Anionic homo‐ and copolymerization of styrenic triple‐tailed polybutadiene macromonomers

Abstract

A number of well‐defined complex macromolecular architectures have been synthesized using an efficient macromonomer technique. Styrenic triple‐tailed polybutadiene (PBd) macromonomers (sTMMB), synthesized by selective reaction (titration) of living PBd tails with the SiCl groups of 2‐(dichloromethylsilyl)ethylchloromethylsilyl‐4‐styrene (TCDSS), were polymerized in situ without isolation of sTMMB with s‐BuLi, using high vacuum techniques. Taking advantage of the living character of the anionic polymerization of sTMMB, the following complex macromolecular architectures were prepared: PBd‐g‐(PBd)3 (triple‐combs), PS‐g‐(PBd)3 (triple‐grafts), [PBd‐g‐(PBd)3]3 (3‐arm triple‐comb stars), and triple molecular brushes (tmbPBd) or triple polymacromonomers (tPMMB). Characterization carried out by size exclusion chromatography (SEC), equipped with refractive index and light scattering detectors, indicated that the synthesized novel architectures have a high degree of molecular and compositional homogeneity. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3513–3523, 2007

Facile syntheses of cylindrical molecular brushes by a sequential RAFT and ROMP “grafting‐through” methodology

“…Of significant interest is the development of synthetic methodologies to prepare complex macromolecular structures that contain functionalities, allowing for stimuli‐responsive characteristics and further chemical modifications 1–6. The cylindrical molecular brush, which is composed of many side chain polymers distributed densely along a backbone, has attracted much attention because its chemical composition, size, and morphology can be controlled precisely by choosing appropriate monomers and tuning the lengths of the backbone and side chains 7–9.…”

The Critical Role of Anionic Polymerization for Advances in the Physics of Polyolefins

“…Much of this sort of work has been done on symmetric stars (i.e., equal arm lengths) [124][125][126], as well as stars with various arm lengths made by the miktoarm techniques of Hadjichristidis et al [127][128][129][130]. Some model PE polymers with multiple branch points, including some pom-pom structures [131][132][133][134], combs [135][136][137][138][139], and dendritic polymers [140][141][142][143][144], have also been studied in this regard. All of them have a local structure identical to an LLDPE with 7 to 10 wt% butene (i.e., 2 to 3 ethyl branches per 100 backbone carbons).…”

Synthesis and self-assembly of fluorene-vinylene alternating copolymers in “Hairy-Rod” architecture: side chain – mediated tuning of conformation, microstructure and photophysical properties

“…alongside, control of the number of branches per branch point was adjusted by appropriately choosing the functionality number of the initiators/reactive intermediate used for the corresponding precursor macromonomer synthesis (Scheme S1). Besides mono-branched macromonomers (Scheme 1), this work also involves the use of what Hadjichristidis et al termed 'double tailed' macromonomers, [46] enabling to systematically change the nature, number, and the substitution pattern of the side chains on the PVFs conjugated backbones (Figure 1).…”