374
copolymer was functionalized with ATRP initiator groups by the hydrosilylation
with 4-vinyl-benzyl chloride in the presence of Pt 2 [(ViSiMe 2 ) 2 O] 3 as a catalyst. It
was used in the ATRP of St, giving a PDMS-g-St copolymer (Pyun and Matyjaszewski
2001). α-n-butyl-ω-Si-H terminated PDMS was applied for the synthesis of ATRP
macroinitiator containing PDMS chains for the polymerization of St and its copolymerization into triblock ABC copolymers containing a surface active segment, followed by grafting onto silicon wafers into polymer brushes with different properties
from glassy to elastomeric materials (Pyun et al. 2004).
Through Pt-catalyzed hydrosilylation of propargyl methacrylate with Q 8 M
H
8 and
T
H
8 cages, the methacrylate-functionalized inorganic-organic hybrids were synthesized, which were thermally photocured (Sellinger and Laine 1996a, b). The
H-silsesquioxane Q 8 M
H
8 has also used for the synthesis of two different initiators for
ATRP: (1) octakis(2-bromo-2-methylpropionoxypropyldimethylsiloxy)octasilsesquioxane and (2) octakis[2-(4-chloromethylphenyl)ethyldimethylsiloxy]octasilsesquioxane. A hybrid 8-arm star PMMA with MWs in the range of 28,000–92,000 g/mol, was
prepared by the ATRP method with (1) as the macroinitiator (Costa et al. 2001, 2002).
Multifunctional poly(alkoxy)siloxanes were synthesized by Ivanovici and
Kickelbick (2008) via hydrosilylation of PDMS-co-PMHS with ViSi(OEt) 3 , which
by the hydrolytic polycondensation in the sol-gel process gave hybrid polysiloxane
NPs. Polysiloxane-metal oxide nanohybrid materials were prepared by adding
PDMS-co-PMHS into allyl acetylacetonate complexes of metal alkoxides (M(OR) 4 ,
M = Ti, Zr, R = Et, i-Pr) (Ivanovici and Kickelbick 2008).
New silicone hydrogels, such as IPN networks with poly(vinyl alcohol) (PVA) were
obtained by crosslinking of α,ω-divinylpoly(dimethyl-co-trifluoropropyl)siloxanes,
photopolymerization of vinyl acetate (in situ), followed by the hydrolysis of acetate
groups. These hydrogels with a considerable transparency (90–92%) and water absorption (20–39%) can be applied for the manufacture of soft contact lenses (Pavlyuchenko
et al. 2009). By hydrosilylation of PMHS with 2-allyloxyethanol, polysiloxanes with
pendant (2-hydroxyethoxy)propyl moieties were synthesized, which were used for the
preparation of silicone-urethane elastomers (Madhavan and Reddy 2006). Triblock
polysiloxane-polyphosphazene copolymers were prepared through hydrosilylation
reaction of α,ω-dihydro-PDMS with allyl-functional polyphosphazenes (Sellinger and
Laine 1996a, b; Prange and Allcock 1999, Allcock and Prange 2001).
Kurian et al. (2002) polymerized D
H 5 into poly(pentmethylcyclopentasiloxane)
(PD 5 ), with water in the presence of Pt 2 [(ViSiMe 2 ) 2 O] 3 as a catalyst, in bulk or in
solution at 100 °C. The Si-H groups of D
H 5 were hydrolyzed into intermediate
Si-OH groups, which underwent the condensation with D
H 5 rings into complex multiring structures. An average three of the five Si-H groups of D
H 5 reacted, and the
final product contained only traces of Si-OH groups. The melting temperature
(T m = −138 °C) and T g (−152 °C) of the monomer were very low. PD 5 was a stiff
and brittle solid, insoluble in common solvents, without a melting endotherm. It had
an extremely low T g (−151 °C) and solid-like properties even at ambient temperature, and was thermally stable up to 700 °C (Kurian et al. 2002). Novel three component amphiphilic membranes were obtained by cohydrosilylation of hydrophilic
J. J. Chruściel
copolymer was functionalized with ATRP initiator groups by the hydrosilylation
with 4-vinyl-benzyl chloride in the presence of Pt 2 [(ViSiMe 2 ) 2 O] 3 as a catalyst. It
was used in the ATRP of St, giving a PDMS-g-St copolymer (Pyun and Matyjaszewski
2001). α-n-butyl-ω-Si-H terminated PDMS was applied for the synthesis of ATRP
macroinitiator containing PDMS chains for the polymerization of St and its copolymerization into triblock ABC copolymers containing a surface active segment, followed by grafting onto silicon wafers into polymer brushes with different properties
from glassy to elastomeric materials (Pyun et al. 2004).
