JPH06293718A - Dihydroxy compound having triphenylamine structure and its production - Google Patents

Abstract

PURPOSE:To obtain a new dihydroxy compound useful as a raw material for various polymers, e.g. a polyarylate resin, a polycarbonate resin, an epoxy resin or a polyester resin. CONSTITUTION:This compound is expressed by formula I [R1 to R8 are H, halogen, alkoxy or alkyl, alkenyl, aryl which may respectively have a substituent group; at least one of R9 and R10 is a group containing a triphenylamine expressed by formula II {R11 to R16 are H, halogen, alkyl, alkenyl, alkoxy, aryl, arylamino, aryl-substituted alkenyl, aryl ether, aminoaryl ether or R11 and R12, R13 and R14 or R15 and R16 are bound to form a carbocyclic or heterocyclic ring; any of R11 to R16 are converted into bivalent group and bound to (CH2)a[(a) is 0-5] to form R9 or R10} and the rest is H, alkyl, alkenyl or aryl], e.g. a compound expressed by formula III. The compound is obtained by reacting phenols expressed by formula IV (at least one of R1 to R5 is H) with ketones or aldehydes expressed by formula V in the presence of an acidic catalyst.

Description

Detailed Description of the Invention

[0001]

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

[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]

Therefore, the present invention provides a novel dihydroxy compound which is useful as a polymer raw material.

[0004]

As a result of intensive studies to solve the conventional problems, the present inventors have found that the dihydroxy compound having a triphenylamine structure shown below is a novel compound not described in the literature. , Polyarylate resin,
It was found to be useful as a polymer raw material for polycarbonate resins, epoxy resins, polyester resins, etc.,
The present invention has been completed based on this finding.

That is, the present invention provides a dihydroxy compound having a triphenylamine structure represented by the following general formula (A) and a method for producing the same.

[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 triphenylamine represented by the following general formula (B), and the remaining one is hydrogen, an optionally substituted alkyl group, an alkenyl group, or an aryl group. , Or R ₉ and R ₁₀ are both the following general formula (B)
Represents a group containing triphenylamine represented by ) General formula (B)

[0008]

[Chemical 6]

(In the formula, R _{11 to} R ₁₆ are hydrogen, halogen, an alkyl group which may have a substituent, an alkenyl group, an alkoxy group, or an aryl group, an arylamino group, an aryl-substituted alkenyl group, an aryl ether. Base,
An aminoaryl ether group, or a group in which R ₁₁ and R ₁₂ or R ₁₃ and R ₁₄ or R ₁₅ and R ₁₆ are combined to form a carbocycle or a heterocycle, and any one of R _{11 to} R ₁₆ It becomes divalent radical, - (CH ₂₎ a- combines with R ₉ or R ₁₀
Form a group. a represents the integer of 0-5. )

The dihydroxy compound having a triphenylamine structure represented by the general formula (A) of the present invention is represented by the following general formula (C) in the presence of an acidic catalyst without solvent or in a solvent. And a ketone or an aldehyde represented by the following general formula (D) can be produced.

[0011]

[Chemical 7]

(In the formula, each of R _{1 to} R ₅ has the same meaning as in the formula (A) except that at least one is hydrogen.)

[0013]

[Chemical 8]

(In the formula, R _{9 to} R ₁₀ have the same meanings as in formula (A) above.)

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 triphenylamine structure represented by the general formula (B). to have a triphenylamine structure compounds as exemplified _{below, - (CH 2) a -} (a is 0
An integer of up to 5) and an alkylene group represented by R
₉ or R ₁₀ is formed. However, it is not limited to these compounds.

[0017]

[Chemical 9]

[0018]

[Chemical 10]

[0019]

[Chemical 11]

The reaction of these phenols with ketones or aldehydes having a triphenylamine structure is
A solvent may or may not be used. When a solvent is used, the solvent used is preferably an inert solvent for the reaction, for example, an aromatic hydrocarbon solvent such as benzene, toluene, xylene and ethylbenzene.

The catalyst used in the reaction is an acidic catalyst such as hydrogen chloride, sulfuric acid, toluenesulfonic acid,
Trifluoroacetic acid, trifluoromethanesulfonic acid, oxalic acid, phosphorus pentachloride, polyphosphoric acid, strong acid cation exchange resin, etc. are used, but among these, hydrogen chloride and strong acid cation are preferred because of their reaction accelerating property and ease of post-treatment. Ion exchange resins are preferred. The amount of the catalyst used varies depending on the type of the catalyst, but in the case of hydrogen chloride, it is usually selected in the range of 0.5 to 10% by weight based on the total amount of the phenols and the ketones or aldehydes.

