ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 5, pp. 866−870. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © V.V. Kireev, E.M. Chistyakov, S.N. Filatov, A.S. Tupikov, D.V. Panﬁ lova, A.I. Chetverikova, 2015, published in Zhurnal Prikladnoi Khimii,
2015, Vol. 88, No. 5, pp. 826−830.
Polymeric Dental Composites Modiﬁ ed
with Carboxy Phosphazene Methacrylates
V. V. Kireev
, E. M. Chistyakov
, S. N. Filatov
, A. S. Tupikov
D. V. Panﬁ lova
, and A. I. Chetverikova
Mendeleev University of Chemical Technology of Russia, Miusskaya pl. 9, Moscow, 125047 Russia
ZAO VladMiVa, Slavyanskaya ul. 15, Belgorod, 308000 Russia
Received May 26, 2015
Abstract—Oligophosphazenes containing carboxy and polymerizable methacrylate groups were prepared by
the reaction of hexa-p-carboxyphenoxycyclotriphosphazene with glycidyl methacrylate. Introduction of these
oligomers in an amount of up to 10 wt % into methacrylate ﬁ lling dental composites enhances their adhesion to
tooth tissues and metals by a factor of 5–7 and the compression strength by 20–30%.
Carboxyl-containing phosphazenes are of much
interest for modern engineering, technologies, science,
and socially signiﬁ cant branches, e.g., for the development
on their basis of incombustible heat-resistant polymers
and composites [1, 2], films , and biodegradable
drug carriers [4–6], for electronics and photonics ,
for supramolecular chemistry , and for dentistry .
Modiﬁ ers based on phosphazenes have been successfully
used in the development of various restoration dental
materials [10–12], because they are nontoxic, exhibit
good afﬁ nity for tooth tissues, only weakly affect the
viscosity of the compounds, and considerably improve
the operation characteristics of the items obtained.
Nevertheless, insufﬁ cient adhesion of the dental material
to metals and tooth tissues is a topical problem of
restoration dentistry, as it requires additional procedures
to be performed in the course of tooth treatment.
Despite the fact that the existing phosphazene additives
considerably enhance the adhesion, its level, nevertheless,
remains insufﬁ cient. Bredov et al.  were able to prepare
methacrylate compounds based on alkoxyphosphazenes
with enhanced adhesion, but the modiﬁ ers used tend to
undergo phosphazene–phosphazane rearrangement and,
as a consequence, gradual degradation. In contrast to
alkoxy derivatives, aryloxyphosphazenes do not tend
to undergo this rearrangement. Therefore, previously
 we synthesized maleic acid derivatives based
on aryloxycyclotriphosphazene (MDP), exhibiting
considerably enhanced adhesion owing to the presence
of carboxy groups:
However, synthesis of these compounds is labor-
consuming, and incomplete acylation of hydroxy groups
and presence of difﬁ cultly polymerizable multiple bonds
in the maleate fragment of MDP lead to incomplete
incorporation of the modifier into the polymeric
methacrylate matrix, which negatively influences
the characteristics of the compounds being modiﬁ ed.
Therefore, we synthesized aryloxyphosphazenes
containing both carboxy and methacrylate groups (MCP)
following the scheme presented below: