JP2529230B2 - 1,1-bis (3-phenyl-4-hydroxyphenyl) methane derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel dihydroxydiaryl compound. More specifically, the present invention includes, for example, polycarbonate, aromatic polyester, epoxy resin,
The present invention relates to a novel 1,1-bis (3-phenyl-4-hydroxyphenyl) methane derivative useful as a raw material for high molecular weight polymers such as polysulfone.

[Conventional technology]

Conventionally, bisphenols obtained by the reaction of phenols with aldehydes or ketones are known to be important compounds as raw materials for various high molecular weight polymers such as polycarbonate, epoxy resins, aromatic polyesters, polysulfones, and the like. Among them, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) obtained from phenol and acetone is used in large quantities as a raw material for the above-mentioned polymer.

As the bisphenols, various compounds have been found so far. For example, as a compound obtained by the reaction of phenol with various aldehydes or ketones, bis (phenol) and formaldehyde other than the bisphenol A can be obtained. Hydroxyphenyl) methane isomer mixture (bisphenol F), 1,1-bis (4-hydroxyphenyl) ethane obtained from phenol and acetaldehyde (bisphenol AD), 1,1-bis (4'-obtained from phenol and cyclohexanone
Hydroxyphenyl) cyclohexane and the like are known.

Further, bisphenols having a substituent on the benzene ring include, for example, o-cresol, o-ethylphenol, o-isopropylphenol, 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-diisopropylphenol. , Ot-dodecylphenol and other alkylphenols, compounds obtained by reaction of halogenated phenols with aldehydes or ketones, or different substitutions on the respective benzene rings by reaction of alkylphenols with isopropenylphenols. Bisphenols having a group are known [U.S. Pat. No. 4,304,899, "Collection Czec
hoslov.Chem.Commun., 34, 2843 (1969
Year)〕.

Furthermore, it is also known that one phenyl group is introduced into each benzene ring, and one phenyl group is introduced into one side of the benzene ring [[Collection Czechoslov.
em.Commun. ", Volume 34, Page 2843 (1969)].

Among these bisphenols, bisphenol F
Is industrially used as a raw material of liquid epoxy resin, 3,3 ', 5,5'-tetramethylbisphenol A is used as a modifier of polycarbonate, and mono- or dialkyl-substituted bisphenols are used as gas barrier agents. It has attracted attention as an excellent raw material for polycarbonate (US Pat. No. 4,304,899).

By the way, in recent years, with the expansion of applications of high-molecular polymers, the use under severe conditions has increased, and high-molecular polymers having more excellent physical properties are desired, such as polycarbonate, epoxy resin, aromatic polyester, and polysulfone. In the field as well, development of new raw materials is being actively attempted in order to obtain products with better physical properties.

[Problems to be solved by the invention]

The object of the present invention is polycarbonate, epoxy resin,
It is an object of the present invention to provide a novel dihydroxydiaryl compound which is useful as a raw material for high molecular weight polymers such as aromatic polyesters, porformal resins and polysulfones.

[Means for solving problems]

The present inventors have conducted extensive research to develop a novel dihydroxydiaryl compound useful as a raw material for the above-mentioned polymer, and as a result, 1,1-bis (obtained from o-phenylphenol and ketones The 3-phenyl-4-hydroxyphenyl) methane derivative is a novel compound that has not been published in the literature and is useful as a raw material for high molecular weight polymers such as polycarbonate, epoxy resin, aromatic polyester, polyformal resin, and polysulfone. The present invention has been completed based on this finding.

That is, the present invention has the general formula (Wherein R ¹ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ² is a phenyl group, a phenoxyphenyl group or an alkoxyphenyl group having 7 to 11 carbon atoms)
A 1-bis (3-phenyl-4-hydroxyphenyl) methane derivative is provided.

The 1,1-bis (3 represented by the general formula (I) of the present invention
-Phenyl-4-hydroxyphenyl) methane derivative is, for example, in the presence of an acidic catalyst in the absence of a solvent or in a solvent, and a compound represented by the general formula (R ₁ and R ₂ in the formula have the same meanings as described above), and can be produced.

In the compound represented by the general formula (II), R ₁ has ₁ carbon atom.
To 6 are alkyl groups or phenyl groups, and R ₂ is a phenyl group, and typical examples of such groups include:
Acetophenone, propiophenone, benzophenone,
4'-phenoxyacetophenone, 4'-methoxyacetophenone, 4'-ethoxyacetophenone and the like.

