Chapter 1

Introduction

Chemical and Bioengineering

Konkuk University

Sep. 12, 2008

0820 Polymer

The term polymer was coined in 1833 by Jöns Jakob Berzelius

Nitrated cellulose – marketed as celluloid and guncottonCommercial 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

Macromolecule

1. chemical: dyeing, oxidation, degradation

reaction.

2. physical: melting & crystallization

possibility

3. mechanical : elasticity metamorphosis 및

배향 가능

4. The molecular cohesion

5. The number average molecular weight:

over 10,000

1-1. Small molecules chemistry& Large molecules chemistry

Definitions of Polymer & basis condition

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. 다 분 자 성 : The identical structure unit, different

molecular weight distribution

The average molecular

weight

1-1. Small molecules material & Large molecules material

1. The origin of Polymer     polymer : poly+ mer (poly= many + meros = parts = unit) 

2. Polymer’s example    1) poly ethylene (P.E)        

What is a polymer?

CH2H2C + CH2H2C CH2 CH2 CH2CH2ex)

2) poly propylene (P.P)

3) poly isoprene

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=CH2CH3CH2

Polymers – with reactive end groups – telechelic polymers

(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)

(1)PolymerThe large molecules made up of simple repeating units.

The basic terminology

•Total number of structural units including end groups

•Related to chain length and molecular weight

(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.)             

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 actate and poly(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 and poly(vinyl acetate) introduction.

1937      polyethylene synthesis (O. Bayer).

1938      nylon 6 and epoxy resin development. LDPE synthesis.

1941      PET synthesis (J.R. Whinfield and J.T. Dickinson).

1942      The commercialization of PAN fiber.

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, denaturation PPO 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.

1-2. The development of the Polymer

1)Polymerization of monomer

단량체 (momomer)   고분자 (polymer)

1-3. The formation of polymer compound

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

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

1-3. The formation 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

1-4. The structure of polymer compound

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

CuringCrosslinkingVulcanization (rubber)

Thermoplastic

Branched structure of polymer

star combladder

Semi-ladder

polyrotaxane polycatenane

Dendrimer (cascade polymer)

Non-covalent bonds

  Conjugated Diene, isoprene monomer : addition

polymerization.

Isomer of polymer

The steric feature of polymer (Tacticity)

  vinyl polymers with a substituent X

( CH2-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

  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) 20 세기 초 rubber tree culture: Sri Lanka, Malaysia cf) the place of orgin:

Brazil 브라질 3) mechanical : high extensibility (800%)

  3. 생체고분자 (Biopolymers)

    1) ex: protein, polyamide, polysaccharide

    2) appliocation: adhesive, 인공피부 , Drug, functional foods

3) muscle, collagen, ligament

Natural polymers

ex: Polysaccharide

Polymerization of

monomer

C:H:O=1:2:1

(CH2O)n

Biopolymers

  1. 섬유 (Fibers)    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

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                   

Synthetic Polymers

CH2 CH CH CH2 + CH2 CH CH CH2 CH2 CH CH CH2 n

CH2 CH CH CH2 CH2 CH+ CH2 CH CH CH2 CH2 CHn

  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

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)

Synthetic Polymers

CHH2Cn

CH2 CH

Cln

2) Resins      ① phenol-formaldehyde resin

          1907year: Baekeland 가 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)

      ② melamine resin

       - application: table wear, toys

       - prooperty: thermosetting resin( no melt at the heat and solution : stable ).

•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

1-5. Nomenclature of polymer compound

    1) common name: Poly + monomer name

CH2CH2 Polyethylene

Polytetrafluoroethylene

Polystylene

n

CF2CF2 n

CH2CH n

CH2CH

CH3

nCH2CH

CH2CH2CH3

nCH2CH

COOHn

Poly(acrylic acid)Poly(-methylstyrene)

Poly(1-pentene)

ex)

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.

    2) IUPAC: i. 최소 구성단위 (CRU) 정의ii. 주쇄의 치환체에 가장 낮은 번호 부여iii. CRU 명을 괄호안에 넣고 그 앞에 poly 붙임

CH2CH2 Polyethylene

Polytetrafluoroethylene

Polystylene

n

CF2CF2 n

CH2CH n

CH2CH

CH3

nCH2CH

CH2CH2CH3

nCH2CH

COOHn

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]

NH (CH2)6 NHCO (CH2)8 CO n

O CH2 CH2 OCO COn

Condensation polymer (from two monomers)

Poly(hexamethylene sebacamide)

Poly(ethylene terephthalate)

IUPAC: Poly(oxyethylene oxyterephthaloyl)

Poly(ethylene-co-methyl acrylate)

Copolymer (from two or more monomers)

among the monomers’s name –co- insertion

CH2 CH2 CH2 CH

COOCH3

yxCH2 CH CH2 CH

COOCH3

x y

Poly(styrene-co-methyl acrylate)

among the repeating units –alt-, –b-, –g- insertion

x y z

Poly(styrene-b-isoprene-b-styrene)

CH2 CH CH2 CH CH CH2

CH3

CH2 CH

The sturcture monomer repeating unit common name IUPAC

Naming

Nylon: Polyamide

NH (CH2)6 NHCO (CH2)8 CO n

Nylon 610: Poly(hexamethylene sebacamide)

Dacron: Polyester

Nylon 66: Poly(hexamethylene adipamide)

Teflon: Poly(tetrafluoroethylene)

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

Research subject of polymer field

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

nGlucose : Galactose : Mannose 2 3 2

O

OHHO

CH2OH

O

OH

HOH2CO O

OHOH2C

OH

O

OHOH

MethylanMethylan ChitosanChitosan

A cationic polymer with NH2 group

Biocompatibility and bioactivity

Easy derivatization

n

O

NH2

HO

CH2OH

O

OH

HOH2CO O

H

NH2

MW: 2,000,000

Methylan Methylan Chitosan Chitosan

MW: 1,000,000

Aminoderivatized Cationic Polysaccharide

Ionic and Hydrophobic Interactions

Ionic and Hydrophobic Interactions

Anticomplementary ActivityAnticomplementary Activity

Bile Acid Sequestering Capacity

Antimicrobial Activity

Antitumor Activity

Bile Acid Sequestering Capacity

Antimicrobial Activity

Antitumor Activity

+

+n

O

O

CH2OR

H

HO

N

H

H(CH3)3

CH3+

+n

O

O

CH2N

H

HO

N

H

H(CH3)3

(CH3)3

quaternized DEAE-Polysaccharide quaternized NH2-Polysaccharide

Biotechnol. Appl. Biochem. 35, 2002; Biosci. Biotechnol. Biochem. 63(5) 2003

Bile acid absorption = 12-32 g/day

(Efficiency >95%)

Pool = 2-4 gCycles/day = 6 -10

Fecal excretion= 0.2-0.6 g/day

CholesterolCholesterol

Hepatic synthesis= 0.2 - 0.6 g/day

Bile acidsBile acids

Intestine

3. Increase of Bile Acid hepatic synthesis from Cholesterol 3. Increase of Bile Acid hepatic synthesis from Cholesterol

1. Prescription of Bile acid sequestrant 1. Prescription of Bile acid sequestrant

2. Increase of Bile acid fecal excretion 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): 833-839, 2003

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 37oC

Chitosan Derivatives (g/ml)

0 20 40 60 80 100

Via

ble

Liv

er C

ance

r C

ell

(%)

0

20

40

60

80

100

ChitosanAmino-Chitosan

qAmino-Chitosan

DEAE-Chitosan

qDEAE-Chitosan

Bioorganic Medicinal Chemistry Lett. 12(20) 2004