Method for producing organic zinc compound

Abstract

Provided is a method for producing an organic zinc compound, wherein a container that contains an inorganic zinc compound and an aliphatic dicarboxylic acid is rotated so as to react the inorganic zinc compound with the aliphatic dicarboxylic acid in the container without using a pulverization medium and without using a solvent.

Description

Method for producing organozinc compounds

[0001] This invention relates to a method for producing organozinc compounds.

[0002] Organozinc compounds are industrially used as polymerization catalysts for synthesizing various polymers. For example, zinc aliphatic dicarboxylic acid salts, which are reaction products of zinc and aliphatic dicarboxylic acids, are used as polymerization catalysts in the production of polyalkylene carbonates from alkylene oxides and carbon dioxide, and in the production of polyethers from alkylene oxides. The catalytic activity of organozinc compounds used as polymerization catalysts is an important factor that affects the productivity of the target polymer product, and therefore, research is being conducted to improve the catalytic activity of organozinc compounds.

[0003] Patent Document 1 discloses a novel organozinc catalyst having high polymerization activity, which is an organozinc catalyst used in a reaction to obtain polyalkylene carbonate from carbon dioxide and epoxide, and is obtained by reacting a zinc compound with an aliphatic dicarboxylic acid and an aliphatic monocarboxylic acid in a molar ratio of 0.0001 to 0.1 with respect to the aliphatic dicarboxylic acid.

[0004] Japanese Patent Publication No. 2007-302731

[0005] However, according to the inventors' research, conventional organozinc compounds had room for improvement in terms of catalytic activity.

[0006] This invention has been made in view of the above circumstances, and aims to provide a method for producing organozinc compounds with excellent catalytic activity.

[0007] As a result of intensive studies, the present inventors have found that the above problems can be solved by a method of reacting an inorganic zinc compound with an aliphatic dicarboxylic acid under specific conditions, and have completed the present invention described below. That is, the present invention relates to the following [1] to [9]. [1] A method for producing an organozinc compound, comprising rotating a container containing an inorganic zinc compound and an aliphatic dicarboxylic acid to react the inorganic zinc compound with the aliphatic dicarboxylic acid in the container without using grinding media and in the absence of a solvent. [2] The method for producing an organozinc compound according to [1] above, wherein the aliphatic dicarboxylic acid is one or more selected from the group consisting of glutaric acid and adipic acid. [3] The inorganic zinc compound includes zinc oxide (ZnO), zinc sulfate (ZnSO ４ ), zinc chlorate (Zn(ClO ３ ) ２ ), zinc nitrate (Zn(NO ３ ) ２ ), zinc formate (Zn(HCOO) ２ ), zinc formate dihydrate (Zn(HCOO) ２ ·2H ２ O), zinc acetate (Zn(OAc) ２ ), zinc carbonate (ZnCO ３ ) and zinc hydroxide (Zn(OH) ２The process for producing an organozinc compound according to [1] or [2] above, wherein the one or more members are selected from the group consisting of). [4] The process for producing an organozinc compound according to any one of [1] to [3] above, wherein the inorganic zinc compound and the aliphatic dicarboxylic acid in the rotated container are in a powder form. [5] The process for producing an organozinc compound according to any one of [1] to [4] above, wherein a molar ratio [inorganic zinc compound / aliphatic dicarboxylic acid] of the inorganic zinc compound to the aliphatic dicarboxylic acid contained in the container is not less than 1.00 / 1.20 and not more than 1.00 / 0.80. [6] The process for producing an organozinc compound according to any one of [1] to [5] above, wherein the reaction is carried out in air. [7] The process for producing an organozinc compound according to any one of [1] to [6] above, wherein the reaction is carried out at 5 to 150°C. [8] The process for producing an organozinc compound according to any one of [1] to [7] above, wherein a reaction rate of the aliphatic dicarboxylic acid is 95.0 to 100.0%. [9] The process for producing an organozinc compound according to any one of [1] to [8] above, wherein the organozinc compound is a catalyst for synthesizing aliphatic polycarbonate or aliphatic polyether.

[0008] According to the present invention, a process for producing an organozinc compound excellent in catalytic activity can be provided.

