Method for making bisphenol , United States Patent 4375567A method is provided for making bisphenol-A based

on the condensation of acetone and phenol in the presence of an ion-exchange resin. Improved yields of 2,2-bis(4hydroxyphenyl)propane is achieved by recycling bisphenol-A reaction mixture containing significant amounts of 2,4'dihydroxy-2,2-diphenyl propane based on the use of a macroreticular ion-exchange resin.
What I claim as new and desire to secure by Letters Patent of the United States is:
1. In a continuous process for making bisphenol by condensing phenol and acetone in the presence of an ionexchange catalyst resulting in the production of effluent comprising 2,2-bis(4-hydroxyphenyl)propane and a
contaminating amount of 2,4'-dihydroxy-2,2-diphenyl propane, whereby said effluent is transported to a bisphenol-A
concentrator, a crystallizer and a solid/liquid separator to effect the separation of bisphenol-A from its reaction byproduct and starting reactants which are recycled to an isomerization zone containing an ion-exchange catalyst to
effect the conversion of said 2,4'-dihydroxy-2,2-diphenyl propane to 4,4'-bis(4-hydroxyphenyl)propane which is recyled
to a bisphenol feed tank, the improvement which comprises, utilizing as the ion-exchange resin in the isomerization
zone a macroreticular cationic-exchange catalyst whereby improved conversion of 2,4'-dihydroxy-2,2-diphenyl propane
to
2,2-bis-(4-hydroxyphenyl)propane
is
achieved.
2. A method in accordance with claim 1, where the macroreticular cationic-exchange catalyst is a sulfonated
polystyrene-divinylbenzene ion-exchange resin.
Description:
CROSS
REFERENCE
TO
RELATED
APPLICATIONS
Reference is made to copending applications Ser. No. 226,271, filed Jan. 19, 1981, for Method for Salvaging Bisphenol
Values, of Ashok Mendiratta, assigned to the same assignee as the present invention.
BACKGROUND

OF

THE

INVENTION

As shown by F. N. Apel et al, U.S. Pat. Nos. 3,049,568, 3,049,569 and 3,153,001 and A. R. Grover et al, U.S. Pat. No.
3,221,061, ion-exchange resins have been found to be useful for effecting the condensation of acetone and phenol for
making 2,2-bis-(4-hydroxyphenyl)propane of the formula, ##STR1## commonly referred to as "bisphenol-A" and
referenced to hereinafter as the "4,4'-isomer". Experience has shown that, during the condensation reaction of acetone
and phenol, in the presence of an ion-exchange catalyst, significant amounts of 2,4'-dihydroxy-2,2-diphenyl propane
can be formed having the formula, ##STR2## referred to hereinafter as the 2,4-isomer.
When strong mineral acids, such as hydrochloric acid, are employed as catalysts in the condensation reaction, the 2,4isomer can rearrange to the desired 4,4'-isomer under the reaction conditions. However, these reaction conditions
result in the formation of significant amounts of tars which are difficult to salvage. These tars result in the formation of
complex color forming aromatics which can adversely affect the utility of the desired 2,2-bis(4-hydroxyphenyl)propane
monomer. As a result, efforts are constantly being sought to improve the effectiveness of ion-exchange catalysts for the
formation of bisphenol-A in place of mineral acid catalyst, while minimizing the production of undesirable amounts of
the 2,4'-dihydroxy-2,2-diphenyl propane, which can impair the purity of the desired bisphenol-A monomer.
One solution to the "isomer" problem when using an ion-exchange catalyst is to recycle the reaction by-products
effluent from the bisphenol-A reaction stream after a concentration and recrystallization step. The by-product stream is
then recycled to an isomerization zone to convert 2,4'-dihydroxy-2,2-diphenyl propane, hereinafter referred to as the
"2,4'-isomer" to bisphenol-A, or the "4,4'-isomer" which can be further recycled to a feed tank along with makeup
acetone and phenol and thereafter introducing the resulting isomerized mixture along with makeup feed to the reactor.
Although in theory, the use of an isomerization step for the by-product feed which can be recycled to the reactor has
achieved some degree of success as measured by improved rates of bisphenol-A production, the effectiveness of such
isomerization procedure has often not achieved the degree of success desired. Improved isomerization procedures to
convert the 2,4'-isomer to the 4,4'-isomer and accordingly more effective techniques to improve the rate of formation of
bisphenol-A
are
constantly
being
sought.
As taught by Reed, U.S. Pat. No. 4,263,407, the term "macroreticular" as opposed to "microreticular" means porous
adsorbance in which the pores are larger than atomic distances and are not part of the polymer structure per se.
Rather, the pores are microscopic channels resulting from the squeezing out of an organic precipitant from a
copolymer mass. As a consequence, the pore structure is not dependent upon environment and therefore is retained

despite

contact

with

various

concentrations

of

electrolyte,

solvent

and

exchangable

ions.

