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

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Presentation on theme: "Chapter 1 Introduction Chemical and Bioengineering Konkuk University Sep. 12, 2008 08 20 Polymer."— Presentation transcript:

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

2 The term polymer was coined in 1833 by Jöns Jakob BerzeliusJöns 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.colloidsassociation theory In 1922, Hermann Staudinger proposed that polymers consisted of long chains of atoms held together by covalent bonds.Hermann Staudinger Work by Wallace Carothers in the 1920s also demonstrated that polymers could be synthesized rationally from their constituent monomersWallace Carothers

3 Macromolecule 1.chemical: dyeing, oxidation, degradation reaction. 2.physical: melting & crystallization possibility 3.mechanical : elasticity metamorphosis 4.The molecular cohesion 5.The number average molecular weight: over 10, Small molecules chemistry& Large molecules chemistry Definitions of Polymer & basis condition

4 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. : The identical structure unit, different molecular weight distribution The average molecular weight 1-1. Small molecules material & Large molecules material

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

6 Oligomer – few monomer units joined together LMW Structural unit enclosed by brackets – repeating unit (monomeric unit) End groups- structural units that terminate polymer chains [CH 2 CH 2 ]CH=CH 2 CH 3 CH 2 Polymers – with reactive end groups – telechelic polymers

7 (2) (monomer) The small molecules that may become chemically bonded to other monomers to form a polymer ( For Polymerization Processes) (3) (repeating unit, constitutional repeating unit, CRU) The minimum repeating unit for the molecule chain. The structure of polymer is -[M] n - (repeating unit: M) (1)Polymer The large molecules made up of simple repeating units. The basic terminology

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

9 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 concepts proposal cellulose actate and poly(vinyl chloride) introduction poly(methyl methacrylate) commercialization (O. Rohm) polystyrene production Neoprene rubber production (W. H. Carothers, DuPont Co.) 1935 nylon 66 production (W. H. Carothers) PANN, SAN and poly(vinyl acetate) introduction polyethylene synthesis (O. Bayer) nylon 6 and epoxy resin development. LDPE synthesis PET synthesis (J.R. Whinfield and J.T. Dickinson) The commercialization of PAN fiber.H. StaudingerW. H. Carothers 1-2. The development of the Polymer

10 1948 ABS resin production 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 Guilio Natta(Development of catalysts and synthesis of polymers) 1964 EVA, ionomer, polyimide, denaturation PPO come polysulfone production H. G. Khorana, The experimental synthesis of DNA (The Nobel Prize in Physiology or Medicine) 1970 The development of Plasticity elastic body Liquid crystal polymer product The development of the Polymer

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

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

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

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

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

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

17 The steric feature of polymer (Tacticity) vinyl polymers with a substituent X ( CH 2 -CHX ) n type which has liner polymer Isotactic Syndiotactic Atactic Tacticity: substituent X- the relative stereochemistry of adjacent chiral centers within a macromolecule strength Isotactic > syndiotactic > Atactic

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

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


21 Biopolymers

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

23 2. (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 - the inner tube of tire use. - Defect: the crystallization at the low temp. - Amorphous Synthetic Polymers

24 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 polymers example 1) polyethylene ~ 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 Synthetic Polymers

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

26 2) Resins phenol-formaldehyde resin 1907year: Baekeland invention patent. Synthetic Polymers 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) melamine resin - application: table wear, toys - prooperty: thermosetting resin( no melt at the heat and solution : stable ).

27 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 (CH 2 =CH-, vinyl group) Polymers derived from simple alkenes (ethylene or propylene)- polyolefins Vinyl and non vinyl polymers 1-5. Nomenclature of polymer compound

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

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 2) IUPAC: i. (CRU) ii. iii. CRU poly Polyethylene Polytetrafluoroethylene Polystylene n n n n n n Poly(acrylic acid) Poly( -methylstyrene) Poly(1-pentene) Poly(methylene) Poly(difluoromethylene) Poly(1-phenylethylene) Poly(1-carboxylethylene) Poly(1-methyl-1-phenylethylene) Poly[1-(1-propyl)ethylene]

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

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


34 The sturcture monomer repeating unit common name IUPAC

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

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

37 Biopolymer: Polysaccharide (Chitosan, Methylan) Methylobacterium organophilum Extracellular anionic polysaccharide Reducing Sugar (76.9%), Uronic Acid (12.4%), Pyruvic Acid (5.1%), Acetic Acid (0.6%), Protein (6.1%) DO-stat Culture, Scale-up n Glucose : Galactose : Mannose O OH HO CH 2 OH O OH HOH 2 C OO O HOH 2 C OH O OH OH Methylan Chitosan A cationic polymer with NH 2 group Biocompatibility and bioactivity Easy derivatization n O NH 2 HO CH 2 OH O OH HOH 2 C OO H NH2H2 MW: 2,000,000 Methylan Chitosan MW: 1,000,000

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

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

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

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