Tapered (cone-shaped) bottlebrush polymers were synthesized for the first time by ring-opening metathesis polymerization (ROMP) using a sequential-addition of macromonomers (SAM) strategy. Polystyrene macromonomers with molecular weights that increased from 1 to 10 kg mol −1 were polymerized in sequence to high conversion, yielding tapered bottlebrush polymers that could be visualized by atomic force microscopy (AFM).

A systematic series of 16 amphiphilic bottlebrush block copolymers (BCPs) containing polystyrene and poly(N-acryloylmorpholine) (PACMO) side chains were prepared by a combination of atom-transfer radical polymerization (ATRP), photoiniferter polymerization, and ring-opening metathesis polymerization (ROMP). The grafting-through method used to prepare the polymers enabled a high degree of control over backbone and side-chain molar masses for each block. Surface tension measurements on the self-assembled amphiphilic bottlebrush BCPs in water revealed an ultralow critical micelle concentration (cmc), 1−2 orders of magnitude lower than linear BCP analogues on a molar basis, even for micelles with >90% PACMO content. Combined with coarse-grained molecular dynamics simulations, fitting of small-angle neutron scattering traces (SANS) allowed us to evaluate solution conformations for individual bottlebrush BCPs and micellar nanostructures for self-assembled macromolecules. Bottlebrush BCPs showed an increase in anisotropy with increasing PACMO content in toluene-d 8 , which is a good solvent for both blocks, reflecting an extended conformation for the PACMO block. SANS traces of bottlebrush BCPs assembled into micelles in D 2 O, a selective solvent for PACMO, were fitted to a core−shell−shell model, suggesting the presence of a partially hydrated inner shell. Results showed an average micelle diameter of 40 nm with combined shell diameters ranging from 16 to 18 nm. A general trend of increased stability of micelles (i.e., resistance to precipitation) was observed with increases in PACMO content. These results demonstrate the stability of bottlebrush polymer micelles, which self-assemble to form spherical micelles with ultralow (<70 nmol/L) cmc's across a broad range of compositions.

Dynamically cross-linkable bottlebrush polymer adhesives were synthesized by the grafting-from strategy through a combination of ring-opening metathesis polymerization (ROMP) and photoiniferter polymerization. A norbornene-containing trithiocarbonate was first polymerized by ROMP to form the bottlebrush polymer backbone; this was followed by blue-light-mediated photoiniferter polymerization of butyl acrylate initiated by the poly(trithiocarbonate) to form the bottlebrush polymer. This strategy afforded well-defined bottlebrush polymers with molar masses in excess of 11 000 kg/mol. For un-cross-linked bottlebrush polymers, 180° peel tests revealed a cohesive failure mode and showed similar peel strengths (∼30 g/mm) regardless of the backbone polymer degree of polymerization (DP). The bottlebrush polymers were then treated with butylamine to remove the trithiocarbonate, liberating thiols on each side-chain terminus. In the presence of oxygen, these thiols readily cross-linked via disulfide bond formation. The cross-linked bottlebrush polymers with a backbone DP of 400 showed a greater than sixfold improvement in peel strength, whereas those with a backbone DP of 100 exhibited a twofold enhancement compared with un-cross-linked samples along with a change to adhesive failure. Triphenylphosphine readily reduced the disulfide bonds, effectively removing all cross-links in the bottlebrush network and allowing for recasting of the adhesive, which showed similar adhesive and rheological properties to the original un-cross-linked samples.

The synthesis of polymeric materials using elemental sulfur (S 8 ) as the chemical feedstock has recently been developed using a process termed inverse vulcanization. The preparation of chemically stable sulfur copolymers was previously prepared by the inverse vulcanization of S 8 and 1,3diisopropenylbenzene (DIB); however, the development of synthetic methods to introduce new chemical functionality into this novel class of polymers remains an important challenge. In this report the introduction of polythiophene segments into poly(sulfur-random-1,3-diisopropenylbenzene) is achieved by the inverse vulcanization of S 8 with a styrenic functional 3,4propylenedioxythiophene (ProDOT-Sty) and DIB, followed by electropolymerization of ProDOT side chains. This methodology demonstrates for the first time a facile approach to introduce new functionality into sulfur and high sulfur content polymers, while specifically enhancing the charge conductivity of these intrinsically highly resistive materials.

We report the design of a simple, inexpensive photoreactor for photoiniferter polymerization of vinyl monomers mediated by thiocarbonylthio compounds. This photoreactor allowed for the synthesis of block copolymers and well-defined bottlebrush polymers by grafting-from and grafting-through.