JP2010241701A - Method for producing 2,2'-alkylene bis(4,6-dialkylphenol) - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for simply producing a high-purity 2,2'-alkylene bis(4,6-dialkylphenol). <P>SOLUTION: The method for producing a 2,2'-alkylene bis(4,6-dialkylphenol) represented by formula (I) (wherein R<SP>1</SP>is hydrogen or alkyl; and R<SP>2</SP>and R<SP>3</SP>are each alkyl) includes a condensation step of subjecting an aldehyde represented by formula (II): R<SP>1</SP>-CHO (wherein R<SP>1</SP>is as shown above) and a dialkylphenol to condensation reaction in the presence of an anionic surfactant, water and a hydrocarbon. The condensation step is carried out in the presence of 90-200 pts.wt. of water and 5-30 pts.wt. of a hydrocarbon and 100 pts.wt. of a dialkylphenol represented by specific formula and the reaction temperature in the condensation step is ≥40°C and <80°C. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing 2,2'-alkylenebis (4,6-dialkylphenol).

（式中、Ｒ¹ は水素又は炭素数１〜３のアルキル基を表し、Ｒ² 及びＲ³ はそれぞれ独立に炭素数２〜５のアルキル基を表す。）
で表される２，２’−アルキレンビス（４，６−ジアルキルフェノール）（以下、ビスフェノール（I）と記すことがある。）は、天然ゴム、合成ゴム、ポリオレフィンなどの熱可塑性樹脂や油脂などの酸化防止剤などに汎用されている。
ビスフェノール（I）の１種である２，２’−メチレンビス（６−ｔｅｒｔ−ブチル−４−エチルフェノール）の製造方法としては、例えば、２−ｔｅｒｔ−ブチル−４−エチルフェノール及びパラホルムアルデヒドを粉状シリカゲルアルミナ及びｎ−ヘキサン存在下に副生する水を反応系外に除去しながら加熱還流して、純度が８９．２重量％の２，２’−メチレンビス（６−ｔｅｒｔ−ブチル−４−エチルフェノール）を得ることが特許文献１に記載されている。 Formula (I)

(In the formula, R ¹ represents hydrogen or an alkyl group having 1 to 3 carbon atoms, and R ² and R ³ each independently represents an alkyl group having 2 to 5 carbon atoms.)
2,2′-alkylenebis (4,6-dialkylphenol) (hereinafter sometimes referred to as bisphenol (I)) is a thermoplastic resin such as natural rubber, synthetic rubber, polyolefin, and fats and oils. It is widely used for antioxidants.
As a method for producing 2,2′-methylenebis (6-tert-butyl-4-ethylphenol), which is one kind of bisphenol (I), for example, 2-tert-butyl-4-ethylphenol and paraformaldehyde are powdered. The mixture was heated to reflux while removing water produced as a by-product in the presence of the silica gel alumina and n-hexane out of the reaction system, and 2,2′-methylenebis (6-tert-butyl-4-) having a purity of 89.2 wt% was obtained. Patent Document 1 discloses that ethylphenol is obtained.

Japanese Patent Laid-Open No. 51-110547 (Example 1)

  There is a demand for a method for producing high-purity 2,2'-alkylenebis (4,6-dialkylphenol) more simply.

（式中、Ｒ² 及びＲ³ はそれぞれ独立に炭素数２〜５のアルキル基を表す。）
で示されるジアルキルフェノール（以下、ジアルキルフェノール（III）と記すことがある。）とを、陰イオン系界面活性剤、水及び炭化水素の存在下に縮合反応させる縮合工程を含む式（I）

（式中、Ｒ¹ 、Ｒ² 及びＲ³ は前記と同じ意味を表す。）
で表される２，２’−アルキレンビス（４，６−ジアルキルフェノール）の製造方法であり、上記縮合工程が、式(III)で示されるジアルキルフェノール１００重量部に対し、水９０〜２００重量部及び炭化水素５〜３０重量部の存在下で行われ、上記縮合工程における反応温度が４０℃以上、８０℃未満であることを特徴とする製造方法； Under such circumstances, as a result of intensive studies by the present inventors,
[1]: Formula (II)
R ¹ —CHO (II)
(In the formula, R ¹ represents hydrogen or an alkyl group having 1 to 3 carbon atoms.)
An aldehyde (hereinafter, sometimes referred to as aldehyde (II)), and a formula (III)

(In the formula, R ² and R ³ each independently represents an alkyl group having 2 to 5 carbon atoms.)
And a dialkylphenol represented by formula (I) (hereinafter, may be referred to as dialkylphenol (III)) in the presence of an anionic surfactant, water and hydrocarbon.

