Alkyne-Functional Homopolymers and Block Copolymers through Nitroxide-Mediated Free Radical Polymerization of 4-(Phenylethynyl)styrene

Sessions, Laura B.; Mı̂inea, Liliana A.; Ericson, Kjell D.; Glueck, David S.; Grubbs, Robert B.

doi:10.1021/ma048793n

Cited by 32 publications

(33 citation statements)

References 24 publications

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“…The vinylic protons of the methacrylate moiety of the monomer also vanished. Alkyne functions are known to polymerize by free RP19 and during the nitroxide‐mediated polymerization40 process, whereas they are stable during the RAFT polymerization 41, 42. To prove that the triple bonds stay unaffected during the RAFT polymerization, 13 C NMR spectra were recorded.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and characterization of polymethacrylates containing conjugated oligo(phenylene ethynylene)s as side chains

Breul

Schäfer

Teichler

et al. 2012

J. Polym. Sci. A Polym. Chem.

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In order to form suitable systems designed for resonance energy transfer, a series of monodisperse methacrylate‐based monomers containing rigid π‐conjugated oligo(phenylene ethynylenes) with different sizes of the conjugated systems (M1–M3), and therefore different optoelectronic properties, were synthesized and subsequently polymerized using the reversible addition–fragmentation chain transfer polymerization technique (P1–P3). In addition, these oligomers were also copolymerized with methyl methacrylate. The obtained polymers were characterized by 1H NMR spectroscopy, size exclusion chromatography, and analytical ultracentrifugation. The photophysical properties of the polymers were studied by UV–vis absorption and emission spectroscopy in diluted solutions as well as in thin films and compared to the photophysics of the corresponding monomers. Thereby, changes going from monomeric to polymeric systems could be detected in fluorescence quantum yields and lifetimes pointing to energy trapping, e.g., energy transfer. Donor–acceptor copolymers containing different numbers of monomeric units within the side chain exhibit differences in the emission spectra, indicating that energy trapping in polymers is very sensitive to structural properties such as the chain length. UV–vis absorption spectroscopy as well as time‐resolved lifetime studies indicate intrapolymer and interpolymer energy transfer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

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Section: Resultsmentioning

confidence: 99%

Synthesis and characterization of polymethacrylates containing conjugated oligo(phenylene ethynylene)s as side chains

Breul

Schäfer

Teichler

et al. 2012

J. Polym. Sci. A Polym. Chem.

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“…91,94,95 As initial copolymer species, we are examining ABC triblock copolymers containing alkyne-functional groups in one block, for the specific covalent attachment of metal complexes, along with the PVP blocks used in many of the studies described previously for metal coordination. 96 The connection of these two blocks with a nonfunctional center (B) block such as PS should allow the formation of a self-assembled polymer architecture, which might then enable the incorporation of two different metal species and facilitate, for example, the discrete inclusion of gold (complexed with the PVP block as the pyridinium tetrachloroaurate salt) and cobalt species (linked to the alkyne-functional block as the dicobalt hexacarbonyl complex) 97,98 within separate ordered nanometer-scale domains of the bulk block copolymer (Fig.…”

Section: Toward the Arrangement Of Multiple Metalsmentioning

confidence: 99%

“…3), through nitroxide-mediated living free-radical polymerization methods. 95,106,107 Although the component blocks of the ultimately targeted triblock copolymers can all be prepared by living anionic polymerization, specific block sequences in which a PS block sits between PVP and poly(alkyne-functional monomer) blocks are only readily accessible through radical methodologies. 108,109 Initial studies of these alkyne-functional monomers proved successful for the preparation of polymers with predictable molecular weights and narrow molecular weight distributions, but only at low-to-moderate monomer conversions.…”

Section: Toward the Arrangement Of Multiple Metalsmentioning

confidence: 99%

“…A limited range of polystyrene-block-poly(alkynefunctional monomer) diblock copolymers were successfully prepared through polymerization to incomplete conversion before it was found that free nitroxide and alkyne-functional monomers are capable of undergoing oxidative side reactions that introduce potential initiating sites into monomer units and decrease the concentration of free nitroxide in the polymerization system. 95 Likewise, a range of PVP-PS-PAFm triblock copolymers have been prepared by the polymerization of alkyne-functional styrene derivatives (Fig. 3) from alkoxyamine-terminal PVP-PS diblock copolymers prepared by the sequential nitroxide-mediated polymerization of 2-vinylpyridine and styrene.…”

