JPH05237394A - Fixed pt cluster complex catalyst and its production - Google Patents

Fixed pt cluster complex catalyst and its production

Info

Publication number
JPH05237394A
JPH05237394A JP4039312A JP3931292A JPH05237394A JP H05237394 A JPH05237394 A JP H05237394A JP 4039312 A JP4039312 A JP 4039312A JP 3931292 A JP3931292 A JP 3931292A JP H05237394 A JPH05237394 A JP H05237394A
Authority
JP
Japan
Prior art keywords
phosphine
catalyst
cluster complex
reaction
complex
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
Application number
JP4039312A
Other languages
Japanese (ja)
Inventor
Takumi Okazaki
巧 岡崎
Takafumi Shito
貴文 紫藤
Masaru Ichikawa
勝 市川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arakawa Chemical Industries Ltd
Original Assignee
Arakawa Chemical Industries Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Arakawa Chemical Industries Ltd filed Critical Arakawa Chemical Industries Ltd
Priority to JP4039312A priority Critical patent/JPH05237394A/en
Publication of JPH05237394A publication Critical patent/JPH05237394A/en
Pending legal-status Critical Current

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Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Hydrogen, Water And Hydrids (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

PURPOSE:To produce a catalyst useful for reaction in heterogeneous system which is practically important by producing ether linkage of phosphine on a silica carrier and then chemically fixing a Pt cluster complex to the phosphine position. CONSTITUTION:A silica carrier is impregnated with phosphine (e.g. tris(hydroxymethyl)phosphine) in the presence of an org. solvent (e.g. ethanol) and heated to produce ether bonds of phosphine. Then a Pt cluster complex (e.g. [N(C2H5)4]2[Pt12(CO)24]) is fixed to the phosphine position in the presence of a solvent (e.g. tetrahydrofuran) which can dissolve the complex. The amt. of phosphine deposited is 0.5-40wt.% to the whole weight of the catalyst and the amt. of the Pt cluster complex deposited is 0.03-40wt.% calculated as metal weight to the whole weight of the catalyst. This catalyst is useful as a catalyst for reaction in heterogeneous system which is practically important.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、新規な固定化Ｐｔクラ
スター錯体触媒及びその製造方法に関する。TECHNICAL FIELD The present invention relates to a novel immobilized Pt cluster complex catalyst and a method for producing the same.

【０００２】[0002]

【従来の技術及びその課題】金属錯体を用いた均一系触
媒反応では、作用機構の解明、触媒反応のデザインを比
較的容易に行うことができ、更にはその低温における高
活性・高選択性等という特徴を生かした不斉合成にみら
れるように、高度な反応設計が可能となる等の利点があ
る。該利点を有効利用した均一系触媒工業プロセスがす
でに幾つも工業化されている。2. Description of the Related Art In a homogeneous catalytic reaction using a metal complex, it is possible to elucidate the mechanism of action and design the catalytic reaction relatively easily, and further, it has high activity and high selectivity at low temperature. As seen in asymmetric synthesis that takes advantage of this feature, there are advantages such as enabling sophisticated reaction design. A number of homogeneous catalyst industrial processes have been commercialized that effectively utilize the advantages.

【０００３】しかし、均一系反応であるため、触媒、生
成物、未反応原料相互の分離が困難であること、熱的に
は必ずしも安定でないこと、酸素・湿気等に敏感であ
り、触媒寿命が固体触媒より短いこと等、プロセス操業
上の不利がある。However, since it is a homogeneous reaction, it is difficult to separate the catalyst, the product, and the unreacted raw materials from each other, is not always thermally stable, is sensitive to oxygen and moisture, etc., and has a long catalyst life. It has disadvantages in process operation such as being shorter than the solid catalyst.

【０００４】これらの問題点、特に触媒分離の困難さを
克服するために、無機固体、有機高分子等に金属錯体触
媒を担持・固定化して不均一系触媒とすることにより、
触媒活性を有効に発現するとともに触媒の分離回収効率
を高める試みがこれまでなされてきた。一般的には、金
属錯体の固定化担持の方法として下記方法が採用されて
きた。In order to overcome these problems, particularly the difficulty of catalyst separation, a metal complex catalyst is supported and immobilized on an inorganic solid, an organic polymer or the like to form a heterogeneous catalyst.
Attempts have been made so far to effectively develop the catalytic activity and enhance the efficiency of separation and recovery of the catalyst. Generally, the following method has been adopted as a method for immobilizing and supporting a metal complex.

【０００５】（１）金属酸化物表面の水酸基（−Ｏ
Ｈ+ 、−ＯＨ- ）、ルイス酸（Ｍn+）、塩基点（Ｏ2-、
Ｏ- ）等と金属錯体や配位子との表面反応を利用した金
属−担体直接結合により固定化する方法。(1) Hydroxyl group (--O on the surface of metal oxide)
H +, -OH -), a Lewis acid (M n +), a base point (O 2-,
A method of immobilizing by a direct metal-carrier bond utilizing the surface reaction of O − ) or the like with a metal complex or a ligand.

【０００６】（２）ゼオライト等の「分子篩」の細孔内
に金属錯体を合成、捕捉する方法。(2) A method of synthesizing and capturing a metal complex in the pores of a "molecular sieve" such as zeolite.

【０００７】（３）アミノ基、ホスフィン基等で修飾し
た有機高分子に、配位子交換反応や直接反応により固定
化する方法。(3) A method of immobilizing an organic polymer modified with an amino group, a phosphine group or the like by a ligand exchange reaction or a direct reaction.

