JP4155212B2 - Cyclic carbonate catalyst and process for producing the same, and process for producing cyclic carbonate using the catalyst - Google Patents

Description

  The present invention relates to a catalyst for producing cyclic carbonate, a method for producing the catalyst, and a method for efficiently producing cyclic carbonate from an epoxy compound and carbon dioxide using the catalyst.

  Various methods for producing a cyclic carbonate have been disclosed, and for example, it has been introduced as a review (Non-Patent Document 1). Among these various methods, as an industrial production method, a method of producing from a reaction between an epoxy compound and carbon dioxide is becoming mainstream from the viewpoint of environmental harmony.

  As a catalyst for producing a cyclic carbonate from a reaction between an epoxy compound and carbon dioxide, there are many homogeneous catalysts such as alkali metal bromides or iodides as disclosed in, for example, (Patent Document 1). . However, when this method is adopted, the process becomes complicated, and there are various problems such as decomposition of the catalyst during the separation of the reaction product and the catalyst and generation of by-products.

  In particular, in recent years, solid catalyst systems have been directed and proposed to solve these problems. For example, thallium (III) oxide (Patent Document 2), a solid strongly basic anion exchanger resin having a quaternary ammonium salt whose water content is below a specific level (Patent Document 3), quaternary phosphonium Anion exchange resin having salt as an exchange group (Patent Document 4), heteropolyacid consisting of tungsten or molybdenum or a metal salt thereof (Patent Document 5), magnesium oxide calcined under specific conditions (Non-Patent Document 2), in zeolite A specific metal phthalocyanine complex encapsulated in a catalyst (Non-patent Document 3), or a catalyst related to the present inventors, that is, a hydrotalcite-based catalyst composed of magnesium or aluminum metal (Patent Document 6) prepared from specific conditions. Can be mentioned.

  However, these conventional techniques have been achieved in terms of solidification of the catalyst, but have at least one problem regarding heat resistance, complexity of catalyst preparation and management, amount of catalyst used, cost, and yield. It was.

JP-A-9-235252 JP 59-167578 A Japanese Patent Publication 8-32700 JP-A-9-235252 JP-A-7-206847 JP-A-11-226413 Chem. Rev. 96, 951, 1996 Chem. Commun. 1129, 1997 Catalysis Letters, 89, 81, 2003

  An object of the present invention is to provide a cyclic carbonate production catalyst that can be easily separated from a reaction product or a solution thereof after completion of the reaction and can be used repeatedly, and a simple production method thereof, and using the catalyst. Gives high yields of cyclic carbonates from epoxy compounds and carbon dioxide under low pressure conditions and reduced catalyst usage. Furthermore, when optically active epoxy compounds are used, the configuration of the epoxy asymmetric carbon is highly advanced. It is an object of the present invention to provide a production method for providing a cyclic carbonate held in a metal.

That is, the present invention is a cyclic carbonate production catalyst characterized in that a part of calcium ions constituting hydroxyapatite represented by the following general formula (1) is ion-exchanged with zinc ions.

  Moreover, this invention is a manufacturing method of the catalyst for cyclic carbonate manufacture characterized by mixing hydroxyapatite (1) and zinc salt aqueous solution, carrying out an ion exchange reaction, isolate | separating and drying a solid phase.

  Furthermore, the present invention is a method for producing a cyclic carbonate, characterized by using the above-mentioned catalyst for producing a cyclic carbonate and reacting an epoxy compound and carbon dioxide in the presence of a basic auxiliary agent.

  According to the present invention, it is possible to produce a catalyst from a general-purpose material by a simple means without the need for a sintering process, etc., and the obtained catalyst is solid and easy to handle and can be reused. Furthermore, a cyclic carbonate can be obtained in a high yield with a small amount of catalyst used.

First, the cyclic carbonate production catalyst and its production method will be described.
Hydroxyapatite (1) used as a raw material for preparing the catalyst in the present invention is a substance substantially composed of Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ , and a commercially available product can be obtained. For example, an explanation about the substance is described on page 140 of “Chemical Handbook Application”.

