Iodine transfer copolymerization of vinylidene fluoride and α‐trifluoromethacrylic acid in emulsion process without any surfactants
Identifieur interne : 002595 ( Istex/Corpus ); précédent : 002594; suivant : 002596Iodine transfer copolymerization of vinylidene fluoride and α‐trifluoromethacrylic acid in emulsion process without any surfactants
Auteurs : Cyrille Boyer ; Bruno AméduriSource :
- Journal of Polymer Science Part A: Polymer Chemistry [ 0887-624X ] ; 2009-09-15.
English descriptors
- KwdEn :
- Acf2i, Ach2i, Ameduri, Aqueous medium, Aqueous solution, Autoclave, Boutevin, Boyer, Cfat, Chain transfer agent, Chain transfer agents, Chem, Coelho, Copolymer, Copolymerization, Emulsion, Emulsion process, European patent, Feed composition, Feed ratio, Functional groups, Functionality, Good agreement, Iodine transfer copolymerization, Iodine transfer polymerization, Macromol chem phys, Macromolecule, Modern fluoropolymers, Molecular weights, Monomer, Percec, Polym, Polym chem, Polymer, Polymer chain, Polymer chemistry, Polymer science, Popov, Radical copolymerization, Radical polymerization, Reactivity ratios, Rvdf, Surfactant, Tfma, Tfma monomer, Tfma units, Uoride, Uorinated, Vinylidene.
- Teeft :
- Acf2i, Ach2i, Ameduri, Aqueous medium, Aqueous solution, Autoclave, Boutevin, Boyer, Cfat, Chain transfer agent, Chain transfer agents, Chem, Coelho, Copolymer, Copolymerization, Emulsion, Emulsion process, European patent, Feed composition, Feed ratio, Functional groups, Functionality, Good agreement, Iodine transfer copolymerization, Iodine transfer polymerization, Macromol chem phys, Macromolecule, Modern fluoropolymers, Molecular weights, Monomer, Percec, Polym, Polym chem, Polymer, Polymer chain, Polymer chemistry, Polymer science, Popov, Radical copolymerization, Radical polymerization, Reactivity ratios, Rvdf, Surfactant, Tfma, Tfma monomer, Tfma units, Uoride, Uorinated, Vinylidene.
Abstract
The synthesis of poly(VDF‐co‐TFMA) copolymers (where VDF and TFMA stand for vinylidene fluoride and α‐trifluoromethacrylic acid, respectively) by iodine transfer polymerization without any surfactant is presented. First, the synthesis and the control of the copolymerization of VDF and TFMA were investigated in the presence of two chain transfer agents, 1‐perfluorohexyl iodide (C6F13I) and 1,4‐diodoperfluorobutane (IC4F8I). TFMA monomer was incorporated in the copolymer in good yields. Moreover, the molecular weights of the resulting poly(VDF‐co‐TFMA) copolymers were in good agreement with the theoretical values for feed of TFMA/VDF ratios that ranged from 50/50 to 0/100 mol %, showing that TFMA does not disturb the controlled radical polymerization of VDF. The microstructures of the produced copolymers were characterized by 1H and 19F NMR to assess the amount of each comonomer, and the molecular weights and the end‐groups of the copolymers. The results on the control of the copolymerization were compared to those obtained with and without the presences of TFMA and surfactant. The addition of a low amount of TFMA improved the control of the polymerization of VDF without using any surfactant. Also, the size of particles, assessed by light scattering, was smaller than 200 nm. The addition of TFMA in low proportions, that is, 5 to 10 mol %, enabled us to stabilize the particle size and to decrease the size by one order of magnitude. The emulsifying behavior of TFMA (in low amount in the copolymer, that is, <10 mol %) was similar to those achieved when a surfactant was added. Indeed, neither sedimentation nor destabilization was observed after several days. The reactivity ratios for rTFMA and rVDF were 0 and 1.6 at 80 °C, respectively. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4710–4722, 2009
Url:
DOI: 10.1002/pola.23525
Links to Exploration step
ISTEX:CB81A00FF3C2902991F528E781CCD9AE74ACC92ALe document en format XML
