MacromolecularSymposia| 248 Radical Polymerization: Kinetics and Mechanism SelectedContributions fromtheconferencein IlCiocco(Italy),September3–8,2006 SymposiumEditors: M.Buback(Germany), A.M.v.Herk(TheNetherlands) Macromolecular Symposia Related Titles M.Matsuo,K.Tashiro,Y.Bin(Eds.) 14thAnnualPolycharWorldForum onAdvancedMaterials Vol.242 J.M.Guenet,A.K.Nandi(Eds.) FibrillarNetworksasAdvanced Materials Vol.241 ISBN3-527-31748-1 D.Baskaran,S.Sivaram(Eds.) RecentTrendsinIonic Polymerization Vol.240 ISBN3-527-31747-3 K.Matyjaszewski,YvesGnanou, LudwikLeibler MacromolecularEngineering ISBN3-527-31446-6 M.Lazzari,G.Liu,S.Lecommandoux BlockCopolymersinNanoscience ISBN3-527-31309-5 D.O.Hummel IRHummelDefinedPolymers BasicCollection ISBN3-527-31628-0 Macromolecular Symposia Vol. 248 Radical Polymerization: Kinetics and Mechanism SelectedContributions fromtheconferencein IlCiocco(Italy),September3–8,2006 SymposiumEditors: M.Buback(Germany), A.M.v.Herk(TheNetherlands) (cid:1)2007Wiley-VCHVerlagGmbH&Co.KGaA, Weinheim ISBN103-527-32056-3 ISBN13978-3-527-32056-1 iv|| Masthead Fulltextandfurtherinformation:www.ms-journal.de Editors(allMacromolecularJournals): ExecutiveAdvisoryBoard: SandraKalveram M.Antonietti,Golm,Germany StefanSpiegel D.L.Kaplan,Medford,USA MaraStaffilani S.Kobayashi,Kyoto,Japan AssistantEditor: K.Kremer,Mainz,Germany CarmenTeutsch T.P.Lodge,Minneapolis,MN,USA EditorialAssistant: H.E.H.Meijer,Eindhoven,Netherlands SibylleMeyer R.Mu¨lhaupt,Freiburg,Germany Administration: T.P.Russell,Amherst,USA IngeDittmer A.J.Ryan,Sheffield,UK PetraPinto A.D.Schlu¨ter,Zu¨rich,Switzerland Production: J.B.P.Soares,Waterloo,Canada KatjaKornmacher H.W.Spiess,Mainz,Germany EditorialOffice: N.Tirelli,Manchester,UK [email protected] G.Wegner,Mainz,Germany C.Wu,HongKong,China MacromolecularSymposia ispublished14timesayear Annualsubscriptionrates2007 Ordersmaybeplacedthroughyourbookseller MacromolecularFullPackage ordirectlyatthepublishers: (All seven Macromolecular Journals; 101 issues in WILEY-VCHVerlagGmbH&Co.KGaA, total): P.O.Box101161,69451Weinheim,Germany, Europe Euro 8,445 9,290 Tel.þ49(0)6201/606-400, Switzerland Sfr 13,995 15,395 Faxþ49(0)6201/606184, Allotherareas US$ 11,145 12,260 E-mail:[email protected] printonlyor printand electroniconly electronic CopyrightPermission: Postageandhandlingchargesincluded. Fax:þ49(0)6201/606-332, AllWiley-VCHpricesareexclusiveofVAT. E-mail:[email protected] Pricesaresubjecttochange. Individualsubscriptions,singleissuesandback copiesareavailable. Pleaseaskfordetailsat:[email protected] ForUSAandCanada:MacromolecularSymposia(ISSN1022-1360)ispublishedwith14volumes peryearbyWILEY-VCHVerlagGmbH&Co.KGaA,Boschstr.12,69451Weinheim,Germany.Air freightandmailingintheUSAbyPublicationsExpeditingInc.,200MeachamAve.,Elmont,NY 11003,USA.ApplicationtomailatPeriodicalsPostagerateispendingatJamaica,NY11431,USA. POSTMASTERpleasesendaddresschangesto:MacromolecularSymposia,c/oWiley-VCH,IIIRiver Street,Hoboken,NJ07030,USA. Printedonacid-freepaper. Typesetting:ThomsonPress(India)Ltd.,India Printing:StraussOffsetdruck,Mo¨rlenbach Binding:Litges&Dopf,Heppenheim (cid:1)2007Wiley-VCHVerlagGmbH&Co.KGaA, Weinheim Table of Contents |v Macromolecular Articlespublishedonthewebwillappear severalweeksbeforetheprintedition. Symposia Theyareavailablethrough: www.interscience.wiley.com Cover:TheIUPAC-sponsoredInternational important step forward toward the better Symposium on ‘‘Radical Polymerization: understandingofthekineticsandmechanism Kinetics and Mechanism’’ was held in Il ofradicalpolymerization,whichisextremely Ciocco(Italia)duringtheweekSeptember3- relevant for both conventional and con- 8, 