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Published on October 15, 2007

Author: Gourangi

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Polymers A historic Perspective Dr ir Stefan Bon Year I - 2005:  Polymers A historic Perspective Dr ir Stefan Bon Year I - 2005 Course info::  Course info: Download lecture slides on: www.stefanbon.com Do online test before end week 10 Week 9 lecture CANCELLED Week 10: 2 lectures from 15:00-17:00 Introduction to polymer chemistry & polymer physics Polymers - poly = many, meros = parts Plastic - plasticos = to shape or form:  Polymers - poly = many, meros = parts Plastic - plasticos = to shape or form Polymer science is relatively new: Macromolecules were not recognized as such until the 1920s (Staudinger) Exponential industrial growth since Worldwar II (1939-1945) In 1998 annual polymer consumption in Europe: 30,381,000 ton (On average each European citizen consumed 75.8 kg of polymer in 1998) From the mid 1980s recycling becomes big business (In 1996 in the USA 9.4 wt% of disposable waste was synthetic polymers) Worldwide Polymer Production:  Worldwide Polymer Production Chemical Industry USA Employment:  Chemical Industry USA Employment 1975 1985 1995 Inorganic Chemistry 9.5% 8.1% 6.7% Drugs 10.7% 11.6% 13.5% Soaps, detergents 9.1% 8.4% 7.9% Organic Chemistry 9.6% 9.0% 7.4% Agriculture 4.2% 3.4% 2.8% Synthetic Polymers 56.9% 59.5% 61.7% Total ( × 1000) 1561 1769 1924 Categories of Polymers:  Categories of Polymers Natural Polymers Origin commodity Synthetic Polymers engineering specialty Thermoplastics Crosslinks Elastomers Thermosets 1900 BC (VII Dynasty)– 395 AD (Roman) Egyptians - Mummification:  1900 BC (VII Dynasty)– 395 AD (Roman) Egyptians - Mummification Pistacia Terebinthus Photopolymerization of Resins Buckley, S.A., Evershed, R.P. Nature 2001, 413, 837 Hairfield, H.H.Jr., Hairfield, E.M., Anal.Chem. 1990, 62, 41A 1600 BC – 1550 AD Mesoamericans - Rubber:  1600 BC – 1550 AD Mesoamericans - Rubber Manati rubber balls (1600 BC – 1150 AD) Rubber tool handles and figures (600-900 AD) medicinal chewing gum, rubber boots and clothes (1400 AD) Hosler, D., Burkett, S.L., Tarkanian, M.J., Science 1999, 284, 1988. El Manati Springs (Mexico) Olmec 1500 BC Meso-American Rubber:  Meso-American Rubber Latex from Castilla Elastica Liquid extracted from Ipomoea Alba (morning glory vine) Mixing causes: Latex coagulation and purification Introduction of plasticizers Thermal curing: Crystalline entanglements Chemical crosslinking via sulfonyl chlorides and acids 1839 AD - Re-invention of Rubber. New -vulcanisation with Sulphur - Charles Goodyear (PATENT No 3,633 1844):  1839 AD - Re-invention of Rubber. New -vulcanisation with Sulphur - Charles Goodyear (PATENT No 3,633 1844) pneumatic tire (Real: 1845 Thomson, but ‘copy’1888 Dunlop) 1846 Gun Cotton by Christian Schönberg :  1846 Gun Cotton by Christian Schönberg 1866 - Celluloid Wesley Hyatt & Alexander Parkes billiard balls 1885 – Celluloid Photographic Film – George Eastman – 1908 Cellulose Acetate Safety Film (Oscar awarded to Eastman company in 1950) “Unknown” discoveries of Polymers:  “Unknown” discoveries of Polymers 1839 Polystyrene by Eduard Simon 1872 Poly(vinyl chloride) (PVC) by Eugen Baumann 1907 - Bakelite Leo Baekeland:  1907 - Bakelite Leo Baekeland 1924 Concept of Macromolecules Hermann .Staudinger (Nobel Prize 1953):  1924 Concept of Macromolecules Hermann .Staudinger (Nobel Prize 1953) “Es ist aber wichtig den Molekülbegriff hier anzuwenden, trotzdem er sehr stark von dem bei dem molekular-dispersen System gebrauchten abweicht; denn wenn wir die Kolloidteilchen als Moleküle des Kautshuks bezeichnen, so soll damit ausgedrückt werden, daß die einzelnen Isoprenreste, die das Kolloidteilchen aufbauen, durch normale chemische Bindungen zusammengehalten werden, und daß wir im strukturchemischen Sinn es mit sehr langen Kohlenstoffketten zu tun haben…..Für solche Kolloidteilchen….schlagen wir zum unterschied die Bezeichnung Makromolekül vor.” taken from: Berichte der Deutschen Chemische Gesellschaft, 1924, 57, 1208-1208. 