In microreticular resins (gel-type) the pores are not really pores at all because they are extremely small, usually below
30 A in diameter and will disappear from the polymer structure when the polymer is dry. The microreticular gel resin has
a continuous polymer phase while the macroreticular resin is clearly shown to consist of conglomerates of granularly
packed macrospheres with both a continuous polymer phase and a continuous void phase. Thus the expression
"porous" as used herein refers to channels or openings between conglomerates of minute spherical particles.
The present invention is based on the discovery that macroreticular cation-exchange catalyst have been found to be
particularly useful for directly converting the 2,4'-isomer to the 4,4'-isomer. Accordingly, an improved procedure for
isomerizing
the
2,4'-isomer
to
the
4,4'-isomer
has
now
been
found.
STATEMENT

OF

THE

INVENTION

There is provided by the present invention a continuous process for making bisphenol-A by condensing phenol and
acetone in the presence of an ion-exchange catalyst, resulting in the production of effluent comprising 2,2-bis(4hydroxyphenyl)propane and a contaminating amount of 2,4'-dihydroxy-2,2-diphenyl propane, whereby said effluent is
transported to a bisphenol-A concentrator, a crystallizer and a solid/liquid separator to effect the separation of
bisphenol-A from its reaction by-product and starting reactants which are recycled to an isomerization zone containing
an ion-exchange catalyst to effect the conversion of said 2,4'-dihydroxy-2,2-diphenyl propane to 2,2-bis(4hydroxyphenyl)propane which is recycled to a bisphenol feed tank, the improvement which comprises, utilizing as the
ion-exchange resin in the isomerization zone, a macroreticular cationic-exchange catalyst whereby improved
conversion of 2,4'-dihydroxy-2,2-diphenyl propane to 2,2-bis-(4-hydroxyphenyl)propane is achieved.
In order that those skilled in the art will be better able to practice the invention, reference is made to the drawing.
There is shown in the schematic a feed tank which conveys reaction mixture to a reactor which is joined to a
concentrator and the bottoms of the concentrator is fed into a recrystallizer and a separator from which substantially
pure 4,4'-isomer of bisphenol-A is collected and which recycles isomer feed to an isomerizer.
More particularly, there is shown at 10 a feed tank having feed ports at 11 and 12 allowing for the introduction of
acetone and phenol and recycled isomer feed at 61. Reactant mixture is fed to the reactor at 20 through line 13.
Reaction mixture is directed through lines 21 to concentrator 30 which separates unreacted phenol and acetone at 31
for recycle and bisphenol-A reaction stream at 32. The bisphenol-A reaction stream is led into a crystallizer at 40 to
produce a solid and liquid mixture which is fed to the separator at 50. The bisphenol-A solids are fed at 51 to a melter
and evaporator not shown, while the liquid by products are fed to the isomerizer at 60 through line 52. The isomerized
mixture
is
then
recycled
to
the
feed
tank
at
10
through
line
61.
In the practice of the invention, a mixture of acetone and phenol are fed into the feed tank which also has ports,
allowing for the entry of feed from the isomerization zone and recycled feed from the concentrator. The rates at which
the makeup acetone and phenol along with the recycled feed and isomerization feed are maintained to allow for the
production of a mixture which is fed into the reactor having the proper material balance to achieve optimum rate of
production of the 4,4'-isomer. The "total feed mixture" is heated prior to its introduction into the reactor. The reactor can
be equipped with an ion-exchange bed, for example, a sulfonated insoluble polystyrene, such as Dowex 50W-4
modified with a mercaptan. The residence time can vary widely, and typically can be 60 minutes more or less.
The acetone-phenol reaction is preferably carried out utilizing a stoichiometric excess of phenol. Preferably a
temperature in the range of about 55.degree. C. to 125.degree. C. is preferred in order to avoid plugging of the reactor.
Reaction is initiated by heating the phenol and acetone under substantially anhydrous conditions, that is less than 2%
by weight of water and preferably less than 0.2% water content by weight, to reaction temperature. The reactants are
passed through a fixed porous bed of ion-exchange resin, at a slight pressure to maintain adequate flow, although
gravity pressure is also found to be satisfactory. The effluent is then passed into a concentrator where all of the water,
phenol and acetone are removed as an overhead fraction. The bottoms from the concentrator are then passed to a
crystallization zone, where crystallization is carried out by chilling the bottoms from the concentrator to a temperature

