U.S. patent application number 09/783920 was filed with the patent office on 2002-01-03 for method of producing an epoxycyclododecane compound.
This patent application is currently assigned to Ube Industries, Ltd.. Invention is credited to Funatsu, Joji, Ii, Nobuhiro, Kugimoto, Junichi, Kuroda, Nobuyuki, Nakamura, Takato.
Application Number | 20020002293 09/783920 |
Document ID | / |
Family ID | 26585357 |
Filed Date | 2002-01-03 |
United States Patent
Application |
20020002293 |
Kind Code |
A1 |
Kuroda, Nobuyuki ; et
al. |
January 3, 2002 |
Method of producing an epoxycyclododecane compound
Abstract
An epoxycyclododecane compound is produced by a catalytic
hydrogenation reaction of 1,2-epoxy-5,9-cyclododecadiene, using a
specific platinum-containing catalyst having a long life, under a
hydrogen gas pressure of 0.8 to 9 MPa, and with a high yield of the
target compound.
Inventors: |
Kuroda, Nobuyuki; (Ube-shi,
JP) ; Kugimoto, Junichi; (Ube-shi, JP) ;
Nakamura, Takato; (Ube-shi, JP) ; Ii, Nobuhiro;
(Ube-shi, JP) ; Funatsu, Joji; (Ube-shi,
JP) |
Correspondence
Address: |
MORGAN, LEWIS & BOCKIUS
1800 M STREET NW
WASHINGTON
DC
20036-5869
US
|
Assignee: |
Ube Industries, Ltd.
|
Family ID: |
26585357 |
Appl. No.: |
09/783920 |
Filed: |
February 16, 2001 |
Current U.S.
Class: |
549/546 |
Current CPC
Class: |
C07D 303/04
20130101 |
Class at
Publication: |
549/546 |
International
Class: |
C07D 33/02 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 15, 2000 |
JP |
2000-36160 |
Oct 17, 2000 |
JP |
2000-316243 |
Claims
1. A method of producing an epoxycyclododecane compound comprising
hydrogenating 1,2-epoxy-5,9-cyclododecadiene with a hydrogen gas in
the presence of a platinum group metal-containing catalyst, the
hydrogen gas having a pressure of 0.8 to 9 MPa, and the platinum
group metal-containing catalyst being a platinum-containing
catalyst.
2. The method of producing an epoxycyclododecane compound as
claimed in claim 1, wherein the hydrogen gas pressure for the
hydrogenation is in the range of from 3 to 7 MPa.
3. The method of producing an epoxycyclododecane compound as
claimed in claim 1, wherein the hydrogenation is carried out under
a hydrogen gas pressure of 0.8 to 9 MPa at a temperature higher
than 50.degree. C.
4. The method of producing an epoxycyclododecane compound as
claimed in any of claims 1 to 3, wherein the platinum containing
catalyst is employed in an amount, in terms of platinum, of 0.0005
times or less the molar amount of
1,2-epoxy-5,9-cyclododecadiene.
5. The method of producing an epoxycyclododecane compound as
claimed in any of claims 1 to 4, wherein the platinum-containing
catalyst comprises a platinum-containing catalytic component
carried on an inert carrier component comprising at least one
member selected from activated carbon, alumina, silica,
silicaalumina, zeolite, and spinel.
6. The method of producing an epoxycyclododecane compound as
claimed in claim 5, wherein the carrier component for the
platinum-containing catalyst consists of activated carbon.
7. The method of producing an epoxycyclododecane compound as
claimed in claim 5, wherein the platinum-containing catalytic
component is present in an amount, in terms of platinum, of 0.1 to
10% by weight, based on the weight of the inert carrier component.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a method of producing an
epoxycyclododecane compound. More particularly, the present
invention relates to a method of producing an epoxycyclododecane
compound by catalytically and selectively hydrogenating double
bonds of 1,2-epoxy-5,9-cyclododecadiene.
[0003] An epoxycyclododecane compound is useful for producing not
only a resin component for paints and adhesives, but also a lactam
compound, a lactone compound or a dibasic carboxylic acid through a
cyclododecanone derived from the epoxycyclododecane by a
conventional method and, thus, it is an important intermediate for
polyamide 12 and polyesters which are useful materials for
producing synthetic resins and synthetic fibers.
[0004] 2. Description of the Related Art
[0005] It is known to produce an epoxycyclododecane compound by a
catalytic reaction of 1,2-epoxy-5,9-cyclododecadiene with hydrogen
in the presence of a platinum group metal-containing catalyst.
