JPS6143095B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention consists of a rhodium carbonyl cluster compound represented by Rh ₄ (CO) ₁₂ or Rh ₆ (CO) ₁₆ and a polymer having an arylphosphine group.
This invention relates to catalysts for oxo reactions. To explain the method for producing the catalyst of the present invention, the rhodium carbonyl cluster compound is mixed with a chemically inert solvent, such as a polar solvent such as chloroform, dichloromethane, tetrahydrofuran, dimethyl sulfoxide, or a nonpolar solvent made of a hydrocarbon such as hexane or pentane. Dissolved in a neutral solvent,
A polymer having an arylphosphine group is added preferably under an inert atmosphere, and the support by carbonyl substitution is completed after sufficient stirring. It can then be produced by separating and recovering a polymer containing rhodium carbonyl clusters by decantation filtration or distillation of the solvent. In the manufacturing method, the inert atmosphere is under reduced pressure (10 ^-1 to ^{10 -5} cm
Hg) and an inert gas such as nitrogen, helium, or argon. The polymer having an arylphosphine group used in the present invention is a polymer represented by the following general formula (), () or () containing a phosphine group as a functional substituent, which is produced by a conventional method. etc. Contains phosphine group (In the formula, R ¹ to R ⁶ are aryl groups, and Z represents a residue obtained by removing a hydroxyl group from silica, alumina, or zeolite molecular sieve.) Although the ratio is not particularly limited, substantially 0.001 to 100 mmol per 1 g, especially 1 to 10 m
A mol range is preferred. The loading rate of the rhodium carbonyl cluster compound on the polymer depends on the concentration of phosphine groups contained in the polymer, but substantially 1 g of the polymer
The molar amount of the supported rhodium carbonyl cluster compound is preferably in the range of 0.001 to 100 mmol. Examples of the rhodium carbonyl cluster compound used include Rh ₄ (CO) ₁₂ −() Rh ₆ (CO) ₁₆ −(). Although the supported state of the polymer containing the rhodium carbonyl cluster of the present invention produced in this way is not completely clear, (1) during the supporting process, the stoichiometric amount (equimolar) is (2)
According to observation by infrared spectroscopy, the carbonyl coordination state peculiar to carbonyl cluster compounds is still supported even after being supported, and (3) after being supported, there are no substances other than the rhodium carbonyl cluster compound, which is the starting material, in the residual solution. Since no metal decomposition products or carbonyl complex compounds were found, it is presumed that the cluster structure is maintained, one to several carbonyl groups are substituted, and the polymer is supported and fixed on the polymer. The conventional oxo reaction (hydroformylation reaction) uses as a catalyst an iron group metal compound, especially a cobalt carbonyl compound, and an iron group whose carbonyl groups are partially or fully substituted by basic compounds (e.g. alkyl or arylphosphines and nitrogen compounds). Using organometallic compounds in polar or non-polar solvents
A homogeneous oxo synthesis method performed at 25-500 atm and 150-250°C is known [W.Reppe, Liebigs Ann.
Chem., 582 , 122 (1953)]. In addition, a homogeneous oxo synthesis method has recently been developed using a rhodium carbonyl complex in a solvent under medium-low pressure with increased selectivity by adding a basic compound [CKBrown, et al.
al., Tetrahedron Letters, 22 , 1725 (1969),
D. Evans, et al., J. Chem. Soc., 2660
(1968)]. However, in the homogeneous oxo synthesis method, the separation and recovery of the effective metal catalyst is complicated and there are economical problems in industrialization. For example, when using cobalt carbonyl as a catalyst, it is necessary to perform the reaction at high temperature and high pressure. Since a high oxo conversion rate cannot be obtained, there are disadvantages such as problems with the reactor and reaction operation. In order to solve these drawbacks, an oxo synthesis method using a heterogeneous catalyst under milder conditions was investigated, and a rhodium carbonyl complex with high oxo activity was immobilized on a polymer having a phosphine group to make the catalyst insolubilized. Several synthetic methods have been reported so far [W.
See O.Haag.et al., Belgian Patent No. 721686, French Patent No. 760556]. However, in this method, rhodium did not flow out in the liquid phase or condensed phase, but rhodium flowed out under high pressure conditions, and the oxo conversion rate per rhodium unit was lower than that of a homogeneous rhodium catalyst. In addition, it is known that conventional cobalt metal-supported catalysts and rhodium metal-supported catalysts have no or almost no gas-phase oxo synthesis activity. No legislation has been developed. The present inventor used a polymer containing rhodium carbonyl clusters according to the present invention, which is composed of a rhodium carbonyl cluster compound containing a plurality of groups of rhodium atoms and a polymer having an arylphosphine group, to produce olefins under reduced pressure to normal pressure. We succeeded in selective vapor phase synthesis of aldehydes from a mixed gas of carbon monoxide, hydrogen and carbon monoxide in the temperature range of room temperature to 120℃. It has been well known that a rhodium carbonyl cluster compound reacts with an alkyl or arylphosphine compound in a solvent to produce a derivative in which a portion of the carbonyl group is substituted with a phosphine group. However, these phosphine derivatives are highly reactive but unstable, and in the presence of carbon monoxide, hydrogen, or oxo gas in a homogeneous phase, it is difficult to decompose them and make them work as catalysts. The present inventor has developed a catalyst in which a rhodium carbonyl cluster compound is chemically activated and immobilized (insolubilized) in a polymer having an arylphosphine group by substitution of carbonyl groups while maintaining the structure of the rhodium carbonyl cluster. The effectiveness of this method was discovered by applying it to reactions. Catalysts made of polymers containing rhodium carbonyl clusters are effective in gas-phase oxo reactions at room temperature and pressure, and have particularly high aldehyde selectivity, with the by-products of alcohol and paraffin being negligible. The catalytic activity lasted for a long time and no decrease in activity was observed. Since the rhodium carbonyl cluster compound itself does not have gas-phase oxo activity, it is chemically activated by carbonyl substitution and support fixation on a polymer having an arylphosphine group, and works effectively as a gas-phase oxo catalyst. It became clear. In addition, rhodium carbonyl complex (Rh(CO) _4-x
(PR _{3 )} It was also found that catalysts made of polymers containing carbonyl clusters have 100 to 1000 times higher catalytic activity (see Reference Examples below). This explains the effectiveness of catalyst preparation by cluster support. The reaction operation method for the oxo reaction is to fill a closed circulation reactor, a flow circulation reactor, a normal pressure or pressurized flow fixed bed reactor with a catalyst (pellet form or powder form), A mixed gas of carbon and hydrogen is mixed at a predetermined mixing ratio and introduced under reduced pressure to normal pressure or increased pressure (1 to 150 atmospheres), and the temperature is substantially room temperature to 150°C (taking into account the thermal stability of the carrier). However, this does not apply when using a carrier with phosphination of the silica surface.)
It collects oxo products. Depending on the shape of the catalyst, it can also be applied to a fluidized bed type flow reactor or a batch type reactor in which the catalyst is dispersed in a polar or nonpolar solvent. As the olefin which is a raw material for producing the aldehyde of the present invention, monoolefins such as ethylene, propylene, butene, hexene, etc., diolefins such as butadiene, etc., and cyclic olefins such as cyclohexene, etc. can be used. The mixing ratio of olefin, carbon monoxide, and hydrogen is not particularly limited, but usually olefin: carbon monoxide = 1:10.
~10:1 and carbon monoxide:hydrogen = 1:10~10:1
(molar ratio) is preferred. Next, the method for producing a polymer containing a rhodium carbonyl cluster according to the present invention and the catalytic ability of the product to catalyze an aldehyde synthesis reaction will be explained in more detail using Examples. Example 1 0.20 g of Rh ₆ (CO) ₁₆ was dissolved in 250 ml of chloroform with thorough stirring to obtain a deep reddish brown solution. Diphenylphosphine lithium [(C ₆ H ₅ ) ₂ PLi], thoroughly washed and dried under reduced pressure.) 7.0 g was added in an argon stream. When an equivalent amount of carbon monoxide had been generated while stirring at room temperature, the polymer resin turned brown and the solution was decolored. Replace _Rh6 (CO) ₁₆ ,
The supported and fixed polystyrene powder was filtered using a glass filter in an argon stream, washed repeatedly with chloroform and methanol, and then vacuum dried. Since the catalyst made of a polymer containing rhodium carbonyl clusters produced in this way is easily oxidized, the production and filling operations are preferably carried out under an inert atmosphere. This catalyst was packed into a glass closed circulation reactor (total volume 420 ml) and reacted at room temperature.
After evacuation for 10 minutes, an oxo mixed gas of ethylene and propylene was introduced, and aldehyde was rapidly and selectively generated at a temperature of 50 to 110 °C. The oxo product was collected in a dry ice lap and confirmed by gas chromatography. Gas phase analysis was based on activated alumina gas chromatography, but the formation of paraffin due to hydrogenation of olefin was negligible during the measurement period. Tables 1 and 2 illustrate ethylene and propylene oxo activities.