(In the formula, R ¹ , R ² and R ³ represent the same meaning as described above.)
In the method for producing 2,2′-alkylenebis (4,6-dialkylphenol) represented by the formula (1), the condensation step comprises 90 to 200 weight parts of water with respect to 100 weight parts of dialkylphenol represented by formula (III). And the reaction temperature in the condensation step is 40 ° C. or higher and lower than 80 ° C., in the presence of 5 parts by weight and 5-30 parts by weight of hydrocarbon;

[2]: The anionic surfactant is at least one anionic surfactant selected from the group consisting of sodium naphthalene sulfonate and alkyl diphenyl disulfonate that may be substituted with an alkyl group. [1] The production method according to
[3] The hydrocarbon is at least one hydrocarbon selected from the group consisting of aliphatic hydrocarbons having 5 to 10 carbon atoms and aromatic hydrocarbons having 6 to 12 carbon atoms [1] Or the production method according to [2];
[4] The production method according to any one of [1] to [3], wherein the dialkylphenol represented by the formula (III) is 2-t-butyl-4-ethylphenol;
[5] The production method according to any one of [1] to [4], wherein the condensation step is a step further performed in the presence of an acid;
[6]: The production method according to any one of [1] to [5], further comprising the following steps;
A dilution step of mixing the reaction solution obtained in the condensation step with hydrocarbons;
The step of neutralizing the reaction solution obtained in the dilution step with a base The crystallization step of cooling the reaction solution obtained in the neutralization step

And so on.

  According to the present invention, highly pure bisphenol (I) can be more easily produced.

Hereinafter, the present invention will be described in detail.
In the present invention, R ¹ is hydrogen or an alkyl group having 1 to 3 carbon atoms, and examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl and the like.
Examples of aldehyde (II) include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, and isobutyraldehyde. Preferable examples include formaldehyde and acetaldehyde.
The aldehyde (II) may be an anhydrous aldehyde (II) such as paraformaldehyde or an aldehyde (II) in an aqueous solution.

  Preferable use amount of aldehyde (II) is, for example, 0.5 to 1 mol, and more preferably 0.5 to 0.8 mol, with respect to 1 mol of dialkylphenol (III). Is mentioned.

The alkyl group represented by R ² and R ³ is an alkyl group having 2 to 5 carbon atoms, for example, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n -Pentyl, t-pentyl and the like can be mentioned. R ² and R ³ may be the same or different.
Preferred examples of R ² include ethyl. Moreover, as preferable R < ³ >, sec-butyl, t-butyl, t-pentyl etc. can be mentioned, for example, More preferably, t-butyl, t-pentyl etc. are mentioned.
Preferred dialkylphenol (III) includes, for example, 2-t-butyl-4-ethylphenol, 2-t-butyl-4-propylphenol, and more preferably 2-t-butyl. Examples include -4-ethylphenol.

  Examples of the anionic surfactant used in the present invention include sodium naphthalene sulfonate which may have an alkyl group having 1 to 20 carbon atoms, sodium alkyl diphenyl disulfonate having 1 to 20 carbon atoms, carbon number Examples thereof include sodium dialkylbenzene sulfonate having 1 to 20 and sodium dialkyl sulfosuccinate having 1 to 20 carbon atoms. Preferable examples include sodium monoalkylnaphthalene sulfonate and sodium alkyldiphenyl disulfonate, and more preferable examples include sodium dialkylbenzene sulfonate.

  As sodium monoalkylnaphthalene sulfonate, “Perex NB-L (registered trademark of Kao Corporation)” is commercially available, and the commercially available product may be used as it is. As sodium alkyldiphenyldisulfonate, “Sandet AL (registered trademark of Sanyo Chemical Co., Ltd.)” is commercially available, and the commercially available product may be used as it is. As sodium dialkylbenzenesulfonate, “Sendale S (registered trademark of Daiichi Kogyo Seiyaku Co., Ltd.)” is commercially available, and the commercially available product may be used as it is. As the sodium dialkylsulfosuccinate, “Neopelex OT-P (registered trademark of Kao Corporation)” is commercially available, and the commercially available product may be used as it is.

