[Stanisław Penczek, Polimery, Polimery i hydrożele
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//-->YThhhPolymer ScienceFortschritte der Hochpolymeren-ForschungEdited by H.-J. CANTOW, Freiburg i. Br. • G. DALL'ASTA, ColleferroK. DU~EK, Prague • J. D. FERRY, Madison • H. FUJITA, OsakaM. GORDON, Colchester • J. P. KENNEDY, A k r o n • W. KERN, MainzS.OKAMURA,Kyoto • C. G.OVERBERGER,A n n A r b o rT.SAEGUSA,K y o t o • G. V. SCHULZ, Mainz • W. P.SLICHTER,Murray HillJ. K. STILLE, Fort CollinsWith 19 FiguresSpringer-VerlagBerlin Heidelberg New York 1980EditorsProf. HANS-JOACHIM CANTOW, Institut fiir Makromolekulare Chemie der Universit/it, Stefan-Meier-Str. 31, 7800 Freiburg i. Br., BRDProf. GINO DALL'ASTA, SNIA V I S C O S A - Centro Studi Chimico, Colleferro (Roma), ItaliaProf. KAREL DU~EK, Institute of Macromolecular Chemistry, Czechoslovak Academy of Scien-ces, 16206 Prague 616, ~SSRProf. JOHN D. FERRY, Department of Chemistry, The University of Wisconsin, Madison,Wisconsin 53706, U.S.A.Prof. HIROSHI FUJITA, Department of Polymer Science, Osaka University, Toyonaka,Osaka, JapanProf. MANFRED GORDON, Department of Chemistry, University of Essex, Wivenhoe Park,Colchester C 04 3 SQ, EnglandProf. JOSEPH P. KENNEDY, Institute of Polymer Science, University of Akron, Akron, Ohio44325, U.S.A.Prof. WERNER KERN, Institut ftir Organische Chemic der Universit/it, 6500 Mainz, BRDProf. SEIZOOKAMURA,NO. 24, Minami-Goshomachi, Okazaki, Sakyo-Ku, Kyoto 606, JapanProf. CHARLES G.OV.ERBERGER,Macromolecular Research Center, Institute of Scienceand Technology, The University of Michigan, Ann Arbor, Michigan 48 104, U.S.A.Prof. TAKEO SAEGUSA, Department of Synthetic Chemistry, Faculty of Engineering,Kyoto University, Kyoto, JapanProf. GONTER VICTOR SCHULZ, Institut fiir Physikalische Chemie der Universit~it, 6500 Mainz,BRDDr. WILLIAMP. SLICHTER, Chemical Physics Research Department, Bell TelephoneLaboratories, Murray Hill, New Jersey 07 971, U.S.A.Prof. JOHN K.STILLE,Department of Chemistry, Colorado State University, Fort Collins,Colorado 805 23, U.S.A.ISBN 3-540-10209-4 Springer-Verlag Berlin Heidelberg New YorkISBN 0-387-10209-4 Springer-Verlag New York Heidelberg BerlinLibraryof CongressCatalogCard Number61-642This workis subjectto copyright.All rightsare reserved,whetherthe wholeor part of the materialis concerned,specificallythoseof translation,reprinting, re-useof illustrations,broadcasting,reproductionby photocopyingmachineor similarmeans,and storagein data banks. Under§ 54 of the GermanCopyrightLawwherecopiesare madeforother than private use,a fee is payableto the publisher,the amountto the fee to be determinedby agreementwiththe publisher.© by Springer-VerlagBerlin Heidelberg 1980Printed in GermanyThe use of generaldescriptivenames,trademarks,etc. in thispublication,evenif the formerare not especiallyidenti-fied, is not to be taken as a signthat suchnames,as understoodby the Trade Marksand MerchandiseMarksAct, mayaccordinglybe usedfreelyby anyone.Typesetting and printing: SchwetzingerVerlagsdruekereiGmbH.Bookbinding: BrfihlscheUniversitatsdruckerei, Giessen2152/3140 - 543210Cationic Ring-Opening Polymerizationof Heterocyclic MonomersI. M e c h a n i s m sStanisCaw P e n c z e k , P r z e m y s C a w K u b i s a a n d K r z y s z t o f M a t y j a s z e w s k iCentre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Boczna 5,PL-90-362L6d'~Table ofContents1 Introduction . . . . . . . . . . . . . . . . . . . . .2 Monomer Structures, Ring Strains and Nucleophilicities (Basicities)2.1. Conformation of Heterocyclic Monomers . . . . . . . . . .2.2 Factors Affecting Reactivities . . . . . . . . . . . . . .3 Initiation . . . . . . . . . . . . . . . . . . . . .3.1 Protonic Acids . . . . . . . . . . . . . . . . .3.1.1Protonic Acids with Complex Anions. . . . . .3.1.2Protonic Acids with Non-Complex Anions . . . . .3.1.3Direct Identification of the Initiation Products(Initial Species) . . . . . . . . . . . . . .3.2 Initiation with Stable Carbenium or Onium Ions and withTheir Covalent Precursors ("Hidden Ions"). . . . . . .3.2.1Carbenium Ions. . . . . . . . . . . . .3.2.2Carbenium Ion-Onium Ion Equilibria. . . . . .3.2.3Structure of Monomers and Rate of Hydride Transfer3.2.4Alkoxycarbenium Ions . . . . . . . . . . .3.2.51,3-Dioxolan-2-ylium (Dioxolenium) Salts . . . . .3.2.6Oxocarbenium Ions . . . . . . . . . . . .3.2.7Onium Ions . . . . . . . . . . . . . . .3.2.8Covalent Initiators ("Hidden Cations") . . . . . .3.2.9Friedel-Crafts (F-C) Initiators . . . . . . . . .3.2.10 Cations Formed by Electron Transfer. . . . . .3.2.11 Organometallic Initiators. . . . . . . . . .3.3 Kinetics of Initiation . . . . . . . . . . . . . . .