Studies on chemical oxidative copolymerization of aniline and o -alkoxysulfonated anilines II. Mechanistic approach and monomer reactivity ratios
Identifieur interne : 000898 ( Istex/Corpus ); précédent : 000897; suivant : 000899Studies on chemical oxidative copolymerization of aniline and o -alkoxysulfonated anilines II. Mechanistic approach and monomer reactivity ratios
Auteurs : V. Prévost ; A. Petit ; F. PlaSource :
- European Polymer Journal [ 0014-3057 ] ; 1999.
English descriptors
- KwdEn :
- Acidic medium, Alkoxysulfonated, Alkoxysulfonated aniline, Alkoxysulfonated aniline derivatives, Alkoxysulfonated anilines, Ammonium persulfate, Aniline, Aniline molecule, Aniline monomer, Apbus, Apprs, Aqueous solutions, Block copolymers, Bulky alkoxysulfonated groups, Chem, Chemical copolymerization, Chemical oxidative copolymerization, Copolymer, Copolymer compositions, Copolymer samples, Copolymer yields, Copolymerization, Copolymerization parameters, Copolymerization process, Derivative, Electrical properties, Electroanal chem, Electrochim acta, Electrophilic attack, Elsevier science, European polymer journal, Experimental data, Initial feed composition, Macromolecule, Mole, Mole fraction, Monomer, Monomer reactivity ratios, Nancy cedex, Other hand, Phys chem, Polym chem, Polymer, Polymerization degree, Polymerization degrees, Present work, Propagation process, Propagation step, Propagation steps, Reactivity ratios, Steric hindrance, Synth.
- Teeft :
- Acidic medium, Alkoxysulfonated, Alkoxysulfonated aniline, Alkoxysulfonated aniline derivatives, Alkoxysulfonated anilines, Ammonium persulfate, Aniline, Aniline molecule, Aniline monomer, Apbus, Apprs, Aqueous solutions, Block copolymers, Bulky alkoxysulfonated groups, Chem, Chemical copolymerization, Chemical oxidative copolymerization, Copolymer, Copolymer compositions, Copolymer samples, Copolymer yields, Copolymerization, Copolymerization parameters, Copolymerization process, Derivative, Electrical properties, Electroanal chem, Electrochim acta, Electrophilic attack, Elsevier science, European polymer journal, Experimental data, Initial feed composition, Macromolecule, Mole, Mole fraction, Monomer, Monomer reactivity ratios, Nancy cedex, Other hand, Phys chem, Polym chem, Polymer, Polymerization degree, Polymerization degrees, Present work, Propagation process, Propagation step, Propagation steps, Reactivity ratios, Steric hindrance, Synth.
Abstract
Abstract: The copolymerization of aniline (An) with o-alkoxysulfonated anilines, i.e. 1-(o-amino)-propane-3-sulfonic acid (APPrS) and 1-(o-amino)-butane-4-sulfonic acid (APBuS), was a new way to produce water-soluble and self-doped polyaniline derivatives. Poly(An-co-APPrS) and poly(An-co-APBuS) were synthesized, in H2SO4 acidic medium, by chemical oxidation using ammonium persulfate. The mechanistic study showed that, during their copolymerization, aniline and alkoxysulfonated-derivatives exhibit two opposite behaviors towards the initial mechanism of dimerization and the following growing process. Because of the steric hindrance of the bulky alkoxysulfonated groups, the dimerization process involved at least one molecule of aniline. On the contrary, in the course of the propagation step, due to the electron-donating effect of the substituent, both alkoxysulfonated anilines exhibited much greater reactivity than aniline and hence were easily incorporated into the growing polymer chains. The comonomer reactivity ratios, computed by using the extended Kelen–Tüdös method, were as follows: rAn=0.04±0.01, rAPPrS=27±9 and rAn=0.04±0.01, rAPBuS=12±6. These findings strongly suggest the formation of block copolymers.
