JP2540590B2 - Method for producing aromatic carbonate compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an aromatic carbonate compound, and more particularly to a phenol compound and a di-aliphatic carbonate or an aliphatic aromatic carbonate. The present invention relates to a method for producing an aromatic carbonate compound in which the reaction is carried out under a high temperature condition of 220 to 350 ° C., and the reaction time, yield, and selectivity are efficient, in the method for producing an aromatic carbonate by reacting

(Prior Art and Its Problems) A phenolic compound is reacted with a dialiphatic carbonate or an aliphatic aromatic carbonate to produce an aromatic carbonate compound composed of an aliphatic aromatic carbonate, a diaromatic carbonate or a mixture thereof. It is well known that this reaction is represented by the following formula:

Or 2ROCO ₂ ArArOCO ₂ Ar + ROCO ₂ R (3) However, in the reactions (1) and (2), the equilibrium constants K ₁ and K ₂ shown below are low and the equilibrium is biased toward the raw material system. And the reaction rate is slow, ROCO ₂ Ar and A
It has the disadvantage that the yield of rOCO ₂ Ar is very low.

Therefore, some proposals have been made to improve the yield in this reaction system.

That is, in the invention disclosed in JP-A-60-169444, when the produced alcohol is removed from the system by distillation so that the equilibrium point is continuously shifted until the reaction completely reaches the end point, the reaction proceeds. It is described that it can proceed with advantage. Further, JP-A-61-291545 discloses a method of distilling off MeOH produced in a reaction system as a mixture with benzene using benzene as an azeotrope-forming agent, and JP-A-54-291545. -48733, a mode in which at least one kind of organic tin compound having no tin-halogen bond is used as a catalyst, MeOH formed in the reaction system is mixed with heptane, and azeotropically removed ( Example 1) is disclosed, and JP-A-58-185536 proposes a method of removing the produced MeOH by adsorbing it with a molecular sieve.

However, in these methods, although the yield of the aromatic carbonate compound is improved, the reaction rate is slow in all of them, and it is difficult to say that they are industrially efficient production methods.

On the other hand, a method of changing the molar ratio of ROCO ₂ R / ArOH or ROCO ₂ Ar / ArOH has also been proposed in order to increase the reaction rate and the yield. For example, JP-A-60-169444 discloses the invention based on the finding that ArOCO ₂ Ar can be satisfactorily produced by reducing the molar ratio to 1/2 or less and making ArOH excessive. However, in the examples, an example in which a large excess of PhOH is used, that is, EtOCO ₂ Et / PhOH = 1/8, is shown. Further, in Japanese Patent Laid-Open No. 51-105032, MeOCO ₂ Me / PhOH = 5/1, which means that MeOCO ₂ Me
The reaction rate and the yield of MeOCO ₂ Ph are improved by making a large excess.

As described above, it is natural that the yield is improved by greatly excessing any one of the raw materials, although it is naturally possible from the principle of chemical equilibrium. Excessive use means production rate per reactor volume (STY = product g / (reactor volume (l)
× Retention time of reaction solution or reaction time h)) is reduced, and enlargement of the apparatus is unavoidable, which is not necessarily an excellent manufacturing method.

Therefore, an object of the present invention is to produce an aromatic carbonate compound in a short time and in a high yield by reacting a phenol compound with a dialiphatic carbonate or an aliphatic aromatic carbonate without having the above-mentioned drawbacks. It is to provide a manufacturing method.

(Means for Solving Problems) The present invention utilizes the principle of equilibrium in the reactions (1) and (2) by using one of the raw materials in a large excess to improve the yield and the reaction rate. Unlike the conventional method that we were aiming for,
This was achieved as a result of conducting research focusing on the reaction temperature rather than the amount of raw material.

That is, according to the present invention, selected from aliphatic aromatic carbonates, diaromatic carbonates and mixtures thereof by reacting a phenolic compound with a dialiphatic carbonate or an aliphatic aromatic carbonate in the presence of a catalyst. A method for producing an aromatic carbonate compound according to claim 1, wherein the reaction temperature is 255 to 320 ° C.

