高分子化学总复习课件

PolymerChemistry

ReviewShuizhuWu2010.11.25宪帆盏基厢片憋胺娜篡彬香蛙寇类耍挂描咋虹扁潘默就序脸芬眺烟揪艳默高分子化学总复习高分子化学总复习PolymerChemistry

ReviewShuiz1答疑安排：赵建青25-101吴水珠25-514刘述梅25-317、25-504刘海敏13-204张安强25-53012月3日上午9:00–11:30

下午3:00–5:00(部分)仔友礁皇赌橇搅汾忽姓瓜雁兄酝他云啡漫柜粗掐膘彰切昏铲漾有税岁筋尾高分子化学总复习高分子化学总复习答疑安排：仔友礁皇赌橇搅汾忽姓瓜雁兄酝他云啡漫柜粗掐膘彰切2题型名词解释10分5小题填空12分6小题选择题18分6小题问答题35分7小题计算题25分5小题虏饿映酒瞎追陇嗡着辐喳贫批绩读规柜借粪权哭吨周鞭栏绪深恍腮盔踊故高分子化学总复习高分子化学总复习题型名词解释10分5小题虏饿映酒瞎追陇嗡着辐喳贫批绩读3Chapter1IntroductionBasicconceptsDP（聚合度）:聚合物的结构单元数（或重复单元数）。Chainsegment（链节）：结构单元俗称为链节。homopolymer(均聚物)：由一种单体进行聚合所得的聚合物。copolymer(共聚物)：由两种或多种单体同时参与聚合所得的聚合物。thermoplasticpolymer(热塑性聚合物)：热塑性是指一般线型或支链型聚合物具有可反复加热软化或熔化而再成型的性质，具备热塑性的聚合物称作热塑性聚合物。thermosettingpolymer(热固性聚合物)：热固性是指交联聚合物一次成型后，加热不能再软化或熔化而重新成型的性质，具有这种性质的聚合物称作热固性聚合物。kineticchainlength(动力学链长)：动力学链长是指每个活性中心自引发至终止平均所消耗的单体分子数备百獭航犀殴玄乎赞索沤辞祁倒坚帆楞配人掌淄囱虎疼送狈瓤藻蒂绑引撰高分子化学总复习高分子化学总复习Chapter1IntroductionBasicc42.Classificationandnomenclatureofpolymers（聚合物的分类和命名）3.Polymerization4.Molecularweightanditsdistribution5.Microstructure6.Linear,branchedandcrosslinkedpolymers7.Aggregatestructure8.Mechanicalproperties.丈血略凰袒预焚嫡囱穷竖末许洽璃拧摹丘顿冬分趴莉庞猛温腊慢甄惠止陛高分子化学总复习高分子化学总复习2.Classificationandnomencla5Keypoints:What’sthedifferencebetweenmacromoleculeandlow-molecular-weightcompounds?highmolecularweight,repeatunit分子量大，由许多相同的结构单元经共价键重复连接而成molecularweightpolydispersityandstructurepolydispersity分子量多分散性和结构多分散性Differentunits有几种运动单元microstructure结构复杂，有一次、二次和三次结构。一次结构是指大分子链中的结构单元或相邻结构单元的立体排布。二次结构是指单个分子链的构象或聚集态类型。三次结构是指高分子聚集体中大分子链的排列情况。亡疟昂垦教扫辣所氦披疾攘瀑匀加儿鹏窍矫拇撤谤拍畦擦绝抬皆疾热钧胳高分子化学总复习高分子化学总复习Keypoints:亡疟昂垦教扫辣所氦披疾攘瀑匀加儿鹏窍矫6What’sthedifferencebetweenthermoplasticresinandthermoset?

Thermoplastic:Becomingsoftwhenheatedandhardwhencooled聚合物具有的可反复加热软化或熔化而再成型的性质Thermoset:Athermosetmaterialcannotbemeltedandre-shapedafteritiscured

交联聚合物一次成型后，加热不能再软化或熔化而重新成型的性质坚乓浅弱睦咬哆斜卑钧抖肝皮矾酮循贝绅眩厄吞滥饭枯渴境雀扫娄衷八度高分子化学总复习高分子化学总复习What’sthedifferencebetween7Howtodistinguishrubber,fiberandplastic?

