KR101437876B1 - Catalyst compositoin for preparing aromatic carbonate compound, and method for preparing aromatic carbonate compound by using the same - Google Patents

Abstract

(상기에서 X는 탄소수 1-10의 알콕시, 알킬 페녹시 또는 페녹시임)
[화학식 2]

(상기에서 R1 및 R2는 각각 독립적으로 서로 같거나 다른 수소, 탄소수 1~6의 알킬기임 )
[화학식 3]

(상기에서 Y는 산소 또는 알콕시임)
[화학식 4]

(상기에서 Z는 알콕시임).
[화학식 5]

(상기에서 M은 할로겐 또는 알콕시임).The catalyst composition for synthesizing an aromatic carbonate compound of the present invention comprises at least one samarium-based primary catalyst represented by the following formula 1 or 2: And at least one cocatalyst represented by the following general formula (3), (4), or (5), wherein the aromatic carbonate compound is prepared by using the catalyst composition, wherein the aliphatic carbonate compound and the aromatic hydroxy compound are In the presence of at least one samarium-based primary catalyst represented by Formula 1 or 2 and at least one cocatalyst represented by Formula 3, Formula 4, or Formula 5, And a cocatalyst to produce an aromatic carbonate compound and a polycarbonate resin having high selectivity stably.
[Chemical Formula 1]

(Wherein X is alkoxy of 1 to 10 carbon atoms, alkylphenoxy or phenoxy)
(2)

(Wherein R1 and R2 are each independently of the other hydrogen or an alkyl group having 1 to 6 carbon atoms)
(3)

(Wherein Y is oxygen or alkoxy)
[Chemical Formula 4]

(Wherein Z is alkoxy).
[Chemical Formula 5]

(Wherein M is halogen or alkoxy).

Description

TECHNICAL FIELD [0001] The present invention relates to a catalyst composition for synthesizing an aromatic carbonate compound and a method for producing an aromatic carbonate compound using the same. BACKGROUND ART [0002]

The present invention relates to a catalyst composition for synthesizing an aromatic carbonate compound and a process for producing an aromatic carbonate compound using the same. More particularly, the present invention relates to a method for producing an aromatic carbonate compound using a catalyst composition comprising a samarium-based primary catalyst and a cocatalyst.

Aromatic carbonate compounds are useful monomers for the production of polycarbonate, and many studies have been conducted on their preparation. Conventionally, it has been mainly prepared by the phosgene method in which an aromatic carbonic ester is obtained by reacting phenol and phosgene in the presence of an alkali. However, this method has a problem in that it is necessary to use poisonous phosgene and neutral salt which is a by-product must be treated by the reaction.

Therefore, in order to solve such a problem, Korean Patent No. 0726925, Japanese Patent Laid-Open No. 1996-259504 and Japanese Laid-open Patent Application No. 1995-033714 disclose an aromatic carbonic acid ester produced by reacting an aliphatic carbonic ester such as dimethyl carbonate with phenol An ester exchange method is disclosed. Such ester exchange processes are generally carried out in the presence of a catalyst and PbO, TiX ₄ (X = alkoxy group or aryloxy group) and SnR ₂ (OPh) ₂ (R = alkyl group) are known as catalysts to be used. However, the stability of PbO catalyst is high, but the reaction rate is very slow due to the low activity of the catalyst. TiX ₄ and SnR ₂ (OPh) ₂ have higher activity than PbO catalyst but have insufficient stability and a considerable amount of ether is obtained as a by-product .

On the other hand, a method of producing an aromatic carbonate by carbonylating an aromatic hydroxy compound using carbon monoxide and oxygen has been developed. However, the method of synthesizing carbon monoxide with carbon monoxide as a reaction material has a considerable decrease in reactivity, There is a problem that it is difficult to commercialize it.

Therefore, in order to solve the above-mentioned problems, it is necessary to develop a method for producing an aromatic carbonate compound which is stable and has high conversion and high selectivity through a carbonic ester reaction between an aliphatic carbonate compound and an aromatic hydroxy compound to be.

An object of the present invention is to provide a catalyst composition for synthesizing an aromatic carbonate compound containing a main catalyst and a cocatalyst.

Another object of the present invention is to provide a process for producing an aromatic carbonate compound which is stable and has a high selectivity by using the catalyst composition.

