Novel photoinduced carbon-carbon bond formation via metal-alkyl and -enolate porphyrins-visible light-mediated polymerization of alkyl methacrylate catalyzed by aluminum porphyrin

Kuroki, Masahiko; Aida, Takuzo; Inoue, Shohei

doi:10.1021/ja00249a056

Cited by 100 publications

(43 citation statements)

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“…[7][8][9] However, only few metal porphyrins, which are well-soluble in organic media, mainly, cobalt, rhodium, aluminum complexes, allowing the radical polymerization of vinyl monomers under controlled mode, have been studied by now. [7][8][9][10][11] The goal of this work was the study of radical polymerization of vinyl monomers (by the example of methyl methacrylate (MMA) and styrene) initiated by azo-bis-isobutironitrile (AIBN) or benzoyl peroxide (BP) in the presence of various porphyrins and their metal complexes. М -Fe III , X -Cl (6); M -Co II (9) Porphyrins in Radical Polymerization Experimental MMA (Fluka) and styrene (Fluka) were distilled two times under reduced pressure: b.p.…”

Section: Introductionmentioning

confidence: 99%

Porphyrins and Their Metal Complexes in Radical Polymerization of Vinyl Monomers

Islamova¹,

Nazarova²,

Койфман³

2011

MHC

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Section: Introductionmentioning

confidence: 99%

Porphyrins and Their Metal Complexes in Radical Polymerization of Vinyl Monomers

Islamova¹,

Nazarova²,

Койфман³

2011

MHC

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“…A second main-group metal counterion strategy for living behavior was developed by Inoue and coworkers, who reported in 1987 that MMA could be polymerized to high yield and low polydispersity (< 1.2) with (tetraphenylporphinato)aluminum methyl [(TPP)AlMe] (122,123). This process utilizes visible light to activate the propagating aluminum-enolate bond through the porphyrin ring (Scheme 6), and was successfully employed for the preparation of block copolymers of MMA with «-butyl and r-butyl acrylate, methacrylonitrile, 8-valerolactone, and propylene oxide (122,124,125).…”

Section: Aluminum Porphyrin Initiatorsmentioning

confidence: 99%

“…This process utilizes visible light to activate the propagating aluminum-enolate bond through the porphyrin ring (Scheme 6), and was successfully employed for the preparation of block copolymers of MMA with «-butyl and r-butyl acrylate, methacrylonitrile, 8-valerolactone, and propylene oxide (122,124,125). Subsequently, it was found that aluminum-based Lewis acid additives could be used in place of visible light as activating agents (126).…”

Section: Aluminum Porphyrin Initiatorsmentioning

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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“…Sequential polymerizations of different epoxides with aluminum porphyrin initiator give the corresponding AB-and ABC-type block-copolyethers of controlled block lengths. Aluminum porphyrins also bring about living polymerizations of other monomers such as lactones with various ring sizes,(ll) lactide, (12) vinyl monomers such as methacrylic-, (13) acrylic esters and methacrylonitrile, and living alternating copolymerizations of epoxides with cyclic anhydrides (14) or carbon dioxide. (15) By virtue of such a wide applicability of the aluminum porphyrin …”

Section: With Metalloporphyrin Initiators Living and Immortal Polymementioning

confidence: 99%

Anionic Ring-Opening Polymerization

Inoue

Aida

1992

New Methods for Polymer Synthesis

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Novel photoinduced carbon-carbon bond formation via metal-alkyl and -enolate porphyrins-visible light-mediated polymerization of alkyl methacrylate catalyzed by aluminum porphyrin

Cited by 100 publications

References 0 publications

Porphyrins and Their Metal Complexes in Radical Polymerization of Vinyl Monomers

Porphyrins and Their Metal Complexes in Radical Polymerization of Vinyl Monomers

The Organometallic Polymerization of (Meth)acrylates: An Overview

Anionic Ring-Opening Polymerization

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