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First, the synthesis and the control of the copolymerization of VDF and TFMA were investigated in the presence of two chain transfer agents, 1‐perfluorohexyl iodide (C6F13I) and 1,4‐diodoperfluorobutane (IC4F8I). TFMA monomer was incorporated in the copolymer in good yields. Moreover, the molecular weights of the resulting poly(VDF‐co‐TFMA) copolymers were in good agreement with the theoretical values for feed of TFMA/VDF ratios that ranged from 50/50 to 0/100 mol %, showing that TFMA does not disturb the controlled radical polymerization of VDF. The microstructures of the produced copolymers were characterized by 1H and 19F NMR to assess the amount of each comonomer, and the molecular weights and the end‐groups of the copolymers. The results on the control of the copolymerization were compared to those obtained with and without the presences of TFMA and surfactant. The addition of a low amount of TFMA improved the control of the polymerization of VDF without using any surfactant. Also, the size of particles, assessed by light scattering, was smaller than 200 nm. The addition of TFMA in low proportions, that is, 5 to 10 mol %, enabled us to stabilize the particle size and to decrease the size by one order of magnitude. The emulsifying behavior of TFMA (in low amount in the copolymer, that is, <10 mol %) was similar to those achieved when a surfactant was added. Indeed, neither sedimentation nor destabilization was observed after several days. The reactivity ratios for rTFMA and rVDF were 0 and 1.6 at 80 °C, respectively. © 2009 Wiley Periodicals, Inc. 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First, the synthesis and the control of the copolymerization of VDF and TFMA were investigated in the presence of two chain transfer agents, 1‐perfluorohexyl iodide (C6F13I) and 1,4‐diodoperfluorobutane (IC4F8I). TFMA monomer was incorporated in the copolymer in good yields. Moreover, the molecular weights of the resulting poly(VDF‐co‐TFMA) copolymers were in good agreement with the theoretical values for feed of TFMA/VDF ratios that ranged from 50/50 to 0/100 mol %, showing that TFMA does not disturb the controlled radical polymerization of VDF. The microstructures of the produced copolymers were characterized by 1H and 19F NMR to assess the amount of each comonomer, and the molecular weights and the end‐groups of the copolymers. The results on the control of the copolymerization were compared to those obtained with and without the presences of TFMA and surfactant. The addition of a low amount of TFMA improved the control of the polymerization of VDF without using any surfactant. Also, the size of particles, assessed by light scattering, was smaller than 200 nm. The addition of TFMA in low proportions, that is, 5 to 10 mol %, enabled us to stabilize the particle size and to decrease the size by one order of magnitude. The emulsifying behavior of TFMA (in low amount in the copolymer, that is, >10 mol %) was similar to those achieved when a surfactant was added. Indeed, neither sedimentation nor destabilization was observed after several days. The reactivity ratios for rTFMA and rVDF were 0 and 1.6 at 80 °C, respectively. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4710–4722, 2009</abstract><qualityIndicators><refBibsNative>true</refBibsNative><abstractWordCount>290</abstractWordCount><abstractCharCount>1842</abstractCharCount><keywordCount>6</keywordCount><score>10</score><pdfWordCount>6019</pdfWordCount><pdfCharCount>37375</pdfCharCount><pdfVersion>1.3</pdfVersion><pdfPageCount>13</pdfPageCount><pdfPageSize>612 x 810 pts</pdfPageSize></qualityIndicators><title>Iodine transfer copolymerization of vinylidene fluoride and α‐trifluoromethacrylic acid in emulsion process without any surfactants</title><genre><json:string>article</json:string></genre><host><title>Journal of Polymer Science Part A: Polymer Chemistry</title><language><json:string>unknown</json:string></language><doi><json:string>10.1002/(ISSN)1099-0518</json:string></doi><issn><json:string>0887-624X</json:string></issn><eissn><json:string>1099-0518</json:string></eissn><publisherId><json:string>POLA</json:string></publisherId><volume>47</volume><issue>18</issue><pages><first>4710</first><last>4722</last><total>13</total></pages><genre><json:string>journal</json:string></genre><subject><json:item><value>Article</value></json:item></subject></host><namedEntities><unitex><date><json:string>2009</json:string><json:string>4720</json:string></date><geogName></geogName><orgName><json:string>US Environment Protection Agency</json:string><json:string>Wiley Periodicals, Inc.