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WO2021140869A1 - Method for producing organozinc catalyst - Google Patents

Method for producing organozinc catalyst Download PDF

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Publication number
WO2021140869A1
WO2021140869A1 PCT/JP2020/047342 JP2020047342W WO2021140869A1 WO 2021140869 A1 WO2021140869 A1 WO 2021140869A1 JP 2020047342 W JP2020047342 W JP 2020047342W WO 2021140869 A1 WO2021140869 A1 WO 2021140869A1
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Prior art keywords
acid
reaction
catalyst
mass
organozinc
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PCT/JP2020/047342
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French (fr)
Japanese (ja)
Inventor
匠 藤野
直久 早水
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住友精化株式会社
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Priority to KR1020227015128A priority Critical patent/KR20220122599A/en
Priority to JP2021569803A priority patent/JPWO2021140869A1/ja
Publication of WO2021140869A1 publication Critical patent/WO2021140869A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/06—Zinc compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/235—Saturated compounds containing more than one carboxyl group
    • C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates

Definitions

  • the present disclosure relates to a method for producing an organozinc catalyst, an organozinc catalyst produced by the production method, and the like.
  • the contents of all documents described herein are incorporated herein by reference.
  • an organozinc compound obtained by reacting an inorganic zinc compound with an aliphatic dicarboxylic acid and an aliphatic monocarboxylic acid is used as an organozinc catalyst for catalyzing a reaction for obtaining a polyalkylene carbonate from carbon dioxide and epoxide.
  • the present inventors studied for the purpose of efficiently obtaining the organozinc catalyst.
  • the present inventors In producing an organozinc catalyst, the present inventors have found that the amount of water in the reaction system when reacting an inorganic zinc compound with an aliphatic carboxylic acid may affect the yield of the obtained organozinc catalyst. , Further examination was repeated.
  • Item 1 Including reacting inorganic zinc compounds and aliphatic carboxylic acids The water content of the reaction system at the start of the reaction is 0.05 to 10% by mass with respect to the inorganic zinc compound.
  • Method for producing organozinc compound Item 2.
  • Item 2. The production method according to Item 1, wherein the inorganic zinc compound is at least one selected from the group consisting of zinc oxide and zinc hydroxide.
  • Item 3. Item 2. The production method according to Item 1 or 2, wherein the aliphatic carboxylic acid is at least one selected from the group consisting of an aliphatic dicarboxylic acid and an aliphatic monocarboxylic acid.
  • Item 8. An organozinc compound obtained by the production method according to any one of Items 1 to 7.
  • Item 9. Item 8.
  • an inorganic zinc compound is reacted with an aliphatic carboxylic acid in producing an organozinc compound which can be preferably used as a catalyst (particularly, a catalyst in a reaction for obtaining a polyalkylene carbonate from carbon dioxide and epoxide).
  • an organozinc compound which can be preferably used as a catalyst (particularly, a catalyst in a reaction for obtaining a polyalkylene carbonate from carbon dioxide and epoxide).
  • the yield of the obtained polypropylene carbonate can be improved.
  • the present disclosure preferably includes, but is not limited to, a method for producing a specific organozinc compound, an organozinc compound produced by the method, and the use of the organozinc compound as a catalyst.
  • the present disclosure includes everything disclosed herein and recognizable to those skilled in the art.
  • the method for producing an organozinc compound included in the present disclosure includes reacting an inorganic zinc compound with an aliphatic carboxylic acid, and the water content of the reaction system at the start of the reaction is 0 with respect to the zinc compound. It is a manufacturing method of .05 to 10% by mass.
  • the production method included in the present disclosure may be referred to as "the organic zinc compound production method of the present disclosure”.
  • the organozinc compound may be referred to as "organozinc compound of the present disclosure”.
  • the organozinc compound of the present disclosure can be used as a catalyst (particularly, a catalyst in a reaction for obtaining a polyalkylene carbonate from carbon dioxide and an epoxide).
  • the catalyst may be referred to as "the catalyst of the present disclosure”.
  • the organozinc compound of the present disclosure is obtained by reacting an inorganic zinc compound with an aliphatic carboxylic acid.
  • the organozinc compound of the present disclosure can be said to be a reaction product of an inorganic zinc compound and an aliphatic carboxylic acid.
  • Examples of the inorganic zinc compound include zinc oxide, zinc sulfate, zinc chlorate, zinc nitrate, zinc acetate, and zinc hydroxide, and zinc oxide and zinc hydroxide are more preferable.
  • the inorganic zinc compound may be used alone or in combination of two or more.
  • an aliphatic carboxylic acid for example, an aliphatic monocarboxylic acid, an aliphatic dicarboxylic acid, an aliphatic tricarboxylic acid and the like can be used. Of these, it is preferable to use an aliphatic dicarboxylic acid.
  • the aliphatic carboxylic acid can be used alone or in combination of two or more. Of these, it is preferable to use an aliphatic dicarboxylic acid, or to use an aliphatic dicarboxylic acid and an aliphatic monocarboxylic acid.
  • the molar ratio of the aliphatic monocarboxylic acid to the aliphatic dicarboxylic acid is about 0.0001 to 0.1 or 0.001 to 0.05. It is preferable to use it so as to be a degree.
  • 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) is preferable. More specifically, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid and the like can be mentioned.
  • the aliphatic monocarboxylic acid has 1 to 15 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15).
  • Monocarboxylic acids are preferred, and more specific examples include formic acid, acetic acid, propionic acid, trifluoroacetic acid and the like.
  • an aliphatic tricarboxylic acid having 3 to 15 carbon atoms is preferable, and more specific.
  • examples thereof include tricarbaryl acid and 3,3', 3''-nitrilotripropionic acid.
  • malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, formic acid, acetic acid, and propionic acid are particularly preferable.
  • the water content of the reaction system at the start of the reaction is 0.05 to 10% by mass with respect to the inorganic zinc compound.
  • the lower limit of the range may be, for example, about 0.1, 0.15, 0.2, or 0.25% by mass.
  • the upper limit of the range may be, for example, about 9.5, 9, 8.5, 8, 7.5, 7, 6.5, or 6% by mass.
  • the water content of the reaction system at the start of the reaction is measured as follows. That is, after charging the raw materials (inorganic zinc compound, aliphatic carboxylic acid and other components (for example, solvent)) into the reaction vessel, the mixture is stirred, and 0.5 g of the mixture is sampled within 1 minute from the start of stirring. 5 g of methanol is added to the mixture and mixed. After filtering the mixed solution with a 0.45 ⁇ m filter, the filtrate is introduced into a Karl Fischer moisture meter to measure the water content.
  • the raw materials inorganic zinc compound, aliphatic carboxylic acid and other components (for example, solvent)
  • the ratio of the inorganic zinc compound and the aliphatic carboxylic acid used is preferably about 0.1 to 1.5 mol, preferably about 0.5 to 1.2 mol, with respect to 1 mol of the inorganic zinc compound. Is more preferable, and about 0.8 to 1.0 mol is further preferable.
  • the reaction between the inorganic zinc compound and the aliphatic carboxylic acid a known reaction can be used, and for example, the reaction conditions described in Patent Document 1 or 2 can be used. More specifically, for example, the reaction solvent is not particularly limited, and various organic solvents can be used. Specific examples of such an organic solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene, aliphatic solvent such as hexane, heptane and cyclohexane, dichloromethane, chloroform, 1 and 2.
  • aromatic hydrocarbon solvents such as benzene, toluene and xylene
  • aliphatic solvent such as hexane, heptane and cyclohexane
  • dichloromethane chloroform
  • -Halogen-based hydrocarbon solvents such as dichloroethane, alcohol-based solvents such as methanol, ethanol and isopropanol, ether-based solvents such as diethyl ether, tetrahydrofuran and dioxane, ester-based solvents such as ethyl acetate and butyl acetate, acetone and methylethiel ketone.
  • Ketone-based solvents such as methyl isobutyl ketone
  • carbonate-based solvents such as dimethyl carbonate, diethyl carbonate and propylene carbonate
  • acetonitrile dimethylformamide, dimethylsulfoxide, hexamethylphosphotriamide and the like.
  • aromatic hydrocarbon solvents such as benzene, toluene, and xylene are preferable from the viewpoint of facilitating the reaction.
  • the amount of the reaction solvent used is not particularly limited, but from the viewpoint of facilitating the reaction and obtaining an effect commensurate with the amount used, for example, 500 to 10000 parts by mass with respect to 100 parts by mass of the inorganic zinc compound. Is preferable.
  • the reaction temperature is not particularly limited, but is preferably 0 to 110 ° C, more preferably 20 to 100 ° C, and even more preferably 50 to 80 ° C.
  • the reaction temperature is 0 ° C. or higher, the reaction can proceed more efficiently. Further, when the reaction temperature is 110 ° C. or lower, side reactions are less likely to occur, and a decrease in yield can be suppressed.
