Reversible-Deactivation Radical Polymerization of Methyl Methacrylate and Styrene Mediated by Alkyl Dithiocarbamates and Copper Acetylacetonates
Identifieur interne : 001C19 ( PascalFrancis/Corpus ); précédent : 001C18; suivant : 001C20Reversible-Deactivation Radical Polymerization of Methyl Methacrylate and Styrene Mediated by Alkyl Dithiocarbamates and Copper Acetylacetonates
Auteurs : YAOZHONG ZHANG ; Kristin Schröder ; Yungwan Kwak ; Pawel Krys ; Aurélie N. Morin ; Tomislav Pintauer ; Rinaldo Poli ; Krzysztof MatyjaszewskiSource :
- Macromolecules : (Print) [ 0024-9297 ] ; 2013.
Descripteurs français
- Pascal (Inist)
- Méthacrylate de méthyle polymère, Styrène polymère, Polymère vivant, Polymérisation radicalaire, Polymérisation masse, Transfert chaîne, Dithiocarbamate organique, Complexe de cuivre, Cinétique chimique, Mécanisme réaction, Modélisation, Méthode fonctionnelle densité, Etude expérimentale, Inifer, Polymérisation radicalaire désactivation réversible.
English descriptors
- KwdEn :
Abstract
Reversible-deactivation radical polymerization (RDRP) of methyl methacrylate (MMA) and styrene (St) was successfully mediated by copper(II) acetylacetonate, [Cu-(acac)2], or copper(II) hexafluoroacetylacetonate, [Cu(hfa)2], in conjunction with 1-cyano-1-methylethyl diethyldithiocarbamate (MAN-DC) or 2-(N,N-diethyldithiocarbamyl)ethyl isobutyrate (EMA-DC) initiators/transfer agents in the absence of additional reducing agents. Linear first-order kinetic plots were obtained for the polymerization of MMA in the presence of [Cu(hfa)2] or [Cu(acac)2] and MAN-DC. [Cu(hfa)2] provided better control than [Cu(acac)2] for the polymerization of MMA, leading to PMMA with narrow molecular weight distribution, Mw/Mn ∼ 1.1. Polymerization of St was successfully carried out with either MAN-DC or EMA-DC in the presence of [Cu(hfa)2], also resulting in polymers with low Mw/Mn values. In the absence of alkyl dithiocarbamates or copper acetylacetonates, the polymerizations resulted in only trace amounts of polymers or polymers with high values of Mw/Mn. Thus, the combination of alkyl dithiocarbamates and copper(II) acetylacetonates provides a convenient way to prepare well-controlled PMMA and PSt. NMR analysis of low-MW polymers reveals the presence of DC groups as chain ends. DFT calculations show that DC group transfer from a H-MMA-DC model of the growing chain to the Cu(II) complexes is energetically accessible and more favorable than Br atom transfer, thus rationalizing the need for the Cu(II)/dithiocarbamate combination for successful control and suggesting that the process takes place by reversible DC group transfer involving a CuII/CuIII couple. Attempts to synthesize complexes [Cu(acac)2(DC)] and [Cu(hfa)2(DC)], in combination with DFT calculations, suggest that these complexes are thermodynamically unstable relative to the bis(diketonate)copper(II) and dithiuram disulfide, but this does not preclude the involvement of the Cu(III) species as a spin trap in RDRP controlled by DC group transfer.
Notice en format standard (ISO 2709)
Pour connaître la documentation sur le format Inist Standard.
| pA |
|
|---|
Format Inist (serveur)
| NO : | PASCAL 13-0278832 INIST |
|---|---|
| ET : | Reversible-Deactivation Radical Polymerization of Methyl Methacrylate and Styrene Mediated by Alkyl Dithiocarbamates and Copper Acetylacetonates |
| AU : | YAOZHONG ZHANG; SCHRÖDER (Kristin); KWAK (Yungwan); KRYS (Pawel); MORIN (Aurélie N.); PINTAUER (Tomislav); POLI (Rinaldo); MATYJASZEWSKI (Krzysztof) |
| AF : | Center for Macromolecular Engineering, Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue/Pittsburgh, Pennsylvania 15213/Etats-Unis (1 aut., 2 aut., 4 aut., 8 aut.); Silberline Manufacturing Co., Inc., 36 Progressive Avenue/Tamaqua, Pennsylvania 18252/Etats-Unis (3 aut.); Laboratoire de Chimie de Coordination (LCC), CNRS 8241, Université de Toulouse, UPS, INPT, 205 Route de Narbonne/31077 Toulouse/France (5 aut., 6 aut., 7 aut.); Department of Chemistry and Biochemistry, Duquesne University, 600 Forbes Avenue, 308 Mellon Hall/Pittsburgh, Pennsylvania 15282/Etats-Unis (6 aut.); Institut Universitaire de France, 103, bd Saint-Michel/75005 Paris/France (7 aut.) |
