Determination of the Propagation Rate Coefficient of Vinyl Pivalate Based on EPR Quantification of the Propagating Radical Concentration
The propagation rate coefficient (kp) of the vinyl pivalate (VPi) has been determined from an EPR quantification of the concentration of propagating radicals. The polymerizations followed first‐order kinetics with respect to the monomer, and the concentration of propagating radicals did not vary wit...
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| Veröffentlicht in: | Macromolecular chemistry and physics 2007-11, Vol.208 (22), p.2403-2411 |
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| container_title | Macromolecular chemistry and physics |
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| creator | Kubota, Narimi Kajiwara, Atsushi Zetterlund, Per B. Kamachi, Mikiharu Treurnicht, Jeanne Tonge, Matthew P. Gilbert, Robert G. Yamada, Bunichiro |
| description | The propagation rate coefficient (kp) of the vinyl pivalate (VPi) has been determined from an EPR quantification of the concentration of propagating radicals. The polymerizations followed first‐order kinetics with respect to the monomer, and the concentration of propagating radicals did not vary with time. The chain lengths were estimated to be sufficiently large to not affect kp. The resulting Arrhenius parameters for kp of VPi in heptane are Ap = 1.39 × 107 dm3 · mol−1 · s−1 and Ep = 20.5 kJ · mol−1. They are very similar to those of vinyl acetate as previously determined by the PLP method. The present results thus indicate that EPR gives consistent kp values for vinyl esters. |
| doi_str_mv | 10.1002/macp.200700185 |
| format | Article |
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The polymerizations followed first‐order kinetics with respect to the monomer, and the concentration of propagating radicals did not vary with time. The chain lengths were estimated to be sufficiently large to not affect kp. The resulting Arrhenius parameters for kp of VPi in heptane are Ap = 1.39 × 107 dm3 · mol−1 · s−1 and Ep = 20.5 kJ · mol−1. They are very similar to those of vinyl acetate as previously determined by the PLP method. The present results thus indicate that EPR gives consistent kp values for vinyl esters.</description><identifier>ISSN: 1022-1352</identifier><identifier>EISSN: 1521-3935</identifier><identifier>DOI: 10.1002/macp.200700185</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag</publisher><subject>Applied sciences ; Arrhenius parameters ; chain length ; ESR/EPR ; Exact sciences and technology ; Organic polymers ; Physicochemistry of polymers ; Polymerization ; Preparation, kinetics, thermodynamics, mechanism and catalysts ; pulsed laser polymerization ; radical polymerization</subject><ispartof>Macromolecular chemistry and physics, 2007-11, Vol.208 (22), p.2403-2411</ispartof><rights>Copyright © 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2008 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c3885-b9f271d5950c2ea77297179c50643035f3058908b229242e931338ab407bb6563</citedby><cites>FETCH-LOGICAL-c3885-b9f271d5950c2ea77297179c50643035f3058908b229242e931338ab407bb6563</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fmacp.200700185$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fmacp.200700185$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=19373485$$DView record in Pascal Francis$$Hfree_for_read</backlink></links><search><creatorcontrib>Kubota, Narimi</creatorcontrib><creatorcontrib>Kajiwara, Atsushi</creatorcontrib><creatorcontrib>Zetterlund, Per B.</creatorcontrib><creatorcontrib>Kamachi, Mikiharu</creatorcontrib><creatorcontrib>Treurnicht, Jeanne</creatorcontrib><creatorcontrib>Tonge, Matthew P.</creatorcontrib><creatorcontrib>Gilbert, Robert G.</creatorcontrib><creatorcontrib>Yamada, Bunichiro</creatorcontrib><title>Determination of the Propagation Rate Coefficient of Vinyl Pivalate Based on EPR Quantification of the Propagating Radical Concentration</title><title>Macromolecular chemistry and physics</title><addtitle>Macromol. Chem. Phys</addtitle><description>The propagation rate coefficient (kp) of the vinyl pivalate (VPi) has been determined from an EPR quantification of the concentration of propagating radicals. The polymerizations followed first‐order kinetics with respect to the monomer, and the concentration of propagating radicals did not vary with time. The chain lengths were estimated to be sufficiently large to not affect kp. The resulting Arrhenius parameters for kp of VPi in heptane are Ap = 1.39 × 107 dm3 · mol−1 · s−1 and Ep = 20.5 kJ · mol−1. They are very similar to those of vinyl acetate as previously determined by the PLP method. The present results thus indicate that EPR gives consistent kp values for vinyl esters.