Dr. Muhammad Irfan, PhD & Post Doc.

Assistant Professor

Department of Chemical & Energy Engineering

MECHANISMS OF POLYMERIZATION

REACTIONS
 Reactions of Polymers

Addition Polymerization (Chain Growth)

Step Growth Polymerization (Condensation)
Differences between step-growth polymerization and
chain-growth polymerization
Step-growth polymerization Chain-growth polymerization
Growth throughout matrix Growth by addition of monomer only at
one end of chain
Rapid loss of monomer early in the Some monomer remains even at long
reaction reaction times
Same mechanism throughout Different mechanisms operate at
different stages of reaction (i.e.
Initiation, propagation and
termination)
Average molecular weight increases Molar mass of backbone chain increases
slowly at low conversion and high rapidly at early stage and remains
extents of reaction are required to approximately the same throughout the
obtain high chain length polymerization
Ends remain active (no termination) Chains not active after termination
No initiator necessary Initiator required
Step of Radical Chain Polymerization

• Initiation

• Propagation

• Termination
INITIATION
PROPAGATION
 TERMINATION
Dead Polymer
i.) Coupling or Combination;

ii.) Disproportionation
CHAIN TRANSFER
REACTIONS
Transfer to monomer reaction

Transfer to initiator reaction

Transfer to solvent reaction

 IONIC CHAIN
POLYMERIZATION
• Using catalyst, not initiator

• Highest reaction rate

• Termination step is just disproportionation

• Environment must be pure

• Reaction occurs in the cold

Anionic Polymerization=Living Polymerization

If the starting reagents are pure and the

polimerization reactor is purged of all

oxygen and traces of water, polimerization

can proceed until all monomer is

consumed.
 CONDENSATION
POLYMERIZATION
• Using catalyst

• Minumum two functional groups required

• Usually linear

• Molecular weight increases slowly at low

conversion

• High extents of reaction are required to obtain

 KINETICS OF
POLYMERIZATION
• Reaction rate of ionic polimerization more
than radicalic polimerization

• So kinetics of ionic polimerization are not

calculated

• But kinetics of radicalic polimerization can

be analysed
 Kinetic of Radicalic
Polymerization
Initiation;

Propagation;

Termination;
Kinetic of Condensation
Polymerization
• Equivalent reactivity of
functional groups.

• It may be first, second

or third order by
depending upon.
 POLYMERIZATION
PROCESSES
• Bulk Polymerization

• Solvent Polymerization

• Suspention Polymerization

• Emulsion Polymerization

• Special Processes

 Electrochemical Polymerization
 Radiation Polymerization
 Grow-discharge (Plasma)
 Bulk Polymerization
• The simplest technique

• It gives the highest-purity polymer

 Ingredients : monomer,

monomer-soluble initiator,

perhaps a chain transfer agent

Advantages Disadvantages
High yield per reactor volume Difficult of removing the lost
traces of monomer
Easy polymer recovery Dissipating heat produced during
the polimerization
Final product form
 Solution Polymerization
• Heat can be removed by conducting the polymerization in an organic solvent or water

• Initiator or monomer must be soluble in solvent

• Solvents have acceptable chain-transfer characteristics

• Solvents have suitable melting or boiling points for the conditions of polymerization

 Ingredients : monomer

initiator

solvent

Advantages Disadvantages
Temperature control is easy Small yield per reactor volume
Easy removed Solvent recovery
 Suspention Polymerization
• Coalescense of sticky droplets is prevented by PVA

• Near the end of polymerization, the particles harder and they can be

removed by filtration, then washing

 Ingredients : water-insoluble monomer,
water-insoluble initiator,
sometimes chain transfer agent
suspention medium (water-usually)

Advantages (according to bulk Disadvantages

polymerization)
Forming process not using Polymer purity is low

Stirring is easy Reactor capital costs are higher

than for solution polymerization

Separation process is easy

 Emulsion Polymerization
• Particles are formed monosize with emulsion polymerization

• Polymerization is initiated when the water-soluble radical enters a

monomer-containing micelles.