| DT : | Publication en série; Niveau analytique |
| SO : | Macromolecules : (Print); ISSN 0024-9297; Coden MAMOBX; Etats-Unis; Da. 2013; Vol. 46; No. 14; Pp. 5512-5519; Bibl. 37 ref. |
| LA : | Anglais |
| EA : | Reversible-deactivation radical polymerization (RDRP) of methyl methacrylate (MMA) and styrene (St) was successfully mediated by copper(II) acetylacetonate, [Cu-(acac)2], or copper(II) hexafluoroacetylacetonate, [Cu(hfa)2], in conjunction with 1-cyano-1-methylethyl diethyldithiocarbamate (MAN-DC) or 2-(N,N-diethyldithiocarbamyl)ethyl isobutyrate (EMA-DC) initiators/transfer agents in the absence of additional reducing agents. Linear first-order kinetic plots were obtained for the polymerization of MMA in the presence of [Cu(hfa)2] or [Cu(acac)2] and MAN-DC. [Cu(hfa)2] provided better control than [Cu(acac)2] for the polymerization of MMA, leading to PMMA with narrow molecular weight distribution, Mw/Mn ∼ 1.1. Polymerization of St was successfully carried out with either MAN-DC or EMA-DC in the presence of [Cu(hfa)2], also resulting in polymers with low Mw/Mn values. In the absence of alkyl dithiocarbamates or copper acetylacetonates, the polymerizations resulted in only trace amounts of polymers or polymers with high values of Mw/Mn. Thus, the combination of alkyl dithiocarbamates and copper(II) acetylacetonates provides a convenient way to prepare well-controlled PMMA and PSt. NMR analysis of low-MW polymers reveals the presence of DC groups as chain ends. DFT calculations show that DC group transfer from a H-MMA-DC model of the growing chain to the Cu(II) complexes is energetically accessible and more favorable than Br atom transfer, thus rationalizing the need for the Cu(II)/dithiocarbamate combination for successful control and suggesting that the process takes place by reversible DC group transfer involving a CuII/CuIII couple. Attempts to synthesize complexes [Cu(acac)2(DC)] and [Cu(hfa)2(DC)], in combination with DFT calculations, suggest that these complexes are thermodynamically unstable relative to the bis(diketonate)copper(II) and dithiuram disulfide, but this does not preclude the involvement of the Cu(III) species as a spin trap in RDRP controlled by DC group transfer. |
| CC : | 001D09D02B |
| FD : | Méthacrylate de méthyle polymère; Styrène polymère; Polymère vivant; Polymérisation radicalaire; Polymérisation masse; Transfert chaîne; Dithiocarbamate organique; Complexe de cuivre; Cinétique chimique; Mécanisme réaction; Modélisation; Méthode fonctionnelle densité; Etude expérimentale; Inifer; Polymérisation radicalaire désactivation réversible |
| ED : | Methyl methacrylate polymer; Styrene polymer; Living polymer; Free radical polymerization; Bulk polymerization; Chain transfer; Organic dithiocarbamate; Copper complex; Chemical reaction kinetics; Reaction mechanism; Modeling; Density functional method; Experimental study |
| SD : | Metacrilato de metilo polímero; Estireno polímero; Polímero viviente; Polimerización radicalar; Polimerización masa; Transferencia en cadena; Ditiocarbamato orgánico; Cobre complejo; Cinética química; Mecanismo reacción; Modelización; Estudio experimental |
| LO : | INIST-13789.354000506569750130 |
| ID : | 13-0278832 |
Links to Exploration step
Pascal:13-0278832Le document en format XML
