Higher TG Based On Triple Hydrogen Bond Interactions - Jean Claude MBULU AGALIA

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MemoireOnlinePreparationofPolystyrenewithHigherTgBasedonTripleHydrogenBondInteractionsJeanClaudeMBULUAGALIA
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PreparationofPolystyrenewithHigherTgBasedonTripleHydrogenBond
Interactions
(Tlchargerlefichieroriginal)
parJeanClaudeMBULUAGALIA
BeijingUniversityofChemicalTechnologyMasteresScience2008
Disponibleenmode
multipage
PREPARATIONOFPOLYSTYRENEWITHHIGHERTgBASEDONTRIPLEHYDROGENBONDINTERACTION
MBULUAGALIA
MATERIALSSCIENCE
\u26085 \u26399: \u20108 \u9675 \u9675 \u20061 \u24180 \u19968 \u26376 \u20108
\u26085
Contents
Abstract.................................................................................2
AbstractinChinese...................................................................4
Chapter1Introduction.........................................5
1.1Glasstransitiontemperature.............................................................5
1.2StyreneandMaleimidecopolymer....................................................14
1.3Melamineandchemistry.............................................................23
1.4Diaminopyridinemolecule..............................................................26
1.5thethesiswork...........................................................................27
Chapter2ExperimentationSection.............................................31
2.1Materials.................................................................................31
2.2Instruments..............................................................................31
2.3Synthesisofrandomcopolymersofstyreneandmaleimide......................32
2.4SynthesisofBlendsofStyrene/Maleimidecopolymerandmelamine...........32
2.5SynthesisofBlendsofthecopolymerand2,6diaminopyridine.................33
Chapter3Resultsanddiscussion................................................34
3.1Characterizationofcopolymerofstyreneandmaleimide..........................34
3.2Copolymerizationofstyreneandmaleimide........................................33
3.3Blendsofthestyrene/maleimidecopolymersandmelamine............................38
3.4Blendsofthecopolymerand2,6diaminopyridine..................................43
Chapter4Conclusion.................................................................46
http://www.memoireonline.com/09/09/2681/PreparationofPolystyrenewithHigherTgBasedonTripleHydrogenBondInteractions.html
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Reference...................................................................................47
PREPARATIONOFPOLYSTYRENEWITHHIGHERTgBASEDONHYDROGENBONDINTERACTION
ABSTRACT
Polystyreneisoneofacommonpolymer.Butitsglasstransitiontemperature(Tg)isonly100oCwhichleadstolimitits
applications.Inthethesis,improvementofitsTgwasdoneviaincreaseofitschaininteractionstorestrictthechain
flexibility.
Styrenewascopolymerizedwithmaleimide,imideofwhichactasahydrogenbondinteractionsiteinthecopolymer,
by free radical polymerization method in DMSO solution at different temperature, and different ratio of styrene to
maleimide, and different reaction time, using different amount of AIBN as an initiator. To make the imide distribute
randomlyinthechains,maleimidewasdroppedslowlyduringthepolymerization.Melamineanddiaminopyridinewere
selectedtobeasinteraction molecule because they can form the triplehydrogenbondwithimide in the copolymer.
Addition of melamine or diaminopyridine into the copolymer results in a dramatic increase of Tg. Polystyrene with
imide molar concentration of 5.05% has Tg of 122oC in the presence of melamine, 22 oC higher than polystyrene,
whichwillextendapplicationofpolystyrene.Athighratioofmelaminetoimide,twoTgsareobserved,oneishigher
than 122oC but another much lower. The existence of two Tg is due to the fact that free melamine is acting as
plasticizer.
DiaminopyridinealsoincreaseTgofpolystyrene,butnoteffectivelythanmelamineowingtolackofcrosslinking.Inthis
case, the blend of Diaminopyridine with polystyrene containing imide looks like a copolymer of styrene with a big
monomer,complexofmaleimideandDiaminopyridine.
ThesecondaryinteractioncharacteristicsbetweenmelamineorDiaminopyridinewithpolystyrenecontainingimideis
confirmedbytheirblendsreadilysolubleinDMSOandinCH2Cl2.
Chapter1Introduction
1.1Glasstransitiontemperature
Manyplasticslosetheirstrengthatrelativelylowtemperature.Continuousservicetemperaturecomparisonofplastics
reveals that most common plastics can endure temperature more than 150oC when under low or no stress. Glass
transitiontemperatureorGlasspoint(Tg)isthepointatwhichpolymersactasglassorbecomeviscousliquids.That's
averyimportantfactorforpolymerstoevaluatetheirprocessingandapplicationperformances.
TheGlasstransitionisareversiblechangethatoccurswhenaresinpolymerisheatedtoacertaintemperature(Tg),
resultinginasuddenchangeortransitionfromrigidpolymertoaflexible,rubberymaterialoraviscousliquid.When
the polymer is cooled below this temperature, it becomes hard and brittle, like glass. Certainly there are a few
polymersusedabovetheirGlasstransitiontemperatures,howevermajorityofpolymersareusedbelow.Popularhard
plastics like polystyrene (Tg=100oC) is used below their glass transition temperatures that is its glassy state. Their
Glasstransitiontemperaturesarewellaboveroomtemperature,bothataround100oC.
RubberselastomerslikepolyisopreneandpolyisobutyleneareusedabovetheirGlasstransitiontemperaturesthatis
intherubberysatewheretheyaresoftandflexible.
The glass transition differs from the melting transition by the fact that the former is a transition which happens to
amorphouspolymersandthelatterisatransitionwhichoccursincrystallinepolymers.Butevencrystallinepolymers
will have some amorphous portions this portion usually makes up 4070% of the polymer sample. This is why the
same sample of a polymer can have both a Glass transition temperature and a melting temperature. But only the
amorphousportionundergoestheglasstransitionandonlythecrystallineportionundergoesmelting.Thischangein
mobilitywithtemperaturehappensbecauseheatisreallyaformofkineticenergy.
