Chain transfer in pulsed laser polymerization of methylmethacrylate in the presence of different cobalt (II) [Co(dmg-2H)2 (BF2)2] and [Co(afdo-2H)2 (BF2)2] complexes

M. Sakhawat Hussain; S. A. Awan; Z. S. Seddigi; M. W. Ashraf; M. A. Khan

doi:10.1016/j.jphotochem.2006.03.032

Chain transfer in pulsed laser polymerization of methylmethacrylate in the presence of different cobalt (II) [Co(dmg-2H)₂ (BF₂)₂] and [Co(afdo-2H)₂ (BF₂)₂] complexes

M. Sakhawat Hussain
, S. A. Awan
, Z. S. Seddigi
, M. W. Ashraf
, M. A. Khan^*

^*Corresponding author for this work

King Fahd University of Petroleum & Minerals

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

Abstract

Methylmethacrylate (MMA) was polymerized at 25 °C with excimer laser (λ = 308 nm) in the presence of different Co(II) chain transfer agents, bis(boron difluorodimethylglyoximate) cobaltate(II) [Co(dmg-2H)₂ (BF₂)₂] (henceforth called catalyst (1)) and bis(boron difluorodialphafurilglyoximate) cobaltate(II) [Co(afdo-2H)₂ (BF₂)₂] (henceforth called catalyst (2)) used separately, with 2,2′-Azobis-(2-methylpropionitrile) [AIBN] as an initiator. The polymer (PMMA) formed in this study was characterized using GPC, ¹H NMR, ¹³C NMR, and DEPT 135. The value of chain transfer constant (C_s) was higher for catalyst (1) than catalyst (2) by a factor of 5. The higher character of "living free radical polymerization", as evident from the low values of polydispersity index (PDI), was observed mainly for catalyst (2). Both steric and electronic factors supported by IR and UV-vis spectra for the two catalysts indicate that catalyst (2) is a weaker nucleophile as compared to catalyst (1) forming a weaker Co-C bond between this catalyst and growing polymer chain indicating more living polymerization for the catalyst (2).

Original language	English
Pages (from-to)	58-65
Number of pages	8
Journal	Journal of Photochemistry and Photobiology A: Chemistry
Volume	184
Issue number	1-2
DOIs	https://doi.org/10.1016/j.jphotochem.2006.03.032
State	Published - 15 Nov 2006

Bibliographical note

Funding Information:
We gratefully acknowledge the support provided by KFUPM, and the Laser Research Laboratories (College of Sciences) for use of the excimer laser, and the Center for Refining and Petrochemicals of the Research Institute for GPC analysis.

Keywords

Chain transfer constant
Cobalt (II) catalysts
Methylmethacrylate
Pulsed laser polymerization

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering
General Physics and Astronomy

Access to Document

10.1016/j.jphotochem.2006.03.032

Cite this

Hussain, M. S., Awan, S. A., Seddigi, Z. S., Ashraf, M. W., & Khan, M. A. (2006). Chain transfer in pulsed laser polymerization of methylmethacrylate in the presence of different cobalt (II) [Co(dmg-2H)₂ (BF₂)₂] and [Co(afdo-2H)₂ (BF₂)₂] complexes. Journal of Photochemistry and Photobiology A: Chemistry, 184(1-2), 58-65. https://doi.org/10.1016/j.jphotochem.2006.03.032

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title = "Chain transfer in pulsed laser polymerization of methylmethacrylate in the presence of different cobalt (II) [Co(dmg-2H)2 (BF2)2] and [Co(afdo-2H)2 (BF2)2] complexes",

abstract = "Methylmethacrylate (MMA) was polymerized at 25 °C with excimer laser (λ = 308 nm) in the presence of different Co(II) chain transfer agents, bis(boron difluorodimethylglyoximate) cobaltate(II) [Co(dmg-2H)2 (BF2)2] (henceforth called catalyst (1)) and bis(boron difluorodialphafurilglyoximate) cobaltate(II) [Co(afdo-2H)2 (BF2)2] (henceforth called catalyst (2)) used separately, with 2,2′-Azobis-(2-methylpropionitrile) [AIBN] as an initiator. The polymer (PMMA) formed in this study was characterized using GPC, 1H NMR, 13C NMR, and DEPT 135. The value of chain transfer constant (Cs) was higher for catalyst (1) than catalyst (2) by a factor of 5. The higher character of {"}living free radical polymerization{"}, as evident from the low values of polydispersity index (PDI), was observed mainly for catalyst (2). Both steric and electronic factors supported by IR and UV-vis spectra for the two catalysts indicate that catalyst (2) is a weaker nucleophile as compared to catalyst (1) forming a weaker Co-C bond between this catalyst and growing polymer chain indicating more living polymerization for the catalyst (2).",