  As a preferable usage-amount of an anionic surfactant, 0.01-1 weight part etc. can be mentioned with respect to 100 weight part of dialkylphenol (III), for example. More preferably, for example, 0.05 to 1 part by weight and the like can be mentioned, and more particularly, for example, 0.1 to 0.9 part by weight and the like can be mentioned.

Examples of the hydrocarbon present in the condensation step of the present invention include 5 to 10 carbon atoms such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, cycloheptane, and cyclohexane. Aliphatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, cymene, chlorobenzene and the like, and aromatic hydrocarbons having 6 to 12 carbon atoms.
Preferable examples include n-hexane and n-heptane, and more preferable examples include n-hexane.

 The amount of hydrocarbon present in the condensation step is 5 to 30 parts by weight per 100 parts by weight of dialkylphenol (III). Preferably, 7-25 weight part etc. are mentioned, More preferably, it is 9-2 weight part.

The amount of water in the condensation step is 90 to 200 parts by weight with respect to 100 parts by weight of dialkylphenol (III). Preferably, 95-160 weight part etc. are mentioned, More preferably, it is 100-150 weight part.
In addition, when using aldehyde (II) of aqueous solution, since water is contained in aldehyde (II) of aqueous solution, the weight of the water contained in aldehyde (II) of aqueous solution is water as the said weight range. included.

In the condensation step, the reaction is preferably further performed in the presence of an acid. Examples of the acid include mineral acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, and organic acids such as toluenesulfonic acid. Preferable examples include hydrochloric acid and sulfuric acid, and more preferable examples include sulfuric acid and the like.
As usage-amount of an acid, 0.01-0.1 mol etc. can be mentioned with respect to 1 mol of dialkylphenol (III), for example. Preferably, 0.015-0.10 mol etc. are mentioned, for example, More preferably, 0.017-0.09 mol etc. are mentioned. The acid may be diluted with water or the like or may have a high concentration.

  The reaction temperature in the condensation step is 40 ° C. or higher and lower than 80 ° C., and preferably 60 ° C. or higher and lower than 80 ° C., for example.

The condensation step may be performed under atmospheric pressure, under pressure, or under reduced pressure, but is preferably performed under atmospheric pressure.
Moreover, although the reaction time in a condensation process changes with kinds of aldehyde, 10 minutes-24 hours etc. can be mentioned, for example. Preferably, for example, 2 to 18 hours and the like are mentioned, and more preferably, for example, 1 hour to 15 hours and the like are mentioned.

  In the condensation step, it is preferable that the crystalline bisphenol (I) is present in advance as a seed crystal. Examples of the amount of seed crystals added include 0.005 to 0.5 parts by weight with respect to 100 parts by weight of dialkylphenol (III).

  Examples of the bisphenol (I) obtained by the production method of the present invention include 2,2′-methylenebis (4-ethyl-6-t-butylphenol) and 2,2′-methylenebis (4-propyl-6-t-). Butylphenol), 2,2′-ethylenebis (4-ethyl-6-tert-butylphenol), 2,2′-ethylenebis (4-propyl-6-tert-butylphenol) and the like. Preferable examples include 2,2'-methylenebis (4-ethyl-6-t-butylphenol).

The reaction solution obtained in the condensation step may be further purified by, for example, column chromatography, recrystallization, repulping and the like. The production method of the present invention preferably includes the following dilution step, neutralization step, and crystallization step.
The dilution step is a step of mixing the reaction solution obtained in the condensation step and a hydrocarbon. Here, as the hydrocarbon, the hydrocarbons exemplified above can be exemplified as well. Preferred hydrocarbons include, for example, hydrocarbons used in the condensation step.
As a usage-amount of the hydrocarbon in a dilution process, 10-100 weight part etc. can be mentioned with respect to 100 weight part of dialkylphenol (III), for example. Preferable examples include 10 to 90 parts by weight, and more preferable examples include 10 to 80 parts by weight.

The neutralization step is a step of neutralizing the reaction solution obtained in the dilution step with a base.
Here, examples of the base include ammonia, sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium hydrogen carbonate, potassium carbonate, and the like. Preferably, for example, ammonia, sodium hydroxide, sodium hydrogen carbonate, sodium carbonate and the like can be mentioned, and more preferably, for example, ammonia and the like can be mentioned.
As the base, for example, the base may be used as it is, or may be used after being dissolved in water. Preferable examples include an aqueous solution containing 1 to 40% by weight as a base, preferably an aqueous solution containing 10 to 35% by weight, and more preferably 20 to 35% by weight. % Aqueous solution and the like.
As pH of the water obtained at the neutralization process, 5-7.5 etc. can be mentioned, for example, More preferably, 5.0-7.3 etc. are mentioned.

