What is the Difference Between Cationic and Anionic Polymerization

The main difference between cationic and anionic polymerization is that cationic polymerization is initiated by a cationic species, whereas anionic polymerization is initiated by anionic species.

Polymerization is a chemical process in which small molecules called monomers react with each other to form long chains or networks known as polymers. This reaction occurs through the bonding of monomers, which create repeating units that make up the polymer structure. Cationic and anionic polymerization are two types of polymerization.

Key Areas Covered

1. What is Cationic Polymerization
      – Definition, Initiation, Monomer Reactivity 
2. What is Anionic Polymerization
      – Definition, Initiation, Monomer Reactivity 
3. Similarities – Cationic and Anionic Polymerization
      – Outline of Common Features
4. Difference Between Cationic and Anionic Polymerization
      – Comparison of Key Differences

Key Terms

Cationic Polymerization, Anionic Polymerization

Difference Between Cationic and Anionic Polymerization - Comparison Summary

What is Cationic Polymerization

Cationic polymerization is a chain growth polymerization mechanism where the polymerization is initiated through the formation of a carbocation intermediate. This carbocation serves as the active center for polymerization. Subsequently, monomer molecules react with carbocation, resulting in the propagation of the polymer chain. Then this process is continued until termination, which can occur through various mechanisms such as a reaction with a nucleophile or a combination with another active chain end. The most commonly used cations are strong Lewis acids or protic acids such as aluminium chloride or sulfuric acid.

Cationic polymerization has a wide range of uses. This process can be used to produce polymers with controlled molecular weight, narrow polydispersity, and unique architectures. These characteristics help in the development of advanced materials such as adhesives, coatings, and photoresists. Cationic polymerization can be used in the production of elastomers, which are materials that exhibit high elasticity and resilience. These can be used in applications such as gaskets, seals, and tires.

Cationic vs Anionic Polymerization

Figure 2: Cationic Polymerization

Cationic polymerization allows for the synthesis of elastomers with excellent mechanical properties, high elongation, and low glass transition temperatures. This process is also used in the fabrication of macrostructures and microdevices. By utilizing photoinitiators, light can trigger cationic polymerization, enabling precise control over the polymerization process. This photo-induced cationic polymerization has been employed in the fabrication of microelectromechanical systems, microfluidic devices, and optical components due to its ability to generate well-defined structures with high resolution. Cationic polymerization is useful in the synthesis of block copolymers, as well.

What is Anionic Polymerization

Anionic polymerization is a type of polymerization process that relies on the reactivity of negatively charged species called anions to initiate and propagate the polymerization reaction. It involves the use of strong bases or organometallic compounds as initiators. In anionic polymerization, the initiator abstracts a proton from a monomer molecule, leading to the formation of a reactive carbanion. The carbanion then attracts another monomer molecule, resulting in the growth of the polymer chain. Termination of the anionic polymerization can be achieved through various mechanisms, including protonation of the carbocation by a protic solvent or reaction with impurities present in the reaction mixture.

Compare Cationic and Anionic Polymerization - What's the difference?

Figure 2: Anionic Polymerization

There are many applications of anionic polymerization. It also helps to produce block copolymers. Another application of anionic polymerization is the production of synthetic rubber. Properties of rubber, such as elastomeric properties, make them useful in the making of applications such as tires, seals, and gaskets. Anionic polymerization enables the creation of elastomers with excellent mechanical properties such as high elasticity, low glass transition temperatures, and resistance to heat and chemicals. Another use of anionic polymerization is in the development of functional polymers. It also helps in the fabrication of various nanomaterials.

Similarities Between Cationic and Anionic Polymerization

  • Both cationic and anionic polymerization rely on the reactivity of the charged species to initiate the polymerization process.

Difference Between Cationic and Anionic Polymerization

Definition

Cationic polymerization is a chain growth polymerization mechanism where the polymerization is initiated through the formation of a carbocation intermediate, while anionic polymerization is a type of polymerization process that relies on the reactivity of anions to initiate and propagate the polymerization reaction.

Initiation Mechanism

The initiation step in cationic polymerization involves the reaction of the cation with a monomer, leading to the formation of a reactive carbocation, while anionic polymerization involves the initiation of polymerization through the abstraction of a proton from a monomer by a strong base or organometallic compound.

Monomer Reactivity

Cationic polymerization involves monomers that are electron-rich and can stabilize the positive charge of the carbocation, while anionic polymerization involves monomers that are electron-deficient and can stabilize the negative charge of the carbanion.

Conclusion

Cationic and anionic polymerization are two types of polymerization. The main difference between cationic and anionic polymerization is that cationic species initiate cationic polymerization, while anionic species initiate anionic polymerization.

Reference:

1. “Anionic Polymerization – Overview.” Science Direct. 
2. “Cationic Polymerization – Overview.” Science Direct. 

Image Courtesy:

1. “Anionic polymerization of styrene initiated by sec-BuLi” By Efanmm – Own work(CC BY-SA 3.0) via Commons Wikimedia
2. “ROP cationic.” By MatChem121 – Own work (CC BY 3.0) via Commons Wikimedia

About the Author: Hasini A

Hasini is a graduate of Applied Science with a strong background in forestry, environmental science, chemistry, and management science. She is an amateur photographer with a keen interest in exploring the wonders of nature and science.

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