Beginning with a precise and well-defined monomer and polymer we can control the secondary structure, single chain organization, and the tertiary structure or multi-chain organization. These controlled tertiary structures can then assemble into unique polymer morphologies and have unique behaviors and physical properties. This concept has been applied extensively in homopolymers using acyclic diene metathesis (ADMET) polymerization.<br/>Precise block polymers remain largely unstudied due to synthetic difficulties of creating a precise block polymer with functional groups spaced further than every few backbone carbons. ADMET cannot be used since the double bonds in the polymer backbone remain reactive so can undergo insertion if a new monomer is added (<b>Figure 1</b>). Selective acyclic diene metathesis (SADMET) polymerization is the solution to this. It creates a polymer with nonreactive double bonds in the backbone, allowing for sequential addition of monomers and creating block polymers.&lt;span style="font-size:10.8333px"&gt; &lt;/span&gt;Unfortunately, this technique has been limited to only a small number of functional groups, primarily acrylates.The work described aims at addressing this oversight.<br/>We have studied electron deficient olefins such as acrylates, acrylamide, and conjugated ketones as well as sterically hindered olefins with allylic alcohols and methyl groups to find other types of monomers that will undergo SADMET polymerizations. Alternating and block polymers are then created utilizing these functional group, creating some of the first block polymer with precisely placed functional groups utilizing a nonliving, nonchain-growth polymerization mechanism.

Selective acyclic diene metathesis polymerization: New functional groups to create precise alternating and block polymers

255th National Meeting (2018)

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