Url:
DOI: 10.1016/S0014-3057(98)00211-0
Links to Exploration step
ISTEX:EBAA4A1F067E192D17839858D1AB4F6C5C406EBCLe document en format XML
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Pla</name><affiliation><mods:affiliation>Laboratoire des Sciences du Génie Chimique, CNRS UPR 6811, ENSIC-INPL, 1, rue Grandville, BP 451, 54001 Nancy cedex, France</mods:affiliation></affiliation></author></titleStmt><publicationStmt><idno type="wicri:source">ISTEX</idno><idno type="RBID">ISTEX:EBAA4A1F067E192D17839858D1AB4F6C5C406EBC</idno><date when="1999" year="1999">1999</date><idno type="doi">10.1016/S0014-3057(98)00211-0</idno><idno type="url">https://api.istex.fr/document/EBAA4A1F067E192D17839858D1AB4F6C5C406EBC/fulltext/pdf</idno><idno type="wicri:Area/Istex/Corpus">000898</idno><idno type="wicri:explorRef" wicri:stream="Istex" wicri:step="Corpus" wicri:corpus="ISTEX">000898</idno></publicationStmt><sourceDesc><biblStruct><analytic><title level="a">Studies on chemical oxidative copolymerization of aniline and o -alkoxysulfonated anilines II. Mechanistic approach and monomer reactivity ratios</title><author><name sortKey="Prevost, V" sort="Prevost, V" uniqKey="Prevost V" first="V." last="Prévost">V. Prévost</name><affiliation><mods:affiliation>Laboratoire des Sciences du Génie Chimique, CNRS UPR 6811, ENSIC-INPL, 1, rue Grandville, BP 451, 54001 Nancy cedex, France</mods:affiliation></affiliation></author><author><name sortKey="Petit, A" sort="Petit, A" uniqKey="Petit A" first="A." last="Petit">A. Petit</name><affiliation><mods:affiliation>Laboratoire de Chimie-Physique Macromoléculaire, CNRS UMR 7568, ENSIC-INPL, 1, rue Grandville, BP 451, 54001 Nancy cedex, France</mods:affiliation></affiliation></author><author><name sortKey="Pla, F" sort="Pla, F" uniqKey="Pla F" first="F." last="Pla">F. Pla</name><affiliation><mods:affiliation>Laboratoire des Sciences du Génie Chimique, CNRS UPR 6811, ENSIC-INPL, 1, rue Grandville, BP 451, 54001 Nancy cedex, France</mods:affiliation></affiliation></author></analytic><monogr></monogr><series><title level="j">European Polymer Journal</title><title level="j" type="abbrev">EPJ</title><idno type="ISSN">0014-3057</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1999">1999</date><biblScope unit="volume">35</biblScope><biblScope unit="issue">7</biblScope><biblScope unit="page" from="1229">1229</biblScope><biblScope unit="page" to="1236">1236</biblScope></imprint><idno type="ISSN">0014-3057</idno></series></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0014-3057</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Acidic medium</term><term>Alkoxysulfonated</term><term>Alkoxysulfonated aniline</term><term>Alkoxysulfonated aniline derivatives</term><term>Alkoxysulfonated anilines</term><term>Ammonium persulfate</term><term>Aniline</term><term>Aniline molecule</term><term>Aniline monomer</term><term>Apbus</term><term>Apprs</term><term>Aqueous solutions</term><term>Block copolymers</term><term>Bulky alkoxysulfonated groups</term><term>Chem</term><term>Chemical copolymerization</term><term>Chemical oxidative copolymerization</term><term>Copolymer</term><term>Copolymer compositions</term><term>Copolymer samples</term><term>Copolymer yields</term><term>Copolymerization</term><term>Copolymerization parameters</term><term>Copolymerization process</term><term>Derivative</term><term>Electrical properties</term><term>Electroanal chem</term><term>Electrochim acta</term><term>Electrophilic attack</term><term>Elsevier science</term><term>European polymer journal</term><term>Experimental data</term><term>Initial feed composition</term><term>Macromolecule</term><term>Mole</term><term>Mole fraction</term><term>Monomer</term><term>Monomer reactivity ratios</term><term>Nancy cedex</term><term>Other hand</term><term>Phys chem</term><term>Polym chem</term><term>Polymer</term><term>Polymerization degree</term><term>Polymerization degrees</term><term>Present work</term><term>Propagation process</term><term>Propagation step</term><term>Propagation steps</term><term>Reactivity ratios</term><term>Steric hindrance</term><term>Synth</term></keywords><keywords