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

- Structure-dynamics relations are studied in long-range ordered alkoxylated polyesters.
- A cooperative dynamics of CH2 units within alkyl nanodomains is commonly observed.
- The influence of domain size, density and interfacial constraints is investigated.
- Geometrical confinement resulting in a hindered glass transition is most important.
- Long-range ordered regio-regular poly(3-alkyl thiophenes) show similar behavior.

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 αPE 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 αPE 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 αPE 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 αPE 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.

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