Molecular Dynamics and Self-Assembly in Double Hydrophilic Block and Random Copolymers
Artikel i vetenskaplig tidskrift, 2024

We investigate the self-assembly and dynamics of double hydrophilic block copolymers (DHBCs) composed of densely grafted poly[oligo(ethylene glycol) methacrylate] (POEGMA) and poly(vinyl benzyl trimethylammonium chloride) (PVBTMAC) parent blocks by means of calorimetry, small- and wide-angle X-ray scattering (SAXS/WAXS), and dielectric spectroscopy. A weak segregation strength is evident from X-ray measurements, implying a disordered state and reflecting the inherent miscibility between the host homopolymers. The presence of intermixed POEGMA/PVBTMAC nanodomains results in homogeneous molecular dynamics, as evidenced through isothermal dielectric and temperature-modulated DSC measurements. The intermixed process undergoes a glass transition at a temperature approximately 40 K higher than the vitrification of bulk POEGMA segments, and it shifts to an even higher temperature by increasing the content of the hard block. At temperatures below the intermixed glass transition temperature, the confined POEGMA segments between the glassy intermixed regions contribute to a segmental process featuring (i) reduced glass transition temperature (Tg), (ii) reduced dielectric strength, (iii) broader distribution of relaxation times, and (iv) reduced fragility compared to the POEGMA homopolymer. We also observe two glass transition temperatures of dry PVBTMAC, which we attribute to the backbone and side chain segmental relaxation. To the best of our knowledge, this is the first time in the literature that these glass transitions of dry PVBTMAC have been reported. Finally, this study shows that excellent mixing of the two homopolymers is obtained, and this implies that different properties of this copolymer system can be tailored by adjusting the concentration of each homopolymer.

Författare

Achilleas Pipertzis

Chalmers, Fysik, Nano- och biofysik

Angeliki Chroni

Theoretical and Physical Chemistry

Stergios Pispas

Theoretical and Physical Chemistry

Jan Swenson

Chalmers, Fysik, Nano- och biofysik

Journal of Physical Chemistry B

1520-6106 (ISSN) 1520-5207 (eISSN)

Vol. 128 45 11267-11276

Ämneskategorier

Polymerkemi

DOI

10.1021/acs.jpcb.4c05398

Mer information

Senast uppdaterat

2024-12-02