Basic Science

Petroleum Chemistry program

Lecture 4: Polymer Chemistry & Technology (CHE312)

Ass. Prof. : Omayma Fawzy Date : 11 / 03 / 2024

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 Let’s do a quick revision

The ionic mechanism of polymerization

Cationic polymerization and Anionic polymerization

 Retardation and Inhibition of Polymerization Reactions

If the transfer reaction process leads to a lower reactivity radical than that of the

original growing chains, the rate of polymerization will decrease, and the substance

involved in the transfer process is known as Retarder.

If the reactivity is so weak, that no polymerization can be detected, the substance is

known as Inhibitor.
Retardation refers to the slowing down of the polymerization reaction.

Retarders are substances that are added to slow down or delay the polymerization

process.

Retarders are typically used when it is necessary to control the reaction rate or when a

longer processing time is desired.

Retardation can occur due to various factors and can have both intentional and

unintentional consequences.

Let's explore some common causes of retardation in polymerization reactions:

1.Inhibitors:

Inhibitors are chemical substances intentionally added to polymerization reactions to

control the reaction rate. They work by scavenging or reacting with the reactive species

involved in the polymerization process, such as free radicals or initiators. By consuming

these reactive species, inhibitors interrupt the chain reaction and slow down the

polymerization process. Common inhibitors include hydroquinone, phenols, and nitro

compounds.
2. Temperature:
The reaction temperature plays a crucial role in polymerization reactions. Lowering the
temperature can retard the reaction by reducing the mobility and reactivity of the
polymerization species. Slower molecular motion at lower temperatures decreases the
collision frequency and thus slows down the reaction rate.

3. Oxygen:
The presence of oxygen can retard certain types of polymerization reactions, particularly those
that involve free radical mechanisms. Oxygen acts as a scavenger for free radicals, which are
crucial for the propagation of the reaction. Oxygen reacts with the free radicals and
deactivates them, inhibiting the polymerization process.
4. Chain transfer agents:

Chain transfer agents can also cause retardation in polymerization reactions. These agents

react with the growing polymer chain and effectively terminate its growth. By terminating

the chain prematurely, the overall polymerization rate is slowed down.

5. Impurities:

The presence of impurities in the reaction mixture can interfere with the polymerization

process and cause retardation. Impurities can either react with the reactive species or

hinder their mobility, leading to a slower reaction rate.

Inhibition reactions in polymerization processes refer to the complete suppression or

prevention of the polymerization reaction. Inhibition can occur unintentionally,

leading to undesired outcomes, or it can be intentionally induced to control the reaction

or prevent unwanted polymerization.

Here are a few common causes of inhibition in polymerization reactions:

1.Inhibitors:

While inhibitors can be used as retarders, they can also cause inhibition at higher

concentrations. Inhibitors interfere with the initiation or propagation steps of the

polymerization process by scavenging or reacting with the reactive species responsible for

the reaction, such as initiators or monomers. In higher concentrations, inhibitors can

completely block the reaction, resulting in inhibition.

2. Oxygen:

Oxygen is known to inhibit certain types of polymerization reactions, particularly those that

involve free radical mechanisms. Oxygen can react with and deactivate the reactive

species, preventing them from initiating polymerization or participating in the reaction.

Oxygen inhibition is commonly observed in processes such as UV-curing or free radical

polymerizations.
3. Catalyst poisons:

Some polymerization reactions rely on the presence of catalysts to proceed. However, certain

substances, known as catalyst poisons, can inhibit the activity of these catalysts. Catalyst

poisons can bind to the catalysts, rendering them inactive and inhibiting the

polymerization process.

4. Incompatible impurities:

The presence of impurities in the reaction mixture can hinder the polymerization process and

cause inhibition. These impurities can either react with the reactive species or interfere

with their mobility, resulting in a suppressed or blocked reaction.

5. Temperature:

Extreme temperatures, both high and low, can inhibit polymerization reactions. High

temperatures can cause premature termination of the polymer chains or result in side

reactions that disrupt the polymerization process. On the other hand, low temperatures

can reduce the mobility and reactivity of the reactants, leading to slower or inhibited

reactions.
It's important to note that while inhibition can be undesired in most cases, it can also

be intentionally induced to control the polymerization process or prevent unwanted

reactions. Understanding the specific polymerization mechanism, reaction conditions, and

the nature of the reactants and inhibitors used is crucial in managing and avoiding

inhibition reactions in polymerization processes.

Advantages of Retarders:
1. Control over reaction rate:
Retarders provide the ability to control the polymerization reaction rate. By adjusting the
concentration of retarders or their application, the rate of polymerization can be slowed
down, allowing for better control over the process.

2. 2. Extended processing time:

Retarders can extend the processing time, which can be beneficial in situations where
longer processing times are desired. This can be particularly useful in large-scale industrial
processes where longer reaction times may be required for practical reasons.
3. Improved product quality:

Slowing down the polymerization reaction rate can often lead to improved product

quality. It allows for better control over molecular weight distribution, chain

branching, and other polymer properties, resulting in products with desired

characteristics.
Disadvantages of Retarders:
1.Potential loss of productivity:
The use of retarders can lead to longer reaction times, which can reduce the productivity of
the polymerization process. This can be a disadvantage in situations where high production
rates are desired or when there are time constraints.

2. Increased reaction complexity:

The addition of retarders can introduce additional complexity to the polymerization process. It
requires careful consideration of the concentration and timing of retarder addition, as well
as potential interactions with other additives or reactants, adding complexity to process
optimization and control.
Advantages of Inhibitors:
1.Prevention of undesired polymerization:
Inhibitors can be used to completely suppress or prevent polymerization reactions when
necessary. This can be beneficial in situations where unwanted or premature
polymerization needs to be avoided, such as during storage or transportation of
monomers or reactive mixtures.
2. Safety and stability:
Inhibitors can enhance the safety and stability of reactive systems. By inhibiting the
polymerization reaction, they reduce the risk of uncontrolled reactions (self-
polymerization), heat generation, and potential hazards associated with highly reactive
materials.
Disadvantages of Inhibitors:
1.Complete suppression of reaction:
Inhibitors can completely suppress the polymerization reaction, which may not be desirable
in all cases. In situations where controlled polymerization is needed, excessive inhibition can
hinder the desired reaction and lead to incomplete or unsatisfactory polymerization.

2. Challenges in achieving the desired inhibition level:

Determining the optimal concentration and type of inhibitor to achieve the desired level of
inhibition can be challenging. Insufficient inhibition may result in undesired
polymerization, while excessive inhibition can completely stop the reaction.
3. Additional costs and complexity:
The use of inhibitors introduces additional costs and complexity to the polymerization
process. Inhibitors need to be carefully selected, added, and monitored, adding to the
overall process complexity and potentially increasing production costs.

It's important to note that the advantages and disadvantages of retarders and inhibitors can
vary depending on the specific polymerization process, reactants, and desired
outcomes. Careful consideration of these factors is necessary when deciding to use
retarders or inhibitors in polymerization processes.
 Quiz 1

Question [1]: Define:

1. Degree of polymerization.

2. Glass transition temperature.

Question [2]: Write down the equation of Styrene free radical polymerization initiated by

potassium persulfate.
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