European Patent Application: Process For Producing Dialkyl Carbonate and Diol

&
(19)
(11) EP 1 760 059 A1

(12) EUROPEAN PATENT APPLICATION
published in accordance with Art. 158(3) EPC
(43) Date of publication: (51) Int Cl.:

07.03.2007 Bulletin 2007/10 C07C 27/02 (2006.01) C07C 29/128 (2006.01)
C07C 31/20 (2006.01) C07C 68/06 (2006.01)
(21) Application number: 05751558.7 C07C 69/96 (2006.01)
(22) Date of filing: 17.06.2005 (86) International application number:

PCT/JP2005/011107
(87) International publication number:

WO 2005/123638 (29.12.2005 Gazette 2005/52)
(84) Designated Contracting States: (72) Inventors:

AT BE BG CH CY CZ DE DK EE ES FI FR GB GR • TOJO, Masahiro
HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR Okayama, 7100847 (JP)
• MIYAJI, Hironori
(30) Priority: 17.06.2004 JP 2004179799 Okayama, 7100847 (JP)
(71) Applicant: Asahi Kasei Chemicals Corporation (74) Representative: Strehl, Peter
Tokyo 100-8440 (JP) Strehl Schübel-Hopf & Partner
Maximilianstrasse 54
80538 München (DE)
(54) PROCESS FOR PRODUCING DIALKYL CARBONATE AND DIOL
(57) A method for producing a dialkyl carbonate and action mixture, followed by separation of the dialkyl car-
a diol, comprising: (a) effecting a transesterification re- bonate from the dialkyl carbonate-containing liquid, and
action between a cyclic carbonate and an aliphatic mono- (c) withdrawing a diol -containing liquid from the reaction
hydric alcohol in the presence of a transesterification cat- mixture, followed by separation of the diol from the diol-
alyst, thereby obtaining a reaction mixture containing a containing liquid, wherein the cyclic carbonate contains
product dialkyl carbonate and a product diol, (b) with- a cyclic ether in an amount of from 0.1 to 3,000 ppm by
drawing a dialkyl carbonate-containing liquid from the re- weight, and the product dialkyl carbonate contains a car-
bonate ether of not more than 10,000 ppm by weight.
EP 1 760 059 A1
Printed by Jouve, 75001 PARIS (FR)

EP 1 760 059 A1
Description
Field of the Invention
5 [0001] The present invention relates to a method for producing a dialkyl carbonate and a diol. More particularly, the
present invention is concerned with a method for producing a dialkyl carbonate and a diol, comprising: (a) effecting a
transesterification reaction between a cyclic carbonate and an aliphatic monohydric alcohol in the presence of a trans-
esterification catalyst, thereby obtaining a reaction mixture containing a product dialkyl carbonate and a product diol,
(b) withdrawing a dialkyl carbonate-containing liquid from the reaction mixture, followed by separation of the dialkyl
10 carbonate from the dialkyl carbonate-containing liquid, and (c) withdrawing a diol-containing liquid from the reaction
mixture, followed by separation of the diol from the diol-containing liquid, wherein the cyclic carbonate contains a cyclic
ether in an amount of from 0.1 to 3,000 ppm by weight, and the product dialkyl carbonate contains a carbonate ether in
an amount of not more than 10,000 ppm by weight. In the dialkyl carbonate produced by the method of the present
invention, the content of a carbonate ether (which is a conventionally unknown impurity) is reduced to a specific low
15 range. The dialkyl carbonate obtained by the method of the present invention can be used to produce a transesterification
aromatic carbonate. The transesterification aromatic carbonate produced can be very advantageously used to produce
a colorless, high molecular weight aromatic polycarbonate.
Background of the Invention

20
[0002] With respect to the method for producing a dialkyl carbonate and a diol by reacting a cyclic carbonate with an
aliphatic monohydric alcohol, various proposals have been made. Most of those proposals relate to the development of
catalysts for the above reaction. Examples of such catalysts include alkali metals or basic compounds containing alkali
metals (see Patent Documents 1 and 2), tertiary aliphatic amines (see Patent Document 3), thallium compounds (see
25 Patent Document 4), tin alkoxides (see Patent Document 5), alkoxides of zinc, aluminum and titanium (see Patent
Document 6), a mixture of a Lewis acid with a nitrogen -containing organic base (see Patent Document 7), phosphine
compounds (see Patent Document 8), quaternary phosphonium salts (see Patent Document 9), cyclic amidines (see
Patent Document 10), compounds of zirconium, titanium and tin (see Patent Document 11), a solid, strongly basic anion-
exchanger containing a quaternary ammonium group (see Patent Document 12), a solid catalyst selected from the group
30 consisting of a tertiary amine- or quaternary ammonium group-containing ion-exchange resin, a strongly acidic or a
weakly acidic ion-exchange resin, a silica impregnated with a silicate of an alkali metal or an alkaline earth metal, and
a zeolite exchanged with ammonium ion (Patent Document 13), and a homogeneous catalyst selected from the group
consisting of tertiary phosphine, tertiary arsine, tertiary stibine, a divalent sulfur compound and a selenium compound
(see Patent Document 14).
35 [0003] With respect to the method for conducting the above-mentioned reaction between a cyclic carbonate and a
diol, the below-mentioned four types of methods (1) to (4) have conventionally been proposed. Hereinbelow, explanation
is made with respect to such methods (1) to (4), taking as an example the production of dimethyl carbonate and ethylene
glycol by the reaction between ethylene carbonate and methanol, which is a representative example of reactions between
cyclic carbonates and diols.
40 [0004] First method (hereinafter referred to as "method (1)") is a completely batchwise method in which ethylene
carbonate, methanol and a catalyst are fed to an autoclave as a batchwise reaction vessel, and a reaction is performed
at a reaction temperature higher than the boiling point of methanol under pressure for a predetermined period of time
(see Patent Documents 1, 2 and 5 to 9).
[0005] Second method (hereinafter referred to as "method (2)") is a batchwise method, using an apparatus comprising
45 a reaction vessel provided at an upper portion thereof with a distillation column, in which ethylene carbonate, methanol
and a catalyst are fed to the reaction vessel, and a reaction is performed by heating the contents of the reaction vessel
to a predetermined temperature. In this method, in order to compensate for the methanol distilled as an azeotropic
mixture of the methanol and the produced dimethyl carbonate, the continuous or batchwise addition of supplemental
methanol to the reaction vessel is optionally conducted. However, irrespective of whether or not such an addition of
50 supplemental methanol is conducted, the reaction per se is performed only in a batch-type reaction vessel. That is, in
this method, the reaction is batchwise performed under reflux for a prolonged period of time as long as 3 to 20 odd
hours. (Patent Documents 15, 3 and 4).
[0006] Third method (hereinafter referred to as "method (3)") is a liquid flow method in which a solution of ethylene
carbonate in methanol is continuously fed to a tubular reactor to perform a reaction at a predetermined reaction tem-
55 perature in the tubular reactor, and the resultant reaction mixture in a liquid form containing the unreacted materials (i.e.,
ethylene carbonate and methanol) and the reaction products (i.e., dimethyl carbonate and ethylene glycol) is continuously
withdrawn through an outlet of the reactor. This method has conventionally been conducted in two different manners in
accordance with the two types of catalyst used. That is, one of the manners consists in passing a mixture of a solution
2
EP 1 760 059 A1
of ethylene carbonate in methanol and a solution of a homogenous catalyst in a solvent through a tubular reactor to
perform a reaction, thereby obtaining a reaction mixture, and separating the catalyst from the obtained reaction mixture
(see Patent Documents 11 and 14). The other manner consists in performing the reaction in a tubular reactor having a
heterogeneous catalyst securely placed therein (see Patent Documents 12 and 13). Since the reaction between ethylene
5 carbonate and methanol to produce dimethyl carbonate and ethylene glycol is an equilibrium reaction, the flow method
using a tubular reactor cannot achieve a higher conversion of ethylene carbonate than the conversion of ethylene
carbonate at the equilibrium state of reaction (the latter conversion depends on the composition ratio of the feedstocks
fed to the reactor and the reaction temperature). For example, in Example 1 of Patent Document 11 which is directed
to a continuous flow reaction method using a tubular reactor and wherein the flow reaction is conducted at 130 °C using
10 a feedstock mixture having a methanol/ethylene carbonate molar ratio of 4/1, the conversion of ethylene carbonate is
only 25 %. This means that large amounts of unreacted ethylene carbonate and unreacted methanol, which are contained
in the reaction mixture, need to be separated and recovered, which in turn are recycled to the reactor. Actually, in the
method disclosed in Patent Document 13, various apparatuses are used for the separation, purification, recovery and
recycling of the unreacted compounds.
15 [0007] Fourth method (hereinafter referred to as "method (4)") is a reactive distillation method in which each of ethylene
carbonate and methanol is continuously fed to a multi-stage distillation column to perform a reaction in a plurality of
stages of the distillation column in the presence of a catalyst, while continuously effecting separation between the
produced dimethyl carbonate and the produced ethylene glycol (Patent Documents 16 to 19).
[0008] Thus, the conventional methods for producing a dialkyl carbonate and a diol by reacting a cyclic carbonate
20 with an aliphatic monohydric alcohol, can be classified into the following four methods:
(1) A completely batchwise method;