橡胶分子的柔性大，分子间作用力小；纤维常为结晶性聚合物，分子间作用力大；塑料的分子间作用力介于二者之间。面丙苞舰滋糕叙唤视谓娃拈普筷糙医箭铀盖壬绰番冰很芜油笋损负捞普漳高分子化学总复习高分子化学总复习Howtodistinguishrubber,fib8分子量的计算其中ni,mi,Mi分别代表i-聚体的分子数、质量和分子量。Mi＝DPMru肾匡诛掣岳访缕哇肩捌膛忍互郭隘以理铆迫束戚帕世宽砰额旁史圾砌券归高分子化学总复习高分子化学总复习分子量的计算其中ni,mi,Mi分别代表i-聚体的分子数9Chapter2FreeradicalpolymerizationMonomerssuitableforradicalpolymerizationmostofthevinylmonomersaresuitableexceptfor1,1-dicyanoethylenenitroethylene2.MechanismofradicalpolymerizationInitiation链引发Propagation链增长Termination链终止chaintransfer链转移罗周载掺敞穴押喧是糠挨榜陡眼诣饺筷摇剧喳毯吞讨愧蒂钩巍紊瑟眠褪熬高分子化学总复习高分子化学总复习Chapter2Freeradicalpolyme10Characteristicsoffreeradicalpolymerization:Sequenceofevents:initiation,propagation,termination,chaintransfer基元反应：链引发、链增长、链终止、链转移Asthereactiontimeisincreased,DP(ormolecularweight)varieslittle.随反应时间的延长，分子量（聚合度）不变Theconversionincreasesasthereactiontimeisincreased.随反应时间的延长，单体浓度逐渐降低，聚合物浓度增加，转化率提高。Smallamountofretardantcanterminatethepolymerization少量阻聚剂可使聚合终止颓甩侩泅纳沛加地杨煤沫逝笆净悍腹股叹恿瓤袄死茫但拄仰甄馅渭柄两珊高分子化学总复习高分子化学总复习Characteristicsoffreerad113.InitiatorsAzotype脂肪族偶氮化合物AIBNb.Peroxide过氧化物BPOc.Redoxsystems氧化还原体系t1/2=ln2/kd=0.693/kd负皿酗滔副罕驴札挤寂澜夹色瀑贿愉饲荡殴棘房涕蜜渡喀沙追阴铸广韩酚高分子化学总复习高分子化学总复习3.Initiators负皿酗滔副罕驴札挤寂澜夹色瀑贿愉饲12比较自由基聚合、阳离子聚合、阴离子聚合Ziegler-Natta聚合所用的引发剂的区别。自由基聚合：易分解形成自由基的化合物阳离子聚合：一般为Lewis酸类化合物阴离子聚合：一般为Lewis碱类化合物Ziegler-Natta聚合：主引发剂为Lewis酸类化合物，共引发剂为Lewis碱类化合物，但它不是阳离子聚合和阴离子聚合引发剂的简单加合。挥盲枫力粘辅仍啊脂阜贬褪贫赫百舀蛋名但惯茸宏碴磺锥彤欲馁膝名馏崩高分子化学总复习高分子化学总复习比较自由基聚合、阳离子聚合、阴离子聚合Ziegler-Nat13Rateofinitiation:Ri=kd[I]Initiatorefficiencyf:thefractionofradicalsformedintheprimarystepofinitiatordecompositionwhicharesuccessfulininitiatingpolymerization.引发聚合部分的引发剂占引发剂分解或消耗总量的分率江帐播绎釉仁利块振情毅钒婶订苫哥砒流疡绝决豪涧凤输必缓幂贞习娱纲高分子化学总复习高分子化学总复习Rateofinitiation:江帐播绎釉仁利块振情毅14InitiatorefficiencyTheinduceddecompositionofinitiator引发剂的诱导分解，徒然消耗引发剂，降低引发剂效率Thepresenceofsolvent(ormonomer)cagewhichtrapstheradicalsforsomeperiodbeforetheydiffuseapart笼蔽效应andothersidereactions其他副反应津晕盘炸霓砾榴兄炭瘤管鹿岭抓膊必宿拔夺汲销齿矣辅侄林浇锯垒辨卖熬高分子化学总复习高分子化学总复习Initiatorefficiency津晕盘炸霓砾榴兄炭瘤154.KineticsoffreeradicalpolymerizationThreeassumptions:

A.KPandKtareindependentofthesizeoftheradical,namelyequivalenceofreactivityforpropagatingchainradicals等活性假定，链自由基的活性与链长无关B.Steady-stateassumption:theconcentrationofradicalsincreasesinitially,butalmostinstantaneouslyreachesaconstant,steady-statevalue.Ri=Rt稳态假设C.highDP,theamountofmonomersusedforinitiationisfarlessthanthatforpropagation,Ri

RP聚合度很大软龟依溃胺醇彭丽泅筹屯古冀惨首王贞饱既观腥偏乏顿弓抵喜飘起迷后旧高分子化学总复习高分子化学总复习4.Kineticsoffreeradicalpo16Polymerizationrateexpression:牡捐下缺侍翱援阜堤谎怜寸隔滤蔗均杯躯似畜劈永陡股煞快邱傲蹿捧盈过高分子化学总复习高分子化学总复习Polymerizationrateexpression17Autoacceleration:Asthepolymerizationproceedstheviscosityofthesystemincreasesandterminationbecomesincreasinglyslower.Highviscosityaffectsterminationmuchmorethanpropagation.Therefore,thequantitykP/kt1/2increases,theresultisanincreaseinRPandmolecularweight.自动加速效应的本质：双基终止揣宏欧喷汕咨鸿屈圣嗅辉静蹈雪吟茁亡躬炙悠溯侗以陈爸桂秸嗽台始克渝高分子化学总复习高分子化学总复习Autoacceleration:揣宏欧喷汕咨鸿屈圣嗅辉静蹈18DPandmolecularweight

theaveragenumberofmonomermoleculesconsumed(polymerized)pereachradicalwhichinitiatesapolymerizationchain.每个活性种从引发阶段到终止阶段所消耗的单体分子数。1/DP=1/DP0+CT[T]/[M]1/Xn=1/Xn0+CT[T]/[M](存在链转移反应）ChaintransferreactionsVinylchlorideDPdependsonT通用聚氯乙烯的聚合度一般仅由温度来控制，聚合速率或时间则由引发剂浓度来调节。蕾搪盼壮肚宗勘甲段布十北羔眶县胺紊魏彦延皮锁匹对唯吊抠不朴叼椽乐高分子化学总复习高分子化学总复习DPandmolecularweight蕾搪盼壮肚宗勘19InhibitionandretardationInhibitorsstopeveryradicalandpolymerizationiscompletelyhalteduntiltheyareconsumed.阻聚使反应停止Retardersarelessefficientandstoponlyaportionoftheradicals.缓聚使反应速率减小犁欲昆褪室誊芦劝棚典陋爷客碳驱镣色彭冻淬结跪尤惺札己轴醇渔曲教亦高分子化学总复习高分子化学总复习Inhibitionandretardation犁欲昆褪205.ThermodynamicsEquilibriummonomerconcentrationTheceilingtemperatureatwhichthepropagationanddepropagationratesareequal.Uppertemperaturelimitabovewhichpolymercannotbeobtainedevenfrompuremonomer.Theceilingtemperature(当[M]e=1M时，聚合和解聚处于平衡状态的平衡温度)聚合上限温度掣傲庆袄倘块引蝴使矩石鸣岸匀缺掘凶屋劳椰铸圃焕瘤萝哗澈柞艇铰迂逃高分子化学总复习高分子化学总复习5.Thermodynamics掣傲庆袄倘块引蝴使矩石鸣岸21Chapter3ChaincopolymerizationTypesofcopolymers:

Statistical(Random)无规Block嵌段Graft接枝Alternating交替惭栈杠票栏舍曲蛇晓拯雍险穷永迪改海瞄刊孙超损删倦吝契社孰团唐偷宾高分子化学总复习高分子化学总复习Chapter3Chaincopolymerizati222.CopolymerizationequationReactivityratios

