AustralieFrV1, Main, Exploration, bibRecord, 009750

Ab initio study of the penultimate effect for the ATRP activation step using propylene, methyl acrylate, and methyl methacrylate monomers

Identifieur interne : 009750 ( Main/Exploration ); précédent : 009749; suivant : 009751

Ab initio study of the penultimate effect for the ATRP activation step using propylene, methyl acrylate, and methyl methacrylate monomers

Auteurs : CHING YEH LIN [Australie] ; Michelle L. Coote [Australie] ; Alban Petit [France] ; Philippe Richard [France] ; Rinaldo Poli [France] ; Krzysztof Matyjaszewski [États-Unis]

Source :

Macromolecules [ 0024-9297 ] ; 2007.

RBID : Pascal:07-0396107

Descripteurs français

Pascal (Inist)
- Méthacrylate de méthyle polymère, Acrylate de méthyle polymère, Propène polymère, Polymère vivant, Polymérisation transfert atome, Activation, Constante équilibre, Chaleur réaction, Modélisation, Méthode MO, Méthode ab initio, Etude théorique, Effet unité préterminale.

English descriptors

KwdEn :
- Ab initio method, Activation, Atom transfer polymerization, Equilibrium constant, Heat of reaction, Living polymer, MO method, Methyl acrylate polymer, Methyl methacrylate polymer, Modeling, Propylene polymer, Theoretical study.

Abstract

High-level ab initio molecular orbital calculations are used to study the magnitude and origin of the penultimate unit effect in atom transfer radical polymerization (ATRP) of dimers involving the comonomers methyl acrylate (MA), methyl methacrylate (MMA), and propylene (P). The penultimate unit effects depend on the nature of the terminal unit and the halogen and can be significant, with the MMA unit in particular altering the equilibrium constant for the bond dissociation equilibrium by as much as 2 orders of magnitude. Specifically, the ratios of the equilibrium constants (K) for the bond dissociation reactions of H-M₂-M₁-Cl at 298 K, relative to the equilibrium constant (K₀) of the corresponding unimer H-M₁-Cl, for penultimate units M₂ = P, MA, and MMA are respectively 0.81, 1.27, and 92.46 for M₁ = P; 8.73, 2.64, and 32.69 for M₁ = MA; and 5.73, 0.78, and 1.57 for M₁ = MMA. For the bromides, H-M₂-M₁-Br, the corresponding ratios K/K₀ for M₂ = P, MA, and MMA are respectively 0.55, 0.70, and 54.79 (M₁ = P); 5.44, 0.63, and 2.38 (M₁ = MA); and 0.24, 12.18, and 43.77 (M₁ = MMA). It is shown that the penultimate unit effects arise in both the entropy and enthalpy of the equilibrium and are the result of a complex interplay of stereoelectronic effects which, for the ester linkages, are heavily influenced by intramolecular hydrogen bonding. The penultimate unit effects have important implications for initiator design; for example, they can account for the experimental observation that the isobutyrate halide is an inefficient initiator for MMA polymerization. The results also imply that penultimate unit effects need to be taken into account in the synthesis of block, gradient, and random copolymers.

Affiliations:

