oxide) [47]. In the work by Wang et al. [42], hydroxyl groups terminating the
polyether moieties were subsequently transformed into the quaternary ammonium
salts (QAS) in the reaction with SOCl 2 followed by the one with trimethylamine.
Kang and Fang [49] converted the dimethylamine groups present in their functionalized polymer to QAS by treatment with methyl iodide. Incorporation of
polyether groups into the studied polysiloxanes was corroborated by FTIR (the
band at 1095 cm
−1 , C–O–C bond stretching [42]),
1 H NMR (signal at d = 3.8 ppm,
protons of polyether blocks [43]), and
13 C NMR (lines at d = *70 ppm, carbon
atoms in polyether blocks [48]) spectra. The amounts of the polyether moieties in
the systems were calculated based on the
1 H NMR spectra [41, 43]. These spectra
were also used to determine the shares of the Markovnikov, anti-Markovnikov
hydrosilylation adducts as well as side products (cis and trans isomers of the
internal alkene derivative derived from the hydrosilylated allyl compound, propanal
resulting from its decomposition) formed during the reactions [41, 45]. Moreover,
FTIR and
1 H NMR spectroscopic studies allowed Ganicz et al. [41] to conclude that
only one of the studied rhodium catalysts showed slightly higher activity than
Karstedt’s complex, but it gave significantly more undesired a-adduct. Among the
Pt catalysts investigated by Chung and Kim [45]—Karstedt’s, Speier’s,
Lamoreaux’s, i.e., Pt-octanal/octanol complex, and Pt/C, Speier’s turned out to be
the best. Surface properties [43, 44], ionic conductivity [47–49], and a model drug
(tocopherol) loading capacity [42] of the resultant materials were examined in view
of their potential use as surfactants, polymer electrolytes, and drug carriers,
respectively.
Methoxy-substituted aromatic pendant fragments (Table 12.1, S13—R = CH 3 ,
R 3 = H, R 4 = H or OCH 3 ) were introduced into PHMS by its reaction with
4-allyl-1-methoxybenzene or 4-allyl-1,2-dimethoxybenzene (Karstedt’s or Speier’s
catalyst, toluene, 60 °C) [50]. FTIR and
1 H NMR spectra of the synthesized polymers showed that Karstedt’s catalyst was more efficient: in its presence, all Si–H
groups of the polymer were substituted. The Si–H groups which remained in the
polymer after the process performed using Speier’s catalyst were responsible for
partial gelation of the reaction mixture giving rise to the IR band at 1185 cm
−1
characteristic for silsesquioxane bonds. Presence of methoxy-substituted aromatic
fragments in the modified polymer was evidenced by the IR bands at: 835 cm
−1
(1,4-disubstituted benzene ring, polymer with S13 in Table 12.1, R 3 = R 4 = H), 728,
841 cm
−1 (1,2,4-trisubstituted benzene ring, polymer with S13 in Table 12.1,
R 3 = H, R 4 = OCH 3 ), 1505–1600 cm
−1 , and 3020–3060 cm
−1 (vibrations of C=C
and C–H bonds in aromatic ring, respectively).
1 H NMR spectra indicated that the
hydrosilylation proceeded according to both Markovnikov and anti-Markovnikov
rules; ratios of the anti-Markovnikov and Markovnikov adducts were equal to 8:1
(polymer with S13 in Table 12.1, R 3 = R 4 = H) and 6:1 (polymer with S13 in
Table 12.1, R 3 = H, R 4 = OCH 3 ). Moreover,
1 H NMR spectra confirmed the presence of phenyl rings (multiple signal in the range of d = 6.78–7.29 ppm) and
methoxy groups (signal at d = 3.81 ppm, OCH 3 ) in the polymer structures.
