WO2013039105A1 - Method for producing aluminum alkoxide - Google Patents
Method for producing aluminum alkoxide Download PDFInfo
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- WO2013039105A1 WO2013039105A1 PCT/JP2012/073336 JP2012073336W WO2013039105A1 WO 2013039105 A1 WO2013039105 A1 WO 2013039105A1 JP 2012073336 W JP2012073336 W JP 2012073336W WO 2013039105 A1 WO2013039105 A1 WO 2013039105A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- aluminum alkoxide
- aluminum
- normal
- alcohol
- producing
- Prior art date
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 98
- -1 aluminum alkoxide Chemical class 0.000 title claims abstract description 80
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 13
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 12
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052738 indium Inorganic materials 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 10
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 8
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 claims description 8
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000005244 neohexyl group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 19
- 239000002184 metal Substances 0.000 abstract description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002472 indium compounds Chemical class 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/062—Al linked exclusively to C
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/68—Preparation of metal alcoholates
- C07C29/70—Preparation of metal alcoholates by converting hydroxy groups to O-metal groups
Definitions
- the present invention relates to a method for producing aluminum alkoxide. Specifically, the present invention relates to a method for producing aluminum alkoxide by a solid-liquid reaction between metallic aluminum and alcohol.
- Aluminum alkoxides are widely used as raw materials for high-purity alumina, organic synthesis catalysts, dehydrating condensing agents, surface treatment agents, additives for modification such as paints, inks, adhesives, water repellents, and functional glass. It's being used.
- high-purity alumina in fields where high growth is expected, such as display materials, energy, automobiles, semiconductors, and computers, has been increasing, and it is required to efficiently produce aluminum alkoxide as the raw material. ing.
- Patent Document 1 discloses a method in which a solid-liquid reaction is carried out under the condition that at least one of gallium, indium or a compound of these metals is present in an amount of 0.02 to 50 ppm (in terms of metal) relative to the liquid phase.
- Patent Document 2 discloses a method in which granular aluminum having a diameter of 2 mm to 100 mm is used as metallic aluminum in the absence of a catalyst, and a solid-liquid reaction is performed under a condition where the moisture in the alcohol used is 2000 ppm or less. ing.
- an object of this invention is to provide the manufacturing method of aluminum alkoxide which can manufacture aluminum alkoxide efficiently by the solid-liquid reaction of metal aluminum and alcohol.
- the present inventors have intensively studied to solve the above problems. As a result, in the mixed solution containing aluminum alkoxide at a predetermined ratio, the present inventors have obtained new knowledge that the reaction is likely to proceed when the metal aluminum and the alcohol are subjected to a solid-liquid reaction in the presence of a catalyst. It came to complete.
- a method for producing an aluminum alkoxide comprising steps (a) and (b).
- Aluminum alkoxide is a manufacturing method of the aluminum alkoxide of the said (1) or (2) description represented by following formula (i).
- Al (OR 1 ) 3 (i) [Wherein R 1 is independently methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, neobutyl, normal pentyl, isopentyl, neopentyl, normal hexyl, isohexyl, neohexyl, normal heptyl, isoheptyl, neoheptyl, normal It is at least one selected from the group consisting of octyl, isooctyl and neooctyl.
- R 2 OH (ii)
- R 2 is methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, neobutyl, normal pentyl, isopentyl, neopentyl, normal hexyl, isohexyl, neohexyl, normal heptyl, isoheptyl, neoheptyl, normal octyl, isooctyl and It is at least one selected from the group consisting of neooctyl.
- the aluminum alkoxide is represented by the formula (iii), and the alcohol is represented by the formula (iv).
- Al (OR 3 ) 3 (iii) R 3 OH (iv) wherein R 3 is methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, neobutyl, normal pentyl, isopentyl, neopentyl, normal hexyl, isohexyl, neohexyl, normal heptyl, isoheptyl, neoheptyl, normal octyl, isooctyl and It is at least one selected from the group consisting of neooctyl.
- the method for producing an aluminum alkoxide of the present invention comprises a step (a) of preparing a mixture by mixing alcohol and aluminum alkoxide, and a step (b) of reacting the alcohol and metal aluminum in the presence of a catalyst.
- the purity of the metallic aluminum used as a raw material is not particularly limited.
- aluminum alkoxide obtained by the production method of the present invention is used as a raw material for high-purity alumina having a purity of 99.99% or more, 99.99. It is preferable that the purity is 99% or more. If the purity is within the above range, the impurity concentration of iron, silicon, copper, magnesium, etc. in the metal aluminum is 100 ppm or less with respect to the total weight of the metal aluminum, so that the resulting aluminum alkoxide can be purified. It becomes unnecessary.
- the metallic aluminum before the solid-liquid reaction is at least one selected from gallium and indium, preferably 0.02 to 50 ppm, more preferably 0.1 to 40 ppm, particularly preferably based on the total weight of the metallic aluminum.
- the content is preferably 0.5 to 20 ppm.
- the shape of the metal aluminum is not particularly limited, and examples thereof include ingots, pellets, plates, foils, wires, and powders.
- the aluminum alkoxide is not particularly limited, and it is preferable to use the same compound as the aluminum alkoxide intended for production.
- Specific examples of the aluminum alkoxide include aluminum alkoxide represented by the following formula (i), and among them, aluminum isopropylide is preferable.
- R 1 is independently methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, neobutyl, normal pentyl, isopentyl, neopentyl, normal hexyl, isohexyl, neohexyl, normal heptyl, isoheptyl, neoheptyl, normal It is at least one selected from the group consisting of octyl, isooctyl and neooctyl, preferably isopropyl, and more preferably the same as R 2 in formula (ii) described later. ]
- the alcohol that forms the mixed solution is preferably a monohydric alcohol having 1 to 8 carbon atoms. Among them, the longer the carbon chain, the lower the reactivity with metallic aluminum.
- the alcohol represented by the formula (ii) is more preferable, and isopropyl alcohol is particularly preferable.
- R 2 is methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, neobutyl, normal pentyl, isopentyl, neopentyl, normal hexyl, isohexyl, neohexyl, normal heptyl, isoheptyl, neoheptyl, normal octyl, isooctyl and It is at least one selected from the group consisting of neooctyl, and among them, isopropyl is preferable. ]
- the alcohol may contain a solvent such as benzene and toluene as long as the above-described solid-liquid reaction is not adversely affected.
- the liquid containing alcohol may contain ketones such as acetone, but the content of the ketone is within the range of 130 ppm or less with respect to the total weight of the liquid containing alcohol. It is preferable because it does not adversely affect the liquid reaction.
- the catalyst is at least one selected from gallium and indium. These may exist as compounds. Examples of gallium and indium compounds include alkoxide compounds such as methoxide, ethoxide and isopropoxide; allyloxide compounds such as phenoxide; carboxylate compounds such as formate and acetate; anhydrous halides such as acetylacetonate compounds and chlorides Is mentioned. Among these catalysts, those having solubility in the alcohol or other solvent used can be used alone or in combination.
- step (a) Alcohol / aluminum alkoxide is mixed with alcohol / aluminum alkoxide in a weight ratio of 5/95 to 85/15, preferably 5/95 to 80/20, more preferably 5/95 to 70 /. Mix to obtain 30 to obtain a mixed solution. If the weight ratio is within the above range, the progress of the solid-liquid reaction can be effectively promoted.
- the mixing order and mixing method of alcohol and aluminum alkoxide in preparing the mixed solution are not particularly limited, and may be performed while stirring or may be performed while heating.
- the temperature of the mixture is preferably 15 to 65 ° C., more preferably 20 to 60 ° C. If the temperature is within the above range, the reaction can be further promoted.
- Step (b)> metallic aluminum is introduced into the mixed liquid obtained as described above, and the alcohol and the metallic aluminum are subjected to solid-liquid reaction in the presence of the catalyst.
- the ratio of the amount of alcohol and metal aluminum used is not unambiguous depending on the reaction mode such as batch or continuous and the desired concentration of aluminum alkoxide, but the amount of metal aluminum depends on the total weight of the mixture. On the other hand, it may be 1 to 70% by weight, preferably 1.5 to 65% by weight, particularly preferably 1.5 to 60% by weight.
- the amount of metallic aluminum is within the above range, the solid-liquid reaction between metallic aluminum and alcohol can be further promoted, and aluminum alkoxide can be produced more efficiently.
- the content of the catalyst is preferably based on the weight of Al contained in the mixed liquid in contact with the metal aluminum (however, in the case of a compound of gallium and indium, it is a value in terms of metal), preferably. It is 0.02 to 50 ppm, more preferably 0.1 to 40 ppm. When the catalyst content is less than 0.02 ppm, the reaction promoting effect may not be sufficient. On the other hand, when it exceeds 50 ppm, the resulting aluminum alkoxide is used as a raw material for fine ceramic powders such as high-purity alumina. In addition, gallium and indium may move to the final product as impurities, which may cause inconveniences such as deterioration of sinterability and optical characteristics.
- the method for causing the catalyst to be present in the mixed solution is not particularly limited as long as the concentration of the catalyst in the mixed solution is within the above range, and, for example, more effective promotion at the solid-liquid interface
- a method in which the catalyst is contained by a known method such as mixing and dispersing in advance or solid solution, and the metal aluminum and alcohol are reacted while dispersing or eluting the catalyst in the mixed solution during the solid-liquid reaction is preferable.
