JP2002080484A - Phosphorus containing hydroquinone derivative, method for producing the same and flame retardant - Google Patents

Abstract

(57) [Problem] To provide a phosphorus-containing hydroquinone derivative useful as an intermediate material for a reactive flame retardant or a phosphorus-containing epoxy resin. A phosphorus-containing hydroquinone derivative represented by the following general formula (1). Embedded image (R ¹ and R ^{2 each} represent a linear or branched alkyl group which may be substituted, and one or more methylene groups in the alkyl group may be replaced by -CH = CH-. And R ¹ and R ² may form a cyclic substance containing or not containing P. X represents an oxygen atom Y and Z each represent a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, an aralkyl group, an alkoxy group, an allyl group, an aryl group or a cyano group, and Y and Z form a cyclic substance. May be used.)

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphorus-containing hydroquinone derivative, a method for producing the same, and a flame retardant. The present invention relates to the manufacturing method.

[0002]

2. Description of the Related Art Epoxy resins are widely used in electronic parts, electric equipment, automobile parts, FRP, sporting goods, etc. because of their excellent adhesiveness, heat resistance and moldability. Of these, flame retardants, particularly brominated epoxy resins and antimony compounds, are used for copper-clad laminates and sealing materials used for electric components and electric equipment. However, halogen-containing compounds and antimony compounds are feared for their safety to the human body. Therefore, environmentally friendly flame retardants are desired.

[0003] Conventionally, as a method for making an epoxy resin flame-retardant, an addition-type flame retardant is kneaded and mixed with an epoxy resin, or a reactive flame retardant is used to chemically bond the epoxy resin and the flame retardant to form the epoxy resin. A reforming method and the like have been proposed.

As a method of using an addition type flame retardant, for example, a method of using hydrated alumina (JP-A-05-253)
No. 69), a method using a modified red phosphorus (JP-A-63-1988).
156860) and a method using a modified red phosphorus and hydrated alumina (Japanese Patent Application Laid-Open No. 58-198521). However, when these additive-type flame retardants are used, the amount of the flame retardant added increases, and there is a problem in the moldability of the obtained material.

On the other hand, various methods using a reactive flame retardant have been proposed because the amount of the flame retardant to be added is small.

For example, a method using tris (hydroxypropyl) phosphine oxide (JP-A-57-1951)
No. 41), the following general formula (4)

[0007]

Embedded image

(Where x = 0 to 2, y = 1 to 3;
And x + y = 3, and R represents a methylene group or an ethylene group. Using a phosphine oxide derivative represented by the following formula (JP-A-63-95223);

[0009]

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Alternatively, the following general formula (6)

[0011]

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Wherein R is an alkyl group having 1 to 6 carbon atoms;
a method using an organophosphorus compound represented by the following formula (n represents 0 to 4) (JP-A-11-279258, JP-A-11-279258)
No. 166035), a method using an epoxy ester compound of phosphonic acid obtained by reacting phosphonic acid with a polyepoxy compound having an oxirane group or epihalohydrin (JP-A-51-143620, JP-A-03-84025). JP-A-02-272014 and JP-A-02-269730) have been proposed.

[0013]

SUMMARY OF THE INVENTION In addition, Japanese Patent Application Laid-Open No. 2000-2000
No. 80251 discloses the following general formula (7)

[0014]

Embedded image

(Wherein R ′ represents two or more phenolic O
A compound containing an H group, n ′ is an integer of 0 to 3, and R ″
Is a linear or branched alkyl group having 1 to 8 carbon atoms, a cyclohexyl group, a cyclopentyl group or an aryl group or an alkyl or alkoxy-substituted alkyl group or an aryl group having 1 to 18 carbon atoms, R ″ may form a ring together with the P atom, and m is 0 or 1.) This publication discloses a method using a phosphorus-containing compound represented by the following formula: Although it is described that a wide range of phosphorus-containing compounds is included, compounds that have been confirmed to actually exhibit flame retardancy include compounds having a phosphorus atom-oxygen atom (PO) bond. I'm just there.

[0016] However, as described above, various methods for making an epoxy resin flame-retardant with a reactive flame retardant have been proposed, but it is difficult to increase the phosphorus content of the epoxy resin until the flame-retardant effect is exhibited. In addition, those having a phosphorus atom-oxygen atom (PO) bond have a problem that they are inferior in moisture resistance and chemical resistance.

That is, an object of the present invention is to provide a novel phosphorus-containing hydroquinone derivative useful as a reactive flame retardant having a phenolic OH group that reacts with an epoxy resin or epichlorohydrin, and to produce the phosphorus-containing hydroquinone derivative industrially. An object of the present invention is to provide a manufacturing method that can be manufactured by an advantageous method.