<record><TEI><teiHeader><fileDesc><titleStmt><title xml:lang="en" level="a">Reversible-Deactivation Radical Polymerization of Methyl Methacrylate and Styrene Mediated by Alkyl Dithiocarbamates and Copper Acetylacetonates</title><author><name sortKey="Yaozhong Zhang" sort="Yaozhong Zhang" uniqKey="Yaozhong Zhang" last="Yaozhong Zhang">YAOZHONG ZHANG</name><affiliation><inist:fA14 i1="01"><s1>Center for Macromolecular Engineering, Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue</s1><s2>Pittsburgh, Pennsylvania 15213</s2><s3>USA</s3><sZ>1 aut.</sZ><sZ>2 aut.</sZ><sZ>4 aut.</sZ><sZ>8 aut.</sZ></inist:fA14></affiliation></author><author><name sortKey="Schroder, Kristin" sort="Schroder, Kristin" uniqKey="Schroder K" first="Kristin" last="Schröder">Kristin Schröder</name><affiliation><inist:fA14 i1="01"><s1>Center for Macromolecular Engineering, Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue</s1><s2>Pittsburgh, Pennsylvania 15213</s2><s3>USA</s3><sZ>1 aut.</sZ><sZ>2 aut.</sZ><sZ>4 aut.</sZ><sZ>8 aut.</sZ></inist:fA14></affiliation></author><author><name sortKey="Kwak, Yungwan" sort="Kwak, Yungwan" uniqKey="Kwak Y" first="Yungwan" last="Kwak">Yungwan Kwak</name><affiliation><inist:fA14 i1="02"><s1>Silberline Manufacturing Co., Inc., 36 Progressive Avenue</s1><s2>Tamaqua, Pennsylvania 18252</s2><s3>USA</s3><sZ>3 aut.</sZ></inist:fA14></affiliation></author><author><name sortKey="Krys, Pawel" sort="Krys, Pawel" uniqKey="Krys P" first="Pawel" last="Krys">Pawel Krys</name><affiliation><inist:fA14 i1="01"><s1>Center for Macromolecular Engineering, Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue</s1><s2>Pittsburgh, Pennsylvania 15213</s2><s3>USA</s3><sZ>1 aut.</sZ><sZ>2 aut.</sZ><sZ>4 aut.</sZ><sZ>8 aut.</sZ></inist:fA14></affiliation></author><author><name sortKey="Morin, Aurelie N" sort="Morin, Aurelie N" uniqKey="Morin A" first="Aurélie N." last="Morin">Aurélie N. Morin</name><affiliation><inist:fA14 i1="03"><s1>Laboratoire de Chimie de Coordination (LCC), CNRS 8241, Université de Toulouse, UPS, INPT, 205 Route de Narbonne</s1><s2>31077 Toulouse</s2><s3>FRA</s3><sZ>5 aut.</sZ><sZ>6 aut.</sZ><sZ>7 aut.</sZ></inist:fA14></affiliation></author><author><name sortKey="Pintauer, Tomislav" sort="Pintauer, Tomislav" uniqKey="Pintauer T" first="Tomislav" last="Pintauer">Tomislav Pintauer</name><affiliation><inist:fA14 i1="03"><s1>Laboratoire de Chimie de Coordination (LCC), CNRS 8241, Université de Toulouse, UPS, INPT, 205 Route de Narbonne</s1><s2>31077 Toulouse</s2><s3>FRA</s3><sZ>5 aut.</sZ><sZ>6 aut.</sZ><sZ>7 aut.</sZ></inist:fA14></affiliation><affiliation><inist:fA14 i1="04"><s1>Department of Chemistry and Biochemistry, Duquesne University, 600 Forbes Avenue, 308 Mellon Hall</s1><s2>Pittsburgh, Pennsylvania 15282</s2><s3>USA</s3><sZ>6 aut.</sZ></inist:fA14></affiliation></author><author><name sortKey="Poli, Rinaldo" sort="Poli, Rinaldo" uniqKey="Poli R" first="Rinaldo" last="Poli">Rinaldo Poli</name><affiliation><inist:fA14 i1="03"><s1>Laboratoire de Chimie de Coordination (LCC), CNRS 8241, Université de Toulouse, UPS, INPT, 205 Route de Narbonne</s1><s2>31077 Toulouse</s2><s3>FRA</s3><sZ>5 aut.</sZ><sZ>6 aut.</sZ><sZ>7 aut.</sZ></inist:fA14></affiliation><affiliation><inist:fA14 i1="05"><s1>Institut Universitaire de France, 103, bd Saint-Michel</s1><s2>75005 Paris</s2><s3>FRA</s3><sZ>7 aut.</sZ></inist:fA14></affiliation></author><author><name sortKey="Matyjaszewski, Krzysztof" sort="Matyjaszewski, Krzysztof" uniqKey="Matyjaszewski K" first="Krzysztof" last="Matyjaszewski">Krzysztof Matyjaszewski</name><affiliation><inist:fA14 i1="01"><s1>Center for Macromolecular Engineering, Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue</s1><s2>Pittsburgh, Pennsylvania 15213</s2><s3>USA</s3><sZ>1 aut.</sZ><sZ>2 aut.</sZ><sZ>4 aut.</sZ><sZ>8 aut.</sZ></inist:fA14></affiliation></author></titleStmt><publicationStmt><idno type="wicri:source">INIST</idno><idno type="inist">13-0278832</idno><date when="2013">2013</date><idno type="stanalyst">PASCAL 13-0278832 INIST</idno><idno type="RBID">Pascal:13-0278832</idno><idno type="wicri:Area/PascalFrancis/Corpus">001C19</idno></publicationStmt><sourceDesc><biblStruct><analytic><title xml:lang="en" level="a">Reversible-Deactivation Radical Polymerization of Methyl Methacrylate and Styrene Mediated by Alkyl Dithiocarbamates and Copper Acetylacetonates</title><author><name sortKey="Yaozhong Zhang" sort="Yaozhong Zhang" uniqKey="Yaozhong Zhang" last="Yaozhong Zhang">YAOZHONG ZHANG</name><affiliation><inist:fA14 i1="01"><s1>Center for Macromolecular Engineering, Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue</s1><s2>Pittsburgh, Pennsylvania 15213</s2><s3>USA</s3><sZ>1 aut.