Molecular Dynamics of Amphiphilic Random Copolymers in the Bulk: A ¹H and ¹⁹F NMR Relaxometry Study

Abstract

A set of amphiphilic random copolymers of poly(ethylene glycol) methacrylate (PEGMA) and perfluorohexylethyl acrylate (FA) with different compositions synthesized by atom transfer radical polymerization (ATRP) is investigated by 1H and 19F NMR relaxometry. In particular, a thorough investigation of T1 and T2 relaxation times at variable temperature and copolymer composition provides the first complete and detailed characterization of the dynamics of both the main chain backbone and the side chains of the PEGMA‐co‐FA copolymers. The results highlight an intramolecular segregation of rigid main chain and mobile side chains, and an additional self‐assembling of the PEGMA and FA side chains into distinct nanodomains, driven by the hydrophobic interactions between FA side chains. The obtainment and observation of nanoscale phase separation in random copolymers is a promising achievement to the aim of controlling self‐assembly in the bulk by suitably modulating copolymers composition, which can open novel avenues to easier fabrications and applications in nanotechnologies.

Amphiphilic Polyphosphonate Copolymers as New Additives for PDMS-Based Antifouling Coatings

“…SiMA- co -PEGMA28 exhibited only the SiMA related transition at −119 °C. Since the PEGMA homopolymer with the same length of the oxyethylenic side chain is reported to have a T g of −54 °C [ 49 ], its absence in the thermogram was ascribed to the low weight fraction of PEGMA in the copolymer. Copolymer SiMA- co -MPC20 did not present any other glass transition temperatures, other than the one at −119 °C due to the SiMA units.…”

Behavior of Protein-Inspired Synthetic Random Heteropolymers

“…Several popular methods in SCNP literature rely on methacrylate-based monomer building blocks due to the variety of available synthesis and functionalization methods, as well as inherent amphiphilicity of these constituents. 5,40,42,[48][49][50][51][52] These methacrylate-based heteropolymers have been used to demonstrate the dramatic effect side chain chemistry can have on polymer collapse and resulting nanoparticle behavior, as revealed through common experimental SCNP analysis techniques. 48,53 Inspired by the recent functionalities observed in RHPs, [6][7][8] here we study the molecular structure and dynamics of complex RHPs containing up to four different monomers using molecular dynamics as well as X-ray scattering.…”

The Effect of Poly(ethylene glycol) (PEG) Length on the Wettability and Surface Chemistry of PEG-Fluoroalkyl-Modified Polystyrene Diblock Copolymers and Their Two-Layer Films with Elastomer Matrix

“…In particular, amphiphilic surface-active additives, composed of polysiloxane and/or fluoropolymer chains as the hydrophobic components, and poly(ethylene glycol) (PEG) chains as the hydrophilic components, have been investigated in different fields of nanotechnology [ 3 , 34 , 36 , 37 , 38 , 39 ]. The self-assembly of such amphiphilic copolymers in fact is also possible in the bulk copolymer itself [ 40 , 41 ], or when dissolved in a selective solvent, determining a variety of nanostructures ranging from single chain nanoparticles to large aggregates [ 42 , 43 , 44 , 45 , 46 ]. A surface reconstruction process of amphiphilic polymers generally involves an increase in hydrophilicity of the film surface after immersion in polar solvents, notably water, and a reversible restoration of the surface hydrophobicity after contact with air [ 4 , 17 ].…”