Another object of the present invention is to provide a reactive flame retardant using the phosphorus-containing hydroquinone derivative.

[0019]

The problem is solved by the following general formula (1)

[0020]

Embedded image

(Wherein R ¹ and R ² represent an optionally substituted linear or branched alkyl group, and one or more methylene groups in the alkyl group may be -CHＣＨC
May be replaced by H-, R ¹ and R ² may be the same or different groups, and R ¹ and R ² may be cyclic with or without P May be formed. X represents an oxygen atom or a sulfur atom.

Y and Z each represent a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, an aralkyl group, an alkoxy group, an allyl group, an aryl group or a cyano group, and one or more of the alkyl groups Methylene group is -CH = CH-
And Y and Z may be the same or different groups, and Y and Z may form a cyclic substance. This is achieved by a phosphorus-containing hydroquinone derivative represented by the following formula:

The cyclic substance formed by R ¹ and R ² is preferably represented by the following general formula (12) or (13).

[0024]

Embedded image (In the formula, R ³ represents an alkylene group which may be substituted.)

[0025]

Embedded image (In the formula, R ⁴ represents a cycloalkylene group or an arylene group which may be substituted.)

The first method for producing the phosphorus-containing hydroquinone derivative represented by the general formula (1) is represented by the following general formula (2)

[0027]

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(Wherein R ^1, R ² and X are as defined above), and at least one selected from secondary phosphine derivatives represented by the following general formula (3):

[0029]

Embedded image

(Wherein, Y and Z have the same meanings as described above).

The second method for producing the phosphorus-containing hydroquinone derivative represented by the general formula (1) includes the following general formulas (2) and (2a).

[0032]

Embedded image

(Wherein R ^1, R ² and X have the same meanings as described above), and at least one selected from secondary phosphine derivatives represented by the following general formula (3):

[0034]

Embedded image

(Wherein, Y and Z have the same meanings as described above).

Further, the present invention is a flame retardant comprising the above-mentioned phosphorus-containing hydroquinone derivative.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The phosphorus-containing hydroquinone derivative of the present invention is represented by the following general formula (1).

[0038]

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In the general formula (1), R ¹ and R ^{2 each} represent a linear or branched alkyl group which may be substituted, and the alkyl group has 1 to 18 carbon atoms, preferably It is an alkyl group of Formulas 1 to 8, and specific examples thereof include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a tertiary butyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. . Also,
R ¹ and R ² in the formula may be the same or different groups. One or more methylene groups in the alkyl group may be replaced by -CH = CH-, and specific examples include a vinyl group, an allyl group, and an isopropenyl group.

R ¹ and R ² may be substituted, and examples of the substituent include a phenyl group, an alkoxy group, a cyano group and a hydroxyl group. Specific examples of the substituted R ¹ and R ² include an aralkyl group such as a benzyl group, a cyanoalkyl group, a cyanoalkenyl group, a hydroxyalkyl group, and a hydroxyalkenyl group.

Further, R ¹ and R ² may form a cyclic substance containing P or not containing P. R ¹ and R ²
Forms a cyclic substance containing P, the following general formula (1)
Cyclic substances formed by the bond represented by 2). .

Embedded image

In the general formula (12), R ³ represents an optionally substituted alkylene group.

The alkylene group is an alkylene group having 3 to 9 carbon atoms, preferably 4 to 6 carbon atoms, and specifically includes a propylene group, a butylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, Examples include an octamethylene group and a nonamethylene group. R ³ may be substituted, and examples of the substituent include a phenyl group, an alkoxy group, a cyano group, and a hydroxyl group.

When R ¹ and R ² do not contain P to form a cyclic substance, a cyclic substance formed by a bond represented by the following general formula (13) can be mentioned.

[0045]

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In the general formula (13), R ⁴ represents a cycloalkylene group or an arylene group which may be substituted.

The cycloalkylene group has 4 to 4 carbon atoms.
9, preferably a cycloalkylene group having 5 to 7 carbon atoms, and specific examples thereof include a cyclobutylene group, a cyclopentamethylene group, a cyclohexamethylene group, a cycloheptamethylene group, a cyclooctylene group, and a cyclononylene group. be able to.

Examples of the arylene group include a phenylene group, a biphenylene group and a naphthylene group.

R ⁴ may be substituted, and examples of the substituent include a phenyl group, an alkoxy group, a cyano group and a hydroxyl group. Further, in the substituents of R ³ and R ⁴ , a hetero atom such as an oxygen atom, a sulfur atom and a nitrogen atom may be contained.

