US007812189B2

(12) United States Patent (10) Patent No.: US 7,812,189 B2

Fukuoka et al. (45) Date of Patent: *Oct. 12, 2010
(54) INDUSTRIAL PROCESS FOR PRODUCTION 5,747,609 A 5/1998 Komiya et al.
OF HIGH-PURITY DIPHENYL CARBONATE 5,872,275 A 2/1999 Komiya et al.
6,093,842 A 7/2000 Oyevaar et al.
(75) Inventors: Shinsuke Fukuoka, Tokyo (JP); Hiroshi 6, 197916 B1 3/2001 Pressman et al.
Hachiya, Tokyo (JP); Kazuhiko 6,262,210 B1* 7/2001 Tojo et al. ................... 526,270
Matsuzaki, Tokyo (JP); Hironori 6,346,638 B1 2/2002 Tojo et al.
Miyaji, Tokyo (JP) 6.479,689 B1 1 1/2002 Tojo et al.
6,861,494 B2 3/2005 Debruin
(73) Assignee: Asahi Kasei Chemicals Corporation, 7,417,161 B2 * 8/2008 Woo et al. ................... 558,270
Tokyo (JP) 7.622,601 B2 * 1 1/2009 Fukuoka et al. ............. 558,270
2001, 0021786 A1 9, 2001 Bruin et al.
(*) Notice: Subject to any disclaimer, the term of this 2002/0107355 A1 8/2002 Bouwens et al.
patent is extended or adjusted under 35 2004/0236136 A1 11/2004 Schlosberg et al.
U.S.C. 154(b) by 719 days. 2004/0266974 A1 12/2004 Murthy et al.
2007/0219387 A1 9, 2007 Fukuoka et al.
This patent is Subject to a terminal dis 2007/0255069 A1 11/2007 Fukuoka et al.
claimer. 2007,0260083 A1 11/2007 Fukuoka et al.
2007,0260084 A1 11/2007 Fukuoka et al.
(21) Appl. No.: 11/660,362 2007/0260095 A1 11/2007 Fukuoka et al.
2007,0265461 A1 11/2007 Fukuoka et al.
(22) PCT Filed: Aug. 24, 2005 2007/027O604 A1 11/2007 Fukuoka et al.
2008/0051595 A1 2/2008 Fukuoka et al.
(86). PCT No.: PCT/UP2005/O15343
2008, OO64846 A1 3/2008 Fukuoka et al.
2008, 0221348 A1 9, 2008 Fukuoka et al.
S371 (c)(1), 2008/0223711 A1 9, 2008 Fukuoka et al.
(2), (4) Date: Feb. 16, 2007
(87) PCT Pub. No.: WO2006/022294
FOREIGN PATENT DOCUMENTS
PCT Pub. Date: Mar. 2, 2006 DE T36063 6, 1943
(65) Prior Publication Data EA O10066 8, 2007
EA OO9715 B1 2, 2008
US 2008/OO41712 A1 Feb. 21, 2008 EP O 461 274 A1 12, 1991
EP O530615 A2 3, 1993
(30) Foreign Application Priority Data EP O56O159 A1 9, 1993
Aug. 25, 2004 (JP) ............................. 2004-245758 EP O569812 A1 11F1993
EP O582930 A2 2, 1994
(51) Int. Cl. EP O582931 A2 2, 1994
CD7C 69/96 (2006.01) EP O722931 A1 T 1996
(52) U.S. Cl. ....................................... 558/270; 558/274
(58) Field of Classification Search ................. 558/270,
558/274 (Continued)
See application file for complete search history. Primary Examiner Rei-tsang Shiao
(56) References Cited (74) Attorney, Agent, or Firm—Birch, Stewart, Kolasch &
U.S. PATENT DOCUMENTS
Birch, LLP
4,045,464 A 8, 1977 Romano et al. (57) ABSTRACT
4,182,726 A 1, 1980 Illuminati et al.
4,252,737 A 2f1981 Krimm et al.
4.410.464 A 10/1983 Hallgren According to the present invention, there are provided a high
4,552,704 A 11, 1985 Mark boiling point material separating column A and a diphenyl
4,554,110 A 11, 1985 Mark carbonate purifying column Beach comprising a continuous
4,609,501 A 9, 1986 Mark multi-stage distillation column having specified structures,
5,210,268 A 5, 1993 Fukuoka et al. and there is provided a specific process that enables a high
5,231,212 A 7/1993 Buysch et al. purity diphenyl carbonate which is important as a raw mate
5,282,965 A 2f1994 Urairi et al. rial of a high-quality and high-performance polycarbonate to
5,284.965 A 2/1994 Buysch be produced stably for a prolonged period of time on an
5,334,742 A 8, 1994 Schon et al. industrial scale of not less than 1 ton/hr from a reaction
5,344,954 A 9, 1994 Schon et al.
5,359,118 A 10/1994 Wagner et al.
mixture containing the diphenyl carbonate using an apparatus
5,362.901 A 1 1/1994 Wagner et al. in which these two continuous multi-stage distillation col
5,426.207 A 6, 1995 Harrison et al. umns are connected together.
5,495,038 A 2/1996 Buysch et al.
5,705,673 A 1/1998 Rivetti et al. 6 Claims, 1 Drawing Sheet
 US 7,812,189 B2
Page 2

FOREIGN PATENT DOCUMENTS JP T-304713 A 11, 1995

JP 9-40616 A 2, 1997
EP O781760 A1 T 1997 JP 9-59224 A 3, 1997
EP O784O48 A1 T 1997 JP 9-59225. A 3, 1997
EP O855384 A1 T 1998 JP 9-1 10805. A 4f1997
EP O892001 A1 1, 1999 JP 9-165357 A 6, 1997
EP 1016648 A1 7, 2000 JP 9-169704 A 6, 1997
EP 1086940 A1 3f2001 JP 9-173819. A 7/1997
EP 11744.06 A1 1, 2002 JP 9-176094. A 7/1997
EP 1760 069 A1 3/2007 JP 9-194435 A 7/1997
EP 1762559 A1 3f2007 JP 9-194436. A 7/1997
EP 1762560 A1 3f2007 JP 9-194437 A 7/1997
EP 1767518 3, 2007 JP 9-255772 A 9, 1997
EP 1783. 112 A1 5/2007 JP 10-245366 A 9, 1998
EP 1787 977 A1 5/2007 JP 11-12230 A 1, 1999
EP 1792890 A1 6, 2007 JP 11-49727 A 2, 1999
EP 1795.523 A1 6, 2007 JP 11-92429 A 4f1999
IT 1255746 B 11, 1995 JP 11-228,504. A 8, 1999
JP 51-75044 6, 1976 JP 2000-191596. A T 2000
JP 51-105032 9, 1976 JP 2000-191597 A T 2000
JP 54-48732 A 4f1979 JP 2001-64234 A 3, 2001
JP 54-48733. A 4f1979 JP 2001-64235 A 3, 2001
JP 54-63O23 A 5, 1979 JP 2003-113144 A 4/2003
JP 56-25138 A 3, 1981 JP 2003-119168 A 4/2003
JP 56-123948 A 9, 1981 JP 2003-155264 A 5, 2003
JP 56-123949 A 9, 1981 JP 2003-516376 A 5, 2003
JP 57-176932 A 10, 1982 JP 2003-300936 A 10, 2003
JP 57-183745. A 11, 1982 JP 2003-342209. A 12/2003
JP 58-185536 A 10, 1983 JP 2004-131421 A 4/2004
JP 60-169444 A 9, 1985 JP 2004-323384 A 11, 2004
JP 60-169445 A 9, 1985 JP 2006-182683 A T 2006
JP 60-173016 A 9, 1985 JP 2006-199643 A 8, 2006
JP 61-172852 A 8, 1986 JP 2006-206497. A 8, 2006
JP 61-291545. A 12/1986 RU 2 041869 C1 8, 1995
JP 62-277345 A 12/1987 WO WO-91,09832 A1 7, 1991
JP 1-93560 A 4f1989 WO WO-92, 18458 A1 10, 1992
JP 1-265062 A 10, 1989 WO WO-97,11049 A1 3, 1997
JP 1-265063. A 10, 1989 WO WO-99,64382 A1 12, 1999
JP 1-265064. A 10, 1989 WO WO-99.64492 A1 12, 1999
JP 3-291257. A 12, 1991 WO WO-00, 18720 A1 4, 2000
JP 4-93.58 A 1, 1992 WO WO-OOf 51954 A1 9, 2000
JP 4-100824 A 4f1992 WO WO-01/42.187 A1 6, 2001
JP 4-198141 A 7, 1992 WO WO-02? 40439 A2 5, 2002
JP 4-211038 A 8, 1992 WO WO-O3,O16257 A1 2, 2003
JP 4-224,547 A 8, 1992 WO WOO3,066.569 8, 2003
JP 4-230242 A 8, 1992 WO WO-2005/123638 A1 12/2005
JP 4-235951 A 8, 1992 WO WO-2006/001256 A1 1/2006
E. 5. A E. WO WO-2006/022294 A1 3f2006
JP 6-9507 A 1, 1994 WO WO-2006/025424 A1 3f2006
JP 6-41022 A 2, 1994 WO WO-2006-025478 A 3, 2006
JP 6-157424. A 6, 1994 WO WO-2006/041075 A1 4, 2006
JP 6-184058 A T 1994
JP 7-101908 A 4f1995 * cited by examiner
U.S. Patent Oct. 12, 2010 US 7,812,189 B2

FG.1

FROM COLUMN
BOTTOM OF THE 11 31
SECOND REACTIVE
DISTILLATION
COLUMN

HGHBOLING POINT MATERIAL DIPHENY CARBONATE

SEPARATING COLUMNA PURIFYING COLUMNB
 US 7,812,189 B2
1. 2
INDUSTRAL PROCESS FOR PRODUCTION Laid-Open No. 51-75044 (corresponding to West German
OF HIGH-PURITY OPHENYL CARBONATE Patent Application No. 2552907, and U.S. Pat. No. 4,045,
464)), tin compounds such as organotin alkoxides and orga
TECHNICAL FIELD notin oxides (see Patent Documents 2: Japanese Patent Appli
cation Laid-Open No. 54-48733 (corresponding to West
The present invention relates to an industrial process for German Patent Application No. 2736062), Japanese Patent
the production of a high-purity diphenyl carbonate. More Application Laid-Open No. 54-63023, Japanese Patent
particularly, the present invention relates to an industrial pro Application Laid-Open No. 60-169444 (corresponding to
cess for the production of a high-purity diphenyl carbonate, U.S. Pat. No. 4,554.110), Japanese Patent Application Laid
which is useful as a raw material of a transesterification 10 Open No. 60-169445 (corresponding to U.S. Pat. No. 4,552,
method polycarbonate, by using two continuous multi-stage 704), Japanese Patent Application Laid-Open No.
distillation columns having specified structures, from a reac 62-277345, Japanese Patent Application Laid-Open No.
tion mixture containing a diphenyl carbonate obtained by 1-265063), salts and alkoxides of alkali metals and alkaline
carrying out a transesterification reaction between a dialkyl earth metals (see Patent Document 3: Japanese Patent Appli
carbonate and a phenol and/or a disproportionation reaction 15 cation Laid-Open No. 57-176932), lead compounds (see
of an alkyl phenyl carbonate and/or a transesterification reac Patent Documents 4: Japanese Patent Application Laid-Open
tion between an alkyl phenyl carbonate and a phenol. No. 57-176932, Japanese Patent Application Laid-Open No.
