JPH0925254A - Production of nuclear substituted bisphenol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a mono- and/or di-substituted compound extremely useful for a resin raw material in a high purity. SOLUTION: This nuclear substituted bisphenol represented by formula I R1 , R2 are each H, a 1-6C alkyl, etc.; X is -O-, -S-, etc.; R3 is H or a 1-12C hydrocarbon; R4 is H or a 1-12C hydrocarbon; R5 is a 3-10C divalent hydrocarbon, Ra , Rb are each H, etc.} is obtained by reacting a bisphenol compound of formula II, e.g. 2,2-bis(4-hydroxyphenyl)propane, with a phenyl alkenyl compound of formula III R5, R7 are each a 1-7C hydrocarbon, etc.; R8 is a 1-8C hydrocarbon, etc.; R9 , R10 are each a 1-7C hydrocarbon, etc.; R11 is a 3-7C divalent hydrocarbon; Ar<1> , Ar<2> are each a 6-15C aromatic group} and formula IV, e.g. α-methylstyrene in the presence of (A) aluminum alkoxide, e.g. aluminum tripropoxide and/or (B) a reaction product of (A) with a compound of formula II.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a process for producing a nuclear-substituted bisphenol which is extremely useful as a resin raw material. More specifically, it relates to a process for producing a nuclear-substituted bisphenol, which comprises reacting a bisphenol compound with an aluminum alkoxide and / or an aluminum alkoxide and an aromatic alkenyl compound in the presence of a reactant of the bisphenol compound.

[0002]

It is known to alkylate bisphenols with aromatic alkenyl compounds, especially styrene or α-methylstyrene, in the presence of a catalyst (Dokl.
Akad.Nauk. B. SSR. (1976), 20 (9) 809-12, Bolbotu
nova, TN, etc.). As the catalyst in this case, an acidic catalyst such as sulfuric acid, P-toluenesulfonic acid, phosphoric acid or the like is generally known.

However, when a bisphenol compound such as bisphenol A is reacted in the presence of an acidic catalyst, a considerable proportion of bisphenol A is decomposed and at the same time P-
Phenylalkylated phenol was produced as a by-product, and it was difficult to obtain the target nuclear-substituted bisphenol with high yield and high purity.

It is also known to carry out the reaction using aluminum phenolate as a catalyst, and it is disclosed in JP-A-52-19.
According to Japanese Patent No. 643, when the reaction is carried out in the presence of aluminum phenolate, the bisphenol compound is
It is described as being alkylated by phenylalkenyl compounds without undergoing any significant decomposition.

Further, when aluminum phenolate is used as a catalyst, decomposition of the bisphenol compound can be suppressed as compared with the case where an acidic catalyst is used, and further, a side reaction (dimerization, trimerization, free reaction) of the phenylalkenyl compound itself is possible. It is described that it also has the advantage that the (Delcraft reaction) is not observed.

However, when the above-mentioned aluminum phenolate catalyst is used, monoalkyl-group-substituted and dialkyl-group-substituted bisphenols (hereinafter referred to as monoalkylated compounds,
It is abbreviated as a dialkylated product. It is difficult to selectively and efficiently obtain a monoalkylated product with high industrial utility, which is a mixture of

For example, in the above-mentioned publication, the preferable conditions for obtaining the monoalkylated product are used, and even if the reaction is carried out at a high temperature for a short time by using a large amount of catalyst (Example 4 of the above-mentioned publication), the monoalkylated product in the product is obtained. Is at most 5
The content is only 9.2% by weight, 38% by weight of the raw material bisphenol and 3% by weight of the dialkylated product.

It is relatively easy to remove the raw material bisphenol from these mixtures by using a suitable solvent, for example, a toluene / hexane mixed solvent.

However, it is extremely difficult to efficiently take out the monoalkylated product from the product obtained by removing the raw material bisphenol, particularly when the dialkylated product is contained in an amount of 4 to 5% by weight or more, and fractional distillation is performed. In order to fractionally distill the monoalkylated product, for example, under reduced pressure of 0.1 torr, 195
It must be distilled at a high temperature of ~ 200 ° C. When exposed to such a high temperature, a part of the mono- and / or di-alkylated product causes undesired side reactions such as decomposition and color polymerization, and is mixed as an impurity in the product.

The aluminum phenolate catalyst described in German Patent 2,534,559 has a monoalkylated product selectivity of 90% as described in the specification.
In order to maintain at, the reaction rate of bisphenol is at most 56%
Must be kept (Example 1). Further, in Example 2, when the reaction rate of bisphenol was increased to 83%, the selectivity of monoalkylated product was only 53% at most, and the mixture was almost equivalent to monoalkylated product and dialkylated product.

