etc. Especially when used for applications such as encapsulants and insulating powder coatings, in addition to the above-mentioned curing accelerator, a filler, a colorant, a flame retardant, a release agent, a coupling agent, etc. are added to the epoxy resin composition. Can be used for desired purposes by using various additives; tar, pitch, amino resin, alkyd resin and the like in combination. Examples of the filler include crystalline silica powder, fused silica powder, alumina powder, takule, quartz glass powder, calcium carbonate powder, glass fiber and the like.

Since the epoxy resin composition using the curing agent for epoxy resin of the present invention is excellent in not only its excellent performance but also solvent solubility and the like, it should exhibit high performance also in applications such as laminates. You can For use as a laminate, it can be carried out, for example, by impregnating a glass cloth or the like with the epoxy resin composition solution containing the curing agent for an epoxy resin of the present invention, and laminating and molding a dried prepreg. At this time, a halogenated phenol resin or the like may be simply blended in the composition, or may be subjected to an addition reaction with a halogenated polyepoxy compound or the like to newly be used as a modified phenol resin or an epoxy resin. .

The curing agent for maleimide resin of the present invention contains the above allylated polyphenols A or C. In particular the allylation polyphenols A or C, in order to improve the workability, -C contained in ^{R 1, R 2, R 4} 5 H
The ratio of ₁₀ − is 50% or more, and the carbon number of Ar is 6, n
It is preferred to use allylated polyphenols A or C which is = 0 or R ² or R ⁴ with no mixed chains. The content of the allylated polyphenols A or C is preferably 10 to 100% by weight, particularly preferably 30 to 100% by weight. When the amount is less than 10% by weight, the curability is lowered when the maleimide resin cured product is prepared, and the desired cured product is not provided with desired moldability, flexibility, impact resistance and water resistance. There is a fear that it is not preferable.

In addition to the above-mentioned essential components, the maleimide resin curing agent of the present invention may be used in combination with the known compatible phenol resins listed in the above-mentioned epoxy resin curing agent. The mixing ratio of the phenol resin is preferably in the range of 0 to 90% by weight based on the total amount of the curing agent for maleimide resin.

In order to prepare a maleimide resin cured product by using the maleimide resin curing agent of the present invention, a maleimide resin curing agent, a maleimide compound and, if necessary, a curing accelerator are mixed and preferably used. Can be obtained by a method such as a curing reaction at a reaction temperature of 130 to 250 ° C. for 10 minutes to 24 hours. At this time, the compounding ratio of the curing agent for maleimide resin is such that the imide group in the obtained maleimide resin is 1
With respect to the equivalent weight, the allyl group in the allylated polyphenols A or C in the curing agent for maleimide resin is 0.5 to
It is preferable that the compounding amount be 1.5 equivalents.

The maleimide compound is not particularly limited as long as it contains at least one N-substituted maleimide group represented by the following formula 12 as a structural unit in one molecule. For example, the following general formula 13 Preferable examples are the compounds represented.

[0052]

[Chemical 12]

[0053]

[Chemical 13]

(In the formula, R ⁵ is an unsubstituted or halogen-substituted divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and 6 to 2 carbon atoms.
0 unsubstituted or halogen-substituted divalent aromatic hydrocarbon group,
An unsubstituted or halogen-substituted alkylenearylene group composed of these, or a substituent having a functional group such as ether, thioether, sulfoxide, and sulfone as a part of these divalent organic groups is shown. ) Examples of R ⁵ include groups represented by the following chemical formula 14.

[0055]

[Chemical 14]

N represented by the above formulas 12 and 13
Specific examples of the maleimide compound having a -substituted maleimide group include N, N'-diphenylmethane bismaleimide, N, N'-phenylene bismaleimide,
N, N'-diphenyl ether bismaleimide, N,
N'-diphenylsulfone bismaleimide, N, N'-
Dicyclohexylmethane bismaleimide, N, N'-xylene bismaleimide, N, N'-tolylene bismaleimide, N, N'-xylylene bismaleimide, N, N '
-Diphenylcyclohexane bismaleimide, N, N '
-Dichloro-diphenyl bismaleimide, N, N'-diphenylmethane bismethyl maleimide, N, N'-diphenyl ether bismethyl maleimide, N, N'-diphenyl sulfone bismethyl maleimide, N, N'-ethylene bismaleimide, N, N N-N'-bismaleimide such as'-hexamethylene bismaleimide; a prepolymer having an N, N'-bismaleimide skeleton at the end obtained by adding N, N'-bismaleimide and diamines You can

Examples of the maleimide compound include a maleimide compound represented by the above formula 13 and a maleimide compound of aniline and formalin condensate represented by the following general formula 15, N-substituted monomaleimide such as phenylmaleimide, and N. It is also possible to mix and use -substituted trimaleimide, N-substituted tetramaleimide or a compound obtained by modifying these maleimide compounds with silicone.