</sZ><sZ>2 aut.</sZ><sZ>4 aut.</sZ><sZ>8 aut.</sZ></inist:fA14></affiliation></author><author><name sortKey="Schroder, Kristin" sort="Schroder, Kristin" uniqKey="Schroder K" first="Kristin" last="Schröder">Kristin Schröder</name><affiliation><inist:fA14 i1="01"><s1>Center for Macromolecular Engineering, Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue</s1><s2>Pittsburgh, Pennsylvania 15213</s2><s3>USA</s3><sZ>1 aut.</sZ><sZ>2 aut.</sZ><sZ>4 aut.</sZ><sZ>8 aut.</sZ></inist:fA14></affiliation></author><author><name sortKey="Kwak, Yungwan" sort="Kwak, Yungwan" uniqKey="Kwak Y" first="Yungwan" last="Kwak">Yungwan Kwak</name><affiliation><inist:fA14 i1="02"><s1>Silberline Manufacturing Co., Inc., 36 Progressive Avenue</s1><s2>Tamaqua, Pennsylvania 18252</s2><s3>USA</s3><sZ>3 aut.</sZ></inist:fA14></affiliation></author><author><name sortKey="Krys, Pawel" sort="Krys, Pawel" uniqKey="Krys P" first="Pawel" last="Krys">Pawel Krys</name><affiliation><inist:fA14 i1="01"><s1>Center for Macromolecular Engineering, Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue</s1><s2>Pittsburgh, Pennsylvania 15213</s2><s3>USA</s3><sZ>1 aut.</sZ><sZ>2 aut.</sZ><sZ>4 aut.</sZ><sZ>8 aut.</sZ></inist:fA14></affiliation></author><author><name sortKey="Morin, Aurelie N" sort="Morin, Aurelie N" uniqKey="Morin A" first="Aurélie N." last="Morin">Aurélie N. Morin</name><affiliation><inist:fA14 i1="03"><s1>Laboratoire de Chimie de Coordination (LCC), CNRS 8241, Université de Toulouse, UPS, INPT, 205 Route de Narbonne</s1><s2>31077 Toulouse</s2><s3>FRA</s3><sZ>5 aut.</sZ><sZ>6 aut.</sZ><sZ>7 aut.</sZ></inist:fA14></affiliation></author><author><name sortKey="Pintauer, Tomislav" sort="Pintauer, Tomislav" uniqKey="Pintauer T" first="Tomislav" last="Pintauer">Tomislav Pintauer</name><affiliation><inist:fA14 i1="03"><s1>Laboratoire de Chimie de Coordination (LCC), CNRS 8241, Université de Toulouse, UPS, INPT, 205 Route de Narbonne</s1><s2>31077 Toulouse</s2><s3>FRA</s3><sZ>5 aut.</sZ><sZ>6 aut.</sZ><sZ>7 aut.</sZ></inist:fA14></affiliation><affiliation><inist:fA14 i1="04"><s1>Department of Chemistry and Biochemistry, Duquesne University, 600 Forbes Avenue, 308 Mellon Hall</s1><s2>Pittsburgh, Pennsylvania 15282</s2><s3>USA</s3><sZ>6 aut.</sZ></inist:fA14></affiliation></author><author><name sortKey="Poli, Rinaldo" sort="Poli, Rinaldo" uniqKey="Poli R" first="Rinaldo" last="Poli">Rinaldo Poli</name><affiliation><inist:fA14 i1="03"><s1>Laboratoire de Chimie de Coordination (LCC), CNRS 8241, Université de Toulouse, UPS, INPT, 205 Route de Narbonne</s1><s2>31077 Toulouse</s2><s3>FRA</s3><sZ>5 aut.</sZ><sZ>6 aut.</sZ><sZ>7 aut.</sZ></inist:fA14></affiliation><affiliation><inist:fA14 i1="05"><s1>Institut Universitaire de France, 103, bd Saint-Michel</s1><s2>75005 Paris</s2><s3>FRA</s3><sZ>7 aut.</sZ></inist:fA14></affiliation></author><author><name sortKey="Matyjaszewski, Krzysztof" sort="Matyjaszewski, Krzysztof" uniqKey="Matyjaszewski K" first="Krzysztof" last="Matyjaszewski">Krzysztof Matyjaszewski</name><affiliation><inist:fA14 i1="01"><s1>Center for Macromolecular Engineering, Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue</s1><s2>Pittsburgh, Pennsylvania 15213</s2><s3>USA</s3><sZ>1 aut.</sZ><sZ>2 aut.</sZ><sZ>4 aut.</sZ><sZ>8 aut.</sZ></inist:fA14></affiliation></author></analytic><series><title level="j" type="main">Macromolecules : (Print)</title><title level="j" type="abbreviated">Macromolecules : (Print)</title><idno type="ISSN">0024-9297</idno><imprint><date when="2013">2013</date></imprint></series></biblStruct></sourceDesc><seriesStmt><title level="j" type="main">Macromolecules : (Print)</title><title level="j" type="abbreviated">Macromolecules : (Print)</title><idno type="ISSN">0024-9297</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Bulk polymerization</term><term>Chain transfer</term><term>Chemical reaction kinetics</term><term>Copper