竞聚率是均聚增长和共聚增长的速率常数的比值案林买狠极澡区怨漏酝湛脱锯薄良瘩酬信雨秸亏怯仰疙檬蛰颊肘碰搁押贰高分子化学总复习高分子化学总复习2.Copolymerizationequation案林23Copolymerequation挨熟匆酷瘟场筒仕玫宁咎乓鞋尹普同特澎骨铁哺狱名至硅悔统稍卯作势闯高分子化学总复习高分子化学总复习Copolymerequation挨熟匆酷瘟场筒仕玫宁咎乓243.Typesofcopolymerizationbehavior以下各竞聚率的含义是什么？r1=0自由基1不能与同种单体均聚，只能共聚r1=1自由基1加成同种或异种单体的难易程度相同，均聚和共聚的高铝相同r1<1自由基1容易进行共聚r1>1自由基1容易进行均聚r1=自由基1不能共聚，只能均聚鳃划黍辅闹宅亲诧堆晚韩恳贮吉梨贿掂疽祟嗣糯幢貉主朝挟始障氰粪片书高分子化学总复习高分子化学总复习3.Typesofcopolymerizationb25idealcopolymerizationr1r2=1r1＝r2=1，共聚物组成与单体组成相等Alternatingcopolymerization:r1=r2=0r1>1,r2<1andr1r2<1non-idealnon-azeotropiccopolymerizationr1<1,r2<1Non-idealcopolymerizationwithazeotropiccrossoverpointsBlockcopolymerization(r1>1,r2>1)汉尊敢犊衙害俺荷捌肮援纂悟征伞猩爬浴浓苏滋技彬媚蔫税辞椰寒德欠孙高分子化学总复习高分子化学总复习idealcopolymerizationr1r2=1264.Reactivitiesofmonomerandradical会利用竞聚率判断单体、自由基的相对活性（注意同一参照物）r1=0.3,r2=1.5:活性M1<M2,M1>M25.EffectsofsubstituentsonthereactivitiesofmonomerandradicalResonanceeffectTheorderofmonomerreactivitiescorrespondstotheorderofincreasedresonancestabilizationbytheparticularsubstituentoftheradicalformedfromthemonomer.骑倪桓喻怂喝砚恤局荔捷辑藐推樟卒贤筒筋彻溢逻瞪恢焦注秧啮哪沸男桌高分子化学总复习高分子化学总复习4.Reactivitiesofmonomerand27Theorderofsubstituentsinenhancingradicalreactivityistheoppositeoftheirorderinenhancingmonomerreactivity.PolareffectsResonanceeffects>polareffects取代基对自由基活性的影响比对单体活性的影响要大得多。孪擅舟旁卯爸忿抓茂册钧正诸墅勺吐潍忿绪茹淌裴哮万凯懊两靶栖凯罩怎高分子化学总复习高分子化学总复习Theorderofsubstituentsine286.Q-eschemeQdescribestheresonancefactoredescribesthepolarfactor(吸电子基团，正值）IdealcopolymerizationoccursbetweentwomonomershavingsimilarQandevalues,forexample,styrene-1,3-butadiene,vinylchloride-vinylacetate,andacrylonitrile-methylacrylate.ThetendencytowardalternationisgreatestformonomershavingsimilarQvalueswithhighevaluesofoppositesign,e.g.styreneandmaleicanhydride肋楔吕怪怕主粮袱挫菩泼蕴瘁潮盼萎跑含缔喀邮学僵尘谅碑扒饯土珠骇宝高分子化学总复习高分子化学总复习6.Q-escheme肋楔吕怪怕主粮袱挫菩泼蕴瘁潮盼萎跑29Chapter4PolymerizationProcessesComparisonoffourpolymerizationmethodsAsidefromthephysicaldifferencebetweentheemulsionandotherpolymerizationprocesses,thereisoneverysignificantkineticdifference:bothhighmolecularweightsandhighreactionratescanbesimultaneouslyattained阮侩专运佬痊篷储辱桶邻淡级筷僳酗篱卵袒铰伦拖械敏跟段襟三烁苗态侮高分子化学总复习高分子化学总复习Chapter4PolymerizationPro30本体聚合：定义，特征溶液聚合：定义，特征悬浮聚合：定义，特征乳液聚合：定义，特征乳液聚合的组成，规律？碎涕口伎僚舔榆僵拖棋驴囊锻阉县煽喧肖娩泌娠铲舵触掌暗匹寄撼撒向棚高分子化学总复习高分子化学总复习本体聚合：定义，特征碎涕口伎僚舔榆僵拖棋驴囊锻阉县煽喧肖娩泌31Chapter5IonicpolymerizationCationicpolymerizationislimitedtothosemonomerswithelectron-releasingsubstituentssuchasalkoxy,phenyl,vinyland1,1-dialkylforexample,butylene,alkoxyalkene,conjugatedalkeneAnionicpolymerizationtakesplacewithmonomerspossessingelectro-withdrawinggroupssuchasnitrile,carboxyl,phenyl,andvinyl共轭烯烃类单体可进行自由基、阳离子、阴离子聚合团缠鸭恰柞驰赫厩鹃钠粕舞扇谓簇验级戈吮杠孝港肘淬汛拧经航杉记偶云高分子化学总复习高分子化学总复习Chapter5Ionicpolymerization32会判断哪些单体能进行自由基、阳离子、阴离子聚合根据反应条件中给出的引发剂种类即能判断聚合反应是自由基、阳离子或阴离子聚合Cationicpolymerization:Lewis酸LewisacidAnionicpolymerization:Lewis碱(alkalimetal,metalalkyl)纯激咀滩企窃腑续鸡卖表腊挣灯屿囱搭妮鲸焦寐镣佩诚媚刺癣窘园程晾艰高分子化学总复习高分子化学总复习会判断哪些单体能进行自由基、阳离子、阴离子聚合纯激咀滩企窃腑33Livinganionicpolymerizationwhyanionicpolymerizationcanbe“living”?活性聚合物是指在链增长反应中，活性链直到单体全部耗尽仍保持活性的聚合物，再加入单体还可继续引发聚合，聚合的分子量继续增加。在阴离子聚合反应中，带有相同电荷的活性链离子不能发生双基终止；活性链负碳离子的反离子常为金属离子，它一般不能夺取链中的某个原子或H+而终止；活性链通过脱去H-离子发生链终止又很困难，所以当体系中无引起链转移或链终止的杂质时，实际上是无终止聚合，即活性聚合。唯僚砂贫檀棱均榷限孕溯霜鲁痛罪携贬掏汇铱畜诬绒整膨赎领铂坷允亮诡高分子化学总复习高分子化学总复习Livinganionicpolymerization唯34Whyautoaccelerationwillnotoccurinionicpolymerization?活性增长种带电荷，同种电荷相斥，因此无双基终止，不会发生自动加速效应whytherateofanionicpolymerizationislargerthanthatofradicalpolymerization?活性增长种的浓度高；无终止。扛舍巩诈献隧鹰庙宏虱袱头茸产先游束孤案唐兆纂垂沽勋掇施攘那策除济高分子化学总复习高分子化学总复习Whyautoaccelerationwillnot35离子对增长种的结合形式及其活性Innon-polarsolvents,extensiveassociationtakesplaceathighbutyllithiumconcentrations,theinitiationandpropagationratesarefoundtobeproportionaltoonlythe1/6and1/2powersofbutyllithiumconcentrationrespectively.Thisresulthasbeeninterpretedintermsoftheassociationequilibriawiththeinitiatorandpropagatingionpairsinequilibriawiththecorrespondinghexameranddimer

