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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
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Common Polyolefins

Monomer
Ethylene

CH3
Propylene
Ph
Styrene

Polymer

Polyethylene

Polypropylene

Polystyrene

CH3

H3C

n

Vinyl Chloride
F2C CF2
Tetrafluoroethylene

CH3

n

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

n

Ph

n

F2
C

Ph

Ph
CH3

Cl

C
nF
2

Cl
F2
C

C
F2

Cl
F2
C

C
F2

CF3

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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

n

Ester
O

NH2
OH H2N
4
1,6-Diaminohexane

H2 H2
O C C O H

HO

O

HO
4
Adipic Acid

O

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

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Monomer

Isoprene
H OH
HO
HO

Natural Polymers

Polymer

Polyisoprene:
Natural rubber

HO

H OH
H

H

OH
H
H
ß-D-glucose

OH

Poly(ß-D-glycoside):
cellulose

H

O

Polyamino acid:
protein

R
Amino Acid

O P O
O

O
O

H3N

OH
Nucleotide
Base = C, G, T, A

Base
oligonucleic acid
DNA

H

OH

OH
H

O

H
N

R1
DNA

O

HO

O
HO

O
H3N

n

Rn+1

n

O

H
N
n

OH
Rn+2

O
O P O

O

O
O

DNA

Base

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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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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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Polymerization Processes
• Addition Polymerization
– No Byproducts
– Usually heat driven

• Condensation Polymerization

– Byproducts produced
– Removal of byproduct controls rate

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Polymer Synthesis
• There are two major classes of polymer formation
mechanisms
1. 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
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Polymer Synthesis
2. 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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Anatomy of Addition Polymerizations
• Initiation
– Generation of active initiator
– Type of Initiator:
• Azo (-N=N-)
• Disulphide (-S-S)
• Peroxide (-O-O)

– Example :

• Benzoyl Peroxide
• AIBN

– Reaction with monomer to form growing
chains

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Anatomy of Addition Polymerizations
• Propagation
– Chain extension by incremental monomer
addition
• Chain Termination
– Conversion of active growing chains to inert
polymer
– Combination or disproportionation
– Chain Transfer :Transfer of active growing site
by terminating one chain and reinitiating a new
chain.
– Chain transfer to monomer, to solvent and to
polymer
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Addition Polymerization
In*

A
Initiation

In

A*

A

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Addition Polymerization
Propagation
In*

A
Initiation

In

A A*

A

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Addition Polymerization
Propagation

In*

A
Initiation

In

A A A*

A

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Addition Polymerization
In*

A

In

Initiation

A A A A*

nA

A

In

*A
In

A A A A A
A*

In

Propagation

A A A A A*
n

A A A A
m

m

A A A A A

In

n

n

*A

A A A A

A A A A A
n

A A A A A

Combination

B A A A A

m

m

Chain Transfer
New reactive site
is produced

Disproportionation

Termination
Reactive site is consumed

MW

MW 
0

% conversion

100

k propagation
k ter mination

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Types of Addition Polymerizations

Anionic

C3H7

Li

Ph

C4H9

Ph

Li+

C4H9
Ph

n

Ph

PhCO2
Ph

Cationic

Cl3Al OH2

Ph

Ph

Radical

PhCO2•

n

Li+

Ph

Ph

n
H
Ph

HOAlCl3

PhCO2

Ph

H
Ph

n

n

n

Ph

Ph

HOAlCl3
Ph

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Branching: High and low density
Polyethylene

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19

20

21

22

23

24

25

26

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Commodity Polyolefins
Polyethylene
High Density (1954)
HDPE
Bottles, drums, pipe, conduit, sheet, film

Low Density (1939-1945)
LDPE
Packaging Film, wire and cable coating, toys, flexible
bottles, house wares, coatings
Linear Low Density (1975)
Shirt bags, high strength films

LLDE
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• BRANCHING OF POLYMER CHAINS

55%

85-95%

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Commodity Polyolefins

Polypropylene (1954)
PP
dishwasher safe plastic ware, carpet yarn, fibers and ropes,
webbing, auto parts
Polyisobutylene (1940)
PIB
inner tubes, flexible adhesives, raincoats
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Commodity Vinyl Polymers

Polystyrene (1920)
PS
Styrofoam, clear plastic cups
envelop windows, toys
Cl

Poly(vinyl chloride) (1927)

Cl

Cl

Cl

PVC
garden hose, pipe, car trim, seat covers, records,
floor tiles
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Semi-Commodity Polymers
CO2CH3

Poly(methyl methacrylate) (1931)

CO2CH3
CO2CH3

CO2CH3

CO2CH3

PMMA
plexiglas, embedding resin, resist for X-ray applications
F

Polytetrafluoroethylene. (1943)
teflon, non stick cookware, no grease bearings,
pipe-seal tape

F

F
F

F
F

F
F

F
F

F
F

F
F

F
F

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Step-Growth Polymerization
n

Stage 1

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.
Degree of Polymerization

1000

Xn = Degree of polymerization
p = mole fraction monomer
conversion

Xn 

1
1 p

100


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
4

Cl

Adipoyl chloride

H2N

4

NH2

O

NaOH
Cl

O
HO

N
H

4

1,6-Diaminohexane

Adipoyl chloride
in hexane

O
4

H

O
N
H

4

Nylon 6,6
Diamine, NaOH, in H2O

N
H

6 carbon
diacid

4

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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Condensation Reaction

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Commodity Condensation Polymers
O
N

C

H

Nylon 6 /
bearings, molded parts
carpet yarn
marine rope
cooking/boiling bags

H
N
H

N

O
C

C

O

Nylon 66 (1939)
Fibers, tire cord, fishing line

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Commodity Condensation Polymers

O

O

C

C
O

O

Polyester (1941)
PET, dacron, mylar, kodel
fibers, film-backing, magnetic tapes, soft drink bottles, tire
cord, moldings
O

Polycarbonate (1957)
PC, Lexan
shatter proof glass, cd-disks, car doors and roofs,
appliance housings

O

O

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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.

• Viscosity average M.W. (Mv):
Average determined by viscosity
measurements. Closer to Mw than
M

Mv Mn
Mw

#
o
f
m
o
le
cu
le
s

• 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

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

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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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2.1 Number Average and Weight Average Molecular Weight
A. The molecular weight of polymers
 
a. Some natural polymer (monodisperse) :
All polymer molecules have same molecular weights.
b. Synthetic polymers (polydisperse) :
The molecular weights of polymers are distributed
c. Mechanical properties are influenced by molecular weight
much lower molecular weight ; poor mechanical property
much higher molecular weight ; too tough to process
optimum molecular weight ; 105 -106 for vinyl polymer
15,000 - 20,000 for polar functional group containing polymer (polyamide)
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B. Determination of molecular weight

a. Absolute method :
mass spectrometry
colligative property
end group analysis
light scattering
ultracentrifugation.
b. Relative method : solution viscosity
c. Fractionation method : GPC

POLYMER CHEMISTRY

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C. Definition of average molecular weight
a. number average molecular weight ( Mn )
  Mn=

    
Ni      i
M
    Ni

(colligative property and end group analysis)
b. weight average molecular weight ( Mw)

WiMi
 Mw= W
i
(light scattering)
POLYMER CHEMISTRY

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C. Definition of average molecular weight
c. z average molecular weight ( MZ )

MZ =

NiMi3
NiMi2

(ultracentrifugation)
d. general equation of average molecular weight :

M =
( a=0 , Mn  

NiMia+1
NiMia
a=1 , Mw

a=2 , Mz   

)

e. Mz >  Mw >  Mn   
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D. Polydispersity index : width of distribution

polydispersity index (PI) = Mw / Mn ≥ 1

POLYMER CHEMISTRY

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E. Example of molecular weight calculation

a. 9 moles, molecular weight (Mw) = 30,000
5 moles, molecular weight ( Mw) = 50,000

M n=

Mw =

(9 mol x 30,000 g/mol) + (5 mol x 50,000 g/mol)

= 37,000 g/mol

9 mol + 5 mol

9 mol(30,000 g/mol)2 + 5 mol(50,000 g/mol)2
9 mol(30,000 g/mol) + 5 mol(50,000 g/mol)

= 40,000 g/mol

POLYMER CHEMISTRY

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E. Example of molecular weight calculation

b. 9 grams, molecular weight ( Mw ) = 30,000
5 grams, molecular weight ( Mw ) = 50,000
Mn =

Mw =

9g+5g
(9 g/30,000 g/mol) + (5 g/50,000 g/mol)
(9 g/30,000 g/mol) + (5 g/50,000 g/mol)
9g+5g

= 35,000 g/mol

= 37,000 g/mol

POLYMER CHEMISTRY

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Molecular Weight:
Number Average

Weight Average

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

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)

C NMR spectrum of CH3 region
of atactic polypropylene
13

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Levels of Polymer Architecture



Monomer Type
Molecule Length – molecular weight
Mixture of Monomers – copolymers
Monomer Arrangement - Isomers

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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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Isomerism/Polymer Tacticity
Isotactic

Sindiotactic

Random
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Polymer Categories
Thermoplastic – only secondary bonds between
molecules.
-”Plastic” or reshapable
- Melted and formed under pressure
- Higher tooling costs

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Polymer Categories
Thermoplastic – only secondary bonds between
molecules.
-”Plastic” or reshapable
- Melted and formed under pressure
- Higher tooling costs
Thermoset – primary and secondary bonds between
molecule segments.
- Cannot be reshaped
- Low viscosity in processing
- Cheaper tooling
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Thermoset
Epoxy Reaction:
Primary Amine

If an Amine is on
both ends you get a
“crosslink”
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Polyester Reaction

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Thermoset

Frequent Cross-links Create 3-D Network

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Amorphous Polymer – Lightly Crosslinked

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Semicrystalline Thermoplastic

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Levels of Polymer Architecture





Monomer Type
Molecule Length – molecular weight
Mixture of Monomers – copolymers
Monomer Arrangement – Isomers
Bond/Network Structure
Molecular Conformation

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Amorphous

Example:
Polycarbonate

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Crystalline

Example: Polyethylene

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Crystals

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Chains assume folded
chain conformation

These collect into
lamellar crystallite

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Two crystalline morphologies
(collections of lamellar crystalites)

Spherulite (no shear)

Row Nucleated (shear )
Shish-kebab

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Polymer Blends
• Mixture of compatible
polymers
• No primary bonds
• Intermediate properties
• May be phase separation

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Levels of Polymer Architecture







Monomer Type
Molecule Length – molecular weight
Mixture of Monomers – copolymers
Monomer Arrangement – Isomers
Bond/Network Structure
Molecular Conformation
Blends/Alloys
Additives

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Polymer Categories: Network
Thermoset
Network
Fixed

vs
vs

Thermoplastic
Linear

vs

Reshapeable

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Polymer Categories: Price
Commodity

<$1/pound

Engineering

$1.5-$5/pound

Specialty

> $5/pound

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Polymer Categories: Application




Plastics
Adhesives
Films
Fibers
Elastomers

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Self-Test
• Draw the monomer structure of polyethylene.
• What crystalline morphology forms under shear?
• Which type of polymer cannot be reshaped by
heat and pressure?

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