(2) A batchwise method using a reaction vessel provided at an upper portion thereof with a distillation column;
(3) A liquid flow method using a tubular reactor; and
25 (4) A reactive distillation method. However, the above-mentioned conventional methods (1) to (4) have their respec-
tive problems as described below.
[0009] In the case of each of the completely batchwise method (1) and the flow method (3) using a tubular reactor,
the maximum conversion of a cyclic carbonate depends on the composition ratio of the feedstocks fed to the reactor
30 and the reaction temperature. Therefore, it is impossible to convert all of the feedstocks into the products and the
conversion of the cyclic carbonate becomes low. Further, in the batchwise method (2), for improving the conversion of
a cyclic carbonate, the produced dialkyl carbonate must be removed using a largely excess amount of an aliphatic
monohydric alcohol, and a long reaction time is needed.
[0010] In the case of the reactive distillation method (4), it is possible to perform a reaction with high conversion, as
35 compared to the conversions in methods (1), (2) and (3). However, needless to say, even in the case of method (4),
production of a dialkyl carbonate and a diol is performed by a reversible, equilibrium reaction. Accordingly, even when
it is possible to achieve a substantially 100 % conversion of a cyclic carbonate by method (4), it is impossible to prevent
a trace amount of the cyclic carbonate from remaining unreacted in a produced diol. Therefore, for obtaining a high
purity diol by method (4), in general, it is necessary to separate the cyclic carbonate from the diol by performing a
40 distillation under strictly controlled conditions. In Patent Document 20, it is attempted to solve this problem by hydrolyzing
the unreacted cyclic carbonate to convert it into a diol. Further, in Patent Document 21, it is attempted to solve this
problem by reacting the unreacted cyclic carbonate with a diol to convert it into an ether.
[0011] In addition, there have been proposed methods in which water or water having an oxygen content of not more
than 100 ppm is introduced into the process for distillation purification of a diol, to thereby obtain a high purity diol having
45 high UV transmission or low aldehyde content (see Patent Documents 22 and 23).
[0012] In the method for producing a dialkyl carbonate and a diol by reacting a cyclic carbonate with an aliphatic
monohydric alcohol, the presence of a carbonate ether described in the present invention was not known in the art. The
present inventors have for the first time found that a dialkyl carbonate obtained by the above-mentioned method contains
a carbonate ether and that when a dialkyl carbonate contains a carbonate ether in an amount exceeding a specific level,
50 the reaction using such a dialkyl carbonate as a raw material poses various problems. For example, it has become
apparent that when a transesterification aromatic carbonate is produced from such a conventional dialkyl carbonate and
phenol, the produced aromatic carbonate will contain impurities.
[0013] As can be understood from the above, no method has heretofore been proposed for producing a dialkyl car-
bonate and a diol from a cyclic carbonate and an aliphatic monohydric alcohol, wherein the produced dialkyl carbonate
55 contains a carbonate ether only in a content which is reduced to a specific low range.
[0014]
Patent Document 1: U.S. Patent No. 3,642,858
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EP 1 760 059 A1
Patent Document 2: Unexamined Japanese Patent Application Laid-Open Specification No. Sho 54-48715 (corre-
sponding to U.S. Patent No. 4,181,676)
Patent Document 3: Unexamined Japanese Patent Application Laid-Open Specification No. Sho 51-122025 (cor-
responding to U.S. Patent No. 4,062,884)
5 Patent Document 4: Unexamined Japanese Patent Application Laid-Open Specification No. Sho 54-48716 (corre-
sponding to U.S. Patent No. 4,307,032)
Patent Document 5: Unexamined Japanese Patent Application Laid-Open Specification No. Sho 54-63023
10 Patent Document 8: Unexamined Japanese Patent Application Laid-Open Specification No. Sho 55-64551
15 Patent Document 12: Unexamined Japanese Patent Application Laid-Open Specification No. Sho 63-238043
20 Patent Document 16: Unexamined Japanese Patent Application Laid-Open Specification No. Hei 4-198141
Patent Document 17: Unexamined Japanese Patent Application Laid-Open Specification No. Hei 4-230243
Patent Document 18: Unexamined Japanese Patent Application Laid-Open Specification No. Hei 5-213830 (corre-
sponding to German Patent No. 4,129,316)
Patent Document 19: Unexamined Japanese Patent Application Laid-Open Specification No. Hei 6-9507 (corre-
25 sponding to German Patent No. 4,216,121)
Patent Document 20: International Publication No. WO 97/23445
Patent Document 21: International Publication No. WO 00/51954
Patent Document 22: Unexamined Japanese Patent Application Laid-Open Specification No. 2002-308804
Patent Document 23: Unexamined Japanese Patent Application Laid-Open Specification No. 2004-131394
30
Disclosure of the Invention
Problems to Be Solved by the Invention
35 [0015] An object of the present invention is to provide a method for producing a dialkyl carbonate containing a carbonate
ether (which is a conventionally unknown impurity) only in an amount which is reduced to a specific low range, wherein
the dialkyl carbonate can be used to produce a transesterification aromatic carbonate which can be very advantageously
used to produce a colorless, high molecular weight aromatic polycarbonate.
40 Means to Solve the Problems
[0016] In this situation, for solving the above -mentioned problems, the present inventors have made extensive and
intensive studies. As a result, they have unexpectedly found that, in a method for producing a dialkyl carbonate and a
diol, comprising effecting a transesterification reaction between a cyclic carbonate and an aliphatic monohydric alcohol
45 in the presence of a transesterification catalyst, thereby producing a product dialkyl carbonate and a product diol, when
the cyclic carbonate as a raw material contains a cyclic ether, a carbonate ether is by-produced and enters the dialkyl
carbonate produced. They have also found that, by reducing the cyclic ether content of the cyclic carbonate as a raw
material, the carbonate ether content of the dialkyl carbonate produced can be reduced. Specifically, the present inventors
have found that the above-mentioned problems can be solved by a method for producing a dialkyl carbonate and a diol,
50 comprising: (a) effecting a transesterification reaction between a cyclic carbonate and an aliphatic monohydric alcohol
in the presence of a transesterification catalyst, thereby obtaining a reaction mixture containing a product dialkyl carbonate
and a product diol, (b) withdrawing a dialkyl carbonate-containing liquid from the reaction mixture, followed by separation
of the dialkyl carbonate from the dialkyl carbonate-containing liquid, and (c) withdrawing a diol-containing liquid from the
reaction mixture, followed by separation of the diol from the diol-containing liquid, wherein the cyclic carbonate contains
55 a cyclic ether in an amount of from 0.1 to 3,000 ppm by weight, and the product dialkyl carbonate contains a carbonate
ether in an amount of not more than 10,000 ppm by weight. Based on these findings, the present invention has been
completed.
[0017] The foregoing and other objects, features and advantages of the present invention will be apparent from the
4
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following detailed description taken in connection with the accompanying drawing, and the appended claims.
Effects of the Invention
5 [0018] In the dialkyl carbonate produced by the method of the present invention, the content of a carbonate ether
(which is a conventionally unknown impurity) is reduced to a specific low range. The dialkyl carbonate obtained by the
method of the present invention can be used to produce a transesterification aromatic carbonate. The transesterification
aromatic carbonate produced can be very advantageously used to produce a colorless, high molecular weight aromatic
polycarbonate.
10
Brief Description of the Drawing
[0019] [Fig. 1] A diagram showing the system which was used for practicing the Examples and Comparative Example
of the present application.
15
Description of Reference Numerals
[0020]
20 1 continuous multi-stage distillation column

3, 6 preheater
4, 18, 42, 72 top of column
7, 19, 45, 75 condenser
10, 26, 43, 73 bottom of column
25 12, 28, 50, 80 reboiler
17 low boiling point mixture separation column
22 carbon dioxide separation column
41 diol (ethylene glycol (EG)) purification column
71 DMC separation column
30 2, 2’, 5, 8, 9, 11, 13, 14, 16, 20, 21, 23, 24, 25, 27, 29, 30, 46, 47, 48, 49, 51, 52, 56, 76, 77, 78, 79, 81, 82 conduit
Best Mode for Carrying Out the Invention
[0021] According to the present invention, there is provided a method for producing a dialkyl carbonate and a diol,
35 comprising:
(a) effecting a transesterification reaction between a cyclic carbonate and an aliphatic monohydric alcohol in the
presence of a transesterification catalyst, thereby obtaining a reaction mixture containing a product dialkyl carbonate
and a product diol,
40 (b) withdrawing a dialkyl carbonate-containing liquid from the reaction mixture, followed by separation of the dialkyl
carbonate from the dialkyl carbonate-containing liquid, and
(c) withdrawing a diol-containing liquid from the reaction mixture, followed by separation of the diol from the diol-
containing liquid,
the steps (b) and (c) being performed in either order or simultaneously,
45
wherein:
the cyclic carbonate contains a cyclic ether represented by the formula (1) below in an amount of from 0.1 to 3,000
ppm by weight, and
50 the product dialkyl carbonate contains a carbonate ether represented by the formula (2) below in an amount of not
more than 10,000 ppm by weight,
[0022]
55
5
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wherein R1 represents a divalent group represented by the formula: -(CH2)m- wherein m is an integer of from 2 to 6, and
10 at least one hydrogen atom of R1 is optionally replaced by at least one substituent group selected from the group
consisting of a C1-10 alkyl group and a C6-10 aryl group, and
[0023]
R2OR1OCOOR2 (2)
15
wherein R1 is as defined above for formula (1), R2 represents a C1-12 monovalent aliphatic group, and at least one
hydrogen atom of R2 is optionally replaced by at least one substituent group selected from the group consisting of a
C1-10 alkyl group and a C6-10 aryl group.
[0024] For easier understanding of the present invention, the essential features and various preferred embodiments
20 of the present invention are enumerated below.
[0025]
1. A method for producing a dialkyl carbonate and a diol, comprising:
25 (a) effecting a transesterification reaction between a cyclic carbonate and an aliphatic monohydric alcohol in
the presence of a transesterification catalyst, thereby obtaining a reaction mixture containing a product dialkyl
carbonate and a product diol,
(b) withdrawing a dialkyl carbonate-containing liquid from the reaction mixture, followed by separation of the
dialkyl carbonate from the dialkyl carbonate-containing liquid, and
30 (c) withdrawing a diol-containing liquid from the reaction mixture, followed by separation of the diol from the
diol-containing liquid,
the steps (b) and (c) being performed in either order or simultaneously,
wherein:
35 the cyclic carbonate contains a cyclic ether represented by the formula (1) below in an amount of from 0.1
to 3,000 ppm by weight, and
the product dialkyl carbonate contains a carbonate ether represented by the formula (2) below in an amount
of not more than 10,000 ppm by weight,
40 [0026]
45
50 [0027] wherein R1 represents a divalent group represented by the formula: -(CH2)m- wherein m is an integer of from
2 to 6, and at least one hydrogen atom of R1 is optionally replaced by at least one substituent group selected from the
group consisting of a C1-10 alkyl group and an aryl group, and
[0028]
55 R2OR1OCOOR2 (2)
hydrogen atom of R2 is optionally replaced by at least one substituent group selected from the group consisting of a
6
EP 1 760 059 A1
C1-10 alkyl group and an aryl group.

