A novel, ester-free initiator for surface-initiated free
radical
polymerization has been synthesized and tested. The structurally non-symmetrical
azo-based initiator features a chemically stable alkane linker between
the initiating group and the silane anchoring group, setting it apart
from the majority of surface initiators that are linked by hydrolyzable
moieties, such as esters. The novel design of the initiator is bolstered
by an original synthetic approach, leading to a greater yield and
a dramatic reduction in cyanide usage relative to previous methods.
Here we demonstrate the capability of this novel initiator for surface-initiated
free radical polymerization (SI-FRP), reverse ATRP, and RAFT, noting
that Arrhenius behavior of SI-FRP differs significantly from that
of FRP in the bulk. Furthermore, we show that polymer brushes formed
from the novel initiator are more stable than those formed from ester-based
initiators.
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