KR20220125215A - Method for preparing organic zinc catalyst composition - Google Patents

Abstract

A means for stably obtaining polyalkylene carbonate in high yield by reacting carbon dioxide with an epoxide is provided. More specifically, a zinc catalyst composition obtained by reacting a zinc compound and an aliphatic carboxylic acid, wherein the aliphatic carboxylic acid content is less than 5% by mass relative to the composition is provided.

Description

Method for preparing organic zinc catalyst composition

The present disclosure relates to a method for preparing a zinc catalyst composition, a zinc catalyst composition prepared by the method, and the like. In addition, the contents of all documents described herein are incorporated herein by reference.

As an organozinc catalyst that catalyzes the reaction for obtaining polyalkylene carbonate from carbon dioxide and epoxide, it is known to use an organozinc compound obtained by reacting an inorganic zinc compound, an aliphatic dicarboxylic acid, and an aliphatic monocarboxylic acid (for example, , Patent Documents 1 and 2).

Patent Document 1: Japanese Patent Laid-Open No. 2007-302731 Patent Document 2: International Publication No. 2011/142259

After reacting a zinc compound with an aliphatic carboxylic acid, the present inventors use the reaction composition as a catalyst to perform a reaction to obtain a polyalkylene carbonate from carbon dioxide and an epoxide, the yield of the polyalkylene carbonate is stable found that it was not. Then, the method of obtaining polyalkylene carbonate in high yield stably was examined.

The present inventors reacted a zinc compound with an aliphatic carboxylic acid to obtain a reaction composition (zinc catalyst composition), and then used the reaction composition as a catalyst when reacting carbon dioxide with an epoxide. When the amount of reactive aliphatic carboxylic acid was in a specific range, the possibility that polyalkylene carbonate could be obtained especially in a high yield by reaction of a carbon dioxide and an epoxide was discovered, and further examination was repeated.

The present disclosure includes, for example, the subject matter described in the following paragraphs.

Section 1.

A zinc catalyst composition obtained by reacting a zinc compound and an aliphatic carboxylic acid, wherein the content of the aliphatic carboxylic acid is less than 5% by mass relative to the composition.

Section 2.

The composition according to item 1, wherein the zinc compound is at least one selected from the group consisting of zinc oxide and zinc hydroxide.

Section 3.

The composition according to item 1 or 2, wherein the aliphatic carboxylic acid is at least one selected from the group consisting of aliphatic dicarboxylic acids and aliphatic monocarboxylic acids.

Section 4.

The composition according to item 3, wherein the aliphatic monocarboxylic acid is at least one selected from the group consisting of formic acid, acetic acid, propionic acid and trifluoroacetic acid.

Section 5.

The composition according to any one of claims 1 to 4, wherein the aliphatic carboxylic acid comprises at least an aliphatic dicarboxylic acid.

Section 6.

The composition according to any one of Items 3 to 5, wherein the aliphatic dicarboxylic acid is at least one selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and sebacic acid.

Section 7.

A method for producing a polyalkylene carbonate comprising reacting carbon dioxide with an epoxide in the presence of the zinc catalyst composition according to any one of claims 1 to 6.

A zinc catalyst composition capable of obtaining polyalkylene carbonate in high yield by using it as a catalyst in a reaction for obtaining polyalkylene carbonate from carbon dioxide and epoxide is provided. In addition, if it is the zinc catalyst composition, a polyalkylene carbonate having a relatively high molecular weight (that is, a relatively high molecular weight) can be obtained.

1 is a TG/DTA apparatus for measuring glutaric acid in the residual slurry after reacting a zinc compound (specifically, zinc oxide) and an aliphatic carboxylic acid (specifically, glutaric acid) in Example 5; It is a schematic diagram showing extracts of TG results among the results.

Hereinafter, each embodiment included in the present disclosure will be described in more detail. The present disclosure preferably includes, but is not limited to, a specific zinc catalyst composition, a method for producing the zinc catalyst composition, a method for producing a polyalkylene carbonate using the zinc catalyst composition, and the like, and the present disclosure is not limited thereto. Disclosed are all that would be appreciated by one of ordinary skill in the art.