  • the reaction time varies depending on the reaction temperature and cannot be unequivocally determined, but is, for example, about 1 to 50 hours.
  • reaction is preferably carried out in an atmosphere of an inert gas (for example, nitrogen).
  • an inert gas for example, nitrogen
  • an organozinc compound obtained by reacting at least zinc oxide and glutaric acid can be mentioned as a particularly preferable form of the organozinc compound of the present disclosure.
  • the organozinc compound was reacted with only zinc oxide as the inorganic zinc compound, reacted with only glutaric acid as the aliphatic carboxylic acid, or reacted with only zinc oxide and glutaric acid. Those are preferably included.
  • the organozinc compound 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.
  • the present disclosure also preferably includes a method for producing a polyalkylene carbonate by reacting carbon dioxide and an epoxide in the presence of the organozinc compound of the present disclosure (copolymerization reaction).
  • the epoxide is not particularly limited, but for example, ethylene oxide, propylene oxide, 1-butane oxide, 2-butane oxide, isobutylene oxide, 1-pentene oxide, 2-pentene oxide, 1-hexene oxide, 1-.
  • the working pressure of carbon dioxide is not particularly limited, but is usually preferably 0.1 to 20 MPa, more preferably 0.1 to 10 MPa, and even more preferably 0.1 to 5 MPa. Carbon dioxide may be supplied in a lump sum, intermittently, or continuously.
  • the amount of the organozinc catalyst used is, for example, preferably 0.001 to 50 parts by mass, more preferably 0.01 to 40 parts by mass, and 0.1 to 30 parts by mass with respect to 100 parts by mass of the epoxide. It is more preferably a part.
  • the solvent used in the copolymerization reaction is not particularly limited, and various organic solvents can be used.
  • organic solvent include aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; dichloromethane and chloroform.
  • 1,2-Dichloroethane chlorobenzene, bromobenzene and other halogenated hydrocarbon solvents
  • ethyl acetate isopropyl acetate, butyl acetate and other ester solvents
  • tetrahydrofuran, 1,4-dioxane and other ether solvents dimethyl carbonate
  • carbonate solvents such as diethyl carbonate and propylene carbonate.
  • the amount of the solvent used is not particularly limited, but is, for example, 100 to 10000 parts by mass with respect to 100 parts by mass of the epoxide from the viewpoint of smoothing the reaction and obtaining an effect commensurate with the amount used. Is preferable. Moreover, it is not necessary to use a solvent.
  • the method for producing the polyalkylene carbonate has different polymerization forms such as solution polymerization and precipitation polymerization depending on the type and amount of the solvent used, but the copolymerization reaction proceeds without any problem in any of the polymerization forms. , Their reaction efficiency is very high.
  • the reaction temperature of the copolymerization reaction is not particularly limited, but is preferably, for example, 20 to 100 ° C, more preferably 40 to 80 ° C.
  • the reaction time cannot be unequivocally determined because it varies depending on the reaction temperature, but is, for example, 2 to 40 hours.
  • the method for mixing the organozinc catalyst 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 organozinc catalyst with epoxide. ..
  • the polyalkylene carbonate thus obtained is dried by using a vacuum drying method or the like after removing the catalyst or the like by filtration or washing with a dilute acid aqueous solution or a dilute alkaline aqueous solution, if necessary, and then reprecipitating.
  • a vacuum drying method or the like after removing the catalyst or the like by filtration or washing with a dilute acid aqueous solution or a dilute alkaline aqueous solution, if necessary, and then reprecipitating.
  • ⁇ Analyzer TG / DTA 7220 (manufactured by Hitachi High-Tech Science Corporation) -Sample pretreatment: 1 g of slurry is collected and dried at 70 ° C. under reduced pressure (1 kPa ⁇ abs) for 1 Hr.
  • ⁇ Analytical conditions 30 to 300 ° C. 10 ° C./min Atmosphere N 2 200 mL / min, Sample 5 mg ⁇ 1 mg -Analysis conditions: Since the catalyst using zinc oxide and glutaric acid is described in this example, the case of zinc oxide and glutaric acid is also shown as an example for the analysis conditions such as the calculation method.
  • the tangent at 100 ° C was T 1
  • the tangent at 250 ° C was T 2
  • the tangent at the inflection point between 100 and 250 ° C was T 3 .
  • the mass W 1 at the intersection of the tangents T 1 and T 3 was obtained.
  • the mass W 2 at the intersection of the tangents T 2 and T 3 was obtained.
  • the mass difference between the intersections (W 1- W 2 ) is defined as 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 is calculated.
  • the content of glutaric acid (aliphatic carboxylic acid) was used (see FIG. 1 and Formula 1).
  • R CA glutaric acid (aliphatic carboxylic acids) according to Equation 2.
  • R CA [%] (1-C CA / C 0 ) x 100 (Equation 2)
  • R CA Glutaric acid (aliphatic carboxylic acid) reaction rate [%]
  • C CA Glutaric acid (aliphatic carboxylic acid) content [%]
  • C 0 Glutaric acid (aliphatic carboxylic acid) content at the time of preparation [%]
  • C 0 (glutaric acid (aliphatic carboxylic acid) content at the time of preparation) was calculated from the following formula 3.
  • C 0 [%] ⁇ W CA / (W CA + W Zn ) ⁇ ⁇ 100 (Equation 3)
  • C 0 Glutaric acid (aliphatic carboxylic acid) content at the time of preparation [%]
  • W CA Amount of charged glutaric acid (aliphatic carboxylic acid) [g]
  • W Zn Amount of zinc oxide (zinc compound) charged [g]
  • Example 1 Production of Organozinc Compound 81 g (1.00 mol) of zinc oxide, 132 g (1.00 mol) of glutaric acid, and 1000 g of toluene were charged into a 1.5 L volume separable flask equipped with a cooling tube / thermometer and a stirrer. When the mixed solution was sampled and the water content was measured, the water content with respect to zinc oxide (100% by mass) was 0.1% by mass. Then, the temperature was raised to 60 ° C. under a nitrogen atmosphere, and the mixture was stirred and reacted at the same temperature for 6 hours. The mixed solution after the reaction was sampled, the amount of residual glutaric acid was measured, and the reaction rate was calculated.
  • the powder was used as an organozinc catalyst in the production of polypropylene carbonate.
  • the powder is also referred to as a catalytic dry powder.
  • Example 2 In the production of the catalyst of Example 1, 195 g of dry catalyst powder was obtained in the same manner as in Example 1 except that 0.20 g of water was added at the time of preparation. The water content at the initial stage of the reaction was 0.26% by mass with respect to zinc oxide, and the reaction rate of the reaction 6Hr was 98.0% by mass. Using this catalyst, polymerization was carried out in the same manner as in Example 1 to obtain 87 g of polypropylene carbonate (yield 85% by mass, molecular weight Mw 351,000).
  • Example 3 In the production of the catalyst of Example 1, 195 g of dry catalyst powder was obtained in the same manner as in Example 1 except that 0.4 g of water was added at the time of preparation. The water content at the initial stage of the reaction was 0.42% by mass with respect to zinc oxide, and the reaction rate of the reaction 6 hours was 98.0% by mass. Using this catalyst, polymerization was carried out in the same manner as in Example 1 to obtain 84 g of polypropylene carbonate (yield 82% by mass, molecular weight Mw 336,000).
  • Example 4 In the production of the catalyst of Example 1, 195 g of dry catalyst powder was obtained in the same manner as in Example 1 except that 4.00 g of water was added at the time of preparation. The water content at the initial stage of the reaction was 5.12% by mass with respect to zinc oxide, and the reaction rate of the reaction 6Hr was 97.5% by mass. Using this catalyst, polymerization was carried out in the same manner as in Example 1 to obtain 86 g of polypropylene carbonate (yield 84% by mass, molecular weight Mw 317,000).
  • Example 5 In the production of the catalyst of Example 1, 196 g of dry catalyst powder was obtained in the same manner as in Example 1 except that 7.00 g of water was added at the time of preparation. The water content at the initial stage of the reaction was 8.55% by mass with respect to zinc oxide, and the reaction rate of the reaction 6Hr was 95.6% by mass. Using this catalyst, polymerization was carried out in the same manner as in Example 1 to obtain 84 g of polypropylene carbonate (yield 82% by mass, molecular weight Mw 326,000).
  • Example 2 In the production of the catalyst of Example 1, 197 g of dry catalyst powder was obtained in the same manner as in Example 1 except that 9.00 g of water was added at the time of preparation. The water content at the initial stage of the reaction was 11.50% by mass with respect to zinc oxide, and the reaction rate of the reaction 6 hours was 90.9% by mass. Using this catalyst, polymerization was carried out in the same manner as in Example 1 to obtain 78 g of polypropylene carbonate (yield 76% by mass, molecular weight Mw 289,000).