1-93560), complexes of metals such as copper, iron and Zir
BACKGROUND ART conium (see Patent Document 5:Japanese Patent Application
Laid-Open No. 57-183745), titanic acid esters (see Patent
A high-purity diphenyl carbonate is important as a raw Documents 6: Japanese Patent Application Laid-Open No.
material for the production of an aromatic polycarbonate, 58-185536 (corresponding to U.S. Pat. No. 4.410.464), Japa
which is the most widely used engineering plastics, without nese Patent Application Laid-Open No. 1-265062), mixtures
using toxic phosgene. As a process for producing an aromatic of a Lewis acid and protonic acid (see Patent Document 7:
carbonate, a process of reacting an aromatic monohydroxy 25 Japanese Patent Application Laid-Open No. 60-173016 (cor
compound with phosgene has been known from long ago, and responding to U.S. Pat. No. 4,609.501)), compounds of Sc,
has also been the Subject of a variety of studies in recent years. Mo, Mn, Bi, Te or the like (see Patent Documents 8: Japanese
However, this process has the problem of using phosgene, and Patent Application Laid-Open No. 1-265064), ferric acetate
in addition chlorinated impurities that are difficult to separate (see Patent Document 9: Japanese Patent Application Laid
out are present in the aromatic carbonate produced using this 30 Open No. 61-172852), and so on have been proposed.
process, and hence this aromatic carbonate cannot be used as Since the problem of the disadvantageous equilibrium can
a raw material for the production of the aromatic polycarbon not be solved merely by developing the catalyst, as the other
ate. Because such chlorinated impurities markedly inhibit the type of the proposals, attempts have been made to devise a
polymerization reaction in the transesterification method reaction system so as to shift the equilibrium toward the
which is carried out in the presence of an extremely small 35 product system as much as possible, thus improving the aro
amount of a basic catalyst; for example, even if such chlori matic carbonate yield. For example, for the reaction between
nated impurities are present in an amount of only 1 ppm, the dimethyl carbonate and phenol, there have been proposed a
polymerization hardly proceeds at all. To make the aromatic method in which methanol produced as a by-product is dis
carbonate capable of using as a raw material of a transesteri tilled off by azeotropy together with an azeotrope-forming
fication method polycarbonate, a troublesome multi-stage 40 agent (see Patent Documents 10: Japanese Patent Application
separation/purification processes such as enough washing Laid-Open No. 54-48732 (corresponding to West German
with a dilute aqueous alkaline solution and hot water, oil/ Patent Application No. 736063, and U.S. Pat. No. 4.252,
water separation, distillation and so on are thus required. 737)), and a method in which the methanol produced as a
Furthermore, the yield of aromatic carbonate decreases due to by-product is removed by being adsorbed onto a molecular
hydrolysis loss and distillation loss during this separation/ 45 sieve (see Patent Documents 11: Japanese Patent Application
purification processes. Therefore, there are many problems in Laid-Open No. 58-185536 (corresponding to U.S. Pat. No.
carrying out this method economically on an industrial scale. 410.464)). Moreover, a method has also been proposed in
On the other hand, a process for producing aromatic car which, using an apparatus in which a distillation column is
bonates through transesterification reactions between dialkyl provided on top of a reactor, an alcohol produced as a by
carbonates and aromatic monohydroxy compounds are also 50 product in the reaction is separated off from the reaction
known. However, Such transesterification reactions are all mixture, and at the same time an unreacted Starting material
equilibrium reactions. Since the equilibriums are biased that evaporates is separated off by distillation (see Patent
extremely toward the original system and the reaction rates Documents 12: examples in Japanese Patent Application
are slow, there have been many difficulties in producing the Laid-Open No. 56-123948 (corresponding to U.S. Pat. No.
aromatic carbonate industrially in large amounts using this 55 4,182.726), examples in Japanese Patent Application Laid
method. Two types of proposals have been made to improve Open No. 56-25138, examples in Japanese Patent Applica
on the above difficulties. One of these relates to development tion Laid-Open No. 60-169444 (corresponding to U.S. Pat.
of a catalyst to increase the reaction rate, and many metal No. 4,554.110), examples in Japanese Patent Application
compounds have been proposed as the catalyst for the above Laid-Open No. 60-169445 (corresponding to U.S. Pat. No.
type of the transesterification reactions. For example, Lewis 60 4.552.704), examples in Japanese Patent Application Laid
acids such as transition metalhalides and Lewis acid-forming Open No. 60-173016 (corresponding to U.S. Pat. No. 4,609,
compounds (see Patent Documents 1: Japanese Patent Appli 501), examples in Japanese Patent Application Laid-Open
cation Laid-Open No. 51-105032, Japanese Patent Applica No. 61-172852, examples in Japanese Patent Application
tion Laid-Open No. 56-123948, Japanese Patent Application Laid-Open No. 61-291545, examples in Japanese Patent
Laid-Open No. 56-123949 (corresponding to West German 65 Application Laid-Open No. 62-277345).
Patent Application No. 2528412, British Patent No. 1499530, However, these reaction systems have basically been batch
and U.S. Pat. No. 4,182,726), Japanese Patent Application system or Switchover system. Because there are limitations in
 US 7,812,189 B2
3 4
the improvement of the reaction rate through catalyst devel responding to European Patent No. 0560159, and U.S. Pat.
opment for Such transesterification reactions, and the reaction No. 5.282,965), Patent Document 20: Japanese Patent Appli
rates are still slow, and thus it has been thought that the batch cation Laid-Open No. 6A41022 (corresponding to European
system is preferable to a continuous system. Of these, a con Patent No. 0572870, and U.S. Pat. No. 5,362.901), Patent
tinuous stirring tank reactor (CSTR) system in which a dis Documents 21: Japanese Patent Application Laid-Open No.
tillation column is provided on the top of the reactor has been 6-157424 (corresponding to European Patent No. 0582931,
proposed as the continuous system, but there are problems and U.S. Pat. No. 5,334.742), Japanese Patent Application
Such as the reaction rate being slow, and a gas-liquid interface Laid-Open No. 6-184058 (corresponding to European Patent
in the reactor being Small, based on the Volume of the liquid. No.0582930, and U.S. Pat. No. 5,344,954), Patent Document
Hence it is not possible to make the reaction ratio high. 10 22: Japanese Patent Application Laid-Open No. 7-304713,
Accordingly, it is difficult to attain the object of producing the Patent Document 23': Japanese Patent Application Laid
aromatic carbonate continuously in large amounts stably for a Open No. 940616, Patent Document 24: Japanese Patent
prolonged period of time by means of the above-mentioned Application Laid-Open No. 9-59225, Patent Document 25:
methods, and many issues remain to be resolved before eco Japanese Patent Application Laid-OpenNo. 9-110805, Patent
nomical industrial implementation is possible. 15 Document 26: Japanese Patent Application Laid-Open No.
The present inventors have developed reactive distillation 9-165357, Patent Document 27: Japanese Patent Application
methods in which such a transesterification reaction is carried Laid-Open No. 9-173819, Patent Documents 28: Japanese
out in a continuous multi-stage distillation column simulta Patent Application Laid-OpenNo. 9-176094, Japanese Patent
neously with separation by distillation, and have been the first Application Laid-Open No. 2000-191596, Japanese Patent
in the world to disclose that such a reactive distillation system Application Laid-OpenNo. 2000-191597, Patent Documents
is useful for Such a transesterification reaction, for example, a 29: Japanese Patent Application Laid-Open No. 9-194436
reactive distillation method in which a dialkyl carbonate and (corresponding to European Patent No. 0785184, and U.S.
an aromatic hydroxy compound are continuously fed into the Pat. No. 5,705,673), Patent Documents 30: International Pub
multi-stage distillation column, and the reaction is carried out lication No. 00/18720 (corresponding to U.S. Pat. No. 6,093,
continuously inside the column in which a catalyst is present, 842), International Publication No. 01/042187 (correspond
while continuously withdrawing a low boiling point compo 25 ing to Published Japanese Translation of PCT Application
nent containing an alcohol produced as a by-product by dis No. 2003-516376), Patent Documents 31: Japanese Patent
tillation and continuously withdrawing a component contain Application Laid-Open No. 2001-64234, Japanese Patent
ing a produced alkyl aryl carbonate from a lower portion of Application Laid-Open No. 2001-64235, Patent Document
the column (see Patent Document 13: Japanese Patent Appli 32: International Publication No. 02/40439 (corresponding to
cation Laid-Open No. 3-291257), a reactive distillation 30 U.S. Pat. No. 6,596,894, U.S. Pat. No. 6,596,895, and U.S.
method in which an alkyl aryl carbonate is continuously fed Pat. No. 6,600,061)).
into the multi-stage distillation column, and the reaction is Among the reactive distillation systems, the present appli
carried out continuously inside the column in which a catalyst cants have further proposed, as a method that enables highly
is present, while continuously withdrawing a low boiling pure aromatic carbonates to be produced stably for a pro
point component containing a dialkyl carbonate produced as 35 longed period of time without a large amount of a catalyst
a by-product by distillation, and continuously withdrawing a being required, a method in which a high boiling point mate
component containing a produced diaryl carbonate from a rial containing a catalyst component is reacted with a nactive
lower portion of the column (see Patent document 14: Japa Substance and then separated off, and the catalyst component
nese Patent Application Laid-Open No. 4-9358), a reactive is recycled (see Patent Documents 33: International Publica
distillation method in which these reactions are carried out 40 tion No. 97/11049 (corresponding to European Patent No.
using two continuous multi-stage distillation columns, and 0855384, and U.S. Pat. No. 5,872,275)), and a method carried
hence a diaryl carbonate is produced continuously while effi out while keeping the weight ratio of a polyhydric aromatic
ciently recycling a dialkyl carbonate produced as a by-prod hydroxy compound in the reaction system to a catalyst metal
uct (see Patent document 15: Japanese Patent Application at not more than 2.0 (see Patent Documents 34: Japanese
Laid-Open No. 4-211038), and a reactive distillation method Patent Application Laid-Open No. 11-92429 (corresponding
45
in which a dialkyl carbonate and an aromatic hydroxy com to European Patent No. 1016648, and U.S. Pat. No. 6,262,
pound or the like are continuously fed into the multi-stage 210)). Furthermore, the present inventors have also proposed
distillation column, and a liquid that flows down through the a method in which 70 to 99% by weight of phenol produced
column is withdrawn from a side outlet provided at an inter as a by-product in a polymerization process is used as a
mediate stage and/or a lowermost stage of the distillation starting material, and diphenyl carbonate can be produced by
column, and is introduced into a reactor provided outside the 50 means of the reactive distillation method. This diphenyl car
distillation column so as to bring about reaction, and is then bonate can be used as the raw material for polymerization to
introduced back through a circulating inlet provided at a stage produce aromatic polycarbonates (see Patent Documents 35:
above the stage where the outlet is provided, whereby reac Japanese Patent Application Laid-Open No. 9-255772 (cor
tion is carried out in both the reactor and the distillation responding to European Patent No. 0892001, and U.S. Pat.
column (see Patent Documents 16:Japanese Patent Applica 55 No. 5,747.609)).
tion Laid-Open No. 4-224.547, Japanese Patent Application However, in all of these prior art documents in which the
Laid-Open No. 4-230242, Japanese Patent Application Laid production of the aromatic carbonates using the reactive dis
Open No. 4-235951). tillation method is proposed, there is no disclosure whatso
These reactive distillation methods proposed by the present ever of a specific process or apparatus enabling mass produc
inventors are the first to enable aromatic carbonates to be 60 tion on an industrial scale (e.g. more than 1 ton perhr), nor is
produced continuously and efficiently, and many similar there any description Suggesting Such a process or apparatus.
reactive distillation systems based on the above disclosures For example, the descriptions regarding heights (H and H:
have been proposed thereafter (see Patent Documents 17 to cm), diameters (D and D. cm), the numbers of stages (N
32: Patent Document 17: International Publication No. and N), and the feeding rates of the raw materials (Q. and Q.:
00/18720 (corresponding to U.S. Pat. No. 5,362.901), Patent 65
kg/hr) for two reactive distillation columns disclosed for pro
Document 18: Italian Patent No. 01255746, Patent Document ducing mainly diphenyl carbonate (DPC) from dimethyl car
19: Japanese Patent Application Laid-Open No. 6-9506 (cor bonate and phenol are as Summarized in the following table.
