JPH0770155A - Production of organic acid titanium salt - Google Patents
Production of organic acid titanium saltInfo
- Publication number
- JPH0770155A JPH0770155A JP24199093A JP24199093A JPH0770155A JP H0770155 A JPH0770155 A JP H0770155A JP 24199093 A JP24199093 A JP 24199093A JP 24199093 A JP24199093 A JP 24199093A JP H0770155 A JPH0770155 A JP H0770155A
- Authority
- JP
- Japan
- Prior art keywords
- organic acid
- aqueous solution
- titanium
- acid
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、反応触媒、セラミック
ス用添加剤、電子材料用二酸化チタンの薄膜前駆体とし
て有用な有機酸チタン塩の製造方法に関するものであ
る。TECHNICAL FIELD The present invention relates to a method for producing a titanium salt of an organic acid useful as a reaction catalyst, an additive for ceramics, and a thin film precursor of titanium dioxide for electronic materials.
【０００２】[0002]
【従来の技術】従来有機酸金属塩の製造方法としては、
飽和脂肪族モノカルボン酸、脂環式モノカルボン酸、芳
香族モノカルボン酸、又は樹脂酸などの有機酸と、金属
を加熱して直接反応させる直接法（例えばオクチル酸と
鉄を反応する方法）、有機酸と金属酸化物、金属水酸化
物、金属炭酸塩、又は酢酸金属塩を混合加熱して反応さ
せる溶融法（例えばナフテン酸と酸化亜鉛を反応する方
法、オクチル酸と炭酸コバルトと反応する方法など）、
有機酸のアルカリ金属塩水溶液と金属塩化物、金属硫酸
塩、又は金属硝酸塩などの水溶液を加熱混合して反応す
る複分解法（例えばオクチル酸ナトリウム水溶液と塩化
コバルト水溶液を反応する方法、ナフテン酸ナトリウム
水溶液と硫酸マンガン水溶液を反応する方法）などが知
られている。2. Description of the Related Art As a conventional method for producing an organic acid metal salt,
Direct method of directly reacting an organic acid such as a saturated aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, or resin acid by heating a metal (for example, a method of reacting octylic acid with iron) A melting method in which an organic acid and a metal oxide, a metal hydroxide, a metal carbonate, or a metal acetate are mixed and heated to react (for example, a method of reacting naphthenic acid and zinc oxide, a reaction of octylic acid and cobalt carbonate) Method),
A metathesis method in which an aqueous solution of an alkali metal salt of an organic acid and an aqueous solution of a metal chloride, a metal sulfate, a metal nitrate or the like are heated and mixed to react (for example, a method of reacting an aqueous solution of sodium octylate with an aqueous solution of cobalt chloride, an aqueous solution of sodium naphthenate And a manganese sulfate aqueous solution) are known.
【０００３】[0003]
【発明が解決しようとする課題】しかし、チタンに関し
ては例えば二酸化チタン、又はチタン金属粉末と有機酸
を長時間加熱攪拌しても反応しない。一般的に良く知ら
れている複分解法については、硫酸チタンとアルカリ金
属塩水溶液を反応しても、二酸化チタンの懸濁液になる
のみで目的とする有機酸チタン塩は得られない。そのた
め、チタン含有量が高く、夾雑物が少なく安定性の良
い、有機酸チタン塩を経済的に製造する方法は見いださ
れていない。従って、本発明の目的は簡単な製法でチタ
ン含有量が高く、貯蔵安定性の良い有機酸チタン塩を経
済的に得ようとするものである。However, with respect to titanium, for example, titanium dioxide or titanium metal powder and organic acid do not react even if heated and stirred for a long time. According to the generally well-known metathesis method, even if titanium sulfate is reacted with an aqueous solution of an alkali metal salt, only a suspension of titanium dioxide is obtained, and the desired titanium salt of an organic acid cannot be obtained. Therefore, a method for economically producing a titanium salt of an organic acid having a high titanium content, a small amount of impurities, and good stability has not been found. Therefore, an object of the present invention is to economically obtain an organic acid titanium salt having a high titanium content and good storage stability by a simple production method.