  • the water content of the reaction system at the start of the reaction is 0.05 with respect to the inorganic zinc compound. It was found that the reaction occurred with high efficiency when the content was ⁇ 10% by mass. Furthermore, it was found that a polyalkylene carbonate having a relatively large molecular weight can be obtained in a high yield by using an organozinc compound produced under these conditions as a catalyst when reacting carbon dioxide with an epoxide.

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Abstract

Provided is a method for efficiently obtaining an organozinc catalyst. More specifically, the present invention provides a method for producing an organozinc catalyst that includes reacting an inorganic zinc compound and an aliphatic carboxylic acid and in which the moisture content of the reaction system at the time the reaction is started is 0.05-10 mass% with respect to the inorganic zinc compound.

Description

有機亜鉛触媒の製造方法Manufacturing method of organozinc catalyst
　本開示は、有機亜鉛触媒の製造方法及び当該製造方法で製造された有機亜鉛触媒等に関する。なお、本明細書に記載される全ての文献の内容は参照により本明細書に組み込まれる。 The present disclosure relates to a method for producing an organozinc catalyst, an organozinc catalyst produced by the production method, and the like. The contents of all documents described herein are incorporated herein by reference.
　二酸化炭素とエポキシドとからポリアルキレンカーボネートを得る反応を触媒する有機亜鉛触媒として、無機亜鉛化合物と脂肪族ジカルボン酸と脂肪族モノカルボン酸とを反応させて得られる有機亜鉛化合物を用いることが開示されている（例えば特許文献１、２、及び非特許文献１）。 It is disclosed that an organozinc compound obtained by reacting an inorganic zinc compound with an aliphatic dicarboxylic acid and an aliphatic monocarboxylic acid is used as an organozinc catalyst for catalyzing a reaction for obtaining a polyalkylene carbonate from carbon dioxide and epoxide. (For example, Patent Documents 1 and 2, and Non-Patent Document 1).
特開２００７－３０２７３１号広報Public relations of JP-A-2007-302731 国際公開第２０１１／１４２２５９号International Publication No. 2011/142259
　本発明者らは、当該有機亜鉛触媒を効率よく得ることを目的に検討した。 The present inventors studied for the purpose of efficiently obtaining the organozinc catalyst.
　本発明者らは、有機亜鉛触媒を製造するにあたり、無機亜鉛化合物と脂肪族カルボン酸を反応させるときの、反応系内の水分量が、得られる有機亜鉛触媒の収量に影響する可能性を見いだし、さらに検討を重ねた。 In producing an organozinc catalyst, the present inventors have found that the amount of water in the reaction system when reacting an inorganic zinc compound with an aliphatic carboxylic acid may affect the yield of the obtained organozinc catalyst. , Further examination was repeated.
　本開示は例えば以下の項に記載の主題を包含する。
項１．
無機亜鉛化合物及び脂肪族カルボン酸を反応させることを含み、
当該反応開始時における当該反応系の水分含有量が、当該無機亜鉛化合物に対して０．０５～１０質量％である、
有機亜鉛化合物の製造方法。
項２．
無機亜鉛化合物が、酸化亜鉛及び水酸化亜鉛からなる群より選択される少なくとも１種である、項１に記載の製造方法。
項３．
脂肪族カルボン酸が、脂肪族ジカルボン酸及び脂肪族モノカルボン酸からなる群より選択される少なくとも１種である、項１又は２に記載の製造方法。
項４．
脂肪族モノカルボン酸が、ギ酸、酢酸、及びプロピオン酸よりなる群より選択される少なくとも１種である、項３に記載の製造方法。
項５．
脂肪族カルボン酸が、少なくとも脂肪族ジカルボン酸を含む、項１～４のいずれかに記載の製造方法。
項６．
脂肪族ジカルボン酸が、マロン酸、コハク酸、グルタル酸、アジピン酸、及びセバシン酸からなる群より選択される少なくとも１種である、項３～５のいずれかに記載の製造方法。
項７．
前記有機亜鉛化合物が有機亜鉛触媒である、項１～６のいずれかに記載の製造方法。
項８．
項１～７のいずれかに記載の製造方法により得られる有機亜鉛化合物。
項９．
項８に記載の有機亜鉛化合物の存在下で、二酸化炭素とエポキシドとを反応させることを含む、ポリアルキレンカーボネートの製造方法。 The present disclosure includes, for example, the subjects described in the following sections.
Item 1.
Including reacting inorganic zinc compounds and aliphatic carboxylic acids
The water content of the reaction system at the start of the reaction is 0.05 to 10% by mass with respect to the inorganic zinc compound.
Method for producing organozinc compound.
Item 2.
Item 2. The production method according to Item 1, wherein the inorganic zinc compound is at least one selected from the group consisting of zinc oxide and zinc hydroxide.
Item 3.
Item 2. The production method according to Item 1 or 2, wherein the aliphatic carboxylic acid is at least one selected from the group consisting of an aliphatic dicarboxylic acid and an aliphatic monocarboxylic acid.
Item 4.
Item 3. The production method according to Item 3, wherein the aliphatic monocarboxylic acid is at least one selected from the group consisting of formic acid, acetic acid, and propionic acid.
Item 5.
Item 8. The production method according to any one of Items 1 to 4, wherein the aliphatic carboxylic acid contains at least an aliphatic dicarboxylic acid.
Item 6.
Item 6. The production method according to any one of Items 3 to 5, wherein the aliphatic dicarboxylic acid is at least one selected from the group consisting of malonic acid, succinic acid, glutaric acid, adipic acid, and sebacic acid.
Item 7.
Item 8. The production method according to any one of Items 1 to 6, wherein the organozinc compound is an organozinc catalyst.
Item 8.
An organozinc compound obtained by the production method according to any one of Items 1 to 7.
Item 9.
Item 8. A method for producing a polyalkylene carbonate, which comprises reacting carbon dioxide with an epoxide in the presence of the organozinc compound according to Item 8.
　触媒（特に、二酸化炭素とエポキシドとからポリアルキレンカーボネートを得る反応における触媒）として好ましく用いることができる、有機亜鉛化合物を製造するにあたり、無機亜鉛化合物と脂肪族カルボン酸を反応させるときの反応系内水分量を適当量とすることによって、得られる有機亜鉛化合物の収量を向上させることができる。 In the reaction system when an inorganic zinc compound is reacted with an aliphatic carboxylic acid in producing an organozinc compound which can be preferably used as a catalyst (particularly, a catalyst in a reaction for obtaining a polyalkylene carbonate from carbon dioxide and epoxide). By setting the water content to an appropriate amount, the yield of the obtained organic zinc compound can be improved.
　また、このようにして得られた有機亜鉛化合物を、二酸化炭素とエポキシドとからポリアルキレンカーボネートを得る反応における触媒として用いることで、得られるポリプロピレンカーボネートの収率も改善され得る。 Further, by using the organozinc compound thus obtained as a catalyst in a reaction for obtaining a polyalkylene carbonate from carbon dioxide and an epoxide, the yield of the obtained polypropylene carbonate can be improved.
無機亜鉛化合物（具体的には酸化亜鉛）及び脂肪族カルボン酸（具体的にはグルタル酸）を反応させた後、残存スラリー中のグルタル酸をＴＧ／ＤＴＡ装置により測定した結果の例を示す。An example of the result of measuring the glutaric acid in the residual slurry by the TG / DTA device after reacting the inorganic zinc compound (specifically, zinc oxide) and the aliphatic carboxylic acid (specifically, glutaric acid) is shown.
　以下、本開示に包含される各実施形態について、さらに詳細に説明する。本開示は、特定の有機亜鉛化合物の製造方法、当該製造方法で製造される有機亜鉛化合物、及び当該有機亜鉛化合物の触媒としての使用等を好ましく包含するが、これらに限定されるわけではなく、本開示は本明細書に開示され当業者が認識できる全てを包含する。 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 method for producing a specific organozinc compound, an organozinc compound produced by the method, and the use of the organozinc compound as a catalyst. The present disclosure includes everything disclosed herein and recognizable to those skilled in the art.
