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Broadband dielectric spectroscopy is employed to probe dynamics in low molecular weight poly(cis-1,4-isoprene) (PI) confined in unidirectional silica nanopores with mean pore diameter, D, of 6.5nm. Three molecular weights of PI (3, 7 and 10kg/mol) were chosen such that the ratio of D to the polymer radius of gyration, Rg, is varied from 3.4, 2.3 to 1.9, respectively. It is found that the mean segmental relaxation rate remains bulk-like but an additional process arises at lower frequencies with increasing molecular weight (decreasing D/Rg). In contrast, the mean relaxation rates of the end-to-end dipole vector corresponding to chain dynamics are found to be slightly slower than that in the bulk for the systems approaching D/Rg ∼ 2, but faster than the bulk for the polymer with the largest molecular weight. The analysis of the spectral shapes of the chain relaxation suggests that the resulting dynamics of the 10 kg/mol PI confined at length-scales close to that of the Rg are due to non-ideal chain conformations under confinement decreasing the chain relaxation times. The understanding of these faster chain dynamics of polymers under extreme geometrical confinement is necessary in designing nanodevices that contain polymeric materials within substrates approaching the molecular scale. 

Flexible alkyl side chain in conjugate polymers (CPs) improves the solubility and promotes solution processability, in addition, it affects interchain packing and charge mobilities. Despite the well-known charge mobility and morphology correlation for these semi-crystalline polymers, there is a lack of fundamental understanding of the impact of side chain on their crystallization kinetics. In the present work, isothermal crystallization of five poly(3-alkylthiophene-2,5-diyl) (P3ATs) with different side-chain structures were systematically investigated. To suppress the extremely fast crystallization and trap the sample into amorphous glass, an advanced fast scanning chip calorimetry technique, which is able to quench the sample with few to tens thousands of K/s, was applied. Results show that the crystallization of P3ATs was greatly inhibited after incorporation of branched side chains, as indicated by a dramatic up to six orders of magnitude decrease in the crystallization rate. The suppressed crystallization of P3ATs were correlated with an increased π–π stacking distance due to unfavorable side-chain steric interaction. This work provides a pathway to use side-chain engineering to control the crystallization behavior for CPs, thus to control device performance. 

ABSTRACT Thermomechanical properties of polymers highly depend on their glass transition temperature (T_g). Differential scanning calorimetry (DSC) is commonly used to measureT_gof polymers. However, many conjugated polymers (CPs), especially donor–acceptor CPs (D–A CPs), do not show a clear glass transition when measured by conventional DSC using simple heat and cool scan. In this work, we discuss the origin of the difficulty for measuringT_gin such type of polymers. The changes in specific heat capacity (Δc_p) atT_gwere accurately probed for a series of CPs by DSC. The results showed a significant decrease in Δc_pfrom flexible polymer (0.28 J g⁻¹K⁻¹for polystyrene) to rigid CPs (10⁻³J g⁻¹K⁻¹for a naphthalene diimide‐based D–A CP). When a conjugation breaker unit (flexible unit) is added to the D–A CPs, we observed restoration of the Δc_patT_gby a factor of 10, confirming that backbone rigidity reduces the Δc_p. Additionally, an increase in the crystalline fraction of the CPs further reduces Δc_p. We conclude that the difficulties of determiningT_gfor CPs using DSC are mainly due to rigid backbone and semicrystalline nature. We also demonstrate that physical aging can be used on DSC to help locate and confirm the glass transition for D‐A CPs with weak transition signals. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys.2019, 57, 1635–1644