ORGANIC SYNTHESIS AND INDUSTRIAL
Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 12, pp. 2093−2099.
Pleiades Publishing, Ltd., 2011.
Original Russian Text © I.V. Korolev, N.G. Kuzina, L.N. Mashlyakovskii, 2011, published in Zhurnal Prikladnoi Khimii, 2011, Vol. 84, No. 12, pp. 1209−1215.
Effect of the Molecular Structure
of Perﬂ uoroligoetherurethaneethoxystyrenes on Surface
Properties of Coatings Based on Powdered UV-Curable
I. V. Korolev, N. G. Kuzina, and L. N. Mashlyakovskii
St. Petersburg State Technological Institute, St. Petersburg, Russia
Received September 26, 2011
Abstract—Efﬁ ciency of synthesized perﬂ uoroligoetherurethaneethoxystyrenes as surface hydrophobizers for
coatings based on solid UV-curable oligoetherdimethacrylate was studied. Surface and physicomechanical
properties of composite coatings were examined in relation to the structure of styrene derivatives and composition
of powder formulations.
Previously, the inﬂ uence exerted by the concentra-
tion of perﬂ uoroligoetherbisurethaneethoxystyrenes
(PObUS) and by the concentration of their ﬂ uorine-con-
taining fragment on the surface properties (wetting an-
gle, wear resistance, dirt retention) of coatings based on
UV-curable oligoetherdimethacrylate has been studied
and it was shown that, depending on the modiﬁ er struc-
ture, the wetting angle of the coatings increases from
60° (starting ﬁ lm-forming agent) to 82–98°. However,
considerable amounts of a modiﬁ er (4–6 wt %) were to
be used to impart hydrophobic properties to the coatings.
This circumstance, combined with speciﬁ c features of
coating formation from powders under UV curing con-
ditions (high melt viscosity, short curing time), impaired
the strength of there adhesion to the metallic substrate.
At the same time, it is known [2–5] that perﬂ uoroalkyl
acrylates and perﬂ uoroether urethane acrylates with
a single unsaturated group can strongly affect surface
properties of coatings deposited from liquid formulations
at substantially lower concentrations. According to [2, 3],
this is due to the strong inﬂ uence exerted on the surface
properties not only by the ﬂ uorine content of a ﬁ lm, but
also by the molecular structure of a modiﬁ er (presence
of a perﬂ uoroalkyl or perﬂ uoropolyether radical, its
length, existence of a terminal triﬂ uoromethyl group
and a freely “uspended” ﬂ uorinated chain).
In this communication, results of a synthesis of
monofunctional perﬂ uoroligoetherurethaneethoxysty-
renes with a single terminal double bond and a perﬂ uo-
roligoether radical are presented and the effect of their
molecular structure on the surface properties of coatings
produced by 3D radical copolymerization with a UV-
curable powdered oligoetherdimethacrylate is exam-
ined. Also, the efﬁ ciency of these modiﬁ ers is analyzed
in comparison with those having a similar structure, but
containing two terminal double bonds in the oligomer
We synthesized perﬂ uoroligoetherurethaneethoxy-
styrenes (POUSs) from 1H,1H-perﬂ uoro-3,6,9-
trioxytridecan-1-ol (MOL; SynQuest Labs) with
a molecular mass of 548, hexamethylene diisocyanate
(HMDI), isophorone diisocyanate (IPDI, Merck), and
para-hydroxyethoxystyrene (para-HES). The synthesis
was performed in two stages (see the scheme).
Perﬂ uoroligoetherurethaneethoxystyrenes were
synthesized in a mixed solvent, meta-hexaﬂ uoroxylene–