High-Conversion Free-Radical Bulk Polymerization of Styrene:  Termination Kinetics Studied by Electron Spin Resonance, Fourier Transform Near-Infrared Spectroscopy, and Gel Permeation Chromatography

High-Conversion Free-Radical Bulk Polymerization of Styrene:  Termination Kinetics Studied by Electron Spin Resonance, Fourier Transform Near-Infrared Spectroscopy, and Gel Permeation Chromatography

The free-radical bulk polymerization of styrene initiated by dimethyl 2,2‘-azobisisobutyrate at 70 °C has been studied employing the techniques of Fourier transform near-infrared spectroscopy, electron spin resonance spectroscopy and gel permeation chromatography. The initiator efficiency (f) as a f...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Macromolecules 2001-10, Vol.34 (22), p.7686-7691
Hauptverfasser: Zetterlund, Per B, Yamazoe, Hirotomo, Yamada, Bunichiro, Hill, David J. T, Pomery, Peter J
Format: Artikel
Sprache:eng
Schlagworte:
Applied sciences
Exact sciences and technology
Organic polymers
Physicochemistry of polymers
Polymerization
Preparation, kinetics, thermodynamics, mechanism and catalysts
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
container_end_page 7691
container_issue 22
container_start_page 7686
container_title Macromolecules
container_volume 34
creator Zetterlund, Per B
Yamazoe, Hirotomo
Yamada, Bunichiro
Hill, David J. T
Pomery, Peter J
description The free-radical bulk polymerization of styrene initiated by dimethyl 2,2‘-azobisisobutyrate at 70 °C has been studied employing the techniques of Fourier transform near-infrared spectroscopy, electron spin resonance spectroscopy and gel permeation chromatography. The initiator efficiency (f) as a function of monomer conversion was estimated via an equation relating the instantaneous and the cumulative number average degrees of polymerization. The result was subsequently employed to calculate the conversion dependence of the termination rate coefficient (k t) from zero to the limiting conversion for different initiator concentrations. Over the course of the reaction, k t decreases by 5 orders of magnitude (107−102 M-1 s-1). At conversion levels approaching the limiting value, k t shows a marked dependence on initiator concentration; higher initiator concentration shifts the k t vs conversion curves toward higher conversion levels. The reaction diffusion constant was found to decrease with increasing conversion in the high-conversion regime.
doi_str_mv 10.1021/ma010560y
format Article
fullrecord <record><control><sourceid>istex_cross</sourceid><recordid>TN_cdi_crossref_primary_10_1021_ma010560y</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>ark_67375_TPS_MV9KNQ01_Z</sourcerecordid><originalsourceid>FETCH-LOGICAL-a390t-253b46f4c503cfe0251af558092390ff2a9df0c725624d331b20d3dfd64e20203</originalsourceid><addsrcrecordid>eNptkc9u1DAQxiMEEkvhwBv4AAekBsZ2vLvhBqtuW7WUpbtw4BJ5nXHXbWJH4ywinLjyZjwHT4JLULlwmsP3--abP1n2lMNLDoK_ajVwUFMY7mUTrgTkai7V_WwCIIq8FOXsYfYoxmsAzlUhJ9nPE3e1yxfBf0GKLni2JMT8UtfO6Ia93Tc3bBWaoUVy33R_CwTL1v1A6PH1r-8_2AapdX6UzpzH3pmYgH3tsGbbgR01aHpK4rpznl1iDF57g4dsGfbkkNiGtI82UMsuUFN-6i1pSt5198cYTeiGQ6Z9zY6xYasUh2PaYkeh1X24It3thsfZA6ubiE_-1oPs4_JoszjJz98fny7enOdaltDnQsltMbWFUSCNRRCKa6vUHEqRdGuFLmsLZibUVBS1lHwroJa1racFChAgD7IXY1-TZouEturItZqGikN1-4Lq7gWJfTaynY7pnGkxb1z8Z-CymINKWD5iLvb49U7WdFNNZ3Kmqs1qXb37VJ5dfABefU7885HXJlbX6Yw-Lfyf-N-Mn6YU</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>High-Conversion Free-Radical Bulk Polymerization of Styrene:  Termination Kinetics Studied by Electron Spin Resonance, Fourier Transform Near-Infrared Spectroscopy, and Gel Permeation Chromatography</title><source>American Chemical Society Journals</source><creator>Zetterlund, Per B ; Yamazoe, Hirotomo ; Yamada, Bunichiro ; Hill, David J. T ; Pomery, Peter J</creator><creatorcontrib>Zetterlund, Per B ; Yamazoe, Hirotomo ; Yamada, Bunichiro ; Hill, David J. T ; Pomery, Peter J</creatorcontrib><description>The free-radical bulk polymerization of styrene initiated by dimethyl 2,2‘-azobisisobutyrate at 70 °C has been studied employing the techniques of Fourier transform near-infrared spectroscopy, electron spin resonance spectroscopy and gel permeation chromatography. The initiator efficiency (f) as a function of monomer conversion was estimated via an equation relating the instantaneous and the cumulative number average degrees of polymerization. The result was subsequently employed to calculate the conversion dependence of the termination rate coefficient (k t) from zero to the limiting conversion for different initiator concentrations. Over the course of the reaction, k t decreases by 5 orders of magnitude (107−102 M-1 s-1). At conversion levels approaching the limiting value, k t shows a marked dependence on initiator concentration; higher initiator concentration shifts the k t vs conversion curves toward higher conversion levels. The reaction diffusion constant was found to decrease with increasing conversion in the high-conversion regime.