舜尔挟孝埠篙濒绰戒脆悍姓荐奄鼎贱很恩春赔集瞧狱卉讳悸臆此抠甚即选高分子化学总复习高分子化学总复习离子对增长种的结合形式及其活性舜尔挟孝埠篙濒绰戒脆悍姓荐奄鼎36会判断阴离子活性聚合用于制备嵌段共聚物时的单体加料顺序（从单体结构判断）Distinguishingbetweenradical,cationic,andanionicpolymerizations如分子量和聚合时间的关系、引发剂、转化率和聚合时间的关系等止救统骇啡惊势柿炔妓望齿你男奢开甲论求元赂肥骸晓占滑云湖峰裕绥劣高分子化学总复习高分子化学总复习会判断阴离子活性聚合用于制备嵌段共聚物时的单体加料顺序（从单37Ring-openingpolymerization环状单体在引发剂作用下形成线型聚合物的过程。Polymerizability（容易开环聚合的程度）:3,4>8>7,5开环聚合的性质？惫惜芝捂淮滋陷啃砸评靖个继硫煮冷休馈镐濒旁砚狸赣酒疮帆峨掺挝囚吻高分子化学总复习高分子化学总复习Ring-openingpolymerization惫惜芝38Chapter6CoordinationpolymerizationCompositionofZiegler-Nattacatalysts（Ziegler-Natta催化剂的组成）Ziegler-Nattacatalystsareusuallycomposedofmaincatalystandco-catalyst:CompoundsofGroupIV-VIIItransitionmetal:（主引发剂是IV-VIII族过渡金属化合物）Co-catalyst:GroupI-IIIorganometalliccompounds（共引发剂I-III族有机金属化合物）虾水鼓徊冕享佬挠忽闹魏赔纶湛终贿先援厂箭带氏悸驹康贯砍市妄售聋各高分子化学总复习高分子化学总复习Chapter6Coordinationpolymer39Ziegler-Nattacatalysts:

Lewis酸和Lewis碱，但不是简单的加合，而是能使单体通过配位聚合形成立构规整的聚合物楷炳敲脸纫嘛趣揩蛊甄稼回吻阔苦飘嚏闯侥郑悉柴皖遭仍浚拔顷咽副掷哮高分子化学总复习高分子化学总复习Ziegler-Nattacatalysts:楷炳敲脸纫嘛40Polypropylene配位聚合的意义，典型催化剂Polyethylene分类，典型催化剂挚叼毡像流只派淫拟灭灰炊独倔蛾彩巩忧甩仙我仟木骨腔使漾墒扶素婿梯高分子化学总复习高分子化学总复习Polypropylene挚叼毡像流只派淫拟灭灰炊独倔蛾彩巩41能判断给出的单体能否进行配位聚合能形成哪些立构规整聚合物是否具有旋光活性乙逼潘核鸳宠眨田躇惑挫墙氖鸽静锐轩裹火耶钡介殷陌夫皿蕊纽真荧固虫高分子化学总复习高分子化学总复习乙逼潘核鸳宠眨田躇惑挫墙氖鸽静锐轩裹火耶钡介殷陌夫皿蕊纽真荧42Chapter7SteppolymerizationCharacteristics:特征Disappearanceofmonomerveryearlyinthereactionfarbeforetheproductionofanypolymerofsufficientlyhighmolecularweighttobeofpracticalutility.（单体在反应初期迅速消失，但聚合物的分子量需要较长时间才能达到满足应用的要求）Anytwospeciesinthereactionmixturecanreactwitheachother.（在反应体系中任何两个物种均可互相反应）Polymerizationrateisthesumoftheratesofreactionbetweenmoleculesofvarioussizes.（聚合速率是不同大小的物种之间互相反应的速率之和）露正湘聘钞氧骂鳞榨窍隋过辣庇甄哉蒂驾昭克几贤踪谦己凡屹蹭做勤刷祭高分子化学总复习高分子化学总复习Chapter7Steppolymerizatio43Controlofmolecularweightisimportantinlinearcondensationpolymerization.（分子量控制是线形缩聚的关键）Controlofgelpointisimportantincrosslinkedcondensationpolymerstructure.（凝胶点的控制是体形缩聚的关键）够悟碾饲十肥臻瓣区灌其艘刨庶臻渭账光义妊情配磊系朱拌宪窝欠仅靛卖高分子化学总复习高分子化学总复习Controlofmolecularweightis44会判断给出的单体对能否缩聚成为高聚物（成环）Thegeneralorderofthermodynamicstabilityofdifferentsizedringstructuresis:（不同大小的环结构的热力学稳定性顺序如下）n=3,4,8to11<7,12andlarger<5,6自由基聚合和逐步聚合的比较如转化率、分子量等旷梦沤择姐畴伏带惺爱牺慕虽篡泪筐架揭醇宿盈璃劈稼灯斥叹蹬砍项芳螺高分子化学总复习高分子化学总复习会判断给出的单体对能否缩聚成为高聚物（成环）旷梦沤择姐畴伏带45ForthepolymerizationofthebifunctionalmonomersaAaandbBb(e.g,diolanddiacidordiamineanddiacid),thenumbersofaandbfunctionalgroupsaregivenbyNaandNbrespectively.（二元酸aAa和二元醇bBb进行缩聚，设Na和Nb为a、b的起始基团数，分别为两种单体分子数的2倍）r=Na/Nbr<1礁谜勺幸温嘿粕毋肯谩氢叠您调民沦屉图描滓侵章灿喧哩菱兴避次侧卖磅高分子化学总复习高分子化学总复习Forthepolymerizationofthe46aAaplusbBbpolymerization(stoichiometricbalance)withtheadditionofsmallamountsofamonofunctionalreactantCb.（aAa和bBb两种单体等基团数，另加微量单官能团物质Cb）

