Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2000-07-03
2002-04-02
Padmanabhan, Sreeni (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S445000, C568S817000, C568S822000, C568S838000, C568S909000
Reexamination Certificate
active
06365782
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method of producing dialdehydes (tricyclodecane dicarbaldehyde and/or pentacyclopentadecane dicarbaldehyde) by hydroformylation of dicyclopentadiene and/or tricyclopentadiene, and a method of producing dimethanols (tricyclodecane dimethanol and pentacyclopentadecane dimethanol) by hydrogenating the dialdehydes.
Tricyclodecane dimethanol and pentacyclopentadecane dimethanol which are produced by reducing tricyclodecane dicarbaldehyde and pentacyclopentadecane dicarbaldehyde with hydrogen are useful as materials for producing polyesters, polyester carbonates, acrylic resins, methacrylic resins, etc. Particularly, polycarbonate resins having constitutional units derived from tricyclodecane dimethanol and/or pentacyclopentadecane dimethanol have excellent properties as optical materials for manufacturing optical disks, optical fibers, spectacle lenses, lenses for industrial use, etc. With such usefulness, it has been demanded to develop industrial method of easily producing the dialdehydes. In addition, tricyclodecane dimethanamine and pentacyclopentadecane dimethanamine which are produced by reductive amination of tricyclodecane dicarbaldehyde and pentacyclopentadecane dicarbaldehyde are useful as materials for producing polyamide resins and isocyanates.
The present invention further relates to a method of recovering high-boiling dialdehydes produced by rhodium/organophosphorus-catalyzed hydroformylation of dicyclopentadiene and/or tricyclopentadiene in a hydroformylation solvent comprising a hydrocarbon compound. More particularly, the present invention relates to a method of recovering a high-boiling dialdehyde from a reaction product liquid containing a rhodium-organophosphorus catalyst, a dialdehyde and a hydroformylation solvent obtained from liquid reaction product-take-off, hydroformylation process. The hydroformylation is well-known in the art as a method of converting olefins into aldehydes having one carbon more than the starting olefins by the addition of one molecule each of hydrogen and carbon monoxide to one carbon-carbon double bond. If the organic substrate contains two or more carbon-carbon double bonds, two or more formyl groups can be added to the substrate, thereby increasing the number of carbon atoms in the substrate by two or more. As a result, both the molecular weight and the boiling point of the aldehyde produced increase significantly when the starting olefin has a substituent group such as carboxyl, aldehyde and hydroxyl as well as when the starting olefin constituted only by hydrogen and carbon has six or more carbon atoms. Therefore, there are demands for establishing industrial process for easily recovering the high-boiling aldehydes.
2. Description of the Prior Art
The production of tricyclodecane dicarbaldehyde by hydroformylation of dicyclopentadiene is known. British Patent No. 750144 discloses to hydroformylate dicyclopentadiene in the presence of a diluent, a polymerization inhibitor, a stabilizer and a catalyst comprising a cobalt compound.
EP-A-186075 teaches to hydroformylate dicyclopentadiene in the presence of a catalyst comprising a rhodium compound and a quaternary ammonium salt of phosphine having a sulfonic acid group.
WO93/02024 describes the extraction of high-boiling aldehydes produced by rhodium-catalyzed hydroformylation of olefins with an extraction solvent comprising a primary alkanol and water.
U.S. Pat. No. 5,260,490 describes to separate and recover rhodium catalysts with an aqueous solution of complex-forming organic phosphine, thereby recycling and reusing the recovered rhodium catalysts.
Japanese Patent Application Laid-Open Nos. 11-80067 and 11-80068 teach hydroformylation of dicyclopentadiene in the presence of a rhodium catalyst of extremely reduced concentration using a phosphite ligand while controlling a conjugated diene concentration.
The production of aldehydes by hydroformylation has been industrially practiced using a rhodium-organophosphorus compound catalyst on lower olefins such as ethylene and propylene. In this production, the aldehyde produced are separated from the catalyst components by distillation. Since the rhodium-organophosphorus compound catalyst is poor in heat stability, the low-boiling aldehydes produced in the above process are recovered as vapor from the mixture containing high-boiling products by gas stripping using unreacted gas. This method is successful for aldehydes having relatively low boiling points due to their relatively high vapor pressure at hydroformylation temperatures employed. However, the flow rate of stripping gas should be increased with increasing boiling point of aldehyde to obtain the aldehyde in the same yield, this making the process less practical. In another method of recovering the products, the high-boiling products are separated from the catalyst by distilling the high-boiling residue containing the catalyst under reduced pressure at high temperatures. However, the problem of this method is a loss of expensive rhodium metal from hydroformylation process by its deposition onto the surface of apparatus due to poor heat stability of the catalyst.
As alternative method to the distillation for recovering the high-boiling aldehyde, proposed are extraction separation, membrane separation and immobilization of catalyst (general reviews in J. of Mol. Cat. A., 104(1995), pp 17-85; J. of Mol. Cat. A., 116(1997), pp39-42; and J. of Cat. Soc. of Japan, vol. 39, No. 5(1997), pp341-346).
As a process utilizing extraction separation, put into practice is a hydroformylation of propylene in a two-phase organic solvent/water system using a rhodium catalyst containing water-soluble trisulfonated-triphenylphosphine sodium salt as ligands. The water layer containing the catalyst from phase separation after the reaction is reused in the next run. This hydroformylation process in organic solvent/water two-phase system is taught to be applicable to the hydroformylation of butene isomer mixtures. However, olefins become less soluble to water with increasing number of carbon atoms, and therefore, the process is not practical for higher olefins due to low reaction rate.
WO93/02024, as mentioned above, describes the extraction of high-boiling aldehydes produced by rhodium-catalyzed hydroformylation of olefins with an extraction solvent comprising a primary alkanol and water.
The membrane separation for separating the catalyst components and the high-boiling aldehyde, i.e., a hydroformylation product of dicyclopentadiene is described in EP0374615, U.S. Pat. Nos. 5,817,884 and 5,773,667. The proposed methods are two-stage membrane separation by aromatic polyamide membrane using a rhodium complex compound containing a quaternary ammonium salt of high-molecular sulfonated-triphosphine as ligands.
U.S. Pat. Nos. 4,144,191 and 4,262,147 immobilize rhodium catalysts by the bonds with amine groups of polymer.
One pot sequential production of tricyclodecane dimethanol by hydroformylation of dicyclopentadiene followed by hydrogenation of the resultant dialdehyde is also known.
For example, British Patent No. 1170226 obtains tricyclodecane dimethanol by hydrogenation of hydroformylation product by increasing temperature and pressure after the hydroformylation.
Japanese Patent Application Laid-Open No. 55-118429 obtains tricyclodecane dimethanol by extraction with water and a polar solvent after hydroformylation and hydrogenation in a hydrocarbon solvent in the presence of a cobalt-phosphine catalyst.
Japanese Patent Application Laid-Open No. 63-119429 describes the reuse of the solution containing the catalyst separated from the tricyclodecane dimethanol layer after the hydroformylation and hydrogenation in a hydrocarbon solvent.
U.S. Pat. No. 2,880,241 produces tricyclodecane dimethanol by hydrogenating tricyclodecane dicarbaldehyde obtained by hydroformylation in an alcohol solvent. In the proposed method, the dialdehyde obtained by hydroformylation of dicyclopentadiene is converted into a acetal derivative stable
Fujii Takashi
Motoi Takashi
Nakamura Ken'ichi
Yamada Kazuhiro
Antonelli Terry Stout & Kraus LLP
Mitsbushi Gas Chemical Company, Inc.
Padmanabhan Sreeni
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