 Ingredients : water-insoluble monomer,

water-soluble initiator,
chain transfer agent,
dispersing medium (water),
fatty acid,
surfactant such as sodium salt of a long chain
Polymer Building Blocks
• Hydrogen
• Carbon (key)
• Oxygen
• Nitrogen
• Fluorine
• Silicon
• Sulfur
• Chlorine
 Carbon Is Key
Atomic number: 6
Valence: 2s22p2
Hybrid orbital- sp

Will share up to four electrons,

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

• Condensation Polymerization
– Byproducts produced
– Removal of byproduct controls rate
Addition Polymerization
Condensation Reaction
 Effects of Polymerization Scheme

• Polymer may contain residual byproduct.

• Addition polymerization done in solvent
may have residual solvent
• Cleanest polymers are gas phase or aqueous
solution polymers
Basic Steps in Polymerization

Initiation: Formation of
free radical

Propagation: Combining of
mers to form
chains

Termination: Elimination of
free radicals
 Polymerization Step Effects
• The actual method of initiation,
propagation, termination will affect final
properties.

• You cannot easily switch suppliers or resin

once a particular material and factory have
been qualified.
 Properties
• Behavior determined by a combination of
primary backbone bonds and secondary
bonds.

• Different monomers will have different

secondary bond strengths.
 Levels of Polymer Architecture
• Monomer Type
Families based on an ethenic backbone are vinyl
polymers or vinylydines

Polyethylene
PE

Polypropylene
PP
Polystyrene
PS

Polyvinylchloride
PVC
 Levels of Polymer Architecture
• Monomer Type
• Molecule Length
 Synthetic and Biological Polymers

Polymers: Macromolecules formed by the covalent

attachment of a set of small molecules termed monomers.

Polymers are classified as:

(1) Man-made or synthetic polymers that are
synthesized in the laboratory;
(2) Biological polymer that are found in nature.

Synthetic polymers: nylon, poly-ethylene, poly-styrene

Biological polymers: DNA, proteins, carbohydrates

34
 Methods for making polymers

Addition polymerization and condensation polymerization

Addition polymerization: monomers react to form a

polymer without net loss of atoms.

Most common form: free radical chain reaction of

ethylenes

n monomers one polymer molecule

35
Example of addition polymers

36
Free-Radical AdditionPolymerization of
Ethylene
H2C CH2

200 °C O2
2000 atm peroxides

CH2 CH2 CH2 CH2 CH2 CH2 CH2

polyethylene
Free-Radical Polymerization of Propene

H2C CHCH3

CH CH CH CH CH CH CH
CH3 CH3 CH3 CH3 CH3 CH3 CH3

polypropylene
 ..
RO
.. • Mechanism
H2C CHCH3
 ..
RO: Mechanism
H2C CHCH3
•
 ..
RO: Mechanism
H2C CHCH3
•

H2C CHCH3
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3
•
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3
•

H2C CHCH3
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3

H2C CHCH3
•
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3

H2C CHCH3
•

H2C CHCH3
 Likewise...

•H2C=CHCl polyvinyl chloride

•H2C=CHC6H5 polystyrene
•F2C=CF2 Teflon
Important
constitutions
for synthetic
polymers

47
Supramolecular
structure of
polymers

48
Structural
properties of
linear
polymers:
conformationa
l flexibility
and strength

49
Cross linking adds
tensile strength

50
 Condensation polymerization

Condensation polymerization: the polymer grows from

monomers by splitting off a small molecule such as
water or carbon dioxide.

Example: formation of amide links and loss of water

Monomers

First unit of polymer + H2O

51
Rembember from GChem?

Nylon is a condensation polymer

made of the monomers adipic acid
and hexamethylene diamine.

O OH
O

OH
Qu i c k T i m e ™ an d a
Ph ot o - J PEG de c o m p re s s o r
are n ee de d t o s ee th i s pi c ture.

