U.S. patent application number 10/571134 was filed with the patent office on 2007-03-29 for process for producing bisphenol a.
Invention is credited to Kenji Fujiwara, Yuko Maruyama, Toshihiro Takai, Takashi Terajima.
Application Number | 20070073091 10/571134 |
Document ID | / |
Family ID | 34308498 |
Filed Date | 2007-03-29 |
United States Patent
Application |
20070073091 |
Kind Code |
A1 |
Terajima; Takashi ; et
al. |
March 29, 2007 |
Process for producing bisphenol a
Abstract
The present invention provides a process for producing bisphenol
A by reacting phenol with acetone, wherein reaction is performed at
higher temperatures while maintaining high selectivity, and thus
high productivity is obtained. The invention relates to a
cation-exchange resin, wherein a cation-exchange group is
introduced into a syndiotactic polystyrene polymer and the amount
of acid is 0.8 milliequivalent/g or more, to a catalyst comprising
the cation-exchange resin, and to a process for producing bisphenol
A using the cation-exchange resin catalyst.
Inventors: |
Terajima; Takashi;
(Sodegaura-shi, JP) ; Maruyama; Yuko;
(Sodegaura-shi, JP) ; Takai; Toshihiro;
(Sodegara-shi, JP) ; Fujiwara; Kenji;
(Sodegara-shi, JP) |
Correspondence
Address: |
BIRCH STEWART KOLASCH & BIRCH
PO BOX 747
FALLS CHURCH
VA
22040-0747
US
|
Family ID: |
34308498 |
Appl. No.: |
10/571134 |
Filed: |
September 1, 2004 |
PCT Filed: |
September 1, 2004 |
PCT NO: |
PCT/JP04/12634 |
371 Date: |
March 9, 2006 |
Current U.S.
Class: |
568/728 |
Current CPC
Class: |
B01J 2231/347 20130101;
C07C 37/20 20130101; C07C 37/20 20130101; C07C 39/16 20130101; C08F
8/36 20130101; C08F 8/32 20130101; C08F 8/36 20130101; C08F 8/36
20130101; C08F 8/32 20130101; C08F 212/08 20130101; C07C 39/16
20130101; B01J 31/10 20130101; C08F 12/08 20130101 |
Class at
Publication: |
568/728 |
International
Class: |
C07C 39/16 20060101
C07C039/16 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 10, 2003 |
JP |
2003-317759 |
Claims
1. A cation-exchange resin catalyst comprising a cation-exchange
resin, wherein a cation-exchange group is introduced into a
syndiotactic polystyrene polymer, and the amount of acid is 0.8
milliequivalent/g or more.
2. The cation-exchange resin catalyst according to claim 1, wherein
the crystallinity is 5% or more.
3. The cation-exchange resin catalyst according to claim 1, wherein
the syndiotacticity of the polystyrene polymer is 70% or more.
4. The cation-exchange resin catalyst according to claim 1, wherein
the catalyst is used in the reaction of phenol and acetone to
produce bisphenol A.
5. A process for producing bisphenol A by reacting phenol with
acetone, wherein the cation-exchange resin catalyst according to
claim 1 is used as a catalyst.
Description
TECHNICAL FIELD
[0001] The present invention relates to a catalyst comprising a
cation-exchange resin with a polystyrene polymer skeleton.
[0002] The present invention also relates to a process for
producing bisphenol A. More specifically, the invention relates to
a process for producing bisphenol A by reacting acetone with phenol
in the presence of a cation-exchange resin catalyst.
BACKGROUND ART
[0003] Bisphenol A [2,2-bis(4-hydroxyphenyl)propane] is usually
produced by reacting phenol with acetone in the presence of a
homogeneous acid or a solid acid catalyst. The reaction mixture
includes unreacted acetone, unreacted phenol, water and other
by-products formed by the reaction, in addition to bisphenol A. The
main component of the by-products is
2-(2-hydroxyphenyl)-2-(4-hydroxyphenyl)propane (hereinafter,
referred to as o,p'-BPA), and in addition, it includes trisphenol,
a polyphenol compound, a chroman compound, colored impurities and
the like.
[0004] Examples of a homogeneous acid to be used as a catalyst,
include hydrochloric acid, sulfuric acid and the like. In the case
where the homogeneous acid is used, since it is possible to proceed
the reaction while precipitating crystals of an adduct of phenol
with bisphenol A by reacting them at lower temperatures, bisphenol
A can be produced with a high conversion of acetone and a high
selectivity by decreasing the amount of the by-produced o,p'-BPA as
an isomer thereof. However, the catalyst of the homogeneous acid
such as hydrochloric acid requires a process for removing the
catalyst from a reaction mixture or for neutralizing the catalyst,
and thus the operation becomes complicated. Homogeneous dissolution
of the acid in the reaction solution further causes corrosion of an
apparatus or the like used in the reaction. Therefore, the reaction
apparatus should use expensive and anti-corrosive materials, thus
being uneconomical.
[0005] As a solid acid catalyst, a sulfonic acid-type
cation-exchange resin is usually used. The reaction for producing
bisphenol A essentially proceeds only with an acid catalyst, but if
such a solid acid catalyst is used, the process in which acetone
diffuses from the surface of the catalyst particles to an active
site on the catalyst is involved, and thus the reaction rate is
low. Thus, there is a general method used for improving the
catalytic activity and the selectivity by allowing a compound
containing a mercapto group to coexist in the reaction system (For
example, JP-B Nos. 45-10337, 46-19953, etc.).
[0006] Further, it is proposed in JP-A No. 62-178532 to use a
sulfonic acid-type cation-exchange resin in a fine particle or a
fine powder having an effective diameter of 0.3 mm or less for
obtaining a sufficient reaction conversion.