</json:string><json:string>France and Brussels, Belgium</json:string><json:string>University of New South Wales</json:string><json:string>Polymer Laboratories</json:string><json:string>US Environmental Protection Agency</json:string><json:string>France Received</json:string><json:string>Wiley Periodicals, Inc</json:string></orgName><orgName_funder></orgName_funder><orgName_provider></orgName_provider><persName><json:string>Yoshida</json:string><json:string>Kawada</json:string><json:string>Charles Gerhardt</json:string><json:string>Pierre Benite</json:string><json:string>B. 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xml:id="author-0000"><persName><forename type="first">Cyrille</forename><surname>Boyer</surname></persName><affiliation>Centre for Advanced Macromolecular Design (CAMD), School of Chemical Sciences and Engineering, The University of New South Wales, Sydney, NSW 2052, Australia<address><country key="AU"></country></address></affiliation><affiliation>Current Address: Centre for Advanced Macromolecular Design (CAMD), School of Chemical Sciences and Engineering, The University of New South Wales, Sydney, NSW 2052, Australia<address><country key="AU"></country></address></affiliation></author><author xml:id="author-0001" role="corresp"><persName><forename type="first">Bruno</forename><surname>Améduri</surname></persName><email>bruno.ameduri@enscm.fr</email><affiliation>Ingénierie et Architecture Macromoléculaire, Institut Charles Gerhardt, Ecole Nationale Supérieure de Chimie de Montpellier (UMR 5253‐CNRS), 8, rue de l'Ecole Normale, 34296 Montpellier Cedex 1, France<address><country key="FR"></country></address></affiliation><affiliation>Ingénierie et Architecture Macromoléculaire, Institut Charles Gerhardt, Ecole Nationale Supérieure de Chimie de Montpellier (UMR 5253‐CNRS), 8, rue de l'Ecole Normale, 34296 Montpellier Cedex 1, France</affiliation></author><idno type="istex">CB81A00FF3C2902991F528E781CCD9AE74ACC92A</idno><idno type="ark">ark:/67375/WNG-0JD60VWR-K</idno><idno type="DOI">10.1002/pola.23525</idno><idno type="unit">POLA23525</idno><idno type="toTypesetVersion">file:POLA.POLA23525.pdf</idno></analytic><monogr><title level="j" type="main">Journal of Polymer Science Part A: Polymer Chemistry</title><title level="j" type="alt">JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY</title><idno type="pISSN">0887-624X</idno><idno type="eISSN">1099-0518</idno><idno type="book-DOI">10.1002/(ISSN)1099-0518</idno><idno type="book-part-DOI">10.1002/pola.v47:18</idno><idno type="product">POLA</idno><imprint><biblScope unit="vol">47</biblScope><biblScope unit="issue">18</biblScope><biblScope unit="page" from="4710">4710</biblScope><biblScope unit="page" to="4722">4722</biblScope><biblScope unit="page-count">13</biblScope><publisher>Wiley Subscription Services, Inc., A Wiley Company</publisher><pubPlace>Hoboken</pubPlace><date type="published" when="2009-09-15"></date></imprint></monogr></biblStruct></sourceDesc></fileDesc><profileDesc><abstract xml:lang="en" style="main"><head>Abstract</head><p>The synthesis of poly(VDF‐<hi rend="italic">co</hi>‐TFMA) copolymers (where VDF and TFMA stand for vinylidene fluoride and α‐trifluoromethacrylic acid, respectively) by iodine transfer polymerization without any surfactant is presented. First, the synthesis and the control of the copolymerization of VDF and TFMA were investigated in the presence of two chain transfer agents, 1‐perfluorohexyl iodide (C<hi rend="subscript">6</hi>F<hi rend="subscript">13</hi>I) and 1,4‐diodoperfluorobutane (IC<hi rend="subscript">4</hi>F<hi rend="subscript">8</hi>I). TFMA monomer was incorporated in the copolymer in good yields. Moreover, the molecular weights of the resulting poly(VDF‐<hi rend="italic">co</hi>‐TFMA) copolymers were in good agreement