JP4221588B2 - Method for stabilizing iridium catalyst solution - Google Patents
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本発明は、ヒドロシリル化反応用触媒等として有用なイリジウム触媒の溶液状態での安定化方法に関する。 The present invention relates to a method for stabilizing an iridium catalyst useful as a hydrosilylation catalyst or the like in a solution state.
イリジウム触媒はヒドロシリル化反応用触媒として有用であり、特定の系においては白金触媒より反応性、反応選択性が良好であり、有用な触媒である。その具体例としては、特公平２−５７０７６号公報（特許文献１）、特許第２７６８１５９号公報（特許文献２）記載のハロゲン化アリルとハイドロジェンアルコキシシランとの反応、特許第２９３８７３１号公報（特許文献３）、特開２００１−３２２９９３号公報（特許文献４）記載のハロゲン化アリルとジメチルクロロシランとの反応、特開２００３−９６０８６号公報（特許文献５）記載のカルボン酸アリルエステルとジメチルクロロシランとの反応等への使用が例示される。これらの反応において、用いられる触媒は実施例によると固体として添加している。これらの実施例は小スケールであるため、この方法が容易に採用できるが、工業的規模では少量の固体を定量的に添加することは困難であり、少量の固体を添加する場合は、溶媒に溶解させ、溶液として添加する方法が用いられる。 The iridium catalyst is useful as a catalyst for hydrosilylation reaction. In a specific system, the iridium catalyst has better reactivity and reaction selectivity than a platinum catalyst, and is a useful catalyst. Specific examples thereof include reaction of allyl halide and hydrogen alkoxysilane described in JP-B-2-57076 (Patent Document 1) and Patent 2768159 (Patent Document 2), and Japanese Patent No. 2938731 (Patent Document). Reference 3), reaction of allyl halide and dimethylchlorosilane described in JP-A-2001-322993 (Patent Document 4), carboxylic acid allyl ester and dimethylchlorosilane described in JP-A-2003-96086 (Patent Document 5) Is used for the reaction and the like. In these reactions, the catalyst used is added as a solid according to the examples. Since these examples are small-scale, this method can be easily adopted, but it is difficult to quantitatively add a small amount of solid on an industrial scale, and when adding a small amount of solid, The method of dissolving and adding as a solution is used.
しかしながら、上記のイリジウム触媒を溶媒に溶解、例えばトルエン等の芳香族炭化水素系溶媒に溶解すると、溶解性はよいが、そのまま放置しておくと、窒素下で保存しても、溶媒中の溶存酸素によりイリジウム触媒が酸化され、沈澱が生成し、触媒活性が失われてしまう。そのため、溶液として安定に保存するためには、溶媒中の溶存酸素を完全に脱気し、かつ空気を完全に遮断する必要があり、工業的に実施するには困難であった。 However, when the above iridium catalyst is dissolved in a solvent, for example, in an aromatic hydrocarbon solvent such as toluene, the solubility is good, but if left as it is, it can be dissolved in the solvent even if stored under nitrogen. Oxygen oxidizes the iridium catalyst, produces a precipitate, and the catalytic activity is lost. Therefore, in order to store stably as a solution, it is necessary to completely deaerate dissolved oxygen in the solvent and completely shut off the air, which is difficult to implement industrially.
本発明は上記事情に鑑みなされたもので、長期に亘ってイリジウム触媒溶液を、触媒活性を保持した状態で安定に保存する方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for stably storing an iridium catalyst solution while maintaining catalytic activity over a long period of time.
本発明者は、上記目的を達成するため鋭意検討を重ねた結果、イリジウム触媒を、例えばトルエン等の芳香族炭化水素系溶媒に溶解してイリジウム触媒溶液を調製する際に、驚くべきことに水酸基を有する化合物を共存させると、脱気していない溶媒を用いて空気中で溶液を調製しても沈澱の生成がなく、また触媒活性が低下しないことを知見し、本発明を完成するに至ったものである。 As a result of intensive studies to achieve the above object, the present inventors have surprisingly found that when preparing an iridium catalyst solution by dissolving an iridium catalyst in an aromatic hydrocarbon solvent such as toluene, Coexistence of a compound having a non-degassed solvent and the preparation of a solution in the air does not produce a precipitate and the catalytic activity does not decrease, leading to the completion of the present invention. It is a thing.
