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
2

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

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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Polymerization Processes
Addition Polymerization
No Byproducts
Usually heat driven

Condensation Polymerization

Byproducts produced
Removal of byproduct controls rate

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
9

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

10

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

11

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
12

Addition Polymerization
In*

A
Initiation

In

A*

13

Addition Polymerization
Propagation
In*

A
Initiation

In

A A*

14

Addition Polymerization
Propagation

In*

A
Initiation

In

A A A*

15

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

16

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

17

Branching: High and low density

Polyethylene

18

19

20

21

22

23

24

25

26

27

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
28

 BRANCHING OF POLYMER CHAINS

55%

85-95%

29

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
30

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
31

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

32

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
33

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

Mole Fraction Conversion (p)

34

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

35

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

36

37

Condensation Reaction

38

Commodity Condensation Polymers

O
N

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

H
N
H

O
C

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

39

Commodity Condensation Polymers

C
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

40

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

41

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

42

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)
POLYMER CHEMISTRY

44

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

45

C. Definition of average molecular weight

a. number average molecular weight ( Mn)
Mn=

Nii
M
Ni

(colligative property and end group analysis)

b. weight average molecular weight ( Mw)

WiMi
Mw= W
i
(light scattering)
POLYMER CHEMISTRY

46

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
POLYMER CHEMISTRY

47

D. Polydispersity index : width of distribution

polydispersity index (PI) = Mw / Mn 1

POLYMER CHEMISTRY

48

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

49

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

51

52

53

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

54

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

55

Levels of Polymer Architecture

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

56

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
57

Isomerism/Polymer Tacticity
Isotactic

Sindiotactic

Random
58

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

59

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
60

Thermoset
Epoxy Reaction:
Primary Amine

If an Amine is on
both ends you get a
crosslink
61

Polyester Reaction

62

Thermoset

Frequent Cross-links Create 3-D Network

63

Amorphous Polymer Lightly Crosslinked

64

Semicrystalline Thermoplastic

65

Levels of Polymer Architecture

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

66

Amorphous

Example:
Polycarbonate

67

Crystalline

Example: Polyethylene

68

Crystals

69

Chains assume folded

chain conformation

These collect into

lamellar crystallite

70

71

Two crystalline morphologies

(collections of lamellar crystalites)

Spherulite (no shear)

Row Nucleated (shear )

Shish-kebab

72

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

73

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

74

Polymer Categories: Network

Thermoset
Network
Fixed

vs
vs

Thermoplastic
Linear

vs

Reshapeable

75

Polymer Categories: Price

Commodity

<$1/pound

Engineering

$1.5-$5/pound

Specialty

> $5/pound

76

Polymer Categories: Application

Plastics
Adhesives
Films
Fibers
Elastomers

77

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?

78