X in the formula represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom. Y and Z in the formula are a hydrogen atom,
A hydroxyl group, a linear or branched alkyl group, an aralkyl group such as a benzyl group, an aryl group such as an allyl group or a phenyl group, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a phenyloxy group; . The alkyl group has 1 to 18 carbon atoms, preferably 1 carbon atom.
And specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a tertiary butyl group, and a cyclohexyl group. One or more methylene groups in the alkyl group is -CH = C
It may be replaced by H-. Y and Z may be the same or different groups.

Further, Y and Z may be groups forming a cyclic substance, and examples of the group wherein Y and Z form a cyclic substance include the cyclic groups represented by the following formulas and names.

[0052]

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However, the name in parentheses indicates the name of the ring containing hydroquinone. Further, these substituents may contain a hetero atom such as an oxygen atom, a sulfur atom and a nitrogen atom.

Specific examples of the phosphorus-containing hydroquinone derivative represented by the general formula (1) include dimethylphosphonyl-1,4-hydroquinone, diethylphosphonyl-1,4-hydroquinone, and di-n- Propylphosphonyl-1,4-hydroquinone, di-iso-propylphosphonyl-1,4-hydroquinone, di-n-butylphosphonyl-1,4-hydroquinone, di-sec
-Butylphosphonyl-1,4-hydroquinone, di-t
tert-butylphosphonyl-1,4-hydroquinone,
Dibenzylphosphonyl-1,4-hydroquinone,

Methylethylphosphonyl-1,4-hydroquinone, methyl-n-propylphosphonyl-1,4-
Hydroquinone, methyl-n-butylphosphonyl-1,
4-hydroquinone, methyl-iso-butylphosphonyl-1,4-hydroquinone, methyl-sec-butylphosphonyl-1,4-hydroquinone, methyl-ter
t-butylphosphonyl-1,4-hydroquinone, ethyl-n-propylphosphonyl-1,4-hydroquinone, ethyl-iso-propylphosphonyl-1,4-hydroquinone, ethyl-tert-butylphosphonyl-
1,4-hydroquinone,

N-propyl-iso-propylphosphonyl-1,4-hydroquinone, n-propyl-n-butylphosphonyl-1,4-hydroquinone, n-propyl-sec-butylphosphonyl-1,4-hydroquinone, n-butyl -Sec-butylphosphonyl-1,4-
Hydroquinone, n-butyl-tert-butylphosphonyl-1,4-hydroquinone,

Propylenephosphonyl-1,4-hydroquinone, butylenephosphonyl-1,4-hydroquinone, pentamethylenephosphonyl-1,4-hydroquinone, hexamethylenephosphonyl-1,4-hydroquinone,

1,4-cyclopentylenephosphonyl-
1,4-hydroquinone, 1,4-cyclooctylenephosphonyl-1,4-hydroquinone, 1,5-cyclooctylenephosphonyl-1,4-hydroquinone,

2- (diethylphosphonyl) -1,4-naphthalenediol, 2- (dimethylphosphonyl) -1,
4-naphthalenediol, 2- (diethylphosphonyl)
-1,4-naphthalenediol, 2- (di-n-propylphosphonyl) -1,4-naphthalenediol, 2-
(Di-iso-propylphosphonyl) -1,4-naphthalenediol, 2- (di-n-butylphosphonyl)-
1,4-naphthalenediol, 2- (di-sec-butylphosphonyl) -1,4-naphthalenediol, 2-
(Di-tert-butylphosphonyl) -1,4-naphthalenediol, 2- (dibenzylphosphonyl) -1,4
-Naphthalene diol,

2- (methylethylphosphonyl) -1,4
-Naphthalenediol, 2- (methyl-n-propylphosphonyl) -1,4-naphthalenediol, 2- (methyl-n-butylphosphonyl) -1,4-naphthalenediol, 2- (methyl-iso-butylphosphonyl)-
1,4-naphthalenediol, 2- (methyl-sec-
Butylphosphonyl) -1,4-naphthalenediol, 2
-(Methyl-tert-butylphosphonyl) -1,4-
Naphthalene diol, 2- (ethyl-n-propylphosphonyl) -1,4-naphthalene diol, 2- (ethyl-iso-propylphosphonyl) -1,4-naphthalene diol, 2- (ethyl-tert-butylphosphonyl) -1,4-naphthalene diol,

2- (n-propyl-iso-propylphosphonyl) -1,4-naphthalenediol, 2- (n-
Propyl-n-butylphosphonyl) -1,4-naphthalenediol, 2- (n-propyl-sec-butylphosphonyl) -1,4-naphthalenediol, 2- (n-butyl-sec-butylphosphonyl) -1,4-naphthalene Diols, 2- (n-butyl-tert-butylphosphonyl) -1,4-naphthalenediol,