The zinc catalyst composition included in the present disclosure is a zinc catalyst composition obtained by reacting a zinc compound and an aliphatic carboxylic acid, wherein the content of the aliphatic carboxylic acid is less than 5% by mass relative to the composition. The zinc catalyst composition is sometimes referred to as "the catalyst composition of the present disclosure."

As described above, the zinc catalyst composition of the present disclosure is obtained by reacting a zinc compound and an aliphatic carboxylic acid. In other words, the catalyst composition of the present disclosure may be said to be a reaction composition of a zinc compound and an aliphatic carboxylic acid.

As a zinc compound, an inorganic zinc compound is preferable. Examples of the inorganic zinc compound include zinc oxide, zinc sulfate, zinc chlorate, zinc nitrate, zinc acetate, and zinc hydroxide. Among them, zinc oxide and zinc hydroxide are preferred, and zinc oxide This is particularly preferred. A zinc compound can be used individually by 1 type or in combination of 2 or more types.

As aliphatic carboxylic acid, aliphatic monocarboxylic acid, aliphatic dicarboxylic acid, aliphatic tricarboxylic acid, etc. can be used, for example. Especially, it is preferable to use an aliphatic dicarboxylic acid. Aliphatic carboxylic acid can be used individually by 1 type or in combination of 2 or more type. Especially, it is preferable to use an aliphatic dicarboxylic acid, or to use an aliphatic dicarboxylic acid and an aliphatic monocarboxylic acid. Moreover, when using an aliphatic dicarboxylic acid and an aliphatic monocarboxylic acid, it is preferable to use the aliphatic monocarboxylic acid so that the molar ratio with respect to the said aliphatic dicarboxylic acid may become about 0.0001-0.1 or about 0.001-0.05.

The aliphatic dicarboxylic acid is preferably an aliphatic dicarboxylic acid having 2 to 15 carbon atoms (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15); More specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, etc. are mentioned, for example. Moreover, as an aliphatic monocarboxylic acid, C1-C15 (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15) aliphatic monocarboxyl. An acid is preferable, and more specifically, formic acid, acetic acid, propionic acid, trifluoroacetic acid, etc. are mentioned, for example. The aliphatic tricarboxylic acid is preferably an aliphatic tricarboxylic acid having 3 to 15 carbon atoms (3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15), and more specifically As examples, tricarballylic acid and 3,3',3''-nitrilotripropionic acid etc. are mentioned. Among the aliphatic carboxylic acids, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, formic acid, acetic acid and propionic acid are particularly preferable.

As described above, in the catalyst composition of the present disclosure, the content of the aliphatic carboxylic acid is less than 5% by mass relative to the composition. For example, 4.5 mass% or less, 4 mass% or less, 3.5 mass% or less, 3 mass% or less, 2.5 mass% or less, 2 mass% or less, 1.5 mass% or less, 1 mass% or less, or 0.5 mass% or less good night. Moreover, the minimum in particular of content of this aliphatic carboxylic acid is although it does not restrict|limit, For example, 0.01 mass % or more, 0.02 mass % or more, or 0.05 mass % or more is illustrated.

Moreover, in the catalyst composition of this indication, when content of an aliphatic carboxylic acid is 2.5 mass % or more (less than 5 mass %) with respect to a composition, the value of the mass average molecular weight of the polyalkylene carbonate obtained using this catalyst composition tends to be relatively high. For this reason, when it is desired to obtain a polyalkylene carbonate having a mass average molecular weight of, for example, 1 million or more (more specifically, about 1 to 2 million), the carboxylic acid content in the catalyst composition is It is preferable to set it as 5 mass % or more.

The aliphatic carboxylic acid may remain unreacted when the zinc compound and the aliphatic carboxylic acid are reacted, or may be added to the zinc catalyst. Therefore, when using an unreacted thing, content of the aliphatic carboxylic acid in the catalyst composition of this indication can be adjusted by adjusting the reaction conditions of a zinc compound and an aliphatic carboxylic acid. More specifically, for example, by lengthening the time for making a zinc compound and aliphatic carboxylic acid react, content of the aliphatic carboxylic acid in the catalyst composition obtained can be reduced.

