U.S. patent application number 09/729123 was filed with the patent office on 2001-10-18 for method and catalyst system for producing aromatic carbonates.
Invention is credited to Patel, Ben Purushotam, Shalyaev, Kirill Vladimirovich, Soloveichik, Grigorii Lev, Whisenhunt, Donald Wayne JR..
Application Number | 20010031888 09/729123 |
Document ID | / |
Family ID | 24057957 |
Filed Date | 2001-10-18 |
United States Patent
Application |
20010031888 |
Kind Code |
A1 |
Patel, Ben Purushotam ; et
al. |
October 18, 2001 |
Method and catalyst system for producing aromatic carbonates
Abstract
A method and catalyst system for producing aromatic carbonates
from aromatic hydroxy compounds. In one embodiment, the method
includes the step of contacting at least one aromatic hydroxy
compound with oxygen and carbon monoxide in the presence of a
carbonylation catalyst system having an effective amount of an iron
source in the absence of a Group VIII B metal source. In various
alternative embodiments, the carbonylation catalyst system can
include at least one inorganic co-catalyst, as well as a halide
composition and/or a base.
Inventors: |
Patel, Ben Purushotam;
(Albany, NY) ; Soloveichik, Grigorii Lev; (Latham,
NY) ; Whisenhunt, Donald Wayne JR.; (Niskayuna,
NY) ; Shalyaev, Kirill Vladimirovich; (Clifton Park,
NY) |
Correspondence
Address: |
GENERAL ELECTRIC COMPANY
CRD PATENT DOCKET ROOM 4A59
P O BOX 8
BUILDING K 1 SALAMONE
SCHENECTADY
NY
12301
US
|
Family ID: |
24057957 |
Appl. No.: |
09/729123 |
Filed: |
December 4, 2000 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09729123 |
Dec 4, 2000 |
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09517000 |
Mar 1, 2000 |
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6187942 |
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Current U.S.
Class: |
558/274 ;
562/406 |
Current CPC
Class: |
C07C 68/01 20200101;
C07C 68/01 20200101; C07C 69/96 20130101; C07C 68/01 20200101; C07C
69/96 20130101 |
Class at
Publication: |
558/274 ;
562/406 |
International
Class: |
C07C 069/96; C07C
051/15 |
Claims
What is claimed is:
1. A method of carbonylating an aromatic hydroxy compound, said
method comprising the step of contacting at least one aromatic
hydroxy compound with oxygen and carbon monoxide in the presence of
a carbonylation catalyst system comprising an effective amount of
an iron source in the absence of an effective amount of a Group
VIII B metal source.
2. The method of claim 1, wherein the carbonylation catalyst system
further comprises a catalytic amount of an inorganic
co-catalyst.
3. The method of claim 2, wherein the inorganic co-catalyst is a
copper source.
4. The method of claim 2, wherein the inorganic co-catalyst is a
lead source.
5. The method of claim 1, wherein the carbonylation catalyst system
further comprises a combination of inorganic co-catalysts.
6. The method of claim 5, wherein the combination of inorganic
co-catalysts comprises a catalytic amount of a copper source and a
catalytic amount of a zirconium source.
7. The method of claim 5, wherein the combination of inorganic
co-catalysts comprises a catalytic amount of a titanium source and
a catalytic amount, of a cerium source.
8. The method of claim 5, wherein the combination of inorganic
co-catalysts comprises a catalytic amount of a lead source and a
catalytic amount of a titanium source.
9. The method of claim 5, wherein the combination of inorganic
co-catalysts comprises a catalytic amount of a lead source and a
catalytic amount of a zirconium source.
10. The method of claim 5, wherein the combination of inorganic
co-catalysts comprises a catalytic amount of a copper source and a
catalytic amount of a titanium source.
11. The method of claim 5, wherein the combination of inorganic
co-catalysts comprises a catalytic amount of a copper source and a
catalytic amount of a lead source.
12. The method of claim 5, wherein the combination of inorganic
co-catalysts comprises a catalytic amount of a titanium source and
a catalytic amount of a zirconium source.
13. The method of claim 1, wherein the carbonylation catalyst
system further comprises an effective amount of a halide
composition.
14. The method of claim 13, wherein the halide composition is an
onium bromide composition.
15. The method of claim 13, wherein the halide composition is an
onium chloride composition.