[0007] Various improvements on the structure of a resin product,
which is the base material of a sulfonic acid-type cation-exchange
resin, have been made. The sulfonic acid-type cation-exchange resin
is a resin obtained by sulfonating a styrene-divinylbenzene
copolymer which is obtained by radically copolymerizing styrene and
divinylbenzene. The divinylbenzene in polymerization does not only
prevent a polystyrene chain from dissolving in an organic solvent,
but the content thereof is also an important factor in controlling
the size of a pore, i.e., the size of a gel micropore within the
sulfonic acid-type cation-exchange resin formed by capturing a
polar solvent, or the mechanical strength of the sulfonic acid-type
cation-exchange resin.
[0008] In other words, a sulfonic acid-type cation-exchange resin
with a low content of divinylbenzene has a high catalytic activity
due to a large gel micropore, but the mechanical strength is low.
In addition, in the case where the content thereof is high, the
mechanical strength increases, but the gel micropore size
decreases, which causes decreased activity. JP-A Nos. 5-97741 and
6-320009 describe a method which complements the respective defects
by simultaneous filling a sulfonic acid-type cation-exchange resin
having a low content of divinylbenzene and a sulfonic acid-type
cation-exchange resin having a high content of divinylbenzene into
a reactor. Further, it is reported in WO 00/00454 that an
improvement on a reaction conversion, which suggests a sulfonic
acid-type cation-exchange resin having large gel micropores by
using large molecules such as divinylbiphenyl instead of
divinylbenzene.
[0009] The sulfonic acid-type cation-exchange resin in these
methods described above comprises as a base material, atactic
polystyrene which is obtained by radically copolymerizing styrene
and a polyvinyl aromatic compound such as divinylbenzene. Since the
atactic polystyrene is an amorphous resin without having a sharp
melting point, a commercially available ion-exchange resin
comprising the atactic polystyrene having a sulfone group
introduced thereinto has room for improvement in heat resistance
and is thus known to generate an effluent when it is used under the
heating condition of 80.degree. C. or higher. Thus, this causes
problems such as deterioration in mechanical strength, decrease in
the activity due to clogging of gel micropores, and deterioration
over a prolonged period, and thereby there is an obstacle in using
thereof at higher temperatures.
[0010] In order to overcome such problems, a method has been used
which increases the degree of crosslinking and improves heat
resistance in an atactic polymer chain. Since the diffusion within
the ion-exchange resin particles is extremely lowered as the degree
of crosslinking is increased, a large hole referred to as a
"macroporous" is formed within the particles by a physical
treatment in order to improve the diffusion within the
particles.
[0011] However, in the case where an ion-exchange resin having this
macroporous adsorbs a molecule having high polarity, such as water,
a crosslinked structure tends to inhibit the bulge of particles
caused by the swelling, which eventually collapses when it can no
longer endure the swelling. Therefore, the development of a
heat-resistant ion-exchange resin, which can be treated with an
aqueous solvent, is demanded.
[0012] It is described in U.S. Pat. No. 3,342,755 that halogen is
substituted for hydrogen on the tertiary carbon adjacent to the
benzene ring of the styrene moiety in order to overcome the above
described problem. However, the substitution of halogen for
hydrogen leads to elution of chlorine from the resin, and thus a
new problem occurs of incorporating halogen into a reaction
mixture.
[0013] Further, as a highly heat-resistant ion-exchange resin, a
perfluorosulfonic acid-based resin such as nafion is known, in
which the maximum amount of acid is about 1.0 milliequivalent/g.
Since this polymer skeleton is formed by copolymerization of
tetrafluoroethylene and a trifluorovinyl alcohol derivative, an
introduction exceeding a given amount of the trifluorovinyl alcohol
derivative is problematic in terms of the polymerization
technologies, which means that it is impossible to increase the
amount of acid.
[0014] Further, it is described in the respective papers of Polymer
Preprints, Vol. 34, p. 852 (1993), Macromolecules, Vol. 27, p. 287
(1994), Polymer International, Vol. 50, p. 421 (2001) or the like,
a process for synthesizing a crystalline polymer containing a
sulfone group, in which a sulfone group is introduced into
syndiotactic polystyrene, and then crystallized. It is believed
that it is necessary to remarkably suppress the amount of acidic
functional groups to be introduced, in order to crystallize the
sulfonated syndiotactic polystyrene later. Therefore, in this
example, the maximum amount of acid is only 1.0 milliequivalent/g,
thus being inadequate for a practical catalyst use.
[0015] As such, any ion-exchange resin product which has heat
resistance and a high amount of acid, and can be used as a catalyst
has not been exemplified. If an ion-exchange resin having heat
resistance and a high amount of acid can be developed, the
ion-exchange resin can be used as a solid catalyst at a high
temperature in the reaction using a conventional ion-exchange resin
at a low temperature or using a mineral acid as a catalyst, for
example, the hydration of isobutene and propylene, the synthesis of
bisphenol A from phenol and acetone, the synthesis of
methylenedianiline from aniline and formaldehyde, and the like,
thus it being an extremely useful catalyst in the industry.
[0016] [Patent Document 1] U.S. Pat. No. 3,342,755
[0017] [Patent Document 2] JP-A No. 2004-55165
[0018] [Non-Patent Document 1] Polymer Preprints, Vol. 34, p. 852
(1993)
[0019] [Non-Patent Document 2] Macromolecules, Vol. 27, p. 287
(1994)
[0020] [Non-Patent Document 3] Polymer International, Vol. 50, p.
421 (2001)
DISCLOSURE OF THE INVENTION
(Problems to be Solved by the Invention)
[0021] The present invention provides a cation-exchange resin
catalyst comprising a polystyrene cation-exchange resin, which has
excellent heat resistance and a sufficient amount of acid. Further,
the invention provides a process for producing bisphenol A by
reacting phenol with acetone, wherein a high heat resistance
cation-exchange resin is used as a catalyst in order to solve the
above described problems, reaction is performed at higher
temperatures while maintaining high selectivity, and as a result,
high productivity is obtained.
