JP6635575B2 - Phenolic compound having good stability and method for producing the same - Google Patents

Description

The present invention relates to heat and / or heat produced from aldehydes (hereinafter sometimes simply referred to as aldehyde) or ketones (hereinafter sometimes simply referred to as ketone) and phenols (hereinafter sometimes simply referred to as phenol). It relates to a phenol compound having good stability to oxygen.

Bisphenol and phenol novolak resins are widely used as epoxy resins by reacting with epichlorohydrin to form glycidyl ether. These phenolic compounds are known to be sensitive to heat and oxygen, and upon exposure to heat and / or oxygen, these phenolic compounds form decomposition products, which are more abundant than phenolic compounds containing these decomposition products. It also has an adverse effect on the physical properties of the manufactured epoxy resin. In particular, bisphenol F and phenol novolak resins are produced by adding formalin to phenol and condensing it using an acid catalyst, but when these are stored for a long period of time, coloring is remarkable. Further, the epoxy resin obtained by using such a colored phenol compound is also colored, which significantly impairs the product value. Therefore, it has been proposed to prevent the coloring of the phenol compound obtained by controlling the dissolved oxygen in the reaction solution, which is now a standard method, and the hue of the obtained phenol compound is clear (Patent Document 1) ). However, even the phenol compound obtained by that method does not solve the tendency to color when stored for a long period of time or the decomposability when heated.

Therefore, in order to stabilize these phenol compounds, a method of adding lactic acid, malic acid, glyceric acid or a metal salt thereof (Patent Document 2), or adding phthalic anhydride or a phthalic anhydride derivative as a stabilizer is used. A method (Patent Document 3) and a method of adding L-ascorbic acid or DL-α-tocopherol (Patent Document 4) have been proposed. However, in these methods, since the stabilizer is mixed as an impurity, in the so-called indirect method, a method for producing an epoxy resin obtained by a reaction between a low-molecular epoxy resin and a phenol compound, the stabilizer is mixed into the epoxy resin, Physical properties may be deteriorated.
Further, in a production method in which bisphenol F and a phenol novolak resin are co-produced, since a distillation step is always included, there is a high possibility of being affected by heat, but the conventional method has not been a production method in which special consideration has been given ( Patent Document 5, Patent Document 6).

JP-A-62-195509 Japanese Patent No. 2820746 JP-A-55-151526 Japanese Patent No. 308374 JP-A-6-128183 JP 2011-68760 A

The present invention has been developed in view of the above circumstances, and it is an object of the present invention to provide a phenol compound produced from an aldehyde or ketone and phenol without heat and / or oxygen without using a special stabilizer. An object of the present invention is to obtain a phenol compound having good stability.

The present inventors use a special stabilizer in phenol compounds produced from aldehydes or ketones and phenol, if the concentration of metal ions and dissolved oxygen in the phenol compounds is controlled within a certain range that is significantly reduced from the conventional level. It has been found that a phenol compound having good stability to heat and / or oxygen can be obtained without performing the method, and the present invention has been completed.

That is, the present invention
A method for producing a phenolic compound (1) for an epoxy resin raw material , which is obtained from an aldehyde or a ketone and a phenol in the presence of a catalyst, wherein the metal ion concentration in the raw material used is 0.1 to 10 mg. / Kg, while the phenolic compound (1) in a molten state is added with oxygen other than oxygen so that the dissolved oxygen concentration in the phenolic compound (1) is in the range of 0.01 to 1.0 mg / L. B) bubbling the gas or degassing the phenolic compound (1) in a molten state under reduced pressure, characterized in that the phenolic compound for an epoxy resin raw material has good heat and / or oxygen stability ( This is the manufacturing method of 1).

The phenol compound is preferably bisphenol F or phenol novolak resin,

The phenolic compound is more preferably bisphenol F and a phenol novolak resin obtained by a production method that produces bisphenol F and a phenol novolak resin together.

The aldehydes are preferably formaldehyde, and the phenols are preferably phenol.

The heat and / or oxygen stable phenolic compound of the present invention does not require a special stabilizer, so that a phenolic compound having little adverse effect upon subsequent use can be obtained. It is a phenolic compound suitable as a raw material in a method for producing an epoxy resin.

