Controlled Radical Polymerization of Methyl Methacrylate Initiated by an Alkyl Halide in the Presence of the Wilkinson Catalyst

Moineau, Georges; Granel, Claude; Dubois, Philippe; Jérôme, Robert; Teyssié, Philippe

doi:10.1021/ma971123f

Cited by 196 publications

(147 citation statements)

References 9 publications

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“…The resulting increase in the concentration of persistent radicals makes the subsequent trapping of all new transient radicals selective for the cross-coupled product. In addition to nitroxides used in NMP, other persistent radical species commonly used in living radical polymerization include metal complexes in atom transfer radical polymerization [64][65][66][67][68][69][70][71][72][73][74][75][76] and tertiary thiocarbonylderived radicals in reversible addition-fragmentation transfer [77][78][79][80] polymerization. In the course of polymerization, the concentration of transient polymeric carbon radicals remains very low, whereas the concentration of the persistent species remains higher.…”

Section: Introductionmentioning

confidence: 99%

Nitroxide decomposition: Implications toward nitroxide design for applications in living free‐radical polymerization

Nilsen

Braslau

2005

J. Polym. Sci. A Polym. Chem.

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ABSTRACT:Nitroxides bearing an a-hydrogen decompose upon heating in a bimolecular reaction. A new mechanism is proposed for the decomposition of t-butylisopropylphenyl nitroxide (TIPNO) involving the formation of a head-to-tail dimer, single electron transfer to form an oxammonium salt, epimerization to the corresponding nitrone, and elimination to form a conjugated oxime. This mechanism may provide insights into designing new nitroxides for use in controlled polymerization.

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Section: Introductionmentioning

confidence: 99%

Nitroxide decomposition: Implications toward nitroxide design for applications in living free‐radical polymerization

Nilsen

Braslau

2005

J. Polym. Sci. A Polym. Chem.

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“…Various ligands such as 2,2'-bipyridyl (bipy) are added to the reaction mixture or incorporated into the discrete metal components to solubilize and stabilize active species during polymerization. In addition to copper(I)-based systems, "living" radical polymerizations of (meth)acrylates can be carried out with complexes of ruthenium / aluminum oxide (132,133), nickel (134), rhodium (135), palladium (136), iron (137,138), and cobalt (139). The process may be carried out in solution, bulk, emulsion or dispersion in water, and on solid supports at a variety of temperatures.…”

Section: Atom Transfer Radical Polymerizationmentioning

confidence: 99%

The Organometallic Polymerization of (Meth)acrylates: An Overview

Boffa

2000

ACS Symposium Series

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Metal-mediated (meth)acrylate polymerizations provide a good example of the versatility and importance of transition metal catalysis in polymer design. This chapter surveys several of these processes with respect to "living" behavior, experimental condition and monomer restrictions, and types of polymer architectures available.In addition to anionic methods, Group Transfer Polymerization (GTP) with silyl enolates or zirconocenes, organolanthanide-and aluminum porphyrin-initiated polymer ization, and Atom Transfer Radical Polymerization (ATRP) are discussed.Polymethacrylate and polyacrylate materials play an important role in our society. Almost two billion pounds of polymer products based on acrylic esters are produced each year for applications such as window plastics, dental materials, paints, contact lenses, fibers, and viscosity modifiers.Polymethacrylates-particularly poly(methyl methacrylate) (PMMA)-possess high strength, high impact resistance, excellent heat and chemical stability, and a highly amorphous nature which results in excellent optical clarity. For these reasons, they are used widely as building plastics (Plexiglas, Lucite). Polyacrylates are less rigid due to their lower glass transition temperatures, and as latex emulsions form the basis for durable automobile and house paints and coatings. Random copolymers of (meth)acrylates with vinylidene chloride (Sarari), acrylonitrile, and ethylene find applications as clothing fibers, tubing, gaskets, disposable gloves, and heat-and oil-resistant automotive elastomers.Despite the commercial utility of polymethacrylates and polyacrylates, refinements in synthetic methodology these macromolecules have lagged behind that of other polymers. The great majority of acrylic ester products in use today are still produced by radical polymerization, which allows little if any control over the fine points of the polymerization process. This is the result of the traditionally illcontrolled nature of acrylate polymerization. While chain termination and transfer side reactions may be largely eliminated for other monomers, such as styrene and dienes, through the use of controlled anionic polymerization, the (meth)acrylate ester

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“…5 These hybrid species often display enhanced permeability and stability. 6,7 ''Living'' polymerization techniques, including nitroxide-mediated radical polymerization (NMRP), 8,9 atom transfer radical polymerization, [10][11][12][13][14][15][16][17][18][19] and reversible addition fragmentation transfer, [20][21][22][23][24][25] allow for the formation of polymers with predictable structures and molecular weights. The use of unimolecular initiators affords the opportunity to install synthetic handles on the polymer termini that can be used for pre-or postpolymerization modification.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of arylethyl‐functionalized N‐alkoxyamine initiators and use in nitroxide‐mediated radical polymerization

Hill

Braslau

2007

J. Polym. Sci. A Polym. Chem.

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New functionalized initiators have been synthesized and evaluated for use in nitroxide‐mediated radical polymerization. Well‐defined polymers have been made of polystyrene and poly(tert‐butyl acrylate). These functionalized initiators carry convenient handles for pre‐ or post‐polymerization modification. In particular, primary alcohol, protected carboxylic acid, and amine groups are ideally suited for coupling to peptides or oligosaccharides to prepare polymer–biomolecule hybrids.

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Controlled Radical Polymerization of Methyl Methacrylate Initiated by an Alkyl Halide in the Presence of the Wilkinson Catalyst

Cited by 196 publications

References 9 publications

Nitroxide decomposition: Implications toward nitroxide design for applications in living free‐radical polymerization

Nitroxide decomposition: Implications toward nitroxide design for applications in living free‐radical polymerization

The Organometallic Polymerization of (Meth)acrylates: An Overview

Synthesis of arylethyl‐functionalized N‐alkoxyamine initiators and use in nitroxide‐mediated radical polymerization

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