WO2009028724A1

WO2009028724A1 - Method for producing phenol dimer

Info

Publication number: WO2009028724A1
Application number: PCT/JP2008/065921
Authority: WO
Inventors: Yoshihito Okubo; Hideyuki Higashimura
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2007-08-31
Filing date: 2008-08-28
Publication date: 2009-03-05
Also published as: JP2009073824A

Abstract

Disclosed is a method for producing a phenol dimer, which comprises a step for mixing a first solution and a second solution by using an internal collision-type mixer which comprises at least a first line for supplying the first solution containing a phenol (I), a second line for supplying the second solution containing a transition metal compound, and a discharge line for discharging the liquid supplied from the first line and the second line.

Description

Description Method for producing phenolic dimers Technical Field

The present invention relates to a method for producing a phenol dimer. Background art

Phenolic dimers obtained by oxidative pulling of phenols such as phenol are used in a wide range of fields as synthetic raw materials for engineering plastics, epoxy resins, photoresists, antioxidants, and the like.

As an oxidation coupling method for phenols, a method using a transition metal compound is generally an inexpensive and useful method. At this time, the transition metal compound is used as an oxidizing agent or a catalyst. However, in the production of phenol dimers, generally, the phenol dimer produced is more easily oxidized than phenols, and even if the phenol dimer is formed, it immediately becomes a high molecular weight. there were.

In order to solve such a problem, a two-phase mixed solvent of an organic solvent and water is used, phenol is dissolved in the organic solvent, and Ce (NH ₄ ) ₂ (N 0 ₃ ) ₆ is dissolved in the water. In other words, Patent Document 1 discloses a method in which these are stirred and oxidatively coupled. In addition, this document also discloses that the yield of phenol dimers is low when a homogeneous solvent mixture of methanol and water is used.

[Patent Document 1] Japanese Patent Laid-Open No. 2 00 0-2 3 9 2 0 3 (Table 2) Disclosure of Invention

Under such circumstances, it has been desired to develop a method for producing a phenol dimer that can improve the yield of the phenol dimer even when a phase-mixed solvent is used. The present inventors examined the production method and found that the yield of the phenol dimer can be improved by mixing the transition metal compound and the phenol by a certain method. That is, the present invention provides the following [1] to [5].

[1]. A first line for supplying a first solution containing phenols represented by the following formula (I), a second line for supplying a second solution containing a transition metal compound, a first line and A phenolic dimer comprising a step of mixing the first solution and the second solution using an internal collision mixer having at least a discharge line for discharging the liquid supplied from the second line. Manufacturing method.

(In the formula (I), R ^{1 to} R ⁵ are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. And at least one group of R ¹ , R ³ and R ⁵ is a hydrogen atom. )

[2]. The flow velocity in the discharge line is u. The production method according to [1], wherein _ut (m / s) and the inner diameter d (m) of the discharge line flow path satisfy the following formula.

u. _ut / ά ≥ 10, 000 (s- ¹ )

[3] The method according to [1] or [2], wherein the first solution, the second solution, or both the first solution and the second solution are water-containing solutions.

[4]. The production method according to any one of [1] to [3], wherein the first solution is a solution containing at least one solvent selected from the group consisting of alcohols having 1 to 3 carbon atoms and acetone. .

[5] The production method according to any one of [1] to [4], wherein the transition metal compound is Ce (NH ₄ ) ₂ (N0 ₃ ) ₆ . Brief Description of Drawings

FIG. 1 is a schematic diagram showing a schematic configuration of a reaction apparatus used in the production method of the present embodiment.

2 is a cross-sectional view of the center of the internal collision mixer in the reaction apparatus shown in FIG. 1 cut from the paper surface direction.