They're nylons, Benjamin.

adipic acid
+
NH2
H2N

hexamethylene diamine

nylon
52
 Hydrogen bonds between chains

Supramolecular
Structure of
nylon

Intermolecular
hydrogen bonds
give nylon
enormous tensile
strength

53
 Biopolymers

Nucleic acid polymers (DNA, RNA)

Amino acids polymers (Proteins)

Sugar polymers (Carbohydrates)

Genetic information for the cell: DNA

Structural strength and catalysis: Proteins

Energy source: Carbohydrates

54
 Proteins: amino acid monomers

The basic structure of an amino acid monomer

HO NH2
H
O R

The difference between amino acids is the R group

56
 Proteins: condensation polymers

Formed by condensation polymerization of amino acids

Monomers: 20 essential amino acids

NH2 General structure of an amino acid
H R
CO2H R is the only variable group

Glycine (R = H) + Glycine First step toward poly(glycine)

57
Representation of the
constitution of a protein

58
Three D representation of the structure of a protein

59
DNA
 Thymine (T)
The monomers:

Adenine (A)
Cytosine (C)

Guanine (G)

Phosphate-
Sugar (backbone) of
DNA
61
Phosphate-
sugar
backbone
holds the DNA
macromolecule
together

62
One strand
unwinds to
duplicate its
complement via a
polymerization of
the monomers
C, G, A and T

63
Carbohydrates
65
1.1 Introduction and Historical Development

A. Development of civilization

Stone age → Bronze age → Iron age → Polymer age

B. Application of polymeric materials

ｏ PE milk bottles

ｏ Polyamide bulletproof vests

ｏ Polyurethane artificial heart

ｏ Fluorinated phosphazene elastomer for arctic

environments
E. Examples of monomers and polymers

Monomer Polymer

CH2 CH2
CH2CH2

CH2 CHCl CH2CH2

Cl
O
H2C CH2 CH2CH2O

HOCH 2CH2OH CH2CH2O

HO CO2H O C
1.2 Definitions

A. Acoording to the amount of repeating units

monomer : one unit

oligomer : few

polymer : many (poly – many, mer – part)

telechelic polymer : polymer containing reactive end group

(tele = far, chele = claw)

telechelic oligomer : oligomer containing reactive end group

macromer(=macro monomer) : monomer containing long chain

1.2 Definitions
B. DP : Degree of polymerization

The total number of repeating units

contained
terminal group

C. The kinds of applied monomers

One kind :
Homopolymer
Two kinds : Copolymer
Three kinds :
Terpolymer
D. Types of copolymer

Homopolymer : -A-A-A-A-A-A-A-A-

Random copolymer : -A-B-B-A-B-A-A-B-

Alternating copolymer : -A-B-A-B-A-B-A-B-

Block copolymer : -A-A-A-A-B-B-B-B-

Graft copolymer : -A-A-A-A-A-A-A-A-

B-B-B-B-B-
E. Representation of polymer types

(a) linear (b) branch

(c) network
F. Representation of polymer architectures

(a) star (b) comb polymer

polymer

(c)ladder polymer (d) semi- ladder

(or stepladder) polymer
F. Representation of polymer architectures

(e) polyrotaxane (f) polycatenane

(g) dendrimer
 G. Thermoplastic and thermoset (reaction to
temperature)

Thermoplastic : Linear or branched polymer

Thermoset : Network polymer

1.3 Polymerization Processes

A. Classification of polymers to be suggested by Caroth

Addition polymers : repeating units and monomers are same

Condensation polymers : repeating units and monomers

are not equal, to be split out sm
 Other examples

1. Polyester from lactone (1.7) &

from ω-hydroxycarboxylic acid

(1.8)
O O
(1.7)
O C O R C

O (1.8)
OH R CO2H O R C + H2O
 Other examples

2. Polyamide from lactam (1.9), and

from ω-aminocarboxylic acid (1.10)

O O
(1.9)
NH C NH R C
R

O
+ H2O (1.10)
H2N R CO2H NH R C
 Other examples

3. Polyurethane from diisocyanate and dialcohol(1.11)

and from diamine and bischloroformate(1.12):

OCN R NCO + HO R' OH

O O
'
(1.11)
CNH R NHCO R O

O O

H2N R NH 2 + ClCO R' OCCl

(1.12)
O O

CNH R NHCO R' O + 2HCl

 Other examples

4. Hydrocarbon polymer from ethylene (1.13), and

from α,ω-dibromide (1.14)

initiator
CH2 CH2 CH2CH2 (1.13)

2Na
BrCH2(CH2)8CH2Br CH2CH2 + 2NaBr (1.14)
5
 1.3 Polymerization Processes
B. Modern classification of polymerization
according to
polymerization mechanism

Step growth polymerization : Polymers build up

stepwise
Chain growth polymerization : Addition polymerizatio
molecular weights increase successively,
one by one monomer

Ring-opening polymerization may be either step

or chain reaction
1.4 Step-reaction Polymerization

A. Monomer to have difunctional group

1. One having both reactive functional groups in one molecule

A R B R X

HO R CO2H O R C + H2O (1.8)

O
+ H2O (1.10)
H2N R CO2H NH R C
2. Other having two difunctional monomers

A R A + B R' B R X R' X

OCN R NCO + HO R' OH

O O
(1.11)
CNH R NHCO R' O

O O

H2N R NH 2 + ClCO R' OCCl

(1.12)
O O

CNH R NHCO R' O + 2HCl

 B. Reaction : Condensation reaction using functional
group
Example - Polyesterification

n HO CO2H O C + nH2O (1.3)

n

nHO2C CO2H + nHOCH2CH2OH

(1.4)

O O

C COCH2CH2O n
+ 2nH2O
C. Carothers equation

( NO : number of molecules
N : total molecules after a given reaction period.
NO – N : The amount reacted
P : The reaction conversion )

NO
P =N Or N = NO(1 P)
NO

( DP is the average number of repeating units of all molecules prese

DP = NO/N

1
DP =
1-P

For example 1
DP =
At 98% conversion 1- 0.98
 (A) Unreacted monomer
A A A A A A A A A A A A
(a)
B B B B B B B B B B B B

(B) 50% reacted, DP = 1.3

A A A A A A A A A A A A
(b)
B B B B B B B B B B B B

(C) 75% reacted, DP = 1.7

A A A A A A A A A A A A
(c)
B B B B B B B B B B B B

(D) 100% reacted, DP = 3

A A A A A A A A A A A A
(d)
B B B B B B B B B B B B
1.5 Chain-reaction Polymerization

A. Monomer : vinyl monomer

χCH2=CH2

B. Reaction : Addition reaction initiated by active species

C. Mechanism :

Initiation
.
R + CH2=CH2 → RCH2CH2 .
.
Propagation
RCH2CH2 + CH2=CH2 → RCH2CH2CH2CH2 .
 TABLE 1.1 Comparison of Step-Reaction and
Chain-Reaction Polymerization

Step Reaction Chain Reaction

Growth occurs throughout matrix by Growth occurs by successive addition of

monomer units to limited number of
reaction between monomers, oligomers,
growing chains
and polymers
DP can be very high
DPa low to moderate
Monomer consumed relatively slowly, but
Monomer consumed rapidly while
molecular weight increases rapidly
molecular weight increases slowly
Initiation and propagation mechanisms diff
No initiator needed; same reaction Usually chain-terminating step involved
mechanism throughout Polymerizaion rate increases initially as
No termination step; end groups still initiator units generated; remains relati
reactive
constant until monomer depleted
Polymerization rate decreases steadily as
functional groups consumed
aDP, average degree of polymerization.
1.6 Step-reaction Addition and
Chain-reaction Condensation

A. Step-reaction Addition.

(CH2)6 +

O
O

(CH2)6 (1.15)

O
1.6 Step-reaction Addition and
Chain-reaction
Condensation
B. Chain-reaction Condensation

BF3
CH2N2 CH2 + N2 (1.16
)