【０００４】[0004]
【課題を解決するための手段】本発明は有機酸のアルカ
リ金属塩水溶液、及び／又は有機酸アミン塩水溶液、及
び／又は有機酸アンモニウム塩水溶液と三塩化チタン水
溶液をｐＨ３〜１０の範囲で反応し、さらに反応物を酸
化することにより、安定な有機酸チタン塩が得られるこ
とを見いだしたものである。According to the present invention, an aqueous solution of an alkali metal salt of an organic acid and / or an aqueous solution of an organic acid amine salt, and / or an aqueous solution of an organic acid ammonium salt is reacted with an aqueous solution of titanium trichloride within a pH range of 3 to 10. However, it has been found that a stable organic acid titanium salt can be obtained by further oxidizing the reaction product.
【０００５】反応条件としては、まず最初に所定量の有
機酸と水を３０〜１００℃に加熱・攪拌しながら、所定
量のアルカリ金属塩水溶液、及び／又はアミン、及び／
又はアンモニア水を加え、５〜１０分以上反応すること
により、有機酸のアルカリ金属塩水溶液、及び／又は有
機酸アミン水溶液、及び／又は有機酸アンモニウム塩水
溶液が得られる。続いて２０〜１００℃望ましくは５０
〜７０℃でｐＨ３〜１０望ましくは６．５〜７．５を保
ちながら三塩化チタン水溶液の所定量を少しずつ添加
し、ｐＨ３〜１０の範囲で５〜６０分反応後、引き続い
て反応物を酸化することにより、有機酸チタンが得られ
る。その酸化の方法は制限が無く、反応系へ酸素又は空
気を吹き込む方法、過酸化水素等の酸化剤を添加する方
法等があるが、反応物を水と分離して空気と接触させる
方法が望ましい。ｐＨが低すぎる場合は反応物の分解が
著しいため、製品の収率が極端に低下すると同時に、製
品中の未反応の有機酸が極端に多くなる。逆にｐＨが高
すぎる場合は安定な有機酸チタン塩が得られない。As reaction conditions, first, a predetermined amount of an organic acid and water are heated and stirred at 30 to 100 ° C., and a predetermined amount of an aqueous solution of an alkali metal salt, and / or an amine, and / or
Alternatively, by adding aqueous ammonia and reacting for 5 to 10 minutes or more, an aqueous solution of an alkali metal salt of an organic acid, and / or an aqueous solution of an organic acid amine, and / or an aqueous solution of an organic acid ammonium salt can be obtained. Then 20 to 100 ° C., preferably 50
A predetermined amount of titanium trichloride aqueous solution is added little by little while maintaining the pH at 3 to 10 ° C, preferably at 6.5 to 7.5, and after reacting at pH 3 to 10 for 5 to 60 minutes, the reaction product is continuously added. By oxidizing, organic titanium oxide is obtained. There is no limitation on the oxidation method, and there are a method of blowing oxygen or air into the reaction system, a method of adding an oxidizing agent such as hydrogen peroxide, and the like, but a method of separating the reaction product from water and contacting with air is preferable. . If the pH is too low, the decomposition of the reaction product is significant, resulting in an extremely low yield of the product and, at the same time, an excessive amount of unreacted organic acid in the product. Conversely, if the pH is too high, a stable organic acid titanium salt cannot be obtained.
