苏州大学聚合物合成与改性作业答案Word文档格式.docx
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苏州大学聚合物合成与改性作业答案Word文档格式.docx
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PTFE(polytetrafluroethylene)
3、Pleaselistthesourcestogeneratefreeradicals.
Thermaldecomposition、photochemicaldecomposition、oxidation-reductionreaction、highenergyparticleradiation、sonication、plasmainitiation、electrolyticinitiation.
4、Pleaselistmainreactionsofradicals.
Radicaladditionreaction、radicalcouplingreaction、radicaldisproportionationreaction、radicaldissociationreaction、radicaltransferreaction.
5、Pleaselistthreemonomerswhichcanbepolymerizedviaradical,ionicandcoordinationpolymerizations.
Radical:
styrene、vinylchloride、ethylene、acrylonitrile、methacrylamide;
Ionic:
isobutylene、isoprene、iospropylvinylether、styrene;
Coordination:
propene、styrene、ethylene、isoprene;
6、Can1,1-diphenylethylenebesubjectedtopolymerization?
Why?
No,sincethephenylsubstitutesgroupsarebulkywhichcancausestrongstericeffects,1,1-diphenylethylenecanonlyformdimer.
7、Pleasedrawchemicalstructuresofpoly(styrene-alt-maleicanhydride).
8、Pleaselistelementalreactionsofchainpolymerization.
Chaininitiation、chainpropagation、chaintermination、chaintransfer.
9、Pleaselistthetypesofmicrostructuresformonosubstitutedvinylmonomers.
Head-to-tail(1,3-placement,thesubstitutesareonalternatecarbonatoms):
Head-to-head(1,2-placement):
10、Pleaselistthetypesofchaintransferreactioninfreeradicalpolymerizationandgivetwoexamplesofchaintransferagents.
Chaintransfertomonomer,solvent(chaintransferagent),initiator,andpolymer;
Chaintransferagent:
carbontetrachloride,1-butanethiol,carbontetrabromide,triethylamine.
11、Whatarethecharacteristicsofradicalpolymerization?
Itconsistsoffourelementaryreactions——initiation,propagation,termination,andtransfer;
Therateofinitiationisthelowestone,whichcontrolstheoverallrateofpolymerization;
Slowinitiation,fastpropagation,fasttermination,andeasytermination;
Theproductsonlyconsistsofmonomer,polymers(activespecies,ifpossible);
Highpolymersexistasthepolymerizationbegins;
Conversionisincreasedbytheextensionofpolymerizationtime;
Thereisnoreactionbetweenmonomer-monomer,monomer-polymer,andpolymer-polymer;
Theconcentrationofmonomerdecreasesandpolymerincreasesasthepolymerizationgoeson.
12、Notions:
efficiencyofinitiation,kineticchainlength,autoacceleration(geleffect),radicallife,polymerizationrate,inhibition,retardation.
Efficiencyofinitiation:
theratioofinitiatorswhichareusedtoinitiatepolymerizationtoinitiatorsthatdecomposeinthewholeprocessofpolymerization;
Kineticchainlength:
theaveragenumberofmonomermoleculesconsumedpereachradicalwhichinitiatesapolymerchain,anditcanbegivenbytheratioofpolymerizationratetoinitiationrate;
Autoacceleration:
autoaccelerationisacommonphenomenonwherethepolymerizationrateincreasesforcertainperiodinradicalpolymerizationwhichiscausedbytheincreaseofthesystemviscosity,thusisalsocalledgeleffect;
Radicallife:
thetimefromproductiontoterminationofradicals;
Polymerizationrate:
describehowthepolymerizationconcentrationorconversionchangeswiththereactiontime,whichconsistsofthreeelementaryreactions—initiation,propagation,andtermination,andcanbeexpressedbythefollowingequation:
Inhibition:
aphenomenoninwhichthereactivityofradicalsandstoppedandthepolymerizationiscompletelyhaltedduetotheadditionofinhibitors;
Retardation:
aphenomenoninwhichonlyaportionoftheradicalsarestoppedandpolymerizationoccursatalowerrateandlowerpolymermolecularweightduetotheadditionofretarders;
13、Chemicalstructures:
AIBN,BPO,KPS,cumylhydroperoxide.
AIBN(2,2-azobisisobutyronitrile)BPO(benzylperoxide)
KPS(potassiumpersulfate)cumylhydroperoxide
14、Pleaselisttherelationbetweendegreeofpolymerizationandkineticchainlength.
Whennochaintransferoccurs:
Couplingtermination:
;
Disproportionationtermination:
Thetwomodescoexist:
C、Drepresentthepercentageofcouplinganddisproportionation
Whenchaintransferoccurs:
15、Pleaseexplainbasicprinciplesofdilatometermethod.