【０００８】これらの方法によって、金属錯体をそれぞ
れの担体に固定化できることは明らかであるが、いずれ
の方法も未だ問題点を有している。即ち、上記（１）及
び（２）の方法では、固定化時に、無機担体の表面反応
基の作用により金属錯体の構造変化（異性化、分解等）
が起り、金属錯体固有の構造を保持したまま固定化する
ことははなはだ困難である。また、（３）の方法では、
担体が有機化合物であるために、固定化触媒自体が熱に
よって変化したり、溶媒に溶解する問題があり、実用
上、触媒の使用条件に大きな制限があった。殊に、上記
公知の固定化方法を金属クラスター錯体に適用した場合
には、その有効な構造中心ひいては高活性能を保持した
まま固定化することが困難であった。It is clear that the metal complex can be immobilized on each carrier by these methods, but all of them still have problems. That is, in the above methods (1) and (2), the structural change (isomerization, decomposition, etc.) of the metal complex is caused by the action of the surface reactive group of the inorganic carrier during immobilization.
Therefore, it is very difficult to immobilize the metal complex while retaining its unique structure. Also, in the method of (3),
Since the carrier is an organic compound, there are problems that the immobilized catalyst itself is changed by heat and that it is dissolved in a solvent, which practically limits the conditions of use of the catalyst. In particular, when the above-mentioned known immobilization method is applied to a metal cluster complex, it is difficult to immobilize the metal cluster complex while maintaining its effective structural center and thus high activity.

【０００９】[0009]

【課題を解決するための手段】本発明の目的は、上記従
来方法で得られる固定化金属錯体触媒が有する課題を解
決し得る新規な固定化金属クラスター錯体触媒を提供す
ることにある。即ち、種々の触媒反応に際して高性能・
高効率なＰｔクラスター錯体触媒を、該錯体本来の構造
及び触媒性能を充分に保持したままシリカの無機担体上
に固定化した固定化金属クラスター錯体触媒を提供する
ことにある。An object of the present invention is to provide a novel immobilized metal cluster complex catalyst capable of solving the problems of the immobilized metal complex catalyst obtained by the above conventional method. That is, high performance in various catalytic reactions
An object of the present invention is to provide an immobilized metal cluster complex catalyst in which a highly efficient Pt cluster complex catalyst is immobilized on an inorganic carrier of silica while sufficiently retaining the original structure and catalytic performance of the complex.

【００１０】本発明者は、有機金属錯体の一種であるＰ
ｔクラスター錯体触媒を固定化するに当り、上記従来技
術の課題に鑑み金属錯体の固定化法につき鋭意研究し
た。その結果、驚くべきことにＰｔクラスター錯体を特
定の配位子を介してシリカ担体に固定化することによ
り、前記課題を悉く解決し得る固体触媒（不均一系触
媒）を収得し得るという新たな知見を得た。本発明は、
かかる新知見に基づき完成されたものである。The inventor of the present invention, P, which is a kind of organometallic complex,
In immobilizing the t-cluster complex catalyst, in view of the above-mentioned problems of the prior art, an intensive study was conducted on a method of immobilizing a metal complex. As a result, surprisingly, by immobilizing a Pt cluster complex on a silica carrier through a specific ligand, a new solid catalyst (heterogeneous catalyst) that can solve the above problems can be obtained. I got the knowledge. The present invention is
It was completed based on this new knowledge.

【００１１】即ち本発明は、シリカ担体がホスフィンに
よりエーテル結合を介して修飾され、且つ該ホスフィン
部位にＰｔクラスター錯体が化学的に固定化されてなる
ことを特徴とする固定化Ｐｔクラスター錯体触媒に係
る。That is, the present invention provides an immobilized Pt cluster complex catalyst characterized in that a silica carrier is modified with phosphine through an ether bond, and a Pt cluster complex is chemically immobilized on the phosphine site. Pertain.

【００１２】更に本発明は、シリカ担体上にホスフィン
をエーテル結合させ、次いで該ホスフィン部位にＰｔク
ラスター錯体を化学的に固定化することを特徴とする固
定化Ｐｔクラスター錯体触媒の製造方法に係る。Further, the present invention relates to a method for producing an immobilized Pt cluster complex catalyst, characterized in that a phosphine is ether-bonded onto a silica carrier, and then a Pt cluster complex is chemically immobilized on the phosphine site.

【００１３】本発明で使用されるシリカとしては、特に
限定はされないが、触媒性能面から見てその表面積及び
細孔容積が大きいことが好ましい。担体の形状は、粉
末、ペレット、球状、押出成型品等の通常のものでよ
く、担体の大きさも約１０μｍから６ｍｍ程度のものが
好適であるが、特に制限されるものではない。この担体
シリカはホスフィンで修飾するに先立ち、シリカ表面に
吸着している水や吸着ガスを除くために加熱排気処理す
ることが望ましい。該加熱温度は、特に制限されない
が、一般的には約１００℃から約８００℃の間とされ
る。１００℃より低すぎると脱水が不十分となる傾向に
あり、又８００℃より高すぎるとシリカ表面の水酸基量
が減少し引き続くホスフィンの固定化反応に関与する反
応性表面水酸基の数が少なくなる傾向にあるので、いず
れも好ましくない。なお、一般的には、２００℃以上の
加熱によって、シリカに物理的に吸着した水はほとんど
除去できるとされている。The silica used in the present invention is not particularly limited, but it is preferable that it has a large surface area and a large pore volume from the viewpoint of catalytic performance. The shape of the carrier may be a usual one such as powder, pellet, sphere, or extrusion molded product, and the size of the carrier is preferably about 10 μm to 6 mm, but is not particularly limited. Prior to modifying the carrier silica with phosphine, it is desirable that the carrier silica be heated and exhausted to remove water and adsorbed gas adsorbed on the silica surface. The heating temperature is not particularly limited, but is generally between about 100 ° C and about 800 ° C. If it is lower than 100 ° C, dehydration tends to be insufficient, and if it is higher than 800 ° C, the amount of hydroxyl groups on the silica surface decreases and the number of reactive surface hydroxyl groups involved in the subsequent phosphine immobilization reaction tends to decrease. Therefore, both are not preferable. In general, it is said that by heating at 200 ° C. or higher, most of the water physically adsorbed on silica can be removed.