(Means for Solving the Problems)
[0022] The present inventors have conducted extensive studies to
solve the problems, and as a result, they have found that by using
a cation-exchange resin which can be obtained by introducing an
acidic functional group into a crystalline polymer as a catalyst, a
reaction can be performed at higher temperatures without
deteriorating the activity, selectivity and durability, and thereby
bisphenol A can be obtained with high productivity. Thus, they have
completed the invention.
[0023] In other words, the invention relates to a cation-exchange
resin catalyst as follows:
[0024] (1) A cation-exchange resin catalyst comprising a
cation-exchange resin, wherein a cation-exchange group is
introduced into a syndiotactic polystyrene polymer, and the amount
of acid is 0.8 milliequivalent/g or more.
[0025] Furthermore, hereinbelow, the preferable embodiments and the
production processes for the cation-exchange resin catalyst of the
invention will be described.
[0026] (2) The cation-exchange resin catalyst as described in (1)
above, wherein the crystallinity is 5% or more.
[0027] (3) The cation-exchange resin catalyst as described in (1)
above, wherein the syndiotacticity of the polystyrene polymer is
70% or more.
[0028] (4) The cation-exchange resin catalyst as described in (1)
above, wherein the catalyst is used in the reaction of phenol and
acetone to produce bisphenol A.
[0029] (5) A process for producing bisphenol A by reacting phenol
with acetone, wherein the cation-exchange resin catalyst as
described in (1) above is used as a catalyst.
(Effects of the Invention)
[0030] According to the present invention, a cation-exchange resin
catalyst, which has a high amount of acid and excellent activity,
and can be used at a high temperature, is provided.
[0031] According to the process of the invention, bisphenol A can
be produced with high yield and selectivity, and bisphenol A can be
produced with remarkably excellent in safety, processability and
economic aspects.
BEST MODE FOR CARRYING OUT THE INVENTION
[0032] The cation-exchange resin catalyst of the present invention
is produced by subjecting the styrene polymer to chemical treatment
for introduction of an acidic functional group.
[0033] The styrene polymer includes .alpha. or .beta. substituted
polystyrenes such as polystyrene and poly(.alpha.-methylstyrene),
and phenyl substituted polystyrenes such as poly(p-methylstyrene).
Among these, unsubstituted polystyrene is preferred.
[0034] For example, syndiotactic polystyrene in which the phenyl
groups which are the side-chain with respect to the main chain
formed by a carbon-carbon bond of the polystyrenes obtained by the
copolymerization of a styrenic monomer alone or the
copolymerization of a styrenic monomer and a polyvinyl aromatic
compound, are alternately located in the opposite direction, and
isotactic polystyrene in which the phenyl groups are located in the
same direction are preferable from the viewpoint that they have
crystallinity, and syndiotactic polystyrene are more preferable
from the viewpoint that it rapidly crystallizes.
[0035] Syndiotactic polystyrene may be commercially available one,
or may be a polymer obtained by polymerization of a styrenic
monomer alone or a polymer obtained by copolymerization of a
styrenic monomer and a polyvinyl aromatic monomer. The
polymerization method is not particularly limited, but in either
cases of using a polymer obtained by the polymerization of a
styrenic monomer alone or of using a polymer obtained by the
copolymerization of a styrenic monomer and a polyvinyl aromatic
monomer, a polymer having high stereoregularity can be obtained by
using the method as disclosed in, for example, JP-A No. 8-151492,
JP-A No. 8-151414, JP-A No. 8-143729, JP-A No. 8-134122, JP-B No.
7-77790, JP-B No. 7-57767, JP-B No. 7-55994, or the like.
[0036] The tacticity indicating the stereoregularity of
syndiotactic polystyrene can be measured by a 13C-NMR method and
can be represented by the existence ratios of the plural
consecutive constitutional units, for example, a dyad in the case
of where two constitutional units exist, a triad in the case of
where three constitutional units exist, and a pentad in the case of
where five constitutional units exist, and in the racemic dyad, the
ratio is preferably 70% or more, and more preferably 75% or
more.
[0037] Other ones with stereostructures such as isotatic polymers
may be mixed with the syndiotactic polystyrene as long as they do
not adversely affect the scope of the invention.
[0038] The polymer used in the invention may have a crosslinked
structure. The crosslinked structure means the structure such that
the main chain or side chain of a polymer molecule is linked with
the main chain or side chain of another polymer molecule via a
crosslinking structure by means of any kind of methods for
introducing the crosslinked structure. For example, if styrene
having one vinyl group and divinylbenzene which is polyvinyl
aromatics are copolymerized, a main chain of the polymer can be
generated, as well as a crosslinked structure can be introduced.
Further, a polymer having no crosslinked structure may be
crosslinked later by the method as disclosed in JP-A No.
2002-363116.
[0039] In the case of using a polymer obtained by the
copolymerization of a styrenic monomer and a polyvinyl aromatic
monomer, the degree of crosslinking, which is represented by, for
example, (weight of polyvinyl aromatic monomer)/(weight of total
monomers), is from 0.01% to 20% (inclusive), preferably from 0.1%
to 15% (inclusive), and particularly preferably from 0.1% to 10%
(inclusive).
[0040] Elution of the thus obtained ion-exchange resin is
suppressed, and its physical strength is enhanced while maintaining
the diffusibility of the material in the ion-exchange resin. As a
result, it is possible to maintain its catalytic activity over a
prolonged period.
