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Addition Polymerization

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Addition polymerization is a chain-growth process forming polymers without by-products. It involves initiation by free radicals, cations, or anions, followed by propagation where monomers add to the growing chain, and termination that halts the chain. This method produces polymers such as polyethylene, polypropylene, and PVC, which are vital in various industries. Understanding the detailed mechanism is key to controlling polymer properties.

Fundamentals of Addition Polymerization

Addition polymerization is a type of chain-growth polymerization where unsaturated monomer molecules, such as alkenes or alkynes, join together without the loss of small molecules or atoms. This process unfolds through three essential stages: initiation, where an active species such as a free radical, cation, or anion is formed; propagation, where the active species adds to an unsaturated monomer, creating a new active species that adds to more monomers, thus growing the polymer chain; and termination, which occurs when the active species is deactivated, halting further chain growth. Unlike condensation polymerization, addition polymerization does not generate by-products, making it a more efficient process for certain applications.
Chemical laboratory with flasks, vertical condenser for distillation, magnetic stirrer and digital thermometer in beaker with blue solution.

The Mechanism of Addition Polymerization

The mechanism of addition polymerization begins with the generation of an active species that initiates the polymerization process. This species can be a free radical, cation, or anion, depending on the type of initiation. The active species attacks the pi bond of an unsaturated monomer, opening it up and attaching the monomer to the active site. The newly formed active species at the end of the growing chain can then react with additional monomer molecules, perpetuating the chain growth. Termination can occur through various mechanisms, such as combination (where two active chain ends join), disproportionation (transfer of hydrogen from one chain to another), or chain transfer (transfer of the active site to another molecule), concluding the polymerization process.

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00

The ______ stage of addition polymerization stops the growth of the polymer chain by deactivating the active species.

termination

01

Types of active species in addition polymerization

Free radical, cation, or anion; type depends on initiation method.

02

Termination mechanisms in addition polymerization

Combination, disproportionation, or chain transfer; ends polymer growth.

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