JP3282330B2 - Polyhydric phenolic compound and method for producing polyhydric phenolic compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polyhydric phenol compound and a method for producing the polyhydric phenol compound.

[0002]

2. Description of the Related Art Polyhydric phenol compounds are useful compounds used as curing agents for epoxy resins or as raw materials for epoxy resins.

In recent years, in the field where polyhydric phenolic compounds are used, particularly in the field of electric and electronic materials, with higher integration of electronic circuits and the spread of surface mounting methods, more heat resistance,
A resin excellent in chemical resistance, mechanical properties, and the like has been desired.

Heretofore, phenol novolak resins and ortho-cresol novolak resins have been mainly used as such polyhydric phenol compounds, but handling is generally inconvenient. In addition, polyhydric phenolic compounds generally used as curing agents for epoxy resins do not contain low-molecular-weight compounds in view of heat resistance, chemical resistance, mechanical properties, and the like of the obtained cured products, and have a molecular weight distribution width. However, it is thought that phenol novolak resins and the like, which are conventionally known, are composed of a mixture of linear molecules having a low molecular weight and a wide molecular weight distribution. However, it is difficult to obtain a cured product having a high crosslinking density, and as a result, no satisfactory cured product has been obtained.

[0005]

The object of the present invention is to provide a branched-chain polyhydric phenolic compound having a relatively low viscosity and good handleability, containing no low molecular weight substance, and having a narrow molecular weight distribution. With the goal.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems of the prior art, and as a result, a polyhydric phenol compound having a specific structure represented by the following general formula (1): However, they found that the object of the present invention was met, and completed the present invention.

That is, the present invention provides a compound represented by the general formula (1):

[0008]

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Wherein R ₁ is an alkyl group having 1 to 12 carbon atoms, and R ₂ is a hydrogen atom, a hydroxy group or a C ₁ to C 12
4 represents an alkyl group, and n represents an integer of 1 or 2. A) a polyhydric phenolic compound represented by the general formula (2):

[0010]

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(Wherein, R ₁ represents an alkyl group having 1 to 12 carbon atoms), and 2,6-diformyl-4-alkylphenol represented by the following general formula (3):

[0012]

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(Wherein R ₂ represents a hydrogen atom, a hydroxy group or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 or 2) in the presence of an acid catalyst. And a general formula (1) characterized by reacting
To a method for producing a polyhydric phenol compound.

Specific examples of the polyhydric phenolic compound represented by the general formula (1) of the present invention include the following compounds.

[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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In the above Chemical Formulas 8 to 14, R ₁ represents an alkyl group having 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms, and R ₂ represents a hydroxy group or an alkyl group having 1 to 4 carbon atoms. R
_When the number of carbon atoms of ₁ exceeds 12, the heat resistance of a cured product obtained when used as a curing agent for an epoxy resin or the like is undesirably reduced. When the carbon number of R ₂ exceeds 4, the reactivity with 2,6-diformyl-4-alkylphenol decreases, which is not preferable. The polyhydric phenolic compounds shown in Chemical formulas 8 to 14 are examples when one kind of compound having the same orientation is used as phenols, but R _{2 in} one molecule is the same substituent. This need not be the case, and a mixture using phenols having different substituents may be used. Also, although not illustrated,
When two or more compounds having different orientations are used as phenols, a mixture of several kinds of polyhydric phenol compounds according to the orientation of each phenol is obtained.

The novel polyphenolic compound represented by the general formula (1) is represented by the general formula (2):

[0024]

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(Wherein R ₁ represents an alkyl group having 1 to 12 carbon atoms), and 2,6-diformyl-4-alkylphenol represented by the general formula (3):

[0026]

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(Wherein R ₂ represents a hydrogen atom, a hydroxy group or an alkyl group having 1 to 4 carbon atoms), and is easily prepared by a condensation reaction in the presence of an acid catalyst. Can be manufactured.

Specific examples of 2,4-diformyl-4-alkylphenol represented by the general formula (2) include 2,6
-Diformyl-4-methylphenol, 2,6-diformyl-4-ethylphenol, 2,6-diformyl-4
-N-propylphenol, 2,6-diformyl-4-
i-propylphenol, 2,6-diformyl-4-n
-Butylphenol, 2,6-diformyl-4-t-butylphenol, 2,6-diformyl-4-octylphenol, 2,6-diformyl-4-nonylphenol, 2,6-diformyl-4-dodecylphenol and the like. The 2,6-diformyl-4-alkylphenol is produced by oxidizing a 2,6-dimethylol-4-alkylphenol in the presence of a catalyst such as palladium, platinum, manganese dioxide, etc. 29371, Japanese Patent Publication No. 4-43059).