The content of the aliphatic carboxylic acid in the catalyst composition of the present disclosure is determined from TG (thermogravimetry) data. Specifically, TG (thermogravimetry) is performed on the dried catalyst composition at 30 to 300°C 10°C/min atmosphere N ₂ 200 mL/min, and sample 5 mg±1 mg. In the TG (thermogravimetric measurement) data, T ₁ is a tangent at 100° C., T ₂ is a tangent at 250° C., and T ₃ is a tangent at an inflection point between 100 and 250° C. Next, the mass W ₁ at the intersection of the tangents T ₁ and T ₃ is obtained. In addition, the mass W ₂ at the intersection of the tangents T ₂ and T ₃ is obtained. Let the mass difference (W1 _- W2) between intersections be aliphatic carboxylic acid content, and let the value which divided _the aliphatic carboxylic acid content by the mass (W1) _of the intersection on the low-temperature side be an aliphatic carboxylic acid content rate. The carboxylic acid content (C _CA [%]) is expressed as follows.

C _CA [%] = (W ₁ -W ₂ )/W ₁ × 100

C _CA : Glutaric acid (aliphatic carboxylic acid) content [%]

W ₁ : mass of low temperature side [mg]

W ₂ : mass of high temperature side [mg]

The use ratio of the zinc compound and the aliphatic carboxylic acid is, for example, about 0.1 to 1.2 mol of the aliphatic carboxylic acid, more preferably about 0.5 to 1.2 mol, and about 0.8 to 1.0 mol, per 1 mol of the zinc compound. is more preferable.

As reaction of a zinc compound and an aliphatic carboxylic acid, a well-known reaction can be used, For example, the reaction conditions described in the said patent document 1 or 2 can be used. Moreover, it does not specifically limit as a reaction catalyst, For example, More specifically, various organic solvents can be used. Specific examples of such an organic solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene, aliphatic hydrocarbon solvents such as hexane, heptane and cyclohexane, dichloromethane, chloroform, 1,2-dichloroethane, and the like. of halogenated hydrocarbon solvents, alcohol solvents such as methanol, ethanol and isopropanol, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, ester solvents such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, Ketone solvents, such as methyl isobutyl ketone, carbonate solvents, such as dimethyl carbonate, diethyl carbonate, and propylene carbonate, acetonitrile, dimethylformamide, dimethyl sulfoxide, hexamethylphosphotriamide, etc. are mentioned. Among them, an aromatic hydrocarbon-based solvent such as benzene, toluene or xylene is preferable from the viewpoint of smoothly proceeding the reaction.

The amount of the reaction solvent used is not particularly limited, but it is preferably 500 to 10000 parts by mass based on 100 parts by mass of the zinc compound, for example, from the viewpoint of facilitating the reaction and obtaining an effect suitable for the amount used.

Although reaction temperature is not specifically limited, For example, it is preferable that it is 0-110 degreeC, It is more preferable that it is 20-100 degreeC, It is still more preferable that it is 50-80 degreeC. When the reaction temperature is 0°C or higher, the reaction can proceed more efficiently. In addition, when the reaction temperature is 110° C. or less, a side reaction becomes more difficult to occur, and a decrease in the yield can be suppressed. Since the reaction time varies with the reaction temperature, it cannot be said uniformly, but is, for example, 1 to 20 hours. A zinc catalyst composition having a desired amount of aliphatic carboxylic acid can be obtained by washing the obtained catalyst with an organic solvent such as acetone or methanol.

In addition, it is preferable to carry out the reaction in an inert gas (for example, nitrogen) atmosphere.

Although not particularly limited, a particularly preferred embodiment of the zinc catalyst composition of the present disclosure includes a zinc catalyst composition obtained by reacting at least zinc oxide and glutaric acid. The zinc catalyst composition preferably includes, for example, a zinc compound in which only zinc oxide is reacted, an aliphatic carboxylic acid in which only glutaric acid is reacted, and a zinc oxide and glutaric acid alone are reacted.

