Chapter 1 Introduction

1. 20 Polymer 08 Sep. 12, 2008 Chapter 1Introduction Chemical and Bioengineering Konkuk University

2. The term polymer was coined in 1833 by Jöns Jakob Berzelius Nitrated cellulose–marketed as celluloid and guncotton Commercial synthetic polymer–phenol formaldehyde resin-Bakelite • Scientists believed that polymers - clusters of small molecules (called colloids), without definite molecular weights, held together by an unknown force, a concept known as association theory. • In 1922, Hermann Staudinger proposed that polymers consisted of long chains of atoms held together by covalent bonds. • Work by Wallace Carothers in the 1920s also demonstrated that polymers could be synthesized rationally from their constituent monomers

3. 1-1. Small molecules chemistry& Large molecules chemistry Definitions of Polymer&basiscondition • Macromolecule • chemical: dyeing, oxidation, degradationreaction. • physical: melting&crystallizationpossibility • mechanical : elasticitymetamorphosis 및 배향 가능 • The molecularcohesion • The number average molecular weight: over 10,000

4. 1-1. Small molecules material & Large molecules material 1. The size of molecules (molecular weight):       Polymerover 10,000 , nonlinear (coiled comformation) 2. Viscosity:     Polymerthe specitic higher viscosity of Colloid solution 3. Separation: dialysis using the molecular weight difference 4. Volatility: Polymer nonvolatile 5. The melting point: Polymer  A wide range 6. 다분자성: The identicalstructure unit, differentmolecular weightdistribution  The average molecular weight

5. What is a polymer? 1. The origin of Polymer polymer : poly+ mer (poly= many + meros = parts = unit)  2. Polymer’s example 1) poly ethylene (P.E)   2) poly propylene (P.P) 3) poly isoprene

6. [CH2CH2] CH=CH2 CH3CH2 Oligomer – few monomer units joined together LMW Structural unit enclosed by brackets – repeating unit (monomeric unit) End groups- structural units that terminate polymer chains Polymers – with reactive end groups – telechelic polymers

7. The basic terminology • Polymer • The large molecules made up of simple repeating units. (2) 단량체 (monomer)           The small molecules that may become chemically bonded to other monomers to form a polymer ( For Polymerization Processes) (3) 반복 단위 (repeating unit, constitutional repeating unit, CRU)  The minimum repeating unit for the molecule chain. The structure of polymer is -[M]n- (repeating unit: M)

8. (4) 중합도 (Degree of Polymerization), DP DP: The number of repeat units (monomer) in an average polymer chain. p: 반응도 (extent of reaction), 카로더스 식 (Carothers eq.)             • Total number of structural units including end groups • Related to chain length and molecular weight

9. 1-2. The development of the Polymer 1839      Vulcanized rubber development(C. Goodyear) 1868      nitrocellulose synthesis(J.W. Hyatt) 1888      The preumatic tire(bicycle) development (J. B. Dunlop) 1909      phenol-formaldehyde resin production(L.H. Baekeland)1922      H. Staudinger-Polymer concept’s proposal. 1927      cellulose actateandpoly(vinyl chloride) introduction.1928      poly(methyl methacrylate) commercialization(O. Rohm). 1930      polystyrene production. 1931      Neoprene rubber production(W. H. Carothers, DuPont Co.) 1935      nylon 66 production(W. H. Carothers). 1936      PANN, SAN andpoly(vinyl acetate) introduction. 1937      polyethylene synthesis(O. Bayer). 1938      nylon 6andepoxy resindevelopment. LDPE synthesis. 1941      PET synthesis(J.R. WhinfieldandJ.T. Dickinson). 1942      The commercialization of PAN fiber.

10. 1-2. The development of the Polymer 1948      ABS resin production. 1952      The development of the polymerization catalyst(under low pressure) was made by the K. Ziegler(ethylene)1953      Hermann Staudinger, who won the Nobel Prizs(Work on macromolecules) 1955      The development of stereoregular polymer using Ziegler catalyst. (G. Natta )1956      poly(phenylene oxide)development(A. S. Hay) 1958      polyacetal resin production opening.              F. Sanger, The determination method of peptide bond in amino acids (The Novel Prize)1960     J. D. Watson&F. H. C. Crick, Discovery of the DNA Double Helix (The Nobel Prize in Physiology or Medicine) 1962      phenoxy resin, EPR Production. 1963      Guilio Natta(Development of catalysts and synthesis of polymers) 1964      EVA, ionomer, polyimide, denaturationPPO come. 1965      polysulfone production. 1968      H. G. Khorana, The experimental synthesis of DNA (The Nobel Prize in Physiology or Medicine) 1970      The development of Plasticity elastic body. 1985      Liquid crystal polymer product.