[Explanation of symbols]

1 Internal collision type mixer

1 a entrance

1 b entrance

1 c exit

2 a pump

2b pump

5 Reaction vessel

D Inner diameter of outlet-side flow path at branch of internal collision type mixer (d) Mode for carrying out the invention

Hereinafter, the present invention will be described in detail. In this specification, “weight” is treated as a synonym for “mass”, and “weight%” is treated as a synonym for “mass%”. In addition, “A to B” indicating the range indicates A or more and B or less. Also, the reaction rate of the two phenols used in this specification is:

Reaction rate (%) = (1— (unreacted phenols [mo 1] Z amount of phenols [mo 1])) X 1 00

And the selectivity for phenol dimers

Selectivity (%) = (2 X Amount of phenolic monomer produced [mo 1] Amount of phenol reacted with Z [m ο 1]) X 100

Means. FIG. 1 is a schematic diagram showing an example of a schematic configuration of a reaction apparatus used in the production method of the present invention. FIG. 2 is an example of a cross-sectional view in which the center of the internal collision type mixer 1 in the reaction apparatus is cut from the paper surface direction. The method for producing a phenol dimer according to the present invention uses a transition metal compound to convert a phenol represented by the formula (I) (hereinafter sometimes referred to as a phenol) into an oxidized cutlet. A method for producing a phenol dimer that undergoes a pulling reaction, the first line supplying a first solution containing the phenols, the second line supplying a second solution containing the transition metal compound, and In an internal collision type mixer having at least a discharge line for discharging the liquid supplied from the first line and the second line, the first solution and the second solution are caused to collide with each other. Includes steps.

Specifically, as illustrated in FIGS. 1 and 2, the internal collision mixer 1 includes at least one outlet lc and two inlets 1a and 1b, and the inlet la has a pump 2a. The first solution is supplied at a predetermined flow rate, the second solution is supplied to the inlet 1b at a predetermined speed by the pump 2b, and the supplied first solution and the second solution collide internally. It is mixed and collided inside the mold mixer 1 and discharged from the outlet lc to the discharge line. Here, in the internal collision mixer 1, the flow velocity in the discharge line is u. _ut (m / s), where d (m) is the inner diameter of the discharge line, the following equation is satisfied.