従って、本発明は下記のイリジウム触媒の溶液状態での安定化方法を提供する。
（Ｉ）下記一般式（２）
［Ｉｒ（Ｒ 2 ）Ｘ］ 2 （２）
（式中、Ｒ 2 はジエン化合物、Ｘは塩素、臭素、ヨウ素のいずれかである。）
で示されるイリジウム触媒を溶液とする際に、イリジウム触媒に対し、下記一般式（１）
Ｒ1ＯＨ （１）
（式中、Ｒ1は炭素数１〜２０の置換又は非置換の一価炭化水素基を示す。）
で示される一価アルコール又は多価アルコールをイリジウム触媒に対し、１モル〜１００，０００モル添加することを特徴とするイリジウム触媒溶液の安定化方法。
（ＩＩ）イリジウム触媒を溶液とする際に、溶媒として芳香族炭化水素系溶媒を用いることを特徴とする（Ｉ）記載のイリジウム触媒溶液の安定化方法。
Accordingly, the present invention provides a method for stabilizing the following iridium catalyst in solution.
(I) The following general formula (2)
[Ir (R 2 ) X] 2 (2)
(In the formula, R 2 is a diene compound, and X is chlorine, bromine, or iodine.)
When the iridium catalyst represented by formula (1) is used as a solution, the following general formula (1)
R 1 OH (1)
(In the formula, R 1 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.)
A method for stabilizing an iridium catalyst solution, comprising adding 1 mol to 100,000 mol of a monohydric alcohol or polyhydric alcohol represented by formula (1) to an iridium catalyst.
(II) The method for stabilizing an iridium catalyst solution according to (I), wherein an aromatic hydrocarbon solvent is used as a solvent when the iridium catalyst is used as a solution .
本発明によれば、ヒドロシリル化反応等に有効なイリジウム触媒を溶液とする際に、水酸基を有する化合物を添加することにより、空気中で溶液を調製しても、触媒活性を損なうことなく溶液状態で安定に保存することができる。 According to the present invention, when an iridium catalyst effective for hydrosilylation reaction or the like is used as a solution, even if the solution is prepared in the air by adding a compound having a hydroxyl group, the solution state is maintained without impairing the catalytic activity. Can be stored stably.
本発明のイリジウム触媒溶液の安定化方法は、イリジウム触媒を溶液としたときに下記一般式（１）
Ｒ1ＯＨ （１）
（式中、Ｒ1は炭素数１〜２０の置換又は非置換の一価炭化水素基を示す。）
で示される水酸基を有する化合物を添加するものである。
The stabilization method of the iridium catalyst solution of the present invention is the following general formula (1) when the iridium catalyst is used as a solution.
R 1 OH (1)
(In the formula, R 1 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.)
A compound having a hydroxyl group represented by is added.
ここで、イリジウム触媒としては、イリジウム塩、イリジウム錯体等が例示される。イリジウム塩としては具体的には、三塩化イリジウム、四塩化イリジウム、塩化イリジウム酸、塩化イリジウム酸ナトリウム、塩化イリジウム酸カリウム等が例示される。イリジウム錯体としては下記一般式（２）
［Ｉｒ（Ｒ2）Ｘ］2 （２）
（式中、Ｒ2はジエン化合物、Ｘは塩素、臭素、ヨウ素のいずれかである。）
で示される化合物等が好ましい。
Here, examples of the iridium catalyst include iridium salts and iridium complexes. Specific examples of the iridium salt include iridium trichloride, iridium tetrachloride, iridium chloride, sodium chloroiridate, and potassium iridium chloride. As the iridium complex, the following general formula (2)
[Ir (R 2 ) X] 2 (2)
(In the formula, R 2 is a diene compound, and X is chlorine, bromine, or iodine.)
The compound etc. which are shown by these are preferable.
