Confined relaxation dynamics in long range ordered polyesters with comb-like architecture

The cooperative relaxation dynamics of methylene units in self-assembled amorphous alkyl nanodomains with typical dimensions in the range 5–20 Å is studied in a series of poly(1,4-phenylene-2,5-n-dialkyloxy terephthalate)s (PPAOTs) with C = 6–12 alkyl carbons per side chain. These comb-like polymers are long range ordered on the nanoscale since domains where main chains are stacked in a crystal-like manner alternate with alkyl nanodomains formed by aggregated side chains. Dynamic mechanical data for the investigated PPAOTs show polyethylene-like glass transitions α_PE which are similar to those for many other polymer series with comb-like architecture containing long alkyl side groups. Hence, self-assembled PPAOTs are excellent model systems for studies focusing on a detailed understanding of the influence of (i) alkyl nanodomain size, (ii) average volume per CH₂ unit and (iii) number of alkyl groups per interfacial area on the cooperative dynamics of methylene units seen as α_PE process. Structural parameters as obtained from X-ray diffraction experiments allow to deduce quantitative information about these influencing factors. The results are compared with those for regio-regular poly(3-alkyl thiophenes) with similar molecular architecture. The comparison shows that important features of the α_PE process within amorphous alkyl nanodomains are main chain independent even in case of long-range ordered polymers with quite different main chain packing. It is concluded that the alkyl nanodomain size is the most important factor determining the α_PE dynamics of the methylene units. Main chain dependent aspects like average volume per CH₂ unit and interfacial constraints do only weakly influence the relaxation behavior within the alkyl nanodomains.