  In the catalyst according to the present invention, the ratio in which calcium ions are replaced with zinc ions by an ion exchange reaction is preferably 0.0001 to 0.5 milligram atoms, more preferably 1 milligram atoms of calcium constituting the hydroxyapatite (1). It is in the range of 0.001 to 0.1 milligram atoms, most preferably 0.01 to 0.08 milligram atoms.

  The catalyst of the present invention may be prepared by mixing hydroxyapatite (1) and an aqueous zinc salt solution, ion exchange reaction, separating and drying the solid phase. For example, a cyclic carbonate production catalyst can be obtained by adding hydroxyapatite (1) to a zinc salt aqueous solution having a concentration of 0.1 to 20 mmol / L, stirring or standing, and then separating and drying the solid phase. .

  Examples of zinc salts that can be used include salts composed of inorganic anions such as zinc nitrate, zinc sulfate, zinc chloride and zinc bromide, and salts composed of inorganic anions such as zinc acetate and zinc oxalate. It is done.

  The amount of zinc ions in the aqueous zinc salt solution is in the range of 0.001 to 5 mmol, preferably 0.01 to 1 mmol, more preferably 0.1 to 0.8 mmol, per 1 g of hydroxyapatite. Although there is no restriction | limiting in particular in the density | concentration of zinc salt aqueous solution, Usually, it can use in the range of 0.1-20 mmol zinc / L.

  The temperature and time for the ion exchange reaction are not particularly limited, but for example, the reaction temperature is in the range of 0 to 100 ° C. and the reaction time is within 48 hours.

  After the ion exchange reaction, the solid phase may be separated from the obtained slurry-like reaction solution by a usual means, for example, filtration may be performed. Also, the drying method after separation is not particularly limited, but it is preferably performed in the air at a drying temperature in the range of 20 to 200 ° C., and may be appropriately performed under reduced pressure.

  The behavior of zinc ions in the catalyst prepared by the above method can be observed by measuring the K-shell EXAFS spectrum of zinc. As a result, it can be confirmed that the unit structure of zinc-oxygen-zinc having a bond length of about 3 mm is substantially not included, which indicates the fact that zinc ions are substituted as phosphates in the catalyst according to the present invention.

（上式中、Ｒ₁、Ｒ₂、Ｒ₃およびＲ₄は、水素または置換基を有してもよい炭素数２０以下のアルキル基、アリール基、アルケニル基、シクロアルキル基、アリールアルキル基、エポキシ基を表し、それぞれ互いに同一の基でも異なる基でもよく、互いに結合して環状構造を形成してもよい。またここで言う置換基とはハロゲン原子、カルボキシル基、アルコキシ基、アリーロキシ基、カルボニル基、水酸基、エポキシ基を意味する。） Next, the manufacturing method of the cyclic carbonate using the catalyst of this invention is demonstrated.
The epoxy compound used in the present invention is a compound represented by the following general formula (2). The epoxy compound includes those having two or more epoxy groups.

(In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen or an optionally substituted alkyl group having 20 or less carbon atoms, aryl group, alkenyl group, cycloalkyl group, arylalkyl group, Represents an epoxy group, which may be the same or different from each other, and may be bonded to each other to form a cyclic structure, and the substituents mentioned here are halogen atoms, carboxyl groups, alkoxy groups, aryloxy groups, carbonyls Group, hydroxyl group, and epoxy group.)

  Specifically, as an epoxy compound having one epoxy group in a molecule, alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, and octylene oxide, and epoxy compounds having these substituents , Cyclohexylene oxide, cyclohexylene oxide having a substituent, alicyclic epoxy compounds such as norbornene epoxide, dicyclopentadiene epoxide, styrene oxide having a substituent such as styrene oxide, α-methylstyrene oxide, etc. Aryl alkylene oxides, alkylene oxides substituted with halogen such as epichlorohydrin, methyl glycidyl ether, butyl glycidyl ether, benzyl glycidyl ether, etc. Glycidyl ether alkylene oxides having an alkoxy substituent, glycidyl ethers having an allyloxy substituent such as phenyl glycidyl ether, glycidyl ester alkylene oxides having a carbonyl substituent such as glycidyl acetate, glycidyl propionate, hydroxyl groups such as glycidol Examples include alkylene oxides having a substituent.

