Silicon 1,2-migration

Figure 7. Silver Migration, Silicon Rubber Backseai. Reiative Humidity as...

Weak boundary layer. WBL theory proposes that a cohesively weak region is present at the adhesive-substrate interface, which leads to poor adhesion. This layer can prevent the formation of adhesive bonds, or the adhesive can preferentially form bonds with the boundary layer rather that the surface it was intended for. Typically, the locus of failure is interfacial or in close proximity to the silicone-substrate interface. One of the most common causes of a WBL being formed is the presence of contaminants on the surface of the substrate. The formation of a WBL can also result from migration of additives from the bulk of the substrate, to the silicone-substrate interface. Alternatively, molecular... 

Silyl groups have found broad appeal as protective groups because their reactivity and stability can be tailored by varying the nature of the substituents on the silicon. Their ability to migrate from one hydroxyl to another is a property that can be used to advantage, but more often, it is a nuisance. The migratory apti-... 

Semiconducting devices, switches and miniaturised v.h.f. circuits are all particularly sensitive to the slightest reaction on critical surfaces, and in devices calling for the highest levels of reliability even the most inert of the phenolic, epoxide and silicone resins are not considered to be fully acceptablecorrosion of electronic assemblies may often be enhanced by migration of ions to sensitive areas under applied potentials, and by local heating effects associated with current flows. 

In the presence of catalytic amounts of Pd(0), silicon-substituted vinyloxiranes can rearrange into the corresponding ot-silyl- 3,y-unsaturated aldehydes (Scheme 9.34) [151]. Treatment of 80 with Pd(OAc)2 and P(OPh)3 results in the formation of 7t-allylpalladium complex 81. Bond rotation to give 82, followed by migration of the silyl moiety, affords aldehyde 83, which is trapped in situ to provide the Felkin-Anh product 84. The reaction proceeds with retention of configuration and the ee of the starting material is retained in the product. The size of the silicon substituents is critical for the outcome of the reaction, as is the choice of ligands on palladium. 

Other peculiarities have occurred. As an example of a potential problem that can occur is when a silicone release agent is used when injection molding electrical connectors, etc. It can behave like the metal migration just reviewed. 

We suggest that the ejected thiyl radical undergoes a fast 1,2-migration of silyl group from silicon to sulfur (Reaction 85), affording a new silyl radical that either reacts with (TMSlsSiH (Reaction 86) which completes the reaction cycle, or replaces the (TMSlsSi radical in the above described reaction sequence. 

In addition, silicone polymers in both gel and elastomer forms have been shown to induce a typical subcutaneous foreign body reaction and fibro sarcoma development in rats. The lower-molecular weight silicone polymers may migrate into the adjacent tissues or stimulate other cellular and immunological response. 

The blends, irrespective of the concentration of fluororubber, show surface energy lower than neat rubbers. This is attributed to the migration of silicone mbber to the surface. The presence of silicone rubber on the surface of the blends also contributes to their lower limited oxygen index compared to that of fluoroelastomers. 

The B - C migration can also be induced by other types of electrophiles. Trimethylsilyl chloride or trimethylsilyl triflate induces a stereospecific migration to form (3-trimethylsilyl alkenylboranes having cis silicon and boron substituents.34 It has been suggested that this stereospecificity arises from a silicon-bridged intermediate. 

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