高分子近代史課件

1、鄭 強(qiáng) 教 授Dr. Prof Qiang ZHENG 2004/9Development of Polymer Science高分子科學(xué)的形成與發(fā)展What is polymer其分子量(molecular weight) 104107 小分子 (small molecule)“點(diǎn)”(point)高分子(polymer)“一條鏈” (chain) “一串珠” (bead)MacromoleculePolymerHigh Polymer高 分 子高分子是指其分子主鏈上的原子都直接以價(jià)鍵連接，且鏈上的成鍵原子都共享成鍵原子的化合物價(jià) 鍵 bond缺電子鍵 electron-defect bond

2、配位鍵 coordinate-covalent bond共價(jià)鍵 covalent bondEarlierGoodyear(1839,美)天然橡膠（nature rubble）Parks (1855,美)硝化纖維素（guncotton）樟腦 （camphor）人造絲（rayon）de Chardonnet (1883,法)賽璐璐 (celluloid）Hyatt (1870)高分子和我們的關(guān)系 Oil industry data shows that only about 9% of all crude oil is used for petrochemicals.The largest use

3、 of crude oil is in fuel for transport(about53%).Of the oil used for petrochemicals,about half goes into plastics,so that the complete abolition of plastics would have a tiny effect on oil consumption.Indeed,plastics production uses oil fractions that might otherwise be flared;polymerization of ethy

4、lene ,propylene,dienes and cyclo-olefins to lightweight,high-added-value engineering materials,which keep the carbon content locked in a solid form, is a very “green” activity.Modern 高分子科學(xué) Polymer Science高分子化學(xué)Polymer Chemistry高分子物理Polymer Physics高分子材料Polymer Material歷史人物Storied Characters H .Staudin

5、ger (German，18811965)1.Organic Chemist and Polymer Chemist1881.Mar. 23, born in Worms 1965.Sep. 8, died in Freeburg . 1903, he studied at Darmstadt, Munich and Halle and obtained his doctorate . 1912, he was appointed associate professor at the Polytechnic in Karlsruhe, moved to Zurich and finally t

6、o the University of Freeburg in 1926. In 1910,he recognised that the current theories for the structure of natural rubber were incorrect. The controversies surrounding naturally occurring large molecules and experimental difficulties in studying them led him to look at materials based on simpler mol

7、ecules such as styrene. He introduced the concept of macromolecules, a term which he coined, and polymerisation in May 1922, in a report which appeared in Helvetica Chimica Acta. He met Wallace Carothers at a conference in Cambridge in 1935, following which he included polyesters in his studies of t

8、he properties of dilute polymer solutions - from which he discovered the relationship between viscosity and molecular weight. Towards the end of his career he turned his attention back to biological macromolecules and what is now called molecular biology.1920 On Polymer 論聚合 首次提出聚合就是小分子依靠化學(xué)鍵結(jié)合起來，形成大分

9、子的過程的理論，并提出了聚苯乙烯、聚甲醛、天然橡膠的線型長鏈結(jié)構(gòu)式1932 The high-molecular compounds 高分子有機(jī)化合物 首次提出了合成大分子具有多分散性，且物理性質(zhì)具有分子量依賴性，標(biāo)志著高分子化學(xué)的誕生。1953 Nobel Prize in Chemistry For his discoveries in the field of macromolecular chemistry.“鏈狀大分子物質(zhì)的發(fā)現(xiàn)”K .Ziegler (German，19891973)2.1898.Nov. 26, born in Helsa in Germany . 1973.Au

10、g. 12, died in otto Hahn. 1920, graduated under Prof. von Auwers at the University of Marburg/Lahn. 1936, he became Professor and Director of the Chemisches Institut at the University of Halle/Saale. 1943-1969, he was Director of the Max-Planck-Institut fur Kohlenforschung.Organic Chemist His earlie

11、r work involved the clarification of rubber synthesis reactions, cyclic carbon compounds used in perfumes and lithium in organic reactions. Zieglers most important discovery was made in 1953 from his work on organo-aluminium compounds. With E. Holzkamp, a student, he found that substances made by mi