Theexacttemperatureatwhichthepolymerchainundergoesthisbigchangeinmobilitydependsonthestructureof
thepolymer.ApolymerchainthatcanmovearoundfairlyeasilywillhaveaverylowTg,whileonethatdoesn'tmove
sowellwillhaveahighone.Themoreeasilyapolymercanmovethelessheatittakesforthechainstocommence
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wigglingandbreakoutoftherigidglassystateandintothesoftrubberystate.Agivenpolymersampledoesnothave
auniquevalueofTgbecausetheglassphaseisnotatequilibrium.
1.1.1FactorsgoverningTg
The height of the glassrubber transition temperature is, in the first instance, governed by the competition between
thermalmotionandtheattractionforcesbetweenthechains.
Thethermalmotionisdependonthefreedomofthechaintoundergochangesinconformation.Whenthisfreedomis
higher,thechainissubjectedtoastrongerthermalmotionthanachainwhich,e.g.asresultofhindranceinrotation,is
morerigid,thechainstiffnessplaysanimportantrole.
Theprimarycriteriaare:
chainflexibility
chaininteractions
1.1.2Chainflexibility
Higherchainstiffnessresultsfromasmallernumberofpossiblechainconformationsthiscanbecausedby:
greaterstiffnessofthemainchain
biggersidegroups
crosslinks
Someexamplesofthechainstiffnessdifferencesinthemainchainare:
Someexamplesoftheeffectofsidegroupsonthechainflexibilityare:
TheincreasingsizeofthesidegroupeffectsadecreaseofchainflexibilityandanincreaseofTg.
1.1.3Chaininteractions
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Thestrongestofmolecularinteractionarethedipoleforces.TheireffectonTgisillustratedbytheseriesPP,PVCand
PAN,inwhichthechainmobilityhardlyvariesbecausethesidegroupsareofaboutequalsize,butinwhich,inthe
orderofsequencementioned,thedipoleinteractionincrease.
Interactioncanbedecreasedbyincreasingthedistancebetweenthechains,forinstancewithlongsidechains,which
lowerTg.Thiseffectappearstobegreaterthantheincreaseofchainstiffness,asshownintheexamplesbelow:
Approximateglasstransitiontemperaturesandmeltingpointofafewpolymersareshownbelow:
Table11glasstransitiontemperaturesofcommonpolymers
Polymer LDPE HDPE PP PVC PS PAN PTFE PMMA PMMA

Tm(oC)
110
130
175 180 175 >200 330
180
30
Tg(oC)
110
110
20
105
70
80 100
95
110
1.1.4Intermolecularinteraction
Therearethreetypesofintermolecularforces:
VanDerWaalsforces
Dipoleforces
Hydrogenbondinteractions
Althoughallsuchforcesarisefromthesamefundamentalsourcei.e.,interactionofnegativelychargedelectronsand
positivelychargednucleusyettheydifferinmagnitude,effectiverangeandmodeofoperation.Usuallytheyaremuch
smallerthantheforcesresponsibleforchemicalbonding.
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1.1.5VanDerWaalsinteractions
These interactions arise due to transfer polarization of neutral molecules and are also known as London forces.
Usuallyneutralmoleculeshavebalancednumberofnegativeelectronsandpositivechargeonthenucleus.Yetsince
electronsareinmotion,thecentreofdensityofnegativechargemaynotcoincidewiththecentreofdensityofpositive
charge continuously. A molecular thus acquires an electric dipole and can exert an attraction for other similar
molecules.SuchinteractionisknownasvanDerWaalsinteraction.
A polarized molecule may induce the electric dipole in a neutral molecule. However such polarized molecule
continuallyrevertsbacktoneutralstateanddipoleisonlytransient.Thegreaterthenumberofelectronsinamolecule
and farther their distance from nucleus, the greater will be the case of polarization and consently stronger Van Der
Waalsforces.Theseforcesvaryinverselywiththeseventhpowerofthedistancebetweenmolecules.
V.F.1/d7
Where V.F. is Van Der Waals forces and d is distance separating the molecules. They are effective only over short
intermoleculardistances.
1.1.6DipoleDipoleInteractions
Unequal sharing of electrons in covalent bonds results in bonds dipoles and their magnitudes are indicated by the
bond moments. As may be expected the bond dipoles in different molecules attract each other resulting in dipole
dipoleinteraction.Theseforces(D.F,)aregovernedbytheexpression:D.F.1/d4
Wheredisthedistancebetweenmolecules,thustheseforcesalsoareeffectivesonlyovershortdistancesbuthave
largerrangethanVanDerWaalsforces.
1.1.7HydrogenBonds
Ithasbeenobservedthatwhenahydrogenatominacompoundisbondedtoahighlyelectronegativeatomssuchas
N,O,F,thenmarkeddifferencesareobservedinitsusualpropertieslikeboilingpoint,solubilityetc.Forexamplethe
boiling point of organic compounds usually increases with increase in molecular weight but, though ethyl alcohol
C2H5OH(b.p.78.2o)anddimethyletherCH3OCH3(b.p.24.9o)havethesamemolecularweight,yetthereislarge
differenceintheirboilingpoints.
The chemical properties of these compounds also differ as compared to similar compounds not having hydrogen
attachedtoN,O,F.
Itisarguedthatwhenhydrogenisattachedtosuchelectronegativeatomsthebondingelectronsaredrawnstrongly
towards the electronegative atom creating a dipole in the molecule. The hydrogen atom therefore, acquires a small
positive charge and becomes extraordinarily capable of attracting a negatively charged atom of a molecule. This
attractionresultsinassociationofsuchmoleculesthoughtheHatomknownasHydrogenBond.Thisisrepresented
byadottedline.Ithasmuchlessstrengththancovalentbondandisessentiallytheresultofelectrostaticinteractions,
delocalizationeffectsanddispersioneffects.
Hydrogenbondsareattractiveinteractionsbetweenapositivelychargedhydrogenatombondedtoanelectronegative
element(thedonor:
),andanegativelychargedatomwithalonepairofelectrons(theacceptor:
Table12Functionalgroupthatcanformhydrogenbonds,arrangedbyelement
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Thestrongesthydrogenbondingisformedbetweenastrongdonor(likeFHandOHinacid)andastrongacceptor.