[0009] In the present specification, with respect to preferred numerical ranges, the stepwisely described lower limits and upper limits can be combined independently of each other. For example, from the description "preferably 10 to 90, more preferably 30 to 60", the "preferred lower limit (10)" and the "more preferred upper limit (60)" can be combined to obtain "10 to 60".

[0010] It should be noted that the mechanism of action described herein is a conjecture, and does not limit the mechanism that achieves the effects of the present invention.

[0011] [Method for producing organozinc compound] The method for producing an organozinc compound of the present embodiment (hereinafter sometimes simply referred to as "the production method of the present embodiment") is a method for producing an organozinc compound, which comprises rotating a container containing an inorganic zinc compound and an aliphatic dicarboxylic acid to react the inorganic zinc compound and the aliphatic dicarboxylic acid in the container without using grinding media and without a solvent. Hereinafter, the raw materials used in the production method of the present embodiment and the reaction conditions of the production method of the present embodiment will be described.

[0012] <Raw Materials> In the production method of the present embodiment, an inorganic zinc compound and an aliphatic dicarboxylic acid are used as raw materials. For each of the inorganic zinc compound and the aliphatic dicarboxylic acid, one type may be used alone, or two or more types may be used in combination.

[0013] (Inorganic Zinc Compound) The inorganic zinc compound used in the production method of the present embodiment is not particularly limited as long as it is an inorganic zinc compound having reactivity with an aliphatic dicarboxylic acid. Examples of the inorganic zinc compound include zinc oxide (ZnO), zinc sulfate (ZnSO ４ ), zinc chlorate (Zn(ClO ３ ) ２ ), zinc nitrate (Zn(NO ３ ) ２ ), zinc formate (Zn(HCOO) ２ ), zinc formate dihydrate (Zn(HCOO) ２ ·2H ２ O), zinc acetate (Zn(OAc) ２ ), zinc carbonate (ZnCO ３ ) and zinc hydroxide (Zn(OH) ２ ), one or more selected from the group consisting of the above. Among these, zinc oxide (ZnO) is preferable from the viewpoint of reactivity with an aliphatic dicarboxylic acid.

[0014] (Aliphatic Dicarboxylic Acid) The aliphatic dicarboxylic acid used in the production method of the present embodiment is not particularly limited as long as it is an aliphatic dicarboxylic acid having reactivity with an inorganic zinc compound. One type of the aliphatic dicarboxylic acid may be used alone, or two or more types may be used in combination.

[0015] The number of carbon atoms in the aliphatic dicarboxylic acid is preferably 2 to 15, more preferably 3 to 12, even more preferably 4 to 10, and even more preferably 5 to 7, from the viewpoint of reactivity with inorganic zinc compounds and catalytic activity of the resulting organozinc compound. Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid. Among these, one or more selected from the group consisting of glutaric acid and adipic acid are preferred from the viewpoint of reactivity with inorganic zinc compounds and catalytic activity of organozinc compounds, glutaric acid is more preferred from the viewpoint of catalytic activity, and adipic acid is more preferred from the viewpoint of economic efficiency.

[0016] (Solvent) In the production method of this embodiment, the reaction between the inorganic zinc compound and the aliphatic dicarboxylic acid is carried out without a solvent. By reacting the inorganic zinc compound and the aliphatic dicarboxylic acid without a solvent, the reaction rate between the inorganic zinc compound and the aliphatic dicarboxylic acid is increased, and an organozinc compound with excellent catalytic activity and a composition close to the stoichiometric ratio can be formed. Furthermore, by reacting the inorganic zinc compound and the aliphatic dicarboxylic acid without a solvent, the step of separating the organozinc compound product from the solvent can be eliminated, thereby reducing the yield of the product and the cost of carrying out this step. In addition, the environmental burden and impact on the human body due to the use of organic solvents can be reduced.

[0017] Here, in this embodiment, "solvent-free" means that there is no solvent present or substantially no solvent in the container containing the inorganic zinc compound and the aliphatic dicarboxylic acid. "Substantially no solvent" means that the solvent content in the container containing the inorganic zinc compound and the aliphatic dicarboxylic acid is 1 part by mass or less, 0.5 parts by mass or less, 0.1 parts by mass or less, 0.01 parts by mass or less, or 0.001 parts by mass or less, per 100 parts by mass of the total amount of the inorganic zinc compound and the aliphatic dicarboxylic acid. However, water generated by the reaction between the inorganic zinc compound and the aliphatic dicarboxylic acid is not included in the concept of solvent.