- the desired amount of gallium and / or indium may be used in combination in consideration of the elution amount from metallic aluminum and the amount added directly into the mixed solution.
- the reaction temperature in the solid-liquid reaction between metallic aluminum and alcohol is not particularly limited as long as the reaction proceeds, and is preferably 75 to 110 ° C, more preferably 80 to 100 ° C. In particular, from the viewpoint of accelerating the reaction, it is preferable to carry out the reaction under conditions where the liquid mixture used is boiled and refluxed.
- the present invention may further include a step of recovering aluminum alkoxide from the mixture obtained in the step (b) described above.
- Example 1 In a 2 liter separable flask equipped with a reflux condenser, 100 parts by weight of a mixed solution in which isopropyl alcohol (A) and aluminum isopropoxide (B) were mixed so that the weight ratio (A / B) was 15/85 was added. Added. Next, 2.3 parts by weight of an aluminum piece (size: about a diameter) having a stirring rotor blade at the lower end and attached to the peripheral surface of the polytetrafluoroethylene-coated shaft using a polytetrafluoroethylene tube.
- A isopropyl alcohol
- B aluminum isopropoxide
- Example 2 The same operation as in Example 1 was performed except that the weight ratio of isopropyl alcohol to aluminum isopropoxide in the mixed solution was 60/40 and the reaction time was 717 minutes. After the reaction for 717 minutes, the aluminum piece was taken out, and the dissolution amount of the aluminum piece was 20.6%.
- Example 3 The same operation as in Example 1 was performed except that the weight ratio of isopropyl alcohol to aluminum isopropoxide in the mixed solution was 55/45 and the reaction time was 716 minutes. After the reaction for 716 minutes, the aluminum piece was taken out, and the amount of dissolution of the aluminum piece was 14.7%.
- Example 4 The same operation as in Example 1 was performed except that the weight ratio of isopropyl alcohol to aluminum isopropoxide in the mixed solution was 50/50 and the reaction time was 715 minutes. After reacting for 715 minutes, the aluminum piece was taken out, and the dissolution amount of the aluminum piece was 16.0%.
- Example 1 The same operation as in Example 1 was performed except that the weight ratio of isopropyl alcohol to aluminum isopropoxide in the mixed solution was 100/0 and the reaction time was 716 minutes. Almost no generation of hydrogen gas was confirmed. After the reaction for 716 minutes, the aluminum piece was taken out, and the dissolution amount of the aluminum piece was 0.0%.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention addresses the problem of providing a method for producing aluminum alkoxide, whereby aluminum alkoxide can be produced efficiently through a solid-liquid reaction between metal aluminum and an alcohol. This method for producing aluminum alkoxide comprises: a step (a) of mixing an alcohol and aluminum alkoxide to prepare a mixed solution in which the alcohol/aluminum alkoxide weight ratio is 5/95 to 85/15; and a step (b) of reacting alcohol and metal aluminum within the mixed solution in the presence of at least one species selected from gallium and indium.
Description
本特許出願は、日本国特許出願第２０１１－１９９４３０号（２０１１年９月１３日出願）に基づくパリ条約上の優先権を主張するものであり、ここに引用することによって、上記出願に記載された内容の全体が、本明細書中に組み込まれるものとする。
本発明は、アルミニウムアルコキサイドの製造方法に関する。詳しくは、本発明は、金属アルミニウムとアルコールとの固液反応によりアルミニウムアルコキサイドを製造する方法に関する。 This patent application claims priority under the Paris Convention based on Japanese Patent Application No. 2011-199430 (filed on September 13, 2011), and is incorporated herein by reference. The entire contents of which are incorporated herein.
The present invention relates to a method for producing aluminum alkoxide. Specifically, the present invention relates to a method for producing aluminum alkoxide by a solid-liquid reaction between metallic aluminum and alcohol.
本発明は、アルミニウムアルコキサイドの製造方法に関する。詳しくは、本発明は、金属アルミニウムとアルコールとの固液反応によりアルミニウムアルコキサイドを製造する方法に関する。 This patent application claims priority under the Paris Convention based on Japanese Patent Application No. 2011-199430 (filed on September 13, 2011), and is incorporated herein by reference. The entire contents of which are incorporated herein.
The present invention relates to a method for producing aluminum alkoxide. Specifically, the present invention relates to a method for producing aluminum alkoxide by a solid-liquid reaction between metallic aluminum and alcohol.
アルミニウムアルコキサイドは、高純度アルミナの原料、有機合成触媒、脱水縮合剤、表面処理剤や、塗料、インキ、接着剤などの改質用添加剤、或いは撥水剤、機能性ガラスなどとして幅広く利用されている。
近年、表示材料、エネルギー、自動車、半導体やコンピューターといった高い成長が期待される分野での高純度アルミナの需要が拡大しており、その原料となるアルミニウムアルコキサイドを効率よく製造することが求められている。 Aluminum alkoxides are widely used as raw materials for high-purity alumina, organic synthesis catalysts, dehydrating condensing agents, surface treatment agents, additives for modification such as paints, inks, adhesives, water repellents, and functional glass. It's being used.
In recent years, the demand for high-purity alumina in fields where high growth is expected, such as display materials, energy, automobiles, semiconductors, and computers, has been increasing, and it is required to efficiently produce aluminum alkoxide as the raw material. ing.
近年、表示材料、エネルギー、自動車、半導体やコンピューターといった高い成長が期待される分野での高純度アルミナの需要が拡大しており、その原料となるアルミニウムアルコキサイドを効率よく製造することが求められている。 Aluminum alkoxides are widely used as raw materials for high-purity alumina, organic synthesis catalysts, dehydrating condensing agents, surface treatment agents, additives for modification such as paints, inks, adhesives, water repellents, and functional glass. It's being used.
In recent years, the demand for high-purity alumina in fields where high growth is expected, such as display materials, energy, automobiles, semiconductors, and computers, has been increasing, and it is required to efficiently produce aluminum alkoxide as the raw material. ing.
アルミニウムアルコキサイドの製造方法として、金属アルミニウムとアルコールとを固液反応させる製造方法が知られている。特許文献１には、ガリウム、インジウム或いはこれら金属の化合物の少なくとも１種が液相に対し０．０２～５０ｐｐｍ（金属換算）存在する条件下で固液反応させる方法が開示されている。特許文献２には、触媒の非存在下で、金属アルミニウムとして、直径が２ｍｍ～１００ｍｍの粒状アルミニウムを用い、使用するアルコール中の水分が２０００ｐｐｍ以下である条件下で固液反応させる方法が開示されている。
As a method for producing aluminum alkoxide, a production method in which metal aluminum and alcohol are subjected to a solid-liquid reaction is known. Patent Document 1 discloses a method in which a solid-liquid reaction is carried out under the condition that at least one of gallium, indium or a compound of these metals is present in an amount of 0.02 to 50 ppm (in terms of metal) relative to the liquid phase. Patent Document 2 discloses a method in which granular aluminum having a diameter of 2 mm to 100 mm is used as metallic aluminum in the absence of a catalyst, and a solid-liquid reaction is performed under a condition where the moisture in the alcohol used is 2000 ppm or less. ing.
しかしながら、特許文献１、２に記載の方法では、アルミニウムアルコキサイドを効率よく製造することはできない。従って、従来の方法よりも、さらに効率よくアルミニウムアルコキサイドを製造することが求められている。
そこで、本発明は、金属アルミニウムとアルコールとの固液反応によって、アルミニウムアルコキサイドを効率よく製造することができるアルミニウムアルコキサイドの製造方法を提供することを目的とする。 However, the methods described in Patent Documents 1 and 2 cannot efficiently produce aluminum alkoxide. Therefore, it is required to produce aluminum alkoxide more efficiently than the conventional method.
Then, an object of this invention is to provide the manufacturing method of aluminum alkoxide which can manufacture aluminum alkoxide efficiently by the solid-liquid reaction of metal aluminum and alcohol.
そこで、本発明は、金属アルミニウムとアルコールとの固液反応によって、アルミニウムアルコキサイドを効率よく製造することができるアルミニウムアルコキサイドの製造方法を提供することを目的とする。 However, the methods described in Patent Documents 1 and 2 cannot efficiently produce aluminum alkoxide. Therefore, it is required to produce aluminum alkoxide more efficiently than the conventional method.
Then, an object of this invention is to provide the manufacturing method of aluminum alkoxide which can manufacture aluminum alkoxide efficiently by the solid-liquid reaction of metal aluminum and alcohol.
本発明者らは上記課題を解決すべく鋭意検討を行った。その結果、アルミニウムアルコキサイドを所定割合で含有する混合液中で、触媒の存在下、金属アルミニウムとアルコールとを固液反応させると、反応が進行しやすいとの新たな知見を得、本発明を完成するに至った。
The present inventors have intensively studied to solve the above problems. As a result, in the mixed solution containing aluminum alkoxide at a predetermined ratio, the present inventors have obtained new knowledge that the reaction is likely to proceed when the metal aluminum and the alcohol are subjected to a solid-liquid reaction in the presence of a catalyst. It came to complete.
