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"I just want to say one word to

you -- just one word -- 'plastics.'"


Advice to Dustin Hoffman's
character in The Graduate

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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
– Natural Polymers: Polysaccharides, DNA, proteins 3
Common Polyolefins
Monomer Polymer
CH3
H3C
Polyethylene n
Ethylene Repeat unit

CH3
CH3 n
Polypropylene CH3 CH3 CH3 CH3 CH3 CH3 CH3
Propylene

CH3
Ph n
Polystyrene Ph Ph Ph Ph Ph Ph Ph
Styrene

CH3
Cl n
Poly(vinyl chloride) Cl Cl Cl Cl Cl Cl Cl
Vinyl Chloride
F2 F2 F2 F2 F2 F2
F2C CF2 C C C C C C CF3
F3C C C C C C C
F2 F2 F2 nF F2 F2
Tetrafluoroethylene Poly(tetrafluoroethylene): Teflon 2

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Polyesters, Amides, and Urethanes
Monomer Polymer
O O
H2 H2
HO2C CO2H OH HO O C C O H
HO
Ethylene Poly(ethylene terephthalate n
Terephthalic
acid glycol Ester

O O O O
H
HO 4
OH H2N 4
NH2 HO N 4 N
4
Adipic Acid 1,6-Diaminohexane Nylon 6,6 H H n
Amide
O O
H H
HO2C CO2H H2N NH2 HO N N H
Kevlar n
Terephthalic 1,4-Diamino
acid benzene
H2
OCN C NCO OH
HO
Ethylene Spandex
4,4-diisocyantophenylmethane
glycol
O O
H H2 H H2 H2
HO N C N O C C O H Urethane linkage
n
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Natural Polymers
Monomer Polymer

Isoprene Polyisoprene:
Natural rubber n
H OH H OH
HO H HO
HO O
HO OH HO OH
H OH Poly(ß-D-glycoside): H OH
H H cellulose H H n

ß-D-glucose
O O O O
H H
H3N H3N N N OH
O Polyamino acid:
protein R1 Rn+1 n Rn+2
R
Amino Acid
O O
DNA
O P O Base O P O
O Base
O O O
oligonucleic acid
OH DNA
O
Nucleotide DNA
Base = C, G, T, A 6
What Makes Polymers Unique?
• Really big molecules (macromolecules) like
polymers have very different properties than
small molecules
– Chain entanglement: Long
polymer chains get entangled with
each other.
• When the polymer is melted, the
chains can flow past each other.
• Below the melting point, the chains
can move, but only slowly. Thus the
plastic is flexible, but cannot be
easily stretched.
• Below the glass transition point, the
chains become locked and the
polymer is rigid
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Physical Properties
Linear Polymer

Stretch

The chains can be stretched, which causes


them to flow past each other. When released,
the polymer will not return to its original form.
Cross-Linked Polymer

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

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Addition Polymerization
A
In* In A* A
Initiation

10
Addition Polymerization
Propagation

A
In* In A A* A
Initiation

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Addition Polymerization
Propagation

A
In* In A A A* A
Initiation

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Addition Polymerization
A nA
In* In A A A A* In A A A A A*
Initiation Propagation n

*A A A A A
A *A A A A A m
m

In A A A A A In A A A A A A A A A A
In A A A A A n
n n m

A* Combination
B A A A A
m
Chain Transfer Disproportionation
New reactive site
is produced
Termination
Reactive site is consumed
MW

k propagation
MW 
k ter mination

0 100 13
% conversion
Types of Addition Polymerizations
Anionic

n Li+
Ph Li+ Ph
C4H9 C4H9
C3H7 Li n
Ph Ph Ph
Radical

n
Ph Ph
PhCO2• PhCO2 PhCO2
n
Ph Ph Ph
Cationic

n
Ph Ph
Cl3Al OH2 H H HOAlCl3
n
Ph Ph Ph
HOAlCl3

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Step-Growth Polymerization
Stage 1
n n
Consumption
of monomer

Stage 2

Combination
of small fragments

Stage 3

Reaction of
oligomers to give
high molecular
weight polymer

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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

1
Degree of Polymerization
Xn 
1 p
100


10

Xn = Degree of polymerization
p = mole fraction monomer 1
conversion 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 O O O
NaOH
Cl Cl H2N NH2 H
4 4 Cl 4
N 4 N
H H
Adipoyl chloride 1,6-Diaminohexane

O O
Adipoyl chloride H
in hexane HO N N
4 4
H H n
Nylon 6,6
6 carbon 6 carbon
diacid diamine
Diamine, NaOH, in H2O
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.

Adipoyl chloride
in hexane

Nylon 6,6

Diamine, NaOH, in H2O

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Molecular Weight of Polymers
Unlike small molecules, polymers are typically a mixture of differently
sized molecules. Only an average molecular weight can be defined.
• Measuring molecular weight
• Size exclusion chromatography
• Viscosity
• Measurements of average molecular Mv Mn
weight (M.W.)
• Number average M.W. (Mn): Total Mw
weight of all chains divided by # of
chains
• Weight average M.W. (Mw):

m
Weighted average. Always larger
#
o
o
le
cu
le
s
f
than Mn
• Viscosity average M.W. (Mv): increasing molecular weight
Average determined by viscosity
measurements. Closer to Mw than
Mn 19
What the Weights Mean
Mn: This gives you the true average weight
Let's say you had the following polymer sample:
2 chains: 1,000,000 Dalton 2,000,000
5 chains: 700,000 Dalton 3,500,000
10 chains: 400,000 Dalton 4,000,000
4 chains: 100,000 Dalton 400,000
2 chains: 50,000 Dalton 100,000
10,000,000
10,000,000/23 = 435,000 Dalton

1 Dalton = 1 g/mole

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Weight Average Molecular Weight
Mw: Since most of the polymer mass is in the heavier fractions, this
gives the average molecular weight of the most abundant polymer
fraction by mass.
2,000,000
 0.20  1,000,000  200,000
10,000,000
3,500,000
 0.35  700,000  245,000
10,000,000
4,000,000
 0.40  400,000  160,000
10,000,000
400,000
 0.04  100,000  4,000
10,000,000
100,000
 0.01 50,000  500
10,000,000
Total  609,500

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Polymer Microstructure
Polyolefins with side chains have stereocenters on every other carbon

CH3
n
CH3 CH3 CH3 CH3 CH3 CH3 CH3

With so many stereocenters, the stereochemistry can be complex.


There are three main stereochemical classifications for polymers.
Atactic: random orientation

Isotactic: All stereocenters have same orientation

Syndiotactic: Alternating stereochemistry

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How to Determine Microstructure?
13C NMR is a very powerful way to determine the microstructure of
a polymer.

2 1 1 2
13C NMR shift is sensitive to the two
stereocenters on either side on sptectrometers
> 300 MHz. This is called pentad resolution.

r m m r m r

mmrm pentad
m = meso (same orientation)
r = racemic (opposite orientation)
13C NMR spectrum of CH3 region
of atactic polypropylene
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Why is this important?
• Tacticity affects the physical properties
– Atactic polymers will generally be amorphous, soft,
flexible materials
– Isotactic and syndiotactic polymers will be more
crystalline, thus harder and less flexible
• Polypropylene (PP) is a good example
– Atactic PP is a low melting, gooey material
– Isoatactic PP is high melting (176º), crystalline, tough
material that is industrially useful
– Syndiotactic PP has similar properties, but is very
clear. It is harder to synthesize

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