高分子化学总复习课件

1、Polymer ChemistryReviewShuizhu Wu2010.11.25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第1页，共56页。 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25-530 12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第2页，共56页。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

2、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第3页，共56页。Chapter 1 Introduction Basic concepts DP（聚合度）: 聚合物的结构单元数（或重复单元数）。Chain segment（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。 thermoplastic polymer(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

3、的性质，具备热塑性的聚合物称作热塑性聚合物。 thermosetting polymer (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。 kinetic chain length(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第4页，共56页。2. Classification and nomenclature of polymers（聚合物的分类和命名）3. Polymerization4

4、. Molecular weight and its distribution5. Microstructure6. Linear, branched and crosslinked polymers7. Aggregate structure8. Mechanical properties.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第5页，共56页。Key points:Whats the difference between macromolecule and low-molecular-weight compounds?high mo

5、lecular weight, repeat unit 分子量大，由许多相同的结构单元经共价键重复连接而成molecular weight polydispersity and structure polydispersity分子量多分散性和结构多分散性Different units 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

6、总复习第6页，共56页。Whats the difference between thermoplastic resin and thermoset? Thermoplastic: Becoming soft when heated and hard when cooled 聚合物具有的可反复加热软化或熔化而再成型的性质Thermoset: A thermoset material cannot be melted and re-shaped after it is cured 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

7、衷八度高分子化学总复习高分子化学总复习第7页，共56页。How to distinguish rubber, fiber and plastic? 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第8页，共56页。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。MiDPMru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第9页，共56页。Chapter 2 Free

8、radical polymerizationMonomers suitable for radical polymerization most of the vinyl monomers are suitable except for 1,1-dicyanoethylene nitroethylene2. Mechanism of radical polymerizationInitiation 链引发Propagation 链增长Termination 链终止 chain transfer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第

9、10页，共56页。 Characteristics of free radical polymerization:Sequence of events: initiation, propagation, termination, chain transfer 基元反应：链引发、链增长、链终止、链转移As the reaction time is increased, DP (or molecular weight) varies little. 随反应时间的延长，分子量（聚合度）不变The conversion increases as the reaction time is increas

10、ed. 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。Small amount of retardant can terminate the polymerization 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第11页，共56页。3. InitiatorsAzo type 脂肪族偶氮化合物 AIBNb. Peroxide 过氧化物 BPOc. Redox systems 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

11、学总复习高分子化学总复习第12页，共56页。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第13页，共56页。Rate of initiation: Ri=kdIInitiator efficiency f

12、: the fraction of radicals formed in the primary step of initiator decomposition which are successful in initiating polymerization. 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第14页，共56页。Initiator efficiencyThe induced decomposition of initiator 引发剂的诱导分解，徒然消耗引发剂，降低引发剂效率The

13、 presence of solvent (or monomer) cage which traps the radicals for some period before they diffuse apart 笼蔽效应 and other side reactions 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第15页，共56页。4. Kinetics of free radical polymerizationThree assumptions: A. KP and Kt are independent of the size

14、 of the radical, namely equivalence of reactivity for propagating chain radicals 等活性假定，链自由基的活性与链长无关 B. Steady-state assumption: the concentration of radicals increases initially, but almost instantaneously reaches a constant, steady-state value. Ri=Rt 稳态假设 C. high DP, the amount of monomers used for

15、 initiation is far less than that for propagation, 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第16页，共56页。Polymerization rate expression: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第17页，共56页。Autoacceleration: As the polymerization proceeds the viscosity of the system increases and

16、termination becomes increasingly slower. High viscosity affects termination much more than propagation. Therefore, the quantity kP/kt1/2 increases, the result is an increase in RP and molecular weight.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第18页，共56页。DP and molecular weight the

17、 average number of monomer molecules consumed (polymerized) per each radical which initiates a polymerization chain. 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 + CTT/M 1/Xn= 1/Xn0 + CTT/M (存在链转移反应）Chain transfer reactions Vinyl chloride DP depends on T 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

18、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第19页，共56页。Inhibition and retardation Inhibitors stop every radical and polymerization is completely halted until they are consumed.阻聚使反应停止 Retarders are less efficient and stop only a portion of the radicals. 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

19、习第20页，共56页。5. Thermodynamics Equilibrium monomer concentration The ceiling temperature at which the propagation and depropagation rates are equal.Upper temperature limit above which polymer cannot be obtained even from pure monomer.The ceiling temperature ( 当Me=1 M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

20、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第21页，共56页。Chapter 3 Chain copolymerization Types of copolymers: 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第22页，共56页。2. Copolymerization equationReactivity ratios 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

21、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第23页，共56页。Copolymer equation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第24页，共56页。3. Types of copolymerization behavior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

22、习高分子化学总复习第25页，共56页。ideal copolymerization r1r2=1 r1r2=1， 共聚物组成与单体组成相等Alternating copolymerization: r1=r2=0 r11, r21 and r1r21 non-ideal non-azeotropic copolymerizationr11, r21, r21)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第26页，共56页。4. Reactivities of monomer and radical 会利用竞聚率判断单体、自由基的相对活性（注意

23、同一参照物） r1=0.3, r2=1.5: 活性M1 M25. Effects of substituents on the reactivities of monomer and radicalResonance effectThe order of monomer reactivities corresponds to the order of increased resonance stabilization by the particular substituent of the radical formed from the monomer.骑倪桓喻怂喝砚恤局荔捷辑藐推樟卒贤筒筋彻

24、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第27页，共56页。The order of substituents in enhancing radical reactivity is the opposite of their order in enhancing monomer reactivity.Polar effectsResonance effects polar effects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第28页，共56页。6. Q-e scheme

25、 Q describes the resonance factor e describes the polar factor(吸电子基团，正值）Ideal copolymerization occurs between two monomers having similar Q and e values, for example, styrene-1,3-butadiene, vinyl chloride-vinyl acetate, and acrylonitrile-methyl acrylate.The tendency toward alternation is greatest fo

26、r monomers having similar Q values with high e values of opposite sign, e.g. styrene and maleic anhydride 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第29页，共56页。Chapter 4 Polymerization ProcessesComparison of four polymerization methodsAside from the physical difference between the emulsion and o

27、ther polymerization processes, there is one very significant kinetic difference:both high molecular weights and high reaction rates can be simultaneously attained 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第30页，共56页。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

28、撼撒向棚高分子化学总复习高分子化学总复习第31页，共56页。Chapter 5 Ionic polymerizationCationic polymerization is limited to those monomers with electron-releasing substituents such as alkoxy, phenyl, vinyl and 1,1-dialkyl for example, butylene, alkoxy alkene, conjugated alkeneAnionic polymerization takes place with monomers

29、possessing electro-withdrawing groups such as nitrile, carboxyl, phenyl, and vinyl 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第32页，共56页。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Cationic polymerization: Lewis酸Lewis acidAnionic polymerization: Lewis碱 (alk

30、ali metal, metal alkyl)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第33页，共56页。Living anionic polymerization why anionic polymerization can be “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

31、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第34页，共56页。Why autoacceleration will not occur in ionic polymerization? 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why the rate of anionic polymerization is larger than that of radical polymerization? 活性增长种的浓度高；无终止。扛舍巩

32、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第35页，共56页。离子对增长种的结合形式及其活性In non-polar solvents, extensive association takes place at high butyllithium concentrations, the initiation and propagation rates are found to be proportional to only the 1/6 and 1/2 powers of butyllithium concentration respectiv

33、ely. This result has been interpreted in terms of the association equilibria with the initiator and propagating ion pairs in equilibria with the corresponding hexamer and dimer 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第36页，共56页。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）Distinguishing between radica

34、l, cationic, and anionic polymerizations 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第37页，共56页。Ring-opening polymerization 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第38页，共56页。Chapter 6 Coord

35、ination polymerizationComposition of Ziegler-Natta catalysts （ Ziegler-Natta催化剂的组成）Ziegler-Natta catalysts are usually composed of main catalyst and co-catalyst:Compounds of Group IV-VIII transition metal: （主引发剂是IV-VIII族过渡金属化合物）Co-catalyst: Group I-III organometallic compounds （共引发剂I-III族有机金属化合物）虾水鼓

36、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第39页，共56页。Ziegler-Natta catalysts: 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第40页，共56页。Polypropylene 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第41页，共56页。能判断给出的单体能否进

37、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第42页，共56页。Chapter 7 Step polymerizationCharacteristics: 特征 Disappearance of monomer very early in the reaction far before the production of any polymer of sufficiently high molecular weight to be of practical utility. （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） Any two species in the reaction mixture can react with each other. （在反应体系中任何两个物种均可互相反应） Polymerization rate is the sum of the rates of reaction between molecules of various sizes. （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