ISSN 1070-4272, Russian Journal of Applied Chemistry, 2016, Vol. 89, No. 9, pp. 1490−1493. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © M.K. Mamedov, V.S. Qedirli,
2016, published in Zhurnal Prikladnoi Khimii, 2016, Vol. 89, No. 9, pp. 1201−1204.
AND POLYMERIC MATERIALS
Polymerization of Carboxyl-Containing Bicyclic (Meth)acrylates
M. K. Mamedov and V. S. Qedirli*
Mamedaliyev Institute of Petrochemical Processes, National Academy of Sciences of Azerbaijan,
pr. Khodzhaly 30, Baku,
* e-mail: email@example.com
Received April 18, 2016
Abstract—Radical polymerization of 5-carboxybicyclo[2.2.1]hept-2-yl acrylate and 5-carboxy-5-methylbicy-
clo[2.2.1]hept-2-yl methacrylate in the presence of various initiators was studied. Di-tert-butyl peroxide radical
initiator showed high performance in the process and ensured the maximal yield of the polymers. The polymers
can be used as ﬁ lm-forming agents.
Growing attention in the ﬁ eld of organic and
petrochemical synthesis is paid to norbornyl-containing
acrylic monomers. Acrylic polymers are ideally
transparent, colorless, can be readily dyed, and are readily
soluble. They have found wide use in the development
of diverse materials. The interest in these compounds
is largely due to the fact that they are active monomers
capable of polymerization by various mechanisms.
There are two ways to control the properties of polymers
obtained from them: choice of initiators ensuring one
of possible polymerization pathways (metathesis
or additive) and thus one or another structure of the
backbone and variation of substituents in the monomeric
unit. Polymers for diverse purposes (from ﬁ bers,
adhesives, and heat-resistant coatings to materials for
optoelectronics and gas-separation membranes) have
been prepared by now from norbornyl (meth)acrylates
[1–3]. Therefore, synthesis of new monomers of this
type and preparation of new polymers from them is an
important problem of the modern polymer chemistry.
Taking into account prospects for using bicyclic
(meth)acrylates, we developed an efﬁ cient procedure
for preparing 5-carboxybicyclo[2.2.1]hept-2-yl acrylate
(CBHA) and 5-carboxy-5-methylbicyclo[2.2.1]hept-
2-yl methacrylate (CMBHMA) by thermal addition of
acrylic acids to cyclopentadiene .
A valuable feature of this reaction is that it is stereo-
and regiospeciﬁ c. The products, CBHA and CMBHMA,
have exclusively the exo orientation of the ring relative
to the norbornane moiety. This is particularly important
for involvement of these monomers into polymerization,
because exo-substituted norbornenes are considerably
more active in polymerization than endo isomers.
This study deals with radical polymerization of
CBHA and CMBHMA in the presence of various
organic and inorganic initiators.
CBHA and CMBHMA were synthesized according
to  and had the following constants after puriﬁ cation
by distillation: CBHA, bp 70–72°С/1 mmHg,
1.4805; CMBHMA, bp 96–
97°С/1 mmHg, d
The purity, according to the chromatographic data
(Tsvet-100), was 99.7%.
Polymerization of CBHA and CMBHMA was
performed in sealed ampules in an inert gas atmosphere
in the presence of various initiators: di-tert-butyl
peroxide (DTBP), ammonium persulfate (NH
(AP), tert-butyl perbenzoate (TBP), benzoyl peroxide
(BP) and azobis(isobutyronitrile) (AIBN), at different
temperatures determined by the initiator decomposition
AP had the following characteristics: mp 120°С
1.9820; BP of analytically pure grade