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Ishizu, Koji; Sawada, Naotaka; Satoh, Junichiro; Sogabe, Atsushi

doi:10.1023/a:1025352601751

Cited by 30 publications

(29 citation statements)

References 14 publications

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“…In aqueous solution, they self‐assemble into large, rod‐like aggregates. By employing a similar synthetic strategy, alternating copolymer brushes consisting of PPO and PEO segments were also prepared, which self‐assemble into rod‐like or irregular aggregates in aqueous solution, depending on the overall polymer concentration 126…”

Section: Comb‐shaped Copolymer Brushesmentioning

confidence: 99%

Supramolecular Self‐Assembly of Nonlinear Amphiphilic and Double Hydrophilic Block Copolymers in Aqueous Solutions

Liu

2009

Macromol. Rapid Commun.

103

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Supramolecular self-assembly of block copolymers in aqueous solution has received ever-increasing interest over the past few decades due to diverse biological and technological applications in drug delivery, imaging, sensing and catalysis. In addition to relative block lengths, molecular weights and solution conditions, chain architectures of block copolymers can also dramatically affect their self-assembling properties in selective solvents. This feature article mainly focuses on recent developments in the field of supramolecular self-assembly of amphiphilic and double hydrophilic block copolymers (DHBCs) possessing nonlinear chain topologies, including miktoarm star polymers, dendritic-linear block copolymers, cyclic block copolymers and comb-shaped copolymer brushes.

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Section: Comb‐shaped Copolymer Brushesmentioning

confidence: 99%

Supramolecular Self‐Assembly of Nonlinear Amphiphilic and Double Hydrophilic Block Copolymers in Aqueous Solutions

Liu

2009

Macromol. Rapid Commun.

103

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“…Ishizu's groups have also reported the synthesis and surfactant behavior of prototype amphiphilic copolymer brushes composed of PEO and poly(propylene oxide) (PPO). 17 Methacryloyl-terminated PPO macromonomer (PPO-MC; M n ¼ 1200) was synthesized by Figure 2. Plot of effective diffusion coefficient D eff against polymer concentration on PS/PEO prototype copolymer brushes P1 and P2 in benzene at 25 C. the reaction of commercially available poly(propylene glycol)monobutyl ether with methacryloyl chloride in THF in the addition of triethyl amine as an acid acceptor.…”

Section: Prototype Copolymer Brushesmentioning

confidence: 99%

Architecture of Multi-Component Copolymer Brushes: Synthesis, Solution Properties and Application for Nanodevices

Ishizu

2004

Polym J

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ABSTRACT:In this review article, we describe the architecture of multi-component copolymer brushes. These copolymer brushes can be classified into tree types, i.e., double-cylinder-type, prototype, and block-type. Double-cylinder-type copolymer brushes were prepared by free-radical polymerization of corresponding diblock macromonomer or by the ''grafting from'' approach using atom transfer radical polymerization (ATRP). Alternating free-radical copolymerization of the mixture of two macromonomers provided prototype copolymer brushes. ATRP was applied to the synthesis of AB-type brush-block-brush (block-type) copolymers. All copolymer brushes were molecularly dissolved in a dilute solution due to densely branched side chains and took geometrically anisotropic conformation such as cylinder with increasing aspect ratio. In self-assembly process of amphiphilic prototype copolymer brushes in water, hierarchical generations from small rods to large rods were observed, because copolymer brushes exhibited phase-separated hydrophobic/hydrophilic domains. Moreover, binding of anionic/nonionic polyeletrolyte prototype brushes with cationic linear polyelectrolyte formed an interesting complex of a high order by electrostatic interaction. On the other hand, the molecular wires in electronic nanodevices were prepared by forming conducting polypyrroles with an internal core of double-cylider-type copolymer brushes as templates, where as the outer cylinder parts play the role of an insulator. [DOI 10.1295/polymj.36.775] KEY WORDS Multi-component Copolymer Brush / Double-cylinder-type / Prototype / Blocktype / Macromonomer / ATRP / Aternating Copolymerization / Molecular Wire / Binding / Nanostructured polymers are of rapidly growing interest because of their sized-coupled properties. Generally, the branched polymer has a smaller hydrodynamic dimension than a linear polymer with the same molecular weight. The interest in branched polymers arises from their compactness and their enhanced segment density. Recently, a new class of branched architectural polymers, such as nanocylinders, is attracting attention with expectation that their unique structures may result in unusual properties. It is well known that comb polymers with densely grafted side chains in a good solvent can adopt a worm-like cylinder brush conformations, in which the side chains are stretched in the direction normal to the backbone, owing to the excluded-volume interaction. The polymerization of macromonomers provides regular multi-branched polymers with dense branching. Since both the degree of polymerization (DP n ) and the length of branches are varied, poly(macromonomer)s, often so-called ''polymer brushes'', are interesting models for the study of branched polymers.1-9 More recently, we have systematically investigated the architecture of multi-component copolymer brushes. Figure 1 shows the illustration of three types of multi-component copolymer brushes. Various strategies can be designed to construct such structures. For example, one strategies for the...

