360
siloxanes in the presence of Pt 2 [(ViSiMe 2 ) 2 O] 3 as a catalyst. By hydrosilylation
of end alkeneloxy poly(arylsilalkylene) containing CF 3 groups with linear
α,ω- dihydrooligodimethylsiloxanes (HMe 2 Si(OSiMe 2 ) n OSiHMe 2 , M
H 2 D n ) or
bis(hydrodimethylsilyl)ethylene (HMe 2 SiCH 2 CH 2 SiMe 2 H) or 1,4-bis-(hydrodimethylsilyl)benzene have also been prepared fluorine containing copolymers.
However, higher MWs have been obtained in shorter reaction times under supercritical carbon dioxide (scCO 2 ) conditions compared to toluene medium (Zhou
et al. 2003).
Poly(imidesiloxane)s have been synthesized by reaction of appropriate N,N′diallylyldiimide with M
H
D n M
H
in the presence of Cp 2 PtCl 2 (Wenski et al. 1991).
Exactly alternating poly(imide-co-siloxane) thermoplastic elastomers have
been obtained from allyl-end oligoimides and α,ω-dihydropolysiloxanes (Andre
et al. 2001). In line with this, poly(silarylene-siloxane)polyimide copolymers have
also been prepared from α,ω-allyl- oligoimides and Si-H functional silarylene siloxanes (Homrighausen et al. 2005).
Poly(ethoxy)-substituted terpolymers were synthesized by Zhou et al. (2008) via
hydrosilylation of HMe 2 SiC 6 CH 4 SiMe 2 H and its homologs with 1,3- divinyltetraphe
nyldisiloxane and 1,3-divinyl(tetraethoxy)disiloxane in toluene or scCO 2 . The novel
oligomeric divinyl-telechelic aromatic ether-containing resin was polymerized
using silane coupling agents, resulting in transparent and clear polymers exhibiting
high thermooxidative stability (Laskoski and Keller 2009).
A commercially available hybrid liquid silicone fluoroelastomer was prepared
via hydrosilylation of the vinyl terminated silicone perfluoroether with a perfluoroalkylene or perfluoroether crosslinkers containing 2, 4 or 6 Si-H end groups (Uritani
and Kishita 2002). Due to its excellent properties, it can be used in O-rings, diaphragms and in aerospace industry.
New fullerene (C 60 )-modified polysiloxane materials were prepared by grafting
C 60 molecules onto PMHS and further crosslinking (West et al. 1994, 2009) or by
the addition of allyl bromide into PDMS-co-PMHS, followed by reactions with
sodium azide (NaN 3 ) and C 60 . The latter poly(siloxane) was used as a stationary
phase for a capillary gas chromatography which showed high termostability and
excellent selectivity for various compounds (Fang et al. 2000).
Isocyanate-functionalized siloxanes have also been prepared via reaction of different functional Si-H substrates with m-isopropenyl-α,α-dimethylbenzylisocyanate
(m- TMI), and using Pt 2 [(ViSiMe 2 ) 2 O] 3 as a catalyst (Zhou and Smid 1991).
Multifunctional isocyanate derivatives made from silsesquioxanes have also been
prepared by the hydrosilylation of m-TMI with Q 8 M
H 8 in THF medium and using
Pt 2 [(ViSiMe 2 ) 2 O] 3 as a catalyst. This new type of octaisocyanate-POSS macromer
was used as a crosslinking agent and nanofiller for the fabrication of the hybrid
crosslinked poly(urethane) (PU) nanomaterial with POSS molecules dispersed into
the polymer matrix. The isocyanate-POSS nanofiller was also suitable for the synthesis of other hybrid dendritic or star copolymers (Neumann et al. 2002).
An optically active isotactic poly(silethylenesiloxane) was obtained via selfhydrosilylation of a chiral 1-hydro-3-vinyl-disiloxane (Li and Kawakami 1998;
Tang et al. 1998).
