Polymerization method

Polymers
All plastics whether made by addition or
condensation polymerization an be divided into 2
groups, called thermoplastic and thermosets.

Thermoplastic
Solid at room temperature that can be melted @
softened by heating, placed into a mold or other
shaping device, and then cooled to give the desired
shape.
Can be reshaped at anytime by reheating the part
Example: choc bar…
Example of thermoplastic
H H
C =C
X H
Monomer

H H polymer, where X can be

C= C H,CH3,Cl , and
X H n ,
Thermoset
Can be either liquid/solids at room
temperature.
When placed into a mould and then heated,
they initially drop in viscosity (liquify) but then
cure(harden) upon further heating, thus giving
the desired shape and solid properties.
But after curing, if thermoset are reheated,
they will soften somewhat do not melt and
therefore it cannot be reshaped.
Example: baking a cake
 Types of Polymer
Elastomer Thermoplastic elastomer

Known as rubber Special group of

Elastic deformation > polymer
200% Processing - easy
Thermoset @ lightly
such as
crosslinked thermoplastics.
thermosets Behaviour – elastic
Polymer chain consist
as elastomer.
of coil like molecules
that can reversiblly
stretch by applying a
force.
 polymer categories
Behaviour General Example
Structure
Thermoplastic Flexible linear polyethylene,
chains (straight/ polystyrene
branched )
Thermosetting Rigid three Polyurethanes,
dimensional Epoxy,
network( chains polyester
maybe linear /
branched)
Elastomer Thermoplastics or Natural Rubber
lightly cross-
linked
thermosets,
consist of spring –
Polymer
Thermoplastic Thermoset Elastomer
Polyethylene •Phenolics (PF) Natural Rubber
LDPE Isoprene Rubber
HDPE •Amino Plastic (synthetic rubber)
LLDPE (linear low (urea
density) formaldehyde)
(melamine
Formaldehyde)
polypropylene Epoxies Butadiene
rubber(BR)
Styrene Butadiene
Rubber(SBR)
Polyvinyl chloride Imides/polyimides Ethylene-Propylene
(PVC) Elastomer (EPM and
EPDM)
Polystyrene (PS) Polyurethanes Silicones
Polyamide/ nylons Polyester
(PA)
POLYMERIZATION
Process - ‘creating a polymer’

The two carbon atoms are joined by a

double covalent bond.
Each carbon atom shares two of its
electrons with the second carbon atom and
two hydrogen atoms are bonded to each of
carbon atom.
Replace one of the hydrogen atoms in CH2
with CH3, benzene ring @ chlorine
Polymer Synthesis
Polymer synthesis is a complex procedure and
can take place in a variety of ways.
 Polymerization

Addition Condensation

@ @
Chain growth Step growth
polymerization polymerization
Chain Growth @ Addition Polymerization
Chain-growth polymerization (or addition
polymerization) involves the linking together of
molecules incorporating double or triple
chemical bonds.
These unsaturated monomers (the identical
molecules that make up the polymers) have extra
internal bonds that are able to break and link up
with other monomers to form the repeating chain.
This process involved reaction in which monomers
are added one after another to a rapidly growing
chains.
The growing polymer proceeds via a chain
mechanism
Like all chain reactions, three fundamental steps are
involved: initiation, propagation and termination.

Chain-growth polymerization is involved in the

manufacture of polymers such as polyethylene,
polypropylene, and polyvinyl chloride (PVC).

A special case of chain-growth polymerization leads

to living polymerization.
Polyethylene, polypropylene, and poly(vinyl
chloride) are addition polymers formed by
adding monomers to a growing polymer chain.

Addition polymers can be recognized by

noting that the repeating unit always has the
same formula as the monomer from which the
polymer is formed.
 Polyethylene

Polypropylene

Poly(vinyl chloride)
Addition polymerization
describes the method where
monomers are added one by
one to an active site on the
growing chain.
There are three significant
reactions that take place in
addition polymerization:
initiation (birth),
propagation (growth),
and termination (death).
 Initiation Reaction
The first step in producing polymers by free
radical polymerization is initiation.
This step begins when an initiator
decomposes into free radicals in the presence
of monomers.
Peroxides, which contain an O-O bond, are
often used in this role
Initiator = dibenzyl peroxide
A peroxide is a compound containing an oxygen–
oxygen single bond or the peroxide anion, O 2-2.The
O−O group is called the peroxide group or
peroxo group.
The peroxide group is marked as O , R1 and R2
mark hydrocarbon radicals.
[O – O]-2
R – O – O – R
R – O - O – H
Example of peroxide is Hydrogen peroxide
(H-O-O-H)
The instability of carbon-carbon
double bonds in the monomer makes
them susceptible to reaction with
the unpaired electrons in the radical.
In this reaction, the active center of
the radical "grabs" one of the
electrons from the double bond of
the monomer, leaving an unpaired
electron to appear as a new active
center at the end of the chain.
Propagation Reaction
After a synthesis reaction has been initiated, the
propagation reaction takes over.
In the propagation stage, monomer will react with free
radical of initiator.