[0058]

[Chemical 15]

The maleimide compounds may be used alone or as a mixture, and among them, N-substituted bismaleimide, N-substituted trimaleimide and the like are preferable,
Particularly, N, N'-diphenylmethane bismaleimide and the like are preferable, and most preferably N, N'-tetramethyldiphenylmethane bismaleimide and the like are used.

Examples of the curing accelerator include tertiary amines, quaternary ammonium salts, BF ₃ salts, imidazoles, peroxides, phosphorus compounds such as triphenylphosphine, and the like. Is preferably 0.1 to 5.0% by weight with respect to the total amount of the raw materials.

The curing agent for maleimide resin of the present invention is, for example, CFRP matrix resin, multilayer printed circuit board, IC
Sealing material, powder coating material, electrical insulation material, precision molding material,
It can be used as a curing agent for a maleimide resin composition useful as an adhesive or the like, and depending on the application, it may be used in combination with the epoxy resin described above and various additives similar to those used in the epoxy resin composition described above. It can also be used.

[0062]

The allylated polyphenols of the present invention are
Since it has a very low viscosity, it is easy to handle and can be used for various applications such as an epoxy resin intermediate and a curing agent for epoxy resin and maleimide resin. In addition, such a novel allylated polyphenol can be easily obtained by the production method thereof. On the other hand, since the epoxy resin curing agent of the present invention contains the above-mentioned allylated polyphenols, it can be used as an epoxy for printed wiring boards, IC encapsulants, conductive pastes, powder coatings, solder resists, laminated boards, etc. It is useful as a curing agent for resin compositions, imparts excellent solvent solubility, and the like, and can impart cured products with excellent moldability, flexibility, bending strength, impact strength, moisture resistance, and the like. Further, the curing agent for maleimide resin of the present invention,
Since it contains the allylated polyphenols, for example, curing of a maleimide resin composition that can be used as a CFRP matrix resin, a multilayer printed circuit board, an IC encapsulant, a powder coating material, an electrical insulating material, a precision molding material, an adhesive, etc. It is useful as an agent, imparts excellent solvent solubility and the like, and can give a cured product excellent moldability, flexibility, bending strength, impact strength, moisture resistance and the like.

[0063]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[0064]

Example 1 Synthesis of polyphenols Phenol 4 was added to a four-necked flask equipped with a stirrer and a thermometer.
700 g and BF ₃ -phenol complex 20 g were charged and mixed well. Next, while maintaining the system temperature at 70 ° C., 680 g of isoprene was added over 2.5 hours, and then the system temperature was maintained at 140 ° C. and heated and stirred for 3 hours. After completion of the reaction, 350 g of a 2 wt% sodium hydroxide aqueous solution was added to the obtained reaction product solution, and the mixture was stirred for 2 hours to deactivate the catalyst. After standing for 2 hours, add 3000 g of toluene,
The washing operation with water was repeated 3 times to collect the organic layer. Then, unreacted phenol was removed by distillation to obtain 1810 g of a brown polyphenol (I).

When the obtained polyphenols (I) were distilled under reduced pressure, 1540 g of transparent polyphenols (II) were obtained. Then, the OH equivalent of the polyphenols (II) was measured by the method of back titration of the residual acid amount after esterification with acetic anhydride, and it was 130 g / eq. Also, F
When the molecular weights of the components in the polyphenols were determined by D-MS, it was found that the molecular weight of 256 was the main component, and some of the components of the molecular weight of 324 were included. Polyphenols having a molecular weight of 256 were obtained by adding 2 molecules of phenol to 1 unit of isoprene, and polyphenols having a molecular weight of 324 were obtained by adding 2 molecules of phenol to 2 units of isoprene. Moreover, when the ratio of each component was determined by capillary gas chromatography analysis, polyphenols having a molecular weight of 256 were 90% by weight and polyphenols having a molecular weight of 324 were 1%.
It was contained in an amount of 0% by weight. From the ¹ H-NMR analysis of the distillate as well, absorption supporting the existence and proportion of each of these components was observed. In the ¹ H-NMR analysis of the polyphenols (II), no proton absorption was observed at δ 4.5 to 6 ppm. Therefore, a double bond is not present in the alkylene chain of 2 units of isoprene of the polyphenols having a molecular weight of 324. It was found that there was one cycloalkylene group.