The zinc catalyst composition of the present disclosure is particularly preferably used for catalyzing a reaction (copolymerization reaction) for obtaining a polyalkylene carbonate from carbon dioxide and an epoxide. In addition, the present disclosure preferably includes a method of preparing polyalkylene carbonate by reacting carbon dioxide and epoxide in the presence of the zinc catalyst composition of the present disclosure (copolymerization reaction).

Although it does not specifically limit as an epoxide, For example, ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, isobutylene oxide, 1-pentene oxide, 2-pentene oxide , 1-hexene oxide, 1-octene oxide, 1-decene oxide, cyclopentene oxide, cyclohexene oxide, styrene oxide, vinylcyclohexane oxide, 3-phenylpropylene oxide, 3, 3, 3-trifluoropropylene oxide, 3-naphthylpropylene oxide, 3-phenoxypropylene oxide, 3-naphthoxypropylene oxide, butadiene monooxide, allyl glycidyl ether, 3-vinyloxy propylene oxide Seed, 3-trimethylsilyloxypropylene oxide, etc. are mentioned. Especially, from a viewpoint of having high reactivity, ethylene oxide and propylene oxide are preferable. These epoxides may be used individually, respectively, and may be used in combination of 2 or more type.

Although the working pressure of carbon dioxide is not specifically limited, Usually, it is preferable that it is 0.1-20 MPa, It is more preferable that it is 0.1-10 MPa, It is still more preferable that it is 0.1-5 MPa. Carbon dioxide may be supplied collectively, and may be supplied intermittently or continuously.

The usage-amount of the said zinc catalyst composition is, for example, it is preferable that it is 0.001-50 mass parts with respect to 100 mass parts of epoxides, It is more preferable that it is 0.01-40 mass parts, It is still more preferable that it is 0.1-30 mass parts.

It does not specifically limit as a solvent used for the said copolymerization reaction, Various organic solvents can be used. Specific examples of such an organic solvent include aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; halogenated hydrocarbon solvents such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene and bromobenzene; ester solvents such as ethyl acetate, isopropyl acetate, and butyl acetate; ether solvents such as tetrahydrofuran and 1,4-dioxane; and carbonate solvents such as dimethyl carbonate, diethyl carbonate and propylene carbonate.

The amount of the solvent used is not particularly limited, but from the viewpoint of facilitating the reaction and obtaining an effect appropriate to the amount used, for example, it is preferably 500 to 10000 parts by mass based on 100 parts by mass of the epoxide. Moreover, it is not necessary to use a solvent.

In addition, the production method of the polyalkylene carbonate may be in other polymerization forms such as solution polymerization and precipitation polymerization depending on the type and amount of the solvent used. is very high

Although the reaction temperature of this copolymerization reaction is although it does not specifically limit, For example, it is preferable that it is 20-100 degreeC, and it is more preferable that it is 40-80 degreeC. Since the reaction time varies with the reaction temperature, it cannot be said uniformly, but is, for example, 2 to 40 hours.

A method of mixing the zinc catalyst composition with carbon dioxide and epoxide is not particularly limited, but for ease of mixing, for example, there is a method of adding carbon dioxide after mixing the zinc catalyst composition with the epoxide.

In addition, the polyalkylene carbonate obtained in this way can be isolated by, for example, filtering or washing with a dilute acid aqueous solution or a diluted alkali aqueous solution to remove a catalyst, etc. can

In addition, as used herein, “comprising” includes “consisting essentially of” and “consisting of” (The term “comprising” includes “consisting essentially of” and “consisting of.”). In addition, this disclosure includes all combinations of any of the elements described herein.

In addition, various characteristics (properties, structures, functions, etc.) described with respect to each embodiment of the present disclosure described above may be combined in any way in specifying the subject matter included in the present disclosure. That is, the present disclosure includes all subject matter that consists of all combinations of each combinable characteristic described herein.