12、xing organo-metallic compounds with certain heavy metals permitted rapid polymerisation of ethylene at atmospheric pressure. This significant contribution established that very high molecular weight polyethylene could be produced with linear chain structure and give valuable production, property and

13、 application potential. The catalyst was derived from triethyl aluminium and titanium tetrachloride. Although many other catalyst systems and polymerisation methods were devised, this work formed the basis of later developments in the production of long chain polymers from olefins such as propylene

14、and butadiene. The modern polyethylene range of specifically structured polymers has provided products readily formed as films, fibers and mouldings applicable in many areas of modern life. Blow moulded bottles (eg for milk and household cleaners), injection moulded containers, toys and appliance co

15、mponents are daily reminders of Zieglers outstanding and original work.烯烴的催化二聚作用,合成高級烯烴乙烯經(jīng)烷基鋁催化合成高級伯醇由烯烴合成萜醇由烷基鋁經(jīng)電化學(xué)或其他方法合成其他金屬的烷基化合物利用氫化烷基鋁和三烷基鋁做有機(jī)物官能團(tuán)的還原劑以三烷基鋁與四氯化鈦為催化劑(稱為ziegler-natta催化劑 )使乙烯在常溫常壓下聚合成線型聚乙烯 ,這項(xiàng)研究為高分子化學(xué)和配位催化作用開辟了廣闊的研究領(lǐng)域。 主要貢獻(xiàn)G .Natta (Italian，19031979)1903.Feb. , born in Imperia, I

16、taly. 1979.May ,died in Bergamo. 1924, he graduated in Chemical Engineering at the Polytechnic of Milan and teach there in 1927. 1936-1938, full-professor and director of the Institute of Industrial Chemistry at the Polytechnic of Turin. Since 1938, he has been full-professor and director of the Dep

17、artment of Industrial Chemistry at the Milan Polytechnic.Italian Chemist Prof. Natta began his career with a study of solids by means of X-rays and electron diffraction. He then used the same methods for studying catalysts and the structure of some high organic polymers. His kinetic research on meth

18、anol synthesis, on selective hydrogenation of unsaturated organic compounds and on oxosynthesis led to an understanding of the mechanism of these reactions and to an improvement in the selectivity of catalysts. He developed new uses for the commercial synthesis of methanol, formaldehyde, succinic ac

19、id and butyraldehyde. His intensive interest in and studies of polymers in conjunction with the Italian firm Montecatini led in 1953 to his use of Ziegler catalysts for the polymerisation of propylene. He also developed catalyst systems for producing syndiotactic polypropylene. he contribution of Na

20、tta to the development of high polymers of profound use in the manufacture of films, fibres, synthetic rubber, etc., has provided a major building block towards our current domestic and commercial society.以丁烯脫氫制成丁二烯 ,發(fā)展了合成橡膠單體 的制備方法以三氯化鈦和烷基鋁為催化劑 ,丙烯在低壓下高收率地聚合,生成 分子結(jié)構(gòu)高度規(guī)整的立體定向聚合物 聚丙烯進(jìn)一步成功地將其催化劑分別用于丁烯

21、和4-甲基-1-戊烯的立體定向聚合,首先制成了分子結(jié)構(gòu)高度規(guī)整的聚丁烯和聚甲基戊烯以釩鹵化物和烷基鋁為催化劑,使乙烯和丙烯共聚合制成無規(guī)結(jié)構(gòu)的乙丙橡膠主要貢獻(xiàn)立體規(guī)整聚合Plastic、Rubble、FibreNobel Prize in Chemistry聚丙烯聚合環(huán)烯烴環(huán)烯烴聚合非烯單體1963，Ziegler、Natta在高分子合成化學(xué)和工藝領(lǐng)域中的發(fā)現(xiàn)for their discoveries in the field of the chemistry and technology of high polymers Ziegler-Natta polymerization is a m

22、ethod of vinyl polymerization. Its important because it allows one to make polymers of specific tactivity. It was named for Karl Ziegler and Giulio Natta, who were pioneers in this type of polymerization, though history and a federal court have decided that Robert L. Banks and J. Paul Hogan were the

