苏州大学聚合物合成与改性作业答案Word文档格式.docx

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