Living Radical Polymerization of Acrylates by Organocobalt Porphyrin Complexes

Wayland, Bradford B.; Poszmik, George; Mukerjee, Shakti L.; Fryd, Michael

doi:10.1021/ja00096a080

Cited by 522 publications

(426 citation statements)

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“…1 In comparison, Wayland et al reported alkylcobalt(III) porphyrin polymerization study, in which acrylic ester polymer bound cobalt porphyrin species were observed in 1 H nmr and those showed the controlled/living polymerization. 12,14 The difference between two metal porphyrins might come from the metal-carbon bond energies. The bond energy of the cobalt-carbon is typically 10 kcal/mole greater than that for the iron-carbon.…”

Section: Resultsmentioning

confidence: 99%

“…[11][12][13][14][15] However, substantial differences might exist for the two metals, as the cobalt-carbon bond energy is typically 10 kcal/mole greater than that for the iron-carbon bond in any given porphyrin and alkyl group. Also, as demonstrated in this report, iron(II) porphyrin is less prone to effect β-hydrogen abstraction in the growing polymer radical.…”

Section: Introductionmentioning

confidence: 99%

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Olefin Polymerization Activity and Crystal Structure of Alkyliron(Ⅲ) Porphyrin Complexes

Oh¹,

Swenson²,

Goff³

2003

Bulletin of the Korean Chemical Society

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Alkyliron(III) porphyrins, n-butyliron(III) tetraphenylporphyrin, (TPP)Fe-Bu and n-butyliron(III) tetrakis-(pentafluorophenyl)porphyrin, (F 20 TPP)Fe-Bu have been evaluated as suitable for olefin free-radical polymerization. Butyl radicals dissociated from n-butyliron(III) porphyrin initiated the polymerization reaction, but the ratio of the propagation was low. The GCMS analysis of the reaction mixture of nbutyliron(III) porphyrin and styrene has revealed several products containing two butyl groups, while traces of β-hydrogen-abstracted products were observed. The crystal structure of (TPP)Fe-Bu has been determined. The structure of the n-butyliron(III) porphyrin reveals the compound containing five-coordinated iron with the average Fe-N distance of 1.973(1) Å and Fe-C of 2.030(2) Å. The iron atom is displaced by 0.137Å from a four nitrogen mean plane. Crystal system is triclinic, and space group is P-1.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Olefin Polymerization Activity and Crystal Structure of Alkyliron(Ⅲ) Porphyrin Complexes

Oh¹,

Swenson²,

Goff³

2003

Bulletin of the Korean Chemical Society

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“…Cobalt mediated radical polymerization (CMRP) [45,46] is extensively studied especially for its high ability to control the polymerization of a large range of monomers including acrylic monomers [47][48][49][50] and vinyl esters [12,17,46,51,52]. Depending on the reaction conditions, the CMRP process follows a reversible termination (RT) mechanism (Eq.…”

Section: Introductionmentioning

confidence: 99%

In situ bidentate to tetradentate ligand exchange reaction in cobalt-mediated radical polymerization

Kermagoret

Jérôme

Detrembleur

et al. 2015

European Polymer Journal

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a b s t r a c tOrganometallic-mediated radical polymerization (OMRP) has seen a significant growth in the last years notably due to the development of new metal complexes, especially cobalt derivatives. Despite of this, none of the reported complexes offers optimal control for monomers with very different reactivity, which somewhat limits the synthesis of copolymers. In order to expand the scope of cobalt-mediated radical polymerization (CMRP), we investigated an in situ ligand exchange reaction for modulating the properties of the cobalt complex at the polymer chain-end and adjusting the CACo bond strength involved in the control process. With the aim of improving the synthesis of poly(vinyl acetate)-b-poly (n-butyl acrylate) copolymers, bidentate acetylacetonate ligands, which impart high level of control to the polymerization of vinyl acetate (VAc), were replaced in situ at the PVAcAcobalt chain-end by tetradentate Salen type ligands that are more suited to acrylates.

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“…Poly(styrene-b-poly(methyl methacrylate)-b-styrene) triblock copolymers were synthesized by anionic polymerization of MMA using a difunctional initiator, followed by the cationic polymerization of styrene [ 12,13]. Nitroxide-based initiators effectively polymerize styrenic monomers by a living free radical mechanism, while acrylates are polymerized efficiently by organo cobalt complexes [14]. In addition, copper halides complexed with either 2, 2'-bipyridine or a 4, 4'-disubstituted 2, 2'-bipyridine can catalyze the polymerization of both styrene and acrylate with a suitable initiator [15].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and thermal properties of triblock copolymers of methyl methacrylate using combination of anionic and controlled radical polymerization: Poly(methyl methacrylate) center block bearing different microstructures

Song

Pelletier

et al. 2012

E-Polymers

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ABA and/or ABC type triblock copolymers were synthesized by living anionic and controlled radical polymerization in which poly(methyl methacrylate) was used as central block. The structural composition of these block copolymers were determined by 1 H NMR. The block length/molecular weight and microstructure of these polymers were measured by SEC. The microstructure of resultant central alkyl methacrylate block can be tailored from highly syndiotactic to highly isotactic structure by varying the solvent and/or initiator. The thermal and rheological properties of center poly(methyl methacrylate) block and poly(styreneb-methyl methacrylate-b-styrene) tri block copolymers were studied in detail.

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Living Radical Polymerization of Acrylates by Organocobalt Porphyrin Complexes

Cited by 522 publications

References 0 publications

Olefin Polymerization Activity and Crystal Structure of Alkyliron(Ⅲ) Porphyrin Complexes

Olefin Polymerization Activity and Crystal Structure of Alkyliron(Ⅲ) Porphyrin Complexes

In situ bidentate to tetradentate ligand exchange reaction in cobalt-mediated radical polymerization

Synthesis and thermal properties of triblock copolymers of methyl methacrylate using combination of anionic and controlled radical polymerization: Poly(methyl methacrylate) center block bearing different microstructures

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