Hereinafter, embodiments of the present invention will be described in detail.
The phenolic compound of the present invention is a phenolic compound represented by the following general formula (1) and produced from aldehydes or ketones and phenols, and the metal ion concentration in the phenolic compound is 0.1%. 1 to 10 mg / kg, and refers to a phenol compound having a dissolved oxygen concentration of 0.01 to 1.0 mg / L.

（式中、Ｒ_１はそれぞれ独立に炭素数１〜１２の炭化水素基であり、Ｒ_２は炭素数１〜１３の炭化水素基、または−Ｃ（ＣＦ_３）−であり、ｋはそれぞれ独立に０〜２の整数であり、ｎは１以上の整数である。）

(Wherein, R ₁ is each independently a hydrocarbon group having 1 to 12 carbon atoms, R ₂ is a hydrocarbon group having 1 to 13 carbon atoms, or —C (CF ₃ ) —, and k is each independently Is an integer of 0 to 2, and n is an integer of 1 or more.)

In addition to phenol, the raw material phenols include, for example, alkyl phenols such as cresol, ethyl phenol, butyl phenol, octyl phenol, nonyl phenol, dodecyl phenol, and their (ortho, meta, para) position-substituted products, (n-, sec-, tert) Substituent structural isomers (eg-) can also be used. Among them, phenol is preferred from the viewpoint of reactivity and ease of recovery by distillation. Phenol may be used alone or in combination of two or more.

Examples of the raw material aldehydes include, but are not limited to, formaldehyde (formalin), acetaldehyde, propionaldehyde, benzaldehyde, and the like.

Ketones as a raw material include, for example, acetone, butanone, cyclohexanone, benzophenone, hexafluoroacetone and the like, but are not limited thereto.

In the production of the phenol compound of the present invention, it is preferable to use a catalyst as in the production of a general phenol compound. Specific examples of the catalyst that can be used include acid catalysts such as inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as salicylic acid, paratoluenesulfonic acid, and oxalic acid; sodium hydroxide, lithium hydroxide, and water. Basic catalysts such as hydroxides of alkali metals such as potassium oxide, tertiary amines such as aqueous ammonia and triethylamine, oxides and hydroxides of alkaline earth metals such as calcium, magnesium and barium, and sodium carbonate and the like. . Further, it may be a fixed bed of a solid catalyst such as an ion exchange resin. In the present invention, although there is no particular limitation on the catalyst, an acid catalyst is preferable, and specifically, oxalic acid and p-toluenesulfonic acid are preferable.

  The reaction temperature and the reaction time in the production vary depending on the type, amount or reaction molar ratio of the catalyst used (phenols / aldehydes or ketones), etc., but the reaction temperature is usually 50 to 110 ° C. Is usually 0.5 to 10 hours.

Specific phenolic compounds include bisphenol A obtained from phenol and acetone, bisphenol F obtained from phenol and formalin, bisphenol AP obtained from phenol and acetophenone, bisphenol AF obtained from phenol and hexafluoroacetone, phenol and butanone Bisphenol B obtained from phenol and benzophenone, bisphenol C obtained from cresol and acetone, bisphenol E obtained from phenol and acetaldehyde, bisphenol G obtained from 2-isopropylphenol and acetone, 2-phenylphenol Such as bisphenol PH obtained from phenol and acetone, and bisphenol Z obtained from phenol and cyclohexanone. Phenol or phenol novolak derived from phenol and formaldehyde, cresol novolac obtained from cresol and formaldehyde, although phenol novolac such as octylphenol novolak obtained from octylphenol and formaldehyde and the like, but is not limited thereto. The phenol compound in the specification refers to these phenol compounds of the present invention unless otherwise specified. When a phenol compound other than the present invention or a phenol compound other than the present invention is contained, it is clearly distinguished in each case.

If the concentration of metal ions contained in these phenol compounds is in the range of 0.1 to 10 mg / kg and the concentration of dissolved oxygen in the phenol compounds satisfies the range of 0.01 to 1.0 mg / L, A phenol compound is a phenol compound having good stability to heat and / or oxygen, does not discolor even during long-term storage, and hardly undergoes thermal decomposition even when kept at a high temperature.