上記一般式（２）で示されるイリジウム錯体としては、具体的にはジ−μ−クロロビス（μ−１，５−ヘキサジエン）二イリジウム、ジ−μ−ブロモビス（μ−１，５−ヘキサジエン）二イリジウム、ジ−μ−ヨードビス（μ−１，５−ヘキサジエン）二イリジウム、ジ−μ−クロロビス（μ−１，５−シクロオクタジエン）二イリジウム、ジ−μ−ブロモビス（μ−１，５−シクロオクタジエン）二イリジウム、ジ−μ−ヨードビス（μ−１，５−シクロオクタジエン）二イリジウム、ジ−μ−クロロビス（μ−２，５−ノルボルナジエン）二イリジウム、ジ−μ−ブロモビス（μ−２，５−ノルボルナジエン）二イリジウム、ジ−μ−ヨードビス（μ−２，５−ノルボルナジエン）二イリジウム等が例示される。 Specific examples of the iridium complex represented by the general formula (2) include di-μ-chlorobis (μ-1,5-hexadiene) diiridium, di-μ-bromobis (μ-1,5-hexadiene) Iridium, di-μ-iodobis (μ-1,5-hexadiene) diiridium, di-μ-chlorobis (μ-1,5-cyclooctadiene) diiridium, di-μ-bromobis (μ-1,5- Cyclooctadiene) diiridium, di-μ-iodobis (μ-1,5-cyclooctadiene) diiridium, di-μ-chlorobis (μ-2,5-norbornadiene) diiridium, di-μ-bromobis (μ -2,5-norbornadiene) diiridium, di-μ-iodobis (μ-2,5-norbornadiene) diiridium, and the like.
上記イリジウム触媒を溶解する溶媒は、例えばベンゼン、トルエン、キシレン等の芳香族炭化水素系溶媒が使用される。この場合、他の溶媒、例えばペンタン、ヘキサン、シクロヘキサン、ヘプタン、イソオクタン等の非芳香族系の炭化水素系溶媒、ジエチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、酢酸エチル、酢酸ブチル等のエステル系溶媒、アセトニトリル、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド等の非プロトン性極性溶媒、ジクロロメタン、クロロホルム等の塩素化炭化水素系溶媒等が例示される。これらの溶媒は単独で使用してもよく、あるいは２種以上を混合して使用してもよい。
また、触媒の更なる安定化のために、ヘキセン、シクロヘキセン、シクロオクタジエン、ノルボルナジエン等の不飽和炭化水素化合物を添加してもよい。
As the solvent for dissolving the iridium catalyst, for example, an aromatic hydrocarbon solvent such as benzene, toluene or xylene is used. In this case, other solvents such as non-aromatic hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane and isooctane, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, and ester solvents such as ethyl acetate and butyl acetate. Examples include solvents, aprotic polar solvents such as acetonitrile, N, N-dimethylformamide and dimethyl sulfoxide, and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used alone or in combination of two or more.
Further, an unsaturated hydrocarbon compound such as hexene, cyclohexene, cyclooctadiene, norbornadiene may be added for further stabilization of the catalyst.
本発明においては、更に下記一般式（１）
Ｒ1ＯＨ （１）
で示される水酸基を有する化合物が上記溶媒に添加される。
In the present invention, the following general formula (1)
R 1 OH (1)
A compound having a hydroxyl group represented by is added to the solvent.
この場合、Ｒ1は炭素数１〜２０、特に１〜１０の置換又は非置換の一価炭化水素基であり、具体的には直鎖状、分岐状、環状のアルキル基、アルケニル基、アルキニル基、アラルキル基等が挙げられ、またこれらの非置換一価炭化水素基において、炭素原子に結合した水素原子の一部を水酸基、アルコキシ基、ハロゲン原子等で置換したもの、エーテル結合、カルボニル基等を含むものなどの置換一価炭化水素基が挙げられる。
従って、上記一般式（１）の化合物としては、一価アルコールのほか、多価アルコールを含む。
In this case, R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms, specifically, a linear, branched or cyclic alkyl group, alkenyl group, alkynyl. group, and a aralkyl group and the like, also in these unsubstituted monovalent hydrocarbon groups, those obtained by substituting a part of hydrogen atoms bonded to a carbon atom a hydroxyl group, an alkoxy group, a halogen atom or the like, an ether bond, a carbonyl Substituted monovalent hydrocarbon groups such as those containing groups and the like can be mentioned.
Therefore, the compounds of the general formula (1), in addition to monohydric alcohols, including polyhydric alcohol.
