SET-LRP of methyl acrylate to complete conversion with zero termination

Nga H. Nguyen; Martin E. Levere; Virgil Percec

doi:10.1002/pola.25838

SET-LRP of methyl acrylate to complete conversion with zero termination

Nga H. Nguyen, Martin E. Levere, Virgil Percec

Faculty of Science

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109 Citations (Scopus)

Abstract

The single electron transfer-living radical polymerization of methyl acrylate (MA) initiated by bis(2-bromopropionyl)ethane (BPE) in dimethyl sulfoxide was carried out to 100% monomer conversion and complete absence of bimolecular termination under the following reaction conditions: [MA]/[BPE]/[Me ₆-TREN]/[CuBr ₂] = 60/1/0.21/0.01 and [MA]/[BPE]/[TREN]/[CuBr ₂] = 60/1/0.25/0.05. These polymerizations were mediated by 0.5 cm of hydrazine-activated Cu(0) wire of 20 gauge (0.812 cm in diameter), corresponding to a surface area of 0.14 cm ² of Cu(0) per 3 mL reaction volume (2/1 v/v monomer/solvent). A higher extent of bimolecular termination (5-13%) was observed at complete conversion when longer lengths of Cu(0) wire were used. In the absence of CuBr ₂ the activated Cu(0) wire/Me ₆-TREN catalyst in dimethyl sulfoxide also allowed the synthesis of perfectly bifunctional and monofunctional PMAs at complete conversion. This was also demonstrated by the quantitative reinitiation experiments from the chain(s) end(s) of these macroinitiators.

Original language	English
Pages (from-to)	860-873
Number of pages	14
Journal	Journal of Polymer Science, Part A: Polymer Chemistry
Volume	50
Issue number	5
DOIs	https://doi.org/10.1002/pola.25838
Publication status	Published - 1 Mar 2012

Keywords

chain-end analysis
kinetics (polym.)
MALDI
single electron transfer-living radical polymerization (SET-LRP)
termination

ASJC Scopus subject areas

Materials Chemistry
Polymers and Plastics
Organic Chemistry

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10.1002/pola.25838

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title = "SET-LRP of methyl acrylate to complete conversion with zero termination",

abstract = "The single electron transfer-living radical polymerization of methyl acrylate (MA) initiated by bis(2-bromopropionyl)ethane (BPE) in dimethyl sulfoxide was carried out to 100% monomer conversion and complete absence of bimolecular termination under the following reaction conditions: [MA]/[BPE]/[Me 6-TREN]/[CuBr 2] = 60/1/0.21/0.01 and [MA]/[BPE]/[TREN]/[CuBr 2] = 60/1/0.25/0.05. These polymerizations were mediated by 0.5 cm of hydrazine-activated Cu(0) wire of 20 gauge (0.812 cm in diameter), corresponding to a surface area of 0.14 cm 2 of Cu(0) per 3 mL reaction volume (2/1 v/v monomer/solvent). A higher extent of bimolecular termination (5-13%) was observed at complete conversion when longer lengths of Cu(0) wire were used. In the absence of CuBr 2 the activated Cu(0) wire/Me 6-TREN catalyst in dimethyl sulfoxide also allowed the synthesis of perfectly bifunctional and monofunctional PMAs at complete conversion. This was also demonstrated by the quantitative reinitiation experiments from the chain(s) end(s) of these macroinitiators.",

keywords = "chain-end analysis, kinetics (polym.), MALDI, single electron transfer-living radical polymerization (SET-LRP), termination",

author = "Nguyen, {Nga H.} and Levere, {Martin E.} and Virgil Percec",

year = "2012",

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doi = "10.1002/pola.25838",

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T1 - SET-LRP of methyl acrylate to complete conversion with zero termination

AU - Nguyen, Nga H.

AU - Levere, Martin E.

AU - Percec, Virgil

PY - 2012/3/1

Y1 - 2012/3/1

N2 - The single electron transfer-living radical polymerization of methyl acrylate (MA) initiated by bis(2-bromopropionyl)ethane (BPE) in dimethyl sulfoxide was carried out to 100% monomer conversion and complete absence of bimolecular termination under the following reaction conditions: [MA]/[BPE]/[Me 6-TREN]/[CuBr 2] = 60/1/0.21/0.01 and [MA]/[BPE]/[TREN]/[CuBr 2] = 60/1/0.25/0.05. These polymerizations were mediated by 0.5 cm of hydrazine-activated Cu(0) wire of 20 gauge (0.812 cm in diameter), corresponding to a surface area of 0.14 cm 2 of Cu(0) per 3 mL reaction volume (2/1 v/v monomer/solvent). A higher extent of bimolecular termination (5-13%) was observed at complete conversion when longer lengths of Cu(0) wire were used. In the absence of CuBr 2 the activated Cu(0) wire/Me 6-TREN catalyst in dimethyl sulfoxide also allowed the synthesis of perfectly bifunctional and monofunctional PMAs at complete conversion. This was also demonstrated by the quantitative reinitiation experiments from the chain(s) end(s) of these macroinitiators.

AB - The single electron transfer-living radical polymerization of methyl acrylate (MA) initiated by bis(2-bromopropionyl)ethane (BPE) in dimethyl sulfoxide was carried out to 100% monomer conversion and complete absence of bimolecular termination under the following reaction conditions: [MA]/[BPE]/[Me 6-TREN]/[CuBr 2] = 60/1/0.21/0.01 and [MA]/[BPE]/[TREN]/[CuBr 2] = 60/1/0.25/0.05. These polymerizations were mediated by 0.5 cm of hydrazine-activated Cu(0) wire of 20 gauge (0.812 cm in diameter), corresponding to a surface area of 0.14 cm 2 of Cu(0) per 3 mL reaction volume (2/1 v/v monomer/solvent). A higher extent of bimolecular termination (5-13%) was observed at complete conversion when longer lengths of Cu(0) wire were used. In the absence of CuBr 2 the activated Cu(0) wire/Me 6-TREN catalyst in dimethyl sulfoxide also allowed the synthesis of perfectly bifunctional and monofunctional PMAs at complete conversion. This was also demonstrated by the quantitative reinitiation experiments from the chain(s) end(s) of these macroinitiators.

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