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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.
Radical Chain-Growth Polymerization: Chain Branching01:17

Radical Chain-Growth Polymerization: Chain Branching

The skeletal structure of polymers synthesized via radical polymerization is always branched. For example, the polymerization of ethylene by radical polymerization results in a low-density grade of polyethylene with a heavily branched skeletal structure. Here, the radical site abstracts hydrogen from the growing chain, and the radical site shifts from the end (a primary carbon center) to anywhere within the growing chain (a secondary carbon center). Consequently, the part of the chain from the...
Polymer Classification: Architecture01:14

Polymer Classification: Architecture

Polymers are classified as linear or branched on the basis of their chain architecture. The polymer chains in linear polymers have a long chain-like structure with minimal to no branching at all. Even if a polymer features large substituent groups on the monomer, which appear as branches to the skeleton, it is not considered a branched polymer. A branched polymer contains secondary polymer chains that arise from the main polymer chain. The branching occurs when the polymer growth shifts from...
Nomenclature of Alkenes02:29

Nomenclature of Alkenes

The IUPAC naming system for alkenes replaces -an- with -en- in the corresponding parent alkanes. Accordingly, a simple alkene replaces the -ane suffix of the alkane with -ene.
As per the IUPAC rules, the longest carbon chain containing the maximum number of double bonds is identified as the parent chain and is numbered such that the doubly bonded carbon atoms receive the lowest possible numbers. The location of the double bond is indicated by the number of its first carbon atom. In branched...
Characteristics and Nomenclature of Homopolymers01:00

Characteristics and Nomenclature of Homopolymers

Polymers that are made up of identical monomer units are called homopolymers. Only one repeating unit is involved in the construction of the homopolymer structure. For example, as depicted in Figure 1, polypropylene is a homopolymer constituted of propylene monomers. Here, the only repeating unit in the polymer chain is propylene.
Anionic Chain-Growth Polymerization: Mechanism01:04

Anionic Chain-Growth Polymerization: Mechanism

The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael acceptor.

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Related Experiment Video

Updated: Jun 17, 2026

Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization
07:28

Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization

Published on: November 27, 2015

How long are the ends of polyene chains?

T G Schmalz1, L L Griffin

  • 1Texas A&M University at Galveston, 5007 Avenue U, Galveston, Texas 77551, USA. schmalzt@tamug.edu

The Journal of Chemical Physics
|December 17, 2009
PubMed
Summary

Conjugation in polyene chains shows that bond lengths stabilize in the middle but are affected by chain ends. Significant conjugation effects extend through six neighboring double bonds, providing extra stabilization energy.

Area of Science:

  • Computational Chemistry
  • Polymer Science
  • Organic Chemistry

Background:

  • Conjugation in polyene chains influences electronic and structural properties.
  • Bond length alternation is a key characteristic of conjugated systems.
  • Understanding chain-end effects is crucial for predicting polymer behavior.

Purpose of the Study:

  • To investigate the length scale of conjugation interactions in all-trans polyene chains.
  • To determine how chain length affects bond length alternation and stabilization energy.
  • To quantify the influence of end effects on conjugated systems.

Main Methods:

  • Computational modeling using MP2/cc-pVTZ level of theory.
  • Optimization of geometries for polyene oligomers up to n=11 repeat units.

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Covalent Attachment of Single Molecules for AFM-based Force Spectroscopy
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Last Updated: Jun 17, 2026

Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization
07:28

Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization

Published on: November 27, 2015

MALDI-ToF MS Method for the Characterization of Synthetic Polymers with Varying Dispersity and End Groups
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MALDI-ToF MS Method for the Characterization of Synthetic Polymers with Varying Dispersity and End Groups

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Covalent Attachment of Single Molecules for AFM-based Force Spectroscopy
10:37

Covalent Attachment of Single Molecules for AFM-based Force Spectroscopy

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  • Analysis of bond lengths, energy increments, and stabilization energies.
  • Main Results:

    • Bond length alternation diminishes towards the center of polyene chains, approaching a constant value for infinite chains.
    • End effects significantly influence bond lengths near the chain termini, even in long chains.
    • Conjugation effects extend through approximately six neighboring double bonds, contributing about 8 kcal/mol stabilization energy per monomer.

    Conclusions:

    • The study establishes the length scale for conjugation interactions in polyenes.
    • End effects play a significant role in the properties of finite conjugated chains.
    • Computational methods provide valuable insights into the behavior of conjugated systems.