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Related Concept Videos

Polymers02:34

Polymers

The word polymer is derived from the Greek words “poly” which means “many” and “mer” which means “parts”. Polymers are long chains of molecules composed of repeating units of smaller molecules, known as monomers. They either occur naturally, such as DNA and proteins, or can be constructed synthetically, like plastics. They have varied structural characteristics, such as linear chains, branched chains, or complex networks, that contribute to the properties that they exhibit. Additionally,...
Polymers02:34

Polymers

The word polymer is derived from the Greek words “poly” which means “many” and “mer” which means “parts”. Polymers are long chains of molecules composed of repeating units of smaller molecules, known as monomers. They either occur naturally, such as DNA and proteins, or can be constructed synthetically, like plastics. They have varied structural characteristics, such as linear chains, branched chains, or complex networks, that contribute to the properties that they exhibit. Additionally,...
Polymers02:34

Polymers

The word polymer is derived from the Greek words “poly” which means “many” and “mer” which means “parts”. Polymers are long chains of molecules composed of repeating units of smaller molecules, known as monomers. They either occur naturally, such as DNA and proteins, or can be constructed synthetically, like plastics. They have varied structural characteristics, such as linear chains, branched chains, or complex networks, that contribute to the properties that they exhibit. Additionally,...
Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the generated carbocation,...
Free-Radical Chain Reaction and Polymerization of Alkenes02:35

Free-Radical Chain Reaction and Polymerization of Alkenes

The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
Characteristics and Nomenclature of Copolymers01:24

Characteristics and Nomenclature of Copolymers

Copolymers are the products obtained from the polymerization of multiple monomer species. So, in a polymer chain itself, there can be multiple repeating units that come from different monomers. The process of synthesizing a polymer from different monomer species is called copolymerization. When two monomers are involved, the polymer is known as a bipolymer. Polymers with three and four monomers are termed terpolymers and quaterpolymers, respectively. Figure 1 depicts the copolymerization of...

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Related Experiment Video

Updated: May 17, 2026

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level
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Published on: September 26, 2016

Polymerization by classical and frustrated Lewis pairs.

Eugene Y-X Chen1

  • 1Department of Chemistry, Colorado State University, Fort Collins, CO, 80523-1872, USA, eugene.chen@colostate.edu.

Topics in Current Chemistry
|October 26, 2012
PubMed
Summary
This summary is machine-generated.

Strong Lewis acid and Lewis base pairs efficiently polymerize polar alkenes. Different transition metal systems yield polymers with unique microstructures via ion-pairing or H-shuttling mechanisms.

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Area of Science:

  • Polymer Chemistry
  • Organometallic Chemistry
  • Catalysis

Background:

  • Main-group classical and frustrated Lewis pairs (CLPs and FLPs) are effective catalysts for polymerizing conjugated polar alkenes.
  • These systems, particularly those involving Al(C6F5)3, yield high molecular weight polymers with narrow distributions.

Purpose of the Study:

  • To explore the polymerization of conjugated polar alkenes using Lewis pairs (LPs) and transition metal nucleophile/electrophile pairs.
  • To elucidate the mechanisms of polymerization, including initiation, propagation, and chain transfer.

Main Methods:

  • Utilized strong Lewis acids (LAs) like Al(C6F5)3 and various Lewis bases (LBs) including phosphines, N-heterocyclic carbenes, and phosphazene superbases.
  • Investigated transition metal systems with LAs (E = Al, B) to generate different polymerization behaviors.

Main Results:

  • CLPs and FLPs facilitate cooperative monomer addition, forming zwitterionic species for initiation and bimetallic mechanisms for propagation.
  • Transition metal systems with Al(C6F5)3 resulted in ion-pairing polymerization, producing polymers with unique stereo-multiblock microstructures.
  • Transition metal systems with B(C6F5)3 generated ion-pairs that catalyzed polymerization via an H-shuttling mechanism.

Conclusions:

  • Lewis pairs offer versatile catalytic systems for controlled polymerization of polar alkenes.
  • The choice of Lewis acid dictates the polymerization mechanism and resulting polymer microstructure.
  • H-shuttling mechanism provides a novel pathway for catalytic polymerization using transition metal ion-pairs.