INFRARED STUDY ON MOLECULAR-ORIENTATION AND PHASE-TRANSITION IN LANGMUIR-BLODGETT-FILMS OF AN AMPHIPHILIC MICROGEL COPOLYMER WITH THE BRANCHING OF OCTADECYL GROUPS
B. Zhao et al., INFRARED STUDY ON MOLECULAR-ORIENTATION AND PHASE-TRANSITION IN LANGMUIR-BLODGETT-FILMS OF AN AMPHIPHILIC MICROGEL COPOLYMER WITH THE BRANCHING OF OCTADECYL GROUPS, JOURNAL OF PHYSICAL CHEMISTRY B, 102(34), 1998, pp. 6515-6520
Molecular orientation, structure, and phase transition in Langmuir-Blo
dgett (LB) films of an amphiphilic polymer consisting of a flexible hy
drophilic epichlorohydrin-ethylenediamine slightly cross-linking micro
gel and a number of hydrophobic stearic chains (ES-3) have been studie
d by infrared (IR) transmission and reflection-absorption (RA) spectro
scopy. The infrared study indicates that the LB films of ES-3 possess
crystalline, tightly packed methylene chains and extended interchain h
ydrogen bonds between the amide groups, which connect the alkyl chains
with the microgel. A comparison of the band intensities between the t
ransmission and RA spectra suggests that the hydrocarbon chains are hi
ghly oriented with a small tilt angle and that N-H and C=O bonds of th
e amide groups and the interchain hydrogen bonds between the N-H and C
=O bonds are nearly parallel to the surface. It is indicated from infr
ared spectra of LB films of ES-3 prepared under different surface pres
sures that the alkyl chains are highly ordered even in the film deposi
ted under nearly zero surface pressure, while the microgel core shows
some mobility. The phase transitions have been observed in narrow temp
erature ranges near 65, 105, and 140 degrees C for multilayer LB films
of ES-3. The three temperatures are very close to those for the phase
transitions of bulk materials of ES-3, but the transitions occur more
sharply for the LB films. Of note is that the transition temperatures
of the LB films are markedly different from those of the self-assembl
ing (SA) films previously reported. This may be due to structural diff
erences in the alkyl chains between the two kinds of films; the SA fil
ms have partial interdigitation of the alkyl tails, while the LB films
do not have it. In contrast to LB films of low molecular weight organ
ic dyes, even a one-monolayer LB film of ES-3 shows clear phase transi
tions at slightly higher temperatures. Probably, the microgels prevent
the direct interaction between the substrate and the alkyl chains in
the first layer, providing the one-monolayer LB film with clear phase
transitions.