Ruthenium catalyzed synthesis of alternating copolymers and their characterization

Dihydridocarbonyltris(triphenylphosphine)ruthenium catalyzes the addition of aryl carbon-hydrogen bonds which are ortho to a carbonyl group across the carbon-carbon double bond of alkenes. Chapter 1 describes the preparation of mono and disubstituted ortho alkyl aceto-phenones. In a similar reaction, benzophenone is tetrafunctional with respect to carbon-hydrogen bonds ortho to the carbonyl group. Nevertheless, the ruthenium-catalyzed reaction with styrene and benzophenone exclusively yields 2, 8-bis(2{dollar}spprime{dollar}-phenylethyl)benzophenone. Regarding aromatic electrophilic substitution, xanthone is deactivated at the 2 and 9 positions. However, in an analogous ruthenium-catalyzed reaction between xanthone and styrene, 2,9-bis(2{dollar}spprime{dollar}-phenylethyl)xanthone is formed. In the reaction between acetophenone and norbornene, an ortho carbon and hydrogen of acetophenone becomes attached with a stereochemical orientation endo to the 2 position of the norbornyl group while the hydrogen is attached to the 3 position.; Chapter 2 describes the modification of unsaturated polysiloxanes with pendant or terminal vinyl groups. Dihydridocarbonyltris(triphenylphosphine)ruthenium catalyzes the addition of the ortho carbon-hydrogen bond of 2{dollar}spprime{dollar}-methylacetophenone across the carbon-carbon double bond of pendant and terminal vinyl groups of copoly(dimethylsiloxane/vinylmethylsiloxane) and polydimethylsiloxane terminated with vinyldimethylsiloxy groups. Both polydimethylsiloxane terminated with 2-(2{dollar}spprime{dollar}acetyl-3{dollar}spprime{dollar}-methyl phenyl)ethyldimethylsiloxy groups and copoly (dimethylsiloxane/2-(2{dollar}spprime{dollar}- acetyl-3{dollar}spprime{dollar}-methylphenyl)ethylmethylsiloxane) were synthesized.; Neither fluorenone nor xanthone have been previously used as difunctional monomers in polymer synthesis. Chapter 3 reports the reaction of xanthone and fluorenone with 3,3,6,6-tetramethyl-3,6-disila-1,7-octadiene to yield copoly (1,8-xanthonylene/3,3,6,6-tetramethyl-3,6-disila-1,8-octanylene) and copoly (1,8-fluorenonylene/3,3,6,6-tetramethyl-3,6-disila-1,8-octanylene) respectively.; The ruthenium catalyzed copolymerization of acetophenone with {dollar}alpha,omega{dollar}-dienes is sensitive to electronic effects in the acetophenone. Specifically, electron donating para-dialkylamino groups facilitate copolymerization and result in a higher degree of polymerization than copolymers synthesized from acetophenone. Chapter 4 describes the reaction between 4{dollar}spprime{dollar}-piperidinoacetophenone and 4{dollar}spprime{dollar}-morpholinoacetophenone with 3,3,6,6-tetramethyl-3,6-disila-1,7-octadiene to yield copoly(3,3,6,6-tetra-methyl-{dollar}3, 6{dollar}-disila-1,8-octanylene/2-aceto-5-piperidino-1,3-phenylene) and copoly(3,3,6,6-tetramethyl-{dollar}3, 6{dollar}-disila-1,8-octanylene/2-aceto-5-morpholino-1,3-phenylene) respectively.; Chapter 5 describes the synthesis of polysiloxane copolymers containing 4-(dialkylamino)pyridine and their ability to hydrolyze p-nitro-phenyl alkanoates. Poly (1,1,3,3-tetramethyl-{dollar}1, 3{dollar}-disila-2-oxa-7-(4{dollar}spprime{dollar}-pyridinyl)-aza-1,10-decanylene) has been synthesized from 4-(diallyl-amino)pyridine and 1,1,3,3-tetramethyldisiloxane using Pt and {dollar}rm BFsb3OEtsb2.{dollar} Overall yields are improved compared to those polymerizations which do not utilize {dollar}rm BFsb3OEtsb2.{dollar} The polysiloxane catalyst's ability to hydrolyze p-nitrophenyl alkanoates was followed by absorption spectroscopy.