Green Polymerization Methods: Renewable Starting Materials, Catalysis and Waste Reduction PDF
Preview Green Polymerization Methods: Renewable Starting Materials, Catalysis and Waste Reduction
Editedby RobertT.Mathersand MichaelA.R.Meier GreenPolymerizationMethods Related Titles HandbookofGreen Chemistry Lapkin,A.,Constable,D.(eds.) GreenChemistryMetrics Hardcover 12volumes ISBN:978-1-4051-5968-5 ISBN:978-3-527-31404-1 Perosa,A.,Zecchini,F. Loos,K.(ed.) MethodsandReagentsforGreen BiocatalysisinPolymerChemistry Chemistry 2011 AnIntroduction ISBN:978-3-527-32618-1 2007 Lendlein,Andreas/Schroeter,Michael(eds.) ISBN:978-0-471-75400-8 HandbookofBiodegradable Sheldon,R.A.,Arends,I.,Hanefeld,U. Polymers Isolation,Synthesis,Characterizationand GreenChemistryandCatalysis Applications 2007 2011 ISBN:978-3-527-30715-9 ISBN:978-3-527-32441-5 Matyjaszewski,K.,Gnanou,Y.,Leibler,L.(eds.) Dubois,P.,Coulembier,O.,Raquez,J.-M.(eds.) MacromolecularEngineering HandbookofRing-Opening PreciseSynthesis,MaterialsProperties, Polymerization Applications 2009 4volumes ISBN:978-3-527-31953-4 2007 Hardcover Janssen,Leon/Moscicki,Leszek(eds.) ISBN:978-3-527-31446-1 ThermoplasticStarch Cornils,B.,Herrmann,W.A.,Muhler,M., AGreenMaterialforVariousIndustries Wong,C.-H.(eds.) CatalysisfromAtoZ 2009 ISBN:978-3-527-32528-3 AConciseEncyclopedia 3volumes Fessner,W.-D.,Anthonsen,T.(eds.) 2007 ModernBiocatalysis ISBN:978-3-527-31438-6 StereoselectiveandEnvironmentallyFriendly Reactions 2009 ISBN:978-3-527-32071-4 Edited by Robert T. Mathers and Michael A. R. Meier Green Polymerization Methods Renewable Starting Materials, Catalysis and Waste Reduction TheEditors AllbookspublishedbyWiley-VCHare carefullyproduced.Nevertheless,authors, Prof.Dr.RobertT.Mathers editors,andpublisherdonotwarrantthe PennsylvaniaStateUniversity informationcontainedinthesebooks, DepartmentofChemistry includingthisbook,tobefreeoferrors. 3550SeventhStreetRd. Readersareadvisedtokeepinmindthat NewKensington,PA15068 statements,data,illustrations,procedural USA detailsorotheritemsmayinadvertentlybe inaccurate. Prof.Dr.MichaelA.R.Meier KarlsruheInstituteofTechnology(KIT) LibraryofCongressCardNo.:appliedfor InstituteofOrganicChemistry Fritz-Haber-Weg6,Building30.42 BritishLibraryCataloguing-in-Publication 76131Karlsruhe Data Germany Acataloguerecordforthisbookisavailable fromtheBritishLibrary. Bibliographicinformationpublishedbythe DeutscheNationalbibliothek TheDeutscheNationalbibliothek liststhispublicationintheDeutsche Nationalbibliografie;detailedbibliographic dataareavailableontheInternetat <http://dnb.d-nb.de>. 2011WILEY-VCHVerlag&Co.KGaA, Boschstr.12,69469Weinheim,Germany Allrightsreserved(includingthoseof translationintootherlanguages).Nopart ofthisbookmaybereproducedinany form–byphotoprinting,microfilm,orany othermeans–nortransmittedortranslated intoamachinelanguagewithoutwritten permissionfromthepublishers.Registered names,trademarks,etc.usedinthisbook, evenwhennotspecificallymarkedassuch, arenottobeconsideredunprotectedbylaw. Composition LaserwordsPrivateLtd., Chennai,India PrintingandBinding betz-druckGmbH, Darmstadt CoverDesign SchulzGrafik-Design, Fußgo¨nheim PrintedintheFederalRepublicofGermany Printedonacid-freepaper ISBN:978-3-527-32625-9 V Contents ListofContributors XIII PartI Introduction 1 1 WhyareGreenPolymerizationMethodsRelevanttoSociety,Industry, andAcademics? 