2- (propylenephosphonyl) -1,4-
Naphthalene diol, 2- (butylenephosphonyl)-
1,4-naphthalenediol, 2- (pentamethylenephosphonyl) -1,4-naphthalenediol, 2- (hexamethylenephosphonyl) -1,4-naphthalenediol,

2- (1,4-cyclopentylenephosphonyl) -1,4-naphthalenediol, 2- (1,4-cyclooctylenephosphonyl) -1,4-naphthalenediol, 2- (1, 5-cyclooctylenephosphonyl)-
Examples thereof include 1,4-naphthalene diol and the like.

In the present invention, the above-mentioned phosphorus-containing hydroquinone derivative may be a mixture of the phosphorus-containing hydroquinone derivatives derived from the reaction raw materials.

Next, a method for producing the phosphorus-containing hydroquinone derivative of the present invention will be described. The phosphorus-containing hydroquinone derivative represented by the general formula (1) of the present invention includes at least one selected from secondary phosphine derivatives represented by the following general formula (2) and a compound represented by the following general formula (3). Is characterized by reacting with a benzoquinone derivative.

The following general formula (2)

[0067]

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[0068] secondary wherein phosphine derivative represented by, R ¹ and R ² respectively correspond to R ¹ and R ² in the formula of the phosphorus-containing hydroquinone derivative represented by the general formula (1) Group. R ¹ and R ² represent a linear or branched alkyl group which may be substituted, and the alkyl group is an alkyl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms. Specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a tertiary butyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group can be exemplified.

In the formula, R ¹ and R ² may be the same or different. One or more methylene groups in the alkyl group are -CH
= CH-. Also, R
¹ and R ² may be substituted.

Further, R ¹ and R ² may form a cyclic substance containing P or not containing P. R ¹ and R ²
Forms a cyclic material containing P, the above-mentioned general formula (1)
Cyclic substances formed by the bond represented by 2).
When R ¹ and R ² do not contain P to form a cyclic substance, a cyclic substance formed by the bond represented by the general formula (13) may be mentioned. X in the formula corresponds to X in the formula of the phosphorus-containing hydroquinone derivative represented by the general formula (1), and represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom.

The secondary phosphine derivative represented by the general formula (2) can be produced by a known method. For example, the following reaction formula (1) shows an example of a cycloalkylenephosphine oxide in which R ¹ and R ² form a ring containing no P.

[0072]

Embedded image

By reacting phosphine (compound (8)) with 1,5-cyclooctadiene (compound (9)) in the presence of a radical generating catalyst,
1,4-cyclooctylenephosphine (compound (1
0)) and a mixture of 1,5-cyclooctylenephosphine (compound (11)) (JP-A-55-12279).
No. 0), and by oxidizing it, the desired 1,4-cyclooctylenephosphine oxide and 1,1
A mixture of 5-cyclooctylenephosphine oxides can be obtained.

In the method for producing a phosphorus-containing hydroquinone derivative represented by the general formula (1) of the present invention, the secondary phosphine derivative represented by the general formula (2) is
Since a tautomer is formed, instead of the secondary phosphine derivative represented by the above general formula (2) as a reaction raw material, the following general formula (2a)

[0075]

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(Wherein R ^1, R ² and X have the same meanings as described above).

Further, the general formula (2) and the general formula (2)
The tautomer of the secondary phosphine derivative represented by a) becomes one derivative depending on the temperature, and the secondary phosphine derivative represented by the general formula (2) or (2a) is used as a reaction raw material. , Or a mixture of both.

The secondary phosphine derivative represented by the general formula (2a) can be produced by a known method. For example, "KOZOLAPOFF",
Vol 4, page 475.

The other reaction raw material has the following general formula (3)

[0080]

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In the formula of the benzoquinone derivative represented by the formula:
And Z are groups corresponding to Y and Z in the formula of the phosphorus-containing hydroquinone derivative represented by the general formula (1).

Y and Z each represent a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, an aralkyl group such as a benzyl group,
An aryl group such as an allyl group and a phenyl group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group and a phenyloxy group; or a cyano group. The alkyl group has 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms, and specifically includes an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a tertiary butyl group, and a cyclohexyl group. Examples can be given. Y and Z may be the same or different groups.

Further, Y and Z may be groups forming a cyclic substance. Examples of the group wherein Y and Z form a cyclic substance include the same groups as the above-mentioned cyclic groups. Further, these substituents may contain a hetero atom such as an oxygen atom, a sulfur atom and a nitrogen atom.