For example, if X were a methyl group, the monomer

would be propylene and the polymer, polypropylene .
Thousands of monomers are added to the
chain within this time. The entire process
stops when the termination reaction occurs.
This is a rapid process.
Termination Reaction
In theory, the propagation reaction could
continue until the supply of monomers is
exhausted.
Most often the growth of a polymer chain
is halted by the termination reaction.
The addition polymerization stop
when 2 free radicals combine and no
new radicals are formed.
Termination typically occurs in two
ways:combination and disproportionation.
Combination occurs when the polymer's
growth is stopped by free electrons from two
growing chains that join and form a single
chain. The following diagram depicts
combination, with the symbol (R)
representing the rest of the chain.
Disproportionation halts the propagation
reaction when a free radical strips a hydrogen
atom from an active chain. A carbon-carbon
double bond takes the place of the missing
hydrogen.
Disproportionation can also occur when the
radical reacts with an impurity. This is why it is
so important that polymerization be carried out
under very clean conditions.
Termination by disproportionation is shown in
the diagram
Addition Polymerization
https://youtu.be/HpPHN7fcLHI

https://youtu.be/0yOJajPJptA
Three components of chain
polymerizations:
Initiation
Propagation
Termination
All chain polymerizations (of any kind) have at
least the first two components; most have all
three. The exceptions are living
polymerizations that lack termination.
Cationic polymerization
Cationic polymerization is a type of chain
growth polymerization in which a cationic
initiator transfers charge to a monomer which
becomes reactive.
This reactive monomer goes on to react
similarly with other monomers to form a
polymer.
Poly(isobutylene) used in inner tubes is the
only polymer being commercially produced
via cationic polymerization.
Monomer scope for cationic polymerization is limited to two
main types: olefins and heterocyclic monomers.
Cationic polymerization of both types of monomers occurs only
if the overall reaction is thermally favorable.

In the case of olefins, this is due to isomerization (same

atom different arrangement) of the monomer double bond;
for heterocycles, this is due to release of monomer ring strain
and, in some cases, isomerization of repeating units.

Monomers for cationic polymerization are nucleophilic

( chemical species that donates an electron pair to
an electrophile to form a chemical bond in relation to
a reaction)and form a stable cation upon polymerization. )
Anionic addition polymerization is a form
of chain-growth polymerization or addition
polymerization that involves the
polymerization of vinyl monomers with strong
electronegative groups.
This polymerization is carried out through a
carbon ion active species.
Like all chain-growth polymerizations, it takes
place in three steps: chain initiation, chain
propagation, and chain termination.
Anionic polymerizations are used in the
production of polydiene synthetic rubbers,
solution styrene/butadiene rubbers (SBR), and
styrenic thermoplastic elastomers.
Condensation
To condense means to make something more
dense, or compact.
Polymers formed when a small molecule
condenses out during the polymerization
reaction are therefore called condensation
polymers.
Silicone, for example, is a condensation
polymer formed by polymerizing (silanol)
(CH3)2Si(OH)2. Each time a monomer is added to
the polymer chain, a molecule of water is
condensed out, as shown in the figure below.
Step Growth @ Condensation
Polymerization

Step-growth polymers = polymers formed

by the stepwise reaction between
functional groups of monomers.
Most step-growth polymers are also
classified as condensation polymers,
Step-growth polymers increase in
molecular weight at a very slow rate at
lower conversions and reach moderately
high molecular weights only at very high
conversion (i.e. >95%).
Condensation polymers are formed from a
series of reaction, in which two species
(monomer) can react at any time leading to a
larger molecule.
In this reaction, stepwise reaction occurs
between the chemically reactive groups or
functional groups on the reacting molecules.
In the process, a small molecule, usually water /
ammonia is eliminated
Example: formation of polyester through
reaction of glycol and dicarboxylic acid.
A condensation polymer is defined
as a polymer that involves loss of
small molecules during its
synthesis, or contains functional
groups as part of its backbone
chain, or its repeat unit does not
contain all the atoms present in
the monomer to which it can be
degraded.
Example: Polyester , Polyimide
The monomers that are involved in
condensation polymerization are not the same
as those in addition polymerization.

