KR101720090B1 - Phenol compound with high reliability and a method of manufacturing the same - Google Patents

Phenol compound with high reliability and a method of manufacturing the same Download PDF

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KR101720090B1
KR101720090B1 KR1020160105902A KR20160105902A KR101720090B1 KR 101720090 B1 KR101720090 B1 KR 101720090B1 KR 1020160105902 A KR1020160105902 A KR 1020160105902A KR 20160105902 A KR20160105902 A KR 20160105902A KR 101720090 B1 KR101720090 B1 KR 101720090B1
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phenol
mg
oxygen
compound
phenolic compound
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세이고 다쿠와
고타 인데
히로키 노구치
히데유키 무라이
야스오 요시무라
신태규
이진수
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국도화학 주식회사
신닛테츠 수미킨 가가쿠 가부시키가이샤
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
    • C07C39/15Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
    • C07C39/16Bis-(hydroxyphenyl) alkanes; Tris-(hydroxyphenyl)alkanes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/16Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/20Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/02Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
    • C07C39/04Phenol
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00Compounds having —CHO groups
    • C07C47/02Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
    • C07C47/04Formaldehyde

Abstract

Aldehydes or ketones and phenol compounds prepared from phenols do not require special stabilizers and provide phenolic compounds that are highly stable to heat and / or oxygen.
An aldehyde or a ketone and a phenol compound having a concentration of metal ions contained in the phenol compound of 0.1 to 10 mg / kg and a concentration of dissolved oxygen in the phenol compound of 0.01 to 1.0 mg / L Or phenolic compounds which are highly stable to oxygen and / or oxygen.

Description

[0001] The present invention relates to a process for producing a phenol compound having high stability,

The present invention relates to a process for the production of a catalyst for thermal and / or oxygen production of aldehydes (hereinafter sometimes simply referred to as aldehydes) or ketones (hereinafter sometimes simply referred to as ketones) and phenols (hereinafter referred to simply as phenols) To a process for producing a highly stable phenolic compound.

Bisphenol and phenol novolak resins react with epichlorohydrin to form glycidyl ether and are widely used as epoxy resins. These phenolic compounds are widely known to react sensitively to heat and oxygen, and these phenolic compounds when exposed to heat and / or oxygen form decomposition products, and epoxy resins prepared from phenol compounds containing these decomposition products But also the physical properties of the resin. Particularly, bisphenol F and phenol novolac resins are prepared by adding formalin to phenol and condensing them using an acid catalyst. However, if they are stored for a long time, the color becomes remarkable. Also, the epoxy resin obtained by using the phenol compound thus colored is also colored, which seriously damages the product value. Thus, a proposal has been made to prevent the phenol compound from being obtained by controlling the dissolved oxygen of the reaction solution, and at present, it is a standard method, and the color of the obtained phenol compound is clear (Patent Document 1). However, the phenol compounds obtained by the method did not solve the tendency of coloration or decomposition of heat time (heat) when stored for a long period of time.

In order to stabilize such a phenolic compound, a method of adding sulfuric acid, malic acid, glyceric acid or a metal salt thereof as a stabilizer (Patent Document 2), a method of adding phthalic anhydride and phthalic anhydride derivatives (Patent Document 3) and L- A method of adding an acid or DL-? -Tocopherol (Patent Document 4) has been proposed. However, in these methods, stabilizers are mixed with impurities, so that a stabilizer may be incorporated into an epoxy resin to cause deterioration of physical properties in a method of producing an epoxy resin obtained by a reaction between a low-molecular epoxy resin and a phenol compound called so-called indirect method.

In addition, as a method for producing bisphenol F and phenol novolac resin, a distillation process is necessarily included, which is highly likely to be affected by heat, but this has not been solved by a conventional method (Patent Document 5).

Patent Publication Sho 62-195009 Patent No. 2820746 Patent Publication Sho 55-151526 Patent 3008374 Patent Publication Hei 6-128183 Patent Publication No. 2011-68760

.

SUMMARY OF THE INVENTION The present invention has been developed in view of the above circumstances, and an object of the present invention is to obtain a phenol compound which is produced by aldehyde or ketone and phenol with high heat and / or oxygen stability without using a special stabilizer.

The present inventors have found that when phenol compounds prepared from aldehydes, ketones and phenols are controlled within a certain range in which the concentrations of metal ions and dissolved oxygen in the phenol compounds are significantly lower than those of conventional ones, Phenol compound can be obtained, thereby completing the present invention.

