JP2886012B2 - Novel aromatic diol compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel aromatic diol compound, 4,4'-bis (3-hydroxyphenoxy) -p-terphenyl, and a process for producing the same. More specifically, 4,4'-bis (3-hydroxyphenoxy) -p-terphenyl which can be used as a raw material monomer of a polymer material excellent in heat resistance, chemical resistance, and the like, and a method for industrially producing the same About.

[0002]

2. Description of the Related Art Conventionally, diol components which are one of the raw materials of organic polymer compounds include aliphatic or alicyclic diols such as ethylene glycol, propylene glycol, cyclohexane dimethanol, hydroquinone, resorcinol, 2,6 and the like. -Hydroxynaphthalene, 2,5-hydroxynaphthalene, 4,4'-dihydroxydiphenyl,
Aromatic diols such as bisphenol A and bisphenol S are used. These are used as components of resins such as polyester, polyurethane, polycarbonate, polyether, and polyetherketone.

In order to improve the heat resistance, chemical resistance and mechanical properties of these resins, it is conceivable to introduce a structural unit having a higher aromaticity, for example, a component containing a terphenyl structure. A polymer derived from a phenyl compound or a monomer having a higher aromaticity than the phenyl compound has a problem that only a polymer having a high melting point and insolubility and poor uniform polymerizability and moldability can be obtained.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel aromatic diol compound useful as a diol component of a high-performance organic polymer material and a method for producing the same.

[0005]

The novel aromatic diol compound of the present invention is represented by the following formula (I):
4,4'-bis- (3-hydroxyphenoxy) -p-
Terphenyl.

[0006]

Embedded image

The 4,4'-bis- (3-hydroxyphenoxy) -p-terphenyl of the present invention comprises a 4,4'-dihalogenoterphenyl represented by the following formula (II) and a compound represented by the following formula (III):

[0008]

Embedded image

Wherein X is a chlorine or bromine atom, R is an alkyl group having 1 to 5 carbon atoms, and m-alkoxyphenol represented by the formula: Reacting in the presence of the compound,
It can be produced by 4'-bis- (3-alkoxyphenoxy) -p-terphenyl, which is then dealkylated.

In the present invention, 4,4'-dihalogenoterphenyl is reacted with m-alkoxyphenol in the presence of an alkali metal hydroxide or carbonate and copper or a copper compound. The halogen group of the 4,4'-dihalogenoterphenyl used herein may contain chlorine or bromine or a mixture of both, but disubstituted bromine is particularly preferably used because of its high reactivity. Further, as the m-alkoxyphenol, m-methoxyphenol is preferable.

On the other hand, sodium, potassium, lithium and the like can be used as the alkali metal, but potassium is particularly preferably used because of its high reactivity. As copper or a copper compound, activated copper powder, copper chloride, copper bromide, copper oxide, or a pyridine complex or a quinoline complex of copper chloride or copper bromide can be used. Further, a crown ether or the like may be used in combination as a cation scavenger.

In the production method of the present invention, the above components are mixed and reacted by heating. At this time, m-alkoxyphenol is used in a molar amount of 2 to 3 times, more preferably 2.0 to 2.2 times, based on 4,4'-dihalogenoterphenyl. The equivalent of the alkali metal is used with respect to the m-alkoxyphenol. The amount of copper or copper compound used may be a catalytic amount.

In the reaction, the components of 4,4'-dihalogenoterphenyl, m-alkoxyphenol, hydroxide or carbonate of alkali metal, copper or copper compound may be mixed and heated at the same time. Preferably, m-alkoxyphenol is reacted in advance with a hydroxide or carbonate of an alkali metal to form a phenolate, and then 4,4'-
A method of adding dihalogen notterphenyl and copper or a copper compound can also be used.

The etherification reaction between m-alkoxyphenol and 4,4'-dihalogenoterphenyl is 200 to 25.
The reaction is preferably performed at 0 ° C., and the reaction time is 1 to 10 hours.
The reaction is preferably performed for 2 to 5 hours. In the reaction, a solvent that does not inhibit the reaction can be used. Examples of such a solvent include benzophenone, diphenylsulfone, sulfolane, N-methylpyrrolidone, N-hexylpyrrolidone and the like.

Thus, the 4,4'-bis- (3-alkoxyphenoxy)-is obtained by the etherification of m-alkoxyphenol with 4,4'-dihalogenoterphenyl.
p-Terphenyl is synthesized.

Next, the obtained 4,4'-bis- (3-
Dealkylation of (alkoxyphenoxy) -p-terphenyl gives 4,4'-bis (3-hydroxyphenoxy) -p-terphenyl of the present invention.