scheme="Teeft" xml:lang="en"><term>Acidic medium</term><term>Alkoxysulfonated</term><term>Alkoxysulfonated aniline</term><term>Alkoxysulfonated aniline derivatives</term><term>Alkoxysulfonated anilines</term><term>Ammonium persulfate</term><term>Aniline</term><term>Aniline molecule</term><term>Aniline monomer</term><term>Apbus</term><term>Apprs</term><term>Aqueous solutions</term><term>Block copolymers</term><term>Bulky alkoxysulfonated groups</term><term>Chem</term><term>Chemical copolymerization</term><term>Chemical oxidative copolymerization</term><term>Copolymer</term><term>Copolymer compositions</term><term>Copolymer samples</term><term>Copolymer yields</term><term>Copolymerization</term><term>Copolymerization parameters</term><term>Copolymerization process</term><term>Derivative</term><term>Electrical properties</term><term>Electroanal chem</term><term>Electrochim acta</term><term>Electrophilic attack</term><term>Elsevier science</term><term>European polymer journal</term><term>Experimental data</term><term>Initial feed composition</term><term>Macromolecule</term><term>Mole</term><term>Mole fraction</term><term>Monomer</term><term>Monomer reactivity ratios</term><term>Nancy cedex</term><term>Other hand</term><term>Phys chem</term><term>Polym chem</term><term>Polymer</term><term>Polymerization degree</term><term>Polymerization degrees</term><term>Present work</term><term>Propagation process</term><term>Propagation step</term><term>Propagation steps</term><term>Reactivity ratios</term><term>Steric hindrance</term><term>Synth</term></keywords></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">Abstract: The copolymerization of aniline (An) with o-alkoxysulfonated anilines, i.e. 1-(o-amino)-propane-3-sulfonic acid (APPrS) and 1-(o-amino)-butane-4-sulfonic acid (APBuS), was a new way to produce water-soluble and self-doped polyaniline derivatives. Poly(An-co-APPrS) and poly(An-co-APBuS) were synthesized, in H2SO4 acidic medium, by chemical oxidation using ammonium persulfate. The mechanistic study showed that, during their copolymerization, aniline and alkoxysulfonated-derivatives exhibit two opposite behaviors towards the initial mechanism of dimerization and the following growing process. Because of the steric hindrance of the bulky alkoxysulfonated groups, the dimerization process involved at least one molecule of aniline. On the contrary, in the course of the propagation step, due to the electron-donating effect of the substituent, both alkoxysulfonated anilines exhibited much greater reactivity than aniline and hence were easily incorporated into the growing polymer chains. The comonomer reactivity ratios, computed by using the extended Kelen–Tüdös method, were as follows: rAn=0.04±0.01, rAPPrS=27±9 and rAn=0.04±0.01, rAPBuS=12±6. 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Prévost</name><affiliations><json:string>Laboratoire des Sciences du Génie Chimique, CNRS UPR 6811, ENSIC-INPL, 1, rue Grandville, BP 451, 54001 Nancy cedex, France</json:string></affiliations></json:item><json:item><name>A. Petit</name><affiliations><json:string>Laboratoire de Chimie-Physique Macromoléculaire, CNRS UMR 7568, ENSIC-INPL, 1, rue Grandville, BP 451, 54001 Nancy cedex, France</json:string></affiliations></json:item><json:item><name>F. Pla</name><affiliations><json:string>Laboratoire des Sciences du Génie Chimique, CNRS UPR 6811, ENSIC-INPL, 1, rue Grandville, BP 451, 54001 Nancy cedex, France</json:string></affiliations></json:item></author><subject><json:item><lang><json:string>eng</json:string></lang><value>Aniline</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>o-alkoxysulfonated aniline</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Chemical oxidative copolymerization</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Reactivity ratio</value></json:item></subject><language><json:string>eng</json:string></language><originalGenre><json:string>Full-length article</json:string></originalGenre><abstract>The copolymerization of aniline (An) with o-alkoxysulfonated anilines, i.e. 1-(o-amino)-propane-3-sulfonic acid (APPrS) and 1-(o-amino)-butane-4-sulfonic acid (APBuS), was a new