  Examples of the epoxy compound having two or more epoxy groups in the molecule include acyclic or cyclic diepoxy compounds such as butadiene diepoxide, vinylcyclohexene diepoxide, norbornadiene diepoxide, dicyclopentadiene diepoxide, bisphenol A, bisphenol F, and the like. And diepoxy compounds containing an aryl group such as

  The present invention is not limited to these epoxy compounds, but includes at least one 3-membered ring formed by two carbon atoms and one oxygen atom in the structural formula, so-called epoxy system. Any compound can be used.

  Among the above-exemplified epoxy compounds, alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, and octylene oxide, cyclohexylene oxides having a substituent, norbornene epoxide, dicyclopentadiene epoxide, etc. Alicyclic epoxy compounds, styrene oxides such as styrene oxide and α-methylstyrene oxide, glycidyl ethers having an allyloxy substituent such as epichlorohydrin, phenylglycidyl ether, methyl glycidyl ether, butyl glycidyl ether, benzyl glycidyl Carbohydrates such as glycidyl ether alkylene oxides having an alkoxy substituent such as ether, glycidyl acetate, glycidyl propionate, etc. Preferred examples include alkylene oxides having a hydroxyl substituent such as glycidyl ester-based alkylene oxides and glycidol having a substituent, particularly ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, octylene oxide, and cyclohexylene. Oxide, norbornene epoxide, dicyclopentadiene epoxide, styrene oxide, α-methylstyrene oxide, epichlorohydrin, phenyl glycidyl ether, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, benzyl glycidyl ether, glycidyl acetate An epoxy compound selected from glycidyl propionate and glycidol is preferred.

（上式中、Ｒ₁、Ｒ₂、Ｒ₃ および Ｒ₄ はそれぞれ上記と同じである。） In the present invention, one or more of these epoxy compounds are subjected to the reaction. Therefore, the cyclic carbonate produced in the present invention is a carbonate produced from the epoxy compound and is a cyclic carbonate represented by the following general formula (3).

(In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are the same as above.)

  Specifically, ethylene carbonate, propylene carbonate, butylene carbonate, hexylene carbonate, octylene carbonate, vinyl ethylene carbonate, chloromethyl ethylene carbonate, cyclohexane carbonate, cyclopentane carbonate, styrene carbonate, methoxymethyl ethylene carbonate, phenoxymethyl ethylene carbonate And benzyloxyethylene carbonate, vinylcyclohexene dicarbonate, dicyclopentadiene dicarbonate, diallyldiphenylmethane dicarbonate, and the like.

By the way, the epoxy compound used as a raw material is hydrogen in the carbon atom of the three-membered ring constituting the epoxy compound except for the case where all of R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms in the general formula (1). When R ₁ , R ₂ , R ₃ and R ₄ substituents other than atoms are bonded, the carbon atom constitutes a molecule as an asymmetric carbon atom. In general, when the raw material epoxy compound is an optically active molecule derived from this carbon atom, when performing the carbonation reaction, part or all of the asymmetric configuration is often lost. By substituting the specific examples of the non-optically active substance with the raw material of the optically active substance, substantially all of the optical configuration of the epoxy compound to which the R ₁ , R ₂ , R ₃ , and R ₄ substituents are bonded is combined. A corresponding cyclic carbonate can be produced with high efficiency.

  Examples of the optically active epoxy compound that can be used include alkylene oxides such as propylene oxide, 1,2-butylene oxide, 1,2-pentene oxide, 1,2-hexylene oxide, 1,2-octylene oxide, and the like. Arylalkylene oxides such as epoxide compounds having substituents, alicyclic epoxy compounds including cyclohexylene oxides having substituents, styrene oxides having substituents such as styrene oxide and α-methylstyrene oxide , Alkylene oxides substituted with halogen such as epichlorohydrin, glycidyl ether alkylene oxides having an alkoxy substituent such as methyl glycidyl ether, butyl glycidyl ether, benzyl glycidyl ether, Glycidyl ethers having an allyloxy substituent such as E alkenyl glycidyl ether, glycidyl acetate, glycidyl esters having a carbonyl substituent glycidyl propionate, and alkylene oxides having a hydroxyl substituent such as glycidol and the like. Glycidyl ether alkylene oxides having an alkoxy substituent such as benzyl glycidyl ether are particularly preferred.