　本開示に包含される有機亜鉛化合物の製造方法は、無機亜鉛化合物及び脂肪族カルボン酸を反応させることを含み、当該反応開始時における当該反応系の水分含有量が、当該亜鉛化合物に対して０．０５～１０質量％である、製造方法である。以下、本開示に包含される当該製造方法を「本開示の有機亜鉛化合物製造方法」ということがある。また、当該有機亜鉛化合物を「本開示の有機亜鉛化合物」ということがある。また、本開示の有機亜鉛化合物は、触媒（特に、二酸化炭素とエポキシドとからポリアルキレンカーボネートを得る反応における触媒）として用いることができる。本開示の有機亜鉛化合物を特に触媒として用いる場合、当該触媒を「本開示の触媒」ということがある。 The method for producing an organozinc compound included in the present disclosure includes reacting an inorganic zinc compound with an aliphatic carboxylic acid, and the water content of the reaction system at the start of the reaction is 0 with respect to the zinc compound. It is a manufacturing method of .05 to 10% by mass. Hereinafter, the production method included in the present disclosure may be referred to as "the organic zinc compound production method of the present disclosure". In addition, the organozinc compound may be referred to as "organozinc compound of the present disclosure". In addition, the organozinc compound of the present disclosure can be used as a catalyst (particularly, a catalyst in a reaction for obtaining a polyalkylene carbonate from carbon dioxide and an epoxide). When the organozinc compound of the present disclosure is particularly used as a catalyst, the catalyst may be referred to as "the catalyst of the present disclosure".
　上記の通り、本開示の有機亜鉛化合物は、無機亜鉛化合物及び脂肪族カルボン酸を反応させて得られる。言い換えれば、本開示の有機亜鉛化合物は、無機亜鉛化合物及び脂肪族カルボン酸の反応物と言うこともできる。 As described above, the organozinc compound of the present disclosure is obtained by reacting an inorganic zinc compound with an aliphatic carboxylic acid. In other words, the organozinc compound of the present disclosure can be said to be a reaction product of an inorganic zinc compound and an aliphatic carboxylic acid.
　無機亜鉛化合物としては、例えば、酸化亜鉛、硫酸亜鉛、塩素酸亜鉛、硝酸亜鉛、酢酸亜鉛、または水酸化亜鉛が好ましく挙げられ、酸化亜鉛及び水酸化亜鉛がより好ましい。無機亜鉛化合物は、１種単独で又は２種以上を組み合わせて用いることができる。 Examples of the inorganic zinc compound include zinc oxide, zinc sulfate, zinc chlorate, zinc nitrate, zinc acetate, and zinc hydroxide, and zinc oxide and zinc hydroxide are more preferable. The inorganic zinc compound may be used alone or in combination of two or more.
　脂肪族カルボン酸としては、例えば脂肪族モノカルボン酸、脂肪族ジカルボン酸、及び脂肪族トリカルボン酸等を用いることができる。中でも脂肪族ジカルボン酸を用いることが好ましい。脂肪族カルボン酸は、１種単独で又は２種以上を組み合わせて用いることができる。中でも、脂肪族ジカルボン酸を用いるか、あるいは脂肪族ジカルボン酸及び脂肪族モノカルボン酸を用いることが好ましい。なお、脂肪族ジカルボン酸及び脂肪族モノカルボン酸を用いる場合には、脂肪族モノカルボン酸は、該脂肪族ジカルボン酸に対するモル比率が０．０００１～０．１程度又は０．００１～０．０５程度となるように用いることが好ましい。 As the aliphatic carboxylic acid, for example, an aliphatic monocarboxylic acid, an aliphatic dicarboxylic acid, an aliphatic tricarboxylic acid and the like can be used. Of these, it is preferable to use an aliphatic dicarboxylic acid. The aliphatic carboxylic acid can be used alone or in combination of two or more. Of these, it is preferable to use an aliphatic dicarboxylic acid, or to use an aliphatic dicarboxylic acid and an aliphatic monocarboxylic acid. When an aliphatic dicarboxylic acid and an aliphatic monocarboxylic acid are used, the molar ratio of the aliphatic monocarboxylic acid to the aliphatic dicarboxylic acid is about 0.0001 to 0.1 or 0.001 to 0.05. It is preferable to use it so as to be a degree.
　脂肪族ジカルボン酸としては、炭素数２～１５（２、３、４、５、６、７、８、９、１０、１１、１２、１３、１４、又は１５）の脂肪族ジカルボン酸が好ましく、より具体的には、例えば、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸及びセバシン酸等が挙げられる。また、脂肪族モノカルボン酸としては、炭素数１～１５（１、２、３、４、５、６、７、８、９、１０、１１、１２、１３、１４、又は１５）の脂肪族モノカルボン酸が好ましく、より具体的には、例えば、ギ酸、酢酸、プロピオン酸、およびトリフルオロ酢酸等が挙げられる。脂肪族トリカルボン酸としては、炭素数３～１５（３、４、５、６、７、８、９、１０、１１、１２、１３、１４、又は１５）の脂肪族トリカルボン酸が好ましく、より具体的には、例えば、トリカルバリル酸および３，３’，３’’－ニトリロトリプロピオン酸等が挙げられる。脂肪族カルボン酸のなかでも、特にマロン酸、コハク酸、グルタル酸、アジピン酸、セバシン酸、ギ酸、酢酸、及びプロピオン酸が好ましい。 As the aliphatic dicarboxylic acid, 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) is preferable. More specifically, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid and the like can be mentioned. The aliphatic monocarboxylic acid has 1 to 15 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15). Monocarboxylic acids are preferred, and more specific examples include formic acid, acetic acid, propionic acid, trifluoroacetic acid and the like. As the aliphatic tricarboxylic acid, an aliphatic tricarboxylic acid having 3 to 15 carbon atoms (3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15) is preferable, and more specific. Examples thereof include tricarbaryl acid and 3,3', 3''-nitrilotripropionic acid. 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.
　上記の通り、本開示の有機亜鉛触媒製造方法においては、当該反応開始時における当該反応系の水分含有量が、当該無機亜鉛化合物に対して０．０５～１０質量％である。当該範囲の下限は、例えば０．１、０．１５、０．２、又は０．２５質量％程度であってもよい。また、当該範囲の上限は、例えば９．５、９、８．５、８、７．５、７、６．５、又は６質量％程度であってもよい。 As described above, in the organic zinc catalyst production method of the present disclosure, the water content of the reaction system at the start of the reaction is 0.05 to 10% by mass with respect to the inorganic zinc compound. The lower limit of the range may be, for example, about 0.1, 0.15, 0.2, or 0.25% by mass. Further, the upper limit of the range may be, for example, about 9.5, 9, 8.5, 8, 7.5, 7, 6.5, or 6% by mass.
　反応開始時における当該反応系の水分含有量は、次のようにして測定される。すなわち、原料（無機亜鉛化合物及び脂肪族カルボン酸並びにその他の成分（例えば溶媒））を反応容器に仕込んだ後、撹拌し、撹拌開始から１分以内に当該混合物を０．５ｇサンプリングして、これにメタノール５ｇを添加して混合する。当該混合液を０．４５μｍのフィルターでろ過した後、濾液をカール・フィッシャー水分計に導入して水分量を測定する。 The water content of the reaction system at the start of the reaction is measured as follows. That is, after charging the raw materials (inorganic zinc compound, aliphatic carboxylic acid and other components (for example, solvent)) into the reaction vessel, the mixture is stirred, and 0.5 g of the mixture is sampled within 1 minute from the start of stirring. 5 g of methanol is added to the mixture and mixed. After filtering the mixed solution with a 0.45 μm filter, the filtrate is introduced into a Karl Fischer moisture meter to measure the water content.
　無機亜鉛化合物及び脂肪族カルボン酸の使用割合としては、例えば、無機亜鉛化合物１モルに対して、脂肪族カルボン酸０．１～１．５モル程度が好ましく、０．５～１．２モル程度がより好ましく、０．８～１．０モル程度がさらに好ましい。 The ratio of the inorganic zinc compound and the aliphatic carboxylic acid used is preferably about 0.1 to 1.5 mol, preferably about 0.5 to 1.2 mol, with respect to 1 mol of the inorganic zinc compound. Is more preferable, and about 0.8 to 1.0 mol is further preferable.