In the production method of the present invention, at least one selected from the secondary phosphine derivatives represented by the general formulas (2) and (2a) and the benzoquinone derivative represented by the general formula (3) Is reacted in the presence of an inert solvent to obtain the desired phosphorus-containing hydroquinone derivative represented by the general formula (1).

The molar ratio of the benzoquinone derivative represented by the general formula (3) to the secondary phosphine derivative represented by the general formula (2) or (2a) is based on 1 mol of the secondary phosphine derivative. And usually 1.0 to 1.5, preferably 1.0 to 1.2.

The reaction temperature depends on the type of the reactants,
At 300 ° C. or higher, the target product represented by the general formula (1)
Since the phosphorus-containing hydroquinone derivative represented by is decomposed, usually 0 to 150 ° C, preferably 25 to 100 ° C
It is preferable that

The reaction time is generally 1 to 8 hours, preferably 2 to 5 hours.

The inert solvent is not particularly limited as long as the reaction raw material and the target product are inert solvents. For example, aromatic hydrocarbons such as benzene, toluene and xylene, petroleum ethers and the like can be used. Examples include aliphatic hydrocarbons, ethers such as dialkyl ethers, nitriles such as acetonitrile and propionitrile, halogenated aromatic hydrocarbons such as chlorobenzene, and haloalkanes such as methylene chloride and chloroform. Alternatively, two or more kinds can be used in combination.

In the production method of the present invention, the reaction can be promoted by using an acid catalyst or a basic catalyst, if desired. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, oxalic acid, phosphoric acid, perchloric acid, periodic acid, hydrogen fluoride, methanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, glacial acetic acid and the like. Alternatively, two or more kinds can be used in combination.

As the basic catalyst, for example, sodium,
Use of one or a combination of two or more of alkali metals such as potassium or lithium, alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide, and alkyl metal compounds such as t-butyllithium and lithium diisopropylamide Can be done. In this case, the amount of the catalyst to be added is generally 1 to 10 mol%, preferably 1 to 10 mol%, of the compound represented by the general formula (3).
5 mol%.

After completion of the reaction, the product can be filtered and dried to obtain a product. However, if desired, the product may be purified by a conventional purification means. By doing so, the above general formula (1)
The phosphorus-containing hydroquinone derivative represented by the following formula can be produced.

The phosphorus-containing hydroquinone derivative of the present invention can be used as a flame retardant, especially a reactive flame retardant. Specifically, since the phosphorus-containing hydroquinone derivative has a phenolic OH group, for example, it is directly reacted with an epoxy resin, and the derivative is introduced into the epoxy resin to form a phosphorus-containing epoxy resin, or It can be reacted with chlorohydrin to form a phosphorus-containing epoxy resin, and the phosphorus-containing epoxy resin can be cured and used as a flame-retardant epoxy resin composition.

A flame-retardant epoxy resin composition obtained by adding a curing agent or a polymerization initiator to a phosphorus-containing epoxy resin is as follows:
As a safe plastic material, it can be used as a printed wiring board, a copper-clad laminate used for an electric circuit board, a sealing material used for electric components, a molding material, a casting material, an adhesive, an electrically insulating paint material, and the like. When the flame-retardant epoxy resin composition is used as a sealing resin for a sealing material, it is preferable that the composition is uniformly mixed and kneaded. As a method of kneading, for example, a sealing resin is manufactured by heating using a roll, a kneader, a mixer, or the like, and then cooling, pulverizing, and tableting.

Then, when a semiconductor element, a lead frame, and the like are sealed by performing transfer molding or the like using the sealing resin obtained above, a semiconductor device having excellent flame retardancy and humidity electric resistance is obtained. . The method of molding is not particularly limited except that the above sealing resin is used, and molding can be performed by a general method.

A resin varnish can be obtained by dissolving the above flame-retardant epoxy resin composition in a solvent. The prepared resin varnish is applied to a substrate such as paper, glass woven fabric, glass nonwoven fabric, or a cloth having a component other than glass, impregnated, and dried in a drying oven at 80 to 200 ° C. A prepreg can be prepared, and a predetermined number of the prepregs can be stacked and heated and pressed to produce a laminate or a metal-clad laminate for a printed wiring board.

[0096]

The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.

