1. Chemical and Bioengineering20
Polymer 08
Sep. 12, 2008
Chapter 1 Introduction
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 & basis condition
Macromolecule
chemical: dyeing, oxidation, degradation reaction.
physical: melting & crystallization possibility
mechanical : elasticity metamorphosis 및 배향 가능
The molecular cohesion
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 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 LMW
Structural unit enclosed by brackets – repeating unit (monomeric unit)
End groups- structural units that terminate polymer chains
[CH2CH2]
CH=CH2
CH3CH2
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)
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), 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)      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 the
K. 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 DNA
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: 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 Polymer
Thermoplastic
b. Branched Polymer
c. Network or Crosslinked Polymer:
Infusible, insoluble, swelling
Thermosetting resin
Linear Polymer
Branched Polymer
Network Polymer
Curing
Crosslinking
Vulcanization (rubber)

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 which has liner polymer
Isotactic
Tacticity:
substituent X- 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, 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: 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
    
1) Man-made fiber: artificial silk
cellulose’s chemical 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
      - 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, 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. 1) common name: Poly + monomer name
Polyethylene
ex) n n
Polytetrafluoroethylene n
Polystylene n
Poly(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 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. iii. CRU명을 괄호안에 넣고 그 앞에 poly 붙임
    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 n
Polytetrafluoroethylene
Poly(difluoromethylene) n
Polystylene
Poly(1-phenylethylene) n
Poly(acrylic acid)
Poly(a-methylstyrene)
Poly(1-pentene)
Poly[1-(1-propyl)ethylene]
Poly(1-carboxylethylene)
Poly(1-methyl-1-phenylethylene)

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

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

34. The sturcture monomer repeating unit common name IUPAC

35. Naming Nylon: Polyamide Dacron: Polyester
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. Biopolymer: Polysaccharide (Chitosan, Methylan)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%),
Pyruvic Acid (5.1%), Acetic Acid (0.6%), Protein (6.1%) u u
DO-stat Culture, Scale-up n
Glucose : Galactose : Mannose O H C 2 n O
NH2 H C 2 N H2
Methylan
Chitosan
MW: 2,000,000
MW: 1,000,000

38. Aminoderivatized Cationic Polysaccharide+ n O C H 2 R N ( 3 )
(CH3)3
quaternized DEAE-Polysaccharide
quaternized NH2-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
= g/day
Intestine
Pool = 2-4 g
Bile acid absorption
Cycles/day = 6 -10
= g/day
(Efficiency >95%)
Fecal excretion
= g/day
1. Prescription of Bile acid sequestrant
2. Increase of Bile acid fecal excretion
Biosci. Biotechnol. Biochem. 63(5): , 2003

40. Morphology Change of HepG2 by the Chitosan Derivatives
(A) Control HepG2
100 80
Chitosan 60
Amino-Chitosan
Viable Liver Cancer Cell (%)
qAmino-Chitosan
DEAE-Chitosan 40
qDEAE-Chitosan
(B) qDEAE-chitosan treated HepG2 20 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