Further, according to the present invention, the aliphatic aromatic carbonate produced by the above method, or a mixture of the aliphatic aromatic carbonate and the diaromatic carbonate is further heated in the presence of a catalyst to give the diaromatic carbonate. A method of manufacturing is provided.

The reaction temperature of 255 to 320 ° C. is far higher than the conventional common sense as the reaction temperature of the phenol compound and the dialiphatic carbonate or the aliphatic aromatic carbonate, and thus the reaction at a high temperature can be performed. The fact that an aromatic carbonate having improved reaction rate, yield, and selectivity is obtained by carrying out the reaction, and that the equilibrium constant changes with the reaction temperature and becomes significantly higher with the increase in temperature, It is the first knowledge obtained by.

(Function) The present invention comprises reacting a phenol compound with a di-aliphatic carbonate or an aliphatic aromatic carbonate to produce an aromatic carbonate compound, wherein the reaction is
This is based on the findings of the present inventors that the equilibrium constant can be significantly increased by performing the reaction at a high temperature of 5 to 320 ° C., and thus the reaction rate and the yield can be improved.

(Explanation of Preferred Embodiments) Phenol Compound The phenol compound in the present invention is represented by the general formula [I] ArOH ... [1], wherein Ar represents an aromatic compound residue, and substituted or unsubstituted benzene. It represents a ring, a naphthalene ring, an anthracene ring, a tetralin ring or the like.

Specifically, phenol, o, m, p-cresol, o, m, p
-Chlorophenol, o, m, p-Ethylphenol, o, m, p
-(Iso) propylphenol, o, m, p-phenoxyphenol, o, m, p-phenylphenol, o, m, p-methoxyphenol, o, m, p-nitrophenol, 2,6-dimethylphenol, 2,4-Dimethylphenol, 3,4-dimethylphenol, 2,6-dibutylphenol, α-naphthol, β-naphthol and β-anthrol can be exemplified, and among them, phenol can be most preferably used.

Dialiphatic carbonate The dialiphatic carbonate in the present invention has the general formula [II] (In the formula, R ′ is a monovalent aliphatic hydrocarbon group), more specifically, R ′ is preferably an alkyl group or a cycloalkyl group, and two R ′ May be linked to each other, and the alkyl group is a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples thereof include a butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, and an octyl group. The cycloalkyl group has 4 to 7 ring carbon atoms, for example,
Examples thereof include a cyclobutyl group, a cyclopentyl group, a methylcyclohexyl group, a cyclohexyl group, and a cycloheptyl group. Further, an example in which two R's are linked to each other is an ethylene group.

Specifically as the compound represented by the above formula [II],
Dimethyl carbonate, diethyl carbonate, dinormal butyl carbonate, dicyclohexyl carbonate, dibenzyl carbonate, dinormal octyl carbonate, diisopropyl carbonate, ethylene carbonate and the like are exemplified, and among them, dimethyl carbonate is preferably used.

Aliphatic Aromatic Carbonate The aliphatic aromatic carbonate in the present invention has the general formula [III] Wherein Ar is the same as the above formula [I] and R ′ is the same as the above formula [II]. Specifically, phenylmethyl carbonate, phenylethyl carbonate,
Examples thereof include phenylcyclohexyl carbonate and tolyl methyl carbonate.

Aromatic Carbonate Compound The product aromatic carbonate compound in the present invention is selected from aliphatic aromatic carbonates, diaromatic carbonates and mixtures thereof,
Of these, the diaromatic carbonate has the formula (Ar is the same as the above formula [I]), and specifically,
Examples include diphenyl carbonate, di (methylphenyl) carbonate, di (dimethylphenyl) carbonate, and dinaphthyl carbonate.

In the present invention, the phenol compound and a dialiphatic carbonate or an aliphatic aromatic carbonate are reacted in the presence of a catalyst to produce an aromatic carbonate compound, but the reaction temperature is 255 to 320 ° C. The most important feature is that it is performed under high temperature conditions.

