chapter 1 introduction chemical and bioengineering konkuk university sep. 12, 2008 08 20 polymer
TRANSCRIPT
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