[0029] 2. The method according to item 1 above, wherein the amount of the cyclic ether in the cyclic carbonate is from
3 to 1,500 ppm by weight.
[0030] 3. The method according to item 2 above, wherein the amount of the cyclic ether in the cyclic carbonate is from
5 10 to 1,000 ppm by weight.
[0031] 4. The method according to any one of items 1 to 3 above, wherein the cyclic carbonate is ethylene carbonate.
[0032] 5. The method according to any one of items 1 to 4 above, wherein the transesterification reaction is performed
in a reactive distillation column.
[0033] 6. A dialkyl carbonate produced by the method of any one of items 1 to 5 above, which contains a carbonate
10 ether represented by the formula (2) of item 1 above in an amount of from 1 to 10,000 ppm by weight.
[0034] 7. The dialkyl carbonate according to item 6 above, wherein the amount of the carbonate ether in the dialkyl
carbonate is from 3 to 5,000 ppm by weight.
[0035] 8. The dialkyl carbonate according to item 7 above, wherein the amount of the carbonate ether in the dialkyl
carbonate is from 10 to 3,000 ppm by weight.
15 [0036] Hereinbelow, the present invention will be explained in detail.
The reaction performed in the present invention is a reversible, equilibrium transesterification reaction represented by
the following reaction scheme (I), in which a dialkyl carbonate (C) and a diol (D) are produced from a cyclic carbonate
(A) and an aliphatic monohydric alcohol (B):
[0037]
20
25
30
35 [0038] wherein R1 and R2 are as defined above.