The reaction between these compounds and o-phenylphenol may be performed without using a solvent or may be performed using a solvent. As the solvent to be used, those inert to the reaction, for example, aromatic hydrocarbon solvents such as benzene, toluene, xylene and ethylbenzene are preferable. Examples of the catalyst include acidic catalysts such as hydrogen chloride, sulfuric acid, toluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, oxalic acid, phosphorus pentachloride, and polyphosphoric acid. Among them, hydrogen chloride is particularly preferable. It is preferable from the viewpoints of accelerating reaction and easiness of post-treatment. The amount of these catalysts used cannot be unconditionally limited because it depends on the type of catalyst used, but when hydrogen chloride is used, it is usually 0.5 to 10 wt% relative to the total amount of o-phenylphenol and ketones. It is selected in the range of%.

In this reaction, it is preferable to use a compound containing a mercapto group as a promoter together with the acidic catalyst. Examples of the mercapto group-containing compound include methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, octyl mercaptan, alkyl mercaptans such as dodecyl mercaptan, aromatic mercaptans such as thiophenol and thiocresol, and mercaptoacetic acid (thioglycol Acid) and mercapto organic acids such as mercaptopropionic acid. These cocatalysts are usually used in the range of 0.1 to 5% by weight based on the total amount of o-phenylphenol and ketones.

Regarding the usage ratio of o-phenylphenol and ketones, it is preferable to use o-phenylphenol in excess of the theoretical amount.
Phenylphenol is used in a proportion of 2.2 to 6 mol.

The reaction temperature varies depending on the type of aldehyde or ketones used and the type of catalyst used, and cannot be specified unconditionally, but it is generally selected in the range of 20 to 150 ° C. The reaction pressure is not particularly limited and may be any of reduced pressure, normal pressure and increased pressure, but it is usually advantageous to carry out the reaction under normal pressure. Furthermore, the reaction time depends on the type of raw material, the type and amount of catalyst and cocatalyst, the reaction temperature, etc.
It is usually about 5 to 200 hours.

Next, as an example of a suitable method for producing the 1,1-bis (3-phenyl-4-hydroxyphenyl) methane derivative of the present invention, the structural formula 1-phenyl-1,1-bis (3-phenyl-
Explaining the production of 4-hydroxyphenyl) ethane, first, o-phenylphenol and acetophenone are mixed in a predetermined ratio, for example, in a molar ratio of 3: 1 and heated and dissolved. A predetermined amount of a catalyst is added, and then the catalyst is allowed to react for 20 to 50 hours at a temperature in the range of 40 to 80 ° C. while blowing hydrogen chloride gas into the reaction system.

Next, the reaction-terminated liquid is washed with warm water or the like to remove hydrogen chloride gas, and then unreacted o-phenylphenol is distilled off under reduced pressure to obtain a crude reaction product, which is then purified by a conventional method. The desired 1-phenyl-
1,1-bis (3-phenyl-4-hydroxyphenyl)
You get ethane.

This 1-phenyl-1,1-bis (3-phenyl-4-
Hydroxyphenyl) ethane is a novel compound that has not been published in the literature, and its melting point is 67 to 68 ° C.

In the same manner, the following novel compounds can be produced.

1-phenyl-1,1-bis (3-phenyl-4-hydroxyphenyl) propane Melting point: 72-75 ° C 1,1-diphenyl-1,1-bis (3-phenyl-4-hydroxyphenyl) methane 1- (4-phenoxyphenyl-1,1-bis (3-phenyl-4-hydroxyphenyl) ethane 1- (4-methoxyphenyl) -1,1-bis (3-phenyl-4-hydroxyphenyl) ethane These 1,1-bis (3-phenyl-4-hydroxyphenyl) methane derivatives are useful as raw materials for high molecular weight polymers such as polycarbonate, epoxy resin, aromatic polyester, polyformal resin and polysulfone.

For example, a polycarbonate can be obtained by reacting the 1,1-bis (3-phenyl-4-hydroxyphenyl) methane derivative with phosgene by a known method. Further, at this time, by coexisting bisphenol A, a copolymer polycarbonate with bisphenol A can be obtained.

Furthermore, an epoxy resin is obtained by reacting the 1,1-bis (3-phenyl-4-hydroxyphenyl) methane derivative with epichlorohydrin by a known method. In addition, the 1,1-bis (3
An aromatic polyester by condensing a (phenyl-4-hydroxyphenyl) metal derivative with an aromatic polycarboxylic acid such as terephthalic acid, and a polyformal resin by reacting with methylene chloride
Polysulfone is obtained by condensing with (4-chlorophenyl) sulfone.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples.
The present invention is not limited in any way by these examples.