The monomers for condensation

polymerization have two main characteristics:
1. Instead of double bonds, these monomers
have functional groups (like alcohol, amine,
or carboxylic acid groups).
2. Each monomer has at least two reactive
sites, which usually means two functional
groups.
Glycol means that a molecule has more than one
alcohol (-OH) group.
Amine means that a molecule has an amino (-NH 2)
group. Diamine (or diamino) means that a
molecule contains two amino groups.
 Acid means that a molecule contains a carboxylic
acid group (-COOH).
The carboxylic acid group

The amino group

 The alcohol group
The Amide Linkage:
When a carboxylic acid and an amine react,
a water molecule is removed, and an amide
molecule is formed.
The Ester Linkage:
When a carboxylic acid and an alcohol react, a
water molecule is removed, and an ester
molecule is formed
Monomers involved in condensation
polymerization have functional groups.
These functional groups combine to form amide
and ester linkages.
When this occurs, a water molecule in
removed. Since water is removed, we call these
reactions condensation reactions (water
condenses out).
When involved condensation process in the
polymerization = condensation polymerization.
A water molecule is removed as the ester
linkage is formed. Notice the acid and the
alcohol groups that are still available for
bonding.

Because the monomers above are all joined by

ester linkages, the polymer chain is a polyester.
Condensation polymerization
https://youtu.be/-d14DmSBuAQ
https://youtu.be/usRnJP8lDxM
https://youtu.be/mIKdQG5Mp9k
Curing
https://youtu.be/ZEjXmHwEWFc
STEP GROWTH/ CONDENSATION CHAIN GROWTH / ADDITION
POLYMERIZATION POLYMERIZATION
 STEP POLYMERIZATION
CHAIN/GROWTH
POLYMERIZATION

 Any two molecular species  Growth occurs only by

can react. addition of monomer to
 Monomer disappears early. active chain end.
 Monomer is present
 Polymer MW rises
throughout, but its
throughout. concentration decreases.
 Growth of chains is usually  Polymer begins to form
slow (minutes to days). immediately.
 Long reaction times  Chain growth is usually
increase MW, but yield of very rapid (second to
microseconds).
polymer hardly changes.  MW and yield depend on
mechanism details.
 ADDITION/CHAIN GROWTH
STEP POLYMERIZATION
POLYMERIZATION

All molecular species Only monomer and

are present polymer are present
throughout. during reaction.
Usually (but not Usually (but not
always) polymer always) polymer
repeat unit has fewer repeat unit has the
atoms than had the same atoms as had
monomer. the monomer
 Condensation / Step Addition / chain-
growth growth
polymerization Polymerization
Polymer growth step by step reaction Chain reaction
mechanism
Dependence No – independent Yes- sequential
events dependent events
Initiator No Yes
Type of Bifunctional ( has Contains carbon –
monomer reacting functional carbon
groups on the ends) Double bond
Polymer chain Many, not very long A few ,long chains
characteristics chains
Branching Unlikely Possible
Name of Poly + name of new Poly +name of
polymer bond monomer
New type of Yes No
bond formed
Living Polymerization
There exists a type of addition polymerization
that does not undergo a termination reaction.
This so-called "living polymerization"
continues until the monomer supply has been
exhausted.
Condensation vs. Addition
Carothers originally classified polymers based
on a comparison of the atoms in the monomer
to the atoms in the polymer repeat unit. (Wallace
Hume Carothers (April 27, 1896 – April 29, 1937) was an American
chemist)
Condensation polymers had fewer atoms in
the repeat unit (i.e., some small molecule was
emitted during polymerization).
Addition polymers had the same atoms as
their monomers.
What is needed:
Extremely pure ingredients.
Clean, very high yield
reactions.
At least moderate reaction
rates.
Precise balance of functional
groups.
Polymerization - What Can
Go Wrong
Impurities containing only one functional
group.
Impurities that poison the catalyst (if used).
Decomposition of monomer.
Unwanted side reactions.
Physical loss of monomer during reaction.
Reversibility (unfavorable equilibrium).
Stoichiometric imbalance (for syndioregic
mode).