Conventionally, when producing an aromatic carbonate, the reaction of the phenol compound and the di-aliphatic carbonate or the aliphatic aromatic carbonate should be carried out at a temperature in the range of 50 to 250 ° C. (JP-A-54-48733). Alternatively, it is disclosed that the temperature is in the range of 20 to 300 ° C. (Japanese Patent Laid-Open No. 54-63023). However, in these conventional techniques, if the reaction temperature is too high, it is explained that it is not preferable because it leads to deactivation of the catalyst and decomposition of the formed carbonate, and the preferable temperature is 250 ° C. or lower. In addition, in the examples given as manufacturing examples, in practice,
The reaction was carried out at a temperature below 0 ° C.

In fact, according to the knowledge of the present inventors, as is clear from the comparison between Example 1 and Comparative Example 1 or Example 2 and Comparative Example 2 described later, when the temperature in the reaction is increased. It was found that the selectivity dropped sharply from around 200 ° C.

However, it has been found that the selectivity is increased again when the reaction temperature is further increased, the reaction rate is significantly increased, and therefore the reaction time is shortened.

The recognition that the deactivation of the catalyst occurs when the reaction temperature is too high in the prior art is considered to be based on the fact that the selectivity decreases in the vicinity of 200 ° C., and thus,
No example has been known of pursuing a reaction at a higher temperature than that, for example, a reaction at a higher temperature of 255 ° C or more.

In addition, when the reaction temperature is higher than 320 ° C., in addition to the target aromatic carbonate, the ether compound ArOR ′
(Ar is the same as the formula [I] and R ′ is the same as the formula [II]) again, or the raw material di-aliphatic carbonate or aliphatic aromatic carbonate begins to decompose, and the selectivity of the aromatic carbonate is again increased. Tends to decline.

Especially when the reaction temperature is higher than 350 ° C., the above tendency becomes remarkable and an aromatic carbonate having excellent physical properties cannot be obtained.

And when looking at the above-mentioned prior art, all of them had a drawback that the amount of catalyst used was large and the reaction time was long, so that there were many side reactions and the selectivity of the target aromatic carbonate was low. Is.

The above-mentioned findings by the present inventors are completely new beyond the conventional wisdom in the conventional method for producing aromatic carbonates, and the effect of shortening the reaction time with a marked increase in yield and reaction rate is described in Examples described later. And it will become clear from the description of the comparative examples.

Furthermore, surprisingly, the temperature of the present invention is 255 to 320 ° C.
By carrying out the reaction under high temperature conditions, the amount of the catalyst used is 0.5 mol% or less, preferably 0.2 to 10 ^-3 mol% with respect to the phenol compound, which is an extremely small amount as compared with the conventional production method. The yield and the reaction rate can be increased, and the reaction between the phenol compound and the di-aliphatic carbonate or the aliphatic-aromatic carbonate is
It is preferably carried out in the vicinity of an equimolar ratio, and unlike the conventional method, it is not necessary to use a large excess of either of them, so that the production rate per reactor volume (STY) is increased, which is a significant industrial advantage. There is.

In the present invention, the reaction of the phenol compound and the di-aliphatic carbonate or the aliphatic aromatic carbonate is carried out in a molar ratio of 5: 1 to 1: 5, preferably 2.5: 1 to 1: 2.5 equimolar. A reaction in the vicinity of the specific ratio is recommended in order to obtain an aromatic carbonate compound having high selectivity and high STY.