23、 first to discover the process. Ziegler-Natta is especially useful, because it can make polymers that cant be made any other way, such as linear unbranched polyehtylene and isotactic polypropylene.Free radical vinyl polymerization can only give branched polyethylene, and propylene wont polymerize at

24、 all by free radical polymerization. So this is a pretty important polymerization reaction, this Zieglar-Natta stuff. 3. P. J. Flory (USA，19101985)Polymer scientist1910.Jun. 19, born in Sterling, Illinois, of Huguenot-German parentage. 1931, graduated from the Manchester College. 1934, obtained his

25、doctorate and joined the Central Research Department of the DuPont Company. 1937, joined the Basic Science Research Laboratory of the University of Cincinnati. 1943-1948, at the Research Laboratory of the Goodyear Tire and Rubber Company. 1961, accepted a professorship in the Department of Chemistry

26、 at Stanford University Kinetic studies of condensation polymerization enabled him to calculate the most probable distribution of molecular sizes in the polymer by assuming, contrary to conventional wisdom of the time, that reactivity is largely independent of molecular chain length. Other major con

27、tributions include the concept of chain transfer in the kinetics of vinyl polymerization, a statistical theory of gel formation from monomers with more than two functional groups, the Flory-Huggins theory of polymer solution thermodynamics, and the excluded volume effect which causes significant exp

28、ansion of polymer coils over what had been previously theorized, theories of rubber elasticity and of liquid crystals, and many more. Flory, more than any other individual, showed that the physical and chemical properties of macromolecules are as understandable as those of nonpolymers via the basic

29、principles of kinetics, thermodynamics, and statistical mechanics.縮聚過程的分子量分布理論 molecular weight distribution theory of polycondensation自由基聚合的鏈轉(zhuǎn)移理論 chain transfer theory of free radical polymerization凝膠化理論 gelification theory主要貢獻(xiàn)非晶態(tài)高聚物本體構(gòu)象概念 conception of bulk conformation of amorphous polymer高分子溶液熱力

30、學(xué)理論 thermodynamic theory of polymer solution溶液或熔體粘度與分子結(jié)構(gòu)關(guān)系 the relation between molecular structure and solution or melt viscosity液晶高分子理論 liquid crystal polymer theory1953 Principles of Polymer Chemistry 高分子化學(xué)原理Became bibles in the field A comprehensive guide to Polymers by the Nobel winning Flory h

31、imself! The book is an essential read for anyone interested in polymer science, and knowledge of how Flory developed and demonstrated several key ideas used in everyday polymer science. Not recommended as a textbook for beginners, but as reference book for anyone planning to delve deeper into the su

32、bject! 1969 Statistical Mechanics of Chain Molecules 鏈分子的統(tǒng)計(jì)力學(xué) It is the recommended introduction into the subject of rotational isomeric state theory for the novice and the most important work of reference for those seeking to rationally deduce the conformational characteristics of macromolecules fr

33、om a detailed knowledge of the chain structure.1974 Nobel Prize in Chemistry For his fundamental achievements, both theoretical and experimental, in the physical chemistry of the macromolecules4. P. G. de Gennes (French，1932)1932, Born in Paris. 1955, majored from the Ecole Normale Suprieure 1955-19

34、59, research engineer at the Atomic Energy Center. 1961, assistant professor in Orsay and soon started the Orsay group on supraconductors. 1968, switched to liquid crystals. 1971, became Professor at the Collge de France, and participated to STRASCOL on polymer physics. Gennes investigated how extre

35、mely complex forms of matter behave during the transition from order to disorder. He showed how electrically or mechanically induced phase changes transform liquid crystals from a transparent to an opaque state, the phenomenon exploited in liquid-crystal displays. His research on polymers contribute

36、d to understanding how the long molecular chains in molten polymers move, making it possible for scientists to better determine and control polymer properties. Simple View on Condensed Matter 凝聚物質(zhì)概述 The works presents a personal selection of the major works of de Gennes. It comes complete with after