16. The method of claim 1, wherein the aromatic hydroxy compound is
phenol.
17. The method of claim 2, wherein the carbonylation catalyst
system further comprises an effective amount of a base.
18. A method of carbonylating an aromatic hydroxy compound, said
method comprising the step of: contacting at least one aromatic
hydroxy compound with oxygen and carbon monoxide in the presence of
a carbonylation catalyst system comprising the following
components: an effective amount of an iron source in the absence of
an effective amount of a Group VIII B metal source; a catalytic
amount of an inorganic co-catalyst; and an effective amount of a
halide composition.
19. A carbonylation catalyst system, comprising an effective amount
of an iron source in the absence of an effective amount of a Group
VIII B metal source.
20. The carbonylation catalyst system of claim 19, further
comprising a catalytic amount of an inorganic co-catalyst.
21. The carbonylation catalyst system of claim 20, wherein the
inorganic co-catalyst is a copper source.
22. The carbonylation catalyst system of claim 20, wherein the
inorganic co-catalyst is a lead source.
23. The carbonylation catalyst system of claim 19, further
comprising a combination of inorganic co-catalysts.
24. The carbonylation catalyst system of claim 23, wherein the
combination of inorganic co-catalysts comprises a catalytic amount
of a copper source and a catalytic amount of a zirconium
source.
25. The carbonylation catalyst system of claim 23, wherein the
combination of inorganic co-catalysts comprises a catalytic amount
of a titanium source and a catalytic amount of a cerium source.
26. The carbonylation catalyst system of claim 23, wherein the
combination of inorganic co-catalysts comprises a catalytic amount
of a lead source and a catalytic amount of a titanium source.
27. The carbonylation catalyst system of claim 23, wherein the
combination of inorganic co-catalysts comprises a catalytic amount
of a lead source and a catalytic amount of a zirconium source.
28. The carbonylation catalyst system of claim 23, wherein the
combination of inorganic co-catalysts comprises a catalytic amount
of a copper source and a catalytic amount of a titanium source.
29. The carbonylation catalyst system of claim 23, wherein the
combination of inorganic co-catalysts comprises a catalytic amount
of a copper source and a catalytic amount of a lead source.
30. The carbonylation catalyst system of claim 23, wherein the
combination of inorganic co-catalysts comprises a catalytic amount
of a titanium source and a catalytic amount of a zirconium
source.
31. The carbonylation catalyst system of claim 19, further
comprising an effective amount of a halide composition.
32. The carbonylation catalyst system of claim 31, wherein the
halide composition is an onium bromide composition.
33. The carbonylation catalyst system of claim 31, wherein the
halide composition is an onium chloride composition.
34. The carbonylation catalyst system of claim 20, wherein the
carbonylation catalyst system further comprises an effective amount
of a base.
35. A carbonylation catalyst system, comprising an effective amount
of an iron source in the absence of an effective amount of a Group
VIII B metal source; a catalytic amount of an inorganic
co-catalyst; and an effective amount of a halide composition.
Description
BACKGROUND
[0001] 1. Field of the Invention
[0002] The present invention is directed to a method and catalyst
system for producing aromatic carbonates and, more specifically, to
a method and catalyst system for producing diaryl carbonates
through the carbonylation of aromatic hydroxy compounds.
[0003] 2. Discussion of Related Art
[0004] Aromatic carbonates find utility, inter alia, as
intermediates in the preparation of polycarbonates. For example, a
popular method of polycarbonate preparation is the melt
transesterification of aromatic carbonates with bisphenols. This
method has been shown to be environmentally superior to previously
used methods which employed phosgene, a toxic gas, as a reagent and
chlorinated aliphatic hydrocarbons, such as methylene chloride, as
solvents.
[0005] Various methods for preparing aromatic carbonates have been
previously described in the literature and/or utilized by industry.
A method that has enjoyed substantial popularity in the literature
involves the direct carbonylation of aromatic hydroxy compounds
with carbon monoxide and oxygen. In general, practitioners have
found that the carbonylation reaction requires a rather complex
catalyst system. For example, in U.S. Pat. No. 4,187,242, which is
assigned to the assignee of the present invention, Chalk reports
that a carbonylation catalyst system should contain a Group VIII B
metal, such as ruthenium, rhodium, palladium, osmium, iridium,
platinum, or a complex thereof. Further refinements to the
carbonylation reaction include the identification of organic
co-catalysts, such as terpyridines, phenanthrolines, quinolines and
isoquinolines in U.S. Pat. No. 5,284,964 and the use of certain
halide compounds, such as quaternary ammonium or phosphonium
halides in U.S. Pat. No. 5,399,734, both patents also being
assigned to the assignee of the present invention.