すなわち、本発明は以下の構成からなる。
（１）工程（ａ）及び（ｂ）を有することを特徴とするアルミニウムアルコキサイドの製造方法。
（ａ）：アルコールとアルミニウムアルコキサイドを混合して、アルコール／アルミニウムアルコキサイドが重量比で５／９５～８５／１５である混合液を調製する工程。
（ｂ）：混合液中で、アルコールと金属アルミニウムとを、ガリウム及びインジウムから選ばれる少なくとも１種の存在下で反応させる工程。
（２）ガリウム及びインジウムから選ばれる少なくとも１種を含有した金属アルミニウムを用い、金属アルミニウムとアルコールとの固液反応を行う前記（１）記載のアルミニウムアルコキサイドの製造方法。
（３）アルミニウムアルコキサイドは、下記式（i）で表わされる前記（１）または（２）記載のアルミニウムアルコキサイドの製造方法。
Ａｌ（ＯＲ1）3 （i）
［式中、Ｒ1は、それぞれ独立に、メチル、エチル、ノルマルプロピル、イソプロピル、ノルマルブチル、イソブチル、ネオブチル、ノルマルペンチル、イソペンチル、ネオペンチル、ノルマルヘキシル、イソヘキシル、ネオヘキシル、ノルマルヘプチル、イソヘプチル、ネオヘプチル、ノルマルオクチル、イソオクチル及びネオオクチルからなる群より選ばれる少なくとも１つである。］
（４）アルコールは、式（ii）で表される前記（１）～（３）いずれかに記載のアルミニウムアルコキサイドの製造方法。
Ｒ2ＯＨ （ii）
［式中、Ｒ2は、メチル、エチル、ノルマルプロピル、イソプロピル、ノルマルブチル、イソブチル、ネオブチル、ノルマルペンチル、イソペンチル、ネオペンチル、ノルマルヘキシル、イソヘキシル、ネオヘキシル、ノルマルヘプチル、イソヘプチル、ネオヘプチル、ノルマルオクチル、イソオクチル及びネオオクチルからなる群より選ばれる少なくとも１つである。］
（５）アルミニウムアルコキサイドは、式（iii）で表わされ、かつアルコールは、式（iv）で表される前記（１）または（２）記載のアルミニウムアルコキサイドの製造方法
。
Ａｌ（ＯＲ3）3 （iii）
Ｒ3ＯＨ （iv）
［式中、Ｒ3は、メチル、エチル、ノルマルプロピル、イソプロピル、ノルマルブチル、イソブチル、ネオブチル、ノルマルペンチル、イソペンチル、ネオペンチル、ノルマルヘキシル、イソヘキシル、ネオヘキシル、ノルマルヘプチル、イソヘプチル、ネオヘプチル、ノルマルオクチル、イソオクチル及びネオオクチルからなる群より選ばれる少なくとも１つである。］
（６）Ｒ1が、イソプロピルである前記（３）記載のアルミニウムアルコキサイドの製造方法。
（７）Ｒ2が、イソプロピルである前記（４）記載のアルミニウムアルコキサイドの製造方法。
（８）工程（ａ）における混合液の調製は、温度１０～７０℃で行われる前記（１）～（７）記載いずれかにアルミニウムアルコキサイドの製造方法。
（９）工程（ｂ）における反応は、温度７５～１１０℃で行われる前記（１）～（８）記載いずれかにアルミニウムアルコキサイドの製造方法。
（１０）金属アルミニウムの量は、混合液に対し１重量％～６０重量％である前記（１）～（９）いずれかに記載のアルミニウムアルコキサイドの製造方法。
（１１）さらに工程（ｃ）を有する前記（１）～（１０）いずれかに記載のアルミニウムアルコキサイドの製造方法。
（ｃ）：工程（ｂ）にて得られる混合物からアルミニウムアルコキサイドを回収する工程。 That is, the present invention has the following configuration.
(1) A method for producing an aluminum alkoxide, comprising steps (a) and (b).
(A): A step of mixing alcohol and aluminum alkoxide to prepare a mixed solution in which the alcohol / aluminum alkoxide has a weight ratio of 5/95 to 85/15.
(B): A step of reacting alcohol and metallic aluminum in the mixed solution in the presence of at least one selected from gallium and indium.
(2) The method for producing an aluminum alkoxide according to (1), wherein a metal-aluminum containing at least one selected from gallium and indium is used and a solid-liquid reaction between the metal aluminum and alcohol is performed.
(3) Aluminum alkoxide is a manufacturing method of the aluminum alkoxide of the said (1) or (2) description represented by following formula (i).
Al (OR 1 ) 3 (i)
[Wherein R 1 is independently methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, neobutyl, normal pentyl, isopentyl, neopentyl, normal hexyl, isohexyl, neohexyl, normal heptyl, isoheptyl, neoheptyl, normal It is at least one selected from the group consisting of octyl, isooctyl and neooctyl. ]
(4) The method for producing an aluminum alkoxide according to any one of (1) to (3), wherein the alcohol is represented by formula (ii).
R 2 OH (ii)
Wherein R 2 is methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, neobutyl, normal pentyl, isopentyl, neopentyl, normal hexyl, isohexyl, neohexyl, normal heptyl, isoheptyl, neoheptyl, normal octyl, isooctyl and It is at least one selected from the group consisting of neooctyl. ]
(5) The aluminum alkoxide is represented by the formula (iii), and the alcohol is represented by the formula (iv). The method for producing an aluminum alkoxide according to the above (1) or (2).
Al (OR 3 ) 3 (iii)
R 3 OH (iv)
Wherein R 3 is methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, neobutyl, normal pentyl, isopentyl, neopentyl, normal hexyl, isohexyl, neohexyl, normal heptyl, isoheptyl, neoheptyl, normal octyl, isooctyl and It is at least one selected from the group consisting of neooctyl. ]
(6) The method for producing an aluminum alkoxide according to (3), wherein R 1 is isopropyl.
(7) The method for producing an aluminum alkoxide according to (4), wherein R 2 is isopropyl.
(8) The method for producing an aluminum alkoxide according to any one of (1) to (7), wherein the preparation of the mixed solution in the step (a) is performed at a temperature of 10 to 70 ° C.
(9) The method for producing aluminum alkoxide according to any one of (1) to (8), wherein the reaction in the step (b) is carried out at a temperature of 75 to 110 ° C.
(10) The method for producing aluminum alkoxide according to any one of (1) to (9), wherein the amount of metallic aluminum is 1% by weight to 60% by weight with respect to the mixed solution.
(11) The method for producing an aluminum alkoxide according to any one of (1) to (10), further comprising a step (c).
(C): A step of recovering aluminum alkoxide from the mixture obtained in step (b).
（１）工程（ａ）及び（ｂ）を有することを特徴とするアルミニウムアルコキサイドの製造方法。
（ａ）：アルコールとアルミニウムアルコキサイドを混合して、アルコール／アルミニウムアルコキサイドが重量比で５／９５～８５／１５である混合液を調製する工程。
（ｂ）：混合液中で、アルコールと金属アルミニウムとを、ガリウム及びインジウムから選ばれる少なくとも１種の存在下で反応させる工程。
（２）ガリウム及びインジウムから選ばれる少なくとも１種を含有した金属アルミニウムを用い、金属アルミニウムとアルコールとの固液反応を行う前記（１）記載のアルミニウムアルコキサイドの製造方法。
（３）アルミニウムアルコキサイドは、下記式（i）で表わされる前記（１）または（２）記載のアルミニウムアルコキサイドの製造方法。
Ａｌ（ＯＲ1）3 （i）
［式中、Ｒ1は、それぞれ独立に、メチル、エチル、ノルマルプロピル、イソプロピル、ノルマルブチル、イソブチル、ネオブチル、ノルマルペンチル、イソペンチル、ネオペンチル、ノルマルヘキシル、イソヘキシル、ネオヘキシル、ノルマルヘプチル、イソヘプチル、ネオヘプチル、ノルマルオクチル、イソオクチル及びネオオクチルからなる群より選ばれる少なくとも１つである。］
（４）アルコールは、式（ii）で表される前記（１）～（３）いずれかに記載のアルミニウムアルコキサイドの製造方法。
Ｒ2ＯＨ （ii）
［式中、Ｒ2は、メチル、エチル、ノルマルプロピル、イソプロピル、ノルマルブチル、イソブチル、ネオブチル、ノルマルペンチル、イソペンチル、ネオペンチル、ノルマルヘキシル、イソヘキシル、ネオヘキシル、ノルマルヘプチル、イソヘプチル、ネオヘプチル、ノルマルオクチル、イソオクチル及びネオオクチルからなる群より選ばれる少なくとも１つである。］
（５）アルミニウムアルコキサイドは、式（iii）で表わされ、かつアルコールは、式（iv）で表される前記（１）または（２）記載のアルミニウムアルコキサイドの製造方法
。
Ａｌ（ＯＲ3）3 （iii）
Ｒ3ＯＨ （iv）
［式中、Ｒ3は、メチル、エチル、ノルマルプロピル、イソプロピル、ノルマルブチル、イソブチル、ネオブチル、ノルマルペンチル、イソペンチル、ネオペンチル、ノルマルヘキシル、イソヘキシル、ネオヘキシル、ノルマルヘプチル、イソヘプチル、ネオヘプチル、ノルマルオクチル、イソオクチル及びネオオクチルからなる群より選ばれる少なくとも１つである。］
（６）Ｒ1が、イソプロピルである前記（３）記載のアルミニウムアルコキサイドの製造方法。
（７）Ｒ2が、イソプロピルである前記（４）記載のアルミニウムアルコキサイドの製造方法。
（８）工程（ａ）における混合液の調製は、温度１０～７０℃で行われる前記（１）～（７）記載いずれかにアルミニウムアルコキサイドの製造方法。
（９）工程（ｂ）における反応は、温度７５～１１０℃で行われる前記（１）～（８）記載いずれかにアルミニウムアルコキサイドの製造方法。
（１０）金属アルミニウムの量は、混合液に対し１重量％～６０重量％である前記（１）～（９）いずれかに記載のアルミニウムアルコキサイドの製造方法。
（１１）さらに工程（ｃ）を有する前記（１）～（１０）いずれかに記載のアルミニウムアルコキサイドの製造方法。
（ｃ）：工程（ｂ）にて得られる混合物からアルミニウムアルコキサイドを回収する工程。 That is, the present invention has the following configuration.