　無機亜鉛化合物及び脂肪族カルボン酸の反応としては、公知の反応を用いることができ、例えば上記特許文献１又は２に記載の反応条件を用いることができる。また、より具体的には、例えば、反応溶媒としては、特に限定されるものではなく、種々の有機溶媒を用いることができる。このような有機溶媒としては、具体的には、例えば、ベンゼン、トルエン、キシレン等の芳香族炭化水素系溶媒、ヘキサン、ヘプタン、シクロヘキサン等の脂肪族炭化水素系溶媒、ジクロロメタン、クロロホルム、１，２－ジクロロエタン等のハロゲン系炭化水素溶媒、メタノール、エタノール、イソプロパノール等のアルコール系溶媒、ジエチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、酢酸エチル、酢酸ブチル等のエステル系溶媒、アセトン、メチルエチエルケトン、メチルイソブチルケトン等のケトン系溶媒、及び、ジメチルカーボネート、ジエチルカーボネート、プロピレンカーボネート等のカーボネート系溶媒、並びに、アセトニトリル、ジメチルホルムアミド、ジメチルスルホキシド、ヘキサメチルホスホトリアミド等が挙げられる。中でも、反応を円滑に進める観点から、ベンゼン、トルエン、キシレン等の芳香族炭化水素系溶媒が好ましい。 As the reaction between the inorganic zinc compound and the aliphatic carboxylic acid, a known reaction can be used, and for example, the reaction conditions described in Patent Document 1 or 2 can be used. More specifically, for example, the reaction solvent is not particularly limited, and various organic solvents can be used. Specific examples of such an organic solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene, aliphatic solvent such as hexane, heptane and cyclohexane, dichloromethane, chloroform, 1 and 2. -Halogen-based hydrocarbon solvents such as dichloroethane, alcohol-based solvents such as methanol, ethanol and isopropanol, ether-based solvents such as diethyl ether, tetrahydrofuran and dioxane, ester-based solvents such as ethyl acetate and butyl acetate, acetone and methylethiel ketone. , Ketone-based solvents such as methyl isobutyl ketone, carbonate-based solvents such as dimethyl carbonate, diethyl carbonate and propylene carbonate, and acetonitrile, dimethylformamide, dimethylsulfoxide, hexamethylphosphotriamide and the like. Of these, aromatic hydrocarbon solvents such as benzene, toluene, and xylene are preferable from the viewpoint of facilitating the reaction.
　反応溶媒の使用量は、特に制限されるものではないが、反応を円滑にさせる観点および使用量に見合うだけの効果を得る観点から、例えば無機亜鉛化合物１００質量部に対して５００～１００００質量部であることが好ましい。 The amount of the reaction solvent used is not particularly limited, but from the viewpoint of facilitating the reaction and obtaining an effect commensurate with the amount used, for example, 500 to 10000 parts by mass with respect to 100 parts by mass of the inorganic zinc compound. Is preferable.
　反応温度は、特に限定されないが、例えば、０～１１０℃であるのが好ましく、２０～１００℃であるのがより好ましく、５０～８０℃がさらに好ましい。反応温度が０℃以上であることで、反応がより効率よく進行し得る。また、反応温度が１１０℃以下であることで、副反応がより起こり難くなり、収率の低下が抑制され得る。反応時間は、反応温度により異なるために一概には言えないが、例えば１～５０時間程度である。 The reaction temperature is not particularly limited, but is preferably 0 to 110 ° C, more preferably 20 to 100 ° C, and even more preferably 50 to 80 ° C. When the reaction temperature is 0 ° C. or higher, the reaction can proceed more efficiently. Further, when the reaction temperature is 110 ° C. or lower, side reactions are less likely to occur, and a decrease in yield can be suppressed. The reaction time varies depending on the reaction temperature and cannot be unequivocally determined, but is, for example, about 1 to 50 hours.
　また、反応は、不活性ガス（例えば窒素）雰囲気下で行うことが好ましい。 Further, the reaction is preferably carried out in an atmosphere of an inert gas (for example, nitrogen).
　特に制限される訳ではないが、本開示の有機亜鉛化合物の特に好ましい一形態として、少なくとも酸化亜鉛及びグルタル酸を反応させて得られる有機亜鉛化合物が挙げられる。当該有機亜鉛化合物には、例えば、無機亜鉛化合物としては酸化亜鉛のみを反応させたもの、及び脂肪族カルボン酸としてはグルタル酸のみを反応させたものや、酸化亜鉛およびグルタル酸のみを反応させたものが、好ましく包含される。 Although not particularly limited, an organozinc compound obtained by reacting at least zinc oxide and glutaric acid can be mentioned as a particularly preferable form of the organozinc compound of the present disclosure. For example, the organozinc compound was reacted with only zinc oxide as the inorganic zinc compound, reacted with only glutaric acid as the aliphatic carboxylic acid, or reacted with only zinc oxide and glutaric acid. Those are preferably included.
　本開示の有機亜鉛化合物は、特に、二酸化炭素とエポキシドとからポリアルキレンカーボネートを得る反応（共重合反応）を触媒するために好ましく用いられる。また、本開示は、本開示の有機亜鉛化合物存在下で、二酸化炭素とエポキシドとを反応（共重合反応）させてポリアルキレンカーボネートを製造する方法も好ましく包含する。 The organozinc compound 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. The present disclosure also preferably includes a method for producing a polyalkylene carbonate by reacting carbon dioxide and an epoxide in the presence of the organozinc compound of the present disclosure (copolymerization reaction).
　エポキシドとしては、特に限定されるものではないが、例えば、エチレンオキシド、プロピレンオキシド、１－ブテンオキシド、２－ブテンオキシド、イソブチレンオキシド、１－ペンテンオキシド、２－ペンテンオキシド、１－ヘキセンオキシド、１－オクテンオキシド、１－デセンオキシド、シクロペンテンオキシド、シクロヘキセンオキシド、スチレンオキシド、ビニルシクロヘキサンオキシド、３－フェニルプロピレンオキシド、３，３，３－トリフルオロプロピレンオキシド、３－ナフチルプロピレンオキシド、３－フェノキシプロピレンオキシド、３－ナフトキシプロピレンオキシド、ブタジエンモノオキシド、アリルグリシジルエーテル、３－ビニルオキシプロピレンオキシドおよび３－トリメチルシリルオキシプロピレンオキシド等が挙げられる。中でも、高い反応性を有する観点から、エチレンオキシドおよびプロピレンオキシドが好ましい。これらのエポキシドは、それぞれ単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 The epoxide is not particularly limited, but for example, ethylene oxide, propylene oxide, 1-butane oxide, 2-butane 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, Examples thereof include 3-naphthoxypropylene oxide, butadiene monooxide, allylglycidyl ether, 3-vinyloxypropylene oxide and 3-trimethylsilyloxypropylene oxide. Of these, ethylene oxide and propylene oxide are preferable from the viewpoint of having high reactivity. These epoxides may be used alone or in combination of two or more.
　二酸化炭素の使用圧力は、特に限定されないが、通常、０．１～２０ＭＰａであることが好ましく、０．１～１０ＭＰａであることがより好ましく、０．１～５ＭＰａであることがさらに好ましい。二酸化炭素は、一括で供給してもよいし、間欠的に、もしくは、連続的に供給してもよい。 The working pressure of carbon dioxide is not particularly limited, but is usually preferably 0.1 to 20 MPa, more preferably 0.1 to 10 MPa, and even more preferably 0.1 to 5 MPa. Carbon dioxide may be supplied in a lump sum, intermittently, or continuously.
　前記有機亜鉛触媒の使用量は、例えばエポキシド１００質量部に対して０．００１～５０質量部であることが好ましく、０．０１～４０質量部であることがより好ましく、０．１～３０質量部であることがさらに好ましい。 The amount of the organozinc catalyst used is, for example, preferably 0.001 to 50 parts by mass, more preferably 0.01 to 40 parts by mass, and 0.1 to 30 parts by mass with respect to 100 parts by mass of the epoxide. It is more preferably a part.
　前記共重合反応に用いられる溶媒としては、特に限定されるものではなく、種々の有機溶媒を用いることができる。このような有機溶媒としては、具体的には、例えば、ペンタン、ヘキサン、オクタン、デカン、シクロヘキサン等の脂肪族炭化水素系溶媒；ベンゼン、トルエン、キシレン等の芳香族炭化水素系溶媒；ジクロロメタン、クロロホルム、１，２－ジクロロエタン、クロロベンゼン、ブロモベンゼン等のハロゲン化炭化水素系溶媒；酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒；テトラヒドロフラン、１，４－ジオキサン等のエーテル系溶媒；ジメチルカーボネート、ジエチルカーボネート、プロピレンカーボネート等のカーボネート類系溶媒等が挙げられる。 The solvent used in the copolymerization reaction is not particularly limited, and 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; dichloromethane and chloroform. , 1,2-Dichloroethane, chlorobenzene, bromobenzene and other halogenated hydrocarbon solvents; ethyl acetate, isopropyl acetate, butyl acetate and other ester solvents; tetrahydrofuran, 1,4-dioxane and other ether solvents; dimethyl carbonate, Examples thereof include carbonate solvents such as diethyl carbonate and propylene carbonate.
　前記溶媒の使用量は、特に制限されるものではないが、反応を円滑にさせる観点および使用量に見合うだけの効果を得る観点から、例えばエポキシド１００質量部に対して１００～１００００質量部であることが好ましい。また、溶媒を使用しなくてもよい。 The amount of the solvent used is not particularly limited, but is, for example, 100 to 10000 parts by mass with respect to 100 parts by mass of the epoxide from the viewpoint of smoothing the reaction and obtaining an effect commensurate with the amount used. Is preferable. Moreover, it is not necessary to use a solvent.