[0006] Unfortunately, due to the significant expense of using a
Group VIII B metal as the primary catalyst in a bulk process, the
economics of the aforementioned carbonylation systems is strongly
dependent on the number of moles of aromatic carbonate produced per
mole of Group VIII B metal utilized (i.e. "catalyst turnover").
Consequently, much work has been directed to the identification of
efficacious co-catalyst combinations that increase primary catalyst
turnover. For example, in U.S. Pat. No. 5,231,210, which is also
assigned to the present assignee, Joyce et al. report the use of a
cobalt pentadentate complex as an inorganic co-catalyst ("IOCC").
In U.S. Pat. No. 5,498,789, Takagi et al. report the use of lead as
an IOCC. In U.S. Pat. No. 5,543,547, Iwane et al. report the use of
trivalent cerium as an IOCC. In U.S. Pat. No. 5,726,340, Takagi et
al. report the use of lead and cobalt as a binary IOCC system.
[0007] Until the work underlying the teachings of the present
disclosure, however, few or no resources have been dedicated to
identifying effective substitutes for the Group VIII B metal
(typically palladium) as the primary catalyst in the carbonylation
reaction. Given the recent, substantial increases in the cost of
palladium, even substitutes exhibiting comparatively low activity
can be economically viable.
[0008] Unfortunately, the literature is not instructive regarding
the role of many catalyst components in the carbonylation reaction
(i.e. the reaction mechanism), and meaningful guidance regarding
the identification of effective combinations of catalyst system
components is cursory at best. Accordingly, due to the lack of
guidance in the literature, the identification of effective
carbonylation catalyst systems has become a serendipitous
exercise.
[0009] As the demand for high performance plastics has continued to
grow, new and improved methods of providing product more
economically are needed to supply the market. In this context,
various processes and catalyst systems are constantly being
evaluated; however, the identities of additional economically
effective catalyst systems for these processes continue to elude
the industry. Consequently, a long felt, yet unsatisfied need
exists for economically superior methods and catalyst systems for
producing aromatic carbonates and the like.
SUMMARY OF THE INVENTION
[0010] Accordingly, the present invention is directed to a method
and catalyst system for producing aromatic carbonates. In one
embodiment, the method includes the step of contacting at least one
aromatic hydroxy compound with oxygen and carbon monoxide in the
presence of a carbonylation catalyst system having an effective
amount of an iron source in the absence of an effective amount of a
Group VIII B metal source.
[0011] In various alternative embodiments, the carbonylation
catalyst system can include catalytic amounts of at least one
inorganic co-catalyst, as well as effective amounts of a halide
composition and/or a base.
BRIEF DESCRIPTION OF THE DRAWING
[0012] Various features, aspects, and advantages of the present
invention will become more apparent with reference to the following
description, appended claims, and accompanying drawing, wherein the
FIGURE is a schematic view of a device capable of performing an
aspect of an embodiment of the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0013] The present invention is directed to a method and catalyst
system for producing aromatic carbonates. In one embodiment, the
method includes the step of contacting at least one aromatic
hydroxy compound with oxygen and carbon monoxide in the presence of
a carbonylation catalyst system having an effective amount of an
iron source in the absence of an effective amount of a Group VIII B
metal source.
[0014] For convenience, the constituents of the catalyst system
described herein arc called "components" irrespective of whether a
reaction between specific components actually occurs either before
or during the carbonylation reaction. Therefore, the catalyst
system may include the components and any reaction products
thereof.
[0015] Unless otherwise noted, the term "effective amount" as used
herein includes that amount of a component capable of either
increasing (directly or indirectly) the yield of the carbonylation
product or increasing selectivity toward an aromatic carbonate.
Optimum amounts of a given component can vary based on reaction
conditions and the identity of other components, yet can be readily
determined in light of the discrete circumstances of a given
application.
[0016] Aromatic hydroxy compounds which may be used in the present
process include aromatic mono or polyhydroxy compounds, such as
phenol, cresol, xylenol, resorcinol, hydroquinone, and bisphenol A.