ThetypeofHbondingresultinginassociationoftwoormoremoleculesofthesameordifferentcompoundisknown
asIntermolecularhydrogenbonding.Intermolecularassociationtroughhydrogenbondresultsinunusuallyhighboiling
points of the liquids. Thus, the high boiling points of water, alcohols, amines and acids as compared to monomeric
moleculesofcomparablemolecularweightmaybeexplainedonthebasisofHbonding.
Intermolecular Hydrogen bonding is the formation of Hbonging within the molecule itself. Ethylacetoacetate,
salicylaldehydeandonitrophenolareexampleofthistype.
1.2StyreneandMaleimidecopolymer
Polystyreneisoneofacommonpolymer.Itisveryeasytoproduceandproceed,soverycheap,andhasmajorityof
propertiesforusageincommonlife.However,itsglasstransitiontemperature(Tg)isonly100degreeCelsius,which
leadstolimititsapplications.
Polymers with high glass transition temperature are attractive for industrial polymer science because of their strong
economicrewardsthatmayarisefromtheirpotentialapplication[1]. As mentioned above, two factors governs Tg of
polymers,chainflexibilityandchaininteraction.Copolymerizationisabestwaytochangebothofthem.Inthecaseof
copolymers,thefinalvalueofagivenpropertye.g.themeltingpointortheglasstransitiontemperaturedoesdepend
onbothofmonomerstructuresandthecompositionofthem,alsotheothers[2].Theexistingmethodsusedtoimprove
Tg of Polystyrene are the copolymerization and control of its configuration. Incorporation of a few of another stiff
monomershowslessimprovementinTgofpolystyrene,becausetheTgisafunctionofcontentofstiffmonomer.More
content of stiff monomer makes Tg of styrene copolymer higher, meanwhile many good properties, for instance,
stiffness, transparent, and processing property, will be lost. Isotactic polystyrene has very high Tg(above 220oC).
However,itisdifficulttoprocessand,furthermore,itisgottenbymuchmorecomplicatedcoordinationpolymerization
route,notbytheeasyfreeradicalpolymerization.
Styrene molecule or derivates are chemically modified by free radical polymerization to obtain new products with
variouspotentialapplicationsandproperties[3].Copolymerizationofmaleimideswithstyreneprovidesthepossibilityof
synthesizinghigherandthermallystablepolymers.Inadditiontothattheprocessabilityofmaleimidepolymercanalso
beenhancedbytheincorporationofmoreflexibleunitswithinthepolymerbackbone[1].
StyreneMaleimidecopolymer(SMA)havebeenfoundtohaveversatileapplicationsinmanyindustriesrangingfrom
aerospace to the microelectronics field [2]. During the past several years many reports and researches in the free
radicalcopolymerizationofstyrenewithmaleimidehaveemerged[25].
1.2.1Generaldescription
Whenapolymerismadebylinkingonlyonetypeofsmallmolecule,ormonomer,together,itiscalledahomopolymer.
Whentwodifferenttypesofmonomersarejoinedinthesamepolymerchain,thepolymeriscalledacopolymer.Two
monomersAandBcanbemadeintoacopolymerinmanydifferentways.
Whenthetwomonomersarearrangedinanalternatingfashion,thepolymeriscalledanalternatingcopolymer:
Inarandomcopolymer,thetwomonomersmayfollowinanyorder:
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Inablockcopolymer,allofonetypeofmonomeraregroupedtogetherandalloftheotheraregroupedtogether.A
blockcopolymercanbethoughtofastwohomopolymersjoinedtogetherattheends:
When chains of a polymer made of monomer B are grafted on to a polymer chain of monomer A we have a graft
copolymer:
Styrene,alsoknownasvinylbenzeneisanorganiccompoundwiththechemicalformulaC6H5CH=CH2.Under
normalconditions,thisaromatichydrocarbonisanoilyliquid.Itevaporateseasilyandhasasweetsmell,although
highconcentrationsconferalesspleasantodor.Styreneistheprecursortopolystyrene,animportantsynthetic
material.StyreneMonomeristherawmaterialforpolystyreneandEPS,accountingforapproximatelytwothirdsof
totalstyrenemonomerproduction.TheremainingstyrenemonomerisusedasafeedstockintheproductionofSAN,
ABSandtheunsaturatedpolyesterresins,SBRandpolymerlatex.Majordownstreamstyrenemarkets(polystyrene
andABS)areunderpressureasaresultofoversupplyandinterpolymercompetition,althoughrationalizationofolder,
smallerstyrenicsunitsshouldhelpbalanceoutthemarket.
MaleimideisthechemicalcompoundwiththeformulaH2C2(CO)2NH.Thisunsaturatedimideisanimportantbuilding
blockinorganicsynthesis.Thenameisacontractionofmaleicacidandimide,theC(O)NHC(O)functionalgroup.
Fig1MoleculeofMaleimide
Maleimideanditsderivativesarepreparedfrommaleicanhydridebytreatmentwithaminesfollowedbydehydration.A
special feature of the reactivity of maleimides is their susceptibility to additions across the double bond either by
MichaeladditionsorviaDielsAlderreactions.
ACopolymerisapolymerchainmadeupoftwomonomersunits,sayAandB.Whenproducedbycopolymerization,
the copolymer chain will comprise a distribution of sequence lengths (S)which will depend upon the monomer feed
ratio [A]/[B] and the reactivity ratio (rAandrB)which reflect the inherent tendencies of a radical to react with its own
monomerrelativetothecomonomer.
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Therefore, because of the feed ratio, the polymerization of two or more monomers will result either to random
copolymers,alternatingcopolymerandblockcopolymers[6,7].