between about 37.degree. C. to 95.degree. C. An adduct of phenol and the 2,2-isomer separates out as crystals which
can be separated from the mother liquor by centrifuging, filtration, etc. The crystals can then be washed with phenol
and the washings along with the mother liquor can then be recycled to the isomerization zone.
The isomerization zone consists of a bed of macroreticular ion-exchange catalysts as distinguished from the reactor
which is a fixed bed of either microreticular or macroreticular ion-exchange resin. The mother liquor and the washings
from the crystallizer are then allowed to pass through the macroreticular ion-exchange resin which can be at a
temperature of from 60.degree. C. to 120.degree. C. for a period of time sufficient to effect rearrangement of the 2,4'isomer to the 4,4'-isomer depending upon such factors as the feed rate, the size of the bed, etc. The isomerized feed is
then fed back to the feed tank along with the makeup acetone and phenol for reuse in the reactor.
In order that those skilled in the art will be better able to practice the present invention, the following examples are
given by way of illustration and not by way of limitation. All parts are by weight.
EXAMPLE

A rate study was made to determine the effectiveness of typical microreticular cation-exchange catalysts, such as
Amberlite-118 of the Rohm and Haas Company, of Philadelphia, PA and Dowex 50WX2 of Dow Chemical Company,
Midland, Mich., both sulfonated insoluble polystyrene resins to isomerize 2,4'-dihydroxy-2,2-diphenyl propane or "2,4'isomer"
to
2,2-bis(4-hydroxyphenyl)propane,
or
"BPA".
The microreticular resins were then compared in the same manner to equivalent weights of Amberlyst-15 and
Amberlyst-XN-1010, commercially available macroreticular resins of Rohm and Haas Company. The following
procedure was used to determine the first order rate constant of isomerization using the various ion-exchange resins.
There was added 5 parts of activated ion-exchange resin and 0.5 part of 2,4'-dihydroxy-2,2-diphenylpropane to 20
parts of dry phenol. The mixture was placed in a preheated oil bath at 70.degree. C. and small aliquats were withdrawn
at specific time intervals, diluted with 20 parts of acetonitrile, followed by high pressure liquid chromatography analysis.
The results of the various ion-exchange catalyst rate studies were plotted on a natural log scale and are shown in the
following table:
TABLE I
______________________________________
Catalyst
k (min.sup.-1 met.sup.-1)
k.sub.rel
______________________________________
Amberlit-118.sup.a 7.58 .times. 10.sup.-5
0.052
Dowex 50WX2.sup.a 72.2 .times. 10.sup.-5
0.402
Amberlyst-15.sup.b 80.9 .times. 10.sup.-5
0.552
Amberlyst XN-1010.sup.b
147. .times. 10.sup.-5
1.0
Amberlyst XN-1010.sup.b + 0.5% H.sub.2 O
118. .times. 10.sup.-5
0.804
Amberlyst XN-1010.sup.b + 1.0% H.sub.2 O
74.3 .times. 10.sup.-5
0.508
Amberlyst XN-1010.sup.b + 2.0% H.sub.2 O
40.8 .times. 10.sup.-5
0.279
Amberlyst XN-1010.sup.b + 3.0% H.sub.2 O
20.0 .times. 10.sup.-5
0.136

______________________________________
.sup.a This catalyst is microreticular
.sup.b This catalyst is macroreticular
The above results show that macroreticular resins as illustrated by Amberlyst-15 and Amberlyst XN-1010 are more
effective as isomerization catalysts for converting the 2,4'-isomer to the 4,4'-isomer than Amberlite-118 or Dowex
50WX2. In addition, the above results also show that the isomerization rate is effected by trace amounts of water.
EXAMPLE