37、thoughts by the author on his main papers, explaining their successes or weaknesses, and the current views on each special problem. This collectors volume contains all the important works of de Gennes which have made a lasting impact on our understanding of condensed matter, and serves as an essenti

38、al reference book for all condensed matter physicists and physical chemists. It also bears testimony to the genius of a remarkable man, and should be a source of inspiration for aspiring scientists around the world This volume of collected works of Pierre-Gilles de Gennes will be a valuable and stim

39、ulating source for many years to come for younger readers and for beginners in the subfields of condensed matter covered in this volume, as well as a useful and compact reference book for all workers in the field. Helmut R Brand Advanced Materials, 1993 A few of the judges on the Nobel committee des

40、cribed Gennes as the Isaac Newton of our time in having successfully applied mathematics to generalized explanations of several different physical phenomena. “當(dāng)代牛頓”被譽(yù)為1991 Nobel Prize in Physics For discovering that methods developed for studying order phenomena in simple systems can be generalized

41、to more complex forms of matter, in particular to liquid crystals and polymersHideki Shirakawa（白川英樹 ） (Japanese，1936)5.1936. Aug. 20 , born in Tokyo 1961, graduated from the Tokyo Institute of Technology with a degree in chemical engineering 1966, received his doctorate in engineering. 1976, went to

42、 the University of Pennsylvania in the United States as a 1982, he became a professor of the faculty of the University of Tsukuba. Organic Chemist2000.Apr, he was appointed professor emeritus. researcherHow can plastic become conductive? Plastics are polymers, molecules that form long chains, repeat

43、ing themselves like pearls in a necklace. In becoming electrically conductive, a polymer has to imitate a metal, that is, its electrons need to be free to move and not bound to the atoms. The first condition for this is that the polymer consists of alternating single and double bonds, called conjuga

44、ted double bonds. However, it is not enough to have conjugated double bonds. To become electrically conductive, the plastic has to be disturbed - either by removing electrons from (oxidation), or inserting them into (reduction), the material. The process is known as doping. What Heeger, MacDiarmid a

45、nd Shirakawa found was that a thin film of polyacetylene could be oxidized with iodine vapor, increasing its electrical conductivity a billion times. This sensational finding was the result of their impressive work, but also of coincidences and accidental circumstances. 白川英樹教授對“發(fā)現(xiàn)導(dǎo)電聚合物”的主要貢獻(xiàn)在于他首次合成出

46、了高性能的膜狀聚乙炔。這是一種具有相當(dāng)規(guī)整結(jié)構(gòu)的材料，有較高的結(jié)晶度，且其表觀密度僅為0.48cm2，這無疑給對其進(jìn)行摻雜提供了極好的基礎(chǔ)。The Society of Polymer Science, Japan (1983)The Society of Polymer Science, Japan (2000)The Order of Culture from Japanese Government(2000)awards2000 Nobel Prize in Chemistry together with Alan J. Heeger and Alan G. MacDiarmid for

47、 the discovery and development of conductive polymers Ryoji Noyori （野依良治 ） (Japanese，1938)6.Organic Chemist1938.Sep. , born in Kobe,Japan. 1961, graduated from the Kyoto University, Faculty of Engineering. 1969-1970, went to Harvard University as a postdoctoral associate. 1972, appointed Professor a

48、t Nagoya University, and assumed his current positions in 2003. Ryoji Noyori and his research group designed and synthesized chiral compounds such as diphosphine-binapthyl or BINAP which, when complexed with transition metals, form chiral hydrogenation catalysts. The BINAP-ruthenium(II) complex was

49、used to produce the anti-inflammatory agent naproxen in high enantiometric purity and in very high yield. For this important work, Ryoji Noyori shared one-half of the Nobel Prize in Chemistry (2001) with William S. Knowles for their work on chirally catalysed hydrogenation reactions. The other half

50、was awarded to K. Barry Sharpless. The Laureates have opened up a completely new field of research in which it is possible to synthesise molecules and material with new properties. Today the results of their basic research are being used in a number of industrial syntheses of pharmaceutical products

