人类的文明史材料的发展史

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1、人类的文明史人类的文明史=材料的发展史材料的发展史 材料包括：材料包括：无机非金属材料无机非金属材料 有机高分子材料有机高分子材料 复合材料复合材料高分子材料学简介第一章第一章：绪论绪论1INTRODUCTION Advancement in technology is directly associated with the development of new materials History is often dated by the materials of most importance to the society,i.e.,the Stone,Bronze,and Iron A

2、ges The most important materials in the modern society are plastics,ceramics,and steel2HISTORYNatural Macromolecules A living organism is a complex machine,most functions of which are performed by macromolecules.DNA,RNA,ribosomers,proteins,cellulose,starches,and a host of other biologically importan

3、t substances are all macromolecules.From the very beginning of civilization,humans made technological use of natural macromolecules:leather,fur,wool,wood,cotton,flax,paper,natural rubber,etc.3Man-made(Synthetic)Macromolecules1839 Elastic property improvement of natural rubber by vulcanization 1870 C

4、ommercialization of celluloid(75%cellulose nitrate+25%camphor)1892 Preparation of rayon textile fibbers1910 Phenol-formaldehyde resins-first fully-synthetic polymers1920 Staudingers hypothesis of macromolecules1930Firm establishment of the concept of polymers4Nobel Prizes for Polymer Science1953 H.S

5、taudingerIntroduction of the concept of polymers(but not colloids)1963 K.Ziegler and G.NattaDiscovery of coordination polymerization catalysts and preparation of stereoregular polymers1974 P.J.FloryTheoretical and experimental contributions to fundamental principles of polymer science1991 G.de Genne

6、sSuccessful mathematical treatment of phase transition phenomena of polymers,liquid crystals,and super-conducting materials2000 A.J.Heeger,A.G.MacDiarmid,and H.Shirakawa Discovery and development of conductive polymers5Polymers Are Everywhere6高分子材料的应用高分子材料的应用衣衣食食行行住住用用科技科技7Polymers Are Everywhere8Na

7、tional Missile Defense9我们骄傲：我们骄傲：高高分分子子概概念念的的形形成成和和高高分分子子科科学学的的出出现现始始于于20世世纪纪20年年代代，但但高高分分子子材料是近材料是近50年发展最快的材料年发展最快的材料1996年年塑塑料料与与金金属属材材料料的的体体积积比比达达到到130%10我们责任重大：我们责任重大：*我国高分子研究起步于我国高分子研究起步于20世纪世纪50年代初年代初*1995年，我国高分子材料进口总量：年，我国高分子材料进口总量：*塑料：塑料：370万吨万吨*合成纤维：合成纤维：207万吨万吨*橡胶：橡胶：31万吨万吨*占国内消耗量的占国内消耗量的50

8、%，投资，投资100亿美元亿美元*1998年年，国国内内高高分分子子材材料料的的总总消消耗耗量量为为1446万万吨吨，占占世世界界总总消消耗耗量量的的1/10，其其中中803万万吨吨为为进进口，人均消耗量仅为发达国家的口，人均消耗量仅为发达国家的1/711现代高分子材料学的三个基础性分支学科l高分子化学高分子物理 （结构与性能关系研究）l高分子工程 （聚合反应工程和高分子成型）1213高高分分子子聚聚合合物物塑料塑料橡胶橡胶纤维纤维涂料涂料 粘合剂粘合剂热固性塑料热固性塑料(酚醛、脲醛酚醛、脲醛)热塑性塑料热塑性塑料(PE,PP,PVC,PS,PMMA,尼尼龙龙)天然橡胶天然橡胶(聚异戊二烯聚