Theprinciplesofdilatometermethodarebasedonthelinearrelationshipbetweenthevolumecontractionandtheconversionofthereactionsystem:
Where
isthespecificvolumeofmonomer,
isthespecificvolumeofpolymer,andKrepresentstherateofchangeofvolumewhentheconversionis100%.
Theconversion(C%)hasalinearrelationshipwiththevolumecontraction:
istheoriginalvolumeofthesystem,and
denotesthecontractionvalueofvolume.
Thedilatometerconsistsoftwoparts:
thelowerpartisthereactor,andtheupperoneiscalibratedcapillary.Bymeasuringthevolumecontractionvalueatdifferenttime,wecangettheconversionchangewithtime,andgetthepolymerizationrate.
Chapter2
1、Whatarebasicfeaturesoflivingpolymerizationsystems?
Constantnumberofpolymerchains;
Nopermanentchainstoppingreactions;
Controlofchaingrowth;
Dormantandactivestates;
Narrowmolecularweightdistribution;
TheplotofMnversusmonomerconversionislinear;
Synthesisofblockcopolymers,starpolymersandcombpolymer;
Synthesisoftelechelicpolymers(controlofendgroups).
2、Pleaselistthemaintypesof“living”/controlledradicalpolymerization.
Reversiblehemolyticcleavage:
NMP(nitroxide-mediatedpolymerization,aspecialkindofSFRP,stablefree-radicalpolymerization)andATRP(atomtransferradicalpolymerization);
Chaintransferprocess:
additionfragmentation,RAFT(reversibleaddition-fragmentationchaintransferpolymerization),CCTP(catalyticchaintransferpolymerization);
Inifertersmethods;
Organotelluriumandboroxyl-basedinitiators.
3、PleaselistthebasicmechanismandapplicationofATRP.
ATRPisakindoftransitionmetalmediatedlivingradicalpolymerization,anditsmechanismisshownbelow:
Or
ApplicationsofATRP:
Topreparewell-definedmacromoleculeswithpredeterminedMwandlowpolydispersity<
Mw/Mn<
300<
Mn<
200,000);
Tocontrolmacromoleculararchitecture(linear,star,polymerbrush,dendritic);
Tocontrolmicrostructureofmacromolecules(homopolymer,alternating,block,graft);
TopreparemacromonomersandfunctionalizedpolymerswithCOOH,OH,NR1R2andvinylgroups(telechelic,multifunctional,end-functionalized).
4、PleaselistthebasicmechanismandapplicationofRAFTpolymerization,anddescribetheprimaryrolesofZandRgroupsofRAFTagent.
Mechanism:
Application:
Synthesisofblockcopolymer,gradientcopolymer,andgraftcopolymer;
Synthesisofpolymerswithdifferentarchitectures,liketelecheliccopolymer,starcopolymer,hyperbranchedcopolymer,andpolymerswithnetwork;
Introducingfunctionalitiesintopolymers.
PrimaryrolesofZandR:
Zservesasstabilizinggroups,likephenyl,alkylgroups;
Rservesasreinitiatinggroups,andshouldbecleavable,likeisopropylphenylgroup.
Chapter5
1、TakeNa-naphthalenebasedanionicpolymerizationofstyreneforexample,pleasedescribethebasicmechanismandapplicationoflivinganionicpolymerization.
Tosynthesizeamonodispersepolymer;
Tomeasuretheanionicpolymerizationrate;
Toprepareablockcopolymer;
Toprepareatelechelicpolymer.
2、Pleasedescribemainsubclassesofdendriticpolymers.
Dendrimers、dendrons、hyperbranchedpolymers、dendrigraftpolymers、dendronizedpolymers.
3、Whatisdendrimer?
Howaboutitsmainapplications?
Dendrimerisrepetitivelybranchedmolecule,whichistypicallysymmetricaroundthecore,andoftenadoptsasphericalthree-dimensionalmorphology.
Dendrimerhaslotofapplications:
suprachemistry,catalyst,drugdelivery,genedelivery,optics,sensors,bloodsubstitution,nanoparticles,andotherfields.
4、Pleaselistthreetypesofdendrimers.WhatistherepeatingunitofTomalia-typepoly(amidoamine)dendrimer?
Tomalia-typepoly(amidoamine)(PAMAM)、Newkome’sarboroldendrimers、Phosphoruscontainingdendrimers、Fré
chet-typepoly(benzylether).
RepeatingunitofPAMAMdendrimers:
5、Pleaselistthemainmethodstosynthesizedendrimers.
Divergentsynthesis:
multiplicativegrowthfromacentralcore;
Convergentsynthesis:
preparationstartingfromwhatwillbecometheperipheryofthemoleculeandprogressinginward;
Clickchemistry:
preparationbasedonDiels-Alderreactions,thiol-enereactions,andazide-alkynereactions.
6、Byassumingthecorefunctionalityism,andeachbranchingpointhasthreelinkingpos
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