As
a kind of well-defined monomer sequence distribution, an alternating
sequence endows polymers with specific properties owing to the precisely
repeating structure. In this study, we report a novel alternating
copolymerization of 1,1-diphenylethylene (DPE) derivatives with 1-cyclopropylvinylbenzene
(CPVB) by means of alternating transformation of anion-migrated ring-opening
polymerization (AMROP for CPVB) and general anionic polymerization
(AP for DPE derivatives) mechanisms. In particular, the kinetics of
the elementary reaction in this copolymerization system were first
investigated, and it was confirmed that alternating copolymerization
with the ideal alternating copolymerization kinetics (k
CD, k
DC > 0; k
DD, k
CC = 0; thus, r
C = r
D = 0 at 20
°C) was achieved. Additionally, neither the lower reactivity
of the DPE derivative nor the excess feeding of CPVB in the reaction
substantially influenced the formation of alternating sequences. Furthermore,
because the DPE derivatives (DPE, 1-[4-[N,N-bis(trimethylsilyl)
amino]phenyl]-1-phenylethylene (DPE-NSi2) and 1-(4-dimethylaminophenyl)-1-phenylethylene
(DPE-NMe2)) exhibited different reactivities, the sequence
distributions of DPE and DPE derivative units in the chain can be
regulated through terpolymerization with CPVB. Therefore, DPE units
with random, gradient, and block distributions in alternating terpolymers, which cannot be achieved
in general polymerization reactions because of kinetic limitations,
can be well regulated based on the abovementioned alternating copolymerization
system. Overall, this study inspires and promotes alternating copolymerization
in the field of polymer chemistry.