Basic Science

Petroleum Chemistry program

Lecture 2: Polymer Chemistry & Technology (CHE312)

Ass. Prof. : Omayma Fawzy Date : 26 / 02 / 2024

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 Let’s do a quick revision

Definition of polymers

Nomenclature

Properties

Classification
 Mechanism of polymerization reactions

Free radical mechanism of polymerization

Free radical polymerization is a chemical reaction mechanism in which monomers

(smaller molecular units) are joined together to form a polymer chain. It relies on the

presence of free radicals, which are highly reactive species with unpaired electrons. This

process involves

the initiation, propagation, and termination steps

2. Initiation:

The process begins with the generation of free radicals. This can occur through various

methods, such as thermal, photochemical, or chemical initiation.

a. Thermal Initiation:

In thermal initiation, the reaction is initiated by the application of heat to the reaction

mixture. This heat provides the necessary energy to break the chemical bonds within a small

fraction of monomer molecules, forming free radicals.

The mechanism of thermal initiation is not well-established. The oxygen dissolved in the

monomers may probably be the actual initiator, through the formation of peroxides with

the monomers which then decompose to form radicals.

This is proved by the fact that the rate of polymerization of certain monomers is largely

increased if they are first saturated with oxygen.

2. Photochemical Initiation:

In photochemical initiation, the reaction is initiated by the absorption of ultraviolet (UV)

light by a photosensitive monomer molecule. The absorbed energy from the UV light

causes the photosensitive molecule to undergo a photochemical reaction, resulting in

the formation of free radicals.

The photosensitive monomer molecule absorbs UV light, which provides the energy

required to break the chemical bonds within the molecule and form free radicals.
Note: Most of the molecules that are convenient radical sources at elevated temperatures

may dissociate photochemically by UV radiation at room temperature or below.

Photopolymerization is carried out using inert gas such as nitrogen as a medium for the

reaction since the presence of oxygen largely decreases the rate of the reaction as it reacts

with the created free radicals.

3. Chemical initiation

Free radical polymerization involves the use of chemical compounds called initiators to

generate free radicals. These initiators undergo a chemical reaction that produces highly

reactive species with unpaired electrons, which then initiate the polymerization process.

There are two main types of chemical initiators used in free radical polymerization:

organic peroxides and azo compounds.

Organic Peroxides:

Organic peroxides are widely used as initiators in free radical polymerization. They contain a

peroxide (-O-O-) functional group that is susceptible to homolytic cleavage, resulting in the

formation of two radicals. The most commonly used organic peroxides include benzoyl

peroxide (BPO), Dicumyl peroxide, and tert-butyl peroxide.

The organic peroxide molecule absorbs heat energy, which weakens the O-O bond. This

leads to the homolytic cleavage of the O-O bond, generating two radicals. For example,

benzoyl peroxide (BPO) can be represented as PhCOO•, where Ph represents the phenyl

group.
Tert-butyl peroxide
Azo Compounds

Azo compounds are another group of initiators frequently used in free radical polymerization.

They contain a nitrogen-nitrogen (N-N) double bond that is susceptible to homolytic cleavage

upon the application of heat or light. Common examples of azo initiators include

azobisisobutyronitrile (AIBN).

The azo compound absorbs heat or light energy, promoting the homolytic cleavage of the N-

N bond. This generates two radicals with unpaired electrons. For example, AIBN can be

represented as [N(C(CH3)2)2]•, where • denotes the radical.

The cage effect

Refers to a phenomenon in which reactive species, such as initiators, encounter other

molecules in their immediate vicinity before they can react with the intended target. This

effect is particularly relevant in free radical polymerization, where initiators play a crucial

role in initiating the polymerization reaction. The cage effect can reduce the efficiency of

initiation and lead to undesirable side reactions.

Mechanism – How to overcome

1.Mechanism of the Cage Effect:

When an initiator molecule undergoes homolytic cleavage to generate radicals, the resulting

radicals are highly reactive and have a short lifetime. However, due to their high reactivity,

they can collide with other molecules present in the reaction mixture before they can initiate

polymerization. These collisions can lead to the following outcomes:

Inert Collisions - Side Reactions

a. Inert Collisions:

The initiator radicals collide with inert molecules that do not participate in the

polymerization reaction. This results in the loss of the radicals and reduces the efficiency of

initiation.

b. Side Reactions:

The initiator radicals react with other molecules in the system, leading to undesired side

reactions. For example, they can react with monomers to form non-polymeric byproducts or

initiate polymerization at unintended sites.

2. Overcoming the Cage Effect:

The cage effect can be overcome if a reducing agent is added to the polymerization system,

which can react with one of the radicals formed, thus preventing their recombination.

For example: H2O2 and K2S2O8

H2O2 + Fe2+ → HO. + HO- + Fe3+

Which initiation method is more effective? why?
2. Propagation

In free radical polymerization, the polymer chain grows through successive addition of

monomer units. It involves the reaction between a growing polymer radical (active

center) and a monomer molecule, resulting in the formation of a longer polymer chain

and a new radical that can continue the process. Here are the details of the propagation

step:

Active Center Formation - Reaction with Monomer - Chain Growth

1.Active Center Formation:

The polymerization process begins with the formation of an active center, also known as a

growing polymer radical. The active center is typically a radical species that possesses an

unpaired electron. It can be generated during the initiation step of the polymerization

mechanism.

