Renewable Fabric Surface-Initiated ATRP Polymerizations: Towards Mixed Polymer Brushes

Raj, Wojciech; Russo, A.; Zhang, Yaoming; Chapelat, Julien; Pietrasik, Joanna

doi:10.3390/nano10030536

Cited by 4 publications

(4 citation statements)

References 46 publications

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“…Notably, ATRP is particularly successful in creating bottlebrush polymers, surface-grafted polymer brushes, and star polymers. [68][69][70][71][72][73]…”

Section: Reversible Addition-fragmentation Chain Transfer Polymerizationmentioning

confidence: 99%

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Non‐linear functional polymers containing selective/cleavable bonds: Synthesis and their biomedical applications

Rahimi,

Gałęziewska,

Jerczyński

et al. 2024

Polymers for Advanced Techs

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The growing interest in functional materials has resulted in the emergence of smart polymers, demonstrating practical performance in various applications especially for biomedical purposes. The properties of functional polymers are mainly determined by the presence of functional groups that differ from those in the main chains. While some polymers are naturally active and considered functional, others require modification for enhanced impact and functionality. Many functional polymers typically have a linear backbone, but very recently the attention has been shifted towards those with specific topologies and architecture, for example, bottlebrushes, stars, dendritic polymers, and gels. Over the past few years, there has been a rising emphasis on integrating selective bonds into complex polymer structures to enhance chain scission in single macromolecules. This review captures the most recent and promising approaches to the design of non‐linear functional polymers containing selective/cleavable bonds and discusses the potential of these materials for biomedical applications.

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“…Notably, ATRP is particularly successful in creating bottlebrush polymers, surface-grafted polymer brushes, and star polymers. [68][69][70][71][72][73]…”

Section: Reversible Addition-fragmentation Chain Transfer Polymerizationmentioning

confidence: 99%

“…This versatility positions ATRP as the most widely used polymerization method for synthesizing functional polymers with diverse architectures. Notably, ATRP is particularly successful in creating bottlebrush polymers, surface‐grafted polymer brushes, and star polymers 68–73 …”

Section: Approaches For Synthesis Of Functional Polymersmentioning

confidence: 99%

Non‐linear functional polymers containing selective/cleavable bonds: Synthesis and their biomedical applications

Rahimi,

Gałęziewska,

Jerczyński

et al. 2024

Polymers for Advanced Techs

Self Cite

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“…Surfaceinitiated atom transfer radical polymerization (SI-ATRP) is the most popular method among SI-RDRPs due to its well-described mechanism, compatibility with various monomers and substrates, as well as commercial availability of necessary reagents [2]. Furthermore, this method allows the formation of polymer brushes with controllable thickness and various architectures, such as homopolymer [3], block copolymer [4], loop [5], mixed [6] or ladderlike brushes [7]. Classical SI-ATRP requires the utilization of high amounts of copper-based catalyst, which is unfavorable in the case of biomedical and electronic applications of the brushes.…”

Section: Introductionmentioning

confidence: 99%

Preparation of Homopolymer, Block Copolymer, and Patterned Brushes Bearing Thiophene and Acetylene Groups Using Microliter Volumes of Reaction Mixtures

et al. 2021

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The synthesis of surface-grafted polymers with variable functionality requires the careful selection of polymerization methods that also enable spatially controlled grafting, which is crucial for the fabrication of, e.g., nano (micro) sensor or nanoelectronic devices. The development of versatile, simple, economical, and eco-friendly synthetic strategies is important for scaling up the production of such polymer brushes. We have recently shown that poly (3-methylthienyl methacrylate) (PMTM) and poly (3-trimethylsilyl-2-propynyl methacrylate) (PTPM) brushes with pendant thiophene and acetylene groups, respectively, could be used for the production of ladder-like conjugated brushes that are potentially useful in the mentioned applications. However, the previously developed syntheses of such brushes required the use of high volumes of reagents, elevated temperature, or high energy UV-B light. Therefore, we present here visible light-promoted metal-free surface-initiated ATRP (metal-free SI-ATRP) that allows the economical synthesis of PMTM and PTPM brushes utilizing only microliter volumes of reaction mixtures. The versatility of this approach was shown by the formation of homopolymers but also the block copolymer conjugated brushes (PMTM and PTPM blocks in both sequences) and patterned films using TEM grids serving as photomasks. A simple reaction setup with only a monomer, solvent, commercially available organic photocatalyst, and initiator decorated substrate makes the synthesis of these complex polymer structures achievable for non-experts and ready for scaling up.

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“…Surface-initiated ATRP techniques have been also successfully used for controlled decoration of various organic and inorganic surfaces leading to: homopolymer [ 18 ], copolymer [ 19 ], ladder-like [ 5 ], loop [ 20 ], gradient [ 21 ], or mixed brushes [ 22 ]. Surface-initiated ATRP techniques that use ppm amount of catalyst very often need addition of sacrificial initiator [ 23 ], which is required to maintain the control over the process, as low concentration of initiating groups on planar surfaces is not sufficient for effective regeneration of deactivator and shifting K ATRP (k a /k d ) towards deactivation process.…”

Section: Introductionmentioning

confidence: 99%

Surface-Initiated Photoinduced Iron-Catalyzed Atom Transfer Radical Polymerization with ppm Concentration of FeBr3 under Visible Light

et al. 2020

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Reversible deactivation radical polymerizations with reduced amount of organometallic catalyst are currently a field of interest of many applications. One of the very promising techniques is photoinduced atom transfer radical polymerization (photo-ATRP) that is mainly studied for copper catalysts in the solution. Recently, advantageous iron-catalyzed photo-ATRP (photo-Fe-ATRP) compatible with high demanding biological applications was presented. In response to that, we developed surface-initiated photo-Fe-ATRP (SI-photo-Fe-ATRP) that was used for facile synthesis of poly(methyl methacrylate) brushes with the presence of only 200 ppm of FeBr3/tetrabutylammonium bromide catalyst (FeBr3/TBABr) under visible light irradiation (wavelength: 450 nm). The kinetics of both SI-photo-Fe-ATRP and photo-Fe-ATRP in solution were compared and followed by 1H NMR, atomic force microscopy (AFM) and gel permeation chromatography (GPC). Brush grafting densities were determined using two methodologies. The influence of the sacrificial initiator on the kinetics of brush growth was studied. It was found that SI-photo-Fe-ATRP could be effectively controlled even without any sacrificial initiators thanks to in situ production of ATRP initiator in solution as a result of reaction between the monomer and Br radicals generated in photoreduction of FeBr3/TBABr. The optimized and simplified reaction setup allowed synthesis of very thick (up to 110 nm) PMMA brushes at room temperature, under visible light with only 200 ppm of iron-based catalyst. The same reaction conditions, but with the presence of sacrificial initiator, enabled formation of much thinner layers (18 nm).

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Renewable Fabric Surface-Initiated ATRP Polymerizations: Towards Mixed Polymer Brushes

Cited by 4 publications

References 46 publications

Non‐linear functional polymers containing selective/cleavable bonds: Synthesis and their biomedical applications

Non‐linear functional polymers containing selective/cleavable bonds: Synthesis and their biomedical applications

Preparation of Homopolymer, Block Copolymer, and Patterned Brushes Bearing Thiophene and Acetylene Groups Using Microliter Volumes of Reaction Mixtures

Surface-Initiated Photoinduced Iron-Catalyzed Atom Transfer Radical Polymerization with ppm Concentration of FeBr3 under Visible Light

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