Architecture and solution properties of AB-type brush–block–brush amphiphilic copolymers via ATRP techniques

Ishizu, Koji; Satoh, Junichiro; Sogabe, Atsushi

doi:10.1016/j.jcis.2004.03.044

Cited by 77 publications

(76 citation statements)

References 28 publications

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“…1 H NMR spectrum shown in Figure 9 confirms the structure of β-CD-(PDMAEMA 28 ) 21 3 (α), -CH 2 -(β), -CH 3 (g), -CH 2 -(f), and -OCH 2 -(e) groups of the PDMAEMA units in the arms, respectively, indicating the presence of PDMAEMA chains [65]. While, in the 1 H NMR spectrum of the star block copolymer (Figure 10 Table 1, entry 5; M n = 97 100, Ð = 1.08) after purification (in CDCl 3 ) arms, respectively, indicating the presence of PBA chains [15].…”

Section: Thementioning

confidence: 54%

“…While, in the 1 H NMR spectrum of the star block copolymer (Figure 10 Table 1, entry 5; M n = 97 100, Ð = 1.08) after purification (in CDCl 3 ) arms, respectively, indicating the presence of PBA chains [15].…”

Section: Thementioning

confidence: 98%

“…Atom transfer radical polymerization (ATRP) is proven to be one of the most versatile reversible deactivation radical polymerization (RDRP) methods that enables the preparation of polymers with controlled molecular weights (MWs), narrow molecular weight distributions (M w /M n , MWDs), and targeted degrees of polymerization (DP) [1][2][3][4][5][6][7][8][9][10][11][12][13]. The advent of low amount catalyst ATRP system, such as simplified electrochemically mediated ATRP (seATRP) [14] offers more environmentally friendly reaction conditions for the synthesis of polymers [15].…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of cationic star polymers by simplified electrochemically mediated ATRP

Chmielarz¹

2016

Express Polym. Lett.

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Abstract. Cyclodextrin-based cationic star polymers were synthesized using β-cyclodextrin (β-CD) core, and 2-(dimethylamino)ethyl methacrylate (DMAEMA) as hydrophilic arms. Star-shaped polymers were prepared via a simplified electrochemically mediated ATRP (seATRP) under potentiostatic and galvanostatic conditions. The polymerization results showed molecular weight (MW) evolution close to theoretical values, and maintained narrow molecular weight distribution (MWD) of obtained stars. The rate of the polymerizations was controlled by applying more positive potential values thereby suppressing star-star coupling reactions. Successful chain extension of the ω-functional arms with a hydrophobic n-butyl acrylate (BA) formed star block copolymers and confirmed the living nature of the β-CD-PDMAEMA star polymers prepared by seATRP. Novelty of this work is that the β-CD-PDMAEMA-b-PBA cationic star block copolymers were synthesized for the first time via seATRP procedure, utilizing only 40 ppm of catalyst complex. The results from 1 H NMR spectral studies support the formation of cationic star (co)polymers.

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Section: Thementioning

confidence: 54%

Section: Thementioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

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Synthesis of cationic star polymers by simplified electrochemically mediated ATRP

Chmielarz¹

2016

Express Polym. Lett.

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“…39 The synthetic scheme is shown in Scheme 5 The procedure included the following steps: (1) ATRP of methacryloyl-terminated PEO (PEO-MC) gave well-defined PEO brush macroinitiator (formula P[(EO) 40 Br]), (2) subsequent ATRP of 2-hydroxyethyl methacrylate (HEMA) with this brush macroinitiator provided PEO brush-block-PHEMA (brush-block-coil) diblock copolymers (formula P[(EO) 40 -b-(HEMA) 30 ]), (3) esterification of the pendant hydroxy groups of PHEMA block with 2-bromoisobutyryl bromide yielded a block-type polyinitiators, brush-block-poly(2-(2-bromoisobutyryloxy)ethyl methacrylate) (PBIEM) (number of initiation sites per PHEMA block, N BIB ¼ 14), (4) ATRP of HEMA using brush-block-PBIEM as polyinitiator provided AB-type brush-block-brush amphiphilic copolymer P23. Table VII lists the characteristics of AB-type PEO brush-block-PHEMA brush copolymer brush P23.…”

Section: Block-type 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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“…However, the micellar behaviors of heterograft copolymers have been rarely studied except that Ishizu et al have synthesized amphiphilic heterograft brushes with PEG and PHEMA side chains, which demonstrated micelles similar to Janus-type. 42 To study the micellar behaviors of the heterograft copolymers herein with different compositions of PCL and PEG, the fluorescence technique has been employed and pyrene was used as a probe. As reported by Wilhelm et al, 47,48 pyrene molecules will transfer into hydrophobic microdomains with a concurrent change in the molecule's photophysical properties.…”

Section: Micellization Of Heterograft Copolymersmentioning

confidence: 99%

Synthesis, characterization and micellization of heterograft copolymers based on phosphoester functionalized macromonomers via “grafting through” method

Zhu

Sun

et al. 2011

J of Applied Polymer Sci

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Novel amphiphilic heterograft copolymers consisting of phosphoester functionalized PEG (phosPEG) and PCL (phosPCL) were synthesized by the ring-opening polymerization via ''grafting through'' method. The heterograft structure and thermal properties of these copolymers with various compositions were characterized by 1 H-NMR, 31 P NMR, size exclusion chromatography (SEC), and differential scanning calorimetry (DSC) in detail. These amphiphilic copolymers could self-assemble into micellar structures in aqueous solution, and their critical micellization concentrations (CMC) were determined to be 0.69-1.25 mg/L by fluorescence technique. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) measurements show that these heterograft copolymer micelles are spherical in shape with the particle size ranging from 20 to 60 nm, which has potential in biomedical application.

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Architecture and solution properties of AB-type brush–block–brush amphiphilic copolymers via ATRP techniques

Cited by 77 publications

References 28 publications

Synthesis of cationic star polymers by simplified electrochemically mediated ATRP

Synthesis of cationic star polymers by simplified electrochemically mediated ATRP

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

Synthesis, characterization and micellization of heterograft copolymers based on phosphoester functionalized macromonomers via “grafting through” method

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