[0041] The styrenic monomer used includes styrene and substituted
styrene such as .alpha.-methylstyrene, vinyltoluene, vinylxylene,
ethylvinylbenzene, vinylnaphthalene, vinylbiphenyl,
methylvinylbiphenyl and the like, and preferred is styrene.
[0042] The polyvinyl aromatic monomer includes, for example,
divinylbenzene, divinyltoluene, divinylchlorobenzene,
diallyphthalate, divinylnaphthalene, divinylxylene, divinylethyl
benzene, trivinylnaphthalene, polyvinylanthracene,
divinylphenanthrene, divinylbiphenyldivinyl terphenyl, divinyl
diphenylmethane, divinyl diphenylmethane and the like, and
preferred is divinylbenzene.
[0043] The styrenic monomer and the polyvinyl aromatic monomer can
be used in any combination, but in order to sufficiently perform
the crosslinking, it is important to adjust the reactivity of
polymerization reactions with a combination of the vinyl groups, as
in styrene and divinylbenzene.
[0044] The invention is characterized in that the polymer is first
crystallized by heat treatment or other methods, and an acidic
functional group is later introduced thereto from the exterior
surface of the polymer particle. With this method, the acidic
functional group can be introduced in any proportion without
adversely affecting the crystallinity of the whole particle.
[0045] In other words, if the operation is sufficiently performed
during the crystallization process, a polymer having high
crystallinity can be obtained, and with a simple and easy
operation, a polymer having low crystallinity can be obtained.
Further, even when an acidic functional group is introduced into
these polymers, the amount of acidic functional group to be
introduced can be controlled by selection of the reaction condition
and the kind of electrophilic reagents. As such, the crystallinity
and the amount of acidic functional group can have any value.
[0046] The method for crystallizing a polymer is not particularly
limited and employs a well-known method, but a method for
performing heat treatment of a crystalline polymer is convenient,
which is preferable. For the heat treatment, mention may be made
of, for example, a method of heating a polymer to its melting point
or higher and then cooling the polymer, a method of heating a
polymer to its melting point or lower, maintaining the polymer at
that temperature and then cooling the polymer, a method of
dissolving or dispersing a polymer in a solvent, heating the
polymer, and then cooling the polymer, and the like, and any such
method may be used. In order to enhance the heat resistance of the
obtained ion-exchange resin, the crystallinity as determined by an
X-ray process is preferably from 5% to 50% (inclusive), and more
preferably from 10% to 50% (inclusive). The X-ray process for
determining the crystallinity of a polymer is a generally known
process, and described in "Kobunshi Jikkengaku, Vol. 17, Solid
Structure of Polymer II, p. 313, Kyoritsu Shuppan (1984)", etc.
[0047] According to the invention, the acidic functional groups to
be introduced into the polymer include a carboxyl group, a sulfonic
acid group and the like, among which the sulfonic acid group is
preferable due to sufficient strength as an acid catalyst, easy
introduction by an electrophilic reaction, or the like.
[0048] A well-known method can be used for introduction of a
sulfonic acid group, and the method includes, for example, a method
wherein a predetermined amount of a reagent such as sulfuric acid,
acetyl sulfuric acid, fuming sulfuric acid and chlorosulfuric acid
is added for sulfonation in the liquid phase in the presence of a
swelling agent or a solvent, a method wherein a sulfonating agent
such as sulfur trioxide is contacted with a polymer in the gas
phase for sulfonation, and the like. From the viewpoint of the
sulfonation rate, a method for sulfonation in the liquid phase is
preferred.
[0049] The solvent or swelling agent used in the sulfonation in the
liquid phase is not particularly limited as long as it does not
react with a sulfonating reagent, but those having too high
solubility in a polystyrene polymer might adversely affect the
crystallinity of the polymer. In addition, when the affinity with
the polystyrene polymer is too low, sulfonation may not proceed
sufficiently. The swelling agent or the solvent can be suitably
chosen in consideration of these points, but in the case of using
polystyrene for the polystyrene polymer, it is preferable to use a
high polarity solvent such as nitrobenzene, glacial acetic acid,
1,4-dioxane and petroleum ether, because sulfonation proceeds from
the surface of the polymer particles.
[0050] In order to obtain a sufficient function as a catalyst, the
amount of acid of the ion-exchange resin after introduction of an
acidic functional group is preferably 0.8 milliequivalent/g or
more, and more preferably 1.1 milliequivalent/g or more. Further,
the amount of acid of the ion-exchange resin can be determined by
stirring 0.2 g of a proton type dry resin in 100 ml of a 10%
aqueous NaCl solution for one hour and back-titrating the whole
amount of the filtrate with a 0.05 N aqueous NaOH solution.
[0051] As the ion-exchange resin obtained in the invention, an
ion-exchange resin which generates a lower amount of the eluate, as
compared with a conventional one in the use of the heating
condition, can be obtained. For example, when 50 g of water and 2 g
of the ion-exchange resin are stirred at 130.degree. C. for 18
hours, the elution of the acid components into water is preferably
1.5% or less, and more preferably 1.1% or less.
[0052] The forms of such ion-exchange resin are defined in the
stages of polystyrene obtained in polymerization. In other words,
if the acidic functional group is introduced as the powder obtained
in polymerization, an ion-exchange resin in the powder form can be
obtained. On the other hand, in the stages of polystyrene, a
particle or a sheet may be formed by a well known method or a
fibrous form may be obtained after spinning, and if an acidic
functional group is introduced to the formed product as a raw
material, an ion-exchange resin maintaining the shape of
polystyrene can be obtained. For the form of polystyrene, a large
powder or particle form having a large specific surface area is
preferred from the points of easy introduction of the acidic
functional group and excellent catalytic activity.