(Example)

Hereinafter, although an example is shown and embodiment of this indication is described more specifically, embodiment of this indication is not limited to the following example.

Each analysis was performed by the following method.

<Measurement of residual glutaric acid>

The mixed slurry remaining after the reaction was dried under reduced pressure at 70°C for 1 hour to obtain a solid. About 5 mg of the obtained solid material was introduce|transduced into the TG/DTA apparatus. It heated up at 10 degreeC/min from 30 degreeC to 300 degreeC in nitrogen atmosphere, and the amount of residual glutaric acid was calculated|required from the weight loss originating in residual glutaric acid.

ㆍAnalysis device: TG/DTA 7220 (manufactured by Hitachi High-Tech Science Co., Ltd.)

ㆍSample pretreatment: 1 g of the slurry was collected and dried at 70°C under reduced pressure (1kPa·abs) for 1Hr

ㆍAnalysis conditions: 30 to 300°C 10°C/min atmosphere N ₂ 200 mL/min, sample 5 mg±1 mg

Analysis conditions: In the TG (thermogravimetric measurement) data, T ₁ was the tangent at 100°C, T ₂ was the tangent at 250°C, and T ₃ was the tangent at the inflection point between 100 and 250°C. Next, the mass W ₁ at the intersection of the tangents T ₁ and T ₃ was calculated. In addition, the mass W ₂ at the intersection of the tangents T ₂ and T ₃ was obtained. Let the mass difference (W ₁ -W ₂ ) between intersections be the glutaric acid (aliphatic carboxylic acid) content, and the value obtained by dividing the glutaric acid (aliphatic carboxylic acid) content by the mass (W ₁ ) of the intersection on the low temperature side It was set as the content rate of glutaric acid (aliphatic carboxylic acid) (refer FIG. 1 and Formula 1).

C _CA [%] = (W ₁ -W ₂ )/W ₁ × 100 (Equation 1)

C _CA : Glutaric acid (aliphatic carboxylic acid) content [%]

W ₁ : mass of low temperature side [mg]

W ₂ : mass of high temperature side [mg]

<Measurement of molecular weight of polyalkylene carbonate>

For the mass average molecular weight of the polyalkylene carbonate described in each Example and Production Example, using a gel permeation chromatography (GPC) measuring device (manufactured by Waters, product name “waters2695” separation module), the following conditions It is the mass average molecular weight in terms of standard polystyrene measured by . The sample was introduced into the measuring device as a N,N-dimethylformamide solution having a polymer concentration of 0.3% by mass.

GPC measurement conditions

ㆍColumn: Showa Denko “Shodex OHpak SB-804 HQ”, “Shodex”

OHpak SB-805” connected sequentially

ㆍColumn temperature: 40℃

ㆍDeveloping solvent: 5 mmol/L LiBr-N, N-dimethylformamide solution

ㆍFlow rate: 1.0mL/min

ㆍDetector: Differential Refractometer

ㆍStandard sample: polystyrene

Example 1

<Production of zinc catalyst>

81 g (1 mol) of zinc oxide, 129 g (98 mmol) of glutaric acid, 1.5 g (2 mmol) of acetic acid and 776 g of toluene were placed in a 1.5 L volume four-necked flask equipped with a cooling tube, a thermometer and a stirrer. Then, it heated up to 55 degreeC in nitrogen atmosphere, and stirred at the same temperature for 20 hours, and made it react. Thereafter, the temperature was raised to 110° C., stirred at the same temperature for 2 hours to azeotrope, water was removed, cooled to room temperature, filtered and dried to obtain a zinc catalyst composition having a free carboxylic acid content of 0.10 mass% 190 g were obtained. In addition, the free carboxylic acid is specifically residual glutaric acid.

<Production of polyalkylene carbonate>

20.5 g of the above organic zinc catalyst, 510 g of dimethyl carbonate, 70 g (1.2 mol) of propylene oxide and carbon dioxide were added to a 1 L volume autoclave equipped with a thermometer and a stirrer, and the reaction system was set to 60 ° C., 0.99 MPa, and consumed The polymerization reaction was performed for 24 hours while supplying carbon dioxide. Thereafter, the autoclave was cooled and depressurized to obtain a white polymer slurry. After filtering this, it refine|purified with methanol, and it dried under reduced pressure and obtained 94.6 g (yield 77.5%) of polypropylene carbonate.