(1) A method for producing an aluminum alkoxide, comprising steps (a) and (b).
(A): A step of mixing alcohol and aluminum alkoxide to prepare a mixed solution in which the alcohol / aluminum alkoxide has a weight ratio of 5/95 to 85/15.
(B): A step of reacting alcohol and metallic aluminum in the mixed solution in the presence of at least one selected from gallium and indium.
(2) The method for producing an aluminum alkoxide according to (1), wherein a metal-aluminum containing at least one selected from gallium and indium is used and a solid-liquid reaction between the metal aluminum and alcohol is performed.
(3) Aluminum alkoxide is a manufacturing method of the aluminum alkoxide of the said (1) or (2) description represented by following formula (i).
Al (OR 1 ) 3 (i)
[Wherein R 1 is independently methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, neobutyl, normal pentyl, isopentyl, neopentyl, normal hexyl, isohexyl, neohexyl, normal heptyl, isoheptyl, neoheptyl, normal It is at least one selected from the group consisting of octyl, isooctyl and neooctyl. ]
(4) The method for producing an aluminum alkoxide according to any one of (1) to (3), wherein the alcohol is represented by formula (ii).
R 2 OH (ii)
Wherein R 2 is methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, neobutyl, normal pentyl, isopentyl, neopentyl, normal hexyl, isohexyl, neohexyl, normal heptyl, isoheptyl, neoheptyl, normal octyl, isooctyl and It is at least one selected from the group consisting of neooctyl. ]
(5) The aluminum alkoxide is represented by the formula (iii), and the alcohol is represented by the formula (iv). The method for producing an aluminum alkoxide according to the above (1) or (2).
Al (OR 3 ) 3 (iii)
R 3 OH (iv)
Wherein R 3 is methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, neobutyl, normal pentyl, isopentyl, neopentyl, normal hexyl, isohexyl, neohexyl, normal heptyl, isoheptyl, neoheptyl, normal octyl, isooctyl and It is at least one selected from the group consisting of neooctyl. ]
(6) The method for producing an aluminum alkoxide according to (3), wherein R 1 is isopropyl.
(7) The method for producing an aluminum alkoxide according to (4), wherein R 2 is isopropyl.
(8) The method for producing an aluminum alkoxide according to any one of (1) to (7), wherein the preparation of the mixed solution in the step (a) is performed at a temperature of 10 to 70 ° C.
(9) The method for producing aluminum alkoxide according to any one of (1) to (8), wherein the reaction in the step (b) is carried out at a temperature of 75 to 110 ° C.
(10) The method for producing aluminum alkoxide according to any one of (1) to (9), wherein the amount of metallic aluminum is 1% by weight to 60% by weight with respect to the mixed solution.
(11) The method for producing an aluminum alkoxide according to any one of (1) to (10), further comprising a step (c).
(C): A step of recovering aluminum alkoxide from the mixture obtained in step (b).
アルコールとアルミニウムアルコキサイドとの重量比が５／９５～８５／１５である混合液中で、触媒の存在下、アルコールと金属アルミニウムとを反応させる本発明の製造方法によれば、効率よくアルミニウムアルコキサイドを製造することができる。
According to the production method of the present invention in which alcohol and metal aluminum are reacted in the presence of a catalyst in a mixed solution in which the weight ratio of alcohol to aluminum alkoxide is 5/95 to 85/15, aluminum is efficiently produced. Alkoxide can be produced.
本発明のアルミニウムアルコキサイドの製造方法は、アルコールおよびアルミニウムアルコキサイドを混合して混合液を調製する工程（ａ）と、アルコールおよび金属アルミニウムを触媒の存在下で反応させる工程（ｂ）とを有する。
The method for producing an aluminum alkoxide of the present invention comprises a step (a) of preparing a mixture by mixing alcohol and aluminum alkoxide, and a step (b) of reacting the alcohol and metal aluminum in the presence of a catalyst. Have
（金属アルミニウム）
原料として用いる金属アルミニウムの純度は、特に限定されないが、例えば、本発明の製造方法により得られるアルミニウムアルコキサイドを純度９９．９９％以上の高純度アルミナの原料として使用する場合には、９９．９９％以上の高純度であるのが好ましい。純度が上記範囲内であれば、金属アルミニウム中の鉄、ケイ素、銅、マグネシウム等の不純物濃度が、金属アルミニウムの総重量に対して、１００ｐｐｍ以下であるので、得られるアルミニウムアルコキサイドの精製が不要となる。
また、固液反応させる前の金属アルミニウムは、ガリウムおよびインジウムから選ばれる少なくとも１種を、金属アルミニウムの総重量に対して、好ましくは０．０２～５０ｐｐｍ、さらに好ましくは０．１～４０ｐｐｍ、特に好ましくは０．５～２０ｐｐｍ含有しているのがよい。これにより、新たに触媒を混合液に添加することなく、または添加量を少なくして反応を行なわせることができる。
金属アルミニウムの形状としては、特に限定されず、例えば、インゴット、ペレット、板、箔、線、粉末などが挙げられる。 (Metal aluminum)
The purity of the metallic aluminum used as a raw material is not particularly limited. For example, when aluminum alkoxide obtained by the production method of the present invention is used as a raw material for high-purity alumina having a purity of 99.99% or more, 99.99. It is preferable that the purity is 99% or more. If the purity is within the above range, the impurity concentration of iron, silicon, copper, magnesium, etc. in the metal aluminum is 100 ppm or less with respect to the total weight of the metal aluminum, so that the resulting aluminum alkoxide can be purified. It becomes unnecessary.
The metallic aluminum before the solid-liquid reaction is at least one selected from gallium and indium, preferably 0.02 to 50 ppm, more preferably 0.1 to 40 ppm, particularly preferably based on the total weight of the metallic aluminum. The content is preferably 0.5 to 20 ppm. As a result, the reaction can be carried out without newly adding a catalyst to the mixed solution or by reducing the addition amount.
The shape of the metal aluminum is not particularly limited, and examples thereof include ingots, pellets, plates, foils, wires, and powders.
原料として用いる金属アルミニウムの純度は、特に限定されないが、例えば、本発明の製造方法により得られるアルミニウムアルコキサイドを純度９９．９９％以上の高純度アルミナの原料として使用する場合には、９９．９９％以上の高純度であるのが好ましい。純度が上記範囲内であれば、金属アルミニウム中の鉄、ケイ素、銅、マグネシウム等の不純物濃度が、金属アルミニウムの総重量に対して、１００ｐｐｍ以下であるので、得られるアルミニウムアルコキサイドの精製が不要となる。
また、固液反応させる前の金属アルミニウムは、ガリウムおよびインジウムから選ばれる少なくとも１種を、金属アルミニウムの総重量に対して、好ましくは０．０２～５０ｐｐｍ、さらに好ましくは０．１～４０ｐｐｍ、特に好ましくは０．５～２０ｐｐｍ含有しているのがよい。これにより、新たに触媒を混合液に添加することなく、または添加量を少なくして反応を行なわせることができる。
金属アルミニウムの形状としては、特に限定されず、例えば、インゴット、ペレット、板、箔、線、粉末などが挙げられる。 (Metal aluminum)
The purity of the metallic aluminum used as a raw material is not particularly limited. For example, when aluminum alkoxide obtained by the production method of the present invention is used as a raw material for high-purity alumina having a purity of 99.99% or more, 99.99. It is preferable that the purity is 99% or more. If the purity is within the above range, the impurity concentration of iron, silicon, copper, magnesium, etc. in the metal aluminum is 100 ppm or less with respect to the total weight of the metal aluminum, so that the resulting aluminum alkoxide can be purified. It becomes unnecessary.
The metallic aluminum before the solid-liquid reaction is at least one selected from gallium and indium, preferably 0.02 to 50 ppm, more preferably 0.1 to 40 ppm, particularly preferably based on the total weight of the metallic aluminum. The content is preferably 0.5 to 20 ppm. As a result, the reaction can be carried out without newly adding a catalyst to the mixed solution or by reducing the addition amount.
The shape of the metal aluminum is not particularly limited, and examples thereof include ingots, pellets, plates, foils, wires, and powders.