complex</term><term>Density functional method</term><term>Experimental study</term><term>Free radical polymerization</term><term>Living polymer</term><term>Methyl methacrylate polymer</term><term>Modeling</term><term>Organic dithiocarbamate</term><term>Reaction mechanism</term><term>Styrene polymer</term></keywords><keywords scheme="Pascal" xml:lang="fr"><term>Méthacrylate de méthyle polymère</term><term>Styrène polymère</term><term>Polymère vivant</term><term>Polymérisation radicalaire</term><term>Polymérisation masse</term><term>Transfert chaîne</term><term>Dithiocarbamate organique</term><term>Complexe de cuivre</term><term>Cinétique chimique</term><term>Mécanisme réaction</term><term>Modélisation</term><term>Méthode fonctionnelle densité</term><term>Etude expérimentale</term><term>Inifer</term><term>Polymérisation radicalaire désactivation réversible</term></keywords></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">Reversible-deactivation radical polymerization (RDRP) of methyl methacrylate (MMA) and styrene (St) was successfully mediated by copper(II) acetylacetonate, [Cu-(acac)<sub>2</sub>], or copper(II) hexafluoroacetylacetonate, [Cu(hfa)<sub>2</sub>], in conjunction with 1-cyano-1-methylethyl diethyldithiocarbamate (MAN-DC) or 2-(N,N-diethyldithiocarbamyl)ethyl isobutyrate (EMA-DC) initiators/transfer agents in the absence of additional reducing agents. Linear first-order kinetic plots were obtained for the polymerization of MMA in the presence of [Cu(hfa)<sub>2</sub>] or [Cu(acac)<sub>2</sub>] and MAN-DC. [Cu(hfa)<sub>2</sub>] provided better control than [Cu(acac)<sub>2</sub>] for the polymerization of MMA, leading to PMMA with narrow molecular weight distribution, M<sub>w</sub>/M<sub>n</sub> ∼ 1.1. Polymerization of St was successfully carried out with either MAN-DC or EMA-DC in the presence of [Cu(hfa)<sub>2</sub>], also resulting in polymers with low M<sub>w</sub>/M<sub>n</sub> values. In the absence of alkyl dithiocarbamates or copper acetylacetonates, the polymerizations resulted in only trace amounts of polymers or polymers with high values of M<sub>w</sub>/M<sub>n</sub>. Thus, the combination of alkyl dithiocarbamates and copper(II) acetylacetonates provides a convenient way to prepare well-controlled PMMA and PSt. NMR analysis of low-MW polymers reveals the presence of DC groups as chain ends. DFT calculations show that DC group transfer from a H-MMA-DC model of the growing chain to the Cu(II) complexes is energetically accessible and more favorable than Br atom transfer, thus rationalizing the need for the Cu(II)/dithiocarbamate combination for successful control and suggesting that the process takes place by reversible DC group transfer involving a Cu<sup>II</sup>/Cu<sup>III</sup> couple. Attempts to synthesize complexes [Cu(acac)<sub>2</sub>(DC)] and [Cu(hfa)<sub>2</sub>(DC)], in combination with DFT calculations, suggest that these complexes are thermodynamically unstable relative to the bis(diketonate)copper(II) and dithiuram disulfide, but this does not preclude the involvement of the Cu(III) species as a spin trap in RDRP controlled by DC group transfer.</div></front></TEI><inist><standard h6="B"><pA><fA01 i1="01" i2="1"><s0>0024-9297</s0></fA01><fA02 i1="01"><s0>MAMOBX</s0></fA02><fA03 i2="1"><s0>Macromolecules : (Print)</s0></fA03><fA05><s2>46</s2></fA05><fA06><s2>14</s2></fA06><fA08 i1="01" i2="1" l="ENG"><s1>Reversible-Deactivation Radical Polymerization of Methyl Methacrylate and Styrene Mediated by Alkyl Dithiocarbamates and Copper Acetylacetonates</s1></fA08><fA11 i1="01" i2="1"><s1>YAOZHONG ZHANG</s1></fA11><fA11 i1="02" i2="1"><s1>SCHRÖDER (Kristin)</s1></fA11><fA11 i1="03" i2="1"><s1>KWAK (Yungwan)</s1></fA11><fA11 i1="04" i2="1"><s1>KRYS (Pawel)</s1></fA11><fA11 i1="05" i2="1"><s1>MORIN (Aurélie N.)</s1></fA11><fA11 i1="06" i2="1"><s1>PINTAUER (Tomislav)</s1></fA11><fA11 i1="07" i2="1"><s1>POLI (Rinaldo)</s1></fA11><fA11 i1="08" i2="1"><s1>MATYJASZEWSKI (Krzysztof)</s1></fA11><fA14 i1="01"><s1>Center for Macromolecular Engineering, Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue</s1><s2>Pittsburgh, Pennsylvania 15213</s2><s3>USA</s3><sZ>1 aut.