The conventional method of shifting the equilibrium to the product system by carrying out the reaction while removing the generated ROH to the outside of the reaction system in order to improve the yield of the aromatic carbonate compound is also applied to the method of the present invention. be able to. However, even in such a case, under the conditions of the present invention, since the equilibrium constants K ₁ and K ₂ in the reaction system are higher than those in the conventional technique in which the reaction is performed at 200 ° C. or lower, the ROH by a method such as distillation is used. When removing, the number of steps is small,
The yield can be improved more effectively. In addition, when using MeOCO ₂ Me as a raw material during distillation,
MeOCO ₂ Me azeotropes, and this azeotrope is separated in a distillation column.
It is necessary to remove only MeOH, but in this case, since the equilibrium constants K ₁ and K ₂ are large, the concentration of ROH becomes high, so that ROH can be easily removed by distillation, and the equipment cost and utility cost are reduced. It will also have the economic advantage of being cheaper. Furthermore, when removing ROH, as in the prior art, by adding an azeotropic agent such as benzene or heptane to the reaction system,
The method of removing as an azeotrope with ROH also enables more efficient removal of ROH.

The catalyst used in the present invention, Ti, Zr, Hf,
V, Nb, Ta, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Zn, Al,
Si, Ge, Sn and Sb compounds, these halogen compounds,
Examples thereof include oxides, hydrides, carboxylic acid compounds, nitric acid compounds, alkoxy compounds, acetylacetonate compounds, sulfuric acid compounds, cyclopentenyl compounds, carbonyl compounds, phosphine complexes, amine complexes and the like. Specifically, Ti (OCH ₃ ) ₄ , Ti (OiC ₃ H ₇ ) ₄ , Ti (OC ₆ H ₅ ) ₄ , TiCl ₄ , T
iCl ₃ , TiO (CH ₃ COCHCOCH ₃ ) ₂ , TiOCl ₂ , TiO ₂ , Ti (OCOCH ₃ ) ₄ , Ti
(dipyridyl) ₃ ； Zr (C ₅ H ₅ ) ₂ Cl ₂ , Zr (CH ₃ COCHCOCH ₃ ) ₄ , ZrO ₂ , ZrF ₄ , ZrCl ₄ , Zr
_{(OC 2 H 5) 4;} HfH 2, HfO 2, HfCl 4; VH, VO 2, VOCl 3, VCl 5, H 2 VO 3, H 2 V 4 O 9, V 2 O 5, Na 3 [VO 4 ], VCl ₃ ,
VCl ₄ ； Nb ₂ O ₅ ,, NbF ₅ , NbCl ₅ , NbOBr ₃ , NbO ₂ F, NbO ₂ ； TaCl ₅ , TaF ₅ , Ta ₂ O ₅ , TaO ₂ F, TaOBr ₃ , TaO ₂ ； ReOCl ₃ (Ph ₃ P) ₂ , Re ₂ (CO) ₁₀ , Re (CO) ₅ Cl, ReO ₂ , ReCl ₄ , Re
₂ O ₇ , KReO ₄ , K ₃ ReO ₅ , Re (pyridine) ₂ Cl ₂ ; Fe (C ₅ H ₅ ) ₂ , Fe (OCH ₃ ) ₃ , Fe (CH ₃ COCHCOCH ₃ ) ₃ , Fe ₂ O ₃ , Fe (OH)
₃ , FeSO ₄・ 7H ₂ O, Fe (CO) ₅ , Fe ₂ (CO) ₉ , Fe ₃ (CO) ₁₂ , K ₂ FeO ₃ , K ₃ F
eO ₄ , FeCl ₂ , FeCl ₃ ； Ru ₃ (CO) ₁₂ , K ₂ RuO ₄ , RuCl ₃ , Ru (Ph ₃ P) ₄ Cl ₂ , Ru (Ph ₃ P) ₃ Cl ₂ ； Os ₃ (CO) ₁₂ , K ₂ OsO ₄ ,, OsF ₆ , OsO ₂ , OsO ₄ , OsCl ₄ ； Co (CH ₃ COCHCOCH ₃ ) ₂ , Co (Ph ₃ P) ₂ Cl ₂ , Co ₃ O ₄ , CoCl ₂ , CO (NH ₃ )
₃ (NO ₂ ) ₃ , Co ₂ (CO) ₈ ； Rh (CO) ₂ (CH ₃ COCHCOCH ₃ ), Rh ₄ (CO) ₁₂ , RhCl ₃ , Rh (Ph ₃ P) ₃ Cl,
Rh ₂ O ₃ ,, K ₂ RhCl ₆ ； Ir ₄ (CO) ₁₂ , IrCl ₃ , IrO ₂ , K ₂ IrCl ₆ , IrO ₃ , IrS ₃ ； Ni (C ₅ H ₅ ) ₂ , Ni (Ph ₃ P) _{2 Cl 2, Ni (CO) 4} , NiO, NiCl 2, NiSO 4; Pd (CH 3 COCHCOCH 3) 2, Pd (Ph 3 P) 2 Cl 2, PdO, PdCl 2, H 2 PdCl 6; Pt (CH 3 COCHCOCH ₃ ) ₂ , PtO, PtCl ₂ , H ₂ PtCl ₆ , PtCl ₄ , (CH ₃ ) ₃ Pt
_{I, (CH 3) 4 Pt} , PtO 3, Pt (NH 3) 2 Cl 2; Cu (CH 3 COCHCOCH 3) 2, Cu 2 O, CuCl, CuBr, CuI, CuSO 4, Cu (NO 3)
₂ , Cu ₂ S; Ag (OCOCH ₃ ), AgCl, AgNO ₃ , Ag ₂ O, Ag ₂ CO ₃ ; Zn (OCOCH ₃ ) ₂ , Na ₂ ZnO ₂ , ZnO, ZnSO ₄ , ZnCl ₂ , ZnS, ZnCO ₃ , Zn (N
_{O 3) 2, Zn 4 O} (OCOCH 3) 6; Al (OiC 3 H 7) 3, Al 2 O 3, Al (OH) 3; Si (C 6 H 5) 2 (OCH 3) 2, Si ( _{OCH 3) 4, HSiCl 3,} (CH 3) 2 SiCl 2, SiCl
_{4, HSi (CH 3) Cl} 2, Si (OC 2 H 5) 4, SiO 2; GeO 2, GeCl 4; SnCl 2, SnCl 4 (C 4 H 9) 2 SnO, SnO 2, Sn (OCOCH 3) ₄ , Sn (CH ₃ ) ₃ (OC
OCH ₃ ), Sn (C ₄ H ₉ ) ₂ (OCOCH ₃ ) ₂ , (C ₄ H ₉ ) ₂ Sn (OCH ₃ ) ₂ , Sn (C ₄ H ₉ )
O (OH), Sn (P ₁ O ₄ ), [Bu ₂ Sn (OC ₆ H ₅ )] ₂ O, [(C ₆ O ₅ ) Sn (OCOC
_{H 3) 2] 2 O;} Sb 2 O 3, SbCl 5; but are exemplified, preferably, Ti, Zr, V, Fe , Co, Zn and Sn
The compounds of the system can be exemplified.