【table】

_[ Table] Reference example: Comparison of oxo activity using a catalyst made by using a _rhodium carbonyl complex instead of a rhodium _carbonyl cluster and supporting and fixing it on a polymer. 5 g of the diphenylphosphine polystyrene resin used in Example 1 was added and stirred to completely fix rhodium carbonyl. After being filtered in an argon stream and washed with benzene, it was packed into a closed circulation reactor (total volume 420 ml). did. Although propylene oxo gas was introduced after hydrogen reduction treatment, the generation of aldehyde in the temperature range of 90 to 110°C was negligible, and compared to a catalyst made of a polymer containing rhodium carbonyl clusters under the same conditions, it was Only 1/700 or less activity was observed. Example 2 0.10g of Rh ₄ (CO) ₁₂ in 100ml of tetrahydrofuran
Add 4.0 g of diphenylphosphineated polystyrene (100-200 mesh, phosphine group content 1.26 mmol/g, 2% divinylbenzene cross-linked) under a nitrogen gas atmosphere, degas the mixture, and stir to remove carbon monoxide. As a result, the red solution was decolorized and completely immobilized on the polymer particles. After 20 minutes, the solvent was removed by filtration under a nitrogen gas atmosphere, and the mixture was filled into a glass closed circulation reactor (total volume: 420 ml). After degassing the gas phase and continuing evacuation at room temperature for 30 minutes, ethylene or propylene oxo gas was introduced under reduced pressure, and aldehydes were selectively obtained at room temperature to 100°C. Oxo activity of this catalyst when changing reaction conditions,
Table 3 shows the results obtained regarding the aldehyde linear chain ratio, by-product paraffinization reaction, and alcoholization activity.

【table】

Claims (1)

[Claims] 1. An oxo reaction catalyst comprising a rhodium carbonyl cluster compound represented by Rh ₄ (CO) ₁₂ or Rh ₆ (CO) ₁₆ and a polymer having an arylphosphine group.