3 RobertT.MathersandMichaelA.R.Meier 1.1 StatusandOutlookforEnvironmentallyBenignProcesses 3 1.2 ImportanceofCatalysis 4 1.3 BriefSummariesofContributions 5 References 6 PartII IntegrationofRenewableStartingMaterials 9 2 PlantOilsasRenewableFeedstockforPolymerScience 11 MichaelA.R.Meier 2.1 Introduction 11 2.2 Cross-LinkedMaterials 12 2.3 Non-Cross-LinkedPolymers 15 2.3.1 MonomerSynthesis 15 2.3.2 PolymerSynthesis 18 2.4 Conclusion 24 References 25 3 FuransasOffspringsofSugarsandPolysaccharidesandProgenitorsof anEmblematicFamilyofPolymerSiblings 29 AlessandroGandini 3.1 Introduction 29 3.2 FirstGenerationFuransandtheirConversionintoMonomers 30 3.2.1 FurfuralandDerivatives 30 3.2.2 MonomersfromFurfural 31 3.2.3 Hydroxymethylfurfural 35 GreenPolymerizationMethods:RenewableStartingMaterials,CatalysisandWasteReduction EditedbyRobertT.MathersandMichaelA.R.Meier Copyright2011WILEY-VCHVerlagGmbH&Co.KGaA,Weinheim ISBN:978-3-527-32625-9 VI Contents 3.3 PolymersfromFurfurylAlcohol 35 3.4 ConjugatedPolymersandOligomers 39 3.5 Polyesters 41 3.6 Polyamides 42 3.7 Polyurethanes 43 3.8 FurylOxirane 45 3.9 ApplicationoftheDiels–AlderReactiontoFuranPolymers 45 3.9.1 LinearPolymerizations 46 3.9.2 Non-LinearPolymerizations 49 3.9.3 ReversiblePolymerCross-Linking 52 3.9.4 MiscellaneousSystems 52 3.10 Conclusions 53 References 53 4 SelectiveConversionofGlycerolintoFunctionalMonomersviaCatalytic Processes 57 Fran¸coisJe´roˆmeandJo¨elBarrault 4.1 Introduction 57 4.2 ConversionofGlycerolintoGlycerolCarbonate 58 4.3 ConversionofGlycerolintoAcrolein/AcrylicAcid 62 4.4 ConversionofGlycerolintoGlycidol 63 4.5 OxidationofGlyceroltoFunctionalCarboxylicAcid 65 4.5.1 CatalyticOxidationofGlyceroltoGlycericAcid 65 4.5.2 Oxidative-AssistedPolymerizationofGlycerol 68 4.5.2.1 CationicPolymerization 68 4.5.2.2 AnionicPolymerization 69 4.6 ConversionofGlycerolintoAcrylonitrile 71 4.7 SelectiveConversionofGlycerolintoPropyleneGlycol 72 4.7.1 ConversionofGlycerolintoPropyleneGlycol 72 4.7.1.1 ReactionintheLiquidPhase 73 4.7.1.2 ReactionintheGasPhase 75 4.7.2 ConversionofGlycerolinto1,3-Propanediol 76 4.8 SelectiveCouplingofGlycerolwithFunctionalMonomers 78 4.9 Conclusion 84 References 84 PartIII SustainableReactionConditions 89 5 MonoterpenesasPolymerizationSolventsandMonomersinPolymer Chemistry 91 RobertT.MathersandStewartP.Lewis 5.1 Introduction 91 5.2 MonoterpenesasMonomers 92 5.2.1 TerpenicResinsOverview 92 5.2.2 ConceptsofCationicOlefinPolymerization 93 Contents VII 5.2.3 CationicPolymerizationofβ-Pinene 98 5.2.4 CationicPolymerizationofDipentene 104 5.2.5 CationicPolymerizationofα-Pinene 106 5.2.6 