　なお、当該ポリアルキレンカーボネートの製造方法は、これら用いる溶媒の種類および使用量により、溶液重合および沈澱重合といった異なる重合形態となるが、いずれの重合形態であっても共重合反応は問題なく進行し、それらの反応効率は非常に高い。 The method for producing the polyalkylene carbonate has different polymerization forms such as solution polymerization and precipitation polymerization depending on the type and amount of the solvent used, but the copolymerization reaction proceeds without any problem in any of the polymerization forms. , Their reaction efficiency is very high.
　当該共重合反応の反応温度は、特に限定されないが、例えば２０～１００℃であるのが好ましく、４０～８０℃であるのがより好ましい。反応時間は、反応温度により異なるために一概には言えないが、例えば、２～４０時間である。 The reaction temperature of the copolymerization reaction is not particularly limited, but is preferably, for example, 20 to 100 ° C, more preferably 40 to 80 ° C. The reaction time cannot be unequivocally determined because it varies depending on the reaction temperature, but is, for example, 2 to 40 hours.
　前記有機亜鉛触媒と二酸化炭素とエポキシドとの混合方法は、特に限定されるものではないが、混合の容易さから、例えば前記有機亜鉛触媒とエポキシドとを混合した後に二酸化炭素を添加する方法がある。 The method for mixing the organozinc catalyst 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 organozinc catalyst with epoxide. ..
　また、かくして得られるポリアルキレンカーボネートは、例えば、ろ過あるいは希酸水溶液や希アルカリ水溶液を用いた洗浄により触媒等を除去した後、必要に応じて再沈殿した後に、減圧乾燥法等を用いて乾燥することにより単離することができる。 Further, the polyalkylene carbonate thus obtained is dried by using a vacuum drying method or the like after removing the catalyst or the like by filtration or washing with a dilute acid aqueous solution or a dilute alkaline aqueous solution, if necessary, and then reprecipitating. Can be isolated by
　なお、本明細書において「含む」とは、「本質的にからなる」と、「からなる」をも包含する（The term "comprising" includes "consisting essentially of” and "consisting of."）。また、本開示は、本明細書に説明した構成要件を任意の組み合わせを全て包含する。 In this specification, "including" also includes "consisting of" and "consisting of" (The term "comprising" includes "consisting essentially of" and "consisting of."). The present disclosure also includes all combinations of the constituent requirements described herein.
　また、上述した本開示の各実施形態について説明した各種特性（性質、構造、機能等）は、本開示に包含される主題を特定するにあたり、どのように組み合わせられてもよい。すなわち、本開示には、本明細書に記載される組み合わせ可能な各特性のあらゆる組み合わせからなる主題が全て包含される。 Further, the various characteristics (property, structure, function, etc.) described for 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 subjects consisting of any combination of each combinable property described herein.
　以下、例を示して本開示の実施形態をより具体的に説明するが、本開示の実施形態は下記の例に限定されるものではない。 Hereinafter, embodiments of the present disclosure will be described in more detail with reference to examples, but the embodiments of the present disclosure are not limited to the following examples.
各分析は以下の方法で行った。
＜水分量測定＞
　各実施例及び比較例に記載する系内水分量（すなわち、反応開始時における当該反応系の水分含有量）については、反応に用いる原料をすべて混合したスラリーをメタノールで希釈して水分を抽出し、カール・フィッシャー水分計（平沼産業製、製品名「ＡＱ－２１００」）を用いて測定した。より詳細には、次のようにして行った。原料を反応容器に仕込んだ後撹拌し、当該撹拌開始から１分以内に混合物（スラリー）０．５ｇを量り取り、メタノール５ｇと混合した。混合液をフィルター（０．４５μｍ）でろ過し、濾液をカール・フィッシャー水分計に導入した。メタノールのみの測定値（ブランク測定値）を差し引いて有機亜鉛触媒内の水分量を算出した。 Each analysis was performed by the following method.
<Measurement of water content>
Regarding the water content in the system described in each Example and Comparative Example (that is, the water content of the reaction system at the start of the reaction), the slurry obtained by mixing all the raw materials used for the reaction was diluted with methanol to extract the water content. , Carl Fisher Moisture Analyzer (manufactured by Hiranuma Sangyo, product name "AQ-2100"). More specifically, it was done as follows. The raw materials were charged into a reaction vessel and then stirred, and within 1 minute from the start of the stirring, 0.5 g of the mixture (slurry) was weighed and mixed with 5 g of methanol. The mixture was filtered through a filter (0.45 μm) and the filtrate was introduced into a Karl Fischer moisture meter. The water content in the organozinc catalyst was calculated by subtracting the measured value of methanol only (blank measured value).
水分計分析条件
・発生液：Ｓｉｇｍａ－Ａｌｄｒｉｃｈ製「ハイドラナール　クーロマットＡＫ」
・対極液：Ｓｉｇｍａ－Ａｌｄｒｉｃｈ製「ハイドラナール　クーロマットＣＧ－Ｋ」 Moisture meter analysis conditions / generated liquid: Sigma-Aldrich "Hydranal Coulomat AK"
・ Counter electrode: Sigma-Aldrich "Hydranal Coulomat CG-K"
＜反応率測定＞
　反応後に残った混合スラリーを７０℃減圧下で１時間乾燥させて固形物を得た。得られた固形物約５ｍｇをＴＧ／ＤＴＡ装置に導入した。窒素雰囲気化で３０℃から３００℃まで１０℃／ｍｉｎで昇温させ、残存グルタル酸に由来する重量減少から、反応率を求めた。 <Measurement of reaction rate>
The mixed slurry remaining after the reaction was dried under reduced pressure at 70 ° C. for 1 hour to obtain a solid substance. About 5 mg of the obtained solid was introduced into the TG / DTA apparatus. The temperature was raised from 30 ° C. to 300 ° C. at 10 ° C./min in a nitrogen atmosphere, and the reaction rate was determined from the weight loss derived from the residual glutaric acid.
・分析装置：ＴＧ／ＤＴＡ　７２２０（株式会社　日立ハイテクサイエンス製）
・サンプル前処理：スラリーを１ｇ採取し、７０℃減圧（１ｋＰａ・ａｂｓ）１Ｈｒ乾燥・分析条件：３０から３００℃　１０℃／ｍｉｎ　雰囲気Ｎ２　２００ｍＬ／ｍｉｎ、試料５ｍｇ±１ｍｇ
・解析条件：本実施例においては酸化亜鉛とグルタル酸を用いた触媒について記載しているため、計算方法等の解析条件についても酸化亜鉛とグルタル酸の場合を例に示す。ＴＧ（熱重量測定）のデータにおいて、１００℃における接線をＴ１、２５０℃における接線をＴ２、及び１００～２５０℃間の変曲点における接線をＴ３とした。次に接線Ｔ１とＴ３の交点における質量Ｗ１を求めた。また、接線Ｔ２とＴ３の交点における質量Ｗ２を求めた。交点間の質量差（Ｗ１－Ｗ２）をグルタル酸（脂肪族カルボン酸）含有量とし、低温側での交点の質量Ｗ１でグルタル酸（脂肪族カルボン酸）含有量を割った値をグルタル酸（脂肪族カルボン酸）含有率とした（図１及び式１を参照）。 ・ Analyzer: TG / DTA 7220 (manufactured by Hitachi High-Tech Science Corporation)
-Sample pretreatment: 1 g of slurry is collected and dried at 70 ° C. under reduced pressure (1 kPa · abs) for 1 Hr. ・ Analytical conditions: 30 to 300 ° C. 10 ° C./min Atmosphere N 2 200 mL / min, Sample 5 mg ± 1 mg
-Analysis conditions: Since the catalyst using zinc oxide and glutaric acid is described in this example, the case of zinc oxide and glutaric acid is also shown as an example for the analysis conditions such as the calculation method. In the TG (thermogravimetric analysis) data, the tangent at 100 ° C was T 1 , the tangent at 250 ° C was T 2 , and the tangent at the inflection point between 100 and 250 ° C was T 3 . Next, the mass W 1 at the intersection of the tangents T 1 and T 3 was obtained. Further, the mass W 2 at the intersection of the tangents T 2 and T 3 was obtained. The mass difference between the intersections (W 1- W 2 ) is defined as 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 is calculated. The content of glutaric acid (aliphatic carboxylic acid) was used (see FIG. 1 and Formula 1).
　ＣＣＡ　［％］＝（Ｗ１－Ｗ２）／Ｗ１　×１００　（式１）
　　ＣＣＡ：グルタル酸（脂肪族カルボン酸）含有率［％］
　　Ｗ１：低温側質量［ｍｇ］
　　Ｗ２：高温側質量［ｍｇ］ C CA [%] = (W 1- W 2 ) / W 1 x 100 (Equation 1)
C CA : Glutaric acid (aliphatic carboxylic acid) content [%]
W 1 : Low temperature side mass [mg]
W 2 : High temperature side mass [mg]
　次に、式２に従ってグルタル酸（脂肪族カルボン酸）の反応率ＲＣＡを計算した。
　ＲＣＡ　［％］＝（１－ＣＣＡ／Ｃ０　）×１００　（式２）
　　ＲＣＡ：グルタル酸（脂肪族カルボン酸）反応率［％］
　　ＣＣＡ：グルタル酸（脂肪族カルボン酸）含有率［％］
　　Ｃ０：仕込時グルタル酸（脂肪族カルボン酸）含有率［％］ It was then calculated reaction rate R CA glutaric acid (aliphatic carboxylic acids) according to Equation 2.
