Thermally-labile segmented hyperbranched copolymers: using reversible-covalent chemistry to investigate the mechanism of self-condensing vinyl copolymerization

Abstract

A thermally-reversible inimer was used to confirm the controlled growth of individual branches during self-condensing vinyl atom transfer radical polymerization (ATRP).

Long‐Chain Hyperbranched Polymers: Synthesis, Properties, and Applications

“…Although some interesting applications in biomedicine, electric conductivity, chemical sensing, and catalytic carrier have been documented, the application field of LCHBPs is rather insufficient, the development of which should not be limited to those several examples reported or the scope of conventional HBPs, and may be regarded as a new type of polymer material that incorporates certain advantageous properties of both linear and hyperbranched polymers, and thus possibly beyond both of them. Moreover, thanks to the long‐chain hyperbranched topologic structures that are much more easy to design and control, some novel and environment‐friendly biodegradable materials should be paid sufficient attention . Therefore, it is pretty believable that a bright prospect of LCHBPs will probably be made in the near future as well as their due functions to be an attractive class of advanced functional materials.…”

“…Sumerlin et al. presented a kind of HBP with thermally‐labile branching points prepared from designed inimer incorporated with a reversible‐covalent linkage between the propagating and initiating groups via SCVP, thus the degradation and reconstruction of thus obtained HBPs were examined, allowing the investigation of the mechanism of SCVP . The SCVP‐based copolymerization process was further widely used to prepare various LCHBPs based on poly(vinyl acetate)s and poly(2‐(dimethylamino)ethyl methacrylate)s …”

“…[1,5,7,8,10,15] This synthetic simplicity along with the fact that many of their physical and mechanical properties of both HBPs and dendrimers are evidenced to be similar make HBPs attractive alternatives to dendrimers and thus the investigation of HBPs encourages considerable attention. The results in a large number of contributions have shown HBPs to be good candidates for a wide range of applications including been adjusted for the preparation of LCHBPs through copolymerization of the traditional small molecular inimer with an additional comonomer, [80][81][82][83][84][85][86][87][88][89][90][91][92][93][94][95][96][97][98][99] or direct homopolymerization of a macroinimer. [100][101][102] Besides their unique synthetic strategies and novel structural features or topologies, LCHBPs have displayed some novel properties in both bulk and solution states.…”

Polymer nanostructures synthesized by controlled living polymerization for tumor-targeted drug delivery

“…Polymers synthesized via this method have larger molar mass dispersities; however, their constituent segments are still somewhat controlled. [86] Examples of inimers include hydroxyl-substituted lactones, acrylic-substituted ATRP initiators, and acrylic-substituted RAFT agents. The latter two inimers are conveniently prepared by the esterification of the acid halide and carboxylic acid groups present on many ATRP initiators and RAFT CTAs, respectively.…”

Ligand effect in the synthesis of hyperbranched polymers via copper‐catalyzed azide‐alkyne cycloaddition polymerization (CuAACP)

“…One goal during the synthesis of hyperbranched polymers is to be able to tune the DB values within a wide range with no change of the polymer's composition . In traditional step‐growth polymerization of AB 2 monomers and step‐growth/chain‐growth polymerization of AB* inimers, the produced hyperbranched polymers exhibit a statistical DB value at DB ~0.5, although the experimental DB values could be less than 0.5 due to the steric effect . To achieve DB > 0.5, two strategies are applied: (1) the use of AB m dendron as monomer (m = 4 and 8, etc.)…”