Production Example 1 1843 g of 1,5-cyclooctadiene (1
6.69 mol) and 3750 ml of toluene were sufficiently purged with nitrogen. Subsequently, 731 g of phosphine (21.
50 mol) and heated to 60 ° C. 58.8 g (0.237 mol) of 2,2-azobis- (2,4-dimethylvaleronitrile) was injected as a radical initiator over 3 hours, aged at 60 ° C. overnight, and 1,4-cyclohexane was added. A toluene solution of a mixture consisting of octylenephosphine and 1,5-cyclooctylenephosphine was obtained. (Purity of mixture: 31.9 wt%, 1,4-cyclooctylenephosphine: 1,5-cyclooctylenephosphine = 3
8.4: 61.6 (GC relative area ratio)

After thoroughly replacing the nitrogen in a 2000 ml four-necked flask equipped with a stirrer, a condenser and a dropping funnel, 434.6 g (0.975 m
ol) at room temperature. In addition, methanol 440
g in an ice bath and cooled to about 5 ° C.
06.5 g (1.05 mol) was added dropwise from the dropping funnel over about 3 hours. The end point of the reaction was determined by gas chromatography. After the completion of the oxidation reaction, the mixture was concentrated with a rotary evaporator to give 152.8 g of a mixture of colorless crystalline 1,4-cyclooctylenephosphine oxide and 1,5-cyclooctylenephosphine oxide (0.966 g).
mol, 1,4-cyclooctylenephosphine oxide: 1,5-cyclooctylenephosphine oxide = 3
9.4: 60.6 (NMR relative area ratio)).

Example 1 In a reaction vessel equipped with a stirring device and a thermometer, 183.5 g of a mixture of 1,4-cyclooctylenephosphine oxide and 1,5-cyclooctylenephosphine oxide was added to 900 ml of toluene at room temperature. Purity 87.0%, 1.
00 mol) and stirred to dissolve. After the temperature of the reaction solution was raised to 70 ° C., 108.7 g (1.00 mol) of 1,4-bensoquinone as a fine powder was added little by little over about 3 hours. After completion of the addition, the mixture was aged at 70 ° C. for about 1 hour, cooled to room temperature, and the resulting precipitate was filtered, washed with cold methanol three times, and dried at 80 ° C. under reduced pressure to give 1,4-cyclooctylene. 192.7 g of a mixture of phosphonyl-1,4-hydroquinone and 1,5-cyclooctylenephosphonyl-1,4-hydroquinone (0.
724 mol) as a pale yellow crystalline powder. Yield 7
2.4%.

¹ H NMR (300 MHz, CD ₃ O
D) [delta] 1.43-2.83 (m, 14H), 6.7.
7-6.91 (m, 3H) ³¹ P NMR (121.5 MHz, CD ₃ OD) δ
42.5 (s), 66.8 (s) FAB-MS (Pos., M / z) 267 [M + H] ⁺ IR (KBr, cm ^-1 ) 3157 (@OH), 3080
(Arom @ C-H), 1225 (@ P = O)

Example 2 In a reaction vessel equipped with a stirring device and a thermometer, 500 ml of toluene and 200 ml of diethylphosphine oxide were added at room temperature.
g (1.89 mol) and heated to 70 ° C.
299 g of fine powdered 1,4-naphthoquinone (1.89 mo
l) was added in small portions over about 3 hours. After the addition,
After reacting at 70 ° C. for about 1 hour, the precipitate formed by cooling to room temperature was filtered, washed three times with cold methanol, and then washed at 80 ° C.
361 g of 2- (diethylphosphonyl) -1,4-naphthalenediol (1.37).
mol) was obtained as a pale yellow crystalline powder. Yield 72.3
%.

¹ H NMR (300 MHz, CD ₃ O
D) δ 0.90 to 1.12 (m, 6H), 2.11
-2.58 (m, 4H), 6.60 (s, 1H), 7.
38 (m, 1H), 7.80 (m, 1H), 8.07
(M, 2H) ³¹ P NMR (121.5 MHz, CD ₃ OD) δ
54.0 (s), 78.5 (S) IR (KBr, cm ^-1 ) 3179 (@OH), 3090
(Arom @ C-H), 1205 (@ P = O)

Example 3 In Example 2, 253 g of ethyl diethyl phosphinate was dissolved in 500 ml of toluene in place of diethyl phosphine oxide, and 500 ml of 3 mol / L hydrochloric acid was added to 500 ml of toluene.
The reaction was performed at 5 ° C. After the completion of the reaction, the reaction solution was separated, and the organic phase was mixed with 500 ml of a 5 mol% aqueous sodium hydrogen carbonate solution.
And 500 ml of water twice. Next, after the temperature was raised to 70 ° C. in the same manner as in Example 2, 299 g (1.89 mol) of 1,4-naphthoquinone as a fine powder was added little by little over about 3 hours. After the addition was completed, after reacting at 70 ° C. for about 1 hour
The precipitate formed upon cooling to room temperature was filtered, washed three times with cold methanol, and dried at 80 ° C. under reduced pressure to obtain 2
320 g (1.21 mol) of-(diethylphosphonyl) -1,4-naphthalenediol were obtained as a pale yellow crystalline powder. Yield 64.0%.

