Basic Science

Petroleum Chemistry program

Lecture 3: Polymer Chemistry & Technology (CHE312)

Ass. Prof. : Omayma Fawzy Date: 04 / 03 / 2024

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 Let’s do a quick revision

Mechanism of polymerization reactions

Free radical mechanism of polymerization

Initiation, Propagation, and Termination

Initiation
Thermal, Photochemical, Chemical

Propagation
Chain growth

Termination
Combination - Disporportionation
 The ionic mechanism of polymerization

Ionic polymerization is a type of polymerization that involves the formation of polymer

chains through the reaction of charged monomers known as ions. It can be classified

into two main categories:

Cationic polymerization and Anionic polymerization

 1. Cationic mechanism of Polymerization

Cationic polymerization involves the propagation of a cationic species, typically a

carbocation.

This polymerization method applies only to monomers with electron-releasing groups

such as Isobutylene, Butadiene, and Vinyl ethers.

The catalyst should be an electron-accepting type. These include strong acids such as

sulfuric and perchloric acids or Lewis acids such as Boron trifluoride or anhydrous

aluminum chloride, which produce the true catalyst with the aid of cocatalysts such as

water for BF3 and ethyl chloride or trace of HCl in case of AlCl3.
 BF3 + HOH → [BF3OH]- + H+

AlCl3 + HCl → [AlCl4]- + H+

AlCl3 + Et-Cl → [AlCl4]- + Et +

The catalyst polarizes the double bond of the monomer to form a carbonium ion.
1. Initiation:

Cationic polymerization begins with the initiation step, where a highly reactive species

called the initiator is generated. The initiator is typically a Lewis acid or a strong protic

acid. The electron pair in the double bond of the monomer attacks the catalyst, forming a

carbocation.

CH3
CH3

H2C C [BF3OH]- H+ CH3 C+ [BF3OH]-

CH3
CH3
2. Propagation:

In the propagation step, the carbocation generated in the initiation step reacts with

another monomer molecule. The electron pair in the double bond of the monomer attacks

the positively charged carbocation, leading to the formation of a new carbocation and

extending the polymer chain. This process proceeds continuously, with each new monomer

molecule adding to the growing chain.

3. Termination:
Termination of cationic polymerization has several possibilities:
1. Occurs when the monomer molecules are no longer available for the propagation chains.
2. Combination Termination: Two active chains react with each other, resulting in the
formation of a polymer molecule with a terminated end.
3. Disproportionation Termination: An active chain reacts with a neutral molecule, typically
a monomer, resulting in the transfer of a proton (H+) from one chain to the other. This
leads to the formation of a polymer molecule with a terminated end.
4. The catalyst is destroyed by the addition of some suitable agent, e.g. ammonia to
neutralize protic acids, and alcohol or water to destroy Lewis acids.
 1. Anionic mechanism of Polymerization

This type of polymerization is characteristic only for monomers having electronegative

substituents such as carboxylic or nitrile or nitro groups e.g. Acrylic acid, Acrylonitrile,

Nitroethene.

• The propagating chain carries a negative charge.

• Catalysts for anionic polymerization are of the electron-donating type such as alkali metals

in liquid ammonia (sodium amide in liquid ammonia) or common bases such as Na 2CO3.
1.Initiation:

Anionic polymerization typically begins with the initiation step, where an anionic initiator

reacts with a monomer to form an active center.

The reaction can be represented as follows:

Catalyst + Monomer → Active center

NaNH2 H2C CH H2N CH2 CH- Na+

NO2 NO2
2.Propagation:

Once the active center is formed, it can react with additional monomer molecules to

propagate the polymer chain. The propagation step involves the addition of monomers to the

active center, leading to the elongation of the polymer chain. The reaction can be represented

as:

Active center + Monomer → Polymer chain with an extended active center

H2N CH2 CH - Na+ H2C CH H2N CH2 CH CH2 CH- Na+
NO2 NO2
NO2 NO2
Notes :

• Unlike free radical polymerization, the anions are always present and are not removed by

rapid termination reactions. In this case, the polymerization is said to be non-terminating

or living.

• The term "living polymerization" refers to a polymerization process where the polymer

chains can grow indefinitely without chain termination or side reactions.

• The living nature of the propagation step in anionic polymerization is attributed to the

stability and reactivity of the active center, which is typically an anionic species.
• The rates of initiation and propagation in anionic polymerization are dependent on the

electronegativity of the catalyst, the electronegativity of the substituents on the

monomer, and the resonance stability of the polymeric carbanions formed.

• Since both the catalyst and the polymeric carbanions react with water, alcohols, CO2,

and O2, the polymerization should be carried out in their absence.