Synthesis of allylated polyphenols In a four-necked flask equipped with a stirrer, thermometer and dropping funnel, n
-800 ml of propanol, the polyphenols (II)
After charging 260 g and dissolving, sodium hydroxide 80
g was added and stirred until a homogeneous solution was obtained. Next, 200 g of allyl chloride was added at a system temperature of 40 ° C. over 1 hour, the temperature was raised to 70 ° C., and stirring was performed for 4 hours. After the completion of the reaction, the reaction solution was filtered to remove the by-produced sodium chloride, and then n-propanol was distilled off under reduced pressure to collect.
Then, the residue was dissolved in methyl isobutyl ketone and washed with water, and then methyl isobutyl ketone was distilled off and recovered. The obtained allyl ether compound was distilled off under reduced pressure to obtain 290 g of an allyl ether compound of polyphenols.

This allyl ether compound was placed in a four-necked flask equipped with a stirrer and a thermometer, and heated at 200 ° C. for 8 hours to obtain transparent allylated polyphenols.
The viscosity of the obtained allylated polyphenols is 900 poise (25 ° C.), 3 poise (70 ° C.), and OH equivalent is 182.
It was g / eq. Figure 1 in carbon tetrachloride - ¹ H-N allylated polyphenols measured in deuterated methanol
An MR spectrum is shown. In FIG. 1, δ 6.5 to 7.
5 ppm aromatic ring proton, δ 5.8 to 6.3 ppm allyl group double bond methine proton, δ 4.7 to 5.4
ppm methylene proton of allyl group double bond, δ3.
From the area ratio of the benzylic methylene proton of the allyl group of 2 to 3.6 ppm and the proton of the alkylene skeleton of δ 0.8 to 3.0 ppm and the OH equivalent of the polyphenols, the allylated polyphenols are aromatic with an allyl group. It was found that one ring was introduced per ring. Figure 2
Shows the FD-MS spectrum of this polyallylphenol. From this, it was found that a component having a molecular weight of 336, that is, an allylated polyphenol represented by the following formula 16 was the main component.

[0068]

[Chemical 16]

[0069]

Example 2 To 100 parts by weight of the allylated polyphenols obtained in Example 1 was added an equivalent amount of a bisphenol A type epoxy resin (trade name "Epicoat 828", manufactured by Yuka Shell Co., Ltd., epoxy equivalent 185). Then 170 ℃, 2
After melt-mixing for 0 minutes, 1 part by weight of triphenylphosphine was added as a curing accelerator. After further thoroughly mixing and degassing for 5 minutes, the mixture is poured into a mold and pre-cured at 100 ° C. for 3 hours, followed by post-curing at 200 ° C. for 6 hours to cure 150 mm × 150 mm, thickness 4 mm. I got a thing. The composition and physical properties of the obtained cured product are shown in Table 1.

[0070]

Comparative Example 1 Instead of the allylated polyphenols synthesized in Example 1, o, o′-diallylbisphenol A was used.
A cured product was obtained in the same manner as in Example 2 except that was used.
The composition and physical properties of the obtained cured product are shown in Table 1.

[0071]

Example 3 100 parts by weight of the allylated polyphenols obtained in Example 1 was mixed with an equivalent amount of a general-purpose bismaleimide (trade name "MB-3000", manufactured by Mitsubishi Petrochemical Co., Ltd.).
Then, after melt-mixing at 155 ° C. for 20 minutes and sufficiently degassing, the mixture is poured into a mold and cured at 180 ° C. for 5 hours,
A cured product having a size of mm × 150 mm and a thickness of 4 mm was obtained. The composition and physical properties of the obtained cured product are shown in Table 1.

[0072]

Comparative Example 2 Instead of the allylated polyphenols synthesized in Example 1, o, o′-diallylbisphenol A was used.
A cured product was obtained in the same manner as in Example 3 except that was used.
The composition and physical properties of the obtained cured product are shown in Table 1.

[0073]

[Table 1]

[Brief description of drawings]

FIG. 1 is a chart showing the measurement results of ¹ H-NMR spectrum of allylated polyphenols prepared in Example 1.

FIG. 2 is a chart showing measurement results of FD-MS spectrum of allylated polyphenols prepared in Example 1.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Otsuki 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Nihon Sekiyu Co., Ltd. Central Technology Research Institute

Claims (5)

[Claims] 1. An allylated polyphenol represented by the following general formula 1. [Chemical 1] 2. An isoprene-containing material in the presence of an acid catalyst,
A polyphenol represented by the following general formula 2 obtained by reacting with a phenol having a benzene ring or a naphthalene ring having 6 to 15 carbon atoms is reacted with an alkali compound and an allyl halide, and then subjected to Claisen rearrangement. A method for producing an allylated polyphenol represented by the following general formula (3). [Chemical 2] [Chemical 3] 3. An allylated polyphenol represented by the following general formula 4. [Chemical 4] 4. A curing agent for an epoxy resin, comprising the allylated polyphenol according to claim 1 or 3. 5. A curing agent for a maleimide resin, which comprises the allylated polyphenol according to claim 1 or 3.