Polyester synthesis using high pressure carbon monoxide

153 Pages·1999·5.7 MB·English

by  Penney, Jonathan M., 1971-

POLYESTERSYNTHESISUSINGHIGHPRESSURECARBONMONOXIDE
By
JONATHANM.PENNEY
ADISSERTATIONPRESENTEDTOTHEGRADUATESCHOOL
OFTHEUNIVERSITYOFFLORIDAINPARTIALFULFILLMENT
OFTHEREQUIREMENTSFORTHEDEGREEOF
DOCTOROFPHILOSOPHY
UNIVERSITYOFFLORIDA
1999
ACKNOWLEDGMENTS
GreatappreciationgoestoDr.JamesBoncellaforallowingmetoworkinhis
researchgroupandforhelpingmeunderstandorganometallicchemistry. Jimhasshown
meboththeeleganceoforganometallicchemistryandtheexcitementofdiscovery.
Thanks gotomycommitteemembers,pastandpresent.Professors Kenneth
Wagener,LisaMcElwee-White,MichaelScott,GuerryMcClellan,WilliamJones,and
DanielTalhamfortheirtimeandencouragement. SpecialthanksgotoProfessorWagener
forbeingmyfosteradviserduringJim'ssabbaticalandforenlighteningmeonpolymer
chemistry. ProfessorMcElwee-Whitealsodeservesextrathanksforkeepingmeawareof
theorganicsideoforganometallicchemistry.
IdeeplyappreciateDr.DanielVanderlende,Dr.WilliamVaughan,andDr.Faisal
Shafiqforteachingmeorganometallicsynthesis,bothbyinstructionandbyexample.
ThanksgotoDr.PercyDoufou,Dr.JerroldMiller,Dr.Shu-YuStevenWang,Dr.David
Knoeppel,Dr.JamesFisher,CarlosOrtiz,PerlaIszak,LeighHuff,JustineRoth,Ryan
Mills, KenWeakley, andTimFoley forprovidingaproductive andfriendly work
environment.
LloydRobesonandAirProductsandChemicals,Inc.helpedtoinitiatethisresearch
andtheirhelpisappreciated.
SpendingtimeworkingoutsideofFloridahasgreatlyexpandedmyknowledgeand
loveforchemistryandIamgratefulfortheopportunities. Dr.WilliamTumasdeserves
thanksforallowingmetospendasemesterworkinginhisresearchgroupatLosAlamos
NationalLaboratoriesandexposingmetosupercriticalfluidchemistry. WhileatLos
Alamos,Dr.StevenBuelowdesignedahighpressurereactorwithoutwhichIwouldhave
accomplishednothing. Dr.RobertHembredeservesthanksforallowingmetospendtime
11
workingatEastmanChemicalCompanyandexposingmetotheareasofbiochemistryand
watersolublecatalysis.
TheworkthatDonnaBalkomhasdoneformehasnotgonewithoutnotice. She
hasshieldedmefromadministrativeredtapeandmadeiteasytogetthingsdone.
IespeciallywanttothankDebbyTindallforherhelpwithmydissertation. She
assistedintheinitialstagesofthisresearchsynthesizingseveralpalladiumcompounds.
Shealsohasbeenaconstantsourceofexpertisewithpolymercharacterizationwithout
whichIwouldhavebeenlost. Herpatienceeditingthisdissertationdeservesmuchpraise.
Finally,ifitweren'tformyfamilyIwouldn'tbehere. Myparents,PaulandJune,
havealwaysstoodby mydecisionsandencouragedmetopursuemydreams. My
brothers,EricandDavid,havesetexamplesofachievementwhichIstrivetoreach.