 US 7,812,189 B2

TABLE 1.
PATENT
H. D. N. Q H. D. N Q, DOCUMENT
600 25 20 66 600 25 2O 23 15
3SO 2.8 O.2 30S S-10 15 + O.6 21
PACKING
SOO S SO 0.6 400 8 50 O.6 23
1OO 4 - 14 200 4 O.8 24
3OO S 40 1.5 5 25 0.7 28
1200 20 40 86 600 25 2O 31 33
34
600 - 20 66 600 - 2O 22 35

15
In other words, the biggest continuous multi-stage distil Another is a method in which the diphenyl carbonate is
lation columns used when carrying out this reaction using the obtained as a column bottom component from a distillation
reactive distillation system are those disclosed by the present column; for example, there is:
applicants in Patent Documents 33 and 34. As can be seen IV) a method in which the reaction mixture containing the
from Table 1, the maximum values of the various conditions catalystis distilled in a distillation column, and thus separated
for the continuous multi-stage distillation columns disclosed into a high boiling point material containing most of the
for the above reaction are H=1200 cm, H=600 cm, D=20 catalyst and a low boiling point material, and then the low
cm, D=25 cm, N=N=50 (Patent Document 25), Q=86 boiling point material is distilled in a distillation column, and
kg/hr, and Q 31 kg/hr, and the total amount of diphenyl the diphenyl carbonate is obtained as a column bottom com
carbonate produced was only approximately 6.7 kg/hr, which 25 ponent (see Patent Document 31).
was not an amount produced on an industrial scale. The other is a method in which the diphenyl carbonate is
obtained as a side cut component from a distillation column;
As methods for separating the diphenyl carbonate from the for example, there are:
reaction mixture containing a diphenyl carbonate that has V) a method in which the reaction mixture containing the
been produced through transesterification reaction and the 30 catalyst is introduced into a third reactive distillation column,
like between a dialkyl carbonate and a phenol as a starting and further reaction and distillation are carried out, whereby
material as described above, and then purifying the diphenyl the diphenyl carbonate is obtained as a side cut component
carbonate, crystallization methods, distillation methods and from the reactive distillation column (see Patent Document
the like have been proposed. With regard to the distillation 21);
methods, three methods have been proposed. One is a method 35 VI) a method in which the reaction mixture containing the
in which the diphenyl carbonate is obtained as a column top catalyst is subjected to flash evaporation, and thus separated
component from a distillation column; for example, there are: into a high boiling point material containing most of the
I) a method in which the reaction mixture containing the catalyst and a low boiling point material, and then the low
catalyst is distilled as is in a batch type distillation column, boiling point material is introduced into a distillation column
and the diphenyl carbonate is obtained as the column top 40 and distillation is carried out, whereby the diphenyl carbonate
component (see example of Patent Document 10, example 2 is obtained as a side cut component from the reactive distil
of Patent Document 19); lation column (see Patent Documents 34 and 35, Patent Docu
ment 39: International Publication No. 92/18458 (corre
II) a method in which the reaction mixture containing the sponding to U.S. Pat. No. 5,426.207);
catalyst is subjected to flash evaporation, and thus separated 45 VII) a method in which the reaction mixture containing the
into a high boiling point material containing most of the catalyst is distilled in a first purifying column, and thus sepa
catalyst and a low boiling point material, and then the low rated into a high boiling point material containing most of the
boiling point material is distilled in a distillation column for catalyst and a low boiling point material, and then the low
starting material recovery, and a catalyst-containing diphenyl boiling point material is introduced into a second purifying
carbonate is obtained as a column bottom material, and then 50 column and distillation is carried out, whereby the diphenyl
this column bottom material is distilled inapurifying column, carbonate is obtained as a side cut component from the second
whereby the diphenyl carbonate is obtained as a column top purifying column (see Patent Document 40: Japanese Patent
component (see Patent Document 37: example 1 in Japanese Application Laid-open No. 11-49727); and
Patent Application Laid-open No. 4-100824, Patent Docu VIII) a method in which diphenyl carbonate containing
ment 38: Japanese Patent Application Laid-open No. 55 phenyl salicylate is introduced into a distillation column hav
9-169704); and ing the number of theoretical stages being from 5 to 15, and
III) a method in which the reaction mixture containing the distillation is carried out at a column bottom temperature of
catalyst is distilled in a distillation column (or evaporator), not less than 150° C., whereby the diphenyl carbonate is
and thus separated into a high boiling point material contain obtained as a side cut component from the distillation column
ing most of the catalyst and a low boiling point material, and 60 (see Patent Document 36: Japanese Patent Application Laid
then the low boiling point material is Subjected to continuous open No. 9-194437 (corresponding to European Patent No.
sequential distillation using a distillation apparatus compris 0784.048)).
ing three columns, i.e. a light fraction separating column, a However, it has been shown that various problems remain
methyl phenyl carbonate separating column, and a diphenyl with Such diphenyl carbonate separation/purification meth
carbonate separating column, whereby diphenyl carbonate is 65 ods using these distillations. More specifically, the purity of
obtained as a column top component (see Patent Document the diphenyl carbonate obtained through the above I) is low,
25). and moreover this is a batch process and hence is not suitable
 US 7,812,189 B2
7 8
for mass production on an industrial scale. Regarding the reaction is carried out with bisphenol A are given as a method
above II), the method of Patent Document 37 is a batch of evaluating the purity of the diphenyl carbonate obtained
method, and the diphenyl carbonate which was obtained through the distillation, but evaluation of whether the diphe
through the method disclosed in Patent Document 38 con nyl carbonate is suitable for polymerization cannot be carried
tains a titanium catalyst, albeit in an amount of not more than 5 out using this test method. This is because even for diphenyl
1 ppm, and hence is not suitable as a raw material for the carbonate of low purity such that a polycarbonate of the
production of a high-purity discolored polycarbonate. With required degree of polymerization cannot be produced, the
the method of the above III), since the diphenyl carbonate is initial reaction in which phenol is eliminated occurs suffi
heated to a high temperature at the bottom of each of two of ciently. Moreover, since with this evaluation method, a large
the distillation columns, i.e. the light fraction separating col 10
amount of 2.3 ppm of NaOH based on the bisphenol A is used
umn and the methyl phenyl carbonate separating column, and as a catalyst, even for diphenyl carbonate containing, for
is then Subjected to a high temperature in the diphenyl car example, 1 ppm of chlorinated impurities, an incorrect evalu
bonate separating column, the diphenyl carbonate is altered, ation that the diphenyl carbonate is of high purity and is
bringing about a decrease in the purity and a decrease in the
yield. 15 suitable as a raw material for a polycarbonate would be
Moreover, the method of the above IV) in which the diphe obtained. As stated earlier, the diphenyl carbonate containing
nyl carbonate is obtained from the column bottom is unsuit 1 ppm of chlorinated impurities cannot be used as the raw
able, because the purity is low and hence a desired polycar material for the polycarbonate at all. In ordinary polymeriza
bonate cannot be produced. tion, since Such a large amount of an alkaline catalyst is not
With the method of the above V), the reaction mixture used, this evaluation method is not suitable for evaluating the
containing the catalyst, the unreacted Starting material and the purity of diphenyl carbonate to be used for producing poly
impurities obtained from the bottom of the second reactive carbonate. Further, in Patent Document 36, there is no spe
distillation column is introduced into the third reactive distil cific description whatsoever of purification of diphenyl car
lation column from an upper portion thereof, and the diphenyl bonate that has been obtained using the transesterification
carbonate is withdrawn from the side of the third reactive 25 method. Since the types and contents of impurities differ
distillation column. Vapor or mist of the catalyst, the starting between diphenyl carbonate obtained through the phosgene
material, the impurities and the like may thus be entrained, method and diphenyl carbonate obtained using the transes
and hence the purity of the diphenyl carbonate is low. With the terification method, it cannot be said that diphenyl carbonate
method of the above VI), the amount of diphenyl carbonate of the same purity will be obtained through the same purifi
produced is 6.7 kg/hr (example 3 of Patent Document 34) or 30
cation method. It thus cannot be said at all that diphenyl
3.9 kg/hr (example 1 of Patent Document 35), which is not on carbonate having the required purity for the raw material of
an industrial scale. The method of the above VII) is a prefer the polycarbonate would be obtained through the purification
able process, but the amount of diphenyl carbonate produced method of Patent Document 36. Furthermore, the amount of
is small at 2 kg/hr (example 8 of Patent Document 40), which purified diphenyl carbonate disclosed in Patent Document 36
is not on an industrial scale. Moreover, the method is carried 35
is 0.57 kg/hr, which is not on an industrial scale.
out with the column top pressure in the first purifying column
at a high vacuum of 200 Pa, and hence industrial implemen A reaction mixture obtained through transesterification
tation would be difficult, because a very large distillation reaction between a dialkyl carbonate and a phenol as a start
column would be required so that the high vacuum could be ing material in the presence of a homogeneous catalyst gen
maintained. 40 erally contains various reaction by-products. In particular, if
Moreover, with the method of the above VIII), although it a diphenyl carbonate containing the amounts of high boiling
is stated that the content of phenyl salicylate is reduced from point by-products having a higher boiling point than that of
3000 ppm to 50 ppm (example 2 of Patent Document 36), the diphenyl carbonate, Such as phenyl salicylate, Xanthone,
nothing is stated whatsoever for other impurities. For phenyl methoxybenzoate, 1-phenoxycarbonyl-2-phenoxy
example, even though the diphenyl carbonate is produced 45 carboxy-phenylene and the like which have not been reduced
using the phosgene method in this example, and hence this is down to a sufficient level is used as the raw material of the
definitely a purification method for diphenyl carbonate con transesterification method polycarbonate, then these high
taining chlorinated impurities, nothing is stated whatsoever boiling point by-products will cause coloration and deterio
with regard to the chlorinated impurities (which have an ration in properties. It is thus preferable to reduce the amounts
adverse effect on the polymerization to produce a polycar 50 of Such impurities as much as possible. However, Such high
bonate and the properties of the polycarbonate even in an boiling point by-products are difficult to separate out, and
extremely small amount of only a few tens of ppb). With this with methods proposed hitherto, it has not been possible to
method, such chlorinated impurities will not be separated out reduce the amounts of Such high boiling point by-products
sufficiently, and hence it will not be possible to use the diphe down to a sufficient level. In particular, there has been no
nyl carbonate as a raw material for a polycarbonate. This is as 55 proposal whatsoever of a process for the production on an
described in comparative example 1 (in which the alkali col industrial scale of not less than 1 ton/hr of a high-purity
umn is not used) of the purification method (in which after diphenyl carbonate required for the raw material of a high
washing twice with alkaline hot water, washing with hot quality and high-performance polycarbonate.