Specific examples of the phenol represented by the general formula (3) include phenol, resorcinol, pyrogallol, etc., cresols such as o-cresol, m-cresol, p-cresol, 2,3-xylenol,
2,4-xylenol, 2,5-xylenol, 2,6
Xylenols such as -xylenol, 3,4-xylenol and 3,5-xylenol, ethylphenol, n
-Propylphenol, i-propylphenol, n-
Various alkylphenols such as butylphenol and t-butylphenol are exemplified. These phenols can be used alone or in combination of two or more.

The amount of the phenol used is usually 2,6-
It is used in an amount of about 4 to 60 parts by mole, preferably 8 to 32 parts by mole, based on 1 part by mole of diformyl-4-alkylphenol. If the amount is less than 4 parts by mole, the production of a high molecular weight substance increases, and if it exceeds 60 parts by mole, the reaction rate becomes slow and the reaction requires a long time, which is not preferable.

Examples of the acid catalyst used in the condensation reaction include organic acids, inorganic acids, metal salts, Lewis acids and the like. Specifically, organic acids include formic acid, oxalic acid, malonic acid,
Succinic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, paratoluenesulfonic acid, benzenesulfonic acid, phenolsulfonic acid, xylenesulfonic acid, trifluoromethanesulfonic acid, and the like.Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, and the like. Examples include perchloric acid, hydrobromic acid, phosphoric acid, and the like. Examples of metal salts include zinc acetate, zinc chloride, and magnesium acetate. Examples of Lewis acids include boron trifluoride, titanium tetrachloride, and aluminum chloride. can give. Among them, it is preferable to use a strong acid catalyst such as p-toluenesulfonic acid or hydrochloric acid, since the selectivity is particularly good and the reaction rate can be appropriately controlled. The amount of the acid catalyst used is usually 0.001 to 10 parts by weight with respect to 100 parts by weight of 2,6-diformyl-4-alkylphenol since the reaction rate is appropriately controlled and the generation of by-products can be suppressed. Degree, preferably 0.01 to 5
Parts by weight.

In using the above-mentioned catalyst,
A suitable co-catalyst may be used. Specific examples of the cocatalyst include thiols such as thioglycolic acid, thioglycerol, and benzenethiol. Of these,
It is preferable to use thioglycolic acid from the viewpoint of ease of post-treatment and solubility. The amount of cocatalyst used controls the reaction rate appropriately and suppresses the generation of by-products,
The amount is usually about 10 parts by weight or less, preferably about 0.001 to 5 parts by weight, based on 100 parts by weight of 2,6-diformyl-4-alkylphenol.

In the condensation reaction of the present invention, a solvent is not particularly required, but the reaction may be carried out using an appropriate solvent. Specific examples of the solvent used include water, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, and isoamyl alcohol; glycol ethers such as ethyl cellosolve acetate, ethyl cellosolve, and methyl cellosolve; hexane, cyclohexane, and heptane. ,
Examples include hydrocarbons such as benzene, toluene, and xylene.

[0034] The reaction temperature is usually about 20 to 200 ° C. The temperature is preferably set to 50 to 100 ° C. since the reaction rate is appropriately controlled and generation of by-products can be suppressed.

After the completion of the reaction, an alkaline substance is added to neutralize the acid catalyst (if a cocatalyst is used, the acid catalyst and the cocatalyst). As the alkaline substance used,
Examples include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkaline earth metal carbonates, ammonia, and organic amines. Among these, alkali metal hydroxides, such as sodium hydroxide, are preferred because they have few side reactions and are easy to handle. The alkaline substance may be added as it is, or may be added as an aqueous solution.
It is good to add as an aqueous solution of about 1 to 50% by weight, preferably 1 to 20% by weight.

After the neutralization, an organic solvent or the like is added to the system to dissolve the reaction product, and the salts and metal ions generated by the neutralization are washed with water. As the organic solvent, ethyl acetate, tetrahydrofuran, chloroform, methyl isobutyl ketone, benzene, toluene, xylene, hexane, heptane, cyclohexane and the like are preferable, and as the water, ion-exchanged water is preferable.

