Spatially Controlled Highly Branched Vinylsilicones

Branched silicones possess interesting properties as oils, including their viscoelastic behavior, or as precursors to controlled networks. However, highly branched silicone polymers are difficult to form reliably using a grafting to strategy because functional groups may be bunched together preventing complete conversion for steric reasons. We report the synthesis of vinyl-functional highly branched silicone polymers based, at their core, on the ability to spatially locate functional vinyl groups along a silicone backbone at the desired frequency. Macromonomers were created and then polymerized using the Piers-Rubinsztajn reaction with dialkoxyvinylsilanes and telechelic HSi-silicones; molecular weights of the polymerized macromonomers were controlled by the ratio of the two reagents. The vinyl groups were subjected to iterative (two steps, one pot) hydrosilylation with alkoxysilane and Piers-Rubinsztajn reactions, leading to high molecular weight, highly branched silicones after one or two iterations. The vinyl-functional products can optionally be converted to phenyl/methyl-modified branched oils or elastomers.

Automated summary

A novel method for synthesizing vinyl-functional highly branched silicone polymers has been reported, which involves spatially locating functional vinyl groups along the silicone backbone at the desired frequency. Iterative reactions lead to high molecular weight silicones, which can be further converted into different properties of branched oils or elastomers.