R CA [%] = (1-C CA / C 0 ) x 100 (Equation 2)
R CA : Glutaric acid (aliphatic carboxylic acid) reaction rate [%]
C CA : Glutaric acid (aliphatic carboxylic acid) content [%]
C 0 : Glutaric acid (aliphatic carboxylic acid) content at the time of preparation [%]
　Ｃ０（仕込時グルタル酸（脂肪族カルボン酸）含有率）は、以下の式３から算出した。　Ｃ０［％］＝｛ＷＣＡ／（ＷＣＡ＋ＷＺｎ）｝×１００　（式３）
　　Ｃ０：仕込時グルタル酸（脂肪族カルボン酸）含有率　［％］
　　ＷＣＡ：仕込みグルタル酸（脂肪族カルボン酸）量　［ｇ］
　　ＷＺｎ：仕込み酸化亜鉛（亜鉛化合物）量　［ｇ］ C 0 (glutaric acid (aliphatic carboxylic acid) content at the time of preparation) was calculated from the following formula 3. C 0 [%] = {W CA / (W CA + W Zn )} × 100 (Equation 3)
C 0 : Glutaric acid (aliphatic carboxylic acid) content at the time of preparation [%]
W CA : Amount of charged glutaric acid (aliphatic carboxylic acid) [g]
W Zn : Amount of zinc oxide (zinc compound) charged [g]
＜ポリアルキレンカーボネートの分子量測定＞
　各実施例および製造例に記載するポリアルキレンカーボネートの重量平均分子量についてはゲル・パーミエーション・クロマトグラフ（ＧＰＣ）測定装置（Ｗａｔｅｒｓ製、製品名「ｗａｔｅｒｓ２６９５」セパレーションモジュール）を用い下記条件にて測定した、標準ポリスチレン換算の質量平均分子量である。サンプルは、ポリマー濃度０．３質量％のＮ，Ｎ－ジメチルホルムアミド溶液として、測定装置へ導入した。 <Measurement of molecular weight of polyalkylene carbonate>
The weight average molecular weight of the polystyrene carbonate described in each Example and Production Example was measured under the following conditions using a gel permeation chromatograph (GPC) measuring device (manufactured by Waters, product name "waters2695" separation module). , Standard polystyrene equivalent mass average molecular weight. The sample was introduced into the measuring device as an N, N-dimethylformamide solution having a polymer concentration of 0.3% by mass.
ＧＰＣ測定条件
　　・カラム　　　：昭和電工製「Ｓｈｏｄｅｘ　ＯＨｐａｋ　ＳＢ－８０４　ＨＱ」、「Ｓｈｏｄｅｘ　ＯＨｐａｋ　ＳＢ－８０５」を順次接続したもの
　　・カラム温度　：４０℃
　　・展開溶媒　　：５ｍｍｏｌ／Ｌ　ＬｉＢｒ－Ｎ，Ｎ－ジメチルホルムアミド溶液
　　・流速　　　　：１．０ｍＬ／ｍｉｎ
　　・検出器　　　：示差屈折計
　　・標準試料　　：ポリスチレン GPC measurement conditions-Column: Showa Denko's "Shodex OHpak SB-804 HQ" and "Shodex OHpak SB-805" connected in sequence-Column temperature: 40 ° C
-Development solvent: 5 mmol / L LiBr-N, N-dimethylformamide solution-Flow velocity: 1.0 mL / min
・ Detector: Differential refractometer ・ Standard sample: Polystyrene
［実施例１］　
有機亜鉛化合物の製造
　冷却管・温度計および撹拌機を備え付けた１．５Ｌ容セパラブルフラスコに、酸化亜鉛８１ｇ（１．００ｍｏｌ）、グルタル酸１３２ｇ（１．００ｍｏｌ）、及びトルエン１０００ｇを仕込んだ。混合液をサンプリングして水分量を測定したところ、酸化亜鉛（１００質量％）に対する水分量は０．１質量％であった。次いで、窒素雰囲気下で６０℃まで昇温し、同温度で６時間撹拌して反応させた。反応後の混合液をサンプリングして残存グルタル酸量を測定して反応率を計算した結果、９６．５質量％であった。その後、室温まで冷却し、吸引濾過を行い、次いで９０℃、１．０ｋＰａ　ａｂｓで１Ｈｒ乾燥させることで、有機亜鉛化合物（グルタル酸亜鉛）１９６ｇ（粉末）を得た。当該粉末を有機亜鉛触媒としてポリプロピレンカーボネートの製造に用いた。以下、当該粉末を触媒乾粉とも表記する。 [Example 1]
Production of Organozinc Compound 81 g (1.00 mol) of zinc oxide, 132 g (1.00 mol) of glutaric acid, and 1000 g of toluene were charged into a 1.5 L volume separable flask equipped with a cooling tube / thermometer and a stirrer. When the mixed solution was sampled and the water content was measured, the water content with respect to zinc oxide (100% by mass) was 0.1% by mass. Then, the temperature was raised to 60 ° C. under a nitrogen atmosphere, and the mixture was stirred and reacted at the same temperature for 6 hours. The mixed solution after the reaction was sampled, the amount of residual glutaric acid was measured, and the reaction rate was calculated. As a result, it was 96.5% by mass. Then, the mixture was cooled to room temperature, suction-filtered, and then dried at 90 ° C. for 1.0 kPa abs for 1 hr to obtain 196 g (powder) of an organic zinc compound (zinc glutarate). The powder was used as an organozinc catalyst in the production of polypropylene carbonate. Hereinafter, the powder is also referred to as a catalytic dry powder.
ポリアルキレンカーボネートの製造
　撹拌機、ガス導入管および温度計を備えた１Ｌ容のオートクレーブの系内をあらかじめ窒素雰囲気に置換した後、有機亜鉛触媒１０ｇ（０．０５ｍｏｌ）、酢酸エチル５００ｇ、プロピレンオキシド５８ｇ（１．００ｍｏｌ）を仕込んだ。６０℃に昇温し、反応系内が１．０ＭＰａとなるまで二酸化炭素を充填し、消費される二酸化炭素を補給しながら１２時間重合反応を行った。その後、オートクレーブを冷却して脱圧し、白色ポリマーの酢酸エチルスラリーを得た。これを濾過し、減圧乾燥してポリプロピレンカーボネート８６ｇ（収率８４質量％、分子量Ｍｗ３４．２万）を得た。 Production of polyalkylene carbonate After replacing the inside of a 1 L autoclave system equipped with a stirrer, a gas introduction tube and a thermometer with a nitrogen atmosphere in advance, 10 g (0.05 mol) of an organozinc catalyst, 500 g of ethyl acetate and 58 g of propylene oxide (1.00 mol) was charged. The temperature was raised to 60 ° C., carbon dioxide was filled until the inside of the reaction system became 1.0 MPa, and the polymerization reaction was carried out for 12 hours while replenishing the consumed carbon dioxide. Then, the autoclave was cooled and depressurized to obtain an ethyl acetate slurry of a white polymer. This was filtered and dried under reduced pressure to obtain 86 g of polypropylene carbonate (yield 84% by mass, molecular weight Mw 342,000).
［実施例２］
　実施例１の触媒製造において、仕込み時に水を０．２０ｇ添加する以外は実施例１と同様にして、触媒乾粉１９５ｇを取得した。反応初期の水分量は酸化亜鉛に対して０．２６質量％で、反応６Ｈｒの反応率は９８．０質量％であった。この触媒を用いて、実施例１と同様の操作で重合を行い、ポリプロピレンカーボネート８７ｇ（収率８５質量％、分子量Ｍｗ３５．１万）を得た。 [Example 2]
In the production of the catalyst of Example 1, 195 g of dry catalyst powder was obtained in the same manner as in Example 1 except that 0.20 g of water was added at the time of preparation. The water content at the initial stage of the reaction was 0.26% by mass with respect to zinc oxide, and the reaction rate of the reaction 6Hr was 98.0% by mass. Using this catalyst, polymerization was carried out in the same manner as in Example 1 to obtain 87 g of polypropylene carbonate (yield 85% by mass, molecular weight Mw 351,000).