As shown in the copending application Ser. No. 226,271 of A. R. Mendiratta, filed Jan. 19, 1981, and assigned to the
same assignee as the present invention, a glass ion-exchange resin column was charged with 45 parts of
macroreticular, sulfonated polystyrenedivinylbenzene ion-exchange resin beads of the Rohm & Haas Company having
a mesh size of 28-48 and furnished commercially under the trademark Amberlyst XN-1010. The resin bed was washed
with 4 bed volumes of 80:20 (by weight) phenol-water solution. This was followed by 3 bed volumes of dry phenol
wash.
An isomer stream consisting of 80.4% of phenol, 8% of bisphenol-A, 3.2% o,p-bisphenol-A and 8.4% of various byproducts by weight was fed into the above ion-exchange resin bed. A total of 18 bed volumes of the isomer feed
mixture was passed through the column. There was obtained an effluent isomer stream having the following
composition by weight: phenl 79.9%; bisphenol-A 8.9%; o,p-bisphenol-A 2.9%; and other products 8.3%.
The above results show that the macroreticular resin of the present invention had a noticable influence on the
composition of the isomer stream with respect to reducing the 2,4-isomer of bisphenol-A.
Although the above examples are directed to only a few of the very many variables of the method of the present
invention, it should be understood that the present invention is directed to a much broader class of macroreticular
resins and to procedures and conditions for separating and recovering the bisphenol-A in the practice of the method of
the present invention.
United
States
Method for maximizing yield and purity of bisphenol A
Issued on August 23, 1988
Abstract

Patent

4766254

Product losses and color formation are sometimes encountered in the synthesis of bisphenol A from phenol and
acetone in the presence of a cation exchange resin, particularly in the crude product stream from which bisphenol A
has been separated via its phenol adduct. Such losses are suppressed and the crude product stream stabilized and
decolorized by contact with an anion exchange resin.
Claims
1. A method for recovering bisphenol A from a product stream which comprises:
forming and separating an adduct of bisphenol A and phenol, leaving a crude liquid stream containing crude bisphenol
A
and
impurities;
removing acidic impuritites from said crude liquid stream by contact with a basic ion exchange resin at a temperature in
the range of about 45-125 C. for a period of time effective to remove said impurities by salt formation with said resin;
and
recovering further bisphenol A from the resin-treated crude liquid stream by distillation.
2. A method according to claim 1 wherein contact with the anion exchange resin is effected at a temperature in the
range
of
about50-75
C.
3. A method according to claim 2 wherein said contact is effected by passing said crude liquid stream through a column
containing
said
resin.
4. A method according to claim 3 which includes the step of regenerating said resin by treatment with aqueous base
after
said
contact
has
been
effected.