51、 such as antibiotics, anti-inflammatory drugs, and heart medicines. 野依良治在威廉諾爾斯的基礎(chǔ)上進(jìn)行了深入而廣泛的研究，并開發(fā)出了性能更為優(yōu)異的手性催化劑。這些催化劑用于氫化反應(yīng)，能使反應(yīng)過程更經(jīng)濟(jì)，同時(shí)大大減少產(chǎn)生的有害廢棄物，有利于環(huán)境保護(hù)。這些工作對手性氫化催化劑在工業(yè)上的應(yīng)用起到極大的推動作用。目前，很多化學(xué)制品、藥物和新材料的制造，都得益于野依良治的研究。awardsThe Chemical Society of Japan Award (1985)The Japan Academy Prize (1995)The

52、Order of Culture (2000)The Wolf Prize in Chemistry (2001)The Roger Adams Award (2001)2001 Nobel Prize in Chemistry with K. Barry Sharpless and William S. Knowles For their work on chirally catalysed hydrogenation reactionsFamous Polymer Scientists in China著名中國高分子科學(xué)家介紹王葆仁院士錢人元院士徐 僖院士于同隱教授馮新德院士沈家驄院士潘祖

53、仁教授沈之荃院士楊士林教授浙江大學(xué)四川 大學(xué)北京 大學(xué)吉林 大學(xué)復(fù)旦 大學(xué)中國科學(xué)院 王葆仁（1906-1986) Chemist 1.1906, born in Yangzhou, Jiangsu province. 1927, graduated from the Chemistry Department of Southeastern University. 1935, got doctor degree of the London University Empire College. 1959, founded the Polymer Chemistry and Physics Dep

54、artment of Chinese Science and Technology University.1980, he was elected as a full member of the Chinese Academy of Sciences. Wang set up the Department of Polymer Chemistry and Physics in the University of Science and Technology of China in 1959. He was one of the chemists in China who first condu

55、cted polymer chemistry research. He studied polymethyl methacrylate and polycaprolactam in the 1950s. He also studied silicone chemistry and did a lot in the synthesis of silicon-carbon-silicon-oxygen type of polymers. He was interested in heterocyclic heat-resistant polymers and did some creative w

56、ork. In the 1970s, he pointed out the importance of strengthening research on polymers which were used in large quantities, such as polypropylene. He also did a lot of research on hydrocarbon chemistry. 王葆仁中國最早從事高分子科學(xué)研究的化學(xué)家之一。50年代開始研究聚甲基丙烯酸甲酯、聚已內(nèi)酰胺。對有機(jī)硅高分子、特別是硅碳硅氧鏈高分子的合成做了深入研究。對耐高溫雜環(huán)高分子的合成及性能進(jìn)行了較廣泛研

57、究，并在應(yīng)用方面作了許多開拓工作。70年代提出加強(qiáng)高分子大品種如聚丙烯等的研究。在烴類化學(xué)方面也做過許多研究。著有有機(jī)合成化學(xué)上下冊。 錢人元（1917.9-2003.12）Chemist2.1919.Sep. 19, he was born in Changshu , Jiangsu province. 1939, graduated from the Chemistry Department of Zhejiang University. 1943, went to the United States to take postgraduate studies mainly in the U

58、niversity of Wisconsin. 1948, associated with Xiamen University and Zhejiang University as professor in physical chemistry.1951, he joined the Chinese Academy of Sciences as research professor in the institute of Physical Chemistry,Institute of Applied Chemistry and then the Institute of Organic Che

59、mistry at Shanghai, where he started his research career in the physics and physical chemistry of polymers. 1977-1981, moved to Beijing and served as the Department Head,Deputy Director. 1981-1985, Director of the Institute. 1982-1986, president of Chinese Chemical Society. 1986-1994, Chairman of Po

60、lymer Division of the Society.1980, he was elected as a full member of the Chinese Academy of Sciences. He has won many awards,such as the State Natural Science Awards, State Science and Technology Progress Award, Qiushi Prize for distinguished Scientists in 1994, and the International Award of the