[0018] (Form of raw materials) In the manufacturing method of this embodiment, the inorganic zinc compound and aliphatic dicarboxylic acid in the rotating container are preferably in powder form. By reacting the powdered inorganic zinc compound and aliphatic dicarboxylic acid in the rotating container, an organozinc compound having a crystalline structure that exhibits good catalytic activity tends to be formed. Furthermore, by reacting the powdered inorganic zinc compound and aliphatic dicarboxylic acid, the organozinc compound can also be obtained in powder form, which improves subsequent handling. The powdered inorganic zinc compound and aliphatic dicarboxylic acid react well in the solid phase without a solvent. This is because the powdered inorganic zinc compound and aliphatic dicarboxylic acid react with water (H) upon contact with each other. ２ It is presumed that this is due to the generation of O) and the resulting good molecular-level contact by the water. The average particle size (D) of the powdered inorganic zinc compound. ５０ The average particle size (D) of the powdered aliphatic dicarboxylic acid is preferably 0.01 to 100 μm, more preferably 0.05 to 30 μm, and even more preferably 0.1 to 10 μm. ５０ The average particle size (D) of the powdered inorganic zinc compound and aliphatic dicarboxylic acid is preferably 1 to 5000 μm, more preferably 10 to 3000 μm, even more preferably 40 to 1500 μm, even more preferably 100 to 1000 μm, and particularly preferably 200 to 800 μm. ５０ By setting the average particle size (D) of powdered inorganic zinc compounds and aliphatic dicarboxylic acids within the above range, it is possible to suppress dust damage to workers' health and other issues, and to improve handling during manufacturing. ５０ ) refers to the particle size corresponding to 50% of the cumulative volume frequency calculated from the smallest particle size in the particle distribution measured using a laser diffraction particle size distribution analyzer.

[0019] <Reaction Conditions> In the manufacturing method of this embodiment, the inorganic zinc compound and the aliphatic dicarboxylic acid are reacted by rotating a container containing the inorganic zinc compound and the aliphatic dicarboxylic acid. The conditions of this reaction will be described below. The container containing the inorganic zinc compound and the aliphatic dicarboxylic acid may be referred to as the "reaction vessel" below.

[0020] (Reaction Vessel) The material of the reaction vessel is not particularly limited and includes, for example, glass; ceramics such as alumina, zirconia, mullite, and magnesia; plastics such as polyolefin and polyester; and metals such as stainless steel. The shape of the reaction vessel can be appropriately selected depending on the method of rotating the reaction vessel and includes, for example, cylindrical and polygonal prism shapes. Among these, a cylindrical reaction vessel is preferred from the viewpoint of being easy to rotate and allowing a homogeneous reaction to proceed easily.

[0021] (Molar ratio of raw materials) The molar ratio [inorganic zinc compound / aliphatic dicarboxylic acid] of the inorganic zinc compound to the aliphatic dicarboxylic acid contained in the reaction vessel is preferably 1.00 / 1.20 or more and 1.00 / 0.80 or less, more preferably 1.00 / 1.10 or more and 1.00 / 0.85 or less, even more preferably 1.00 / 1.00 or more and 1.00 / 0.90 or less, even more preferably greater than 1.00 / 1.00 and 1.00 / 0.93 or less, and even more preferably 1.00 / 0.98 or more and 1.00 / 0.95 or less.

[0022] (Reaction Atmosphere) The atmosphere inside the reaction vessel may be an air atmosphere or an inert gas atmosphere. Examples of inert gases include nitrogen, argon, and helium. Among these, an air atmosphere is preferred from the viewpoint of production cost. That is, in the production method of this embodiment, it is preferable to carry out the reaction between the inorganic zinc compound and the aliphatic dicarboxylic acid in air. The atmosphere inside the reaction vessel may be sealed or open. The pressure inside the reaction vessel is not particularly limited and may be under pressurized, reduced pressure, or atmospheric pressure.