If a feed ratio of
is taken, then the reactivity ratios will indicate the inherent tendency of a system to
produce particular sequence length distributions and hence the characteristic average sequence lengths. As an
example,foraperfectlyalternatingcopolymer,rA=rB=0andthemonomersalternatealongthechain.Alternatively,for
acompletelyrandomcopolymerrA=rB=1andSA=SB=2
Oneofthemostcommonandusefulreactionformakingpolymersisfreeradicalpolymerization.
It is used to make polymers from vinyl monomers, that is, from small molecules containing carboncarbon double
bonds. Polymers made by free radical polymerization include polystyrene, poly (methyl methacrylate), poly (vinyl
acetate)andbranchedpolyethylene.
Copolymerizationofmaleimidewithstyrenemonomersresultsinapolymerizationmechanismoccurringviaacharge
transfer complex or via the penultimate model, but it is obvious that polymerization of an electron rich monomer
(styrene)withanelectronpoormonomer(maleimide)leadstoa,predominantly,alternatingcopolymer[8,9].
Fig11chargetransfercomplexduringthepolymerizationofstyrenemaleimidecopolymer
Fig12StyreneMaleimideCopolymers
1.2.2TheinitiatorofStyreneMaleimidecopolymer
Thewholeprocessstartsoffwithamoleculecalledaninitiator.Thisisamoleculelikebenzoylperoxideor2,2'azobis
isobutyrylnitrile(AIBN).
Whatisspecialaboutthesemoleculesisthattheyhaveanuncannyabilitytofallapart,inaratherunusualway.When
theysplit,thepairofelectronsinthebondwhichisbrokenwillseparate.Thisisunusualaselectronsliketobeinpairs
whenever possible. When this split happens, we're left with two fragments, called initiator fragments, of the original
molecule, each of which has one unpaired electron. Molecules like this, with unpaired electrons are called free
radicals.
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Thecarboncarbondoublebondinavinylmonomer,likeethylene,hasapairofelectronswhichisveryeasilyattacked
bythefreeradical.Theunpairedelectron,whenitcomesnearthepairofelectrons,can'thelpbutswipeoneofthemto
pairwithitself.Thisnewpairofelectronsformsanewchemicalbondbetweentheinitiatorfragmentandoneofthe
double bond carbons of the monomer molecule. This electron, having nowhere else to go, associates itself with the
carbonatomwhichisnotbondedtotheinitiatorfragment.Youcanseethatthiswillleadusbackwherewestarted,as
wenowhaveanewfreeradicalwhenthisunpairedelectroncomestoroostonthatcarbonatom.Thiswholeprocess,
thebreakdownoftheinitiatormoleculetoformradicals,followedbytheradical'sreactionwithamonomermoleculeis
calledtheinitiationstepofthepolymerization.
Thisprocess,theaddingofmoreandmoremonomermoleculestothegrowingchains,iscalledpropagation.
Becausewekeepremakingtheradical,wecankeepaddingmoreandmoreethylenemolecules,andbuildalong
chainofthem.Selfperpetuatingreactionslikethisonearecalledchainreactions.
Coupling is one of two main types of termination reaction. Termination is the third and final step of a chaingrowth
polymerization.
1.3Melaminemoleculeandchemistry
As we known, the physical properties of polymers are significantly altered upon addition of low molecular weight
compounds,e.g.theadditionofplastizers,whichincreasechainmobility,andenhancetheprocessabilityofpolymeric
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materials[4]. However, a low molecular weight compounds is easy to distribute in polymers and have a strong
interactionwithpolymersinsomecases.It'sknownthattheusedofsecondaryinteraction(suchashydrogenbond,ion
ion, dipoledipole or Van Der Waals forces ) is also a wellaccepted strategy to enhance miscibility of immiscible
polymers,andmisciblepolymersmixturebasedonhydrogenbonding[5]. Mostsignificantly, secondary interaction for
the selfassembly of macromolecules has been investigated more recently in detail for liquid crystallinity, rotaxanes,
catenanesandamphiphilicstructures [5].Recently,Lehnetal.introducedtheconceptofusingwelldefinedsecondary
interactionsbasedonhydrogenbondinginthesynthesisofliquidcrystallinepolymer,inwhichtherepeatingunitsare
linkedbytriplehydrogenbondinginsteadofbycovalentbonding[6].
Ronald F.M. Lange et al. have studied the interaction between the alternating copolymer of styrene/maleimide with
unsubstituted melamine . They observed that addition of melamine results in a dramatic decrease of Tg up to
melamineconcentrationof20%(w/w)atwhichtheTgremainsconstantataround215oC[5,7].
1.3.1StructureofMelamine
MelamineisanorganicbasewiththechemicalformulaC3H6N6,withtheIUPACname1,3,5triazine2,4,6triamine.It
isonlyslightlysolubleinwater.Melamineisatrimerofcyanamide.Likecyanamide,itis66%nitrogen(bymass)and
providesfireretardantpropertiestoresinformulasbyreleasingnitrogenwhenburnedorcharred.
Fig131,3,5Triazine2,4,6triamine
1.3.2ChemistryofMelamine
Itiswellknownthatmelamineformsa11crystallinecomplex[5,7,12]withcyanuricacid.Thestructureofthiscomplex
isproposedtobeaninfinitetwodimensionallatticeasisshowinginthefigure5
Fig14infinitetwodimensionallattices,proposedforthe1:1complexofmelamineandcyanuricacid.
This 1:1 melaminecyanuric acid lattice has been a source of inspiration in the development of supramolecular
chemistryandthetheoryofsecondaryinteraction[7,12].
Variousmodelstudies(e.g.complexationofunsubstitutedmelaminewithalowmolecularweightimideaswellaswith
variousimidescontainingpolymers)havebeenperformedtomimicthistriplehydrogenbondformation[12].
However,fewattemptshavebeenmadetomimicthistriplehydrogenbondformationusinghighmolecularpolymeric
materials.InordertomimicthistriplehydrogenbondformationonlyalternatingcopolymersofSMAhavebeenusedin
thesynthesisofblendbetweenSMAwitheithermelamineor2.4diaminotriazine[12]
1.42,6diaminopyridinemolecule
2,6diaminopyridineisanalogousmelamine.ItcanalsoformthetriplehydrogenbondwithSMA.
