were introduced into PHMS and its copolymers by hydrosilylation of
1-allyloxy-2,3-epoxypropane (allyl glicydyl ether, AGE). In some cases, this process was conducted in the presence of another unsaturated organic compound to
afford a polymer containing two types of pendant groups. Spectroscopic studies of
the functionalized polymers allowed for verification of their chemical structures,
determination of the functionalization degrees or served as the basis for kinetic
investigations.
In several studies, polysiloxanes were modified exclusively by 3-(2,3epoxypropoxy)propyl moieties (Table 12.1, S1) originating from AGE and transformed to other ones in the next step. Srividhya et al. [30] and Safa et al. [31]
hydrosilylated AGE with PHMS (toluene, 80–90 °C, Speier’s catalyst). Then the
obtained polymers grafted with epoxy groups were converted to the ones containing
imide [30] or bulky tris(trimethylsilyl)methyl [31] substituents in the reactions with
amine-terminated imides or tris(trimethylsilyl)methyl lithium, respectively. Racles
and Cozan [32] prepared glucose-modified and El-Sukkary et al. [33]—hydroxyamide functionalized polysiloxanes by treatment of the epoxy groups from AGE
incorporated into PHMS-DMS copolymers (Karstedt’s catalyst, toluene, 75 or
120 °C) with D-glucose in the presence of a strongly acidic gel-type resin
(Amberlite IR-120 plus) or with the excess of various a,x-alkanediamines followed
by the reactions of the amine-modified polysiloxanes thus generated with d-gluconolactone, respectively. In all investigations, the synthesized materials were examined by FTIR and
1 H NMR spectroscopies, in [30, 32]—additionally by
13 C NMR
spectroscopy. FTIR spectra of the polymers modified by AGE moieties showed the
bands at 907 and 1237 cm
−1 (symmetric and asymmetric stretching vibrations of
epoxy groups, respectively),
1 H NMR spectra—the lines at d = 2.5, 2.7, 3.1 ppm
(protons of epoxy groups), and at d = 0.5, 1.5, 3.4 ppm (protons of silylpropyl
groups),
13 C NMR spectra—the signals at d = 44.2 and 50.8 ppm (carbon atoms of
epoxy ring). Spectral features of the epoxy ring disappeared after the next processes
conducted and the new ones, confirming the presence of new moieties in the
polymers, showed up. Final functionalized materials were applied as the components
of cross-linked PDMS-based membranes that exhibited high thermal stability and
high tensile strength [30] or studied as potential surfactants [33].
Kowalewska and Stańczyk [34], Rutnakornpituk [35], and Min et al. [36] prepared polysiloxanes with two types of side groups: tris(trimethylsilyl)
hexyl (Table 12.1, S2) and glycidoxypropyl (Table 12.1, S1) [34], cyanopropyl
(Table 12.1, S3) and glycidoxypropyl (Table 12.1, S1) [35] or dodecyl
(Table 12.1, S4) and glycidoxypropyl (Table 12.1, S1) [36] by hydrosilylating the
mixture of appropriate alkene derivatives (6,6,6-tris(trimethylsilyl)hex-1-ene and
AGE, allyl cyanide and AGE, dodec-1-ene and AGE) with PHMS [34] or
PHMS-DMS copolymers [34–36] using Karstedt’s [34] or Speier’s catalyst [35,
36]. Progress of the hydrosilylation process was monitored by
1 H NMR [34] or
FTIR spectroscopy [35]. NMR spectra (
1 H,
13 C and
29 Si) proved modification of
the polymers by the moieties originating from the alkene derivatives applied; in the
work by Rutnakornpituk [35], the functionalized polysiloxanes were additionally
characterized by FTIR spectroscopy.
29 Si NMR spectra of polysiloxanes with
370
A. Chechelska-Noworyta et al.
1-allyloxy-2,3-epoxypropane (allyl glicydyl ether, AGE). In some cases, this process was conducted in the presence of another unsaturated organic compound to
afford a polymer containing two types of pendant groups. Spectroscopic studies of
the functionalized polymers allowed for verification of their chemical structures,
determination of the functionalization degrees or served as the basis for kinetic
investigations.
In several studies, polysiloxanes were modified exclusively by 3-(2,3epoxypropoxy)propyl moieties (Table 12.1, S1) originating from AGE and transformed to other ones in the next step. Srividhya et al. [30] and Safa et al. [31]
hydrosilylated AGE with PHMS (toluene, 80–90 °C, Speier’s catalyst). Then the
obtained polymers grafted with epoxy groups were converted to the ones containing
imide [30] or bulky tris(trimethylsilyl)methyl [31] substituents in the reactions with
amine-terminated imides or tris(trimethylsilyl)methyl lithium, respectively. Racles
and Cozan [32] prepared glucose-modified and El-Sukkary et al. [33]—hydroxyamide functionalized polysiloxanes by treatment of the epoxy groups from AGE
incorporated into PHMS-DMS copolymers (Karstedt’s catalyst, toluene, 75 or
120 °C) with D-glucose in the presence of a strongly acidic gel-type resin
(Amberlite IR-120 plus) or with the excess of various a,x-alkanediamines followed
by the reactions of the amine-modified polysiloxanes thus generated with d-gluconolactone, respectively. In all investigations, the synthesized materials were examined by FTIR and
1 H NMR spectroscopies, in [30, 32]—additionally by
13 C NMR
spectroscopy. FTIR spectra of the polymers modified by AGE moieties showed the
bands at 907 and 1237 cm
−1 (symmetric and asymmetric stretching vibrations of
epoxy groups, respectively),
1 H NMR spectra—the lines at d = 2.5, 2.7, 3.1 ppm
(protons of epoxy groups), and at d = 0.5, 1.5, 3.4 ppm (protons of silylpropyl
groups),
13 C NMR spectra—the signals at d = 44.2 and 50.8 ppm (carbon atoms of
epoxy ring). Spectral features of the epoxy ring disappeared after the next processes
conducted and the new ones, confirming the presence of new moieties in the
polymers, showed up. Final functionalized materials were applied as the components
of cross-linked PDMS-based membranes that exhibited high thermal stability and
high tensile strength [30] or studied as potential surfactants [33].
Kowalewska and Stańczyk [34], Rutnakornpituk [35], and Min et al. [36] prepared polysiloxanes with two types of side groups: tris(trimethylsilyl)
hexyl (Table 12.1, S2) and glycidoxypropyl (Table 12.1, S1) [34], cyanopropyl
(Table 12.1, S3) and glycidoxypropyl (Table 12.1, S1) [35] or dodecyl
(Table 12.1, S4) and glycidoxypropyl (Table 12.1, S1) [36] by hydrosilylating the
mixture of appropriate alkene derivatives (6,6,6-tris(trimethylsilyl)hex-1-ene and
AGE, allyl cyanide and AGE, dodec-1-ene and AGE) with PHMS [34] or
PHMS-DMS copolymers [34–36] using Karstedt’s [34] or Speier’s catalyst [35,
36]. Progress of the hydrosilylation process was monitored by
1 H NMR [34] or
FTIR spectroscopy [35]. NMR spectra (
1 H,
13 C and
29 Si) proved modification of
the polymers by the moieties originating from the alkene derivatives applied; in the
work by Rutnakornpituk [35], the functionalized polysiloxanes were additionally
characterized by FTIR spectroscopy.
29 Si NMR spectra of polysiloxanes with
370
A. Chechelska-Noworyta et al.