JPS642577B2 - - Google Patents

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention provides dihydric phenol derivatives useful as raw materials for producing various high-performance thermoplastic polymers, surfactants, resin modifiers, stabilizers, etc. and its manufacturing method.

<Prior Art> Bisphenols are important starting materials for various high-performance thermoplastic polymers, such as polycarbonates, polyesters, and epoxy resins.
generally well known.

However, polymers using bisphenols are desired to have further improved heat-resistant adhesive performance depending on the application.

In addition, divalent phenol compounds such as resorcinol and catechol, or their derivatives, are widely used as non-toxic vulcanization accelerators for rubber.
Further improvements in performance are desired.

<Problems to be Solved by the Invention> In view of the current situation, the present inventors have conducted intensive studies on divalent phenol-based compounds, and as a result, it is an object of the present invention to provide a novel divalent phenol derivative.

<Means for solving the problem> That is, the present invention has the following structural formula: or A divalent phenol derivative represented by the formula (B) and its production method, that is, resorcinol or catechol, and the formula (B) and formula (C) and formula (D) (In formulas (B), (C) and (D), the substituents on the benzene nucleus are located at the 1, 3 or 1, 4 positions of the benzene nucleus) with an acidic condensing agent. The above dihydric phenols (A-1), (A-2),
The present invention relates to a method for producing a divalent phenol derivative, which comprises recovering (A-3) or (A-4).

Specific examples of the compound of formula (B) are 1,3-diisopropenylbenzene and 1,4-diisopropenylbenzene.

Specific examples of the compound of formula (C) are 3-(2-hydroxy-2-propyl)-isopropenylbenzene, 4
-(2-hydroxy-2-propyl)-isopropenylbenzene.

Specific examples of the compound of formula (D) are 1,3-di(2-hydroxy-2-propyl)benzene and 1,4-di(2-hydroxy-2-propyl)-benzene.

In addition, the manufacturing method of the compound selected from the group consisting of formulas (B), (C), and (D) is not particularly limited, but the industrially common manufacturing method is formula (E). (In formula (E), the substituents on the benzene nucleus are located at the 1, 3 or 1, 4 positions of the benzene nucleus.) A compound of formula (B) obtained by dehydrogenation of a hydrocarbon compound represented by , or by air oxidation.

Formula (F) (In formula (F), the substituents on the benzene nucleus are located at the 1, 3 or 1, 4 positions of the benzene nucleus) and/or formula (G) (In formula (G), the substituents on the benzene nucleus are located at the 1, 3 or 1, 4 positions of the benzene nucleus.) Formula obtained by reducing hydroperoxide with sodium sulfite, hydrogen, etc. Compounds of formula (B) and (C) can be produced by dehydrating the compound of (D) or the compound of formula (D) in the presence of an acid catalyst.

These compounds can be subjected to the reaction in the range of 1,3-disubstituted products or 1,4-disubstituted products, singly or as a mixture of two or more.

Furthermore, these compounds are provided as a mixture of two or more of the 1,3-disubstituted product and the 1,4-disubstituted product, and after the reaction, the difference in physical properties (such as melting point) of the desired reaction product can be utilized. However, it is also possible to separate and produce each desired reaction product.

In carrying out the present invention, resorcinol or catechol is usually used in a molar amount of 2.0 to 10 times, preferably 2.0 times, per mole of the compound represented by formula (B), (C), or (D).
~6 times the molar amount and the stoichiometric amount or more,
Used in excess.

As the acidic condensing agent, common sulfuric acid, hydrochloric acid, hydrogen chloride gas, boron trifluoride, hydrogen fluoride, trifluoroacetic acid, acid clay, acidic ion exchange resin, etc. can be used.

In order to assist this condensation reaction, the reaction can be carried out more efficiently if "S" compounds such as hydrogen sulfide, mercaptans, and thiophenols are used in combination.

In order to carry out the reaction smoothly, it is also possible to use a suitable organic solvent such as benzene, toluene, chlorobenzene, etc. as a solvent.

The reaction temperature is usually in the range of -20 to 100°C.

The reaction pressure can usually be carried out under atmospheric pressure, but when the acidic condensing agent is a gas, it is carried out under increased pressure. Furthermore, when water is produced in the reaction, since the acidic condensing agent is diluted with water, the reaction can be carried out under reduced pressure in order to remove the produced water from the reaction system in order to maintain its effectiveness. At this time, it is also possible to coexist an organic solvent and remove water under reduced pressure and azeotropy.

The dihydric phenol derivative of the present invention can be precipitated as a solid from the reaction mixture, or when an organic solvent is used, can be precipitated as a solid and recovered as a crude product by cooling the organic layer.

After removing unreacted resorcin or catechol from this crude product by a conventional method such as hot water washing or distillation, it is treated with water, alcohol, acetic acid, chloroform, benzene, toluene, etc., or a mixture thereof. It can be recovered as a highly pure solid by recrystallization from a solvent.