（アルミニウムアルコキサイド）
アルミニウムアルコキサイドとしては、特に限定されず、製造目的とするアルミニウムアルコキサイドと同一の化合物を用いることが好ましい。アルミニウムアルコキサイドの例としては、具体的には、下記式（i）で表されるアルミニウムアルコキサイドなどが挙げられ、なかでも、アルミニウムイソプロキサイドが好ましい。
Ａｌ（ＯＲ1）3 （i）
［式中、Ｒ1は、それぞれ独立に、メチル、エチル、ノルマルプロピル、イソプロピル、ノルマルブチル、イソブチル、ネオブチル、ノルマルペンチル、イソペンチル、ネオペンチル、ノルマルヘキシル、イソヘキシル、ネオヘキシル、ノルマルヘプチル、イソヘプチル、ネオヘプチル、ノルマルオクチル、イソオクチル及びネオオクチルからなる群より選ばれる少なくとも１つであり、なかでも、好ましくはイソプロピルであり、より好ましくは後述する式（ii）のおけるＲ2と同一のものである。］ (Aluminum alkoxide)
The aluminum alkoxide is not particularly limited, and it is preferable to use the same compound as the aluminum alkoxide intended for production. Specific examples of the aluminum alkoxide include aluminum alkoxide represented by the following formula (i), and among them, aluminum isopropylide is preferable.
Al (OR 1 ) 3 (i)
[Wherein R 1 is independently methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, neobutyl, normal pentyl, isopentyl, neopentyl, normal hexyl, isohexyl, neohexyl, normal heptyl, isoheptyl, neoheptyl, normal It is at least one selected from the group consisting of octyl, isooctyl and neooctyl, preferably isopropyl, and more preferably the same as R 2 in formula (ii) described later. ]
アルミニウムアルコキサイドとしては、特に限定されず、製造目的とするアルミニウムアルコキサイドと同一の化合物を用いることが好ましい。アルミニウムアルコキサイドの例としては、具体的には、下記式（i）で表されるアルミニウムアルコキサイドなどが挙げられ、なかでも、アルミニウムイソプロキサイドが好ましい。
Ａｌ（ＯＲ1）3 （i）
［式中、Ｒ1は、それぞれ独立に、メチル、エチル、ノルマルプロピル、イソプロピル、ノルマルブチル、イソブチル、ネオブチル、ノルマルペンチル、イソペンチル、ネオペンチル、ノルマルヘキシル、イソヘキシル、ネオヘキシル、ノルマルヘプチル、イソヘプチル、ネオヘプチル、ノルマルオクチル、イソオクチル及びネオオクチルからなる群より選ばれる少なくとも１つであり、なかでも、好ましくはイソプロピルであり、より好ましくは後述する式（ii）のおけるＲ2と同一のものである。］ (Aluminum alkoxide)
The aluminum alkoxide is not particularly limited, and it is preferable to use the same compound as the aluminum alkoxide intended for production. Specific examples of the aluminum alkoxide include aluminum alkoxide represented by the following formula (i), and among them, aluminum isopropylide is preferable.
Al (OR 1 ) 3 (i)
[Wherein R 1 is independently methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, neobutyl, normal pentyl, isopentyl, neopentyl, normal hexyl, isohexyl, neohexyl, normal heptyl, isoheptyl, neoheptyl, normal It is at least one selected from the group consisting of octyl, isooctyl and neooctyl, preferably isopropyl, and more preferably the same as R 2 in formula (ii) described later. ]
（アルコール）
混合液を形成するアルコールとしては、炭素数が１～８個の一価アルコールであるのが好ましく、なかでも、炭素鎖が長くなるほど金属アルミニウムとの反応性が低下するおそれがあることから、下記式（ii）で表されるアルコールがより好ましく、イソプロピルアルコールが特に好ましい。
Ｒ2ＯＨ （ii）
［式中、Ｒ2は、メチル、エチル、ノルマルプロピル、イソプロピル、ノルマルブチル、イソブチル、ネオブチル、ノルマルペンチル、イソペンチル、ネオペンチル、ノルマルヘキシル、イソヘキシル、ネオヘキシル、ノルマルヘプチル、イソヘプチル、ネオヘプチル、ノルマルオクチル、イソオクチル及びネオオクチルからなる群より選ばれる少なくとも１つであり、なかでも、好ましくはイソプロピルである。］ (alcohol)
The alcohol that forms the mixed solution is preferably a monohydric alcohol having 1 to 8 carbon atoms. Among them, the longer the carbon chain, the lower the reactivity with metallic aluminum. The alcohol represented by the formula (ii) is more preferable, and isopropyl alcohol is particularly preferable.
R 2 OH (ii)
Wherein R 2 is methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, neobutyl, normal pentyl, isopentyl, neopentyl, normal hexyl, isohexyl, neohexyl, normal heptyl, isoheptyl, neoheptyl, normal octyl, isooctyl and It is at least one selected from the group consisting of neooctyl, and among them, isopropyl is preferable. ]
混合液を形成するアルコールとしては、炭素数が１～８個の一価アルコールであるのが好ましく、なかでも、炭素鎖が長くなるほど金属アルミニウムとの反応性が低下するおそれがあることから、下記式（ii）で表されるアルコールがより好ましく、イソプロピルアルコールが特に好ましい。
Ｒ2ＯＨ （ii）
［式中、Ｒ2は、メチル、エチル、ノルマルプロピル、イソプロピル、ノルマルブチル、イソブチル、ネオブチル、ノルマルペンチル、イソペンチル、ネオペンチル、ノルマルヘキシル、イソヘキシル、ネオヘキシル、ノルマルヘプチル、イソヘプチル、ネオヘプチル、ノルマルオクチル、イソオクチル及びネオオクチルからなる群より選ばれる少なくとも１つであり、なかでも、好ましくはイソプロピルである。］ (alcohol)
The alcohol that forms the mixed solution is preferably a monohydric alcohol having 1 to 8 carbon atoms. Among them, the longer the carbon chain, the lower the reactivity with metallic aluminum. The alcohol represented by the formula (ii) is more preferable, and isopropyl alcohol is particularly preferable.
R 2 OH (ii)
Wherein R 2 is methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, neobutyl, normal pentyl, isopentyl, neopentyl, normal hexyl, isohexyl, neohexyl, normal heptyl, isoheptyl, neoheptyl, normal octyl, isooctyl and It is at least one selected from the group consisting of neooctyl, and among them, isopropyl is preferable. ]
アルコールは、前記した固液反応に悪影響を及ぼさない範囲で、ベンゼン、トルエン等の溶媒を含んでいてもよい。
また、アルコールを含む液にアセトン等のケトン類が含まれていてもよいが、該ケトン類はアルコールを含む液の総重量に対して含有量が１３０ｐｐｍ以下となる範囲内であるのが、固液反応に悪影響を及ぼさないうえで好ましい。 The alcohol may contain a solvent such as benzene and toluene as long as the above-described solid-liquid reaction is not adversely affected.
In addition, the liquid containing alcohol may contain ketones such as acetone, but the content of the ketone is within the range of 130 ppm or less with respect to the total weight of the liquid containing alcohol. It is preferable because it does not adversely affect the liquid reaction.
また、アルコールを含む液にアセトン等のケトン類が含まれていてもよいが、該ケトン類はアルコールを含む液の総重量に対して含有量が１３０ｐｐｍ以下となる範囲内であるのが、固液反応に悪影響を及ぼさないうえで好ましい。 The alcohol may contain a solvent such as benzene and toluene as long as the above-described solid-liquid reaction is not adversely affected.
In addition, the liquid containing alcohol may contain ketones such as acetone, but the content of the ketone is within the range of 130 ppm or less with respect to the total weight of the liquid containing alcohol. It is preferable because it does not adversely affect the liquid reaction.
（触媒）
触媒は、ガリウム及びインジウムから選ばれる少なくとも１つである。これらは化合物として存在してもよい。ガリウム、インジウムの化合物としては、例えば、メトキサイド、エトキサイド、イソプロポキサイドなどのアルコキサイド化合物；フェノキサイドなどのアリロキサイド化合物；フォルメート、アセテートなどのカルボキシレート化合物；アセチルアセトネート化合物、塩化物などの無水ハロゲン化物が挙げられる。これら触媒の中から使用するアルコール或いは他の溶媒に溶解度のあるものを単独或いは混合して用いることができる。 (catalyst)
The catalyst is at least one selected from gallium and indium. These may exist as compounds. Examples of gallium and indium compounds include alkoxide compounds such as methoxide, ethoxide and isopropoxide; allyloxide compounds such as phenoxide; carboxylate compounds such as formate and acetate; anhydrous halides such as acetylacetonate compounds and chlorides Is mentioned. Among these catalysts, those having solubility in the alcohol or other solvent used can be used alone or in combination.
触媒は、ガリウム及びインジウムから選ばれる少なくとも１つである。これらは化合物として存在してもよい。ガリウム、インジウムの化合物としては、例えば、メトキサイド、エトキサイド、イソプロポキサイドなどのアルコキサイド化合物；フェノキサイドなどのアリロキサイド化合物；フォルメート、アセテートなどのカルボキシレート化合物；アセチルアセトネート化合物、塩化物などの無水ハロゲン化物が挙げられる。これら触媒の中から使用するアルコール或いは他の溶媒に溶解度のあるものを単独或いは混合して用いることができる。 (catalyst)
The catalyst is at least one selected from gallium and indium. These may exist as compounds. Examples of gallium and indium compounds include alkoxide compounds such as methoxide, ethoxide and isopropoxide; allyloxide compounds such as phenoxide; carboxylate compounds such as formate and acetate; anhydrous halides such as acetylacetonate compounds and chlorides Is mentioned. Among these catalysts, those having solubility in the alcohol or other solvent used can be used alone or in combination.