way to produce water-soluble and self-doped polyaniline derivatives. Poly(An-co-APPrS) and poly(An-co-APBuS) were synthesized, in H2SO4 acidic medium, by chemical oxidation using ammonium persulfate. The mechanistic study showed that, during their copolymerization, aniline and alkoxysulfonated-derivatives exhibit two opposite behaviors towards the initial mechanism of dimerization and the following growing process. Because of the steric hindrance of the bulky alkoxysulfonated groups, the dimerization process involved at least one molecule of aniline. On the contrary, in the course of the propagation step, due to the electron-donating effect of the substituent, both alkoxysulfonated anilines exhibited much greater reactivity than aniline and hence were easily incorporated into the growing polymer chains. The comonomer reactivity ratios, computed by using the extended Kelen–Tüdös method, were as follows: rAn=0.04±0.01, rAPPrS=27±9 and rAn=0.04±0.01, rAPBuS=12±6. These findings strongly suggest the formation of block copolymers.</abstract><qualityIndicators><score>4.997</score><pdfVersion>1.2</pdfVersion><pdfPageSize>543 x 745 pts</pdfPageSize><refBibsNative>true</refBibsNative><keywordCount>4</keywordCount><abstractCharCount>1219</abstractCharCount><pdfWordCount>3161</pdfWordCount><pdfCharCount>21238</pdfCharCount><pdfPageCount>8</pdfPageCount><abstractWordCount>153</abstractWordCount></qualityIndicators><title>Studies on chemical oxidative copolymerization of aniline and o -alkoxysulfonated anilines II. Mechanistic approach and monomer reactivity ratios</title><pii><json:string>S0014-3057(98)00211-0</json:string></pii><genre><json:string>research-article</json:string></genre><host><title>European Polymer Journal</title><language><json:string>unknown</json:string></language><publicationDate>1999</publicationDate><issn><json:string>0014-3057</json:string></issn><pii><json:string>S0014-3057(00)X0048-1</json:string></pii><volume>35</volume><issue>7</issue><pages><first>1229</first><last>1236</last></pages><genre><json:string>journal</json:string></genre></host><categories><wos><json:string>science</json:string><json:string>polymer science</json:string></wos><scienceMetrix><json:string>natural sciences</json:string><json:string>chemistry</json:string><json:string>polymers</json:string></scienceMetrix><inist><json:string>sciences appliquees, technologies et medecines</json:string><json:string>sciences biologiques et medicales</json:string><json:string>sciences biologiques fondamentales et appliquees. psychologie</json:string></inist></categories><publicationDate>1999</publicationDate><copyrightDate>1999</copyrightDate><doi><json:string>10.1016/S0014-3057(98)00211-0</json:string></doi><id>EBAA4A1F067E192D17839858D1AB4F6C5C406EBC</id><score>1</score><fulltext><json:item><extension>pdf</extension><original>true</original><mimetype>application/pdf</mimetype><uri>https://api.istex.fr/document/EBAA4A1F067E192D17839858D1AB4F6C5C406EBC/fulltext/pdf</uri></json:item><json:item><extension>zip</extension><original>false</original><mimetype>application/zip</mimetype><uri>https://api.istex.fr/document/EBAA4A1F067E192D17839858D1AB4F6C5C406EBC/fulltext/zip</uri></json:item><istex:fulltextTEI uri="https://api.istex.fr/document/EBAA4A1F067E192D17839858D1AB4F6C5C406EBC/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a">Studies on chemical oxidative copolymerization of aniline and o -alkoxysulfonated anilines II. Mechanistic approach and monomer reactivity ratios</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>ELSEVIER</publisher><availability><p>©1999 Elsevier Science Ltd</p></availability><date>1999</date></publicationStmt><notesStmt><note type="content">Scheme. SC1:</note><note type="content">Scheme. SC2:</note><note type="content">Scheme. SC3:</note><note type="content">Fig. 1: Experimental data for the chemical oxidative copolymerization of aniline (An) with o-alkoxysulfonated aniline: (A) 1-(o-amino)-propane-3-sulfonic acid (APPrS); (B) 1-(o-amino)-butane-4-sulfonic acid (APBuS).