</description><subject>Applied sciences</subject><subject>Arrhenius parameters</subject><subject>chain length</subject><subject>ESR/EPR</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><subject>pulsed laser polymerization</subject><subject>radical polymerization</subject><issn>1022-1352</issn><issn>1521-3935</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2007</creationdate><recordtype>article</recordtype><recordid>eNqFkM1OGzEURkdVkUqhW9azobsJ177j2F6S8CulkEZtWVoexwOGiSfYEyBvwGPXYSLaRaWubPme71z5y7IDAgMCQI8W2iwHFIADEME-ZLuEUVKgRPYx3YHSgiCjn7LPMd4DgADJd7PXE9vZsHBed671eVvn3Z3Np6Fd6tv-aaY7m49bW9fOOOu7DfPL-XWTT92TbjbTkY52nif2dDrLv6-071yC_230t8k4T9MmSb1JwvAG7mc7tW6i_bI997KfZ6c_xhfF5Pr8cnw8KQwKwYpK1pSTOZMMDLWacyo54dIwGJYIyGoEJiSIilJJS2olEkShqxJ4VQ3ZEPeyr713GdrHlY2dWrhobNNob9tVVJhqEYKyBA560IQ2xmBrtQxuocNaEVCbwtWmcPVeeAocbs06pu_VQXvj4p-URI7lGyd77tk1dv0fq_p2PJ7-vaPosy529uU9q8ODGnLkTN1cnatyhCcU-USN8DcxCaBo</recordid><startdate>20071120</startdate><enddate>20071120</enddate><creator>Kubota, Narimi</creator><creator>Kajiwara, Atsushi</creator><creator>Zetterlund, Per B.</creator><creator>Kamachi, Mikiharu</creator><creator>Treurnicht, Jeanne</creator><creator>Tonge, Matthew P.</creator><creator>Gilbert, Robert G.</creator><creator>Yamada, Bunichiro</creator><general>WILEY-VCH Verlag</general><general>WILEY‐VCH Verlag</general><general>Wiley</general><scope>BSCLL</scope><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope></search><sort><creationdate>20071120</creationdate><title>Determination of the Propagation Rate Coefficient of Vinyl Pivalate Based on EPR Quantification of the Propagating Radical Concentration</title><author>Kubota, Narimi ; Kajiwara, Atsushi ; Zetterlund, Per B. ; Kamachi, Mikiharu ; Treurnicht, Jeanne ; Tonge, Matthew P. ; Gilbert, Robert G. ; Yamada, Bunichiro</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3885-b9f271d5950c2ea77297179c50643035f3058908b229242e931338ab407bb6563</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2007</creationdate><topic>Applied sciences</topic><topic>Arrhenius parameters</topic><topic>chain length</topic><topic>ESR/EPR</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><topic>pulsed laser polymerization</topic><topic>radical polymerization</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kubota, Narimi</creatorcontrib><creatorcontrib>Kajiwara, Atsushi</creatorcontrib><creatorcontrib>Zetterlund, Per B.</creatorcontrib><creatorcontrib>Kamachi, Mikiharu</creatorcontrib><creatorcontrib>Treurnicht, Jeanne</creatorcontrib><creatorcontrib>Tonge, Matthew P.</creatorcontrib><creatorcontrib>Gilbert, Robert G.</creatorcontrib><creatorcontrib>Yamada, Bunichiro</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Macromolecular chemistry and physics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kubota, Narimi</au><au>Kajiwara, Atsushi</au><au>Zetterlund, Per B.</au><au>Kamachi, Mikiharu</au><au>Treurnicht, Jeanne</au><au>Tonge, Matthew P.</au><au>Gilbert, Robert G.</au><au>Yamada, Bunichiro</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Determination of the Propagation Rate Coefficient of Vinyl Pivalate Based on EPR Quantification of the Propagating Radical Concentration</atitle><jtitle>Macromolecular chemistry and physics</jtitle><addtitle>Macromol. Chem. Phys</addtitle><date>2007-11-20</date><risdate>2007</risdate><volume>208</volume><issue>22</issue><spage>2403</spage><epage>2411</epage><pages>2403-2411</pages><issn>1022-1352</issn><eissn>1521-3935</eissn><abstract>The propagation rate coefficient (kp) of the vinyl pivalate (VPi) has been determined from an EPR quantification of the concentration of propagating radicals. The polymerizations followed first‐order kinetics with respect to the monomer, and the concentration of propagating radicals did not vary with time. The chain lengths were estimated to be sufficiently large to not affect kp. The resulting Arrhenius parameters for kp of VPi in heptane are Ap = 1.39 × 107 dm3 · mol−1 · s−1 and Ep = 20.5 kJ · mol−1. They are very similar to those of vinyl acetate as previously determined by the PLP method. The present results thus indicate that EPR gives consistent kp values for vinyl esters.</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag</pub><doi>10.1002/macp.200700185</doi><tpages>9</tpages></addata></record> |
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| subjects | Applied sciences Arrhenius parameters chain length ESR/EPR Exact sciences and technology Organic polymers Physicochemistry of polymers Polymerization Preparation, kinetics, thermodynamics, mechanism and catalysts pulsed laser polymerization radical polymerization |
| title | Determination of the Propagation Rate Coefficient of Vinyl Pivalate Based on EPR Quantification of the Propagating Radical Concentration |
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