Through Pt-catalyzed hydrosilylation of propargyl methacrylate with Q 8 M
H
8 and
T
H
8 cages, the methacrylate-functionalized inorganic-organic hybrids were synthesized, which were thermally photocured (Sellinger and Laine 1996a, b). The
H-silsesquioxane Q 8 M
H
8 has also used for the synthesis of two different initiators for
ATRP: (1) octakis(2-bromo-2-methylpropionoxypropyldimethylsiloxy)octasilsesquioxane and (2) octakis[2-(4-chloromethylphenyl)ethyldimethylsiloxy]octasilsesquioxane. A hybrid 8-arm star PMMA with MWs in the range of 28,000–92,000 g/mol, was
prepared by the ATRP method with (1) as the macroinitiator (Costa et al. 2001, 2002).
Multifunctional poly(alkoxy)siloxanes were synthesized by Ivanovici and
Kickelbick (2008) via hydrosilylation of PDMS-co-PMHS with ViSi(OEt) 3 , which
by the hydrolytic polycondensation in the sol-gel process gave hybrid polysiloxane
NPs. Polysiloxane-metal oxide nanohybrid materials were prepared by adding
PDMS-co-PMHS into allyl acetylacetonate complexes of metal alkoxides (M(OR) 4 ,
M = Ti, Zr, R = Et, i-Pr) (Ivanovici and Kickelbick 2008).
New silicone hydrogels, such as IPN networks with poly(vinyl alcohol) (PVA) were
obtained by crosslinking of α,ω-divinylpoly(dimethyl-co-trifluoropropyl)siloxanes,
photopolymerization of vinyl acetate (in situ), followed by the hydrolysis of acetate
groups. These hydrogels with a considerable transparency (90–92%) and water absorption (20–39%) can be applied for the manufacture of soft contact lenses (Pavlyuchenko
et al. 2009). By hydrosilylation of PMHS with 2-allyloxyethanol, polysiloxanes with
pendant (2-hydroxyethoxy)propyl moieties were synthesized, which were used for the
preparation of silicone-urethane elastomers (Madhavan and Reddy 2006). Triblock
polysiloxane-polyphosphazene copolymers were prepared through hydrosilylation
reaction of α,ω-dihydro-PDMS with allyl-functional polyphosphazenes (Sellinger and
Laine 1996a, b; Prange and Allcock 1999, Allcock and Prange 2001).
Kurian et al. (2002) polymerized D
H 5 into poly(pentmethylcyclopentasiloxane)
(PD 5 ), with water in the presence of Pt 2 [(ViSiMe 2 ) 2 O] 3 as a catalyst, in bulk or in
solution at 100 °C. The Si-H groups of D
H 5 were hydrolyzed into intermediate
Si-OH groups, which underwent the condensation with D
H 5 rings into complex multiring structures. An average three of the five Si-H groups of D
H 5 reacted, and the
final product contained only traces of Si-OH groups. The melting temperature
(T m = −138 °C) and T g (−152 °C) of the monomer were very low. PD 5 was a stiff
and brittle solid, insoluble in common solvents, without a melting endotherm. It had
an extremely low T g (−151 °C) and solid-like properties even at ambient temperature, and was thermally stable up to 700 °C (Kurian et al. 2002). Novel three component amphiphilic membranes were obtained by cohydrosilylation of hydrophilic
J. J. Chruściel