CharacteristicsofTerpenicResins 112 5.2.7 ApplicationsofTerpenicResins 113 5.2.8 CommercialProductionandMarketsofTerpenicResins 113 5.2.9 EnvironmentalAspectsofTerpenicResinProduction 115 5.3 MonoterpenesasSolventsandChainTransferAgents 116 5.3.1 PossibilitiesforReplacingPetroleumSolvents 116 5.3.2 Ring-OpeningPolymerizationsinMonoterpenes 117 5.3.3 MetallocenePolymerizationsinMonoterpenes 121 5.4 Conclusion 124 Acknowledgments 124 References 125 6 ControlledandLivingPolymerizationinWater:ModernMethodsand ApplicationtoBio-SyntheticHybridMaterials 129 DebasisSamanta,KatrinaKratz,andToddEmrick 6.1 Introduction 129 6.2 Ring-OpeningMetathesisPolymerization(ROMP) 130 6.2.1 WaterSolubleROMPCatalysts 133 6.3 LivingFreeRadicalMethodsforBio-SyntheticHybridMaterials 136 Acknowledgments 141 References 141 7 TowardsSustainableSolutionPolymerization:Biodieselasa PolymerizationSolvent 143 MarcA.Dube´andSomaiehSalehpour 7.1 Introduction 143 7.2 SolutionPolymerizationandGreenSolvents 144 7.3 BiodieselasaPolymerizationSolvent 144 7.4 ExperimentalSection 146 7.4.1 Materials 146 7.4.2 Polymerization 147 7.4.3 Characterization 148 7.5 EffectofFAMESolventonPolymerizationKinetics 148 7.5.1 ChainTransfertoSolventConstant 149 7.5.2 RateConstant 151 7.6 EffectofBiodieselFeedstock 155 7.6.1 PolymerizationKinetics 157 7.6.2 PolymerComposition 158 7.7 Conclusion 160 References 160 VIII Contents PartIV CatalyticProcesses 163 8 Ring-OpeningPolymerizationofRenewableSix-MemberedCyclic Carbonates.MonomerSynthesisandCatalysis 165 DonaldJ.Darensbourg,AdrianaI.Moncada,andStephanieJ.Wilson 8.1 Introduction 165 8.2 Preparationof1,3-PropanediolfromRenewableResources 166 8.3 PreparationofDimethylcarbonatefromRenewableResources 169 8.4 SynthesisofTrimethyleneCarbonate 171 8.5 Six-MemberedCyclicCarbonates:ThermodynamicPropertiesof Ring-OpeningPolymerization 171 8.6 CatalyticProcessesUsingGreenCatalystsMethods 172 8.6.1 CationicRing-OpeningPolymerization 173 8.6.2 AnionicRing-OpeningPolymerization 176 8.6.3 EnzymaticRing-OpeningPolymerization 178 8.6.4 Coordination–InsertionRing-OpeningPolymerization 181 8.6.4.1 Groups13-and14BasedCatalysts 182 8.6.4.2 Groups4–12BasedCatalysts 186 8.6.4.3 Lanthanide-BasedCatalysts 190 8.6.4.4 Groups1and2BasedCatalysts 191 8.6.5 OrganocatalyticRing-OpeningPolymerization 193 8.7 ThermoplasticElastomersandtheirBiodegradationProcesses 194 8.8 ConcludingRemarks 197 Acknowledgments 197 References 197 9 Poly(lactide)sasRobustRenewableMaterials 201 JanM.BeckerandAndrewP.Dove 9.1 Introduction 201 9.1.1 TheLactideCycle 202 9.2 Ring-OpeningPolymerizationofLactide 204 9.2.1 Coordination–InsertionPolymerization 205 9.2.2 OrganocatalyticRing-OpeningPolymerization 208 9.3 Poly(lactide)Properties 210 9.3.1 PLAPropertiesandProcessingEffects 211 9.3.2 PolymerBlends 213 9.3.2.1 Poly(Lactide)/Poly(ε-Caprolactone)Blends 213 9.3.2.2 OtherBiodegradable/RenewablePolyesters 214 9.4 ThermoplasticElastomers 214 9.5 FutureDevelopments/Outlook 216 References 216 Contents IX 10 