</sZ><sZ>2 aut.</sZ><sZ>4 aut.</sZ><sZ>8 aut.</sZ></fA14><fA14 i1="02"><s1>Silberline Manufacturing Co., Inc., 36 Progressive Avenue</s1><s2>Tamaqua, Pennsylvania 18252</s2><s3>USA</s3><sZ>3 aut.</sZ></fA14><fA14 i1="03"><s1>Laboratoire de Chimie de Coordination (LCC), CNRS 8241, Université de Toulouse, UPS, INPT, 205 Route de Narbonne</s1><s2>31077 Toulouse</s2><s3>FRA</s3><sZ>5 aut.</sZ><sZ>6 aut.</sZ><sZ>7 aut.</sZ></fA14><fA14 i1="04"><s1>Department of Chemistry and Biochemistry, Duquesne University, 600 Forbes Avenue, 308 Mellon Hall</s1><s2>Pittsburgh, Pennsylvania 15282</s2><s3>USA</s3><sZ>6 aut.</sZ></fA14><fA14 i1="05"><s1>Institut Universitaire de France, 103, bd Saint-Michel</s1><s2>75005 Paris</s2><s3>FRA</s3><sZ>7 aut.</sZ></fA14><fA20><s1>5512-5519</s1></fA20><fA21><s1>2013</s1></fA21><fA23 i1="01"><s0>ENG</s0></fA23><fA43 i1="01"><s1>INIST</s1><s2>13789</s2><s5>354000506569750130</s5></fA43><fA44><s0>0000</s0><s1>© 2013 INIST-CNRS. All rights reserved.</s1></fA44><fA45><s0>37 ref.</s0></fA45><fA47 i1="01" i2="1"><s0>13-0278832</s0></fA47><fA60><s1>P</s1></fA60><fA61><s0>A</s0></fA61><fA64 i1="01" i2="1"><s0>Macromolecules : (Print)</s0></fA64><fA66 i1="01"><s0>USA</s0></fA66><fC01 i1="01" l="ENG"><s0>Reversible-deactivation radical polymerization (RDRP) of methyl methacrylate (MMA) and styrene (St) was successfully mediated by copper(II) acetylacetonate, [Cu-(acac)<sub>2</sub>], or copper(II) hexafluoroacetylacetonate, [Cu(hfa)<sub>2</sub>], in conjunction with 1-cyano-1-methylethyl diethyldithiocarbamate (MAN-DC) or 2-(N,N-diethyldithiocarbamyl)ethyl isobutyrate (EMA-DC) initiators/transfer agents in the absence of additional reducing agents. Linear first-order kinetic plots were obtained for the polymerization of MMA in the presence of [Cu(hfa)<sub>2</sub>] or [Cu(acac)<sub>2</sub>] and MAN-DC. [Cu(hfa)<sub>2</sub>] provided better control than [Cu(acac)<sub>2</sub>] for the polymerization of MMA, leading to PMMA with narrow molecular weight distribution, M<sub>w</sub>/M<sub>n</sub> ∼ 1.1. Polymerization of St was successfully carried out with either MAN-DC or EMA-DC in the presence of [Cu(hfa)<sub>2</sub>], also resulting in polymers with low M<sub>w</sub>/M<sub>n</sub> values. In the absence of alkyl dithiocarbamates or copper acetylacetonates, the polymerizations resulted in only trace amounts of polymers or polymers with high values of M<sub>w</sub>/M<sub>n</sub>. Thus, the combination of alkyl dithiocarbamates and copper(II) acetylacetonates provides a convenient way to prepare well-controlled PMMA and PSt. NMR analysis of low-MW polymers reveals the presence of DC groups as chain ends. DFT calculations show that DC group transfer from a H-MMA-DC model of the growing chain to the Cu(II) complexes is energetically accessible and more favorable than Br atom transfer, thus rationalizing the need for the Cu(II)/dithiocarbamate combination for successful control and suggesting that the process takes place by reversible DC group transfer involving a Cu<sup>II</sup>/Cu<sup>III</sup> couple. Attempts to synthesize complexes [Cu(acac)<sub>2</sub>(DC)] and [Cu(hfa)<sub>2</sub>(DC)], in combination with DFT calculations, suggest that these complexes are thermodynamically unstable relative to the bis(diketonate)copper(II) and dithiuram disulfide, but this does not preclude the involvement of the Cu(III) species as a spin trap in RDRP controlled by DC group transfer.