That is,

Wherein the concentration of the metal ion contained in the phenol compound is 0.1 to 10 mg / kg and the concentration of dissolved oxygen in the phenol compound is 0.01 to 1.0 mg / L Characterized in that it is a phenolic compound having high heat and / or oxygen stability,

The phenolic compound is preferably bisphenol F or phenol novolac resin,

The phenol compounds are more preferably bisphenol F and phenol novolac resins obtainable by a method of blending bisphenol F and phenol novolac resins.

The present invention also relates to a process for producing the phenolic compound.

Since the phenolic compound having high heat and / or oxygen stability of the present invention does not require a special stabilizer, it is possible to obtain a phenolic compound which hardly adversely affects further use. Thus, It is a phenolic compound suitable as a raw material for the method.

Hereinafter, embodiments of the present invention will be described in detail.

The phenolic compound of the present invention is a phenol compound produced from aldehydes or ketones and phenols represented by the following general formula (1), wherein the concentration of metal ions in the phenolic compound is 0.1 to 10 mg / kg and the dissolved oxygen concentration is 0.01 To 1.0 mg / L.

Figure 112016081021115-pat00001

(Formula 1)

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

The raw phenols include phenol, alkylphenols such as cresol, ethylphenol, butylphenol, octylphenol, nonylphenol and dodecylphenol, and substituted (n-, sec-, tert- Etc.), substituent structural isomers may be used. Among them, phenol is preferable in terms of reactivity and ease of distillation. The phenol may be used alone or in combination of two or more.

The aldehydes as raw materials include, for example, formaldehyde (formalin), acetaldehyde, propionaldehyde, benzaldehyde and the like, but are not limited thereto.

Examples of ketones as raw materials include, but are not limited to, acetone, butaneone, cyclohexanone, benzophenone, and hexafluoroacetone.

The production of the phenolic compounds of the present invention is preferably carried out in the same manner as in the preparation of general phenolic compounds. 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, and hydroxides such as hydroxides of alkali metals such as sodium hydroxide, lithium hydroxide and potassium hydroxide, Tertiary amines such as triethylamine, oxides and hydroxides of alkaline earth metals such as calcium, magnesium and barium, and basic catalysts such as sodium carbonate. It may also be a fixed bed of a solid catalyst such as an ion exchange resin. In the present invention, the catalyst is not particularly specified, but an acid catalyst is preferable, and specifically, oxalic acid and para-toluenesulfonic acid are preferable.

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

Specific examples of the phenol 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, 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-isopropyphenol and acetone, 2 Bisphenol PH obtained from phenol and acetone, bisphenol such as bisphenol Z obtained from phenol and cyclohexanone, phenol novolak obtained from phenol and formalin, cresol novolak obtained from cresol and formalin, octylphenol and formalin Octylphenol novol And phenol novolac such as lactic acid, but are not limited thereto. Incidentally, in the specification, phenol compounds refer 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, the time is clearly distinguished.

When the concentration of dissolved oxygen in the phenol compound satisfies the range of 0.01 to 1.0 mg / L, the phenol compounds have a heat and / or oxygen concentration in the range of 0.1 to 10 mg / kg. Is a stable phenolic compound. It is not colored even by long-term storage, and pyrolysis does not occur even if it is maintained at a high temperature.

If the concentration of the metal ion in the phenol compound is in the range of 0.1 to 10 mg / kg, the stability against heat is improved, and pyrolysis is difficult. Pyrolysis largely affects the remaining amount of the acid catalyst, and when the amount of residual catalyst is large, pyrolysis tends to occur. Although the amount by which thermal decomposition easily occurs varies depending on the kind of the acid catalyst, in the present invention, a range in which thermal decomposition is difficult to occur is found by controlling the metal ion concentration corresponding thereto irrespective of the kind thereof. The range of the metal ion concentration in the phenol compound is 0.1 to 10 mg / kg, more preferably 0.1 to 7 mg / kg, still more preferably 0.1 to 5 mg / kg, and particularly preferably 0.1 to 3 mg / kg. The metal ion concentration is an index of the amount of the acid catalyst remaining in the synthesis of the phenolic compound. The smaller the amount of the metal ion is, the smaller the amount of the remaining acid catalyst is. However, in order to reduce the metal ion concentration forcibly, a process such as rinsing is required, so that the process is complicated and the water absorption rate is lowered. In most cases, the total amount of metal ions in the raw phenol, aldehyde, or ketone remains in the phenol compound as it is. Therefore, the control of the amount of metal ions in the raw material is practically feasible and the total metal ion concentration of the raw material used is in the range of 0.1 to 10 mg / kg .

