Anionic Copolymerization Enables the Scalable Synthesis of Alternating (AB) Multiblock Copolymers with High Molecular Weight in /2 Steps.

Based on the highly disparate reactivities of isoprene (I, = 25.4) and 4-methylstyrene (4MS, = 0.007) in the anionic copolymerization in nonpolar media, a general strategy for the rapid and scalable synthesis of tapered multiblock copolymers with an extremely steep gradient has been developed.

One-Step Anionic Copolymerization Enables Formation of Linear Ultrahigh-Molecular-Weight Block Copolymer Films Featuring Vivid Structural Colors in the Bulk State.

Ultrahigh-molecular-weight (UHMW) tapered block copolymers (BCPs) consisting of polyisoprene- block-poly(4-methylstyrene) featuring overall molar masses in the range of 1101-2033 kg mol ( M) are synthesized via a convenient one-step anionic copolymerization protocol. The obtained UHMW BCPs are investigated by differential scanning calorimetry, size exclusion chromatography, and H NMR spectroscopy. Microphase separation for the UHMW BCPs in the bulk state is investigated by transmission electron microscopy (TEM) measurements and scanning electron microscopy (SEM), revealing well-ordered lamellar and spherical domains with large domain sizes in the range of 100-200 nm.

Controlling the Polymer Microstructure in Anionic Polymerization by Compartmentalization.

An ideal random anionic copolymerization is forced to produce gradient structures by physical separation of two monomers in emulsion compartments. One monomer (M) is preferably soluble in the droplets, while the other one (D) prefers the continuous phase of a DMSO-in-cyclohexane emulsion. The living anionic copolymerization of two activated aziridines is thus confined to the DMSO compartments as polymerization occurs selectively in the droplets.