Synthesis and Surface Characterization of Hydrophilic-Hydrophobic Block Copolymers Containing Poly(2,3-dihydroxypropyl methacrylate)

Mori, Hideharu; Hirao, Akira; Nakahama, Seiichi; Senshu, Kazuhisa

doi:10.1021/ma00093a010

Cited by 78 publications

(72 citation statements)

References 6 publications

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“…The change of the surface composition and properties of these amphiphilic graft as well as block copolymers, depending on the environment, particularly in contact with water, appears to be an important factor in their usefulness as biocompatible materials (4,5,20).…”

Section: Copolymerization Of the Macromonomers And Preparation Of Gramentioning

confidence: 99%

Syntheses and interfacial characterization of graft copolymers from styrene and 2-hydroxyethyl methacrylate that comprise either trunks or branches

Yoshida¹,

Itsuno²,

Ito³

1995

Can. J. Chem.

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Polystyrene (PS) and poly(2-hydroxyethyl methacrylate) (PHEMA) macromonomers with either p-vinylbenzyl or methacrylate end groups were prepared by living anionic polymerizations of styrene and 2-(trimethylsilyloxy)ethyl methacrylate, respectively, followed by appropriate end-capping. They were radically copolymerized with 2-hydroxyethyl methacrylate and styrene, respectively, to afford PS-g-PHEMA and PHEMA-g-PS, having PS trunks with PHEMA branches or the reverse architecture. 1H NMR spectra of the graft copolymers in deuterated methanol showed their micelle formation with PS and PHEMA chains as the core and the shell, respectively. In chloroform the reverse micelles were observed. Contact angle measurements of water on the graft copolymer films revealed that PS chains were generally dominant on the free surface. The films either cast from methanol or after immersion into water, however, were apparently wettable, indicating dominant PHEMA chains on the surface. Keywords: styrene, 2-hydroxyethyl methacrylate, graft copolymer, micelle formation, wettability.

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Section: Copolymerization Of the Macromonomers And Preparation Of Gramentioning

confidence: 99%

Syntheses and interfacial characterization of graft copolymers from styrene and 2-hydroxyethyl methacrylate that comprise either trunks or branches

Yoshida¹,

Itsuno²,

Ito³

1995

Can. J. Chem.

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“…This responsive behavior is similar to that exhibited by surfaces modified with grafted amphiphilic block copolymer molecules upon exposure to solvents or temperature. [21][22][23][24][25][26][27][28] Micelles offer additional advantages for surface modification because they are individual nanoscale entities that can be readily coated over a wide range of substrates.…”

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confidence: 99%

Block Copolymer Micelles as Switchable Templates for Nanofabrication

et al. 2006

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Block copolymer inverse micelles from polystyrene-block-poly-2-vinylpyridine (PS-b-P2VP) deposited as monolayer films onto surfaces show responsive behavior and are reversibly switchable between two states of different topography and surface chemistry. The as-coated films are in the form of arrays of nanoscale bumps, which can be transformed into arrays of nanoscale holes by switching through exposure to methanol. The use of these micellar films to act as switchable etch masks for the structuring of the underlying material to form either pillars or holes depending on the switching state is demonstrated.Block copolymers have been explored extensively as templates for nanofabrication. 1-3 Nanostructures form as a result of the microphase separation driven by chemical incompatibility between the constituent blocks of the copolymer. The morphology and dimensions of the nanostructures thus obtained are tunable with the suitable choice and length of the constituent polymer blocks. Nanoscale polymer etch masks were obtained from microphase-separated block copolymer thin films by selective degradation and removal of one of the blocks, whereas the other block serves as a lithographic mask to etch the underlying substrate. [4][5][6][7] Surface micelles that form through the preferred adsorption of one polymer block onto the surface have also been used to structure surfaces, and the as-coated film offers an inherent mass thickness contrast necessary for transferring structures by etching. 8,9 Block copolymers are furthermore well known to form micelles in solution when dissolved in selective solvents. 10,11 The soluble block forms a swollen corona in the solution phase shielding the insoluble block that forms a highly condensed core. These micelles can be spherical, cylindrical, or wormlike depending on the block ratios, the interfacial energy between the blocks, and the solvent quality. There have been several reports on the deposition of spherical micelles on surfaces to obtain arrays of functional centers that were used for making nanoparticle arrays 12-14 and other functional 15 or responsive 14,16 surfaces.Micellar films loaded with metal salts or nanoparticles derived from them have been used as etch masks to structure the underlying substrate. In the remarkable case of PS-b-P2VP micelles loaded with AuCl 4 -, the authors found an inversion of the relative etch rates upon reducing the included salt to gold nanoparticles, allowing the inversion of the etch contrast depending on the redox state of the mask. 17 We report in this letter the responsive behavior of an amphiphilic diblock copolymer micellar array that can be switched between two complementary surface topographies and polarities by simple means as well as its use as an etch mask for the structuring of the underlying silicon substrate. The complementary topographies obtained from the micellar film lead to complementary topographies in the silicon, resulting in either arrays of pillars or holes depending on the switching state of the micellar film (Figures...

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“…Mori et al [96] reported the switchability of amphiphilic block copolymers containing PS, poly(4-octylstyrene) or polyisoprene as a hydrophobic segment and poly(2,3-dihydroxypropyl methacrylate) [polyA C H T U N G T R E N N U N G (DIMA)] as a hydrophilic segment. Their copolymers were hydrophobic in air due to the enriched number of hydrophobic segments on the surface, but when soaked in water, hydrophilic groups were enriched on the surface.…”

Section: Environmental Switchingmentioning

confidence: 99%

Intelligent Control of Surface Hydrophobicity

et al. 2007

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Switchable surfaces are highly useful materials with surface properties that change in response to external stimuli. These surfaces can be employed in both research and industrial applications, where the ability to actively control surface properties can be used to develop smart materials and intelligent surfaces. Herein, we review a range of surfaces in which hydrophobicity can be controlled. We present the principal ideas of surface switching, discuss recent developments, explore experimental issues and examine factors that influence surface switching, including the nature of the stimuli, the underlying material, the morphology of the surface and the surrounding environment. We have categorised switchable surfaces according to the stimuli that trigger changes in surface hydrophobicity. These are electrically, electrochemically, thermally, mechanically, photo- and environmentally inducible surfaces. In addition, we review the use of chemical reactions to modify the properties of switchable surfaces and produce changes in the molecular structure and nanoscale features of the surface.

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Synthesis and Surface Characterization of Hydrophilic-Hydrophobic Block Copolymers Containing Poly(2,3-dihydroxypropyl methacrylate)

Cited by 78 publications

References 6 publications

Syntheses and interfacial characterization of graft copolymers from styrene and 2-hydroxyethyl methacrylate that comprise either trunks or branches

Syntheses and interfacial characterization of graft copolymers from styrene and 2-hydroxyethyl methacrylate that comprise either trunks or branches

Block Copolymer Micelles as Switchable Templates for Nanofabrication

Intelligent Control of Surface Hydrophobicity

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