water is carried out, and then the diphenyl carbonate is dehy
drated through distillation and then passed through a column 60 DISCLOSURE OF INVENTION
filled with a solid alkali, before being subjected to reduced
pressure distillation in the multi-stage distillation column) of It is an object of the present invention to provide a specific
Patent Document 41 (Japanese Patent Application Laid-Open process that enables a high-purity diphenyl carbonate that can
No. 9-194437), which was filed more than one year after the be used as a raw material of a high-quality and high-perfor
filing of Patent Document 36. 65 mance polycarbonate to be produced stably for a prolonged
Furthermore, in Patent Document 36, the temperature and period of time on an industrial scale of not less than 1 ton/hr
time at which phenol starts to be distilled off in the case that from a reaction mixture containing a catalyst and reaction
 US 7,812,189 B2
10
by-products that has been obtained through transesterifica is n (n+n2+ns), wherein L. D., n., n2 ns, and n, satisfy
tion reaction and the like using a dialkyl carbonate and a the following formulae (4) to (9);
phenol as a starting material. 1000s La 5000 (4)
Since the present inventors disclosed a process for produc
ing aromatic carbonates using the continuous multi-stage 5
100s Da1000 (5)
distillation column, various proposals regarding processes for
the production of reaction mixtures containing aromatic car 5ans20 (6)
bonates by means of the reactive distillation method have
been made. However, these have all been on a small scale and 12sn's 40 (7)
a short operating time laboratory level, and there have been no 10
disclosures on a specific process or apparatus enabling mass 3 ense 15 (8)
production on an industrial scale from Sucha reaction mixture
to a high-purity diphenyl carbonate that can be used as the raw 20sn's 70 (9):
material of a high-quality and high-performance polycarbon
ate. In view of these circumstances, the present inventors 15 (d) a distillation operation of said diphenyl carbonate puri
carried out studies aimed at discovering a specific process fying column B is carried out under conditions of a column
enabling a high-purity diphenyl carbonate which is important bottom temperature T in a range of from 185 to 280° C., and
as the raw material of the high-quality and high-performance a column top pressure P in a range of from 1000 to 20000 Pa;
and
polycarbonate to be produced stably for a prolonged period of
time on an industrial scale of not less than 1 ton/hr. As a result, (e) not less than 1 ton/hr of the high-purity diphenyl car
the present inventors have reached to the present invention. bonate is obtained continuously as the side cut component Bs.
That is, in the first aspect of the present invention, there is 2. The process according to item 1, wherein L, D, and n for
provided: said high boiling point material separating column A satisfy
1. In an industrial process for the production of a high-purity the following formulae: 1000sLs2500, 200sDs 600,
diphenyl carbonate which is produced continuously from a 25 and 30sn's 70, respectively,
reaction mixture containing a diphenyl carbonate, which has L. D., n., n2 ns, and n for said diphenyl carbonate purify
been obtained by carrying out a transesterification reaction ing column B satisfy the following formulae:
between a dialkyl carbonate and a phenol and/or a dispropor 1500sLis3000, 150s.D. s.500, 7sn's 15, 12sn-s30,
tionation reaction of an alkyl phenyl carbonate and/or a trans 30 3sns 10, and 25snis55, respectively,
esterification reaction between an alkyl phenyl carbonate and T is in a range of from 190 to 240°C., P is in a range of from
a phenol in the presence of a homogeneous catalyst, by con 2000 to 15000 Pa,
tinuously introducing said reaction mixture into a high boil
ing point material separating column A, and continuously T is in a range of from 190 to 240°C., and P is in a range of
carrying out separation by distillation into a column top com 35
from 2000 to 15000 Pa.
ponent A containing the diphenyl carbonate and a column 3. The process according to item 1 or 2, wherein each of said
bottom component A containing the catalyst, and then con high boiling point material separating column A and said
tinuously introducing said column top component A into a diphenyl carbonate purifying column B is a distillation col
diphenyl carbonate purifying column B having a side cut umn having a tray and/or a packing as said internal.
outlet, and continuously carrying out separation by distilla 40
tion into a column top component B, a side cut component 4. The process according to item 3, wherein said internal of
Bs and a column bottom component B, the improvement each of said high boiling point material separating column A
which comprises: and said diphenyl carbonate purifying column B is a packing.
(a) said high boiling point material separating column A 5. The process according to item 4, wherein said packing is a
comprises a continuous multi-stage distillation column hav 45 structured packing which is at least one selected from the
ing a length L (cm), an inside diameter D (cm), and an group consisting of Mellapak, Gempak, TECHNO-PAK,
internal with a number of stages in thereinside, wherein L. FLEXI-PAK, a Sulzer packing, a Goodroll packing, and a
D, and n satisfy the following formulae (1) to (3): Glitchgrid.
800s. La3000 (1) In the second aspect of the present invention, there is pro
50 vided:
100s De 1000 (2)
6. A high-purity diphenyl carbonate containing a halogen
20ans 100 (3): content of not more than 0.1 ppm, and a content of by
(b) a distillation operation of said high boiling point mate products having a higher boiling point than that of the diphe
rial separating column A is carried out under conditions of a 55
nyl carbonate of not more than 100 ppm, produced by the
column bottom temperature T in a range of from 185 to 280° process according to any one of claims 1 to 5.
C., and a column top pressure P in a range of from 1000 to 7. The high-purity diphenyl carbonate according to item 6.
20000 Pa; wherein the halogen content is not more than 10 ppb, and the
(c) said diphenyl carbonate purifying column B comprises content of each of phenyl salicylate, Xanthone, phenyl meth
a continuous multi-stage distillation column having a length 60 oxybenzoate, and 1-phenoxycarbonyl-2-phenoxycarboxy
L (cm), an inside diameter D (cm), an internal thereinside, phenylene, which are the by-products having the higher boil
an inlet B1 at a middle portion of the column, and a side cut ing point than that of the diphenyl carbonate, is not more than
outlet B2 between said inlet B1 and the column bottom, in 30 ppm.
which a number of stages of the internal above the inlet B1 is 8. The high-purity diphenyl carbonate according to item 7.
n, a number of stages of the internal between the inlet B1 and 65 wherein the content of the by-products having the higher
the side cut outlet B2 is n, a number of stages of the internals boiling point than that of the diphenyl carbonate is not more
below the side cut outlet B2 is n, and a total number of stages than 50 ppm.
 US 7,812,189 B2
11 12
9. The high-purity diphenyl carbonate according to item 8. temperature T in a range of from 185 to 280° C., and a
wherein the halogen content is not more than 1 ppb, and the column top pressure P in a range of from 1000 to 20000 Pa.
content of the by-products having the higher boiling point 13. The apparatus according to any one of items 10 to 12,
than that of the diphenyl carbonate is not more than 10 ppm. wherein not less than 1 ton/hr of the high-purity diphenyl
In the third aspect of the present invention, there is pro carbonate is obtained as the side cut component Bs.
vided:
14. The apparatus according to any one of items 10 to 13,
10. An apparatus for producing a high-purity diphenyl car wherein L, D, and n for said high boiling point material
bonate which is produced from a reaction mixture containing separating column A satisfy the following formulae:
a diphenyl carbonate, which has been obtained by carrying 10 1000sLs2500, 200sDs600, and 30sn's 70, respec
out a transestrification reaction between a dialkyl carbonate tively,
and a phenol and/or a disproportionation reaction of an alkyl
carbonate and/or a transesterification reaction between an L. D., n., n2 ns, and n for said diphenyl carbonate purify
alkyl phenyl carbonate and a phenol in the presence of a ing column B satisfy the following formulae:
homogeneous catalyst, the apparatus comprises; 1500sLis3000, 150sDs.500, 7sn's 15, 12sn-s30,
a high boiling point material separating column A which 15 3sns 10, and 25snis55, respectively,
receives said reaction mixture, and which carries out separa T is in a range of from 190 to 240°C., P is in a range of from
tion by distillation into a column top component A contain 2000 to 15000 Pa,
ing the diphenyl carbonate and a column bottom component
A containing the catalyst; and T is in a range of from 190 to 240°C., and P is in a range of
a diphenyl carbonate purifying column B having a side cut from 2000 to 15000 Pa
outlet B2, which is connected with said high boiling point 15. The apparatus according to any one of items 10 to 14.
material separating column A, and which receives said col wherein each of said high boiling point material separating
umn top component A, therefrom, wherein separation by column A and said diphenyl carbonate purifying column B is
distillation is carried out into a column top component B, a a distillation column having a tray and/or a packing as said
side cut component Bs and a column bottom component B. 25 internal.
wherein
(a) said high boiling point material separating column A 16. The apparatus according to item 15, wherein said internal
comprises a continuous multi-stage distillation column hav of each of said high boiling point material separating column
ing a length L (cm), an inside diameter D (cm), and an A and said diphenyl carbonate purifying column B is a pack
internal with a number of stages in thereinside, wherein L, 30 ing.
D, and n satisfy the following formulae (1) to (3):
17. The apparatus according to item 16, wherein said packing
800s Lis3000 (1) is a structured packing which is at least one selected from the
group consisting of Mellapak, Gempak, TECHNO-PAK,
100s De 1000 (2) FLEXI-PAK, a Sulzer packing, a Goodroll packing, and a
35 Glitchgrid.
20ans 100 (3):
In another aspect of the process according to the present
(b) said diphenyl carbonate purifying column B comprises invention, there is provided:
a continuous multi-stage distillation column having a length
L (cm), an inside diameter D (cm), an internal thereinside, 18. A process for the production of a high-purity diphenyl
an inlet B1 at a middle portion of the column, and the side cut 40 carbonate, the process comprising the steps of:
outlet B2 between said inlet B1 and the column bottom, in (i) carrying out a transestrification reaction between a
which a number of stages of the internal above the inlet B1 is dialkyl carbonate and a phenol and/or a disproportionation
n, a number of stages of the internal between the inlet B1 and reaction of an alkyl carbonate and/or a transesterification
the side cut outlet B2 is n, a number of stages of the internals reaction between an alkyl phenyl carbonate and a phenol in
below the side cut outlet B2 is n, and a total number of stages 45 the presence of a homogeneous catalyst, so as to form a
is n (n+n2+n), wherein L. D., n., n2 ns, and no satisfy reaction mixture containing a diphenyl carbonate;
the following formulae (4) to (9): (ii) carrying out separation by distillation in a high boiling
1000s. LaS000 (4)
point material separating column A into a column top com
ponent A containing the diphenyl carbonate and a column
100s Das 1000 (5) 50 bottom component A containing the catalyst
(iii) carrying out separation by distillation of said column
5ans20 (6) top component A in a diphenyl carbonate purifying column
B having a side cut outlet into a column top component B, a
12sn's 40 (7)
side cut component Bs and a column bottom component B,
55
said column top component Aintroducing from the side cut
3 sn's 15 (8)
outlet into the column B; wherein
(a) said high boiling point material separating column A
20sn's 70 (9): comprises a continuous multi-stage distillation column
having a length L (cm), an inside diameter D (cm), and
11. The apparatus according to item 10, wherein a distillation 60 an internal with a number of stages in thereinside,
operation of said high boiling point material separating col wherein L, D, and n satisfy the following formulae
umn A is carried out under conditions of a column bottom (1) to (3):
temperature T in a range of from 185 to 280° C., and a 800s. La3000 (1)
column top pressure P in a range of from 1000 to 20000 Pa.
