Abstract

The influence of chain microstructure on thermorheological behaviour of two series of comb

poly n-butyl acrylates (PBA) is investigated. The combs were synthesized by three step atom
transfer radical polymerization using the grafting from approach. For different model PBA a
broad range of time scales has been investigated regarding the thermorheological behaviour by
using an overlay of creep recovery and dynamic data. The WLF shift factors were determined
for different stages of the frequency/time spectrum and evaluated regarding their differences
for linear and branched model PBA. It was found that for linear PBA, the same shift factor is
used to superpose the rheological data overall the viscoelastic spectrum. For branched PBA
combs with side branches of one or more entanglement, different shift factors are required to
bring the viscoelastic data into superposition, and hence thermorheological complexity is
observed. To quantify the temperature dependence, activation energy is determined from the
WLF shift factors. For linear PBA combs constant value of activation energy value was obtained
which is in quite good agreement with values obtained from literature. A comparison of the so-
called activation energy spectrum versus frequency for two combs with the same backbone
length and number of branching shows that activation energy increases with decrease in
frequency with samples having the highest arm length exhibiting steeper transition in the
activation energy values from high to low frequencies. Comparison of the molecular weight
dependence of zero shear viscosity for the branched PBA shows deviation from 3.4 power law
exponent established for linear PBA. The height above the linear base increases with an increase
length of side branches.