Cationic Interracial Polymerization of<i>p</i>-Methoxystyrene by Means of Triphenylmethylium Halide-Aerosil Initiation

Spange, Stefan; Heublein, G.; Simon, Frank

doi:10.1080/00222339108052149

Cited by 12 publications

(3 citation statements)

References 30 publications

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“…In recent years, surface modifications by polymers have been increasingly important for various applications ranging from biotechnology to advanced microelctronics. Graft polymerization starting with the initiating sites fixed on a surface is one of the most effective and versatile methods for this purpose, since surface properties can be widely changed by graft-polymerizing a variety of functional monomers. − Recently, some living polymerization techniques were successfully applied to surface-initiated graft polymerization to prepare a dense polymer brush. − We were the first to succeed in applying atom transfer radical polymerization (ATRP) to the graft polymerization on a solid surface and yielding a graft layer of low-polydispersity polymer with the highest graft density reported to date . Furthermore, we revealed that in such a graft layer polymer chains were highly extended in a good solvent, nearly to their full lengths, and that the properties of this high-density polymer brush were quite different and unpredictable from those of the “moderately dense” polymer brushes previously studied. 9c,d In addition to such parameters as graft density and the chain length and length distribution of graft polymer, the morphology of the grafted surface is also an important factor determining such surface properties as chemical reactivity, wettability, permeability, lubricity, biocompatibility, and electrical properties.…”

Section: Introductionmentioning

confidence: 99%

“…Graft polymerization starting with the initiating sites fixed on a surface is one of the most effective and versatile methods for this purpose, since surface properties can be widely changed by graftpolymerizing a variety of functional monomers. [1][2][3][4][5][6][7] Recently, some living polymerization techniques were successfully applied to surface-initiated graft polymerization to prepare a dense polymer brush. [8][9][10][11][12][13][14][15][16] We were the first to succeed in applying atom transfer radical polymerization (ATRP) 17 to the graft polymerization on a solid surface and yielding a graft layer of lowpolydispersity polymer with the highest graft density reported to date.…”

Section: Introductionmentioning

confidence: 99%

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Fabrication of Patterned High-Density Polymer Graft Surfaces. 1. Amplification of Phase-Separated Morphology of Organosilane Blend Monolayer by Surface-Initiated Atom Transfer Radical Polymerization

et al. 2002

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Patterned films of a low-polydispersity polymer densely end-grafted on a silicon substrate were fabricated for the first time by the combined use of the Langmuir−Blodgett (LB) and the surface-initiated atom transfer radical polymerization (ATRP) techniques: a blend monolayer of 2-(4-chlorosulfonylphenyl)ethyltrimethoxysilane (CTS: ATRP initiator) and n-octadecyltrimethoxysilane (OTS: noninitiator) was immobilized on a silicon wafer by the LB technique, and then the ATRP of methyl methacrylate was carried out on the modified wafer in the presence of the Cu/ligand complexes. Atomic force microscopic studies revealed that the CTS/OTS blend was immiscible and phase-separated into two monolayer phases: most OTS molecules aggregate with each other, forming a condensed-type monolayer domain with CTS molecules excluded from there almost perfectly, and the remaining OTS molecules are incorporated in the matrix region. This 2-dimensionally phase-separated structure was successfully amplified by the controlled growth of a high-density graft layer only on the matrix phase of CTS as a main component. The amplification by the ATRP technique was characterized by a sharp boundary between the grafted and ungrafted domains; as a measure of the spatial resolution, the boundary sharpness Δw was evaluated to be ca. 100 nm. The domain size in the phase-separated structure was independent of the mole fraction of CTS, while it could be changed by changing the pH of the subphase water: namely, the higher was the pH, the larger was the domain size. It was deduced that a change in pH of the subphase water gave rise to a change in the hydrolysis rate of the methoxysilyl groups into silanol groups and hence a change in the rate of condensation of the silanol groups into domains.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Fabrication of Patterned High-Density Polymer Graft Surfaces. 1. Amplification of Phase-Separated Morphology of Organosilane Blend Monolayer by Surface-Initiated Atom Transfer Radical Polymerization

et al. 2002

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“…Normally, the combination of silica and soluble polymers obtained by common cationic polymerization would be a system of low reactivity. However, it has been shown that cationic surface polymerization of cyclopentadiene (CPD) onto silica particles is a powerful tool to obtain new materials with advanced properties [9][10][11].…”

Section: Introductionmentioning

confidence: 99%

The versatile surface properties of poly(cyclopentadiene)-modified silica particles (PCPD-silica): XPS and electrokinetic studies

Simon

Jacobasch

Spange

1998

Colloid & Polymer Science

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Surface properties of poly(cyclopentadiene)-silica hybrid particles (PCPD-silica) were studied by means of XPS and electrokinetic measurements. The surfaces of PCPD-silica particles exhibit two different areas with different properties: bare silica holes and PCPD patches. The PCPD chains contain different functional groups such as alcohol and carbonyl groups that were identified by XPS. The PCPD chains are grafted covalently onto the silica surface via Si-O-C bonds created by the reaction of silanol groups and active PCPD chains. The amount of Si-O-C was examinated by means of XPS.The Br+nsted acidity of the residual silanol groups was determined by means of electrokinetic measurements. It was found that the pK values of the residual silanol groups increase with increasing polymer content on the particle surface.The surface acceptor strengths of the hybrid particles in non-aqueous liquids were investigated by the solvatochromic indicator bis(1,10-phenanthroline)-cis-dicyano-iron-II in 1,2-dichloroethane.

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Cationic coating polymerization of cyclopentadiene onto silica particles

Spange

Langhammer

1997

Macro Chemistry & Physics

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The cationic polymerization of cyclopentadiene (CPD) initiated by different initiators (triphenylmethyl chloride, triphenylmethyl bromide, methyl triflate, and trifluoroacetic acid) onto silica particles yields polycyclopentadiene (PCPD)-silica composites in high yield beside small amounts of soluble polymers. The novel PCPD-silica particles are characterized by UVNIS reflectance spectra and IR spectra. The percentage of coating (PG) is determined by combustion analysis and depends on the reaction temperature and the technical procedure of the polymerization. The influence of the initiator used and initiator/monomer ratio on the PG of the silica particles are investigated, too. It can be shown that the total amount of coating strongly depends on the initiator used. In case of trifluoroacetic acid initiation, particle aggregation takes place if the carbon content of the PCPD particles exceeds 15% carbon weight due to crosslinking between the PCPD layers of the coated silica particles, as evidenced by electron scanning microscopy.

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Cationic Interracial Polymerization ofp-Methoxystyrene by Means of Triphenylmethylium Halide-Aerosil Initiation

Cited by 12 publications

References 30 publications

Fabrication of Patterned High-Density Polymer Graft Surfaces. 1. Amplification of Phase-Separated Morphology of Organosilane Blend Monolayer by Surface-Initiated Atom Transfer Radical Polymerization

Fabrication of Patterned High-Density Polymer Graft Surfaces. 1. Amplification of Phase-Separated Morphology of Organosilane Blend Monolayer by Surface-Initiated Atom Transfer Radical Polymerization

The versatile surface properties of poly(cyclopentadiene)-modified silica particles (PCPD-silica): XPS and electrokinetic studies

Cationic coating polymerization of cyclopentadiene onto silica particles

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