Formation of conjugated polymer brushes by surface-initiated catalyst-transfer polycondensation

Sontag, S. Kyle; Marshall, Nicholas; Locklin, Jason

doi:10.1039/b907264k

Cited by 93 publications

(106 citation statements)

References 23 publications

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“…It was also demonstrated that the SI-KCTP from functional block copolymers is a promising tool to nanostructure thin films with polymer brushes (Scheme 11). Sontag et al [49] and Marshall et al [50] used mixtures of Ni(cod) 2 and phosphorous ligands to generate Ni(0) species Scheme 11. Approaches to surface-initiated KCTP: grafting from P4VP-b-PS(I) adsorbed on silica surfaces.…”

Section: Polymer Brushes and Surface Initiated Polymerizationmentioning

confidence: 99%

Kumada Catalyst‐Transfer Polycondensation: Mechanism, Opportunities, and Challenges

Kiriy

Senkovskyy

Sommer

2011

Macromol. Rapid Commun.

225

178

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Kumada catalyst-transfer polycondensation (KCTP) is a new but rapidly developing method with great potential for the preparation of well-defined conjugated polymers (CPs). The recently discovered chain-growth mechanism is unique among the various transition metal-catalyzed polycondensations, and has thus attracted much attention among researchers. Most progress is found in the areas of mechanism and external initiation via new initiators, but also the number of monomers other than thiophene that can be polymerized is steadily increasing. Accordingly, the variety of CP chain architectures is increasing as well, and a considerable contribution of KCTP toward more efficient materials can be expected in the future. This review critically focuses on very recent progress in the synthesis of CPs and the mechanism of KCTP, and is finally aimed at providing a comprehensive picture of this exciting polymerization method.

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Section: Polymer Brushes and Surface Initiated Polymerizationmentioning

confidence: 99%

Kumada Catalyst‐Transfer Polycondensation: Mechanism, Opportunities, and Challenges

Kiriy

Senkovskyy

Sommer

2011

Macromol. Rapid Commun.

225

178

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“…Then, lauryl methacrylate monomers were clicked onto the monoliths using either heat or UV initiation. Thiol-yne and CuAAC reactions were also utilized to achieve reactive porous polymer monoliths [8,124]. Zhang and coworkers produced poly(glycidyl methacrylate-codivinylbenzene), poly(GMA-co-DVB), and poly(vinylbenzyl chloride-codivinylbenzene), (poly(VBC-co-DVB), monoliths to provide the reactive sites for click chemistry [29].…”

Section: Polymeric Monolithic Columnsmentioning

confidence: 99%

Post-polymerization Modification of Surface-Bound Polymers

Théato

2015

Controlled Radical Polymerization at and From Solid Surfaces

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Surfaces that have been intricately functionalized with reactive polymers have attracted scientific attention recently because of their potential use in a broad range of applications. Polymers containing chemically reactive functional groups can be utilized for subsequent modification of various surfaces. Reactive polymeric surfaces can be produced by surface-initiated polymerization, such as atom transfer radical polymerization, nitroxide-mediated polymerization, and ring-opening metathesis polymerization. Such surfaces can subsequently undergo postpolymerization modification to alter their physicochemical properties. Postpolymerization modification has a number of advantages, including the fact that diverse polymer structures are rapidly accessible without individual synthesis; polymerization of new functional monomers can produce a variety of surfaces and interfaces; and other materials can be easily modified, which would be difficult using conventional direct polymerization. In addition, the libraries of chemical reactions and materials that can be used in post-polymerization modifications are abundant. Therefore, post-polymerization modification opens up new platforms for the facile and versatile modification of various surfaces. This chapter focuses on a discussion of post-polymerization modification of various surface-bound polymers, from planar surfaces to three-dimensional objects, and on the extended applications of the reactive surfaces.

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“…The preparation of such high-molecular-weight materials are also supportive of a chain growth mechanism. Ni(COD) 2 , in the presence of PPh 3 , has also been used to prepare initiators from surface-bound thienyl bromides [72]. Kiriy and coworkers have also investigated the use of external initiators containing aryl bromide groups to determine the extent of the ''ring walk'' of the associated Ni(0) catalyst (Scheme 7.11) [73].…”

Section: Initiation and Catalyst Transfer Propagationmentioning

confidence: 99%

The Synthesis of Conjugated Polythiophenes by K umada Cross‐Coupling

Koch

Heeney

2012

Materials Science and Technology

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Conjugated polymers have been the subject of intensive research efforts over the past few decades. Much of this interest has stemmed from the fact that such materials combine the inherent processibility and mechanical robustness associated with polymers, with the electronic properties more typically associated with inorganic semiconductors. Thus, such materials may allow the fabrication of electronic devices on a variety of flexible or conformable surfaces, by a range of potentially low-cost and large-area deposition techniques such as printing. Possible applications include field effect transistors for display backplanes, organic solar cells, electrochromic displays, chemical sensors, and polymeric light-emitting diodes [1].Within the realms of conjugated polymer research, thiophene-containing materials have been one of the most widely investigated classes for many of the above applications [2,3]. Thiophene is a cheap and widely available electron-rich, planar aromatic heterocycle which is readily functionalized by range of chemistries. As a result, it can be copolymerized with a variety of aromatic comonomers to generate polymers with extended π-electron delocalization along the backbone. The alternating double and single bonds of the delocalized conjugated system are nondegenerate, leading to an energy band gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). For many of the optoelectronic applications outlined above, the absolute energy levels of the HOMO and LUMO, as well as the band gap between them, are important parameters affecting device performance. As such, major research efforts have been devoted to understanding how chemical structure can influence the electronic delocalization of conjugated polymers. Whilst these factors are complex, they can be related to points such as the attachment of electron-donating/-withdrawing substituents to the polymer backbone, the degree of backbone planarity (and, therefore, the π-electron overlap and delocalization), and the nature and aromaticity of any comonomers included in the polymer backbone.

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Formation of conjugated polymer brushes by surface-initiated catalyst-transfer polycondensation

Abstract: Electroactive conjugated polymer brushes of poly(thiophene) and poly(phenylene) have been prepared via a surface-initiated Kumada-type polycondensation reaction, yielding films with a thickness up to 42 nm.

Cited by 93 publications

References 23 publications

Kumada Catalyst‐Transfer Polycondensation: Mechanism, Opportunities, and Challenges

Kumada Catalyst‐Transfer Polycondensation: Mechanism, Opportunities, and Challenges

Post-polymerization Modification of Surface-Bound Polymers

The Synthesis of Conjugated Polythiophenes by K umada Cross‐Coupling

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