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Fig15PotentialprecursorsofthetriplehydrogenbondedStyreneMaleimidecouple
Fig162,6Diaminopyridine
PYRIDINEisaheterocyclicaromatictertiaryaminecharacterizedbyasixmemberedringstructurecomposedoffive
carbonatomsandnitrogenwhichreplaceonecarbonhydrogenunitinthebenzenering(C5H5N).Thesimplest
memberofthepyridinefamilyispyridineitself.Itiscolorless,flammable,toxicliquidwithaunpleasantodor,miscible
withwaterandwithmostorganicsolvents,boilsat115oC.Itsaqueoussolutionisslightlyalkaline.Itsconjugateacidis
calledpyridiniumcation,C5H5NH+,usedasaoxidationagentfororganicsynthesis.Pyridineisabasewithchemical
propertiessimilartotertiaryamines.Nitrogenintheringsystemhasanequatoriallonepairofelectronsthatdoesnot
participateinthearomaticpibond.Itsaqueoussolutionisslightlyalkaline.Itisincompatibleandreactivewithstrong
oxidizersandstrongacids,andreactsviolentlywithchlorosulfonicacid,maleicanhydride,oleum,perchromates,b
propiolactone,formamide,chromiumtrioxide,andsulfuricacid.Liquidpyridineeasilyevaporatesintotheair.Ifitis
releasedtotheair,itmaytakeseveralmonthstoyearsuntilitbreaksdownintoothercompounds.Usually,pyridineis
derivedfromcoaltarorsynthesizedfromotherchemicals,mainlyacetaldehydeandammonia.
Pyridineanditsderivativesareveryimportantinindustrialfieldaswellasinbiochemistry.2,6Pyridinediamineisused
as an intermediate for the synthesis of analgesic drugs. Phenazopyridine is an example derived from 2,6
Pyridinediamine.
1.5Thethesiswork
The use of secondary interactions a wellaccepted strategy to enhance the miscibility of immiscible polymers, and
miscible polymer mixtures based on hydrogen bonding. This is result in interesting and enhanced polymeric
properties[12,13].Theuseofhydrogenbondsofferstheadvantagethattheyinvolvedistinctdonorandacceptorsites,
andareverydirectional.Inthatwaytheyoffermorepossibilitiesforstructuraldesignthanforcesthataresymmetric
andnondirectionalase.g.ionioninteractions.
In our case, we will improve Tg of polystyrene based on secondary interactions. Knowledgably crosslinking can
increaseTgofpolymers.However,nobodytriedtousethemethodbecausefewcrosslinkageinpolystyrenewilllead
toworserheologicalproperty.
Thearrangementofhydrogenbonddonorsandacceptorsofmaleimide,whichareinvolvedinhydrogenbondinginthe
complexwithmelamine,suggestthatitshouldbepossibletocomplexonemelaminemoleculetothreeimidesunits.
Fig17ProposedStructureofMaleimide/styreneinteractionswithmelamine
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Fig18ProposedStructureofMaleimide/styreneinteractionswith2,6diaminopyridine
Ingeneral,thebindingstrengthofmultiplehydrogenbondedcomplexesisdependingonthestrengthoftheindividual
hydrogenbondsinthearray,andthenumberofhydrogenbond.DifferenthydrogenDonor(D)andhydrogenacceptor
(A)arrayscanbeobtainede.g.atriplebond(DDDAAAarray,DDAAADarray,DADADAarray)[12].The DADADA
triplehydrogenbondarrayisfrequentlyusedinorganicchemistryduetoitssyntheticavailability.
Theuseofahydrogenbondingunitpossessingtwoormoreinteractionsitesshouldresultinnetworkformation.Itisa
new, simple, economical method to prepare polystyrene with higher Tg based on hydrogen bonding crosslinkage
betweenmelamineandimideinthepolystyrenepreparedbyfreeradicalcopolymerizationofstyreneandfewamount
of maleimide. The thermoreversible properties of hydrogen bond make the polystyrene have good rheological
propertieswithhigherTg.
Inordertorevealtheinteractionbetweenimideandmelamine,weused2,6diaminopyridinetoreplacemelamineto
complexwithimidefromSMA.BothofthemshouldcomplexwithimidebyDADADAarraysshownintheFig.17and
Fig.18.
Chapter2Experimental
2.1Materials
Styrene was distilled under vacuum and stored in a freezer until use. Maleimide 2,6diaminopyridine were used
commercially.AIBN(2,2'azobutironitrile)wasrecrystallisedfrommethanolbeforeuse.DMSOwaspurifiedanddried
bystandardtechniquesbeforeuse.CH3OHandCH2Cl2wereusedcommercially.
2.2Instruments
1HNMR of copolymer samples were taken in CDCl on a Bruker 600 MHz spectrophotometer with DMSO as a
3
solvent. The glass temperature transition was determined by differential scanning calorimeter (DSC) and was
performedonaPerkinElmerPyris1undernitrogenwithascanrateof10oC/min.TheglasstemperaturetransitionTg
isthemidpointintheheatcapacitychange.
2.3Synthesisofrandomcopolymersofstyreneandmaleimide
Copolymer of styrene and maleimide were prepared by a free radical copolymerization using AIBN as the radical
initiator and DMSO as solvent. The synthesis of random copolymers of styrene and maleimide (Fig. 21) which can
serveasanexamplewasperformedasfollow:
StyreneandMaleimidesolutionwaspreparedinDMSO.StyrenesolutionwasaddedwithAIBN(80%w/wofthetotal
monomerconcentration)ina3neckedroundbottomedflaskequippedwitharefluxcondenser,mechanicalstirrerand
nitrogen inlet (septum and a long needle). Maleimide solution was added dropwise with AIBN (20% w/w of the total
monomerconcentration)shortlyandslowly.Thepolymersolutionwasprecipitatedinwaterandtheresultingpolymer
wasdissolveinCH2Cl2andprecipitatedinCH3OH,thendriedinvacuumat60oC.