【００１４】本発明で使用されるホスフィンは、特に限
定されないが、シリカ表面をエーテル結合により修飾し
得るものであることが必要である。より具体的には、シ
リカ表面の水酸基との間で脱水縮合反応によりエーテル
結合を生成して固定化される観点から、ホスフィン分子
中に少なくとも１個の水酸基を有することが必要であ
る。かかるホスフィンの具体例としては、例えばトリス
（ヒドロキシメチル）ホスフィン〔Ｐ（ＣＨ2 Ｏ
Ｈ）3 、以下ＴＨＰという〕、トリス（ヒドロキシフェ
ニル）ホスフィン〔Ｐ（Ｃ6 Ｈ4 ＯＨ）3 〕等が挙げら
れる。The phosphine used in the present invention is not particularly limited, but it is necessary that the surface of silica can be modified by an ether bond. More specifically, it is necessary to have at least one hydroxyl group in the phosphine molecule from the viewpoint of forming an ether bond by a dehydration condensation reaction with the hydroxyl group on the silica surface and immobilizing it. Specific examples of such a phosphine include, for example, tris (hydroxymethyl) phosphine [P (CH 2 O
H) 3 , hereinafter referred to as THP], tris (hydroxyphenyl) phosphine [P (C 6 H 4 OH) 3 ] and the like.

【００１５】シリカに対するホスフィンの添加量も、特
に限定されないが、通常は触媒の全重量に対して約０．
５〜４０重量％程度、好ましくは約２〜２０重量％とさ
れる。０．５重量％未満ではホスフィンの添加効果が充
分に発現しないので好ましくない。即ち、後述するＰｔ
クラスター錯体が直接的に担体シリカ表面と反応し、ク
ラスター構造が変化し易くなるため好ましくない。ま
た、４０重量％を越えると、ホスフィンとシリカ表面と
の反応が不十分となり、ホスフィンの固定化が完結しな
い場合があるので好ましくない。The amount of phosphine added to silica is also not particularly limited, but is usually about 0.
It is about 5 to 40% by weight, preferably about 2 to 20% by weight. If it is less than 0.5% by weight, the effect of adding phosphine is not sufficiently exhibited, which is not preferable. That is, Pt described later
The cluster complex directly reacts with the surface of the carrier silica, and the cluster structure is likely to change, which is not preferable. On the other hand, if it exceeds 40% by weight, the reaction between the phosphine and the silica surface becomes insufficient and immobilization of phosphine may not be completed, which is not preferable.

【００１６】ホスフィンのシリカ表面への固定化反応
は、シリカ担体上にホスフィンを有機溶媒存在下に含浸
させた後に加熱処理してシリカ担体上にホスフィンをエ
ーテル結合させることにより、行うことができる。より
具体的には、ホスフィンを無水の有機溶媒に溶解し、シ
リカと共に室温で撹拌した後溶媒を留去してホスフィン
を含浸担持させ、更に通常加熱排気処理してシリカ表面
の水酸基とホスフィンの水酸基とを脱水縮合反応させて
エーテル結合を形成することによって、好適に達成され
る。使用する有機溶媒としては、水酸基を有するホスフ
ィンを溶解すること及びシリカ表面水酸基と反応しない
ことの２要件を満足するものであり、例えばエタノー
ル、プロパノール、イソプロパノール等の無水のものが
好適である。なお、水が混入した有機溶媒を使用した場
合には、水がホスフィンより先にシリカ表面水酸基と反
応し、ホスフィンとシリカ表面水酸基との脱水縮合反応
が実質的に阻害され固定化が十分に達成されない。ま
た、該固定化反応に際しては、水酸基を有するホスフィ
ンが一般に吸湿性が高いため、十分に乾燥した空気又は
窒素等の不活性ガス中で取扱うことが望ましい。The immobilization reaction of phosphine on the silica surface can be carried out by impregnating the phosphine on the silica carrier in the presence of an organic solvent and then heat-treating the phosphine to form an ether bond with the phosphine on the silica carrier. More specifically, phosphine is dissolved in an anhydrous organic solvent, stirred with silica at room temperature, then the solvent is distilled off to impregnate and carry phosphine, and further, it is usually heated and exhausted to give a hydroxyl group on the silica surface and a hydroxyl group of phosphine. It is preferably achieved by subjecting and to a dehydration condensation reaction to form an ether bond. The organic solvent used is one that satisfies the two requirements of dissolving a phosphine having a hydroxyl group and not reacting with the hydroxyl group on the silica surface. For example, an anhydrous solvent such as ethanol, propanol or isopropanol is preferable. When an organic solvent mixed with water is used, water reacts with the hydroxyl groups on the silica surface before the phosphine, and the dehydration condensation reaction between the phosphine and the silica surface hydroxyl groups is substantially inhibited and immobilization is sufficiently achieved. Not done. In addition, since phosphine having a hydroxyl group generally has high hygroscopicity in the immobilization reaction, it is desirable to handle it in sufficiently dry air or an inert gas such as nitrogen.