According to the present invention, a novel polyhydric phenolic compound represented by the above general formula (1) can be obtained. Usually, the polyhydric phenolic compound is contained in the reaction product obtained by the present invention. In addition, unreacted phenols and the like are contained. Such unreacted phenols can be easily removed by distillation under reduced pressure, steam distillation or the like, and the novel polyhydric phenolic compound represented by the general formula (1) can be easily isolated. The novel polyhydric phenolic compound represented by the general formula (1) is a high molecular weight compound obtained by condensing the polyhydric phenolic compound with unreacted 2,6-diformyl-4-alkylphenol together with phenols and the like. Etc. may be included. Such high molecular weight substances and the like can be removed by means such as reprecipitation and recrystallization, but they can be used for various applications as a mixture with a novel polyhydric phenol compound as it is.

[0038]

According to the present invention, the viscosity is relatively low,
In addition, a novel polyhydric phenol-based compound of a branched chain molecule having a narrow molecular weight distribution and containing no low molecular weight substance can be provided. Such a novel polyhydric phenol compound of the present invention can be used as a curing agent for an epoxy resin, a raw material for an epoxy resin, and the like, and can provide a cured product having a high crosslinking density. Further, the novel polyphenolic compound of the present invention is a polyester,
It can also be used as a polyol component of polycarbonate and polyurethane.

[0039]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 A reactor equipped with a stirrer and a reflux condenser was placed under a stream of nitrogen under nitrogen atmosphere.
7.5 g of 6-diformyl-4-methylphenol (0.
05 mol) and 150.6 g (1.6 mol) of phenol, and the mixture was heated to 80 ° C. while stirring. To this, 0.075 g (0.43 g) of paratoluenesulfonic acid was used as an acid catalyst.
6 × 10 ⁻³ mol) and reacted for 1 hour. Then, 0.075 g (0.436 × 1) of thioglycolic acid was used as a co-catalyst.
0 ^-3 mol), and the mixture was further reacted for 5 hours to complete the reaction. After completion of the reaction, while maintaining the temperature at 80 ° C., 1.308 g (1.3% by weight) of a 4% by weight aqueous sodium hydroxide solution was used.
08 × 10 ^-3 mol) to neutralize the catalyst.
After stirring for 300 minutes, 300 ml of methyl isobutyl ketone and 100 ml of water were added, and the mixture was cooled to room temperature. This was transferred to a separating funnel, left for a while, and then separated. Further, the organic layer was washed with ion-exchanged water until the washing liquid became neutral.
Thereafter, the solvent in the organic layer was removed by distillation, and excess phenol was subsequently removed from 120 ° C to 180 ° C (750 mm
Hg to 5 mmHg), and the objective polyhydric phenolic compound (compound corresponding to Chemical formula 8) 7
A resin containing 0% was obtained. The resin was further purified by recrystallization in a chloroform solution to obtain 12.67 g of the objective polyhydric phenol compound (compound corresponding to the above formula 8) having a purity of 99.9% by GPC (2,6- (In a yield of 52% from diformyl-4-methylphenol)
Obtained. The NMR data of the obtained polyhydric phenol compound is shown below. FIG. 1 shows a GPC chart of the obtained polyhydric phenol compound.

( ¹ H-NMR spectrum data) Solvent: deuterated dimethyl sulfoxide δ (ppm): 2.01 (3H, s), 5.71 (2)
H, s), 6.43 (2H, s), 6.67 (8H,
d), 6.82 (8H, d), 8.01 (1H, s),
9.18 (4H, s)

( ¹³ C-NMR spectrum data) Solvent: deuterated dimethyl sulfoxide δ (ppm): 20.91, 47.53, 114.8
9, 120.08, 126.89, 128.07, 13
2.22, 134.70, 149.43, 155.36

Example 2 A reactor equipped with a stirrer and a reflux condenser was placed under a stream of nitrogen under nitrogen flow.
7.5 g of 6-diformyl-4-methylphenol (0.
05 mol) and 173.0 g (1.6 mol) of o-cresol, and the mixture was heated to 80 ° C. while stirring. Then, 0.075 g of paratoluenesulfonic acid was used as an acid catalyst.
(0.436 × 10 ⁻³ mol) and reacted for 1 hour, and then 0.075 g of thioglycolic acid (0.
(436 × 10 ⁻³ mol), and the reaction was further continued for 11 hours to complete the reaction. After the completion of the reaction, while maintaining the temperature at 80 ° C., 1.30% by weight of a 4% by weight aqueous sodium hydroxide solution.
8 g (1.308 × 10 ⁻³ mol) was added to neutralize the catalyst, and the mixture was stirred for 5 minutes. Then, 300 ml of methyl isobutyl ketone and 100 ml of water were added, and the mixture was cooled to room temperature. This was transferred to a separating funnel, left for a while, and then separated. Further, the organic layer was washed with ion-exchanged water until the washing liquid became neutral. Thereafter, the solvent in the organic layer was removed by distillation, and the excess o-cresol was subsequently removed from 120 ° C. to 1 ° C.
Distillation was performed under the conditions of 80 ° C. (750 mmHg to 5 mmHg) to obtain a resin containing 69% of the objective polyhydric phenol compound (compound corresponding to the above formula 9). This resin is purified by heating and dissolving it in a chloroform solution and reprecipitating it from a carbon tetrachloride solution. 0.32 g (49% yield from 2,6-diformyl-4-methylphenol) were obtained. The NMR data of the obtained polyhydric phenol compound is shown below. FIG. 2 shows a GPC chart of the obtained polyhydric phenol compound.