J. J. Chruściel
siloxanes in the presence of Pt 2 [(ViSiMe 2 ) 2 O] 3 as a catalyst. By hydrosilylation
of end alkeneloxy poly(arylsilalkylene) containing CF 3 groups with linear
α,ω- dihydrooligodimethylsiloxanes (HMe 2 Si(OSiMe 2 ) n OSiHMe 2 , M
H 2 D n ) or
bis(hydrodimethylsilyl)ethylene (HMe 2 SiCH 2 CH 2 SiMe 2 H) or 1,4-bis-(hydrodimethylsilyl)benzene have also been prepared fluorine containing copolymers.
However, higher MWs have been obtained in shorter reaction times under supercritical carbon dioxide (scCO 2 ) conditions compared to toluene medium (Zhou
et al. 2003).
Poly(imidesiloxane)s have been synthesized by reaction of appropriate N,N′diallylyldiimide with M
H
D n M
H
in the presence of Cp 2 PtCl 2 (Wenski et al. 1991).
Exactly alternating poly(imide-co-siloxane) thermoplastic elastomers have
been obtained from allyl-end oligoimides and α,ω-dihydropolysiloxanes (Andre
et al. 2001). In line with this, poly(silarylene-siloxane)polyimide copolymers have
also been prepared from α,ω-allyl- oligoimides and Si-H functional silarylene siloxanes (Homrighausen et al. 2005).
Poly(ethoxy)-substituted terpolymers were synthesized by Zhou et al. (2008) via
hydrosilylation of HMe 2 SiC 6 CH 4 SiMe 2 H and its homologs with 1,3- divinyltetraphe
nyldisiloxane and 1,3-divinyl(tetraethoxy)disiloxane in toluene or scCO 2 . The novel
oligomeric divinyl-telechelic aromatic ether-containing resin was polymerized
using silane coupling agents, resulting in transparent and clear polymers exhibiting
high thermooxidative stability (Laskoski and Keller 2009).
A commercially available hybrid liquid silicone fluoroelastomer was prepared
via hydrosilylation of the vinyl terminated silicone perfluoroether with a perfluoroalkylene or perfluoroether crosslinkers containing 2, 4 or 6 Si-H end groups (Uritani
and Kishita 2002). Due to its excellent properties, it can be used in O-rings, diaphragms and in aerospace industry.
New fullerene (C 60 )-modified polysiloxane materials were prepared by grafting
C 60 molecules onto PMHS and further crosslinking (West et al. 1994, 2009) or by
the addition of allyl bromide into PDMS-co-PMHS, followed by reactions with
sodium azide (NaN 3 ) and C 60 . The latter poly(siloxane) was used as a stationary
phase for a capillary gas chromatography which showed high termostability and
excellent selectivity for various compounds (Fang et al. 2000).
Isocyanate-functionalized siloxanes have also been prepared via reaction of different functional Si-H substrates with m-isopropenyl-α,α-dimethylbenzylisocyanate
(m- TMI), and using Pt 2 [(ViSiMe 2 ) 2 O] 3 as a catalyst (Zhou and Smid 1991).
Multifunctional isocyanate derivatives made from silsesquioxanes have also been
prepared by the hydrosilylation of m-TMI with Q 8 M
H 8 in THF medium and using
Pt 2 [(ViSiMe 2 ) 2 O] 3 as a catalyst. This new type of octaisocyanate-POSS macromer
was used as a crosslinking agent and nanofiller for the fabrication of the hybrid
crosslinked poly(urethane) (PU) nanomaterial with POSS molecules dispersed into
the polymer matrix. The isocyanate-POSS nanofiller was also suitable for the synthesis of other hybrid dendritic or star copolymers (Neumann et al. 2002).
An optically active isotactic poly(silethylenesiloxane) was obtained via selfhydrosilylation of a chiral 1-hydro-3-vinyl-disiloxane (Li and Kawakami 1998;
Tang et al. 1998).
J. J. Chruściel