</note><note type="content">Scheme. SC4:</note><note type="content">Scheme. SC5:</note><note type="content">Fig. 2: Mole conversion rates of aniline (⋅) and aniline-derivative (○) vs the feed composition: (A) aniline/1-(o-amino)-propane-3-sulfonic acid; (B) aniline/1-(o-amino)-butane-4-sulfonic acid, for 0.16</note> <note type="content">Fig. 3: Kelen–Tüdös plots for the chemical oxidative copolymerization of aniline (An) with: (A) 1-(o-amino)-propane-3-sulfonic acid (APPrS); and (B) 1-(o-amino)-butane-4-sulfonic acid (APBuS). Constants of Kelen–Tüdös equation: α=946 and 410 for (A) and (B), respectively.</note><note type="content">Fig. 4: Composition diagrams for the chemical oxidative copolymerization of aniline (An) with alkoxysulfonated aniline: (A) 1-(o- amino)-propane-3-sulfonic acid (APPrS); (B) 1-(o-amino)-butane-4-sulfonic acid (APBuS). ▵: experimental data corrected according to the extended Kelen–Tüdös method; solid line: curve calculated from terminal-unit model with rAn=0.04, rAPPrS=27 (A) and rAn=0.04, rAPBuS=12 (B).</note><note type="content">Table 1: Chemical copolymerization of aniline (An) with 1-(o-amino)-propane-3-sulfonic acid (APPrS) and 1-(o-amino)-butane-4-sulfonic acid (APBuS)a</note><note type="content">Table 2: Reactivity ratios for the chemical oxidative copolymerization of aniline (An) with 1-(o-amino)-propane-3-sulfonic acid (APPrS) and 1-(o-amino)-butane-4-sulfonic acid (APBuS)a</note></notesStmt><sourceDesc><biblStruct type="inbook"><analytic><title level="a">Studies on chemical oxidative copolymerization of aniline and o -alkoxysulfonated anilines II. Mechanistic approach and monomer reactivity ratios</title><author xml:id="author-0000"><persName><forename type="first">V.</forename><surname>Prévost</surname></persName><affiliation>Laboratoire des Sciences du Génie Chimique, CNRS UPR 6811, ENSIC-INPL, 1, rue Grandville, BP 451, 54001 Nancy cedex, France</affiliation></author><author xml:id="author-0001"><persName><forename type="first">A.</forename><surname>Petit</surname></persName><note type="correspondence"><p>Corresponding author: Tel.: (33) 03 83 17 50 95; fax: (33) 03 83 37 99 77</p></note><affiliation>Laboratoire de Chimie-Physique Macromoléculaire, CNRS UMR 7568, ENSIC-INPL, 1, rue Grandville, BP 451, 54001 Nancy cedex, France</affiliation></author><author xml:id="author-0002"><persName><forename type="first">F.</forename><surname>Pla</surname></persName><affiliation>Laboratoire des Sciences du Génie Chimique, CNRS UPR 6811, ENSIC-INPL, 1, rue Grandville, BP 451, 54001 Nancy cedex, France</affiliation></author><idno type="istex">EBAA4A1F067E192D17839858D1AB4F6C5C406EBC</idno><idno type="DOI">10.1016/S0014-3057(98)00211-0</idno><idno type="PII">S0014-3057(98)00211-0</idno></analytic><monogr><title level="j">European Polymer Journal</title><title level="j" type="abbrev">EPJ</title><idno type="pISSN">0014-3057</idno><idno type="PII">S0014-3057(00)X0048-1</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1999"></date><biblScope unit="volume">35</biblScope><biblScope unit="issue">7</biblScope><biblScope unit="page" from="1229">1229</biblScope><biblScope unit="page" to="1236">1236</biblScope></imprint></monogr></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>1999</date></creation><langUsage><language ident="en">en</language></langUsage><abstract xml:lang="en"><p>The copolymerization of aniline (An) with o-alkoxysulfonated anilines, i.e. 1-(o-amino)-propane-3-sulfonic acid (APPrS) and 1-(o-amino)-butane-4-sulfonic acid (APBuS), was a new way to produce water-soluble and self-doped polyaniline derivatives. Poly(An-co-APPrS) and poly(An-co-APBuS) were synthesized, in H2SO4 acidic medium, by chemical oxidation using ammonium persulfate. The mechanistic study showed that, during their copolymerization, aniline and alkoxysulfonated-derivatives exhibit two opposite behaviors towards the initial mechanism of dimerization and the following growing process. Because of the steric hindrance of the bulky alkoxysulfonated groups, the dimerization process involved at least one molecule of aniline. On the contrary, in the course of the propagation step, due to the electron-donating effect of the substituent, both alkoxysulfonated anilines exhibited much greater reactivity than aniline and hence were easily incorporated into the growing polymer chains. The comonomer reactivity ratios, computed by using the extended Kelen–Tüdös method, were as follows: rAn=0.04±0.01, rAPPrS=27±9 and rAn=0.04±0.01, rAPBuS=12±6. These findings strongly suggest the formation of block copolymers.