Another object of the present invention is to provide an aromatic carbonate compound produced by the above production method and a polycarbonate resin prepared by polymerization thereof.

The technical objects to be achieved by the present invention are not limited to the above-mentioned technical problems, and other technical subjects which are not mentioned can be understood by those skilled in the art from the following description.

One aspect of the present invention relates to an aromatic carbonate compound prepared by subjecting an aliphatic carbonate compound and an aromatic hydroxy compound to a carbonic ester reaction in the presence of a main catalyst and a cocatalyst, and a process for producing the same.

In one embodiment of the present invention, the aromatic carbonate compound is prepared by reacting an aliphatic carbonate compound and an aromatic hydroxy compound with at least one samarium-based primary catalyst represented by the following general formula (1) or (2) In the presence of at least one cocatalyst represented by the following formula: < RTI ID = 0.0 >

(Wherein X is alkoxy of 1 to 10 carbon atoms, alkylphenoxy or phenoxy)

(Wherein R1 and R2 are each independently of the other hydrogen or an alkyl group having 1 to 6 carbon atoms)

(Wherein Y is oxygen or alkoxy)

(Wherein Z is alkoxy).

delete

(Wherein M is halogen or alkoxy).

The present invention can produce an aromatic carbonate compound and a polycarbonate having a high selectivity by carrying out a carbonic ester reaction between an aliphatic carbonate compound and an aromatic hydroxy compound in the presence of a main catalyst and a cocatalyst.

In addition, the aromatic carbonate compound and the polycarbonate having a stable and high conversion ratio can be produced by limiting the molar ratio of the main catalyst to the cocatalyst and the total concentration of the catalyst.

The process for producing an aromatic carbonate compound of the present invention comprises reacting an aliphatic carbonate compound and an aromatic hydroxy compound with at least one samarium-based primary catalyst represented by the following formula (1) or (2) and at least one In the presence of a cocatalyst of the species.

Catalyst composition

The catalyst composition of the present invention comprises a samarium-based primary catalyst and a Pb, Al, or Nb-based cocatalyst.

The samarium-based primary catalyst may be a compound represented by the following Chemical Formula 1 or 2, or a hydrate thereof.

[Chemical Formula 1]

(Wherein X is alkoxy of 1 to 10 carbon atoms, alkylphenoxy or phenoxy)

(2)

(Wherein R1 and R2 are each independently of the other hydrogen or an alkyl group having 1 to 6 carbon atoms)

In an embodiment, X in Formula 1, which is the main catalyst, may be methoxy, ethoxy, isopropoxy, butoxy, phenoxy, 2.6-di-tertiary-butyl-4-methylphenoxy, and the like. These may be used alone or in combination of two or more.

In the specific examples, R1 and R2 in formula (2), which are the main catalysts, independently may be the same or different, and may be hydrogen, an alkyl group having 1 to 6 carbon atoms, and the like. These may be used alone or in combination of two or more.

In the specific examples, the main catalysts represented by the above-mentioned formula (1) or (2) may be used singly or in combination.

The cocatalyst may be represented by the following general formula (3), (4), or (5).

(3)

(Wherein Y is oxygen or alkoxy)

[Chemical Formula 4]

(Wherein Z is alkoxy).

delete

[Chemical Formula 5]

(Wherein M is halogen or alkoxy).

In an embodiment, the cocatalyst Y in formula (3) may be oxygen or methoxy, ethoxy, isopropoxy, butoxy, and the like. These may be used alone or in combination of two or more.

In embodiments, Z in formula (4), which is the cocatalyst, may be methoxy, ethoxy, isopropoxy, butoxy, and the like. These may be used alone or in combination of two or more.

In an embodiment, M in formula (5) as the cocatalyst may be halogen, alkoxy, or the like. These may be used alone or in combination of two or more.

In a specific example, the cocatalyst represented by the above formula (3), (4) or (5) may be mixed and used.

In embodiments, the molar ratio of the cocatalyst to the main catalyst is preferably from 1: 1 to 3: 1. If the molar ratio of the cocatalyst to the main catalyst is less than 1: 1, the effect of the main catalyst is not exhibited, and if the molar ratio of the cocatalyst to the main catalyst exceeds 3: 1, the equilibrium conversion rate is no longer increased Therefore, the problem of an increase in cost may occur when an excessive amount is included. Accordingly, the molar ratio of the cocatalyst to the main catalyst is preferably 1: 1 to 3: 1.