Example 2

<Production of zinc catalyst>

A zinc catalyst composition having a free carboxylic acid content of 0.35 mass % in the same manner as in Example 1 except that the reaction time was changed to 20 hours and reacted for 10 hours, and the zinc catalyst was washed using 600 g of acetone in the filtration step after the reaction. got

<Production of polyalkylene carbonate>

Using the obtained zinc catalyst composition, it carried out similarly to Example 1, and obtained 87.0 g (yield 71.3%) of polypropylene carbonate.

Example 3

<Production of zinc catalyst>

The zinc catalyst composition whose free carboxylic acid amount is 0.65 mass % was obtained like Example 2 except not washing|cleaning the sample by acetone in the filtration process after reaction.

<Production of polyalkylene carbonate>

Using the obtained zinc catalyst composition, it carried out similarly to Example 1, and obtained 92.0 g (yield 75.4%) of polypropylene carbonate.

Example 4

<Production of organic zinc catalyst>

Except for changing the reaction time to 20 hours and making it react for 6 hours, it carried out similarly to Example 1, and obtained the zinc catalyst composition whose free carboxylic acid amount is 2.00 mass %.

<Production of polyalkylene carbonate>

Using the obtained zinc catalyst composition, it carried out similarly to Example 1, and obtained 84.0 g (yield 68.9%) of polypropylene carbonate.

Example 5

<Production of zinc catalyst>

Glutaric acid was added to the catalyst composition obtained in Example 4 to obtain a zinc catalyst composition having an amount of free carboxylic acid of 3.00 mass%.

<Production of polyalkylene carbonate>

Using the obtained zinc catalyst composition, it carried out similarly to Example 1, and obtained 79.6g (yield 65.3%) of polypropylene carbonate.

Comparative Example 1

<Production of zinc catalyst>

Except for changing the reaction time into 20 hours and making it react for 1 hour, it carried out similarly to Example 1, and obtained the zinc catalyst composition whose free carboxylic acid amount is 5.00 mass %.

<Production of polyalkylene carbonate>

Using the obtained zinc catalyst composition, it carried out similarly to Example 1, and obtained 20 g of polypropylene carbonates.

The above results and the molecular weight of each obtained polypropylene carbonate are summarized and shown in Table 1.

residual free carboxylic acid
(mass%) Polyalkylene carbonate yield (%) Mass average molecular weight (Mw)
(only) Example 1 0.10 77.8 30.4 Example 2 0.35 71.3 32.8 Example 3 0.65 75.4 35.5 Example 4 2.00 68.9 28.9 Example 5 3.00 65.3 125.5 Comparative Example 1 5.00 42.4 13.5

Claims (7)

A zinc catalyst composition obtained by reacting a zinc compound and an aliphatic carboxylic acid, wherein the content of the aliphatic carboxylic acid is less than 5% by mass with respect to the composition.
composition.
According to claim 1,
The zinc compound is at least one selected from the group consisting of zinc oxide and zinc hydroxide.
composition.
3. The method of claim 1 or 2,
The aliphatic carboxylic acid is at least one selected from the group consisting of aliphatic dicarboxylic acids and aliphatic monocarboxylic acids.
composition.
4. The method of claim 3,
The aliphatic monocarboxylic acid is at least one selected from the group consisting of formic acid, acetic acid, propionic acid and trifluoroacetic acid.
composition.
5. The method according to any one of claims 1 to 4,
wherein the aliphatic carboxylic acid comprises at least an aliphatic dicarboxylic acid.
composition.
6. The method according to any one of claims 3 to 5,
The aliphatic dicarboxylic acid is at least one selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and sebacic acid.
composition.
A method comprising reacting carbon dioxide with an epoxide in the presence of the zinc catalyst composition according to any one of claims 1 to 6
A method for producing polyalkylene carbonate.

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