</description><identifier>ISSN: 0024-9297</identifier><identifier>EISSN: 1520-5835</identifier><identifier>DOI: 10.1021/ma010560y</identifier><identifier>CODEN: MAMOBX</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Applied sciences ; Exact sciences and technology ; Organic polymers ; Physicochemistry of polymers ; Polymerization ; Preparation, kinetics, thermodynamics, mechanism and catalysts</subject><ispartof>Macromolecules, 2001-10, Vol.34 (22), p.7686-7691</ispartof><rights>Copyright © 2001 American Chemical Society</rights><rights>2001 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a390t-253b46f4c503cfe0251af558092390ff2a9df0c725624d331b20d3dfd64e20203</citedby><cites>FETCH-LOGICAL-a390t-253b46f4c503cfe0251af558092390ff2a9df0c725624d331b20d3dfd64e20203</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ma010560y$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ma010560y$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&amp;idt=1134805$$DView record in Pascal Francis$$Hfree_for_read</backlink></links><search><creatorcontrib>Zetterlund, Per B</creatorcontrib><creatorcontrib>Yamazoe, Hirotomo</creatorcontrib><creatorcontrib>Yamada, Bunichiro</creatorcontrib><creatorcontrib>Hill, David J. T</creatorcontrib><creatorcontrib>Pomery, Peter J</creatorcontrib><title>High-Conversion Free-Radical Bulk Polymerization of Styrene:  Termination Kinetics Studied by Electron Spin Resonance, Fourier Transform Near-Infrared Spectroscopy, and Gel Permeation Chromatography</title><title>Macromolecules</title><addtitle>Macromolecules</addtitle><description>The free-radical bulk polymerization of styrene initiated by dimethyl 2,2‘-azobisisobutyrate at 70 °C has been studied employing the techniques of Fourier transform near-infrared spectroscopy, electron spin resonance spectroscopy and gel permeation chromatography. The initiator efficiency (f) as a function of monomer conversion was estimated via an equation relating the instantaneous and the cumulative number average degrees of polymerization. The result was subsequently employed to calculate the conversion dependence of the termination rate coefficient (k t) from zero to the limiting conversion for different initiator concentrations. Over the course of the reaction, k t decreases by 5 orders of magnitude (107−102 M-1 s-1). At conversion levels approaching the limiting value, k t shows a marked dependence on initiator concentration; higher initiator concentration shifts the k t vs conversion curves toward higher conversion levels. The reaction diffusion constant was found to decrease with increasing conversion in the high-conversion regime.</description><subject>Applied sciences</subject><subject>Exact sciences and technology</subject><subject>Organic polymers</subject><subject>Physicochemistry of polymers</subject><subject>Polymerization</subject><subject>Preparation, kinetics, thermodynamics, mechanism and catalysts</subject><issn>0024-9297</issn><issn>1520-5835</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2001</creationdate><recordtype>article</recordtype><recordid>eNptkc9u1DAQxiMEEkvhwBv4AAekBsZ2vLvhBqtuW7WUpbtw4BJ5nXHXbWJH4ywinLjyZjwHT4JLULlwmsP3--abP1n2lMNLDoK_ajVwUFMY7mUTrgTkai7V_WwCIIq8FOXsYfYoxmsAzlUhJ9nPE3e1yxfBf0GKLni2JMT8UtfO6Ia93Tc3bBWaoUVy33R_CwTL1v1A6PH1r-8_2AapdX6UzpzH3pmYgH3tsGbbgR01aHpK4rpznl1iDF57g4dsGfbkkNiGtI82UMsuUFN-6i1pSt5198cYTeiGQ6Z9zY6xYasUh2PaYkeh1X24It3thsfZA6ubiE_-1oPs4_JoszjJz98fny7enOdaltDnQsltMbWFUSCNRRCKa6vUHEqRdGuFLmsLZibUVBS1lHwroJa1racFChAgD7IXY1-TZouEturItZqGikN1-4Lq7gWJfTaynY7pnGkxb1z8Z-CymINKWD5iLvb49U7WdFNNZ3Kmqs1qXb37VJ5dfABefU7885HXJlbX6Yw-Lfyf-N-Mn6YU</recordid><startdate>20011023</startdate><enddate>20011023</enddate><creator>Zetterlund, Per B</creator><creator>Yamazoe, Hirotomo</creator><creator>Yamada, Bunichiro</creator><creator>Hill, David J. T</creator><creator>Pomery, Peter J</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20011023</creationdate><title>High-Conversion