[0053] The reaction for producing Bisphenol A essentially proceeds
with an acid catalyst only, but typically a method for improving
the catalytic activity and the selectivity by allowing a mercapto
group-containing compound coexist therewith as a cocatalyst, can be
adopted. Also, in the invention, it is preferable for allowing a
mercapto group-containing compound to coexist. Such methods include
a method wherein a small amount of a mercapto group-containing
compound such as alkyl mercaptan is mixed with a mixture of phenol
and acetone which are raw materials, and the resultant mixture is
used, a method wherein a mercapto group-containing compound is
bound to an acidic functional group of a cation-exchange resin, and
the like, and any such method may be used.
[0054] The mercapto group-containing compound to be mixed with the
mixture of phenol and acetone is not particularly limited in the
structure, as long as it contains a mercapto group in its molecule,
and it includes, for example, mercapto alkyl groups such as a
mercaptomethyl group, a 2-mercaptoethyl group and a
3-mercapto-n-propyl group, alicyclic hydrocarbon groups such as a
4-mercaptocyclohexyl group and a 4-mercaptomethyl cyclohexyl group,
mercapto aromatic groups such as a p-mercaptophenyl group and a
p-mercaptomethylphenyl group, and the like. Further, these
aromatic, aliphatic or alicyclic hydrocarbon groups may be
hydrocarbon groups having a substituent such as a halogen atom, an
alkoxy group, a nitro group and a hydroxyl group, in addition to
the mercapto group. The amount of this mercapto group-containing
compound to be added to the mixture of phenol and acetone is
preferably in the range of 100 wtppm to 5 wt %. By this, it is
possible to exhibit the cocatalyst effect to a maximum extent with
a small amount of a cocatalyst.
[0055] The mercapto group-containing compound to be bound to a part
of the acidic functional group of the cation-exchange resin is not
particularly limited, but the compound may be any one which forms
an ionic bond with the acidic functional group of the
cation-exchange resin. This compound includes mercapto alkylamines
such as 2-mercaptoethylamine (cysteamine), 3-mercaptopropylamine
and N,N-dimethyl-3-mercaptopropylamine, mercaptoalkyl pyridines
such as 3-mercaptomethylpyridine, 3-mercaptoethyl pyridine and
4-mercaptoethyl pyridine, thiazolidines such as thiazolidine,
2,2-dimethylthiazolidine, 2-methyl-2-phenylthiazolidine and
3-methylthiazolidine, and the like. The ratio for the acidic
functional group to be bound to the mercapto group-containing
compound is 2 to 50%, and preferably 5 to 30% of the total sulfonic
acid groups of the sulfonic acid-type cation-exchange resin. By
this, it is possible to exhibit the cocatalyst effect to a maximum
extent without causing the decrease in the activity due to the
decrease in an amount of acid. For the method wherein a mercapto
group-containing compound is bound to a cation-exchange resin,
there may be used a conventionally known method as disclosed in
JP-B No. 46-19953, or the like.
[0056] In the invention, for phenol to be used as a raw material
for producing bisphenol A, a generally available industrial phenol
can be used. The industrial phenol includes one prepared by a
cumene method, a toluene oxidation method, or the like, any of
which may be used. Generally, phenol having a purity of 98% or more
is commercially available. Such the industrial phenol may be used
as it is in the synthesis reaction of bisphenol A, but preferably
phenol which is preliminarily treated with a strong acid-type
cation-exchange resin in a continuous or batch mode before carrying
out the reaction at a treatment temperature of 50 to 120.degree. C.
during a contact time of 5 minutes to 10 hours, is used. Even more
preferably, one obtained by the process wherein the industrial
phenol is brought into contact with a strong acid-type
cation-exchange resin as described above and is then subjected to a
distillation treatment under the condition of a normal pressure to
a reduced pressure of 10 mmHg, at a temperature of 70 to
200.degree. C., is used.
[0057] Acetone used in the invention is not particularly limited,
but it may be a commercially available industrial acetone.
Generally, acetone having a purity of 99% or more is available.
[0058] The amounts (quantitative ratios) of phenol and acetone,
used as raw materials, to be used, are not particularly limited,
but the molar ratio of phenol/acetone is recommended preferably in
the range of 0.1 to 100, and more preferably in the range of 0.5 to
50. If the amount of phenol is too small, it is difficult to
accomplish a high conversion of acetone as a raw material, if the
amount of phenol is too large, the reactor becomes unreasonably
larger because phenol is used as the higher amount than required,
and moreover, massive circulation of phenol is also required, even
though a high conversion of acetone can be accomplished. Thus,
efficient production cannot be accomplished.
[0059] In the invention, the reaction temperature is not
particularly limited, but it is preferably in the range of 0 to
300.degree. C., and more preferably in the range of 30 to
200.degree. C. If the reaction temperature is extremely low, the
reaction rate decreases and thus the productivity of a reaction
product also decreases. On the other hand, if the reaction
temperature is extremely high, an undesirable side reaction, or the
like proceeds, thus leading to the increase in the amount of
by-products, and to the decrease in stability of phenol and acetone
as a raw material and further bisphenol A as a product, and the
reaction selectivity. Therefore, it is not economical.
[0060] The reaction can be carried out under any of a reduced
pressure, an applied pressure and a normal pressure. From the
viewpoint of the reaction efficiency (reaction efficiency per unit
volume), it is not preferable to carry out the reaction under too
low of pressure. Usually, the pressure for carrying out the
reaction is preferably in the range of 0.1 to 200 atm, and more
preferably in the range of 0.5 to 100 atm. Of course, the invention
is not limited to such pressure ranges.
[0061] In addition, when carrying out the invention, the amount of
the catalyst to be used is not particularly limited, but for
example, when carrying out the reaction in a batch mode, it is
recommended to carry out the invention such that the amount of the
catalyst is preferably in the range of 0.001 to 200% by weight, and
more preferably in the range of 0.1 to 50% by weight with respect
to phenol as a raw material.
