Synthesis of Well-Defined Miktoarm Star-Branched Polymers Consisting of Perfluorinated Segments by a Novel Methodology Using Soluble In-Chain-Benzyl Bromide-Functionalized AB Diblock Copolymers as Key Building Blocks

Abstract

In order to synthesize miktoarm star-branched polymers consisting of poly(2-(perfluorooctyl)ethyl methacrylate) (P(F 8 H 2 -MA)) segments insoluble in most organic solvents, a novel methodology based on a new concept by using a THF-soluble in-chain-benzyl bromide (BnBr)-functionalized AB diblock copolymer, polystyrene (PS)-block-P(F 8 H 2 -MA), as a key building blocks is proposed. The methodology involves the following three reaction steps: (1) preparation of in-chain-(3-tert-butyldimethylsilyloxymethylphenyl) (SiOMP)-functionalized PS-block-P(F 8 H 2 -MA) by means of living anionic polymerization, (2) a transformation reaction of the SiOMP group into BnBr function, and (3) a coupling reaction of the resulting in-chain-BnBr-functionalized PS-block-P(F 8 H 2 -MA) with another living anionic polymer(s). With this methodology, a variety of well-defined 3-arm ABC, 4-arm A 3 B, ABC 2 , and ABCD miktoarm star-branched polymers consisting of P(F 8 H 2 -MA) (B) segments was successfully synthesized. Thus, the proposed methodology satisfactorily works and opens a new route for the synthesis of miktoarm star-branched polymers consisting of insoluble arm segment(s).

Controlled copolymerization of n-butyl acrylate with semifluorinated acrylates by RAFT polymerization

“…Therefore, fluorine containing materials have found various promising applications, and are current topics of active research. [1][2][3][4][5][6][7][8][9][10] There has been a growing realization of synthetic (semi) fluorinated polymers and materials in both fundamental and applied research over the last couple of decades, relying on a multitude of polymerization techniques (such as polycondensation, 11 living anionic, [12][13][14][15][16][17] living cationic, 18 conventional radical [19][20][21][22] or living radical polymerization, atom transfer radical polymerization (ATRP), [23][24][25][26][27][28][29] single-electron transfer living radical polymerization (SET-LRP), 30 nitroxide-mediated radical polymerization (NMP), 31 reversible addition-fragmentation chain transfer (RAFT) and Macromolecular Design via the Interchange of Xanthates (MADIX) polymerization [32][33][34][35][36] techniques). Especially the formation of semicrystalline polymers is often an important characteristic of many homofluoropolymers, [37][38][39] together with their high chemical resistance.…”

Successive Synthesis of Multiarmed and Multicomponent Star‐Branched Polymers by New Iterative Methodology Based on Linking Reaction between Block Copolymer In‐Chain Anion and α‐Phenylacrylate‐Functionalized Polymer

“…In order to well elucidate the relationships of properties and behavior with such morphologies and supramolecular assemblies, the synthesis of μ‐star polymers with well‐defined structures is essential. Although most such μ‐star polymers have so far been synthesized by the methodologies using living anionic polymerization, the synthesis of μ‐star polymers having arms composed of more than three different components is very limited by the following two requirements and, therefore, still challenging even at the present time: Firstly, multistep reactions in a number that corresponds to all the different arms are required. Second and most importantly, several selective reactions and/or several different reaction sites selectively working for the introduction of all the different arms are required.…”

Versatile Synthesis of Multiarm and Miktoarm Star Polymers with a Branched Core by Combination of Menschutkin Reaction and Controlled Polymerization

“…Synthesis and properties of complex macromolecular architectures such as multiarm and miktoarm stars have attracted much attention in the past decades due to their unique topologies and physicochemical properties. − Owing to their compact structure and variable functionality, star polymers usually exhibit bulk, solution, and interface properties different from their linear analogues and have potential applications in many fields. − Moreover, miktoarm stars with at least two kinds of polymer arms are liable to form higher order multiscale self-assemblies involving multicompartment micelles originating from their branched architectures and heterophase structures, and thus they can hold great promise as next-generation advanced functional polymers. − …”