In this work, branching studies were carried out regarding
reversible
addition–fragmentation chain transfer (RAFT) copolymerization
and its kinetic simulations for preparing branched (typically, hyperbranched
and star) polymers using various feeding strategies in the batch,
semibatch, and continuous reactor operation. Critical properties like
branching/cyclization density, which are difficult to detect, can
be tracked in real time through the kinetic modeling study. The simulation
results for continuous preparation of star polymers by the arm-first
method match the experimental results, demonstrating the validity
of the model. Various feeding strategies were evaluated, turning out
that the arm-first system could achieve better control over chain
length and molecular weight. The semibatch operation with multistep
feeding can achieve the optimum branch density by adjusting the amount
of cross-linkers in each step. Moreover, branched polymers with optimized
properties are excepted to be continuously prepared by tubular rectors
with distributed side injections.
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