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Fig21SynthesisCopolymerizationofStyreneandMaleimide
2.4preparationofBlendsofStyrene/Maleimidecopolymerandmelamine
or2,6diaminopyridine
Coprecipitation method was used to blend melamine or 2,6diaminopyridinewithimidescontaining copolymers. A
series of experiments was done to blend StyreneMaleimide copolymers with melamine or 2,6diaminopyridine.
Copolymersbasedonstyrenemaleimideweremixedhomogenouslywithvariousamountsofmelamineandcarefully
dissolvedinDMSOfor30minutes,thencoprecipitatedinwater.TheresultingpolymerwasdissolveinCH2Cl2and
precipitatedagaininCH3OHthendriedinvacuumat50oC.Afterfiltration,washinganddryingtheyieldoftheblend
wasdetermined[7].
Fig22blendofStyreneMaleimideandMelamine
Fig23BlendofStyreneMaleimideand2,6diaminopyridine
Chapter3Resultsanddiscussion
3.1Characterizationofcopolymerofstyreneandmaleimide
3.1.11HNMRSpectra
Inordertocharacterizetherandomstyrenemaleimidecopolymer, 1HNMRmeasurementwasperformedonaBruker
600MHzspectrophotometerwithDMSOasasolvent.
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1/12/2017
Atypical1HNMRspectrumofcopolymerMaleimideStyreneisshowninfigure31.
Fig311HNMRspectrumofrandomcopolymerStyreneMaleimideatratio18.8/1
ThecharacteristicspectrumwasfoundfordifferentratioofStyreneMaleimide
The1HNMRspectrumshowstheexpectedresonanceforthearomaticprotonsofpolystyrene(cande~6.07.6ppm
protonsignalsoftheCH=groupofStyrene)andimineprotonsofMaleimide(b~11.2ppm).
Thebroadsignalsfrom1to3ppmareassignabletoCH(aandf)andCH2(d)protonsofthemainchain.Therefore,
thisspectrumconfirmsthepresenceofMaleimidestyrenecopolymer[15].
Allofthe1HNMRspectraofrandomcopolymerofStyreneMaleimideatdifferentcompositionshaveshownthesame
characteristicsbands.
3.1.2Copolymercomposition
1H
NMR spectroscopic analysis has been established as a powerful tool for the determination of copolymer
compositionsbecauseofitssimplicity,rapidityandsensitivity.Theaveragecompositionratioofthecopolymersamples
was determined from the corresponding 1H NMR spectra. The assignment of the resonance peaks in the 1H NMR
spectrum leads to the accurate evaluation of the content of each kind of monomeric unit incorporated into the
copolymerchains.
Thus,theCopolymerratioofSMAwascalculatedbymeasuringtheintegratedpeakareasofaromaticprotonsof
styreneunit(signalcande)andimineprotonofMaleimide(signalb).LetBbetheintegratedpeakareasofaromatic
protonsofstyrenemonomerandAistheintegratedpeakareasofimineprotonofMaleimide.Thepolystyreneunit
containsfivearomaticprotonsactiveinresonanceandthemaleimideunitcontainsoneimineproton,thefollowing
expressionisusedtodeterminethecompositionofcopolymer:
Table31CalculationofintegratedpeakareaofprotonsandmolecompositionsofcopolymersIV
Copolymer IAromatic IImide
I
II
28.832
14.843
1.000
0.5473
1.000
1.000
[Styr]/[Mal]
1.000 43.675
8.7
0.0233 0.0233 1.5473
13.2
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1/12/2017
1.000
III
0.0167 0.0167 1.5741
18.8
0.0122 0.0152 1.5581
25.5
0.0153 0.0153 1.3540
17.7
0.5741
1.000
IV
0.5581
1.000
IV
0.3540
IAromaticIntegratedpeakareaofaromaticprotonsofstyreneunit.
ImideIntegratedpeakareaofanimineprotonofMaleimide.
3.2Copolymerizationofstyreneandmaleimide
TherandomcopolymerstyrenemaleimidewaseasilyobtainedbyradicalpolymerizationinDMSOusingAIBNasthe
initiator.Tocontrolthecontentofmaleimideincopolymer,weperformedthesynthesisatdifferentconditionsto
copolymerizeMaleimideandStyrene,andobtainedcopolymerswithidenticalmainchainstructurebutwithadifferent
yieldfrom37.3%to89%.Aswementionedbefore,MaleimideandStyrenecouldconstitutethechargetransfer
complex,sowechosedropwiseadditionofmaleimideduringthepolymerization.
Table32Effectofstyrene/maleimideratioonyield
Experience [Styr]/[Mal] Reactiontime/h Temp/oC MasseAIBN/% MonomerConc./M Yield/% [st]/[imide]
1
10/1
15/1
20/1
13
30/1
80
0.0476
39.4
8.7/1
44.5
13.2/1
80.0
18.8/1
89.0
25.5/1
Table33Effectofinitiatoronyield
Experience [Styr]/[Mal] Reactiontime/h Temp/oC MasseAIBN/% MonomerConc./M Yield/%
4
5
6
1
20/1
37.3
80
0.0476
48.8
59.8
80.0
Table34Effectoftemperatureonyield
7
8
3
60
20/1
20.8
70
80
0.0476
90
40.0
80.0
85.0
Table35Effectofreactiontimeonyield
10
20/1
80
0.0476
67.0
11
72.0
80.0
12
81.0
Fromtheseresultsweconcludethattheratioofthecopolymerizationaffectsmuchmoretheyield.
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1/12/2017
Table 32 show that the yield of the copolymer increase with the ratio of [Styrene]/[Maleimide]. That indicates
maleimideintroductionslowsthepolymerizationrateofstyrene.However,theratioof[St]/[imide]inthecopolymeris
lessthantheirmonomerratiocounterpart,whichmeansMaleimideiseasytocopolymerizewithstyrene.