【００１７】上記固定化反応において、加熱処理を施す
理由は、シリカ表面の水酸基とホスフィンの水酸基との
脱水縮合反応を進行させると共に、反応生成水を系外に
留去して化学平衡的に反応を促進でき、且つ生成水のシ
リカ表面への吸着を防止できるためである。ここで、加
熱温度は、通常２００℃以下程度が好ましく、７０〜１
５０℃程度がより好ましい。２００℃を越えて加熱すれ
ばホスフィンの分解が起り始める傾向にあるからであ
る。加熱処理時間については、特に限定されるものでは
ないが、シリカ表面水酸基とホスフィンの水酸基の反応
が終結するに足る時間とするのが良く、通常１〜５時間
程度とするのが適当である。該反応の終点はＩＲスペク
トルにより決定できる。即ち、ホスフィンを有機溶媒中
でシリカと共に室温で撹拌した後溶媒を留去したもので
は、ホスフィン及びシリカに存在する水酸基の伸縮振動
吸収が３０００〜３８００cm-1に大きく観測されるが、
加熱処理により水酸基間の脱水縮合反応が進行しこの吸
収強度が減少するからであり、反応終点はこのＩＲ吸収
の変化が無くなった時点として容易に認識できる。In the above immobilization reaction, the heat treatment is performed because the dehydration condensation reaction between the hydroxyl group on the silica surface and the hydroxyl group on phosphine proceeds, and the reaction product water is distilled out of the system to react chemically equilibrium. This is because the adsorption of generated water on the silica surface can be prevented. Here, the heating temperature is usually preferably about 200 ° C. or lower, and 70 to 1
About 50 ° C is more preferable. This is because the decomposition of phosphine tends to begin to occur when heated at over 200 ° C. The heat treatment time is not particularly limited, but it is good enough to complete the reaction between the hydroxyl groups on the silica surface and the phosphine hydroxyl groups, and usually about 1 to 5 hours is appropriate. The end point of the reaction can be determined by IR spectrum. That is, when phosphine is stirred with silica in an organic solvent at room temperature and then the solvent is distilled off, stretching vibration absorption of hydroxyl groups present in phosphine and silica is largely observed at 3000 to 3800 cm -1 ,
This is because the dehydration condensation reaction between the hydroxyl groups progresses by the heat treatment and this absorption intensity decreases, and the reaction end point can be easily recognized as the time when this IR absorption change disappears.

【００１８】この固定化反応により、シリカ担体がホス
フィンによりエーテル結合を介して修飾されている、ホ
スフィン修飾シリカが調製される。By this immobilization reaction, phosphine-modified silica in which the silica carrier is modified with phosphine through an ether bond is prepared.

【００１９】本発明触媒は、上記で得たホスフィン修飾
シリカの該ホスフィン部位にＰｔクラスター錯体が化学
的に固定化されてなるものである。ここで、化学的に固
定化とは、Ｐｔクラスター錯体の配位子であるＣＯとホ
スフィン修飾シリカ上のＰ原子との配位子交換反応によ
って、Ｐｔクラスター錯体と該Ｐ原子との間に化学的な
配位結合が生成していることを意味する。The catalyst of the present invention is obtained by chemically fixing a Pt cluster complex on the phosphine site of the phosphine-modified silica obtained above. Here, the chemical immobilization means that a ligand exchange reaction between CO, which is a ligand of the Pt cluster complex, and a P atom on the phosphine-modified silica causes a chemical reaction between the Pt cluster complex and the P atom. Means that a specific coordinate bond is generated.

【００２０】本発明の触媒の製造において使用されるＰ
ｔクラスター錯体としては、特に限定されないが、例え
ばＫ2 〔Ｐｔ6 （ＣＯ）12〕、〔Ｎ（Ｃ2 Ｈ5 ）4 〕2
〔Ｐｔ9 （ＣＯ）18〕、〔Ｎ（Ｃ2 Ｈ5 ）4 〕2 〔Ｐｔ
12（ＣＯ）24〕、〔Ｎ（Ｃ2Ｈ5 ）4 〕2 〔Ｐｔ15（Ｃ
Ｏ）30〕等の一連のアニオンタイプのものや、例えば
〔Ｐｔ3 （ＣＯ）3 （Ｐ（Ｃ6 Ｈ5 ）3 ）4 〕等の中性
タイプのもの等を好適に使用できる。これらの内、特に
好ましいものは、〔Ｎ（Ｃ2 Ｈ5 ）4 〕2 〔Ｐｔ12（Ｃ
Ｏ）24〕等である。該Ｐｔクラスター錯体を前記ホスフ
ィン修飾シリカ上へ化学的に固定化する方法は、特に限
定されるものではないが、例えば、次の方法を採用でき
る。即ち、Ｐｔクラスター錯体を不活性ガス気流下で該
クラスター錯体を溶解し得る溶媒（例えばテトラヒドロ
フラン等）に溶解した後、通常室温にてホスフィン修飾
シリカに添加、撹拌、混合することにより、該錯体がホ
スフィン修飾シリカに固定化される。Ｐｔクラスター錯
体の添加量は、ホスフィン修飾シリカ中のホスフィンの
モル量に対して等モル量以下とするのが好ましい。等モ
ル量を越えて添加すると、Ｐｔクラスター錯体がホスフ
ィン部位以外の部分即ちシリカ上にも固定化され、Ｐｔ
クラスターの構造が変化する場合があるからである。固
定化の際の温度条件は、必要に応じて、１００℃程度以
下の比較的低い温度に加熱することもできる。一般的
に、金属クラスター錯体は熱的に不安定であるからであ
る。Ｐｔクラスター錯体固定化後は、溶媒を留去し、減
圧下又は不活性ガス気流下で乾燥すれば目的とする固定
化Ｐｔクラスター錯体触媒を得ることができる。P used in the preparation of the catalyst of the present invention
The t-cluster complex is not particularly limited, but for example, K 2 [Pt 6 (CO) 12 ], [N (C 2 H 5 ) 4 ] 2
[Pt 9 (CO) 18 ], [N (C 2 H 5 ) 4 ] 2 [Pt
12 (CO) 24 ], [N (C 2 H 5 ) 4 ] 2 [Pt 15 (C
O) 30] ones and series of anion types such as, for example, [Pt 3 (CO) 3 (P (C 6 H 5) 3) 4 ] that such a neutral type, such as can be suitably used. Of these, particularly preferred are [N (C 2 H 5 ) 4 ] 2 [Pt 12 (C
O) 24 ]. The method for chemically immobilizing the Pt cluster complex on the phosphine-modified silica is not particularly limited, but for example, the following method can be adopted. That is, after the Pt cluster complex is dissolved in a solvent (for example, tetrahydrofuran) capable of dissolving the Pt cluster complex under an inert gas stream, the complex is usually added to phosphine-modified silica at room temperature, followed by stirring and mixing to give the complex. It is immobilized on phosphine-modified silica. The addition amount of the Pt cluster complex is preferably equal to or less than the molar amount of phosphine in the phosphine-modified silica. If added in excess of the equimolar amount, the Pt cluster complex will be immobilized on the part other than the phosphine site, that is, on silica,
This is because the cluster structure may change. The temperature condition for immobilization may be heating to a relatively low temperature of about 100 ° C. or lower, if necessary. This is because the metal cluster complex is generally thermally unstable. After the Pt cluster complex is immobilized, the solvent is distilled off and the target immobilized Pt cluster complex catalyst can be obtained by drying under reduced pressure or under an inert gas stream.