12. The apparatus according to item 10 or 11, wherein a 65 100s Da1000 (2)
distillation operation of said diphenyl carbonate purifying
column B is carried out under conditions of a column bottom 20ans 100 (3):
 US 7,812,189 B2
13 14
(b) said diphenyl carbonate purifying column B comprises been obtained by carrying out a transesterification reaction
a continuous multi-stage distillation column having a between a dialkyl carbonate and a phenol and/or a dispropor
length L. (cm), an inside diameter D (cm), an internal tionation reaction of an alkyl phenyl carbonate and/or a trans
thereinside, an inlet B1 at a middle portion of the col esterification reaction between the alkyl phenyl carbonate
umn, and a side cut outlet B2 between said inlet B1 and and the phenol in the presence of a homogeneous catalyst.
the column bottom, in which a number of stages of the
internal above the inlet B1 is n, a number of stages of BRIEF DESCRIPTION OF DRAWING
the internal between the inlet B1 and the side cut outlet
B2 is n, a number of stages of the internals below the FIG. 1 is a schematic view of an example showing a con
side cut outlet B2 is n, and a total number of stages is no 10 tinuous separating/purifying apparatus for carrying out the
(n+n2+ns), wherein L. D., n.1, n2 ns, and n, Satisfy present invention in which a high boiling point material sepa
the following formulae (4) to (9); rating column A and a diphenyl carbonate purifying column B
1000s LeS000 (4)
are connected together. As one example, each of these con
tinuous multi-stage distillation columns has installed therein
100s Das 1000 (5) 15 an internal comprising a structured packing having a prede
termined number of stages.
5ans20 (6) A1 and B1; inlet; B2: outlet; 11: outlet for a column bottom
component of high boiling point material column A; 13 and
12sn's 40 (7) 23: column top gas outlet; 14, 24, 18, 28, and 38: heat
exchanger; 15 and 25; reflux liquid inlet; 16: outlet for a
3 ense 15 (8) column top component of high boiling point material column
A; 17 and 27; column bottom liquid outlet; 26: outlet for a
20sn's 70 (9): column top component of diphenyl carbonate purifying col
umn B:31: outlet for a column bottom component of diphenyl
19. The process according to item 18, wherein not less than 1 25 carbonate purifying column B; 33: outlet for a side cut com
ton/hr of the high-purity diphenyl carbonate is obtained as the ponent of diphenyl carbonate purifying column B.
side cut component Bs.
20. The process according to item 18 or 19, wherein L. D. BEST MODE FOR CARRYING OUR THE
and n for said high boiling point material separating column INVENTION
A satisfy the following formulae: 1000sLs2500, 30
200sDs 600, and 30sns70, respectively, In the following, the present invention is described in
detail.
L. D., n., n., n., and n for said diphenyl carbonate purify A dialkyl carbonate used in the present invention is a com
ing column B satisfy the following formulae: pound represented by the general formula (10);
1500sLis3000, 150sDs 500, 7sn's 15, 12sn-s30, 35 ROCOOR (10)
3sns 10, and 25sns55, respectively,
T is in a range of from 190 to 240°C., P is in a range of from wherein R' represents an alkyl group having 1 to 10 carbon
2000 to 15000 Pa, atoms, an alicyclic group having 3 to 10 carbon atoms, or an
T is in a range of from 190 to 240°C., and P is in a range of
aralkyl group having 6 to 10 carbon atoms. Examples of R'
from 2000 to 15000 Pa.
40 include an alkyl group Such as methyl, ethyl, propyl (iso
mers), allyl, butyl (isomers), butenyl (isomers), pentyl (iso
21. The process according to any one of items 18 to 20, mers), hexyl (isomers), heptyl (isomers), octyl (isomers),
wherein each of said high boiling point material separating nonyl (isomers), decyl (isomers) and cyclohexylmethyl; an
column A and said diphenyl carbonate purifying column B is alicyclic group Such as cyclopropyl, cyclobutyl, cyclopentyl,
a distillation column having a tray and/or a packing as said 45 cyclohexyl and cycloheptyl; and an aralkyl group Such as
internal. benzyl, phenethyl (isomers), phenylpropyl (isomers), phe
22. The process according to item 21, wherein said internal of nylbutyl (isomers) and methylbenzyl (isomers). The above
each of said high boiling point material separating column A mentioned alkyl groups, alicyclic group and aralkyl group
and said diphenyl carbonate purifying column B is a packing. may be substituted with other substituents such as Ia ower
50 alkyl group, a lower alkoxy group, a cyano group or a halogen
23. The process according to item 22, wherein said packing is atom, and may also contain an unsaturated bond therein.
a structured packing which is at least one selected from the Examples of dialkyl carbonates having such R' include
group consisting of Mellapak, Gempak, TECHNO-PAK, dimethyl carbonate, diethyl carbonate, dipropyl carbonate
FLEXI-PAK, a Sulzer packing, a Goodroll packing, and a (isomers), diallyl carbonate, dibutenyl carbonate (isomers),
Glitchgrid. 55 dibutyl carbonate (isomers), dipentyl carbonate (isomers),
dihexyl carbonate (isomers), diheptyl carbonate (isomers),
ADVANTAGEOUSEFFECT OF THE INVENTION dioctyl carbonate (isomers), dinonyl carbonate (isomers),
didecyl carbonate (isomers), dicyclopentyl carbonate, dicy
It has been discovered that by implementing the present clohexyl carbonate, dicycloheptyl carbonate, dibenzyl car
invention, a high-purity diphenyl carbonate that can be used 60 bonate, diphenethyl carbonate (isomers), di(phenylpropyl)
as a raw material of a high-quality and high-performance carbonate (isomers), di(phenylbutyl) carbonate (isomers),
polycarbonate can be produced on an industrial scale of not di(chlorobenzyl) carbonate (isomers), di(methoxybenzyl)
less than 1 ton/hr, preferably not less than 2 ton/hr, more carbonate (isomers), di(methoxymethyl)carbonate, di(meth
preferably not less than 3 ton/hr, stably for a prolonged period oxyethyl) carbonate (isomers), di(chloroethyl) carbonate
of time of not less than 2000 hours, preferably not less than 65 (isomers) and di(cyanoethyl)carbonate (isomers).
3000 hours, more preferably not less than 5000 hours, from a Of these dialkyl carbonates, ones preferably used in the
reaction mixture containing the diphenyl carbonate that has present invention are dialkyl carbonates in which R" is an
 US 7,812,189 B2
15 16
alkyl group having not more than four carbon atoms and not catalyst with the dialkyl carbonate and the phenol as a starting
containing a halogen atom. A particularly preferable one is material may be any process, but one particularly preferable
dimethyl carbonate. Moreover, of preferable dialkyl carbon for industrial implementation is a process in which two con
ates, particularly preferable ones are dialkyl carbonates pro tinuous multi-stage distillation columns are used as reactive
duced in a state Substantially not containing a halogen, for 5 distillation columns as previously proposed by the present
example ones produced from an alkylene carbonate Substan inventors. This is a process in which a transesterification
tially not containing a halogen and an alcohol Substantially reaction between the dialkyl carbonate and the phenol is
not containing a halogen. carried out in the presence of the homogeneous catalyst in the
A phenol used in the present invention is one in which one first continuous multi-stage distillation column to obtain a
hydroxyl group is bonded to a phenyl group, and may be 10 column bottom reaction mixture having an alkyl phenyl car
phenol itself or a substituted phenol. Examples of the substi bonate as a main product therein, and this column bottom
tuted phenols include various alkylphenols such as cresol reaction mixture is introduced into the second continuous
(isomers), Xylenol (isomers), trimethylphenol (isomers), tet multi-stage distillation column, where conversion of the alkyl
ramethylphenol (isomers), ethylphenol (isomers), propy phenyl carbonate into the diphenyl carbonate and the dialkyl
lphenol (isomers), butylphenol (isomers), diethylphenol (iso 15 carbonate occurs mainly through a disproportionation reac
mers), methylethylphenol (isomers), methylpropylphenol tion. The diphenyl carbonate may of course also be produced
(isomers), dipropylphenol (isomers), methylbutylphenol through a transesterification reaction between the alkylphe
(isomers), pentylphenol (isomers), hexylphenol (isomers) nyl carbonate and the phenol in the reactive distillation col
and cyclohexylphenol (isomers); various alkoxyphenols such umns. The column bottom reaction mixture from the second
as methoxyphenol (isomers) and ethoxyphenol (isomers); continuous multi-stage distillation column thus obtained is
and arylalkylphenols such as phenylpropylphenol (isomers). preferably taken as the reaction mixture containing the diphe
Of unsubstituted phenol and such substituted phenols, unsub nyl carbonate used in the present invention.
stituted phenol is particularly preferable used in the present Note that since the disproportionation reaction is a trans
invention. Moreover, of these phenols, ones substantially not esterification reaction between two of the same molecular
containing a halogen are preferably used in the present inven 25 species, the “reaction mixture containing the diphenyl car
tion. bonate, which has been obtained by carrying out a transes
The molar ratio of the dialkyl carbonate to the phenol used terification reaction between a dialkyl carbonate and a phenol
in the starting material for use in the present invention must be and/or a disproportionation reaction of an alkyl phenyl car
in a range of from 0.1 to 10. Outside this range, the amount of bonate and/or a transesterification reaction between the alkyl
unreacted Starting material remaining relative to a prescribed 30 phenyl carbonate and the phenol in the presence of a homo
amount of the desired diphenyl carbonate produced becomes geneous catalyst” used in the present invention can also be
high, which is not efficient, and moreover much energy is referred to as a "reaction mixture containing the diphenyl
required to recover the unreacted starting material. For that carbonate, which has been obtained through transesterifica
reason, the above molar ratio is more preferably in a range of tion reaction between a dialkyl carbonate and a phenol as a
from 0.5 to 5, yet more preferably from 1 to 3. 35 starting material in the presence of a homogeneous catalyst’.
A catalyst used in the present invention is a homogeneous When “reaction mixture' is used merely in the present inven
catalyst which contains a metal such as Pb, Cu, Zn, Fe, Co, Ni, tion, Such a reaction mixture is meant.
Al, Ti, V. Sn and the like, and which dissolves in the reaction In addition to the diphenyl carbonate, the reaction mixture
system. A catalyst in which Such a metallic component is used in the present invention contains the catalyst, unreacted
bonded to organic groups can thus be preferably used. The 40 starting materials, the alkyl phenyl carbonate, by-products
catalyst component may of course have been reacted with an and so on. As the by-products, there are relatively low boiling
organic compound present in the reaction system such as point by-products such as an alkyl phenyl ether, and the high
aliphatic alcohols, phenols, alkyl phenyl carbonates, diphenyl boiling point by-products such as Fries rearrangement prod
carbonates or dialkyl carbonates, or may have been Subjected ucts of the alkyl phenyl carbonate or the diphenyl carbonate
to heating treatment with the starting material or products 45 and derivatives thereof, degeneration products of the diphe
prior to the reaction. The catalyst used in the present invention nyl carbonate, and other high boiling point material of an
is preferably one that has a high solubility in the reaction unknown structure.
liquid under the reaction conditions. Examples of preferable For example, in the case of producing diphenyl carbonate
catalysts in this sense include PbO, Pb(OH), and Pb(OPh): using dimethyl carbonate and phenol as a starting material,
TiCl, Ti(OMe), (MeO)Ti(OPh), (MeO),Ti(OPh), 50 reaction by-products are anisole, methyl salicylate, phenyl
(MeO) Ti(OPh) and Ti(OPh); SnCl, Sn(OPh), BuSnO salicylate, Xanthone, phenyl methoxybenzoate, 1-phenoxy
and BuSn(OPh); FeCls, Fe(OH) and Fe(OPh); and such carbonyl-2-phenoxycarboxy-phenylene and so on, and typi
catalysts that have been treated with phenol, the reaction cally a small amount of high boiling point by-products of
liquid and the like. unknown structure thought to be produced through further
In the present invention, it is particularly preferable to use 55 reaction of these reaction by-products is also contained.
