1

"I just want to say one word to

you -- just one word -- 'plastics.'"
Advice to Dustin Hoffman's
character in The Graduate
2
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
3
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
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Common Polyolefins
Monomer Polymer
Ethylene
H
3
C
CH
3
n
Repeat unit
Polyethylene
CH
3
CH
3
n
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
Propylene
Polypropylene
Ph
CH
3
n
Ph Ph Ph Ph Ph Ph Ph
Styrene
Polystyrene
Cl
CH
3
n
Cl Cl Cl Cl Cl Cl Cl
Vinyl Chloride
Poly(vinyl chloride)
F
2
C CF
2
Tetrafluoroethylene
F
3
C
F
2
C
C
F
2
F
2
C
C
F
2
F
2
C
C
F
2
F
2
C
C
F
2
F
2
C
C
F
2
F
2
C
C
F
2
CF
3
n
Poly(tetrafluoroethylene): Teflon
5
Polyesters, Amides, and Urethanes
Monomer Polymer
CO
2
H HO
2
C
HO
OH
O O
HO O
H
2
C
H
2
C O
n
Terephthalic
acid
Ethylene
glycol
Poly(ethylene terephthalate
H
Ester
HO OH
O O
4
H
2
N NH
2
4
Adipic Acid 1,6-Diaminohexane
Nylon 6,6
HO N
H
N
H
H
O O
4
4
n
CO
2
H HO
2
C
Terephthalic
acid
NH
2
H
2
N
1,4-Diamino
benzene
Kevlar
O
HO
O
H
N
H
N H
n
Amide
HO
OH
Ethylene
glycol
H
2
C OCN NCO
4,4-diisocyantophenylmethane
Spandex
H
2
C
H
N
H
N
O
HO
O
O
H
2
C
H
2
C O H
n
Urethane linkage
6
Natural Polymers
Monomer Polymer
Isoprene
n
Polyisoprene:
Natural rubber
O
H
HO
H
HO
H
H
OH
H
OH
OH
Poly(-D-glycoside):
cellulose
O
H
O
H
HO
H
H
OH
H
OH
OH
H
n
-D-glucose
H
3
N
O
O
R
Polyamino acid:
protein
H
3
N
O
H
N
R
1
O
H
N
R
n+1
O
OH
R
n+2
n
Amino Acid
Base
O
OH
O P
O
O
O
oligonucleic acid
DNA
Nucleotide
Base = C, G, T, A
Base
O
O
O P
O
O
O
DNA
DNA
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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
Stretch
Linear 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
Cross-Linked Polymer
The cross-links hold the chains together.
When released, the polymer will return to it's
original form.
Relax
9
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
In*
A
Initiation
In A*
A
11
Addition Polymerization
Propagation
In*
A
Initiation
In A A* A
12
Addition Polymerization
Propagation
A
In*
A
Initiation
In A A A*
13
Addition Polymerization
Propagation
nA
In A A A A
n
A*
A A A A A
m
In A A A A
n
A
*A A A A A
m
Combination
*A A A A A
m
In A A A A
n
A
B A A A A
m
Disproportionation
Termination
Reactive site is consumed
A
In A A A A
n
A
A*
Chain Transfer
New reactive site
is produced

MW
k
propagation
k
ter mination
MW
% conversion
0 100
In*
A
Initiation
In A A A A*
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Types of Addition Polymerizations
Ph
Anionic
C
3
H
7
Li
C
4
H
9
Ph
Li
+
Ph
n
C
4
H
9
Ph Ph
Li
+
n
Ph
Radical
PhCO
2

Ph
n
Ph
Cationic
Cl
3
Al OH
2
H
Ph
HOAlCl
3
Ph
n
H
Ph Ph
n
HOAlCl
3
PhCO
2
Ph
PhCO
2
Ph Ph
n
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Step-Growth Polymerization
Stage 1
Consumption
of monomer
n n
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.

X
n

1
1 p
X
n
= Degree of polymerization
p = mole fraction monomer
conversion
1
10
100
1000
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole Fraction Conversion (p)
D
e
g
r
e
e

o
f

P
o
l
y
m
e
r
i
z
a
t
i
o
n
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Nylon-6,6
Cl Cl
O O
4
H
2
N NH
2
4
Adipoyl chloride 1,6-Diaminohexane
Cl N
H
N
H
H
O O
4
4
NaOH
HO N
H
N
H
H
O O
4
4
n
6 carbon
diacid
6 carbon
diamine
Nylon-6,6
Diamine, NaOH, in H
2
O
Adipoyl chloride
in hexane
Nylon 6,6
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Nylon-6,6
Diamine, NaOH, in H
2
O
Adipoyl chloride
in hexane
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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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
weight (M.W.)
Number average M.W. (M
n
): Total
weight of all chains divided by # of
chains
Weight average M.W. (M
w
):
Weighted average. Always larger
than M
n

Viscosity average M.W. (M
v
):
Average determined by viscosity
measurements. Closer to M
w
than
M
n

# of molecules
M
n
M
w
increasing molecular weight
M
v
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What the Weights Mean
M
n
: 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
M
w
: 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
10,000,000
0.201,000,000 200,000
3,500,000
10,000,000
0.35 700,000 245,000
4,000,000
10,000,000
0.40 400,000 160,000
400,000
10,000,000
0.04100,000 4,000
100,000
10,000,000
0.01 50,000 500
Total 609,500
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Polymer Microstructure
Polyolefins with side chains have stereocenters on every other carbon
CH
3
n
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
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?
13
C NMR is a very powerful way to determine the microstructure of
a polymer.

13
C 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)
1 2 1 2
13
C NMR spectrum of CH
3
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 (176), crystalline, tough
material that is industrially useful
Syndiotactic PP has similar properties, but is very clear.
It is harder to synthesize