9、异戊二烯)合成橡胶合成橡胶(顺丁顺丁,丁苯丁苯,丁腈丁腈,丁基丁基橡胶橡胶)腈纶腈纶(PAN),丙纶丙纶(PP),聚酯纤维聚酯纤维(PET),尼龙尼龙研研究究对对象象14研究对象之一研究对象之一塑料的发展塑料的发展1869年31岁的印刷工人约翰海阿特发明赛璐珞取取代代象象牙牙的的塑塑料料151909年贝克兰发明酚醛树脂年贝克兰发明酚醛树脂16酚酚醛醛塑塑料料制制作作的的门门把把手手171909年贝克兰合成年贝克兰合成酚醛树脂，酚醛树脂，1911年年英国的马修斯合成英国的马修斯合成出聚苯乙烯，出聚苯乙烯，1912年聚氯乙烯被合成，年聚氯乙烯被合成，1927年合成出聚甲年合成出聚甲基丙烯酸甲酯，基

10、丙烯酸甲酯，1933年高压聚乙烯年高压聚乙烯问世，问世，1938年四氟年四氟乙烯被聚合乙烯被聚合聚合产生的奇迹聚合产生的奇迹18 1953年齐格勒在低压条件下年齐格勒在低压条件下合成出聚乙烯，随后纳塔合成出合成出聚乙烯，随后纳塔合成出聚丙烯，聚丙烯，1963齐格勒、纳塔获得齐格勒、纳塔获得诺贝尔化学奖。诺贝尔化学奖。19研究对象之二研究对象之二橡胶的发展橡胶的发展橡橡树树之之泪泪202122丑却受宠的合成橡胶丑却受宠的合成橡胶23蚕说：还是人类有能耐蚕说：还是人类有能耐1855年瑞士人奥年瑞士人奥蒂玛斯把纤维素蒂玛斯把纤维素放在硝酸中得到放在硝酸中得到硝化纤维素溶液，硝化纤维素溶液，制得第一根

11、人造制得第一根人造纤维；纤维；1884年查年查唐纳脱把硝化纤唐纳脱把硝化纤维素放在酒精和维素放在酒精和乙醚中得到溶液，乙醚中得到溶液，得到人造丝；得到人造丝；研究对象之三研究对象之三纤维的发展纤维的发展24252627 从上面所叙述材料的发展可从上面所叙述材料的发展可以看到，科学发展是无止境的，以看到，科学发展是无止境的，一时的满足和安于现状就会导致一时的满足和安于现状就会导致落后，不断进取、不断创新才更落后，不断进取、不断创新才更有所作为。有所作为。人类需求是推动科学发展的人类需求是推动科学发展的动力。动力。28绪论绪论一、高聚物的基本概论一、高聚物的基本概论高聚物高聚物高聚物（high p

12、olymer）是高分子化合物（macromolecular compound）的简称，是由成千上万个原子通过化学键连接而成的高分子（macromolecule）所组成的化合物。高聚物的基本特点高聚物的基本特点相对分子质量大高聚物的基本特点分子链长相对分子质量具有多分散性常用的术语常用的术语单体结构单元重复结构单元聚合度常用的术语29绪论绪论实例分析实例分析以氯乙烯（VC）为单体，通过聚合生成聚氯乙烯（PVC）。n CH2CHCH2CHCH2CHCH2CHCH2CH以对苯二甲酸、乙二醇为单体，通过聚合生成聚对苯二甲酸乙二酯（的确良）。ClClClClCl简写ClCH2CHn结构单元重复结构单元n

13、 HOCH2CH2OHn HOOCCOOH HOCCOCH2CH2OHOOn重复结构单元结构单元结构单元30绪论绪论单体（单体（monomer）能够形成结构单元的分子所组成的化合物，即聚合时的小分子原料。结构单元（结构单元（structural unit）组成高聚物重复结构单元的基本单元。重复结构单元（重复结构单元（structural repeat unit）高分子链中重复出现的单元，即链节（chain element）。聚合度（聚合度（degree of polymerization）重复结构单元数目，即链节数。单独提出用DP或Xn表示，在结构式中用n表示。三个关系的处理三个关系的处理结构