keywords = "Chain transfer constant, Cobalt (II) catalysts, Methylmethacrylate, Pulsed laser polymerization",

author = "Hussain, \{M. Sakhawat\} and Awan, \{S. A.\} and Seddigi, \{Z. S.\} and Ashraf, \{M. W.\} and Khan, \{M. A.\}",

note = "Funding Information: We gratefully acknowledge the support provided by KFUPM, and the Laser Research Laboratories (College of Sciences) for use of the excimer laser, and the Center for Refining and Petrochemicals of the Research Institute for GPC analysis. ",

year = "2006",

month = nov,

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doi = "10.1016/j.jphotochem.2006.03.032",

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Chain transfer in pulsed laser polymerization of methylmethacrylate in the presence of different cobalt (II) [Co(dmg-2H)₂ (BF₂)₂] and [Co(afdo-2H)₂ (BF₂)₂] complexes. / Hussain, M. Sakhawat; Awan, S. A.; Seddigi, Z. S. et al.
In: Journal of Photochemistry and Photobiology A: Chemistry, Vol. 184, No. 1-2, 15.11.2006, p. 58-65.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Chain transfer in pulsed laser polymerization of methylmethacrylate in the presence of different cobalt (II) [Co(dmg-2H)2 (BF2)2] and [Co(afdo-2H)2 (BF2)2] complexes

AU - Hussain, M. Sakhawat

AU - Awan, S. A.

AU - Seddigi, Z. S.

AU - Ashraf, M. W.

AU - Khan, M. A.

N1 - Funding Information: We gratefully acknowledge the support provided by KFUPM, and the Laser Research Laboratories (College of Sciences) for use of the excimer laser, and the Center for Refining and Petrochemicals of the Research Institute for GPC analysis.

PY - 2006/11/15

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N2 - Methylmethacrylate (MMA) was polymerized at 25 °C with excimer laser (λ = 308 nm) in the presence of different Co(II) chain transfer agents, bis(boron difluorodimethylglyoximate) cobaltate(II) [Co(dmg-2H)2 (BF2)2] (henceforth called catalyst (1)) and bis(boron difluorodialphafurilglyoximate) cobaltate(II) [Co(afdo-2H)2 (BF2)2] (henceforth called catalyst (2)) used separately, with 2,2′-Azobis-(2-methylpropionitrile) [AIBN] as an initiator. The polymer (PMMA) formed in this study was characterized using GPC, 1H NMR, 13C NMR, and DEPT 135. The value of chain transfer constant (Cs) was higher for catalyst (1) than catalyst (2) by a factor of 5. The higher character of "living free radical polymerization", as evident from the low values of polydispersity index (PDI), was observed mainly for catalyst (2). Both steric and electronic factors supported by IR and UV-vis spectra for the two catalysts indicate that catalyst (2) is a weaker nucleophile as compared to catalyst (1) forming a weaker Co-C bond between this catalyst and growing polymer chain indicating more living polymerization for the catalyst (2).

AB - Methylmethacrylate (MMA) was polymerized at 25 °C with excimer laser (λ = 308 nm) in the presence of different Co(II) chain transfer agents, bis(boron difluorodimethylglyoximate) cobaltate(II) [Co(dmg-2H)2 (BF2)2] (henceforth called catalyst (1)) and bis(boron difluorodialphafurilglyoximate) cobaltate(II) [Co(afdo-2H)2 (BF2)2] (henceforth called catalyst (2)) used separately, with 2,2′-Azobis-(2-methylpropionitrile) [AIBN] as an initiator. The polymer (PMMA) formed in this study was characterized using GPC, 1H NMR, 13C NMR, and DEPT 135. The value of chain transfer constant (Cs) was higher for catalyst (1) than catalyst (2) by a factor of 5. The higher character of "living free radical polymerization", as evident from the low values of polydispersity index (PDI), was observed mainly for catalyst (2). Both steric and electronic factors supported by IR and UV-vis spectra for the two catalysts indicate that catalyst (2) is a weaker nucleophile as compared to catalyst (1) forming a weaker Co-C bond between this catalyst and growing polymer chain indicating more living polymerization for the catalyst (2).

KW - Chain transfer constant

KW - Cobalt (II) catalysts

KW - Methylmethacrylate

KW - Pulsed laser polymerization

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