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dc.contributor.authorZetterlund, PB
dc.contributor.authorBusfield, WK
dc.contributor.authorJenkins, ID
dc.date.accessioned2017-05-03T11:07:34Z
dc.date.available2017-05-03T11:07:34Z
dc.date.issued2002
dc.date.modified2009-12-04T05:18:39Z
dc.identifier.issn0024-9297
dc.identifier.doi10.1021/ma020325v
dc.identifier.urihttp://hdl.handle.net/10072/6560
dc.description.abstractThe first 15 addition products in the free radical polymerization of styrene initiated by AIBN have been trapped using a nitroxide trapping technique. In this experiment, the concentration of trap is maintained at a level sufficiently high to prevent the formation of high polymer yet low enough to allow competitive monomer addition to form the lower members of the propagation series before being trapped to form the oligomeric addition products. These oligomers have been identified and quantified by electrospray ionization mass spectrometry (ESI-MS) in series with HPLC-UV. The observation of single chromatographic peaks for each oligomer indicates that the rate of formation of branched products is negligible. The results have allowed the first 14 individual propagation rate coefficients, kSn (n = 1-14), to be estimated based on the assumption that the successive trapping rate coefficients are constant. RSn堫 S RSn+1宠The results show that at 75 àkSn increases significantly from n = 1 to n = 3 and then stays constant to n = 7. The value of kSn for n = 3-7 is 6.5 ᠲ נ104 M-1 s-1. In the range n = 7-14, the value decreases steadily by a factor of about 2. The value at n = 14 is significantly higher than the IUPAC recommended value for high polymer of 565 M-1 s-1 at 75 î The rate coefficient for the addition of cyanoisopropyl radicals to styrene (n = 0) is 1.0 ᠰ.4 נ104 M-1 s-1 at 75 î
dc.description.peerreviewedYes
dc.description.publicationstatusYes
dc.languageEnglish
dc.language.isoeng
dc.publisherAmerican Chemical Society
dc.publisher.placeUS
dc.publisher.urihttp://pubs.acs.org/journal/mamobx
dc.relation.ispartofpagefrom7232
dc.relation.ispartofpageto7237
dc.relation.ispartofjournalMacromolecules
dc.relation.ispartofvolume35
dc.subject.fieldofresearchChemical sciences
dc.subject.fieldofresearchEngineering
dc.subject.fieldofresearchcode34
dc.subject.fieldofresearchcode40
dc.titleFree Radical Polymerisation of Styrene: Mass Spectrometric Identification of the first 15 Nitroxide-Trapped Oligomers and Estimated Propagation Rate Coefficients
dc.typeJournal article
dc.type.descriptionC1 - Articles
dc.type.codeC - Journal Articles
gro.facultyGriffith Sciences, Griffith Institute for Drug Discovery
gro.date.issued2002
gro.hasfulltextNo Full Text
gro.griffith.authorJenkins, Ian D.
gro.griffith.authorBusfield, Ken K.
gro.griffith.authorZetterlund, Per B.


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