In this reaction, a compound containing a mercapto group may be used as a promoter 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 triphenylamine structure, it is desirable to use the phenols in excess of the theoretical amount. Usually, phenols are usually added to 1 mol of the ketones or aldehydes. It is used in a proportion of 3 to 30 mol.

The reaction temperature varies depending on the type of the ketones or aldehydes and the 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.

[0025]

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 (301 g) of bis (4-methylphenyl) -4-formylphenylamine, and the mixture was stirred while maintaining the temperature at about 60 ° C. Blow to 2% in the mixture. The reaction is continued for 8 hours. Next, the hydrogen chloride gas was rapidly removed under reduced pressure, and hydrochloric acid in the liquid was removed.
Crystals of dihydric phenol mixed with phenol were obtained by adjusting the concentration to 0.005%, cooling to 40 ° C., and filtering. Phenol was removed from this crystal by vacuum distillation at about 30 mmHg and 170 ° C.
The remaining crystals are thoroughly washed with methanol. Then, the crystals were washed with water several times and dried under reduced pressure to obtain 312 g of dihydric phenol crystals represented by the following structural formula (1) (yield 6
6.2%) obtained. Elemental analysis, IR spectrum, M that this crystal is a dihydric phenol represented by the structural formula (1)
It was identified by S (mass spectrum).

[0027]

[Chemical 12]

Elemental analysis Calculated value: C; 84.05% Analytical value: C; 83.82% H; 6.20% H; 6.31% N; 2.97% N; 3.03%

The strong absorption in the IR spectrum 3300cm ^-1 near the (-OH derived from) 1320cm around ^-1 (aromatic tertiary amine) was observed. No strong absorption peak around 1700 cm ^-1 (aromatic aldehyde). Molecular weight (m +) 471

Example 2 As Example 1 except that 1 mol (329 g) of bis (4-methylphenyl) -4-acetonylphenylamine was used in place of bis (4-methylphenyl) -4-formylphenylamine. I went the same way. The yield of the obtained dihydric phenol represented by the following structural formula (2) was 354 g (yield 70.9%).

[0031]

[Chemical 13]

Elemental analysis Calculated value: C; 84.12% Analytical value: C; 84.21% H; 6.66% H; 6.71% N; 2.80% N; 2.90%

The strong absorption in the IR spectrum 3300cm ^-1 near the (-OH derived from) 1320cm around ^-1 (aromatic tertiary amine) was observed. No strong absorption peak was observed near 1700 cm ^-1 (aliphatic ketone). Molecular weight (m +) 499

Example 3 Same as Example 1 except that 1 mol (315 g) of bis (4-methylphenyl) -4-acetylphenylamine was used instead of bis (4-methylphenyl) -4-formylphenylamine. Went to. The yield of the obtained dihydric phenol represented by the following structural formula (3) was 297 g (yield 61.2%).

[0035]

[Chemical 14]

Elemental analysis Calculated value: C; 84.10% Analytical value: C; 83.9% H; 6.43% H; 6.47% N; 2.88% N; 3.00%

The strong absorption in the IR spectrum 3300cm ^-1 near the (-OH derived from) 1320cm around ^-1 (aromatic tertiary amine) was observed. No strong absorption peak was observed near 1700 cm ^-1 (aromatic ketone). Molecular weight (m +) 485

Example 4 Bis (4-methylphenyl) -4- (3) instead of bis (4-methylphenyl) -4-formylphenylamine
Example 1 was repeated except that 1 mol (343 g) of -oxobutyl) phenylamine was used. The yield of the obtained dihydric phenol represented by the following structural formula (4) was 370 g (yield 72.1%).

[0039]

[Chemical 15]

Elemental analysis Calculated value: C; 84.18% Analytical value: C; 84.02% H; 6.87% H; 6.75% N; 2.73% N; 2.74%

The strong absorption in the IR spectrum 3300cm ^-1 near the (-OH derived from) 1320cm around ^-1 (aromatic tertiary amine) was observed. No strong absorption peak was observed near 1700 cm ^-1 (aliphatic ketone). Molecular weight (m +) 513

Example 5 1 mol of 1,3-bis (4-bis (4-methylphenyl) aminophenyl) -2-propanone (60) instead of bis (4-methylphenyl) -4-formylphenylamine
Example 1 was repeated except that 0 g) was used. The yield of the obtained dihydric phenol of the following structural formula (5) was 411 g (yield
53.4%).