[0006] For example, Soviet Union (SU) Patent No. 380,650 discloses
a method of synthesizing an epoxycyclododecane compound by reducing
1,2-epoxy-5,9-cyclododecadiene with hydrogen in a cyclohexane
medium in the presence of a catalytic component comprising a
platinum-group metal (a metal of Group VIII of the Periodic Table)
carried on a carrier consisting of alumina or activated carbon, at
a reaction temperature of 70 to 200.degree. C. under a hydrogen gas
pressure of 101,325 to 263,445 kPa (100 to 260 atmospheres). In
this method, however, the yield of the target epoxycyclododecane
compound was 82 to 95% which was unsatisfactory. Also, this method
is disadvantageous in that the necessary amount of the catalyst
based on the amount of 1,2-epoxy-5,9-cyclododecadiene fed into the
reaction procedure is too high.
[0007] Also, "Russian Journal of General Chemistry", Vol. 67, No. 6
(1997), pages 921 to 926, discloses a result of a reaction of
1,2-epoxy-5,9-cyclododecadiene with hydrogen in the presence of a
catalyst comprising a catalytic component comprising a platinum
group metal (for example, palladium or platinum) carried on a
carrier component comprising an activated carbon, alumina or a
silica gel. In an embodiment of the method, the reaction was
carried out in the presence of a catalyst in which palladium is
carried on a carrier-comprising an activated carbon, alumina or a
silica gel, at a reaction temperature of 30 to 90.degree. C. under
a hydrogen gas pressure of 0.1 to 4.0 MPa, and the target
epoxycyclododecane compound was obtained in a yield of 80 to 99%.
In another embodiment, the reaction was carried out in the presence
of a catalyst in which platinum was carried on a silica gel
carrier, at a reaction temperature of 50.degree. C. under a
hydrogen gas pressure of 1.3 to 2.5 MPa, and the target
epoxycyclododecane compound was obtained in a yield of 84%. This
report is, however, quite silent as to the length of the life of
the catalyst.
[0008] Generally, when a catalyst containing a platinum group metal
which is an expensive noble metal is used in industry, it is
necessary that the resultant catalyst enables the target product to
be produced in a high yield; the catalytic reaction can be effected
at a high reaction rate; and the resultant catalyst has a long
duration of life.
[0009] However, the prior art literature and patent publications
did not teach or suggest how to impart a long life to the
catalyst.
SUMMARY OF THE INVENTION
[0010] An object of the present invention is to provide a method
which enables an epoxycyclododecane compound to be industrially
produced with a high yield at a high reaction rate, by a reaction
of 1,2-epoxy-5,9-cyclododecadiene with hydrogen in the presence of
a catalyst with a long life thereof.
[0011] The above-mentioned object can be attained by the method of
the present invention.
[0012] The method of the present invention for producing
epoxycyclododecane compound comprises hydrogenating
1,2-epoxy-5,9-cyclododecadiene with a hydrogen gas in the presence
of a platinum group metal-containing catalyst,
[0013] the hydrogen gas having a pressure of 0.8 to 9 MPa, and
[0014] the platinum group metal-containing catalyst being a
platinum-containing catalyst.
[0015] In the method of the present invention for producing an
epoxycyclododecane compound, the hydrogen gas pressure for the
hydrogenation is in the range of from 3 to 7 MPa.
[0016] In the method of the present invention for producing an
epoxycyclododecane compound, the hydrogenation is carried out under
a hydrogen gas pressure of 0.8 to 9 MPa at a temperature higher
than 50.degree. C.
[0017] In the method of the present invention for producing an
epoxycyclododecane compound, the platinum containing catalyst is
employed in an amount, in terms of platinum, of 0.0005 times or
less the molar amount of 1,2-epoxy-5,9-cyclododecadiene.
[0018] In the method of the present invention for producing an
epoxycyclododecane compound, the platinum-containing catalyst
comprises a platinum-containing catalytic component carried on an
inert carrier component comprising at least one member selected
from activated carbon, alumina, silica, silicaalumina, zeolite, and
spinel.
[0019] In the method of the present invention for producing an
epoxycyclododecane compound, the carrier component for the
platinum-containing catalyst consists of activated carbon.
[0020] In the method of the present invention for producing an
epoxycyclododecane compound, the platinum-containing catalytic
component is present in an amount, in terms of platinum, of 0.1 to
10% by weight, based on the weight of the inert carrier
component.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0021] The 1,2-epoxy-5,9-cyclododecadiene usable, as a starting
material, for the method of present invention can be produced by,
for example, epoxidizing a cyclododecatriene with an organic
carboxylic acid and hydrogen peroxide. In the resultant
1,2-epoxy-5,9-cyclododecadiene, the epoxy group and the double bond
may be located in any of a cis-form, a trans-form or an other
form.
