Polymers and Plastics

1. Polymers and Plastics History Uses Big Six Special Plastics Problems and Issues

3. Timeline - Precursors 1839 - Natural Rubber - method of processing invented by Charles Goodyear Timeline - Beginning of the Plastic Era with Semi Synthetics 1839 - Polystyrene (PS) discovered - Eduard Simon 1862 - Parkesine - Alexander Parkes 1863 - Cellulose Nitrate or Celluloid - John Wesley Hyatt 1872 - PVC - first created by Eugen Baumann 1894 - Viscose Rayon - Charles Frederick Cross, Edward John Bevan Timeline - Thermosetting Plastics and Thermoplastics 1908 - Cellophane ® - Jacques E. Brandenberger 1909 - First true plastic Phenol-Formaldehyde tradenamed Bakelite -Leo Hendrik Baekeland 1926 - PVC - Walter Semon invented a plasticized PVC. 1927 - Cellulose Acetate 1933 - Polyvinylidene chloride or Saran also called PVDC - accidentally discovered by Ralph Wiley, a Dow Chemical lab worker. 1935 - LDPE - Reginald Gibson and Eric Fawcett 1936 - Acrylic or Polymethyl Methacrylate 1937 - Polyurethanes for plastics materials and Perlon for fibers. - Otto Bayer and co-workers discovered and patented the chemistry of polyurethanes 1938 – Polystyrene(PS) made practical 1938 - Polytetrafluoroethylene or PTFE tradenamed Teflon - Roy Plunkett 1939 - Nylon and Neoprene -Wallace Hume Carothers 1941 - Polyethylene Terephthalate or PET - Whinfield and Dickson 1942 - LDPE 1942 - Unsaturated Polyester also called PET patented by John Rex Whinfield and James Tennant Dickson 1951 - HDPE - Paul Hogan and Robert Banks 1951 - PP - Paul Hogan and Robert Banks 1953 - Saran Wrap introduced by Dow Chemicals. 1954 - Styrofoam a polystyrene foam was invented by Ray McIntire for Dow Chemicals 1964 - Polyimide 1970 - Thermoplastic Polyester (includes Dacron, Mylar, Melinex, Teijin, and Tetoron) 1978 - Linear Low Density Polyethylene 1985 - Liquid Crystal Polymers

5. 1940’s Nylon

6. Nylon stocking • Nylon 은 DuPont 사 Wallace Carothers 에 의해 발명(1938) • 1940년 5월 15일 미국 뉴욕시에서 나일론으로 만든 4백만 켤레의 스타킹은 판매시작 수 시간만에 매진 • 이차대전 때 군사용품으로 전환되어 민간수요는 1945년 이후에 보급 • X200 SEM/EDX image • Dee Breger ,Mgr. SEM/EDX Facility, Lamont-Doherty Earth Observatory

7. History of Polymers • 1870년 미국 John Hyatt 셀루로이드(nitrocellulose + camphor) 개발 • 영국의 Alexander Parkes가 최초 개발한 Parksine을 응용 • 상아 대체 - 당구공 제조회사의 만 달러 공모 • 1907년 Leo Baekeland가 Bakelite(페놀-포름알데히드수지)개발, 대량 생산 • 1938년 Dow사는 폴리스티렌 대량생산 • 1939년 듀퐁사는 나일론(nylon-6,6)을 대량생산하여 스타킹 판매 시작. 고분자 화학 발달에 계기

8. History of Polymers • 1839년 Charles Goodyear 가 천연고무(latex)에 황을 가하여 타이어용의 고무 대량생산 • 고무의 내열 특성 때문에 타이어에 적합

9. Wallace Carothers, inventor of Nylon (1930 at DuPont). (1896 - 1937)

10. Hermann Staudinger(1953 Nobel Prize for chemistry) • In a landmark paper published in 1920, Staudinger concluded the structure of rubber and other polymeric substances: “polymers were long chains of short repeating molecular units linked by covalent bonds.” • Staudinger termed makromoleküls paved the way for the birth of the field of polymer chemistry.

11. Nobel laureates in polymer science K. Ziegler G. Natta (1897-1973) (1903-1979) P.J.Flory (1936- ) 화학 H. Staudinger (1881-1965) 1953 1963 1974 A.J.Heeger A.G. MacDiarmid H.Shirakawa (1910-1985) (1927- ) (1936- ) P.-G de Gennes (1932- ) 물리 2000 1991

12. polymer = poly(많은)+meros (부분) • 동일한 구조( 단위체, monomer )의 반복단위로 된 화합물 • 중합체라고도 불린다.

13. Tacticity Tacticity – stereoregularity of chain isotactic – all R groups on same side of chain syndiotactic – R groups alternate sides atactic – R groups random

14. cis/trans Isomerism cis cis-isoprene (natural rubber) bulky groups on same side of chain trans trans-isoprene (gutta percha) bulky groups on opposite sides of chain

15. ( CH CH2 CH2 CH CH CH2 )n ( CH2 CH )n Teflon Polyethylene Cl ( CF2 CF2 )n ( CH2 CH2 )n PVC Homopolymer is a polymer made up of only one type of monomer Copolymer is a polymer made up of two or more monomers Styrene-butadiene rubber

16. Copolymers random two or more monomers polymerized together • random – A and B randomly vary in chain • alternating – A and B alternate in polymer chain • block – large blocks of A alternate with large blocks of B • graft – chains of B grafted on to A backbone A – B – alternating block graft

17. Thermoplastics vs. Thermosets T Callister, rubber viscous Fig. 16.9 mobile Tm liquid tough liquid plastic Tg partially crystalline crystalline solid solid Molecular weight • Thermoplastics: -- little crosslinking -- ductile -- soften w/heating -- polyethylene polypropylene polycarbonate polystyrene • Thermosets: -- large crosslinking (10 to 50% of mers) -- hard and brittle -- do NOT soften w/heating -- vulcanized rubber, epoxies, polyester resin, phenolic resin Adapted from Fig. 15.19, Callister 7e. (Fig. 15.19 is from F.W. Billmeyer, Jr., Textbook of Polymer Science, 3rd ed., John Wiley and Sons, Inc., 1984.)

