propyl cinnamate group-containing material to UV radiation (Fig. 12.8) which was
connected with photopolymerization of these moieties [101]. Formation of polylactide arms and completeness of hydrosilylation in the mPLLA-Q 8 M 8
H system
was verified by FTIR and
1 H NMR spectroscopies [102].
It should be noted that Igarashi et al. [100] treated T 8
H with allyl ethyl ether
(AEE) and N,N-dimethylallylamine (DMAA) in the same conditions as those in the
reactions of T 8
H and AA already described. The molecules modified by groups S17
and S18 (Table 12.3) resulted from these processes. Based on spectroscopic studies,
it was found that addition of PPh 3 to the reaction mixture had no effect on selectivity and conversion of Si–H groups in the case of AEE while for DMAA both
parameters decreased.
Spherosilicate/silsesquioxane-polyether hybrids were investigated by Mya et al.
[103], Markovic et al. [104], and Pozza et al. [105]. They were synthesized by
hydrosilylation of allyl poly(ethylene oxide) with Q 8 M 8
H in toluene using
Karstedt’s catalyst (at 80 °C [103]), Q 8 M 8
H or T 8
H (at room temperature [104]) or
hydrosilylation of a-methoxy-x-undecenyl poly(ethylene oxide) with Q 8 M 8
H (at
40 °C [105]). Products of the reactions were characterized by FTIR and
1 H NMR
[103], FTIR and
1 H,
13 C,
29 Si NMR [104, 105] which confirmed the presence of
polyether units (Table 12.3, S19 or S20) in the systems. Incomplete functionalization of Q 8 M 8
H was found in [103, 105]. Ratios of integral intensities of the
1 H
NMR signals at d = *0.6 ppm (protons of CH 2 groups in PEO) and at
d = *0.1 ppm (protons of CH 3 groups in Q 8 M 8
H ) showed that the average number
of polyether chains attached to one cubic core was equal to 6 [103] or 7.2 [105].
12.5.3 T 8
H and Q 8 M 8
H Modified by Fluorocarbon Groups
Although cage molecules with introduced fluorocarbon substituents exhibit
attractive properties, reports on their preparation via hydrosilylation are scarce.
Dutkiewicz et al. [106] applied a rhodium siloxide complex as a homogeneous
catalyst in the hydrosilylation of 1,1,2,2,3,3,4,4-octafluoropentyl allyl ether with
Q 8 M 8
H conducted in toluene at 110 °C—this process led to the molecules with
eight fluorocarbon substituents (Table 12.3, S4). Then, spherosilicates with various
amounts of fluorocarbon and epoxy groups (Table 12.3, S1 and S4) were synthesized by successive hydrosilylation of AGE and 1,1,2,2,3,3,4,4-octafluoropentyl
allyl ether at various ratios with Q 8 M 8
H in the same conditions. Spectroscopic
analyses (
1 H,
13 C,
29
Si NMR) unambiguously corroborated formation of the targeted, octasubstituted cage molecules.
Wang et al. [107] prepared a series of spherosilicates with incorporated fluorinated ether, fluorinated oligoether, or perfluoroaromatic units (Table 12.3, S21–
S23) by the reactions between Q 8 M 8
H and various fluorinated alkene derivatives
which were synthesized in the work (Karstedt’s catalyst, toluene, room temperature). Progress of the hydrosilylation processes was followed by monitoring the
390
A. Chechelska-Noworyta et al.
connected with photopolymerization of these moieties [101]. Formation of polylactide arms and completeness of hydrosilylation in the mPLLA-Q 8 M 8
H system
was verified by FTIR and
1 H NMR spectroscopies [102].
It should be noted that Igarashi et al. [100] treated T 8
H with allyl ethyl ether
(AEE) and N,N-dimethylallylamine (DMAA) in the same conditions as those in the
reactions of T 8
H and AA already described. The molecules modified by groups S17
and S18 (Table 12.3) resulted from these processes. Based on spectroscopic studies,
it was found that addition of PPh 3 to the reaction mixture had no effect on selectivity and conversion of Si–H groups in the case of AEE while for DMAA both
parameters decreased.
Spherosilicate/silsesquioxane-polyether hybrids were investigated by Mya et al.
[103], Markovic et al. [104], and Pozza et al. [105]. They were synthesized by
hydrosilylation of allyl poly(ethylene oxide) with Q 8 M 8
H in toluene using
Karstedt’s catalyst (at 80 °C [103]), Q 8 M 8
H or T 8
H (at room temperature [104]) or
hydrosilylation of a-methoxy-x-undecenyl poly(ethylene oxide) with Q 8 M 8
H (at
40 °C [105]). Products of the reactions were characterized by FTIR and
1 H NMR
[103], FTIR and
1 H,
13 C,
29 Si NMR [104, 105] which confirmed the presence of
polyether units (Table 12.3, S19 or S20) in the systems. Incomplete functionalization of Q 8 M 8
H was found in [103, 105]. Ratios of integral intensities of the
1 H
NMR signals at d = *0.6 ppm (protons of CH 2 groups in PEO) and at
d = *0.1 ppm (protons of CH 3 groups in Q 8 M 8
H ) showed that the average number
of polyether chains attached to one cubic core was equal to 6 [103] or 7.2 [105].
12.5.3 T 8
H and Q 8 M 8
H Modified by Fluorocarbon Groups
Although cage molecules with introduced fluorocarbon substituents exhibit
attractive properties, reports on their preparation via hydrosilylation are scarce.
Dutkiewicz et al. [106] applied a rhodium siloxide complex as a homogeneous
catalyst in the hydrosilylation of 1,1,2,2,3,3,4,4-octafluoropentyl allyl ether with
Q 8 M 8
H conducted in toluene at 110 °C—this process led to the molecules with
eight fluorocarbon substituents (Table 12.3, S4). Then, spherosilicates with various
amounts of fluorocarbon and epoxy groups (Table 12.3, S1 and S4) were synthesized by successive hydrosilylation of AGE and 1,1,2,2,3,3,4,4-octafluoropentyl
allyl ether at various ratios with Q 8 M 8
H in the same conditions. Spectroscopic
analyses (
1 H,
13 C,
29
Si NMR) unambiguously corroborated formation of the targeted, octasubstituted cage molecules.
Wang et al. [107] prepared a series of spherosilicates with incorporated fluorinated ether, fluorinated oligoether, or perfluoroaromatic units (Table 12.3, S21–
S23) by the reactions between Q 8 M 8
H and various fluorinated alkene derivatives
which were synthesized in the work (Karstedt’s catalyst, toluene, room temperature). Progress of the hydrosilylation processes was followed by monitoring the
390
A. Chechelska-Noworyta et al.