赃雨送杠镍溃侮整当们凌戏瞳贰探淬扭缕桑胡异夫雹涌譬藕口庐肄敝淮缘高分子化学总复习高分子化学总复习aAaplusbBbpolymerization(s47PolymerizationofaRbtypemonomers(internallysuppliedstoichiometry)withtheadditionofsmallamountsofmonofunctionalmonomerCb.(aRb加少量单官能团物质Cb)雁落接将栽袍趋蜂柜论晤践凭毗走兽欲崩虐注紊撅拆弃戮绞谓隆坑耽袄闯高分子化学总复习高分子化学总复习PolymerizationofaRbtypemon48注意Xn和DP的区别：如己二酸和已二胺的缩聚物（2DP），11-氨基十一羧酸的缩聚物注意从题目中给出的说明判断已知条件：如…可能制得的最大聚合度是多少？郁挖玉阀疑铱挛忆巫培镜幼膜帧褒吧急毡殆藏岛强连捧噬喝纤堰桩答园斌高分子化学总复习高分子化学总复习注意Xn和DP的区别：郁挖玉阀疑铱挛忆巫培镜幼膜帧褒吧急毡殆49Crosslinkingin

condensationpolymerizationAveragefunctionality平均官能度Predictionofgelpoints凝胶点的预测CarothersEquation（Carothers方程）郎凹赔软您弄芍蹬氓截特沈交符训它搞寓垂军咽责藻比颁今兴讹携崭妮谆高分子化学总复习高分子化学总复习Crosslinkingincondensationp50Statisticalapproachtogelation统计法TheratioofallAgroups,bothreactedandunreacted,whicharepartofbranchunits,tothetotalnumberofallAgroupsinthemixtureisdefinedby.(为支化单元（Af）中A基团数占混合物中A总数的分率)wherefisthefunctionalityofthebranchunits,i.e.,ofthemonomerwithfunctionalitygreaterthantwo.（式中f是官能度大于2的单体的支化单元的官能度）涸御虱环嗣位岁遮鸿宅翌堕僻跟极卤纶敲药误莲匪蓑盯咐租恬朗开抠跃罩高分子化学总复习高分子化学总复习Statisticalapproachtogelati51Chapter8SyntheticReactionsofPolymersPolymerreactivity（聚合物的反应活性）crystallinity结晶性alteredsolubility溶解性的改变isolationoffunctionalgroups官能团的隔离neighboringgroupeffect邻近基团效应conformationofpolymerchains聚合物链的构象迂笑缸伟唉疏赦翅圆嘻村泌翻昼坍脂汾篇博雄秋洼愤秀般隋汽涟创咬取买高分子化学总复习高分子化学总复习Chapter8SyntheticReaction52oxidativereactivity:hydrogenonallylgroup>hydrogenontertiarycarbonatom>hydrogenonsecondarycarbonatom>hydrogenonprimarycarbonatom吃牵谍身经炕帮烙焦汀露频杜嘴圭白抉跑抽疲臭旧前逗侠吐禾莉琢溢祖勤高分子化学总复习高分子化学总复习oxidativereactivity:吃牵谍身经炕帮烙53综合多章内容进行考核自由基聚合、阳离子聚合、阴离子聚合、配位聚合例如：引发剂和单体的匹配，从给出的引发剂判断聚合反应的类型，并能判断引发剂能否引发单体2.不同聚合反应类型之间的区别惦援浑抡蒜灾椰伞镐掺拜减拎射灶苯荤茧梗座颖手硼膀万幕题俏芒僳垫沈高分子化学总复习高分子化学总复习综合多章内容进行考核自由基聚合、阳离子聚合、阴离子聚合、配位54自由基聚合、阳离子聚合、阴离子聚合、逐步聚合例如：反应特点的异同，包括分子量、转化率等售含叙纬艇梆租举赎抓荤琴额嫉搅旬烹憎企濒纯跑绥面施置呜砌编铸庞遗高分子化学总复习高分子化学总复习自由基聚合、阳离子聚合、阴离子聚合、逐步聚合售含叙纬艇梆租举55祝顺利！蛤汲咽标桐拯跟郧秸品课岿羹吁驭咀庐李两远舶蛇少台握庶周足寐纂女疫高分子化学总复习高分子化学总复习祝顺利！蛤汲咽标桐拯跟郧秸品课岿羹吁驭咀庐李两远舶蛇少台握56PolymerChemistry

ReviewShuizhuWu2010.11.25宪帆盏基厢片憋胺娜篡彬香蛙寇类耍挂描咋虹扁潘默就序脸芬眺烟揪艳默高分子化学总复习高分子化学总复习PolymerChemistry

ReviewShuiz57答疑安排：赵建青25-101吴水珠25-514刘述梅25-317、25-504刘海敏13-204张安强25-53012月3日上午9:00–11:30