[0062] When carrying out the invention, it is possible to add a
solvent or gas which is inert to a catalyst and a reaction reagent
in the reaction system, which can be used in the diluted state.
Specifically, aliphatic hydrocarbons such as methane, ethane,
propane, butane, hexane and cyclohexane, and an inert gas such as
nitrogen, argon and helium, and if necessary, hydrogen can be used
as a diluent.
[0063] When carrying out the invention, the method can be carried
out in any of a batch, semi-batch or continuous flow system. It can
be carried out in any of a liquid phase, a gas phase, a gas-liquid
mixed phase. Preferably, from the viewpoint of the reaction
efficiency, it is recommended that the reaction is carried out in
the liquid phase. For a way for charging a catalyst, various kinds
of ways using, for example, a fixed bed, a fluidized bed, a
suspended bed and a plate fixed bed can be employed, any of which
can be used.
[0064] The reaction time (retention time or catalytic contact time
in the flow system) is not particularly limited, but it is usually
0.1 second to 30 hours, and preferably 0.5 second to 15 hours.
After the reaction, the reaction product can be separated and
recovered from the catalysts, or the like, by a separation method
such as filtration, extraction and distilling-off. Bisphenol A as a
target product can be separated, purified and obtained from the
reaction mixture separated and recovered by performing a sequential
treatment of solvent extraction, distillation, alkali treatment,
acid treatment and the like or an ordinary separation and
purification method suitably combining them. In addition, unreacted
raw materials can be recovered and recycled into the reaction
system for use.
[0065] In the case of a batch reaction, the catalyst which is
separated and recovered from the reaction product after the
reaction, can be used as it is, or partially or wholly reproduced
to be repeatedly used for the reaction. In the case of carrying out
the reaction in a fixed bed or a fluidized bed flow system, if the
catalyst is provided to the reaction and thereby a part or all of
the catalysts is inactivated or is deteriorated in the activity,
the reaction is interrupted, and thereafter the catalyst can be
reproduced and then provided to the reaction. Alternatively, a part
of the catalyst can be withdrawn continuously or intermittently and
reproduced, and then recycled to the reactor for re-use. Further, a
fresh catalyst can be intermittently supplied to the reactor. When
carrying out the reaction in a moving-bed flow system, the catalyst
can be separated, recovered and, if necessary, reproduced, as in
the batch reaction.
EXAMPLES
[0066] Hereinbelow, the present invention will be described in more
detail in reference to Examples. However, the invention is not
intended to be limited to Examples.
Example 1
(1) Synthesis of Styrenic Polymer
[0067] 180 ml of toluene, 45 ml of styrene, 24 ml of a 10% methyl
aluminoxane/toluene solution, and 3.6 ml of a 0.5%
cyclopentadienyltitanium trichloride/toluene solution were charged
and reacted at 50.degree. C. for 2 hours under a nitrogen
atmosphere. Thereafter, the recovered polymer was washed and dried.
By .sup.13C-NMR measurement of the obtained polymer, it was
confirmed that this polymer was syndiotactic polystyrene. Further,
peaks of Tc (crystallization) could be found at 222.degree. C. by
DSC measurement of 5 mg of this polymer at 10.degree. C./min.
(2) Heat Treatment of Styrenic Polymer
[0068] The sufficiently dried styrenic polymer was maintained at
200.degree. C. for 4 hours under a nitrogen atmosphere and then
slowly cooled under a nitrogen atmosphere.
(3) Sulfonation of Styrenic Polymer
[0069] 130 g of nitrobenzene, 10 g of styrenic polymer which had
been heat-treated in (2), and 50 g of sulfuric acid were charged
and reacted at 80.degree. C. for 3 hours. After the reaction, the
resin fraction was separated by filtration, sufficiently washed
with ion-exchange water and further dried under reduced pressure at
80.degree. C. for 24 hours to obtain a cation-exchange resin 1. The
amount of acid of the obtained cation-exchange resin 1 was 1.1
milliequivalents/g. Further, peaks were found at 20 of 6.7, 11.7,
13.5 and 20.4.degree. by XRD measurement of this cation-exchange
resin 1 with a CuK.alpha.-ray. The crystallinity was 21%.
Example 2
[0070] 130 g of nitrobenzene, 10 g of styrenic polymer which had
been heat-treated in (2) of Example 1, and 50 g of sulfuric acid
were charged and reacted at 80.degree. C. for 6 hours. After the
reaction, the resin fraction was separated by filtration,
sufficiently washed with ion-exchange water and further dried under
reduced pressure at 80.degree. C. for 24 hours to obtain a
cation-exchange resin 2. The amount of acid of the obtained
cation-exchange resin 2 was 1.7 milliequivalents/g. Further, peaks
were found at 20 of 6.7, 11.7, 13.5 and 20.40 by XRD measurement of
this cation-exchange resin 2 with a CuK.alpha.-ray. The
crystallinity was 14.9%.
Example 3
[0071] The procedure was performed under the same conditions as in
Example 1, except that a combination of 45 ml of styrene and 0.7 ml
of 80% divinylbenzene was used instead of 45 ml of styrene, to
obtain cation-exchange resin 3. By .sup.13C-NMR measurement of the
styrenic polymer prior to heat treatment, it was confirmed that
this polymer was syndiotactic polystyrene. Further, peaks of Tc
(crystallization) were found at 217.degree. C. by DSC measurement
of 5 mg of the styrenic polymer prior to heat treatment at
10.degree. C./min. The amount of acid of the cation-exchange resin
3 was 3.7 milliequivalents/g. Further, peaks were found at 2.theta.
of 6.7, 11.7, 13.5 and 20.4.degree. by XRD measurement of this
cation-exchange resin 3 with a CuK.alpha.-ray. The crystallinity
was 10.5%.
