高分子化學(xué)總復(fù)習(xí)課件

PolymerChemistry

ReviewShuizhuWu2010.11.25憲帆盞基廂片憋胺娜篡彬香蛙寇類耍掛描咋虹扁潘默就序臉芬眺煙揪艷默高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)PolymerChemistry

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下午3:00–5:00(部分)仔友礁皇賭橇攪汾忽姓瓜雁兄醞他云啡漫柜粗掐膘彰切昏鏟漾有稅歲筋尾高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)答疑安排：仔友礁皇賭橇攪汾忽姓瓜雁兄醞他云啡漫柜粗掐膘彰切2題型名詞解釋10分5小題填空12分6小題選擇題18分6小題問答題35分7小題計(jì)算題25分5小題虜餓映酒瞎追隴嗡著輻喳貧批績讀規(guī)柜借糞權(quán)哭噸周鞭欄緒深恍腮盔踴故高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)題型名詞解釋10分5小題虜餓映酒瞎追隴嗡著輻喳貧批績讀3Chapter1IntroductionBasicconceptsDP（聚合度）:聚合物的結(jié)構(gòu)單元數(shù)（或重復(fù)單元數(shù)）。Chainsegment（鏈節(jié)）：結(jié)構(gòu)單元俗稱為鏈節(jié)。homopolymer(均聚物)：由一種單體進(jìn)行聚合所得的聚合物。copolymer(共聚物)：由兩種或多種單體同時(shí)參與聚合所得的聚合物。thermoplasticpolymer(熱塑性聚合物)：熱塑性是指一般線型或支鏈型聚合物具有可反復(fù)加熱軟化或熔化而再成型的性質(zhì)，具備熱塑性的聚合物稱作熱塑性聚合物。thermosettingpolymer(熱固性聚合物)：熱固性是指交聯(lián)聚合物一次成型后，加熱不能再軟化或熔化而重新成型的性質(zhì)，具有這種性質(zhì)的聚合物稱作熱固性聚合物。kineticchainlength(動(dòng)力學(xué)鏈長)：動(dòng)力學(xué)鏈長是指每個(gè)活性中心自引發(fā)至終止平均所消耗的單體分子數(shù)備百獺航犀毆玄乎贊索漚辭祁倒堅(jiān)帆楞配人掌淄囪虎疼送狽瓤藻蒂綁引撰高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Chapter1IntroductionBasicc42.Classificationandnomenclatureofpolymers（聚合物的分類和命名）3.Polymerization4.Molecularweightanditsdistribution5.Microstructure6.Linear,branchedandcrosslinkedpolymers7.Aggregatestructure8.Mechanicalproperties.丈血略凰袒預(yù)焚嫡囪窮豎末許洽璃擰摹丘頓冬分趴莉龐猛溫臘慢甄惠止陛高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)2.Classificationandnomencla5Keypoints:What’sthedifferencebetweenmacromoleculeandlow-molecular-weightcompounds?highmolecularweight,repeatunit分子量大，由許多相同的結(jié)構(gòu)單元經(jīng)共價(jià)鍵重復(fù)連接而成molecularweightpolydispersityandstructurepolydispersity分子量多分散性和結(jié)構(gòu)多分散性Differentunits有幾種運(yùn)動(dòng)單元microstructure結(jié)構(gòu)復(fù)雜，有一次、二次和三次結(jié)構(gòu)。一次結(jié)構(gòu)是指大分子鏈中的結(jié)構(gòu)單元或相鄰結(jié)構(gòu)單元的立體排布。二次結(jié)構(gòu)是指單個(gè)分子鏈的構(gòu)象或聚集態(tài)類型。三次結(jié)構(gòu)是指高分子聚集體中大分子鏈的排列情況。亡瘧昂墾教掃辣所氦披疾攘瀑勻加兒鵬竅矯拇撤謗拍畦擦絕抬皆疾熱鈞胳高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Keypoints:亡瘧昂墾教掃辣所氦披疾攘瀑勻加兒鵬竅矯6What’sthedifferencebetweenthermoplasticresinandthermoset?

Thermoplastic:Becomingsoftwhenheatedandhardwhencooled聚合物具有的可反復(fù)加熱軟化或熔化而再成型的性質(zhì)Thermoset:Athermosetmaterialcannotbemeltedandre-shapedafteritiscured

交聯(lián)聚合物一次成型后，加熱不能再軟化或熔化而重新成型的性質(zhì)堅(jiān)乓淺弱睦咬哆斜卑鈞抖肝皮礬酮循貝紳眩厄吞濫飯枯渴境雀掃婁衷八度高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)What’sthedifferencebetween7Howtodistinguishrubber,fiberandplastic?

橡膠分子的柔性大，分子間作用力??；纖維常為結(jié)晶性聚合物，分子間作用力大；塑料的分子間作用力介于二者之間。面丙苞艦滋糕敘喚視謂娃拈普筷糙醫(yī)箭鈾蓋壬綽番冰很蕪油筍損負(fù)撈普漳高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Howtodistinguishrubber,fib8分子量的計(jì)算其中ni,mi,Mi分別代表i-聚體的分子數(shù)、質(zhì)量和分子量。Mi＝DPMru腎匡誅掣岳訪縷哇肩捌膛忍互郭隘以理鉚迫束戚帕世寬砰額旁史圾砌券歸高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)分子量的計(jì)算其中ni,mi,Mi分別代表i-聚體的分子數(shù)9Chapter2FreeradicalpolymerizationMonomerssuitableforradicalpolymerizationmostofthevinylmonomersaresuitableexceptfor1,1-dicyanoethylenenitroethylene2.MechanismofradicalpolymerizationInitiation鏈引發(fā)Propagation鏈增長Termination鏈終止chaintransfer鏈轉(zhuǎn)移羅周載摻敞穴押喧是糠挨榜陡眼詣餃筷搖劇喳毯吞討愧蒂鉤巍紊瑟眠褪熬高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Chapter2Freeradicalpolyme10Characteristicsoffreeradicalpolymerization:Sequenceofevents:initiation,propagation,termination,chaintransfer基元反應(yīng)：鏈引發(fā)、鏈增長、鏈終止、鏈轉(zhuǎn)移Asthereactiontimeisincreased,DP(ormolecularweight)varieslittle.隨反應(yīng)時(shí)間的延長，分子量（聚合度）不變Theconversionincreasesasthereactiontimeisincreased.隨反應(yīng)時(shí)間的延長，單體濃度逐漸降低，聚合物濃度增加，轉(zhuǎn)化率提高。Smallamountofretardantcanterminatethepolymerization少量阻聚劑可使聚合終止頹甩儈泅納沛加地楊煤沫逝笆凈悍腹股嘆恿瓤襖死茫但拄仰甄餡渭柄兩珊高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Characteristicsoffreerad113.InitiatorsAzotype脂肪族偶氮化合物AIBNb.Peroxide過氧化物BPOc.Redoxsystems氧化還原體系t1/2=ln2/kd=0.693/kd負(fù)皿酗滔副罕驢札擠寂瀾夾色瀑賄愉飼蕩毆棘房涕蜜渡喀沙追陰鑄廣韓酚高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)3.Initiators負(fù)皿酗滔副罕驢札擠寂瀾夾色瀑賄愉飼12比較自由基聚合、陽離子聚合、陰離子聚合Ziegler-Natta聚合所用的引發(fā)劑的區(qū)別。自由基聚合：易分解形成自由基的化合物陽離子聚合：一般為Lewis酸類化合物陰離子聚合：一般為Lewis堿類化合物Ziegler-Natta聚合：主引發(fā)劑為Lewis酸類化合物，共引發(fā)劑為Lewis堿類化合物，但它不是陽離子聚合和陰離子聚合引發(fā)劑的簡單加合。揮盲楓力粘輔仍啊脂阜貶褪貧赫百舀蛋名但慣茸宏碴磺錐彤欲餒膝名餾崩高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)比較自由基聚合、陽離子聚合、陰離子聚合Ziegler-Nat13Rateofinitiation:Ri=kd[I]Initiatorefficiencyf:thefractionofradicalsformedintheprimarystepofinitiatordecompositionwhicharesuccessfulininitiatingpolymerization.引發(fā)聚合部分的引發(fā)劑占引發(fā)劑分解或消耗總量的分率江帳播繹釉仁利塊振情毅釩嬸訂苫哥砒流瘍絕決豪澗鳳輸必緩冪貞習(xí)娛綱高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Rateofinitiation:江帳播繹釉仁利塊振情毅14InitiatorefficiencyTheinduceddecompositionofinitiator引發(fā)劑的誘導(dǎo)分解，徒然消耗引發(fā)劑，降低引發(fā)劑效率Thepresenceofsolvent(ormonomer)cagewhichtrapstheradicalsforsomeperiodbeforetheydiffuseapart籠蔽效應(yīng)andothersidereactions其他副反應(yīng)津暈盤炸霓礫榴兄炭瘤管鹿嶺抓膊必宿拔奪汲銷齒矣輔侄林澆鋸壘辨賣熬高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Initiatorefficiency津暈盤炸霓礫榴兄炭瘤154.KineticsoffreeradicalpolymerizationThreeassumptions:

A.KPandKtareindependentofthesizeoftheradical,namelyequivalenceofreactivityforpropagatingchainradicals等活性假定，鏈自由基的活性與鏈長無關(guān)B.Steady-stateassumption:theconcentrationofradicalsincreasesinitially,butalmostinstantaneouslyreachesaconstant,steady-statevalue.Ri=Rt穩(wěn)態(tài)假設(shè)C.highDP,theamountofmonomersusedforinitiationisfarlessthanthatforpropagation,Ri

RP聚合度很大軟龜依潰胺醇彭麗泅籌屯古冀慘首王貞飽既觀腥偏乏頓弓抵喜飄起迷后舊高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)4.Kineticsoffreeradicalpo16Polymerizationrateexpression:牡捐下缺侍翱援阜堤謊憐寸隔濾蔗均杯軀似畜劈永陡股煞快邱傲躥捧盈過高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Polymerizationrateexpression17Autoacceleration:Asthepolymerizationproceedstheviscosityofthesystemincreasesandterminationbecomesincreasinglyslower.Highviscosityaffectsterminationmuchmorethanpropagation.Therefore,thequantitykP/kt1/2increases,theresultisanincreaseinRPandmolecularweight.自動(dòng)加速效應(yīng)的本質(zhì)：雙基終止揣宏歐噴汕咨鴻屈圣嗅輝靜蹈雪吟茁亡躬炙悠溯侗以陳爸桂秸嗽臺(tái)始克渝高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Autoacceleration:揣宏歐噴汕咨鴻屈圣嗅輝靜蹈18DPandmolecularweight

theaveragenumberofmonomermoleculesconsumed(polymerized)pereachradicalwhichinitiatesapolymerizationchain.每個(gè)活性種從引發(fā)階段到終止階段所消耗的單體分子數(shù)。1/DP=1/DP0+CT[T]/[M]1/Xn=1/Xn0+CT[T]/[M](存在鏈轉(zhuǎn)移反應(yīng)）ChaintransferreactionsVinylchlorideDPdependsonT通用聚氯乙烯的聚合度一般僅由溫度來控制，聚合速率或時(shí)間則由引發(fā)劑濃度來調(diào)節(jié)。蕾搪盼壯肚宗勘甲段布十北羔眶縣胺紊魏彥延皮鎖匹對(duì)唯吊摳不樸叼椽樂高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)DPandmolecularweight蕾搪盼壯肚宗勘19InhibitionandretardationInhibitorsstopeveryradicalandpolymerizationiscompletelyhalteduntiltheyareconsumed.阻聚使反應(yīng)停止Retardersarelessefficientandstoponlyaportionoftheradicals.緩聚使反應(yīng)速率減小犁欲昆褪室謄蘆勸棚典陋爺客碳驅(qū)鐐色彭凍淬結(jié)跪尤惺札己軸醇漁曲教亦高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Inhibitionandretardation犁欲昆褪205.ThermodynamicsEquilibriummonomerconcentrationTheceilingtemperatureatwhichthepropagationanddepropagationratesareequal.Uppertemperaturelimitabovewhichpolymercannotbeobtainedevenfrompuremonomer.Theceilingtemperature(當(dāng)[M]e=1M時(shí)，聚合和解聚處于平衡狀態(tài)的平衡溫度)聚合上限溫度掣傲慶襖倘塊引蝴使矩石鳴岸勻缺掘兇屋勞椰鑄圃煥瘤蘿嘩澈柞艇鉸迂逃高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)5.Thermodynamics掣傲慶襖倘塊引蝴使矩石鳴岸21Chapter3ChaincopolymerizationTypesofcopolymers:

Statistical(Random)無規(guī)Block嵌段Graft接枝Alternating交替慚棧杠票欄舍曲蛇曉拯雍險(xiǎn)窮永迪改海瞄刊孫超損刪倦吝契社孰團(tuán)唐偷賓高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Chapter3Chaincopolymerizati222.CopolymerizationequationReactivityratios

競聚率是均聚增長和共聚增長的速率常數(shù)的比值案林買狠極澡區(qū)怨漏醞湛脫鋸薄良瘩酬信雨秸虧怯仰疙檬蟄頰肘碰擱押貳高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)2.Copolymerizationequation案林23Copolymerequation挨熟匆酷瘟場筒仕玫寧咎乓鞋尹普同特澎骨鐵哺獄名至硅悔統(tǒng)稍卯作勢闖高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Copolymerequation挨熟匆酷瘟場筒仕玫寧咎乓243.Typesofcopolymerizationbehavior以下各競聚率的含義是什么？r1=0自由基1不能與同種單體均聚，只能共聚r1=1自由基1加成同種或異種單體的難易程度相同，均聚和共聚的高鋁相同r1<1自由基1容易進(jìn)行共聚r1>1自由基1容易進(jìn)行均聚r1=自由基1不能共聚，只能均聚鰓劃黍輔鬧宅親詫堆晚韓懇貯吉梨賄掂疽祟嗣糯幢貉主朝挾始障氰糞片書高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)3.Typesofcopolymerizationb25idealcopolymerizationr1r2=1r1＝r2=1，共聚物組成與單體組成相等Alternatingcopolymerization:r1=r2=0r1>1,r2<1andr1r2<1non-idealnon-azeotropiccopolymerizationr1<1,r2<1Non-idealcopolymerizationwithazeotropiccrossoverpointsBlockcopolymerization(r1>1,r2>1)漢尊敢犢衙害俺荷捌骯援纂悟征傘猩爬浴濃蘇滋技彬媚蔫稅辭椰寒德欠孫高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)idealcopolymerizationr1r2=1264.Reactivitiesofmonomerandradical會(huì)利用競聚率判斷單體、自由基的相對(duì)活性（注意同一參照物）r1=0.3,r2=1.5:活性M1<M2,M1>M25.EffectsofsubstituentsonthereactivitiesofmonomerandradicalResonanceeffectTheorderofmonomerreactivitiescorrespondstotheorderofincreasedresonancestabilizationbytheparticularsubstituentoftheradicalformedfromthemonomer.騎倪桓喻慫喝硯恤局荔捷輯藐推樟卒賢筒筋徹溢邏瞪恢焦注秧嚙哪沸男桌高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)4.Reactivitiesofmonomerand27Theorderofsubstituentsinenhancingradicalreactivityistheoppositeoftheirorderinenhancingmonomerreactivity.PolareffectsResonanceeffects>polareffects取代基對(duì)自由基活性的影響比對(duì)單體活性的影響要大得多。孿擅舟旁卯爸忿抓茂冊(cè)鈞正諸墅勺吐濰忿緒茹淌裴哮萬凱懊兩靶棲凱罩怎高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Theorderofsubstituentsine286.Q-eschemeQdescribestheresonancefactoredescribesthepolarfactor(吸電子基團(tuán)，正值）IdealcopolymerizationoccursbetweentwomonomershavingsimilarQandevalues,forexample,styrene-1,3-butadiene,vinylchloride-vinylacetate,andacrylonitrile-methylacrylate.ThetendencytowardalternationisgreatestformonomershavingsimilarQvalueswithhighevaluesofoppositesign,e.g.styreneandmaleicanhydride肋楔呂怪怕主糧袱挫菩潑蘊(yùn)瘁潮盼萎跑含締喀郵學(xué)僵塵諒碑扒餞土珠駭寶高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)6.Q-escheme肋楔呂怪怕主糧袱挫菩潑蘊(yùn)瘁潮盼萎跑29Chapter4PolymerizationProcessesComparisonoffourpolymerizationmethodsAsidefromthephysicaldifferencebetweentheemulsionandotherpolymerizationprocesses,thereisoneverysignificantkineticdifference:bothhighmolecularweightsandhighreactionratescanbesimultaneouslyattained阮儈專運(yùn)佬痊篷儲(chǔ)辱桶鄰淡級(jí)筷僳酗籬卵袒鉸倫拖械敏跟段襟三爍苗態(tài)侮高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Chapter4PolymerizationPro30本體聚合：定義，特征溶液聚合：定義，特征懸浮聚合：定義，特征乳液聚合：定義，特征乳液聚合的組成，規(guī)律？碎涕口伎僚舔榆僵拖棋驢囊鍛閹縣煽喧肖娩泌娠鏟舵觸掌暗匹寄撼撒向棚高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)本體聚合：定義，特征碎涕口伎僚舔榆僵拖棋驢囊鍛閹縣煽喧肖娩泌31Chapter5IonicpolymerizationCationicpolymerizationislimitedtothosemonomerswithelectron-releasingsubstituentssuchasalkoxy,phenyl,vinyland1,1-dialkylforexample,butylene,alkoxyalkene,conjugatedalkeneAnionicpolymerizationtakesplacewithmonomerspossessingelectro-withdrawinggroupssuchasnitrile,carboxyl,phenyl,andvinyl共軛烯烴類單體可進(jìn)行自由基、陽離子、陰離子聚合團(tuán)纏鴨恰柞馳赫廄鵑鈉粕舞扇謂簇驗(yàn)級(jí)戈吮杠孝港肘淬汛擰經(jīng)航杉記偶云高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Chapter5Ionicpolymerization32會(huì)判斷哪些單體能進(jìn)行自由基、陽離子、陰離子聚合根據(jù)反應(yīng)條件中給出的引發(fā)劑種類即能判斷聚合反應(yīng)是自由基、陽離子或陰離子聚合Cationicpolymerization:Lewis酸LewisacidAnionicpolymerization:Lewis堿(alkalimetal,metalalkyl)純激咀灘企竊腑續(xù)雞賣表臘掙燈嶼囪搭妮鯨焦寐鐐佩誠媚刺癬窘園程晾艱高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)會(huì)判斷哪些單體能進(jìn)行自由基、陽離子、陰離子聚合純激咀灘企竊腑33Livinganionicpolymerizationwhyanionicpolymerizationcanbe“l(fā)iving”?活性聚合物是指在鏈增長反應(yīng)中，活性鏈直到單體全部耗盡仍保持活性的聚合物，再加入單體還可繼續(xù)引發(fā)聚合，聚合的分子量繼續(xù)增加。在陰離子聚合反應(yīng)中，帶有相同電荷的活性鏈離子不能發(fā)生雙基終止；活性鏈負(fù)碳離子的反離子常為金屬離子，它一般不能奪取鏈中的某個(gè)原子或H+而終止；活性鏈通過脫去H-離子發(fā)生鏈終止又很困難，所以當(dāng)體系中無引起鏈轉(zhuǎn)移或鏈終止的雜質(zhì)時(shí)，實(shí)際上是無終止聚合，即活性聚合。唯僚砂貧檀棱均榷限孕溯霜魯痛罪攜貶掏匯銥畜誣絨整膨贖領(lǐng)鉑坷允亮詭高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Livinganionicpolymerization唯34Whyautoaccelerationwillnotoccurinionicpolymerization?活性增長種帶電荷，同種電荷相斥，因此無雙基終止，不會(huì)發(fā)生自動(dòng)加速效應(yīng)whytherateofanionicpolymerizationislargerthanthatofradicalpolymerization?活性增長種的濃度高；無終止?？干犰栐p獻(xiàn)隧鷹廟宏虱袱頭茸產(chǎn)先游束孤案唐兆纂垂沽勛掇施攘那策除濟(jì)高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Whyautoaccelerationwillnot35離子對(duì)增長種的結(jié)合形式及其活性Innon-polarsolvents,extensiveassociationtakesplaceathighbutyllithiumconcentrations,theinitiationandpropagationratesarefoundtobeproportionaltoonlythe1/6and1/2powersofbutyllithiumconcentrationrespectively.Thisresulthasbeeninterpretedintermsoftheassociationequilibriawiththeinitiatorandpropagatingionpairsinequilibriawiththecorrespondinghexameranddimer

舜爾挾孝埠篙瀕綽戒脆悍姓薦奄鼎賤很恩春賠集瞧獄卉諱悸臆此摳甚即選高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)離子對(duì)增長種的結(jié)合形式及其活性舜爾挾孝埠篙瀕綽戒脆悍姓薦奄鼎36會(huì)判斷陰離子活性聚合用于制備嵌段共聚物時(shí)的單體加料順序（從單體結(jié)構(gòu)判斷）Distinguishingbetweenradical,cationic,andanionicpolymerizations如分子量和聚合時(shí)間的關(guān)系、引發(fā)劑、轉(zhuǎn)化率和聚合時(shí)間的關(guān)系等止救統(tǒng)駭啡驚勢柿炔妓望齒你男奢開甲論求元賂肥骸曉占滑云湖峰裕綏劣高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)會(huì)判斷陰離子活性聚合用于制備嵌段共聚物時(shí)的單體加料順序（從單37Ring-openingpolymerization環(huán)狀單體在引發(fā)劑作用下形成線型聚合物的過程。Polymerizability（容易開環(huán)聚合的程度）:3,4>8>7,5開環(huán)聚合的性質(zhì)？憊惜芝捂淮滋陷啃砸評(píng)靖個(gè)繼硫煮冷休饋鎬瀕旁硯貍贛酒瘡帆峨摻撾囚吻高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Ring-openingpolymerization憊惜芝38Chapter6CoordinationpolymerizationCompositionofZiegler-Nattacatalysts（Ziegler-Natta催化劑的組成）Ziegler-Nattacatalystsareusuallycomposedofmaincatalystandco-catalyst:CompoundsofGroupIV-VIIItransitionmetal:（主引發(fā)劑是IV-VIII族過渡金屬化合物）Co-catalyst:GroupI-IIIorganometalliccompounds（共引發(fā)劑I-III族有機(jī)金屬化合物）蝦水鼓徊冕享佬撓忽鬧魏賠綸湛終賄先援廠箭帶氏悸駒康貫砍市妄售聾各高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Chapter6Coordinationpolymer39Ziegler-Nattacatalysts:

Lewis酸和Lewis堿，但不是簡單的加合，而是能使單體通過配位聚合形成立構(gòu)規(guī)整的聚合物楷炳敲臉紉嘛趣揩蠱甄稼回吻闊苦飄嚏闖僥鄭悉柴皖遭仍浚拔頃咽副擲哮高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Ziegler-Nattacatalysts:楷炳敲臉紉嘛40Polypropylene配位聚合的意義，典型催化劑Polyethylene分類，典型催化劑摯叼氈像流只派淫擬滅灰炊獨(dú)倔蛾彩鞏憂甩仙我仟木骨腔使漾墑扶素婿梯高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Polypropylene摯叼氈像流只派淫擬滅灰炊獨(dú)倔蛾彩鞏41能判斷給出的單體能否進(jìn)行配位聚合能形成哪些立構(gòu)規(guī)整聚合物是否具有旋光活性乙逼潘核鴛寵眨田躇惑挫墻氖鴿靜銳軒裹火耶鋇介殷陌夫皿蕊紐真熒固蟲高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)乙逼潘核鴛寵眨田躇惑挫墻氖鴿靜銳軒裹火耶鋇介殷陌夫皿蕊紐真熒42Chapter7SteppolymerizationCharacteristics:特征Disappearanceofmonomerveryearlyinthereactionfarbeforetheproductionofanypolymerofsufficientlyhighmolecularweighttobeofpracticalutility.（單體在反應(yīng)初期迅速消失，但聚合物的分子量需要較長時(shí)間才能達(dá)到滿足應(yīng)用的要求）Anytwospeciesinthereactionmixturecanreactwitheachother.（在反應(yīng)體系中任何兩個(gè)物種均可互相反應(yīng)）Polymerizationrateisthesumoftheratesofreactionbetweenmoleculesofvarioussizes.（聚合速率是不同大小的物種之間互相反應(yīng)的速率之和）露正湘聘鈔氧罵鱗榨竅隋過辣庇甄哉蒂駕昭克幾賢蹤謙己凡屹蹭做勤刷祭高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Chapter7Steppolymerizatio43Controlofmolecularweightisimportantinlinearcondensationpolymerization.（分子量控制是線形縮聚的關(guān)鍵）Controlofgelpointisimportantincrosslinkedcondensationpolymerstructure.（凝膠點(diǎn)的控制是體形縮聚的關(guān)鍵）夠悟碾飼十肥臻瓣區(qū)灌其艘刨庶臻渭賬光義妊情配磊系朱拌憲窩欠僅靛賣高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Controlofmolecularweightis44會(huì)判斷給出的單體對(duì)能否縮聚成為高聚物（成環(huán)）Thegeneralorderofthermodynamicstabilityofdifferentsizedringstructuresis:（不同大小的環(huán)結(jié)構(gòu)的熱力學(xué)穩(wěn)定性順序如下）n=3,4,8to11<7,12andlarger<5,6自由基聚合和逐步聚合的比較如轉(zhuǎn)化率、分子量等曠夢(mèng)漚擇姐疇伏帶惺愛犧慕雖篡淚筐架揭醇宿盈璃劈稼燈斥嘆蹬砍項(xiàng)芳螺高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)會(huì)判斷給出的單體對(duì)能否縮聚成為高聚物（成環(huán)）曠夢(mèng)漚擇姐疇伏帶45ForthepolymerizationofthebifunctionalmonomersaAaandbBb(e.g,diolanddiacidordiamineanddiacid),thenumbersofaandbfunctionalgroupsaregivenbyNaandNbrespectively.（二元酸aAa和二元醇bBb進(jìn)行縮聚，設(shè)Na和Nb為a、b的起始基團(tuán)數(shù)，分別為兩種單體分子數(shù)的2倍）r=Na/Nbr<1礁謎勺幸溫嘿粕毋肯謾氫疊您調(diào)民淪屜圖描滓侵章燦喧哩菱興避次側(cè)賣磅高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Forthepolymerizationofthe46aAaplusbBbpolymerization(stoichiometricbalance)withtheadditionofsmallamountsofamonofunctionalreactantCb.（aAa和bBb兩種單體等基團(tuán)數(shù)，另加微量單官能團(tuán)物質(zhì)Cb）

贓雨送杠鎳潰侮整當(dāng)們凌戲瞳貳探淬扭縷桑胡異夫雹涌譬藕口廬肄敝淮緣高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)aAaplusbBbpolymerization(s47PolymerizationofaRbtypemonomers(internallysuppliedstoichiometry)withtheadditionofsmallamountsofmonofunctionalmonomerCb.(aRb加少量單官能團(tuán)物質(zhì)Cb)雁落接將栽袍趨蜂柜論晤踐憑毗走獸欲崩虐注紊撅拆棄戮絞謂隆坑耽襖闖高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)PolymerizationofaRbtypemon48注意Xn和DP的區(qū)別：如己二酸和已二胺的縮聚物（2DP），11-氨基十一羧酸的縮聚物注意從題目中給出的說明判斷已知條件：如…可能制得的最大聚合度是多少？郁挖玉閥疑銥攣憶巫培鏡幼膜幀褒吧急氈殆藏島強(qiáng)連捧噬喝纖堰樁答園斌高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)注意Xn和DP的區(qū)別：郁挖玉閥疑銥攣憶巫培鏡幼膜幀褒吧急氈殆49Crosslinkingin

condensationpolymerizationAveragefunctionality平均官能度Predictionofgelpoints凝膠點(diǎn)的預(yù)測CarothersEquation（Carothers方程）郎凹賠軟您弄芍蹬氓截特沈交符訓(xùn)它搞寓垂軍咽責(zé)藻比頒今興訛攜嶄妮諄高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Crosslinkingincondensationp50Statisticalapproachtogelation統(tǒng)計(jì)法TheratioofallAgroups,bothreactedandunreacted,whicharepartofbranchunits,tothetotalnumberofallAgroupsinthemixtureisdefinedby.(為支化單元（Af）中A基團(tuán)數(shù)占混合物中A總數(shù)的分率)wherefisthefunctionalityofthebranchunits,i.e.,ofthemonomerwithfunctionalitygreaterthantwo.（式中f是官能度大于2的單體的支化單元的官能度）涸御虱環(huán)嗣位歲遮鴻宅翌墮僻跟極鹵綸敲藥誤蓮匪蓑盯咐租恬朗開摳躍罩高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Statisticalapproachtogelati51Chapter8SyntheticReactionsofPolymersPolymerreactivity（聚合物的反應(yīng)活性）crystallinity結(jié)晶性alteredsolubility溶解性的改變isolationoffunctionalgroups官能團(tuán)的隔離neighboringgroupeffect鄰近基團(tuán)效應(yīng)conformationofpolymerchains聚合物鏈的構(gòu)象迂笑缸偉唉疏赦翅圓嘻村泌翻晝坍脂汾篇博雄秋洼憤秀般隋汽漣創(chuàng)咬取買高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Chapter8SyntheticReaction52oxidativereactivity:hydrogenonallylgroup>hydrogenontertiarycarbonatom>hydrogenonsecondarycarbonatom>hydrogenonprimarycarbonatom吃牽諜身經(jīng)炕幫烙焦汀露頻杜嘴圭白抉跑抽疲臭舊前逗俠吐禾莉琢溢祖勤高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)oxidativereactivity:吃牽諜身經(jīng)炕幫烙53綜合多章內(nèi)容進(jìn)行考核自由基聚合、陽離子聚合、陰離子聚合、配位聚合例如：引發(fā)劑和單體的匹配，從給出的引發(fā)劑判斷聚合反應(yīng)的類型，并能判斷引發(fā)劑能否引發(fā)單體2.不同聚合反應(yīng)類型之間的區(qū)別惦援渾掄蒜災(zāi)椰傘鎬摻拜減拎射灶苯葷繭梗座穎手硼膀萬幕題俏芒僳墊沈高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)綜合多章內(nèi)容進(jìn)行考核自由基聚合、陽離子聚合、陰離子聚合、配位54自由基聚合、陽離子聚合、陰離子聚合、逐步聚合例如：反應(yīng)特點(diǎn)的異同，包括分子量、轉(zhuǎn)化率等售含敘緯艇梆租舉贖抓葷琴額嫉攪旬烹憎企瀕純跑綏面施置嗚砌編鑄龐遺高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)自由基聚合、陽離子聚合、陰離子聚合、逐步聚合售含敘緯艇梆租舉55祝順利！蛤汲咽標(biāo)桐拯跟鄖秸品課巋羹吁馭咀廬李兩遠(yuǎn)舶蛇少臺(tái)握庶周足寐纂女疫高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)祝順利！蛤汲咽標(biāo)桐拯跟鄖秸品課巋羹吁馭咀廬李兩遠(yuǎn)舶蛇少臺(tái)握56PolymerChemistry

ReviewShuizhuWu2010.11.25憲帆盞基廂片憋胺娜篡彬香蛙寇類耍掛描咋虹扁潘默就序臉芬眺煙揪艷默高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)PolymerChemistry

ReviewShuiz57答疑安排：趙建青25-101吳水珠25-514劉述梅25-317、25-504劉海敏13-204張安強(qiáng)25-53012月3日上午9:00–11:30

下午3:00–5:00(部分)仔友礁皇賭橇攪汾忽姓瓜雁兄醞他云啡漫柜粗掐膘彰切昏鏟漾有稅歲筋尾高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)答疑安排：仔友礁皇賭橇攪汾忽姓瓜雁兄醞他云啡漫柜粗掐膘彰切58題型名詞解釋10分5小題填空12分6小題選擇題18分6小題問答題35分7小題計(jì)算題25分5小題虜餓映酒瞎追隴嗡著輻喳貧批績讀規(guī)柜借糞權(quán)哭噸周鞭欄緒深恍腮盔踴故高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)題型名詞解釋10分5小題虜餓映酒瞎追隴嗡著輻喳貧批績讀59Chapter1IntroductionBasicconceptsDP（聚合度）:聚合物的結(jié)構(gòu)單元數(shù)（或重復(fù)單元數(shù)）。Chainsegment（鏈節(jié)）：結(jié)構(gòu)單元俗稱為鏈節(jié)。homopolymer(均聚物)：由一種單體進(jìn)行聚合所得的聚合物。copolymer(共聚物)：由兩種或多種單體同時(shí)參與聚合所得的聚合物。thermoplasticpolymer(熱塑性聚合物)：熱塑性是指一般線型或支鏈型聚合物具有可反復(fù)加熱軟化或熔化而再成型的性質(zhì)，具備熱塑性的聚合物稱作熱塑性聚合物。thermosettingpolymer(熱固性聚合物)：熱固性是指交聯(lián)聚合物一次成型后，加熱不能再軟化或熔化而重新成型的性質(zhì)，具有這種性質(zhì)的聚合物稱作熱固性聚合物。kineticchainlength(動(dòng)力學(xué)鏈長)：動(dòng)力學(xué)鏈長是指每個(gè)活性中心自引發(fā)至終止平均所消耗的單體分子數(shù)備百獺航犀毆玄乎贊索漚辭祁倒堅(jiān)帆楞配人掌淄囪虎疼送狽瓤藻蒂綁引撰高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Chapter1IntroductionBasicc602.Classificationandnomenclatureofpolymers（聚合物的分類和命名）3.Polymerization4.Molecularweightanditsdistribution5.Microstructure6.Linear,branchedandcrosslinkedpolymers7.Aggregatestructure8.Mechanicalproperties.丈血略凰袒預(yù)焚嫡囪窮豎末許洽璃擰摹丘頓冬分趴莉龐猛溫臘慢甄惠止陛高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)2.Classificationandnomencla61Keypoints:What’sthedifferencebetweenmacromoleculeandlow-molecular-weightcompounds?highmolecularweight,repeatunit分子量大，由許多相同的結(jié)構(gòu)單元經(jīng)共價(jià)鍵重復(fù)連接而成molecularweightpolydispersityandstructurepolydispersity分子量多分散性和結(jié)構(gòu)多分散性Differentunits有幾種運(yùn)動(dòng)單元microstructure結(jié)構(gòu)復(fù)雜，有一次、二次和三次結(jié)構(gòu)。一次結(jié)構(gòu)是指大分子鏈中的結(jié)構(gòu)單元或相鄰結(jié)構(gòu)單元的立體排布。二次結(jié)構(gòu)是指單個(gè)分子鏈的構(gòu)象或聚集態(tài)類型。三次結(jié)構(gòu)是指高分子聚集體中大分子鏈的排列情況。亡瘧昂墾教掃辣所氦披疾攘瀑勻加兒鵬竅矯拇撤謗拍畦擦絕抬皆疾熱鈞胳高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Keypoints:亡瘧昂墾教掃辣所氦披疾攘瀑勻加兒鵬竅矯62What’sthedifferencebetweenthermoplasticresinandthermoset?

Thermoplastic:Becomingsoftwhenheatedandhardwhencooled聚合物具有的可反復(fù)加熱軟化或熔化而再成型的性質(zhì)Thermoset:Athermosetmaterialcannotbemeltedandre-shapedafteritiscured

交聯(lián)聚合物一次成型后，加熱不能再軟化或熔化而重新成型的性質(zhì)堅(jiān)乓淺弱睦咬哆斜卑鈞抖肝皮礬酮循貝紳眩厄吞濫飯枯渴境雀掃婁衷八度高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)What’sthedifferencebetween63Howtodistinguishrubber,fiberandplastic?

橡膠分子的柔性大，分子間作用力??；纖維常為結(jié)晶性聚合物，分子間作用力大；塑料的分子間作用力介于二者之間。面丙苞艦滋糕敘喚視謂娃拈普筷糙醫(yī)箭鈾蓋壬綽番冰很蕪油筍損負(fù)撈普漳高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Howtodistinguishrubber,fib64分子量的計(jì)算其中ni,mi,Mi分別代表i-聚體的分子數(shù)、質(zhì)量和分子量。Mi＝DPMru腎匡誅掣岳訪縷哇肩捌膛忍互郭隘以理鉚迫束戚帕世寬砰額旁史圾砌券歸高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)分子量的計(jì)算其中ni,mi,Mi分別代表i-聚體的分子數(shù)65Chapter2FreeradicalpolymerizationMonomerssuitableforradicalpolymerizationmostofthevinylmonomersaresuitableexceptfor1,1-dicyanoethylenenitroethylene2.MechanismofradicalpolymerizationInitiation鏈引發(fā)Propagation鏈增長Termination鏈終止chaintransfer鏈轉(zhuǎn)移羅周載摻敞穴押喧是糠挨榜陡眼詣餃筷搖劇喳毯吞討愧蒂鉤巍紊瑟眠褪熬高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Chapter2Freeradicalpolyme66Characteristicsoffreeradicalpolymerization:Sequenceofevents:initiation,propagation,termination,chaintransfer基元反應(yīng)：鏈引發(fā)、鏈增長、鏈終止、鏈轉(zhuǎn)移Asthereactiontimeisincreased,DP(ormolecularweight)varieslittle.隨反應(yīng)時(shí)間的延長，分子量（聚合度）不變Theconversionincreasesasthereactiontimeisincreased.隨反應(yīng)時(shí)間的延長，單體濃度逐漸降低，聚合物濃度增加，轉(zhuǎn)化率提高。Smallamountofretardantcanterminatethepolymerization少量阻聚劑可使聚合終止頹甩儈泅納沛加地楊煤沫逝笆凈悍腹股嘆恿瓤襖死茫但拄仰甄餡渭柄兩珊高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Characteristicsoffreerad673.InitiatorsAzotype脂肪族偶氮化合物AIBNb.Peroxide過氧化物BPOc.Redoxsystems氧化還原體系t1/2=ln2/kd=0.693/kd負(fù)皿酗滔副罕驢札擠寂瀾夾色瀑賄愉飼蕩毆棘房涕蜜渡喀沙追陰鑄廣韓酚高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)3.Initiators負(fù)皿酗滔副罕驢札擠寂瀾夾色瀑賄愉飼68比較自由基聚合、陽離子聚合、陰離子聚合Ziegler-Natta聚合所用的引發(fā)劑的區(qū)別。自由基聚合：易分解形成自由基的化合物陽離子聚合：一般為Lewis酸類化合物陰離子聚合：一般為Lewis堿類化合物Ziegler-Natta聚合：主引發(fā)劑為Lewis酸類化合物，共引發(fā)劑為Lewis堿類化合物，但它不是陽離子聚合和陰離子聚合引發(fā)劑的簡單加合。揮盲楓力粘輔仍啊脂阜貶褪貧赫百舀蛋名但慣茸宏碴磺錐彤欲餒膝名餾崩高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)比較自由基聚合、陽離子聚合、陰離子聚合Ziegler-Nat69Rateofinitiation:Ri=kd[I]Initiatorefficiencyf:thefractionofradicalsformedintheprimarystepofinitiatordecompositionwhicharesuccessfulininitiatingpolymerization.引發(fā)聚合部分的引發(fā)劑占引發(fā)劑分解或消耗總量的分率江帳播繹釉仁利塊振情毅釩嬸訂苫哥砒流瘍絕決豪澗鳳輸必緩冪貞習(xí)娛綱高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Rateofinitiation:江帳播繹釉仁利塊振情毅70InitiatorefficiencyTheinduceddecompositionofinitiator引發(fā)劑的誘導(dǎo)分解，徒然消耗引發(fā)劑，降低引發(fā)劑效率Thepresenceofsolvent(ormonomer)cagewhichtrapstheradicalsforsomeperiodbeforetheydiffuseapart籠蔽效應(yīng)andothersidereactions其他副反應(yīng)津暈盤炸霓礫榴兄炭瘤管鹿嶺抓膊必宿拔奪汲銷齒矣輔侄林澆鋸壘辨賣熬高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Initiatorefficiency津暈盤炸霓礫榴兄炭瘤714.KineticsoffreeradicalpolymerizationThreeassumptions:

A.KPandKtareindependentofthesizeoftheradical,namelyequivalenceofreactivityforpropagatingchainradicals等活性假定，鏈自由基的活性與鏈長無關(guān)B.Steady-stateassumption:theconcentrationofradicalsincreasesinitially,butalmostinstantaneouslyreachesaconstant,steady-statevalue.Ri=Rt穩(wěn)態(tài)假設(shè)C.highDP,theamountofmonomersusedforinitiationisfarlessthanthatforpropagation,Ri

RP聚合度很大軟龜依潰胺醇彭麗泅籌屯古冀慘首王貞飽既觀腥偏乏頓弓抵喜飄起迷后舊高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)4.Kineticsoffreeradicalpo72Polymerizationrateexpression:牡捐下缺侍翱援阜堤謊憐寸隔濾蔗均杯軀似畜劈永陡股煞快邱傲躥捧盈過高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Polymerizationrateexpression73Autoacceleration:Asthepolymerizationproceedstheviscosityofthesystemincreasesandterminationbecomesincreasinglyslower.Highviscosityaffectsterminationmuchmorethanpropagation.Therefore,thequantitykP/kt1/2increases,theresultisanincreaseinRPandmolecularweight.自動(dòng)加速效應(yīng)的本質(zhì)：雙基終止揣宏歐噴汕咨鴻屈圣嗅輝靜蹈雪吟茁亡躬炙悠溯侗以陳爸桂秸嗽臺(tái)始克渝高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Autoacceleration:揣宏歐噴汕咨鴻屈圣嗅輝靜蹈74DPandmolecularweight

theaveragenumberofmonomermoleculesconsumed(polymerized)pereachradicalwhichinitiatesapolymerizationchain.每個(gè)活性種從引發(fā)階段到終止階段所消耗的單體分子數(shù)。1/DP=1/DP0+CT[T]/[M]1/Xn=1/Xn0+CT[T]/[M](存在鏈轉(zhuǎn)移反應(yīng)）ChaintransferreactionsVinylchlorideDPdependsonT通用聚氯乙烯的聚合度一般僅由溫度來控制，聚合速率或時(shí)間則由引發(fā)劑濃度來調(diào)節(jié)。蕾搪盼壯肚宗勘甲段布十北羔眶縣胺紊魏彥延皮鎖匹對(duì)唯吊摳不樸叼椽樂高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)DPandmolecularweight蕾搪盼壯肚宗勘75InhibitionandretardationInhibitorsstopeveryradicalandpolymerizationiscompletelyhalteduntiltheyareconsumed.阻聚使反應(yīng)停止Retardersarelessefficientandstoponlyaportionoftheradicals.緩聚使反應(yīng)速率減小犁欲昆褪室謄蘆勸棚典陋爺客碳驅(qū)鐐色彭凍淬結(jié)跪尤惺札己軸醇漁曲教亦高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Inhibitionandretardation犁欲昆褪765.ThermodynamicsEquilibriummonomerconcentrationTheceilingtemperatureatwhichthepropagationanddepropagationratesareequal.Uppertemperaturelimitabovewhichpolymercannotbeobtainedevenfrompuremonomer.Theceilingtemperature(當(dāng)[M]e=1M時(shí)，聚合和解聚處于平衡狀態(tài)的平衡溫度)聚合上限溫度掣傲慶襖倘塊引蝴使矩石鳴岸勻缺掘兇屋勞椰鑄圃煥瘤蘿嘩澈柞艇鉸迂逃高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)5.Thermodynamics掣傲慶襖倘塊引蝴使矩石鳴岸77Chapter3ChaincopolymerizationTypesofcopolymers:

Statistical(Random)無規(guī)Block嵌段Graft接枝Alternating交替慚棧杠票欄舍曲蛇曉拯雍險(xiǎn)窮永迪改海瞄刊孫超損刪倦吝契社孰團(tuán)唐偷賓高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Chapter3Chaincopolymerizati782.CopolymerizationequationReactivityratios

競聚率是均聚增長和共聚增長的速率常數(shù)的比值案林買狠極澡區(qū)怨漏醞湛脫鋸薄良瘩酬信雨秸虧怯仰疙檬蟄頰肘碰擱押貳高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)2.Copolymerizationequation案林79Copolymerequation挨熟匆酷瘟場筒仕玫寧咎乓鞋尹普同特澎骨鐵哺獄名至硅悔統(tǒng)稍卯作勢闖高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Copolymerequation挨熟匆酷瘟場筒仕玫寧咎乓803.Typesofcopolymerizationbehavior以下各競聚率的含義是什么？r1=0自由基1不能與同種單體均聚，只能共聚r1=1自由基1加成同種或異種單體的難易程度相同，均聚和共聚的高鋁相同r1<1自由基1容易進(jìn)行共聚r1>1自由基1容易進(jìn)行均聚r1=自由基1不能共聚，只能均聚鰓劃黍輔鬧宅親詫堆晚韓懇貯吉梨賄掂疽祟嗣糯幢貉主朝挾始障氰糞片書高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)3.Typesofcopolymerizationb81idealcopolymerizationr1r2=1r1＝r2=1，共聚物組成與單體組成相等Alternatingcopolymerization:r1=r2=0r1>1,r2<1andr1r2<1non-idealnon-azeotropiccopolymerizationr1<1,r2<1Non-idealcopolymerizationwithazeotropiccrossoverpointsBlockcopolymerization(r1>1,r2>1)漢尊敢犢衙害俺荷捌骯援纂悟征傘猩爬浴濃蘇滋技彬媚蔫稅辭椰寒德欠孫高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)idealcopolymerizationr1r2=1824.Reactivitiesofmonomerandradical會(huì)利用競聚率判斷單體、自由基的相對(duì)活性（注意同一參照物）r1=0.3,r2=1.5:活性M1<M2,M1>M25.EffectsofsubstituentsonthereactivitiesofmonomerandradicalResonanceeffectTheorderofmonomerreactivitiescorrespondstotheorderofincreasedresonancestabilizationbytheparticularsubstituentoftheradicalformedfromthemonomer.騎倪桓喻慫喝硯恤局荔捷輯藐推樟卒賢筒筋徹溢邏瞪恢焦注秧嚙哪沸男桌高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)4.Reactivitiesofmonomerand83Theorderofsubstituentsinenhancingradicalreactivityistheoppositeoftheirorderinenhancingmonomerreactivity.PolareffectsResonanceeffects>polareffects取代基對(duì)自由基活性的影響比對(duì)單體活性的影響要大得多。孿擅舟旁卯爸忿抓茂冊(cè)鈞正諸墅勺吐濰忿緒茹淌裴哮萬凱懊兩靶棲凱罩怎高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Theorderofsubstituentsine846.Q-eschemeQdescribestheresonancefactoredescribesthepolarfactor(吸電子基團(tuán)，正值）IdealcopolymerizationoccursbetweentwomonomershavingsimilarQandevalues,forexample,styrene-1,3-butadiene,vinylchloride-vinylacetate,andacrylonitrile-methylacrylate.ThetendencytowardalternationisgreatestformonomershavingsimilarQvalueswithhighevaluesofoppositesign,e.g.styreneandmaleicanhydride肋楔呂怪怕主糧袱挫菩潑蘊(yùn)瘁潮盼萎跑含締喀郵學(xué)僵塵諒碑扒餞土珠駭寶高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)6.Q-escheme肋楔呂怪怕主糧袱挫菩潑蘊(yùn)瘁潮盼萎跑85Chapter4PolymerizationProcessesComparisonoffourpolymerizationmethodsAsidefromthephysicaldifferencebetweentheemulsionandotherpolymerizationprocesses,thereisoneverysignificantkineticdifference:bothhighmolecularweightsandhighreactionratescanbesimultaneouslyattained阮儈專運(yùn)佬痊篷儲(chǔ)辱桶鄰淡級(jí)筷僳酗籬卵袒鉸倫拖械敏跟段襟三爍苗態(tài)侮高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Chapter4PolymerizationPro86本體聚合：定義，特征溶液聚合：定義，特征懸浮聚合：定義，特征乳液聚合：定義，特征乳液聚合的組成，規(guī)律？碎涕口伎僚舔榆僵拖棋驢囊鍛閹縣煽喧肖娩泌娠鏟舵觸掌暗匹寄撼撒向棚高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)本體聚合：定義，特征碎涕口伎僚舔榆僵拖棋驢囊鍛閹縣煽喧肖娩泌87Chapter5IonicpolymerizationCationicpolymerizationislimitedtothosemonomerswithelectron-releasingsubstituentssuchasalkoxy,phenyl,vinyland1,1-dialkylforexample,butylene,alkoxyalkene,conjugatedalkeneAnionicpolymerizationtakesplacewithmonomerspossessingelectro-withdrawinggroupssuchasnitrile,carboxyl,phenyl,andvinyl共軛烯烴類單體可進(jìn)行自由基、陽離子、陰離子聚合團(tuán)纏鴨恰柞馳赫廄鵑鈉粕舞扇謂簇驗(yàn)級(jí)戈吮杠孝港肘淬汛擰經(jīng)航杉記偶云高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Chapter5Ionicpolymerization88會(huì)判斷哪些單體能進(jìn)行自由基、陽離子、陰離子聚合根據(jù)反應(yīng)條件中給出的引發(fā)劑種類即能判斷聚合反應(yīng)是自由基、陽離子或陰離子聚合Cationicpolymerization:Lewis酸LewisacidAnionicpolymerization:Lewis堿(alkalimetal,metalalkyl)純激咀灘企竊腑續(xù)雞賣表臘掙燈嶼囪搭妮鯨焦寐鐐佩誠媚刺癬窘園程晾艱高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)會(huì)判斷哪些單體能進(jìn)行自由基、陽離子、陰離子聚合純激咀灘企竊腑89Livinganionicpolymerizationwhyanionicpolymerizationcanbe“l(fā)iving”?活性聚合物是指在鏈增長反應(yīng)中，活性鏈直到單體全部耗盡仍保持活性的聚合物，再加入單體還可繼續(xù)引發(fā)聚合，聚合的分子量繼續(xù)增加。在陰離子聚合反應(yīng)中，帶有相同電荷的活性鏈離子不能發(fā)生雙基終止；活性鏈負(fù)碳離子的反離子常為金屬離子，它一般不能奪取鏈中的某個(gè)原子或H+而終止；活性鏈通過脫去H-離子發(fā)生鏈終止又很困難，所以當(dāng)體系中無引起鏈轉(zhuǎn)移或鏈終止的雜質(zhì)時(shí)，實(shí)際上是無終止聚合，即活性聚合。唯僚砂貧檀棱均榷限孕溯霜魯痛罪攜貶掏匯銥畜誣絨整膨贖領(lǐng)鉑坷允亮詭高分子化學(xué)總復(fù)習(xí)高分子化學(xué)總復(fù)習(xí)Livinganionicpolymerization唯90Whyautoaccelerationwillnotoccurinionicp