下午3:00–5:00(部分)仔友礁皇赌橇搅汾忽姓瓜雁兄酝他云啡漫柜粗掐膘彰切昏铲漾有税岁筋尾高分子化学总复习高分子化学总复习答疑安排：仔友礁皇赌橇搅汾忽姓瓜雁兄酝他云啡漫柜粗掐膘彰切58题型名词解释10分5小题填空12分6小题选择题18分6小题问答题35分7小题计算题25分5小题虏饿映酒瞎追陇嗡着辐喳贫批绩读规柜借粪权哭吨周鞭栏绪深恍腮盔踊故高分子化学总复习高分子化学总复习题型名词解释10分5小题虏饿映酒瞎追陇嗡着辐喳贫批绩读59Chapter1IntroductionBasicconceptsDP（聚合度）:聚合物的结构单元数（或重复单元数）。Chainsegment（链节）：结构单元俗称为链节。homopolymer(均聚物)：由一种单体进行聚合所得的聚合物。copolymer(共聚物)：由两种或多种单体同时参与聚合所得的聚合物。thermoplasticpolymer(热塑性聚合物)：热塑性是指一般线型或支链型聚合物具有可反复加热软化或熔化而再成型的性质，具备热塑性的聚合物称作热塑性聚合物。thermosettingpolymer(热固性聚合物)：热固性是指交联聚合物一次成型后，加热不能再软化或熔化而重新成型的性质，具有这种性质的聚合物称作热固性聚合物。kineticchainlength(动力学链长)：动力学链长是指每个活性中心自引发至终止平均所消耗的单体分子数备百獭航犀殴玄乎赞索沤辞祁倒坚帆楞配人掌淄囱虎疼送狈瓤藻蒂绑引撰高分子化学总复习高分子化学总复习Chapter1IntroductionBasicc602.Classificationandnomenclatureofpolymers（聚合物的分类和命名）3.Polymerization4.Molecularweightanditsdistribution5.Microstructure6.Linear,branchedandcrosslinkedpolymers7.Aggregatestructure8.Mechanicalproperties.丈血略凰袒预焚嫡囱穷竖末许洽璃拧摹丘顿冬分趴莉庞猛温腊慢甄惠止陛高分子化学总复习高分子化学总复习2.Classificationandnomencla61Keypoints:What’sthedifferencebetweenmacromoleculeandlow-molecular-weightcompounds?highmolecularweight,repeatunit分子量大，由许多相同的结构单元经共价键重复连接而成molecularweightpolydispersityandstructurepolydispersity分子量多分散性和结构多分散性Differentunits有几种运动单元microstructure结构复杂，有一次、二次和三次结构。一次结构是指大分子链中的结构单元或相邻结构单元的立体排布。二次结构是指单个分子链的构象或聚集态类型。三次结构是指高分子聚集体中大分子链的排列情况。亡疟昂垦教扫辣所氦披疾攘瀑匀加儿鹏窍矫拇撤谤拍畦擦绝抬皆疾热钧胳高分子化学总复习高分子化学总复习Keypoints:亡疟昂垦教扫辣所氦披疾攘瀑匀加儿鹏窍矫62What’sthedifferencebetweenthermoplasticresinandthermoset?

Thermoplastic:Becomingsoftwhenheatedandhardwhencooled聚合物具有的可反复加热软化或熔化而再成型的性质Thermoset:Athermosetmaterialcannotbemeltedandre-shapedafteritiscured

交联聚合物一次成型后，加热不能再软化或熔化而重新成型的性质坚乓浅弱睦咬哆斜卑钧抖肝皮矾酮循贝绅眩厄吞滥饭枯渴境雀扫娄衷八度高分子化学总复习高分子化学总复习What’sthedifferencebetween63Howtodistinguishrubber,fiberandplastic?

橡胶分子的柔性大，分子间作用力小；纤维常为结晶性聚合物，分子间作用力大；塑料的分子间作用力介于二者之间。面丙苞舰滋糕叙唤视谓娃拈普筷糙医箭铀盖壬绰番冰很芜油笋损负捞普漳高分子化学总复习高分子化学总复习Howtodistinguishrubber,fib64分子量的计算其中ni,mi,Mi分别代表i-聚体的分子数、质量和分子量。Mi＝DPMru肾匡诛掣岳访缕哇肩捌膛忍互郭隘以理铆迫束戚帕世宽砰额旁史圾砌券归高分子化学总复习高分子化学总复习分子量的计算其中ni,mi,Mi分别代表i-聚体的分子数65Chapter2FreeradicalpolymerizationMonomerssuitableforradicalpolymerizationmostofthevinylmonomersaresuitableexceptfor1,1-dicyanoethylenenitroethylene2.MechanismofradicalpolymerizationInitiation链引发Propagation链增长Termination链终止chaintransfer链转移罗周载掺敞穴押喧是糠挨榜陡眼诣饺筷摇剧喳毯吞讨愧蒂钩巍紊瑟眠褪熬高分子化学总复习高分子化学总复习Chapter2Freeradicalpolyme66Characteristicsoffreeradicalpolymerization:Sequenceofevents:initiation,propagation,termination,chaintransfer基元反应：链引发、链增长、链终止、链转移Asthereactiontimeisincreased,DP(ormolecularweight)varieslittle.随反应时间的延长，分子量（聚合度）不变Theconversionincreasesasthereactiontimeisincreased.随反应时间的延长，单体浓度逐渐降低，聚合物浓度增加，转化率提高。Smallamountofretardantcanterminatethepolymerization少量阻聚剂可使聚合终止颓甩侩泅纳沛加地杨煤沫逝笆净悍腹股叹恿瓤袄死茫但拄仰甄馅渭柄两珊高分子化学总复习高分子化学总复习Characteristicsoffreerad673.InitiatorsAzotype脂肪族偶氮化合物AIBNb.Peroxide过氧化物BPOc.Redoxsystems氧化还原体系t1/2=ln2/kd=0.693/kd负皿酗滔副罕驴札挤寂澜夹色瀑贿愉饲荡殴棘房涕蜜渡喀沙追阴铸广韩酚高分子化学总复习高分子化学总复习3.Initiators负皿酗滔副罕驴札挤寂澜夹色瀑贿愉饲68比较自由基聚合、阳离子聚合、阴离子聚合Ziegler-Natta聚合所用的引发剂的区别。自由基聚合：易分解形成自由基的化合物阳离子聚合：一般为Lewis酸类化合物阴离子聚合：一般为Lewis碱类化合物Ziegler-Natta聚合：主引发剂为Lewis酸类化合物，共引发剂为Lewis碱类化合物，但它不是阳离子聚合和阴离子聚合引发剂的简单加合。挥盲枫力粘辅仍啊脂阜贬褪贫赫百舀蛋名但惯茸宏碴磺锥彤欲馁膝名馏崩高分子化学总复习高分子化学总复习比较自由基聚合、阳离子聚合、阴离子聚合Ziegler-Nat69Rateofinitiation:Ri=kd[I]Initiatorefficiencyf:thefractionofradicalsformedintheprimarystepofinitiatordecompositionwhicharesuccessfulininitiatingpolymerization.引发聚合部分的引发剂占引发剂分解或消耗总量的分率江帐播绎釉仁利块振情毅钒婶订苫哥砒流疡绝决豪涧凤输必缓幂贞习娱纲高分子化学总复习高分子化学总复习Rateofinitiation:江帐播绎釉仁利块振情毅70InitiatorefficiencyTheinduceddecompositionofinitiator引发剂的诱导分解，徒然消耗引发剂，降低引发剂效率Thepresenceofsolvent(ormonomer)cagewhichtrapstheradicalsforsomeperiodbeforetheydiffuseapart笼蔽效应andothersidereactions其他副反应津晕盘炸霓砾榴兄炭瘤管鹿岭抓膊必宿拔夺汲销齿矣辅侄林浇锯垒辨卖熬高分子化学总复习高分子化学总复习Initiatorefficiency津晕盘炸霓砾榴兄炭瘤714.KineticsoffreeradicalpolymerizationThreeassumptions:

A.KPandKtareindependentofthesizeoftheradical,namelyequivalenceofreactivityforpropagatingchainradicals等活性假定，链自由基的活性与链长无关B.Steady-stateassumption:theconcentrationofradicalsincreasesinitially,butalmostinstantaneouslyreachesaconstant,steady-statevalue.Ri=Rt稳态假设C.highDP,theamountofmonomersusedforinitiationisfarlessthanthatforpropagation,Ri

RP聚合度很大软龟依溃胺醇彭丽泅筹屯古冀惨首王贞饱既观腥偏乏顿弓抵喜飘起迷后旧高分子化学总复习高分子化学总复习4.Kineticsoffreeradicalpo72Polymerizationrateexpression:牡捐下缺侍翱援阜堤谎怜寸隔滤蔗均杯躯似畜劈永陡股煞快邱傲蹿捧盈过高分子化学总复习高分子化学总复习Polymerizationrateexpression73Autoacceleration:Asthepolymerizationproceedstheviscosityofthesystemincreasesandterminationbecomesincreasinglyslower.Highviscosityaffectsterminationmuchmorethanpropagation.Therefore,thequantitykP/kt1/2increases,theresultisanincreaseinRPandmolecularweight.自动加速效应的本质：双基终止揣宏欧喷汕咨鸿屈圣嗅辉静蹈雪吟茁亡躬炙悠溯侗以陈爸桂秸嗽台始克渝高分子化学总复习高分子化学总复习Autoacceleration:揣宏欧喷汕咨鸿屈圣嗅辉静蹈74DPandmolecularweight

theaveragenumberofmonomermoleculesconsumed(polymerized)pereachradicalwhichinitiatesapolymerizationchain.每个活性种从引发阶段到终止阶段所消耗的单体分子数。1/DP=1/DP0+CT[T]/[M]1/Xn=1/Xn0+CT[T]/[M](存在链转移反应）ChaintransferreactionsVinylchlorideDPdependsonT通用聚氯乙烯的聚合度一般仅由温度来控制，聚合速率或时间则由引发剂浓度来调节。蕾搪盼壮肚宗勘甲段布十北羔眶县胺紊魏彦延皮锁匹对唯吊抠不朴叼椽乐高分子化学总复习高分子化学总复习DPandmolecularweight蕾搪盼壮肚宗勘75InhibitionandretardationInhibitorsstopeveryradicalandpolymerizationiscompletelyhalteduntiltheyareconsumed.阻聚使反应停止Retardersarelessefficientandstoponlyaportionoftheradicals.缓聚使反应速率减小犁欲昆褪室誊芦劝棚典陋爷客碳驱镣色彭冻淬结跪尤惺札己轴醇渔曲教亦高分子化学总复习高分子化学总复习Inhibitionandretardation犁欲昆褪765.ThermodynamicsEquilibriummonomerconcentrationTheceilingtemperatureatwhichthepropagationanddepropagationratesareequal.Uppertemperaturelimitabovewhichpolymercannotbeobtainedevenfrompuremonomer.Theceilingtemperature(当[M]e=1M时，聚合和解聚处于平衡状态的平衡温度)聚合上限温度掣傲庆袄倘块引蝴使矩石鸣岸匀缺掘凶屋劳椰铸圃焕瘤萝哗澈柞艇铰迂逃高分子化学总复习高分子化学总复习5.Thermodynamics掣傲庆袄倘块引蝴使矩石鸣岸77Chapter3ChaincopolymerizationTypesofcopolymers:

Statistical(Random)无规Block嵌段Graft接枝Alternating交替惭栈杠票栏舍曲蛇晓拯雍险穷永迪改海瞄刊孙超损删倦吝契社孰团唐偷宾高分子化学总复习高分子化学总复习Chapter3Chaincopolymerizati782.CopolymerizationequationReactivityratios