11. 1-3.The formation of polymer compound • Polymerization of monomer • 단량체 (momomer)   고분자 (polymer) 중합 (polymerization) • Monomer & polymer • A. 단량체 (monomer) •     ① Low molecular weight, monomer: Polymer consist of the repeating unit. •     ② monosaccharide, ethylene, amino acid, nucleotide •     ③ The simplicity: monosaccharide, fatty acid, amino acid (20aa) •  B. 중합체 (polymer) •     ① The large molecule composed of repeating structural unit. •     ② polysaccharide, lipid, protein, nucleic acid •     ③ The diversity: The composition of a few monomer., the diversity of linking order

12. 1-3. The formation of polymer compound 2) 작용기 (functional group): The chemical reaction among the monomers. 3) Repeating unit: ex. Polystyrene: -CH2-CHO- Nylon 6: -NH-(CH2)5-CO- Polyethylene: -CH2-CH2- 4) The number of the repeating unit - n: Degree of Polymerization(DP) 5) Molecular weight= the molecular weight of the structural unit(Mm) X DP(n)   6) The display of chemical structure: the structural unit &DP 7) Oligomer: DP5-20

13. 1-4. The structure of polymer compound     1) Homopolymer ( a single monomer)      ① linear polymer    ex) -A-A-A-A-A-    ② branch polymer   ex) -A-A-A-A-A-                                        A-A-A-A-A-A     2) Copolymer (two or more monomers)       ① alternating copolymer  ex) -ABABABABABAB-       ② random copolymer     ex) -ABAABBA       ③ block copolymer       ex) -AAAABBBBAAAA-     ④ graft copolymer       ex) -AAAAAAAAAAAA-                                             BBBBBBBBBB

14. Linear Polymer Branched Polymer Network Polymer Curing Crosslinking Vulcanization (rubber) The structure of polymer a. Linear Polymer Thermoplastic b. Branched Polymer c. Network or Crosslinked Polymer: Infusible, insoluble, swelling Thermosetting resin

15. Branched structure of polymer ladder star comb Semi-ladder polyrotaxane polycatenane Non-covalent bonds Dendrimer (cascade polymer)

16. Isomer of polymer Conjugated Diene,isoprene monomer : addition polymerization.

17. The steric feature of polymer (Tacticity) vinyl polymers with a substituent X ( CH2-CHX )n type whichhas liner polymer Isotactic Tacticity: substituentX-the relative stereochemistry of adjacent chiral centers within a macromolecule Syndiotactic Atactic strength Isotactic > syndiotactic > Atactic

18. Natural polymers 1. 섬유 (Fibers)     1) ex: cotton, wool, et al (application: clothes and industry)     3) molecular structure: oriented long-chain molecule of cellulose, crystallinity     4) mechanical : 고인장강도 (high tensile strength)   2. 고무 (Rubber)     1) ex: Polyisoprene     2) 20세기 초 rubber tree culture: Sri Lanka, Malaysiacf) the place of orgin: Brazil브라질 3) mechanical : high extensibility (800%)   3. 생체고분자 (Biopolymers)     1) ex: protein, polyamide, polysaccharide     2) appliocation: adhesive, 인공피부, Drug, functional foods 3) muscle, collagen, ligament

19. ex: Polysaccharide Polymerization of monomer C:H:O=1:2:1(CH2O)n

21. Biopolymers

22. Synthetic Polymers 1. 섬유 (Fibers) 1) Man-made fiber: artificial silk cellulose’schemical treatment. soluble cellulose derivative: cellulose acetate, cellulose xanthate 2) Artificial fiber from monomer       ① nylon:  Nylon 66       ② polyester: Terylene       ③ acrylic fiber: Orlon       ④ polypropylene: Ulstron

23. Synthetic Polymers 2. 고무 (Rubbers)     1) Buna rubber: The Germany develop at the World War II.     2) GR-S : The USA develop at the World War II 3) Butyl rubber       - theinner tube of tire use. - Defect: the crystallization at the low temp. - Amorphous

24. Synthetic Polymers 3. Crystalline Polymers     i. the intermediate property between glass and rubber. - semi crystalline: crystallinity + amorphous     ii. synthetic fiber      - sub-group of crystalline polymer     iii. crystalline polymer’s example 1) polyethylene        - 110 ~ 130℃, application: wire, packing materials, bottle and household goods 2) polypropylene        - 170℃, stronger and more durable than polyethylene .       3) nylon        - 265℃, application: fiber, plastic, gear, zipper, the gasoline tank ( Melting temp. is high ) 4) teflon        - 365℃, application : frying pan, coating materials, bearing

25. Synthetic Polymers 4. Glasses and resins 1) glassy polymer         ① property: transparency, brittleness         ② structure: amorphous like rubbers         ③ single-crystal (quartz, diamond, rock salt) : clearness ④attractive force of the molecular: glassy polymer (strong) > rubber (weak) ⑤ glassy polymer’s ex.: - polystyrene(P.S)           - poly(methylmethacrylate)(PMMA)(=perspex)           - poly(vinylchloride)(PVC)

26. Synthetic Polymers 2) Resins      ① phenol-formaldehyde resin           1907year: Baekeland가 invention patent. Structure of synthetic resin of the phenol-formadehyde (bakelite) type         - short segment with many branch. network         - incorporation with wood-flour: filler or reinforcing material, pigment         - application: the electronic socket, board et al ( an insulator)      ② melamine resin - application: table wear, toys - prooperty: thermosetting resin( no melt at the heat and solution : stable ).

