(CH 2 ) 2 Si(OCH 2 CH 3 ) 3 , and d = 3.8 ppm (Si(CH 2 ) 2 Si(OCH 2 CH 3 ) 3 [52]. The prepared fluoroester group-modified polysiloxanes were applied to fabricate icephobic
coatings on Al plates [52] or as additives in paint formulations for generation of
antigraffiti coatings on Sn plates [60]. Using X-ray photoelectron spectroscopy
(XPS), it was revealed that in both cases the surface of the cured coatings was
enriched in fluorine which ensured their desired properties.
PHMS functionalized by a perfluoroalkylhydroxyl, namely hexafluoroisopropanolyl group (Table 12.1, polymer A-S19), was synthesized via hydrosilylation
of 1,1,1,3,3,3-hexafluoro-2-vinylpropan-2-ol with PHMS (Karstedt’s catalyst,
toluene, room temperature) [61]. In another approach, PHMS was applied as the
hydrosilylating agent for 2-allylphenol (reflux in toluene, Karstedt’s catalyst); then the
polymer with incorporated hydroxyphenyl rings was subjected to the reaction with
hexafluoroacetone which yielded polysiloxane with introduced hexafluoroisopropanolyl groups attached to hydroxyphenyl ring (Table 12.1, polymer A-S20) [62].
Structures of the polymer functionalized in both ways were confirmed by FTIR and
1
H
NMR spectroscopies. IR bands at 3444 and 1224 cm
−1 , corresponding to stretching
vibrations of O–H and C–F bonds, respectively, demonstrated the presence of
hexafluoroisopropanolyl moieties, whereas the one at 3026 cm
−1 originating from
stretching vibrations of aromatic C–H bonds—the presence of aromatic rings in the
polymer A-S20 (Table 12.1). In neither case, the IR Si–H band at *2100 cm
−1 was
observed showing that complete functionalization of PHMS occurred.
1 H NMR
spectra contained all the expected signals: at d = 3.76 ppm (OH), d = 1.26 ppm
(SiCH 2 ), d = 1.83 ppm (CCH 2 ), d = 0.17 ppm (SiCH 3 ), and d = 5.11 ppm (protons
of hydroxyphenyl group, the signal seen in the spectrum of polymer A-S20). Sensing
properties of the materials toward organic vapors were evaluated [61, 62].
Photocrosslinkable polysiloxanes bearing either perfluoroalkyl (Table 12.1, S21)
or perfluoroalkylether (Table 12.1, S22) and methacrylate side groups (Table 12.1,
S6) were obtained by a two-step hydrosilylation [57, 58]. First, allylperfluorooctane
[57] or allyl 2-(perfluorohexyl)ethyl ether [58] reacted with PHMS-DMS copolymer; then allyl methacrylate was added to the product formed. Speier’s catalyst was
applied in the reactions which were performed at 90 °C without solvent. IR and
1
H
NMR spectra of the polymers functionalized with two organic groups showed no
maxima corresponding to Si–H moieties indicating their complete conversion.
Incorporation of methacrylate groups was manifested by an intense IR band at
*1720 cm
−1 and
1 H NMR signals at d = 1.9 ppm (C(CH 3 )=CH 2 ) as well as at
d = 5.5 and d = 6.1 ppm (C(CH 3 ) = CH 2 ). In the
29 Si NMR spectra of the polymer
containing perfluoroalkyl groups (Table 12.1, polymer B-S21), the expected
maxima in the range of −23.3 to −20.0 ppm ([Si(O 2 )C 3 H 6 ] units formed upon
hydrosilylation) and at 8.0 ppm ([Si(CH 3 ) 3 O], polymer terminal units) were visible.