上記一般式（１）で示される水酸基を有する化合物としては、具体的にはメタノール、エタノール、１−プロパノール、２−プロパノール、１−ブタノール、２−ブタノール、２−メチル−１−プロパノール、２−メチル−２−プロパノール、１−ペンタノール、２−ペンタノール、２−メチル−１−ブタノール、ｔｅｒｔ−アミルアルコール、１−ヘキサノール、４−メチル−２−ペンタノール、１−オクタノール、２−エチル−１−ヘキサノール、１−デカノール、シクロヘキサノール、メチルシクロヘキサノール、メントール、アリルアルコール、プロパルギルアルコール、エチレングリコール、プロピレングリコール、グリセリン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ベンジルアルコール、フェネチルアルコール等のアルコール類が例示される。 Specific examples of the compound having a hydroxyl group represented by the general formula (1) include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2- Methyl-2-propanol, 1-pentanol, 2-pentanol, 2-methyl-1-butanol, tert-amyl alcohol, 1-hexanol, 4-methyl-2-pentanol, 1-octanol, 2-ethyl- 1-hexanol, 1-decanol, cyclohexanol, methylcyclohexanol, menthol, allyl alcohol, propargyl alcohol, ethylene glycol, propylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, benzyl alcohol, and phenethyl alcohol are exemplified.
上記一般式（１）の化合物の添加量は特に限定されないが、イリジウム触媒１モルに対し、１モル〜１００，０００モル、特に５モル〜１０，０００モルの範囲が好ましい。 Although the addition amount of the compound of the general formula (1) is not particularly limited, it is preferably in the range of 1 mol to 100,000 mol, particularly 5 mol to 10,000 mol with respect to 1 mol of the iridium catalyst.
以下、実施例と比較例を示して本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
［実施例１］ 水酸基を有する化合物としてメタノールを添加したイリジウム触媒溶液の安定性評価
サンプル瓶にジ−μ−クロロビス（μ−１，５−シクロオクタジエン）二イリジウム（以下、［ＩｒＣｌ（ｃｏｄ）］2と略す）０．１８ｇを秤量し、更にメタノール１．０ｇ、トルエン５．０ｇを順に空気中で添加し、触媒を溶解させた。サンプル瓶の蓋を閉め、そのまま室温にて１週間放置した。１週間後、沈澱は生成しておらず、均一溶液であった。
[Example 1] Stability evaluation of iridium catalyst solution added with methanol as a compound having a hydroxyl group Di-μ-chlorobis (μ-1,5-cyclooctadiene) diiridium (hereinafter referred to as [IrCl (cod) The abbreviated 2 ) 0.18 g was weighed, and further 1.0 g of methanol and 5.0 g of toluene were sequentially added in the air to dissolve the catalyst. The lid of the sample bottle was closed and left at room temperature for one week. After 1 week, no precipitate was formed and the solution was homogeneous.
更に、この触媒溶液を用いて、塩化アリルとジメチルクロロシランとのヒドロシリル化反応を行い、触媒活性が保たれているか調べた。撹拌機、還流器、滴下ロート及び温度計を備えたフラスコに、塩化アリル１５３．０ｇ（２．０モル）、上記調製法で調製し、１週間放置したイリジウム触媒溶液１．２ｇ、１，５−シクロオクタジエン０．４３ｇ（０．００４モル）を仕込み、３５℃に加熱した。内温が安定した後、ジメチルクロロシラン１８９．２ｇ（２．０モル）を６時間かけて滴下した。滴下時、常に発熱が見られた。滴下終了後、反応液をガスクロマトグラフィーにて組成を分析したところ、クロロプロピルジメチルクロロシランが９８％であった。原料である塩化アリル、ジメチルクロロシランはほぼ消費されており、触媒活性は保たれていることが明らかとなった。 Further, using this catalyst solution, a hydrosilylation reaction between allyl chloride and dimethylchlorosilane was conducted to examine whether the catalytic activity was maintained. In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 153.0 g (2.0 mol) of allyl chloride, 1.2 g of iridium catalyst solution prepared by the above preparation method and allowed to stand for 1 week, 1, 5 -0.43 g (0.004 mol) of cyclooctadiene was charged and heated to 35 ° C. After the internal temperature was stabilized, 189.2 g (2.0 mol) of dimethylchlorosilane was added dropwise over 6 hours. When dripping, there was always an exotherm. After completion of the dropwise addition, the composition of the reaction solution was analyzed by gas chromatography. As a result, chloropropyldimethylchlorosilane was 98%. The raw materials, allyl chloride and dimethylchlorosilane, were almost consumed, and it became clear that the catalytic activity was maintained.
［実施例２〜４、比較例１〜２］
表１に示す配合比でイリジウム触媒溶液を調製し、その溶液安定性、触媒活性を実施例１と同様の評価法で評価した。表１における各成分の配合量の単位はｇである。
評価基準
・溶液安定性：○ １週間後でも沈澱は生成せず、均一溶液である。
× ２４時間後で多量に沈澱が生成している。
・触媒活性： ○ 反応がほぼ定量的に進行
× 反応が全く進行しない
[Example 2-4, Comparative Example 1-2]
An iridium catalyst solution was prepared at a blending ratio shown in Table 1, and the solution stability and catalytic activity were evaluated by the same evaluation method as in Example 1. The unit of the amount of each component in Table 1 is g.