＜工程（ａ）＞
工程（ａ）では、アルコールとアルミニウムアルコサイドとを、アルコール／アルミニウムアルコサイドが重量比で５／９５～８５／１５、好ましくは５／９５～８０／２０、さらに好ましくは５／９５～７０／３０となるように混合して、混合液を得る。
重量比が上記範囲内であれば、効果的に固液反応の進行を促進することができる。 <Process (a)>
In the step (a), alcohol / aluminum alkoxide is mixed with alcohol / aluminum alkoxide in a weight ratio of 5/95 to 85/15, preferably 5/95 to 80/20, more preferably 5/95 to 70 /. Mix to obtain 30 to obtain a mixed solution.
If the weight ratio is within the above range, the progress of the solid-liquid reaction can be effectively promoted.
工程（ａ）では、アルコールとアルミニウムアルコサイドとを、アルコール／アルミニウムアルコサイドが重量比で５／９５～８５／１５、好ましくは５／９５～８０／２０、さらに好ましくは５／９５～７０／３０となるように混合して、混合液を得る。
重量比が上記範囲内であれば、効果的に固液反応の進行を促進することができる。 <Process (a)>
In the step (a), alcohol / aluminum alkoxide is mixed with alcohol / aluminum alkoxide in a weight ratio of 5/95 to 85/15, preferably 5/95 to 80/20, more preferably 5/95 to 70 /. Mix to obtain 30 to obtain a mixed solution.
If the weight ratio is within the above range, the progress of the solid-liquid reaction can be effectively promoted.
混合液を調製する際の、アルコールおよびアルミニウムアルコキサイドの混合順序や混合方法は、特に限定されず、必要に応じて撹拌しながら行ってもよいし、加熱しながら行ってもよい。
混合液を加熱して調製する場合は、混合液の温度は、好ましくは１５～６５℃、より好ましくは２０～６０℃であるのがよい。温度が上記範囲内なら、反応をより促進させることができる。 The mixing order and mixing method of alcohol and aluminum alkoxide in preparing the mixed solution are not particularly limited, and may be performed while stirring or may be performed while heating.
When the mixture is prepared by heating, the temperature of the mixture is preferably 15 to 65 ° C., more preferably 20 to 60 ° C. If the temperature is within the above range, the reaction can be further promoted.
混合液を加熱して調製する場合は、混合液の温度は、好ましくは１５～６５℃、より好ましくは２０～６０℃であるのがよい。温度が上記範囲内なら、反応をより促進させることができる。 The mixing order and mixing method of alcohol and aluminum alkoxide in preparing the mixed solution are not particularly limited, and may be performed while stirring or may be performed while heating.
When the mixture is prepared by heating, the temperature of the mixture is preferably 15 to 65 ° C., more preferably 20 to 60 ° C. If the temperature is within the above range, the reaction can be further promoted.
＜工程（ｂ）＞
工程（ｂ）では、例えば、上述のようにして得られた混合液中に、金属アルミニウムを投入して、触媒の存在下で、アルコールと金属アルミニウムとを固液反応させる。
固液反応に際し、アルコールと金属アルミニウムの使用量比は回分式或いは連続式等の反応様式や所望するアルミニウムアルコキサイドの濃度により一義的でないが、金属アルミニウムの量は、混合液の総重量に対して、１～７０重量％、好ましくは１．５～６５重量％、特に好ましくは１．５～６０重量％とするのがよい。金属アルミニウムの量が上記範囲内であれば、金属アルミニウムとアルコールとの固液反応をより促進することができ、より効率的にアルミニウムアルコキサイドを製造することができる。 <Step (b)>
In the step (b), for example, metallic aluminum is introduced into the mixed liquid obtained as described above, and the alcohol and the metallic aluminum are subjected to solid-liquid reaction in the presence of the catalyst.
In the solid-liquid reaction, the ratio of the amount of alcohol and metal aluminum used is not unambiguous depending on the reaction mode such as batch or continuous and the desired concentration of aluminum alkoxide, but the amount of metal aluminum depends on the total weight of the mixture. On the other hand, it may be 1 to 70% by weight, preferably 1.5 to 65% by weight, particularly preferably 1.5 to 60% by weight. When the amount of metallic aluminum is within the above range, the solid-liquid reaction between metallic aluminum and alcohol can be further promoted, and aluminum alkoxide can be produced more efficiently.
工程（ｂ）では、例えば、上述のようにして得られた混合液中に、金属アルミニウムを投入して、触媒の存在下で、アルコールと金属アルミニウムとを固液反応させる。
固液反応に際し、アルコールと金属アルミニウムの使用量比は回分式或いは連続式等の反応様式や所望するアルミニウムアルコキサイドの濃度により一義的でないが、金属アルミニウムの量は、混合液の総重量に対して、１～７０重量％、好ましくは１．５～６５重量％、特に好ましくは１．５～６０重量％とするのがよい。金属アルミニウムの量が上記範囲内であれば、金属アルミニウムとアルコールとの固液反応をより促進することができ、より効率的にアルミニウムアルコキサイドを製造することができる。 <Step (b)>
In the step (b), for example, metallic aluminum is introduced into the mixed liquid obtained as described above, and the alcohol and the metallic aluminum are subjected to solid-liquid reaction in the presence of the catalyst.
In the solid-liquid reaction, the ratio of the amount of alcohol and metal aluminum used is not unambiguous depending on the reaction mode such as batch or continuous and the desired concentration of aluminum alkoxide, but the amount of metal aluminum depends on the total weight of the mixture. On the other hand, it may be 1 to 70% by weight, preferably 1.5 to 65% by weight, particularly preferably 1.5 to 60% by weight. When the amount of metallic aluminum is within the above range, the solid-liquid reaction between metallic aluminum and alcohol can be further promoted, and aluminum alkoxide can be produced more efficiently.
触媒の含有量は、金属アルミニウムと接触している混合液中に含まれるＡｌの重量に対して（但し、ガリウム、インジウムの化合物の場合には、金属換算での値である。）、好ましくは０．０２～５０ｐｐｍであり、より好ましくは０．１～４０ｐｐｍである。触媒の含有量が０．０２ｐｐｍ未満であると反応促進効果が十分でない場合があり、他方、５０ｐｐｍを越えると、得られるアルミニウムアルコキサイドを高純度アルミナ等のファインセラミックス粉末の原料として用いる場合に、ガリウム、インジウムが不純物として最終製品に移行し、焼結性や光学特性を悪化させるなどの不都合を生じるおそれがある。
The content of the catalyst is preferably based on the weight of Al contained in the mixed liquid in contact with the metal aluminum (however, in the case of a compound of gallium and indium, it is a value in terms of metal), preferably. It is 0.02 to 50 ppm, more preferably 0.1 to 40 ppm. When the catalyst content is less than 0.02 ppm, the reaction promoting effect may not be sufficient. On the other hand, when it exceeds 50 ppm, the resulting aluminum alkoxide is used as a raw material for fine ceramic powders such as high-purity alumina. In addition, gallium and indium may move to the final product as impurities, which may cause inconveniences such as deterioration of sinterability and optical characteristics.
触媒を混合液中に存在させる方法としては、混合液中の触媒の濃度が上記範囲内となるようにすることができる方法であれば特に限定されず、例えば、固液界面においてより有効に促進効果を発揮させる観点から、触媒をあらかじめ混合分散或いは固溶させる等の公知の方法で含有させ、固液反応時に触媒を混合液中に分散或いは溶出させつつ金属アルミニウムとアルコールを反応させる方法が好適に用いられる。
また、所望のガリウムおよび／またはインジウム量は、金属アルミニウム中からの溶出量と直接混合液中に添加する量を勘案して、併用してもよい。 The method for causing the catalyst to be present in the mixed solution is not particularly limited as long as the concentration of the catalyst in the mixed solution is within the above range, and, for example, more effective promotion at the solid-liquid interface From the viewpoint of exerting the effect, a method in which the catalyst is contained by a known method such as mixing and dispersing in advance or solid solution, and the metal aluminum and alcohol are reacted while dispersing or eluting the catalyst in the mixed solution during the solid-liquid reaction is preferable. Used for.
Further, the desired amount of gallium and / or indium may be used in combination in consideration of the elution amount from metallic aluminum and the amount added directly into the mixed solution.
また、所望のガリウムおよび／またはインジウム量は、金属アルミニウム中からの溶出量と直接混合液中に添加する量を勘案して、併用してもよい。 The method for causing the catalyst to be present in the mixed solution is not particularly limited as long as the concentration of the catalyst in the mixed solution is within the above range, and, for example, more effective promotion at the solid-liquid interface From the viewpoint of exerting the effect, a method in which the catalyst is contained by a known method such as mixing and dispersing in advance or solid solution, and the metal aluminum and alcohol are reacted while dispersing or eluting the catalyst in the mixed solution during the solid-liquid reaction is preferable. Used for.
Further, the desired amount of gallium and / or indium may be used in combination in consideration of the elution amount from metallic aluminum and the amount added directly into the mixed solution.
金属アルミニウムとアルコールの固液反応における反応温度は、反応が進行しさえすれば特に限定されず、好ましくは７５～１１０℃であり、さらに好ましくは８０～１００℃である。特に、反応を促進させる観点から、用いる混合液が沸騰、還流する条件下で反応を行うことが好ましい。
The reaction temperature in the solid-liquid reaction between metallic aluminum and alcohol is not particularly limited as long as the reaction proceeds, and is preferably 75 to 110 ° C, more preferably 80 to 100 ° C. In particular, from the viewpoint of accelerating the reaction, it is preferable to carry out the reaction under conditions where the liquid mixture used is boiled and refluxed.