Comparative Example 1
(1) Sulfonation of Styrenic Polymer
[0072] 130 g of nitrobenzene, 10 g of styrenic polymer which had
been obtained in (1) of Example 1, and 50 g of sulfuric acid were
charged and reacted at 80.degree. C. for 3 hours. After the
reaction, the resin fraction was separated by filtration,
sufficiently washed with ion-exchange water and further dried under
reduced pressure at 80.degree. C. for 24 hours to obtain a
cation-exchange resin 4. The amount of acid as measured was 1.1
milliequivalents/g.
(2) Heat Treatment of Cation-Exchange Resin 4
[0073] The sufficiently dried cation-exchange resin 4 was
maintained at 200.degree. C. for 4 hours under a nitrogen
atmosphere and then slowly cooled under a nitrogen atmosphere. No
clear peak was observed upon XRD measurement of this heat-treated
cation-exchange resin 4 with a CuK.alpha.-ray.
Comparative Example 2
[0074] Heat treatment was performed in the same manner as in (2) of
Example 1, except that Amberlyst 31, which had been sufficiently
washed and dried, was used instead of the styrenic polymer. No
clear peak was observed upon XRD measurement thereof with a
CuK.alpha.-ray.
Example 4
[0075] Into a 70 ml pressure-resistant reactor, 50 g of distilled
water, and 2 g of the cation-exchange resin 1 produced in Example 1
were charged, and pressurized with nitrogen gas under 5 kg/cm.sup.2
of a gauge pressure inside the reactor, and then heated with
stirring at 130.degree. C. for 18 hours. Thereafter, the resultant
was cooled to room temperature. After the pressure discharge, all
the contents were taken out, and separated by filtration with a
membrane filter having a pore diameter of 0.1 .mu.m. Then, the
amount of acids of the filtrate and the residue were measured,
respectively. As a result, about 1.1% of the amount of acid to be
put was detected in the filtrate, and the remaining amounts were
detected in the residue.
Example 5
[0076] The same procedure as in Example 4 was performed, except
that the cation-exchange resin 2 produced in Example 2 was used
instead of the cation-exchange resin 1. As a result, about 1.0% of
the amount of acid to be put was detected in the filtrate, and the
remaining amounts were detected in the residue.
Example 6
[0077] The same procedure as in Example 4 was performed, except
that the cation-exchange resin 3 produced in Example 3 was used
instead of the cation-exchange resin 1. As a result, about 0.7% of
the amount of acid to be put was detected in the filtrate, and the
remaining amounts were detected in the residue.
Comparative Example 3
[0078] The same procedure as in Example 4 was performed, except
that the cation-exchange resin 4 produced in Comparative Example 1
was used instead of the cation-exchange resin 1. As a result, about
3.0% of the amount of acid to be put was detected in the filtrate,
and the remaining amounts were detected in the residue.
Comparative Example 4
[0079] The same procedure as in Example 4 was performed, except
that Amberlyst 31, which had been sufficiently washed and dried,
was used instead of the cation-exchange resin 1. As a result, about
2.0% of the amount of acid to be put was detected in the filtrate,
and the remaining amounts were detected in the residue.
Example 7
Modification of Cation-Exchange Resin
[0080] 5 g of the cation-exchange resin 3 obtained in Example 3 was
dispersed in 100 ml of ion-exchange water, and an arbitrary amount
of a 0.85% aqueous solution of aminoethanethiol hydrochloride was
added dropwise with stirring for 1 hour. Thereafter, the resultant
was stirred at a room temperature for 5 hours, and then the resin
fraction was separated by filtration, sufficiently washed with
ion-exchange water and further dried under reduced pressure at
80.degree. C. for 24 hours to obtain a modified cation-exchange
resin A. (Here, the obtained modified cation-exchange resin A was a
modified cation-exchange resin in which 35% of the sulfonic acid
groups bound to aminoethanethiol.)
Example 8
[0081] Into a 70 ml pressure-resistant reactor, 1.59 g of acetone,
28.41 g of phenol and 0.75 g of the cation-exchange resin A
produced in Example 7 were charged, and pressurized with nitrogen
gas under 5 kg/cm.sup.2 of a gauge pressure inside the reactor, and
then heated with stirring at 75.degree. C. for 2 hours. After
completion of the reaction, the resultant was cooled to room
temperature. After the pressure discharge, the reaction solution
was taken out, and subjected to quantitative analysis by means of
liquid chromatography. The results are shown in Table 1.
Example 9
[0082] Under the same conditions as in Example 8, except that the
amount of phenol to be charged was changed to 20.66 g, and the
reaction temperature was changed to 85.degree. C., the reaction was
performed. The results are shown in Table 1.
Example 10
[0083] Under the same conditions as in Example 8, except that the
amount of phenol to be charged was changed to 12.91 g, and the
reaction temperature was changed to 100.degree. C., the reaction
was performed. The results are shown in Table 1. TABLE-US-00001
TABLE 1 Amount of Amount of Reaction acetone to phenol to temper-
Conversion Selectivity to be charged be charged ature of acetone
bisphenol A (g) (g) (.degree. C.) (%) (%) Exam- 1.59 28.41 75 65.2
92.8 ple 8 Exam- 1.59 20.66 85 61.5 90.9 ple 9 Exam- 1.59 12.91 100
64.4 86.8 ple 10
Comparative Example 5
[0084] Under the same conditions as in Example 8, except that a
modified Amberlyst 31 obtained by ion-exchange of 35% of the
sulfonic acid groups of a commercially available Amberlyst 31 with
aminoethanethiol was used as a catalyst, the reaction was
performed. The results are shown in Table 2.