When the metal ion concentration in the phenol compound is in the range of 0.1 to 10 mg / kg, stability against heat is particularly improved, and thermal decomposition hardly occurs. Thermal decomposition is greatly affected by the amount of residual acid catalyst, and if the residual amount is large, thermal decomposition tends to occur. In addition, the amount by which thermal decomposition is likely to occur varies depending on the type of acid catalyst, but in the present invention, regardless of the type, by controlling the concentration of the metal ion that forms the pair, a range in which thermal decomposition does not easily occur was found. . The range of the metal ion concentration in the phenol compound is 0.1 to 10 mg / kg, preferably 0.1 to 7 mg / kg, more preferably 0.1 to 5 mg / kg, and 0.1 to 3 mg / kg. kg is particularly preferred. This metal ion concentration is an index of the remaining amount of the acid catalyst used in synthesizing the phenol compound. Regardless of the type of the acid catalyst, the smaller the metal ion, the smaller the remaining amount of the acid catalyst. However, in order to forcibly reduce the metal ion concentration, a step such as washing with water is required. In most cases, the total amount of metal ions in the raw material phenol, aldehyde, or ketone remains in the phenol compound as it is, so it is realistic to control the amount of metal ions in the raw material, and the total metal ion concentration of the raw material used Is preferably adjusted to the range of 0.1 to 10 mg / kg.

Although the metal ion concentration is determined by the fluorescent X-ray method, since most of the metal ions are not detected, a total sum of the concentrations of lithium ion, sodium ion, potassium ion, magnesium ion, and calcium ion may be used. In that case, a simple quantitative method by ion chromatography may be used.

When the concentration of dissolved oxygen in the phenol compound is in the range of 0.01 to 1.0 mg / L, stability against heat is improved, thermal decomposition is unlikely to occur, and stability against oxygen is improved. No coloration even after storage for a period. Dissolved oxygen tends to cause thermal decomposition, and the more it is, the more the thermal decomposition is promoted. Further, the dissolved oxygen greatly affects the coloring factor of the phenol compound, and the coloring is considered to be due to oxidation. Therefore, conventionally, oxidation was suppressed by adding an antioxidant, but in the present invention, it was found that by controlling the range of dissolved oxygen in the phenol compound, the oxidation itself hardly occurred and coloring was difficult. The range of the concentration of dissolved oxygen in the phenol compound is 0.01 to 1.0 mg / L, preferably 0.01 to 0.7 mg / L, more preferably 0.01 to 0.5 mg / L, and 0.01 to 0.3 mg / L is more preferred. This dissolved oxygen concentration is a measure of the degree of coloring during long-term storage. In the range of 0.01 to 1.0 mg / L, even if stored at 60 ° C., coloring is hardly recognized for 60 days. However, as the amount of dissolved oxygen increases, the period during which coloring starts is shortened accordingly. This dissolved oxygen may be replaced by a gas other than oxygen, specifically, a gas such as water vapor (water), carbon dioxide, helium, nitrogen, etc. before commercialization of the phenol compound. The gas used is preferably nitrogen. For the purpose of reducing dissolved oxygen, there is no problem with water vapor, but the phenolic compound obtained by that method cannot be used in applications where the amount of water is not desired. It is also conceivable that the phenol compound is melted and liquefied and deaerated by decompression, but the efficiency is lower than the gas replacement method. Either method may be used, but it is important that the concentration of dissolved oxygen in the phenol compound be 0.01 to 1.0 mg / L.

In addition, the dissolved oxygen concentration in the phenol compound is determined by the following measuring method.
70 parts by mass of the phenol compound are precisely weighed and put into a sealable container. 30 parts by mass of N, N-dimethylformamide, which has been precisely weighed in advance, are gently added to the same container so as not to entrap air. At this time, the porosity of the container is set to 5% by volume or less. After sealing the container, dissolve completely with a shaker. Dissolved oxygen is measured using a dissolved oxygen meter at 25 ° C. of a completely dissolved N, N-dimethylformamide solution of a phenol compound having a nonvolatile content of 70% by mass. Separately, the dissolved oxygen of the used N, N-dimethylformamide is measured by the same dissolved oxygen meter. As N, N-dimethylformamide, nitrogen bubbling is performed for 10 minutes or more to reduce dissolved oxygen. The dissolved oxygen concentration in the phenol compound is calculated by the following equation.

