(Table 12.1, S7) resulted in polysiloxanes with carboxyl side groups. This was
demonstrated by significant decrease in the intensity of the band at *1740 cm
−1
with simultaneous appearance of the band at 1711 cm
−1 and the broad peak at
*3300 cm
−1 (carbonyl and OH groups in organic acids, respectively) in the IR
spectra.
Mukbaniani et al. [39] investigated the reactions of acrylic and methacrylic acids
with PHMS catalyzed by H 2 PtCl 6 . Based on the analysis of FTIR and NMR (
1 H,
13 C) spectroscopic data, they concluded that apart from the 1,2- and
1,4-hydrosilylation, dehydrogenative condensation ( ! Si–H + HO(O)C– ! ! Si–
O(O)C– + H 2 ) takes place in the systems. According to the results presented in the
paper, reactions between PHMS and acrylic acid involve predominantly
1,2-addition with the formation of anti-Markovnikov (b) product and dehydrocondensation. Reactions of PHMS with methacrylic acid proceed in more directions: They lead to 1,2-Markovnikov and anti-Markovnikov, 1,4-addition and
dehydrocondensation products. Some of these compounds undergo further transformations which result in a very complex product mixture [39].
Polysiloxanes modified by other oxygen-containing substituents, namely ester or
benzylamide-terminated long-chain hydrocarbon groups (Table 12.1, S8–S9), were
prepared by the reaction between PHMS-DMS copolymer and methyl undecylenate
or undecylenic acid benzylamide (Karstedt’s catalyst, toluene, 20 °C [40]).
Completeness of the reactions was established by the disappearance of the signals
from the Si–H and CH=CH 2 groups in
1 H NMR spectra which were also used to
confirm the presence of functional groups in the polymer structures. Their signals
were seen at d = 3.69 ppm (C(O)OCH 3 , d = 4.47 ppm (C(O)NHCH 2 Ph),
d = 5.90–6.30 ppm (C(O)NHCH 2 Ph), and d = 7.25 ppm (C(O)NHCH 2 Ph). In the
work, the influence of the type and content of pendant groups on the
low-temperature and rheological properties of the functionalized copolymers as
compared to PDMS was established.
In a number of studies, polysiloxanes were modified by polyether side groups.
PHMS-DMS copolymers were applied as hydrosilylating agents for terminal allyl
poly(ethylene oxide) derivatives bearing different groups at the other chain end:
hydroxyl [41, 42], acetate [43], methyl [44–46] (Table 12.1, S10: R=OH, CH 3 CO,
CH 3 , respectively). Into PHMS, in turn, functional groups originating from tri
(ethylene oxide) allyl methyl ether (Table 12.1, S10—x = 3, R = CH 3 ) [47],
allyltrimethoxysilane and, subsequently, tetra(ethylene oxide) allyl methyl ether
[48] (Table 12.1, S11 and S10—x = 4, R = CH 3 ) or, simultaneously, poly(ethylene
oxide) allyl methyl ether and N,N-dimethylallylamine (Table 12.1, S10—R = CH 3 ,
S12) [49] were introduced. Processes were conducted with various rhodium catalysts and (for comparison) with Karstedt’s catalyst [41], various Pt catalysts [45],
Speier’s catalyst [42–44, 46], Karstedt’s catalyst [47, 48], and dichloro(dicyclopentadienyl)platinum(II) complex, Cp 2 PtCl 2 [49]. Progress of the reactions was
followed by FTIR [41, 44–46] or
1 H NMR spectroscopy [48]. Some of the prepared
polymers containing polyether groups were then cross-linked using the incorporated methoxy groups [48] or in the second hydrosilylation reaction that involved
the Si–H groups remaining in the modified polymer and a,x-diallyl(polyethylene
374
A. Chechelska-Noworyta et al.
demonstrated by significant decrease in the intensity of the band at *1740 cm
−1
with simultaneous appearance of the band at 1711 cm
−1 and the broad peak at
*3300 cm
−1 (carbonyl and OH groups in organic acids, respectively) in the IR
spectra.
Mukbaniani et al. [39] investigated the reactions of acrylic and methacrylic acids
with PHMS catalyzed by H 2 PtCl 6 . Based on the analysis of FTIR and NMR (
1 H,
13 C) spectroscopic data, they concluded that apart from the 1,2- and
1,4-hydrosilylation, dehydrogenative condensation ( ! Si–H + HO(O)C– ! ! Si–
O(O)C– + H 2 ) takes place in the systems. According to the results presented in the
paper, reactions between PHMS and acrylic acid involve predominantly
1,2-addition with the formation of anti-Markovnikov (b) product and dehydrocondensation. Reactions of PHMS with methacrylic acid proceed in more directions: They lead to 1,2-Markovnikov and anti-Markovnikov, 1,4-addition and
dehydrocondensation products. Some of these compounds undergo further transformations which result in a very complex product mixture [39].
Polysiloxanes modified by other oxygen-containing substituents, namely ester or
benzylamide-terminated long-chain hydrocarbon groups (Table 12.1, S8–S9), were
prepared by the reaction between PHMS-DMS copolymer and methyl undecylenate
or undecylenic acid benzylamide (Karstedt’s catalyst, toluene, 20 °C [40]).
Completeness of the reactions was established by the disappearance of the signals
from the Si–H and CH=CH 2 groups in
1 H NMR spectra which were also used to
confirm the presence of functional groups in the polymer structures. Their signals
were seen at d = 3.69 ppm (C(O)OCH 3 , d = 4.47 ppm (C(O)NHCH 2 Ph),
d = 5.90–6.30 ppm (C(O)NHCH 2 Ph), and d = 7.25 ppm (C(O)NHCH 2 Ph). In the
work, the influence of the type and content of pendant groups on the
low-temperature and rheological properties of the functionalized copolymers as
compared to PDMS was established.
In a number of studies, polysiloxanes were modified by polyether side groups.
PHMS-DMS copolymers were applied as hydrosilylating agents for terminal allyl
poly(ethylene oxide) derivatives bearing different groups at the other chain end:
hydroxyl [41, 42], acetate [43], methyl [44–46] (Table 12.1, S10: R=OH, CH 3 CO,
CH 3 , respectively). Into PHMS, in turn, functional groups originating from tri
(ethylene oxide) allyl methyl ether (Table 12.1, S10—x = 3, R = CH 3 ) [47],
allyltrimethoxysilane and, subsequently, tetra(ethylene oxide) allyl methyl ether
[48] (Table 12.1, S11 and S10—x = 4, R = CH 3 ) or, simultaneously, poly(ethylene
oxide) allyl methyl ether and N,N-dimethylallylamine (Table 12.1, S10—R = CH 3 ,
S12) [49] were introduced. Processes were conducted with various rhodium catalysts and (for comparison) with Karstedt’s catalyst [41], various Pt catalysts [45],
Speier’s catalyst [42–44, 46], Karstedt’s catalyst [47, 48], and dichloro(dicyclopentadienyl)platinum(II) complex, Cp 2 PtCl 2 [49]. Progress of the reactions was
followed by FTIR [41, 44–46] or
1 H NMR spectroscopy [48]. Some of the prepared
polymers containing polyether groups were then cross-linked using the incorporated methoxy groups [48] or in the second hydrosilylation reaction that involved
the Si–H groups remaining in the modified polymer and a,x-diallyl(polyethylene
374
A. Chechelska-Noworyta et al.