Effect of the Penultimate Unit on Radical Stability and Reactivity in Free-Radical Polymerization
Ab initio molecular orbital calculations have been used to study the effect of γ substituents (X = H, F, or CN) on the addition of 1-Y,3-X-disubstituted propyl radicals (Y = F or CN) to ethylene. It is found that, although the γ substituent (i.e. penultimate unit) can exert a significant effect on t...
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| Veröffentlicht in: | Macromolecules 1999-05, Vol.32 (9), p.2935-2940 |
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| container_title | Macromolecules |
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| creator | Coote, Michelle L Davis, Thomas P Radom, Leo |
| description | Ab initio molecular orbital calculations have been used to study the effect of γ substituents (X = H, F, or CN) on the addition of 1-Y,3-X-disubstituted propyl radicals (Y = F or CN) to ethylene. It is found that, although the γ substituent (i.e. penultimate unit) can exert a significant effect on the stability of the propagating radical, only a small fraction of this effect appears to carry over to the reaction barrier. Furthermore, it appears that when penultimate unit effects on radical stability are large enough to result in significant penultimate unit effects on the reaction barrier, polar interactions are also likely to be significant. The implications of these results for the implicit penultimate model in free-radical copolymerization are discussed. |
| doi_str_mv | 10.1021/ma9818073 |
| format | Article |
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It is found that, although the γ substituent (i.e. penultimate unit) can exert a significant effect on the stability of the propagating radical, only a small fraction of this effect appears to carry over to the reaction barrier. Furthermore, it appears that when penultimate unit effects on radical stability are large enough to result in significant penultimate unit effects on the reaction barrier, polar interactions are also likely to be significant. 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It is found that, although the γ substituent (i.e. penultimate unit) can exert a significant effect on the stability of the propagating radical, only a small fraction of this effect appears to carry over to the reaction barrier. Furthermore, it appears that when penultimate unit effects on radical stability are large enough to result in significant penultimate unit effects on the reaction barrier, polar interactions are also likely to be significant. The implications of these results for the implicit penultimate model in free-radical copolymerization are discussed.</description><subject>Applied sciences</subject><subject>Copolymerization</subject><subject>Exact sciences and technology</subject><subject>Organic polymers</subject><subject>Physicochemistry of polymers</subject><subject>Preparation, kinetics, thermodynamics, mechanism and catalysts</subject><issn>0024-9297</issn><issn>1520-5835</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1999</creationdate><recordtype>article</recordtype><recordid>eNptkE1vEzEQhi0EEiFw4B_sAZA4LPjbu0dUNYBaiahNBeJijZ2xcNl4i-0gwq_HVUq5cBrNzDMf70vIc0bfMMrZ2x2MAxuoEQ_IgilOezUI9ZAsKOWyH_loHpMnpVxTypiSYkHgNAT0tZtDV79ht8a0n2rcQcXuKsVWT90FbKOHqbus4OIU66GDtO0uEHyNP2_TmLpVRuz_gut5Ouwwx99Q45yekkcBpoLP7uKSXK1ONycf-vNP7z-evDvvQXJWeyHCoB1o0wSMjqNRW6qFRyk0ANXaSee40gyD9jhK44JUwoMzTA5otBNL8uq49ybPP_ZYqt3F4nGaIOG8L5brUTFuxga-PoI-z6VkDPYmN8X5YBm1tybaexMb--JuKZQmLWRIPpZ_A0YPsv2xJP0Ri6Xir_s25O9WG2GU3awv7dnnL2x19nVjdeNfHnnwxV7P-5yaM_85_wfdiIxS</recordid><startdate>19990504</startdate><enddate>19990504</enddate><creator>Coote, Michelle L</creator><creator>Davis, Thomas P</creator><creator>Radom, Leo</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8FD</scope><scope>JG9</scope></search><sort><creationdate>19990504</creationdate><title>Effect of the Penultimate Unit on Radical Stability and Reactivity in Free-Radical Polymerization</title><author>Coote, Michelle L ; Davis, Thomas P ; Radom, Leo</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a421t-33f86ba67a989b2e75d063ce436aa066b4bb2561ef6ce947bf453cab7148e76b3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1999</creationdate><topic>Applied sciences</topic><topic>Copolymerization</topic><topic>Exact sciences and technology</topic><topic>Organic polymers</topic><topic>Physicochemistry of polymers</topic><topic>Preparation, kinetics, thermodynamics, mechanism and catalysts</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Coote, Michelle L</creatorcontrib><creatorcontrib>Davis, Thomas P</creatorcontrib><creatorcontrib>Radom, Leo</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><jtitle>Macromolecules</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Coote, Michelle L</au><au>Davis, Thomas P</au><au>Radom, Leo</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Effect of the Penultimate Unit on Radical Stability and Reactivity in Free-Radical Polymerization</atitle><jtitle>Macromolecules</jtitle><addtitle>Macromolecules</addtitle><date>1999-05-04</date><risdate>1999</risdate><volume>32</volume><issue>9</issue><spage>2935</spage><epage>2940</epage><pages>2935-2940</pages><issn>0024-9297</issn><eissn>1520-5835</eissn><coden>MAMOBX</coden><abstract>Ab initio molecular orbital calculations have been used to study the effect of γ substituents (X = H, F, or CN) on the addition of 1-Y,3-X-disubstituted propyl radicals (Y = F or CN) to ethylene. It is found that, although the γ substituent (i.e. penultimate unit) can exert a significant effect on the stability of the propagating radical, only a small fraction of this effect appears to carry over to the reaction barrier. Furthermore, it appears that when penultimate unit effects on radical stability are large enough to result in significant penultimate unit effects on the reaction barrier, polar interactions are also likely to be significant. The implications of these results for the implicit penultimate model in free-radical copolymerization are discussed.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><doi>10.1021/ma9818073</doi><tpages>6</tpages></addata></record> |
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| subjects | Applied sciences Copolymerization Exact sciences and technology Organic polymers Physicochemistry of polymers Preparation, kinetics, thermodynamics, mechanism and catalysts |
| title | Effect of the Penultimate Unit on Radical Stability and Reactivity in Free-Radical Polymerization |
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