u. _ut Zd ≥ 1 0, 000 (s—) Here, the “inner diameter of the discharge line flow path” is the diameter when the cross-sectional shape of the discharge line flow path is circular, and is not circular For hydrodynamic equivalent diameter (= 4 X cross-sectional area of flow Z dip length [wetting edge length of cross-sectional area of flow]) (for example, “Theory and Calculation of Chemical Mechanical (2nd Edition)” Ed., Toei Sakae, p. 48, 1977, published in industrial books)). U above. _ut Zd is more preferably in the range of ¹⁰ , 000 to 100, 000 (s- ¹ ), particularly preferably in the range of ¹⁰ , 000 to 70, 000 (s- ¹ ). In the internal collision type mixer, the angle of collision of the liquids flowing in from the two inlets is preferably in the range of 45 to: 180 °, more preferably in the range of 90 to 180 °, and 150 to 1 A range of 80 ° is particularly preferred. Examples of internal collision type mixers include internal collision type micro mixers, T-tubes, and IMM's Standard Slit Interdigital Micro Mixer, Cem. Eng. Te canol. 2005, 28, No. 3, p324-330 Center collision type mixer described in 1), T-union made by Swagelok, and Mu mixer of Mu Company Limited. As the above pumps 2a and 2b, conventionally known pumps can be used. For example, there is a pulsation-free micro syringe pump made by Kd Scientific or a large amount capable of supplying a large flow rate at a high pressure. A liquid feeding unit for preparative high performance liquid chromatography can be mentioned. The concentration of phenols in the first solution is usually in the range of 0.01 to 500 g / L, preferably in the range of 0.05 to 300 gZL, particularly preferably Within the range of 0.1 to 200 g / L. In addition, the concentration of the transition metal compound in the second solution is usually in the range of 0.5 to 3 mol, preferably in the range of 0.6 to 2 mol, with respect to 1 mol of phenols. And particularly preferably in the range of 0.7 to 1.5 mol. The temperature at the time of mixing the first solution and the second solution is a temperature at which the first solution and the second solution both show a liquid, and the boiling point is higher than the boiling point of the organic solvent or water. In this case, the reaction may be performed under pressure. A preferable temperature range is 0 to 100 ° C., more preferably 5 to 80 ° C., and further preferably 10 to 60 ° C. The mixing ratio (flow rate ratio) between the first solution and the second solution is usually set to be within the range of the molar ratio of the transition metal and the phenols. In the present embodiment, the first solution containing the phenols and the second solution containing the transition metal compound are mixed and collided with each other. More preferably, the reaction is completed by aging under or under stirring. The aging time is usually in the range of about 0.1 to 24 hours, preferably in the range of 1 to 5 hours. The temperature at the time of standing can be performed within a range of 10 to 30 ° C., for example. In the method for producing a phenol dimer according to the present embodiment, an oxidative coupling reaction of a phenol represented by the formula (I) is performed using a transition metal compound. In formula (I), R ¹ to R ⁵ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Here, examples of the hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, and a nonyl group; A cycloalkyl group having about 3 to 10 carbon atoms having a cyclic structure such as a cyclopropyl group, a cyclobutyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclonyl group; an ethenyl group, a probe 1— Nyl group, probe-2-nyl group, prop-3-nyl group, 3 1-but-1-yl group, 2-but-1-yl group, 2-pent-1-yl group, 2 — Hexane 1-nyl group, 2-none 1 1 1 2 yl group and the like alkenyl group having about 2 to 10 carbon atoms; ethynyl group, prop 1 1 1 1 2 group, prop 1 -2-nyl group, 3—petit 1 1-nyl group, 2—petit 1 1 1 2 group, 2—pent 1 1 1 2 1 Alkenyl group having about 2 to 10 carbon atoms, such as 2-hexyl 1 12-yl group, 2-nonyl 1 12-yl group, etc .; phenyl group, 1 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-arylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-t-butylphenyl group, etc. Groups: phenylmethyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenyl-1-propyl group, 1-phenyl-2-propyl group, 2-phenyl-2-propyl group, 1-phenyl group Examples thereof include aralkyl groups having about 7 to 10 carbon atoms such as a 2-luo 3-propyl group and a 1-phenyl 4-butyl group. The hydrocarbon group is preferably a hydrocarbon group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Group, more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group. In addition, at least one group of R ¹ , R ³ and R ⁵ is a hydrogen atom, and preferably R ³ is a hydrogen atom. Specific examples of the phenols include phenol, o-cresol, m-cresol, ρ-cresol, 2,6-dimethylphenol, 2,4-dimethylphenol and the like. As the transition metal compound used in the present invention, for example, a transition metal compound described in Japanese Patent Application Laid-Open No. 2000-233920, a transition metal compound that can be used as an oxidizing agent, and the like can be used. The transition metal compound acts as an oxidant or catalyst. Here, the transition metal compound is a compound of a group 3 to 12 element of the periodic table (I UPAC Inorganic Chemical Nomenclature Revised Edition 1 989). Examples of the transition element include scandium, titanium, vanadium, chromium, manganone, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cerium, platinum, gold, etc. It can be illustrated. The transition metal compound only needs to have the ability to oxidize the phenols, and the standard oxidation-reduction potential (25 ° C) is usually 0 V or more. Specifically, the Chemical Society of Japan “Revised 4th edition, Chemical Handbook Fundamentals II” P 46 5— 468 Transition metals whose standard electrode potential (2 5 :) is 0 V or more in aqueous solution as shown in Table 1 Examples thereof include compounds containing compounds and transition metal ions. Preferred examples include transitions such as pentavalent vanadium ions, trivalent manganese ions, trivalent iron ions, trivalent cobalt ions, divalent copper ions, monovalent silver ions, monovalent gold ions, and tetravalent cerium ions. Metal ions, fluoride ions, chloride ions, bromide ions, iodide ions, sulfate ions, nitrate ions, carbonate ions, perchlorate ions, tetrafluoroborate ions, hexafluorophosphies Ion ion, methanesulfonate ion, trifluoromethanesulfonate ion, toluenesulfonate ion, acetate ion, trifluoroacetate ion, propionate ion, benzoate ion, hydroxide ion, oxide ion, methoxide ion, ethoxide ion Counteranions such as alkali metal ions, alkaline earth metal ions Down, counter evening one cationic or Ranaru transition metal compound such as ammonium Niu beam ions. The standard oxidation-reduction potential (25 ° C) of the transition metal compound is preferably not less than 0.01 V, more preferably not less than 0.05 V, and further preferably not less than 0.1 V. The amount of the transition metal compound used is usually 0.5 to 3 mol, preferably 0.6 to 2 mol, particularly preferably 0.7 to 1.5 mol, relative to 1 mol of the phenol. Is a mole. Examples of transition metal compounds used as catalysts include monodentate ligands / transition metal complexes described in JP-A-10-53649; bidentate ligands described in JP-A-10-168 179 Z transition metal complexes: Tridentate ligands / transition metal complexes described in JP-A-9-144449, JP-A-10-45904, JP-A-9-324040; JP-A-9-324042 A tetradentate or pentadentate ligand Z-transition metal complex described above; a hexadentate or higher ligand Z-transition metal complex described in JP-A-9324043; Can be mentioned. In the method according to the present embodiment, the reaction may be performed in the presence of a normal oxidizing agent in addition to the transition metal compound. Examples of the oxidant to be coexistent include oxygen or peroxide. The oxygen may be a mixture with an inert gas or air. Examples of peroxides include hydrogen peroxide, t-butyl halide peroxide, di-t-butyl peroxide, cumene octaoxide, dicumyl peroxide, peracetic acid, perbenzoic acid and the like. Monkey. The amount of the transition metal compound used as a catalyst is not particularly limited, but is preferably within the range of 0.00000 1 to 1.0 mole per mole of the phenol, 0.0 000 1 It is more preferably within a range of ˜0.3 mol, and still more preferably within a range of 0.0001 to 0.2 mol. When the transition metal compound is used, the reaction may be performed in the presence of a normal oxidant. When the transition metal compound is used as a catalyst, the reaction is performed in the presence of a normal oxidant.

