Platinum-catalyzed polymerization poly

Polyaddition of organosilicon dihydrides, mainly dihydro(poly)siloxanes to dialkenyl-substituted organic compounds also known as hydrosilylation copolymerization, leads to polycarbosiloxanes with functionalized organic segments (359). Platinum-catalyzed polymerization hydrosilylation of a,allyl-substituted bisphenols, imides, or amides leads to the synthesis of block copolymers that are useful thermoplastic elastomers (Scheme 40). 

Uenishi K, Imae I, Shirakawa E, Kawakami Y (2002) Synthesis of steieoregular and optically active poly[ methyl(l-naphthyl)silylene (o-phenylene)methylene] by platinum-catalyzed ring-opening polymerization. Macromolecules 35 2455-2460... 

Pyridine was found to polymerize on a Pt electrode from a solution of 1 M pyridine in 1 M LiC104/CH3CN at potentials above 0.8 V vs Ag/AgCl. A colorless film was formed, but it could be oxidized and reduced when placed in plain electrolyte solution. The infrared spectrum of the electrochemically formed poly(pyridine) film is shown in Figure 5. It displays a very intense, narrow band at 1500 cm indicative of C=C stretches that are perpendicular to the surface. 3,5 Lutidine also was polymerized on a platinum electrode under the same conditions, and its infrared spectrum is similar to that for the surface catalyzed poly(lutidine). The C=C stretching band for the poly(lutidine)... 

Another polymerization that proceeds under the influence of a photogenerated catalyst is the hydrosilylation reaction. In a patent, Drahnak described the photoinduced addition of Si-H functional silanes to poly(dimethylsiloxane)s containing pendant and terminal vinyl double bonds. This reaction is catalyzed by the in situ generation of a colloidal platinum hydrosilylation catalyst, [Pt(0)] c/ by the photolysis of T -cyclopentadienyl(trimethyl)platinum complex, 7. The proposed mechanism is shown in eqns [11] and [12] of Scheme 4. Reportedly, this chemistry has been used to generate crosslinked silicone elastomers. ... 

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