In addition, since the metal ion concentration requires fluorescence X-ray method, most of the metal ions are less than the detection, and therefore, it is also possible to use a comprehensive system of respective concentrations of lithium ion, sodium ion, potassium ion, magnesium ion and calcium ion. In such a case, a 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, the stability to heat is improved and the thermal decomposition hardly occurs, and the stability against oxygen is improved, so that it is not stained even for a long period of storage. Dissolved oxygen is likely to cause pyrolysis, and the more pyrolysis is accelerated. Dissolved oxygen is strongly related to the coloring factors of phenol compounds, and the coloring is considered to be due to oxidation. Thus, in the past, oxidation inhibition was suppressed by adding an antioxidant. In the present invention, it has been found that by controlling the range of dissolved oxygen in a phenol compound, oxidation itself is difficult to occur and hardly colored. 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 even more preferably 0.01 to 0.3 mg / L. This dissolved oxygen concentration is a standard for the degree of coloring during long-term storage. If the concentration is in the range of 0.01 to 1.0 mg / L, coloration hardly occurs for 60 days even when stored at 60 ° C. However, as the amount of dissolved oxygen increases, the period for starting coloring becomes shorter. This dissolved oxygen may be replaced by a gas other than oxygen, specifically water vapor, water, carbon dioxide, helium, or nitrogen, prior to commercialization of the phenol compound. When considering the cost and ease of securing the gas, desirable. There is no problem with water vapor for the purpose of reducing dissolved oxygen, but the phenol compound obtained by this method can not be used in applications that do not like water. In addition, it is possible to consider deaeration by decompression by melting and liquefying phenol compounds, but the efficiency is worse than the gas substitution method. Any method may be used, but it is important to set the dissolved oxygen concentration in the phenol compound to 0.01 to 1.0 mg / L.

In addition, the dissolved oxygen concentration in the phenol compound is determined according to the following measurement method. And 70 parts by weight of a phenol compound are precisely weighed and placed in a hermetically sealed container. 30 parts by mass of N, N-dimethylformamide which has been previously determined is carefully added to the same container so as not to attract air. At this time, the porosity of the container should be 5% by volume or less. Seal this container and completely dissolve it with a vibrator. Dissolved oxygen is measured at 25 캜 by using a dissolved oxygen meter in a N, N-dimethylformamide solution of a completely dissolved phenol compound of 70% by mass of nonvolatile matter. Dissolved oxygen is also measured with a dissolved oxygen system, such as N, N-dimethylformamide, which is used separately. N, N-dimethylformamide is preliminarily subjected to nitrogen bubbling for 10 minutes or more to reduce dissolved oxygen. The dissolved oxygen concentration in the phenolic compound is calculated according to the following formula.

Figure 112016081021115-pat00002

(Equation 1)

only,

DO: Dissolved oxygen concentration in phenol compound (mg / L)

DO 1 : Dissolved oxygen concentration (mg / L) of N, N-dimethylformamide solution of phenolic compound

DO 0 : Dissolved oxygen concentration of N, N-dimethylformamide (mg / L)

w: mass part of phenol compound (kg)

w 0 : parts by weight of N, N-dimethylformamide (kg)

ρ: density of phenolic compound (kg / L)

ρ 0 : density of N, N-dimethylformamide, 0.944 (kg / L)

The present invention is effective for bisphenol F and phenol novolac resins having poor stability, and is particularly effective for a production method for obtaining high purity bisphenol F by distilling bisphenol F and a production method for blending bisphenol F and phenol novolac resin. If the bisphenol F used in the process for obtaining high purity bisphenol F by distilling bisphenol F is the phenol compound of the present invention, high purity bisphenol F can be obtained without causing any degree of coloring and decomposition. In addition, in the production method in which bisphenol F and phenol novolac resin are blended, bisphenol F and phenol novolak resin which are not decomposed by coloring and decomposition can be obtained when the phenol compound of the present invention is fed to a distillation step, that is, a step of separating bisphenol F and phenol novolak resin Can be obtained.

Example

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited thereto. In the Examples, "part" denotes the mass part and "%" denotes the mass%, unless otherwise specified. The various characteristic values of Examples and Comparative Examples were measured according to the following methods (1) to (3).