Examples of the oxidizing agent to be coexisted include oxygen and peroxide. Oxygen may be a mixture with an inert gas or air. Examples of peroxides include hydrogen peroxide, tert-butyl hydride peroxide, di-tert-butyl peroxide, cumene octide peroxide, dicumyl peroxide, peracetic acid, perbenzoic acid, and the like. Can show. The amount of the oxidizing agent used is usually 0.15 mol or more in excess of 1 mol of the phenols when oxygen is used, and usually 1 mol of the phenols when peroxide is used. 0. Use within the range of 3 to 1 mole. As the transition metal compound, a transition metal compound capable of being an oxidizing agent by itself is preferable, and Ce (NH ₄ ) ₂ (N0 ₃ ) ₆ is particularly preferable. The present invention includes a step of mixing and colliding a first solution containing phenols with a second solution containing a transition metal compound. The solvent of the first solution (hereinafter referred to as “first solvent”) is inactive with respect to the phenols and the transition metal compound, and is a liquid in the collision step, and dissolves the phenols. Can do. Preferably, it is a solvent that is uniformly mixed without causing phase separation when mixed with the solvent of the second solution (hereinafter referred to as “second solvent”). The second solvent is inactive with respect to the phenols and the transition metal compound. It is a liquid in the collision process and can dissolve the transition metal compound. Preferably, the solvent is mixed uniformly without causing phase separation when mixed with the first solvent. Examples of the first solvent include aromatic hydrocarbons having about 6 to 10 carbon atoms such as benzene, toluene, xylene, mesitylene, ethylbenzene, cumene, and 1-butylbenzene; pentane, hexane, heptane, and octane. Aliphatic hydrocarbons having about 5 to 10 carbon atoms such as cycloaliphatic hydrocarbons having about 5 to 10 carbon atoms such as cycloheptane and cyclohexane, dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, 1,2-Dichloro-necked benzene, 1_chloronaphthalene and other octahalogenated hydrocarbons having about 1 to 10 carbon atoms; dimethyl ether, jetyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, etc. ~ 10 ethers; acetone, methyl ethyl ketone, methyl butyl ketone, cyclohexanone, Ketones having 3 to 10 carbon atoms such as tophenone; nitriles such as acetonitrile and benzonitrile; alcohols such as methanol, ethanol, n-propyl alcohol, is 0-propyl alcohol; dioxane, terahydrofuran, ethylene Ethers such as glycol dimethyl ether; Amides such as N, N-dimethylformamide and N-methylpyrrolidone; Two-necked compounds such as nitromethane and ditrobenzene; Water and the like. These can be used alone or as a mixture. Among these, polar solvents that are uniform even if they contain a large amount of water such as alcohols having 1 to 3 carbon atoms such as methanol, ethanol, n-propanol, and isopropanol, tetrahydrofuran, and aceton are preferable. Preference is given to at least one solvent selected from the group consisting of alcohols and acetones of the numbers 1 to 3. As the second solvent, water is usually used, and it may be water containing a polar solvent that is uniform even if it contains a large amount of water such as alcohol having 1 to 3 carbon atoms and acetone.