[0043]

[Chemical 16]

Elemental analysis calculated value: C; 85.68% Analytical value: C; 83.80% H; 6.54% H; 6.41% N; 3.63% N; 3.53%

The strong absorption in the IR spectrum 3300cm ^-1 near the (-OH derived from) 1320cm around ^-1 (aromatic tertiary amine) was observed. No strong absorption peak was observed near 1700 cm ^-1 (aliphatic ketone). Molecular weight (m +) 770

Example 6 Instead of bis (4-methylphenyl) -4-formylphenylamine, 1 mol of 9,9'-dimethyl-2- (N-phenyl-N- (4-acetylphenyl) aminofluorene ( The same procedure as in Example 1 was performed except that 403 g) was used, and the yield of the obtained dihydric phenol represented by the following structural formula (6) was 452 g (yield: 78.8%).

[0047]

[Chemical 17]

Elemental analysis Calculated value: C; 85.83% Analytical value: C; 85.77% H; 6.15% H; 6.22% N; 2.44% N; 2.45%

The strong absorption in the IR spectrum 3300cm ^-1 near the (-OH derived from) 1320cm around ^-1 (aromatic tertiary amine) was observed. No strong absorption peak was observed near 1700 cm ^-1 (aliphatic ketone). Molecular weight (m +) 573

Example 7 1 mol (403 g) of 4- (N-phenyl-N- (4-acetylphenyl) amino-4'-methylstilbene instead of bis (4-methylphenyl) -4-formylphenylamine Was carried out in the same manner as in Example 1. The yield of the obtained dihydric phenol of the following structural formula (7) was 431 g (yield 75.2%).

[0051]

[Chemical 18]

Elemental analysis Calculated value: C; 85.83% Analytical value: C; 85.89% H; 6.15% H; 6.30% N; 2.44% N; 2.54%

[0053] strong absorption in the IR spectrum 3300cm ^-1 near the (-OH derived from) 1320cm around ^-1 (aromatic tertiary amine) was observed. No strong absorption peak was observed near 1700 cm ^-1 (aliphatic ketone). Molecular weight (m +) 573

Example 7 Instead of bis (4-methylphenyl) -4-formylphenylamine, N- (4-acetylphenyl):
Example 1 was repeated except that 1 mol (403 g) of N ', N-bis (4-biphenylyl) amine was used.
The yield of the obtained dihydric phenol represented by the following structural formula (8) was 4
It was 06 g (yield 66.7%).

[0055]

[Chemical 19]

Elemental analysis Calculated value: C; 86.67% Analytical value: C; 86.81% H; 5.79% H; 5.68% N; 2.30% N; 2.45%

[0057] strong absorption in the IR spectrum 3300cm ^-1 near the (-OH derived from) 1320cm around ^-1 (aromatic tertiary amine) was observed. No strong absorption peak was observed near 1700 cm ^-1 (aliphatic ketone). Molecular weight (m +) 609

[0058]

The dihydroxy compound having a triphenylamine structure of the present invention is, for example, a polyarylate resin,
It is useful as a raw material for polymers such as polycarbonate resin, epoxy resin and polyester resin.

Claims (3)

[Claims] 1. A dihydroxy compound having a triphenylamine structure represented by the following general formula (A). [Chemical 1] (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 group containing triphenylamine represented by the formula (B), wherein the other one is hydrogen, an alkyl group which may have a substituent, an alkenyl group, or an aryl group, or
Both R ₉ and R ₁₀ represent a group containing triphenylamine represented by the following general formula (B). ) General formula (B): (In the formula, R _{11 to} R ₁₆ are hydrogen, halogen, an alkyl group which may have a substituent, an alkenyl group, an alkoxy group, or an aryl group, an arylamino group, an aryl-substituted alkenyl group, an aryl ether group, and amino. An aryl ether group or a group in which R ₁₁ and R ₁₂ or R ₁₃ and R ₁₄ or R ₁₅ and R ₁₆ are bonded to form a carbocycle or a heterocycle, and one of R _{11 to} R ₁₆ is Becomes a valence group,
(CH ₂₎ a- combine with forming the R ₉ or R ₁₀ groups. a represents the integer of 0-5. ) 2. The dihydroxy compound according to claim 1, wherein the hydroxyl group of the dihydroxy compound of the general formula (A) is bound to the para position. 3. A phenol represented by the following general formula (C) and a ketone or an aldehyde represented by the following general formula (D) are reacted under an acidic catalyst. A method for producing a dihydroxy compound having a triphenylamine structure according to the description. [Chemical 3] (In the formula, each of R _{1 to} R ₅ has the same meaning as in the above formula (A) except that at least one is hydrogen.) (In the formula, each of R _{9 to} R ₁₀ has the same meaning as in the formula (A).)