with the theoretical values for feed of TFMA/VDF ratios that ranged from 50/50 to 0/100 mol %, showing that TFMA does not disturb the controlled radical polymerization of VDF. The microstructures of the produced copolymers were characterized by <hi rend="superscript">1</hi>H and <hi rend="superscript">19</hi>F NMR to assess the amount of each comonomer, and the molecular weights and the end‐groups of the copolymers. The results on the control of the copolymerization were compared to those obtained with and without the presences of TFMA and surfactant. The addition of a low amount of TFMA improved the control of the polymerization of VDF without using any surfactant. Also, the size of particles, assessed by light scattering, was smaller than 200 nm. The addition of TFMA in low proportions, that is, 5 to 10 mol %, enabled us to stabilize the particle size and to decrease the size by one order of magnitude. The emulsifying behavior of TFMA (in low amount in the copolymer, that is, <10 mol %) was similar to those achieved when a surfactant was added. Indeed, neither sedimentation nor destabilization was observed after several days. The reactivity ratios for <hi rend="italic">r</hi><hi rend="subscript">TFMA</hi> and <hi rend="italic">r</hi><hi rend="subscript">VDF</hi> were 0 and 1.6 at 80 °C, respectively. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4710–4722, 2009</p></abstract><abstract xml:lang="en" style="graphical"><p>The polymerization of vinylidene fluoride (VDF), hydrophobic monomer, was carried out in emulsion process without addition of surfactant using iodine transfer polymerization. The incorporation of α‐trifluoromethacrylic acid (TFMA) units in the poly(VDF) by copolymerization allows to improve the stability of these emulsions. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.] <figure type="box"><media mimeType="image" url="urn:x-wiley:0887624X:media:POLA23525:gra001"></media><media mimeType="image/gif" url="" rendition="webLoRes"></media><media mimeType="image/jpeg" url="" rendition="webOriginal"></media><media mimeType="image/jpeg" url="" rendition="webHiRes"></media></figure></p></abstract><textClass><keywords xml:lang="en"><term xml:id="kwd1">emulsion polymerization</term><term xml:id="kwd2">fluoropolymers</term><term xml:id="kwd3">functionalization of polymers</term><term xml:id="kwd4">NMR</term><term xml:id="kwd5">radical polymerization</term><term xml:id="kwd6">surfactants</term></keywords><keywords rend="articleCategory"><term>Article</term></keywords><keywords rend="tocHeading1"><term>Articles</term></keywords></textClass><langUsage><language ident="en"></language></langUsage></profileDesc></teiHeader></istex:fulltextTEI><json:item><extension>txt</extension><original>false</original><mimetype>text/plain</mimetype><uri>https://api.istex.fr/document/CB81A00FF3C2902991F528E781CCD9AE74ACC92A/fulltext/txt</uri></json:item></fulltext><metadata><istex:metadataXml wicri:clean="Wiley, elements deleted: body"><istex:xmlDeclaration>version="1.0" encoding="UTF-8" standalone="yes"</istex:xmlDeclaration><istex:document><component version="2.0" type="serialArticle" xml:lang="en"><header><publicationMeta level="product"><publisherInfo><publisherName>Wiley Subscription Services, Inc., A Wiley Company</publisherName><publisherLoc>Hoboken</publisherLoc></publisherInfo><doi registered="yes">10.1002/(ISSN)1099-0518</doi><issn type="print">0887-624X</issn><issn type="electronic">1099-0518</issn><idGroup><id type="product" value="POLA"></id></idGroup><titleGroup><title type="main" xml:lang="en" sort="JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY">Journal of Polymer Science Part A: Polymer Chemistry</title><title type="short">J. Polym. Sci. A Polym. Chem.