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Institute of Chemical Technology and Polymer Chemistry [email protected] http://www.itcp.kit.edu/wilhelm/ Introduction to Polymerscience Prof. Dr. Manfred Wilhelm private copy 01/2019 KIT – Universität des Landes Baden-Württemberg und nationales Forschungszentrum in der Helmholtz-Gemeinschaft www.kit.edu Content 1 Introduction 1 1.1 Literature 1 1.2 Definition, materials 3 1.3 Definition, polymers 3 1.4 History and nomenclature 12 2 Polymer chemistry 13 2.1 Molecular architectures 13 2.2 Separation/classification of polymers into classes 16 2.3 Typical monomers, polymers 19 2.4 Synthesis 28 2.5 Carothers equations 30 2.6 Kinetics 31 2.7 Size distribution in linear polymers for step reaction 34 2.8 Chain growth reaction, e.g. radical 38 2.9 The ceiling temperature 42 2.10 Suspension polymerization 43 2.11 Emulsion polymerization 44 2.12 Ionic polymerization 45 2.13 Anionic polymerization 47 2.14 Kinetics and molecular weight distribution of ionic polymerization 49 2.15 Copolymers 54 2.16 Coordinative polymerization 57 2.17 Constitution, conformation and configuration isomers 58 3 Polymer physics, physical chemistry 62 3.1 The lonesome chain 62 3.1.1 End to end distance, contour length 62 3.1.2 Radius of gyration 64 3.1.3 Random-walk and Gaussian chain 65 3.1.4 Entropy-Elasticity, basic idea 68 3.1.5 Deviation from simple-statistics for end to end distance 70 3.1.6 Kuhn segment 72 3.1.7 Persistence length (“how stiff is a polymer”) 73 3.2 Polymer physics of melts 75 3.2.1 The reptation model 75 3.2.2 The amorhous state 79 3.2.3 The crystalline state 88 3.2.4 Kinetics of crystallization 100 3.2.5 How to reach 100% crystallinity in a solid polymer 102 4 Molecules and characterisation 104 4.1 Distribution of molar mass and determination of molar mass of polymers 104 4.2 Experimental determination of molecular weight and distribution 108 4.3 GPC, gel permeation chromatography 110 4.4 Ultracentrifuge 113 4.5 Light scattering of polymer solutions 116 4.6 IR-Spectroscopy 126 4.7 Mass spectroscopy 135 4.8 NMR-spectroscopy 149 5 Engineering properties 160 5.1 Mechanical properties 160 5.2 Dielectric properties 166 5.3 Processing of thermoplast; extrusion, injection molding, calendaring 169 6 Special topics 6.1 Polyelectrolytes 176 6.1.1 Definition, examples 176 6.1.2 Theory: Poisson-Boltzmann, Debeye-Hückel, Skolnick-Fixmann-Odijk 177 6.1.3 Experiments 183 6.1.4 Application: super absorbing polymers (SAP) 184 6.1.5 Application: oil production 187 6.1.6 Conclusion polyelectrolytes 189 6.1.7 Literature, polyelectrolytes 190 6.2 Spatially heterogeneous systems, e.g. blends or blockcopolymers 191 6.2.1 Definition 191 6.2.2 Why does the introduction of heterogeneity make sense? 191 6.2.3 How can heterogeneity be achieved 192 6.2.4 Theory of mixing, Flory-Huggins theory 196 7 Appendix 203 Staudinger - Nobel Lecture, December 11, 1953 Ziegler - Nobel Lecture, December 12, 1963 Natta - Nobel Lecture, December 12, 1963 Flory - Nobel Lecture, December 11, 1974 De Gennes - Nobel Lecture, December 9, 1991 Material classes, development and history of polymers 1 1 Introduction 1.1 Literature: 1) History: - Polymers, The origin and growth of a science, Herbert Morawetz, Dover Pub. 1985 2) Introduction: - Große Moleküle, Hans-Georg Elias, Springer 1985 - Introduction to polymers, R.J. Young, CRC Press 1991 3) Chemistry: - Grundriss der Makromolekularen Chemie, Bruno Vollmert, E. Vollmert- Verlag 1988 - Makromolekulare Chemie, Bernd Tieke, VCH 2005 - Makromolekulare Chemiei, Lechner, Gehrke, Nordmeier, Springer 2003, incl. CD - I.M.G. Cowie, V. Arrighi, Polymers: Chemistry and Physics of modern Materials, CRC Press, 2008 4) Polymer and engineering: - Material science for Polymers for engineers, Oswald/ Menges, Hanser 1995 - Polymermechanik, Schwarzel, Springer 1990 5) Encyclopaedia, dictionary: - Concise, Encyclopaedia of polymer science and engineering, Kroschwitz (editor) Wiley 1990 - I-IV von H.G. Elias, Chemie + Physik + Industrie + Anwendung,Wiley VCH 6-te Edition 1999-2003 6) Physics: - Physik kondensierter Materie, G. Strobl, Springer 2001 - The physics of polymers, 1995, G. Strobl, Springer 1996 - Polymer physics, U.W. Gedde, Chapman & Hall 1996 7) Characterisation: - Principles of instrumental analysis, Skoog, Leavy, Saunders College Publishing 1992 - Polymer Charakterisierung, Arndt/ Müller, Hanser 1996 - Polymer characterisation, B.J. Hunt, M.I. James, Blackie academy 1997 i Title is misleading; covers very detailed all aspects, in German. Material classes, development and history of polymers 2 - Polymer characterisation- physical techniques, D. Campell, R.A. Pethrick, I.R. White, Staley-Thornes 2000 - Spectroscopy of polymers, J.L. Koenig, Elsevier 1999 8) Polymer technology: - Handbuch der technischen Polymerchemie, A. Echte, VCH 1993 9) Internet: - http://scholar.google.com - www.vke.de (Verband der Kunststofferzeugenden Industrie) - www.pslc.ws/macrorg.htm - web.umr.edu/~mwlf/ Material classes, development and history of polymers 3 1.2 Definition, materials - Materials are synthetically or biologically built chemicals that we generally use due to there