14、单元与重复结构单元的关系结构单元与重复结构单元的关系单一单一高分子的相对分子质量与聚合度、重复结构单元相对分子质量的关系高分子的相对分子质量与聚合度、重复结构单元相对分子质量的关系重复结构单元重复结构单元结构单元结构单元31绪论绪论单一相对分子质量与平均相对分子质量的关系单一相对分子质量与平均相对分子质量的关系单一相对分子质量只对个体高分子，平均相对分子质量是体系内所有个体相对分子质量的平均值。个体高分子的个体高分子的相对分子质量没有实用价值，真正有价值的是平均平均相对分子质量的大小。原因：原因：高聚物是由相对分子质量不等的同系聚合物组成的混合物，即高聚物的相对分子质量具有多分散性。多分散性的

15、描述：多分散性的描述：分布曲线法、分散系数HI法。常见三大合成材料的相对分子质量范围常见三大合成材料的相对分子质量范围塑料相对分子质量橡胶相对分子质量纤维相对分子质量高密度聚乙烯聚氯乙烯聚苯乙烯聚碳酸酯630万515万1030万26万天然橡胶丁苯橡胶顺丁橡胶氯丁橡胶2040万1620万2530万1012万锦纶-66涤纶维尼纶腈纶1.21.8万1.82.3万67.5万58万32绪论绪论二、高聚物的命名与分类二、高聚物的命名与分类高聚物的命名高聚物的命名通俗命名法通俗命名法“聚聚”单体名称单体名称实例聚聚氯乙烯、聚聚乙烯、聚聚丙烯、聚聚苯乙烯、聚聚甲基丙烯酸甲酯、聚聚四四氟乙烯、聚聚异异丁烯、聚聚

16、偏偏二氯乙烯等。注意：取代基的位置用文字代替。原料名称简字原料名称简字“树脂树脂”实例酚醛树脂树脂、脲醛树脂树脂（聚合单体简字）扩充：聚氯乙烯树脂树脂、聚乙烯树脂树脂等（成型加工原料）高聚物的命名习惯或商品命名法系统命名法通俗命名法树脂命名法橡胶命名法结构特征命名法“聚”单体名称33绪论绪论单体简字单体简字“橡胶橡胶”实例丁苯橡胶橡胶、丁腈橡胶橡胶、氯丁橡胶橡胶、顺丁橡胶橡胶结构特征命名结构特征命名具有“酯COO结构”的高聚物称为聚聚酯酯；具有“酰胺CONH结构”的高聚物称为聚聚酰酰胺胺；具有“醚O结构”的高聚物称为聚聚醚醚。习惯名称与商品名称习惯名称与商品名称高聚物的重复结构单元通俗名称系统

17、名称习惯或商品名称英文缩写CH2CH2CH2CH(CH3)CH2CH(Cl)CH2C(CH3)-COOCO(CH2)2O-NH(CH2)5CO聚乙烯聚丙烯聚氯乙烯聚甲基丙烯酸甲酯聚对苯二甲酸乙二酯聚已内酰胺聚亚乙基聚亚丙基聚(1-氯亚乙基)聚(1-甲氧基酰基)-1-甲基亚乙基聚(氧亚乙基对苯二酰)高密度聚乙烯低密度聚乙烯（丝用）丙纶（丝用）氯纶有机玻璃涤纶锦纶-6或尼龙-6HDPELDPEPPPVCPMMAPETPPA-6COOCH334绪论绪论高聚物的分类高聚物的分类按高分子主链结构分类碳链高聚物（carbon chain polymer）杂链高聚物（carbon chain polymer

18、）元素有机高聚物（carbon chain polymer）无机高聚物（carbon chain polymer）按高聚物用作分类塑料（plastics）橡胶（rubber）纤维（fiber）涂料黏合剂按高分子链几何形状分类线型高聚物体型高聚物支链型高聚物按高分子链排列情况分类结晶高聚物非晶高聚物35绪论绪论三、高聚物的形成反应三、高聚物的形成反应高聚物的形成反应（高聚物的形成反应（formation reaction of polymer）是指由低分子单体形成高聚物的化学反应。广义还应包括利用高聚物的化学变化转化为另一种高聚物的反应。高聚物形成反应的类型高聚物形成反应的类型按元素组成和结构变