Ill
TABLEOFCONTENTS
ACKNOWLEDGMENTS
u
LISTOFTABLES vi
LISTOFFIGURES vii
ABSTRACT xi
CHAPTERS
INTRODUCTIONANDBACKGROUND
1 1
PolyethyleneTerephthalate 1
Poly-p-hydroxybutyrate 5
TransitionMetalCatalyzedPolyesterifications 9
Metal Catalyzed Homopolymerization ofEpoxides 10
Copolymerization ofEpoxides with Carbon Dioxide 12
CopolymerizationofCarbonMonoxidewithOlefins 16
2 DESIGNOFCATALYSTSFORTHECOPOLYMERIZATIONOF
EPOXIDESANDCARBONMONOXIDE 22
PrecedentforPolymerizationofEpoxideswithCarbonMonoxide 22
TestingTransitionMetalComplexesasPotentialCatalystsforthe
CopolymerizationofCarbonMonoxidewithEpoxides 24
AttempttouseCationicLateTransitionMetalsasCatalysts 25
AttemptedCopolymerizationofEpoxideswithCarbonMonoxideUsinga
CationicTitaniump^-AcylComplex 28
AttemptedCopolymerizationofEpoxideswithCarbonMonoxideUsing
Anionic Iron Complexes 30
AttemptedCopolymerizationofEpoxideswithCarbonMonoxideUsingNeutral
CobaltandRhodiumComplexes 33
CopolymerizationofEpoxideswithCarbonMonoxideCatalyzedbyCobalt
ComplexeswithAlkylaluminumCocatalysts 35
CopolymerizationofEpoxideswithCarbonMonoxideUsingNeutralCobalt
Complexes 41
SummaryandConclusions 48
3 POLYESTERSYNTHESIS USINGCARBOALKOXYLATION 50
Cai'boalkoxylation 50
MechanismofCarboalkoxylation 53
PolyesterSynthesisUsingDienesandDiols 57
SynthesisofPoly(alkylenedodecanedioate)s 57
IV
Polymer Synthesis Using Unsaturated Alcohols 62
SynthesisofPoly(co-undecylenoate) 63
SummaryandConclusions 68
4 SYNTHESIS,STRUCTURE,ANDREACTIVITYOFCOBALT(III)
COMPLEXES 69
SynthesisofCobaltComplexes 69
P-DiiminateLigands 74
SynthesisandCharacterizationofCobaltComplexes 76
EnamidoKetonateCobaltComplexes 79
P-DiimidateCobaltComplexes 83
SummaryandConclusions 92
5 EXPERIMENTAL PROCEDURES 93
MaterialsandMethods 93
PolymerizationReactions 94
(CH2CH(CH3)C(0)0)xsynthesis 94
a)UsingaCobaltComplexwithAluminumCocatalyst 94
b)UsingaWellDefinedCobaltComplex 95
((((CCHH22))1i0oCC((O0))OOCCHH22CCHH22OCCH(2O0)C)(x0))x 9956
((CH2)10C(O)OCH2CH2CH2CH2OC(O))x 96
((CH2)iiC(0)0)x 97
CH30C(0)CH2CH(CH3)0H 98
LiCH3C(NCH3)CHC(0)CH3 98
LiCH3C(NPh)CHC(0)CH3 98
Li(o-(PhNCH)(0)C6H4) 99
LiCH3C(p-0CH3PhN)CHC(0)CH3 99
LiCH3C(NPh)CHC(NPh)CH3 99
LiCH3C(p-OCH3PhN)CHC(p-OCH3PhN)CH3 100
CH3C(NCH3)CHC(0)CH3CoC8Hi2,20 100
CH3C(NPh)CHC(0)CH3CoCsHi2 21 101
o-(PhNCH)(0)C6H4CoC8Hi2,26 101
CH3C(p-BrPhN)CHC(0)CH3CoC8Hi2,24 102
CH3C(p-OCH3PhN)CHC(0)CH3CoC8Hi2,25 102
CH3C(NPh)CHC(NPh)CH3CoC8Hi2,12 102
CH3C(p-OCH3PhN)CHC(p-OCH3PhN)CH3CoC8Hi2,22 103
TpCoC8Hi2,23 104
CH3C(0)CHC(0)CH3Co(P(CH3)3)C8Hi2,13 104
APPENDIX:TABLESOFCRYSTALLOGRAPHICDATA 105
REFERENCES 134
BIOGRAPHICALSKETCH 140
LISTOFTABLES
Table page
3.1Linearesteryieldsforvariouscatalystsystems 56
3.2Polymercharacterizationdata 64
4.1 Preparedenamidoketone,p-diiminesandtheirlithiatesalts 76
4.2 SelectedBondLengths (A) andAngles (°) for21 83