Example 4 In a device similar to that of Example 1, 750 ml of toluene was added at room temperature.
263.6 g of a mixture of 1,4-cyclooctylenephosphine oxide and 1,5-cyclooctylenephosphine oxide (total purity 90.0%, 1.50 mol)
Was stirred and dissolved by stirring. After the temperature of this solution was raised to 100 ° C., 237.4 g of 1,4-naphthoquinone (1.
A slurry of 50 mol) and 1100 ml of toluene were added dropwise little by little over about 6 hours. After dropping,
Aged at 100 ° C. for 2 hours, then cooled to room temperature, and the resulting precipitate was filtered, washed three times with cold methanol, and then washed at 80 ° C.
And dried under reduced pressure to give 2- (1,4-cyclooctylenephosphonyl) -1,4-naphthalenediol and 2- (1,5-cyclooctylenephosphonyl) -1,4.
302.22 g of a mixture of naphthalene diols (0.9
55 mol) as a pale yellow crystalline powder. Yield 6
3.6%.

¹ H NMR (300 MHz, CD ₃ O
D) [delta] 1.67-2.70 (m, 14H), 6.6.
3 (s, 1H), 7.40 (m, 1H), 7.81
(M, 1H), 8.10 (m, 2H) ³¹ P NMR (121.5 MHz, CD ₃ OD) δ
55.3 (s), 79.8 (s) DI-EI (m / z) 316 IR (KBr, cm ^-1 ) 3179 (@OH), 3090
(Arom @ C-H), 1205 (@ P = O)

Example 5 The same operation as in Example 2 was carried out except that 200 g of dibenzylphosphine oxide was used instead of 200 g of diethylphosphine oxide, and 2- (dibenzylphosphonyl)
135.9 g of -1,4-naphthalene diol was obtained. Yield 70.0%.

Example 6 The procedure of Example 2 was repeated, except that 44.0 g of tetramethylenephosphine oxide was used instead of 200 g of diethylphosphine oxide, to give 2- (tetramethylenephosphonyl) -1,4-. Naphthalene diol 88.6
g was obtained. Yield 72.1%.

Example 7 A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a Dean-Stark was placed in a reaction vessel prepared in Example 1 to prepare 1,4-cyclooctylenephosphonyl-1,4-hydroquinone and 1,5-cycloquinone. 100 g (0.376 mol) of a mixture of octylenephosphonyl-1,4-hydroquinone and 83.4 g (0.902 mol) of epichlorohydrin were added, and the mixture was heated to 120 ° C. under reflux while stirring. There, 115 g of 40 wt% aqueous sodium hydroxide solution (1.
00 mol) was added dropwise such that gentle reflux continued. During this time, the water accumulated in Dean Stark was properly discarded. After the completion of the dropwise addition of the aqueous sodium hydroxide solution, excess epichlorohydrin was removed under reduced pressure, and 500 ml of toluene was added. The toluene suspension was washed three times with 500 ml of water,
Further, toluene was distilled off under reduced pressure to obtain a phosphorus-containing epoxy resin. 97% yield. Epoxy equivalent 202 g / eq. P
Content 8.1% by weight.

IR (KBr, cm ^-1 ): 3080 (ar
om @ C--H), 1225 (@ P = O), 910 (epoxy group)

Next, the synthesized phosphorus-containing epoxy resin
0 g and meta-xylylenediamine 6.2 g (45.6 m
mol) was cured at room temperature for 3 hours, and then cured at 100 ° C. for 2 hours to obtain a cured epoxy resin.

IR (KBr, cm ^-1 ): 3300 (ΔN
-H), 3080 (arom @ C-H), 1225
(ΥP = O) Tg (DSC method): 82 ° C.

<Flame Retardancy Test> The flame retardancy test was performed on the cured epoxy resin (P content: 5.7% by weight, glass transition temperature: 82 ° C.) with a length of 125 mm and a width of 13 mm.
mm × 3mm thickness, vertical burning test of materials classified as UL94 (94V-0, 94V-1 and 94V-
Tested according to 2). As a result, UL-94 is V-0
Met.