【０００６】有機酸、アルカリ金属塩、及び／又はアミ
ン、及び／又はアンモニア水と三塩化チタンの反応モル
比は、有機酸３モルに対し、アルカリ金属塩、及び／又
はアミン、及び／又はアンモニア水１〜３モル、三塩化
チタン１〜３モルが望ましいが、有機酸は反応溶媒とし
て過剰に用いても差し支えない。また、アルカリ金属及
び／又はアミン、及び／又はアンモニア水と三塩化チタ
ンの反応モル比は、等モルが望ましいが、反応系のｐＨ
調整の目的でいずれかを過剰に用いることが可能であ
る。また反応系のｐＨ調整のため、炭酸ナトリウムの水
溶液を必要に応じて添加しても差し支えない。The reaction molar ratio of the organic acid, alkali metal salt, and / or amine, and / or aqueous ammonia and titanium trichloride is 3 mol of the organic acid, alkali metal salt, and / or amine, and / or ammonia. 1 to 3 mol of water and 1 to 3 mol of titanium trichloride are preferable, but the organic acid may be used in excess as a reaction solvent. The reaction molar ratio of the alkali metal and / or amine, and / or aqueous ammonia and titanium trichloride is preferably equimolar, but the pH of the reaction system is
Either can be used in excess for adjustment purposes. Further, an aqueous solution of sodium carbonate may be added as necessary for adjusting the pH of the reaction system.
【０００７】また、反応終了後必要に応じ、副生物であ
るアルカリ金属等の塩化物を除くため、温水で洗浄する
ことが望ましく、さらに珪藻土を用いてろ過することに
よりより不純物の少ない品質にすることができる。After the reaction, if necessary, it is desirable to wash with warm water in order to remove by-products such as chlorides of alkali metals, etc., and it is desirable to further filter with diatomaceous earth to reduce the quality of impurities. be able to.
【０００８】有機酸アルカリ金属塩水溶液に用いるアル
カリ金属塩としては、経済性、取扱い性等の観点から金
属ナトリウム、金属カリウム、金属リチウムなどのアル
カリ金属の水酸化物が望ましく、これら以外に酸化物、
過酸化物、及びアルカリ金属そのものなどを用いること
ができるが、これらのみに限定されない。As the alkali metal salt used in the aqueous solution of alkali metal salt of organic acid, alkali metal hydroxides such as metal sodium, metal potassium and metal lithium are preferable from the viewpoints of economy and handleability. ,
A peroxide, an alkali metal itself, and the like can be used, but not limited to these.
【０００９】有機酸アミン塩水溶液の生成に用いるアミ
ンとしては、第１級アミン、第２級アミン、第３級アミ
ン等のモノアミン、エチレンジアミン等のジアミン等を
用いることができる。また、有機酸アンモニウム塩水溶
液の生成にはアンモニア、及び／又はアンモニア水、ア
ルカリアンモニウム水酸化物等を用いることができる。As the amine used for forming the organic acid amine salt aqueous solution, monoamines such as primary amine, secondary amine and tertiary amine, diamines such as ethylenediamine and the like can be used. Ammonia and / or ammonia water, alkali ammonium hydroxide, etc. can be used for the production of the organic acid ammonium salt aqueous solution.
【００１０】本発明に用いる有機酸としては特に制限は
無いが、プロピオン酸、オクタン酸、ノナン酸、アクリ
ル酸、クロトン酸、オレイン酸、ソルビン酸、オクチル
酸、ネオデカン酸、セカノイック酸（エクソン社商品
名）、ステアリン酸等の脂肪族モノカルボン酸、安息香
酸、トルイル酸、ナフトエ酸等の芳香族モノカルボン
酸、アビエチン酸等の多核脂肪酸、ナフテン酸等の脂環
式カルボン酸、シクロヘキサン酸、ケイ皮酸、樹脂酸、
トール油脂肪酸等がありこれらの脂肪酸は単独で、又は
２種類以上のものを併用して用いてもよい。The organic acid used in the present invention is not particularly limited, but propionic acid, octanoic acid, nonanoic acid, acrylic acid, crotonic acid, oleic acid, sorbic acid, octylic acid, neodecanoic acid, secanoic acid (commercially available from Exxon) Name), aliphatic monocarboxylic acids such as stearic acid, benzoic acid, toluic acid, aromatic monocarboxylic acids such as naphthoic acid, polynuclear fatty acids such as abietic acid, alicyclic carboxylic acids such as naphthenic acid, cyclohexanoic acid, silicic acid. Crust acid, resin acid,
There are tall oil fatty acids and the like, and these fatty acids may be used alone or in combination of two or more kinds.