[0039] In the present invention, the reason why the carbonate ether content of the product dialkyl carbonate is reduced
to a specific low range has not yet been fully elucidated. However, it is considered that a carbonate ether is generated
in the reaction system by the reaction between a cyclic ether and an aliphatic monohydric alcohol or a carbonate and,
therefore, the amount of generated carbonate ether can be reduced by lowering the cyclic ether content of the cyclic
40 carbonate.
[0040] In the present invention, the transesterification reaction can be performed by a conventional transesterification
reactor. With respect to the transesterification reactor used in the method of the present invention, there is no particular
limitation, and there can be used any of various conventional types of reactors, such as a reactor comprising a combination
of a fixed bed reactor and a distillation column, an agitation vessel, a multi-stage agitation type reactor comprising
45 multiple agitation vessels, a multi-stage distillation column, and a combination of the above -mentioned reactors. These
reactors can be used in either a batchwise manner or a continuous manner. From the viewpoint of displacing the
equilibrium of the reaction toward the product system, a multi-stage distillation column is preferred, and a continuous
multi -stage distillation column is more preferred. With respect to the multi-stage distillation column, there is no particular
limitation as long as it is a distillation column which has two or more stages of distillation and which is capable of
50 continuous distillation. In the present invention, the term "stages" is intended to include theoretical stages (theoretical
plates). In the case of a distillation column having no substantive stages, such as a packed column, the value obtained
by dividing the packing height by the height per theoretical stage (plate) (H.E.T.P.) (height equivalent to a theoretical
plate) is considered as the number of stages.
[0041] Examples of such continuous multi-stage distillation columns include plate type columns using a tray, such as
55 a bubble-cap tray, a sieve tray, a valve tray or a counterflow tray, and packed type columns packed with various packings,
such as a Raschig ring, a Lessing ring, a Pall ring, a Berl saddle, an Interlox saddle, a Dixon packing, a McMahon
packing, a Heli pack, a Sulzer packing and Mellapak. Any column which is generally used as a continuous multi-stage
distillation column can be utilized. Further, a mixed type of plate column and packed column, which comprises both a
7
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plate portion and a portion packed with packings, can also be preferably used. When a solid catalyst which is insoluble
in the liquid phase in a distillation column is used, a packed column type distillation column, in which the solid catalyst
is used in substitution for part or all of the packings, is preferably employed. As the continuous multi-stage distillation
column to be used in the method of the present invention, the above -mentioned distillation columns can be used
5 individually or in combination. When used in combination, a plurality of distillation columns may be connected in series
or in parallel.
[0042] A cyclic carbonate used as a raw material in the method of the present invention is represented by formula (A)
in reaction scheme (I) mentioned above. Examples of cyclic carbonates include alkylene carbonates, such as ethylene
carbonate and propylene carbonate, 1,3-dioxacyclohexa-2-one, 1,3-dioxacyclohepta-2-one, and the like. Of these cyclic
10 carbonates, ethylene carbonate and propylene carbonate are preferred because of their good availability. Ethylene
carbonate is most preferred.
[0043] In the cyclic carbonate used in the present invention, the content of a cyclic ether represented by the formula
(1) above is preferably 3,000 ppm or less. The lower the cyclic ether content of the cyclic carbonate, the lower the
carbonate ether content of the dialkyl carbonate produced. However, for producing a cyclic carbonate having extremely
15 low cyclic ether content, the cyclic carbonate must be produced by a method employing a special purification method.
Therefore, in the present invention, the cyclic ether content of the cyclic carbonate is in the range of from 0.1 to 3,000
ppm, preferably from 1 to 3,000 ppm, more preferably from 3 to 1,500 ppm, most preferably from 10 to 1,000 ppm.
[0044] With respect to the cyclic ether content of a cyclic carbonate obtained in the prior art, attention is drawn to the
following. When ethylene carbonate (which is a cyclic carbonate) is produced from ethylene oxide (which is a cyclic
20 ether), it is generally known that the conversion of ethylene oxide is 99.0 %, and the selectivity for ethylene carbonate
is 99.2 % (see, e.g., U.S. Patent Nos. 4,166,773, 4,786,741 and 4,314,945). That is, in the prior art, the ethylene carbonate
(cyclic carbonate) produced inevitably contains about 5,000 ppm of ethylene oxide (cyclic ether) which remains unreacted.
Therefore, in the prior art, it is impossible to obtain the cyclic carbonate used in the method of the present invention, the
cyclic carbonate having the cyclic ether content reduced to the above-mentioned specific range (i.e., 0.1 to 3,000 ppm).
25 [0045] In the present invention, when ethylene carbonate is used as a cyclic carbonate, the ethylene carbonate can
be produced by reacting ethylene oxide (which is a cyclic ether) with carbon dioxide. As an example of a method for
producing ethylene carbonate which has the cyclic ether content reduced to the above-mentioned specific range, there
can be mentioned a method in which ethylene carbonate is produced by reacting ethylene oxide with carbon dioxide,
wherein the ethylene oxide content of the ethylene carbonate produced is reduced by any of the following methods (α)
30 to (δ): (α) a method in which a so-called finisher (which is a small reactor) is additionally provided in the production plant
for ethylene carbonate, and ethylene oxide is reacted with carbon dioxide at a conversion as high as 99.5 % or more
while maintaining the selectivity for ethylene carbonate at 99.0 % or more; (β) a method in which, immediately after a
reaction mixture containing ethylene carbonate is taken out from the reactor, a portion of the reaction mixture is distilled
off to the outside of the reaction system simultaneously with evaporation-off of carbon dioxide gas; (γ) a method in which,
35 before performing the purification of a reaction mixture containing ethylene carbonate, unreacted ethylene oxide is
distilled off from the reaction mixture by using a flash tank or the like; and (δ) a method in which a portion of a column
top composition (containing unreacted ethylene oxide) obtained at the top of a distillation column for performing the
purification of ethylene carbonate is taken out of the reaction system. The above-mentioned methods (α) to (δ) may be
used individually; however, from the viewpoint of ease in reducing the cyclic ether content of a cyclic carbonate, it is
40 preferred to use the above-mentioned methods (α) to (δ) in combination.
[0046] Specific examples of cyclic ethers include ethylene oxide, propylene oxide, oxacyclobutane and oxacyclopen-
tane.
[0047] An aliphatic monohydric alcohol used as another raw material in the method of the present invention is a
compound which is represented by formula (B) in reaction scheme (I) mentioned above and has a boiling point lower
45 than that of the diol. The type of an aliphatic monohydric alcohol which can be used in the method of the present invention
varies depending on the type of the cyclic carbonate used. Examples of aliphatic monohydric alcohols include methanol,
ethanol, propanol (isomers), allyl alcohol, butanol (isomers), 3-butene-1-ol, amyl alcohol (isomers), hexyl alcohol (iso-
mers), heptyl alcohol (isomers), octyl alcohol (isomers), nonyl alcohol (isomers), decyl alcohol (isomers), undecyl alcohol
(isomers), dodecyl alcohol (isomers), cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, methylcyclopentanol
50 (isomers), ethylcyclopentanol (isomers), methylcyclohexanol (isomers), ethylcyclohexanol (isomers), dimethylcyclohex-
anol (isomers), diethylcyclohexanol (isomers), phenylcyclohexanol (isomers), benzyl alcohol, phenethyl alcohol (iso-
mers), phenylpropanol (isomers) and the like. The above-mentioned aliphatic monohydric alcohol may be substituted
with at least one substituent, such as a halogen atom, a lower alkoxy group, a cyano group, an alkoxycarbonyl group,
an aryloxycarbonyl group, an acyloxy group or a nitro group.
55 [0048] Of these aliphatic monohydric alcohols, an alcohol having 1 to 6 carbon atoms is preferred. More preferred are
monohydric alcohols having 1 to 4 carbon atoms, i.e., methanol, ethanol, propanol (isomers) and butanol (isomers).
When ethylene carbonate or propylene carbonate is used as a cyclic carbonate, methanol and ethanol are preferred,
and especially preferred is methanol.
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[0049] In the method of the present invention, the transesterification reaction is performed in the presence of a trans-
esterification catalyst. The method for causing a transesterification catalyst to be present in the reactor is not particularly
limited. For example, a homogeneous catalyst which is soluble in the reaction system under the reaction conditions can
be caused to be present in the transesterification reactor by continuously feeding the homogeneous catalyst to the
5 transesterification reactor. Alternatively, a heterogeneous catalyst (solid catalyst) which is insoluble in the reaction system
under the reaction conditions, can be caused to be present in the transesterification reactor by packing the solid catalyst
in the transesterification reactor. The above-mentioned homogeneous and heterogeneous catalysts can be used in
combination.
[0050] When a homogeneous catalyst is continuously fed to the transesterification reactor, it may be fed to the reactor
10 together with a feedstock cyclic carbonate and/or a feedstock aliphatic monohydric alcohol. Alternatively, the homoge-
neous catalyst may be fed to the reactor at a position different from that at which the feedstock is fed. Further, when a
multi-stage distillation column is used as a transesterification reactor, the homogeneous catalyst can be fed to the
distillation column at any position as long as the position is at least one theoretical stage (plate) above the column bottom.
[0051] However, since the region where the reaction actually takes place in the continuous multi-stage distillation
15 column is generally below the position at which the homogeneous catalyst is fed, it is preferred that the homogeneous
catalyst is fed to the distillation column at a position between the top of the column and the position at which the feedstock
is fed.
[0052] When a heterogeneous solid catalyst is used as a catalyst, the catalyst can be packed in a desired amount at
a desired position of the reactor. When a multi-stage distillation column is used as a transesterification reactor, the
20 catalyst layer present in the column has a height which corresponds to at least one theoretical stage (plate), preferably
two or more theoretical stages (plates). A catalyst which can serve as a packing for the multi-stage distillation column
can also be used.
[0053] As a transesterification catalyst used in the present invention, various types of known catalysts can be used.
Examples of such catalysts include alkali metals or alkaline earth metals, such as lithium, sodium, potassium, rubidium,
25 cesium, magnesium, calcium, strontium and barium; basic compounds, such as hydrides, hydroxides, alkoxides, ary-
loxides and amides of alkali metals or alkaline earth metals; basic compounds, such as carbonates and hydrogencar-
bonates of alkali metals or alkaline earth metals and alkali metal or alkaline earth metal salts of organic acids; tertiary
amines, such as triethylamine, tributylamine, trihexylamine and benzyldiethylamine; nitrogen-containing heteroaromatic
compounds, such as N-alkylpyrrole, N-alkylindole, oxazole, N-alkylimidazole, N-alkylpyrazole, oxadiazole, pyridine,
30 alkylpyridine, quinoline, alkylquinoline, isoquinoline, alkylisoquinoline, acridine, alkyl-acridine, phenanthroline, alkylphen-
anthroline, pyrimidine, alkylpyrimidine, pyradine, alkylpyradine, triazine and alkyltriazine; cyclic amidines, such as di-
azabicycloundecene (DBU) and diazabicyclononene (DBN); thallium compounds, such as thallium oxide, thallium hal-
ides, thallium hydroxide, thallium carbonate, thallium nitrate, thallium sulfate and thallium salts of organic acids; tin
compounds, such as tri-butylmethoxytin, tributylethoxytin, dibutyldimethoxytin, diethyldiethoxytin, dibutyldiethoxytin, dib-
35 utylphenoxytin, diphenylmethoxytin, dibutyltin acetate, tributyltin chloride and tin 2-ethylhexanoate; zinc compounds,
such as dimethoxyzinc, diethoxyzinc, ethylenedioxyzinc and dibutoxyzinc; aluminum compounds, such as aluminum
trimethoxide, aluminum triisopropoxide and aluminum tributoxide; titanium compounds, such as tetramethoxy-titanium,
tetraethoxytitanium, tetrabutoxytitanium, dichlorodimethoxytitanium, tetraisopropoxytitanium, titanium acetate and tita-
nium acetylacetonate; phosphorus compounds, such as trimethylphosphine, triethylphosphine, tributylphosphine, triphe-
40 nylphosphine, tributylmethylphosphonium halides, trioctylbutylphos-phonium halides and triphenylmethylphosphonium
halides; zirconium compounds, such as zirconium halides, zirconium acetylacetonate, zirconium alkoxides and zirconium
acetate; lead and lead-containing compounds, e.g., lead oxides, such as PbO, PbO2 and Pb3O4; lead sulfides, such as
PbS, Pb2S3 and PbS2; lead hydroxides, such as Pb(OH)2, Pb3O2(OH)2, Pb2[PbO2(OH)2] and Pb2O(OH)2; plumbites,
such as Na2PbO2, K2PbO2, NaHPbO2 and KHPbO2; plumbates, such as Na2PbO3, Na2H2PbO4, K2PbO3, K2[Pb(OH)6],
45 K4PbO4, Ca2PbO4 and CaPbO3; lead carbonates and basic salts thereof, such as PbCO3 and 2PbCO3·Pb(OH)2; alkox-
ylead compounds and aryloxylead compounds, such as Pb(OCH3)2, (CH3O)Pb(OPh) and Pb(OPh)2; lead salts of organic
acids, and carbonates and basic salts thereof, such as Pb(OCOCH3)2, Pb(OCOCH3)4 and Pb(OCOCH3)2 · PbO · 3H2O;
organolead compounds, such as Bu4Pb, Ph4Pb, Bu3PbCl, Ph3PbBr, Ph3Pb (or Ph6Pb2), Bu3PbOH and Ph2PbO wherein
Bu represents a butyl group and Ph represents a phenyl group; lead alloys, such as Pb-Na, Pb-Ca, Pb-Ba, Pb-Sn and
50 Pb-Sb; lead minerals, such as galena and zinc blende; hydrates of these lead compounds; ion -exchangers, such as
anion-exchange resins having -tertiary amino groups, ion-exchange resins having amide groups, ion-exchange resins
having at least one type of ion-exchange group selected from the group consisting of sulfonate, carboxylate and phosphate
groups, and strongly basic solid anion-exchangers having quaternary ammonium groups as ion-exchange groups; and
solid inorganic compounds, such as silica, silica-alumina, silica-magnesia, aluminosilicate, gallium silicate, various types
55 of zeolites, various types of metal -exchanged zeolites and ammonium-exchanged zeolites.
[0054] Among the above-mentioned solid catalysts, strongly basic anion-exchangers having quaternary ammonium
groups as anion-exchange groups are preferred. Examples of such anion-exchangers include strongly basic anion-
exchange resins having quaternary ammonium groups as anion-exchange groups, cellulose type strongly basic anion-
9
EP 1 760 059 A1
exchangers having quaternary ammonium groups as anion-exchange groups, and strongly basic anion-exchangers
carried on an inorganic carrier which have quaternary ammonium groups as anion-exchange groups.
[0055] Of these strongly basic anion-exchange resins having quaternary ammonium groups as ion-exchange groups,
styrene type strongly basic anion-exchange resins and the like are preferred. A styrene type strongly basic anion-
5 exchange resin is comprised of a styrene/divinyl-benzene copolymer as a base resin, and quaternary ammonium groups
(type I or type II) as anion-exchange groups, examples of which are diagrammatically represented by the following
formulae (II).
[0056]
10
15
20
25
30
35
40
45 [0057] In above formulae (II), X represents an anion. Generally, X is at least one type of anion selected from the group
consisting of F-, Cl-, Br-, I-, HCO3-, CO32-, CH3CO2-, HCO2-, IO3-, BrO3- and ClO3-. It is preferred that X is selected from
the group consisting of Cl-, Br-, HCO3- and CO32-. With respect to the structure of the base resin of the anion-exchange
resin, either a gel type or a macroreticular type (MR type) can be used. However, because of the high resistance to
organic solvents, the MR type is preferred.
50 [0058] Examples of cellulose type strongly basic anion -exchangers having quaternary ammonium groups as ion
-exchange groups include cellulose type strongly basic anion-exchangers having ion-exchange groups of the structure
represented by the formula: -OCH2CH2NR3X, which exchangers are obtained by trialkylaminoethylation of a part or all
of the hydroxyl groups of cellulose. In the above formula, R represents an alkyl group, for example, a methyl group, an
ethyl group, a propyl group, a butyl group, preferably a methyl group or an ethyl group; and X is as defined above.
55 [0059] The inorganic carrier-carried strongly basic anion-exchanger usable in the present invention, which has qua-
ternary ammonium groups as ion-exchange groups, is an anion-exchanger having quaternary ammonium groups rep-
resented by the formula -O(CH2)nNR3X wherein R and X are as defined above and n is usually an integer of from 1 to
6, preferably 2, which anion-exchanger can be prepared by the modification of a part or all of the hydroxyl groups on
10
EP 1 760 059 A1
the surface of the inorganic carrier. Examples of inorganic carriers include silica, alumina, silica-alumina, titania and
zeolite. Of these, silica, alumina and silica-alumina are preferred. Silica is most preferred.
[0060] There is no limitation with respect to the method for the modification of hydroxyl groups on the surface of the
inorganic carrier. For example, such a strongly basic anion-exchanger carried on an inorganic carrier can be obtained
5 by subjecting an inorganic carrier and an aminoalcohol represented by the formula HO(CH2)nNR2 to a dehydration
reaction between them in the presence of a basic catalyst to thereby effect aminoalkoxylation, followed by the reaction
of the resultant aminoalkoxylated inorganic carrier with an alkyl halide represented by the formula RX’, wherein X’
represents a halogen atom, preferably Cl, Br or I, to thereby convert the aminoalkoxy group into a -0(CH2)nNR3X’ group.
The -O(CH2)nNR3X’ group is further converted to a -O(CH2),NR3X group having the desired anion X by an anion exchange
10 reaction. When n is 2, an inorganic carrier is treated with N,N-dialkylaziridine so that the hydroxyl groups on the inorganic
carrier are N,N-dialkylaminoethoxylated to obtain a -OCH2CH2NR2 group, which is then converted to a -O(CH2)nNR3X
group by the above-mentioned method.
[0061] Commercially available solid, strongly basic anion-exchangers having quaternary ammonium groups as ion-
exchange groups can be used in the present invention. When a commercially available solid, strongly basic anion-
15 exchanger is used, it can be treated for anion-exchange with a desired anion species before it is used as a transester-
ification catalyst.
[0062] A solid catalyst comprised of a macroreticular or gel type organic polymer or an inorganic carrier, each having
bonded thereto a heterocyclic group containing at least one nitrogen atom, is preferably used as a transesterification
catalyst. Further, the above -mentioned solid catalyst can be treated for quater-narizing a part or all of the nitrogen-
20 containing heterocyclic groups before it is used.
[0063] The amount of the transesterification catalyst to be used in the present invention varies depending on the type
thereof. The homogeneous catalyst, which is soluble in the reaction system under the reaction conditions, is fed con-
tinuously in an amount of from 0.0001 to 50 % by weight, based on the total weight of the raw material cyclic carbonate
and the raw material aliphatic monohydric alcohol. When the solid catalyst is used, it is used generally in an amount of
25 from 10 to 95 % by volume, preferably from 50 to 90 % by volume, based on the internal volume of the reactor. When
the solid catalyst is packed in a distillation column, it is packed preferably in an amount of from 0.01 to 75 % by volume,
based on the internal volume of the empty distillation column.
[0064] When a multi-stage distillation column is used as a transesterification reactor, there is no particular restriction
