Presentation on theme: "Chemical and Bioengineering"— Presentation transcript:
1 Chemical and Bioengineering 20Polymer08Sep. 12, 2008Chapter 1 IntroductionChemical and BioengineeringKonkuk University
2 The term polymer was coined in 1833 by Jöns Jakob Berzelius Nitrated cellulose – marketed as celluloid and guncottonCommercial synthetic polymer – phenol formaldehyde resin- BakeliteScientists 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 & basis conditionMacromoleculechemical: dyeing, oxidation, degradation reaction.physical: melting & crystallization possibilitymechanical : elasticity metamorphosis 및 배향 가능The molecular cohesionThe 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 solution3. Separation: dialysis using the molecular weight difference4. Volatility: Polymer nonvolatile5. The melting point: Polymer A wide range6. 다분자성: The identical structure unit, different molecular weight distribution The average molecular weight
5 What is a polymer? 1. The origin of Polymer 2. Polymer’s example 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 Polymers – with reactive end groups – telechelic polymers Oligomer – few monomer units joined together LMWStructural unit enclosed by brackets – repeating unit (monomeric unit)End groups- structural units that terminate polymer chains[CH2CH2]CH=CH2CH3CH2Polymers – 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 toform 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)96% 전환할 때, 반복단위의 분자량이 183인 11-amino undecanoamide로 부터 형성된 폴리아미드의 분자량은?
8 Total number of structural units including end groups (4) 중합도 (Degree of Polymerization), DPDP: 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 groupsRelated to chain length and molecular weight
9 1-2. The development of the Polymer 1839 Vulcanized rubber development (C. Goodyear) nitrocellulose synthesis (J.W. Hyatt) The preumatic tire(bicycle ) development (J. B. Dunlop) phenol-formaldehyde resin production(L.H. Baekeland) H. Staudinger- Polymer concept’s proposal cellulose actate and poly(vinyl chloride) introduction poly(methyl methacrylate) commercialization (O. Rohm) polystyrene production Neoprene rubber production (W. H. Carothers, DuPont Co.) 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.
10 1-2. The development of the Polymer 1948 ABS resin production The development of the polymerization catalyst(under low pressure) was made by theK. Ziegler (ethylene) 1953 Hermann Staudinger, who won the Nobel Prizs(Work on macromolecules) The development of stereoregular polymer using Ziegler catalyst . (G. Natta ) 1956 poly(phenylene oxide) development (A. S. Hay) polyacetal resin production opening. F. Sanger, The determination method of peptide bond in amino acids (The Novel Prize) 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) EVA, ionomer, polyimide, denaturation PPO come polysulfone production H. G. Khorana, The experimental synthesis of DNA1970 The development of Plasticity elastic body.1985 Liquid crystal polymer product.
11 1-3. The formation of polymer compound Polymerization of monomer단량체 (momomer) 고분자 (polymer)중합(polymerization)Monomer & polymerA. 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 & DP7) Oligomer: DP 5-20
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 The structure of polymer a. Linear PolymerThermoplasticb. Branched Polymerc. Network or Crosslinked Polymer:Infusible, insoluble, swellingThermosetting resinLinear PolymerBranched PolymerNetwork PolymerCuringCrosslinkingVulcanization (rubber)
15 Branched structure of polymer ladderstarcombSemi-ladderpolyrotaxanepolycatenaneNon-covalent bondsDendrimer (cascade polymer)
17 The steric feature of polymer (Tacticity) vinyl polymers with a substituent X( CH2-CHX )n type which has liner polymerIsotacticTacticity:substituent X- the relative stereochemistry of adjacent chiral centers within a macromoleculeSyndiotacticAtacticstrengthIsotactic > 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, Malaysia cf) 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: PolysaccharidePolymerization of monomerC:H:O=1:2:1 (CH2O)n
22 Synthetic Polymers 1. 섬유 (Fibers) 1) Man-made fiber: artificial silk 1) Man-made fiber: artificial silkcellulose’s chemical treatment.soluble cellulose derivative: cellulose acetate, cellulose xanthate2) 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 - the inner 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 ④ attractive 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, polyEg- polyesters, polyamides.Vinyl polymers – polymers from monomers with carbon-carbon double bonds (CH2=CH-, vinyl group)Polymers derived from simple alkenes (ethylene or propylene)- polyolefinsVinyl and non vinyl polymers
28 1) common name: Poly + monomer name Polyethyleneex)nnPolytetrafluoroethylenenPolystylenenPoly(acrylic acid)Poly(a-methylstyrene)Poly(1-pentene)
29 IUPAC- recommends – names be derived from the structure of the base unit, or constitutional repeating unit (CRU)The smallest structural unit is identifiedSubstituent groups on the backbone are assigned the lowest possible numbersThe name is placed in parentheses (or brackets and parentheses, where necessary), and prefixed with poly.
30 iii. CRU명을 괄호안에 넣고 그 앞에 poly 붙임 2) IUPAC:i. 최소 구성단위 (CRU) 정의ii. 주쇄의 치환체에 가장 낮은 번호 부여iii. CRU명을 괄호안에 넣고 그 앞에 poly 붙임PolyethylenePoly(methylene)nnPolytetrafluoroethylenePoly(difluoromethylene)nPolystylenePoly(1-phenylethylene)nPoly(acrylic acid)Poly(a-methylstyrene)Poly(1-pentene)Poly[1-(1-propyl)ethylene]Poly(1-carboxylethylene)Poly(1-methyl-1-phenylethylene)
32 Copolymer (from two or more monomers) among the monomers’s name –co- insertionyxxyPoly(styrene-co-methyl acrylate)Poly(ethylene-co-methyl acrylate)among the repeating units –alt-, –b-, –g- insertionxyzPoly(styrene-b-isoprene-b-styrene)
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 polymersynthesis of polymer’s specific function2) The environmental friendship polymer- resolvability & recyclingThe treatment problem of the large molecule‘s wastesThe development need of the polymer with decomposition and recycling3) The polymer of the resources and energy saving
39 Enterohepatic Circulation of Bile Acid and Cholesterol Lowering Action of Bile Acid SequestrantCholesterol3. Increase of Bile Acid hepatic synthesis from CholesterolBile acidsHepatic synthesis= g/dayIntestinePool = 2-4 gBile acid absorptionCycles/day = 6 -10= g/day(Efficiency >95%)Fecal excretion= g/day1. Prescription of Bile acid sequestrant2. Increase of Bile acid fecal excretionBiosci. Biotechnol. Biochem. 63(5): , 2003
40 Morphology Change of HepG2 by the Chitosan Derivatives (A) Control HepG210080Chitosan60Amino-ChitosanViable Liver Cancer Cell (%)qAmino-ChitosanDEAE-Chitosan40qDEAE-Chitosan(B) qDEAE-chitosan treated HepG22020406080100Chitosan Derivatives (mg/ml)Chitosan derivatives (100 mg/ml) were treated for 24 hr at 37oCBioorganic Medicinal Chemistry Lett. 12(20) 2004