</s0></fC01><fC02 i1="01" i2="X"><s0>001D09D02B</s0></fC02><fC03 i1="01" i2="X" l="FRE"><s0>Méthacrylate de méthyle polymère</s0><s2>NK</s2><s5>01</s5></fC03><fC03 i1="01" i2="X" l="ENG"><s0>Methyl methacrylate polymer</s0><s2>NK</s2><s5>01</s5></fC03><fC03 i1="01" i2="X" l="SPA"><s0>Metacrilato de metilo polímero</s0><s2>NK</s2><s5>01</s5></fC03><fC03 i1="02" i2="X" l="FRE"><s0>Styrène polymère</s0><s2>NK</s2><s5>02</s5></fC03><fC03 i1="02" i2="X" l="ENG"><s0>Styrene polymer</s0><s2>NK</s2><s5>02</s5></fC03><fC03 i1="02" i2="X" l="SPA"><s0>Estireno polímero</s0><s2>NK</s2><s5>02</s5></fC03><fC03 i1="03" i2="X" l="FRE"><s0>Polymère vivant</s0><s5>03</s5></fC03><fC03 i1="03" i2="X" l="ENG"><s0>Living polymer</s0><s5>03</s5></fC03><fC03 i1="03" i2="X" l="SPA"><s0>Polímero viviente</s0><s5>03</s5></fC03><fC03 i1="04" i2="X" l="FRE"><s0>Polymérisation radicalaire</s0><s5>06</s5></fC03><fC03 i1="04" i2="X" l="ENG"><s0>Free radical polymerization</s0><s5>06</s5></fC03><fC03 i1="04" i2="X" l="SPA"><s0>Polimerización radicalar</s0><s5>06</s5></fC03><fC03 i1="05" i2="X" l="FRE"><s0>Polymérisation masse</s0><s5>07</s5></fC03><fC03 i1="05" i2="X" l="ENG"><s0>Bulk polymerization</s0><s5>07</s5></fC03><fC03 i1="05" i2="X" l="SPA"><s0>Polimerización masa</s0><s5>07</s5></fC03><fC03 i1="06" i2="X" l="FRE"><s0>Transfert chaîne</s0><s5>08</s5></fC03><fC03 i1="06" i2="X" l="ENG"><s0>Chain transfer</s0><s5>08</s5></fC03><fC03 i1="06" i2="X" l="SPA"><s0>Transferencia en cadena</s0><s5>08</s5></fC03><fC03 i1="07" i2="X" l="FRE"><s0>Dithiocarbamate organique</s0><s1>ACT</s1><s5>09</s5></fC03><fC03 i1="07" i2="X" l="ENG"><s0>Organic dithiocarbamate</s0><s1>ACT</s1><s5>09</s5></fC03><fC03 i1="07" i2="X" l="SPA"><s0>Ditiocarbamato orgánico</s0><s1>ACT</s1><s5>09</s5></fC03><fC03 i1="08" i2="X" l="FRE"><s0>Complexe de cuivre</s0><s1>ACT</s1><s5>10</s5></fC03><fC03 i1="08" i2="X" l="ENG"><s0>Copper complex</s0><s1>ACT</s1><s5>10</s5></fC03><fC03 i1="08" i2="X" l="SPA"><s0>Cobre complejo</s0><s1>ACT</s1><s5>10</s5></fC03><fC03 i1="09" i2="X" l="FRE"><s0>Cinétique chimique</s0><s5>12</s5></fC03><fC03 i1="09" i2="X" l="ENG"><s0>Chemical reaction kinetics</s0><s5>12</s5></fC03><fC03 i1="09" i2="X" l="SPA"><s0>Cinética química</s0><s5>12</s5></fC03><fC03 i1="10" i2="X" l="FRE"><s0>Mécanisme réaction</s0><s5>13</s5></fC03><fC03 i1="10" i2="X" l="ENG"><s0>Reaction mechanism</s0><s5>13</s5></fC03><fC03 i1="10" i2="X" l="SPA"><s0>Mecanismo reacción</s0><s5>13</s5></fC03><fC03 i1="11" i2="X" l="FRE"><s0>Modélisation</s0><s5>14</s5></fC03><fC03 i1="11" i2="X" l="ENG"><s0>Modeling</s0><s5>14</s5></fC03><fC03 i1="11" i2="X" l="SPA"><s0>Modelización</s0><s5>14</s5></fC03><fC03 i1="12" i2="3" l="FRE"><s0>Méthode fonctionnelle densité</s0><s5>15</s5></fC03><fC03 i1="12" i2="3" l="ENG"><s0>Density functional method</s0><s5>15</s5></fC03><fC03 i1="13" i2="X" l="FRE"><s0>Etude expérimentale</s0><s5>17</s5></fC03><fC03 i1="13" i2="X" l="ENG"><s0>Experimental study</s0><s5>17</s5></fC03><fC03 i1="13" i2="X" l="SPA"><s0>Estudio experimental</s0><s5>17</s5></fC03><fC03 i1="14" i2="X" l="FRE"><s0>Inifer</s0><s4>INC</s4><s5>32</s5></fC03><fC03 i1="15" i2="X" l="FRE"><s0>Polymérisation radicalaire désactivation réversible</s0><s4>INC</s4><s5>33</s5></fC03><fN21><s1>266</s1></fN21><fN44 i1="01"><s1>PSI</s1></fN44><fN82><s1>PSI</s1></fN82></pA></standard><server><NO>PASCAL 13-0278832 INIST</NO><ET>Reversible-Deactivation Radical Polymerization of Methyl Methacrylate and Styrene Mediated by Alkyl Dithiocarbamates and Copper Acetylacetonates</ET><AU>YAOZHONG ZHANG; SCHRÖDER (Kristin); KWAK (Yungwan); KRYS (Pawel); MORIN (Aurélie N.); PINTAUER (Tomislav); POLI (Rinaldo); MATYJASZEWSKI (Krzysztof)</AU><AF>Center for Macromolecular Engineering, Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue/Pittsburgh, Pennsylvania 15213/Etats-Unis (1 aut., 2 aut., 4 aut., 8 aut.); Silberline Manufacturing Co., Inc., 36 Progressive Avenue/Tamaqua, Pennsylvania 18252/Etats-Unis (3 aut.); Laboratoire de Chimie de Coordination (LCC), CNRS 8241, Université de Toulouse, UPS, INPT, 205 Route de Narbonne/31077 Toulouse/France (5 aut., 6 aut., 7 aut.); Department of Chemistry and Biochemistry, Duquesne University, 600 Forbes Avenue, 308 Mellon Hall/Pittsburgh, Pennsylvania 15282/Etats-Unis (6 aut.); Institut Universitaire de France, 103, bd Saint-Michel/75005 Paris/France (7 aut.)