Aromatic organic mono hydroxy compounds are preferred, with phenol
being more preferred.
[0017] The carbonylation catalyst system contains an effective
amount of an iron source as the primary catalyst component.
Suitable iron sources include iron halides, nitrates, carboxylates,
oxides and iron complexes containing carbon monoxide, amines,
phosphines or olefins. As used herein, the term "complex" includes
coordination or complex compounds containing a central ion or atom.
The complexes may be nonionic, cationic, or anionic, depending on
the charges carried by the central atom and the coordinated groups.
Other common names for these complexes include complex ions (if
electrically charged), Werner complexes, and coordination
complexes. In various applications, it may be preferable to utilize
iron salts of organic acids, including carboxylates with C.sub.2-6
aliphatic acids. Suitable iron sources include iron (II or III)
acetylacetonate and iron (II or III) acetate, as well as iron (III)
bromide anhydrous, iron (II or III) nitrate, ferrocene,
acetylferrocene, tris(2,2,6,6-tetramethyl-3,5-heptanedionate) iron
(III), and iron (II) methylcyclopentadienyl.
[0018] The iron source may be a non-supported iron salt or complex.
As used herein, the term "non-supported" indicates the absence of
industrially conventional catalyst supports based on carbon,
element oxides, element carbides or element salts in various
presentations. Examples of supports containing carbon are coke,
graphite, carbon black and activated carbon. Examples of element
oxide catalyst supports are SiO.sub.2 (natural or synthetic
silicas, quartz), Al.sub.2O.sub.3 (.alpha.-,
.gamma.-Al.sub.2O.sub.3), aluminas, natural and synthetic
aluminosilicates (zeolites), TiO.sub.2 (rutile, anatase), ZrO.sub.2
and ZnO. Examples of element carbides and salts are SiC,
AlPO.sub.4, BaSO.sub.4, and CaCO.sub.3.
[0019] The present iron based catalyst system does not require a
component chosen from the Group VIII B metals (i.e., Ru, Pt, Pd,
Rh, Os, Ir) or a compound thereof. Surprisingly, the presently
disclosed catalyst system effectively catalyzes the carbonylation
reaction in the absence of a costly Group VIII B metal source,
thereby effectively insulating the process from the volatile market
for these elements.
[0020] In various alternative embodiments, the carbonylation
catalyst system can include a catalytic amount of at least one
inorganic co-catalyst (IOCC). It has been discovered that IOCC's
and combinations of IOCC's can effectively catalyze the
carbonylation reaction in the presence of the aforementioned
iron-based catalyst system. Such IOCC's and combinations include
copper, lead, copper and zirconium, titanium and cerium, lead and
titanium, lead and zirconium, copper and titanium, copper and lead,
and titanium and zirconium. Additional IOCC's may be used in the
carbonylation catalyst system, provided the additional IOCC does
not deactivate (i.e. "poison") the original IOCC combination.
[0021] An IOCC can be introduced to the carbonylation reaction in
various forms, including salts and complexes, such as tetradentate,
pentadentate, hexadentate, or octadentate complexes. Illustrative
forms may include oxides, halides, carboxylates, diketones
(including beta-diketones), nitrates, complexes containing carbon
monoxide or olefins, and the like. Suitable beta-diketones include
those known in the art as ligands for the IOCC metals of the
present system. Examples include, but are not limited to,
acetylacetone, benzoylacetone, dibenzoylmethane,
diisobutyrylmethane, 2,2-dimethylheptane-3,5-dione,
2,2,6-trimethylheptane-3,5-dione, dipivaloylmetharie, and
tetramethylheptanedione. The quantity of ligand is preferably not
such that it interferes with the carbonylation reaction itself,
with the isolation or purification of the product mixture, or with
the recovery and reuse of catalyst components. An IOCC may be used
in its elemental form if sufficient reactive surface area can be
provided. It may be preferable that an IOCC is non-supported as
discussed above relative to the iron source.
[0022] IOCC's are included in the carbonylation catalyst system in
catalytic amounts. In this context a "catalytic amount" is an
amount of IOCC (or combination of IOCC's) that increases the number
of moles of aromatic carbonate produced per mole of iron utilized;
increases the number of moles of aromatic carbonate produced per
mole of halide composition utilized; or increases selectivity
toward aromatic carbonate production beyond that obtained in the
absence of the IOCC (or combination of IOCC's). Optimum amounts of
an IOCC in a given application will depend on various factors, such
as the identity of reactants and reaction conditions. For example,
when copper is utilized as an IOCC in the reaction, the molar ratio
of copper relative to iron at the initiation of the reaction is
preferably between about 1 and about 100.