The present invention will be explained in more detail with reference to Examples below, but the scope of the present invention is not limited thereby.

Example 1 Resorcinol 33 in a 500ml glass three-necked flask
g (0.3 mol), 1,3-di(2-hydroxy-2
19.4 g (0.1 mol) of benzene (propyl), 100 ml of benzene, and 100 ml of concentrated hydrochloric acid were charged, and the reaction was carried out at 5°C for 15 hours with stirring.

After the reaction was completed, the ocher oil layer was separated and neutralized with hot aqueous sodium carbonate solution. After the neutralization was completed, unreacted resorcin contained in the oil layer was removed by washing with hot water, and the oil layer was cooled in an ice water bath. A pale ocher solid was precipitated by cooling, and a pale ocher powder was obtained by filtration. White crystals with a melting point of 104-107°C were obtained by benzene recrystallization in a yield of 91%.

Based on this manufacturing method and the infrared absorption spectrum, NMR spectrum, mass spectrum, and elemental analysis of the product, this product has the formula 1,3-di[2-
It was confirmed to be (2,4-dihydroxyphenyl)-2-propyl]benzene.

Example 2 Resorcinol 33 in a 500ml glass three-necked flask
g (0.3 mol), 1,4-di-(2-hydroxy-
19.4 g (0.1 mol) of 2-propyl)benzene, 100 ml of benzene, and 100 ml of concentrated hydrochloric acid were charged, and the reaction was carried out at 5° C. for 15 hours with stirring.

After the reaction was completed, the yellowish brown oil layer was separated and neutralized with a hot aqueous solution of sodium carbonate. After the neutralization was completed, unreacted resorcin contained in the oil layer was removed by washing with hot water, and the oil layer was cooled in an ice water bath. A light yellowish brown solid was precipitated by cooling, and a light yellowish brown powder was obtained by filtration. White crystals with a melting point of 135-139°C were obtained by methanol recrystallization in a yield of 87%.

Based on this manufacturing method and the infrared absorption spectrum, NMR spectrum, mass spectrum, and elemental analysis of the product, this product has the formula 1,4-di[2-
It was confirmed to be (2,4-dihydroxyphenyl)-2-propyl]benzene.

Example 3 Catechol in a 500ml glass three neck flask
33 g (0.3 mol), 100 ml of benzene, and 50 ml of concentrated hydrochloric acid were charged, and the temperature was maintained at 40°C. 16 g (0.1 mol in total) of a mixture of 1,3-diisopropenylbenzene and 3-(2-hydroxy-2-propyl)isopropenylbenzene was gradually added thereto. 8
After an hour of reaction, a reddish-brown oil layer separated.

This oil layer was separated and neutralized with a hot aqueous solution of sodium carbonate. After neutralization, unreacted catechol contained in the oil layer was removed by washing with hot water. A precipitate was observed when the oil layer was cooled, and a pale brown solid was obtained by filtering.

White crystals with a melting point of 133-137°C were obtained by chloroform recrystallization in a yield of 81%.

Based on this manufacturing method and the infrared absorption spectrum, NMR spectrum, mass spectrum, and elemental analysis of the product, this product has the formula 1,3-di[2-
It was confirmed to be (3,4-dihydroxyphenyl)-2-propyl]benzene.

Example 4 Catechol 33 in a 500ml glass three neck flask
g (0.3 mol), 1,4-di(2-hydroxy-2
19.4 g (0.1 mol) of benzene (propyl), 100 ml of benzene, and 100 ml of concentrated hydrochloric acid were charged, and the reaction was carried out at 5°C for 15 hours with stirring. After the reaction was completed, precipitation of crystals was observed. After removing the aqueous layer, the oil layer and crystals were neutralized with a hot aqueous solution of sodium carbonate, and then unreacted catechol was removed by washing with hot water. Subsequently, the mixture was cooled in an ice-water bath to completely precipitate crystals, and filtered to obtain a milky white powder. Benzene recrystallization gave white crystals with a melting point of 192-198°C in a yield of 78%.

Based on this manufacturing method and the infrared absorption spectrum, NMR spectrum, mass spectrum, and elemental analysis of the product, this product has the formula 1,4-di[2-
It was confirmed to be (3,4-dihydroxyphenyl)-2-propyl)benzene.

<Effects of the Invention> A novel dihydric phenol derivative could be obtained by the present invention.

Claims (1)

[Claims] 1. Structural formula Or A divalent phenol derivative represented by 2 Resorcinol or catechol and formula (B) and formula (C) and formula (D) (In formulas (B), (C) and (D), the substituents on the benzene nucleus are located at the 1, 3 or 1, 4 positions of the benzene nucleus) with an acidic condensing agent. The structural formula or A method for producing a divalent phenol derivative, which comprises recovering a divalent phenol derivative represented by: