"I just want to say one word to

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

Advice to Dustin Hoffman's
character in The Graduate
1

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
2

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
Ethylene

CH3
Propylene
Ph
Styrene

Polymer

Polyethylene

Polypropylene

Polystyrene

CH3

H3C

Vinyl Chloride
F2C CF2
Tetrafluoroethylene

CH3

CH3 CH3 CH3 CH3 CH3 CH3 CH3

Ph

Ph

Ph

Ph

Cl
Poly(vinyl chloride)

Repeat unit

Cl

F3C
Poly(tetrafluoroethylene): Teflon

Cl
F2
C

C
F2

Cl
F2
C

C
F2

Cl
F2
C

C
F2

CH3

Ph

F2
C

Ph

Ph
CH3

Cl

C
nF
2

Cl
F2
C

C
F2

Cl
F2
C

C
F2

CF3

Polyesters, Amides, and Urethanes

Monomer
HO2C

CO2H

Terephthalic
acid
O

Polymer
O

OH

HO
Ethylene
glycol

Poly(ethylene terephthalate

HO

Nylon 6,6

O
CO2H H2N

HO2C

NH2

1,4-Diamino
benzene

Terephthalic
acid
H2
C

OCN

NCO

4,4-diisocyantophenylmethane
O
HO

H
N

H2
C

Kevlar

HO

Ester
O

NH2
OH H2N
4
1,6-Diaminohexane

H2 H2
O C C O H

HO

HO
4
Adipic Acid

O
4

N
H

N
4
H
Amide
O

H
N

H
n

H
N H
n

OH
HO
Spandex
Ethylene
glycol
O
H2 H2
H
N
O C C O H
n

Urethane linkage

Monomer

Isoprene
H OH
HO
HO

Natural Polymers

Polymer

Polyisoprene:
Natural rubber

HO

H OH
H

OH
H
H
-D-glucose

OH

Poly(-D-glycoside):
cellulose

Polyamino acid:
protein

R
Amino Acid

O P O
O

O
O

H3N

OH
Nucleotide
Base = C, G, T, A

Base
oligonucleic acid
DNA

OH

OH
H
O

H
N

R1
DNA

HO

O
HO

O
H3N

Rn+1

H
N
n

OH
Rn+2

O
O P O

O
O

DNA

Base

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

Linear Polymer

Physical Properties

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.
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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*

10

Addition Polymerization
Propagation
In*

A
Initiation

In

A A*

11

Addition Polymerization
Propagation
In*

A
Initiation

In

A A A*

12

Addition Polymerization
In*

In

Initiation

A A A A*

nA

In

*A
In

A A A A A
A*

In

Propagation

A A A A A*
n

A A A A
m

A A A A A

In

*A

A A A A

A A A A A
n

A A A A A

Combination

B A A A A

Chain Transfer
New reactive site
is produced

Disproportionation
Termination
Reactive site is consumed

MW

MW
0

% conversion

100

k propagation
k ter mination

13

Types of Addition Polymerizations

Anionic

C3H7

Li

Ph

C4H9

Ph

Li+

C4H9
Ph

Ph

PhCO2
Ph

Cationic

Cl3Al OH2

Ph

Ph

Radical

PhCO2

Li+

Ph

Ph

n
H
Ph

HOAlCl3

PhCO2

Ph

H
Ph

Ph

Ph

HOAlCl3
Ph

14

Step-Growth Polymerization
n

Stage 1

Consumption
of monomer

Stage 2
Combination
of small fragments

Stage 3
Reaction of
oligomers to give
high molecular
weight polymer
15

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

Xn =

1
1 p

100

10

Xn = Degree of polymerization
p = mole fraction monomer
conversion

1
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

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Nylon-6,6
O
Cl

O
4

Cl

Adipoyl chloride

H2N

NH2

NaOH
Cl

O
HO

N
H

1,6-Diaminohexane

Adipoyl chloride
in hexane

O
4

O
N
H

Nylon 6,6
Diamine, NaOH, in H2O

N
H

6 carbon
diacid

N
H

H
n

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.

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
weight (M.W.)
Number average M.W. (Mn): Total
weight of all chains divided by # of
chains
Weight average M.W. (Mw):
Weighted average. Always larger
than Mn
Viscosity average M.W. (Mv):
Average determined by viscosity
measurements. Closer to Mw than
M

Mv Mn
Mw

increasing molecular weight

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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

20

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
n

CH3

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

22

How to Determine Microstructure?

C NMR is a very powerful way to determine the microstructure of
a polymer.
13

13C

NMR shift is sensitive to the two

stereocenters on either side on sptectrometers
> 300 MHz. This is called pentad resolution.

mmrm pentad
m = meso (same orientation)
r = racemic (opposite orientation)

C NMR spectrum of CH3 region

of atactic polypropylene
13

23

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
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