( ¹ H-NMR spectrum data) Solvent: deuterated dimethyl sulfoxide δ (ppm): 2.00 (3H, s), 2.03 (12
H, s), 5.60 (2H, s), 6.41 (2H,
s), 6.59 (4H, d), 6.65 (4H, d),
6.69 (4H, s), 7.80 (1H, s), 9.0
1 (4H, s)

( ¹³ C-NMR spectrum data) Solvent: dimethyl sulfoxide δ (ppm): 16.15, 20.93, 47.60,
114.14, 123.05, 126.61, 127.
12,127.95,131.25,132.08,1
34.63, 149.32, 153.29

Example 3 A reactor equipped with a stirrer and a reflux condenser was placed under a stream of nitrogen under nitrogen flow.
7.5 g of 6-diformyl-4-methylphenol (0.
05 mol) and 173.0 g (1.6 mol) of m-cresol, and the mixture was heated to 80 ° C. with stirring. Then, 0.075 g of paratoluenesulfonic acid was used as an acid catalyst.
(0.436 × 10 ⁻³ mol) and reacted for 1 hour, and then 0.075 g of thioglycolic acid (0.
(436 × 10 ⁻³ mol), and the reaction was further continued for 11 hours to complete the reaction. After the completion of the reaction, while maintaining the temperature at 80 ° C., 1.30% by weight of a 4% by weight aqueous sodium hydroxide solution.
8 g (1.308 × 10 ⁻³ mol) was added to neutralize the catalyst, and the mixture was stirred for 5 minutes. Then, 300 ml of methyl isobutyl ketone and 100 ml of water were added, and the mixture was cooled to room temperature. This was transferred to a separating funnel, left for a while, and then separated. Further, the organic layer was washed with ion-exchanged water until the washing liquid became neutral. Thereafter, the solvent in the organic layer was removed by distillation, and the excess m-cresol was subsequently removed from 120 ° C. by 1 ° C.
Distillation was performed under the conditions of 80 ° C. (750 mmHg to 5 mmHg), and the target polyhydric phenolic compound (the above
A resin containing 70%). This resin is purified by heating and dissolving it in a chloroform solution and reprecipitating it from a carbon tetrachloride solution to obtain a target polyhydric phenol compound having a purity of 92.7% by GPC (compound corresponding to the above chemical formula 10). .86 g to (2,6-
51% yield from diformyl-4-methylphenol
At). The NMR data of the obtained polyhydric phenol compound is shown below. FIG. 3 shows a GPC chart of the obtained polyhydric phenol compound.

( ¹ H-NMR spectrum data) Solvent: deuterated dimethyl sulfoxide δ (ppm): 2.00 (12H, s), 2.18 (3
H, s), 5.73 (2H, s), 6.28 (2H,
s), 6.41 (4H, s), 6.47 (4H, d),
6.57 (4H, s), 8.01 (1H, s), 9.0
0 (4H, s)

( ¹³ C-NMR spectrum data) Solvent: dimethyl sulfoxide δ (ppm): 16.14, 20.91, 47.58,
114.15, 123.03, 126.62, 127.
10,127.97,131.24,132.09,1
34.61, 149.31, 153.30

