JPH06234746A - Dihydroxy compound having pyrazoline structure and its producton - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as a raw material for various polymers such as polyarylate, polycarbonate, epoxy and polyester resins. CONSTITUTION:A compound of formula I [R1 to R8 are H, halogen, alkoxy, substitutable alkyl, alkenyl or aryl; one of R9 and R10 is carbazole (R11 to R14 are H, halogen, (substituted) alkyl), etc.) and the others are H, alkyl, (substituted) aryl, etc., or R9 and R10 are both group of formula II]. The compound is obtained by reacting a phenol of formula III with a ketone or an aldehyde of formula IV in the presence of an acidic catalyst (e.g. hydrogen chloride) in the absence of a solvent or in a solvent (e.g. benzene) at 20-150 deg.C for 5-200 hours. 3-30mols of phenol is used based on 1mol of the ketone or aldehyde.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel dihydroxy compound having a pyrazoline structure and a method for producing the same. The dihydroxy compound of the present invention is useful as a raw material for various polymers such as polyarylate resin, polycarbonate resin, epoxy resin and polyester resin.

[0002]

2. Description of the Related Art Conventionally, bisphenols obtained by reacting phenols with aldehydes or ketones are important compounds as raw materials for various polymers such as polyarylate resins, polycarbonate resins, epoxy resins and polyester resins. Above all, 2,2-bis (4-hydroxyphenyl) obtained from phenol and acetone
Propane (bisphenol A) is used in large quantities as a raw material for the polymer. Bisphenol A is a polymer raw material in which cost, heat resistance, mechanical strength, etc. are well balanced. However, along with the expansion of the use of polymers in recent years, a polymer having more excellent physical properties is desired, and even in polyarylate resin, polycarbonate resin, epoxy resin, polyester resin, etc., in order to obtain more excellent physical properties, New raw material development is required.

[0003]

The present invention provides a novel dihydroxy compound which is useful as a raw material for various polymers.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the conventional problems, the inventors have found that the dihydroxy compound having a pyrazoline structure shown below is a novel compound not described in the literature, They have found that they are useful as a polymer raw material for polyarylate resins, polycarbonate resins, epoxy resins, polyester resins, etc., and have completed the present invention based on this finding.

That is, the present invention is represented by the following general formula (A)

[0006]

[Chemical 5]

(In the formula, R _{1 to} R ₈ are hydrogen, halogen, an alkoxy group, an alkyl group which may have a substituent, respectively,
An alkenyl group or an aryl group is shown. At least one of R ₉ and R ₁₀ is a group containing a pyrazoline represented by the following general formula (B), and the remaining one is hydrogen, an alkyl group, or an alkenyl group, an aryl group which may have a substituent, or , R ₉ and R ₁₀ both represent a group containing a pyrazoline represented by the following general formula (B). ) General formula (B)

[0008]

[Chemical 6]

(In the formula, R _{11 to} R ₁₄ each represent hydrogen, halogen, an alkyl group which may have a substituent, an alkoxy group, an alkenyl group or an aryl group, and R _{11 to} R _14
14 either is divalent radical, - (CH ₂₎ a - combines with to form a R ₉ or R ₁₀ groups. a represents the integer of 0-5. The present invention provides a dihydroxy compound having a pyrazoline structure represented by the formula (1) and a method for producing the same.

The dihydroxy compound having a pyrazoline structure represented by the above general formula (A) of the present invention is, for example, in the presence of an acidic catalyst in the absence of a solvent or a solvent, and the following general formula (C).

[0011]

[Chemical 7]

(Wherein at least one of R _{1 to} R ₅ is hydrogen) has the same meaning as in formula (A) above, and the following general formula ( D)

[0013]

[Chemical 8]

It can be produced by reacting with a ketone or an aldehyde represented by the formula (wherein R _{9 to} R ₁₀ have the same meanings as in the formula (A)).

The phenols represented by the general formula (C) are specifically phenol, O-cresol, m-cresol, P-cresol, O-chlorophenol, m-chlorophenol, P-chlorophenol. , O-bromophenol,
m-bromophenol, P-bromophenol, O-t-butylphenol, 2,3-xylenol, 2,6-xylenol,
2,6-di-t-butylphenol, O-phenylphenol,
2,6-dichlorophenol, 2,6-dibromophenol, 2,
6-diethylphenol, 2,6-diisopropylphenol, eugenol, O-allylphenol, isoeugenol, thymol, m-methoxyphenol, guaiacol, O-fluorophenol, Pt-butylphenol, etc. Those having no substituent at the para position are preferable from the viewpoint of reactivity.

The ketones and aldehydes represented by the general formula (D) are those in which at least one of R ₉ and R ₁₀ has a pyrazoline structure represented by the general formula (B). A compound as exemplified below, which has a pyrazoline structure containing no triphenylamine, hydrazone, benzidine, styryl, carbazole structure, and-(C
H ₂₎ a - (a is bonded to the alkylene group represented by an integer) to 0-5, to form the R ₉ or R _10. However, it is not limited to these compounds. (Below margin)

[0017]

[Chemical 9]

The reaction of these phenols with ketones or aldehydes having a pyrazoline structure may or may not use a solvent. As the solvent used in the present invention, those inert to the reaction, for example, aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene and the like are preferable.

