Abstract
Processes based on four organometallic routes leading to phenylethenyl substituted siloxanes are reviewed. Such materials, exhibiting high refraction indices, can be made by hydrosilylation of phenylacetylenes with Si-H moieties containing siloxane oligomers and polymers. On the other hand reactions between vinyl containing siloxanes with haloaryls or styrenes lead to the same systems via Heck or metathetic and silylative coupling. The effectiveness of the catalytic processes is analyzed from the point of view of side reactions, required catalyst concentration and reaction conditions. At the current state of knowledge the Heck coupling offers synthesis of the desired phenylethenyl substituted silicone fluids using technologically most attractive pathway.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Lewis LN, Nye SA. (1996) Aryl substituted silicone fluids having high refractive indices and method for making. US Patent 5,539,137
Marciniec B. (2002) Catalysis of hydrosilylation of carbon-carbon multiple bonds. Silicon Chem. 1:155–174
Jimenez R, Lopez JM, Cervantes J. (2000) Metal supported catalysts obtained by sol-gel in the hydrosilylation of phenylacetylene with R3SiH organosilanes (R3Ph3, Ph2Me, PhMe2). Can. J.Chem. 1:1491–1495
Jimenez R, Martinez-Rosales JM, Cervantes J. (2003) The activity of Pt/SiO2 catalysts obtained by sol-gel method in the hydrosilylation of alkynes. Can. J. Chem. 1:1370–1375
Ramirez-Oliva E, Hernandes A, Martinez-Rosales JM et al. (2006) ARKIVOC (v):126–136
Lappert MF, Maskell RK. (1984) Carbene transition metal complexes as hydrosilylation catalysts. J.Organomet.Chem. 1:217–228
Bruckmann M, Dieck HT, Klaus J. (1986) Rhodium (I) mono- und diazadienkomplexe, synthese, spektroskopische charakterizirung, oxidative additionsreaktionen und einsatz in der homogenen katalyse zur hydrosililierung. J.Organomet.Chem. 1:209–226
Watanabe H, Kitahara T, Motegi T et al. (1977) The stereoselective addition of phenyldimethylsilane to phenylacetylene by rhodium triphenylphosphine complexes. J.Organomet.Chem. 1:215–222
Salmone JC, Kunzler JF, Ozark RM et al. (2006) High refractive index aromatic-based siloxane difunctional macromonomers. US Patent 7,009,024
Raleigh WJ, Campagna JA, Lucarelli MA. (1996) High refractive index phenol-modified siloxanes. US Patent 5,541,278
Ganicz T, Kowalewska A, Stańczyk WA et al. (2005) A novel organometallic route to phenylethenyl-modified polysiloxanes. J. Mater. Chem. 1:611–619
Marciniec B. (2007) Catalytic coupling of sp2- and sp-hybridized carbon-hydrogen bonds with vinylmetalloid compounds. Acc. Chem. Res. 1:527–538
Marciniec B, Pietraszuk C. (1997) Silylation of styrene with vinylsilanes catalyzed by RuCl(SiR3)(CO)(PPh3)2 and RuHCl(CO)(PPh3)3. Organometallics 1:4320–4326
Itami Y, Marciniec B, Kubicki M. (2003) Functionalization of vinyl-substituted cyclosiloxane and cyclosilazane via ruthenium-catalyzed silylative coupling reaction. Organometallics 1:3717–3722
Marciniec B, Walczuk-Gusciora E, Pietraszuk C. (2001) Activation of the vinylic =C-H bond of styrene by a rhodium siloxide complex: the key step in the silylative coupling of styrene with vinylsilanes. Organometallics 1:3423–3428
Heck RF. (1975) Vinylic substitution reactions. US Patent 3,922,299
Trzeciak AM, Ziól’kowski JJ. (2005) Structural and mechanistic studies of Pd-catalyzed C-C bond formation: the case of carbonylation and Heck reaction. Coord Chem. Rev. 1:2308–2322
DeVries RA, Schmidt GF, Frick HR et al (1993) Process for preparing vinylically unsaturated compounds. US Patent 5,264,646
Czech A, Duczmal W, Ganicz T et al. (2007) Phenylethenyl-substituted silicones via Heck coupling reaction. J. Organomet. Chem.: submitted
Maynard HD, Grubbs RH. (1999) Purification technique for the removal of ruthenium from olefin metathesis reaction products. Tetrahedron Lett. 1:4137–4140
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2008 Springer Science+Business Media B.V.
About this paper
Cite this paper
Stańzyk, W.A., Czech, A., Duczmal, W., Ganicz, T., Noskowska, M., Szeląg, A. (2008). High Refraction Index Polysiloxanes via Organometallic Routes – An Overview. In: Ganachaud, F., Boileau, S., Boury, B. (eds) Silicon Based Polymers. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-8528-4_11
Download citation
DOI: https://doi.org/10.1007/978-1-4020-8528-4_11
Publisher Name: Springer, Dordrecht
Print ISBN: 978-1-4020-8527-7
Online ISBN: 978-1-4020-8528-4
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)