Example 4 A reactor equipped with a stirrer and a reflux condenser was placed under a stream of nitrogen under nitrogen atmosphere.
7.5 g of 6-diformyl-4-methylphenol (0.
05 mol) and 195.5 g of 2,6-xylenol (1.
6 mol) and heated to 80 ° C. while stirring.
To this, 0.075 of p-toluenesulfonic acid was used as an acid catalyst.
g (0.436 × 10 ⁻³ mol) and reacted for 1 hour, and then 0.075 g of thioglycolic acid as a co-catalyst.
(0.436 × 10 ⁻³ mol) was added, and the mixture was further reacted for 25 hours to complete the reaction. After the reaction is completed, the temperature is
While maintaining the temperature, 1.308 g (1.308 × 10 ⁻³ mol) of a 4% by weight aqueous solution of sodium hydroxide was added to neutralize the catalyst, and the mixture was stirred for 5 minutes, and then 300 ml of methyl isobutyl ketone and 100 ml of water were added. In addition, it was cooled to room temperature. This was transferred to a separating funnel, left for a while, and then separated. Further, the organic layer was washed with ion-exchanged water until the washing liquid became neutral. Thereafter, the solvent in the organic layer was removed by distillation, and the excess amount of 2,6-xylenol was subsequently
20 ° C to 180 ° C (750mmHg to 5mmHg)
Then, a resin containing 52% of the objective polyhydric phenol compound (compound corresponding to the above formula 12) was obtained. This resin was purified by heating and dissolving it in a chloroform solution and reprecipitating it from a carbon tetrachloride solution.
12.64 g of a target polyhydric phenolic compound having a purity of 97.9% by PC (a compound corresponding to the above chemical formula 12)
(41% yield from 2,6-diformyl-4-methylphenol). The NMR data of the obtained polyhydric phenol compound is shown below. FIG. 4 shows a GPC chart of the obtained polyhydric phenol compound.

( ¹ H-NMR spectrum data) Solvent: deuterated dimethyl sulfoxide δ (ppm): 2.00 (3H, s), 2.08 (24
H, s), 5.57 (2H, s), 6.44 (2H,
s), 6.55 (8H, s), 7.67 (1H, s),
7.67 (1H, s), 7.95 (4H, s)

( ¹³ C-NMR spectrum data) Solvent: dimethyl sulfoxide δ (ppm): 16.84, 21.03, 47.82,
123.61, 126.60, 128.06, 128.
91, 131.95, 135.03, 149.36, 1
51.13

[Brief description of the drawings]

FIG. 1 shows a GPC chart of a polyhydric phenol compound (compound corresponding to the above formula 8) obtained in Example 1. It can be seen that a polyhydric phenolic compound having a narrow molecular weight distribution and containing no low molecular weight product was obtained. GPC: HLC-8020 manufactured by Tosoh Corporation Column: TSK-GEL (G200 manufactured by Tosoh Corporation)
0HXL + G1000HXL) Solvent: THF

FIG. 2 shows a GPC chart of the polyhydric phenol compound (compound corresponding to the above formula 9) obtained in Example 2. It can be seen that a polyhydric phenolic compound having a narrow molecular weight distribution and containing no low molecular weight product was obtained. GPC: HLC-8020 manufactured by Tosoh Corporation Column: TSK-GEL (G200 manufactured by Tosoh Corporation)
0HXL + G1000HXL) Solvent: THF

FIG. 3 shows a GPC chart of the polyhydric phenol compound (compound corresponding to the above formula 10) obtained in Example 3. It can be seen that a polyhydric phenolic compound having a narrow molecular weight distribution and containing no low molecular weight product was obtained. GPC: Tosoh Corporation HLC-8020 Column: Tosoh Corporation TSK-GEL (G300
0HXL + G2000HXL) Solvent: THF

FIG. 4 shows a GPC chart of the polyhydric phenol compound (compound corresponding to the above formula 12) obtained in Example 4. It can be seen that a polyhydric phenolic compound having a narrow molecular weight distribution and containing no low molecular weight product was obtained. GPC: Tosoh Corporation HLC-8020 Column: Tosoh Corporation TSK-GEL (G300
0HXL + G2000HXL) Solvent: THF

──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07C 39/12 C07C 39/15 C07C 39/16 C07C 37/20 C07B 61/00 300 REGISTRY (STN) CA ( STN) CAOLD (STN)

Claims (2)

(57) [Claims] 1. General formula (1): (Wherein, R ₁ represents an alkyl group having 1 to 12 carbon atoms, R ₂ represents a hydrogen atom, a hydroxy group or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 or 2). Polyhydric phenolic compounds. 2. General formula (2): (In the formula, R ₁ represents an alkyl group having 1 to 12 carbon atoms.)
A 2,6-diformyl-4-alkylphenol represented by the general formula (3): (Wherein, R ₂ represents a hydrogen atom, a hydroxy group or a carbon atom 1)
And n represents an integer of 1 or 2. )
Phenols represented in the presence of an acid catalyst, the general formula, characterized by reacting (1): ## STR4 ## (In the formula, _{R 1} represents an alkyl group having 1 to 12 carbon atoms, _{R 2}
Is a hydrogen atom, a hydroxy group or an alkyl having 1 to 4 carbon atoms
And n represents an integer of 1 or 2. )) .