  In the production of a cyclic carbonate from an epoxy compound and carbon dioxide using the catalyst of the present invention, a basic auxiliary agent is essential.

The basic auxiliaries here are roughly classified into inorganic bases and organic bases.
Among basic auxiliaries, examples of inorganic bases include alkali metals such as Li, Na, K, Rb, and Cs, or alkaline earth metals such as Be, Mg, Ca, Sr, and Ba, (ammonium) Hydroxide (OH), sulfide (S), carbonic acid (CO ₃ ) salt, hydrogen carbonate (HCO ₃ ) salt, hydrogen phosphate (HPO ₄ ) salt, sulfurous acid (SO ₃ ) salt, hyposulfite (S ₂ O) ₃ ), or NH ₄ (ammonium) hydroxide (OH), carbonic acid (CO ₃ ), sulfuric acid (SO ₄ ), hydrazine (onium) sulfuric acid (SO ₄ ), carbonic acid (CO ₃ ) Salt, phosphoric acid (PO ₄ ) salt, ammonia (NH ₃ ) and the like, and particularly Li ₂ CO ₃ , LiHCO ₃ , Na ₂ CO ₃ , NaHCO ₃ , K ₂ CO ₃ , KHCO ₃ , Rb ₂ CO ₃ , RbHCO _{3, Cs 2 CO 3, CsHCO} 3, NH 4 SO 4, _{H 3, LiHPO 4, NaHPO 4} , RbHPO 4, CsHPO 4, NH 3 is preferable. One or two or more inorganic bases including the above examples can be selected and used. Inorganic bases usually have a variety of forms ranging from powder to flakes. In the present invention, any of these forms can be used, but it is preferable to use a powdery inorganic base from the viewpoint of promoting the reaction.

Examples of organic bases among basic auxiliaries include primary amines in which one nitrogen atom is substituted with one aliphatic group, such as methylamine, ethylamine, isopropylamine, butylamine, octylamine, and cyclohexylamine. Secondary amines in which one nitrogen atom is substituted with two identical or different aliphatic groups, such as dimethylamine, diethylamine, ethylisopropylamine, butylamine, methyloctylamine, dicyclohexylamine, trimethylamine, triethylamine, Three linear, branched, or monocyclic aliphatic groups in which one nitrogen atom may be the same or different from each other, such as isopropylamine, ethyldiisopropylamine, methylethylbutylamine, trioctylamine, and tricyclohexylamine. Substituted tertiary amines, aniline, -Amines in which at least one of the primary, secondary or tertiary amines is substituted with an aromatic group, such as methylaniline, phenylethylamine, naphthylethylamine, pyrrolidine, 1- (2-aminoethyl) pyrrolidine 3-aminopyrrolidine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, morpholine, N-methyl Morpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, N-aminomorpholine, N- (2-aminoethyl) morpholine, cyclohexylmorpholinoethylthiourea (CHMETU), etc. may be substituted Amines having one nitrogen atom in the formed monocyclic ring structure, Amines having two or more nitrogen atoms in an optionally substituted saturated monocyclic ring structure, such as azine, N- (2-aminoethyl) piperazine, 1,5-diazabicyclo [4,3,0] Non-5-ene, 1,8-diazabicyclo [5,4,0] undec-7-ene, 1,4-diazabicyclo [2.2.2] octane, hexamethylenetetramine, pyrazoline, 2-imidazoline, 3- Imidazolines 4-imidazolines, 4,4-dimethylimidazolines, and the like, amines having two or more nitrogen atoms in an optionally substituted non-aromatic bicyclic ring structure, indole, pyrrole, pyrazole, 3-amino -5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyridine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2- Dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, quinoline and the like, amines having one nitrogen atom in an aromatic monocyclic ring structure which may be substituted, imidazole 2,4,5-triphenylimidazole, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyridazine, pyrazole, triazole, etc. Amine having two or more nitrogen atoms in an aromatic monocyclic ring structure Guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, guanidine-based amines, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebagate, etc. And hindered amines described in JP-A No. 11-52575, such as quinine and cinchonidine, which are selected from one or more of these amines, but are not limited thereto. .
In addition, when the above-exemplified amines have an asymmetric structure, they may be racemic, meso, or optically active.
Among the amines exemplified above, 4-dimethylaminopyridine, 1,8-diazabicyclo [5,4,0] undec-7-ene, triethylamine, and pyridine are particularly preferable. 4-dimethylaminopyridine is particularly preferable.