Example 1 510 g (3 mol) of o-phenylphenol and 182 g (1 mol) of acetophenone were mixed and heated to about 60 ° C. to dissolve, then 10 g of mercaptoacetic acid was added and hydrochloric acid gas was stirred for 36 hours. Blown in.

After washing the reaction mixture with warm water at about 70 ° C three times,
The organic phase was heated under a reduced pressure of 14 mmHg to an oil bath temperature of 190 ° C. to evaporate the evaporate to obtain 180 g of distillation residue. Next, this was dissolved in 400 ml of methylene chloride, 500 ml of a 2N sodium hydroxide aqueous solution was added, and the mixture was vigorously stirred, followed by cooling with ice to precipitate crystals. Next, the crystals were filtered, washed twice with 400 ml of methylene chloride, and then washed with 500 ml of ice-cooled 2N sodium hydroxide aqueous solution. The crystals were dispersed in 1N hydrochloric acid 2 and stirred vigorously, then the crystals were filtered, washed several times with water and dried under reduced pressure to give 1-phenyl-1,1.
-Bis (3'-phenyl-4'-hydroxyphenyl)
110 g of ethane was obtained. The yield of this product is 25% (vs acetophenone), melting point is 67-68 ° C, purity is 99.1% (from HPLC)
Met.

In addition, ¹ H-NMR (acetone d ₆ ) δ (ppm) was 2.17 (s3
H), 6.89 (d2H), 6.96 (dd2H), 7.21 (m7H), 7.33
(T4H), 7.52 (d4H) and 8.3 (b2H).

 The molecular weight (m +) was 442.

In the same manner, the following compounds were reacted to obtain the desired novel compound.

Example 2 Reaction of o-phenylphenol with propiophenone (IB) Melting point was 72 to 75 ° C, and purity was 98.3% (from HPLC).

In addition, ¹ H-NMR (acetone d ₆ ) δ (ppm) was 0.89 (t3
H), 2.20 (q2H), 6.91 (d2H), 6.97 (dd2H), 7.23
(M7H), 7.33 (t4H), 7.52 (d4H) and 8.4 (b2H).

 The molecular weight (m +) was 456.

Example 3 Reaction (IC) of o-phenylphenol and benzophenone The melting point was 295 to 298 ° C, and the purity was 98.6% (from HPLC).

In addition, ¹ H-NMR (dimethyl sulfoxide d ₆ ) δ (pp
m) is 6.91 (d2H), 6.97 (dd2H), 7.06 (d2H), 7.3
(M6H), 7.39 (dd4H) and 8.5 (b2H).

 The molecular weight (m +) was 504.

Example 4 Reaction of o-phenylphenol with 4'phenoxyacetophenone (ID) 510 g (3 mol) of o-phenylphenol, 212 g (1 mol) of 4'-phenoxyacetophenone and 9.2 g (0.1 mol) of mercaptoacetic acid were mixed. The mixture was heated to about 60 ° C. to dissolve it, 117 g of 98% by weight sulfuric acid was added with stirring, and the mixture was reacted at 70 ° C. for 12 hours.

After the reaction was completed, the product was diluted with methylene chloride 3 and washed with water 2 three times. Then, 500 ml of a 5 N sodium hydroxide aqueous solution was added and ice-cooled to obtain crystals. Next, the crystals were washed with methylene chloride, dispersed in water 3, and hydrochloric acid was added until the pH became 1 or less. Then, the crystals were filtered, washed with water, and recrystallized using a toluene-hexane mixed solvent to give 235 g of 1- (4-phenoxyphenyl) -1,1-bis (3-phenyl-4-hydroxyphenyl) ethane. Got The yield of this product is
44% (vs. 4-phenoxyacetophenone), melting point 125
It was ~ 129 ° C.

In addition, ¹ H-NMR (acetone d ₆ ) δ (ppm) was 2.10 (s3
H), 6.82 (s5H), 6.92 (d2H), 6.97 (dd2H), 7.05
It was -7.23 (m6H), 7.26-7.39 (m6H), 7.90 (dd4H).

 The molecular weight (m +) was 534.

Example 5 Reaction of o-phenylphenol and 4'-methoxyacetophenone (IE) The same as Example 4 except that 150 g (1 mol) of 4'-methoxyacetophenone was used instead of 4'-phenoxyacetophenone.

As a result, 160 g of 1- (4-methoxyphenyl) -1,1-bis (3-phenyl-4-hydroxyphenyl) ethane
I got The yield was 34% (vs. 4'-methoxyacetophenone) and the melting point was 142-145 ° C.