(1) Metal ion concentration: About 1 g of a sample is regularly sampled in a centrifuge tube (fluorine resin product, with a lid, 50 ml), and then 20 ml of methyl isobutyl ketone (hereinafter referred to as MIBK) 10 ml was added, the lid was closed and the mixture was vigorously shaken for 5 minutes or more to extract metal ions from the aqueous layer. The aqueous layer was separated by centrifugation using MIBK layer and water layer using a centrifugal separator, and ion- The respective concentrations of sodium ion, potassium ion, magnesium ion and calcium ion were determined. The sum of the respective ion concentrations was converted into the metal ion concentration in the phenol compound.

(2) Dissolved Oxygen Concentration: The dissolved oxygen concentration was measured according to the aforementioned measurement method.

(3) Gardner chromaticity number: The melting color of the phenol compound was measured in accordance with JISK-0071-2.

Example 1

A stirrer type reactor equipped with a stirrer, a temperature controller, a reflux condenser, a reflux condenser, and a pressure reducing device was charged with 1300 parts of phenol (metal ion concentration: 3.0 mg / kg) and heated to 80 DEG C. Then, 3.9 parts of oxalic acid dihydrate Concentration of 1.1 mg / kg) was added and dissolved by stirring for 10 minutes. Then, 246 parts of 37.5% formalin (metal ion concentration: 3.5 mg / kg) was added dropwise for 30 minutes. Thereafter, the reaction temperature was maintained at 92 DEG C and the reaction was continued for 3 hours. After the reaction was completed, the reaction mixture was dehydrated to a temperature of 110 DEG C, and about 90% of the remaining phenol was recovered under the conditions of 150 DEG C and 60 mmHg. Then, the recovered phenol was recovered under conditions of recovery of 5 mmHg, Was added dropwise over 90 minutes to remove the remaining phenol, and then nitrogen gas in the dissolved phenol novolac resin was bubbled for 60 minutes to obtain a phenol novolak resin.

Example 2

The phenol novolak resin obtained in Example 1 was continuously supplied to a centrifugal thin film evaporator operated at a rotor rotation speed of 250 rpm and a vacuum degree of 3 to 5 mmHg at a rate of 21 kg / hr for 1 hour. The evaporation component and the precipitating component were continuously taken out to obtain bisphenol F And phenol novolak resin. The centrifugal thin film evaporator is equipped with a jacket, and the heating front is 0.21 m 2, and the jacket is filled with fruit of 260 ° C. In addition, the centrifugal thin film evaporator used an external condenser to flow hot water of 120 ° C at a cooling surface of 1.3 m 2 to condense the entire evaporation component.

Example 3

1300 parts of phenol (metal ion concentration: 4.0 mg / kg) was added to an agitator-type reactor equipped with a stirrer, a temperature regulator, a reflux condenser, a reflux condenser and a decompression device. After the temperature was raised to 80 ° C, 3.9 parts of para- toluenesulfonic acid 0.8 mg / kg) was added as a 10 mass% aqueous solution and dissolved by stirring for 10 minutes. 246 parts of 37.5% formalin (metal ion concentration 4.5 mg / kg) was added dropwise over 30 minutes. Thereafter, the reaction temperature was maintained at 92 DEG C and the reaction was continued for 3 hours. After completion of the reaction, the reaction mixture was neutralized with 48% sodium hydroxide aqueous solution and washed once. The reaction solution was dehydrated by raising the temperature to 110 ° C., and about 90% of the remaining phenol was collected under the conditions of 150 ° C. and 60 mmHg. And then 10 parts of water was added dropwise under the conditions of 160 DEG C and 80 mmHg for 90 minutes to remove remaining phenol. Then, nitrogen gas was bubbled into the dissolved phenol novolak resin for 40 minutes to obtain phenol novolac resin .

Example 4

1500 parts of phenol (metal ion concentration: 6.0 mg / kg) was added to an agitator-type reactor equipped with a stirrer, a temperature controller, a reflux condenser, a reflux condenser and a decompression device and the mixture was heated to 80 DEG C, and 65 parts of oxalic acid dihydrate Concentration of 1.1 mg / kg) was added as an aqueous solution of 10 mass% and dissolved by stirring for 10 minutes. Then, 246 parts of 37.5% formalin (metal ion concentration 4.5 mg / kg) was added dropwise for 30 minutes. Thereafter, the reaction was continued for 3 hours while maintaining the reaction temperature at 92 占 폚. After the reaction was completed, the reaction mixture was dehydrated to a temperature of 110 DEG C, and about 90% of the remaining phenol was recovered under the conditions of 150 DEG C and 60 mmHg, collected under the recovery conditions of 5 mmHg, 10 parts were added dropwise over 90 minutes to remove the remaining phenol, and bisphenol F was obtained by bubbling nitrogen gas into the dissolved bisphenol F for 20 minutes.