[0011]

DISCLOSURE OF THE INVENTION The present invention provides a process for producing a nuclear-substituted bisphenol, which can obtain a mono- and / or di-substituted compound with high purity, and in particular, can obtain a mono-nuclear substituted compound with high purity. With the goal.

[0012]

The present invention is characterized by using (A) an aluminum alkoxide and / or (B) a reaction product of the aluminum alkoxide and a bisphenol compound represented by the formula (II) as a catalyst. .

That is, the present invention provides the following formula (I)

[0014]

Embedded image

[In the formula, R ₁ and R ₂ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon atom having 1 to 6 carbon atoms.
6 represents an alkoxy group.

[0016]

Embedded image

(However, R ₃ and R ₄ are the same or different,
Represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R
₅ represents a divalent hydrocarbon group having 3 to 10 carbon atoms. )]
A bisphenol compound represented by the following formula (II) and / or in the presence of a reaction product of (A) an aluminum alkoxide and / or (B) the aluminum alkoxide and the bisphenol compound represented by the above formula (I). (III)

[0018]

Embedded image

[In the formula, R ₆ and R ₇ are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms.
R ₈ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. R ₉ and R ₁₀ are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms. R ₁₁ has 3 to 3 carbon atoms
7 represents a divalent hydrocarbon group. Ar ¹ and Ar ² are the same or different and each represents an aromatic group having 6 to 15 carbon atoms. ] The following formula (IV) characterized by reacting with an aromatic alkenyl compound represented by

[0020]

Embedded image

[In the formula (IV), R ₁ , R ₂ and X are the same as those in the formula (I). Ra and Rb are the same or different and each is a hydrogen atom,

[0022]

Embedded image

Ra and Rb are not both hydrogen atoms
(Wherein, Ar¹, Ar^Two, R₈And R ₉Is the formula (II),
Is the same as (III),

[0024]

Embedded image

A method for producing a nuclear-substituted bisphenol represented by

German Patent 2,534,559 proposes aluminum phenolate as a catalyst, but the compound has low solubility in the reaction system. In this specification, it is proposed to utilize this feature and to filter, recover and reuse the aluminum phenolate catalyst after the reaction.

However, aluminum phenolate has low catalytic activity and low reaction selectivity. As the cause,
(1) Aluminum phenolate has low solubility in the reaction system and a small amount of catalyst is involved in the catalytic reaction, and (2) aluminum phenolate catalyst has low catalytic activity and is chemically stable. It is considered that active catalyst species are less likely to be generated due to the exchange of bisphenol and phenoxy group.

On the other hand, aluminum alkoxide has a high solubility in the reaction system and a high reactivity of the alkoxy group, so that the bisphenol and the alkoxy group are easily exchanged in the reaction system, and the active catalyst is active. Considered a seed,
Compound represented by the following formula (V)

[0029]

Embedded image

It is considered that the catalytic activity is high and the reaction selectivity is also good because it is easy to generate.

As can be easily estimated from the above description,
The active catalyst species represented by (V) may be produced in the reaction system by adding an aluminum alkoxide to the reaction system, or may be produced separately outside the reaction system and added to the reaction system.

1 to 6 carbon atoms of R ₁ and R ₂ of the formula (I)
Examples of the alkyl group and the alkoxy group include a methyl group, an ethyl group, a methoxy group and an ethoxy group.

Examples of the hydrocarbon group of R ₃ and R ₄ include an alkyl group and an aryl group, and a methyl group, a propyl group, a phenyl group and the like.

Examples of the hydrocarbon group for R ₅ include an alkylene group and an arylene group, and examples thereof include a propyl group, a butylene group and a phenylene group.

R ₆ and R _{7 of} formulas (II) and (III)
Examples of the hydrocarbon group include an alkyl group, an aryl group and the like, and a methyl group, a hexyl group, a phenyl group and the like are exemplified.

The hydrocarbon group for R ₈ is an alkyl group,
Examples thereof include an aryl group and the like, and examples include an ethyl group, a propyl group, a phenyl group and the like.

Examples of the hydrocarbon group for R ₉ and R ₁₀ include an alkyl group and an aryl group, and examples thereof include an ethyl group, a propyl group and a phenyl group.

Examples of the hydrocarbon group for R ₁₁ include an alkylene group and the like, and examples thereof include a propylene group and a butylene group.

As the aromatic group of Ar ¹ and Ar ² ,
Aryl groups, arylene groups and the like, phenyl groups,
Examples thereof include a naphthyl group and a phenylene group.

In the formula (IV), examples of the hydrocarbon group represented by Rc include an alkyl group, an aryl group and an aralkyl group, and examples thereof include a propyl group, a phenyl group and a benzyl group.

