Catalysis of chain transfer and oligometer structure in radical polymerization of styrene in the presence of cobalt complexes of porphyrins

Smirnov, B.R.; Plotnikov, V.D.; Ozerkovskii, B.V.; Roshchupkin, V.P.; Yenikolopyan, N.S.

doi:10.1016/0032-3950(81)90056-3

Cited by 32 publications

(41 citation statements)

References 2 publications

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“…All efforts to separate out these products from solution were unsuccessful. It is shown in [2][3][4][5] by Smirnov et al that decrease of molecular masses is due to cobalt porphyrin catalyzed chain transfer reactions on monomer.…”

Section: Cobalt Porphyrins In Radical Polymerization Of Vinyl Monomersmentioning

confidence: 99%

“…[2][3][4][5][6] Thus, catalytic chain transfer to the monomer and catalytic inhibition were discovered in the polymerization of methacrylates carried out in the presence of cobalt porphyrins. [2][3][4][5] It was found by B.B. Wayland and M. Fryd that cobalt complex of tetramesitylporphyrin initiates polymerization of acrylates leading to the formation of homopolymers and block copolymers.…”

Section: Introductionmentioning

confidence: 99%

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Porphyrins and Their Metal Complexes in Radical Polymerization of Vinyl Monomers

Islamova¹,

Nazarova²,

Койфман³

2011

MHC

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Section: Cobalt Porphyrins In Radical Polymerization Of Vinyl Monomersmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Porphyrins and Their Metal Complexes in Radical Polymerization of Vinyl Monomers

Islamova¹,

Nazarova²,

Койфман³

2011

MHC

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“…[1][2][3] The catalyst is usually a low spin Co(II) species which is able to catalyze the chain transfer to monomer reaction in the free-radical homopolymerization [4][5][6] of methacrylates, amethylstyrene, styrenes. Cobaloxime boron fluoride (CoBF, Scheme 1) is a typical example of a highly active CCT catalyst that is frequently used in academic studies.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Chain Transfer Copolymerization of Methyl Methacrylate and Butyl Acrylate

Pierik

Herk

2003

Macro Chemistry & Physics

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In this work it is shown that catalytic chain transfer is a very efficient way of controlling molecular weight in the copolymerization of methyl methacrylate (MMA) and butyl acrylate (BA). The experimental data are compared to a previously developed model based on copolymerization kinetics and the mechanisms for catalytic chain transfer and for cobalt‐mediated living radical polymerization that can describe the observed transfer constants. Secondly, it is shown that the presence of a catalytic chain transfer agent does not affect the reactivity ratios within the concentration range studied. Finally, the effect of conversion and therewith composition drift on the catalytic chain transfer polymerization of MMA and BA is investigated and it is shown that under the conditions employed in the experiments a certain degree of macromer copolymerization is present at high partial conversions of MMA.

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“…In the past two decades catalytic chain transfer (CCT) has emerged as a useful, industrial applicable technique to prepare low molecular weight macromonomers 1–3. The catalyst is usually a low‐spin Co(II) species able to catalyze the chain transfer to monomer reaction in the free‐radical homopolymerization4–6 of methacrylates, α‐methylstyrene, and styrenes, and in the copolymerization with other monomers like acrylates 7.…”

Section: Introductionmentioning

confidence: 99%

High‐conversion catalytic chain transfer polymerization of methyl methacrylate

Pierik

Herk

2003

J of Applied Polymer Sci

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ABSTRACT:In this work the effects of conversion on the apparent catalyst activity in the catalytic chain transfer polymerization of methyl methacrylate are reported. Several mechanisms are discussed that may explain the experimental observations. The discussion is supported with computer simulations using Predici software. It is shown that the experimental decrease in weight average molecular weight with conversion is smaller than the decrease obtained in simulations. The most likely cause for this discrepancy is slow catalyst deactivation. The half-life of CoBF under the reported conditions was determined to be about 10 h. Furthermore, the effect of acetic acid (HAc) and benzoyl peroxide (BPO) on the evolution of the molecular weight distribution is investigated. Both HAc and BPO enhance catalyst deactivation. For HAc, catalyst deactivation scales with the square root of its concentration. BPO-enhanced deactivation depends linearly on its concentration.

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Catalysis of chain transfer and oligometer structure in radical polymerization of styrene in the presence of cobalt complexes of porphyrins

Cited by 32 publications

References 2 publications

Porphyrins and Their Metal Complexes in Radical Polymerization of Vinyl Monomers

Porphyrins and Their Metal Complexes in Radical Polymerization of Vinyl Monomers

Catalytic Chain Transfer Copolymerization of Methyl Methacrylate and Butyl Acrylate

High‐conversion catalytic chain transfer polymerization of methyl methacrylate

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