18. Annual U.S. production of plastics from 1935 to 1997

19. Comparison with Other IndustriesUnited States Plastics industry is the nation’s 4th largest manufacturing industry (shipments): • Motor Vehicles and Equipment • Petroleum Refining • Electronic Components and Accessories • Plastics (Source: Probe Economics, Inc. 2004)

20. 주요국 별 범용 플라스틱 생산 · 소비 현황 <2003 : 1,000 MT> <Source : Plastics Age Dec. 2005>

21. 국내 범용 합성수지 수급 현황 <단위 : 1,000 톤> <자료 : 한국석유화학공업협회, 광공업통계조사보고서 (통계청). >

22. 183 177 153 128 126 123 107 90 92 82 79 주요국 별 1인당 플라스틱 소비량 kg per capita <자료 : Plastics Age Dec. 2005, 광공업 통계조사보고서 (통계청)> ☞ Korea still has potentials of Sustainable Growth in Polymer Industry

23. Out of Crude Oil

24. 42 gallon

25. Polymers • Scientists use one or more of the following strategies to design the molecular feature of the polymer chain: 1. length of the chain (# of monomer units); 2. 3-D arrangement of the chains in the solid; 3. branching of the chain: 4. chemical composition of the monomer units; 5. bonding between the chains; 6. orientation of the monomer units within the chain.

26. Polymers • Polyethylene: most common plastic from the monomer ethylene (C2H4) polyethylene ethylene

27. A. 부가중합 (Addition polymerization) A1. Radical Polymerization • Initiation: homolytic cleavage of e.g. a peroxide. • Termination of the polymerization by reaction of two radicals:

28. A2. Cation Polymerization • Initiators: (Lewis) acids such as H+ and BF3.

29. A3. Anion Polymerization • Initiators: anions such as in C4H9Li or NaOC2H5.

30. SOME VINYL POLYMERS

31. RUBBERS: POLYMERS FROM DIENES

32. POLYMERIZATION PROCESS • Resonance stabilization of allylic radical. • Synthetic rubbers: mixture of structural fragments. • Natural rubbers (latex): regular structure with only Z-double bonds.

33. B. 축합중합 (Condensation polymerization) Polyesters polyethylene terephthalate PET, dacron Polycarbonates Lexan(GE)

34. Polyamides (nylons) Amide from lactam Cf) • Use in fibers, strong threads and clothes.

35. * 중부가 (Poly addition) : No low molecular by-product • Actually not a polycondensation, but a step-growth polymerization • Application as insulation material (PUR foam).

36. C. 부가중합 (Addition condensation)

37. 개환중합 (Ring-opening polymerization)

38. Big Six Polymers • Polyethylene (LDPE, HDPE) • Polypropylene (PP) • Polystyrene (PS) • Polyvinyl chloride (PVC) • Polyethyle terephthalate (PETE) -thermoplastic, meaning they can be melted and reshaped. They also tend to be flexible. -PE and PP have both crystalline and amorphous regions. The others - PS, PVC, and PET - are not crystalline. Their chains are bonded randomly.

40. Uses of the “Big Six” polymers

41. A growing PET polymer chain terephthalic acid ethyleneglycol

42. Polyethylene(PE) Radical polymerization of ethylene

43. Classification of PE • Polyethylenes은 밀도에 따라 분류한다. • 고분자의 가지치기 종류,갯수에 따라 밀도가 변한다. • HDPE (high density PE) - 우유통 • MDPE (medium density PE) - 배관 • LDPE (low density PE) - 플라스틱백, squeeze • LLDPE (linear low density PE) • a substantially linear polymer, with significant numbers of short branches, commonly made by copolymerization of ethylene with longer-chain olefins.

44. LDPE vs. HDPE - branching a HDPE molecule an LDPE molecule

45. Uses of LDPE • 유연성 • 마요네즈나 케찹 용기 등의 플라스틱 squeeze bottle • 강도와 내화학성이 우수 • 약품, 음료, 화장품 용기에도 많이 사용된다 • 발포제품 • 기포를 함유하고 있으므로 완충포장재, 고층건물의 지붕바닥재 및 소음 방지재, 스포츠레저용품 • 우수한 전기절연성, 유연성 • 옥내 외 각종 전선의 절연체, 피복

46. LDPE

47. Properties of LDPE • HDPE보다 가지가 많다 • the chains do not "fit well" together. • mp105 ~ 115 °C • 분자간 힘이 약하게 작용 • as the instantaneous-dipole induced-dipole attraction is less. • a lower density and tensile strength, increased malleability and faster biodegradation created by free radical polymerization

48. FT-IR of LDPE & HDPE

49. HDPE • Branching이 거의 없는 고분자 사슬 • stronger intermolecular forces • mp 120 ~ 130 °C • 제조방법 • by an appropriate choice of • catalysts (e.g. Ziegler catalysts, 노벨화학상, 1963) • reaction conditions.