[0023] The carbonylation catalyst system may further contain an
effective amount of a halide composition, such as an organic halide
salt. In various preferred embodiments, the halide composition can
be an organic bromide or chloride salt. The salt may be a
quaternary ammonium or phosphonium salt, such as tetraethylammonium
bromide, tetraethylammonium chloride, tetrabutylammonium chloride,
or the like. To address economic or regulatory concerns, alkali
metal or alkaline earth metal salts may be preferable in certain
applications. In preferred embodiments, the carbonylation catalyst
system can contain between about 5 and about 2000 moles of halide
per mole of iron employed, and, more preferably, between about 50
and about 1000 molar equivalents of halide are used.
[0024] The carbonylation catalyst system can also include an
effective amount of a base. Any desired bases or mixtures thereof,
whether organic or inorganic may be used. A non-exclusive listing
of suitable inorganic bases include alkali metal hydroxides and
carbonates; C.sub.2-C.sub.12 carboxylates or other salts of weak
acids; and various alkali metal salts of aromatic hydroxy
compounds, such as alkali metal phenolates. Hydrates of alkali
metal phenolates may also be used. Examples of suitable organic
bases include tertiary amines and the like. Preferably, the base
used is an alkali metal salt incorporating an aromatic hydroxy
compound, more preferably an alkali metal salt incorporating the
aromatic hydroxy compound to be carbonylated to produce the
aromatic carbonate. Suitable bases include sodium phenoxide and
sodium hydroxide. In preferred embodiments, between about 5 and
about 1000 molar equivalents of base are employed (relative to
iron), and, more preferably, between about 50 and about 700 molar
equivalents of base are used.
[0025] The carbonylation reaction can be carried out in a batch
reactor or a continuous reactor system. Due in part to the low
solubility of carbon monoxide in organic hydroxy compounds, such as
phenol, it is preferable that the reactor vessel be pressurized. In
preferred embodiments, gas can be supplied to the reactor vessel in
proportions of between about 2 and about 50 mole percent oxygen,
with the balance being carbon monoxide or a combination of at least
one inert gas and carbon monoxide and, in any event, outside the
explosion range for safety reasons. It is contemplated that oxygen
can be supplied in diatomic form or from another oxygen containing
source, such as peroxides and the like. Additional gases may be
present in amounts that do not deleteriously affect the
carbonylation reaction. The gases may be introduced separately or
as a mixture. A total pressure in the range of between about 10 and
about 250 atmospheres is preferred. Drying agents, typically
molecular sieves, may be present in the reaction vessel. Reaction
temperatures in the range of between about 60.degree. C. and about
150.degree. C. are preferred. Gas sparging or mixing can be used to
aid the reaction.
[0026] In order that those skilled in the art will be better able
to practice the present invention reference is made to the FIGURE,
which shows an example of a continuous reactor system for producing
aromatic carbonates. The symbol "V" indicates a valve and the
symbol "P" indicates a pressure gauge.
[0027] The system includes a carbon monoxide gas inlet 10, an
oxygen inlet 11, a manifold vent 12, and an inlet 13 for a gas,
such as carbon dioxide. A reaction mixture can be fed into a low
pressure reservoir 20, or a high pressure reservoir 21, which can
be operated at a higher pressure than the reactor for the duration
of the reaction. The system further includes a reservoir outlet 22
and a reservoir inlet 23. The gas feed pressure can be adjusted to
a value greater than the desired reactor pressure with a pressure
regulator 30. The gas can be purified in a scrubber 31 and then fed
into a mass flow controller 32 to regulate flow rates. The reactor
feed gas can be heated in a heat exchanger 33 having appropriate
conduit prior to being introduced to a reaction vessel 40. The
reaction vessel pressure can be controlled by a back pressure
regulator 41. After passing through a condenser 25, the reactor gas
effluent may be either sampled for further analysis at valve 42 or
vented to the atmosphere at valve 50. The reactor liquid can be
sampled at valve 43. An additional valve 44 can provide further
system control, but is typically closed during the gas flow
reaction.
