Addition Polymerization

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.

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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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1

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

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termination

2

Types of active species in addition polymerization

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

3

Termination mechanisms in addition polymerization

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

4

Chain growth perpetuation in addition polymerization

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Active species at chain end reacts with more monomers, extending the polymer.

5

______, a material essential for packaging films and containers, is created by the polymerization of ______.

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Polyethylene ethylene

6

______, utilized in construction for pipes and in healthcare for medical devices, is produced from the polymerization of ______.

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Polyvinyl chloride (PVC) vinyl chloride monomers

7

By-products of condensation polymerization

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Small molecules like water, ammonia, or alcohol are released during condensation polymerization.

8

Examples of addition polymerization products

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Polyethylene and PVC are synthesized through addition polymerization.

9

Examples of condensation polymerization products

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Nylon, polyesters, and Bakelite are products of condensation polymerization.

10

In the process of ______, an active entity is created that can engage with a monomer to start polymer formation.

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initiation

11

The ______ step in polymerization is when the active entity is deactivated, halting the growth of the polymer chain.

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termination

12

Initiation in free radical polymerization

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Starts with free radical generation, often from chemical initiator decomposition by heat or light.

13

Propagation phase of polymerization

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Monomers add to growing chain one by one, with radicals at the end of the chain reacting with new monomers.

14

Termination mechanisms in polymerization

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Radicals are deactivated by recombination or disproportionation, ending the chain growth.

15

The ______ used and the polymerization conditions can greatly affect the polymer's ______ and ______.

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initiator structure molecular weight

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