[0023] (Reaction Temperature and Reaction Time) In the manufacturing method of this embodiment, the temperature at which the inorganic zinc compound and the aliphatic dicarboxylic acid are reacted is preferably 5 to 150°C, more preferably 10 to 100°C, even more preferably 15 to 60°C, and even more preferably 20 to 50°C, from the viewpoint of reaction rate and ensuring the reaction proceeds homogeneously. The time for rotating the reaction vessel can be set appropriately to allow the reaction to proceed sufficiently, for example, it may be 0.5 to 72 hours, 1 to 48 hours, or 1 to 36 hours.

[0024] (Conditions for rotating the reaction vessel) When rotating the vessel containing the inorganic zinc compound and aliphatic dicarboxylic acid, the rotation speed of the reaction vessel is preferably 5 to 300 rpm, more preferably 8 to 200 rpm, even more preferably 10 to 150 rpm, and even more preferably 13 to 120 rpm, from the viewpoint of reaction rate and ensuring the reaction proceeds homogeneously. In the case of a mixing device that does not use a raw material mixing device installed inside the reaction vessel, such as a mix rotor, the rotation speed of the reaction vessel is preferably 20 to 300 rpm, more preferably 40 to 200 rpm, even more preferably 60 to 150 rpm, and even more preferably 80 to 120 rpm. In the case of a container-rotating type powder mixing device equipped with crushing blades, the rotation speed of the reaction vessel is preferably 5 to 200 rpm, more preferably 8 to 100 rpm, even more preferably 10 to 50 rpm, and even more preferably 13 to 30 rpm.

[0025] In the manufacturing method of this embodiment, the container containing the inorganic zinc compound and the aliphatic dicarboxylic acid is rotated, where "rotation" means rotating 360° or more around an axis inside the reaction vessel (hereinafter also referred to as the "rotation center axis"). The direction of rotation of the reaction vessel during the reaction may be constant, or it may be changed periodically or irregularly as needed. The rotation center axis can be set arbitrarily inside the reaction vessel, but for example, when using a cylindrical reaction vessel, the rotation center axis may be an axis perpendicular to the bottom surface and passing through the center of gravity of the bottom surface. The position and angle of the rotation center axis during the reaction may be constant, or it may be changed periodically or irregularly as needed. The angle of the rotation center axis is not particularly limited, but for example, it may be 0 to 45°, 0.5 to 40°, 1 to 35°, 1.5 to 30°, or 2 to 25° with respect to the horizontal.

[0026] The method for rotating the reaction vessel in the manufacturing method of this embodiment is not particularly limited, but for example, a device can be used to rotate the reaction vessel by placing or setting it on a plurality of rotating rollers. Such devices are sold as, for example, mix rotors, rocking mixers, etc.

[0027] (Grinding Media) In the manufacturing method of this embodiment, the reaction between the inorganic zinc compound and the aliphatic dicarboxylic acid is carried out without using grinding media. By reacting the inorganic zinc compound and the aliphatic dicarboxylic acid without using grinding media, it is possible to suppress the destruction of the crystalline structure that exhibits good catalytic activity by the grinding media. In addition, it is possible to suppress the decrease in yield due to the product adhering to the grinding media. Here, "grinding media" in this embodiment means an object that is placed inside the reaction vessel for the purpose of applying grinding force to the raw materials contained in the vessel. Examples of grinding media shapes include ball-shaped, cylindrical, rod-shaped, etc. Examples of grinding media materials include glass; ceramics such as alumina, zirconia, titania, etc.; metals such as stainless steel, etc.

[0028] (Other Mixing Mechanisms) In the manufacturing method of this embodiment, a raw material mixing device installed in the reaction vessel, such as a stirring blade or stirring bar, may or may not be used. If a raw material mixing device installed in the reaction vessel is not used, it is easier to maintain a crystalline structure that exhibits good catalytic activity. In addition, it is possible to suppress the reduction in yield due to the product becoming lumpy and adhering to the mixing device. On the other hand, if a raw material mixing device installed in the reaction vessel is used, the mixing efficiency can be increased without excessively rotating or vibrating the reaction vessel, thus shortening the reaction time, and it is easier to suppress problems when the manufacturing equipment is enlarged. Examples of known stirring blades include propeller blades, turbine blades, paddle blades, anchor blades, and ribbon blades (single helical ribbons, double helical ribbons). Examples of known stirring bars include magnetic stirring bars.