Examples of the catalyst used in the reaction of the present invention include acidic catalysts such as hydrogen chloride, sulfuric acid, toluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, oxalic acid, phosphorus pentachloride, polyphosphoric acid, and strongly acidic positive catalysts. Ion exchange resins are used, but among these,
Hydrogen chloride and a strongly acidic cation exchange resin are preferable in terms of reaction accelerating property and easy post-treatment. The amount of the catalyst used varies depending on the type of the catalyst, but in the case of hydrogen chloride, it is usually 0.5 to 10 relative to the total amount of phenols and ketones or aldehydes.
It is selected in the range of weight%.

In this reaction, a compound containing a mercapto group may be used as a cocatalyst together with the acidic catalyst. Examples of the compound containing a mercapto group include alkyl mercaptans such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, octyl mercaptan and dodecyl mercaptan, aromatic mercaptans such as thiophenol and thiocresol, mercaptoacetic acid and mercaptopropion. Examples thereof include mercapto organic acids such as acids. These cocatalysts are usually used in the range of 0.1 to 5% by weight based on the total amount of phenols and ketones or aldehydes.

Regarding the usage ratio of the phenols and the ketones or aldehydes having a pyrazoline structure, it is desirable to use the phenols in excess of the theoretical amount,
Usually, phenols are used in a proportion of 3 to 30 mol per mol of ketones or aldehydes.

The reaction temperature varies depending on the type of ketones or aldehydes used and the type of catalyst used, and cannot be specified unconditionally, but it is generally selected in the range of 20 ° C to 150 ° C. There is no particular limitation on the reaction pressure, and reduced pressure,
Either normal pressure or increased pressure may be used, but it is usually advantageous to carry out the reaction under normal pressure. Furthermore, the reaction time is usually about 5 to 200 hours, although it is affected by the kinds of raw materials, the kinds and amounts of catalyst and cocatalyst, the reaction temperature and the like.

[0023]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Example 1 10 mol (940 g) of phenol was added to 1 mol (468 g) of 1- (4-formylphenyl) -3,5-bis (4-diethylaminophenyl) pyrazoline, and the mixture was stirred while maintaining the temperature at about 60 ° C. Blow hydrogen chloride gas until the concentration of hydrochloric acid becomes 2% in the mixed solution. The reaction is continued for 8 hours. Next, the hydrogen chloride gas was rapidly removed under reduced pressure, and the hydrochloric acid in the liquid was adjusted to 0.005%, and then 40 ° C.
After cooling to room temperature and filtering, crystals of dihydric phenol mixed with phenol were obtained. Phenol is removed from this crystal by vacuum distillation at about 30 mmHg and 170 ° C., and the remaining crystal is thoroughly washed with methanol. Then, the crystals were washed with water several times and dried under reduced pressure to obtain 382 g (yield 59.9%) of dihydric phenol crystals represented by the following structural formula (1). It was identified by elemental analysis, IR spectrum and MS that this crystal was a dihydric phenol represented by the structural formula (1).

[0025]

[Chemical 10]

Elemental analysis calculated value: C; 78.96% Analytical value: C; 79.11 %% H; 7.26% H; 7.47% N; 8.77% N; 8.64%

IR spectrum No strong absorption peak around 3300 cm-1 (derived from -OH) around 1320 cm-1 (aromatic tertiary amine) around 1700 cm-1 (aromatic aldehyde). Molecular weight (m +) 638

[0028]

INDUSTRIAL APPLICABILITY The dihydroxy compound having a pyrazoline structure of the present invention is useful as a polymer raw material such as polyarylate resin, polycarbonate resin, epoxy resin and polyester resin.

Claims (3)

[Claims] 1. The following general formula (A): (In the formula, R _{1 to} R _{8 each} represent hydrogen, a halogen, an alkoxy group, or an alkyl group, an alkenyl group, or an aryl group which may have a substituent. R ₉ and R ₁₀ are at least one of the following general formulas: A pyrazoline-containing group represented by the formula (B), the other one of which is hydrogen, an alkyl group, or an alkenyl group, an aryl group which may have a substituent, or R ₉ and R
Both of ₁₀ represent groups containing pyrazoline represented by the following general formula (B). ) General formula (B): (In the formula, R _{11 to} R ₁₄ each represent hydrogen, halogen, an alkyl group which may have a substituent, an alkoxy group, an alkenyl group, or an aryl group, and any one of R _{11 to} R ₁₄ is a divalent group. next, - (CH ₂₎ a - combines with to form a R ₉ or R ₁₀ groups .a dihydroxy compound having a pyrazoline structure represented by represents) an integer of 0 to 5.. 2. The dihydroxy compound according to claim 1, wherein the hydroxyl group of the dihydroxy compound of the general formula (A) is in the para position. 3. The following general formula (C): (In the formula, each has the same meaning as in the above formula (A) except that at least one of R _{1 to} R ₅ is hydrogen.) And the following general formula (D): Chemical 4] (In the formula, R _{9 to} R ₁₀ each have the same meaning as in the formula (A).) A ketone or an aldehyde represented by the formula (A) is condensed under an acidic catalyst. A method for producing a dihydroxy compound having a described pyrazoline structure.