termini of the modified copolymer to obtain PDMS/amine-modified PHMS-DMS/
PDMS triblock copolymer. Afterward, in both studies the synthesized polysiloxanes with amine pendant groups were converted to the QAS by treatment with
1-iodooctane (Table 12.1, S25) [71] or benzyl chloride (Table 12.1, S26 and S27)
[72].
1 H NMR spectra revealed that hydrosilylation of DMAA with PHMS-DMS
copolymers led to both b (signals at d = 0.49 ppm, 1.51 ppm, 2.21 ppm) and a
(lines at d = 0.98, 0.99 ppm, 1.25 ppm, 2.26 ppm) addition products [71].
Quaternization of incorporated amine groups was proved by the presence of new
signals at d values above 3 ppm: 3.35 and 3.49 ppm [71] or 3.14 ppm [72].
Guerra-Contreras et al. [71] confirmed the chemical structures of the synthesized
products also by
13 C and
29 Si NMR spectroscopies, Lei et al. [72]—by FTIR
spectroscopy. The prepared QAS showed good solubility in polar organic solvents,
such as ethanol [71] and high antibacterial activity [72].
Another approach to the preparation of polysiloxanes with introduced QAS
groups was presented by Zhao et al. [73] and Hou et al. [74]. They synthesized
polysiloxanes containing epoxy groups first, then the epoxy ring was opened using
an amine which was quaternized during this reaction or in the next step. Thus, Zhao
et al. [73] hydrosilylated allyl polyether epoxy compound (APEE500) and Hou
et al. [74]—AGE with PHMS-DMS copolymers (Speier’s catalyst, 80–85 °C,
isopropanol [73] or 90 °C, toluene [74]). The obtained polysiloxanes with epoxyether pendant groups were then reacted with N,N-dimethyldodecylamine
(DMDA)/acetic acid mixture [73] or diethyl amine and, subsequently, benzyl
chloride [74] yielding polymers with QAS moieties (Table 12.1, S28 or S29,
respectively). The presence of epoxy groups in the intermediate products obtained
by Zhao et al. [73] was evidenced by the
1 H NMR signals in the d range of 2.56–
3.06 which were replaced by the new signals at d = 3.22 ppm (N
+
(CH 3 ) 2 ),
3.33 ppm (N
+ CH 2 CHOH), and 3.58 ppm (N
+
CH 2 CH 2 ) in the spectra of the final
compounds. FTIR spectra showed the bands at 2870 and 1110 cm
−1 ascribed to the
vibrations of C–H and C–O bond in the polyether group, respectively. After the
reaction with amine, the IR band at 3412 cm
−1 , due to the OH group, appeared in
the spectrum [73].
1 H NMR spectra of polysiloxanes with introduced QAS moieties
prepared by Hou et al. [74] contained additionally the signals at d = 4.71 ppm and
7.36–7.53 ppm corresponding to benzyl groups attached to nitrogen atoms.
Polysiloxanes with quaternary ammonium groups were applied to prepare coatings
on fabrics of antimicrobial properties [73] and as cationic surfactants for waterborne
polypropylene oxide emulsions [74].
Among other nitrogen-containing side groups that were used to modify
polysiloxanes, carbazolyl (Table 12.1, S30–S33), phthalocyanine (Table 12.1,
S34), and cyclam (Table 12.1, S35) should be mentioned. Their specific electronic
structures bring about interesting optical properties of these moieties [75, 76]. Thus,
their incorporation into polysiloxanes may lead to the materials suitable for use in
various optical devices.
Nordin et al. [77, 78] prepared polysiloxanes with various amounts of carbazolyl
side groups (Table 12.1, polymer B-S30) by hydrosilylation of 9-vinylcarbazole
with PHMS-DMS copolymer (Karstedt’s catalyst, toluene, 120 °C). This process
380
A. Chechelska-Noworyta et al.
PDMS triblock copolymer. Afterward, in both studies the synthesized polysiloxanes with amine pendant groups were converted to the QAS by treatment with
1-iodooctane (Table 12.1, S25) [71] or benzyl chloride (Table 12.1, S26 and S27)
[72].
1 H NMR spectra revealed that hydrosilylation of DMAA with PHMS-DMS
copolymers led to both b (signals at d = 0.49 ppm, 1.51 ppm, 2.21 ppm) and a
(lines at d = 0.98, 0.99 ppm, 1.25 ppm, 2.26 ppm) addition products [71].
Quaternization of incorporated amine groups was proved by the presence of new
signals at d values above 3 ppm: 3.35 and 3.49 ppm [71] or 3.14 ppm [72].
Guerra-Contreras et al. [71] confirmed the chemical structures of the synthesized
products also by
13 C and
29 Si NMR spectroscopies, Lei et al. [72]—by FTIR
spectroscopy. The prepared QAS showed good solubility in polar organic solvents,
such as ethanol [71] and high antibacterial activity [72].
Another approach to the preparation of polysiloxanes with introduced QAS
groups was presented by Zhao et al. [73] and Hou et al. [74]. They synthesized
polysiloxanes containing epoxy groups first, then the epoxy ring was opened using
an amine which was quaternized during this reaction or in the next step. Thus, Zhao
et al. [73] hydrosilylated allyl polyether epoxy compound (APEE500) and Hou
et al. [74]—AGE with PHMS-DMS copolymers (Speier’s catalyst, 80–85 °C,
isopropanol [73] or 90 °C, toluene [74]). The obtained polysiloxanes with epoxyether pendant groups were then reacted with N,N-dimethyldodecylamine
(DMDA)/acetic acid mixture [73] or diethyl amine and, subsequently, benzyl
chloride [74] yielding polymers with QAS moieties (Table 12.1, S28 or S29,
respectively). The presence of epoxy groups in the intermediate products obtained
by Zhao et al. [73] was evidenced by the
1 H NMR signals in the d range of 2.56–
3.06 which were replaced by the new signals at d = 3.22 ppm (N
+
(CH 3 ) 2 ),
3.33 ppm (N
+ CH 2 CHOH), and 3.58 ppm (N
+
CH 2 CH 2 ) in the spectra of the final
compounds. FTIR spectra showed the bands at 2870 and 1110 cm
−1 ascribed to the
vibrations of C–H and C–O bond in the polyether group, respectively. After the
reaction with amine, the IR band at 3412 cm
−1 , due to the OH group, appeared in
the spectrum [73].
1 H NMR spectra of polysiloxanes with introduced QAS moieties
prepared by Hou et al. [74] contained additionally the signals at d = 4.71 ppm and
7.36–7.53 ppm corresponding to benzyl groups attached to nitrogen atoms.
Polysiloxanes with quaternary ammonium groups were applied to prepare coatings
on fabrics of antimicrobial properties [73] and as cationic surfactants for waterborne
polypropylene oxide emulsions [74].
Among other nitrogen-containing side groups that were used to modify
polysiloxanes, carbazolyl (Table 12.1, S30–S33), phthalocyanine (Table 12.1,
S34), and cyclam (Table 12.1, S35) should be mentioned. Their specific electronic
structures bring about interesting optical properties of these moieties [75, 76]. Thus,
their incorporation into polysiloxanes may lead to the materials suitable for use in
various optical devices.
Nordin et al. [77, 78] prepared polysiloxanes with various amounts of carbazolyl
side groups (Table 12.1, polymer B-S30) by hydrosilylation of 9-vinylcarbazole
with PHMS-DMS copolymer (Karstedt’s catalyst, toluene, 120 °C). This process
380
A. Chechelska-Noworyta et al.