</p></abstract><textClass><keywords scheme="keyword"><list><head>Keywords</head><item><term>Aniline</term></item><item><term>o-alkoxysulfonated aniline</term></item><item><term>Chemical oxidative copolymerization</term></item><item><term>Reactivity ratio</term></item></list></keywords></textClass></profileDesc><revisionDesc><change when="1999">Published</change></revisionDesc></teiHeader></istex:fulltextTEI><json:item><extension>txt</extension><original>false</original><mimetype>text/plain</mimetype><uri>https://api.istex.fr/document/EBAA4A1F067E192D17839858D1AB4F6C5C406EBC/fulltext/txt</uri></json:item></fulltext><metadata><istex:metadataXml wicri:clean="Elsevier, elements deleted: ce:floats; body; tail"><istex:xmlDeclaration>version="1.0" encoding="utf-8"</istex:xmlDeclaration><istex:docType PUBLIC="-//ES//DTD journal article DTD version 4.5.2//EN//XML" URI="art452.dtd" name="istex:docType"><istex:entity SYSTEM="sc1" NDATA="IMAGE" name="sc1"></istex:entity><istex:entity SYSTEM="sc2" NDATA="IMAGE" name="sc2"></istex:entity><istex:entity SYSTEM="sc3" NDATA="IMAGE" name="sc3"></istex:entity><istex:entity SYSTEM="gr1" NDATA="IMAGE" name="gr1"></istex:entity><istex:entity SYSTEM="sc4" NDATA="IMAGE" name="sc4"></istex:entity><istex:entity SYSTEM="sc5" NDATA="IMAGE" name="sc5"></istex:entity><istex:entity SYSTEM="gr2" NDATA="IMAGE" name="gr2"></istex:entity><istex:entity SYSTEM="gr3" NDATA="IMAGE" name="gr3"></istex:entity><istex:entity SYSTEM="gr4" NDATA="IMAGE" name="gr4"></istex:entity></istex:docType><istex:document><converted-article version="4.5.2" docsubtype="fla"><item-info><jid>EPJ</jid><aid>1311</aid><ce:pii>S0014-3057(98)00211-0</ce:pii><ce:doi>10.1016/S0014-3057(98)00211-0</ce:doi><ce:copyright year="1999" type="full-transfer">Elsevier Science Ltd</ce:copyright></item-info><head><ce:title>Studies on chemical oxidative copolymerization of aniline and <ce:italic>o</ce:italic>-alkoxysulfonated anilines II. Mechanistic approach and monomer reactivity ratios</ce:title><ce:author-group><ce:author><ce:given-name>V.</ce:given-name><ce:surname>Prévost</ce:surname><ce:cross-ref refid="AFF1">a</ce:cross-ref></ce:author><ce:author><ce:given-name>A.</ce:given-name><ce:surname>Petit</ce:surname><ce:cross-ref refid="AFF2">b</ce:cross-ref><ce:cross-ref refid="CORR1">*</ce:cross-ref></ce:author><ce:author><ce:given-name>F.</ce:given-name><ce:surname>Pla</ce:surname><ce:cross-ref refid="AFF1">a</ce:cross-ref></ce:author><ce:affiliation id="AFF1"><ce:label>a</ce:label><ce:textfn>Laboratoire des Sciences du Génie Chimique, CNRS UPR 6811, ENSIC-INPL, 1, rue Grandville, BP 451, 54001 Nancy cedex, France</ce:textfn></ce:affiliation><ce:affiliation id="AFF2"><ce:label>b</ce:label><ce:textfn>Laboratoire de Chimie-Physique Macromoléculaire, CNRS UMR 7568, ENSIC-INPL, 1, rue Grandville, BP 451, 54001 Nancy cedex, France</ce:textfn></ce:affiliation><ce:correspondence id="CORR1"><ce:label>*</ce:label><ce:text>Corresponding author: Tel.: (33) 03 83 17 50 95; fax: (33) 03 83 37 99 77</ce:text></ce:correspondence></ce:author-group><ce:date-received day="20" month="5" year="1998"></ce:date-received><ce:date-accepted day="7" month="8" year="1998"></ce:date-accepted><ce:abstract><ce:section-title>Abstract</ce:section-title><ce:abstract-sec><ce:simple-para>The copolymerization of aniline (An) with <ce:italic>o</ce:italic>-alkoxysulfonated anilines, i.e. 1-(<ce:italic>o</ce:italic>-amino)-propane-3-sulfonic acid (APPrS) and 1-(<ce:italic>o</ce:italic>-amino)-butane-4-sulfonic acid (APBuS), was a new way to produce water-soluble and self-doped polyaniline derivatives. Poly(An-co-APPrS) and poly(An-co-APBuS) were synthesized, in H<ce:inf>2</ce:inf>SO<ce:inf>4</ce:inf> acidic medium, by chemical oxidation using ammonium persulfate. The mechanistic study showed that, during their copolymerization, aniline