The total concentration of the main catalyst and the cocatalyst is preferably 0.022 to 0.044 mmol. When the total concentration of the main catalyst and the cocatalyst is less than 0.022 mmol, the conversion rate is inferior. When the total concentration of the main catalyst and the cocatalyst is more than 0.044 mmol, increase in conversion can not be confirmed due to the reaction equilibrium, The total concentration of the cocatalyst is preferably 0.022 to 0.044 mmol.

METHOD FOR PRODUCING AROMATIC CARBONATE COMPOUND

The present invention provides a process for producing an aromatic carbonate compound by reacting an aliphatic carbonate compound and an aromatic hydroxy compound in the presence of the main catalyst and a cocatalyst.

The aliphatic carbonate may be represented by the following formula (6)

(Wherein R1 and R2 are independently an alkyl group having 1 to 6 carbon atoms, which are the same or different from each other).

In an embodiment, examples of the aliphatic carbonate include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, and the like. A double dimethyl carbonate can be preferably used.

The aromatic hydroxy compound may be represented by the following formula (7): < EMI ID =

(Wherein Ar is a substituted or unsubstituted aryl group).

In an embodiment, Ar may be a phenyl group or a naphthyl group, and the substituent may be alkyl of 1-4 carbon atoms, halogen, alkoxy, nitro, cyano, and the like.

In an embodiment, examples of the aromatic hydroxy compound include, but are not limited to, phenol, naphthol, cresol, chlorophenol, alkylphenol, alkoxyphenol, nitrophenol, cyanophenol and the like. Double phenols are preferably used.

In the specific examples, when the reaction temperature is too low, the reaction activity is low and the reaction time or the contact time is also increased, so that the yield of the aromatic carbonate compound is lowered, while when it is too high, the production of by-products is increased and the pressure inside the reactor may be excessively high . In consideration of this, the reaction can be carried out at a temperature of 100 to 280 ° C, preferably 180 to 240 ° C. It is advantageous to produce the target aromatic carbonate compound with stability in the above range and high yield and high selectivity.

In an embodiment, the carbonic ester reaction can proceed at a pressure of 0.1 to 760 mmHg. Preferably, the carbonic ester reaction can proceed at 1 to 350 mmHg.

In embodiments, the reaction may be conducted in the range of 1 second to 150 minutes. This can shorten the reaction time as compared with the average time required in the conventional synthesis method, and therefore can be economically evaluated.

The aromatic carbonate compound prepared from the above method can be preferably applied to polycarbonate polymerization. Examples of the aromatic carbonate compound include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, and the like. . These may be used alone or in combination of two or more, preferably diphenyl carbonate.

In an embodiment, the aromatic carbonate compound produced by the carbonic ester reaction has a high selectivity of 98% or higher.

In an embodiment, the aliphatic carbonate compound by the carbonic ester reaction has a high conversion rate of 7% or more.

In the present invention, the aromatic carbonate compound obtained from the above can be transesterified together with an aromatic dihydroxy compound to produce a polycarbonate.

In an embodiment, the polycarbonate production method is characterized in that the aliphatic carbonate compound and the aromatic hydroxy compound are represented by the formula (1) or (2) and at least one samarium- In the presence of at least one cocatalyst to produce an aromatic carbonate compound; And a second step of transesterifying the aromatic carbonate compound obtained above with an aromatic dihydroxy compound to produce a polycarbonate.

The aromatic dihydroxy compound may be represented by the following general formula (8).

(Wherein, A is a cycloalkylidene, -S- or -SO ₂ of a single bond, C1-C5-alkylene, alkylidene of C1-C5 a, C5-C6 - represents a).

Specific examples of the aromatic dihydroxy compound of Formula 7 include 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis - (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2- , 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, and the like. Of these, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro- Hydroxyphenyl) -cyclohexane, and the like, and 2,2-bis- (4-hydroxyphenyl) -propane, also referred to as bisphenol-A, is most preferred.

In an embodiment, the second step may be carried out in the presence of a catalyst consisting of an alkali, an alkaline earth metal or a mixture thereof.

In an embodiment, the second step may be carried out under reduced pressure at 150 to 300 캜, preferably 160 to 280 캜. And is preferable in reducing the reaction rate and the side reaction in the above temperature range.