Section: Toward the Arrangement Of Multiple Metalsmentioning

confidence: 99%

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Hybrid metal–polymer composites from functional block copolymers

Grubbs

2005

J. Polym. Sci. A Polym. Chem.

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142

102

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ABSTRACT:The combination of metals and polymers in hybrid materials is a research area of great current interest. A number of methods for controlling the positioning of metallic species within polymer matrices on the nanometer scale have been developed. This highlight focuses on the use of functional block copolymers for the localization of metal species, especially nanoparticles, on the nanometer scale through block copolymer phase segregation. Research from the author's group on the use of alkyne-functional block copolymers for the preparation of cobalt-containing materials is discussed in this context.

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“…Other functional polymer brushes, in addition to active esters, have been synthesized for post-polymerization modification, such as epoxides [60][61][62][63][64][65][66], activated alkenes [67][68][69], thiols [70,71], pyridyldisulfides [32,[72][73][74], aldehydes and ketones [75][76][77][78][79], and alkyne/azide cycloaddition [80][81][82][83][84][85][86][87][88][89][90]. The use of alkyne/azide cycloaddition chemistry in the post-polymerization modification of polymer brushes is an additional functionalization strategy to active esters [91,92].…”

Section: Introduction 355mentioning

confidence: 99%

Post‐polymerization Modification of Polymer Brushes

Orski

Sheppard

Arnold

et al. 2012

Functional Polymers by Post‐Polymerization Modification

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IntroductionPolymer thin films are a highly specialized class of polymers on surfaces that range in thickness from several nanometers to micrometers. The chemical composition and conformation of the polymer chains at the surface can dictate interfacial properties such as adhesion, friction, wetting, and absorption of molecules from the environment. Ultimately, techniques that afford polymer coatings that are easily tunable provide the most versatility to develop a wide array of surfaces. Specialized surfaces such as arrays and sensors provide an insight into the development of small-scale sensors and devices for fields such as biomaterials science and nanotechnology [1][2][3][4][5][6][7].Polymeric thin films are attached to the surface in one of the two ways: through physical deposition of a thin film (physisorption) or by covalent attachment of the polymer chains to the surface (chemisorption). Weak intermolecular forces between the polymer thin film and the substrate govern surface modification by physisorption. Physisorption can lead to failure of the thin film under nonideal conditions by delamination, dewetting, desorption, and displacement [8]. In contrast, covalent attachment of a polymer thin film to the surface provides enhanced stability to polymer surface modification over physical absorption methods. Polymer brushes consist of macromolecular chains, in which covalent bonds tether the chains to the surface with a large grafting density to alter the unperturbed solution dimensions of the chains [9]. Films generated from polymer brushes exhibit unique surface phenomena that are advantageous in controlling physical properties such as wetting, phase segregation, absorption of molecules and macromolecules, lubrication, and diffusion control [7].These unique properties of polymer brushes are dictated by the extended conformation of the dense, ordered grafting on the surface. The polymer chains extend to balance the free energy associated with chain stretching and chain-solvent interactions. The entropic energy associated with a random walk configuration of the polymer chains favors short, low grafting density brushes. In contrast, a brush will extend to be energetically favorable in a highly solvated,

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Alkyne-Functional Homopolymers and Block Copolymers through Nitroxide-Mediated Free Radical Polymerization of 4-(Phenylethynyl)styrene

Cited by 32 publications

References 24 publications

Synthesis and characterization of polymethacrylates containing conjugated oligo(phenylene ethynylene)s as side chains

Synthesis and characterization of polymethacrylates containing conjugated oligo(phenylene ethynylene)s as side chains

Hybrid metal–polymer composites from functional block copolymers

Post‐polymerization Modification of Polymer Brushes

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