【００１１】[0011]
（実施例１）１０００ミリリットル反応用ビーカーに水
２００ｇ、ナフテン酸（酸価２００）５２ｇを仕込み、
攪拌しながら７０〜８０℃に昇温後、１０％カセイソー
ダ水溶液７４．１ｇ添加して２０分反応した。その後炭
酸ナトリウム水溶液で、反応系のｐＨを５〜８に調整し
ながら２０％三塩化チタン水溶液４７．１ｇを約５分で
添加し、その後１０分反応した後、静置して反応物を取
り出し、約３０分静置して酸化した。その後Ｎ−ヘキサ
ン５０ｇで希釈し、珪藻土（ラジオライト９００）でろ
過した後、ローターリーエバポレーターで脱溶媒した結
果、赤褐色透明で粘性のある液体５０ｇ得られた。その
ものはチタン５．４％含有していた。(Example 1) 200 g of water and 52 g of naphthenic acid (acid value 200) were charged into a 1000 ml reaction beaker,
After the temperature was raised to 70 to 80 ° C. with stirring, 74.1 g of 10% caustic soda aqueous solution was added and reacted for 20 minutes. Then, while adjusting the pH of the reaction system to 5 to 8 with an aqueous solution of sodium carbonate, 47.1 g of a 20% titanium trichloride aqueous solution was added in about 5 minutes, and after reacting for 10 minutes, the reaction product was taken out by standing still. It was left to stand for about 30 minutes for oxidation. After that, it was diluted with 50 g of N-hexane, filtered through diatomaceous earth (Radiolite 900), and then desolvated with a rotary evaporator. As a result, 50 g of a reddish brown transparent viscous liquid was obtained. It contained 5.4% titanium.
【００１２】（実施例２）シリカゲルカラムクロマト法
で実施例１の反応物から主成分を分取してチタン含有量
を測定したところ、９．６％であった。また、赤外線吸
収スペクトル分析の結果、１５００〜１６００ｃｍ-1に
有機酸金属塩特有の吸収ピークを認めたが、有機酸特有
の１７００ｃｍ-1の吸収ピークを全く認めなかった。(Example 2) When the titanium content was measured by separating the main component from the reaction product of Example 1 by silica gel column chromatography, the titanium content was 9.6%. The infrared absorption spectrum analysis of the results has been observed organic acid metal salt specific absorption peaks 1500～1600Cm -1, there were no absorption peaks of organic acids unique 1700 cm -1 at all.
【００１３】（実施例３）１０００ミリリットル反応用
ビーカーに水２００ｇ、トール油脂肪酸（酸価１７０）
６５ｇを仕込、攪拌しながら７０〜８０℃に昇温後、１
０％カセイソーダ水溶液８０ｇ添加して３０分反応し
た。その後炭酸ナトリウム水溶液で反応系のｐＨ５〜８
に調整しながら三塩化チタン２０％水溶液５０．９ｇを
約５分で添加し、その後１０分反応した後、ｐＨを６〜
７に保持しながら３％過酸化水素１０ｇを約３分で添加
し、１０分攪拌を続けて酸化してＮ−ヘキサン５０ｇで
希釈した。静置して反応物を取り出し、珪藻土（ラジオ
ライト９００）を用い減圧ろ過後、ローターリーエバポ
レーターで脱溶媒した結果、チタン４．０％含有した赤
褐色透明で粘性のある液体６０ｇが得られた。Example 3 In a 1000 ml reaction beaker, 200 g of water and tall oil fatty acid (acid value 170)
Charge 65 g, raise the temperature to 70-80 ° C. with stirring, and then
80 g of 0% caustic soda solution was added and reacted for 30 minutes. After that, the pH of the reaction system is 5 to 8 with an aqueous solution of sodium carbonate.
