Reaction mechanism of borane/oxygen radical initiators during the polymerization of fluoromonomers

Zhi Cheng Zhang; T. C.Mike Chung

doi:10.1021/ma061393a

Reaction mechanism of borane/oxygen radical initiators during the polymerization of fluoromonomers

Zhi Cheng Zhang, T. C.Mike Chung

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

85 Scopus citations

Abstract

The oxidation adducts of B(C ₂H ₅) ₃ (triethylborane) and B(OCH ₃)(C ₂H ₅) ₂ (diethylmethoxylborane) and the reactions in the presence of vinylidene fluoride (VDF) to form PVDF polymers under various conditions was investigated. The distinctive chemical shifts of PVDF, separated from those of borane oxidation fragments greatly help the end-group analysis by the NMR technique. The unstable intermediates containing free radicals during the intermolecular reaction should in situ initiate the radical polymerization to form poly(vinylidene fluoride) (PVDF) and deposit the adduct in the beginning of the PVDF chain. Plots of the polymer molecular weight vs the monomer conversion, the line is well above the theoretical line for the ideal control polymerization. The combined information from oxidation adducts of two related boranes and the polymer chain endstructure presents the initiation mechanism of borane/oxygen-mediated radical polymerization of fluoromonomers at ambient temperature.

Original language	English (US)
Pages (from-to)	5187-5189
Number of pages	3
Journal	Macromolecules
Volume	39
Issue number	16
DOIs	https://doi.org/10.1021/ma061393a
State	Published - Aug 8 2006

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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10.1021/ma061393a

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title = "Reaction mechanism of borane/oxygen radical initiators during the polymerization of fluoromonomers",

abstract = "The oxidation adducts of B(C 2H 5) 3 (triethylborane) and B(OCH 3)(C 2H 5) 2 (diethylmethoxylborane) and the reactions in the presence of vinylidene fluoride (VDF) to form PVDF polymers under various conditions was investigated. The distinctive chemical shifts of PVDF, separated from those of borane oxidation fragments greatly help the end-group analysis by the NMR technique. The unstable intermediates containing free radicals during the intermolecular reaction should in situ initiate the radical polymerization to form poly(vinylidene fluoride) (PVDF) and deposit the adduct in the beginning of the PVDF chain. Plots of the polymer molecular weight vs the monomer conversion, the line is well above the theoretical line for the ideal control polymerization. The combined information from oxidation adducts of two related boranes and the polymer chain endstructure presents the initiation mechanism of borane/oxygen-mediated radical polymerization of fluoromonomers at ambient temperature.",

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T1 - Reaction mechanism of borane/oxygen radical initiators during the polymerization of fluoromonomers

AU - Zhang, Zhi Cheng

AU - Chung, T. C.Mike

PY - 2006/8/8

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N2 - The oxidation adducts of B(C 2H 5) 3 (triethylborane) and B(OCH 3)(C 2H 5) 2 (diethylmethoxylborane) and the reactions in the presence of vinylidene fluoride (VDF) to form PVDF polymers under various conditions was investigated. The distinctive chemical shifts of PVDF, separated from those of borane oxidation fragments greatly help the end-group analysis by the NMR technique. The unstable intermediates containing free radicals during the intermolecular reaction should in situ initiate the radical polymerization to form poly(vinylidene fluoride) (PVDF) and deposit the adduct in the beginning of the PVDF chain. Plots of the polymer molecular weight vs the monomer conversion, the line is well above the theoretical line for the ideal control polymerization. The combined information from oxidation adducts of two related boranes and the polymer chain endstructure presents the initiation mechanism of borane/oxygen-mediated radical polymerization of fluoromonomers at ambient temperature.

AB - The oxidation adducts of B(C 2H 5) 3 (triethylborane) and B(OCH 3)(C 2H 5) 2 (diethylmethoxylborane) and the reactions in the presence of vinylidene fluoride (VDF) to form PVDF polymers under various conditions was investigated. The distinctive chemical shifts of PVDF, separated from those of borane oxidation fragments greatly help the end-group analysis by the NMR technique. The unstable intermediates containing free radicals during the intermolecular reaction should in situ initiate the radical polymerization to form poly(vinylidene fluoride) (PVDF) and deposit the adduct in the beginning of the PVDF chain. Plots of the polymer molecular weight vs the monomer conversion, the line is well above the theoretical line for the ideal control polymerization. The combined information from oxidation adducts of two related boranes and the polymer chain endstructure presents the initiation mechanism of borane/oxygen-mediated radical polymerization of fluoromonomers at ambient temperature.

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Reaction mechanism of borane/oxygen radical initiators during the polymerization of fluoromonomers

Abstract

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