Cobalt-mediated radical polymerization routes to poly(vinyl ester) block copolymers

David N. Bunck; Gregory P. Sorenson; Mahesh K. Mahanthappa

doi:10.1002/pola.24445

Cobalt-mediated radical polymerization routes to poly(vinyl ester) block copolymers

David N. Bunck, Gregory P. Sorenson, Mahesh K. Mahanthappa

Chemical Engineering and Materials Science

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

29 Scopus citations

Abstract

Cobalt-mediated radical polymerizations (CMRPs) utilizing redox initiation are demonstrated to produce poly(vinyl ester) homopolymers derived from vinyl pivalate (VPv) and vinyl benzoate (VBz), and their block copolymers with vinyl acetate (VAc). Combining anhydrous Co(acac)₂, lauroyl peroxide, citric acid trisodium salt, and VPv at 30 °C results in controlled polymerizations that yield homopolymers with M_n = 2.5-27 kg/mol with M_w/M_n = 1.20-1.30. Homopolymerizations of scrupulously purified VBz proceed with lower levels of control as evidenced by broader polydispersities over a range of molecular weights (M_n = 4-16 kg/mol; M_w/M_n = 1.34-1.65), which may be interpreted in terms of the decreased nucleophilicity of these less electron donating propagating polymer chain ends. Based on these results, we demonstrate that sequential CMRP reactions present a viable route to microphase separated poly(vinyl ester) block copolymers as shown by small-angle X-ray scattering analyses.

Original language	English (US)
Pages (from-to)	242-249
Number of pages	8
Journal	Journal of Polymer Science, Part A: Polymer Chemistry
Volume	49
Issue number	1
DOIs	https://doi.org/10.1002/pola.24445
State	Published - Jan 1 2011

Keywords

biodegradable
block copolymers
cobalt-mediated radical polymerization (CMRP)
degenerate transfer polymerization
radical polymerization
self-assembly
vinyl acetate
vinyl ester

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abstract = "Cobalt-mediated radical polymerizations (CMRPs) utilizing redox initiation are demonstrated to produce poly(vinyl ester) homopolymers derived from vinyl pivalate (VPv) and vinyl benzoate (VBz), and their block copolymers with vinyl acetate (VAc). Combining anhydrous Co(acac)2, lauroyl peroxide, citric acid trisodium salt, and VPv at 30 °C results in controlled polymerizations that yield homopolymers with Mn = 2.5-27 kg/mol with Mw/Mn = 1.20-1.30. Homopolymerizations of scrupulously purified VBz proceed with lower levels of control as evidenced by broader polydispersities over a range of molecular weights (Mn = 4-16 kg/mol; Mw/Mn = 1.34-1.65), which may be interpreted in terms of the decreased nucleophilicity of these less electron donating propagating polymer chain ends. Based on these results, we demonstrate that sequential CMRP reactions present a viable route to microphase separated poly(vinyl ester) block copolymers as shown by small-angle X-ray scattering analyses.",

keywords = "biodegradable, block copolymers, cobalt-mediated radical polymerization (CMRP), degenerate transfer polymerization, radical polymerization, self-assembly, vinyl acetate, vinyl ester",

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AU - Sorenson, Gregory P.

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N2 - Cobalt-mediated radical polymerizations (CMRPs) utilizing redox initiation are demonstrated to produce poly(vinyl ester) homopolymers derived from vinyl pivalate (VPv) and vinyl benzoate (VBz), and their block copolymers with vinyl acetate (VAc). Combining anhydrous Co(acac)2, lauroyl peroxide, citric acid trisodium salt, and VPv at 30 °C results in controlled polymerizations that yield homopolymers with Mn = 2.5-27 kg/mol with Mw/Mn = 1.20-1.30. Homopolymerizations of scrupulously purified VBz proceed with lower levels of control as evidenced by broader polydispersities over a range of molecular weights (Mn = 4-16 kg/mol; Mw/Mn = 1.34-1.65), which may be interpreted in terms of the decreased nucleophilicity of these less electron donating propagating polymer chain ends. Based on these results, we demonstrate that sequential CMRP reactions present a viable route to microphase separated poly(vinyl ester) block copolymers as shown by small-angle X-ray scattering analyses.

AB - Cobalt-mediated radical polymerizations (CMRPs) utilizing redox initiation are demonstrated to produce poly(vinyl ester) homopolymers derived from vinyl pivalate (VPv) and vinyl benzoate (VBz), and their block copolymers with vinyl acetate (VAc). Combining anhydrous Co(acac)2, lauroyl peroxide, citric acid trisodium salt, and VPv at 30 °C results in controlled polymerizations that yield homopolymers with Mn = 2.5-27 kg/mol with Mw/Mn = 1.20-1.30. Homopolymerizations of scrupulously purified VBz proceed with lower levels of control as evidenced by broader polydispersities over a range of molecular weights (Mn = 4-16 kg/mol; Mw/Mn = 1.34-1.65), which may be interpreted in terms of the decreased nucleophilicity of these less electron donating propagating polymer chain ends. Based on these results, we demonstrate that sequential CMRP reactions present a viable route to microphase separated poly(vinyl ester) block copolymers as shown by small-angle X-ray scattering analyses.

KW - biodegradable

KW - block copolymers

KW - cobalt-mediated radical polymerization (CMRP)

KW - degenerate transfer polymerization

KW - radical polymerization

KW - self-assembly

KW - vinyl acetate

KW - vinyl ester

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Cobalt-mediated radical polymerization routes to poly(vinyl ester) block copolymers

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