[0029] <Drying Step> In the manufacturing method of this embodiment, after the reaction between the inorganic zinc compound and the aliphatic dicarboxylic acid is completed, there may be a step of drying the water produced by the reaction between the inorganic zinc compound and the aliphatic dicarboxylic acid. The drying conditions can be appropriately selected to remove the water. The drying temperature is not particularly limited, but may be, for example, 65 to 150°C, 70 to 140°C, or 75 to 130°C. The drying time is not particularly limited, but may be, for example, 0.5 to 24 hours, 0.75 to 12 hours, or 1 to 6 hours. Drying may be carried out under normal pressure or under reduced pressure.

[0030] <Purification Process> In this embodiment, the production method involves reacting an inorganic zinc compound with an aliphatic dicarboxylic acid without a solvent, thus eliminating the need for a step to remove the reaction solvent. Therefore, the organozinc compound obtained by the above reaction can be used as a polymerization catalyst after drying as necessary, without performing a step to remove the reaction solvent. However, the organozinc compound may be purified by washing or other methods as needed.

[0031] <Reaction Rate of Aliphatic Dicarboxylic Acids> The reaction rate of aliphatic dicarboxylic acids in the production method of this embodiment is preferably 95.0 to 100.0%, more preferably 96.0 to 100.0%, even more preferably 97.0 to 100.0%, even more preferably 98.0 to 100.0%, even more preferably 98.3 to 100.0%, even more preferably 98.5 to 100.0%, even more preferably 98.7 to 100.0%, even more preferably 99.0 to 100.0%, even more preferably 99.3 to 100.0%, and even more preferably 99.5 to 100.0%. The reaction rate of aliphatic dicarboxylic acids in this embodiment refers to the value obtained by the method described in the example.

[0032] <Uses of organozinc compounds> The organozinc compounds produced by the manufacturing method of this embodiment are suitable as catalysts for ring-opening polymerization of alkylene oxides, and more specifically, as catalysts for the synthesis of aliphatic polycarbonates or aliphatic polyethers.

[0033] Examples of alkylene oxides include ethylene oxide, propylene oxide, 1,2-butylene oxide, isobutylene oxide, 1-pentene oxide, 2-pentene oxide, 1-hexene oxide, 1-octen oxide, 1-decene oxide, cyclopentene oxide, cyclohexene oxide, and their derivatives. Among these, propylene oxide, derivatives of propylene oxide, 1,2-butylene oxide, or derivatives of 1,2-butylene oxide are preferred, and derivatives of 1,2-butylene oxide are more preferred. Alkylene oxides may be used individually or in combination of two or more.

[0034] Next, a method for producing aliphatic polycarbonate using the organozinc compound of this embodiment as a polymerization catalyst will be described.

[0035] Aliphatic polycarbonates, for example, react with alkylene oxides and carbon dioxide (CO2). ２) can be produced by a polymerization reaction using the organozinc compound of this embodiment as a polymerization catalyst. The conditions for the polymerization reaction can be, for example, those described in International Publication No. 2011 / 142259.

[0036] The amount of organozinc compound used as a polymerization catalyst is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 27 parts by mass, even more preferably 1 to 25 parts by mass, and even more preferably 10 to 22 parts by mass, per 100 parts by mass of alkylene oxide used.

[0037] The method for carrying out the polymerization reaction is not particularly limited as long as the target product is obtained, but for example, an autoclave is used to charge alkylene oxide, an organozinc compound, and a co-catalyst and solvent as needed, mix them, and then react by introducing carbon dioxide under pressure into the resulting mixture. The solvent used as needed in the polymerization reaction is not particularly limited, but an organic solvent is preferred. The amount of solvent used is preferably 50 to 10,000 parts by mass per 100 parts by mass of alkylene oxide.

[0038] The pressure at which carbon dioxide is injected during the polymerization reaction is preferably 0.1 to 20 MPa, more preferably 0.1 to 10 MPa, and even more preferably 0.1 to 5 MPa. If the pressure at which carbon dioxide is injected is above the lower limit, the polymerization reaction proceeds more easily. Also, if the pressure at which carbon dioxide is injected is below the upper limit, excessive use of carbon dioxide is suppressed, improving economic efficiency.

[0039] The reaction temperature during the polymerization reaction is preferably 20 to 100°C, more preferably 25 to 80°C, from the viewpoint of reaction rate and suppression of side reactions. The reaction time for the polymerization reaction can be adjusted as appropriate according to the reaction temperature, but is preferably 2 to 40 hours.