[0022] For the method of the present invention, a trade
1,2-epoxy-5,9-cyclododecadiene may be employed without refining by
distillation, etc., or after refining by distillation, etc. When
the compound is a synthetic product, the compound is preferably
employed after refining by distillation, etc.
[0023] The platinum-containing catalyst usable for the present
invention is preferably selected from solid catalysts, preferably
particulate solid catalysts, more preferably particulate solid
catalyst having an average particle size of several .mu.m to
several hundreds .mu.m, particularly 10 to 300 .mu.m, comprising a
catalytic component comprising a platinum-containing compound and
carried on an inert carrier.
[0024] The inert carrier for the catalyst preferably comprises at
least one member selected from the group consisting of activated
carbon, alumina, silica, silicaalumina, zeolite and spinel, more
preferably, activated carbon, alumina and silicaalumina. Still more
preferably, the inert carrier is formed from activated carbon.
[0025] The platinum-containing catalytic component is preferably
present in an amount, in terms of platinum, of 0.1 to 10% by
weight, more preferably 0.2 to 8% by weight, based on the weight of
the inert carrier component. In the catalyst, the
platinum-containing catalytic component may be carried on the
surface of and/or inside the inert carrier component.
[0026] In the method of the present invention, the specific
platinum-containing catalyst exhibits a long life.
[0027] In the hydrogenation reaction of the method of the present
invention, the platinum-containing catalyst is preferably used in a
molar amount in terms of platinum, of 0.0005 times or less, more
preferably 0.000001 to 0.0005 times, still more preferably 0.000005
to 0.0004 times the molar amount of 1,2-epoxy-5,9-cyclododecadiene
used as a starting material. If the amount of the catalyst is too
little, the time necessary to complete the reaction may be too
long. Also, the use of the catalyst in too large an amount may
cause the yield of the target product to decrease.
[0028] In the catalytic reaction of the method of the present
invention, a reaction medium is not always necessary. When the
reaction medium is used, for example, hydrocarbons, for example,
n-hexane, n-heptane, n-tetradecane, and cyclohexane; ethers, for
example, tetrahydrofurane and dioxane; alcohols, for example,
methyl alcohol, ethyl alcohol, tert-butyl alcohol and tert-amyl
alcohol; and esters, for example, ethyl acetate and butyl acetate,
are employed. These organic compounds for the reaction medium may
be employed alone or in a mixture of two or more thereof. The
reaction medium is preferably employed in an amount of 0 to 20
times, more preferably 0 to 10 times, the weight of
1,2-epoxy-5,9-cyclododecadie- ne employed for the reaction.
[0029] In the method of the present invention, the hydrogenation
for the double bonds of 1,2-epoxy-5,9-cyclododecadiene in the
presence of the platinum containing catalyst is carried out under a
hydrogen gas pressure of 0.8 to 9 MPa, preferably 1 to 8 MPa, more
preferably 3 to 7 MPa. In the method of the present invention, the
reaction temperature is not specifically limited. Preferably, the
reaction temperature is preferably controlled to a level higher
than 50.degree. C., more preferably 70 to 200.degree. C., still
more preferably 70 to 150.degree. C.
[0030] If the reaction hydrogen gas pressure and the reaction
temperature are too low, a long time may be undesirably necessary
to complete the reaction, and a yield of a by-product consisting of
cyclododecanol may be increased, and the yield of the target
compound may be decreased. Also, if the reaction hydrogen gas
pressure and the reaction temperature are too high, an undesirable
reduction of the target compound may be promoted and thus the yield
of the target compound may be decreased.
[0031] In the method of the present invention, after the
hydrogenation reaction procedure is completed, the catalyst is
separated and recovered from the resultant reaction mixture, and
the target epoxycyclododecane is isolated from the remaining
reaction mixture by a refining means, for example, distillation. A
high purity epoxycyclododecane is obtained. In the case where the
resultant epoxycyclododecane is further converted to
cyclododecanone or a dodecanedioic acid, after the catalyst is
removed from the reaction mixture, the remaining reaction mixture
may be subjected to an isomerization reaction of the
epoxycyclododecane or to an oxidation reaction of the
epoxycyclododecane contained in the remaining reaction mixture.
EXAMPLES
[0032] The present invention will be further explained by the
following examples.