</title></titleGroup></publicationMeta><publicationMeta level="part" position="180"><doi origin="wiley" registered="yes">10.1002/pola.v47:18</doi><numberingGroup><numbering type="journalVolume" number="47">47</numbering><numbering type="journalIssue">18</numbering></numberingGroup><coverDate startDate="2009-09-15">15 September 2009</coverDate></publicationMeta><publicationMeta level="unit" type="article" position="200" status="forIssue"><doi origin="wiley" registered="yes">10.1002/pola.23525</doi><idGroup><id type="unit" value="POLA23525"></id></idGroup><countGroup><count type="pageTotal" number="13"></count></countGroup><titleGroup><title type="articleCategory">Article</title><title type="tocHeading1">Articles</title></titleGroup><copyright ownership="publisher">Copyright © 2009 Wiley Periodicals, Inc.</copyright><eventGroup><event type="manuscriptReceived" date="2009-04-07"></event><event type="manuscriptAccepted" date="2009-05-15"></event><event type="firstOnline" date="2009-08-04"></event><event type="publishedOnlineFinalForm" date="2009-08-04"></event><event type="xmlConverted" agent="Converter:JWSART34_TO_WML3G version:2.5.2 mode:FullText source:FullText result:FullText mathml2tex" date="2011-07-06"></event><event type="xmlConverted" agent="Converter:WILEY_ML3G_TO_WILEY_ML3GV2 version:3.8.8" date="2014-02-07"></event><event type="xmlConverted" agent="Converter:WML3G_To_WML3G version:4.1.7 mode:FullText,remove_FC" date="2014-10-30"></event></eventGroup><numberingGroup><numbering type="pageFirst">4710</numbering><numbering type="pageLast">4722</numbering></numberingGroup><correspondenceTo>Ingénierie et Architecture Macromoléculaire, Institut Charles Gerhardt, Ecole Nationale Supérieure de Chimie de Montpellier (UMR 5253‐CNRS), 8, rue de l'Ecole Normale, 34296 Montpellier Cedex 1, France</correspondenceTo><objectNameGroup><objectName elementName="figure">Scheme</objectName></objectNameGroup><linkGroup><link type="toTypesetVersion" href="file:POLA.POLA23525.pdf"></link></linkGroup></publicationMeta><contentMeta><countGroup><count type="figureTotal" number="7"></count><count type="tableTotal" number="2"></count><count type="referenceTotal" number="86"></count><count type="wordTotal" number="8396"></count></countGroup><titleGroup><title type="main" xml:lang="en">Iodine transfer copolymerization of vinylidene fluoride and α‐trifluoromethacrylic acid in emulsion process without any surfactants</title><title type="short" xml:lang="en">Iodine Transfer Copolymerization of VDF and TFMA</title></titleGroup><creators><creator xml:id="au1" creatorRole="author" affiliationRef="#af1" currentRef="#curr1"><personName><givenNames>Cyrille</givenNames><familyName>Boyer</familyName></personName></creator><creator xml:id="au2" creatorRole="author" affiliationRef="#af2" corresponding="yes"><personName><givenNames>Bruno</givenNames><familyName>Améduri</familyName></personName><contactDetails><email>bruno.ameduri@enscm.fr</email></contactDetails></creator></creators><affiliationGroup><affiliation xml:id="af1" countryCode="AU" type="organization"><unparsedAffiliation>Centre for Advanced Macromolecular Design (CAMD), School of Chemical Sciences and Engineering, The University of New South Wales, Sydney, NSW 2052, Australia</unparsedAffiliation></affiliation><affiliation xml:id="af2" countryCode="FR" type="organization"><unparsedAffiliation>Ingénierie et Architecture Macromoléculaire, Institut Charles Gerhardt, Ecole Nationale Supérieure de Chimie de Montpellier (UMR 5253‐CNRS), 8, rue de l'Ecole Normale, 34296 Montpellier Cedex 1, France</unparsedAffiliation></affiliation><affiliation xml:id="curr1" countryCode="AU"><unparsedAffiliation>Centre for Advanced Macromolecular Design (CAMD), School of Chemical Sciences and Engineering, The University of New South Wales, Sydney, NSW 2052, Australia</unparsedAffiliation></affiliation></affiliationGroup><keywordGroup xml:lang="en" type="author"><keyword xml:id="kwd1">emulsion polymerization</keyword><keyword xml:id="kwd2">fluoropolymers</keyword><keyword xml:id="kwd3">functionalization of polymers</keyword><keyword xml:id="kwd4">NMR</keyword><keyword xml:id="kwd5">radical polymerization</keyword><keyword xml:id="kwd6">surfactants</keyword></keywordGroup><abstractGroup><abstract type="main" xml:lang="en"><title type="main">Abstract</title><p>The synthesis of poly(VDF‐<i>co</i>‐TFMA) copolymers (where VDF and TFMA stand for vinylidene fluoride and α‐trifluoromethacrylic acid, respectively) by iodine