2006. Attended by close to 200 people trolledradicalpolymerizationandforpeople fromallovertheworldwithagoodbalance inacademiaaswellasinindustry. betweenattendeesfromindustryandacade- mia, this symposium was the fourth within the series of so-called SML conferences, which are the major scientific forum for addressingkineticandmechanisticaspectsof free-radicalpolymerizationandofcontrolled radical polymerization. The present sympo- sium comprised five major themes: Funda- mentals of free-radical polymerization, Heterogeneous polymerization, Controlled radical polymerization, Polymer reaction engineering, and Polymer characterization. Most of the invited lectures covering these topics are reflected as written contributions in this issue. SML IV again marked an Radical Polymerization: Kinetics and Mechanism Il Ciocco (Italy), September 3–8, 2006 Preface M.Buback,AlexvanHerk FundamentalsofRadicalPolymerization TheCutthroatCompetitionBetween Gregory B.Smith, |1 TerminationandTransfertoShapethe Gregory T. Russell* KineticsofRadicalPolymerization (cid:1)2007Wiley-VCHVerlagGmbH&Co.KGaA,Weinheim www.ms-journal.de vi| Table of Contents TheImportanceofChain-Length Johan P.A. Heuts,* |12 DependentKineticsinFree-Radical Gregory T. Russell, Polymerization:APreliminaryGuide Gregory B.Smith, Alex M.vanHerk PropagationKineticsofFree-Radical SabineBeuermann, |23 MethacrylicAcidPolymerizationin Michael Buback, AqueousSolution.TheEffectof Pascal Hesse, ConcentrationandDegreeofIonization Silvia Kukucˇkova´, IgorLacı´k* InvestigationoftheChainLength Irene Schno¨ll-Bitai,* |33 Dependenceofk :NewResultsObtained Christoph Mader p withHomogeneousandHeterogeneous Polymerization PropagationRateCoefficientofNon- SabineBeuermann, |41 ionizedMethacrylicAcidRadical Michael Buback,* PolymerizationinAqueousSolution.The Pascal Hesse, EffectofMonomerConversion Silvia Kukucˇkova´, IgorLacı´k StudyingtheFundamentalsofRadical Atsushi Kajiware |50 PolymerizationUsingESRinCombination withControlledRadicalPolymerization Methods ControlledRadicalPolymerization CompetitiveEquilibriainAtomTransfer Nicolay V.Tsarevsky, |60 RadicalPolymerization Wade A. Braunecker, Alberto Vacca, Peter Gans, Krzysztof Matyjaszewski* KineticAspectsofRAFTPolymerization Philipp Vana |71 ScopeforAccessingtheChainLength Tara M.Lovestead, |82 DependenceoftheTerminationRate Thomas P.Davis, CoefficientforDisparateLengthRadicals Martina H.Stenzel, inAcrylateFreeRadicalPolymerization Christopher Barner- Kowollik* SynthesisofPoly(methylacrylate)Grafted Youliang Zhao, |94 ontoSilicaParticlesbyZ-supportedRAFT Se´bastien Perrier* Polymerization RAFTPolymerization:Addingtothe Ezio Rizzardo,* |104 Picture Ming Chen,Bill Chong, Graeme Moad, Melissa Skidmore, San H.Thang (cid:1)2007Wiley-VCHVerlagGmbH&Co.KGaA,Weinheim www.ms-journal.de Table of Contents |vii Verdazyl-MediatedPolymerizationof Steven J.Teertstra, |117 Styrene Eric Chen, Delphine Chan-Seng, Peter O.Otieno, Robin G.Hicks,* Michael K. Georges* Germanium-andTin-CatalyzedLiving Atsushi Goto, |126 RadicalPolymerizationsofStyreneand HirokazuZushi, Methacrylates Norihiro Hirai, Tsutomu Wakada, YungwanKwak, Takeshi Fukuda* MechanismandKineticsoftheInduction Jose´Bonilla-Cruz, |132 PeriodinNitroxideMediatedThermal Laura Caballero, Autopolymerizations.Applicationtothe Martha Albores-Velasco,* SpontaneousCopolymerizationofStyrene Enrique Saldı´var-Guerra,* andMaleicAnhydride Judith Percino, Vı´ctor Chapela NMRSpectroscopyintheOptimization Bert Klumperman,* |141 andEvaluationofRAFTAgents JamesB.McLeary, EricT.A.vandenDungen, Gwenaelle Pound ReverseIodineTransferPolymerization Patrick |150 (RITP)inEmulsion Lacroix-Desmazes,* Jeff