［実施例３］
　実施例１の触媒製造において、仕込み時に水を０．４ｇ添加する以外は実施例１と同様にして、触媒乾粉１９５ｇを取得した。反応初期の水分量は酸化亜鉛に対して０．４２質量％で、反応６Ｈｒの反応率は９８．０質量％であった。この触媒を用いて、実施例１と同様の操作で重合を行い、ポリプロピレンカーボネート８４ｇ（収率８２質量％、分子量Ｍｗ３３．６万）を得た。 [Example 3]
In the production of the catalyst of Example 1, 195 g of dry catalyst powder was obtained in the same manner as in Example 1 except that 0.4 g of water was added at the time of preparation. The water content at the initial stage of the reaction was 0.42% by mass with respect to zinc oxide, and the reaction rate of the reaction 6 hours was 98.0% by mass. Using this catalyst, polymerization was carried out in the same manner as in Example 1 to obtain 84 g of polypropylene carbonate (yield 82% by mass, molecular weight Mw 336,000).
［実施例４］
　実施例１の触媒製造において、仕込み時に水を４．００ｇ添加する以外は実施例１と同様にして、触媒乾粉１９５ｇを取得した。反応初期の水分量は酸化亜鉛に対して５．１２質量％で、反応６Ｈｒの反応率は９７．５質量％であった。この触媒を用いて、実施例１と同様の操作で重合を行い、ポリプロピレンカーボネート８６ｇ（収率８４質量％、分子量Ｍｗ３１．７万）を得た。 [Example 4]
In the production of the catalyst of Example 1, 195 g of dry catalyst powder was obtained in the same manner as in Example 1 except that 4.00 g of water was added at the time of preparation. The water content at the initial stage of the reaction was 5.12% by mass with respect to zinc oxide, and the reaction rate of the reaction 6Hr was 97.5% by mass. Using this catalyst, polymerization was carried out in the same manner as in Example 1 to obtain 86 g of polypropylene carbonate (yield 84% by mass, molecular weight Mw 317,000).
［実施例５］
　実施例１の触媒製造において、仕込み時に水を７．００ｇ添加する以外は実施例１と同様にして、触媒乾粉１９６ｇを取得した。反応初期の水分量は酸化亜鉛に対して８．５５質量％で、反応６Ｈｒの反応率は９５．６質量％であった。この触媒を用いて、実施例１と同様の操作で重合を行い、ポリプロピレンカーボネート８４ｇ（収率８２質量％、分子量Ｍｗ３２．６万）を得た。 [Example 5]
In the production of the catalyst of Example 1, 196 g of dry catalyst powder was obtained in the same manner as in Example 1 except that 7.00 g of water was added at the time of preparation. The water content at the initial stage of the reaction was 8.55% by mass with respect to zinc oxide, and the reaction rate of the reaction 6Hr was 95.6% by mass. Using this catalyst, polymerization was carried out in the same manner as in Example 1 to obtain 84 g of polypropylene carbonate (yield 82% by mass, molecular weight Mw 326,000).
［比較例１］
　実施例１の触媒製造において、酸化亜鉛、グルタル酸をあらかじめ乾燥させて、脱水トルエンを使用して、触媒乾粉２００ｇを取得した。反応初期の水分量は酸化亜鉛に対して０．０１質量％で、反応６Ｈｒの反応率は７４．１質量％であった。この触媒を用いて、実施例１と同様の操作で重合を行い、ポリプロピレンカーボネート６２ｇ（収率６１質量％、分子量Ｍｗ２１．５万）を得た。 [Comparative Example 1]
In the production of the catalyst of Example 1, zinc oxide and glutaric acid were dried in advance, and 200 g of dry catalyst powder was obtained using dehydrated toluene. The water content at the initial stage of the reaction was 0.01% by mass with respect to zinc oxide, and the reaction rate of the reaction 6 hours was 74.1% by mass. Using this catalyst, polymerization was carried out in the same manner as in Example 1 to obtain 62 g of polypropylene carbonate (yield 61% by mass, molecular weight Mw 215,000).
［比較例２］
　実施例１の触媒製造において、仕込み時に水を９．００ｇ添加する以外は実施例１と同様にして、触媒乾粉１９７ｇを取得した。反応初期の水分量は酸化亜鉛に対して１１．５０　質量％で、反応６Ｈｒの反応率は９０．９質量％であった。この触媒を用いて、実施例１と同様の操作で重合を行い、ポリプロピレンカーボネート７８ｇ（収率７６質量％、分子量Ｍｗ２８．９万）を得た。 [Comparative Example 2]
In the production of the catalyst of Example 1, 197 g of dry catalyst powder was obtained in the same manner as in Example 1 except that 9.00 g of water was added at the time of preparation. The water content at the initial stage of the reaction was 11.50% by mass with respect to zinc oxide, and the reaction rate of the reaction 6 hours was 90.9% by mass. Using this catalyst, polymerization was carried out in the same manner as in Example 1 to obtain 78 g of polypropylene carbonate (yield 76% by mass, molecular weight Mw 289,000).
　以上の結果を、表１にまとめて示す。 The above results are summarized in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　当該結果から、無機亜鉛化合物及び脂肪族カルボン酸を反応させて有機亜鉛化合物（触媒）を製造するにあたり、反応開始時における当該反応系の水分含有量が、当該無機亜鉛化合物に対して０．０５～１０質量％であることにより、高効率で反応が起こることが分かった。さらに、当該条件で製造した有機亜鉛化合物を、二酸化炭素とエポキシドとを反応させる際に触媒として用いることにより、高収率で比較的分子量の大きいポリアルキレンカーボネートを得られること、が分かった。  From the results, when the organozinc compound and the aliphatic carboxylic acid are reacted to produce the organozinc compound (catalyst), the water content of the reaction system at the start of the reaction is 0.05 with respect to the inorganic zinc compound. It was found that the reaction occurred with high efficiency when the content was ~ 10% by mass. Furthermore, it was found that a polyalkylene carbonate having a relatively large molecular weight can be obtained in a high yield by using an organozinc compound produced under these conditions as a catalyst when reacting carbon dioxide with an epoxide.

Claims (9)

  1. 無機亜鉛化合物及び脂肪族カルボン酸を反応させることを含み、
    当該反応開始時における当該反応系の水分含有量が、当該無機亜鉛化合物に対して０．０５～１０質量％である、
    有機亜鉛化合物の製造方法。     Including reacting inorganic zinc compounds and aliphatic carboxylic acids
    The water content of the reaction system at the start of the reaction is 0.05 to 10% by mass with respect to the inorganic zinc compound.
    Method for producing organozinc compound.
  2. 無機亜鉛化合物が、酸化亜鉛及び水酸化亜鉛からなる群より選択される少なくとも１種である、請求項１に記載の製造方法。 The production method according to claim 1, wherein the inorganic zinc compound is at least one selected from the group consisting of zinc oxide and zinc hydroxide.
  3. 脂肪族カルボン酸が、脂肪族ジカルボン酸及び脂肪族モノカルボン酸からなる群より選択される少なくとも１種である、請求項１又は２に記載の製造方法。 The production method according to claim 1 or 2, wherein the aliphatic carboxylic acid is at least one selected from the group consisting of an aliphatic dicarboxylic acid and an aliphatic monocarboxylic acid.
  4. 脂肪族モノカルボン酸が、ギ酸、酢酸、及びプロピオン酸よりなる群より選択される少なくとも１種である、請求項３に記載の製造方法。 The production method according to claim 3, wherein the aliphatic monocarboxylic acid is at least one selected from the group consisting of formic acid, acetic acid, and propionic acid.
  5. 脂肪族カルボン酸が、少なくとも脂肪族ジカルボン酸を含む、請求項１～４のいずれかに記載の製造方法。 The production method according to any one of claims 1 to 4, wherein the aliphatic carboxylic acid contains at least an aliphatic dicarboxylic acid.
  6. 脂肪族ジカルボン酸が、マロン酸、コハク酸、グルタル酸、アジピン酸、及びセバシン酸からなる群より選択される少なくとも１種である、請求項３～５のいずれかに記載の製造方法。 The production method according to any one of claims 3 to 5, wherein the aliphatic dicarboxylic acid is at least one selected from the group consisting of malonic acid, succinic acid, glutaric acid, adipic acid, and sebacic acid.
  7. 前記有機亜鉛化合物が有機亜鉛触媒である、請求項１～６のいずれかに記載の製造方法。 The production method according to any one of claims 1 to 6, wherein the organozinc compound is an organozinc catalyst.
  8. 請求項１～７のいずれかに記載の製造方法により得られる有機亜鉛化合物。 An organozinc compound obtained by the production method according to any one of claims 1 to 7.
  9. 請求項８に記載の有機亜鉛化合物の存在下で、二酸化炭素とエポキシドとを反応させることを含む、ポリアルキレンカーボネートの製造方法。  A method for producing a polyalkylene carbonate, which comprises reacting carbon dioxide with an epoxide in the presence of the organozinc compound according to claim 8.
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