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Le document en format XML

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<affiliation wicri:level="1"><inist:fA14 i1="03"><s1>Laboratoire de Chimie de Coordination, UPR CNRS 8241 liée par convention à l'Université Paul Sabatier et à l'Institut National Polytechnique de Toulouse, 205 Route de Narbonne</s1>
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<sZ>5 aut.</sZ>
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</affiliation>
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<country>États-Unis</country>
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<orgName type="university">Université Carnegie-Mellon</orgName>
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<series><title level="j" type="main">Macromolecules</title>
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<profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Ab initio method</term>
<term>Activation</term>
<term>Atom transfer polymerization</term>
<term>Equilibrium constant</term>
<term>Heat of reaction</term>
<term>Living polymer</term>
<term>MO method</term>
<term>Methyl acrylate polymer</term>
<term>Methyl methacrylate polymer</term>
<term>Modeling</term>
<term>Propylene polymer</term>
<term>Theoretical study</term>
</keywords>
<keywords scheme="Pascal" xml:lang="fr"><term>Méthacrylate de méthyle polymère</term>
<term>Acrylate de méthyle polymère</term>
<term>Propène polymère</term>
<term>Polymère vivant</term>
<term>Polymérisation transfert atome</term>
<term>Activation</term>
<term>Constante équilibre</term>
<term>Chaleur réaction</term>
<term>Modélisation</term>
<term>Méthode MO</term>
<term>Méthode ab initio</term>
<term>Etude théorique</term>
<term>Effet unité préterminale</term>
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<front><div type="abstract" xml:lang="en">High-level ab initio molecular orbital calculations are used to study the magnitude and origin of the penultimate unit effect in atom transfer radical polymerization (ATRP) of dimers involving the comonomers methyl acrylate (MA), methyl methacrylate (MMA), and propylene (P). The penultimate unit effects depend on the nature of the terminal unit and the halogen and can be significant, with the MMA unit in particular altering the equilibrium constant for the bond dissociation equilibrium by as much as 2 orders of magnitude. Specifically, the ratios of the equilibrium constants (K) for the bond dissociation reactions of H-M<sub>2</sub>
-M<sub>1</sub>
-Cl at 298 K, relative to the equilibrium constant (K<sub>0</sub>
) of the corresponding unimer H-M<sub>1</sub>
-Cl, for penultimate units M<sub>2</sub>
 = P, MA, and MMA are respectively 0.81, 1.27, and 92.46 for M<sub>1</sub>
 = P; 8.73, 2.64, and 32.69 for M<sub>1</sub>
 = MA; and 5.73, 0.78, and 1.57 for M<sub>1</sub>
 = MMA. For the bromides, H-M<sub>2</sub>
-M<sub>1</sub>
-Br, the corresponding ratios K/K<sub>0</sub>
 for M<sub>2</sub>
 = P, MA, and MMA are respectively 0.55, 0.70, and 54.79 (M<sub>1</sub>
 = P); 5.44, 0.63, and 2.38 (M<sub>1</sub>
 = MA); and 0.24, 12.18, and 43.77 (M<sub>1</sub>
 = MMA). It is shown that the penultimate unit effects arise in both the entropy and enthalpy of the equilibrium and are the result of a complex interplay of stereoelectronic effects which, for the ester linkages, are heavily influenced by intramolecular hydrogen bonding. The penultimate unit effects have important implications for initiator design; for example, they can account for the experimental observation that the isobutyrate halide is an inefficient initiator for MMA polymerization. The results also imply that penultimate unit effects need to be taken into account in the synthesis of block, gradient, and random copolymers.</div>
</front>
</TEI>
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<li>France</li>
<li>États-Unis</li>
</country>
<region><li>Midi-Pyrénées</li>
<li>Occitanie (région administrative)</li>
<li>Pennsylvanie</li>
<li>Région Bourgogne</li>
</region>
<settlement><li>Dijon</li>
<li>Pittsburgh</li>
<li>Toulouse</li>
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</orgName>
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<tree><country name="Australie"><noRegion><name sortKey="Ching Yeh Lin" sort="Ching Yeh Lin" uniqKey="Ching Yeh Lin" last="Ching Yeh Lin">CHING YEH LIN</name>
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<name sortKey="Coote, Michelle L" sort="Coote, Michelle L" uniqKey="Coote M" first="Michelle L." last="Coote">Michelle L. Coote</name>
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<country name="France"><region name="Région Bourgogne"><name sortKey="Petit, Alban" sort="Petit, Alban" uniqKey="Petit A" first="Alban" last="Petit">Alban Petit</name>
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<name sortKey="Poli, Rinaldo" sort="Poli, Rinaldo" uniqKey="Poli R" first="Rinaldo" last="Poli">Rinaldo Poli</name>
<name sortKey="Richard, Philippe" sort="Richard, Philippe" uniqKey="Richard P" first="Philippe" last="Richard">Philippe Richard</name>
</country>
<country name="États-Unis"><region name="Pennsylvanie"><name sortKey="Matyjaszewski, Krzysztof" sort="Matyjaszewski, Krzysztof" uniqKey="Matyjaszewski K" first="Krzysztof" last="Matyjaszewski">Krzysztof Matyjaszewski</name>
</region>
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</tree>
</affiliations>
</record>

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Ab initio study of the penultimate effect for the ATRP activation step using propylene, methyl acrylate, and methyl methacrylate monomers

Ab initio study of the penultimate effect for the ATRP activation step using propylene, methyl acrylate, and methyl methacrylate monomers

Source :

Descripteurs français

English descriptors

Abstract

Links toward previous steps (curation, corpus...)

Le document en format XML

Pour manipuler ce document sous Unix (Dilib)

Pour mettre un lien sur cette page dans le réseau Wicri