[0028] In the practice of one embodiment of the invention, the
carbonylation catalyst system and aromatic hydroxy compound are
charged to the reactor system. The system is sealed. Carbon
monoxide and oxygen are introduced into an appropriate reservoir
until a preferred pressure (as previously defined) is achieved.
Circulation of condenser water is initiated, and the temperature of
the heat exchanger 33 (e.g., oil bath) can be raised to a desired
operating temperature. A conduit 46 between heat exchanger 33 and
reaction vessel 40 can be heated to maintain the desired operating
temperature. The pressure in reaction vessel 40 can be controlled
by the combination of reducing pressure regulator 30 and back
pressure regulator 41. Upon reaching the desired reactor
temperature, aliquots can be taken to monitor the reaction.
EXAMPLES
[0029] The following examples are included to provide additional
guidance to those skilled in the art in practicing the claimed
invention. The examples provided are merely representative of the
work that contributes to the teaching of the present application.
Accordingly, these examples are not intended to limit the
invention, as defined in the appended claims, in any manner. Unless
otherwise specified, all parts are by weight, and all equivalents
are relative to iron. Reaction products were verified by gas
chromatography. Unless otherwise noted, all reactions were carried
out in a glass, batch reactor at 100.degree. C. in an approximately
6-9% O.sub.2 in CO atmosphere. The glass reactor was sealed with a
semi-permeable membrane and placed in an autoclave containing the
reaction atmosphere at a pressure of approximately 110 atmosphere
(i.e., negligible pressure differential across the walls of the
glass reaction vessel). Reaction time was 3 hours for each run.
[0030] In the following examples, the aromatic carbonate produced
is diphenylcarbonate (DPC). For convenience, the number of moles of
DPC produced per mole of iron utilized is referred to as the iron
turnover number (Fe TON).
Example 1
[0031] Diphenyl carbonate was produced by adding, at ambient
conditions, a substantially homogeneous catalyst system containing
iron in the form of either iron (III) acetylacetonate
("Fe(acac).sub.3") or iron (III) nitrate ("Fe(NO.sub.3).sub.3") 5
equivalents of titanium in the form of titanium (IV) oxide
acetylacetonate ("TiO(acac).sub.2"), 2 equivalents of cerium in the
form of cerium (III) acetylacetonate ("Ce(acac).sub.3"), differing
amounts of halide compositions in the form of either
tetraethylammonium bromide ("TEAB") or tetraethylammonium chloride
("TEAC"), and 50 equivalents of NaOH to a glass reaction vessel
containing phenol. The components were heated to 100.degree. C. for
3 hours in a reaction atmosphere comprised of 3% oxygen, 6%
nitrogen, and 91% carbon monoxide. Total pressure in the reaction
zone was approximately 102 atm. The following results were
observed:
1 Experiment Fe source Halide Halide No. 1 mM source Equivalents Fe
TON 1 Fe(acac).sub.3 TEAC 200 2 2 Fe(NO.sub.3).sub.3 TEAB 50 3
[0032] The data show that a Fe TON at least as high as 3 can be
obtained utilizing an embodiment of the present catalyst system.
Based on the results of these experiments, it is evident that a
catalyst system containing Fe, Ce, Ti, an onium halide, and a base
can effectively catalyze the carbonylation reaction.
Example 2
[0033] The general procedure of Example 1 was repeated with various
iron sources, such as Fe(acac).sub.3, iron (II) acetate
("Fe(OAc).sub.2"), iron (III) bromide ("FeBr.sub.3"), and iron (II)
methylcyclopentadienyl ("Fe(Cp).sub.2"). Various inorganic
co-catalyst combinations were employed in the presence of 50
equivalents of various halide compositions, including TEAB and
tetrabutylammonium chloride ("TBAC"). Some experimental runs were
carried out in the presence of a base. All reactions were carried
out in a 7.4% oxygen in carbon monoxide atmosphere at a total
pressure of approximately 109 atm. to produce the following
results:
2 Fe Experiment source IOCC IOCC #1 IOCC IOCC #2 NaOH Halide Fe No.
1 mM #1 Equiv. #2 Equiv. Equiv. source TON 1 Fe(acac).sub.3 Pb 5 Ti
1 50 TEAB 3 2 Fe(acac).sub.3 Pb 5 Ti 1 50 TEAB 2 3 Fe(acac).sub.3
Pb 5 Zr 5 50 TBAC 3 4 Fe(acac).sub.3 Cu 1 Ti 5 50 TEAB 3 5
Fe(acac).sub.3 Cu 5 Zr 5 50 TEAB 2 6 Fe(OAc).sub.2 Pb 1 Cu 5 --
TEAB 5 7 Fe(OAc).sub.2 Pb 5 Ti 5 50 TEAB 5 8 Fe(OAc).sub.2 Cu 1 Ti
5 50 TEAB 3 9 Fe(OAc).sub.2 Cu 5 Zr 1 -- TEAB 2 10 Fe(OAc).sub.2 Ti
5 Zr 5 50 TBAC 2 11 Fe(Cp).sub.2 Pb 5 Cu 5 50 TEAB 3 12
Fe(Cp).sub.2 Pb 5 Cu 5 50 TEAB 2 13 Fe(Cp).sub.2 Pb 1 Ti 1 50 TEAB
6 14 Fe(Cp).sub.2 Pb 1 Ti 1 50 TEAB 2 15 Fe(Cp).sub.2 Cu 5 Ti 1 50
TBAC 3 16 Fe(Cp).sub.2 Cu 5 Ti 5 50 TEAB 3 17 Fe(Cp).sub.2 Cu 5 Ti
5 50 TEAB 2 18 Fe(Cp).sub.2 Cu 5 Zr 1 50 TBAC 2 19 Fe(Cp).sub.2 Cu
5 Zr 1 50 TBAC 4 20 Fe(Cp).sub.2 Ti 1 Zr 1 50 TEAB 4 21
Fe(Cp).sub.2 Ti 1 Zr 1 50 TEAB 2 22 FeBr.sub.3 Pb 1 Cu 5 50 TBAC 3
23 FeBr.sub.3 Pb 1 Ti 5 50 TEAB 3 24 FeBr.sub.3 Pb 5 Zr 1 50 TBAC 3
25 FeBr.sub.3 Pb 5 Zr 1 50 TBAC 3 26 FeBr.sub.3 Cu 5 Ti 5 50 TEAB 3
27 FeBr.sub.3 Ti 5 Zr 1 50 TEAB 6 28 FeBr.sub.3 Ti 5 Zr 5 50 TEAB
2
[0034] The results show that various combinations of Fe, IOCC,
onium halide, and base can effectively catalyze the carbonylation
reaction.
Example 3
[0035] The general procedure of Examples 1 and 2 was repeated with
1 mM of various iron sources, 100 equivalents of TEAB, and various
amounts of either lead or copper, Lead was provided as lead (II)
oxide ("PbO") and copper as copper (II) acetylacetonate
("Cu(acac).sub.2"). Iron sources used for these experimental runs
include Fe(acac).sub.3, Fe(OAc).sub.2, FeBr.sub.3, ferrocene
("Fe(C.sub.5H.sub.5).sub.2"), and iron (II) nitrate
("Fe(NO.sub.3).sub.2"). Reactions were carried out in a 7.8% oxygen
in carbon monoxide atmosphere at approximately 110 atm. total
pressure. The following results were observed:
3 Experiment Fe source Cu(acac).sub.2 PbO TEAB Fe No. 1 mM
Equivalents Equivalents Equiv. TON 1 Fe(acac).sub.3 5 -- 100 4 2
Fe(OAc).sub.2 5 -- 100 3 3 Fe(OAc).sub.2 5 -- 100 6 4 FeBr.sub.3 5
-- 100 3 5 FeBr.sub.3 5 -- 100 5 6 Fe(C.sub.5H.sub.5).sub.2 5 --
100 6 7 Fe(acac).sub.3 -- 10 100 3 8 Fe(OAc).sub.2 -- 10 100 5 9
FeBr.sub.3 -- 10 100 4 10 FeBr.sub.3 -- 10 100 11 11
Fe(C.sub.5H.sub.5).sub.2 -- 10 100 4 12 Fe(C.sub.5H.sub.5).sub.2 --
10 100 3 13 Fe(NO.sub.3).sub.2 -- 10 100 11 14 Fe(NO.sub.3).sub.2
-- -- -- 16
[0036] The results show that various combinations of Fe alone, as
well as in combination with an IOCC and onium bromide can
effectively catalyze the carbonylation reaction.