Moreover, although the preferable addition amount of the said basic auxiliary agent used in this invention may be 0.00001-0.2 mol with respect to 1 mol of epoxy compounds, Preferably it is 0.00005-0.1 mol, The range of 0.0001 to 0.1 mol is more preferable.
Moreover, the preferable addition amount of the basic auxiliary agent per 1 gram atom of zinc in the catalyst is in the range of 0.1 to 500 mol, preferably 0.5 mol to 300 mol, more preferably 1 to 100 mol. .

In carrying out the method for producing a cyclic carbonate according to the present invention, preferred addition amounts of carbon dioxide and catalyst, and other preferred conditions are as follows.
That is, the partial pressure of carbon dioxide to be used is not particularly limited, but is preferably 1~200kg / cm ^2, more preferably 1 to 100 kg / cm ^2, and most preferably is suitable 1 to 50 kg / cm ^2.
In this case, the amount of the catalyst used may be 0.0001 to 5 mol%, preferably 0.0005 to 2 mol%, more preferably 0.001 to 1 mol, based on the number of moles of the raw material epoxy compound. A range of mol% is suitable.
The reaction temperature may be 20 to 200 ° C., preferably 40 to 150 ° C., and the reaction time depends on the partial pressure of the raw material epoxy compound and carbon dioxide, but usually 10 minutes to 60 ° C. The time may be 1 to 40 hours, and more preferably 3 to 30 hours.

In the method for producing a cyclic carbonate of the present invention, it can be employed in the presence or absence of a solvent, and it is usually preferable to carry out in the absence of a solvent from the viewpoint of improving the efficiency of the process. For this purpose, or as a countermeasure to the case where the epoxy compound is a solid, it can be carried out in the presence of a solvent, and any method is appropriately adopted. Although there is no restriction | limiting in particular as a solvent, A nonbasic solvent is preferable.
Examples include acyclic or cyclic aliphatic solvents such as pentane, hexane and cyclohexane, aromatic solvents such as benzene, toluene and chlorobenzene, ketone solvents such as acetone and methyl ethyl ketone, alcohol solvents such as methanol and ethanol, chloroform Aprotic polar solvents composed of nitrogen and / or sulfur atoms, such as halogenated hydrocarbons such as methylene chloride, dimethylformamide, and dimethylsulfoxide, and cyclic carbonates of the corresponding products such as ethylene carbonate and propylene carbonate A solvent etc. are mentioned and 1 type (s) or 2 or more types are selected.

  By the way, the catalyst used in the present invention can be easily solid-liquid separated by a method such as filtration after being used in the cyclic carbonation reaction. The separated spent catalyst can be used again in the second or more reactions as it is or after washing with the solvent exemplified as the reaction solvent, as it is, or after removal by a method such as drying. When the recovered catalyst is reused, heat treatment may be performed in the range of 20 to 200 ° C. as necessary.

[Example 1]
(Preparation of catalyst)
Hydroxyapatite (Wako Pure Chemicals; product number 032-10855) (1.0 g) was added to an aqueous solution in which Zn (NO ₃ ) ₂ (0.3 mmol) was dissolved in water (100 g), stirred at room temperature for 24 hours, and then filtered. The catalyst was obtained by drying at 110 ° C. for about 10 hours.
FIG. 1A shows the result of Fourier transform of Zn—K shell EXAFS of the obtained catalyst. For comparison, a spectrum with zinc oxide is shown in FIG. The peak near 3Å of zinc oxide (B) is derived from the Zn-O-Zn bond, but this is not confirmed in the obtained catalyst (A), and Zn-O derived from the peak near 1.7Å. Only a structure composed of mononuclears was confirmed.