Tonnar, Bernard Boutevin AMissingReactionStepin Michael Buback,* |158 Dithiobenzoate-MediatedRAFT Olaf Janssen, Polymerization Rainer Oswald, Stefan Schmatz, Philipp Vana PolymerReactionEngineeringand PolymerMaterials RAFTPolymerizationinBulkand Alessandro Butte`,* |168 Emulsion A. DavidPeklak, Giuseppe Storti, MassimoMorbidelli ReactionCalorimetryfortheDevelopment Maartje F.Kemmere,* |182 ofUltrasound-InducedPolymerization Martijn W.A.Kuijpers, ProcessesinCO -ExpandedFluids Jos T.F.Keurentjes 2 (cid:1)2007Wiley-VCHVerlagGmbH&Co.KGaA,Weinheim www.ms-journal.de viii| Table of Contents Size-ExclusionEffectandProtein ChiakiYoshikawa, |189 RepellencyofConcentratedPolymer Atsushi Goto, BrushesPreparedbySurface-Initiated Norio Ishizuka, LivingRadicalPolymerization Kazuki Nakanishi, Akio Kishida, Yoshinobu Tsujii, Takeshi Fukuda* SynthesisofRod-CoilBlockCopolymers Simone Steig, |199 usingTwoControlledPolymerization Frauke Cornelius, Techniques Andreas Heise, Rutger J.I. Knoop, Gijs J.M.Habraken, Cor E.Koning, Henning Menzel* ProductionofPolyacrylicAcidHomo-and Johanna Bu¨nsow, |207 CopolymerFilmsbyElectrochemically Diethelm Johannsmann* InducedFree-RadicalPolymerization: PreparationandSwellingBehavior PolymerizationinHeterogeneousSystems DesigningOrganic/InorganicColloidsby Elodie Bourgeat-Lami,* |213 HeterophasePolymerization Norma Negrete Herrera, Jean-Luc Putaux, Adeline Perro, Ste´phaneReculusa, Serge Ravaine, Etienne Duguet UnusualKineticsinAqueousHeterophase KlausTauer,* |227 Polymerizations Muyassar Mukhamedjanova, Christian Holtze, Pantea Nazaran, Jeongwoo Lee Surface–FunctionalizedInorganic Oliver To¨pfer, |239 NanoparticlesinMiniemulsion Gudrun Schmidt-Naake* Polymerization ReversibleAdditionFragmentationChain Prakash J.Saikia, |249 TransferMediatedDispersion Jung MinLee, PolymerizationofStyrene ByungH.Lee, Soonja Choe* (cid:1)2007Wiley-VCHVerlagGmbH&Co.KGaA,Weinheim www.ms-journal.de Author Index |ix Albores-Velasco,M. |132 Lee,J. |227 Barner-Kowollik,C. |82 Lovestead,T.M. |82 Beuermann,S. |23,41 Mader,C. |33 Bonilla-Cruz,J. |132 Matyjaszewski,K. |60 Bourgeat-Lami,E. |213 McLeary,J.B. |141 Boutevin,B. |150 Menzel,H. |199 Braunecker,W.A. |60 Moad,G. |104 Buback,M. |23,41,158 Morbidelli,M. |168 Bu¨nsow,J. |207 Mukhamedjanova,M. |227 Butte`,A. |168 Nakanishi,K. |189 Caballero,L. |132 Nazaran,P. |227 Chan-Seng,D. |117 Oswald,R. |158 Chapela,V. |132 Otieno,P.O. |117 Chen,E. |117 Peklak,A.D. |168 Chen,M. |104 Percino,J. |132 Choe,S. |249 Perrier,S. |94 Chong,B. |104 Perro,A. |213 Cornelius,F. |199 Pound,G. |141 Davis,T.P. |82 Putaux,J. |213 Duguet,E. |213 Ravaine,S. |213 Fukuda,T. |126,189 Reculusa,S. |213 Gans,P. |60 Rizzardo,E. |104 Georges,M.K. |117 Russell,G.T. |1,12 Goto,A. |126,189 Saikia,P.J. |249 Habraken,G.J.M. |199 Saldı´var-Guerra,E. |132 Heise,A. |199 Schmatz,S. |158 Herrera,N.N. |213 Schmidt-Naake,G. |239 Hesse,P. |23,41 Schno¨ll-Bitai,I. |33 Heuts,J.P.A. |12 Skidmore,M. |104 Hicks,R.G. |117 Smith,G.B. |1,12 Hirai,N. |126 Steig,S. |199 Holtze,C. |227 Stenzel,M.H. |82 Ishizuka,N. |189 Storti,G. |168 Janssen,O. |158 Tauer,K. |227 Johannsmann,D. |207 Teertstra,S.J. |117 Kajiwara,A. |50 Thang,S.H. |104 Kemmere,M.F. |182 Tonnar,J. |150 Keurentjes,J.T.F. |182 To¨pfer,O. |239 Kishida,A. |189 Tsarevsky,N.V. |60 Klumperman,B. |141 Tsujii,Y. |189 Knoop,R.J.I. |199 Vacca,A. |60 Koning,C.E. |199 vandenDungen,E.T.A. |141 Kuijpers,M.W.A. |182 vanHerk,A.M. |12 Kukucˇkova´,S. |23,41 Vana,P. |71,158 Kwak,Y. |126 Wakada,T. |126 Lacı´k,I. |23,41 Yoshikawa,C. |189 Lacroix-Desmazes,P. |150 Zhao,Y. |94 Lee,B.H. |249 Zushi,H. |126 Lee,J.M. |249 (cid:1)2007Wiley-VCHVerlagGmbH&Co.KGaA,Weinheim www.ms-journal.de x| Preface This volumecontainsarticlesoftheinvited ferences, e.g., the groundbreaking pulsed– speakers at the IUPAC-sponsored Inter- laser polymerization – size-exclusion chro- national Symposium on ‘‘Radical Polymer- matography method for the reliable mea- ization:KineticsandMechanism’’heldinIl surement of propagation rate coefficients, Ciocco (Italia) during the week September whichhasbeenintroducedby ProfessorO. 