19、化分类加聚反应（polyaddition reaction）缩聚反应（polycondensation reaction）高聚物化学转变按反应机理分类连锁聚合反应（chain polymerization）逐步聚合反应（step-reaction polymerization）36绪论绪论四、聚合反应的工业实施方法四、聚合反应的工业实施方法适用于连锁聚合反应的工业实施方法适用于连锁聚合反应的工业实施方法适用于逐步聚合反应的工业实施方法适用于逐步聚合反应的工业实施方法选择聚合实施方法的原则：选择聚合实施方法的原则：根据产品性质要求、单体性质、产品用作等缩合考虑。连锁聚合反应工业实施方法本体聚合（

20、bulk polymerization）溶液聚合（solution polymerization）悬浮聚合（suspension polymerization）乳液聚合（emulsion polymerization）逐步聚合反应工业实施方法熔融缩聚（melt polycondensation）溶液缩聚（solution polycondensation）固相缩聚（solid phase polycondensation）界面缩聚（interface polycondensation）乳液缩聚（emulsion polycondensation）37绪论绪论五、高分子科学的发展概况五、高分子科

21、学的发展概况天然高聚物的利用与改性阶段（天然高聚物的利用与改性阶段（19世纪前世纪前19世纪末）世纪末）合成高分子工业的发展与高分子化学的建立阶段（合成高分子工业的发展与高分子化学的建立阶段（20世纪初世纪初40年代末）年代末）现代高分子科学阶段（现代高分子科学阶段（20世纪世纪50年代初年代初20世纪末）世纪末）2121世纪的高分子科学世纪的高分子科学在合成上在合成上探索新的合成反应与方法；探索和提高高分子链结构有序和实现特定聚集态结构的合成技术；用普通单体通过共聚合成新的高聚物。在结构与性能上在结构与性能上研究高分子链和聚集态各层次的结构和相态特点及对材料宏观性能、功能的影响；研究外场条件

22、对各层次高分子链运动和结构的影响规律，开发潜在性能；研究新型高分子材料结构的特点、规律；研究生物高分子的结构特点、信息传递，合成仿生功能材料。在成型加工上在成型加工上研究高聚物成型原理，实现工业化；搜集高聚物流体数据，用计算机进行成型设计；注意在成型加工过程中控制结构，形成技能。在高分子化学上在高分子化学上精确设计、精确操作，发展完善高分子化学与物理的结合，实现纳米化、功能化、仿生化。38绪论绪论高聚物的基本特点：相对分子质量大、分子链长、相对分子质量的多分散性主要概念：高聚物、单体、结构单元、重复结构单元、链节、聚合度、多分散 性、相对分子质量命名方法：通俗法高聚物的类型：从主链结构上分：碳

23、链高聚物、杂链高聚物、元素有机高聚物、无机高聚物从用途上分：塑料、橡胶、纤维、粘合剂、涂料、离子交换树脂从高分子链排列上分：结晶高聚物、非结晶高聚物从高分子链几何形状上分：线型、支链型、体型高聚物的形成反应：连锁聚合、逐步聚合、高聚物转化聚合的工业实施方法取决于原料性质、产品用途、质量要求。具体的：连锁聚合可用本体聚合、溶液聚合、乳液聚合、悬浮聚合等方法；缩聚可用熔融缩聚、溶液缩聚、固相缩聚、界面缩聚、乳液缩聚等方法。展望21世纪的高分子科学39Basic Definition and NomenclaturePolymer:a substance composed of molecules

24、which have long sequences of one or more species of atoms or groups of atoms linked to each other by primary,usually covalent,bonds.Usually,a molecule is considered to be macromolecular when it exhibits properties typical of high molecular weight substances.Macromolecules are formed by linking toget

