PLP-SEC Study into the Free-Radical Propagation Rate Coefficients of Partially and Fully Ionized Acrylic Acid in Aqueous Solution
Propagation rate coefficients, kp, for acrylic acid (AA) polymerization at 6 °C in aqueous solution were measured via pulsed laser polymerization (PLP) with the degree of ionization, α, varied over the entire range between 0 and 1. These measurements were carried out in conjunction with aqueous‐phas...
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| Published in: | Macromolecular chemistry and physics Vol. 205; no. 8; pp. 1080 - 1087 |
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| Main Authors: | , , |
| Format: | Journal Article |
| Language: | English |
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Weinheim
WILEY-VCH Verlag
01-05-2004
WILEY‐VCH Verlag Wiley |
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| Abstract | Propagation rate coefficients, kp, for acrylic acid (AA) polymerization at 6 °C in aqueous solution were measured via pulsed laser polymerization (PLP) with the degree of ionization, α, varied over the entire range between 0 and 1. These measurements were carried out in conjunction with aqueous‐phase size‐exclusion chromatography (SEC). Strictly speaking, the reported kp's are “apparent” propagation rate coefficients deduced from the PLP‐SEC data under the assumption that the local monomer concentration at the radical site is identical to overall monomer concentration. At an AA concentration of 0.69 mol · L−1, the apparent kp decreases from 111 000 L · mol−1 · s−1 at α = 0 to 13 000 L · mol−1 · s−1 at α = 1.0. The significant lowering of kp with higher α is attributed to the repulsion between both monomer molecules and macroradicals becoming negatively charged. Addition of up to 10 mol‐% (with respect to AA) sodium hydroxide to the fully ionized aqueous AA solution leads to an enhancement of kp up to 57 000 L · mol−1 · s−1.
Dependence of apparent kp values on the degree of ionization of acrylic acid (a) and on pH (b) for aqueous polymerizations of acrylic acid. |
|---|---|
| AbstractList | Propagation rate coefficients,
k
p
, for acrylic acid (AA) polymerization at 6 °C in aqueous solution were measured via pulsed laser polymerization (PLP) with the degree of ionization,
α
, varied over the entire range between 0 and 1. These measurements were carried out in conjunction with aqueous‐phase size‐exclusion chromatography (SEC). Strictly speaking, the reported
k
p
's are “apparent” propagation rate coefficients deduced from the PLP‐SEC data under the assumption that the local monomer concentration at the radical site is identical to overall monomer concentration. At an AA concentration of 0.69 mol · L
−1
, the apparent
k
p
decreases from 111 000 L · mol
−1
· s
−1
at
α
= 0 to 13 000 L · mol
−1
· s
−1
at
α
= 1.0. The significant lowering of
k
p
with higher
α
is attributed to the repulsion between both monomer molecules and macroradicals becoming negatively charged. Addition of up to 10 mol‐% (with respect to AA) sodium hydroxide to the fully ionized aqueous AA solution leads to an enhancement of
k
p
up to 57 000 L · mol
−1
· s
−1
.
Dependence of apparent
k
p
values on the degree of ionization of acrylic acid (a) and on pH (b) for aqueous polymerizations of acrylic acid.
image
Dependence of apparent
k
p
values on the degree of ionization of acrylic acid (a) and on pH (b) for aqueous polymerizations of acrylic acid. Propagation rate coefficients, kp, for acrylic acid (AA) polymerization at 6 °C in aqueous solution were measured via pulsed laser polymerization (PLP) with the degree of ionization, α, varied over the entire range between 0 and 1. These measurements were carried out in conjunction with aqueous‐phase size‐exclusion chromatography (SEC). Strictly speaking, the reported kp's are “apparent” propagation rate coefficients deduced from the PLP‐SEC data under the assumption that the local monomer concentration at the radical site is identical to overall monomer concentration. At an AA concentration of 0.69 mol · L−1, the apparent kp decreases from 111 000 L · mol−1 · s−1 at α = 0 to 13 000 L · mol−1 · s−1 at α = 1.0. The significant lowering of kp with higher α is attributed to the repulsion between both monomer molecules and macroradicals becoming negatively charged. Addition of up to 10 mol‐% (with respect to AA) sodium hydroxide to the fully ionized aqueous AA solution leads to an enhancement of kp up to 57 000 L · mol−1 · s−1. Dependence of apparent kp values on the degree of ionization of acrylic acid (a) and on pH (b) for aqueous polymerizations of acrylic acid. |
| Author | Lacík, Igor Buback, Michael Beuermann, Sabine |
| Author_xml | – sequence: 1 givenname: Igor surname: Lacík fullname: Lacík, Igor email: igor.lacik@savba.sk organization: Polymer Institute of the Slovak Academy of Sciences, Dúbravská cesta 9, 842 36 Bratislava, Slovak Republic – sequence: 2 givenname: Sabine surname: Beuermann fullname: Beuermann, Sabine organization: Institut für Physikalische Chemie, Georg-August-Universität Göttingen, Tammannstraße 6, D-37077 Göttingen, Germany – sequence: 3 givenname: Michael surname: Buback fullname: Buback, Michael organization: Institut für Physikalische Chemie, Georg-August-Universität Göttingen, Tammannstraße 6, D-37077 Göttingen, Germany |
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| Cites_doi | 10.1002/(SICI)1521-3919(20000301)9:3<131::AID-MATS131>3.0.CO;2-7 10.1002/pol.1953.120110211 10.1002/pol.1952.120090310 10.1016/S1381-5148(02)00194-3 10.1002/(SICI)1099-0488(19970930)35:13<2029::AID-POLB4>3.0.CO;2-R 10.1021/ma030365e 10.1021/ma002222n 10.1021/ma991763d 10.1002/macp.1997.021980518 10.3891/acta.chem.scand.43-0496 10.1002/macp.1987.021880716 10.1021/la981190i 10.1002/pol.1957.1202310338 10.1021/ja01104a021 10.1039/tf9514701360 10.1002/polc.5070420120 |
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| Copyright | Copyright © 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim 2004 INIST-CNRS |
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| Issue | 8 |
| Keywords | Polyelectrolyte Free radical polymerization Pulsed laser Acrylic acid polymer Kinetics Ionization level Aqueous solution Rate constant Experimental study Monomer Reaction propagation Solution polymerization |
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| Snippet | Propagation rate coefficients, kp, for acrylic acid (AA) polymerization at 6 °C in aqueous solution were measured via pulsed laser polymerization (PLP) with... Propagation rate coefficients, k p , for acrylic acid (AA) polymerization at 6 °C in aqueous solution were measured via pulsed laser polymerization (PLP) with... |
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| SubjectTerms | acrylic acid Applied sciences Exact sciences and technology kinetics (polym.) Organic polymers Physicochemistry of polymers Polymerization Preparation, kinetics, thermodynamics, mechanism and catalysts propagation rate coefficient pulsed laser polymerization radical polymerization |
| Title | PLP-SEC Study into the Free-Radical Propagation Rate Coefficients of Partially and Fully Ionized Acrylic Acid in Aqueous Solution |
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