transfer polymerization without any surfactant is presented. First, the synthesis and the control of the copolymerization of VDF and TFMA were investigated in the presence of two chain transfer agents, 1‐perfluorohexyl iodide (C<sub>6</sub>F<sub>13</sub>I) and 1,4‐diodoperfluorobutane (IC<sub>4</sub>F<sub>8</sub>I). TFMA monomer was incorporated in the copolymer in good yields. Moreover, the molecular weights of the resulting poly(VDF‐<i>co</i>‐TFMA) copolymers were in good agreement with the theoretical values for feed of TFMA/VDF ratios that ranged from 50/50 to 0/100 mol %, showing that TFMA does not disturb the controlled radical polymerization of VDF. The microstructures of the produced copolymers were characterized by <sup>1</sup>H and <sup>19</sup>F NMR to assess the amount of each comonomer, and the molecular weights and the end‐groups of the copolymers. The results on the control of the copolymerization were compared to those obtained with and without the presences of TFMA and surfactant. The addition of a low amount of TFMA improved the control of the polymerization of VDF without using any surfactant. Also, the size of particles, assessed by light scattering, was smaller than 200 nm. The addition of TFMA in low proportions, that is, 5 to 10 mol %, enabled us to stabilize the particle size and to decrease the size by one order of magnitude. The emulsifying behavior of TFMA (in low amount in the copolymer, that is, <10 mol %) was similar to those achieved when a surfactant was added. Indeed, neither sedimentation nor destabilization was observed after several days. The reactivity ratios for <i>r</i><sub>TFMA</sub> and <i>r</i><sub>VDF</sub> were 0 and 1.6 at 80 °C, respectively. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4710–4722, 2009</p></abstract><abstract type="graphical" xml:lang="en"><p>The polymerization of vinylidene fluoride (VDF), hydrophobic monomer, was carried out in emulsion process without addition of surfactant using iodine transfer polymerization. The incorporation of α‐trifluoromethacrylic acid (TFMA) units in the poly(VDF) by copolymerization allows to improve the stability of these emulsions. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.] <blockFixed type="graphic"><mediaResourceGroup><mediaResource alt="image" eRights="yes" copyright="Wiley Periodicals, Inc." href="urn:x-wiley:0887624X:media:POLA23525:gra001"></mediaResource><mediaResource alt="thumbnail image" rendition="webLoRes" mimeType="image/gif" href=""></mediaResource><mediaResource alt="original image" rendition="webOriginal" mimeType="image/jpeg" href=""></mediaResource><mediaResource alt="magnified image" rendition="webHiRes" mimeType="image/jpeg" href=""></mediaResource></mediaResourceGroup></blockFixed></p></abstract></abstractGroup></contentMeta></header></component></istex:document></istex:metadataXml><mods version="3.6"><titleInfo lang="en"><title>Iodine transfer copolymerization of vinylidene fluoride and α‐trifluoromethacrylic acid in emulsion process without any surfactants</title></titleInfo><titleInfo type="abbreviated" lang="en"><title>Iodine Transfer Copolymerization of VDF and TFMA</title></titleInfo><titleInfo type="alternative" contentType="CDATA" lang="en"><title>Iodine transfer copolymerization of vinylidene fluoride and α‐trifluoromethacrylic acid in emulsion process without any surfactants</title></titleInfo><name type="personal"><namePart type="given">Cyrille</namePart><namePart type="family">Boyer</namePart><affiliation>Centre for Advanced Macromolecular Design (CAMD), School of Chemical Sciences and Engineering, The University of New South Wales, Sydney, NSW 2052, Australia</affiliation><affiliation>Current Address: Centre for Advanced Macromolecular Design (CAMD), School of Chemical Sciences and Engineering, The University of New South Wales, Sydney, NSW 2052, Australia</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Bruno</namePart><namePart type="family">Améduri</namePart><affiliation>Ingénierie et Architecture Macromoléculaire, Institut Charles Gerhardt, Ecole Nationale Supérieure de Chimie de Montpellier (UMR 