Comparative Example 1

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

Comparative Example 2

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

Comparative Example 3

Except that phenol (containing a metal ion concentration of 11 mg / kg), oxalic acid dihydrate (containing a metal ion concentration of 1.1 mg / kg) and 37.5% formalin (containing a metal ion concentration of 13 mg / kg) To obtain a phenol novolak resin.

Comparative Example 4

The raw materials used were dissolved in phenol (containing a metal ion concentration of 11 mg / kg), oxalic acid dihydrate (containing a metal ion concentration of 1.1 mg / kg) and 37.5% formalin (containing a metal ion concentration of 13 mg / Bisphenol F was obtained in the same manner as in Example 4 except that no bubbling with gas was used at all.

Table 1 shows the metal ion concentrations, dissolved oxygen concentrations, and Gardner chromaticity numbers 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, respectively.

Phenol compound Metal ion concentration
(mg / kg)
Dissolved oxygen concentration
(mg / g)
Gardner color depth
Example 1 PN 3.1 0.14 1 or less Example 2 PN 3.5 0.22 1 or less BPF 2.9 0.11 1 or less Example 3 PN 4.6 0.43 1 or less Example 4 BPF 5.9 0.81 1 or less Comparative Example 1 PN 3.2 2.3 2 Comparative Example 2 PN 3.3 2.0 2 BPF 3.1 2.1 3 Comparative Example 3 PN 12 0.15 One Comparative Example 4 BPF 13 2.5 2

Examples 5 to 8 and Comparative Examples 5 to 8

The phenol novolac resins of Examples 1 and 3 and Comparative Examples 1 and 3 and the bisphenol F obtained in Examples 2 and 4 and Comparative Example 2 and Comparative Example 4 were placed in a hermetically sealable container, The coloring degree was checked by storing in a thermostat controlled at constant temperature. The results are shown in Table 2. In the table, PN represents phenol novolac resin and BPF represents bisphenol F.

Phenol compound Gardner color depth Day 0 On the 30th day 60 days Example 5 The PN of Example 1 1 or less One 2 Example 6 PN of Example 3 1 or less 2 3 Example 7 The BPF of Example 2 1 or less One 2 Example 8 The BPF of Example 4 1 or less 2 4 Comparative Example 5 PN of Comparative Example 1 2 3 4 Comparative Example 6 The PN of Comparative Example 3 One 3 5 Comparative Example 7 The BPF of Comparative Example 2 3 4 5 Comparative Example 8 The BPF of Comparative Example 4 2 4 7

Claims (8)

  1. A process for producing a phenol compound (b) obtained from an aldehyde or a ketone and a phenol (a), wherein the aldehyde is formaldehyde, the phenol (a) is phenol and the total metal ion concentration in the starting material is 0.1 to 10 mg (b) is bubbled in the molten phenol compound (b) so that the concentration of dissolved oxygen in the phenol compound (b) is in the range of 0.01 to 1.0 mg / L. (B) a phenolic compound having high heat and / or oxygen stability.
  2. The method for producing a phenolic compound (b) according to claim 1, wherein the metal ion concentration is high with respect to heat and / or oxygen which is a total of respective concentrations of lithium ion, sodium ion, potassium ion, magnesium ion and calcium ion.
  3. delete
  4. The method for producing a phenolic compound (b) according to claim 1, wherein the gas other than oxygen is a nitrogen gas and is highly stable to heat and / or oxygen.
  5. Wherein the aldehyde is formaldehyde, the phenol (a) is phenol, and the total metal ion concentration in the raw materials used is 0.1 to 10 mg / m < 2 > kg and the dissolved phenol compound (b) in a molten state is subjected to vacuum degassing so that the dissolved oxygen concentration of the phenol compound (b) is in the range of 0.01 to 1.0 mg / L. (B) a phenolic compound having high stability to oxygen.
  6. delete
  7. The method according to any one of claims 1 to 4, wherein the obtained phenolic compound (b) has a metal ion concentration of 0.1 to 10 mg / kg and a dissolved oxygen concentration of 0.01 to 1.0 mg / L. (B) a phenolic compound having high stability to oxygen.
  8. The phenolic compound (b) obtained in the above item 1 or 4, wherein the color of the phenolic compound measured according to JIS K-0071-2 when the phenolic compound (b) is stored at 60 ° C for 30 days is 2 or less (B) a phenolic compound having high heat and / or oxygen stability.
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