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Polymers: Introduction
Polymer: High molecular weight molecule made up of a small repeat unit (monomer).
A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A
Monomer: Low molecular weight compound that can be connected together to give a poymer Oligomer: Short polymer chain Copolymer: polymer made up of 2 or more monomers
Random copolymer: A-B-B-A-A-B-A-B-A-B-B-B-A-A-B Alternating copolymer: A-B-A-B-A-B-A-B-A-B-A-B-A-B Block copolymer: A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B
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Types of Polymers
Polymer Classifications
Thermoset: cross-linked polymer that cannot be melted (tires, rubber bands) Thermoplastic: Meltable plastic Elastomers: Polymers that stretch and then return to their original form: often thermoset polymers Thermoplastic elastomers: Elastic polymers that can be melted (soles of tennis shoes)
Polymer Families
Polyolefins: made from olefin (alkene) monomers Polyesters, Amides, Urethanes, etc.: monomers linked by ester, amide, urethane or other functional groups 3 Natural Polymers: Polysaccharides, DNA, proteins
Common Polyolefins
Monomer
Ethylene Polyethylene H3C
Polymer
CH3
n
Repeat unit
CH3
n
Ph
Ph
Ph
Ph
Ph
Ph
Ph
CH3
Cl
Cl
Cl
Cl
F2 C
Cl
F2 C
Cl
F2 C
Cl
CF3
C nF 2
C F2
C F2
Polymer
O OH Poly(ethylene terephthalate Ester
O O
4
CO2H
HO Ethylene glycol
HO
H2 H2 O C C O H
n
HO 4 Adipic Acid
N H O
N 4 H Amide H N
H
n
H N H
n
OCN
H2 C
NCO
4,4-diisocyantophenylmethane O HO H N H2 C
Urethane linkage
Natural Polymers
Monomer Polymer
Isoprene
H OH HO HO HO OH H H -D-glucose H OH
H N
O Rn+1
n
H N
O OH Rn+2
O O
R Amino Acid
O O P O O O O Base
O P O
OH Nucleotide Base = C, G, T, A
DNA
Physical Properties
Linear Polymer
Stretch
Cross-Linked Polymer
The chains can be stretched, which causes them to flow past each other. When released, the polymer will not return to its original form.
Stretch
Relax
The cross-links hold the chains together. When released, the polymer will return to it's original form. 8
Polymer Synthesis
There are two major classes of polymer formation mechanisms
Addition polymerization: The polymer grows by sequential addition of monomers to a reactive site
Chain growth is linear Maximum molecular weight is obtained early in the reaction
Step-Growth polymerization: Monomers react together to make small oligomers. Small oligomers make bigger ones, and big oligomers react to give polymers.
Chain growth is exponential Maximum molecular weight is obtained late in the reaction
Addition Polymerization
In* A Initiation In A*
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Addition Polymerization
Propagation
In* A Initiation In A A*
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Addition Polymerization
Propagation
A In* Initiation In A A A*
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Addition Polymerization
A In* Initiation
nA
In A A A A*
Propagation
In
A A A A A*
n
*A
*A A A A A
m
A A A A
m
In
A A A A A
n
In
A A A A A
n
In
A A A A A
n
A A A A A
m
B A A A A Disproportionation
m
Combination
MW
MW
0 % conversion 100
Ph C3H7 Li
n Ph
C4H9 Ph
n
Li+ Ph
C4H9
Radical
n
PhCO2
Ph
PhCO2 Ph
Ph
PhCO2 Ph
Cationic
Ph
Ph Cl3Al OH2
H Ph HOAlCl3
Ph
H Ph
HOAlCl3
n
Ph
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Step-Growth Polymerization
Stage 1 n n Consumption of monomer
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Step-Growth Polymerization
Because high polymer does not form until the end of the reaction, high molecular weight polymer is not obtained unless high conversion of monomer is achieved.
1000
Degree of Polymerization
Xn
100
1 1 p
10
1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 Mole Fraction Conversion (p)
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Nylon-6,6
O Cl O NaOH
4
O Cl
O
4
Cl
H2N
NH2
Adipoyl chloride
1,6-Diaminohexane
N H
N H
O
Adipoyl chloride in hexane Nylon 6,6 Diamine, NaOH, in H2O
O
4
HO
N H
N H
H
n
6 carbon diacid
6 carbon diamine
Nylon-6,6
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Nylon-6,6
Since the reactants are in different phases, they can only react at the phase boundary. Once a layer of polymer forms, no more reaction occurs. Removing the polymer allows more reaction to occur.
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Mv Mn Mw
# o f m o l e c u l e s
increasing molecular weight
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1 Dalton = 1 g/mole
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Polymer Microstructure
Polyolefins with side chains have stereocenters on every other carbon
CH3
n
With so many stereocenters, the stereochemistry can be complex. There are three main stereochemical classifications for polymers.
Atactic: random orientation
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2 13C
NMR shift is sensitive to the two stereocenters on either side on sptectrometers > 300 MHz. This is called pentad resolution.
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