[0040] After the polymerization reaction is complete, the target aliphatic polycarbonate can be extracted by known methods after performing any known post-treatment procedures as necessary. The obtained aliphatic polycarbonate may also be purified by known methods as necessary.

[0041] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0042] [Production of Aliphatic Zinc Dicarboxylates] Details of the raw materials used in each example are as follows: Zinc oxide: Powder (average particle size (D ５０ ) = 0.6 μm) Glutaric acid: Powder (average particle size (D ５０ ) = 528 μm) Adipic acid: Powder (average particle size (D ５０ ) = 324 μm)

[0043] Example 1 A cylindrical glass container (outer diameter 27 mm) with a capacity of 50 mL and a lid was filled with 2.0 g of zinc oxide and 3.12 g of glutaric acid in air. The container was sealed with the lid without adding any solvent or grinding media. The cylindrical glass container was placed on the rotating roller of a mix rotor (manufactured by AS ONE Corporation, product name "MIX ROTOR VMR-5R", which has a seesaw motion function for its rotating rollers) set on a horizontal stand. The reaction was carried out by rotating the rotor at room temperature (23°C) for 24 hours under the conditions of a set rotation speed of 100 rpm and a container rotation speed of 119 rpm. The rotation axis of the cylindrical glass container is perpendicular to the bottom surface of the cylindrical glass container and passes through the center of gravity of the bottom surface. The angle of the rotation axis (maximum tilt angle of the seesaw motion) is ±2.5° with respect to the horizontal. The resulting white powder was dried in a vacuum dryer at 120°C for 5 hours to obtain an aliphatic dicarboxylate zinc salt.

[0044] Example 2 A zinc aliphatic dicarboxylate salt was obtained in the same manner as in Example 1, except that the amount of zinc oxide used and the type and amount of aliphatic dicarboxylic acid used were changed as shown in Table 1.

[0045] Example 3 2350 g of zinc oxide and 3665 g of glutaric acid were placed in air into a container-rotating oscillating powder mixing machine (manufactured by Aichi Electric Co., Ltd., product name "Rocking Mixer RMDHLV-30 (ST) type"), and the lid was closed to seal it without adding any solvent or grinding media. The reaction was carried out by rotating the machine for 2 hours at room temperature (23°C) under the following conditions: mixing speed 14 rpm (device setting 20 Hz), oscillating angle 20°, oscillating frequency 20 Hz, and crushing blade rotation speed 60 rpm (device setting 60 Hz). The resulting white powder was dried in a vacuum dryer at 120°C for 2 hours to obtain an aliphatic dicarboxylate zinc salt.

[0046] Comparative Example 1 A 3 L separable flask equipped with a condenser, thermometer, and a stirrer with anchor-type impellers (manufactured by AS ONE Corporation, product name "Tornado N (NEXT) PC Control PSTC-102") contained 81 g of zinc oxide, 132 g of glutaric acid, and 1,000 g of toluene. The mixture was then heated to 110°C under a nitrogen atmosphere and stirred at 500 rpm for 24 hours. After that, it was cooled to room temperature (23°C) and filtered by suction. The resulting white powder was placed in a 3 L beaker, 1 L of methanol was added and stirred, and then filtered by suction. The resulting white powder was again placed in a 3 L beaker, 1 L of methanol was added and stirred, and then filtered by suction. The resulting white powder was then dried in a vacuum dryer at 120°C for 5 hours to obtain an aliphatic dicarboxylate zinc salt.

[0047] Comparative Examples 2-4: Aliphatic dicarboxylate zinc salts were obtained in the same manner as in Comparative Example 1, except that the amount of zinc oxide used, the type and amount of aliphatic dicarboxylic acid used, and the type and amount of solvent used were changed as shown in Table 1.

[0048] Comparative Example 5 A 1 L separable flask equipped with a stirrer having an anchor-type stirring blade (manufactured by AS ONE Corporation, product name "Tornado N (NEXT) PC Control PSTC-102") contained 10.0 g of zinc oxide and 15.6 g of glutaric acid. Next, a solid-phase reaction was attempted with the stirrer rotating at 150 rpm. However, the raw materials and products aggregated, forming clumps, and these clumps adhered to the stirrer, making it impossible to continue the stirrer's rotation. Therefore, the reaction was stopped.