3–8, 2006. The conference was attended by F.OlajandhisgroupatSMLI. closeto200peoplefromallovertheworld Distinctivefeaturesoftheconferenceare withagoodbalancebetweenattendeesfrom thatallattendeesstayinthesamehotel,that industryandacademia.About40percentof no parallel sessions are presented and that the attendees were Ph.D. students, who thepostersmaybediscussedthroughoutthe very actively participated in the scientific entire week. A total of 35 invited lectures program. havebeengiven,eightofwhichwereselected Thissymposiumwasthefourthwithinthe from the submitted poster abstracts. More- series of so-called SML conferences, which over,114posterswerepresented,mostlyby arethemajorscientificforumforaddressing research students. Most of the invited lec- kineticandmechanisticaspectsoffree-radical turesarereflectedaswrittencontributionsin polymerization and of controlled radical this issue of Macromolecular Symposia. In polymerization. The first SML meeting was addition, the six groups of authors, who organized by Ken O’Driscoll and Saverio receivedmostofthevotesduringtheelection Russo at Santa Margherita Ligure (Italy) in oftheposterprizewinners,werealsoinvited May1987.ThesecondSMLmeetingwasheld to contribute to this volume. It should be atthesamelocationbythesameorganizersin noted that all conference attendees could 1996.ThethirdSMLmeetingwasorganized participate in the voting procedure for the in 2001 by Michael Buback from Go¨ttingen posterprizes. University and by Ton German from the The symposium comprised five major themes: Technical University of Eindhoven. They selectedtheconferencehotelatIlCioccoas - Fundamentalsoffree-radical thenewsymposiumsite.Thisvenueislocated polymerization inthebeautifulprovinceofLucca.Thus,the - Heterogeneouspolymerization abbreviation SML, which originally referred - Controlledradicalpolymerization to Santa Margherita Ligure, now stands for - Polymerreactionengineering ScientificMeetingLucca. - Polymercharacterization ThefourthSMLmeeting(September3–8, 2006)wasorganizedbyMichaelBubackand We are pleased to see that SML IV again by Alex van Herk from the Technical marked an important step forward toward University of Eindhoven. As has been fore- thebetterunderstandingofthekineticsand seen in the last meeting, the number of mechanismofradicalpolymerization,which contributions oncontrolledradical polymer- is extremelyrelevant for both conventional ization (CRP) has significantly increased. and controlled radical polymerization and Four out of theeight sessions were devoted forpeopleinacademiaaswellasinindustry. to CRP and the organizers consequently The organizers want to acknowledge decided to remove the word ‘Free’ from financial support of the conference by the the conference heading. The symposium ‘‘Foundation Emulsion Polymerization’’ nevertheless remains the number one (SEP) and by the European Graduate forum where kinetic and mechanistic issues Schoolon‘‘MicrostructuralControlinFree- are addressed in detail and depth for the RadicalPolymerization’’. entirefieldofradicalpolymerization.Several important aspects of radical polymerization M.Buback, have first been presented at SML con- A.M.VanHerk (cid:1)2007Wiley-VCHVerlagGmbH&Co.KGaA,Weinheim www.ms-journal.de