Example 4
[0037] The general procedure of Examples 1-3 was repeated with 1 mM
of various iron sources, 100 equivalents of either TEAB or TBAC,
and various amounts of either PbO or Cu(acac).sub.2. Reactions were
carried out in a 7.8% oxygen in carbon monoxide atmosphere at
approximately 56 atm. total pressure. The following results
were
4 Experiment Fe source Cu(acac).sub.2 PbO Halide Fe No. 1 mM
Equivalents Equivalents 100 eq. TON 1 Fe(acac).sub.3 -- 10 TEAB 2 2
Fe(OAc).sub.2 -- 10 TEAB 4 3 Fe(acac).sub.3 5 -- TBAC 4 4
FeBr.sub.3 5 -- TBAC 4 5 Fe(NO.sub.3).sub.2 5 -- TBAC 3 6
Fe(NO.sub.3).sub.2 5 -- TBAC 3
[0038] The results show that various combinations of Fe, IOCC, and
onium halide can effecitively catalyze the carbonylation reaction
at lower pressures.
Example 5
[0039] The general procedure of Examples 1-4 was repeated with
various iron sources, various inorganic co-catalyst combinations,
and 100 equivalents of either TEAC or TEAB. IOCC sources included
TiO(acac).sub.2, PbO, Zr(OBu).sub.4, and Cu(acac).sub.2. Some
experimental runs were carried out in the presence of a base. All
reactions were carried out in a 9% oxygen in carbon monoxide
atmosphere at a total pressure of approximately 102 atm. to produce
the following results:
5 Fe Experiment source IOCC IOCC #1 IOCC IOCC #2 NaOH Halide Fe No.
1 mM #1 Equiv. #2 Equiv. Equiv. source TON 1 FeBr.sub.3 Ti 2 Pb 2
50 TEAC 2 2 FeBr.sub.3 Ti 2 Pb 2 50 TEAC 2 3 Fe(Cp).sub.2 Zr 5 Pb 2
-- TBAB 2 4 Fe(Cp).sub.2 Zr 5 Pb 2 -- TEAB 2 5 Fe(Cp).sub.2 Cu 5 Ti
5 -- TEAB 2 6 Fe(OAc).sub.3 Pb 2 Cu 5 50 TEAB 3 7 Fe(OAc).sub.3 Pb
2 Cu 5 50 TEAB 2 8 Fe(acac).sub.3 Cu 5 Ti 2 50 TEAB 1 9
Fe(acac).sub.3 Pb 5 Cu 2 -- TEAC 2
[0040] The results show that various combinations of Fe, IOCC,
onium halide, and base can effectively catalyze the carbonylation
reaction.
Example 6
[0041] The general procedure of Examples 1-5 was repeated with an
iron source selected from either acetylferrocene
("CH.sub.3COC.sub.5H.sub.4FeC- .sub.5H.sub.5") or
tris(2,2,6,6-tetramethyl-3,5-heptanedionate) iron (III)
("Fe(TMHD).sub.3"). The remainder of the catalyst system included
TEAB, and either Cu(acac).sub.2 or PbO. Reactions were carried out
at approximately 107 atm. in a 7.79% oxygen in CO atmosphere to
produce the following results:
6 Experi- Cu(acac).sub.2 PbO ment Equiva- Equiva- TEAB Fe No. Iron
source lents lents Equiv. TON 1
CH.sub.3COC.sub.5H.sub.4FeC.sub.5H.sub.5 5 -- 75 2 2
CH.sub.3COC.sub.5H.sub.4FeC.sub.5H.sub.5 -- 5 75 3 3 Fe(TMHD).sub.3
-- 5 75 3 4 Fe(TMHD).sub.3 -- 5 75 4
[0042] The results show that various combinations of Fe, IOCC, and
onium bromide can effectively catalyze the carbonylation
reaction.
[0043] It will be understood that each of the elements described
above, or two or more together, may also find utility in
applications differing from the types described herein. While the
invention has been illustrated and described as embodied in a
method and catalyst system for producing aromatic carbonates, it is
not intended to be limited to the details shown, since various
modifications and substitutions can be made without departing in
any way from the spirit of the present invention. For example,
additional effective IOCC compounds can be added to the reaction.
As such, further modifications and equivalents of the invention
herein disclosed may occur to persons skilled in the art using no
more than routine experimentation, and all such modifications and
equivalents are believed to be within the spirit and scope of the
invention as defined by the following claims.
* * * * *