380
observed, especially for sulfur vulcanizates. PDMS and PMHS also showed tendency to migrate to the surface of the elastomer (which was growing with the
decrease in PMHS reactivity) and formed a protective layer on the surface, which
caused an increase in aging resistance of the vulcanized SBR. The improvement of
the dispersibility of silica (and DCP) into the SBR with the increase in the PMHS
reactivity (the content of Si-H groups) took place (Bieliński et al. 2007a, b).
14.6.7 Modification of Properties of Other Polymers
with PMHS
Transparent polysiloxane-polycarbonate copolymers (PMHS-PC) were prepared by
cohydrosilylation of butenylphenylcarbonate with Me 3 SiO(MeHSiO) 35 SiMe 3 and
ViSi(OEt) 3 , followed by hydrolysis catalyzed by DBTDL at RT, and by a radical
polymerization of poly(diethyleneglycol biscarbonate) with benzoil peroxide.
These IPNs and analogous PMHS-PC semi-IPNs were useful as drug delivery systems (Boileau et al. 1998). Poly((4-vinylphenyl)dimethylsilane) of narrow MWDs
(PDI = 1.08–1.19) was prepared in quantitative yields by means of the anionic living polymerization solution from (4-vinylphenyl)dimethylsilane 4-(CH 2 =CH)
C 6 H 4 SiMe 2 H with oligo-(α-methylstyryl)Mt 2 (Mt = Li, Na, K) at −78 °C. By the
living polymerization with St a new block copolymer (poly(St-b-(4-vinylphenyl)
dimethylsilane-b-St)) was obtained (Hirao et al. 1987).
Biodegradable multiblock copolymers were prepared by the hydrosilylation of
poly(α-hydroxy acid)s or PLA terminated with alkyl groups, with (α,ω-dihydro)PDMS (M
H 2 D n ) of Mws M n = 1700–9000 g/mol (Bachari et al. 1995). PMHS having perfluoroalkyl side chains and alkyl disulfide anchoring chains formed
self-organized ultrathin layers on a surface (Sun et al. 1996).
A ‘living’ PSt was functionalized with Si-H groups at end chains (by reaction
with ClSiMe 2 H) or in-chain (by reaction with Cl 2 SiMeH). The Si-H end-capped PSt
was reacted with allyl(N,N-bistrimethylsilyl)amine, allylamine or allyl alcohol, and
using Pt 2 [(ViSiMe 2 ) 2 O] 3 or Bu 4 NPtCl 6 as catalysts (Quirk et al. 2005, 2009; BergerNicoletti et al. 2007). The PSt functionalized with end or pendant Si-H groups, and
PSt-b-PDMS were used for modification by the hydrosilylation with hexadiene or
allyl- and vinyl-POSS derivatives (Chakraborty et al. 2008; Quirk et al. 2008; Zhang
et al. 2009).
Alkyd resins containing pendant unsaturated chains derived from a linseed oil
were modified with α,ω-dihydro-PDMS in the presence of a catalyst RhCl(PPh 3 ) 3 ,
which caused a decrease in T g of modified resins by tens °C (Hou et al. 2000). A
siloxane-modified epoxy resin (SG copolymer), with pendant epoxide rings, was
prepared by the hydrosilylation reaction of PMHS with allyl glycidyl ether. The SG
resin mixed with a commercial epoxy resin (DGEBA) was cured with dicyandiamide. The mobility and the thermostability of the cured resins were thus increased
(Zhang et al. 2012b).
Silicone resins having Si-H, Si-CH=CH 2 and Si-OH groups were cured by the
Pt-catalyzed hydrosilylation and the Al(acac) 3 -catalyzed polymerization.
J. J. Chruściel
observed, especially for sulfur vulcanizates. PDMS and PMHS also showed tendency to migrate to the surface of the elastomer (which was growing with the
decrease in PMHS reactivity) and formed a protective layer on the surface, which
caused an increase in aging resistance of the vulcanized SBR. The improvement of
the dispersibility of silica (and DCP) into the SBR with the increase in the PMHS
reactivity (the content of Si-H groups) took place (Bieliński et al. 2007a, b).
14.6.7 Modification of Properties of Other Polymers
with PMHS
Transparent polysiloxane-polycarbonate copolymers (PMHS-PC) were prepared by
cohydrosilylation of butenylphenylcarbonate with Me 3 SiO(MeHSiO) 35 SiMe 3 and
ViSi(OEt) 3 , followed by hydrolysis catalyzed by DBTDL at RT, and by a radical
polymerization of poly(diethyleneglycol biscarbonate) with benzoil peroxide.
These IPNs and analogous PMHS-PC semi-IPNs were useful as drug delivery systems (Boileau et al. 1998). Poly((4-vinylphenyl)dimethylsilane) of narrow MWDs
(PDI = 1.08–1.19) was prepared in quantitative yields by means of the anionic living polymerization solution from (4-vinylphenyl)dimethylsilane 4-(CH 2 =CH)
C 6 H 4 SiMe 2 H with oligo-(α-methylstyryl)Mt 2 (Mt = Li, Na, K) at −78 °C. By the
living polymerization with St a new block copolymer (poly(St-b-(4-vinylphenyl)
dimethylsilane-b-St)) was obtained (Hirao et al. 1987).
Biodegradable multiblock copolymers were prepared by the hydrosilylation of
poly(α-hydroxy acid)s or PLA terminated with alkyl groups, with (α,ω-dihydro)PDMS (M
H 2 D n ) of Mws M n = 1700–9000 g/mol (Bachari et al. 1995). PMHS having perfluoroalkyl side chains and alkyl disulfide anchoring chains formed
self-organized ultrathin layers on a surface (Sun et al. 1996).
A ‘living’ PSt was functionalized with Si-H groups at end chains (by reaction
with ClSiMe 2 H) or in-chain (by reaction with Cl 2 SiMeH). The Si-H end-capped PSt
was reacted with allyl(N,N-bistrimethylsilyl)amine, allylamine or allyl alcohol, and
using Pt 2 [(ViSiMe 2 ) 2 O] 3 or Bu 4 NPtCl 6 as catalysts (Quirk et al. 2005, 2009; BergerNicoletti et al. 2007). The PSt functionalized with end or pendant Si-H groups, and
PSt-b-PDMS were used for modification by the hydrosilylation with hexadiene or
allyl- and vinyl-POSS derivatives (Chakraborty et al. 2008; Quirk et al. 2008; Zhang
et al. 2009).
Alkyd resins containing pendant unsaturated chains derived from a linseed oil
were modified with α,ω-dihydro-PDMS in the presence of a catalyst RhCl(PPh 3 ) 3 ,
which caused a decrease in T g of modified resins by tens °C (Hou et al. 2000). A
siloxane-modified epoxy resin (SG copolymer), with pendant epoxide rings, was
prepared by the hydrosilylation reaction of PMHS with allyl glycidyl ether. The SG
resin mixed with a commercial epoxy resin (DGEBA) was cured with dicyandiamide. The mobility and the thermostability of the cured resins were thus increased
(Zhang et al. 2012b).
Silicone resins having Si-H, Si-CH=CH 2 and Si-OH groups were cured by the
Pt-catalyzed hydrosilylation and the Al(acac) 3 -catalyzed polymerization.
J. J. Chruściel