and alkoxysulfonated-derivatives exhibit two opposite behaviors towards the initial mechanism of dimerization and the following growing process. Because of the steric hindrance of the bulky alkoxysulfonated groups, the dimerization process involved at least one molecule of aniline. On the contrary, in the course of the propagation step, due to the electron-donating effect of the substituent, both alkoxysulfonated anilines exhibited much greater reactivity than aniline and hence were easily incorporated into the growing polymer chains. The comonomer reactivity ratios, computed by using the extended Kelen–Tüdös method, were as follows: <ce:italic>r</ce:italic><ce:inf>An</ce:inf>=0.04±0.01, <ce:italic>r</ce:italic><ce:inf>APPrS</ce:inf>=27±9 and <ce:italic>r</ce:italic><ce:inf>An</ce:inf>=0.04±0.01, <ce:italic>r</ce:italic><ce:inf>APBuS</ce:inf>=12±6. These findings strongly suggest the formation of block copolymers.</ce:simple-para></ce:abstract-sec></ce:abstract><ce:keywords class="keyword"><ce:section-title>Keywords</ce:section-title><ce:keyword><ce:text>Aniline</ce:text></ce:keyword><ce:keyword><ce:text><ce:italic>o</ce:italic>-alkoxysulfonated aniline</ce:text></ce:keyword><ce:keyword><ce:text>Chemical oxidative copolymerization</ce:text></ce:keyword><ce:keyword><ce:text>Reactivity ratio</ce:text></ce:keyword></ce:keywords></head></converted-article></istex:document></istex:metadataXml><mods version="3.6"><titleInfo><title>Studies on chemical oxidative copolymerization of aniline and o -alkoxysulfonated anilines II. Mechanistic approach and monomer reactivity ratios</title></titleInfo><titleInfo type="alternative" contentType="CDATA"><title>Studies on chemical oxidative copolymerization of aniline and</title></titleInfo><name type="personal"><namePart type="given">V.</namePart><namePart type="family">Prévost</namePart><affiliation>Laboratoire des Sciences du Génie Chimique, CNRS UPR 6811, ENSIC-INPL, 1, rue Grandville, BP 451, 54001 Nancy cedex, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">A.</namePart><namePart type="family">Petit</namePart><affiliation>Laboratoire de Chimie-Physique Macromoléculaire, CNRS UMR 7568, ENSIC-INPL, 1, rue Grandville, BP 451, 54001 Nancy cedex, France</affiliation><description>Corresponding author: Tel.: (33) 03 83 17 50 95; fax: (33) 03 83 37 99 77</description><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">F.</namePart><namePart type="family">Pla</namePart><affiliation>Laboratoire des Sciences du Génie Chimique, CNRS UPR 6811, ENSIC-INPL, 1, rue Grandville, BP 451, 54001 Nancy cedex, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><typeOfResource>text</typeOfResource><genre type="research-article" displayLabel="Full-length article" authority="ISTEX" authorityURI="https://content-type.data.istex.fr" valueURI="https://content-type.data.istex.fr/ark:/67375/XTP-1JC4F85T-7">research-article</genre><originInfo><publisher>ELSEVIER</publisher><dateIssued encoding="w3cdtf">1999</dateIssued><copyrightDate encoding="w3cdtf">1999</copyrightDate></originInfo><language><languageTerm type="code" authority="iso639-2b">eng</languageTerm><languageTerm type="code" authority="rfc3066">en</languageTerm></language><abstract lang="en">Abstract: The copolymerization of aniline (An) with o-alkoxysulfonated anilines, i.e. 1-(o-amino)-propane-3-sulfonic acid (APPrS) and 1-(o-amino)-butane-4-sulfonic acid (APBuS), was a new way to produce water-soluble and self-doped polyaniline derivatives. Poly(An-co-APPrS) and poly(An-co-APBuS) were synthesized, in H2SO4 acidic medium, by chemical oxidation using ammonium persulfate. The mechanistic study showed that, during their copolymerization, aniline and alkoxysulfonated-derivatives exhibit two opposite behaviors towards the initial mechanism of dimerization and the following growing process. Because of the steric hindrance of the bulky alkoxysulfonated groups, the dimerization process involved at least one molecule of aniline. On the contrary, in the course of the propagation step, due to the electron-donating effect of the substituent, both alkoxysulfonated anilines exhibited much greater reactivity than aniline and hence were easily incorporated into the growing polymer chains. The comonomer reactivity ratios, computed by using the extended Kelen–Tüdös method, were as follows: rAn=0.04±0.01, rAPPrS=27±9 and rAn=0.04±0.01, rAPBuS=12±6. These findings strongly suggest the formation of block copolymers.