</AF><DT>Publication en série; Niveau analytique</DT><SO>Macromolecules : (Print); ISSN 0024-9297; Coden MAMOBX; Etats-Unis; Da. 2013; Vol. 46; No. 14; Pp. 5512-5519; Bibl. 37 ref.</SO><LA>Anglais</LA><EA>Reversible-deactivation radical polymerization (RDRP) of methyl methacrylate (MMA) and styrene (St) was successfully mediated by copper(II) acetylacetonate, [Cu-(acac)<sub>2</sub>], or copper(II) hexafluoroacetylacetonate, [Cu(hfa)<sub>2</sub>], in conjunction with 1-cyano-1-methylethyl diethyldithiocarbamate (MAN-DC) or 2-(N,N-diethyldithiocarbamyl)ethyl isobutyrate (EMA-DC) initiators/transfer agents in the absence of additional reducing agents. Linear first-order kinetic plots were obtained for the polymerization of MMA in the presence of [Cu(hfa)<sub>2</sub>] or [Cu(acac)<sub>2</sub>] and MAN-DC. [Cu(hfa)<sub>2</sub>] provided better control than [Cu(acac)<sub>2</sub>] for the polymerization of MMA, leading to PMMA with narrow molecular weight distribution, M<sub>w</sub>/M<sub>n</sub> ∼ 1.1. Polymerization of St was successfully carried out with either MAN-DC or EMA-DC in the presence of [Cu(hfa)<sub>2</sub>], also resulting in polymers with low M<sub>w</sub>/M<sub>n</sub> values. In the absence of alkyl dithiocarbamates or copper acetylacetonates, the polymerizations resulted in only trace amounts of polymers or polymers with high values of M<sub>w</sub>/M<sub>n</sub>. Thus, the combination of alkyl dithiocarbamates and copper(II) acetylacetonates provides a convenient way to prepare well-controlled PMMA and PSt. NMR analysis of low-MW polymers reveals the presence of DC groups as chain ends. DFT calculations show that DC group transfer from a H-MMA-DC model of the growing chain to the Cu(II) complexes is energetically accessible and more favorable than Br atom transfer, thus rationalizing the need for the Cu(II)/dithiocarbamate combination for successful control and suggesting that the process takes place by reversible DC group transfer involving a Cu<sup>II</sup>/Cu<sup>III</sup> couple. Attempts to synthesize complexes [Cu(acac)<sub>2</sub>(DC)] and [Cu(hfa)<sub>2</sub>(DC)], in combination with DFT calculations, suggest that these complexes are thermodynamically unstable relative to the bis(diketonate)copper(II) and dithiuram disulfide, but this does not preclude the involvement of the Cu(III) species as a spin trap in RDRP controlled by DC group transfer.</EA><CC>001D09D02B</CC><FD>Méthacrylate de méthyle polymère; Styrène polymère; Polymère vivant; Polymérisation radicalaire; Polymérisation masse; Transfert chaîne; Dithiocarbamate organique; Complexe de cuivre; Cinétique chimique; Mécanisme réaction; Modélisation; Méthode fonctionnelle densité; Etude expérimentale; Inifer; Polymérisation radicalaire désactivation réversible</FD><ED>Methyl methacrylate polymer; Styrene polymer; Living polymer; Free radical polymerization; Bulk polymerization; Chain transfer; Organic dithiocarbamate; Copper complex; Chemical reaction kinetics; Reaction mechanism; Modeling; Density functional method; Experimental study</ED><SD>Metacrilato de metilo polímero; Estireno polímero; Polímero viviente; Polimerización radicalar; Polimerización masa; Transferencia en cadena; Ditiocarbamato orgánico; Cobre complejo; Cinética química; Mecanismo reacción; Modelización; Estudio experimental</SD><LO>INIST-13789.354000506569750130</LO><ID>13-0278832</ID></server></inist></record>Pour manipuler ce document sous Unix (Dilib)
EXPLOR_STEP=$WICRI_ROOT/Wicri/Amérique/explor/PittsburghV1/Data/PascalFrancis/Corpus
HfdSelect -h $EXPLOR_STEP/biblio.hfd -nk 001C19 | SxmlIndent | more
Ou
HfdSelect -h $EXPLOR_AREA/Data/PascalFrancis/Corpus/biblio.hfd -nk 001C19 | SxmlIndent | more
Pour mettre un lien sur cette page dans le réseau Wicri
{{Explor lien
|wiki= Wicri/Amérique
|area= PittsburghV1
|flux= PascalFrancis
|étape= Corpus
|type= RBID
|clé= Pascal:13-0278832
|texte= Reversible-Deactivation Radical Polymerization of Methyl Methacrylate and Styrene Mediated by Alkyl Dithiocarbamates and Copper Acetylacetonates
}}
| This area was generated with Dilib version V0.6.38. |  |