【００２１】Ｐｔクラスター錯体の担持量は、下限は特
に制限されないが、触媒活性を考慮すれば、Ｐｔ金属重
量に換算して全触媒量に対して約０．０３重量％以上で
あることが好ましい。一方、担持量の上限は、上述の通
り使用したホスフィンのモル量に対してＰｔクラスター
錯体の添加量を等モル量以下とするのが好ましいことか
ら、Ｐｔ金属重量に換算して全触媒量に対して約４０重
量％以下であることが好ましい。The lower limit of the amount of the Pt cluster complex supported is not particularly limited, but considering the catalytic activity, it is preferably about 0.03% by weight or more in terms of Pt metal weight based on the total amount of the catalyst. .. On the other hand, as for the upper limit of the supported amount, it is preferable that the addition amount of the Pt cluster complex be equal to or less than the molar amount of the phosphine used as described above. On the other hand, it is preferably about 40% by weight or less.

【００２２】本発明の触媒の利用分野については、特に
制限されるものではないが、Ｐｔ金属種の触媒作用を考
慮すれば、水素化反応、特に選択的な水素化反応への応
用が可能である。The field of use of the catalyst of the present invention is not particularly limited, but in consideration of the catalytic action of Pt metal species, it can be applied to a hydrogenation reaction, particularly a selective hydrogenation reaction. is there.

【００２３】本発明の触媒を用いた反応様式は、回分式
反応系・流通式反応系のいずれであっても良い。反応原
料が気体であれば、そのまま反応に供すれば良いし、液
体であればそのままで又は適当な溶媒で希釈して反応に
供しても良い。また、原料が常温で固体であれば、適当
な溶媒に溶解して反応に供することができる。The reaction mode using the catalyst of the present invention may be either a batch reaction system or a flow reaction system. If the reaction raw material is a gas, it may be used for the reaction as it is, and if it is a liquid, it may be used for the reaction as it is or after diluted with a suitable solvent. If the raw material is solid at room temperature, it can be dissolved in an appropriate solvent and used for the reaction.

【００２４】好適な反応条件は、原料化合物の物理的性
質に依存し、一概に述べることはできないが、目的とす
る反応において、充分な反応速度が得られ且つ分解等の
副反応が十分に抑制されるような反応温度・反応圧力で
行うことが好ましい。反応温度等の条件については、本
発明触媒がその活性を失わない範囲であれば、制限され
ない。The suitable reaction conditions depend on the physical properties of the raw material compounds and cannot be generally described. However, in the intended reaction, a sufficient reaction rate is obtained and side reactions such as decomposition are sufficiently suppressed. It is preferable to carry out the reaction at such a reaction temperature and reaction pressure. The conditions such as reaction temperature are not limited as long as the catalyst of the present invention does not lose its activity.

【００２５】[0025]

【実施例】以下、実施例及び比較例を挙げて、本発明を
更に具体的に説明するが、本発明はこれら各例に限定さ
れるものではない。尚、各例中、部及び％は、特記しな
い限り、すべて重量基準である。EXAMPLES The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In the examples, all parts and% are by weight unless otherwise specified.

【００２６】[0026]

【実施例１】 本発明触媒の調製 ２００℃で４時間真空乾燥（１Torr以下）したシリカ粉
末（日本アエロジル工業（株）製、商品名アエロジル−
３００、比表面積２８０cm2 ）４．５６ｇを容積５０ml
のシュレンク管に窒素ガス雰囲気下で秤りとり、これに
ＴＨＰ４３９mgを溶解した無水エタノール溶液３０mlを
窒素ガス雰囲気下で加えた。室温で約８時間撹拌の後、
真空ポンプで無水エタノールを減圧留去し、更に該溶媒
が完全に蒸発するまで室温にて減圧乾燥した。Example 1 Preparation of catalyst of the present invention Silica powder vacuum-dried (1 Torr or less) at 200 ° C. for 4 hours (manufactured by Nippon Aerosil Industry Co., Ltd., trade name Aerosil-
300, specific surface area 280 cm 2 ) 4.56 g, volume 50 ml
Was weighed in a Schlenk tube under a nitrogen gas atmosphere, and 30 ml of an absolute ethanol solution containing 439 mg of THP was added thereto under a nitrogen gas atmosphere. After stirring at room temperature for about 8 hours,
Anhydrous ethanol was distilled off under reduced pressure with a vacuum pump, and further dried at room temperature under reduced pressure until the solvent was completely evaporated.

【００２７】次いで、１３０℃まで約１時間で昇温し、
最終的に１３０℃で２時間、減圧下（１Torr以下）で真
空加熱することにより、ＴＨＰ修飾シリカを得た。Then, the temperature is raised to 130 ° C. in about 1 hour,
Finally, by vacuum heating at 130 ° C. for 2 hours under reduced pressure (1 Torr or less), THP-modified silica was obtained.