While adjusting to 5, 50.9 g of a 20% aqueous solution of titanium trichloride was added in about 5 minutes, and after reacting for 10 minutes, the pH was adjusted to 6-
While maintaining at 7, 10 g of 3% hydrogen peroxide was added in about 3 minutes, and stirring was continued for 10 minutes to oxidize and dilute with 50 g of N-hexane. The reaction product was taken out by standing, filtered under reduced pressure using diatomaceous earth (Radiolite 900), and then desolvated with a rotary evaporator. As a result, 60 g of a reddish brown transparent viscous liquid containing 4.0% titanium was obtained.
【００１４】（実施例４）２０００ミリリットル反応用
ビーカーに水８００ｇ、オクチル酸４３．７ｇを仕込、
攪拌しながら６０℃に昇温後、モノエタノールアミン１
８．３ｇを少しずつ添加後約１０分反応した。その後炭
酸ナトリウム水溶液で反応系のｐＨを５〜８に保ちなが
ら、２０％三塩化チタン水溶液７７ｇを約１０分で添加
後、１０分反応し、反応物を水と分離して取り出し約３
０分静置して空気と接触させて酸化した。その後Ｎ−ヘ
キサン５０ｇで希釈し、珪藻土（ラジオライト９００）
を用い減圧ろ過後、ロータリーエバポレーターで脱溶媒
した結果、チタン７．０％含有した赤褐色透明で粘性の
ある液体６３ｇが得られた。(Example 4) A 2000 ml reaction beaker was charged with 800 g of water and 43.7 g of octylic acid.
After heating to 60 ° C with stirring, monoethanolamine 1
After adding 8.3 g little by little, it reacted for about 10 minutes. Then, while maintaining the pH of the reaction system at 5 to 8 with an aqueous solution of sodium carbonate, 77 g of a 20% aqueous solution of titanium trichloride was added in about 10 minutes, followed by reaction for 10 minutes, and the reaction product was separated from water and taken out for about 3 minutes.
It was left to stand for 0 minutes and brought into contact with air to be oxidized. After that, dilute with 50 g of N-hexane and add diatomaceous earth (Radiolite 900).
After filtration under reduced pressure using a solvent, the solvent was removed by a rotary evaporator, and 63 g of a reddish brown transparent viscous liquid containing 7.0% titanium was obtained.
【００１５】（実施例５）１０００ミリリットル反応用
ビーカーに水３００ｇ、安息香酸５０ｇを仕込み攪拌し
ながら７０℃に昇温後、１０％カセイソーダ水溶液１６
５ｇを点かし透明な均一液体になるまで約１５分反応し
た。その後炭酸アンモニウム水溶液で反応系のｐＨを５
〜８に保ちながら、２０％三塩化チタン水溶液１０５ｇ
を少しずつ約５分で添加して１０分反応した。その後Ｎ
ｏ．２ろ紙を用いて減圧ろ過し、ろ紙上の反応物をメチ
ルエチルケトンに溶解後、約４０分静置し空気と接触さ
せて酸化した。さらに珪藻土（ラジオライト９００）を
用いろ過した結果、チタン８．０％含有した黄色透明な
液体８２ｇが得られた。(Embodiment 5) 300 g of water and 50 g of benzoic acid were charged into a 1000 ml reaction beaker and the temperature was raised to 70 ° C. with stirring, followed by 10% caustic soda solution 16
5 g was added and reacted for about 15 minutes until it became a transparent uniform liquid. After that, the pH of the reaction system was adjusted to 5 with an ammonium carbonate aqueous solution.
