J. Huh et al., CORRELATION HOLE EFFECT IN COMB-LIKE COPOLYMER SYSTEMS OBTAINED BY HYDROGEN-BONDING BETWEEN HOMOPOLYMERS AND END-FUNCTIONALIZED OLIGOMERS, Macromolecules, 30(6), 1997, pp. 1828-1835
This paper addresses concentration fluctuations in comblike copolymer
systems obtained by hydrogen bonding between polymers and end-function
alized oligomers. Monodisperse block copolymer systems in the homogene
ous melt exhibit small-angle X-ray scattering peaks at finite nonzero
angle due to characteristic correlation hole concentration fluctuation
s. In comblike copolymer systems obtained by hydrogen bonding, the dom
inant fluctuations have been found by us to vary experimentally betwee
n conventional long wavelength fluctuations (for weak hydrogen bonding
) and finite wavelength fluctuations (strong hydrogen bonding). Monte
Carlo computer simulations show that both regimes occur in one and the
same system depending on the temperature. The transition between both
regimes is directly related to the fraction of free oligomers, which
depends on the temperature and the interactions. The structure factors
are analyzed in terms of the random phase approximation applied to a
mixture of free oligomers and comb copolymers, using a uniform distrib
ution of teeth along the polymer chains and a binomial distribution in
the number of polymers with a given number of teeth, confirmed numeri
cally, as input. The agreement is excellent at both high and low tempe
ratures.