with respect to the method for continuously feeding a cyclic carbonate and an aliphatic monohydric alcohol to the
30 continuous multi-stage distillation column. Any feeding method can be used as long as the feedstocks can be contacted
with the catalyst in a region of the distillation column which corresponds to at least one stage, preferably at least two
stages. That is, the cyclic carbonate and the aliphatic monohydric alcohol can be continuously fed to one or more stages
of the continuous multi-stage distillation column through a desired number of feeding pipes at one or more desired
locations as long as the above requirement is satisfied. The cyclic carbonate and the monohydric alcohol may be fed
35 either to the same stage of the distillation column or to separate stages individually.
[0065] The feedstocks are continuously fed in a liquid form, a gaseous form or a gas-liquid mixture form. In addition
to the feeding of the feedstocks to the continuous multi-stage distillation column as described above, additional feedstocks
can be fed in a gaseous form to the lower portion of the distillation column intermittently or continuously. Also preferred
is a method wherein the cyclic carbonate is continuously fed in a liquid form or a gas-liquid mixture form to a stage at a
40 level higher than the stage where the catalyst is present, while the aliphatic monohydric alcohol is continuously fed to
the lower portion of the distillation column in a gaseous form or a gas-liquid mixture form, or in a gaseous form and in
a liquid form individually. In this case, some of the aliphatic monohydric alcohol may be contained in the cyclic carbonate.
[0066] In the present invention, a small amount of a diol as a desired product may be contained in the raw materials.
Further, the aliphatic monohydric alcohol may contain a concomitant dialkyl carbonate. When the aliphatic monohydric
45 alcohol contains a concomitant dialkyl carbonate, the amount of the concomitant dialkyl carbonate in the aliphatic mono-
hydric alcohol is generally in the range of from 0 to 40 % by weight, preferably from 0.1 to 30 % by weight, more preferably
from 1 to 20 % by weight, based on the total weight of the aliphatic monohydric alcohol and the concomitant dialkyl
carbonate.
[0067] The ratio of the aliphatic monohydric alcohol to the cyclic carbonate to be fed to the transesterification reactor
50 may vary depending on the type and quantity of the transesterification catalyst and the reaction conditions, but, in general,
the molar ratio of the aliphatic monohydric alcohol to the cyclic carbonate may be in the range of from 0.01 to 1,000. For
increasing the conversion of the cyclic carbonate, it is preferred to feed the aliphatic monohydric alcohol in an excess
amount which is 2 times or more by mole the mole of the cyclic carbonate. However, too high a concentration of the
aliphatic monohydric alcohol is undesirable because the size of the reaction equipment needs to be large. Therefore, it
55 is especially preferred to use the aliphatic monohydric alcohol in an amount which is 2 to 20 times by mole the mole of
the cyclic carbonate.
[0068] When carbon dioxide is present in a high concentration in the transesterification reaction system of the method
of the present invention, the reaction rate becomes low. Therefore, the CO2 concentration of the reaction system is
11
EP 1 760 059 A1
generally not higher than 500 ppm by weight, preferably not higher than 200 ppm by weight, more preferably not higher
than 100 ppm by weight.
[0069] Also when water is present in a high concentration in the transesterification reaction system of the method of
the present invention, hydrolysis of a cyclic carbonate takes place simultaneously with the transesterification, resulting
5 in a decrease in the selectivity for dialkyl carbonate. Therefore, the water concentration of the reaction system is generally
not higher than 200 ppm by weight, preferably not higher than 100 ppm by weight.
[0070] In the method of the present invention, when it is attempted to render the conversion of the cyclic carbonate
close to 100 %, the reaction time needs to be prolonged, and the aliphatic monohydric alcohol needs to be used in large
excess. On the other hand, when the conversion of the cyclic carbonate is too low, the size of the apparatus used for
10 separation removal of the unreacted cyclic carbonate needs to be large. Therefore, the conversion of the cyclic carbonate
is generally in the range of from 95 to 99.999 %, preferably from 98 to 99.99 %, more preferably from 99 to 99.99 %.
[0071] In the present invention, the dialkyl carbonate which is one of the products of the present invention is withdrawn
from the transesterification reactor. In general, the dialkyl carbonate is withdrawn from the upper portion of the transes-
terification reactor as a low boiling point mixture in a gaseous form. The low boiling point mixture withdrawn from the
15 upper portion of the reactor may be the dialkyl carbonate alone or a mixture of the dialkyl carbonate and the aliphatic
monohydric alcohol. Further, the withdrawn gaseous mixture may also contain a high boiling point product in a small
amount.
[0072] When a multi-stage distillation column is used as a transesterification reactor, a withdrawal port of the continuous
multi-stage distillation column for withdrawing the gaseous low boiling point mixture containing the dialkyl carbonate is
20 preferably provided at a position between the position from which the feedstocks are fed and the top of the distillation
column, or in the top of the distillation column. It is more preferred to provide the withdrawal port for the low boiling point
mixture in the top of the distillation column. A part of the low boiling point mixture withdrawn from the withdrawal port
may be returned to the upper portion of the distillation column to thereby effect the so-called reflux operation. When the
reflux ratio is increased by conducting this reflux operation, the distillation efficiency of a low boiling product into a vapor
25 phase is increased, thereby advantageously increasing the concentration of a low boiling point product in the withdrawn
gaseous component. However, too much of an increase in the reflux ratio disadvantageously leads to an increase in
the thermal energy required. Thus, the reflux ratio is generally chosen in the range of from 0 to 10, preferably from 0 to
5, more preferably from 0 to 3.
[0073] By continuously feeding the low boiling point mixture withdrawn from the upper portion of the transesterification
30 reactor, containing the dialkyl carbonate, to a dialkyl carbonate separation apparatus and continuously recovering the
dialkyl carbonate from the separation apparatus, the product dialkyl carbonate can be obtained. Examples of such dialkyl
carbonate separation apparatuses include a distillation type separation apparatus, an extractive distillation type sepa-
ration apparatus, a liquid-liquid extraction type separation apparatus, a crystallization type separation apparatus, an
adsorption type separation apparatus and a membrane type separation apparatus. A combination of a plurality of different
35 or identical separation apparatuses may be used. Among these separation apparatuses, a distillation type separation
apparatus is especially preferred.
[0074] When the low boiling point mixture (containing the dialkyl carbonate and the unreacted aliphatic monohydric
alcohol) withdrawn from the upper portion of the multi-stage distillation column is subjected to separation by means of
a distillation type separation apparatus, the low boiling point mixture can be separated into various components, such
40 as the dialkyl carbonate and the unreacted aliphatic monohydric alcohol, wherein some of the separated components
are obtained in the form of one or more column top fractions containing a single component or a plurality of components
and some of the separated components are obtained in the form of a column bottom liquid. As the above-mentioned
column top fraction, an azeotropic mixture may be obtained depending on the types of feedstocks. After the components
in the low boiling point mixture withdrawn from the upper portion of the multi-stage distillation column are separated by
45 means of a distillation type separation apparatus, one or more fractions containing the unreacted aliphatic monohydric
alcohol and/or a column bottom liquid containing the unreacted aliphatic monohydric alcohol is then fed to the transes-
terification reactor.
[0075] As the distillation type separation apparatus, a single continuous multi-stage distillation column or a plurality
of continuous multi-stage distillation columns can be used, wherein each continuous multi-stage distillation column may
50 be of the same type as used as the transesterification reactor. Explained hereinbelow is a mode of the method of the
present invention in which an aliphatic monohydric alcohol and a dialkyl carbonate form a minimum boiling point azeotropic
mixture, and wherein dimethyl carbonate is produced by using methanol as the aliphatic monohydric alcohol. A low
boiling point mixture (containing methanol and dimethyl carbonate) withdrawn from the upper portion of the transester-
ification reactor is continuously fed to a dimethyl carbonate separation column. A low boiling point mixture containing a
55 minimum boiling point azeotropic mixture of methanol and dimethyl carbonate is continuously withdrawn from an upper
portion of the dimethyl carbonate separation column, while continuously withdrawing dimethyl carbonate from a lower
portion of the dimethyl carbonate separation column, thereby obtaining dimethyl carbonate.
[0076] As the dimethyl carbonate separation column, a single continuous multi-stage distillation column or a plurality
12
EP 1 760 059 A1
of continuous multi-stage distillation columns can be used, wherein each continuous multi-stage distillation column may
be of the same type as used as the transesterification reactor. The dimethyl carbonate separation column is generally
operated under reduced pressure, atmospheric pressure or superatmospheric pressure, specifically in the range of from
0.5 105 to 50 105 Pa (0.51 to 51 kg/cm2) in terms of the absolute pressure.
5 [0077] The composition of methanol/dimethyl carbonate minimum boiling point azeotropic mixture may be varied
depending on the operating pressure of the dimethyl carbonate separation column. Therefore, the operating pressure
of the dimethyl carbonate separation column is chosen so that the dimethyl carbonate is obtained from the lower portion
of the dimethyl carbonate separation column. Specifically, an operating pressure higher than an operating pressure
corresponding to the methanol/dimethyl carbonate ratio of the low boiling point mixture withdrawn from the upper portion
10 of the transesterification reactor is chosen for the dimethyl carbonate separation column.
[0078] The dialkyl carbonate obtained by the method of the present invention contains a carbonate ether represented
by the above-mentioned formula (2). The lower the cyclic ether content of the cyclic carbonate, the lower the carbonate
ether content of the dialkyl carbonate produced. However, for producing a cyclic carbonate having extremely low cyclic
ether content, the cyclic carbonate must be produced by a complicated method which is not practical for commercial
15 production. Therefore, in the present invention, the cyclic ether content of the dialkyl carbonate produced is not more
than 10,000 ppm, preferably in the range of from 1 to 10,000 ppm, more preferably from 3 to 5,000 ppm, still more
preferably from 10 to 3,000 ppm.
[0079] The low boiling point mixture (containing a minimum boiling point azeotropic mixture of methanol and dimethyl
carbonate) withdrawn from the upper portion of the above-mentioned dimethyl carbonate separation column may be fed
20 to the transesterification reactor as a feedstock usable in the present invention.
[0080] In the method of the present invention, the upper portion of the continuous multi-stage distillation column means
a portion between the top of the distillation column and a position at approximately half the height of the distillation
column, and the upper portion includes the top of the column. The lower portion of the continuous multi-stage distillation
column means a portion between the bottom of the distillation column and a position at approximately half the height of
25 the distillation column, and the lower portion includes the bottom of the column.
[0081] Further, in the method of the present invention, the diol produced in the transesterification reactor is obtained
as the high boiling point mixture withdrawn in a liquid form from the lower portion of the transesterification reactor. The
high boiling point mixture contains the produced diol and the unreacted cyclic carbonate, and may also contain a part
of the unreacted aliphatic monohydric alcohol or both a part of the unreacted aliphatic monohydric alcohol and a part of
30 the produced dialkyl carbonate.
[0082] The withdrawal port for withdrawing the high boiling point mixture (containing the produced diol) in the liquid
form from the transesterification reactor is positioned at a lower portion of the reactor, preferably at the bottom of the
reactor. A part of the withdrawn liquid mixture may be recycled to the lower portion of the transesterification reactor in
a gaseous form or a gas-liquid mixture form by heating by means of a reboiler.
35 [0083] When a multi-stage distillation column is used as a transesterification reactor, the rate at which a liquid flows
down inside the continuous multi-stage distillation column and the rate at which a vapor ascends inside the distillation
column may be varied depending on the type of the distillation column, and on the type of the packing in the case of a
packed column. However, the distillation column is generally operated so that no flooding or weeping occurs.
[0084] In the method of the present invention, the average residence time of the liquid phase in the transesterification
40 reactor depends on the reaction conditions, and the type and inner structure (for example, the types of the plate and
packing) of the transesterification reactor, but is generally in the range of from 0.001 to 50 hours, preferably from 0.01
to 10 hours, more preferably from 0.05 to 5 hours.
[0085] The reaction temperature varies depending on the types of the raw materials and the reaction pressure, but is
generally chosen in the range of from -20 to 350 °C, preferably from 0 to 200 °C. The reaction pressure in the transes-
45 terification reactor can be selected from reduced pressure, atmospheric pressure and superatomospheric pressure. The
reaction pressure is generally in the range of from 1 Pa to 2 106 Pa, preferably from 1 103 Pa to 1 106 Pa, more
preferably from 1 104 Pa to 5 105 Pa, in terms of the absolute pressure.
[0086] It is also possible to supply a part of the high boiling point mixture withdrawn in a liquid form from the lower
portion of the transesterification reactor to the transesterification reactor, so that a part of the unreacted cyclic carbonate
50 and/or a part of the unreacted aliphatic monohydric alcohol can be recycled to the transesterification reactor.
[0087] When the high boiling point mixture (containing the produced diol) withdrawn from the lower portion of the
transesterification reactor is subjected to separation in the diol purification step, the high boiling point mixture can be
separated into various components. In general, (i) when the high boiling point mixture contains low boiling point com-
ponents (such as an aliphatic alcohol used as a raw material), it is preferred that, before the diol purification step, an
55 aliphatic alcohol and the like are separated from the high boiling point mixture by distillation or the like and, then, the
separated aliphatic alcohol and the like are recycled to the transesterification reactor, and (ii) it is also preferred that,
before the diol purification step, the unreacted cyclic carbonate contained in the high boiling point mixture is separated
therefrom and, then, the remaining part of high boiling point mixture is introduced into the diol purification step. As
13
EP 1 760 059 A1
methods for separating unreacted cyclic carbonate from the high boiling point mixture, there can be mentioned (ii-1)
separation by distillation, (ii-2) hydrolysis to convert unreacted cyclic carbonate to a diol, and (ii-3) elimination of unreacted
cyclic carbonate by the etherification of the cyclic carbonate with a diol. The etherification is especially preferred in the
present invention.
5 [0088] Specifically, as preferred examples of manners in which the high boiling point mixture withdrawn from the
transesterification reactor is treated before subjected to a step for the purification of diol, the following two modes can
be mentioned.
[0089] 1. A mode in which the high boiling point mixture (in the liquid form) withdrawn from the lower portion of the
transesterification reactor contains the low boiling point mixture (including a part of the unreacted aliphatic monohydric
10 alcohol and dialkyl carbonate), and wherein the high boiling point mixture is continuously introduced, prior to the feeding
thereof to the continuous etherification reactor, to a low boiling point mixture separation column which is comprised of
a continuous multi-stage distillation column, and wherein a low boiling point mixture containing the part of the unreacted
aliphatic monohydric alcohol and dialkyl carbonate which is contained in the high boiling point mixture is continuously
withdrawn from an upper portion of the low boiling point mixture separation column, while continuously withdrawing a
15 high boiling point mixture containing the diol and the unreacted cyclic carbonate from the low boiling point mixture
separation column through one or more side-cut withdrawal ports provided in a side wall of the column at one or more
positions thereof corresponding to one or more stages selected from the group consisting of intermediate stages and a
lowermost stage of the low boiling point mixture separation column,
wherein the low boiling point mixture withdrawn from the upper portion of the low boiling point mixture separation column
20 is continuously recycled to the transesterification reactor, while continuously feeding the high boiling point mixture with-
drawn through the side-cut withdrawal port of the low boiling point mixture separation column to the diol separation
apparatus.
[0090] As the low boiling point mixture separation column, a continuous multi-stage distillation column can be used,
and the continuous multi-stage distillation column may be of the same type as used as the transesterification reactor.
25 [0091] 2. A mode in which the high boiling point mixture withdrawn from the lower portion of the transesterification
reactor contains a part of the unreacted aliphatic monohydric alcohol and dialkyl carbonate, and wherein the high boiling
point mixture is continuously introduced, prior to the feeding thereof to the etherification reactor, to a low boiling point
mixture separation column which is comprised of a continuous multi- stage distillation column, and wherein a low boiling
point mixture containing the part of the unreacted aliphatic monohydric alcohol and dialkyl carbonate which is contained
30 in the high boiling point mixture is continuously withdrawn from an upper portion of the low boiling point mixture separation
column, while continuously withdrawing a high boiling point mixture containing the diol and the unreacted cyclic carbonate
from a lower portion of the low boiling point mixture separation column, followed by the etherification of the cyclic
carbonate in the withdrawn high boiling point mixture at the bottom portion of the low boiling point mixture separation
column,
35 wherein the low boiling point mixture withdrawn from the upper portion of the low boiling point mixture separation column
is continuously recycled to the transesterification reactor, while continuously feeding the high boiling point mixture con-
taining the diol and the ether to the diol separation apparatus.
[0092] The above-mentioned etherification can be performed in accordance with the etherification method described
in Patent Document 21. Specifically, the high boiling point mixture containing the produced diol and the unreacted cyclic
40 carbonate is fed to an etherification reactor, to thereby effect an etherification reaction between the unreacted cyclic
carbonate and a part of the produced diol and produce a chain ether represented by the following formula:
HO(R1O)nH
45 wherein R1 is as defined for formula (1) above.