但し、
ＤＯ ：フェノール化合物中の溶存酸素濃度（ｍｇ/Ｌ）
ＤＯ_１：フェノール化合物のＮ，Ｎ−ジメチルホルムアミド溶液の溶存酸素濃度（ｍｇ/Ｌ）
ＤＯ_０：Ｎ，Ｎ−ジメチルホルムアミドの溶存酸素濃度（ｍｇ/Ｌ）
ｗ ：フェノール化合物の質量部（ｋｇ）
ｗ_０：Ｎ，Ｎ−ジメチルホルムアミドの質量部（ｋｇ）
ρ ：フェノール化合物の密度（ｋｇ/Ｌ）
ρ_０：Ｎ，Ｎ−ジメチルホルムアミドの密度、０．９４４（ｋｇ/Ｌ）

However,
DO: concentration of dissolved oxygen in phenolic compound (mg / L)
DO ₁ : dissolved oxygen concentration (mg / L) of N, N-dimethylformamide solution of phenol compound
DO ₀ : dissolved oxygen concentration of N, N-dimethylformamide (mg / L)
w: parts by mass of phenol compound (kg)
w ₀ : parts by mass of N, N-dimethylformamide (kg)
ρ: density of phenol compound (kg / L)
ρ ₀ : density of N, N-dimethylformamide, 0.944 (kg / L)

INDUSTRIAL APPLICABILITY The present invention is effective for bisphenol F or phenol novolak resin having poor stability, and is particularly effective for a method for distilling bisphenol F to obtain high-purity bisphenol F or a method for simultaneously producing bisphenol F and phenol novolak resin. . In the production method of obtaining high-purity bisphenol F by distilling bisphenol F, if bisphenol F used is the phenol compound of the present invention, high-purity bisphenol F can be obtained without coloring or decomposition. In addition, in the production method in which bisphenol F and phenol novolak resin are co-produced, if the phenol compound of the present invention is supplied to the distillation step, ie, the step of separating bisphenol F and phenol novolak resin, bisphenol F and bisphenol F can be produced without coloring or decomposition. A phenol novolak resin is obtained.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto. In Examples, unless otherwise specified, "parts" represents parts by mass, and "%" represents% by mass. The measurement of various characteristic values in the examples and comparative examples was performed by the following methods (1) to (3).

(1) Metal ion concentration: After accurately weighing about 1 g of a sample in a centrifuge tube (made of fluororesin, with a lid, 50 ml), adding 20 ml of methyl isobutyl ketone (hereinafter referred to as MIBK) to completely dissolve, and then purifying with pure water. Add 10 ml, close the lid, shake vigorously for more than 5 minutes to extract metal ions into the aqueous layer, and then centrifuge using a centrifugal separator into the MIBK layer and the aqueous layer. The concentrations of lithium ion, sodium ion, potassium ion, magnesium ion, and calcium ion were determined using a quantitative method by chromatography. The total of each ion concentration was converted to the metal ion concentration in the phenol compound.

(2) Dissolved oxygen concentration: In accordance with the above-described method for measuring the dissolved oxygen concentration.

(3) Gardner color number: The melt color of the phenol compound was measured according to JIS K-0071-2.

Example 1
1300 parts of phenol (metal ion concentration: 3.0 mg / kg) was added to a stirred tank reactor equipped with a stirrer, a temperature control device, a reflux condenser, a full contractor, a decompression device, etc., and the temperature was raised to 80 ° C. After that, 3.9 parts of oxalic acid dihydrate (metal ion concentration: 1.1 mg / kg) was added and dissolved by stirring for 10 minutes, and then 246 parts of 37.5% formalin (metal ion concentration: 3.5 mg / kg) / Kg) was added dropwise over 30 minutes. Thereafter, the reaction was continued for 3 hours while maintaining the reaction temperature at 92 ° C. After the completion of the reaction, the temperature was raised to 110 ° C., dehydration was performed, and about 90% of the remaining phenol was recovered under the conditions of 150 ° C. and 60 mmHg, then recovered under the conditions of 5 mmHg, and then further recovered at 160 ° C. and 80 mmHg. Then, 10 parts of water was added dropwise over 90 minutes to remove residual phenol, and nitrogen gas was bubbled through the molten phenol novolak resin for 60 minutes to obtain a phenol novolak resin.