27. 1-5. Nomenclature of polymer compound • Named according to polymer types, or functional groups in repeating unit with prefix, poly • Eg- polyesters, polyamides. • Vinyl polymers– polymers from monomers with carbon-carbon double bonds (CH2=CH-, vinyl group) • Polymers derived from simple alkenes (ethylene or propylene)- polyolefins • Vinyl and non vinyl polymers

28. n n n n Poly(1-pentene) n Poly(acrylic acid) Poly(a-methylstyrene)     1) common name: Poly + monomer name Polyethylene n ex) Polytetrafluoroethylene Polystylene

29. IUPAC- recommends – names be derived from the structure of the base unit, or constitutional repeating unit (CRU) • The smallest structural unit is identified • Substituent groups on the backbone are assigned the lowest possible numbers • The name is placed in parentheses (or brackets and parentheses, where necessary), and prefixed with poly.

30. n n n n Poly(1-pentene) n Poly(acrylic acid) Poly(a-methylstyrene)     2) IUPAC: i. 최소 구성단위 (CRU) 정의 ii. 주쇄의 치환체에 가장 낮은 번호 부여 iii. CRU명을 괄호안에 넣고 그 앞에 poly 붙임 Polyethylene Poly(methylene) n Polytetrafluoroethylene Poly(difluoromethylene) Polystylene Poly(1-phenylethylene) Poly[1-(1-propyl)ethylene] Poly(1-carboxylethylene) Poly(1-methyl-1-phenylethylene)

31. n n Condensation polymer (from two monomers) Poly(hexamethylene sebacamide) Poly(ethylene terephthalate) IUPAC: Poly(oxyethylene oxyterephthaloyl)

32. y x x Poly(styrene-co-methyl acrylate) y Copolymer (from two or more monomers) • among the monomers’s name–co- insertion Poly(ethylene-co-methyl acrylate) • among the repeating units–alt-, –b-, –g- insertion z x y Poly(styrene-b-isoprene-b-styrene)

34. The sturcture monomerrepeating unitcommon nameIUPAC

35. n Naming • Nylon: Polyamide Nylon 610: Poly(hexamethylene sebacamide) Nylon 66: Poly(hexamethylene adipamide) • Dacron: Polyester • Teflon: Poly(tetrafluoroethylene)

36. Research subject of polymer field 1) The development and use of polymer having the high effectiveness and specific property strongly powerful plastic, heat resistant polymer synthesis of polymer’s specific function 2) The environmental friendship polymer- resolvability & recycling The treatment problem of the large molecule‘s wastes The development need of the polymer with decomposition and recycling 3) The polymer of the resources and energy saving

37. C H O H 2 O O H N H2 O C H O H H O 2 O O O O H NH2 O H H O H C 2 O H O H O H H O O O O H H O H C O O 2 n H O H C 2 n Glucose : Galactose : Mannose 2 3 2 Biopolymer: Polysaccharide (Chitosan, Methylan) Methylan Chitosan u Methylobacterium organophilum u A cationic polymer with NH2 group Biocompatibility and bioactivity Easy derivatization u Extracellular anionic polysaccharide u Reducing Sugar (76.9%), Uronic Acid (12.4%), u Pyruvic Acid (5.1%), Acetic Acid (0.6%), Protein (6.1%) u DO-stat Culture, Scale-up Chitosan Methylan MW: 2,000,000 MW: 1,000,000

38. + H H + (CH3)3 C H O R C H N C H 2 2 3 O O H O H O O O + + H H N N n n H H ( C H ) ( C H ) 3 3 3 3 quaternized DEAE-Polysaccharide quaternized NH2-Polysaccharide Aminoderivatized Cationic Polysaccharide Bile Acid Sequestering Capacity Antimicrobial Activity Antitumor Activity Ionic and Hydrophobic Interactions Anticomplementary Activity Biotechnol. Appl. Biochem. 35, 2002; Biosci. Biotechnol. Biochem. 63(5) 2003

39. Enterohepatic Circulation of Bile Acid and Cholesterol Lowering Action of Bile Acid Sequestrant Cholesterol 3. Increase of Bile Acid hepatic synthesis from Cholesterol Bile acids Hepatic synthesis = 0.2 - 0.6 g/day Intestine Pool = 2-4 g Bile acid absorption Cycles/day = 6 -10 = 12-32 g/day (Efficiency >95%) Fecal excretion = 0.2-0.6 g/day 1. Prescription of Bile acid sequestrant 2. Increase of Bile acid fecal excretion Biosci. Biotechnol. Biochem. 63(5): 833-839, 2003

40. Morphology Change of HepG2 by the Chitosan Derivatives (A) Control HepG2 100 80 Chitosan Amino-Chitosan 60 qAmino-Chitosan Viable Liver Cancer Cell (%) DEAE-Chitosan 40 qDEAE-Chitosan (B) qDEAE-chitosan treated HepG2 20 0 0 20 40 60 80 100 Chitosan Derivatives (mg/ml) Chitosan derivatives (100 mg/ml) were treated for 24 hr at 37oC Bioorganic Medicinal Chemistry Lett. 12(20) 2004