[0093] The reaction conditions for the etherification reaction in the etherification reactor may be varied depending on
the presence or absence of an etherification catalyst. When an etherification catalyst is used, the etherification reaction
conditions may be varied depending on the type and amount of the etherification catalyst. However, in general, the
reaction temperature is from 50 to 350 °C, preferably from 80 to 300 °C, more preferably from 100 to 250 °C. The reaction
50 time may be varied depending on the presence or absence of an etherification catalyst. When an etherification catalyst
is used, the reaction time may be varied depending on the type and amount of the etherification catalyst and the reaction
temperature. However, in general, the reaction time is from 0.001 to 50 hours, preferably from 0.01 to 10 hours, more
preferably from 0.02 to 5 hours, in terms of the average residence time. The reaction pressure may be varied depending
on the reaction temperature. However, in general, the reaction pressure is from 1 103 to 2 107 Pa, preferably from
55 1 104 to 1 107 Pa, in terms of the absolute pressure.
[0094] The conversion of the cyclic carbonate in the etherification reaction is generally from 90 to 100 %, preferably
from 95 to 100 %, more preferably from 98 to 100 %.
[0095] When carbon dioxide enters the transesterification reactor, the transesterification reaction is adversely affected,
14
EP 1 760 059 A1
so that the reaction rate becomes low. Therefore, when the etherification reaction mixture withdrawn from the etherification
reactor contains carbon dioxide, it is preferred that the carbon dioxide is separated from the etherification reaction mixture
by means of a carbon dioxide separation apparatus.
[0096] In addition, there can be used the distillation separation method described in Patent Documents 22 and 23. In
5 this method, water is fed to the distillation separation apparatus in which a reaction mixture containing diol is subjected
to distillation separation.
[0097] In the method of the present invention, it is not necessary to use a solvent. However, for the purposes of, e.g.,
(1) facilitating the reaction operation and (2) separating a dialkyl carbonate and a diol efficiently by performing azeotropic
distillation or extractive distillation, an appropriate inert solvent may be used as a reaction solvent. Examples of inert
10 solvents include an ether, an aliphatic hydrocarbon, an aromatic hydrocarbon, a halogenated aliphatic hydrocarbon and
a halogenated aromatic hydrocarbon.
[0098] An inert gas, such as nitrogen, helium, argon or the like, may be present in the reaction system. Further, for
the purpose of promoting the distilling -off of a generated low boiling point reaction product, the above-mentioned inert
gas or a gaseous form of an inert low boiling point organic compound may be introduced to the reaction system from a
15 lower portion of a continuous multi-stage distillation column.
Examples
[0099] Hereinbelow, the present invention will be described in more detail with reference to the following Examples
20 and Comparative Example, which should not be construed as limiting the scope of the present invention.
[0100] In the following Examples and Comparative Example, the yield (%) of ethylene glycol is determined, based on
the amount of the charged ethylene carbonate; the selectivity (%) for ethylene glycol is determined, based on the amount
of the consumed ethylene carbonate; the yield (%) of dimethyl carbonate is determined, based on the amount of the
charged ethylene carbonate; and the selectivity (%) for dimethyl carbonate is determined, based on the amount of the
25 consumed methanol. The positions of respective stages of a distillation column are represented by the ordinal numbers
for the respective stages as counted from the top stage of the distillation column.
Example 1
30 [0101] Using a production system as shown in Fig. 1, dimethyl carbonate (DMC) and ethylene glycol (EG) were
continuously produced from ethylene carbonate (EC) and methanol (MeOH). Continuous multi-stage distillation column
1 was comprised of a 60-stage Oldershaw distillation column which has an inner diameter of 5 cm. EC (containing 400
ppm of ethylene oxide) was continuously fed in a liquid form to distillation column 1 at the fifth stage thereof through
conduit 2 and preheater 3 at a flow rate of 231 g/h, and an 18 % by weight solution of potassium hydroxide (as a catalyst)
35 in ethylene glycol was also continuously fed in a liquid form to distillation column 1 at the fifth stage thereof through
conduit 2’ at a flow rate of 1.1 g/h, while continuously feeding a mixture of MeOH and DMC (MeOH/DMC weight ratio =
97/3) in a liquid form to distillation column 1 at the 30th stage thereof through conduit 5 and preheater 6 at a flow rate
of 735.0 g/h, to thereby effect a transesterification reaction. Continuous multi-stage distillation column 1 was operated
under conditions wherein the reaction pressure and reaction temperature, each as measured at column top 4 thereof,
40 were atmospheric pressure and 63.8 °C, respectively.
[0102] A low boiling point mixture in a gaseous form distilled from column top 4 of distillation column 1 was condensed
by condenser 7. A part of the resultant condensate was refluxed to column top 4 of distillation column 1 through conduit
8 (reflux ratio: 0.4), while the remainder of the condensate (hereinbelow, the condensate is referred to simply as "column
top condensate from column 1") was fed to DMC separation column 71 at a position 80 cm below the top of column 71
45 through conduit 9 at a flow rate of 803.1 g/h, wherein column 71 was comprised of a packed column type distillation
column having an inner diameter of 2.5 cm and a packing height of 160 cm and having packed therein Dixon packings
(3 mmφ). The column top condensate from column 1 contained MeOH and DMC in concentrations of 67.9 % by weight
and 32.1 % by weight, respectively.
[0103] On the other hand, a liquid was withdrawn from column bottom 10 of distillation column 1 through conduit 11
50 (hereinbelow, the liquid is referred to simply as "bottom liquid of column 1"), and a part of the bottom liquid of column 1
was heated by reboiler 12 to provide the energy required for distillation and returned to column bottom 10 of distillation
column 1 through conduit 13, while the remainder of the bottom liquid of column 1 was withdrawn as a high boiling point
mixture in a liquid form, and fed to low boiling point mixture separation column 17 at a position 100 cm below the top of
column 17 through conduit 14 at a flow rate of 231.3 g/h, wherein column 17 was comprised of a packed column type
55 distillation column having an inner diameter of 2.5 cm and a packing height of 160 cm and having packed therein Dixon
packings (3 mmφ). The high boiling point mixture contained EG, MeOH, EC, DMC and KOH in concentrations of 70.7
% by weight, 29.1 % by weight, 0.099 % by weight, 0.04 % by weight and 0.086 % by weight, respectively. The conversion
of EC in the transesterification reaction was 99.9 %.
15
EP 1 760 059 A1
[0104] DMC separation column 71 was operated under conditions wherein the pressure of column top 72 thereof was
1.4 106 Pa and the temperature of column bottom 73 thereof was 205 °C. A low boiling point mixture in a gaseous
form distilled from column top 72 of column 71 was condensed by condenser 75. A part of the resultant condensate was
refluxed to column top 72 of column 71 through conduit 77 (reflux ratio: 2), while feeding the remainder of the condensate
5 to continuous multi-stage distillation column 1 through conduit 78 (which is connected to conduit 5), conduit 5 and
preheater 6. For stabilizing the composition of the liquid fed to continuous multi-stage distillation column 1 through conduit
5, the composition of the liquid fed to continuous multi-stage distillation column 1 through conduit 5 was gradually changed
from MeOH/DMC to only MeOH.
[0105] A liquid was withdrawn from column bottom 73 of DMC separation column 71 through conduit 79 (hereinbelow,
10 the liquid is referred to simply as "bottom liquid of column 71"), and a part of the bottom liquid of column 71 was heated
by reboiler 80 to provide the energy required for distillation and returned to column bottom 73 of distillation column 71
through conduit 81, while the remainder was withdrawn at a flow rate of 235 g/h from the production system through
conduit 82. The bottom liquid of column 71 contained 99.9 % by weight of DMC and 1,150 ppm of carbonate ether
(CH3OCH2CH2OCOOCH3).
15 [0106] Low boiling point mixture separation column 17 was operated under conditions wherein the pressure of column
top 18 thereof was atmospheric pressure and the temperature of column bottom 26 thereof was 201 °C. At the column
bottom 26 of low boiling point mixture separation column 17, an etherification reaction between EC and EG was effected,
thereby forming diethylene glycol (DEG). The residence time at column bottom 26 of low boiling point mixture separation
column 17 was 1.5 hours. A low boiling point mixture in a gaseous form distilled from column top 18 of column 17 was
20 condensed by condenser 19. A part of the resultant condensate was refluxed to column top 18 of column 17 through
conduit 20 (reflux ratio: 1), while feeding the remainder of the condensate to an upper portion of carbon dioxide separation
column 22 through conduit 21. From conduit 23 provided at the bottom of carbon dioxide separation column 22, nitrogen
gas was introduced into the condensate, thereby bubbling the condensate with the nitrogen gas. The nitrogen gas
entraining carbon dioxide was discharged from conduit 24 provided at the top of column 22. The resultant carbon dioxide-
25 free liquid obtained in column 22 was withdrawn from conduit 25 provided at a lower portion of column 22, and recycled
to continuous multi-stage distillation column 1 at the 30th stage thereof at a flow rate of 70.2 g/h.
[0107] A liquid was withdrawn from the bottom of low boiling point mixture separation column 17 (hereinbelow, the
liquid is referred to simply as "bottom liquid of column 17"). The bottom liquid of column 17 contained EG and DEG in
concentrations of 67.6 % by weight and 17.3 % by weight, respectively. The bottom liquid of column 17 was withdrawn
30 at a flow rate of 163.9 g/h through conduit 30 as an etherification reaction mixture, while the remainder of the bottom
liquid of column 17 was heated by reboiler 28 and returned to column bottom 26 of column 17 through conduit 29. The
etherification reaction mixture contained EG and DEG in concentrations of 99.7 % by weight and 0.17 % by weight,
respectively (EC was not detected).
[0108] The etherification reaction mixture was fed to EG purification column 41 at a position 90 cm below the top of
35 column 41 through conduit 30, wherein column 41 was comprised of a packed column type distillation column having
an inner diameter of 2.5 cm and a packing height of 120 cm and having packed therein Dixon packings (3 mmφ).
[0109] EG purification column 41 was operated under conditions wherein the pressure of column top 42 thereof was
4,000 Pa (30 torr) and the temperature of column bottom 43 thereof was 123.5 °C. A distillate was withdrawn in a liquid
form through conduit 56 provided at a position 50 cm below the top of column 41 at a flow rate of 160.9 g/h, to thereby
40 obtain a side-cut distillate. A mixture distilled from column top 42 of column 41 was condensed by condenser 45. A part
of the resultant condensate was refluxed to column top 42 of column 41 through conduit 47 (reflux ratio: 2), while
withdrawing the remainder of the condensate through conduit 48. A liquid was withdrawn from the bottom of EG purification
column 41 through conduit 49 (hereinbelow, the liquid is referred to simply as "bottom liquid of column 41"). The bottom
liquid of column 41 contained EG and DEG in concentrations of 65.2 % by weight and 20.3 % by weight, respectively.
45 2.8 g of the bottom liquid of column 41 was withdrawn every two hours from the production system through conduit 52,
while the remainder of the bottom liquid of column 41 was returned to column bottom 43 of column 41 through reboiler
50 and conduit 51.
[0110] From the above data, it can be seen that the yield of DMC (containing 1,150 ppm of carbonate ether) was 99.8
%, the selectivity for DMC was not lower than 99 %, and EG was obtained in a yield of 99.8 %.
50 [0111] The above-obtained DMC and phenol were subjected to a transesterification reaction, thereby obtaining diphe-
nyl carbonate (DPC). 235 g of the obtained DPC and 228 g of bisphenol A were charged into a vacuum reactor equipped
with a stirrer. The atmosphere in the vacuum reactor was purged with nitrogen gas, and the temperature was gradually
elevated from 180 °C to 220 °C while stirring. Thereafter, the vacuum reactor was hermetically closed. Then, polymer-
ization was performed while stirring at 100 rpm under a pressure of 8,000 Pa for 30 minutes and, then, under a pressure
55 of 4,000 Pa for 90 minutes. Subsequently, the temperature was elevated to 270 °C, and further polymerization was
performed under a pressure of 70 Pa for 1 hour, thereby obtaining an aromatic polycarbonate. The obtained aromatic
polycarbonate was colorless and transparent, which is good. The number average molecular weight was 10,500.
16
EP 1 760 059 A1
Comparative Example 1
[0112] Production of DMC and EG was performed in substantially the same manner as in Example 1 except that the
ethylene oxide content of EC used as a raw material was changed to 5,000 ppm. As a result, there were obtained DMC
5 (containing 15,300 ppm of carbonate ether) and EG, wherein the yield of DMC was 96.4 %, the selectivity for DMC was
95.2 %, and the yield of EG was 94.3 %. From the obtained DMC, DPC was produced in the same manner as in Example
1. From the obtained DPC, an aromatic polycarbonate was produced in the same manner as in Example 1. The obtained
aromatic polycarbonate was discolored to assume a yellow color and had a number average molecular weight of 6,300.
A comparison between the results of Example 1 and the results of this Comparative Example 1 shows that, from a cyclic
10 carbonate containing a large amount of a cyclic ether, a dialkyl carbonate containing a high concentration of a carbonate
ether is obtained, and that, from such a dialkyl carbonate containing a high concentration of a carbonate ether, it is
impossible to obtain highly reactive diphenyl carbonate necessary for producing a high molecular weight aromatic poly-
carbonate.
15 Example 2
(containing 3,400 ppm of carbonate ether) and EG, wherein the yield of DMC was 99.6 %, the selectivity for DMC was
20 not lower than 99 %, and the yield of EG was 99.6 %. From the obtained DMC, DPC was produced in the same manner
as in Example 1. From the obtained DPC, an aromatic polycarbonate was produced in the same manner as in Example
1. The obtained aromatic polycarbonate was colorless and had a number average molecular weight of 10,200.
Example 3
25
(containing 5,600 ppm of carbonate ether) and EG, wherein the yield of DMC was 99.2 %, the selectivity for DMC was
not lower than 99 %, and the yield of EG was 99.1 %. From the obtained DMC, DPC was produced in the same manner
30 as in Example 1. From the obtained DPC, an aromatic polycarbonate was produced in the same manner as in Example
1. The obtained aromatic polycarbonate was colorless and had a number average molecular weight of 9,100.
INDUSTRIAL APPLICABILITY
35 [0115] In the dialkyl carbonate produced by the method of the present invention, the content of a carbonate ether
(which is a conventionally unknown impurity) is reduced to a specific low range. The dialkyl carbonate obtained by the
method of the present invention can be used to produce a transesterification aromatic carbonate. The transesterification
aromatic carbonate produced can be very advantageously used to produce a colorless, high molecular weight aromatic
polycarbonate.
40
Claims
1. A method for producing a dialkyl carbonate and a diol, comprising:

45
(a) effecting a transesterification reaction between a cyclic carbonate and an aliphatic monohydric alcohol in
the presence of a transesterification catalyst, thereby obtaining a reaction mixture containing a product dialkyl
carbonate and a product diol,
(b) withdrawing a dialkyl carbonate-containing liquid from said reaction mixture, followed by separation of the
50 dialkyl carbonate from the dialkyl carbonate-containing liquid, and
(c) withdrawing a diol-containing liquid from said reaction mixture, followed by separation of the diol from the
diol-containing liquid,
said steps (b) and (c) being performed in either order or simultaneously,
55 wherein:
said cyclic carbonate contains a cyclic ether represented by the formula (1) below in an amount of from 0.1 to
3,000 ppm by weight, and
17
EP 1 760 059 A1
said product dialkyl carbonate contains a carbonate ether represented by the formula (2) below in an amount
of not more than 10,000 ppm by weight,
10
wherein R1 represents a divalent group represented by the formula: -(CH2)m- wherein m is an integer of from 2 to
6, and at least one hydrogen atom of R1 is optionally replaced by at least one substituent group selected from the
15 group consisting of a C1-10 alkyl group and a C6-10 aryl group, and
R2OR1OCOOR2 (2)
20 hydrogen atom of R2 is optionally replaced by at least one substituent group selected from the group consisting of
a C1-10 alkyl group and a C6-10 aryl group.
2. The method according to claim 1, wherein the amount of said cyclic ether in said cyclic carbonate is from 3 to 1,500
ppm by weight.
25
3. The method according to claim 2, wherein the amount of said cyclic ether in said cyclic carbonate is from 10 to 1,000
ppm by weight.
4. The method according to any one of claims 1 to 3, wherein said cyclic carbonate is ethylene carbonate.
30
5. The method according to any one of claims 1 to 4, wherein said transesterification reaction is performed in a reactive
distillation column.
6. A dialkyl carbonate produced by the method of any one of claims 1 to 5, which contains a carbonate ether represented
35 by the formula (2) of claim 1 in an amount of from 1 to 10,000 ppm by weight.
7. The dialkyl carbonate according to claim 6, wherein the amount of said carbonate ether in the dialkyl carbonate is
from 3 to 5,000 ppm by weight.
40 8. The dialkyl carbonate according to claim 7, wherein the amount of said carbonate ether in the dialkyl carbonate is
from 10 to 3,000 ppm by weight.
45
50
55
18
EP 1 760 059 A1
19
EP 1 760 059 A1
20
EP 1 760 059 A1
REFERENCES CITED IN THE DESCRIPTION
This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.
Patent documents cited in the description
• US 3642858 A [0014] • US 4691041 A [0014]

• JP 54048715 A [0014] • US 4734518 A [0014]
• US 4181676 A [0014] • US 3803201 A [0014]
• JP 51122025 A [0014] • JP 4198141 A [0014]
• US 4062884 A [0014] • JP 4230243 A [0014]
• JP 54048716 A [0014] • JP 5213830 A [0014]
• US 4307032 A [0014] • DE 4129316 [0014]
• JP 54063023 A [0014] • JP 6009507 A [0014]
• JP 54148726 A [0014] • DE 4216121 [0014]
• JP 55064550 A [0014] • WO 9723445 A [0014]
• JP 55064551 A [0014] • WO 0051954 A [0014]
• JP 56010144 A [0014] • JP 2002308804 A [0014]
• JP 59106436 A [0014] • JP 2004131394 A [0014]
• JP 63041432 A [0014] • US 4166773 A [0044]
• US 4661609 A [0014] • US 4786741 A [0044]
• JP 63238043 A [0014] • US 4314945 A [0044]
• JP 6431737 A [0014]
21

European Patent Application: Process For Producing Dialkyl Carbonate and Diol

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(11) EP 1 760 059 A1

(43) Date of publication: (51) Int Cl.:

(22) Date of filing: 17.06.2005 (86) International application number:

(87) International publication number:

(84) Designated Contracting States: (72) Inventors:

(54) PROCESS FOR PRODUCING DIALKYL CARBONATE AND DIOL

Printed by Jouve, 75001 PARIS (FR)

Field of the Invention

Background of the Invention

(1) A completely batchwise method;

Patent Document 1: U.S. Patent No. 3,642,858

Problems to Be Solved by the Invention

40 Means to Solve the Problems

Effects of the Invention

20 1 continuous multi-stage distillation column

Best Mode for Carrying Out the Invention

1. A method for producing a dialkyl carbonate and a diol, comprising:

C1-10 alkyl group and an aryl group.

35 [0038] wherein R1 and R2 are as defined above.

45 wherein R1 is as defined for formula (1) above.

1. A method for producing a dialkyl carbonate and a diol, comprising:

REFERENCES CITED IN THE DESCRIPTION

Patent documents cited in the description

• US 3642858 A [0014] • US 4691041 A [0014]

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