Development of Ring-Expansion RAFT Polymerization of <i>tert</i>-Butyl Acrylate with a Cyclic Trithiocarbonate Derivative toward the Facile Synthesis of Cyclic Polymers

Polymers with cyclic topology have no terminal structure and, therefore, exhibit various unique physical and functional properties compared to those of linear analogs. In this paper, we report an innovative methodology for the synthesis of cyclic polymers via ring-expansion RAFT (RE-RAFT) polymerization of vinyl monomers using a cyclic trithiocarbonate derivative (CTTC) as a RAFT agent. RE-RAFT of tert-butyl acrylate (TBA) was performed to yield a mixture of polymers exhibiting a bimodal size exclusion chromatography (SEC) trace. Both the peak top molecular weights shifted to higher-molecular-weight regions as the monomer conversion increased. The structure of the resulting polymer mixture was examined by 1H NMR and MALDI-TOF-MS. Detailed studies indicated that the obtained polymer of higher molecular weight was one of the large-sized cyclic polymers generated by the fusion of smaller-sized cyclic polymers during the RE-RAFT polymerization process. This approach opens the door to the simple synthesis of well-controlled cyclic polymers with complex structures, such as alternating and multi-block repeat unit sequences

Synthesis of Well-Defined Alternating Copolymer Composed of Ethylmaleimide and Hydroxy-Functionalized Vinyl Ether by RAFT Polymerization and Their Thermoresponsive Properties

Here we report the controlled synthesis of alternating copolymers by reversible addition-fragmentation chain transfer (RAFT) polymerization of hydroxy-functionalized vinyl ether (DEGV) and ethylmaleimide (EtMI) using dithiocarbonate derivative (CPDB) as the RAFT reagent. The resulting alternating copolymer poly[ethylmaleimide-alt-(diethylene glycol mono vinyl ether)] (poly(MalMI-alt-DEGV)) had a relatively narrow molecular weight distribution (Mw/Mn &lt; 1.4). These polymers are fully soluble in cold water (5 &deg;C) and an aqueous solution of poly(MalMI-alt-DEGV) became turbid upon heating (using an incident wavelength of 600 nm and 1.0 mg mL&minus;1 (0.1 wt %) polymer concentration), indicating phase separation above the cloud point temperature (Tcp). The Tcp of the polymer solution ranged from 15&ndash;35 &deg;C, depending on the molecular weight and molecular weight distribution of the polymer

Controlled Synthesis and Photoresponsive Properties of Spiropyran End-Functionalized Poly(vinyl ether)s

Due to the need to develop smart materials for a variety of applications such as catalysts and drug delivery, the development of photoresponsive polymers is receiving increasing attention. In particular, the photoisomerization of spiropyran (SP), unlike many other photoresponsive compounds, has attracted attention because it dramatically changes not only the molecular structure but also the polarity of the molecule. However, in most cases where SP is used as a photoresponsive functional group, SP is introduced in the side chain of the polymer, and few cases have been reported in which SP is introduced at the end of the polymer chain. Therefore, we designed a new amphipathic poly(vinyl ether) with an SP moiety at the end of the polymer chain. First, an initiator having an SP moiety was synthesized and used for living cationic polymerization to synthesize a poly(vinyl ether) bearing an SP moiety at the end of the polymer chain. Furthermore, we investigated the photoresponsive properties of the obtained polymers, we found that self-assembly of the amphiphilic polymers could be controlled by photoirradiation

Protecting Group-Free Synthesis of Glycopolymer-Type Amphiphilic Macromonomers and Their Use for the Preparation of Carbohydrate-Decorated Polymer Particles

Polymer particles modified with carbohydrates on their surfaces are of significant interest, because their specific recognition abilities to biomolecules are valuable for developing promising materials in biomedical fields. Carbohydrate-decorated core-shell polymer particles are expected to be efficiently prepared by dispersion polymerization using a glycopolymer-based amphiphilic macromonomer as both a polymeric steric stabilizer and a monomer. To create glycopolymer-type macromonomers, we propose a new strategy combining living cationic polymerization of an alkynyl-functionalized vinyl ether (VE), and the click reaction for the preparation of glycopolymers having a polymerizable terminal group, and investigate their dispersion copolymerization with styrene for generating carbohydrate-decorated polymer particles. This study deals with (i) the synthesis of block copolymer-type amphiphilic macromonomers bearing a methacryloyl group at the &#945;-terminus, and pendant alkynyl groups by living cationic polymerization of alkynyl-substituted VE (VEEP), (ii) the derivatization of maltose-carrying macromonomers by click chemistry of the pendant alkynyl groups of the precursor macromonomers with maltosyl azide without any protecting/deprotecting processes, and (iii) the preparation of maltose-decorated (Mal-decorated) polymer particles through the dispersion copolymerization of glycopolymer-type macromonomers with styrene in polar media. Moreover, this study concerns the specific interactions of the resultant polymer particles with the lectin concanavalin A (Con A)