Preferred aluminum alkoxides used in the present invention include aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum tri-t-butoxide and aluminum tri-n-.
Examples include octyl oxide. Of these, aluminum triisopropoxide is preferred because of its high solubility and reactivity.

A cyclic alkoxide represented by the following formula can also be used.

[0043]

Embedded image

Although a 1,3-diketo complex such as aluminum trisacetylacetonate can be used, its reaction activity is low.

The active catalyst species represented by (I) in which the bisphenol and the alkoxy group are exchanged can be easily synthesized by adding an aluminum alkoxide to the reaction system and can be used without isolation.

When the synthesis is carried out outside the reaction system, known literatures,
(CIENCIA. E. CULTURA, 27 (1), JANEIRO, (1975), P50
-P53 PG DAVID) etc. can be easily synthesized.

As the bisphenol compound (I) used in the present invention, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy) Phenyl)
Hexane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane 2,2-bis (4-hydroxyphenyl) 2-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) ether, and the like.

Examples of the phenylalkenyl compound represented by the formulas (II) and (III) used in the present invention include styrene and α
-Methylstyrene, α-ethylstyrene, P-methylstyrene, Pn-butyl-α-methylstyrene, mn
-Propylstyrene and the like are exemplified.

The molar ratio of the bisphenol compound (I) to the phenylalkenyl compound (II) and / or (III) can be varied within a wide range depending on the kind of the target compound, but when a monoalkyl group-substituted bisphenol is desired, It is preferable to use a slight excess of bisphenol based on the stoichiometry.

However, when a large excess of bisphenol is used, a troublesome operation for separating and recovering a large amount of bisphenol is required. Therefore, the bisphenol compound (I) and the phenylalkenyl compound (II) and / or (III
) Is 5/1 to 0.9 / 1, more preferably 3
The range is from 1/1 to 1/1, and more preferably from 2/1 to 1.1 / 1.

When a dialkyl group-substituted product is desired, it is preferable to use the aromatic alkenyl compound in a slightly larger amount than stoichiometrically required. Therefore, the molar ratio of the bisphenol compound (I) to the aromatic alkenyl compound (II) and / or (III) is 1 / 1.5 to 1/5, preferably 1 / 1.6 to 1/3, more preferably 1 /1.7-1
The range is / 3.

The amount of catalyst used is 0.2 to 25% by weight, preferably 1 to 10% by weight, based on the bisphenol compound (I).

In practicing the present invention, it is preferable to use a solvent. These include, for example, compounds which are inert under the reaction conditions, for example, benzene, toluene, xylene, diurene, tetralin, methylnaphthalene, petroleum ether, ligron, and decalin as the hydrocarbon group.

As halogenated hydrocarbons, chlorobenzene, dichlorobenzene, dichloronaphthalene, 1,2-
Examples thereof include dichloroethane, carbon tetrachloride, P-chlorotoluene and the like.

Examples of the ethers include diphenyl ether and anisole, and examples of the esters include methyl benzoate and butyl acetate. Other examples include nitrobenzene and the like.

[0056]

The present invention will be described below by way of examples.

In the examples, the reaction products were analyzed by a liquid chromatograph manufactured by Toyo Soda, acetonitrile / SA8022.
It analyzed by the gradient elution method in a water mixed solvent. 2,2-bis (4-hydroxy-3) as a quantitative internal standard substance
-Methylphenyl) propane was used.

Reference Example The reaction between aluminum isopropoxide and bisphenol A was carried out as follows.

Aluminum isopropoxide (MW20
4.25) 4.5 g and bisphenol A 16.58
g (1.1 mole times) was boiled with 200 ml of benzene to remove the produced isopropyl alcohol while azeotropically removing the reaction. The end point of the reaction was the time when aluminum isopropoxide was not detected by NMR. After the reaction, benzene was distilled off under reduced pressure, and the remaining solid was used as a catalyst.

[Example 1] Bisphenol A (0.2 mol) (45.8 g) and aluminum isopropoxide (4.5 g) were dispersed in 180 ml of toluene and heated to 115 ° C under a nitrogen stream to obtain α-methylstyrene ( 0.2 mol)
After adding 23.6 g over 1 hour, the reaction was performed at the same temperature for 3 hours. A part of the reaction liquid was taken and analyzed by liquid chromatography. As a result, the conversion of bisphenol A was 83%, 2- (4-hydroxyphenyl) -2- (4 '
-Hydroxy-3- (α, α-dimethylbenzyl) phenyl] propane (monoalkylated product) has a formation selectivity of 9
0% (bisphenol base), 2,2-bis [4-hydroxy-3- (α, α-dimethylbenzyl) ether] propane (dialkylated product) formation selectivity is 10%
Met.