SynthesisofSaccharide-DerivedFunctionalPolymers 221 JulianThimmandJoachimThiem 10.1 Introduction 221 10.2 Polyethers 223 10.3 Polyamides 226 10.4 PolyurethanesandPolyureas 229 10.5 Glycosilicones 230 References 234 11 DegradableandBiodegradablePolymersbyControlled/LivingRadical Polymerization:FromSynthesistoApplication 235 NicolayV.Tsarevsky 11.1 Introduction 235 11.2 (Bio)degradablePolymersbyCRP 238 11.2.1 Linear(Bio)degradablePolymers 239 11.2.1.1 PolymerswithaDegradableFunctionalGroup 239 11.2.1.2 PolymerswithaDegradablePolymericSegment 242 11.2.1.3 PolymerswithMultipleCleavableGroupsorPolymeric Segments 243 11.2.2 DegradableStarPolymers 244 11.2.3 DegradableGraftPolymers(PolymerBrushes) 245 11.2.4 HyperbranchedDegradablePolymers 250 11.2.5 Cross-LinkedDegradablePolymers 252 11.3 Conclusions 254 Abbreviations 254 References 255 PartV BiomimeticMethodsandBiocatalysis 263 12 High-PerformancePolymersfromPhenolicBiomonomers 265 TatsuoKaneko 12.1 Introduction 265 12.2 CoumaratesasPhytomonomers 266 12.3 LCPropertiesofHomopolymers 267 12.3.1 SynthesesandStructures 267 12.3.2 Solubility 268 12.3.3 ThermotropicProperty 269 12.3.4 OrderedStructures 270 12.3.5 CellCompatibility 273 12.4 LCCopolymersforBiomaterials 274 12.4.1 LithocholicAcidasCo-monomer 274 12.4.2 CholicAcidasCo-monomer 276 12.5 LCCopolymersforPhotofunctionalPolymers 279 12.5.1 SynthesesofP(4HCA-co-DHCA)s 279 12.5.2 PhototunableHydrolyzes 279 X Contents 12.5.3 PhotoreactionofNanoparticles 282 12.6 LCCopolymersforHighHeat-ResistantPolymers 282 12.6.1 P(4HCA-co-DHCA)Bioplastics 282 12.6.2 Biohybrids 286 12.7 Conclusion 288 Acknowledgments 289 References 289 13 EnzymaticPolymerSynthesisinGreenChemistry 291 AndreasHeiseandIngevanderMeulen 13.1 Introduction 291 13.2 Polymers 292 13.2.1 Polycondensates 292 13.2.1.1 PolyestersbyRing-OpeningPolymerization 293 13.2.1.2 PolyestersbyCondensationPolymerization 296 13.2.2 Polyphenols 298 13.2.3 VinylPolymers 300 13.2.4 Polyanilines 301 13.3 GreenMediaforEnzymaticPolymerization 303 13.3.1 IonicLiquids 303 13.3.2 SupercriticalCarbonDioxide 304 13.4 ConclusionsandOutlook 306 References 307 14 GreenCationicPolymerizationsandPolymerFunctionalizationfor Biotechnology 313 JuditE.Puskas,ChengchingK.Chiang,andMustafaY.Sen 14.1 Introduction 313 14.2 EnzymeCatalysis 313 14.2.1 Lipases 315 14.2.2 CandidaantarcticaLipaseB 321 14.2.3 CALB-CatalyzedTransesterificationReactions 323 14.3 ‘‘Green’’CationicPolymerizationsandPolymerFunctionalization UsingLipases 325 14.3.1 Ring-OpeningPolymerization 325 14.3.2 Enzyme-CatalyzedPolymerFunctionalization 328 14.4 NaturalRubberBiosynthesis – theUltimateGreenCationic Polymerization 330 14.4.1 AnatomyoftheNRLatex,andStructureofNaturalRubber 331 14.4.1.1 StructureofNaturalRubber 332 14.4.2 BiochemicalPathwayofNRBiosynthesis 333 14.4.2.1 Monomer 333 14.4.2.2 Initiators 334 14.4.2.3 Catalyst:RubberTransferase 335 14.4.3 ChemicalMechanismofNaturalRubberBiosynthesis 337
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