In another work [51], polysiloxanes modified by methoxy- and
hydroxy-substituted aromatic pendant fragments were prepared by the reactions
12 Application of Spectroscopic Methods in the Studies …
375
polyether moieties were subsequently transformed into the quaternary ammonium
salts (QAS) in the reaction with SOCl 2 followed by the one with trimethylamine.
Kang and Fang [49] converted the dimethylamine groups present in their functionalized polymer to QAS by treatment with methyl iodide. Incorporation of
polyether groups into the studied polysiloxanes was corroborated by FTIR (the
band at 1095 cm
−1 , C–O–C bond stretching [42]),
1 H NMR (signal at d = 3.8 ppm,
protons of polyether blocks [43]), and
13 C NMR (lines at d = *70 ppm, carbon
atoms in polyether blocks [48]) spectra. The amounts of the polyether moieties in
the systems were calculated based on the
1 H NMR spectra [41, 43]. These spectra
were also used to determine the shares of the Markovnikov, anti-Markovnikov
hydrosilylation adducts as well as side products (cis and trans isomers of the
internal alkene derivative derived from the hydrosilylated allyl compound, propanal
resulting from its decomposition) formed during the reactions [41, 45]. Moreover,
FTIR and
1 H NMR spectroscopic studies allowed Ganicz et al. [41] to conclude that
only one of the studied rhodium catalysts showed slightly higher activity than
Karstedt’s complex, but it gave significantly more undesired a-adduct. Among the
Pt catalysts investigated by Chung and Kim [45]—Karstedt’s, Speier’s,
Lamoreaux’s, i.e., Pt-octanal/octanol complex, and Pt/C, Speier’s turned out to be
the best. Surface properties [43, 44], ionic conductivity [47–49], and a model drug
(tocopherol) loading capacity [42] of the resultant materials were examined in view
of their potential use as surfactants, polymer electrolytes, and drug carriers,
respectively.
Methoxy-substituted aromatic pendant fragments (Table 12.1, S13—R = CH 3 ,
R 3 = H, R 4 = H or OCH 3 ) were introduced into PHMS by its reaction with
4-allyl-1-methoxybenzene or 4-allyl-1,2-dimethoxybenzene (Karstedt’s or Speier’s
catalyst, toluene, 60 °C) [50]. FTIR and
1 H NMR spectra of the synthesized polymers showed that Karstedt’s catalyst was more efficient: in its presence, all Si–H
groups of the polymer were substituted. The Si–H groups which remained in the
polymer after the process performed using Speier’s catalyst were responsible for
partial gelation of the reaction mixture giving rise to the IR band at 1185 cm
−1
characteristic for silsesquioxane bonds. Presence of methoxy-substituted aromatic
fragments in the modified polymer was evidenced by the IR bands at: 835 cm
−1
(1,4-disubstituted benzene ring, polymer with S13 in Table 12.1, R 3 = R 4 = H), 728,
841 cm
−1 (1,2,4-trisubstituted benzene ring, polymer with S13 in Table 12.1,
R 3 = H, R 4 = OCH 3 ), 1505–1600 cm
−1 , and 3020–3060 cm
−1 (vibrations of C=C
and C–H bonds in aromatic ring, respectively).
1 H NMR spectra indicated that the
hydrosilylation proceeded according to both Markovnikov and anti-Markovnikov
rules; ratios of the anti-Markovnikov and Markovnikov adducts were equal to 8:1
(polymer with S13 in Table 12.1, R 3 = R 4 = H) and 6:1 (polymer with S13 in
Table 12.1, R 3 = H, R 4 = OCH 3 ). Moreover,
1 H NMR spectra confirmed the presence of phenyl rings (multiple signal in the range of d = 6.78–7.29 ppm) and
methoxy groups (signal at d = 3.81 ppm, OCH 3 ) in the polymer structures.
In another work [51], polysiloxanes modified by methoxy- and
hydroxy-substituted aromatic pendant fragments were prepared by the reactions
12 Application of Spectroscopic Methods in the Studies …
375