In addition, ¹ H-NMR (acetone d ₆ ) δ (ppm) was 2.12 (s3
H), 3.54 (s3H), 6.82 (d2H), 6.92 (d2H), 6.98
(Dd2H), 7.04 to 7.22 (m6H), 7.25 to 7.40 (m6H), 7.
It was 90 (dd2H) and 8.1 (dd2H).

 The molecular weight (m +) was 472.

Application Example 1 70 g (0.25 mol) of bisphenol A was dissolved in 480 ml of 6 wt% NaOH aqueous solution, 250 ml of methylene chloride was added thereto, and this was put in a baffled flask of 1 and stirred vigorously while phosgene gas was about 900 ml / 14 at the rate of min
I blew for a minute. After stopping the blowing of gas, let it stand and separate,
A methylene chloride solution of a polycarbonate precursor having a chloroformate group terminal and having a degree of polymerization of 2 to 3 was obtained.

Next, 90 ml of this precursor solution was diluted to 120 ml with methylene chloride, to which 0.8 g of pt-butylphenol and 1-phenyl-1,1-bis (3-phenyl-4-hydroxy) obtained in Example 1 were added. Phenyl) ethane (10.1 g) was added and dissolved.

To this solution was added 1 ml of a 5-fold by weight triethylamine aqueous solution, and 90 ml of a 2N NaOH aqueous solution was added dropwise over 30 minutes with vigorous stirring, and the reaction was carried out for 1 hour after the addition. After completion of the reaction, it was diluted with 500 ml of methylene chloride, water, 0.01 N NaOH aqueous solution, water, 0.1 ml.
After washing with a 01N HCl aqueous solution and water in this order, a methylene chloride solution containing polycarbonate was poured into methanol 5 to obtain a white polycarbonate copolymer.

The reduced viscosity of the obtained polymer was 0.48 (20 ° C, 0.5 g / dl
It was a methylene chloride solution), and the content of 1-phenyl-1,1-bis (3-phenyl-4-hydroxyphenyl) ethane unit was 33 mol% from the NMR spectrum measurement.

Application Example 2 60 g of 1-phenyl-1,1-bis (3-phenyl-4-hydroxyphenyl) ethane obtained in Example 1 and p-
1.0 g of t-butylphenol is dissolved in 500 ml of methylene chloride, 300 ml of water and 1.0 ml of triethylamine are added thereto, and phosgene gas is added to 300 to 400 ml / m while vigorously stirring.
Blow in at a rate of in. At this time, a 12N NaOH aqueous solution was dropped into the reaction system so that the pH did not fall below 10. After blowing gas for 25 minutes, the mixture was reacted for 1 hour while stirring. After the reaction, dilute with 700 ml of methylene chloride and add water 0.01N NaOH.
After washing in order of aqueous solution, water, 0.01N HCl aqueous solution, water,
Inject this methylene chloride solution into methanol 5,
A white polycarbonate polymer was obtained. The polymer obtained had a reduced viscosity of 0.42 (20 ° C., 0.5 g / dl methylene chloride solution).

Application Example 3 1- (4-phenoxyphenyl) -1,1-
Bis (3-phenyl-4-hydroxyphenyl) ethane
267 g (0.5 mol), sodium hydroxide 44 g (1.1 mol), methylene chloride 51 g (0.6 mol) and N as a solvent
-Methylpyrrolidone (500 ml) was added, and the mixture was reacted for 4 hours at the reflux temperature of methylene chloride with stirring. After completion of the reaction, the product was cooled, diluted with methylene chloride 2 and washed with 0.01N hydrochloric acid and water respectively, and the organic layer was separated and poured into methanol to precipitate polyformal resin. Recovered. The yield was 183g. The reduced viscosity [ηsp / c] of a solution of 0.5 g / dl concentration of this product in methylene chloride at 20 ° C was 0.5 dl / g, the glass transition temperature was 120 ° C, and the following repeating units were used. Had.

[Effects of the Invention] The 1,1-bis (3-phenyl-4-hydroxyphenyl) methane derivative of the present invention is a novel compound that has not been published in the literature, and includes, for example, polycarbonate, epoxy resin, aromatic polyester, polyformal It is useful as a raw material for polymers such as resins and polysulfones.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area C08G 64/06 NPT C08G 64/06 NPT

Claims (1)

(57) [Claims] 1. A general formula (Wherein R ¹ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ² is a phenyl group, a phenoxyphenyl group or an alkoxyphenyl group having 7 to 11 carbon atoms)
1-bis (3-phenyl-4-hydroxyphenyl) methane derivative.