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“…In general, comb‐shaped polymer brushes can be categorized into homopolymer brushes and copolymer brushes. Since the pioneering work reported by Tsukahara et al3, 4 in 1989, extensive investigations have been devoted to the synthesis of homopolymer brushes mainly via three approaches including grafting‐through,5–20 grafting‐from,21–39 and grafting‐onto 40–46. In the past decade, the advent of controlled polymerization techniques, such as ring‐opening polymerization (ROP),5, 24, 25, 30, 37, 43 nitroxide‐mediated polymerization (NMP),47–49 atom transfer radical polymerization (ATRP),16, 31–33, 35, 39 and reversible addition‐fragmentation chain transfer (RAFT) polymerization,50, 51 have rendered the grafting‐from approach more appealing, starting with macroinitiators with the initiating sites distributed on every repeating unit.…”

Section: Introductionmentioning

confidence: 99%

“…On the other hand, copolymer brushes typically consist of more than one type of polymer side chains. When two types of polymer grafts are involved, they can be arranged in a random,43, 46, 47 alternating,5, 12–14, 18, 19, 25, 34 block,22, 26, 51, 52 or “centipede” manner 33, 37, 53. Compared to homopolymer brushes, the incorporation of another type of polymer graft endows copolymer brushes with extra structural versatility and unique aggregation properties, resulting from the intrinsic immiscibility between two types of polymer grafts.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of amphiphilic copolymer brushes possessing alternating poly(methyl methacrylate) and poly(N‐isopropylacrylamide) grafts via a combination of ATRP and click chemistry

Yin

Líu

et al. 2009

J. Polym. Sci. A Polym. Chem.

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We report on the synthesis of well‐defined amphiphilic copolymer brushes possessing alternating poly(methyl methacrylate) and poly(N‐isopropylacrylamide) grafts, poly(PMMA‐alt‐PNIPAM), via a combination of atom transfer radical polymerization (ATRP) and click reaction (Scheme ). Firstly, the alternating copolymerization of N‐[2‐(2‐bromoisobutyryloxy)ethyl]maleimide (BIBEMI) with 4‐vinylbenzyl azide (VBA) affords poly(BIBEMI‐alt‐VBA). Bearing bromine and azide moieties arranged in an alternating manner, multifunctional poly(BIBEMI‐alt‐VBA) is capable of initiating ATRP and participating in click reaction. The subsequent ATRP of methyl methacrylate (MMA) using poly(BIBEMI‐alt‐VBA) as the macroinitiator leads to poly(PMMA‐alt‐VBA) copolymer brush. Finally, amphiphilic poly(PMMA‐alt‐PNIPAM) copolymer brush bearing alternating PMMA and PNIPAM grafts is synthesized via the click reaction of poly(PMMA‐alt‐VBA) with an excess of alkynyl‐terminated PNIPAM (alkynyl‐PNIPAM). The click coupling efficiency of PNIPAM grafts is determined to be ∼80%. Differential scanning calorimetry (DSC) analysis of poly(PMMA‐alt‐PNIPAM) reveals two glass transition temperatures (Tg). In aqueous solution, poly(PMMA‐alt‐PNIPAM) supramolecularly self‐assembles into spherical micelles consisting of PMMA cores and thermoresponsive PNIPAM coronas, which were characterized via a combination of temperature‐dependent optical transmittance, micro‐differential scanning calorimetry (micro‐DSC), dynamic and static laser light scattering (LLS), and transmission electron microscopy (TEM). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2608–2619, 2009

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Cited by 30 publications

References 14 publications

Supramolecular Self‐Assembly of Nonlinear Amphiphilic and Double Hydrophilic Block Copolymers in Aqueous Solutions

Supramolecular Self‐Assembly of Nonlinear Amphiphilic and Double Hydrophilic Block Copolymers in Aqueous Solutions

Architecture of Multi-Component Copolymer Brushes: Synthesis, Solution Properties and Application for Nanodevices

Synthesis of amphiphilic copolymer brushes possessing alternating poly(methyl methacrylate) and poly(N‐isopropylacrylamide) grafts via a combination of ATRP and click chemistry

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