4.3 SelectedBondLengths(A) andAngles (°) for12 87
4.4 SelectedBondLengths(A) andAngles (°) for23 89
VI
LISTOFFIGURES
Figure page
1.1 Industrial polyethylene terephthalate synthesis 2
1.2Molecularweightversusconversionforstepandchainpolymerizations 3
1.3Reactionofterephthalicacidwithethyleneoxide 4
1.4SynthesesofPHB 5
1.5 The three stereochemical structures of PHB 6
1.6PathwayforbiologicalconversionofnutrientstoPHB 7
1.7AnionicpolymerizationofP-butyrolactonewithpotassiummethoxide/
18-Crown-6 8
1.8Palladiumcatalyzedpolymerizationofparadisubstitutedbenzene,diolandcarbon
monoxide 9
1.9Proposedmechanismforformationofpolyestersfromterminaldiynes,aliphatic
dihalidesandcarbonmonoxide 10
1.10Reactionofepoxideswithcarbondioxideusingdifferentcatalysts 13
1.11Zinccatalystforcyclohexeneoxide/carbonmonoxidecopolymer 14
1.12Livingpolycarbonatesystemwithpolymergrowingfromtwosidesofthecatalyst..15
1.13Mechanismforcopolymerizationofepoxideswithcarbondioxide 16
1.14Copolymerizationofethylenewithcarbonmonoxide 17
1.15Effectofphosphineonproductselectivity 17
1.16Mechanismforcopolymerizationofolefinswithcarbonmonoxide 19
1.17 Polymerizationof 1,5-hexadiene withcarbonmonoxide 19
1.18Polyketonesformedusingchloroform/methanolsystem 20
2.1Reactionofhydridocobalttetracai'bonylwithcarbonmonoxideandepoxides 22
vii
2.2ReactionofcobaltcarbonylanionwithcarbonmonoxideandepoxidestoproduceP-
hydroxyesters 23
2.3Reactionofepoxideswithcarbonmonoxidetoformlactones 23
2.4DisproportionofcobaltoctacarbonylinthepresenceofTHF 24
2.5 Ring-opening of epoxides by acids 25
2.6Proposedreactionschemeforpolymerizationwithcationictransitionmetals 25
2.7Cationicpalladiumcomplextestedaspotentialcatalysts 26
2.8Homopolymerizationofepoxidesbycationicpalladiumcomplexes 27
2.9Additionalcationicpalladiumcomplexes 28
2.10[Cp2Ti(NCCH3)COCH3]+BPh4- 29
2.11ReactionbetweenCp2Zr(THF)Ph+BPh4’andTHFforming polytetrahydrofuran.29
2.12Reactionofnucleophileswithepoxides 30
2.13Proposedreactionschemeforpolymerizationofepoxideswithcarbonmonoxide
catalyzedbyanionictransitionmetals 31
2.14Resonance structures for (CO)4FeCOCH3' 31
2.15Equilibriumstructuresforbimetallicironcomplexes 32
2.16Proposedmechanismfortheformationofstyrenefromstyreneoxide 33
2.17Proposedmechanismforcarbonylationofepoxideswithneutralcobalt complexes.34
2.18Proposedreactionschemeforpolymerizationofepoxideswithcarbonmonoxide
catalyzedbyacobalt-acylcomplex 34
2.19Furukawa'spolyestersynthesisfromepoxidesandcarbonmonoxide 36
2.20*HNMRofpoly-(3-hydroxybutyratemadefrompropyleneoxideandcarbon
monoxidecatalyzedbyCo(acac)3andAlEt3 37
2.21ProductsformedfromFurukawa'scatalystsystemandCo2(CO)8 39
2.22ReactionofCo(acac)3withdifferentalkylaluminums 40
2.23Reactionoftriethylaluminumwithcobaltcomplexes 40
2.24Reactionoftriethylaluminumwithnickel,rhodiumandironcomplexes 41
2.25ProductsofCo(acac)3withEt2A10Etandphosphine 42
