Nanopatterns of poly(styrene-block-butyl acrylate) block copolymer brushes on the surfaces of exfoliated and intercalated clay layers

Zhao, Hanying; Farrell, Brendan P.; Shipp, Devon A.

doi:10.1016/j.polymer.2004.04.018

Cited by 72 publications

(64 citation statements)

References 35 publications

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“…On the basis of the ion exchange capacity and measurements of the specific surface area, 21 MMT contains ∼1site/nm The synthesis and ion exchange of BMP, an ATRP initiator, with MMT is a simple two-step synthesis that was previously described elsewhere. 5,22 It may be summarized as the addition of 2-bromoisobutyryl bromide to 11-bromo-1-undecanol and the subsequent addition of trimethyl amine to produce a cationic alkyl chain with a terminal halide. The synthesis of an analogous inert compound, DMP, uses 2,2-dimethyl acetyl chloride in place of 2-bromoisobutyryl bromide.…”

Section: Methodsmentioning

confidence: 99%

“…23 Styrene was purchased from Fisher Scientific, purified over basic alumina, and degassed prior to use. The unconfined ATRP of PS from either BBr or ethyl-2-methyl-2-bromopropionate (EBP) followed the procedure described in numerous articles by Matyjaszewski et al [1][2][3] SI-ATRP of PS from MMT was similar to the work of others, 5,22 with the addition of ultrasonication to enhance MMT tactoid dispersion. Monomer, initiator, Cu I Br, Cu II Br 2 , and PMDETA were mixed under N 2 in a round-bottomed flask with molar ratios of 1000:1:1:0.06:1.06, respectively.…”

Section: Methodsmentioning

confidence: 99%

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Influence of Graft Density on Kinetics of Surface-Initiated ATRP of Polystyrene from Montmorillonite

et al. 2009

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Here we report the kinetics of the surface-initiated atom transfer radical polymerization (ATRP) of styrene from the surface of functionalized montmorillonite clay as a function of graft density. Compared with analogous ATRP reactions with free initiator, we observe a seven-fold increase in the polymerization rate at the highest graft density, 1 chain/nm2, whereas bulk kinetics are recovered as the graft density is reduced. We hypothesize that this phenomenon is a consequence of local concentration heterogeneities that shift the ATRP equilibrium in favor of the active state and present a simple phenomenological kinetic model that accounts for our data. These findings present an important consideration relevant to the design of precisely defined molecular architectures from surfaces via surface-initiated ATRP. Disciplines Polymer Science CommentsReprinted with permission from Macromolecules 42 (2009) ReceiVed NoVember 6, 2008; ReVised Manuscript ReceiVed February 3, 2009 ABSTRACT: Here we report the kinetics of the surface-initiated atom transfer radical polymerization (ATRP) of styrene from the surface of functionalized montmorillonite clay as a function of graft density. Compared with analogous ATRP reactions with free initiator, we observe a seven-fold increase in the polymerization rate at the highest graft density, ∼1 chain/nm 2 , whereas bulk kinetics are recovered as the graft density is reduced. We hypothesize that this phenomenon is a consequence of local concentration heterogeneities that shift the ATRP equilibrium in favor of the active state and present a simple phenomenological kinetic model that accounts for our data. These findings present an important consideration relevant to the design of precisely defined molecular architectures from surfaces via surface-initiated ATRP.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Influence of Graft Density on Kinetics of Surface-Initiated ATRP of Polystyrene from Montmorillonite

et al. 2009

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“…The introduction of organic salts changes the chemical properties of silicate layer surfaces and increases their compatibility with polymers. The silicate layer surfaces of montmorillonite (MMT) as typical clay have been modified by various controlled living polymerization techniques, such as atom transfer radical polymerization [15][16][17][18], reversible additionfragmentation chain transfer polymerization [19][20][21], and nitroxide-mediated polymerization [22][23][24]. These polymerizations take place in the galleries with growing polymer chains spreading the distance between the silicate layers.…”

Section: Introductionmentioning

confidence: 99%

Melt-Processable Nanocomposites Grafting-From Platelet Surfaces by Vapor-Assisted Surface Polymerization

Andou

Nishida

2011

ISRN Nanotechnology

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One issue accompanying the melt-processing polymer/clay nanocomposites is the reaggregation of silicate platelets, which induces decreases in advantages of nanocomposites. To address this issue, vapor-assisted surface polymerization (VASP) method was applied with an initiator-attached and copolymerizable surfactant moiety-bound A-C18/C6MMT to obtain the exfoliated and intercalated nanocomposites using methylmethacrylate and styrene as vinyl monomers, respectively. The melt processing of the nanocomposites was carried out by a melt-compression molding method at 200• C. From XRD measurements, the C18/C6MMT-based nanocomposites showed no change in d-spacing even after melt processing, indicating the maintenance of the exfoliation and intercalation states. This maintenance must result from polymer chains grafting from the silicate layer surfaces, thus clearly confirming the anchoring effect of the copolymerizable surfactant moiety units.

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“…[8][9][10][11][12] Extremely fine separation of DNA can be achieved using nanopatterned surfaces. [13] Block copolymers [14][15][16][17][18][19][20][21] or mixtures of polymers [9,22] have been used as starting materials for the generation of nanopatterned and nanotopography controlled surfaces, to withstand environmental changes such as temperature, solvents, reactive chemical etching, absorption, etc. The nanotechniques for manufacturing nanopattern and nanotopography range from extremely simple ones such as rubbing the substrate [23] or Langmuir-Blodgett films, [24] up to modified AFM (electrostatic nanolithography [25] ) or TEM (carbothermal reduction) [26] analytical instrument operation.…”

Section: Introductionmentioning

confidence: 99%

Nanotopography Engineering on Homopolymeric Surfaces Using Cold Plasma Generated Charges

Manolache

Gutierrez

Hall

2010

Macromolecular Symposia

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Summary: Cold plasma as source for charged particles was used to induce nanotopographies on homopolymeric surfaces (nylon 12, PMMA, PMA, etc.). Hydrogen and helium plasmas were successfully used for surface nanoengineering of polymers using inductively coupled or atmospheric pressure non-equilibrium barrier discharge reactors. AFM analyses reveal the presence of nanotopographies on the treated surfaces. Physical factors control the process below the T g and chemical factors dominate the process above T g . Pyrolysis GC/MS analyses have been performed in order to obtain more information about the plasma processes. Cold plasma chemical processes, including charges effects are discussed as tools that open-up new ways for nanoengineering of the polymers' surfaces with specific functionalities and / or topography. Future nanomanufacturing techniques can generate anti-scratch, superhydrophobic or superhydrophilic properties on surface of every day use polymeric products by simple and convenient plasma enhanced processes.

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Nanopatterns of poly(styrene-block-butyl acrylate) block copolymer brushes on the surfaces of exfoliated and intercalated clay layers

Cited by 72 publications

References 35 publications

Influence of Graft Density on Kinetics of Surface-Initiated ATRP of Polystyrene from Montmorillonite

Influence of Graft Density on Kinetics of Surface-Initiated ATRP of Polystyrene from Montmorillonite

Melt-Processable Nanocomposites Grafting-From Platelet Surfaces by Vapor-Assisted Surface Polymerization

Nanotopography Engineering on Homopolymeric Surfaces Using Cold Plasma Generated Charges

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