Comparative Example 6
[0085] Under the same conditions as in Example 9, except that a
modified Amberlyst 31 obtained by ion-exchange of 35% of the
sulfonic acid groups of a commercially available Amberlyst 31 with
aminoethanethiol was used as a catalyst, the reaction was
performed. The results are shown in Table 2.
Comparative Example 7
[0086] Under the same conditions as in Example 10, except that a
modified Amberlyst 31 obtained by ion-exchange of 35% of the
sulfonic acid groups of a commercially available Amberlyst 31 with
aminoethanethiol was used as a catalyst, the reaction was
performed. The results are shown in Table 2. TABLE-US-00002 TABLE 2
Amount of Amount of Reaction acetone to phenol to temper-
Conversion Selectivity to be charged be charged ature of acetone
bisphenol A (g) (g) (.degree. C.) (%) (%) Comp. 1.59 28.41 75 62.8
91.4 Ex. 5 Comp. 1.59 20.66 85 48.4 88.4 Ex. 6 Comp. 1.59 12.91 100
61.1 81.1 Ex. 7
Example 11
[0087] The modified cation-exchange resin A which had been used as
a catalyst in Example 10 was taken out by filtration after the
reaction, the raw material was charged therein again, and the
reaction was performed under the same conditions. The results are
shown in Table 3.
Example 12
[0088] The modified cation-exchange resin A which had been once
reused as a catalyst in Example 11 was taken out by filtration
after the reaction, the raw material was charged therein again, and
the reaction was performed under the same conditions. The results
are shown in Table 3.
Example 13
[0089] The modified cation-exchange resin A which had been twice
reused as a catalyst in Examples 11 and 12 was taken out by
filtration after the reaction, the raw material was charged therein
again, and the reaction was performed under the same conditions.
The results are shown in Table 3. TABLE-US-00003 TABLE 3 Amount of
acetone Amount of phenol Reaction Conversion Selectivity to Number
of times of to be charged to be charged temperature of acetone
bisphenol A reuse of catalyst (g) (g) (.degree. C.) (%) (%) Example
1.sup.st 1.59 12.91 100 63.5 86.5 11 Example 2.sup.nd 1.59 12.91
100 65.0 87.2 12 Example 3.sup.rd 1.59 12.91 100 64.0 87.0 13
Comparative Example 8
[0090] The modified Amberlyst 31 which had been used as a catalyst
in Comparative Example 7 was taken out by filtration after the
reaction, the raw material was charged therein again, and the
reaction was performed under the same conditions. This procedure
was repeated three times. The results are shown in Table 4.
Comparative Example 9
[0091] The modified Amberlyst 31 which had been once reused as a
catalyst in Comparative Example 8 was taken out by filtration after
the reaction, the raw material was charged therein again, and the
reaction was performed under the same conditions. The results are
shown in Table 4.
Comparative Example 10
[0092] The modified Amberlyst 31 which had been twice used as a
catalyst in Comparative Examples 8 and 9 was taken out by
filtration after the reaction, the raw material was charged therein
again, and the reaction was performed under the same conditions.
The results are shown in Table 4. TABLE-US-00004 TABLE 4 Amount of
acetone Amount of phenol Reaction Conversion Selectivity to Number
of times of to be charged to be charged temperature of acetone
bisphenol A reuse of catalyst (g) (g) (.degree. C.) (%) (%) Comp.
1.sup.st 1.59 12.91 100 59.5 80.0 Ex. 8 Comp. 2.sup.nd 1.59 12.91
100 57.8 80.5 Ex. 9 Comp. 3.sup.rd 1.59 12.91 100 55.0 79.5 Ex.
10
Example 14
[0093] Into a 70 ml pressure-resistant reactor, 1.59 g of acetone,
28.41 g of phenol and 0.75 g of the cation-exchange resin 3
produced in Example 3 were charged, and 3-mercaptopropionic acid
was further charged thereto to a concentration of 3000 ppm, and the
resultant was pressurized with nitrogen gas under 5 kg/cm.sup.2 of
a gauge pressure inside the reactor, and then heated with stirring
at 75.degree. C. for 2 hours for reaction. After completion of the
reaction, the resultant was cooled to room temperature. After the
pressure discharge, the reaction solution was taken out, and
subjected to quantitative analysis by means of liquid
chromatography. The results are shown in Table 5.
Example 15
[0094] Under the same conditions as in Example 14, except that the
amount of phenol to be charged was changed to 20.66 g, and the
reaction temperature was changed to 85.degree. C., the reaction was
performed. The results are shown in Table 5. TABLE-US-00005 TABLE 5
Amount of Amount of Reaction acetone to phenol to temper-
Conversion Selectivity to be charged be charged ature of acetone
bisphenol A (g) (g) (.degree. C.) (%) (%) Exam- 1.59 28.41 75 81.2
93. 9 ple 14 Exam- 1.59 20.66 85 79.4 90.5 ple 15
Comparative Example 11
[0095] Under the same conditions as in Example 14, except that a
commercially available Amberlyst 31 was used as a catalyst instead
of the cation-exchange resin produced in Example 1, the reaction
was performed. The results are shown in Table 6.
Comparative Example 12
[0096] Under the same conditions as in Example 15, except that a
commercially available Amberlyst 31 was used as a catalyst instead
of the cation-exchange resin produced in Example 1, the reaction
was performed. The results are shown in Table 6. TABLE-US-00006
TABLE 6 Amount of Amount of Reaction acetone to phenol to temper-
Conversion Selectivity to be charged be charged ature of acetone
bisphenol A (g) (g) (.degree. C.) (%) (%) Comp. 1.59 28.41 75 81.0
91.5 Ex. 11 Comp. 1.59 20.66 85 77.9 87.3 Ex. 12
* * * * *