本発明では、さらに、上述した工程（ｂ）にて得られた混合物からアルミニウムアルコキサイドを回収する工程を有していてもよい。
The present invention may further include a step of recovering aluminum alkoxide from the mixture obtained in the step (b) described above.
以下、実施例を挙げて本発明を詳細に説明するが、本発明は以下の実施例のみに限定されるものではない。
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.
（実施例１）
還流冷却器付き２リットルセパラブルフラスコに、イソプロピルアルコール（Ａ）とアルミニウムイソプロポキサイド（Ｂ）とを、重量比（Ａ/Ｂ）が１５／８５となるように混合した混合液１００重量部を添加した。
次いで、下端部に攪拌用のローターブレードを備え、ポリテトラフルオロエチレン被覆された軸体の周面部にポリテトラフルオロエチレンチューブを用いて取り付けた２．３重量部のアルミニウム片（大きさ：直径約１６．５ｍｍ×長さ約４０ｍｍ、純度；９９．９９９％、Ｇａ／Ａｌ＝２．０ｐｐｍ）を溶液中に投入して、アルミニウム片を軸回りに２００ｒｐｍで攪拌させながら、アルコール混合液の沸騰還流下（約８４℃）で、６３０分間反応させた。反応の進行に伴い水素ガス発生とアルミニウムの溶解が確認された。
６３０分間反応後、アルミニウム片を取り出したところ、アルミニウム片の溶解量は３６．２％であった。 Example 1
In a 2 liter separable flask equipped with a reflux condenser, 100 parts by weight of a mixed solution in which isopropyl alcohol (A) and aluminum isopropoxide (B) were mixed so that the weight ratio (A / B) was 15/85 was added. Added.
Next, 2.3 parts by weight of an aluminum piece (size: about a diameter) having a stirring rotor blade at the lower end and attached to the peripheral surface of the polytetrafluoroethylene-coated shaft using a polytetrafluoroethylene tube. 16.5 mm × length of about 40 mm, purity; 99.999%, Ga / Al = 2.0 ppm) was added into the solution, and the alcohol mixture was boiled and refluxed while stirring the aluminum piece around the axis at 200 rpm. The reaction was allowed to proceed for 630 minutes under (about 84 ° C.). As the reaction progressed, generation of hydrogen gas and dissolution of aluminum were confirmed.
After reacting for 630 minutes, the aluminum piece was taken out, and the dissolution amount of the aluminum piece was 36.2%.
還流冷却器付き２リットルセパラブルフラスコに、イソプロピルアルコール（Ａ）とアルミニウムイソプロポキサイド（Ｂ）とを、重量比（Ａ/Ｂ）が１５／８５となるように混合した混合液１００重量部を添加した。
次いで、下端部に攪拌用のローターブレードを備え、ポリテトラフルオロエチレン被覆された軸体の周面部にポリテトラフルオロエチレンチューブを用いて取り付けた２．３重量部のアルミニウム片（大きさ：直径約１６．５ｍｍ×長さ約４０ｍｍ、純度；９９．９９９％、Ｇａ／Ａｌ＝２．０ｐｐｍ）を溶液中に投入して、アルミニウム片を軸回りに２００ｒｐｍで攪拌させながら、アルコール混合液の沸騰還流下（約８４℃）で、６３０分間反応させた。反応の進行に伴い水素ガス発生とアルミニウムの溶解が確認された。
６３０分間反応後、アルミニウム片を取り出したところ、アルミニウム片の溶解量は３６．２％であった。 Example 1
In a 2 liter separable flask equipped with a reflux condenser, 100 parts by weight of a mixed solution in which isopropyl alcohol (A) and aluminum isopropoxide (B) were mixed so that the weight ratio (A / B) was 15/85 was added. Added.
Next, 2.3 parts by weight of an aluminum piece (size: about a diameter) having a stirring rotor blade at the lower end and attached to the peripheral surface of the polytetrafluoroethylene-coated shaft using a polytetrafluoroethylene tube. 16.5 mm × length of about 40 mm, purity; 99.999%, Ga / Al = 2.0 ppm) was added into the solution, and the alcohol mixture was boiled and refluxed while stirring the aluminum piece around the axis at 200 rpm. The reaction was allowed to proceed for 630 minutes under (about 84 ° C.). As the reaction progressed, generation of hydrogen gas and dissolution of aluminum were confirmed.
After reacting for 630 minutes, the aluminum piece was taken out, and the dissolution amount of the aluminum piece was 36.2%.
（実施例２）
混合液中のイソプロピルアルコールとアルミニウムイソプロポキサイドとの重量比を６０／４０とし、反応時間を７１７分間とした以外は、実施例１と同一の操作を行った。
７１７分間反応後、アルミニウム片を取り出したところ、アルミニウム片の溶解量は２０．６％であった。 (Example 2)
The same operation as in Example 1 was performed except that the weight ratio of isopropyl alcohol to aluminum isopropoxide in the mixed solution was 60/40 and the reaction time was 717 minutes.
After the reaction for 717 minutes, the aluminum piece was taken out, and the dissolution amount of the aluminum piece was 20.6%.
混合液中のイソプロピルアルコールとアルミニウムイソプロポキサイドとの重量比を６０／４０とし、反応時間を７１７分間とした以外は、実施例１と同一の操作を行った。
７１７分間反応後、アルミニウム片を取り出したところ、アルミニウム片の溶解量は２０．６％であった。 (Example 2)
The same operation as in Example 1 was performed except that the weight ratio of isopropyl alcohol to aluminum isopropoxide in the mixed solution was 60/40 and the reaction time was 717 minutes.
After the reaction for 717 minutes, the aluminum piece was taken out, and the dissolution amount of the aluminum piece was 20.6%.
（実施例３）
混合液中のイソプロピルアルコールとアルミニウムイソプロポキサイドとの重量比を５５／４５とし、反応時間を７１６分間とした以外は、実施例１と同一の操作を行った。
７１６分間反応後、アルミニウム片を取り出したところ、アルミニウム片の溶解量は１４．７％であった。 (Example 3)
The same operation as in Example 1 was performed except that the weight ratio of isopropyl alcohol to aluminum isopropoxide in the mixed solution was 55/45 and the reaction time was 716 minutes.
After the reaction for 716 minutes, the aluminum piece was taken out, and the amount of dissolution of the aluminum piece was 14.7%.
混合液中のイソプロピルアルコールとアルミニウムイソプロポキサイドとの重量比を５５／４５とし、反応時間を７１６分間とした以外は、実施例１と同一の操作を行った。
７１６分間反応後、アルミニウム片を取り出したところ、アルミニウム片の溶解量は１４．７％であった。 (Example 3)
The same operation as in Example 1 was performed except that the weight ratio of isopropyl alcohol to aluminum isopropoxide in the mixed solution was 55/45 and the reaction time was 716 minutes.
After the reaction for 716 minutes, the aluminum piece was taken out, and the amount of dissolution of the aluminum piece was 14.7%.
（実施例４）
混合液中のイソプロピルアルコールとアルミニウムイソプロポキサイドとの重量比を５０／５０とし、反応時間を７１５分間とした以外は、実施例１と同一の操作を行った。
７１５分間反応後、アルミニウム片を取り出したところ、アルミニウム片の溶解量は１６．０％であった。 (Example 4)
The same operation as in Example 1 was performed except that the weight ratio of isopropyl alcohol to aluminum isopropoxide in the mixed solution was 50/50 and the reaction time was 715 minutes.
After reacting for 715 minutes, the aluminum piece was taken out, and the dissolution amount of the aluminum piece was 16.0%.
混合液中のイソプロピルアルコールとアルミニウムイソプロポキサイドとの重量比を５０／５０とし、反応時間を７１５分間とした以外は、実施例１と同一の操作を行った。
７１５分間反応後、アルミニウム片を取り出したところ、アルミニウム片の溶解量は１６．０％であった。 (Example 4)
The same operation as in Example 1 was performed except that the weight ratio of isopropyl alcohol to aluminum isopropoxide in the mixed solution was 50/50 and the reaction time was 715 minutes.
After reacting for 715 minutes, the aluminum piece was taken out, and the dissolution amount of the aluminum piece was 16.0%.
（比較例１）
混合液中のイソプロピルアルコールとアルミニウムイソプロポキサイドとの重量比を１００／０とし、反応時間を７１６分間とした以外は、実施例１と同一の操作を行った。水素ガスの発生は殆ど確認されなかった。
７１６分間反応後、アルミニウム片を取り出したところ、アルミニウム片の溶解量は０．０％であった。 (Comparative Example 1)
The same operation as in Example 1 was performed except that the weight ratio of isopropyl alcohol to aluminum isopropoxide in the mixed solution was 100/0 and the reaction time was 716 minutes. Almost no generation of hydrogen gas was confirmed.
After the reaction for 716 minutes, the aluminum piece was taken out, and the dissolution amount of the aluminum piece was 0.0%.
