PROCESS IN THE PRODUCTION OF BIS(4-HYDROXYPHENYL) BIPHENYL DISULFONE

METHODE DE PREPARATION DE BIS(4-HYDROXYPHENYL)- BIPHENYL-DISULFONE

English Abstract

A PROCESS IN THE PRODUCTION OF
BIS(4-HYDROXYPHENYL)BIPHENYL DISULFONE
ABSTRACT OF THE DISCLOSURE
The present invention relates to a process for the
production of bis(4-hydroxyphenyl)biphenyl disulfone.

Claims

The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:
1. A process for the preparation of bis(4-hydroxy-
phenyl)biphenyl disulfone comprising reacting 4,4'-di-
bromobiphenyl with 4-mercaptophenol to produce bis(4-
hydroxyphenyl)biphenyl disulfide and oxidizing said bis(4-
hydroxyphenyl)biphenyl disulfide to bis(4-hydroxyphenyl)
biphenyl disulfone.
2. The process of Claim 1 wherein said 4,4'-dibromo-
biphenyl is reacted with 4-mercaptophenol in the presence
of dimethylformamide and potassium carbonate.
3. The process of Claim 1 wherein said bis(4-
hydroxyphenyl)biphenyl disulfide is oxidized to bis(4-
hydroxyphenyl)-biphenyl disulfone in the presence of
hydrogen peroxide and acetic acid.

Description

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~ PROCESS IN rrHE PRODUCTION OF
BIS (4-l[YDROXYPllE'N~L) BIPHENYI, D:CSULFONE
BACKGROIJND OF TEIE IMVENTION
Bis(4-hydroxyphenyl)biphenyl disulfone has been
found to be a useful monomer in preparing polymers such
as polyure-thanes, polycarbonates, polyethers, polyesters
and polysulfones. Polycarbonates prepared using such a
monomer are disclosed in U.S. Patent 3,2~9,986. Such
polymers are generally useful in films, fibers, injection
molded parts, extruded tubes and molded parts, blow molded
articles and coatings.
The object of the present invention is to provide a
novel process for the preparation of bis(4-hydroxyphenyl)
biphenyl disulfone.
SUMMARY OE'_~IE INVENTION
The present invention pertains to a process for the
preparation of bis(4-hydroxyphenyl)biphenyl disulfone com-
prising reacting 4,4'-dibromobiphenyl with 4-mercapto-
phenol to produce bis(4-hydroxyphenyl)bi.phenyl disulfide
and oxidizing the bis(4-hydroxyphenyl)biphenyl disulfide
to produce bis(4-hydroxyphenyl)biphenyl disulfone; in a
preferred embodi.ment said oxidizing is carried out using
hydrogen peroxide and acetic acid.
DETAILED DESCRIPTION OF THE INVENTION
The process of the invention Eor the preparation of
bis(4-hydroxyphenyl)biphenyl disul-fone may be illustrated
by the following general reaction scheme:
Br ~ Br +HS ~ OH diKetchOylfohrmat ide ,~Ho ~ S ~ ~ S ~ OH
H202
HO ~ S02 ~ S02 ~ OH ~- acetic acid,heat
As indicated above, 4,4'-dibromobiphenyl is reacted
with 4-mercaptophenol in the presence of dimethylformamide
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and potasslum carbonate to produce 1.7is (~~hydrOX~pherlyL)
b:iphe~yL clisul~ide which in turn is reacted in the prescn~e
of hyc1ro~en peroxide and acetic acid to produce the bis(4-
hydroxyphenyl) biphenyl disulfone. The resulting monomer
5 is generally recovered as a precipitate and is then separ-
ated and dried.
The process of the invention is advantageous in that
it produces high purity (99.9-~ %) bis(4-hydroxyphenyl)
biphenyl disulforle in high yields ~80% and higher).
The invention will be further illustrated, but is
not intended to be limited, by the following example.
EXAMPLE
Preparation of bis(4-hydroxyphenyl)biphenyl disulfide (HPSB)
.
Potassium carbonate (75.9 g, 0.55 mol) was charged
15 to a 2 liter flask equipped with a stirrer, condenser,
dropping funnel, thermometer and nitrogen purge. Dimeth~l-
formamide (200 ml) was added and the solution heated to
80-90C. 4-mercaptophenol (69.3 g, 0.55 mol) in 200 ml
of dimethylformamide was added to the stirrer reaction
20 mixture over one hour. ~he reaction mixture was maintained
at 100-110C for two hours. Solid 4,4'-dibromobiphenyl
(78 g, 0.25 mol) was then added over one hour. The
reaction mixture was refluxed for 18 hours, cooled to
room temperature, and poured into 10% HCl. The white to
25 yellow solid was collected with suction and washed with
water. The solid was treated with 5-10% NaOH and fil-
tered once more with suction. The mother liquor was
acidified to pH~2, and the solid collected and recry-
stallized from chlorobenæene/methanol. A 34% yield of
30 pure HPSB was obtained with a melting point of 214~217C.
Calculated analysis of C24H18O2S2:
C, 71.64; H, 4.47; S, 15.92.
Found- C, 71.76; H, 4.61; S, 15.73.
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Preparation oE his(4-hyclroxyphenyL)hiphenyLdisulfone (IIBD)
from bis(4-hydroxyphenyl)biphenyl disulflde (IIPSB)
_ ~
TIPSB (~0.2 g, 0.10 mol) ancl 250 ml of glacial acetic
acid were placed in a liter flask equipped with a stirrer,
5 thermometer, dropping funnel and heating mantle. The
reaction mixture was heated to 70-75C and (113 g, 1.0
mol) 30~ hydrogen peroxide was added over 2 hours. The
reaction mixture was heated for an additional 4 hours
at 70-75~C and 250 ml water were added. The light ye]low
10 solid was collected with suction and washed with water.
After drying 4~.2 g, (91% yield) pure bis(4-hydroxyphenyl)
biphenyl disulfone was obtained having a melting point of
236-240C.
Although the invention has been described in detail
15 in the foregoing for the purpose of illustration, it is
to be understood that such detail is solely for that
purpose and that variations can be made therein by those
skilled in the art without departing from the spirit and
scope of the invention except as it may be limited by the
20 claims.
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