Further, it is more preferable that at least one of the first solvent and the second solvent contains water, and both the first solvent and the second solvent may contain water. The phenol dimer can be obtained in high yield by the production method of the present invention. Here, the phenol dimers include p, p′-biphenol, p, o′—biphenol, o, o′—piphenol, etc. (dioxybiphenol), o-phenoxyphenol, p —Phenoxyphenols such as phenoxyphenol. Separation of phenol dimers from each other can be carried out by a conventionally known method, for example, purification methods such as distillation, sublimation, reprecipitation, extraction, chromatography and the like alone or in combination. The method for producing a phenol dimer according to the present invention can produce a phenol dimer in high yield. In addition, phenolic dimers have excellent selectivity. Therefore, it can be applied to the production of various phenol dimers from lab scale to plant scale. According to the present invention, a phenol dimer can be produced with high yield. Example

Hereinafter, the present invention will be described in more detail based on examples, but it goes without saying that the present invention is not limited to the following examples. Each reaction in the examples was performed at normal pressure and room temperature (about 25) unless otherwise specified.

[Reaction rate of phenols and selectivity of phenol dimers]

Methanol 100 ml is added to the reaction mixture, insoluble matter is filtered, and the filtrate is subjected to high performance liquid chromatography (Product name: LC-1 10A, manufactured by Shimadzu Corporation, detection wavelength: 2 78 nm, column: 丫○ Analyzed with 0 S-AM (AM-3 04), developed solvent: methanol / water) manufactured by 〇 company. The reaction rate of phenols in this example was determined based on the phenol and biphenyl calibration curves prepared in advance, and pifenyl in the reaction mixture was used as an internal standard. Similarly, the selectivity of the phenol dimer is determined based on the five types of phenol dimers (p, p '-biphenol, p, o' -biphenol, o, o, — biphenol, o-phenol) Biphenyl in the reaction mixture was determined as an internal standard based on each calibration curve for siphenol and -phenoxyphenol) and the calibration curve for pifenyl.