Example 1
[0033] An SUS Stainless steel autoclave having a capacity of 100 ml
and equipped with a stirrer was charged with 20 g (0.112 moles) of
1,2-epoxy-5,9-cyclododecadiene and 0.08 g of platinum-containing
catalyst particles comprising 5% by weight of a platinum-containing
catalytic component carried on an activated carbon carrier
(platinum atom amount: 0.0102 millimoles, water content: 50% by
weight, BET specific surface area: 1200 m.sup.2/g, made by N. E.
CHEMCAT).
[0034] The inside of the autoclave was pressurized with a hydrogen
gas to pressure of 5 MPa at room temperature. Then the reaction
mixture was heated to a temperature of 70.degree. C., and stirred
at the above-mentioned temperature under the above-mentioned
pressure until no absorption of hydrogen in the reaction mixture
was established. After the reaction was completed, the reaction
mixture was cooled to room temperature, the catalyst was removed
from the reaction mixture by filtration, and the remaining reaction
mixture was subjected to a gas chromatographic analysis.
[0035] In the results of the analysis, it was confirmed that the
starting 1,2-epoxy-5,9-cyclododecadiene was completely consumed,
the target epoxycyclododecane (which will be represented by ECD
hereinafter) was produced in a yield of 99.6 molar %, and as
by-products, cyclododecanone (which will be represented by CDON
hereinafter) was produced in a yield of 0.04 molar %,
cyclododecanol (which will be represented by CDOL hereinafter), was
produced in a yield of 0.2 molar %, and cylcododecane (which will
be represented by CDAN hereinafter) was produced in a yield of 0.04
molar %.
[0036] Examples 2 to 7 and Comparative Examples 1 to 3
[0037] In each of Examples 2 to 7 and Comparative Examples 1 to 3,
the epoxycyclododecane was produced by the same procedures as in
Example 1, except that the type of the catalyst, the amount of the
catalyst, the reaction temperature, the hydrogen gas pressure and
the reaction time were controlled to those shown in Table 1. The
analysis was carried out in the same manner as in Example 1.
[0038] The results are shown in Table 1.
1 TABLE 1 Item Reaction Hydrogen Tempe- gas Yield (molar %) Example
Catalyst Amount rature pressure Time By-products No. Type (g)
(.degree. C.) (MPa) (min) ECD CDON CDOL CDAN Example 1 5 wt % Pt/AC
(*).sub.1 0.08 70 5 120 99.6 0.04 0.20 0.04 2 5 wt % Pt/AC 0.08 100
5 90 99.3 0.05 0.45 0.04 3 5 wt % Pt/AC 0.04 130 5 80 98.8 0.07
0.95 0.07 4 5 wt % Pt/AC 0.02 130 5 90 98.8 0.09 0.81 0.06 5 0.5 wt
% Pt/AN (*).sub.2 0.20 140 5 120 96.5 0.60 2.60 0.20 6 5 wt % Pt/AC
0.80 130 5 10 95.3 0.65 3.18 0.09 7 2.5 wt % Pt/SI (*).sub.3 0.08
150 5 120 97.6 0.17 1.34 0.70 Compara- tive Example 1 5 wt % Pt/AC
0.04 130 0.5 90 91.3 2.20 6.19 0.10 2 0.5 wt % Pd/AC 0.20 140 1 120
85.1 6.40 7.50 0.10 3 0.5 wt % Pd/AN 0.20 120 1 90 42.4 53.00 2.70
0.10 [Note] (*).sub.1 AC . . . Activated carbon carrier (*).sub.2
AN . . . Alumina carrier (*).sub.3 SI . . . Silica carrier
Example 8
[0039] A SUS stainless steel autoclave having a capacity of 1000 ml
and equipped with a stirrer and a filter located at an outlet for a
liquid fraction was charged with 500 g (2.8 moles) of
1,2-epoxy-5,9-cyclododecad- iene and catalyst particles comprising
5% by weight of a platinum-containing catalytic component carried
on activated carbon carrier particles (platinum atom amount: 0.128
millimoles, water content: 50% by weight, made by N. E. CHEMCAT).
The inside of the autoclave was pressurized with a hydrogen gas to
a pressure of 5 MPa. Then the reaction mixture in the autoclave was
heated to a temperature of 130.degree. C., and stirred at the
above-mentioned temperature under the above-mentioned pressure for
2 hours.
[0040] After the reaction procedure was completed, the resultant
reaction liquid fraction was withdrawn from the autoclave through
the filter and subjected to the same analysis as in Example 1.