【００２８】このＴＨＰ修飾シリカに、〔Ｎ（Ｃ
2 Ｈ5 ）4 〕2 〔Ｐｔ12（ＣＯ）24〕であるＰｔクラス
ター錯体１４４mgを溶解させた無水テトラヒドロフラン
溶液約２０mlを窒素ガス雰囲気下に添加し、約３０分間
室温で撹拌した。その後、真空ポンプで無水テトラヒド
ロフランを室温で減圧留去し、更に該溶媒が完全に蒸発
するまで室温にて減圧（１Torr以下）乾燥した。This THP-modified silica was added with [N (C
About 20 ml of anhydrous tetrahydrofuran solution in which 144 mg of Pt cluster complex which is 2 H 5 ) 4 ] 2 [Pt 12 (CO) 24 ] was dissolved was added under a nitrogen gas atmosphere and stirred at room temperature for about 30 minutes. Then, anhydrous tetrahydrofuran was distilled off under reduced pressure at room temperature with a vacuum pump, and further dried under reduced pressure (1 Torr or less) at room temperature until the solvent was completely evaporated.

【００２９】こうして調製したＰｔクラスター錯体／Ｔ
ＨＰ／ＳｉＯ2 触媒のＦＴ−ＩＲを真空下で測定したと
ころ２０４７cm-1及び１８４２cm-1に〔Ｐｔ12（ＣＯ）
24〕2-に特徴的なＰｔ−Ｃ＝Ｏの伸縮振動に基づく吸収
が観測された。The Pt cluster complex / T thus prepared
The FT-IR of the HP / SiO 2 catalyst was measured under vacuum at 2047 cm -1 and 1842 cm -1 [Pt 12 (CO)
24 ] Absorption based on stretching vibration of Pt—C═O, which is characteristic of 2- , was observed.

【００３０】このことは、Ｐｔクラスター錯体の金属骨
格がその立体構造を保持して選択的にＴＨＰ上に固定化
され、シリカ上には殆ど存在していないことを示唆して
いる。This suggests that the metal skeleton of the Pt cluster complex retains its steric structure, is selectively immobilized on THP, and is hardly present on silica.

【００３１】[0031]

【比較例１】 比較用触媒の調製 ＳｉＯ2 にＴＨＰを固定化することなしに、〔Ｎ（Ｃ2
Ｈ5 ）4 〕2 〔Ｐｔ12（ＣＯ）24〕であるＰｔクラスタ
ー錯体を直接ＳｉＯ2 上に固定化した。即ち、２００℃
で４時間真空乾燥（１Torr以下）したシリカ粉末（日本
アエロジル工業（株）製、商品名アエロジル−３００、
比表面積２８０cm2 ）５ｇを容積５０ｍｌのシュレンク
管に窒素ガス雰囲気下で秤りとり、これに〔Ｎ（Ｃ２
Ｈ5 ）4 〕2〔Ｐｔ12（ＣＯ）24〕１４４mgを溶解させ
た無水テトラヒドロフラン溶液２０mlを窒素ガス雰囲気
下に添加し、約３０分間室温で撹拌した。真空ポンプで
無水テトラヒドロフランを室温で減圧留去し、更に該溶
媒が完全に蒸発するまで室温にて減圧（１Torr以下）乾
燥した。In Comparative Example 1] Preparation of SiO 2 comparative catalyst without immobilized THP, [N (C 2
The Pt cluster complex, which is H 5 ) 4 ] 2 [Pt 12 (CO) 24 ], was directly immobilized on SiO 2 . That is, 200 ° C
Silica powder dried under vacuum (1 Torr or less) for 4 hours (manufactured by Nippon Aerosil Co., Ltd., trade name Aerosil-300,
5 g of a specific surface area of 280 cm 2 was weighed in a Schlenk tube having a volume of 50 ml under a nitrogen gas atmosphere, and [N (C 2
20 ml of anhydrous tetrahydrofuran solution in which 144 mg of H 5 ) 4 ] 2 [Pt 12 (CO) 24 ] was dissolved was added under a nitrogen gas atmosphere, and the mixture was stirred at room temperature for about 30 minutes. Anhydrous tetrahydrofuran was distilled off under reduced pressure at room temperature with a vacuum pump, and further dried under reduced pressure (1 Torr or less) at room temperature until the solvent was completely evaporated.

【００３２】こうして調製したＰｔクラスター錯体／Ｓ
ｉＯ2 触媒のＦＴ−ＩＲを真空下で測定したところ２０
６２cm-1及び１８４４cm-1に〔Ｐｔ12（ＣＯ）24〕2-に
特徴的なＰｔ−Ｃ＝Ｏの伸縮振動に基づく吸収が観測さ
れた。The Pt cluster complex / S thus prepared
When FT-IR of the iO 2 catalyst was measured under vacuum, it was 20.
62cm -1 and 1844cm -1 to [Pt 12 (CO) 24] 2- in based on the stretching vibration characteristic Pt-C = O absorption was observed.

【００３３】ＩＲスペクトルにおける〔Ｐｔ12（ＣＯ）
24〕2-のＰｔ−Ｃ＝Ｏの伸縮振動に基づく吸収は、本来
２０４０cm-1に観測される（G.Longoni 等、J.Am.Chem.
Soc., 98,7227(1976) ）。従って、上記の如く大きく吸
収位置がシフトしていることから、本比較例のＳｉＯ2
担体に直接固定した〔Ｎ（Ｃ2 Ｈ5 ）4 〕2 〔Ｐｔ
12（ＣＯ）24〕はＳｉＯ2 担体より何等かの影響を受け
Ｐｔクラスター錯体の状態が変化しているものと推測さ
れる。[Pt 12 (CO) in the IR spectrum
24 ] The absorption due to stretching vibration of Pt-C = O of 2 -is originally observed at 2040 cm -1 (G. Longoni et al., J. Am. Chem.
Soc., 98 , 7227 (1976)). Therefore, since the absorption position is largely shifted as described above, the SiO 2 of this comparative example is
[N (C 2 H 5 ) 4 ] 2 [Pt fixed directly to the carrier
It is presumed that 12 (CO) 24 ] is affected by the SiO 2 carrier and the state of the Pt cluster complex is changed.

