Xanthate mediated living polymerization of vinyl acetate: A systematic variation in MADIX/RAFT agent structure

Martina H. Stenzel; Lyndal Cummins; G. Evan Roberts; Thomas P. Davis; Philipp Vana; Christopher Barner-Kowollik

doi:10.1002/macp.200390089

Xanthate mediated living polymerization of vinyl acetate: A systematic variation in MADIX/RAFT agent structure

Martina H. Stenzel, Lyndal Cummins, G. Evan Roberts, Thomas P. Davis, Philipp Vana, Christopher Barner-Kowollik

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

327 Citations (Scopus)

Abstract

Eight xanthates were synthesized to induce living free radical polymerization of vinyl acetate. Four compounds, methyl (4-methoxyphenoxy)carbonothioylsulfanyl acetate, methyl (methoxycarbonothioyl)sulfanyl acetate, methyl (ethoxycarbonothioyl)sulfanyl acetate and methyl (isopropoxycarbonothioyl)sulfanyl acetate were identified as suitable MADIX/RAFT agents, yielding low polydispersity (PDI < 1.2) poly(vinyl acetate) of molecular weights exceeding 5 x 10⁴ g·mol^-1. All suitable MADIX/RAFT agents exhibited extended periods of inhibition (0.3 h < t_inh < 10 h) andmoderate rate retardation. The abitity of these compounds to control vinyl acetate polymerization can be correlated with the electron density on the central carbon atom of the xanthate. Electrospray ionization mass spectrometric analysis was performed to complete the investigation on the new MADIX/RAFT agents.

Original language	English
Pages (from-to)	1160-1168
Number of pages	9
Journal	Macromolecular Chemistry and Physics
Volume	204
Issue number	9
DOIs	https://doi.org/10.1002/macp.200390089
Publication status	Published - 16 Jun 2003
Externally published	Yes

Keywords

Kinetics (polym.)
Living polymerization
MADIX
Reversible addition fragmentation chain transfer
Vinyl acetate

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10.1002/macp.200390089

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title = "Xanthate mediated living polymerization of vinyl acetate: A systematic variation in MADIX/RAFT agent structure",

abstract = "Eight xanthates were synthesized to induce living free radical polymerization of vinyl acetate. Four compounds, methyl (4-methoxyphenoxy)carbonothioylsulfanyl acetate, methyl (methoxycarbonothioyl)sulfanyl acetate, methyl (ethoxycarbonothioyl)sulfanyl acetate and methyl (isopropoxycarbonothioyl)sulfanyl acetate were identified as suitable MADIX/RAFT agents, yielding low polydispersity (PDI < 1.2) poly(vinyl acetate) of molecular weights exceeding 5 x 104 g·mol-1. All suitable MADIX/RAFT agents exhibited extended periods of inhibition (0.3 h < tinh < 10 h) andmoderate rate retardation. The abitity of these compounds to control vinyl acetate polymerization can be correlated with the electron density on the central carbon atom of the xanthate. Electrospray ionization mass spectrometric analysis was performed to complete the investigation on the new MADIX/RAFT agents.",

keywords = "Kinetics (polym.), Living polymerization, MADIX, Reversible addition fragmentation chain transfer, Vinyl acetate",

author = "Stenzel, {Martina H.} and Lyndal Cummins and Roberts, {G. Evan} and Davis, {Thomas P.} and Philipp Vana and Christopher Barner-Kowollik",

year = "2003",

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language = "English",

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T2 - A systematic variation in MADIX/RAFT agent structure

AU - Stenzel, Martina H.

AU - Cummins, Lyndal

AU - Roberts, G. Evan

AU - Davis, Thomas P.

AU - Vana, Philipp

AU - Barner-Kowollik, Christopher

PY - 2003/6/16

Y1 - 2003/6/16

N2 - Eight xanthates were synthesized to induce living free radical polymerization of vinyl acetate. Four compounds, methyl (4-methoxyphenoxy)carbonothioylsulfanyl acetate, methyl (methoxycarbonothioyl)sulfanyl acetate, methyl (ethoxycarbonothioyl)sulfanyl acetate and methyl (isopropoxycarbonothioyl)sulfanyl acetate were identified as suitable MADIX/RAFT agents, yielding low polydispersity (PDI < 1.2) poly(vinyl acetate) of molecular weights exceeding 5 x 104 g·mol-1. All suitable MADIX/RAFT agents exhibited extended periods of inhibition (0.3 h < tinh < 10 h) andmoderate rate retardation. The abitity of these compounds to control vinyl acetate polymerization can be correlated with the electron density on the central carbon atom of the xanthate. Electrospray ionization mass spectrometric analysis was performed to complete the investigation on the new MADIX/RAFT agents.

AB - Eight xanthates were synthesized to induce living free radical polymerization of vinyl acetate. Four compounds, methyl (4-methoxyphenoxy)carbonothioylsulfanyl acetate, methyl (methoxycarbonothioyl)sulfanyl acetate, methyl (ethoxycarbonothioyl)sulfanyl acetate and methyl (isopropoxycarbonothioyl)sulfanyl acetate were identified as suitable MADIX/RAFT agents, yielding low polydispersity (PDI < 1.2) poly(vinyl acetate) of molecular weights exceeding 5 x 104 g·mol-1. All suitable MADIX/RAFT agents exhibited extended periods of inhibition (0.3 h < tinh < 10 h) andmoderate rate retardation. The abitity of these compounds to control vinyl acetate polymerization can be correlated with the electron density on the central carbon atom of the xanthate. Electrospray ionization mass spectrometric analysis was performed to complete the investigation on the new MADIX/RAFT agents.

KW - Kinetics (polym.)

KW - Living polymerization

KW - MADIX

KW - Reversible addition fragmentation chain transfer

KW - Vinyl acetate

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U2 - 10.1002/macp.200390089

DO - 10.1002/macp.200390089

M3 - Article

AN - SCOPUS:0038606275

SN - 1022-1352

VL - 204

SP - 1160

EP - 1168

JO - Macromolecular Chemistry and Physics

JF - Macromolecular Chemistry and Physics

IS - 9

ER -

Xanthate mediated living polymerization of vinyl acetate: A systematic variation in MADIX/RAFT agent structure

Abstract

Keywords

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