Evaluation Criteria / Solution Stability: ○ No precipitate was formed even after 1 week, and the solution was homogeneous
X A large amount of precipitate was formed after 24 hours.
・ Catalytic activity: ○ Reaction progresses almost quantitatively
× Reaction does not proceed at all
［実施例５］ メタクリル酸アリルとジメチルクロロシランとのヒドロシリル化反応への使用例
撹拌機、還流器、滴下ロート及び温度計を備えたフラスコに、メタクリル酸アリル（含水量５００ｐｐｍ）１２６．０ｇ（１．０モル）、上記実施例２の配合比で調製し、１週間放置したイリジウム触媒溶液１．２ｇ、１，５−シクロオクタジエン２．２ｇ（０．０２モル）、２，６−ジｔｅｒｔ−ブチル−４メチルフェノール０．３３ｇを仕込み、６０℃に加熱した。内温が安定した後、ジメチルクロロシラン９４．６ｇ（１．０モル）を６時間かけて滴下した。滴下時、常に発熱がみられた。滴下終了後、反応液をガスクロマトグラフィーにて組成を分析したところ、メタクリル酸３−（ジメチルクロロシリル）プロピルエステルが９２％であった。原料であるジメチルクロロシランはほぼ消費されており、触媒活性は保たれていることが明らかとなった。
[Example 5 ] Example of use for hydrosilylation reaction of allyl methacrylate and dimethylchlorosilane In a flask equipped with a stirrer, a refluxer, a dropping funnel and a thermometer, 126.0 g of allyl methacrylate (water content 500 ppm) (1 1.0 mol), 1.2 g of iridium catalyst solution prepared at the blending ratio of Example 2 above, and allowed to stand for 1 week, 2.2 g (0.02 mol) of 1,5-cyclooctadiene, 2,6-ditert -0.33 g of butyl-4-methylphenol was charged and heated to 60 ° C. After the internal temperature was stabilized, 94.6 g (1.0 mol) of dimethylchlorosilane was added dropwise over 6 hours. There was always an exotherm during the addition. After completion of the dropwise addition, the composition of the reaction solution was analyzed by gas chromatography. As a result, 92% of methacrylic acid 3- (dimethylchlorosilyl) propyl ester was found. It was revealed that the raw material dimethylchlorosilane was almost consumed and the catalytic activity was maintained.
［比較例３］
イリジウム触媒溶液として比較例１の配合比で調製し、１週間放置したものを用いた以外は実施例５と同様に行った。メタクリル酸３−（ジメチルクロロシリル）プロピルエステルは全く生成しておらず、触媒活性が失われていることが明らかとなった。
[Comparative Example 3]
An iridium catalyst solution was prepared in the same manner as in Example 5 except that the iridium catalyst solution was prepared at the mixing ratio of Comparative Example 1 and allowed to stand for 1 week. Methacrylic acid 3- (dimethylchlorosilyl) propyl ester was not produced at all, and it was revealed that the catalytic activity was lost.
Claims (3)
［Ｉｒ（Ｒ 2 ）Ｘ］ 2 （２）
（式中、Ｒ 2 はジエン化合物、Ｘは塩素、臭素、ヨウ素のいずれかである。）
で示されるイリジウム触媒を溶液とする際に、イリジウム触媒に対し、下記一般式（１）
Ｒ1ＯＨ （１）
（式中、Ｒ1は炭素数１〜２０の置換又は非置換の一価炭化水素基を示す。）
で示される一価アルコール又は多価アルコールをイリジウム触媒に対し、１モル〜１００，０００モル添加することを特徴とするイリジウム触媒溶液の安定化方法。 The following general formula (2)
[Ir (R 2 ) X] 2 (2)
(In the formula, R 2 is a diene compound, and X is chlorine, bromine, or iodine.)
When the iridium catalyst represented by formula (1) is used as a solution, the following general formula (1)
R 1 OH (1)
(In the formula, R 1 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.)
A method for stabilizing an iridium catalyst solution, comprising adding 1 mol to 100,000 mol of a monohydric alcohol or polyhydric alcohol represented by formula (1) to an iridium catalyst.
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