POLYMER ENGINEERING

ChE (411)
Lecture # 3

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 Polymerization

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Definition of polymerization:

CH2 CH2 [ CH2 CH2 ] n

Ethylene Polyethylene

 Carbon is the most important element in polymers. Because it starts

with only four valence electrons, and wants to share four more,
carbon forms a wide variety of covalent bonds. Most importantly,
carbon forms strong bonds with itself. Long, strong chains or nets
made of thousands of carbon atoms form the backbone of a polymer.
 Polyethylene is the simplest polymer. In addition to the carbon
backbone, only hydrogen atoms are used to achieve four covalent
bonds per carbon atom.
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 Polymerization

Addition (chain growth) condensation (step growth)

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 Polymerization

Addition (chain growth) condensation (step growth)

Free radial cationic Anionic

1-Initiation 1.1-Chemical
1.2 Thermal
1.3 Radiation

2- propagation

3- Termination

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 Polymerization

Addition polymerization yield polymers with repeat

units having identical molecular formula to those of
the monomers from which they are formed.
Condensation polymerizations yield polymers
with repeat units having fewer atoms than
present in the monomers from which they are
formed. This type of chemical reaction involve
the elimination of small molecules such as H2O
and HCl.
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 Examples of Addition Polymers
CH2 CH2 [ CH2 CH2 ] n

Ethylene Polyethylene

CH2 CH [ CH2 CH ] n
HCl Hcl
Polyvinyl Chloride
Vinyl Chloride CH3 CH3

CH2 C [ CH2 C ]
n

C O C O

OCH3 OCH3
methyl methacrylate Poly(methyl methacrylate) (PMMA)
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 CH 2 CH [ CH2 CH ]n
Propylene Polypropylene

CH3 CH3

CF2 CF2 [ CF2 CF2 ] n

Tetraflouroethylene Polytetraflouroethylene

CH2 CH [ CH2 CH ]n

Styrene Polystyrene

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 Examples of Condensation Polymers

OH CH2 CH2 OH [ CH2 CH2 O ]n

Ethylene glycol Polyethylene glycol (PEG)
+ H2 O

Ethylene glycol
+
Poly(ethylene terephthalate) PET
+ H2 O
Terephthalic acid H
H

[ N ( CH2 ) N C ( CH2 ) C ]
Hexamethylene diamine 6 8 n

+ O O
Poly(hexamethylene sebacate)
Sebacic acid Or nylon 6, 10 + H2 O
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 Characteristics of Step-growth Polymerization
 The molecules grow by steps of intermolecular reactions.
 During the reaction, molecules of variable lengths co-exist.
 Monomers can combine with themselves or with other
polymers of variable lengths. The molecules grow throughout
the entire reaction time according to random collisions.
 Slow reaction, favored at high T. In general, reaction products
have low molecular weights compared to other types of
polymerization.
 Usually, linear chains are produced.
 Reversible reaction: remove water from the reaction mixture to
increase the conversion
 Condensation polymers generally have one atom of N or O
in their molecule.

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 Step-growth Polymerization
Any two molecular species present can
react.
Monomer disappears early in the reaction.
Polymer MW rises throughout.
Growth of chains is usually slow (minutes
to days).
Long reaction times increase MW, but yield MW and yield depend on mechanism
of polymer hardly changes.
All molecular species are present
throughout
Usually (but not always) polymer repeat
unit has fewer atoms than had the
monomer
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Chain-growth Polymerization
Growth occurs only by addition of
monomer to active chain end.
Monomer is present throughout, but its
concentration decreases steadily.
Polymer begins to form immediately.
Chain growth is usually very rapid (second
to microseconds)
details.
Only monomer and polymer are present
during reaction.
Usually (but not always) polymer repeat
unit has the same atoms as had the
monomer
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 Step-growth Polymerization

• Monomer + monomer = dimer M1 + M1 M2

• Dimer + monomer = trimer M2 + M1 M3
• Dimer + dimer = tetramer M2 + M2 M4
• Trimer + monomer = tetramer
M3 + M1 M4
• Trimer + dimer = pentamer
• Trimer + trimer = hexamer M4 + M1 M5
•… M3 + M2 M5
M5 + M1 M6
Etc

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 Step-growth Polymerization
Step growth polymerization is a polymerization in which the
polymer chains grow step-wise by reactions that can occur between
any two molecular species.
A type of polymerization mechanism in which bi-functional or
multifunctional monomers react to form first dimers, then trimers,
longer oligomers and eventually long chain polymers.

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 Fundamental differences in reaction mechanism between step
polymerization and chain polymerization.

Formation Step-growth Chain-growth

of Polymerization Polymerization
Dimer O+O O-O I+O I-O
I-O + O I-O-O
Trimer O-O + O O-O-O I+O + O I-O-O-O

Tetramer O-O-O + O O-O-O-O I-O-O+ O I-O-O-O-O

O-O + O-O O-O-O-O
Pentamer O-O-O-O + O O-O-O-O-O I-O-O-O + O 1-O-O-O-O-O
O-O + O-O-O O-O-O-O-O
Hexamer O-O-O-O-O + O O-O-O-O-O-O I-O-O-O-O-O + O I-O-O-O-O-O-O
O-O + O-O-O-O O-O-O-O-O-O
O-O-O + O-O-O O-O-O-O-O-O

etc…..

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 Molar Mass and Degree of Polymerization

Polymers

Depends strongly upon the polymer chain sizes

Characterization by molar mass (M)

Units (g mol-1 or kg mol-1)

The molar mass (M) of a homopolymer degree of polymerization

Here is the number of repeat units in the polymer chain.

(1)

Where Mo is molar mass of the repeat unit.

For copolymers xMo for each type of repeat unit define molar mass.

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 Molar Mass Averages

The number-average molar mass ( n ) is defined as ‘sum of the product of the

molar mass of each fraction multiplied by its mole fraction’.

(2)

Where Xi is the mole fraction of molecules of molar mass Mi and Ni is ratio of to the total
number of molecules.

(3)

Better to use weight fraction in place of number of molecules. Weight fraction (wi) is the
mass of molecules of molar mass Mi divided by the total mass of all the molecules present.

(4)

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 From eq. 4 it can be deduced that….

(5)

Combining eqs. 3 and 5 gives n in terms of weight fractions.

(6)

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 The weight-average molar mass ( w ) is defined as ‘sum of the product of
the molar mass of each fraction multiplied by its weight fraction’.

(7)

Combining eqs. 4 and 7 gives w can be expressed in terms of number of

molecules.

(8)

 Ratio must be greater than unity for a polydisperse polymer and called
as polydispersity or heterogeneity index.
 Used to measure for the breadth of the molar mass distribution.
 is in the range of 1.5-2.0
 Many polymers are having smaller or greater polydispersity other than range 1.5-2.0.
 Perfect monodisperse polymer would have = 1.00
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 Higher molar mass averages
 Molar mass measurement e.g. sedimentation equilibrium gives
z-averages molar mass z.

(9)

Complex molar mass averages can be obtained by dilution

solution viscometery and sedimentation measurements.
 For homopolymers the number-average and weight-average
degree of polymerization are given by

(10)

(11)

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 Example:

By given the molar weight distribution in this figure, evaluate the

molecular weight, and calculate the number average of molecular
weight?
Calculate the weight average of molecular weight?
Calculate the degree of polymerization?

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 = 47.7 Kg/mol
= 47700 g/mol

= 53.9 Kg/mol
= 53900 g/mol

Degree of Polymerization DP=

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