The reaction product was cooled to room temperature, the catalyst and bisphenol A were filtered off, the toluene was distilled off under reduced pressure, the monoalkylated product was extracted with 1000 cc of heptane, and separated by crystallization to obtain 48 g of a white product having a purity of 98% or more. Crystals were obtained.

Example 2 In 180 ml of toluene, 45.8 g of bisphenol A (0.2 mol) and a separately synthesized reaction product of aluminum isopropoxide and bisphenol A were dispersed and heated to 117 ° C. under a nitrogen stream. , Α
-Methylstyrene (0.2 mol) (23.6 g) was added over 1 hour, and the mixture was further reacted at the same temperature for 3 hours. afterwards,
When analyzed in the same manner as in Example 1, the conversion of bisphenol A was 85%, the selectivity of the monoalkylated product was 93%,
The selectivity of the dialkylated product was 7%.

The reaction product was treated in the same manner as in Example 1 to extract a monoalkylated product, and after crystallization and separation, 51 g of purity 98%
Was obtained as white crystals.

Example 3 45.8 g of bisphenol A (0.2 mol) and 4.5 g of aluminum isopropoxide were dispersed in 180 ml of xylene and heated to 130 ° C. under a nitrogen stream to give styrene (0.2 mol). Mole) 20.8 g
Was added over 1/2 hour, and the reaction was performed for another 1/2 hour at the same temperature, and then the product was analyzed by liquid chromatography. As a result, the conversion rate of bisphenol A was 8
4%, the selectivity of the monoalkylated product was 91%, and the selectivity of the dialkylated product was 9%.

The above-mentioned mono-alkylated product is 2- (4-hydroxyphenyl) -2- (4'-viroxy-3- (α
-Methylbenzyl) phenyl] propane, the dimonoalkylated product was 2,2-bis [4-hydroxy-3- (α-methylbenzyl) phenyl] propane.

Example 4 Addition of 45.8 g of bisphenol A (0.2 mol) and 4.5 g of aluminum isopropoxide in 180 ml of xylene under a nitrogen stream 13
Heat to 0 ° C and use α-methylstyrene (0.5 mol) 59
g was added over 1 hour, and the reaction was continued for 1 hour after the addition. As a result, the conversion rate of bisphenol A was 99.
%, The monoalkylated product had a selectivity of 5%, and the dialkylated product had a selectivity of 95%.

[Comparative Example 1] 215.8 g of bisphenol A (0.2 mol) and 4.5 g of aluminum phenolate were dispersed in 180 ml of toluene.
Heated to α-methylstyrene (0.2 mol) 23.
After adding 6 g over 1 hour, the reaction was further performed at the same temperature for 5 hours. The reaction solution was analyzed by liquid chromatography. As a result, the conversion rate of bisphenol A was 59%,
The selectivity of monoalkylated product was 90%, and the selectivity of dialkylated product was 10%.

The reaction product was treated in the same manner as in Example 1 to obtain 30 g of a monoalkylated product crystal (purity: 90%).

Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 43/295 7419-4H C07C 43/295 C 7419-4H D 319/20 319/20 323/20 323/20 // C07B 61/00 300 C07B 61/00 300

Claims (1)

[Claims] 1. The following formula (I):[Wherein, R₁And R_TwoAre the same or different and
Child, an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms
Represents a lucoxy group. Embedded image(However, R_ThreeAnd R_FourAre the same or different,
Represents a hydrocarbon group having 1 to 12 carbon atoms, R_FiveIs the carbon number
It represents a divalent hydrocarbon group of 3 to 10. )]
Sphenol compound (A) aluminum alkoxy
And / or (B) the aluminum alkoxide
Reaction product of bisphenol compound represented by the above formula (I)
In the presence of a product, the following formula (II) and / or (III)[Wherein, R₆And R₇Are the same or different and are hydrogen atoms
Alternatively, it represents a hydrocarbon group having 1 to 7 carbon atoms. R₈Is hydrogen field
Represents a child or a hydrocarbon group having 1 to 8 carbon atoms. R₉and
R_TenAre the same or different and each is a hydrogen atom or has 1 to 7 carbon atoms.
Represents a hydrocarbon group of. R₁₁Is divalent carbonization having 3 to 7 carbon atoms
Represents a hydrogen group. Ar¹And Ar^TwoAre the same or different charcoal
It represents an aromatic group having a prime number of 6 to 15. ] Aromatic
Characterized by reacting with an alkenyl compound
Formula (IV) embedded image[In the formula (IV), R₁, R_TwoAnd X are the same as in formula (I)
It is. Ra and Rb are the same or different and are hydrogen
Child,Ra and Rb are not both hydrogen atoms (in the formula, A
r¹, Ar^Two, R₈And R ₉Is the formula (II), (III) and
Is the same,A method for producing a nuclear-substituted bisphenol represented by.