Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 10, pp. 1783−1794.
Pleiades Publishing, Ltd., 2011.
Original Russian Text © B.A. Zaitsev, I.D. Shvabskaya, 2011, published in Zhurnal Prikladnoi Khimii, 2011, Vol. 84, No. 10, pp. 1691−1702.
AND POLYMERIC MATERIALS
Divinyl Aromatic Compounds and Di(methacrylates) Prepared
by Acid-Catalyzed Transformations
B. A. Zaitsev and I. D. Shvabskaya
Institute of Macromolecular Compounds, Russian Academy of Sciences, St. Petersburg, Russia
Received May 13, 2011
Abstract—The mechanism of formation of divinyl aromatic monomers including p,p'-divinyldiphenylmethane
and 1,2-p,p'-divinyldiphenylethane and of their dimerization via terminal vinyl groups was studied. The factors
affecting the structure, composition, and properties of thermosetting resins of a new class, Rolivsans, containing
methacrylates of secondary aromatic alcohols (diols) and divinyl aromatic compounds with methylene bridges
between benzene rings were examined.
Divinylbenzenes and dimethacrylates of diols are
common monomers and cross-linking agents widely used
for preparing ion-exchange resins, sorbents, polymeric
compounds, and binders for reinforced plastics and
coatings [1–3]. Thermosetting resins containing diphenyl
ethers and biphenyls with terminal vinyl and methacrylate
groups (Rolivsans) have been developed [4–10]. They
form heat-resistant thickly cross-linked polymers which
are widely used in electrical engineering and electronics
as insulating materials intended for operation in
aggressive media [11–13].
The raw materials for preparing new polyfunctional
compounds are diverse aromatic compounds and
unsaturated carboxylic acids [4–8]. A heat-resistant
insulating compound, Rolivsan MV-1, was developed
and found practical use. Its synthesis is based on
transformations of methacrylic acid and bis[4-(1-
hydroxyethyl)phenyl] ether (BHPE), catalyzed by strong
acids, with diphenyl ether (diphenyl oxide) used as the
starting compound [4–7, 13, 14].
The use of toxic and volatile divinylbenzenes
(55–80% mixture of isomers and ethylvinylbenzenes)
can be reduced if more accessible procedures for
preparing divinyl aromatic compounds and Rolivsan-type
formulations, involving the use of less toxic compounds,
will be developed. This will allow enhancement of the
heat resistance and physicomechanical properties of the
polymeric materials and improvement of the sanitary and
hygienic conditions of their production.
The goal of this study was to examine in detail the
synthesis conditions, structure, and properties of divinyl
aromatic compounds with methylene bridges between
benzene rings and of monomer–oligomer formulations
and resins based on them. Diphenylalkanes and their
ﬂ uoro derivatives have low dielectric permittivity [15,
16], and diphenylmethane groups are incorporated in the
structure of a number of heat-resistant polymers [17, 18].
An important problem is the development of dielectrics
for interlayer insulation with a low dielectric constant,
capable to enhance the integration of microcircuits .
Therefore, heat-resistant network polymers exhibiting
the required characteristic and prepared by curing of
unsaturated monomers and oligomers containing di-
phenylalkane groups (in the form of ﬁ lms, compounds,
adhesives, and coatings) may be of interest for micro- and
The preparation methods and molecular design of
Rolivsans [4–8] governed the choice of appropriate
disecondary aromatic diols (DADs), namely, of bis
[4-(1-hydroxyethyl)phenyl]methane and 1,2-bis[4-