377
Silane-modified unsaturated polymers, especially with functional groups, can
find a potential application as adhesives, drug delivery agents and rubber materials
(Marciniec et al. 1992; Marciniec 2002, 2009). The properties of PB containing
93% of pendant vinyl groups were modified with M
H 2 D n of MW = 400 g/mol, in the
presence of a catalyst RhCl(PPh 3 ) 3 . With the increase of a mole ratio [Si-H]/
[CH 2 = CH], the properties of modified polymers changed from a strong rubber to a
viscous material, but in longer reaction times gelation was observed (Baum et al.
1998). A ‘living’ linear PB was terminated in reaction with chlorodimethylsilane
(ClSiMe 2 H). Further addition reaction of the Si-H group to unsaturated PB moieties, with the use of the catalyst Pt 2 [(ViSiMe 2 ) 2 O] 3 , led to the production of
branched PB, which was then modified with monohydrosilanes (R 3 SiH) (Wurm
et al. 2008). The PE-g-PDMS copolymers were obtained by catalytic hydrogenation
of PB-g-PDMS. The latter copolymer was prepared by the hydrosilylation of PB
with ω-HMe 2 Si-PDMS in solution catalyzed by cis-dichloro-bis(diethylsufide)
Pt(II) salt (Ciolino et al. 2004).
By crosslinking of non-conjugated α,ω-dienes: 1,5-hexadiene, 1,7-octadiene and
1,9-decadiene (or 1,5-hexadiene/1,9-decadiene mixtures) with D
H 4 , Q 8 M
H 8 or
Si(OSiMe 2 H) 4 , in the presence of the catalyst Pt 2 [(ViSiMe 2 ) 2 O] 3 at RT, organicinorganic hybrid gels with particle sizes in the range of 0.5–5 nm were prepared,
depending on the stoichiometry of the reagents (Naga et al. 2006, 2007). Similar
hybrid gels with a homogeneous network structure (with 1.4 to 1.6 nm size of mesh)
were prepared by photohydrosilylation of D
H 4 or Q 8 M
H 8 with 1,5-hexadiene and
1,9-decadiene, catalyzed by bis(acetylacetonato)platinum (Naga et al. 2009). The
PB networks were crosslinked with p-bis(dimethylsilyl)benzene catalyzed by Pt(II)
compounds (Aranguren and Macosko 1988). The hydrosilylation of α,ω-dienes,
1,5-hexadiene or 1,7-octadiene with M
H 2 , carried out using Pt 2 [(ViSiMe 2 ) 2 O] 3 as
a catalyst, led to the formation of poly(carbosilanesiloxane)s with a limited MW,
due to an isomerization of end C-C double bonds to unreactive terminal 2-octenyl
or 2-hexenyl end groups (Sargent and Weber 1999).
14.6.6 Modification of Elastomers Properties
with Linear PMHS
PB or other poly(diene)s were crosslinked with PMHS using CPA or
Pt 2 [(ViSiMe 2 ) 2 O] 3 as catalysts (Leibfried 1995). Crosslinked St-isoprene-siloxane
copolymers were prepared by hydrosilylation of St-isoprene prepolymer with
H-siloxanes. They were useful for the preparation of membranes for pervaporative
removal of volatile organic compounds from water (Kerres and Strathmann 1993;
Kujawski et al. 2003). Their properties were much better than properties of the commercial hydrophobic membranes.
Diblock PSt-PB or triblock PSt-PB-PSt copolymers were functionalized via
hydrosilylation with methyldiundec-10-enylsilane (AB 2 monomer) (Marcos et al.
2006). Chain-end and in-chain cyano-functionalized PSts were obtained by
14 Hydrosilyl-Functional Polysiloxanes: Synthesis Reactions and Applications
Silane-modified unsaturated polymers, especially with functional groups, can
find a potential application as adhesives, drug delivery agents and rubber materials
(Marciniec et al. 1992; Marciniec 2002, 2009). The properties of PB containing
93% of pendant vinyl groups were modified with M
H 2 D n of MW = 400 g/mol, in the
presence of a catalyst RhCl(PPh 3 ) 3 . With the increase of a mole ratio [Si-H]/
[CH 2 = CH], the properties of modified polymers changed from a strong rubber to a
viscous material, but in longer reaction times gelation was observed (Baum et al.
1998). A ‘living’ linear PB was terminated in reaction with chlorodimethylsilane
(ClSiMe 2 H). Further addition reaction of the Si-H group to unsaturated PB moieties, with the use of the catalyst Pt 2 [(ViSiMe 2 ) 2 O] 3 , led to the production of
branched PB, which was then modified with monohydrosilanes (R 3 SiH) (Wurm
et al. 2008). The PE-g-PDMS copolymers were obtained by catalytic hydrogenation
of PB-g-PDMS. The latter copolymer was prepared by the hydrosilylation of PB
with ω-HMe 2 Si-PDMS in solution catalyzed by cis-dichloro-bis(diethylsufide)
Pt(II) salt (Ciolino et al. 2004).
By crosslinking of non-conjugated α,ω-dienes: 1,5-hexadiene, 1,7-octadiene and
1,9-decadiene (or 1,5-hexadiene/1,9-decadiene mixtures) with D
H 4 , Q 8 M
H 8 or
Si(OSiMe 2 H) 4 , in the presence of the catalyst Pt 2 [(ViSiMe 2 ) 2 O] 3 at RT, organicinorganic hybrid gels with particle sizes in the range of 0.5–5 nm were prepared,
depending on the stoichiometry of the reagents (Naga et al. 2006, 2007). Similar
hybrid gels with a homogeneous network structure (with 1.4 to 1.6 nm size of mesh)
were prepared by photohydrosilylation of D
H 4 or Q 8 M
H 8 with 1,5-hexadiene and
1,9-decadiene, catalyzed by bis(acetylacetonato)platinum (Naga et al. 2009). The
PB networks were crosslinked with p-bis(dimethylsilyl)benzene catalyzed by Pt(II)
compounds (Aranguren and Macosko 1988). The hydrosilylation of α,ω-dienes,
1,5-hexadiene or 1,7-octadiene with M
H 2 , carried out using Pt 2 [(ViSiMe 2 ) 2 O] 3 as
a catalyst, led to the formation of poly(carbosilanesiloxane)s with a limited MW,
due to an isomerization of end C-C double bonds to unreactive terminal 2-octenyl
or 2-hexenyl end groups (Sargent and Weber 1999).
14.6.6 Modification of Elastomers Properties
with Linear PMHS
PB or other poly(diene)s were crosslinked with PMHS using CPA or
Pt 2 [(ViSiMe 2 ) 2 O] 3 as catalysts (Leibfried 1995). Crosslinked St-isoprene-siloxane
copolymers were prepared by hydrosilylation of St-isoprene prepolymer with
H-siloxanes. They were useful for the preparation of membranes for pervaporative
removal of volatile organic compounds from water (Kerres and Strathmann 1993;
Kujawski et al. 2003). Their properties were much better than properties of the commercial hydrophobic membranes.
Diblock PSt-PB or triblock PSt-PB-PSt copolymers were functionalized via
hydrosilylation with methyldiundec-10-enylsilane (AB 2 monomer) (Marcos et al.
2006). Chain-end and in-chain cyano-functionalized PSts were obtained by
14 Hydrosilyl-Functional Polysiloxanes: Synthesis Reactions and Applications