We explore the phase behaviour, solution conformation, and interfacial properties of bottlebrush polymers with side-chains comprised of poly(N-isopropylacrylamide) (PNIPAAM), a thermally responsive polymer that exhibits a lower critical solution temperature (LCST) in water. PNIPAAM bottlebrush polymers with controlled side-chain length and side-chain end-group structure are prepared using a "gr...

Bottlebrush polymers are highly branched macromolecules with potential applications in antifouling coatings, rheological modifiers, and drug delivery systems. However, the solution conformation of bottlebrush polymers has been studied in only a limited set of materials made primarily by grafting-from polymerization. Here we present small-angle neutron scattering (SANS) measurements on a series ...

A novel dithiocarbamate chain transfer agent (CTA1) with a directly polymerizable Z-group was synthesized for use in reversible addition–fragmentation chain transfer polymerization (RAFT). This CTA effectively mediated RAFT polymerization of styrenic and acrylic monomers with dispersities (Đ) < 1.08. Utilizing the polymerizable Z-group on the ω-chain end that is inherited from the RAFT process,...

Soft, solvent-free poly(dimethylsiloxane) elastomers are fabricated by a one-step process via crosslinking bottlebrush polymers. The bottlebrush architecture prevents the formation of entanglements, resulting in elastomers with precisely controllable low moduli from 1 to 100 kPa, below the lower limit of traditional elastomers; moreover, the solvent-free nature enables their negligible adhesive...

By combining living anionic polymerization and hydrosilylation, densely grafted bottlebrush polymers with controlled spacing of branch points are prepared. Dimethyl(4-vinylphenyl)silane and dimethyl(4-(1-phenylvinyl)phenyl)silane are anionically (co)polymerized to synthesize uniform, alternating, and gradient in-chain silyl-hydride (Si-H) functionalized backbones. The spacing of branch points i...

Block copolymer (BCP) self-assembly is a fundamental process in which incompatible blocks spontaneously form organized microstructures with broad practical applications. Classical understanding that the domain spacing limited by contour length of polymer backbone. Here, using combination molecular design, chemical synthesis, small-/wide-angle X-ray scattering, transmission electron microscopy, ...

Introduction Bottlebrush polymers are macromolecules which consist of a long chain serving as “backbone” onto which flexible side chains are densely grafted. There is a lot of recent interest in both the synthesis of these macromolecules and characterization of physical properties by various experimental techniques (light and neutron scattering, atomic force microscopy, electron microscopy, etc...

Bottlebrush polymer thin films may be attractive for the preparation of antifouling and/or stimuli-responsive surface coatings due to the high grafting density and conformational flexibility of polymeric side chains, but bottlebrush polymer thin films have not been previously reported and their surface properties are unknown. Herein, we report a study of the surface properties of mixed bottlebr...

Polymers with advanced topological architectures are promising materials for wide applications due to their structure-generated unique properties different from that of the linear analogues. The elegant integration of stimuli-responsive polymers with such advanced architectures can create novel materials with virtues from both moieties, are thus a hot subject of research for both fundamental an...

Hydrophobic ultrahigh molecular weight bottlebrush block copolymer and linear block copolymer of polystyrene-polylactide (PS-PLA) were shown to be capable of forming Langmuir monolayers and exhibiting unique assembly behaviors at the air/water interface, which cannot be addressed by the classic theory of Langmuir monolayer of amphiphilic copolymers. New models were proposed to illustrate these ...