The amount of the catalyst is an amount effective for catalyzing the transesterification reaction when reacting the phenol compound with the dialiphatic carbonate or the aliphatic aromatic carbonate, a so-called catalytic amount is used, and this amount is the amount of the phenol compound. To 0.5 mol% or less, preferably 0.2 to 10 ^-3 mol%. When the amount of catalyst is small, the selectivity of aromatic carbonate is high.

According to the present invention, the reaction rate can be increased by increasing the equilibrium constant, and thus the reaction time can be significantly shortened. The reaction time in the present invention is 2 minutes to 3
The target aromatic carbonate can be produced in a short time, preferably 10 minutes to 1 hour, and in a high yield. The reaction time in the conventional method for producing an aromatic carbonate varies depending on the catalyst used, etc., but even a short reaction time is 5 hours.
8-24 hours of reaction time are spent, which is why
Side reactions are also likely to occur, so even if you compare this point,
In the present invention, 2 minutes to 3 hours, preferably 10 minutes to 1
It is understood how effective the reaction time of time is.

The short reaction time is not only an economically great advantage, but also the short heating time leads to high product selectivity and good quality results. In the present invention, the aliphatic aromatic carbonate produced by the method according to claim (1) or the mixture of the aliphatic aromatic carbonate and the diaromatic carbonate is further heated in the presence of a catalyst to give Aromatic carbonates can be produced.