viii
1
2.26Synthesesof10 43
2.27Derivativesmadefrom10 45
2.28Coordinationofligandsto11 45
2.29Poly-P-hydroxybutyrateformationusingCo(III)catalysts 46
2.30Proposedmechanismsforpolyesterpolymerization 47
2.31Formationofmethyl3-hydroxybutyratefrompropyleneoxide,carbonmonoxideand
methanol 48
3.1 Ester synthesis by carboalkoxylation 50
3.2ReactionofdieneswithalcoholsusingAlper'scatalystsystem 51
3.3Formationofmethylmethacrylatefrompropyne,carbonmonoxideand methanol.5
3.4 Lactam formation from an allyl amine 52
3.5Bis-carbonylationofa3-buten-l-ol 52
3.6Proposedmechanismforcarboalkoxylationofa3-buten-l-ol 52
3.7Proposedmechanismforcarboalkoxylationbasedonpalladiumhydride formation..53
3.8Proposedmechanismforcarboalkoxylationbasedonpalladiumcarbonyl formation.54
3.9Insertionofcarbonmonoxideintoaplatinumalkoxidebond 55
3.10Regiochemistryofolefininsertionintopalladium-hydridebond 55
3.11Formationofpoly(alkylenedodecanedioate)s 58
3.12Polymer growth showing endgroup formation 59
3.13Formationofcyclicoligomersinastepreaction 60
3.14 Mechanism for olefin isomerization 61
3.15Cyclizationofallylalcoholand4-butenolforminglactones 62
3.16Formationofpoly(co-undecylenoate),16 63
3.17Increaseofmolecularweightofpolymersbyhightemperatureandlowpressure
condensation 65
3.18 NMR(CDCI3)spectraofa)undecylenylalcohol,b)poly((o-undecylenoate), c)
poly(co-undecylenoate)heatedundervacuum 66
3.19 NMR(CDCI3)spectraofa)undecylenylalcohol,b)poly(co-undecylenoate),c)
poly(o)-undecylenoate)heatedundervacuum 67
ix
4.1PreparationofacylcobaltcomplexesfromNaCo(CO)4andacidhalides 69
4.2Prepai'ationofacylcobaltandalkylcobaltcomplexesfromNaCo(CO)4andalkyl
halides 70
4.3 Friedel-Crafts acylation of 17 70
4.4SynthesisofsubstitutedCpderivativesof17usingCo2(CO)g 71
4.5Reductionproductsof[CpCol2]2,18 72
4.6Generationofcationiccobaltcatalystfora-olefinpolymerization 72
4.7CobaltcomplexespreparedfromCo(acac)3andAIR2OR 73
4.8Preparationofiminesfromthecondensationofketonesoraldehydesandamines 74
4.9Synthesesofeneaminoketonesand(3-diiminesofacetylacetone 75
4.10CoordinationofPMe3to11 77
4.11*HNMRspectraofligandcoordinatedcomplexesof12 78
4.12Synthesisofenamidoketonatecomplexesofcobalt 79
4.13Variabletemperature NMRspectraof21 81
4.14MolecularstructureofCH3C(NPh)CHC(0)CH3CoC8Hi2,21.with50%thermal
ellipsoidsandshowingtheatomnumberingscheme 82
4.15Synthesisof(3-diimidatecomplexesofcobalt 84
4.16IHNMRspectrumofCH3C(NPh)CHC(NPh)CH3CoC8Hi2,12 85
4.17MolecularstructureofCH3C(NPh)CHC(NPh)CH3CoC8Hi2,12.with50%thermal
ellipsoidsandshowingtheatomnumberingscheme 86
4.18Attemptedreactionswith12 88
4.19SynthesisofTpCoC8Hi2,23 88
4.20 NMRspectrumofTpCoCsHi2,23 90
4.21MolecularstructureofTpCoC8Hj2,23.with50%thermalellipsoidsandshowingthe
atomnumberingscheme 91
4.22 IsomerizationofCpCori3,r|l-C8Hi2toCpCor|2,'n2-C8Hi2 92
X