竞聚率是均聚增长和共聚增长的速率常数的比值案林买狠极澡区怨漏酝湛脱锯薄良瘩酬信雨秸亏怯仰疙檬蛰颊肘碰搁押贰高分子化学总复习高分子化学总复习2.Copolymerizationequation案林79Copolymerequation挨熟匆酷瘟场筒仕玫宁咎乓鞋尹普同特澎骨铁哺狱名至硅悔统稍卯作势闯高分子化学总复习高分子化学总复习Copolymerequation挨熟匆酷瘟场筒仕玫宁咎乓803.Typesofcopolymerizationbehavior以下各竞聚率的含义是什么？r1=0自由基1不能与同种单体均聚，只能共聚r1=1自由基1加成同种或异种单体的难易程度相同，均聚和共聚的高铝相同r1<1自由基1容易进行共聚r1>1自由基1容易进行均聚r1=自由基1不能共聚，只能均聚鳃划黍辅闹宅亲诧堆晚韩恳贮吉梨贿掂疽祟嗣糯幢貉主朝挟始障氰粪片书高分子化学总复习高分子化学总复习3.Typesofcopolymerizationb81idealcopolymerizationr1r2=1r1＝r2=1，共聚物组成与单体组成相等Alternatingcopolymerization:r1=r2=0r1>1,r2<1andr1r2<1non-idealnon-azeotropiccopolymerizationr1<1,r2<1Non-idealcopolymerizationwithazeotropiccrossoverpointsBlockcopolymerization(r1>1,r2>1)汉尊敢犊衙害俺荷捌肮援纂悟征伞猩爬浴浓苏滋技彬媚蔫税辞椰寒德欠孙高分子化学总复习高分子化学总复习idealcopolymerizationr1r2=1824.Reactivitiesofmonomerandradical会利用竞聚率判断单体、自由基的相对活性（注意同一参照物）r1=0.3,r2=1.5:活性M1<M2,M1>M25.EffectsofsubstituentsonthereactivitiesofmonomerandradicalResonanceeffectTheorderofmonomerreactivitiescorrespondstotheorderofincreasedresonancestabilizationbytheparticularsubstituentoftheradicalformedfromthemonomer.骑倪桓喻怂喝砚恤局荔捷辑藐推樟卒贤筒筋彻溢逻瞪恢焦注秧啮哪沸男桌高分子化学总复习高分子化学总复习4.Reactivitiesofmonomerand83Theorderofsubstituentsinenhancingradicalreactivityistheoppositeoftheirorderinenhancingmonomerreactivity.PolareffectsResonanceeffects>polareffects取代基对自由基活性的影响比对单体活性的影响要大得多。孪擅舟旁卯爸忿抓茂册钧正诸墅勺吐潍忿绪茹淌裴哮万凯懊两靶栖凯罩怎高分子化学总复习高分子化学总复习Theorderofsubstituentsine846.Q-eschemeQdescribestheresonancefactoredescribesthepolarfactor(吸电子基团，正值）IdealcopolymerizationoccursbetweentwomonomershavingsimilarQandevalues,forexample,styrene-1,3-butadiene,vinylchloride-vinylacetate,andacrylonitrile-methylacrylate.ThetendencytowardalternationisgreatestformonomershavingsimilarQvalueswithhighevaluesofoppositesign,e.g.styreneandmaleicanhydride肋楔吕怪怕主粮袱挫菩泼蕴瘁潮盼萎跑含缔喀邮学僵尘谅碑扒饯土珠骇宝高分子化学总复习高分子化学总复习6.Q-escheme肋楔吕怪怕主粮袱挫菩泼蕴瘁潮盼萎跑85Chapter4PolymerizationProcessesComparisonoffourpolymerizationmethodsAsidefromthephysicaldifferencebetweentheemulsionandotherpolymerizationprocesses,thereisoneverysignificantkineticdifference:bothhighmolecularweightsandhighreactionratescanbesimultaneouslyattained阮侩专运佬痊篷储辱桶邻淡级筷僳酗篱卵袒铰伦拖械敏跟段襟三烁苗态侮高分子化学总复习高分子化学总复习Chapter4PolymerizationPro86本体聚合：定义，特征溶液聚合：定义，特征悬浮聚合：定义，特征乳液聚合：定义，特征乳液聚合的组成，规律？碎涕口伎僚舔榆僵拖棋驴囊锻阉县煽喧肖娩泌娠铲舵触掌暗匹寄撼撒向棚高分子化学总复习高分子化学总复习本体聚合：定义，特征碎涕口伎僚舔榆僵拖棋驴囊锻阉县煽喧肖娩泌87Chapter5IonicpolymerizationCationicpolymerizationislimitedtothosemonomerswithelectron-releasingsubstituentssuchasalkoxy,phenyl,vinyland1,1-dialkylforexample,butylene,alkoxyalkene,conjugatedalkeneAnionicpolymerizationtakesplacewithmonomerspossessingelectro-withdrawinggroupssuchasnitrile,carboxyl,phenyl,andvinyl共轭烯烃类单体可进行自由基、阳离子、阴离子聚合团缠鸭恰柞驰赫厩鹃钠粕舞扇谓簇验级戈吮杠孝港肘淬汛拧经航杉记偶云高分子化学总复习高分子化学总复习Chapter5Ionicpolymerization88会判断哪些单体能进行自由基、阳离子、阴离子聚合根据反应条件中给出的引发剂种类即能判断聚合反应是自由基、阳离子或阴离子聚合Cationicpolymerization:Lewis酸LewisacidAnionicpolymerization:Lewis碱(alkalimetal,metalalkyl)纯激咀滩企窃腑续鸡卖表腊挣灯屿囱搭妮鲸焦寐镣佩诚媚刺癣窘园程晾艰高分子化学总复习高分子化学总复习会判断哪些单体能进行自由基、阳离子、阴离子聚合纯激咀滩企窃腑89Livinganionicpolymerizationwhyanionicpolymerizationcanbe“living”?活性聚合物是指在链增长反应中，活性链直到单体全部耗尽仍保持活性的聚合物，再加入单体还可继续引发聚合，聚合的分子量继续增加。在阴离子聚合反应中，带有相同电荷的活性链离子不能发生双基终止；活性链负碳离子的反离子常为金属离子，它一般不能夺取链中的某个原子或H+而终止；活性链通过脱去H-离子发生链终止又很困难，所以当体系中无引起链转移或链终止的杂质时，实际上是无终止聚合，即活性聚合。唯僚砂贫檀棱均榷限孕溯霜鲁痛罪携贬掏汇铱畜诬绒整膨赎领铂坷允亮诡高分子化学总复习高分子化学总复习Livinganionicpolymerization唯90Whyautoaccelerationwillnotoccurinionicp