25、her monomer molecules through chemical reactions,the process by which this is achieved being known as polymerization.40Linear polymers may be represented by a chain with two ends.Branched polymers have side chains,or branches,of significant length which are bonded to the main chain at branch points,

26、and are characterized in terms of the number and size of the branches.Polymers with well-controlled modes of branching:comblike polymers,star polymers,dendrimers,etc.Network polymers have three-dimensional structures in which each chain is connected to all others,and are characterized by their cross

27、linking density or degree of crosslinking(number of junction points per unit volume).41Homopolymers:Polymers whose structure can be represented by multiple repetition of a single type of repeat unit which may contain one or more species of monomer unit.(M)n M:monomer unit or repeat unit;n:number of

28、repeat units or degree of polymerization(DP)n=2(dimer),3(trimer),4(tetramer),5 (pentamer),6(hexamer),.20:oligomer(e.g.,MW 20 or MW 10,000:polymer42NomenclatureSource-based nomenclature places the prefix poly before the name of the monomer,the monomers name being contained within parentheses unless i

29、t is a simple single word e.g.,poly(methyl methacrylate)(PMMA),polyethylene(PE).In structure-based nomenclature the prefix poly is followed in parentheses by words which describe the chemical structure of the repeat unit e.g.,poly(ethylene terephthalate)(PET).Polyesters:(O-R-CO)n or(O-R-O-CO-R-CO)n

30、e.g.,HO-R-OH+HOCO-R-COOH(diol+diacid)Polycarbonates:(O-R-O-CO)n e.g.,HO-R-OH+COCl2(diol+phosgene)Polyamides:(NH-R-CO)n or(NH-R-NH-CO-R-CO)n e.g.,NH2-R-NH2+HOCO-R-COOH(diamine+diacid)Polyurethanes:(O-R-O-CO-NH-R-NH-CO-)n e.g.,HO-R-OH+OCN-R-NCO(diol+diisocyanate)Polyureas:(NH-R-NH-CO-NH-R-NH-CO-)n e.g

31、.,NH2-R-NH2+OCN-R-NCO(diamine+diisocyanate)Polysiloxanes:Si(R2)-On(silicones)43The word copolymer is commonly used to describe polymers whose molecules contain two or more different types of repeat unit.Statistical copolymers are copolymers in which the sequential distribution of the repeat units ob

32、eys known statistical laws.Random copolymers are a special type of statistical copolymer in which the distribution of repeat units is truly random.-B-A-B-B-A-B-A-A-B-A-B-B-B-A-(For simplicity,illustration is for copolymers containing only A and B.)Alternating copolymers have only two different types

33、 of repeat unit and these are arranged alternately along the polymer chain:-A-B-A-B-A-B-A-B-A-B-A-B-A-B-Statistical,random,and alternating copolymers generally have properties which are intermediate to those of the corresponding homopolymers.44Block copolymers are linear copolymers in which the repe

34、at units exit only in long sequences,or blocks,of the same type.E.g.,AB diblock copolymers -A-A-A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-ABA triblock copolymers-A-A-A-A-A-A-B-B-B-B-B-B-B-A-A-A-A-A-Graft copolymers are branched polymers in which the branches have a different chemical structure to that of the ma

35、in chain.B-B-B-B-B-B-BB-B-B-B-B-B-B-B-B-B-B BB-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-B B B-B-B-B-B-B-B-B-B-B-B B-B-B-B-B-B-B-B-B-B-BBlock and graft copolymers usually show properties characteristic of each of the constituent homopolymers.They also have some unique prope

36、rties arising from the copolymerization.45NomenclatureStatistical copolymer of ethylene and propylene poly(ethylene-stat-propylene)ABA triblock copolymer of styrene(A)and isoprene(B)polystyrene-block-polyisoprene-block-polystyrenealternating copolymer of styrene and maleic anhydride polystyrene-alt-