In the embodiment, it is preferable that the second step is carried out at a reduced pressure of not more than 75 torr, preferably not more than 30 torr for at least 10 minutes, preferably 15 minutes to 24 hours, in order to reduce the reaction rate and the side reaction.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense. The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

Example

Example  1 to 3 and Comparative Example  1 to 2

Example 1

(Acac) in a molar ratio of 1: 1 with phenol (65.88 g, 700 mmol), dimethyl carbonate (31.53 g, 350 mmol) and a total catalytic amount of 0.022 mmol in an internal 200 ml autoclave reactor having an external heater. ₃ x H ₂ O (0.0049 g, 0.011 mmol) and cocatalyst Al (OPh) ₃ (0.0034 g, 0.011 mmol) were introduced into the reactor, and oxygen in the reactor was replaced with nitrogen. The temperature of the reactor was then increased to 230 ° C and maintained for 15 minutes. After cooling with a chiller, selectivity and conversion were determined by gas chromatography.

Example 2

The reaction was carried out in the same manner as in Example 1 except that the main catalyst Sm (acac) ₃ .xH ₂ O (0.0049 g, 0.011 mmol) and the cocatalyst PbO (0.0024 g, 0.011 mmol) in a 1: Respectively.

Example 3

1 as the catalyst: 1 molar ratio of the main catalyst _{Sm (acac) 3 · x H} 2 O (0.0049 g, 0.011 mmol) and cocatalyst Nb (OCH ₂ CH _{3) 5} except that the (0.0035 g, 0.011 mmol) carried The reaction was carried out in the same manner as in Example 1.

Comparative Example 1

The reaction was carried out in the same manner as in Example 1 except that Sm (acac) ₃ x H ₂ O (0.0098 g, 0.022 mmol) was used as a catalyst.

Comparative Example 2

The reaction was carried out in the same manner as in Example 1 except that the catalyst (Salan) Ti (OiPr) ₂ (0.0102 g, 0.022 mmol) was used.

Example  4 to 9 and Comparative Example  3 to 6

The reaction was carried out in the same manner as in Example 1, except that the molar ratio of the main catalyst to the cocatalyst and the total catalyst concentration in Table 2 were used.

Calculation of selectivity and conversion rate

The present invention relates to a process for producing methylphenyl carbonate (MPC) by reacting dimethyl carbonate (DMC), an aliphatic carbonate compound, with phenol, which is an aromatic hydroxy compound, in a gas phase reaction or liquid phase reaction in the presence of a main catalyst and a cocatalyst, (DPC) and anisole as final products by liquid phase reaction in the presence of the main catalyst and cocatalyst, and the selectivity of the final product diphenyl carbonate (DPC) as well as the intermediate product The choice of methylphenyl carbonate (MPC) also has important implications. The selectivity (S) of the intermediate product and the final product and the conversion rate (X) of the initial reactant can be obtained by the following formula.

One) MPC  And DPC The choice of S

S (%) = [number of MPC and DPC moles produced] / [number of moles of MPC, DPC, and anisole produced] × 100

2) DMC Conversion rate X (%)

X = [number of moles of produced MPC, DPC, and anisole] / [number of moles of reacted DMC] x 100

Table 1 and Table 2 show the results of the above Examples and Comparative Examples. Table 1 below shows the effect of selectivity (S) of MPC and DPC on the selectivity (S) when Al, Pb co- Table 2 below shows the effect of the total catalyst concentration and the mole ratio of the main catalyst and the cocatalyst on the conversion (X) of DMC as a reactant.

As shown in Table 1, in Examples 1 to 3 using the cocatalyst together with the main catalyst, it was confirmed that the selectivity of MPC and DPC was higher than that of Comparative Examples 1 and 2 in which only the main catalyst was used and no cocatalyst was used .

Further, as shown in Table 2, when the molar ratio of the main catalyst and the cocatalyst was 1: 1 to 3: 1, and the total concentration of the main catalyst and the cocatalyst exceeded 0.022 mmol, the conversion of DMC was confirmed to be high . It can be seen that the higher the ratio of the main catalyst, the higher the conversion rate. However, when the total concentration of the catalyst is less than 0.022 mmol, the conversion is lowered.

Method for producing polycarbonate resin

In the process for producing a polycarbonate resin, the polycarbonate resin can be produced by an ester exchange reaction between an aromatic carbonate compound produced by the carbonic ester reaction and an aromatic dihydroxy compound.