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .13358810101215151717202122242628303234393941424 Propagation . . . . . . . . . . . . . . . . . . . . .4.1 Chemical Structure of the Growing Species . . . . . . . . .4.1.1Active Species in the Polymerization of Cyclic Acetals .4.1.2Polymerization of Cyclic Acetals Initiated by Protonic Acids .IVPolymerization of Cyclic Acetals Initiated by Preformed or"Hidden" Carbocations . . . . . . . . . . . . .4.1.4Carbenium or Oxonium Ions in the Polymerization of CyclicAcetals? . . . . . . . . . . . . . . . . . .4.1.5Carbenium-Oxonium Ion Equilibria InvolvingAlkoxycarbenium Ions . . . . . . . . . . . . .4.1.6Structure of Tertiary Oxonium Ions in thePolymerization of 1,3-Dioxolane . . . . . . . . . .4.1.7Activated Monomer as Active Species in thePolymerization of Lactams . . . . . . . . . . . .4.1.8The Steric and Electronic Structure of Onium Ions . . . .4.2 Macroions and Macroion Pairs in Propagation. . . . . . . .4.2.1Determination of the Concentration of the GrowingSpecies [P*] . . . . . . . . . . . . . . . . .4.2.2Dissociation of MacroionPairs . . . . . . . . . . .4.2.3Propagation on Macroion Pairs with Different Anions4.2.4Reactivities of Macrocations and Macroion Pairs . . . . .4.2.5Solvent Effects (Polarity, Solvation of Ions, MonomerComplexes) in Propagation . . . . . . . . . . . .4.2.5.1 Equilibria and Properties of Media. . . . . .4.2.5.2 Activation Parameters of Propagation andProperties of Media. . . . . . . . . . .4.3 Rate Constants of Propagation and Structure of Monomers . . . .4.4 Stereochemistry of the Cationic Ring-Opening Propagation . . . .4.4.1Inversion of Configuration and Stereoselectivity . . . . .4.1.34445454648505252535658616162647070Termination and Transfer Processes. . . . . . . . . . . . .775.1 Temporary (Reversible) Termination. . . . . . . . . . .775.1.1Reversible Recombination with Non-Complex Anions775.1.2Competition Between Propagation of Covalent andIonic Species. . . . . . . . . . . . . . . .805.1.3Equilibria Between Covalent and Ionic Growing Species845.1.4Equilibrium Between Covalent Macromolecules and MacroionPairs in the Presence of Macroions. . . . . . . . .875.1.5The Rate of Interconversion of Covalent Macromoleculesand Macroion Pairs. . . . . . . . . . . ., . . 885.1.6Summary of the Kinetics of Propagation Involving Covalentand Ionic Species . . . . . . . . . . . . . . .905.2 Termination by Irreversible Collapse of the Macroion Pair. . . .935.2.1Kinetics of Polymerization Involving UnimolecularUnopposed (Irreversible) First-Order Termination. . . .955.2.2Termination by Recombination Within an Ion Pair andStructure of Anions . . . . . . . . . . . . . .965.3 Transfer and Termination Involving the Polymer Backbone . . . .975.3.1Evidence of Reactions with Polymer Chains . . . . . .985.3.2Intermolecular Chain Transfer (Termination) to PolymerChains . . . . . . . . . . . . . . . . . . .101VChain Transfer to Polymer in Polymerization of T H E .Intermolecular Chain Transfer Followed by ReinitiationIntramolecular Termination. . . . . . . . . . .Intrarnolecular Chain Transfer (Termination) Followed byReinitiation . . . . . . . . . . . . . . . . .5.3.7Kinetics of Chain Transfer to Polymer. Determination ofRate Constants. Summary . . . . . . . . . . . .5.3.8Thermodynamics of the Linear Polymer-MacrocycleEquilibrium . . . . . . . . . . . . . . . . .5.3.9Kinetic Enhancement in Macrocycles. . . . . . . .5.3.10 Propagation in Competition with Condensation . . . . .5.3.11 Induction Periods in Polymerization Due to the End-BitingReaction . . . . . . . . . . . . . . . . . .5.3.12 Kinetic Depression o f Macrocycles. . . . . . . . .5.3.13 Stereochernistry o f Back-Biting Processes.Stereoselectivity . . . . . . . . . . . . . . .5.4 Hydride Ion, Proton and Carbocation Transfer to Monomer . . . .5.4.1Hydride Ion Shift and Transfer Reactions . . . . . . .5.4.2Proton and Carbocation Transfer Reactions. . . . . .Addendum . . . . . . . . . . . . . . . . . . . . . . .Initiation . . . . . . . . . . . . . . . . . . . . . .Propagation. . . . . . . . . . . . . . . . . . . . .Stereocontrol in Polymerization . . . . . . . . . . . . . .Termination and Transfer Processes. . . . . . . . . . . . .Macrocyclization. End-Biting and Back-Biting . . . . . . . . .Termination by Fragmentation o f Complex Anions and Collapseo f the Pairs of Ions . . . . . . . . . . . . . . . . . .Transfer to Polymer . . . . . . . . . . . . . . . . . .5.3.35.3.45.3.55.3.6104106108109111111115117118118119121122124127127130130135135136137138145151References. . . . . . . . . . . . . . . . . . . . . . .Subject Index . . . . . . . . . . . . . . . . . . . . . .Author Index Volumes 1 - 3 7. . . . . . . . . . . . . . . .
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