A small, unexpected signal at *−60 ppm ([SiO 3 C] units) was attributed to the
formation of a by-product that resulted from the elimination of propene from the
allyl methacrylate during hydrosilylation reaction [57]. Coatings on poly(vinylidene
fluoride) or poly(ether sulfone), prepared from polymer B-S21, S6 (Table 12.1),
after cross-linking, were evaluated for organic vapor permeation [57]. High UV
378
A. Chechelska-Noworyta et al.
coatings on Al plates [52] or as additives in paint formulations for generation of
antigraffiti coatings on Sn plates [60]. Using X-ray photoelectron spectroscopy
(XPS), it was revealed that in both cases the surface of the cured coatings was
enriched in fluorine which ensured their desired properties.
PHMS functionalized by a perfluoroalkylhydroxyl, namely hexafluoroisopropanolyl group (Table 12.1, polymer A-S19), was synthesized via hydrosilylation
of 1,1,1,3,3,3-hexafluoro-2-vinylpropan-2-ol with PHMS (Karstedt’s catalyst,
toluene, room temperature) [61]. In another approach, PHMS was applied as the
hydrosilylating agent for 2-allylphenol (reflux in toluene, Karstedt’s catalyst); then the
polymer with incorporated hydroxyphenyl rings was subjected to the reaction with
hexafluoroacetone which yielded polysiloxane with introduced hexafluoroisopropanolyl groups attached to hydroxyphenyl ring (Table 12.1, polymer A-S20) [62].
Structures of the polymer functionalized in both ways were confirmed by FTIR and
1
H
NMR spectroscopies. IR bands at 3444 and 1224 cm
−1 , corresponding to stretching
vibrations of O–H and C–F bonds, respectively, demonstrated the presence of
hexafluoroisopropanolyl moieties, whereas the one at 3026 cm
−1 originating from
stretching vibrations of aromatic C–H bonds—the presence of aromatic rings in the
polymer A-S20 (Table 12.1). In neither case, the IR Si–H band at *2100 cm
−1 was
observed showing that complete functionalization of PHMS occurred.
1 H NMR
spectra contained all the expected signals: at d = 3.76 ppm (OH), d = 1.26 ppm
(SiCH 2 ), d = 1.83 ppm (CCH 2 ), d = 0.17 ppm (SiCH 3 ), and d = 5.11 ppm (protons
of hydroxyphenyl group, the signal seen in the spectrum of polymer A-S20). Sensing
properties of the materials toward organic vapors were evaluated [61, 62].
Photocrosslinkable polysiloxanes bearing either perfluoroalkyl (Table 12.1, S21)
or perfluoroalkylether (Table 12.1, S22) and methacrylate side groups (Table 12.1,
S6) were obtained by a two-step hydrosilylation [57, 58]. First, allylperfluorooctane
[57] or allyl 2-(perfluorohexyl)ethyl ether [58] reacted with PHMS-DMS copolymer; then allyl methacrylate was added to the product formed. Speier’s catalyst was
applied in the reactions which were performed at 90 °C without solvent. IR and
1
H
NMR spectra of the polymers functionalized with two organic groups showed no
maxima corresponding to Si–H moieties indicating their complete conversion.
Incorporation of methacrylate groups was manifested by an intense IR band at
*1720 cm
−1 and
1 H NMR signals at d = 1.9 ppm (C(CH 3 )=CH 2 ) as well as at
d = 5.5 and d = 6.1 ppm (C(CH 3 ) = CH 2 ). In the
29 Si NMR spectra of the polymer
containing perfluoroalkyl groups (Table 12.1, polymer B-S21), the expected
maxima in the range of −23.3 to −20.0 ppm ([Si(O 2 )C 3 H 6 ] units formed upon
hydrosilylation) and at 8.0 ppm ([Si(CH 3 ) 3 O], polymer terminal units) were visible.
A small, unexpected signal at *−60 ppm ([SiO 3 C] units) was attributed to the
formation of a by-product that resulted from the elimination of propene from the
allyl methacrylate during hydrosilylation reaction [57]. Coatings on poly(vinylidene
fluoride) or poly(ether sulfone), prepared from polymer B-S21, S6 (Table 12.1),
after cross-linking, were evaluated for organic vapor permeation [57]. High UV
378
A. Chechelska-Noworyta et al.