a starting material and catalyst not containing a halogen. In In one embodiment of the present invention, such a reac
this case, the diphenyl carbonate produced does not contain a tion mixture is continuously introduced into a high boiling
halogen at all, and hence it is important as a raw material point material separating column A, and continuously sepa
when industrially producing a polycarbonate by means of a rated into a column top component A containing the diphe
transesterification method. The reason is that even if a halo 60 nyl carbonate and a column bottom component A containing
gen is present in the raw material for the polymerization in the catalyst, and then the column top component A is con
even an amount less than, for example, 1 ppm, then this tinuously introduced into a diphenyl carbonate purifying col
halogen does inhibit the polymerization reaction, and cause a umn B having a side cut outlet, and continuously separated by
deterioration in the properties of the polycarbonate produced, distillation into a column top component B, a side cut com
and cause discoloration of the polycarbonate. 65 ponent Bs and a column bottom component B. In this way,
The process for the production of the reaction mixture not less than 1 ton/hr of a high-purity diphenyl carbonate is
containing the diphenyl carbonate using Such a homogeneous obtained continuously as the side cut component Bs. For this
 US 7,812,189 B2
17 18
purpose, the high boiling point material separating column. A Moreover, the distillation conditions for the diphenyl car
and the diphenyl carbonate purifying column B must each be bonate purifying column B must be a column bottom tem
made to be a continuous multi-stage distillation column hav perature T in a range of from 185 to 280°C., and a column
ing a specified structure, and must be used in combination top pressure P in a range of from 1000 to 20000 Pa.
with one another. It has been discovered that by using the high boiling point
The reaction mixture used in the present invention gener material separating column A and the diphenyl carbonate
ally contains 50 to 80% by weight of the diphenyl carbonate purifying column B simultaneously satisfying all of these
based on 100% by weight of the reaction mixture, and hence conditions, a high-purity diphenyl carbonate can be purified
to obtain not less than 1 ton/hr of the high-purity diphenyl and produced on an industrial scale of not less than 1 ton/hr
carbonate, the amount of the reaction mixture continuously 10 stably for a prolonged period of time, for example not less
introduced into the high boiling point material separating than 2000 hours, preferably not less than 3000 hours, more
column A is not less than approximately 1.3 to 2 ton/hr, preferably not less than 5000 hours, from a reaction mixture
although this amount varies depending on the content of the containing the diphenyl carbonate that has been obtained
diphenyl carbonate. It is generally necessary to Subject more through transesterification reaction between a dialkyl carbon
than 2 ton/hr of the reaction mixture to the separation/purifi 15 ate and a phenol as a starting material in the presence of a
cation. homogeneous catalyst. The reason why it has become pos
FIG. 1 illustrates a schematic view of an example showing sible to produce the high-purity diphenyl carbonate on an
a continuous separating?purifying apparatus for carrying out industrial scale with such excellent effects by implementing
the present invention in which a high boiling point material the process of the present invention is not clear, but this is
separating column A and a diphenyl carbonate purifying col supposed to be due to a combined effect between the distil
umn B are connected together. As one example, each of the lation conditions and an effect brought about when the con
high boiling point material separating column A and the ditions of formulae (1) to (9) are combined. Preferable ranges
diphenyl carbonate purifying column comprises a continuous for the respective factors are described below.
multi-stage distillation columns having therein an internal If L (cm) is less than 800, since a height of the internal
comprising, but is not limited to, a structured packing having 25
which can be installed in the high boiling point material
a predetermined number of stages. Note that the columns. A separating column A becomes limited, the separation effi
and B comprise the following structures, respectively, in ciency decreases, and it is thus undesirable for L. (cm). More
order to carry out the producing process according to the over, to keep down the equipment cost while attaining the
present invention. desired separation efficiency, L. must be made to be not more
In the producing process according to the present inven 30
than 3000. A more preferable range for L. (cm) is
tion, the high boiling point material separating column A 1000sLs2500, with 1200sLs2000 being yet more pref
must be a continuous multi-stage distillation column having a erable.
length L (cm), an inside diameter D (cm), and an internal If D (cm) is less than 100, then it is not possible to attain
with a number of stages in thereinside, wherein L, D, and the desired production amount. Moreover, to keep down the
in satisfy the following formulae (1) to (3): 35
equipment cost while attaining the desired production
800s. La3000 (1) amount, D must be made to be not more than 1000. A more
preferable range for D (cm) is 200sDs600, with
100s De 1000 (2) 250sDs450 being yet more preferable.
40 If n is less than 20, then the separation efficiency
20ans 100 (3). decreases, and hence the desired high purity cannot be
Moreover, the distillation conditions for the high boiling attained. Moreover, to keep down the equipment cost while
point material separating column A must be a column bottom attaining the desired separation efficiency, n must be made to
temperature T in a range of from 185 to 280° C., and a be not more than 100. Furthermore, if n is greater than 100,
column top pressure P in a range of from 1000 to 20000 Pa. 45 then the pressure difference between the top and bottom of the
Furthermore, the diphenyl carbonate purifying column B column becomes too great, and hence prolonged stable opera
must be a continuous multi-stage distillation column having a tion of the high boiling point material separating column A
length L. (cm), an inside diameter D (cm), an internal there becomes difficult. Moreover, it becomes necessary to
inside, an inlet B1 at a middle portion of the column, and a increase the temperature in the lower portion of the column,
side cut outlet B2 between said inlet B1 and the column 50 and hence side reactions become liable to occur, which is
bottom, in which a number of stages of the internal above the undesirable. A more preferable range for n is 30sns70,
inlet B1 is n, a number of stages of the internal between the with 35sn's 60 being yet more preferable.
inlet B1 and the side cut outlet B2 is n, a number of stages of If T is less than 185°C., since the column top pressure
the internals below the side cut outlet B2 is n, and a total must be reduced, equipment for maintaining a high vacuum
number of stages is n (n+n+n), wherein L. D., n., n. 55 must be used, and moreover the equipment increases in size.
n, and n satisfy the following formulae (4) to (9): Moreover, it is undesirable for T to be greater than 280°C.,
because the high boiling point by-products are produced dur
1000s. LaS000 (4) ing the distillation. A more preferable range for T is from 190
100s Das 1000 (5)
to 240° C., with from 195 to 230° C. being yet more prefer
60 able.
5ans20 (6) It is undesirable for P to be less than 1000 Pa, since then
large equipment enabling a high vacuum to be maintained
12sn's 40 (7) must be used. Moreover, it is undesirable for P to be greater
than 20000 Pa, since then the distillation temperature must be
3 ense 15 (8) 65 increased and hence production of by-products increases. A
more preferable range for P is from 2000 to 15000 Pa, with
20sn's 70 (9): from 3000 to 13000 Pa being yet more preferable.
 US 7,812,189 B2
19 20
If L (cm) is less than 1000, since a height of the internal a Berl Saddle, an Intalox saddle, a Dixon packing, a McMa
which can be installed in the diphenyl carbonate purifying hon packing or Heli-Pak, or a structured packing such as
column B becomes limited, the separation efficiency Mellapak, Gempak, TECHNO-PAK, Flexipac, a Sulzer pack
decreases, and it is thus undesirable for L. (cm). Moreover, to ing, a Goodroll packing or a Glitchgrid are preferable. The
keep down the equipment cost while attaining the desired 5 multi-stage distillation column having both a tray portion and
separation efficiency, L. must be made to be not more than a portion packed with the packing can also be used. Note that
5000. A more preferable range for L. (cm) is the term “number of stages (n) of an internal’ used in the
1500sLis3000, with 1700sLs2500 being yet more pref present invention means that the total number of trays in the
erable. case of a tray, and the theoretical number of stages in the case
If D (cm) is less than 100, then it is not possible to attain 10 of the packing. Accordingly, in the case of the multi-stage
the desired production amount. Moreover, to keep down the column having both the tray portion and the portion packed
equipment cost while attaining the desired production with the packing, n means the Sum of the total number of trays
amount, D must be made to be not more than 1000. A more and the theoretical number of stages of the packing.
preferable range for D (cm) is 150sDs.500, with It has been ascertained that the high boiling point material
200sDs400 being yet more preferable. 15 separating column A according to the present invention pref
If n is less than 20, then the separation efficiency for the erably comprises the packing as the internal, and furthermore
column as a whole decreases, and hence the desired high a structured packing is preferable as the packing. It has also
purity cannot be attained. Moreover, to keep down the equip been discovered that the diphenyl carbonate purifying col
ment cost while attaining the desired separation efficiency, in umn B according to the present invention preferably com
must be made to be not more than 70. Furthermore, if n is prises the packing as the internal, particularly preferably one
greater than 70, then the pressure difference between the top or more of the structured packing.
and bottom of the column becomes too great, and hence A process in which transesterification reaction is carried
prolonged stable operation of the diphenyl carbonate purify out with a dialkyl carbonate and a phenol as a starting material
ing column B becomes difficult. Moreover, it becomes nec in the presence of a homogeneous catalyst using an apparatus
essary to increase the temperature in the lower portion of the 25 in which two reactive distillation columns are connected
column, and hence side reactions become liable to occur, together is a preferable process for obtaining the reaction
which is undesirable. A more preferable range for n is mixture that acts as the starting material in the present inven
25snes35, with 30snis50 being yet more preferable. Fur tion. In this case, a column bottom liquid continuously with
thermore, it has been ascertained that to obtain the desired drawn from the bottom of the second reactive distillation
high-purity diphenyl carbonate stably for a prolonged period 30 column can be used as the reaction mixture used in the present
of time, n, n, and n must be in the ranges 5sns20. invention. This reaction mixture continuously withdrawn
12snes40, and 3sins 15, respectively. More preferable from the bottom of the second reactive distillation column
ranges are 7sn's 15, 12sn-s30, and 3sins 10. generally contains 0.05 to 2% by weight of the dialkyl car
It is undesirable for T to be less than 185°C., since then bonate, 1 to 20% by weight of the phenol, 0.05 to 2% by
the column top pressure must be reduced, and hence equip 35 weight of an alkyl phenyl ether, 10 to 45% by weight of an
ment for maintaining a high vacuum must be used, and more alkyl phenyl carbonate, 50 to 80% by weight of the diphenyl
over the equipment increases in size. Moreover, it is undesir carbonate, 0.1 to 5% by weight of high boiling point by
able for T to be greater than 280°C., since then high boiling products, and 0.001 to 5% by weight of the catalyst, based on
point by-products are produced during the distillation. A the 100% by weight of the reaction mixture.
more preferable range for T is from 190 to 240°C., with from 40 The composition of the reaction mixture varies depending
195 to 230° C. being yet more preferable. on the conditions of the transesterification reaction between
It is undesirable for P to be less than 1000 Pa, since then the dialkyl carbonate and the phenol, the type and amount of
large equipment enabling a high vacuum to be maintained the catalyst and so on, but so long as the transesterification
must be used. Moreover, it is undesirable for P to be greater reaction is carried out under constant conditions, a reaction
than 20000 Pa, since then the distillation temperature must be 45 mixture of approximately constant composition can be pro
increased and hence production of by-products increases. A duced, and hence the composition of the reaction mixture fed
more preferable range for P is from 2000 to 15000 Pa, with into the high boiling point material separating column A may
from 3000 to 13000 Pa being yet more preferable. be approximately constant. However, in the present inven
For the high boiling point material separating column A tion, so long as the composition of the reaction mixture is
and the diphenyl carbonate purifying column B, so long as D. 50 within the above range, then even if this composition fluctu
and D, are within the above ranges, each of the columns may ates somewhat, the separation can still be carried out with
have the same inside diameter from the upper portion thereof approximately the same separation efficiency. This is one of
to the lower portion thereof, or the inside diameter may differ the characteristic features of the present invention.