Example 2
The phenol novolak resin obtained in Example 1 was continuously supplied at 21 kg / hr for 1 hour to a centrifugal thin-film evaporator operated at a rotor rotation speed of 250 rpm and a degree of vacuum of 3 to 5 mmHg. The discharged components were continuously extracted to obtain bisphenol F and phenol novolak resin, respectively. The centrifugal thin-film evaporator was equipped with a jacket, the heat transfer surface was 0.21 m ² , and a heating medium at 260 ° C. was passed through the jacket. The centrifugal thin-film evaporator had an external condenser, a cooling transfer surface was 1.3 m ² , and heated water at 120 ° C. was flowed to condense and extract all the evaporated components.

Example 3
1300 parts of phenol (metal ion concentration: 4.0 mg / kg) was added to a stirred tank reactor equipped with a stirrer, a temperature control device, a reflux condenser, a full contractor, a decompression device, etc., and the temperature was raised to 80 ° C. After that, 3.9 parts of paratoluenesulfonic acid (metal ion concentration: 0.8 mg / kg) was added as a 10% by mass aqueous solution, and the mixture was stirred and dissolved for 10 minutes, and then 246 parts of 37.5% formalin (metal ion) was added. (A concentration of 4.5 mg / kg) was added dropwise over 30 minutes. Thereafter, the reaction was continued for 3 hours while maintaining the reaction temperature at 92 ° C. After completion of the reaction, the reaction mixture was neutralized with a 48% aqueous sodium hydroxide solution, washed once with water, heated to 110 ° C., dehydrated, and the remaining phenol was recovered at 150 ° C. under a recovery condition of 60 mmHg at about 90%. After collection, the mixture was collected under the collection conditions of 5 mmHg, and then 10 parts of water was added dropwise over 90 minutes at 160 ° C. and 80 mmHg to remove the remaining phenol. Nitrogen gas was bubbled for 40 minutes to obtain a phenol novolak resin.

Example 4
1500 parts of phenol (metal ion concentration: 6.0 mg / kg) was added to a stirred tank reactor equipped with a stirrer, a temperature controller, a reflux condenser, a full contractor, a decompressor, etc., and the temperature was raised to 80 ° C. After that, 65 parts of oxalic acid dihydrate (metal ion concentration: 1.1 mg / kg) was added as a 10% by mass aqueous solution, and the mixture was stirred and dissolved for 10 minutes, and then 246 parts of 37.5% formalin (metal ion) was added. (A concentration of 4.5 mg / kg) was added dropwise over 30 minutes. Thereafter, the reaction was continued for 3 hours while maintaining the reaction temperature at 92 ° C. After the completion of the reaction, the temperature was raised to 110 ° C., dehydration was performed, and about 90% of the remaining phenol was recovered under the conditions of 150 ° C. and 60 mmHg, then recovered under the conditions of 5 mmHg, and then further recovered at 160 ° C. and 80 mmHg. Then, 10 parts of water was added dropwise over 90 minutes to remove residual phenol, and then nitrogen gas was bubbled through the melted bisphenol F for 20 minutes to obtain bisphenol F.

Comparative Example 1
A phenol novolak resin was obtained in exactly the same manner as in Example 1, except that no bubbling with nitrogen gas was performed in the molten phenol novolak resin.

Comparative Example 2
Bisphenol F and a phenol novolak resin were obtained in exactly the same manner as in Example 2, except that the phenol novolak resin obtained in Comparative Example 1 was used.

Comparative Example 3
Raw materials used were phenol (containing 11 mg / kg of metal ion), oxalic acid dihydrate (containing 1.1 mg / kg of metal ion), and 37.5% formalin (containing 13 mg / kg of metal ion) A phenol novolak resin was obtained in exactly the same manner as in Example 1.

Comparative Example 4
The raw materials used were phenol (containing 11 mg / kg of metal ion), oxalic acid dihydrate (containing 1.1 mg / kg of metal ion), 37.5% formalin (containing 13 mg / kg of metal ion), and Bisphenol F was obtained in exactly the same manner as in Example 4, except that no bubbling with nitrogen gas was performed on the molten bisphenol F.

