Scribd
Upload
17 views

Condensation Polymerization

Condensation polymerization is a step-growth process where monomers react to form polymers while eliminating small molecules like water. It can utilize AA + BB or AB type monomers, with the presence of monofunctional molecules potentially terminating the chain and reducing molecular weight. Additionally, ring-opening polymerization (ROP) offers a method for polymer formation without byproducts, often used with cyclic monomers.

Uploaded by

tjilosbw21
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
17 views

Condensation Polymerization

Condensation polymerization is a step-growth process where monomers react to form polymers while eliminating small molecules like water. It can utilize AA + BB or AB type monomers, with the presence of monofunctional molecules potentially terminating the chain and reducing molecular weight. Additionally, ring-opening polymerization (ROP) offers a method for polymer formation without byproducts, often used with cyclic monomers.

Uploaded by

tjilosbw21
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 4

CHE442: Advanced Physical Chemistry - Polymer Chemistry

Condensation Polymerization: Lecture Notes

1. Introduction to Condensation Polymerization

Condensation polymerization is a type of step-growth polymerization where monomers


react to form polymers, with the elimination of a small molecule (such as water, HCl, or
methanol) as a byproduct. Unlike addition polymerization, this process occurs gradually,
forming dimers, trimers, oligomers, and eventually high molecular weight polymers.

2. Key Characteristics of Condensation Polymerization

• Step-growth mechanism: Monomers react in a stepwise manner.

• Requires bifunctional or multifunctional monomers: Each monomer must have at


least two reactive functional groups.

• Elimination of a small molecule: Water, HCl, or methanol is commonly released.

• Slow molecular weight growth: High molecular weight polymers form only after
extensive reaction.

• Common functional groups involved:

o Carboxyl (-COOH) and Hydroxyl (-OH) → Forms polyesters.


o Carboxyl (-COOH) and Amine (-NH₂) → Forms polyamides.

o Diisocyanates (-N=C=O) and Diols (-OH) → Forms polyurethanes.

3. Mechanism of Condensation Polymerization

Condensation polymerization proceeds in a series of steps:

1. Monomer Activation – The functional groups of the monomers undergo initial


reaction.

2. Dimer Formation – Two monomers react, eliminating a small molecule and forming
a dimer.

3. Oligomer Formation – Dimers continue reacting with monomers or other dimers to


form oligomers.

4. Polymer Growth – The reaction progresses to form long polymer chains.

4. Polymer Formation: AA + BB and AB Monomers

Condensation polymerization can occur using two different monomer types:

AA + BB Type Monomers

• In this system, one monomer (AA) contains two identical functional groups (e.g.,
diamine -NH₂) and the other monomer (BB) contains two complementary functional
groups (e.g., dicarboxylic acid -COOH).

• Example: Polyamide (Nylon-6,6)

o Monomers: Adipic acid (HOOC-(CH₂)₄-COOH) and Hexamethylenediamine


(H₂N-(CH₂)₆-NH₂)

o Reaction: Amide bonds (-CONH-) form through the elimination of water,


leading to polymer growth.

AB Type Monomers

• Here, a single monomer contains both functional groups required for polymerization
(e.g., hydroxy acid, amino acid).

• Example: Polyester (Polylactic Acid, PLA)


o Monomer: Lactic acid (HO-CH(CH₃)-COOH) contains both -OH and -COOH
groups.

o Reaction: The hydroxyl group (-OH) of one molecule reacts with the carboxyl
(-COOH) of another, forming ester bonds and eliminating water.

5. Effect of Monofunctional Molecules on Polymerization

• If a monofunctional molecule (a molecule with only one reactive group) is


introduced into the polymerization process, it can act as a chain terminator, capping
the end of a growing polymer chain.

• Example Scenario:

o In polyester formation, if ethanol (CH₃CH₂OH) is added to the reaction, it can


react with a carboxyl (-COOH) group, preventing further chain extension.

• Effect on Degree of Polymerization (DP):

o The presence of monofunctional molecules reduces the average chain


length, leading to lower molecular weight polymers.

o High DP requires strict stoichiometric balance between reactive groups.

6. Polymerization from Cyclic Compounds: Ring-Opening Polymerization (ROP)

Condensation polymerization can also occur via ring-opening polymerization (ROP),


where cyclic monomers polymerize without forming byproducts. This is often observed in
lactones, lactams, and cyclic ethers.

Mechanism of Ring-Opening Polymerization

1. Initiation – A catalyst or initiator breaks the ring structure, creating a reactive species.

2. Propagation – The opened monomer reacts with additional cyclic monomers,


forming a growing polymer chain.

3. Termination – The reaction stops when all monomers are consumed or when chain
termination occurs.
Examples of Polymers via ROP

Polymer Cyclic Monomer Catalyst Applications

Polycaprolactone ε-Caprolactone Tin-based Biodegradable


(PCL) catalysts plastics

Nylon-6 ε-Caprolactam Acid/base Fibers, textiles


initiators

Polylactic acid (PLA) Lactide Metal-based Medical implants,


catalysts packaging

8. Summary

• Condensation polymerization forms polymers via step-growth reactions, eliminating


a small molecule in the process.

• Polymerization can occur through AA + BB monomers (e.g., Nylon-6,6) or AB


monomers (e.g., PLA).

• The presence of monofunctional molecules reduces the degree of


polymerization, leading to lower molecular weight products.

• Ring-opening polymerization (ROP) provides an alternative method for forming


polymers without byproducts, commonly used for lactones and lactams.

You might also like