<Chemical Resistance Test> The epoxy resin cured product of the present invention prepared above (P content: 5.7% by weight, glass transition temperature: 82 ° C.), and Epicoat 828 for comparison
(Yuika Shell Epoxy Co., epoxy equivalent 184-19
215 g (1.58 mol) of metaxylylenediamine as a curing agent was added to 300 g of 4 g / eq), and 10 wt% of tricresyl phosphate was added as an additive type flame retardant. The mixture was cured at room temperature for 3 hours and then at 100 ° C. for 2 hours. Two samples of the cured epoxy resin product (Comparative Example 1) were subjected to a chemical resistance test according to JIS K7114.

Each of the resin cured products was prepared to have a diameter of 50 mm and a thickness of 3 mm.
The test pieces were cut into 5 mm disks to prepare five test pieces. After soaking these test pieces in sulfuric acid of 10 wt% (1000 ml) at 23 ° C. for 7 days, they were sufficiently washed with water,
After drying under reduced pressure at 90 ° C. for 24 hours, the weight and appearance of the test piece were examined.

As a result, the epoxy resin cured product according to the present invention was reduced by 2 wt% on average, but there was no change in appearance in any of the test pieces. The cured resin obtained by mixing tricresyl phosphate in Epicoat 828 at 10 wt% was reduced by 10 wt% or more on average, and the appearance of each test piece was cloudy. This difference is due to the fact that the epoxy resin produced according to the present invention has a very strong chemical resistance because the phosphorus atom is bonded by a PC covalent bond, but the phosphate ester such as tricresyl phosphate has a P-O-C It is considered that since they were bonded by bonding, they were hydrolyzed and eluted from the resin. Therefore, it is considered that the resin weight was significantly reduced and the appearance became cloudy.

[0116]

As described above, according to the present invention, a phosphorus-containing hydroquinone derivative represented by the general formula (1) can be provided. Since the derivative has a phenolic OH group, for example, And an effect that can be used as an intermediate material of a reactive flame retardant or a phosphorus-containing epoxy resin.

Further, according to the production method of the present invention, there is an effect that the phosphorus-containing hydroquinone derivative can be produced by an industrially advantageous method.

Further, the flame retardant comprising the phosphorus-containing hydroquinone derivative of the present invention is useful as a reactive flame retardant for a flame-retardant epoxy resin having chemical resistance, and is particularly used for printed wiring boards and electric circuit boards. Phosphorus-containing epoxy resin useful for flame-retarding copper-clad laminates, sealing materials used for electric parts, molding materials, casting materials, adhesives, electric insulating paint materials, etc. The effect which can be used for an epoxy resin composition is produced.

 ────────────────────────────────────────────────── ─── Continued on the front page F term (reference) 4H028 AA34 AA36 BA01 BA04 4H050 AA01 AA02 AA03 AB80 WA12 WA18 WA26 4J036 AB19 AB20 AC01 DC03 DC10 JA01 JA06 JA07 JA08

Claims (5)

[Claims] [Claim 1] The following general formula (1) (Wherein R ¹ and R ² represent an optionally substituted linear or branched alkyl group, and one or more methylene groups in the alkyl group are replaced by —CH ＝ CH— R ¹ and R ² may be the same or different groups, and R ¹ and R ² may form a cyclic substance containing or not containing P. X represents an oxygen atom or a sulfur atom, and Y and Z each represent a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, an aralkyl group, an alkoxy group, an allyl group, an aryl group or a cyano group; One or more methylene groups in the alkyl group may be replaced by -CH = CH-, Y and Z may be the same or different groups, and Y and Z May form a cyclic substance.) Phosphorus-containing hydroquinone derivatives. 2. The phosphorus-containing hydroquinone derivative according to claim ¹ , wherein the cyclic substance formed by R ¹ and R ² is represented by the following general formula (12) or (13). Embedded image (In the formula, R ³ represents an alkylene group which may be substituted.) (In the formula, R ⁴ represents a cycloalkylene group or an arylene group which may be substituted.) 3. The following general formula (2): (Wherein R ^1, R ² and X have the same meanings as described above) and at least one selected from secondary phosphine derivatives represented by the following general formula (3): Wherein Y and Z have the same meanings as described above, and are reacted with a benzoquinone derivative represented by the following general formula (1): (Wherein, R ¹ and R ² , X, Y, and Z have the same meanings as described above). 4. The following general formula (2) and general formula (2a): (Wherein R ^1, R ² and X are as defined above) and at least one selected from secondary phosphine derivatives represented by the following general formula (3): Wherein Y and Z have the same meanings as defined above, and are reacted with a benzoquinone derivative represented by the following general formula (1): (Wherein, R ¹ and R ² , X, Y, and Z have the same meanings as described above). 5. A flame retardant comprising the phosphorus-containing hydroquinone derivative according to claim 1 or 2.