Table35indicatesthattimeisaparameterveryimportantinthecopolymerization.Aswedescribedabove,maleimide
was added to the solution shortly and slowly to avoid the formation of alternative copolymers and to lead
predominantly to the formation of random copolymer. To extend the time reaction favors the formation of random
copolymer. There is no improvement in yield at reaction time of over 6hrs. that indicates effect of maleimide on
copolymerizationisnegligible.Table33and34haveshownrespectivelyanincreaseofyieldwhentheinitiatorand
thetemperaturearechangeddrastically.Thisresultisdemonstratedbythefactthatthecopolymerizationreactionis
dependingoftheamountofinitiatorusedandthetemperaturerequiredtoactivatethecopolymerization.
3.3Blendsofthestyrene/maleimidecopolymersandmelamine
DSCcurvesoftheblendsofthecopolymersIIV(asshowninTable31)withmelamineareshowninFig32andtheir
TgvaluesarepresentedinTable36.
Table36Effectofimide/melamineratioonTg
Experience [imide]/[Mela] [Styr]/[Mal] Tg/oC
F
1/1
103.3
1/2
113.8
1/3
122.0
1/4
125.6
18.8/1
1/5
1/10
105.5
128.0
78.0
130.0
90.0
Fig32DSCtracesofblendswithdifferentmolarconcentrationratiomelaminetoimideinthecopolymerwith
maleimidemolarconcentrationof5.05%
As shown in Fig32 and in Fig33, addition of melamine results in a dramatic increase of Tg up to melamine
concentrationratioof3timestoimideinthecopolymerwhichcorrespondtoTgequal122oC.Inthiscase,Tgis30oC
higherthanthepurecopolymer.Atthemelamine:imideratioof10:1,even40oCisreachedwithTgof130oC.However
themoreadditionofmelamineresultsinpresenceoftwovalueofTgfromthemelamine:imideratioof4:1toof10:1.It
well known there is triplehydrogen bonding between melamine and imide unit. Recently, Ronald F. M [5,7,12]
proposed that one melamine molecule interacts with three imide units, leading to a threedimensional hydrogen
bondednetwork.
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1/12/2017
Figure33DependenceofTgontheratioofmelaminetoimideinthecopolymer
Tgincreaseofourcopolymerinpresenceofmelamineattributestothiskindofcrosslinkagerestrictingthemotionof
polystyrene segments. The more crosslinkage in the blend corresponds to the higher Tg of the blend. However,
Maleimidecontainsinourcopolymersis20timeslessthanRonald's,andrandomlydistributealongthechain,which
restrictstheimidestogethertointeractwithmelamine.Therefore,moremelamineisneededtobuildacrosslinkingsite.
AsFigure33shown,melamine:imideratioelevationfrom3:1to10:1stillincreasestheTgalthoughslowly,suggesting
crosslinkage density still increases. From the melamine: imide ratio of 4:1 to of 10:1, the presence of another Tg at
lowertemperatureincaseofmelamine:imideratioof4/1,5/1and10/1isreasonablyexplainedasthepresenceoffree
melaminewhichactsasaplasticizer.
In order to increase crosslinkage sites, we prepared a series of blends with different styrene/maleimide ratios. The
resultsweregiveninTable38andFig34.
Table37Effectofstyrene/maleimideratioonTg
Experience [Styr]/[Mal] Tg/oC
A
polystyrene 100.1
8.1/1
84.6
13.2/1
87.4
18.8/1
91.7
25.5/1
93.0
Table38Effectofstyrene/maleimideratioonTg
Experience [Styr]/[imide] [imide]/[Mela] Tg/oC
L
8.1/1
106.9
13.2/1
123.3
18.8/1
128.0
1/5
78.0
146.2
25.5/1
8.1/1
109.0
13.2/1
113.0
18.8/1
25.5/1
89.0
1/3
122.0
127.0
74.0
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1/12/2017
Figure34DependenceofTgonimidecontentsincopolymer(blackspot)
Blendswithmolarratioofmelaminetoimide3:1(redspot)
Figure34revealsthatTgofcopolymerdecreasedinalinearfunctionwithmaleimidecontentduetotheflexibilityof
maleimide units. However, Tg of all blends with melamine: imide ratio of 3:1 is much higher, at least 25C, than a
correspondentcopolymer,and is an exponential decay relationship with imide content. Blend of copolymer with the
fewestimidecontent([styrene]/[imide]25.5/1)hasthehighestTg,127oC.
Atthesamemelamine:imideratioof3:1,melamineisn'tenoughtosaturateimideunitsintheblendswithhigherimide
content. However, melamine is too much to complex with imide unit in the blend with imide content of 25.5/1. It is
confirmedbyappearinganotherTgat74oC.So,Tgofblendswithhigherimidecontentmustbemuchhigherifmore
melamine is used. With melamine: imide ratio of 5:1, we prepared a series of blends and tested their Tg, shown in
Table38.theirTgsaremuchhigherthanonesofblendswithmelamine:imideratioof3:1.
Moreover,intheprocedureofpreparationofblends,itisobservedthatblendsarereadilysolubleinDMSO,evenin
CH2Cl2,thisindicatethatcrosslinlingarepresentinourblendsandisbasedonsecondaryinteractions.
3.4Blendsofthecopolymerand2,6diaminopyridine
In order to evaluate the effect of crosslinking of melamine on the Tg of blend, we prepared a series of blend of
Diaminopyridine(DAP) and Styrene/Maleimide copolymer with different styrene/maleimide ratios. DAP is analogue
structure to melamine. They both can form a complex with imide through a triple hydrogen bonds in the manner of
DADADA arrays, however without crosslinkage is formed in the blends of DAP and Styrene/Maleimide copolymer
owingtodifferenceofDAPandmelamineinstructure,asshowedinFig.17andFig.18.
DSCcurvesoftheblendsofDiaminopyridineandStyrene/MaleimidecopolymerareshowninFigure35andtheirTg
valuesarepresentedinTable39.