The ester reaction preferably has a reaction pressure of 30 torr or less, a reaction temperature of 160 to 280 ° C, and a reaction time of 15 minutes or more and 24 hours or less, and further comprises a catalyst composed of an alkaline earth metal or a mixture thereof, Can be produced.

196 Kg (906 mol) of the aromatic carbonate compound prepared in Example 1, 180 Kg (788 mol) of 2,2-bis (4-hydroxyphenyl) propane, KOH 120 ppb (relative to 1 mol of BPA) was added in turn to the reactor, and then nitrogen was used to remove oxygen in the reactor. The temperature of the reactor was raised to 160 ° C to dissolve the raw material, and then the temperature was raised to 190 ° C and maintained for 6 hours. After 6 hours, the reactor was heated to 220 ° C and the pressure was maintained at 70 mmHg for 1 hour. The temperature was raised to 260 ° C. and maintained at 20 mmHg for 1 hour. The pressure was lowered to 0.5 mmHg and maintained for 1 hour to synthesize a polycarbonate. The molecular weight of the prepared polycarbonate was Mw 22.0 K.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, It is to be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.

Claims (13)

At least one samarium-based primary catalyst represented by the following formula (2); And at least one cocatalyst represented by the following general formula (3), (4) or (5):
(2)

(Wherein R1 and R2 are each independently an alkyl group having 1 to 6 carbon atoms which are the same or different from each other)
(3)

(Wherein Y is oxygen)
[Chemical Formula 4]

(Wherein Z is alkoxy).
[Chemical Formula 5]

(Wherein M is alkoxy).
The catalyst composition for synthesizing an aromatic carbonate compound according to claim 1, wherein the molar ratio of the main catalyst to the cocatalyst is from 1: 1 to 3: 1.
The aliphatic carbonate compound and the aromatic hydroxy compound are reacted in the presence of at least one samarium-based primary catalyst represented by the following formula (2) and at least one cocatalyst represented by the following formula (3), (4) A process for producing an aromatic carbonate compound by:

(2)

(Wherein R1 and R2 are each independently an alkyl group having 1 to 6 carbon atoms which are the same or different from each other)
(3)

(Wherein Y is oxygen)
[Chemical Formula 4]

(Wherein Z is alkoxy).
[Chemical Formula 5]

(Wherein M is alkoxy).
4. The method of claim 3, wherein the molar ratio of the main catalyst to the cocatalyst is from 1: 1 to 3: 1.
5. The method of claim 4, wherein the total concentration of the main catalyst and the cocatalyst is 0.022 to 0.044 mmol.
The aromatic carbonate compound according to claim 3, wherein the aliphatic carbonate compound is a dialkyl carbonate compound represented by the following formula (6)
[Chemical Formula 6]

(Wherein R ₁ and R ₂ are independently an alkyl group having 1 to 6 carbon atoms, which are the same or different from each other).
The aromatic carbonate compound according to claim 3, wherein the aromatic hydroxy compound is a hydroxyaryl compound represented by the following formula (7):
(7)

(Wherein Ar is an aryl group substituted or unsubstituted with alkyl, halogen, alkoxy, nitro or cyano having 1-4 carbons).
The aromatic carbonate compound according to claim 3, wherein the selectivity of the aromatic carbonate compound is 95% or more.
4. The process for producing an aromatic carbonate compound according to claim 3, wherein the conversion of the aliphatic carbonate compound is 7% or more.
delete The aliphatic carbonate compound and the aromatic hydroxy compound are reacted in the presence of at least one samarium-based primary catalyst represented by the following formula (2) and at least one cocatalyst represented by the following formula (3), (4) A first step of producing an aromatic carbonate compound: and
And a second step of transesterifying the aromatic carbonate compound and the aromatic dihydroxy compound to produce a polycarbonate.

(2)

(Wherein R1 and R2 are each independently an alkyl group having 1 to 6 carbon atoms which are the same or different from each other)
(3)

(Wherein Y is oxygen)
[Chemical Formula 4]

(Wherein Z is alkoxy).
[Chemical Formula 5]

(Wherein M is alkoxy).
12. The method for producing polycarbonate resin according to claim 11, further comprising a catalyst made of an alkali, an alkaline earth metal, or a mixture thereof in the second step.
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