5253‐CNRS), 8, rue de l'Ecole Normale, 34296 Montpellier Cedex 1, France</affiliation><affiliation>E-mail: bruno.ameduri@enscm.fr</affiliation><affiliation>Correspondence address: Ingénierie et Architecture Macromoléculaire, Institut Charles Gerhardt, Ecole Nationale Supérieure de Chimie de Montpellier (UMR 5253‐CNRS), 8, rue de l'Ecole Normale, 34296 Montpellier Cedex 1, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><typeOfResource>text</typeOfResource><genre type="article" displayLabel="article" authority="ISTEX" authorityURI="https://content-type.data.istex.fr" valueURI="https://content-type.data.istex.fr/ark:/67375/XTP-6N5SZHKN-D">article</genre><originInfo><publisher>Wiley Subscription Services, Inc., A Wiley Company</publisher><place><placeTerm type="text">Hoboken</placeTerm></place><dateIssued encoding="w3cdtf">2009-09-15</dateIssued><dateCaptured encoding="w3cdtf">2009-04-07</dateCaptured><dateValid encoding="w3cdtf">2009-05-15</dateValid><copyrightDate encoding="w3cdtf">2009</copyrightDate></originInfo><language><languageTerm type="code" authority="rfc3066">en</languageTerm><languageTerm type="code" authority="iso639-2b">eng</languageTerm></language><physicalDescription><extent unit="figures">7</extent><extent unit="tables">2</extent><extent unit="references">86</extent><extent unit="words">8396</extent></physicalDescription><abstract lang="en">The synthesis of poly(VDF‐co‐TFMA) copolymers (where VDF and TFMA stand for vinylidene fluoride and α‐trifluoromethacrylic acid, respectively) by iodine transfer polymerization without any surfactant is presented. First, the synthesis and the control of the copolymerization of VDF and TFMA were investigated in the presence of two chain transfer agents, 1‐perfluorohexyl iodide (C6F13I) and 1,4‐diodoperfluorobutane (IC4F8I). TFMA monomer was incorporated in the copolymer in good yields. Moreover, the molecular weights of the resulting poly(VDF‐co‐TFMA) copolymers were in good agreement with the theoretical values for feed of TFMA/VDF ratios that ranged from 50/50 to 0/100 mol %, showing that TFMA does not disturb the controlled radical polymerization of VDF. The microstructures of the produced copolymers were characterized by 1H and 19F NMR to assess the amount of each comonomer, and the molecular weights and the end‐groups of the copolymers. The results on the control of the copolymerization were compared to those obtained with and without the presences of TFMA and surfactant. The addition of a low amount of TFMA improved the control of the polymerization of VDF without using any surfactant. Also, the size of particles, assessed by light scattering, was smaller than 200 nm. The addition of TFMA in low proportions, that is, 5 to 10 mol %, enabled us to stabilize the particle size and to decrease the size by one order of magnitude. The emulsifying behavior of TFMA (in low amount in the copolymer, that is, <10 mol %) was similar to those achieved when a surfactant was added. Indeed, neither sedimentation nor destabilization was observed after several days. The reactivity ratios for rTFMA and rVDF were 0 and 1.6 at 80 °C, respectively. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4710–4722, 2009</abstract><abstract type="graphical" lang="en">The polymerization of vinylidene fluoride (VDF), hydrophobic monomer, was carried out in emulsion process without addition of surfactant using iodine transfer polymerization. The incorporation of α‐trifluoromethacrylic acid (TFMA) units in the poly(VDF) by copolymerization allows to improve the stability of these emulsions. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]</abstract><subject lang="en"><genre>keywords</genre><topic>emulsion polymerization</topic><topic>fluoropolymers</topic><topic>functionalization of polymers</topic><topic>NMR</topic><topic>radical polymerization</topic><topic>surfactants</topic></subject><relatedItem type="host"><titleInfo><title>Journal of Polymer Science Part A: Polymer Chemistry</title></titleInfo><titleInfo type="abbreviated"><title>J. Polym. Sci. A Polym. 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