[0049] [Evaluation Method] Qualitative analysis and catalytic activity evaluation of the organozinc compounds obtained in each example and comparative example were performed using the following method. The results are shown in Table 1.

[0050] [Measurement of reaction rate of aliphatic dicarboxylic acid] The reaction rate of aliphatic dicarboxylic acid was measured using the following procedure.

[0051] (1) Thermogravimetric Analysis (TGA) The aliphatic dicarboxylate zinc salts produced in each example and comparative example were subjected to thermogravimetric analysis (TGA) under the following conditions. <Measurement Conditions> Measurement device: Shimadzu Corporation, product name "DTG-60" Measurement temperature range: 40 to 550°C Heating rate: 10°C / min Sample weight: 9 mg ± 1 Gas: Air

[0052] (2) Analysis Method The reaction rate of the aliphatic dicarboxylic acid was calculated from the results of thermogravimetric analysis (TGA). The stoichiometric ratio of zinc cation to aliphatic dicarboxylate in the zinc aliphatic dicarboxylic acid salt is 1:1. The meaning of the symbols used in each calculation described later is as follows: M １ : Number of moles (moles) of zinc oxide to be charged (M) ２ : Number of moles (moles) of aliphatic dicarboxylic acid used in the charge (M) ３ The theoretical maximum number of moles (mol) of a zinc aliphatic dicarboxylic acid salt having a stoichiometric composition, produced from zinc oxide and aliphatic dicarboxylic acid: M ４ : Prepared zinc oxide and prepared aliphatic dicarboxylic acid from M ３ When (mol) of aliphatic dicarboxylate zinc salt is produced, the theoretical number of moles (mol) of zinc oxide remaining unreacted is: A: Theoretical weight retention rate (%) B: Theoretical weight loss rate (%) C: Weight loss rate (%) of aliphatic dicarboxylate zinc salt produced in each example and comparative example at 350-550°C, measured by thermogravimetric analysis (TGA) R: Aliphatic dicarboxylate reaction rate (%)

[0053] <Calculation of Theoretical Weight Residue Rate A (%)> In calculating the theoretical weight residue rate A (%), first, it is assumed that the theoretical maximum number of moles of aliphatic dicarboxylate zinc salt having a stoichiometric composition (i.e., an aliphatic dicarboxylate zinc salt with a molar ratio [aliphatic dicarboxylate / zinc cation] of 1.00) are produced from the raw materials zinc oxide and aliphatic dicarboxylic acid, and that the components contained in the product are only aliphatic dicarboxylate zinc salt having a stoichiometric composition and unreacted zinc oxide (however, unreacted zinc oxide may not be included). Then, assuming that when the product is subjected to thermogravimetric analysis, all aliphatic dicarboxylates in the aliphatic dicarboxylate zinc salt disappear, all zinc cations in the aliphatic dicarboxylate zinc salt change to zinc oxide, and unreacted zinc oxide remains as zinc oxide, the weight residue rate in this case can be determined as the theoretical weight residue rate A (%). Specifically, the theoretical weight residue rate A (%) can be calculated by the following formula (I): A (%) = [(M ３ +M ４ ) × Molecular weight of zinc oxide] × 100 / (M ４ × Molecular weight of zinc oxide + M ３ ×Molecular weight of aliphatic dicarboxylate zinc salt having a stoichiometric composition) (I) Note M ３ and M ４ The number of moles of zinc oxide to be charged is M, as follows: １ and the number of moles M of aliphatic dicarboxylic acid used in the charge. ２ It is calculated from M. １ > M ２ If M ３ = M ２ M ４ = M １ -M ２ M １ ≤ M ２ If M ３ = M １ M ４ = 0

[0054] <Calculation of Theoretical Weight Loss Rate B (%)> Next, the theoretical weight loss rate B (%) is calculated from the theoretical weight retention rate A (%) calculated above using the following formula (II). B (%) = 100 - A (II)

