1070-4272/05/7801-0149+2005 Pleiades Publishing, Inc.
Russian Journal of Applied Chemistry, Vol. 78, No. 1, 2005, pp. 149!152. Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 1,
2005, pp. 151!154.
Original Russian Text Copyright + 2005 by Ergozhin, Mukhitdinova, Shoinbekova, Nikitina, Nuranbaeva, Zhunusova.
AND POLYMERIC MATERIALS
Derivatives of ortho- and para-Naphthoquinones
and Monoethanolamine Vinyl Ether in Radical
Copolymerization with Acrylic Acid
E. E. Ergozhin, B. A. Mukhitdinova, S. A. Shoinbekova, A. I. Nikitina,
B. M. Nuranbaeva, and G. N. Zhunusova
Bekturov Institute of Chemical Problems, Ministry of Education and Science of Kazakhstan Republic,
Received May 11, 2004
Abstract-Radical copolymerization of new redox monomers based on derivatives of monoethanolamine
vinyl ether and naphthoquinones with acrylic acid was studied.
With the aim to extend the set of monomers suit-
able for synthesis of redox polymers, new redox
monomers based on monoethanolamine vinyl ether
(MEAVE) and quinones  were prepared, and radical
homo- and copolymerization of some of these mono-
mers was studied . It was found that quinoid
derivatives of MEAVE fairly readily enter into homo-
and copolymerization, contrary to the initial ether,
which practically does not form polymers , and to
quinones being polymerization inhibitors.
In this work we studied the influence of chemical
structure of naphthoquinones on the reactivity of
redox monomers in radical copolymerization with
acrylic acid (AA).
Redox monomers based on MEAVE and 1,2-naph-
thoquinone (MEAVE31,2-NQ), MEAVE and
1,4-naphthoquinone (MEAVE31,4-NQ), and dichloro-
1,4-naphthoquinone (MEAVE3DC-1,4-NQ) were syn-
thesized by the procedure described in . Azobis(iso-
butyronitrile) (AIBN) was recrystallized from dry
methanol; mp 1023103oC.
Copolymerization of redox monomers with AA
was carried out in hermetically sealed tubes in DMF
at 68oC in the presence of 6 wt % AIBN for 0.5 h.
Conversion of monomers was judged from variation
of their concentration, which was determined by the
polarographic method (redox monomers) and titration
The polarographic curves were recorded in a
temperature-controlled cell at 25+0.5oC on a PU-1
polarograph (mercury dripping electrode with the
capillary characteristic at open circuit m
[m is the weight of mercury outlow-
ing from the capillary in 1 s and t is the period of
mercury dropping (s)] with phosphate buffer solution
(pH 7.4) with DMF content of 25 wt % as supporting
electrolyte. The reference electrode was a saturated
calomel electrode. Oxygen was removed from the
solutions used for polarography by bubbling with
Determination of the constants of relative activity
of monomers r
is an important problem both
in direct study of copolymerization and for establish-
ment of the relation between the chemical structure of
unsaturated compounds and their reactivity.
Copolymerization of MEAVE derivatives and vari-
ous naphthoquinones (M
) with AA (M
) was studied
in DMF solutions in the presence of AIBN. The com-
position of the copolymers was evaluated from data
listed in Table 1. As seen from Table 1 and Fig. 1,
none of the systems forms an azeotropic copolymer.
In the case of joint polymerization of MEAVE3
1,2-NQ and MEAVE31,4-NQ with AA (r
1), the composition curves are located above the azeo-
tropic line, i.e., at all the ratios of the initial com-
pounds, the copolymers are significantly enriched
with redox monomer units. For the monomer pair
MEAVE3DC-1,4-NQ and AA (r
> 1), the
composition curve is located below the azeotropic line
and the copolymer is enriched with AA units.
The copolymerization constants were evaluated by
the Mayo3Lewis integral equation of copolymer com-
position . The parameter p in this equation was