混合液中のイソプロピルアルコールとアルミニウムイソプロポキサイドとの重量比を１００／０とし、反応時間を７１６分間とした以外は、実施例１と同一の操作を行った。水素ガスの発生は殆ど確認されなかった。
７１６分間反応後、アルミニウム片を取り出したところ、アルミニウム片の溶解量は０．０％であった。 (Comparative Example 1)
The same operation as in Example 1 was performed except that the weight ratio of isopropyl alcohol to aluminum isopropoxide in the mixed solution was 100/0 and the reaction time was 716 minutes. Almost no generation of hydrogen gas was confirmed.
After the reaction for 716 minutes, the aluminum piece was taken out, and the dissolution amount of the aluminum piece was 0.0%.
Claims (11)
- 工程（ａ）及び（ｂ）を有することを特徴とするアルミニウムアルコキサイドの製造方法。
（ａ）：アルコールとアルミニウムアルコキサイドを混合して、アルコール／アルミニウムアルコキサイドが重量比で５／９５～８５／１５である混合液を調製する工程。
（ｂ）：混合液中で、アルコールと金属アルミニウムとを、ガリウム及びインジウムから選ばれる少なくとも１種の存在下で反応させる工程。 A method for producing an aluminum alkoxide, comprising steps (a) and (b).
(A): A step of mixing alcohol and aluminum alkoxide to prepare a mixed solution in which the alcohol / aluminum alkoxide has a weight ratio of 5/95 to 85/15.
(B): A step of reacting alcohol and metallic aluminum in the mixed solution in the presence of at least one selected from gallium and indium. - ガリウム及びインジウムから選ばれる少なくとも１種を含有した金属アルミニウムを用い、金属アルミニウムとアルコールとの固液反応を行う請求項１に記載のアルミニウムアルコキサイドの製造方法。 The manufacturing method of the aluminum alkoxide of Claim 1 which performs the solid-liquid reaction of metallic aluminum and alcohol using the metallic aluminum containing at least 1 sort (s) chosen from a gallium and an indium.
- アルミニウムアルコキサイドは、下記式（i）で表わされる請求項１または２に記載のアルミニウムアルコキサイドの製造方法。
Ａｌ（ＯＲ1）3 （i）
［式中、Ｒ1は、それぞれ独立に、メチル、エチル、ノルマルプロピル、イソプロピル、ノルマルブチル、イソブチル、ネオブチル、ノルマルペンチル、イソペンチル、ネオペンチル、ノルマルヘキシル、イソヘキシル、ネオヘキシル、ノルマルヘプチル、イソヘプチル、ネオヘプチル、ノルマルオクチル、イソオクチル及びネオオクチルからなる群より選ばれる少なくとも１つである。］ Aluminum alkoxide is a manufacturing method of the aluminum alkoxide of Claim 1 or 2 represented by following formula (i).
Al (OR 1 ) 3 (i)
[Wherein R 1 is independently methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, neobutyl, normal pentyl, isopentyl, neopentyl, normal hexyl, isohexyl, neohexyl, normal heptyl, isoheptyl, neoheptyl, normal It is at least one selected from the group consisting of octyl, isooctyl and neooctyl. ] - アルコールは、式（ii）で表される請求項１～３のいずれかに記載のアルミニウムアルコキサイドの製造方法。
Ｒ2ＯＨ （ii）
［式中、Ｒ2は、メチル、エチル、ノルマルプロピル、イソプロピル、ノルマルブチル、イソブチル、ネオブチル、ノルマルペンチル、イソペンチル、ネオペンチル、ノルマルヘキシル、イソヘキシル、ネオヘキシル、ノルマルヘプチル、イソヘプチル、ネオヘプチル、ノルマルオクチル、イソオクチル及びネオオクチルからなる群より選ばれる少なくとも１つである。］ The method for producing an aluminum alkoxide according to any one of claims 1 to 3, wherein the alcohol is represented by the formula (ii).
R 2 OH (ii)
Wherein R 2 is methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, neobutyl, normal pentyl, isopentyl, neopentyl, normal hexyl, isohexyl, neohexyl, normal heptyl, isoheptyl, neoheptyl, normal octyl, isooctyl and It is at least one selected from the group consisting of neooctyl. ] - アルミニウムアルコキサイドは、式（iii）で表わされ、かつアルコールは、式（iv）で表される請求項１または２に記載のアルミニウムアルコキサイドの製造方法。
Ａｌ（ＯＲ3）3 （iii）
Ｒ3ＯＨ （iv）
［式中、Ｒ3は、メチル、エチル、ノルマルプロピル、イソプロピル、ノルマルブチル、イソブチル、ネオブチル、ノルマルペンチル、イソペンチル、ネオペンチル、ノルマルヘキシル、イソヘキシル、ネオヘキシル、ノルマルヘプチル、イソヘプチル、ネオヘプチル、ノルマルオクチル、イソオクチル及びネオオクチルからなる群より選ばれる少なくとも１つである。］ The method for producing aluminum alkoxide according to claim 1 or 2, wherein the aluminum alkoxide is represented by formula (iii) and the alcohol is represented by formula (iv).
Al (OR 3 ) 3 (iii)
R 3 OH (iv)
Wherein R 3 is methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, neobutyl, normal pentyl, isopentyl, neopentyl, normal hexyl, isohexyl, neohexyl, normal heptyl, isoheptyl, neoheptyl, normal octyl, isooctyl and It is at least one selected from the group consisting of neooctyl. ] - Ｒ1が、イソプロピルである請求項３に記載のアルミニウムアルコキサイドの製造方法。 The method for producing an aluminum alkoxide according to claim 3, wherein R 1 is isopropyl.
- Ｒ2が、イソプロピルである請求項４に記載のアルミニウムアルコキサイドの製造方法。 The method for producing an aluminum alkoxide according to claim 4, wherein R 2 is isopropyl.
- 工程（ａ）における混合液の調製は、温度１０～７０℃で行われる請求項１～７のいずれかに記載のアルミニウムアルコキサイドの製造方法。 The method for producing an aluminum alkoxide according to any one of claims 1 to 7, wherein the mixed solution in step (a) is prepared at a temperature of 10 to 70 ° C.
- 工程（ｂ）における反応は、温度７５～１１０℃で行われる請求項１～８のいずれかに記載のアルミニウムアルコキサイドの製造方法。 The method for producing an aluminum alkoxide according to any one of claims 1 to 8, wherein the reaction in the step (b) is carried out at a temperature of 75 to 110 ° C.
- 金属アルミニウムの量は、混合液に対し１重量％～６０重量％である請求項１～９のいずれかに記載のアルミニウムアルコキサイドの製造方法。 The method for producing an aluminum alkoxide according to any one of claims 1 to 9, wherein the amount of metallic aluminum is 1 to 60 wt% with respect to the mixed solution.
- さらに工程（ｃ）を有する請求項１～１０のいずれかに記載のアルミニウムアルコキサイドの製造方法。
（ｃ）：工程（ｂ）にて得られる混合物からアルミニウムアルコキサイドを回収する工程。 The method for producing an aluminum alkoxide according to any one of claims 1 to 10, further comprising a step (c).
(C): A step of recovering aluminum alkoxide from the mixture obtained in step (b).
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| CN201280044350.7A CN103781750A (en) | 2011-09-13 | 2012-09-12 | Method for producing aluminum alkoxide |
| KR1020147005912A KR20140061434A (en) | 2011-09-13 | 2012-09-12 | Method for producing aluminum alkoxide |
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| JP2011199430A JP2013060390A (en) | 2011-09-13 | 2011-09-13 | Method for producing aluminum alkoxide |
| JP2011-199430 | 2011-09-13 |
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| JP5878043B2 (en) * | 2012-03-06 | 2016-03-08 | 住友化学株式会社 | Method for producing aluminum alkoxide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB993730A (en) * | 1963-01-31 | 1965-06-02 | Wyandotte Chemicals Corp | Method for the preparation of aluminuium isopropoxide |
| JPS62286938A (en) * | 1986-06-05 | 1987-12-12 | インタ−ナショナル ビジネス マシ−ンズ コ−ポレ−ション | Manufacture of aluminum alkoxide or aluminum aryloxide |
| JPH0525070A (en) * | 1991-02-15 | 1993-02-02 | Sumitomo Chem Co Ltd | Production of aluminum alkoxide |
| JP2004156994A (en) * | 2002-11-06 | 2004-06-03 | Sumitomo Chem Co Ltd | Method for determining quantity of transition metal solid solution and transition metal crystallized material in metallic aluminum sample |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785946A (en) * | 2004-12-08 | 2006-06-14 | 章浩龙 | Manufacturing method of aluminium alkoxide |
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2012
- 2012-09-12 WO PCT/JP2012/073336 patent/WO2013039105A1/en active Application Filing
- 2012-09-12 KR KR1020147005912A patent/KR20140061434A/en not_active Application Discontinuation
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB993730A (en) * | 1963-01-31 | 1965-06-02 | Wyandotte Chemicals Corp | Method for the preparation of aluminuium isopropoxide |
| JPS62286938A (en) * | 1986-06-05 | 1987-12-12 | インタ−ナショナル ビジネス マシ−ンズ コ−ポレ−ション | Manufacture of aluminum alkoxide or aluminum aryloxide |
| JPH0525070A (en) * | 1991-02-15 | 1993-02-02 | Sumitomo Chem Co Ltd | Production of aluminum alkoxide |
| JP2004156994A (en) * | 2002-11-06 | 2004-06-03 | Sumitomo Chem Co Ltd | Method for determining quantity of transition metal solid solution and transition metal crystallized material in metallic aluminum sample |
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