[0055] <Calculation of Aliphatic Dicarboxylic Acid Reaction Rate R (%)> Next, the weight residue rate C of the sample at 350°C, which is the disappearance temperature of unreacted aliphatic dicarboxylic acid, is measured by thermogravimetric analysis (TGA). １ (%) and weight retention rate C at 550°C ２ From (%), the weight loss rate C (%) of the sample at 350°C to 550°C, with 350°C as the reference temperature, is calculated using the following formula (III): C (%) = (C １ -C ２ ) / C １ (III) The aliphatic dicarboxylic acid reaction rate R (%) is calculated from the theoretical weight loss rate B calculated by formula (II) above and the weight loss rate C calculated by formula (III) above using the following formula (IV): R (%) = C × 100 / B (IV)

[0056] [Evaluation of catalytic activity of organozinc compounds] An autoclave with the capacity shown in Table 1, equipped with a stirrer and gas inlet pipe, was subjected to an argon atmosphere, and organozinc compounds, monomers, and solvents of the types and amounts shown in Table 1 were added. Subsequently, the temperature was raised to 70°C, and the inside of the autoclave was subjected to the CO2 shown in Table 1. ２ The autoclave was then filled with carbon dioxide until pressure was reached, and stirred for two hours. After that, the autoclave was cooled to depressurize and a white slurry was obtained. The obtained slurry was then subjected to nuclear magnetic resonance spectroscopy ( １ ¹H-NMR (Biospin Avance 500, Bruker) was used as the solvent, with CDClone. ３ The analysis was performed using (containing 0.03 volume% tetramethylsilane) to determine the number of moles (M) of monomer-derived structural units in the polymer. ｐ ) and the number of moles of residual monomer (M ｍ The monomer was quantified and the conversion rate was calculated using the following formula. In Table 1, "<1" means that the monomer conversion rate was less than 1%. Monomer conversion rate (%) = M ｐ ×100 / (M ｐ +M ｍ )

[0057] *1: "GA" stands for glutaric acid, and "AA" stands for adipic acid. *2: "PO" stands for propylene oxide, and "BO" stands for 1,2-butylene oxide. *3: "EA" stands for ethyl acetate, "TL" stands for toluene, "MeOH" stands for methanol, and "IPA" stands for isopropyl alcohol.

[0058] Table 1 shows that the organozinc compounds produced by the manufacturing method of this embodiment exhibit excellent catalytic activity.

Claims

1. A method for producing an organozinc compound, comprising rotating a container containing an inorganic zinc compound and an aliphatic dicarboxylic acid, thereby reacting the inorganic zinc compound and the aliphatic dicarboxylic acid in the container without using grinding media and without a solvent.

2. The method for producing an organozinc compound according to claim 1, wherein the aliphatic dicarboxylic acid is one or more selected from the group consisting of glutaric acid and adipic acid.

3. The method for producing an organozinc compound according to claim 1 or 2, wherein the inorganic zinc compound is one or more selected from the group consisting of zinc oxide (ZnO), zinc sulfate (ZnSO ４ ３ ), zinc chlorate (Zn(ClO ３ ２ ) ２ ３ ), zinc nitrate (Zn(NO ３ ２ ) ２ ２ ), zinc formate (Zn(HCOO) ２ ２ ), zinc formate dihydrate (Zn(HCOO) ２ ·2H ２ O), zinc acetate (Zn(OAc) ２ ), zinc carbonate (ZnCO ３ ), and zinc hydroxide (Zn(OH) ２ ).

4. The method for producing an organic zinc compound according to claim 1 or 2, wherein the inorganic zinc compound and aliphatic dicarboxylic acid in the rotating container are in powder form.

5. The method for producing an organic zinc compound according to claim 1 or 2, wherein the molar ratio [inorganic zinc compound / aliphatic dicarboxylic acid] of the inorganic zinc compound to the aliphatic dicarboxylic acid contained in the container is 1.00 / 1.20 or more and 1.00 / 0.80 or less.

6. A method for producing an organozinc compound according to claim 1 or 2, wherein the reaction is carried out in air.

7. A method for producing an organozinc compound according to claim 1 or 2, wherein the reaction is carried out at 5 to 150°C.

8. A method for producing an organozinc compound according to claim 1 or 2, wherein the reaction rate of the aliphatic dicarboxylic acid is 95.0 to 100.0%.

9. The method for producing an organozinc compound according to claim 1 or 2, wherein the organozinc compound is a catalyst for the synthesis of aliphatic polycarbonate or aliphatic polyether.

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