</abstract><note type="content">Scheme. SC1: </note><note type="content">Scheme. SC2: </note><note type="content">Scheme. SC3: </note><note type="content">Fig. 1: Experimental data for the chemical oxidative copolymerization of aniline (An) with o-alkoxysulfonated aniline: (A) 1-(o-amino)-propane-3-sulfonic acid (APPrS); (B) 1-(o-amino)-butane-4-sulfonic acid (APBuS).</note><note type="content">Scheme. SC4: </note><note type="content">Scheme. SC5: </note><note type="content">Fig. 2: Mole conversion rates of aniline (⋅) and aniline-derivative (○) vs the feed composition: (A) aniline/1-(o-amino)-propane-3-sulfonic acid; (B) aniline/1-(o-amino)-butane-4-sulfonic acid, for 0.16</note> <note type="content">Fig. 3: Kelen–Tüdös plots for the chemical oxidative copolymerization of aniline (An) with: (A) 1-(o-amino)-propane-3-sulfonic acid (APPrS); and (B) 1-(o-amino)-butane-4-sulfonic acid (APBuS). Constants of Kelen–Tüdös equation: α=946 and 410 for (A) and (B), respectively.</note><note type="content">Fig. 4: Composition diagrams for the chemical oxidative copolymerization of aniline (An) with alkoxysulfonated aniline: (A) 1-(o- amino)-propane-3-sulfonic acid (APPrS); (B) 1-(o-amino)-butane-4-sulfonic acid (APBuS). ▵: experimental data corrected according to the extended Kelen–Tüdös method; solid line: curve calculated from terminal-unit model with rAn=0.04, rAPPrS=27 (A) and rAn=0.04, rAPBuS=12 (B).</note><note type="content">Table 1: Chemical copolymerization of aniline (An) with 1-(o-amino)-propane-3-sulfonic acid (APPrS) and 1-(o-amino)-butane-4-sulfonic acid (APBuS)a</note><note type="content">Table 2: Reactivity ratios for the chemical oxidative copolymerization of aniline (An) with 1-(o-amino)-propane-3-sulfonic acid (APPrS) and 1-(o-amino)-butane-4-sulfonic acid (APBuS)a</note><subject><genre>Keywords</genre><topic>Aniline</topic><topic>o-alkoxysulfonated aniline</topic><topic>Chemical oxidative copolymerization</topic><topic>Reactivity ratio</topic></subject><relatedItem type="host"><titleInfo><title>European Polymer Journal</title></titleInfo><titleInfo type="abbreviated"><title>EPJ</title></titleInfo><genre type="journal" authority="ISTEX" authorityURI="https://publication-type.data.istex.fr" valueURI="https://publication-type.data.istex.fr/ark:/67375/JMC-0GLKJH51-B">journal</genre><originInfo><publisher>ELSEVIER</publisher><dateIssued encoding="w3cdtf">199907</dateIssued></originInfo><identifier type="ISSN">0014-3057</identifier><identifier type="PII">S0014-3057(00)X0048-1</identifier><part><date>199907</date><detail type="volume"><number>35</number><caption>vol.</caption></detail><detail type="issue"><number>7</number><caption>no.</caption></detail><extent unit="issue-pages"><start>1187</start><end>1380</end></extent><extent unit="pages"><start>1229</start><end>1236</end></extent></part></relatedItem><identifier type="istex">EBAA4A1F067E192D17839858D1AB4F6C5C406EBC</identifier><identifier type="ark">ark:/67375/6H6-WT5C1Q0W-S</identifier><identifier type="DOI">10.1016/S0014-3057(98)00211-0</identifier><identifier type="PII">S0014-3057(98)00211-0</identifier><accessCondition type="use and reproduction" contentType="copyright">©1999 Elsevier Science Ltd</accessCondition><recordInfo><recordContentSource authority="ISTEX" authorityURI="https://loaded-corpus.data.istex.fr" valueURI="https://loaded-corpus.data.istex.fr/ark:/67375/XBH-HKKZVM7B-M">elsevier</recordContentSource><recordOrigin>Elsevier Science Ltd, ©1999</recordOrigin></recordInfo></mods><json:item><extension>json</extension><original>false</original><mimetype>application/json</mimetype><uri>https://api.istex.fr/document/EBAA4A1F067E192D17839858D1AB4F6C5C406EBC/metadata/json</uri></json:item></metadata><serie></serie></istex></record>Pour manipuler ce document sous Unix (Dilib)
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