Table39Effectofimide/DapratioonTg
Experience [imide]/[Dap] [Styr]/[imide] Tg/oC
control
1/0
94.2
1/1
95.7
1/2
103.9
1/3
105.2
1/4
1/5
1/10
17.7/1
113.0
115.2
78.1
117.2
76.5
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1/12/2017
Figure35DependenceofTgontheratioofDAPtoimideinthecopolymer
ThedependenceofTgontheratioofDAPtoimideshowedthatTgsofblendsareincreasingwithadditionofDAP,as
sameasblendsofthecopolymerwithmelamine.SingleTgisshowntillDAPconcentrationratioof4timestoimide,
whichcorrespondto Tg equal 113oC . Then, two Tg is found although one is still elevated. the behavior is found in
blendsofthecopolymerwithmelamine.
ItisknownthereistriplehydrogenbondingbetweenDAPandimideunit.Tgincreaseofourcopolymerinpresenceof
DAP attributes to this kind of triplehydrogen bonding existing in the blend and restricting the motion of polystyrene
segments,makingthecopolymerlooklikeacopolymerofstyreneandcomplexofmaleimidewithDAP.
However, the Tg increase of the blends is lower ones of blends of the copolymer with melamine. Contrary to the
melamine,DAPmoleculecannothavecrosslinkngwithimideunit.Sotheresultsconfirmtherearetrulycrosslinking
formationinblendsofthecopolymerwithmelamine.
Chapter4Conclusion
Tgofpolystyrene,acommonpolymer,isdramaticallyelevatedbasedoncrosslinkagebetweenintroducedimideunits
andmelamine.Polystyrenewithimidemolarconcentrationof5.05%hasTgof122oCinthepresenceofmelamine,22
oChigherthanpolystyrene,whichwillextendapplicationofpolystyrene.Athighratioofmelaminetoimide,twoTgs
areobserved,oneishigherthan122oCbutanothermuchlower.TheexistenceoftwoTgisduetothefactthatfree
melamineisactingasplasticizer.
DiaminopyridinealsoincreaseTgofpolystyrene.Inthiscase,theblendlookslikeacopolymerofstyrenewithabig
monomer, complex of maleimide and Diaminopyridine. but increment is less than melamine owing to lack of
crosslinkingbetweenthem.
The secondary interactions between melamine or Diaminopyridine with polystyrene containing imide is confirmed by
theirblendsreadilysolubleinDMSOandinCH2Cl2.
ReferencesNotes
[1]
Kaj Backfolk et alDetermination of the glass transition temperature of latex films:comparaison of various
methods,''DepartmentofPhysicalChemistryAkademiUniversity,Finland(2007)
[2]
Victor
Morais,Random
alternate
Comlutense,Madrir,Spain(2005)
[3]
Xinliang Yu, Xueye Wang, Hanlu Wang, Aihong Liu and Cuili Zhang , Journal of Molecular Structure:
THEOCHEM,Volume766,Issues23,15August2006,Pages113117
[4]
XinliangYuetal.PredictionoftheglasstransitiontemperaturesofstyreniccopolymersusingaQSPRbasedon
theDFTmethod,CollegeofChemistry,XiangtanUniversity,people'sofrepublicofChina(2006)
[5]
Kumar A, Galaev IY, Mattiasson B. Affinity precipitation of amylase inhibiter from wheat metal by metal
chelate affinity binding using Cu (\u8545cents) loaded copolymers of 1vinylimidazole with Nisopropy
acrylamide[J].Biotechnol.Bioeng.,1998,59:693704
[6]
Ronald lange and al.Supramolecular Polymer Interaction based on the alternating copolymer of styrene and
and
diblock
copolymers,Departement
Materials,University
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[6]
Ronald lange and al.Supramolecular Polymer Interaction based on the alternating copolymer of styrene and
maleimide,laboratory of organic chemistry ,Eindhoven university,The Netherlands(1994) Supramolecular
Polymer Interaction using melamine, Laboratory of organic chemistry , Eindhoven university,The
Netherlands(1996)
[7]
Kotera,MLehn,J.chem.Soc.,ChemComm.1994,197
[8]
Ronald lange ,Polymer blends based on the imidiaminotriazine triple hydrogen bond ,Laboratory of organic
chemistry,Eindhovenuniversity,TheNetherlands(1997)
[9]
Mirzaagha babazadeh,thermal stability and high glass transition temperature of 4choloromethyl styrene
polymers,DepartementofAppliedChemistry,islamicAzaduniversity,Iran(2006)
[10] Billmeyer,J.R.TextbookofPolymerScience3rdEd.Wileyinterscience,Newyork,USA(1984)
[11] Melamine as a dietary nitrogen source for ruminants", G.L.Newton and P.R.Utley, Journal of Animal Science,
vol.47,p133844,1978
[12] E.E.Simanek,X.Li,I.S.Choi,G.M.Whitesides,"CyanuricAcidandMelamine:APlatformfortheConstruction
of Soluble Aggregates and Crystalline Materials", Comprehensive supramolecular chemistry, J.L. Atwood ed.,
NewYork:Pergamon,Vol.9,495(1996).
[13] Ronald lange and al.Supramolecular polymer chemistry based on melamine and maleimidestyrene
copolymers,laboratoryoforganicchemistryEindhovenuniversity,TheNetherlands(1997)
[14] Coleman,SpecificinteractionandthemiscibilityofpolymerBlends,Technomic,Lancaster(1991)
[15]
Koji Ishizu,Chisato Takashi?????Takeshi Shibuya and Satoshi Unichida, Dept. of organic materilas and
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Recherchersurlesite:
Recherche
MemoireOnline20002015
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Higher TG Based On Triple Hydrogen Bond Interactions - Jean Claude MBULU AGALIA

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WOW !! MUCH LOVE ! SO WORLD

Polymer LDPE HDPE PP PVC PS PAN PTFE PMMA PMMA

175 180 175 >200 330

0.0233 0.0233 1.5473

0.0167 0.0167 1.5741

0.0122 0.0152 1.5581

0.0153 0.0153 1.3540

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