Molecular and Structure–Properties Comparison of an Anionically Synthesized Diblock Copolymer of the PS-b-PI Sequence and Its Hydrogenated or Sulfonated Derivatives

Abstract

An approach to obtaining various nanostructures utilizing a well-studied polystyrene-b-poly(isoprene) or PS-b-PI diblock copolymer system through chemical modification reactions is reported. The complete hydrogenation and partial sulfonation to the susceptible carbon double bonds of the PI segment led to the preparation of [polystyrene-b-poly(ethylene-alt-propylene)] as well as [polystyrene-b-poly(sulfonated isoprene-co-isoprene)], respectively. The hydrogenation of the polyisoprene block results in enhanced segmental immiscibility, whereas the relative sulfonation induces an amphiphilic character in the final modified material. The successful synthesis of the pristine diblock copolymer through anionic polymerization and the relative chemical modification reactions were verified using several molecular and structural characterization techniques. The thin film structure–properties relationship was investigated using atomic force microscopy under various conditions such as different solvents and annealing temperatures. Small-angle X-ray scattering was employed to identify the different observed nanostructures and their evolution upon thermal annealing.

Sulfonated Block Copolymers: Synthesis, Chemical Modification, Self-Assembly Morphologies, and Recent Applications

“…The appearance of the signals at 1042 and 1184 cm −1 and 3.75 ppm in FTIR and 1 H NMR, respectively, gave evidence of the incorporation of the sulfonate groups in the polyisoprene. In addition, the 1 H NMR, allowed us to calculate a degree of sulfonation close to 43% [ 62 ].…”

“…Small-angle X-ray scattering and gravimetric measurements allowed us to establish a correlation of nanostructural changes with macroscopic swelling to establish a fundamental structure–property behavior. Recently, Politakos et al [ 62 ] published an approach for obtaining various nanostructures. They employed a diblock based on poly(styrene-b-isoprene) (PS-b-PI) and made a comparative study with its hydrogenated and sulfonated derivatives.…”

“…Thus, when solidifying, nanodomains of donor and acceptor materials can be formed. Varying significant parameters in BCs such as molecular weight, solvent type, annealing temperature, and sulfonation degree, different morphologies may be obtained, including lamella, gyroid, hexagonally packed cylinders (HEX), and hexagonally perforated lamellae (HPL) [ 62 , 120 ].…”

Thermal and Bulk Properties of Triblock Terpolymers and Modified Derivatives towards Novel Polymer Brushes

“…The modified segment plays the polymer brush role. Note that polydienes constitute a class of materials that can be easily modified, as already reported in the literature [ 28 , 29 , 30 ].…”

Highly Ordered Porous Inorganic Structures via Block Copolymer Lithography: An Application of the Versatile and Selective Infiltration of the “Inverse” P2VP-b-PS System

“…Nevertheless, it has a low Flory–Huggins parameter between the blocks (χ = 0.04), which directly affects the minimum period achiaveable . For that reason, researchers have focused on the development of higher χ BCPs, increasing the thermodynamic incompatibility between the two blocks, and allowing a facile microphase separation and a reduction of feature sizes. , P2VP- b -PS is another system with high χ (0.178 at 25 °C) and an interesting characteristic related to the P2VP block. Pyridine is an excellent chelating agent for several inorganic species, enabling the interaction with nanoparticles and metal ions.…”