Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2002-06-20
2003-07-01
Shippen, Michael L. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S385000, C568S727000, C568S728000, C568S768000
Reexamination Certificate
active
06586640
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to the decomposition of organic hydroperoxides to hydroxy-substituted organic compounds and carbonyl compounds in the presence of a particulate catalyst containing highly fluorinated polymer having sulfonic acid groups.
BACKGROUND OF THE INVENTION
Commercial processes for the manufacture of hydroxy-substituted organic compounds, particularly aromatic compounds such as phenol and hydroquinone, often employ reaction routes that require the decomposition of organic hydroperoxides. For example, phenol is manufactured from cumene by converting it to the hydroperoxide followed by decomposition to phenol and acetone. The hydroperoxide decomposition reaction is an acid-catalyzed reaction and a concentrated sulfuric acid solution at temperatures in the range of 50-100° C. is typically employed in commercial processes.
Though it provides effective catalysis, the use of sulfuric acid for the cumene hydroperoxide decomposition reaction has disadvantages. Since it is a homogenous catalyst, it is necessary to employ one or more process steps to separate it from the product mixture. The spent sulfuric acid must be neutralized and disposed of. Moreover, using sulfuric acid causes the product mixture to contain significant percentages of undesirable side products which reduce yields and require additional process steps for removal.
U.S. Pat. No. 4,322,560 discloses using a thin film of solid acid catalyst of perfluorocarbon polymer containing pendant sulfonic acid groups for the decomposition of organic hydroperoxides. However, the reaction rate is not sufficiently high at desirable process temperatures for the process to be particularly useful commercially. PCT Publication No. WO 96/19288, published Jun. 27, 1996, discloses catalysts which comprise porous microcomposites of perfluorinated ion exchange polymer and a metal oxide network. Numerous reactions are disclosed in this publication including the decomposition of organic hydroperoxides. While decomposition results using catalysts disclosed in this publication, the reaction rate again is not sufficiently high at desirable process temperatures to be particularly useful commercially.
SUMMARY OF THE INVENTION
The invention provides a process for the manufacture of a hydroxy-substituted organic compound comprising decomposing an organic hydroperoxide in the presence of a catalyst containing highly fluorinated polymer having sulfonic acid groups, the catalyst being in the form of particles of which at least about 20 weight % have a particle size less than about 300 &mgr;m. In a preferred form of the invention, the catalyst is selected from the group consisting of (a) particles of highly fluorinated polymer having sulfonic acid groups and (b) particles of porous microcomposite of a metal oxide network and highly fluorinated polymer having sulfonic acid groups. Preferably, the process provides for the manufacture of a hydroxy-substituted aromatic compound comprising by the decomposition of a compound of the formula Ar—C(CH
3
)
2
O
2
H, wherein Ar is a substituted or unsubstituted mononuclear or polynuclear aromatic group.
It has been discovered that a process employing catalyst particles having a particle size in accordance with the present invention increases the rate of the decomposition reaction and can provide higher reaction rates than in existing processes. In addition, hydroxy-substituted organic compounds are produced in high yield at moderate temperatures and in higher purity, i.e., with fewer undesirable side products than in existing commercial processes.
The invention also provides a process for the manufacture of 2,2-Bis(4-hydroxyphenyl)-propane (hereinafter referred to as Bisphenol A). The process includes:
(a) decomposing cumene hydroperoxide in the presence of a catalyst containing highly fluorinated polymer having sulfonic acid groups to form a decomposition product mixture containing phenol and acetone; and
(b) reacting the phenol and acetone of the decomposition product mixture in the presence of catalyst containing highly fluorinated polymer having sulfonic acid groups under conditions which promote the formation bisphenol A.
In a preferred embodiment of the process, at least a portion of the phenol and acetone of the decomposition product mixture is not separated from the catalyst prior to the reaction to form bisphenol A and the catalyst used for the decomposition is the same catalyst that is used for the reaction to bisphenol A.
DETAILED DESCRIPTION
The catalyst employed in accordance with the present invention contains highly fluorinated polymer having sulfonic acid groups. “Highly fluorinated” means that at least 90% of the total number of univalent atoms in the polymer are fluorine atoms. Most preferably, the polymer is perfluorinated.
Preferably, the polymer of the catalyst comprises a polymer backbone with recurring side chains attached to the backbone, the side chains carrying the sulfonic acid groups. Possible polymers include homopolymers or copolymers of two or more monomers. Copolymers are typically formed from one monomer which is a nonfunctional monomer and which provides carbon atoms for the polymer backbone. A second monomer provides carbon atoms for the polymer backbone and also contributes the side chain carrying the sulfonic acid group or its precursor, e.g., a sulfonyl halide group such a sulfonyl fluoride (—SO
2
F), which can be subsequently hydrolyzed to a sulfonic acid functional group. For example, copolymers of a first fluorinated vinyl monomer together with a second fluorinated vinyl monomer having a sulfonyl fluoride group (—SO
2
F) can be used. Possible first monomers include tetrafluoroethylene (TFE), hexafluoropropylene, vinyl fluoride, vinylidine fluoride, trifluoroethylene, chlorotrifluoroethylene, perfluoro (alkyl vinyl ether), and mixtures thereof. Possible second monomers include a variety of fluorinated vinyl ethers with sulfonic acid functional groups or precursor groups which can provide the desired side chain in the polymer. Additional monomers can also be incorporated into these polymers if desired. TFE is a preferred monomer.
A class of preferred polymers for use in the present invention include a highly fluorinated, most preferably perfluorinated, carbon backbone and the side chain is represented by the formula —(O—CF
2
CFR
f
)
a
—O—CF
2
CFR′
f
SO
3
H, wherein R
f
and R′
f
are independently selected from F, Cl or a perfluorinated alkyl group having 1 to 10 carbon atoms, and a=0, 1 or 2. The preferred polymers include, for example, polymers disclosed in U.S. Pat. No. 3,282,875 and in U.S. Pat. Nos. 4,358,545 and 4,940,525. One preferred polymer comprises a perfluorocarbon backbone and the side chain is represented by the formula —O—CF
2
CF(CF
3
)—O—CF
2
CF
2
SO
3
H. Polymers of this type are disclosed in U.S. Pat. No. 3,282,875 and can be made by copolymerization of tetrafluoroethylene (TFE) and the perfluorinated vinyl ether CF
2
═CF—O—CF
2
CF(CF
3
)—O—CF
2
CF
2
SO
2
F, perfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride) (PDMOF), followed by hydrolysis of the sulfonyl halide groups to sulfonate groups, and acid exchange to convert the sulfonate groups to the proton form. One preferred polymer of the type disclosed in U.S. Pat. Nos. 4,358,545 and 4,940,525 has the side chain —O—CF
2
CF
2
SO
3
H. This polymer can be made by copolymerization of tetrafluoroethylene (TFE) and the perfluorinated vinyl ether CF
2
═CF—O—CF
2
CF
2
SO
2
F, perfluoro(3-oxa-4-pentenesulfonyl fluoride) (POPF), followed by hydrolysis and acid exchange.
In this application, “ion exchange ratio” or “IXR” is defined as the number of carbon atoms in the polymer backbone in relation to the cation exchange groups. A wide range of IXR values for the polymer are possible. Typically, however, the IXR range used for the catalyst is usually about 7 to about 33. For perfluorinated polymers of the type described above, the cation exchange capacity of a polymer is often expressed in terms of equivalent weight (EW). For the purposes of this
Harmer Mark Andrew
Howard, Jr. Edward George
Lloyd Ralph Birchard
Sun Qun
E. I. du Pont de Nemours and Company
Shippen Michael L.
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