[0041] As a result, it was confirmed that the starting
1,2-epoxy-5,9-cyclododecadiene was completely consumed, the yield
of ECD was 99.2 molar %, and as by-products, CDON was produced in a
yield of 0.06 molar %, CDOL was produced in a yield of 0.70 molar
%, and CDAN was produced in a yield of 0.04 molar %.
[0042] Then, the autoclave in which the filtered catalyst is
remained was charged with 500 g (2.8 moles) of fresh
1,2-epoxy-5,9-cyclododecadiene, the reaction mixture was subjected
to a reaction procedure at a temperature of 130.degree. C. under a
hydrogen gas pressure of 5 MPa for 2 hours. After the reaction
procedure was completed, the resultant reaction liquid fraction was
withdrawn from the autoclave through the filter, and subjected to
the same analysis as in Example 1. The above-mentioned procedures
were repeated 15 times. The test results are shown in Table 2. In
the fifteenth reaction procedure, the starting
1,2-epoxy-5,9-cyclododecadiene was completely consumed, and no
intermediate product, namely epoxycyclododecene (which will be
represented by ECD' hereinafter) was found in the withdrawn
reaction liquid fraction.
[0043] The results are shown in Table 2.
2TABLE 2 Repeated reaction Cata- Yield (mol %) number lyst ECD CDON
CDOL CDAN ECD' (*).sub.4 1 5 wt % 99.2 0.06 0.7 0.04 0 Pt/AC 5 5 wt
% 99.2 0.05 0.59 0.05 0 Pt/AC 10 5 wt % 99.1 0.06 0.78 0.04 0 Pt/AC
15 5 wt % 99.0 0.07 0.89 0.05 0 Pt/AC [Note] Reaction condition:
ECD" (1,2-epoxy-5,9-cyclododecadiene: 500g, Catalyst: 5 wt %
Pt/Activated carbon (AC) 1.0 g Temperature: 130 .degree. C.
Pressure: 5 MPa Time: 120 min.
Example 9
[0044] The same repeated reaction procedures as in Example 8 were
carried out, except that the 1000 ml autoclave was replaced by a
SUS stainless steel autoclave having a capacity of 100 ml and
equipped with a stirrer and a filter; a catalyst comprising a
catalyst component in an amount of 0.5% by weight, in terms
platinum atoms, carried on alumina carrier particles was employed
in an amount of 0.2 g; 1,2-epoxy-5,9-cyclododecadi- ene was
employed in an amount of 20%; the reaction temperature was changed
to 140.degree. C.; and the repeated reaction number was 10
times.
[0045] The results are shown in Table 3.
3TABLE 3 Repeated reaction Yield (mol %) number Catalyst ECD CDON
CDOL CDAN ECD' 1 0.5 wt % 96.5 0.60 2.60 0.2 0 Pt/Alumina 5 0.5 wt
% 93.0 1.10 4.30 0.50 0 Pt/Alumina 10 0.5 wt % 92.8 1.10 4.20 0.40
0 Pt/Alumina [Note] ECD": 1,2-epoxy-5,9-cyclododecad- iene Reaction
conditions: ECD": 20 g, 0.5 wt % Pt/Alumina catalyst: 0.2 g,
Temperature: 140.degree. C., Pressure: 5 MPa, Time: 120 min.
Comparative Example 4
[0046] The same reaction procedures and analysis as in Example 8
were carried out, except that the catalyst comprised 5 wt % of
Pd-containing catalytic component carried on activated carbon
particles; the reaction temperature was 50.degree. C.; and the
reaction time was 4 hours.
[0047] The results are shown in Table 4.
[0048] In the fifth reaction procedures, a large amount (36.2 molar
%) of unreacted ECD" remained.
4TABLE 4 Repeated reaction Yield (mol %) number Catalyst ECD CDON
CDOL CDAN ECD' 1 5 wt % Pd/AC 95.9 0.64 2.62 0.06 0 5 5 wt % Pd/AC
62.0 0.35 1.38 0.05 36.2 [Note] AC . . . Activated carbon ECD":
1,2-epoxy-5,9-cyclododecadiene Reaction conditions: ECD": 500 g,
Catalyst: 5 wt % Pd/AC: 0.5 g, Temperature: 50.degree. C.,
Pressure: 5 MPa, Time: 240 min.
[0049] epoxycyclododecane compound to be produced by a catalytic
hydrogenation reaction of 1,2-epoxy-5,9-cyclododecadiene at a high
reaction rate with a high yield. The specific platinum-containing
catalyst for the method of the present invention has a long life in
practical use, and thus the method of the present invention has a
high industrial utilizability.
* * * * *