Example 1

T-shaped fitting for chromatograph (trade name: low dead polyyumu type uni ti, model number: SS— 1 F 0— 3 GC, inner diameter at branch: 0.33 mm, manufactured by Swage 1 ok ) Was used as an internal collision type mixer, two opposing channels were used as inlet channels, and the remaining one channel was used as an outlet channel. Phenol 3 76.4 mg (4.00 mmo 1) as phenols and pifenyl 10 Omg as an internal standard substance were dissolved in 100 ml of methanol to prepare a first solution. Further, Ce (NH ₄ ) ₂ (N0 ₃ ) 61.93 g (3.52 mmo 1) was dissolved in 20 ml of distilled water to prepare a second solution. The first solution was fed at a flow rate of 50 ml / min, and the second solution was fed at a flow rate of 10 ml lmin. A liquid pump unit for large-scale preparative liquid chromatography (manufactured by Shimadzu Corporation) For example, LC-1 8 A, LC-10 A, L C-11 A, etc.) were used to mix each solution, and the mixture was allowed to stand for 24 hours without stirring. Table 1 shows the analysis results of the resulting mixture. Example 2

A dimerization reaction of phenols was performed in the same manner as in Example 1 except that the methanol in the first solution was changed to tetrahydrofuran (THF). Table 1 shows the analysis results of the resulting mixture. Example 3

Example 1 with the exception that the methanol in the first solution was changed to acetone. The same operation was performed to carry out a dimerization reaction of phenols. Table 1 shows the results of analysis of the resulting mixture. Example 4

A dimerization reaction of phenols was performed in the same manner as in Example 1 except that the distilled water in the second solution was changed to methanol. Table 1 shows the analysis results of the obtained mixture.

Example 5

The phenol dimerization reaction was performed in the same manner as in Example 1, except that the flow rate of the first solution was changed to 15 ml lmin and the flow rate of the second solution was changed to 3 ml zmin. It was. Table 1 shows the analysis results of the resulting mixture.

Example 6

The phenol dimerization reaction was performed in the same manner as in Example 1 except that the flow rate of the first solution was changed to 100 ml lmin and the flow rate of the second solution was changed to 20 ml / min. It was. Table 1 shows the analysis results of the resulting mixture.

Example 7

The dimerization reaction of phenols was carried out in the same manner as in Example 1 except that the flow rate of the first solution was changed to 5 m 1 / min and the flow rate of the second solution was changed to 1 m 1 / min. went. Table 1 shows the analysis results of the resulting mixture.

Example 8

Perform the same process as in Example 1 except that the flow rate of the first solution was changed to 10 ml / min and the flow rate of the second solution was changed to 2 ml / min. It was. Table 1 shows the analysis results of the resulting mixture.

[¾1]

The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope shown in the claims, and the invention can be obtained by appropriately combining technical means disclosed in different embodiments. Embodiments are also included in the technical scope of the present invention. Industrial applicability

According to the method for producing a phenol dimer of the present invention, the yield of the phenol dimer can be improved.

Claims

The scope of the claims

1. a first line for supplying a first solution containing a phenol represented by the following formula (I), a second line for supplying a second solution containing a transition metal compound, a first line and A method for producing a phenol dimer comprising a step of mixing a first solution and a second solution using an internal collision mixer having at least a discharge line for discharging the liquid supplied from the second line .

(In formula (I), R ^{1 to} R ⁵ are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and at least one group of R ¹ , R ³ and R ⁵ is a hydrogen atom. )

2. u the flow velocity in the discharge line. The manufacturing method according to claim 1, wherein _ut (m / s) and inner diameter d (m) of the flow path of the discharge line satisfy the following formula.

u. _ut / d ≥ 1 0, 000 (s- ¹ )

3. The production method according to claim 1 or 2, wherein the first solution, the second solution, or both the first solution and the second solution are water-containing solutions.

4. The production method according to any one of claims 1 to 3, wherein the first solution is a solution containing at least one solvent selected from the group consisting of an alcohol having 1 to 3 carbon atoms and acetone.

5. Transition metal _{compound, C e (NH 4) 2} (N0 3) 6 The method according to any one of claims 1 to 4 is.