in different portions. For example, for each of the continuous In the present invention, when continuously feeding the
multi-stage distillation columns, the inside diameter of the 55 reaction mixture that acts as the starting material into the high
upper portion of the column may be smaller than, or larger boiling point material separating column A, the reaction mix
than, the inside diameter of the lower portion of the column. ture may be fed in a liquid from into inlet(s) provided in one
Each of the high boiling point material separating column or a plurality of positions below a middle portion of the
A and the diphenyl carbonate purifying column B used in the separating column A, or it is also preferable to feed the reac
present invention is a distillation column having a tray and/or 60 tion mixture into the column via a reboiler of the separating
a packing as the internal. The term “internal used in the column A from piping provided at a lower portion of the
present invention means the parts in the distillation column reboiler. The amount of the reaction mixture fed into the high
where gas and liquid are actually brought into contact with boiling point material separating column A varies depending
one another. As the tray, for example, a bubble-cap tray, a on the amount of the high-purity diphenyl carbonate to be
sieve tray, a valve tray, a counterflow tray, a Superfrac tray, a 65 produced, the concentration of the diphenyl carbonate in the
Maxifrac tray or the like are preferable. As the packing, irregu reaction mixture, the separation conditions for the separating
lar packings Such as a Raschig ring, a Lessing ring, a Pall ring, column A and so on, but the above amount is generally not
 US 7,812,189 B2
21 22
less than 2 ton/hr, preferably not less than 6 ton/hr, more point material separating column A is generally approxi
preferably not less than 10 ton/hr. The upper limit of the mately 90 to 97% of the reaction mixture fed into the sepa
amount of the reaction mixture fed into varies depending on rating column A. This column top component (A) is con
the size of the apparatus, the required production amount and tinuously fed into the diphenyl carbonate purifying column B
so on, but the upper limit is generally 200 ton/hr. The reaction from the inlet B1 provided at an intermediate portion of the
mixture fed continuously into the high boiling point material purifying column B, and is continuously separated into three
separating column A is separated into a column top compo components, i.e. a column top component (B), a side cut
nent (A) containing most of the diphenyl carbonate and most component (Bs), and a column bottom component (B). All
of compounds having a lower boiling point than that of the of components having a lower boiling point than that of the
diphenyl carbonate, Such as unreacted starting material, an 10 diphenyl carbonate contained in the column top component
alkyl phenyl ether and an alkyl phenyl carbonate, and a col (A) from the separating column A fed into the purifying
umn bottom component (A) containing the catalyst, high column B are continuously withdrawn from the top of the
boiling point by-products and a small amount of the diphenyl purifying column B as the column top component (B), and a
carbonate. Small amount of liquid is continuously withdrawn from the
The column bottom component (A) may contain a small 15 bottom of the purifying column B. A small amount of the
amount of the alkyl phenyl carbonate. Such organic material diphenyl carbonate is contained in the column top component
in the column bottom component (A) plays a useful role in (B), this amount generally being 1 to 9%, preferably 3 to 8%,
dissolving the catalyst component and thus maintaining a of the diphenyl carbonate fed in. The diphenyl carbonate in
liquid State of the column bottom component (A). All or the column top component (B) is separated out and thus
Some of the column bottom component (A) is generally recovered in another distillation column used for separating
reused by recycling to the first reactive distillation column as the column top component (B). Alternatively, a method in
a transesterification reaction catalyst component, but in some which this diphenyl carbonate is separated off as the column
cases the catalyst may be recycled after being separated from bottom component from this other distillation column, and is
the organic material in a catalyst recovery process, and then then recovered by being returned into the high boiling point
reused by recycling to the first reactive distillation column. 25 material separating column A and/or the diphenyl carbonate
It is a characteristic feature of the present invention that the purifying column B is also preferable.
catalyst component and by-products having a higher boiling The column bottom component (B) contains the diphenyl
point than that of the diphenyl carbonate Such as phenyl carbonate, and a small amount of high boiling point by
salicylate, Xanthone, phenyl methoxybenzoate and 1-phe products concentrated to approximately a few percent.
noxycarbonyl-2-phenoxycarboxy-phenylene are almost 30 Another characteristic feature of the present invention is that
completely removed as the column bottom component (A) the amount of the diphenyl carbonate in the column bottom
in the high boiling point material separating column A, it component (B) withdrawn from the bottom of the purifying
being easy to make the content thereof in the column top column B can be kept very low. This amount is generally 0.05
component (A) be generally not more than 200 ppm, pref to 0.5% of the diphenyl carbonate fed in.
erably not more than 100 ppm, more preferably not more than 35 The high-purity diphenyl carbonate is continuously with
50 ppm. It is another characteristic feature of the present drawn from the side cut outlet B2 at a flow rate of generally
invention that despite making the column top component not less than 1 ton/hr, preferably not less than 3 ton/hr, more
(A) hardly contain any Such high boiling point by-products, preferably not less than 5 ton/hr. This amount generally cor
most of the diphenyl carbonate in the reaction mixture intro responds to approximately 90 to 96% of the diphenyl carbon
duced can be withdrawn from the top of the column. In the 40 ate fed into the purifying column B.
present invention, not less than 95%, preferably not less than The purity of the diphenyl carbonate obtained as the side
96%, more preferably not less than 98% of the diphenyl cut component (Bs) in the present invention is generally not
carbonate in the reaction mixture continuously fed into the less than 99.9%, preferably not less than 99.99%, more pref
high boiling point material separating column A can be with erably not less than 99.999%. The contents of high boiling
drawn from the top of the column. Moreover, in the present 45 point impurities when carrying out the present invention with
invention, although dependent on the composition of the reac dimethyl carbonate and phenol as the starting material are not
tion mixture fed into the separating column A, typically 90 to more than 30 ppm, preferably not more than 10 ppm, more
97% by weight of the liquid continuously fed in is continu preferably not more than 1 ppm for phenyl salicylate, not
ously withdrawn from the top of the column as the column top more than 30 ppm, preferably not more than 10 ppm, more
component (A), with 10 to 3% being continuously with 50 preferably not more than 1 ppm for Xanthone, not more than
drawn from the bottom of the column as the column bottom 30 ppm, preferably not more than 10 ppm, more preferably
component (A). The composition of the column top compo not more than 1 ppm for phenyl methoxybenzoate, and not
nent (A) is generally 0.05 to 2% by weight of the dialkyl more than 30 ppm, preferably not more than 10 ppm, more
carbonate, 1 to 21% by weight of the phenol, 0.05 to 2% by preferably not more than 5 ppm for 1-phenoxycarbonyl-2-
weight of an alkyl phenyl ether, 11 to 47% by weight of the 55 phenoxycarboxy-phenylene. Moreover, the total content of
alkyl phenyl carbonate, and 52 to 84% by weight of the these high boiling point by-products is not more than 100
diphenyl carbonate, based on 100% by weight of the column ppm, preferably not more than 50 ppm, more preferably not
top component (A). The content of the high boiling point more than 10 ppm. Note that the term “high-purity diphenyl
by-products is generally not more than 200 ppm, preferably carbonate' used in the present invention means that the purity
not more than 100 ppm, more preferably not more than 50 60 of the diphenyl carbonate is not less than 99.9 and the diphe
ppm. nyl carbonate contains not more than 100 ppm of high boiling
In the present invention, the reflux ratio for the high boiling point by-products.
point material separating column A is in a range of from 0.01 Moreover, in the present invention, a starting material and
to 10, preferably from 0.08 to 5, more preferably from 0.1 to catalyst not containing a halogen are generally used, and
3. 65 hence the halogen content of the diphenyl carbonate obtained
As stated above, the amount of the column top component is not more than 0.1 ppm, preferably not more than 10 ppb.
(A) continuously withdrawn from the top of the high boiling more preferably not more than 1 ppb.
 US 7,812,189 B2
23 24
In the present invention, the reflux ratio for the diphenyl duced as is into the purifying column B from the inlet B1. The
carbonate purifying column B is in a range of from 0.01 to 10, column bottom temperature (T) was made to be 213°C. and
preferably from 0.1 to 8, more preferably from 0.5 to 5. the column top pressure (P) was made to be 5000 Pa in the
The material constituting the high boiling point material purifying column B, distillation was carried out continuously
separating column A, the diphenyl carbonate purifying col with a reflux ratio of 1.5, a column top component (B) was
umn B, and other liquid-contacting parts which are used in the continuously withdrawn at 5.3 ton/hr via a conduit 26, a
present invention is generally a metallic material Such as column bottom component (B) was continuously withdrawn
carbon steel or stainless steel. In terms of the quality of the at 0.03 ton/hr via a conduit 31, and a side cut component (Bs)
diphenyl carbonate produced, stainless Steel is preferable. was continuously withdrawn at 7.17 ton/hr via a conduit 33.
10 The compositions of the components at 24 hours after the
EXAMPLES system had become completely stable were as follows.
Hereinbelow, the present invention will be described in A: 0.1% by weight of dimethyl carbonate, 0.1% by weight of
more detail with reference to the following Examples, but the anisole, 6.6% by weight of phenol, 33.8% by weight of
present invention is not limited to the following Examples. 15 methyl phenyl carbonate, 59.4% by weight of diphenyl car
The purity of the diphenyl carbonate, and the contents of bonate;
impurities were measured by means of a gas chromatography A:41.0% by weight of diphenyl carbonate, 59.0% by weight
method, and the halogen content was measured by means of of high boiling point material including a catalyst component
an ion chromatography method. and by-products having a higher boiling point than that of
diphenyl carbonate such as phenyl salicylate, Xanthone, phe
Example 1 nyl methoxybenzoate and 1-phenoxycarbonyl-2-phenoxy
carboxy-phenylene;
High Boiling Point Material Separating Column A B: 0.25% by weight of dimethylcarbonate, 0.25% by weight
A continuous multi-stage distillation column as shown in 25 of anisole, 15.6% by weight of phenol, 79.6% by weight of
FIG. 1 having L-1700 cm and D340 cm, and having methyl phenyl carbonate, 4.3% by weight of diphenyl car
Mellapak with n=30 installed therein as the internal was bonate;
used as the separating column A. B: 95.0% by weight of diphenyl carbonate, 5.0% by weight
<Diphenyl Carbonate Purifying Column B of the high boiling point material.
A continuous multi-stage distillation column as shown in
30 The content of each of phenyl salicylate, Xanthone and
phenyl methoxybenzoate in the side cut component was not
FIG. 1 having L 2200 cm and D, 280 cm, and having three more than 1 ppm, and the content of 1-phenoxycarbonyl-2-
sets of Mellapak with n=12, n=18, and n=5 installed phenoxycarboxy-phenylene was 4 ppm. Moreover, the halo
therein as the internal was used as the purifying column B. gen content was not more than 1 ppb. It was thus found that
<Reactive Distillation> 35 the purity of the diphenyl carbonate obtained from the side cut
An apparatus in which two reactive distillation columns (a was not less than 99.999%. Moreover, the amount of this
first reactive distillation column and a second reactive distill high-purity diphenyl carbonate produced was 7.17 ton/hr.
lation column) were connected together was used, the reac Prolonged continuous operation was carried out under
tion liquid in the first reactive distillation column was made to these conditions. The amount of diphenyl carbonate produced
contain 100 ppm of Pb(OPh) as a catalyst, reactive distilla 40 and the purity were substantially unchanged after 500 hours,
tion was carried out using dimethyl carbonate and phenol as 2000 hours, 4000 hours, 5000 hours, and 6000 hours.
a starting material, and a reaction mixture containing diphe
nyl carbonate was continuously withdrawn at 13.1 ton/hr Example 2
from the column bottom of the second reactive distillation
column. Note that halogens were not detected in the starting 45 Reactive Distillation
material or the catalyst used in the reaction.