physical, dominatingly mechanical and chemical properties, specifically their 2 and 3 dimensional structure. - As a consequence: material science is inherent interdisciplinary: biology, chemistry, physics and mechanical engineering are interacting. - Currently, not only mechanical properties (module, T-stability,) chemical resistance), but also “functional” properties are more and more developed, investigated and applied. For example: magnetic ( storage of data), electric ( computer, CPU), chemical ( medicine) or optical functions are added - Materials can be classified as follows i. Metal (high, low density, conducting, semi-conducting, reactive, …) ii. Glass (organic, inorganic), frozen liquid iii. Ceramics (in general: inorganic, but crystalline) iv. Polymers (organic materials) 1.3 Definition, polymers: Polymers are high molecular weight synthetically or biologically built chemical structures that contain at least one repeat unit that is covalently bound and repeated. The dominant elements are C, H, O, N, Cl, F, S, P, Si,… How much materials do we need (world wide)? 1990 => 510 9 people 510t9 , if one 1t per person and year 9 t kg Steel: 10year 200 person and year Polymer: 60 106 t 12 kg year person and year Al: 15 106 t year 3kg person and year kg Note: Germany 50-70 person and year Factor 15 steel polymers, but: 78, g , 1 g Fe cm3 Polymer cm3 Material classes, development and history of polymers 4 6 Polymers 2002: 227 10 t year Note: There is an empirical correlation between price and production in general price ~ production-0.4 Factor 10 in production factor 2-3 in price Material classes, development and history of polymers 5 Source: Schwarzel 1990 Material classes, development and history of polymers 6 Use of polymers in our environment: Nature: construction, storage, clothing, protection Food: carbon hydrates, proteins Packing: bags, storage tanks (PE for H2, full cell in cars) Traffic: super plastified concrete (1-5% polymers), security glass, belts, airbag, oil additives Clothes: wool, cotton, gore-tex® (teflon), polyester Cosmetics: hairspray Hygiene: super absorber, surfactants Medicine: dialysis, contact lenses, controlled drug release Optics: light conducting fibres, organic LED (O-LED), NLO (non linear optics) Electronics: Photoresists, primer for UV-etching, electrically conducting polymers What do we want? - mechanical => high E, G module, low compressibility, M - low weight, low density - low price, P (For non functional polymers these properties are very important) Additionally: - inert - non toxic - temperature stability - dielectric, magnetical, optical properties - easy to form and shape ! If we assume that the importance for a specific applications scales with a scaling exponent (e.g. MPabc,, ) We might generate a “figure of merit” (Kenngröße), F Ma Fabc0 ;,, Pcb If price does not matter (e.g. space application, formula 1, professional sports) Ma F b Material classes, development and history of polymers 7 Do not take this too literately! Typical production (source: Nachrichten aus der Chemie 2004, p. 324): year 2002: 227 106 t , Germany 20 106 t year year polymer 6 t growth Production 10 y PE 56 (24%) 5,5% PP 32 (14%) 9,1% PET 32 (14%) 8% PVC 20 (12%) 4,7% € € In case we have an average price of 1.5 kg PE: 1 kg Production330 109 € year t€ Assuming a business volume of 200 year and person in a company 16510. 6 people in primary production! average production per person: 150 t year t Typical factory: 100000 1000000 year PE, PP, worldscale factory about 1000 people per factory Why investigating materials “Knowledge is power” Francis Bacon (1561-1626) Two examples: 1) Iron at times of Nebukhadnezar in bible (1125-1104 b.Chr.) Material classes, development and history of polymers 8 Daniel 2 Material classes, development and history of polymers 9 Material classes, development and history of polymers 10 2) PE in WW II Source: Morawetz Material classes, development and history of polymers 11 Read this every year in “Nachrichten aus der Chemie“ or “Macromol. Chem. Phys.“ around Feb. or March Material classes, development and history of polymers 12 1.4 History and nomenclature: Polymer: greek: poly: many; meros: parts Plastic: Polymer + additives Natural rubber: Kautschuk (German) from Cahuchu = “caa” (wood) and “o-chu” (tears) in the native South American language. The word rubber originates from first use to erase lead pencil marks from paper by rubbing Rubber trees first mentioned 1516 Short history: 5000 b.Chr. cotton (mexico) 3000 b.Chr. silk (china) 2000 b.Chr. bitumen (sealing of boats) 1500 a.Chr. rubber 1832-1838 F. Lüdersdorf + Charles Goodyear => vulcanisation of rubber via sulphur 1870 cellulose nitrate by Isaak Hyatt and John Hyatt films, packing, first thermoplast 1907 Bakelite, Leo Baekeland, phenol-formaldehyde resin, fist synthetic thermo set 1924 Hermann Staudinger (Freiburg, Germany) proposed polymers as linear chains built of covalent bonds; this concept was first heavily criticized by colleagues, Nobel price 1953 1930-1940 Wallace Carothers at Du Pont worked on Polyester and polyamids (Nylon®) 1930-1950 H.
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