5. A method according to claim 2 wherein the anion exchange resin is an amine resin.
6. A method according to claim 2 wherein the anion exchange resin is a quaternary ammonium salt resin.
7. A method according to claim 4 wherein the aqueous base treatment is preceded by washing with liquid phenol.
8. A method according to claim 7 wherein the anion exchange resin is an amine resin.
9. A method according to claim 7 wherein the anion exchange resin is a quaternary ammonium salt resin.
Description
This invention relates to the preparation and purification of bisphenol A, and more particularly to the maximization of
product
yield.
Bisphenol A, or 2,2-bis(4-hydroxyphenyl)propane, is a valuable chemical intermediate for the production of various
resinous materials, notably epoxy resins and polycarbonates. It is commercially produced by the acid-catalyzed
condensation of phenol and acetone. A common method of preparation involves employing as the acid catalyst a
sulfonated cation exchange resin in the free acid form, generally in combination with a mercaptan as a reaction rate
accelerator.
The product stream from the reaction is frequently subjected to conditions whereby a solid adduct of bisphenol A and
phenol is separated and subjected to further treatment to isolate a major proportion of the bisphenol A. There remains
a liquid stream (hereinafter "mother liquor") containing crude bisphenol A in combination with various impurities, from
which further bisphenol A is generally recovered by distillation. Typical distillation conditions include temperatures in the
range
of
about
210-220
C.
and
reduced
pressure.
It is sometimes found that substantial product losses occur during this distillation step. Such losses may be as high as
15-40% of the total bisphenol A content of the mother liquor. Moreover, the mother liquor is frequently contaminated
with darkly colored materials which are difficult or impossible to remove during bisphenol A purification. These
situations obviously need correction, since product losses of this magnitude cannot be tolerated when a high rate of
production
is
desired
and
highly
colored
product
is
unacceptable.
It has now been discovered that the loss of and color formation in bisphenol A are caused, at least in part, by acidcatalyzed cracking during the distillation step. Apparently, low molecular weight sulfonic acids are present in the cation
exchange resin, are leached therefrom by the product stream and remain in the mother liquor. Upon heating of said
mother liquor, these low molecular weight sulfonic acids, though present in very small proportions (e.g., about 200
ppm.), cause cracking of the product into phenol, isopropenylphenol and various oligomers and condensation products
of
the
latter,
including
highly
colored
materials.
Accordingly, the present invention is a method for stabilizing a liquid crude bisphenol A product stream which
comprises contacting it with a basic anion exchange resin at a temperature in the range of about 45-125 C.
As previously mentioned, the liquid crude bisphenol A product stream treated by the method of this invention is
ordinarily mother liquor from which a major proportion of the bisphenol A has previously been removed in the form of its
adduct with phenol. Said mother liquor contains, in addition to bisphenol A, numerous impurities which are
subsequently removed by distillation. The purpose of the present invention is to ensure removal of strongly acidic
impurities, including low molecular weight sulfonic acids, prior to distillation in order to minimize color formation and
further
loss
of
product
by
cracking.
The anion exchange resins useful in the method of this invention include essentially all known basic resins of this type.
For the most part, they are amine or quaternary ammonium resins typically containing such moieties as
dimethylbenzylamino groups or corresponding methyl-caternized groups attached to a polymer chain. Amine resins are
often preferred. Many suitable resins are commercially available. For the purpose of the invention, the quaternary
ammonium resins are employed in the free base form; that is, the counterion therein is the hydroxide anion.
Contact between the mother liquor and the anion exchange resin may be effected by any convenient means. It is
generally preferred to pass the mother liquor through a column containing the resin, at temperatures in the range of
about 45-125 C. and preferably about 50-75 C. Passage of the mother liquor through the column may be upward
or
downward.
Upon contact with the anion exchange resin, acidic impurities are removed by salt formation therewith. When the resin
has been exhausted, it may be regenerated by treatment with aqueous base. Such treatment is ordinarily preceded by
washing with liquid phenol, to remove base-insoluble tarry impurities whose presence would decrease the efficiency of
the
resin.
It has been found that the method of this invention is essentially completely successful in suppressing decomposition
of bisphenol A upon distillation of the mother liquor. Mother liquor streams in which product decomposition would occur
to the extent of as high as 50% become completely stable during the distillation operation. Moreover, product color is
substantially
decreased.

The

method

of

this

invention

is

illustrated

by

the

following

examples.

EXAMPLE
1
Two different bisphenol A mother liquor streams were utilized. In order to determine the tendency of each stream to
decompose, 163 grams thereof was distilled to a pot temperature of 210 C. An aliquot was removed and analyzed by
high pressure liquid chromatography to determine the amount of bisphenol A present. The mixture was then heated
under reflux for 4 hours and a second aliquot removed and similarly analyzed, and the percent cracking was
determined
by
comparison
of
the
results
of
the
two
analyses.
A 1-inch by 11-inch glass column equipped with a heated jacket was charged with 30 grams of each of four anion
exchange
resins
in
the
free
base
form,
identified
as
follows:
Resin

1--a

polystyrene

resin

Resin

2--a

polystyrene

backbone

Resins

and

4--two

different

acrylic

with

benzyltrimethylammonium

substituents.

benzyldimethylamine

substituents.

with

backbone

resins

with

benzyldimethylamine

substituents.

A total of 1500 grams of mother liquor was passed upward through said columns at a weight-height space velocity of
6.7 hrs.-1 and a temperature of 50 C. The results are listed in the following table.
______________________________________
% cracking
Resin Before treatment
After treatment
______________________________________
1
14.7
0
2
34.6
0
3
14.7
0
4
14.7
0
______________________________________
EXAMPLE
2
A 6-pound sample of Resin 1, exhausted by mother liquor treatment according to Example 1, was washed with liquid
phenol, water and 23 gallons of 6.5% aqueous sodium hydroxide solution, and then with deionized water until the pH of
the effluent was neutral. The regenerated resin was employed as in Example 1 with a mother liquor which cracked to
the extent of 48%. The effluent showed 0% cracking, and the regenerated resin had a lifetime identical to that of the
original.
EXAMPLE
3
Melt color determinations according to ASTM procedure D1209 were made on two separate bisphenol A mother liquor
streams, before and after passage through a column similar to that of Example 1. The following color results were
obtained.
______________________________________
Before
After
______________________________________
280 200
260 200
______________________________________