Silanol siloxane polymers

The properties of these siloxane-based silanol polymers depended largely on the silanol composition. Polymer materials obtained by the condensation of the silanols led... 

Various studies indicate that certain alkoxysilanes react with surface silanol groups (2, 8), but nothing appears to have been reported for ETES and VTES specifically. The second type reaction is between two adsorbate molecules to form a siloxane polymer linkage. 

The poly(siloxane) polymers are usually prepared by the acid or base hydrolysis of appropriately substituted dichlorosilanes or dialkoxysilanes, or by the catalytic polymerization of small ring cyclic siloxanes [71-75]. The silanol-terminated polymers are suitable for use after fractionation or are thermally treated to increase molecular weight and in some cases endcapped by trimethylsilyl, alkoxy or acetyl groups [76,77]. Poly(siloxanes) synthesized in this way are limited to polymers that contain substituent groups that are able to survive the relatively harsh hydrolysis conditions, such as alkyl, phenyl, 3,3,3-trifluoropropyl groups. Hydrosilylation provides an alternative route to the synthesis of poly(siloxanes) with labile or complicated substituents (e.g. cyclodextrin, oligoethylene oxide, liquid crystal, amino acid ester, and alcohol) [78-81]. In this case... 

A new convenient polymer modification has been developed to synthesize a series of novel silanol-containing polymers by a selective oxidation of Si—containing precursor polymers with a dimethyldioxirane solution in acetone. The silanol hydrogen bonding interactions in polymer blends as well as the silanol self-condensation to form siloxane semi-interpenetrating polymer networks in miscible polymer blends and organic-inorganic polymeric hybrids are discussed. 

Anionic Polymerization of Cyclic Siloxanes. The anionic polymerization of cyclosiloxanes can be performed in the presence of a wide variety of strong bases such as hydroxides, alcoholates, or silanolates of alkaH metals (59,68). Commercially, the most important catalyst is potassium silanolate. The activity of the alkaH metal hydroxides increases in the foUowing sequence LiOH < NaOH < KOH < CsOH, which is also the order in which the degree of ionization of thein hydroxides increases (90). Another important class of catalysts is tetraalkyl ammonium, phosphonium hydroxides, and silanolates (91—93). These catalysts undergo thermal degradation when the polymer is heated above the temperature requited (typically >150°C) to decompose the catalyst, giving volatile products and the neutral, thermally stable polymer. 

The resulting silanol group of a polymer chain condenses with acetoxy siloxy group of another polymer chain to form a siloxane (Si-O-Si) linkage (Scheme 8). Further similar reactions finally result in a crosslinked elastomer. Acetic acid is... 

During the aqueous hydrolysis of dichlorosilanes there is always a very important side reaction. It is the self-condensation of silanols which are formed initially during the hydrolysis. These reactions also give rise to the formation of cyclic siloxanes together with the linear oligomers or polymers (Reaction Scheme III). The amount of cyclic products usually depends on the hydrolysis conditions and the degree of the self-condensation attained as well as concentration considerations. 

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