The method of dealkylation includes (a) reaction under reflux in a mixture of hydrobromic acid and acetic acid, (b) mixing with pyridine hydrogen bromide and heating and melting, (c)
For example, a method of dissolving in a solvent and reacting with boron tribromide can be employed.

The obtained 4,4'-bis- (3-hydroxyphenoxy) -p-terphenyl can be purified by recrystallization. Suitable recrystallization solvents include xylene, toluene, and a mixed solvent of dioxane / xylene.

Further, the obtained 4,4'-bis- (3-hydroxyphenoxy) -p-terphenyl is acetylated by treating it with acetic anhydride to give 4,4'-bis- (4-hydroxyphenoxy) -p-terphenyl.
Purified by recrystallization in the form of (3-acetoxyphenoxy) -p-terphenyl, and hydrolyzed to obtain purified 4,4'-bis- (3-hydroxyphenoxy) -p-
A method for obtaining terphenyl is also preferably used.

The 4,4'-bis- (3-
Hydroxyphenoxy) -p-terphenyl has a melting point of 246 to 247 ° C. and can be identified together with the results of elemental analysis, infrared absorption spectrum analysis, nuclear magnetic resonance spectrum analysis, and the like.

[0021]

According to the present invention, 4,4'-bis-
(3-Hydroxyphenoxy) -p-terphenyl is a novel compound, a novel polyester, polyether,
It is useful as a monomer such as polyether ketone. Since this monomer contains both rigid terphenyl and flexible m-phenoxy in the structural unit, it has a lower melting point than conventional terphenyl-containing polymers without lowering heat resistance. It can be used as an excellent raw material for polymer materials.

[0022]

The present invention will be described below with reference to examples. In the examples, "parts" represents parts by weight.

(A) Synthesis of 4,4'-bis- (3-methoxyphenoxy) -p-terphenyl 124 parts of m-methoxyphenol, potassium hydroxide 30
And 300 parts of xylene were placed in a reaction vessel equipped with a stirrer and a distilling system having a nitrogen inlet, refluxed in a nitrogen stream at normal pressure, and the generated water was azeotroped with xylene. After that, xylene is distilled off, and after cooling, 4,4'-dibiomo-
100 parts of p-terphenyl and 2.5 parts of activated copper are added,
The mixture was melted at 240 ° C. and reacted for 4 hours. After the reaction, the reaction mixture was cooled, and about 1000 parts of a 5% aqueous potassium hydroxide solution was added to dissolve excess m-methoxyphenol. The precipitate was separated by filtration, washed and diluted with dilute hydrochloric acid, and the obtained solid was mixed with about 1000 parts of xylene. Recrystallized using 20 parts of activated carbon,
83 parts of 4'-bis- (3-hydroxyphenoxy) -p-terphenyl were obtained. (The melting point of this product is 161-
164 ° C)

(B) Synthesis of 4,4'-bis- (3-hydroxyphenoxy) -p-terphenyl The obtained 4,4'-bis- (3-methoxyphenoxy)
-P-terphenyl 75 parts, acetic acid 300 parts, acetic anhydride 3
00 parts was placed in a reaction vessel equipped with a stirrer, and 100 parts of a 47% aqueous solution of hydrobromic acid was gradually dropped. After dropping,
Reflux for 20 hours. After the reaction, the mixture was cooled, the precipitate was filtered off, recrystallized from 500 parts of a mixed solvent of dioxane: xylene = 1: 4, and 4,4'-bis- (3-hydroxyphenoxy) -p-terphenyl 22 Got a part. The melting point of this product was 246 to 247 ° C, and the elemental analysis values were as follows. C: 80.4% (80.7%) H: 4.6% (4.9%) The infrared absorption spectrum of this product is as shown in FIG. 1, and the nuclear magnetic resonance spectrum ( ¹³ C: 22.5
MHz) were as shown in FIG.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of 4,4′-bis- (3-hydroxyphenyl) -p-terphenyl according to the present invention.

FIG. 2 shows a nuclear magnetic resonance spectrum of 4,4′-bis- (3-hydroxyphenyl) -p-terphenyl according to the present invention.

──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C07C 43/295 C07C 41/16 C07C 41/26 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A 4,4′-bis (3-hydroxyphenoxy) -p-terphenyl represented by the following formula (I). Embedded image 2. A 4,4′-dihalogenoterphenyl represented by the following formula (II) and m-type represented by the following formula (III):
The alkoxyphenol is reacted with an alkali metal hydroxide or carbonate in the presence of copper or a copper compound to give 4,4'-bis (3-alkoxyphenoxy) -p-terphenyl, which is then removed. The method for producing 4,4'-bis (3-hydroxyphenoxy) -p-terphenyl according to claim 1, which is alkylated. Embedded image (In the formula, X represents a chlorine or bromine atom, and R represents an alkyl group having 1 to 5 carbon atoms.)