【００３４】[0034]

【実施例２】本発明触媒を水素重水素交換反応の触媒と
して使用し、その活性を調べた。Example 2 The catalyst of the present invention was used as a catalyst for hydrogen-deuterium exchange reaction, and its activity was investigated.

【００３５】実施例１で調製したＰｔクラスター錯体／
ＴＨＰ／ＳｉＯ2 触媒を窒素雰囲気下で１５４mg秤量
し、内容積２０mlの閉鎖系回分式反応装置に入れた。そ
の後、反応装置内の窒素ガスを真空排気によって除去
し、引き続きＨ2 とＤ2 をそれぞれ１２５Torrずつ反応
装置に導入し、５０℃にて反応させた。なお、装置内の
ガスはマグネチックスターラにて十分に混合させた。反
応開始後６０分の段階で反応装置内のガスをマススペク
トル分析装置に導入し分析したところ、質量数３即ちＨ
Ｄのピークが確認された。従って、実施例１で得た触媒
は、水素重水素交換反応の触媒活性を有していることが
確認された。このことは、当該触媒が、水素化反応を触
媒する可能性を示唆するものである。Pt cluster complex prepared in Example 1 /
154 mg of THP / SiO 2 catalyst was weighed under a nitrogen atmosphere and placed in a closed batch type reactor having an internal volume of 20 ml. Then, the nitrogen gas in the reactor was removed by vacuum evacuation, and then H 2 and D 2 were introduced into the reactor at 125 Torr each and reacted at 50 ° C. The gas inside the apparatus was thoroughly mixed with a magnetic stirrer. When the gas in the reactor was introduced into the mass spectrum analyzer and analyzed at a stage of 60 minutes after the start of the reaction, the mass number was 3
A D peak was confirmed. Therefore, it was confirmed that the catalyst obtained in Example 1 had catalytic activity for hydrogen-deuterium exchange reaction. This suggests that the catalyst may catalyze the hydrogenation reaction.

【００３６】[0036]

【実施例３】本発明触媒をエチレンの水素化反応の触媒
として使用し、その活性を調べた。実施例１で調製した
Ｐｔクラスター錯体／ＴＨＰ／ＳｉＯ2 触媒を窒素雰囲
気下で１５４mg秤量し、内容積２０mlの閉鎖系回分式反
応装置に入れた。その後、反応装置内の窒素ガスを真空
排気によって除去し、引き続きエチレン５０TorrとＨ2
７５Torrを反応装置に導入し、５０℃にて反応させた。
なお、装置内のガスはマグネチックスターラにて十分に
混合させた。装置内の反応ガスをマススペクトル分析装
置に導入し分析したところ、反応開始後６０分の段階
で、エタンの生成が認められ、最終的に反応時間１５時
間の段階で、エチレンの転化率１００％・エタンの選択
率１００％となった。Example 3 The catalyst of the present invention was used as a catalyst for the hydrogenation reaction of ethylene, and its activity was investigated. 154 mg of the Pt cluster complex / THP / SiO 2 catalyst prepared in Example 1 was weighed in a nitrogen atmosphere and placed in a closed batch type reactor having an internal volume of 20 ml. Then, the nitrogen gas in the reactor was removed by vacuum evacuation, followed by ethylene 50 Torr and H 2
75 Torr was introduced into the reactor and reacted at 50 ° C.
The gas inside the apparatus was thoroughly mixed with a magnetic stirrer. When the reaction gas in the device was introduced into a mass spectrum analyzer and analyzed, ethane was found to be produced at the stage of 60 minutes after the start of the reaction, and finally the conversion of ethylene was 100% at the stage of reaction time of 15 hours.・ 100% ethane selectivity.

【００３７】このことから、当該触媒が、オレフィンの
水素化反応を触媒することが明らかとなった。From this, it became clear that the catalyst catalyzes the hydrogenation reaction of olefin.

【００３８】[0038]

【実施例４】本発明触媒を水性ガスシフト反応の触媒と
して使用し、その活性を調べた。Example 4 The catalyst of the present invention was used as a catalyst for a water gas shift reaction, and its activity was investigated.

【００３９】実施例１で調製したＰｔクラスター錯体／
ＴＨＰ／ＳｉＯ2 触媒を窒素雰囲気下で１４８mg秤量
し、内容積２０mlの閉鎖系回分式反応装置に入れた。そ
の後、反応装置内の窒素ガスを真空排気によって除去
し、引き続きＨ2 Ｏを２８TorrとＣＯを５０Torr反応装
置に導入し、５０℃にて反応させた。なお、装置内のガ
スはマグネチックスターラにて十分に混合させた。反応
開始後６５分の段階で、反応装置内のガスをマススペク
トル分析装置に導入し分析したところ、質量数４４即ち
ＣＯ2 のピーク及び質量数２即ちＨ2 のピークが確認さ
れた。このことから、実施例１で得た触媒は、水性ガス
シフト反応の触媒活性を有していることが明らかとなっ
た。Pt cluster complex prepared in Example 1 /
148 mg of THP / SiO 2 catalyst was weighed under a nitrogen atmosphere and placed in a closed batch type reactor having an internal volume of 20 ml. Then, the nitrogen gas in the reactor was removed by vacuum evacuation, then 28 Torr of H 2 O and 50 Torr of CO were introduced into the reactor and reacted at 50 ° C. The gas inside the apparatus was thoroughly mixed with a magnetic stirrer. When the gas in the reactor was introduced into the mass spectrum analyzer and analyzed at the stage of 65 minutes after the start of the reaction, a mass number 44, that is, a peak of CO 2 and a mass number 2, that is, a peak of H 2 were confirmed. From this, it became clear that the catalyst obtained in Example 1 had a catalytic activity for the water gas shift reaction.