  Table 1 shows the metal ion concentration, dissolved oxygen concentration, and Gardner color number of the phenol compounds obtained in Examples 1 to 4 and Comparative Examples 1 to 4. In the table, PN indicates phenol novolak resin, and BPF indicates bisphenol F.

Examples 5 to 8, Comparative Examples 5 to 8
The phenol novolak resin of Example 1, Example 3, Comparative Example 1, and Comparative Example 3 and the bisphenol F obtained in Example 2, Example 4, Comparative Example 2, and Comparative Example 4 were respectively sealed in containers that can be sealed. It was stored in a thermostat controlled at a constant temperature of 60 ° C., and the degree of coloring was confirmed. The results are shown in Table 2. In the table, PN indicates phenol novolak resin, and BPF indicates bisphenol F.

Claims (8)

A method for producing a phenolic compound (1) for use as an epoxy resin raw material, obtained from an aldehyde or ketone and a phenol in the presence of a catalyst, wherein the concentration of metal ions contained in the phenolic compound (1) is 0 is 0.1 to 10 mg / kg, dissolved oxygen concentration of the phenol compound (1) is a production method is 0.01 to 1.0 mg / L, the total metal ions in the raw materials used. The concentration is adjusted to 1 to 10 mg / kg, and the dissolved oxygen in the phenolic compound (1) is replaced by bubbling a gas other than oxygen before commercialization. A method for producing a phenolic compound (1) for use as an epoxy resin raw material, which has good stability.

(Wherein, R ₁ is each independently a hydrocarbon group having 1 to 12 carbon atoms, R ₂ is a hydrocarbon group having 1 to 13 carbon atoms, or —C (CF ₃ ) —, and k is each independently Is an integer of 0 to 2, and n is an integer of 1 or more.) Good stability to heat and / or oxygen according to claim 1, wherein the gas other than the oxygen is nitrogen gas, the production method of phenol compounds for the epoxy resin material (1). A method for producing a phenolic compound ( 1 ) for use as an epoxy resin raw material, obtained from an aldehyde or ketone and a phenol in the presence of a catalyst, wherein the concentration of metal ions contained in the phenolic compound (1) is Is 0.1 to 10 mg / kg, the dissolved oxygen concentration in the phenolic compound (1) is 0.01 to 1.0 mg / L, and the total metal ion concentration in the raw material used is The phenolic compound (1) in the molten state is adjusted so that the dissolved oxygen concentration of the phenolic compound (1) is in the range of 0.01 to 1.0 mg / L while the concentration is in the range of 0.1 to 10 mg / kg. A) a method for producing a phenolic compound (1) for use as an epoxy resin raw material, which has good stability against heat and / or oxygen and comprises degassing under reduced pressure.

(Wherein, R ₁ is each independently a hydrocarbon group having 1 to 12 carbon atoms, R ₂ is a hydrocarbon group having 1 to 13 carbon atoms, or —C (CF ₃ ) —, and k is each independently Is an integer of 0 to 2, and n is an integer of 1 or more.) The phenolic compound (1) according to any one of claims 1 to 3, which has good thermal stability against heat and / or oxygen and is used as a raw material for an epoxy resin, wherein the phenolic compound (1) is bisphenol F. Manufacturing method. The phenolic compound (1) according to any one of claims 1 to 3, which is excellent in heat and / or oxygen stability and is used as an epoxy resin raw material, wherein the phenolic compound (1) is a phenol novolak resin. Manufacturing method. The heat and / or oxygen according to any one of claims 1 to 3, wherein the phenolic compound (1) is bisphenol F and a phenol novolak resin obtained by a production method that produces bisphenol F and a phenol novolak resin. A method for producing a phenolic compound (1) for use as an epoxy resin raw material, which has good stability. The said metal ion density | concentration is a total sum of each density | concentration of lithium ion, sodium ion, potassium ion, magnesium ion, and calcium ion, The heat with respect to any one of Claims 1-6, and / or heat with respect to oxygen. A method for producing a phenolic compound (1) for use as an epoxy resin raw material, which has good stability. The aldehyde compound is formaldehyde, and the phenol compound is phenol. The phenol compound for epoxy resin raw materials according to any one of claims 1 to 7, having good heat stability with respect to heat and / or oxygen. The manufacturing method of (1).