The crystallization step is a step of cooling the reaction solution obtained in the neutralization step.
As a cooling temperature in a crystallization process, the temperature range of 5-60 degreeC etc. can be mentioned, for example.
Examples of the crystallization step include a cooling step in the above temperature range, for example, 0.5 to 72 hours.

  Examples of bisphenol (I) that can be taken out as crystals in the crystallization step include bisphenol (I) content in the crystal of 95% by weight or more, and preferably 98% by weight or more, for example. It is done.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these.
In the examples, the content of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) in the obtained crystals was determined by high performance liquid chromatography (HPLC).

Example 1
Condensation step: After adjusting 172 g of water to 40 ° C., 0.8 g of Sandet AL (registered trademark of Sanyo Chemical Co., Ltd.) as sodium alkyldiphenyldisulfonate, 2 g of 98% sulfuric acid, 18 g of n-heptane, 4-ethyl-2 149 g of t-butylphenol and 38 g of a 37% formalin aqueous solution were added. The 37% formalin aqueous solution was washed with 18 g of water. After adding 31 mg of 2,2′-methylenebis (4-ethyl-6-t-butylphenol) as a seed crystal, the temperature was raised to an internal temperature of 73 ° C., and the mixture was stirred at a temperature range of 71 ° C. to 75 ° C. for 5 hours.
Dilution step: 54 g of n-heptane was added to the mixed solution containing the crystals obtained in the condensation step.
Neutralization step: 25% aqueous ammonia was added to the mixed solution containing the crystals obtained in the dilution step to adjust the pH to 6.1.
Crystallization step: A mixture containing the crystals obtained in the neutralization step, cooled to an internal temperature of 15 ° C., kept at the same temperature for 20 hours, and then filtered.
Washed with n-heptane and water. Drying yields 2,2'-methylenebis (4-ethyl-6-t-butylphenol) in a yield of 88%, and inclusion of 2,2'-methylenebis (4-ethyl-6-t-butylphenol) in the obtained crystals The amount was 98.4%.

  According to the present invention, high-purity bisphenol (I) can be more easily produced.

Claims (6)

Formula (II)
R ¹ —CHO (II)
(In the formula, R ¹ represents hydrogen or an alkyl group having 1 to 3 carbon atoms.)
An aldehyde represented by formula (III)

(Wherein, it represents an alkyl group having 2 to 5 carbon atoms R ² and R ³ each independently.)
A compound comprising a condensation step in which a dialkylphenol represented by the formula (I) is subjected to a condensation reaction in the presence of an anionic surfactant, water and a hydrocarbon.

(In the formula, R ¹ , R ² and R ³ represent the same meaning as described above.)
In the method for producing 2,2′-alkylenebis (4,6-dialkylphenol) represented by the formula (1), the condensation step comprises 90 to 200 weight parts of water with respect to 100 weight parts of dialkylphenol represented by formula (III). And a reaction temperature in the condensation step is 40 ° C. or higher and lower than 80 ° C., in the presence of 5 parts by weight and 5 to 30 parts by weight of hydrocarbon.   The anionic surfactant is at least one anionic surfactant selected from the group consisting of sodium naphthalene sulfonate and alkyl diphenyl disulfonate which may be substituted with an alkyl group. The manufacturing method according to claim 1.   3. The hydrocarbon according to claim 1, wherein the hydrocarbon is at least one hydrocarbon selected from the group consisting of an aliphatic hydrocarbon having 6 to 10 carbon atoms and an aromatic hydrocarbon having 6 to 12 carbon atoms. Manufacturing method.   The production method according to any one of claims 1 to 3, wherein the dialkylphenol represented by the formula (III) is 2-t-butyl-4-ethylphenol.   The method according to any one of claims 1 to 4, wherein the condensation step is a step of further performing a condensation reaction in the presence of an acid. Furthermore, the following process is included, The manufacturing method in any one of Claims 1-5 characterized by the above-mentioned.
A dilution step of mixing the reaction solution obtained in the condensation step with hydrocarbons;
Step of neutralizing the reaction solution obtained in the dilution step with a base Crystallization step of cooling the reaction solution obtained in the neutralization step