Free-Radical Bulk Polymerization of Styrene:  Termination Kinetics Studied by Electron Spin Resonance, Fourier Transform Near-Infrared Spectroscopy, and Gel Permeation Chromatography</title><author>Zetterlund, Per B ; Yamazoe, Hirotomo ; Yamada, Bunichiro ; Hill, David J. T ; Pomery, Peter J</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a390t-253b46f4c503cfe0251af558092390ff2a9df0c725624d331b20d3dfd64e20203</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2001</creationdate><topic>Applied sciences</topic><topic>Exact sciences and technology</topic><topic>Organic polymers</topic><topic>Physicochemistry of polymers</topic><topic>Polymerization</topic><topic>Preparation, kinetics, thermodynamics, mechanism and catalysts</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Zetterlund, Per B</creatorcontrib><creatorcontrib>Yamazoe, Hirotomo</creatorcontrib><creatorcontrib>Yamada, Bunichiro</creatorcontrib><creatorcontrib>Hill, David J. T</creatorcontrib><creatorcontrib>Pomery, Peter J</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>CrossRef</collection><jtitle>Macromolecules</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Zetterlund, Per B</au><au>Yamazoe, Hirotomo</au><au>Yamada, Bunichiro</au><au>Hill, David J. T</au><au>Pomery, Peter J</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>High-Conversion Free-Radical Bulk Polymerization of Styrene:  Termination Kinetics Studied by Electron Spin Resonance, Fourier Transform Near-Infrared Spectroscopy, and Gel Permeation Chromatography</atitle><jtitle>Macromolecules</jtitle><addtitle>Macromolecules</addtitle><date>2001-10-23</date><risdate>2001</risdate><volume>34</volume><issue>22</issue><spage>7686</spage><epage>7691</epage><pages>7686-7691</pages><issn>0024-9297</issn><eissn>1520-5835</eissn><coden>MAMOBX</coden><abstract>The free-radical bulk polymerization of styrene initiated by dimethyl 2,2‘-azobisisobutyrate at 70 °C has been studied employing the techniques of Fourier transform near-infrared spectroscopy, electron spin resonance spectroscopy and gel permeation chromatography. The initiator efficiency (f) as a function of monomer conversion was estimated via an equation relating the instantaneous and the cumulative number average degrees of polymerization. The result was subsequently employed to calculate the conversion dependence of the termination rate coefficient (k t) from zero to the limiting conversion for different initiator concentrations. Over the course of the reaction, k t decreases by 5 orders of magnitude (107−102 M-1 s-1). At conversion levels approaching the limiting value, k t shows a marked dependence on initiator concentration; higher initiator concentration shifts the k t vs conversion curves toward higher conversion levels. The reaction diffusion constant was found to decrease with increasing conversion in the high-conversion regime.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><doi>10.1021/ma010560y</doi><tpages>6</tpages></addata></record>
fulltext fulltext
identifier ISSN: 0024-9297
ispartof Macromolecules, 2001-10, Vol.34 (22), p.7686-7691
issn 0024-9297
1520-5835
language eng
recordid cdi_crossref_primary_10_1021_ma010560y
source American Chemical Society Journals
subjects Applied sciences
Exact sciences and technology
Organic polymers
Physicochemistry of polymers
Polymerization
Preparation, kinetics, thermodynamics, mechanism and catalysts
title High-Conversion Free-Radical Bulk Polymerization of Styrene:  Termination Kinetics Studied by Electron Spin Resonance, Fourier Transform Near-Infrared Spectroscopy, and Gel Permeation Chromatography
url https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-21T13%3A56%3A44IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-istex_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=High-Conversion%20Free-Radical%20Bulk%20Polymerization%20of%20Styrene:%E2%80%89%20Termination%20Kinetics%20Studied%20by%20Electron%20Spin%20Resonance,%20Fourier%20Transform%20Near-Infrared%20Spectroscopy,%20and%20Gel%20Permeation%20Chromatography&rft.jtitle=Macromolecules&rft.au=Zetterlund,%20Per%20B&rft.date=2001-10-23&rft.volume=34&rft.issue=22&rft.spage=7686&rft.epage=7691&rft.pages=7686-7691&rft.issn=0024-9297&rft.eissn=1520-5835&rft.coden=MAMOBX&rft_id=info:doi/10.1021/ma010560y&rft_dat=%3Cistex_cross%3Eark_67375_TPS_MV9KNQ01_Z%3C/istex_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_id=info:pmid/&rfr_iscdi=true