The composition of the reaction mixture was 0.1% by An apparatus in which two reactive distillation columns (a
weight of dimethyl carbonate, 0.1% by weight of anisole, first reactive distillation column and a second reactive distill
6.3% by weight of phenol, 32.2% by weight of methyl phenyl lation column) were connected together was used, the reac
50
carbonate, 58.6% by weight of diphenyl carbonate, and 2.7% tion liquid in the first reactive distillation column was made to
by weight of high boiling point by-products including the contain 250 ppm of Pb(OPh) as a catalyst, reactive distilla
catalyst. tion was carried out using dimethyl carbonate and phenol as
<Separation/Purification> a starting material, and a reaction mixture containing diphe
nyl carbonate was continuously withdrawn at 11.3 ton/hr
Using an apparatus comprising the high boiling point 55 from the column bottom of the second reactive distillation
material separating column A and the diphenyl carbonate column. Note that halogens were not detected in the starting
purifying column B as shown in FIG. 1, the reaction mixture material or the catalyst used in the reaction.
obtained through the reactive distillation described above was The composition of the reaction mixture was 0.1% by
continuously introduced at 13.1 ton/hr into the separating weight of dimethyl carbonate, 0.1% by weight of anisole,
column A from the inlet A1. The column bottom temperature 60 2.5% by weight of phenol, 33.2% by weight of methyl phenyl
(T) was made to be 206° C. and the column top pressure (P) carbonate, 62.5% by weight of diphenyl carbonate, and 1.6%
was made to be 3800 Pa in the separating column A, distilla by weight of high boiling point by-products including the
tion was carried out continuously with a reflux ratio of 0.6, a catalyst.
column top component (A) was continuously withdrawn at
12.5 ton/hr via a conduit 16, and a column bottom component 65 <Separation/Purification>
(A) was continuously withdrawn at 0.6 ton/hr via a conduit Using an apparatus comprising the high boiling point
11. The column top component (A) was continuously intro material separating column A and the diphenyl carbonate
 US 7,812,189 B2
25 26
purifying column B as shown in Example 1, the reaction Note that halogens were not detected in the starting material
mixture obtained through the reactive distillation described or the catalyst used in the reaction.
above was continuously introduced at 11.3 ton/hr into the The composition of the reaction mixture was 0.2% by
separating column A from the inlet A1. The column bottom weight of dimethyl carbonate, 0.1% by weight of anisole,
temperature (T) was made to be 205° C. and the column top 6.6% by weight of phenol, 30.2% by weight of methyl phenyl
pressure (P) was made to be 4000 Pa in the separating
column A, distillation was carried out continuously with a carbonate, 60.1% by weight of diphenyl carbonate, and 2.8%
reflux ratio of 0.7, a column top component (A) was con by weight of high boiling point by-products including the
tinuously withdrawn at 11.0 ton/hr via the conduit 16, and a catalyst.
column bottom component (A) was continuously with 10
<Separation/Purification>
drawn at 0.3 ton/hr via the conduit 11. The column top com
ponent (A) was continuously introduced as is into the puri Using an apparatus comprising a high boiling point mate
fying column B from the inlet B1. The column bottom rial separating column A and a diphenyl carbonate purifying
temperature (T) was made to be 210°C. and the column top column B as shown in Example 1, the reaction mixture
pressure (P) was made to be 4500 Pa in the purifying column 15
obtained through the reactive distillation described above was
B, distillation was carried out continuously with a reflux ratio continuously introduced at 17.2 ton/hr into the separating
of 2.0, a column top component (B) was continuously with column A from the inlet A1. The column bottom temperature
drawn at 4.7 ton/hr via the conduit 26, a column bottom
component (B) was continuously withdrawn at 0.03 ton/hr (T) was made to be 207 C. and the column top pressure (P)
via the conduit 31, and a side cut component (Bs) was con was made to be 4100 Pa in the separating column A, distilla
tinuously withdrawn at 6.27 ton/hr via the conduit 33. tion was carried out continuously with a reflux ratio of 0.61,
The compositions of the components at 24 hours after the a column top component (A) was continuously withdrawn at
system had become completely stable were as follows. 16.4 ton/hr via the conduit 16, and a column bottom compo
A: 0.1% by weight of dimethylcarbonate, 0.1% by weight of nent (A) was continuously withdrawn at 0.8 ton/hr via the
anisole, 2.6% by weight of phenol. 34.1% by weight of conduit 11. The column top component (A) was continu
methyl phenyl carbonate, 63.1% by weight of diphenyl car ously introduced as is into the purifying column B from the
bonate; inlet B1. The column bottom temperature (T) was made to
A:40.2% by weight of diphenyl carbonate, 59.8% by weight be 220° C. and the column top pressure (P) was made to be
of the high boiling point material including a catalyst com 30 6600 Pain the purifying column B, distillation was carried out
ponent and by-products having a higher boiling point than continuously with a reflux ratio of 1.49, a column top com
that of diphenyl carbonate such as phenyl salicylate, Xan ponent (B) was continuously withdrawn at 7.1 ton/hr via the
thone, phenyl methoxybenzoate and 1-phenoxycarbonyl-2- conduit 26, a column bottom component (B) was continu
phenoxycarboxy-phenylene; ously withdrawn at 0.05 ton/hr via the conduit 31, and a side
B: 0.3% by weight of dimethylcarbonate, 0.2% by weight of 35 cut component (Bs) was continuously withdrawn at 9.25 ton/
anisole, 6.1% by weight of phenol, 79.8% by weight of hr via the conduit 33.
methyl phenyl carbonate, 13.6% by weight of diphenyl car The compositions of the components at 24 hours after the
bonate; system had become completely stable were as follows.
B. 96.0% by weight of diphenyl carbonate, 4.0% by weight 40
A: 0.2% by weight of dimethyl carbonate, 0.1% by weight of
of the high boiling point material. anisole, 6.9% by weight of phenol, 31.7% by weight of
The content of each of phenyl salicylate, Xanthone and methyl phenyl carbonate, 61.1% by weight of diphenyl car
phenyl methoxybenzoate in the side cut component was not
more than 1 ppm, and the content of 1-phenoxycarbonyl-2- bonate;
phenoxycarboxy-phenylene was 3 ppm. Moreover, the halo 45
A: 39.8% by weight of diphenyl carbonate, 61.2% by weight
gen content was not more than 1 ppb. It was thus found that of high boiling point material including a catalyst component
the purity of the diphenyl carbonate obtained from the side cut and by-products having a higher boiling point than that of
was not less than 99.999%. Moreover, the amount of this diphenyl carbonate such as phenyl salicylate, Xanthone, phe
high-purity diphenyl carbonate produced was 6.27 ton/hr.
Prolonged continuous operation was carried out under 50 nyl methoxybenzoate and 1-phenoxycarbonyl-2-phenoxy
these conditions. The amount of diphenyl carbonate produced carboxy-phenylene;
and the purity were substantially unchanged after 500 hours, B: 0.5% by weight of dimethyl carbonate, 0.2% by weight of
1000 hours, and 2000 hours. anisole, 16.0% by weight of phenol, 73.2% by weight of
Example 3 55 methyl phenyl carbonate, 10.1% by weight of diphenyl car
bonate;
Reactive Distillation B: 94.0% by weight of diphenyl carbonate, 6.0% by weight
of high boiling point material.
An apparatus in which two reactive distillation columns (a
first reactive distillation column and a second reactive distill 60 The content of each of phenyl salicylate, Xanthone and
lation column) were connected together was used, the reac phenyl methoxybenzoate in the side cut component was not
tion liquid in the first reactive distillation column was made to more than 1 ppm, and the content of 1-phenoxycarbonyl-2-
contain 150 ppm of Pb(OPh), as a catalyst, reactive distilla phenoxycarboxy-phenylene was 4 ppm. Moreover, the halo
tion was carried out using dimethyl carbonate and phenol as gen content was not more than 1 ppb. It was thus found that
a starting material, and a reaction mixture containing diphe 65 the purity of the diphenyl carbonate obtained from the side cut
nyl carbonate was continuously withdrawn at 17.2 ton/hr was not less than 99.999%. Moreover, the amount produced
from the bottom of the second reactive distillation column. of this high-purity diphenyl carbonate was 9.25 ton/hr.
 US 7,812,189 B2
27 28
Prolonged continuous operation was carried out under having a length L. (cm), an inside diameter D (cm),
these conditions. The amount of diphenyl carbonate produced an internal thereinside, an inlet B1 at a middle portion
and the purity were substantially unchanged after 500 hours, of the column, and a side cut outlet B2 between said
1000 hours, and 2000 hours. inlet B1 and the column bottom, in which a number of
stages of the internal above the inlet B1 is n, a num
INDUSTRIAL APPLICABILITY ber of stages n of the internal between the inlet B1
and the side cut outlet B2 is n, a number of stages in
The present invention can be suitably used in the field of of the internals below the side cut outlet B2 is n, and
producing a high-purity diphenyl carbonate, which can be a total number of stages is n (n+n+n), wherein
used as a raw material of a high-quality and high-performance 10 L. D., n., n2 ns, and in Satisfy the following formu
polycarbonate, stably for a prolonged period of time on an lae (4) to (9);
industrial scale of not less than 1 ton/hr from a reaction
mixture containing a catalyst and reaction by-products that 1000s La 5000 (4)
has been obtained through transesterification reaction or the 100s Da1000 (5)
like using a dialkyl carbonate and a phenol as a starting 15
material. 5ans20 (6)
We claim:
1. A process for the production of a high-purity diphenyl 12sn's 40 (7)
carbonate, the process comprising the steps of:
(i) carrying out a transestrification reaction between a 3 sn's 15 (8)
dialkyl carbonate and a phenol and/or a disproportion
ation reaction of an alkyl carbonate and/or a transesteri 20sn's 70 (9).
fication reaction between an alkyl phenyl carbonate and 2. The process according to claim 1, wherein not less than
a phenol in the presence of a homogeneous catalyst, so 1 ton/hr of the high-purity diphenyl carbonate is obtained as
as to form a reaction mixture containing a diphenyl 25 the side cut component Bs.
carbonate; 3. The process according to claim 1 or 2, wherein L, D,
(ii) carrying out separation by distillation in a high boiling and n for said high boiling point material separating column
point material separating column A into a column top A satisfy the following formulae: 1000sLs2500,
component A containing the diphenyl carbonate and a 200sDs600, and 30sns70, respectively,
column bottom component A containing the catalyst 30
L. D., n., n2 ns, and n for said diphenyl carbonate
(iii) carrying out separation by distillation of said column purifying column B satisfy the following formulae:
top component A in a diphenyl carbonate purifying 1500sLis3000, 150sDs500, 7sn's 15,
column B having a side cut outlet into a column top 12sn-s30, 3sins 10, and 25sn's 55, respectively,
component B, a side cut component Bs and a column
bottom component B, said column top component A 35 T is in a range of from 190 to 240°C., P is in a range of
introducing from the side cut outlet into the column B; from 2000 to 15000 Pa,
wherein T is in a range of from 190 to 240°C., and P is in a range
(a) said high boiling point material separating column A of from 2000 to 15000 Pa.
comprises a continuous multi-stage distillation col 4. The process according to claim 1, wherein each of said
umn having a length L (cm), an inside diameter D. 40 high boiling point material separating column A and said
(cm), and an internal with a number of stages in diphenyl carbonate purifying column B is a distillation col
thereinside, wherein L, D, and n satisfy the fol umn having a tray and/or a packing as said internal.
lowing formulae (1) to (3): 5. The process according to claim 4, wherein said internal
800s. La3000 (1) of each of said high boiling point material separating column
45 A and said diphenyl carbonate purifying column B is a pack
100s De 1000 (2) ing.
6. The process according to claim 5, wherein said packing
20ans 100 (3): is structured packing.
(b) said diphenyl carbonate purifying column B com
prises a continuous multi-stage distillation column