【００４０】[0040]

【発明の効果】本発明によれば、ホスフィンを介してＰ
ｔクラスター錯体をシリカ担体上に化学的に固定化して
なる固定化Ｐｔクラスター錯体触媒及びその製造方法が
提供される。得られる固定化Ｐｔクラスター錯体触媒
は、Ｐｔクラスター錯体本来の構造ひいては高活性能を
保持したまま担体に化学的に固定化されているため、実
用上重要な不均一系反応の触媒として有用である。INDUSTRIAL APPLICABILITY According to the present invention, P
Provided are an immobilized Pt cluster complex catalyst obtained by chemically immobilizing a t cluster complex on a silica support, and a method for producing the same. The obtained immobilized Pt cluster complex catalyst is chemically immobilized on a carrier while retaining the original structure of Pt cluster complex and thus high activity, and thus is useful as a catalyst for practically important heterogeneous reaction. ..

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 9/06 8619−4Ｈ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C07C 9/06 8619-4H

Claims (7)

【特許請求の範囲】[Claims] 【請求項１】シリカ担体がホスフィンによりエーテル結
合を介して修飾され、且つ該ホスフィン部位にＰｔクラ
スター錯体が化学的に固定化されてなることを特徴とす
る固定化Ｐｔクラスター錯体触媒。1. An immobilized Pt cluster complex catalyst, characterized in that a silica carrier is modified with phosphine through an ether bond, and a Pt cluster complex is chemically immobilized on the phosphine site. 【請求項２】前記ホスフィンが、その分子内に少なくと
も１個の水酸基を有するホスフィンである請求項１記載
の触媒。2. The catalyst according to claim 1, wherein the phosphine is a phosphine having at least one hydroxyl group in its molecule. 【請求項３】前記ホスフィンが、トリス（ヒドロキシメ
チル）ホスフィンである請求項２記載の触媒。3. The catalyst according to claim 2, wherein the phosphine is tris (hydroxymethyl) phosphine. 【請求項４】前記Ｐｔクラスター錯体が、〔Ｎ（Ｃ2 Ｈ
5 ）4 〕2 〔Ｐｔ12（ＣＯ）24〕である請求項１記載の
触媒。4. The Pt cluster complex comprises [N (C 2 H
The catalyst according to claim 1, which is 5 ) 4 ] 2 [Pt 12 (CO) 24 ]. 【請求項５】前記ホスフィンの担持量が触媒の全重量に
対し０．５〜４０重量％であり、且つＰｔクラスター錯
体の担持量が触媒の全重量に対し金属重量に換算して
０．０３〜４０重量％である請求項１記載の触媒。5. The supported amount of the phosphine is 0.5 to 40% by weight based on the total weight of the catalyst, and the supported amount of the Pt cluster complex is 0.03 in terms of metal weight based on the total weight of the catalyst. The catalyst according to claim 1, which is about 40% by weight. 【請求項６】シリカ担体上にホスフィンをエーテル結合
させ、次いで該ホスフィン部位にＰｔクラスター錯体を
化学的に固定化することを特徴とする固定化Ｐｔクラス
ター錯体触媒の製造方法。6. A method for producing an immobilized Pt cluster complex catalyst, which comprises ether-bonding phosphine on a silica support and then chemically immobilizing a Pt cluster complex on the phosphine site. 【請求項７】シリカ担体上にホスフィンを有機溶媒存在
下に含浸させた後に加熱処理してシリカ担体上にホスフ
ィンをエーテル結合させ、次いでＰｔクラスター錯体を
該錯体を溶解しうる溶媒の存在下に該ホスフィン部位と
化学的に固定化せしめる請求項６記載の触媒の製造方
法。7. A silica carrier is impregnated with phosphine in the presence of an organic solvent, followed by heat treatment to ether bond the phosphine on the silica carrier, and then the Pt cluster complex in the presence of a solvent capable of dissolving the complex. The method for producing a catalyst according to claim 6, wherein the phosphine moiety is chemically immobilized.
JP4039312A 1992-02-26 1992-02-26 Fixed pt cluster complex catalyst and its production Pending JPH05237394A (en)

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Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP4039312A JPH05237394A (en) 1992-02-26 1992-02-26 Fixed pt cluster complex catalyst and its production

Publications (1)

Publication Number Publication Date
JPH05237394A true JPH05237394A (en) 1993-09-17

Family

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JP4039312A Pending JPH05237394A (en) 1992-02-26 1992-02-26 Fixed pt cluster complex catalyst and its production

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001047801A1 (en) * 1999-12-28 2001-07-05 Daikin Industries, Ltd. Modifying device
JP2021527555A (en) * 2018-04-16 2021-10-14 ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ Composition containing platinum nanoparticle clusters with improved thermal stability

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001047801A1 (en) * 1999-12-28 2001-07-05 Daikin Industries, Ltd. Modifying device
US6814944B1 (en) 1999-12-28 2004-11-09 Daikin Industries, Ltd. Modifying device
CN1310829C (en) * 1999-12-28 2007-04-18 大金工业株式会社 Modifying device
JP4736299B2 (en) * 1999-12-28 2011-07-27 ダイキン工業株式会社 Metamorphic equipment
JP2021527555A (en) * 2018-04-16 2021-10-14 ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ Composition containing platinum nanoparticle clusters with improved thermal stability

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