2.Reaction with Monomer:

The active center (polymer radical) reacts with a monomer molecule (M) through a radical

addition reaction. The reaction involves the following steps:

Radical Attack - Bond Formation - Radical Generation

a.Radical Attack:
The active center (polymer radical) approaches a monomer molecule, bringing the unpaired electron close to a
reactive site on the monomer. The reactive site is often a double bond or another functional group that can undergo
addition.

b. Bond Formation:
The unpaired electron of the active center forms a covalent bond with the reactive site of the monomer, resulting in
the attachment of the monomer unit to the polymer chain. This bond formation extends the length of the polymer
chain.

c. Radical Generation:
As a result of the bond formation, a new radical site is created on the monomer molecule. This new radical can
then continue the propagation process by reacting with another monomer molecule, repeating the steps of radical
attack, bond formation, and radical generation.
3. Chain Growth:

The propagation process continues, with the polymer chain growing as monomer units are

successively added. The polymerization can proceed in a chain-growth fashion, where the

active center continues to react with monomers, leading to an ever-increasing polymer

chain length.
3. Termination

The termination in free radical polymerization is where the polymerization process is

stopped by the neutralization or removal of the active polymer radicals. Termination

occurs when two radicals combine or when a radical reacts with a non-radical species.

There are two main types of termination reactions:

Combination termination and Disproportionation termination

Here are the details of each termination mechanism:

• Combination Termination

Combination termination occurs when two active polymer radicals collide and react

with each other, resulting in the formation of a stable, non-radical species. The steps

involved in combination termination are as follows:

Radical Combination:

The colliding radicals undergo a reaction, where the unpaired electrons from each radical

pair up to form a covalent bond. This bond formation results in the formation of a stable,

non-radical species.

Examples of combination termination include the following reaction:

R• + R• → R-R

In this reaction, R represents the polymer chain with an active radical site.
• Disproportionation Termination:

Disproportionation termination occurs when a polymer radical reacts with a non-radical

species, resulting in the transfer of an electron and the formation of a stable polymer

chain and an inert molecule. The steps involved in disproportionation termination are as

follows:

a. Radical Reaction:

An active polymer radical reacts with a non-radical species, which can be another polymer

radical or a molecule without an unpaired electron.

b. Electron Transfer:

During the reaction, one polymer radical donates an electron to the non-radical species, while the other

polymer radical accepts the electron. This electron transfer leads to the formation of a stable polymer chain

and an inert molecule.

Examples of disproportionation termination include the following reactions:

R• + M → R-M

R• + X-Y → R-X + Y•

In the first reaction, M represents a non-radical molecule that can react with the polymer radical to form a

covalent bond. In the second reaction, X-Y represents a non-radical molecule that can be split into two

fragments upon reaction with the polymer radical.

Both combination and disproportionation termination reactions result in the termination of

the polymerization process by removing or neutralizing the active polymer radicals.

The choice between these termination mechanisms depends on factors such as:

The reaction conditions, the concentration of radicals, and the presence of suitable

terminating agents.

The control of termination is essential to achieving the desired molecular weight and

properties of the resulting polymer.

1.Polymerization of Styrene using Benzoyl Peroxide (BPO) as an initiator:
Styrene (C₆H₅CH=CH₂) is a commonly used monomer in the production of polystyrene. The
polymerization can be initiated using benzoyl peroxide (BPO).
2.Initiation:
BPO → 2 •Benzoyl (BPO homolytic cleavage)
3.Propagation:
•Benzoyl + C₆H₅CH=CH₂ → C₆H₅CH₂CH₂• (Benzyl radical)
Benzyl radical + C₆H₅CH=CH₂ → (C₆H₅CH₂CH₂)• (Growing polymer chain)
4.Termination:
Combination termination:
(C₆H₅CH₂CH₂)• + (C₆H₅CH₂CH₂)• → (C₆H₅CH₂CH₂CH₂CH₂C₆H₅) (Polymer chain with
termination)
2. Polymerization of Methyl Methacrylate (MMA) using AIBN as an initiator:

Methyl methacrylate (CH₂=C(CH₃)COOCH₃) is a common monomer used in the

production of polymethyl methacrylate (PMMA). The polymerization can be initiated using

azobisisobutyronitrile (AIBN).

1.Initiation:

AIBN → 2 •AIBN (AIBN homolytic cleavage)

2. Propagation:

•AIBN + CH₂=C(CH₃)COOCH₃ → CH₂-C(CH₃)COOCH₃• (Methyl methacrylate

radical)

Methyl methacrylate radical + CH₂=C(CH₃)COOCH₃ → (CH₂-C(CH₃)COOCH₃)•

(Growing polymer chain)

3. Termination:

Disproportionation termination:

(CH₂-C(CH₃)COOCH₃)• + CH₂=C(CH₃)COOCH₃ → CH₂-C(CH₃)COOCH₃CH₂-

C(CH₃)COOCH₃ (Polymer chain with termination)

3. Polymerization of Vinyl Chloride using Thermal Initiation:
Vinyl chloride (CH₂=CHCl) is a monomer used in the production of polyvinyl chloride
(PVC). The polymerization can be initiated by heating the reaction mixture.
1.Initiation:
CH₂=CHCl → •CH₂-CHCl (Homolytic cleavage)
2.Propagation:
•CH₂-CHCl + CH₂=CHCl → (CH₂-CHCl-CH₂-CHCl)• (Growing polymer chain)
3.Termination:
Combination termination:
(CH₂-CHCl-CH₂-CHCl)• + (CH₂-CHCl-CH₂-CHCl)• → (CH₂-CHCl-CH₂-CHCl-CH₂-
CHCl-CH₂-CHCl) (Polymer chain with termination)
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