While keeping at ~ 8, 105 g of 20% titanium trichloride aqueous solution
Was added little by little in about 5 minutes and reacted for 10 minutes. Then N
o. The mixture was filtered under reduced pressure using 2 filter papers, and the reaction product on the filter papers was dissolved in methyl ethyl ketone and then allowed to stand for about 40 minutes to contact with air for oxidation. As a result of further filtration using diatomaceous earth (Radiolite 900), 82 g of a yellow transparent liquid containing 8.0% of titanium was obtained.
【００１６】（比較例１）３００ミリリットル反応用ビ
ーカーに水６０ｇ、オクチル酸３０ｇを仕込み７０℃に
昇温し、保温しながら１０％カセイソーダ水溶液８６ｇ
添加して反応後、炭酸ナトリウム水溶液で反応系のｐＨ
を５〜８に調整しながら、３０％硫酸チタン溶液４０ｇ
をすこしずつ添加して約５分反応したところ、反応母液
は白濁した。その後約６０分保温と攪拌を継続したが反
応母液は白濁したままであった。(Comparative Example 1) 60 g of water and 30 g of octylic acid were charged in a beaker for reaction of 300 ml, heated to 70 ° C., and 86 g of 10% caustic soda aqueous solution was heated while keeping the temperature.
After adding and reacting, the pH of the reaction system is adjusted with an aqueous sodium carbonate solution.
Adjusting to 5-8, 40g of 30% titanium sulfate solution
Was added little by little and reacted for about 5 minutes, and the reaction mother liquor became cloudy. After that, the reaction mother liquor remained cloudy although the heat retention and stirring were continued for about 60 minutes.
【００１７】[0017]
【発明の効果】本発明の方法によると通常の反応装置を
用い、単純な条件で、経済的にチタン含有量が高く、他
の有機チタンより安定な有機酸チタン塩を得ることが可
能になった。そのことにより、電気特性に優れた二酸化
チタンの薄膜、及び他の有機酸金属塩と組み合わせて焼
成することにより、複合金属酸化物薄膜等を簡単に形成
することが可能になった。Industrial Applicability According to the method of the present invention, it is possible to obtain an organic acid titanium salt which has a high titanium content economically and is more stable than other organic titanium under a simple condition using a usual reaction apparatus. It was As a result, it became possible to easily form a thin film of composite metal oxide or the like by firing in combination with a thin film of titanium dioxide having excellent electrical characteristics and another organic acid metal salt.
Claims (1)
は有機酸アミン塩水溶液、及び／又は有機酸アンモニウ
ム塩水溶液と三塩化チタン水溶液を、ｐＨ３〜１０の範
囲で反応後、反応物を酸化することを特徴とする有機酸
チタン塩の製造方法。1. A reaction product is oxidized after reacting an aqueous solution of an organic acid alkali metal salt and / or an aqueous solution of an organic acid amine salt and / or an aqueous solution of an organic acid ammonium salt with an aqueous solution of titanium trichloride within a range of pH 3 to 10. A method for producing a titanium salt of an organic acid, comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24199093A JPH0770155A (en) | 1993-09-01 | 1993-09-01 | Production of organic acid titanium salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24199093A JPH0770155A (en) | 1993-09-01 | 1993-09-01 | Production of organic acid titanium salt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0770155A true JPH0770155A (en) | 1995-03-14 |
Family
ID=17082614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24199093A Pending JPH0770155A (en) | 1993-09-01 | 1993-09-01 | Production of organic acid titanium salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0770155A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105541600A (en) * | 2014-10-28 | 2016-05-04 | 日油株式会社 | A method of producing fatty acid titanium |
-
1993
- 1993-09-01 JP JP24199093A patent/JPH0770155A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105541600A (en) * | 2014-10-28 | 2016-05-04 | 日油株式会社 | A method of producing fatty acid titanium |
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