Silicon hydride polysiloxanes

Figure 2.6 Reagents used for the deactivation of silanol groups on glass surfaces. A - disilazanes, B > cyclic siloxanes, and C -silicon hydride polysiloxanes in which R is usually methyl, phenyl, 3,3,3-trifluoropropyl, 3-cyanopropyl, or some combination of these groups. The lover portion of the figure provides a view of the surface of fused silica with adsorbed water (D), fused silica surface after deactivation with a trimethylsilylating reagent (E), and fused silica surface after treatment with a silicon hydride polysiloxane (F).

A variety of agents and procedures have been explored for deactivation purposes (60-74). For subsequent coating with nonpolar and moderately polar stationary phases such as polysiloxanes, fused silica has been deactivated by silylation at elevated temperatures, thermal degradation of polysiloxanes and polyethylene glycols, and the dehydrocondensation of silicon hydride polysiloxanes (71,75-79). 

FIGURE 3.23 Selected reagents used for deactivation of silanol groups (a) disUazanes, (b) cyclic siloxanes, (c) silicon hydride polysiloxanes. Lower portion is a view of fused-silica surface with (d) adsorbed water (e) after deactivation with a trimethylsilylating reagent and (f) after treatment with a silicon hydride polysiloxane. (Reproduced from Reference 83 and reprinted with permission from Elsevier Science Publishers.)... 

Hydrosilylation is by far the most important route for obtaining monomers and other precursors to fluorinated polysiloxanes. Hydrosylilation80 is the addition of silicon hydride moiety across an unsaturated linkage using transition metal complexes of platinum or rhodium such as Speier s catalyst, hexachloroplatinic acid in isopro-... 

Even though the addition of silicon hydrides to vinyl compounds often takes the form of /3-addition, exceptions do exist. For example, the reaction of methyldichlorosilane and styrene catalyzed by chloroplatinic acid or Pt/C yielded 53% /3-addition and 33% a-addition product (Ryan and Speier, 1959). For polysiloxanes, Huang and Wu (1992) studied the synthesis of polymer (3.40) using NMR analysis. The result showed that at 50 °C using chloroplatinic acid as catalyst, the product was actually a copolymer with isomeric structures, 58% of which were from //-addition ((3.40)), the other 42% were from the a-addition (3.41). 

Just as the hydrosilylation reaction is important in the synthesis of silanes, so it also serves as a useful route to functional polysiloxanes. The same variety of chemistry as previously described for silanes is available and two further examples are given in equations 82 and 83. One of the main advantages of this route is that the silicon hydride prepolymers are well characterized and readily available materials, which in turn leads to well-defined organofunctional products. A disadvantage is the low efficiency in the use of the precious metal catalyst and the difficulty of its recovery. This is particularly true for systems containing a low level of functionality but this can be partially overcome by using recyclable platinum catalysts on solid supports216,217. 

Hexachloroplatinic acid and other platinum complexes are mainly used as soluble catalysts for the additive cure. The most active catalyst used recently for vulcanization of silicon rubber is the platinum-alkenylsiloxanes complex, mainly the platinum-vinylsiloxane complex (Karstedt s catalyst) (4). One important approach to the activated cure of silicone rubber makes use of various inhibitors or moderators added to the platinum catalyst to reduce, or temporarily inhibit, its catalytic activity in the presence of the alkenyl- and hydropolysiloxanes (see catalysis by Pt complexes). The catalyst is usually added to the reaction mixture in quantities related to the number of unsaturated (e.g., vinyl) substituents in the polysiloxane. Vinyl-terminated polydimethylsiloxane polymers (viscosity > 200 cSt) are typically cross-linked by methylhydrosiloxane-dimethylsiloxane copolymer with 15-50 mol% of polymethylhydrosiloxane. A typical catalyst is a platinum complex in alcohol, xylene, divinylsiloxanes, or cyclic vinylsiloxanes. The system is usually prepared in two parts (part A, vinylsiloxane -I- Pt (5-10 ppm) part B, hydrosiloxane -I- vinylsiloxane). Inhibitors stop the platinum catalyst they are volatile or react with silicone hydride cross-linker to become a part of the polymer network. Some of them are decomposed by heat or light (UV). A single-component system contains fugitive inhibitors of Pt. 

Hybrid versions of silicone-thermoplastic semi-IPNs have been developed (19). A hybrid interpenetrating network is one in which the cross-linked network is formed by the reaction of two polymers with structurally distinct backbones. Hydride-functionalized siloxanes can be reacted with organic polymers with pendant unsaturated groups such as polybutadienes (5) in the presence of platinum catalysts. Compared with the polysiloxane semi-IPNs discussed earlier, the hydride IPNs tend to maintain mechanical and morphologically derived properties, whereas properties associated with siloxanes are diminished. The probable importance of this technology is in cost-effective ways to induce thermoset characteristics in thermoplastic elastomers. 

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