1924 XRay of Graphite 1928 X-Ray of Cellulose Herman Francis Mark:  1924 XRay of Graphite 1928 X-Ray of Cellulose Herman Francis Mark In a pioneering 1928 paper, Meyer and Mark solved the diffraction pattern to yield a structure in agreement with the chemical evidence--the first polymer crystal structure that has survived the test of time. With K. H. Meyer. Über den Bau des kristallisierten Anteils der Zellulose. Ber. 1928 61:593-613. 1929 Concepts of Addition and Condensation polymers, Wallace Hume Carothers :  1929 Concepts of Addition and Condensation polymers, Wallace Hume Carothers Wallace H. Carothers. J. Am. Chem. Soc.; 1929; 51(8); 2548-2559. Chem. Rev.; 1931; 8(3); 353-426. Neoprene (First Synthetic Rubber) Polyesters Nylons (Polyamides) Nylons:  Nylons Proteins are polyamides:  Proteins are polyamides 1929 Plastisizing and Moulding of PVC by Waldo Semon 1938 TEFLON by Roy Plunkett 1943/1949 Silly Putty (viscoelastic material or dilatant fluid?) by James Wright/Peter Hodgson :  1929 Plastisizing and Moulding of PVC by Waldo Semon 1938 TEFLON by Roy Plunkett 1943/1949 Silly Putty (viscoelastic material or dilatant fluid?) by James Wright/Peter Hodgson 1953/1954 Polyethylene/polypropylene Karl Ziegler & Giulio Natta (Nobel Prize 1963):  1953/1954 Polyethylene/polypropylene Karl Ziegler & Giulio Natta (Nobel Prize 1963) POLYETHYLENE (LDPE):  POLYETHYLENE (LDPE) Molecular Weights: 20,000-100,000; MWD = 3-20 density = 0.91-0.93 g/cm3 Highly branched structure—both long and short chain branches 15-30 Methyl groups/1000 C atoms Tm ~ 105 C, X’linity ~ 40% Applications: Packaging Film, wire and cable coating, toys, flexible bottles, housewares, coatings Ziegler’s Discovery:  Ziegler’s Discovery 1953 K. Ziegler, E. Holzkamp, H. Breil and H. Martin Angew. Chemie 67, 426, 541 (1955); 76, 545 (1964). + Ni(AcAc) Same result + Cr(AcAc) White Ppt. (Not reported by Holzkamp) + Zr(AcAc) White Ppt. (Eureka! reported by Breil) 1953 Discovery of DNA double helix – James Watson and Francis Crick (Nobel Prize 1962):  1953 Discovery of DNA double helix – James Watson and Francis Crick (Nobel Prize 1962) Francis Crick shows James Watson the model of DNA that they started building on Wednesday, 4th March and finished in the evening of Saturday, 7th March, 1953 in their room number 103 of the Austin Wing at the Cavendish Laboratories, Cambridge XRay Nature, 1953, 25th April Slide24:  A quick DNA update…. The four Bases:  The four Bases adenine thymine cytosine guanine Slide26:  1974 Paul J. Flory: "for his fundamental achievements, both theoretical and experimental, in the physical chemistry of the macromolecules"  (1953) Principles of Polymer Chemistry (George Fisher Baker Non-Resident Lec). Cornell University Press. ISBN 0801401348. 1991 Pierre-Gilles de Gennes:"for discovering that methods developed for studying order phenomena in simple systems can be generalized to more complex forms of matter, in particular to liquid crystals and polymers" Some more Nobel Prizes… 2000 Heeger, Macdiarmid, Shirakawa: "for the discovery and development of conductive polymers" :  2000 Heeger, Macdiarmid, Shirakawa: "for the discovery and development of conductive polymers" Trans polyacetylene Doping. Conductivity similar to copper/silver. LED: principle of electroluminescence Slide28:  2002 - John B. Fenn, Koichi Tanaka, Kurt Wüthrich: "for the development of methods for identification and structure analyses of biological macromolecules" 2005 – Yves Chauvin, Robert H. Grubbs, Richard R. Schrock: "for the development of the metathesis method in organic synthesis"

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