[Example 2]
(Production of carbonate)
After adding epichlorohydrin (100 mmol), catalyst prepared in Example 1 (0.01 g, 0.003 mmol based on Zn), 4-dimethylaminopyridine (0.02 mmol) to a stainless steel autoclave (capacity 200 ml), CO ₂ gas was introduced to 10 kg / cm ² . The reaction was carried out at 100 ° C. for 24 hours with stirring. After the reaction, the reaction solution was taken out from the autoclave, components were quantified by gas chromatography, the yield of the produced 3-chloropropylene carbonate was determined on the basis of the raw material epoxide, and the results shown in Table 1 were obtained.

[Example 3-14]
The reaction from epoxide to the corresponding alkylene carbonate was conducted in the same manner as in Example 1 under the conditions shown in Table 1, and the results shown in Table 1 were obtained.

[Example 15]
(Reuse of catalyst)
The reaction solution obtained after the reaction in Example 13 was filtered under reduced pressure, whereby the reaction solution and the catalyst could be easily separated. The solid content obtained as a filtration residue was washed with acetone and then dried under reduced pressure for 15 minutes to obtain a catalyst (C) for reuse. FIG. 1C shows a Fourier transform result of Zn-K shell EXAFS of the catalyst (C). It was confirmed that there was no substantial change from the spectrum (A) of the catalyst before use. The reaction was conducted in the same manner as in Example 13 except that the catalyst (C) was used, and the corresponding carbonate was obtained with a yield of 96%.
Further, the reaction mixture obtained here was filtered in the same manner as described above, and the resulting solid residue was washed with acetone, dried under reduced pressure for 15 minutes, and used again as a catalyst (D). The reaction using the catalyst D was carried out in the same manner as in Example 13, and the corresponding carbonate was obtained with a yield of 95%.

[Example 16]
(Optically active substance)
(R) -phenylglycidyl ether (10 mmol), catalyst (0.15 mol%), DMAP (0.1 mmol), solventless, CO ₂ (5 kg / cm ² ), reaction temperature (100 ° C.), reaction time (24 Hr) And the carbonated reaction was carried out in the same manner as in Example 1 to obtain the corresponding carbonated product. The yield of (R) -carbonate obtained was 82%, and the optical purity was 99% ee or higher.
The optical purity was measured by liquid chromatography using an optical resolution column (Daicel Chemical Chiralcel OF) (solvent: hexane / ethanol = 9/1 (v / v), flow rate: 1.0 ml / min, detection wavelength. 256 nm).
The same reaction and measurement were performed using (S) -phenylglycidyl ether (10 mmol) as a raw material, and the corresponding (S) -3-phenoxypropylene carbonate was obtained in a yield of 84% and an optical purity of 99% or more. .

[Comparative example]
To an aqueous solution in which Na ₂ CO ₃ (0.943 mol) and NaOH (3.5 mol) are dissolved in deionized water (100 ml), Mg (NO ₃ ) ₂ .6H ₂ O (1 mol) is stirred at room temperature. ) And Al (NO ₃ ) ₃ .9H ₂ O (0.2 mol) dissolved in deionized water (100 ml) was added dropwise. After completion of the dropwise addition, the mixture was stirred at 65 ° C. for 18 hours, and the resulting slurry was suction filtered and dried at 110 ° C. overnight to obtain a white powder.
The white powder obtained above was calcined at 400 ° C. for 1 hour in an oxidizing atmosphere to obtain a comparative catalyst.
When methyl glycidyl ether (4 mmol), the above comparative catalyst (0.3 g), DMF solvent (3 ml) was used, and the reaction was carried out in the same manner as in Example 14 except that no base was used, the reaction product was analyzed. The corresponding 3-phenoxypropylene carbonate was produced with a yield of 60%.
In addition, the catalyst amount (0.006 mol%) used in Example 14 corresponds to the catalyst amount (0.003 mol, 0.01 g).

