ISSN 1070-4272, Russian Journal of Applied Chemistry, 2016, Vol. 89, No. 9, pp. 1421−1426. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © A.E. Bal’tser, D.A. Zaitsev, N.G. Zubritskaya, T.V. Ivanova, T.G. Babenko, E.N. Barskova,
2016, published in Zhurnal Prikladnoi Khimii,
2016, Vol. 89, No. 9, pp. 1129−1134.
AND METAL CORROSION PROTECTION
At present, polycarbonates based on bisphenols are
widely used in various industries and are in increasingly
high demand. These materials are optically transparent
and have excellent mechanical and electrical properties.
In addition, polycarbonates are heat and water resistant,
have neither taste nor odor, are impermeable to oils, fats,
and bacteria, and are physiologically inert.
Quite a number of various bisphenols can serve as
raw materials for manufacture of polycarbonates. Until
recently, bisphenols have been industrially obtained
mostly via interaction of phenols with ketones in the
presence of strong mineral acids: hydrochloric, sulfuric,
perchloric acids or hydrogen chloride. In the process,
the catalyst was removed from the reaction mixture
by neutralization, which yielded a large amount of
phenolic wastewater and impaired the quality of the
product. In addition, the strong mineral acid present
in the reaction solution corroded the apparatus, which
required use of expensive corrosion-resistant materials.
These disadvantages are eliminated by using solid
heterogeneous catalysts possessing acid properties. As
catalysts of this kind can serve cation-exchange resins
of the sulfoacid type, which are chemically resistant,
insoluble under the process conditions, and are at present
the main heterogeneous catalysts for industrial synthesis
of bisphenol [1–5].
To improve the activity and prolong the service life
of the catalysts and to obtain a purer bisphenol, the resin
is modiﬁ ed with compounds containing divalent sulfur.
The catalysts produced by promotion with compounds
containing a mercapto group have the best catalytic
properties. Results of the most recent studies conﬁ rmed
the efficiency of catalysts based on KU–23 cation-
exchange resin and Amberlyst 35WET cation exchanger,
both promoted with 2-mercaptoethylamine (cysteamine)
. In the case of the simplest and most frequently
industrially used bisphenol A (BP-A), synthesized from
phenol and acetone, it is possible to perform the reaction
at comparatively low temperatures and thereby to largely
avoid the formation of by-products .
At the same time, it is impossible to obtain these
products with characteristics as good as those for BP-A
in the reactions of phenols with more complex steri-
cally hindered ketones, 3,3,5-trimethylcyclohexanone
(dihydroisophorone) or 9-ﬂ uorenone to give 1,1-bis(4-
BP-TMC) (Scheme 1).
Optimization of Technological Parameters of the Process
for Obtaining Bisphenols on Cation-Exchange Catalyst
in the Presence of Hydrogen Sulﬁ de
A. E. Bal’tser*, D. A. Zaitsev, N. G. Zubritskaya, T. V. Ivanova,
T. G. Babenko, and E. N. Barskova
FSUE Russian Scientiﬁ c Center ‟Prikladnaya Khimiya,” ul. Krylenko 26a, St. Petersburg, 193232 Russia
Received June 15, 2016
Abstract—Method for synthesis of bisphenols on a solid cation-exchange catalyst in the presence of hydrogen
sulﬁ de was optimized with respect to the main technological parameters. This method provides high yields of
bisphenols obtained both on the basis of acetone and in the case of complex sterically hindered ketones: 9-ﬂ uo-
renone and dihydroisophorone.