1070-4272/01/7411-1907$25.00C2001 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 74, No. 11, 2001, pp. 1907!1909. Translated from Zhurnal Prikladnoi Khimii, Vol. 74, No. 11,
2001, pp. 1847!1849.
Original Russian Text Copyright + 2001 by Ergozhin, Mukhitdinova, Shoinbekova, Nikitina.
AND INDUSTRIAL ORGANIC CHEMISTRY
New Monomer Derived from Monoethanolamine Vinyl Ether
and Redox Resin Thereof
E. E. Ergozhin, B. A. Mukhitdinova, S. A. Shoinbekova, and A. I. Nikitina
Bekturov Institute of Chemical Sciences, Ministry of Education and Science
of the Kazakhstan Republic, Almaty, Kazakhstan
Received April 25, 2001
Abstract-A procedure was developed for synthesis of a new monomer from monoethanolamine vinyl ether
and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone. The kinetics of its radical polymerization was studied polaro-
graphically. The optimal polymerization conditions and properties of the resulting redox resin were studied.
It is known that quinones are capable of reversible
reduction3oxidation . Their use in synthesis of
macromolecular compounds allows preparation of
resins exhibiting redox properties, which are widely
used in various branches of science and engineering
as reductants, oxidants, enterosorbents, hemosorbents,
etc. . However, available redox resins do not
always exhibit the necessary properties; therefore,
search for new available and cheap monomers and
development of selective ion-exchange and redox
resins thereof remains an urgent problem.
To extend the range of redox resins and simplify
their preparation, we have developed a single-stage
procedure for synthesis of a new unsaturated monomer
exhibiting redox properties. The starting compound,
monoethanolamine vinyl ether I, is readily available
and cheap; therefore, the cost of the resulting redox
polymers can be reduced. Furthermore, the possibility
of repeatedly using and regenerating the redox resins
will help to pay off them faster.
Previously reported procedures for preparing the
required monomers include 537 stages, with the yields
of the target compounds being relatively low [2, 3].
In this work we prepared a new monomer from
ether I and 2,3-dichloro-5,6-dicyano-1,4-benzoqui-
none II. The kinetics of its radical polymerization was
studied polarographically, the optimal polymerization
conditions were determined, and some properties of
the resulting redox resin were studied.
Monoethanolamine vinyl ether was dried over
freshly calcined K
and distilled from calcium
hydride; bp 114oC, n
cyano-1,4-benzoquinone (Aldrich) was used without
preliminary purification; mp 2133216oC. Azobis(iso-
butyronitrile) III was recrystallized from absolute
methanol, mp 1023103oC. The solvents were purified
by known procedures .
1,4-benzoquinone IV. Amine I was added slowly
with continuous stirring to a solution of quinone II in
3 ml of dimethylformamide (DMF) at room tempera-
ture, until the molar ratio of amine to quinone of 4 : 1
was reached. After 15 min, distilled water was added.
The precipitate was filtered off, repeatedly washed
with water, and dried, first in air and then in a vacuum
oven at 25oC to constant weight. Compound IV was
obtained in 90% yield; bright cherry-colored powder,
Found, %: C 52.25, H 2.93, Cl 12.33, N 14.80.
Calculated, %: C 51.90, H 2.91, Cl 12.77, N 15.13.
Polymer V. The monomer was placed in an am-
pule, and the solvent (DMF, to a concentration C 03
250 g l
) and initiator (III,138 wt % relative to IV)
were added. The ampule was sealed, thoroughly
shaken, and placed in a thermostat preheated to 553
72oC. After reaction completion, the ampule was
opened, and polymer V was precipitated with diethyl
ether. The precipitate was filtered off and dried, first
in air at 20325oC and then in a vacuum at 40350oC.
Yield of the polymer 45362%. Under the optimal
conditions (DMF, 4 wt % III, 360 min), the yield of
the polymer is 62%, [h] = 0.25.
Kinetic runs were performed similarly except that