Russian Journal of Applied Chemistry, 2013, Vol. 86, No. 2, pp. 234−241.
Pleiades Publishing, Ltd., 2013.
Original Russian Text © P.B. Pirozhnikov, I.V. Korolev, L.N. Mashlyakovskii, N.G. Kuzina, 2013, published in Zhurnal Prikladnoi Khimii, 2013, Vol. 86,
No. 2, pp. 253−261.
AND POLYMERIC MATERIALS
Inﬂ uence of the Chemical Structure of Fluorinated Radicals
in Acrylated Derivatives of Boltorn
Hyperbranched Polyesterpolyol on the Surface Energy
of Coatings Prepared from UV-Curable Powder Formulations
P. B. Pirozhnikov, I. V. Korolev, L. N. Mashlyakovskii, and N. G. Kuzina
St. Petersburg State Institute of Technology (Technical University), St. Petersburg, Russia
Received December 27, 2012
Abstract—The surface and physicomechanical properties of polymeric coatings prepared from UV-curable powder
formulations based on oligoester dimethacrylates were studied in relation to the chemical structure of a series of
synthesized ﬂ uorinated modiﬁ ers of new generation, based on Boltorn™ H20 hyperbranched polyesterpolyol.
The surface energy of the coatings depends on the chemical structure of the derivatives obtained. The ﬂ uorinated
derivatives of Boltorn
H20 are effective in low concentrations, 0.5–1.0 wt %.
It was discovered recently that hyperbranched polymers
(HBPs) have unique properties distinguishing them both
from common linear polymers and from network mac-
romolecular structures. These unique properties are due
to the unusual core–shell topological structure of HBPs
with very high local concentration of chain termini in the
shell and of branching sites in the core. All these factors
ensure high performance of HBPs as modiﬁ ers for various
polymeric, in particular, paint-and-varnish, materials .
It was shown in a number of papers that introduction
of HBPs into paint-and-varnish materials enhances the
adhesion strength, hardness, and resistance of coatings to
organic solvents and decreases the internal stress of the
ﬁ lms . Recent papers report on the use of ﬂ uorinated
HBPs in concentrations of 0.01–0.5 wt % for preparing
polymeric coatings with low surface energy. As shown in
[2, 3], the efﬁ ciency of these very low modiﬁ er concentra-
tions is due to self-segregation of the ﬂ uorinated modiﬁ er
and ﬁ lm-forming agent in the course of ﬁ lm formation, re-
sulting in considerable enrichment of the phase boundary
surface in ﬂ uorinated fragments. However, the majority of
studies in this ﬁ eld deal with liquid materials of various
curing modes. Data on the use of such modiﬁ ers in powder
paint-and-varnish materials (PVMs), whose production
was actively growing during the past decades, are practi-
cally lacking. Of particular interest are powder composite
materials capable of curing at low temperatures at high
rates under UV irradiation. It was shown previously [4,
5] that the use of perﬂ uorooligoetherurethaneethoxysty-
renes in amount of 2.7–6.0 wt% allows preparation of
hydrophobic coatings (contact angle with water 90°–96°)
from powder UV-curable formulations.
The goal of this study was to prepare new ﬂ uorinated
acrylated derivatives of Boltorn™ H20 hyperbranched
polymer and to examine the possibility of using them for
modiﬁ cation of the surface properties of coatings formed
from UV-curable powder PVMs.
The following products were used for preparing
ﬂ uorinated methacrylated HBP derivatives: perﬂ uori-
nated alcohol with ethylene spacer group 1Н,1Н,2Н,2Н-
perfluorododecan-1-ol (PFA) (Alfa Aesar), М =
564 g mol
; ﬂ uorinated alcohol 1Н,1Н-perﬂ uoro-3,6,9-
trioxatridecan-1-ol (OFA; SynQuest Labs), М = 548 g