37、(maleic anhydride)46Classification of PolymersThermosetsRigid materials and network polymers in which chain motion is greatly restricted by a high degree of crosslinking.Intractable once formed.Degrade rather than melt upon heating.Elastomers Crosslinked rubbery polymers that can be stretched easily

38、 to high extensions and which rapidly recover their original dimensions when the applied stress is released.Low crosslink density.Thermoplastics(plastics)Linear or branched polymers which can be melted upon the application of heat.(Largest proportion of the polymers used in industry.)47Crystalline p

39、olymersInvariably do not form perfect crystalline materials but instead are semicrystalline with both crystalline and amorphous regions.The crystalline phase of such polymers are characterized by their melting temperature(Tm).Amorphous polymersCharacterized by their glass transition temperature(Tg),

40、the temperature at which they transform abruptly from the glass state(hard)to the rubbery state(soft).This transition corresponds to the onset of chain motion.48Molecular Weight and PolydispersityMolecular Weight Molar mass(M):mass of 1 mole of polymer,in unit of g mol-1.(Practically people use mole

41、cular weight instead of molar mass.)M=xMo where x(or n):degree of polymerization,Mo:molar mass of repeat unit.Molecular Weight DistributionWith very few exceptions(e.g.,some materials of biological origin),polymers consist of macromolecules with a range of molecular weights.49Molecular Weight Averag

42、esTo define any arithmetic mean A,lets assume unit volume of a sample of N polymer molecules comprising:N1 molecules with molecular weight M1,N2 molecules with molecular weight M2,Nj molecules with molecular weight Mj.N=N1+N2+NjThe arithmetic mean molecular weight A is given as usual by the total me

43、asured quality(M)divided by the total number of elements.N1M1+N2M2+NjMjA=(Ni/N)MiN1+N2+NjNumber-average molecular weight(Mn):the sum of the products of the molar mass of each fraction multiplied by its mole fraction.NiMi Mn=Ni50The weight fraction wi is defined as the mass of molecules of molar mass

44、 Mi divided by the total mass of all the molecules presentwi=NiMi/NiMifrom which it can be deduced that(wi/Mi)=Ni/NiMiMn=1/(wi/Mi)Number-average degree of polymerizationxn=Mn/MoAnother method of averaging weights the property by mass(usually called weight)of the material having that property.The wei

45、ght-average molecular weight Mw is defined as the sum of the products of the molar mass of each fraction multiplied by its weight fraction wi.Mw=(wiMi)=NiMi2/NiMi Weight-average degree of polymerizationxw=Mw/Mo51Z-Average Molecular Weight(z stands for centrifuge.German zentrifuge)Mz=NiMi3/NiMi2=wiMi

46、2/wiMiViscosity-Average Molecular WeightM=(NiMi1+a/NiMi)1/a=(wiMia/wiMi)1/aMathematically,Mn Mw Mz,here the equality sign holds only for monodisperse polymers.The ratios of different molecular weight averages Mw/Mn and Mz/Mw are often used as characteristics of polymer polydispersity.For most polyme

47、rs Mw/Mn:1.52.5For monodisperse polymer:Mw/Mn=Mz/Mw=152聚合物结构与性能的关系聚合物结构与性能的关系HOW？研究方法研究方法结构：长链、柔性、缠结、链段运动结构：长链、柔性、缠结、链段运动性能：质轻、易着色、韧性、耐腐蚀、性能：质轻、易着色、韧性、耐腐蚀、易加工、减震、生物兼容、易剪裁易加工、减震、生物兼容、易剪裁53WHY？研究的目的？研究的目的指导大分子设计指导大分子设计指导加工与应用指导加工与应用发展高分子材料发展高分子材料54抗抗高高温温高高压压的的塑塑料料55高高分分子子分分离离膜膜56人工肾人工肾5758生物降解塑料生物降解塑料化学降解塑料化学降解塑料 光降解塑料光降解塑料 5960