(Explanation of Table 1)
1. In the table, the numbers (1) to (6) in the column of “epoxide” mean the following compounds.
(1): epichlorohydrin, (2): methyl glycidyl ether, (3): styrene oxide,
(4): 1-hexene oxide, (5): 1-octene oxide, (6): phenylglycidyl ether In the table, the abbreviations in the “base” column mean the following compounds.
DMAP; 4-dimethylaminopyridine, DBU; 1,8-diazabicyclo [5,4,0] undec-7-ene, TEA; triethylamine In the table, the following relationship was used to calculate the “catalyst amount”. Here, “mol%” of the catalyst represents mol% of the substrate with respect to epoxide.
Catalyst amount: 0.01 g = 0.003 mmol (Zn basis)
4). Other points to note in 1) to 4) are as follows.
1) Yield of corresponding alkylene carbonate 2) Tanne over number (TON) = [(generated carbonate (mmol) / amount of catalyst used in reaction (mmol: Zn standard))
3) Dimethylformamide (5 ml) was used as a solvent.
4) As the reaction vessel, an autoclave of 200 ml was used in Examples 1 and 6 and the other was 100 ml.

The present invention can be used for the production of a cyclic carbonate using an epoxy compound as a main raw material by using a solid catalyst. Furthermore, the present invention can be used for the production of optically active cyclic carbonates having a highly maintained steric configuration that is a useful raw material for pharmaceuticals and pharmaceutical intermediates.
Non-optically active cyclic carbonates are industrially useful substances such as environmentally conscious organic solvents, acrylic fiber processing agents, battery electrolytes, hydroxyalkylating agents, and the like. The optically active epoxy compound is useful as an intermediate for pharmaceuticals or agricultural chemicals.

It is a figure which shows the Fourier transform of K shell EXAFS of zinc (Zn). Example 1

Explanation of symbols

A: Catalyst B obtained in Example 1 of the present invention B: Zinc oxide C: Regenerated catalyst obtained in Example 1 of the present invention once

Claims (10)

A catalyst for producing a cyclic carbonate, characterized in that a part of calcium ions constituting the hydroxyapatite represented by the following general formula (1) is ion-exchanged with zinc ions, and the calcium is produced by the ion exchange reaction. The ratio in which ions are substituted with zinc ions is 0.0001 to 0.5 milligram atom per milligram atom of calcium constituting hydroxyapatite (1), and the cyclic carbonate to be produced is represented by the following general formula ( A catalyst for producing a cyclic carbonate, which is represented by 3).

(In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen or an optionally substituted alkyl group having 20 or less carbon atoms, aryl group, alkenyl group, cycloalkyl group, arylalkyl group, Represents an epoxy group, which may be the same or different from each other, and may be bonded to each other to form a cyclic structure, and the substituents mentioned here are halogen atoms, carboxyl groups, alkoxy groups, aryloxy groups, carbonyls Group, hydroxyl group, and epoxy group.) Mixing hydroxyapatite (1) and the zinc salt solution, by an ion exchange reaction of claim 1, wherein the cyclic carbonate catalyst for producing slurry by separation and drying, characterized by comprising. The catalyst for producing a cyclic carbonate according to claim 1 or 2, wherein a unit structure of zinc-oxygen-zinc at a bond length of 3− is not observed in a K-shell EXAFS spectrum of zinc. The method for producing a catalyst for producing cyclic carbonate according to any one of claims 1 to 3 , wherein the hydroxyapatite (1) and an aqueous zinc salt solution are mixed and subjected to an ion exchange reaction, and the solid phase is separated and dried. A cyclic carbonate represented by the following general formula (3), wherein the catalyst according to any one of claims 1 to 3 is used, and an epoxy compound and carbon dioxide are reacted in the presence of a basic auxiliary agent. Manufacturing method.

(In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are the same as above.) 6. The method for producing a cyclic carbonate according to claim 5 , wherein the addition amount of the catalyst is in the range of 0.0001 to 5 mol% with respect to the number of moles of the epoxy compound to be used. The method for producing a cyclic carbonate according to claim 5 or 6 , wherein the partial pressure of carbon dioxide is 1 to 200 kg / cm ² and the reaction temperature is in the range of 20 to 200 ° C. The method for producing a cyclic carbonate according to any one of claims 5 to 7, wherein the addition amount of the basic auxiliary agent is 0.1 to 500 mol per gram atom of zinc constituting the catalyst. The method for producing a cyclic carbonate according to claim 8, wherein the basic auxiliary agent is an organic nitrogen compound. The method for producing an optically active cyclic carbonate according to any one of claims 5 to 9, wherein the epoxy compound is an optically active substance.

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