• Water and alcohol are used for the termination.

3. Termination:

In anionic polymerization, termination can occur by adding water to the reaction mixture,

which deactivates the active center. The addition of water leads to the protonation of the

anionic active center, resulting in the formation of a stable, non-reactive species. This

termination mechanism is commonly referred to as "quenching" the active center.

H2N CH2 CH CH2 CH- Na+ CH2 CH CH2 CH2

H2O NaOH
NO2 NO2 NO2 NO2
NH3
CH3CH2CHLi CH2=CH
CH3

Write down the anionic polymerization equation of acrylonitrile

 Point of Cationic Polymerization
comparison
Mechanism involves the initiation and propagation of
cationic species, typically formed by the anionic species, typically formed by the reaction
reaction of a Lewis acid catalyst with a of a strong base catalyst with a monomer. The
monomer. The propagation step occurs
through the attack of the cationic species
on the monomer's double bond.
Reactivity tends to be slower and less efficient
compared to anionic polymerization due
to the lower reactivity of carbocations.
Monomer used for various monomers, such as vinyl
Selection ethers, styrene, and isobutylene.
Initiation requires the use of strong Lewis acid
initiators, such as BF3 or SnCl4, which
can be difficult to handle due to their
reactivity and toxicity.
Sensitivity highly sensitive to impurities, moisture,
and oxygen, which can cause premature
termination or side reactions
Anionic Polymerization
involves the initiation and propagation of
propagation step occurs through the attack of
the anionic species on the monomer's double
bond.
generally more efficient and faster than cationic
polymerization due to the higher reactivity of
carbanions.
well-suited for monomers such as styrene,
butadiene, and methyl methacrylate.
requires the use of strong bases, such as alkyl
lithium compounds (e.g., n-BuLi), alkali metals
(e.g., sodium), or alkali metal amides (e.g.,
NaNH2), as initiators.
sensitive to moisture and impurities, which can
lead to premature termination or side reactions.
 Advantages and disadvantages of cationic polymerization

Advantages:
Disadvantages:
• Cationic polymerization offers the ability
• The need for specialized catalysts, and
to polymerize monomers that are not
susceptibility to impurities.
amenable to other polymerization
• The limited availability of monomers
mechanisms.
suitable for cationic polymerization.
• It can also proceed at low temperatures,

allowing for the incorporation of

temperature-sensitive functionalities.
 Advantages and disadvantages of anionic polymerization

Advantages: Disadvantages:

• Anionic polymerization offers precise • Anionic polymerization is limited to

control over molecular weight. It allows monomers that can form stable anionic

for the synthesis of well-defined polymers species.

with controlled architectures and • It is also sensitive to impurities and requires

functionalities. careful handling and purification of

reactants.
 Competitive reactions

These reactions compete with the propagation of the chains thus limiting their growth.

These include transfer, retardation, and inhibition reactions.

Transfer reactions mean the transfer of the reactivity of a growing chain to any other

ingredient in the polymerization system such as initiator, monomer, dead polymeric

chains, and solvent.

All transfer reactions lead to a decrease in the molecular weight of the final polymer, but

the rate of the polymerization will depend on the reactivity of the new center.
1. Transfer to monomer:

• It occurs in radical reactions, it is considered to be one of the most important growth-

limiting processes in cationic polymerization probably due to the greater stability of the

resulting carbonium ion.

• The growing chain attacks unreacted monomer existing in the reaction medium.

• However, the process is highly temperature-dependent, that is why polymers with high

molecular weight are obtained at low temperatures.

• Transfer of anionic activity to a monomer molecule is not important such as in cationic

polymerization.
 CH3 CH3 CH3 CH3

H2C C+ H2C C HC C CH3 C+

CH3 CH3 CH3 CH3

2. Transfer to polymer:

• This type of transfer is characteristic only for radical reactions. Especially at the later stages

of polymerization when almost all monomers have been consumed.

• The growing chain starts to attack dead chains which leads to branching and sometimes

cross-linking to the final polymer.

• The reaction is largely favored at high temperatures.

• To overcome these reactions in some industries use chain transfer agents which are

substances added in small amounts in the polymerization system to prevent branching or

cross-linking and also to control the molecular weight of the final polymer.
3. Transfer to solvent

• This depends on the nature of the solvent and its reactivity.

• The solvent is chosen to be inert

CHCl .
H2C CH . ClCCl3 H2C CCl3

CH3 CH3
4. Transfer to initiator

This usually happens when using a very high concentration of initiators, the reactivity is

transferred from the growing chain radical to the initiator molecules leading to the

formation of a primary radical.

A report about Retardation and Inhibition reactions
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