In this case, the same catalyst as that used in the preceding reaction may be used, but a different catalyst may be used as long as it is within the range of the above-described catalyst.

This reaction is represented by the aforementioned reaction formula (3), and the reaction temperature is 50 to 370 ° C, preferably 150 to 320 ° C.
The temperature is 0 ° C., and the pressure can be increased, normal pressure, or reduced pressure, but it is preferable to perform the reaction under reduced pressure while removing the produced dialiphatic carbonate outside the reaction system.

(Effects of the Invention) Thus, according to the present invention, a phenol compound,
When producing an aromatic carbonate by reacting a di-aliphatic carbonate or an aliphatic aromatic carbonate, by carrying out the above reaction under a high temperature condition of 255 to 320 ° C., both the yield and the reaction rate are increased and the efficiency is improved. The feature is that an aromatic carbonate of excellent quality can be obtained.

(Example) Hereinafter, the present invention will be described in detail based on examples.

Example 1 0.11 mol of phenol, dimethyl carbonate (DMC)
0.11 mol and 0.01 g of Zr (C ₅ H ₅ ) ₂ Cl ₂ were placed in a 50 ml autoclave and heated at 280 ° C. for 30 minutes. Gas chromatographic analysis of the reaction mixture revealed that 0.75% of anisole and 1 of phenylmethyl carbonate (PMC) were found on a phenol basis.
The yield was 5.20% and diphenyl carbonate (DPC) was 1.12%.

Examples 2 to 9 The procedure of Example 1 was repeated except that the catalyst and the reaction conditions were changed as shown in Table 1.

 Table 1 shows the results.

As Comparative Examples 1 to 4 The catalyst, Zr (C ₂ H ₅₎ using _{2 Cl 2, Ti (Oi-} Pr) 4, carried out at a reaction temperature below 255 ° C. As shown in Table 1, other reaction conditions The same procedure as in Example 1 was carried out except that the results shown in Table 1 were used.

 Table 1 shows the results.

Example 10 Phenylmethyl carbonate 8.4 g, Ti (OiC ₃ H ₇ ) ₇ 0.2
8g was heated in an autoclave at 200 ° C for 1 hour. As a result of analyzing the reaction solution by gas chromatography, 12 mmol of phenyl carbonate and 11 mmol of dimethyl carbonate were produced.

Example 11 The procedure of Example 10 was repeated except that Zr (C ₅ H ₅ ) ₂ Cl ₂ was used as the catalyst. Formation of diphenyl carbonate and dimethyl carbonate was confirmed by gas chromatography.

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Claims (8)

(57) [Claims] 1. An aromatic selected from aliphatic aromatic carbonates, diaromatic carbonates and mixtures thereof by reacting a phenolic compound with a dialiphatic carbonate or an aliphatic aromatic carbonate in the presence of a catalyst. In the method for producing a group carbonate compound,
A method characterized in that the reaction temperature is set to 255 to 320 ° C. 2. The method according to claim 1, wherein the molar ratio of the phenol compound and the di-aliphatic carbonate or the aliphatic-aromatic carbonate is 2.5: 1 to 1: 2.5. 3. The method according to claim 1, wherein the phenol compound is phenol. 4. The method according to claim 1, wherein the dialiphatic carbonate is dimethyl carbonate. 5. The method according to claim 1, wherein the aliphatic aromatic carbonate is methylphenyl carbonate. 6. The catalyst concentration is 0.2 with respect to the phenol compound.
The method according to claim 1, wherein the content is from mol% to 0.001 mol%. 7. The method according to claim 1, wherein the reaction time is 10 minutes to 1 hour. 8. An aliphatic aromatic carbonate produced by the method according to claim 1 or a mixture of an aliphatic aromatic carbonate and a diaromatic carbonate is further heated in the presence of a catalyst. A method for producing a diaromatic carbonate.