ISSN 1070-4272, Russian Journal of Applied Chemistry, 2008, Vol. 81, No. 4, pp. 672!675. + Pleiades Publishing, Ltd., 2008.
Original Russian Text + K.G. Guliev, 2008, published in Zhurnal Prikladnoi Khimii, 2008, Vol. 81, No. 4, pp. 636 ! 639.
AND POLYMERIC MATERIALS
Synthesis of 2-Formyl-1-( p-vinylphenyl)cyclopropane
and Its Polymerization and Copolymerization with Styrene
K. G. Guliev
Institute of Polymeric Materials, National Academy of Sciences of Azerbaijan, Sumgaiyt, Azerbaijan
Received July 5, 2007
Abstract-2-Formyl-1-( p-vinylphenyl)cyclopropane was prepared, and its homopolymerization and co-
polymerization with styrene were performed. The effect of the substituent on the monomer reactivity and
the photosensitivity of the copolymer obtained were examined.
Functional polymers find growing use in micro-
electronics owing to their high heat resistance, good
electrical properties, and high deformation-and-strength
characteristics. Such a set of properties makes some
functional polymers useful for preparing protective
and insulating layers in the production of microelec-
tronic devices and circuits. A topological pattern is
usually created in a polymer film by optical photo-
lithography using a multilayer system of resists, or by
appropriate modification of the polymer to make it
photosensitive . The latter alternative has a num-
ber of significant advantages, as it considerably sim-
plifies and reduces the process of pattern formation
and increases the resolving power of lithography.
The aim of this study was to prepare a new formyl-
substituted cyclopropylstyrene monomer, 2-formyl-1-
( p-vinylphenyl)cyclopropane (FVPC), and to examine
its radical polymerization and copolymerization with
styrene. We also intended to study systematically
the influence exerted on the photosensitivity of cyclo-
propane-containing polymers by the substituent at
the cyclopropane ring in the pendant chain of the
macromolecule [6, 7].
2-Formyl-1-( p-vinylphenyl)cyclopropane is a new
promising monomer for preparing polymers with
valuable properties for microelectronics. FVPC was
synthesized as follows. First, we prepared 2-ethoxy-
carbonyl-1-( p-vinylphenyl)cyclopropane. Then, this
ester was reduced to 2-hydroxymethyl-1-( p-vinyl-
phenyl)cyclopropane , which was subsequently oxi-
dized to FVPC according to :
The structure of the aldehyde prepared was deter-
mined from the IR and
H NMR spectra. The results
of spectroscopic studies and GLC analysis show that
FVPC is a mixture of two geometric isomers, cis and
trans, in a 30 : 70 ratio.
The IR spectrum of FVPC shows absorption bands
at 163531640, 103531045, 1500, and 1605 cm
characteristic of the vinyl group in cyclopropane and
benzene rings. It also contains a band at 3010 cm
characteristic of the aldehyde C3H bond and a band
at 1709 cm
corresponding to the C=O group.
H NMR spectrum, the vinyl proton signals
are observed at 6.76 (H
), 5.38 (H
), and 5.80 ppm
). The aromatic ring protons are manifested at
6.6037.30 ppm. The aldehyde proton appears as a sin-
glet at 9.1 ppm.
The vinyl proton signals are shifted downfield rela-
tive to unsubstituted styrene (H
, 6.4; H
, 5.11; H
5.58 ppm). This shift is mainly caused by the meso-
meric effect of substituents; specific distribution of
the electron density in the cyclopropane ring also
has a certain effect. The spectra suggest that all
the synthesis steps leave the vinyl group and cyclo-
propane ring intact.