Green Polymerization Methods: Renewable Starting Materials, Catalysis and Waste Reduction

365 Pages·2011·13.188 MB·English

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
Copyright2011WILEY-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