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Related Concept Videos

Radical Chain-Growth Polymerization: Overview01:10

Radical Chain-Growth Polymerization: Overview

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Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the reaction proceeds via a free-radical intermediate. The free radical is formed from radical initiators, which spontaneously generate free radicals by homolytic fission. Organic peroxides (such as dibenzoyl peroxide, as shown in Figure 1) or azo compounds are popular radical initiators. A low concentration ratio of radical initiator to monomer is...
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Radical Chain-Growth Polymerization: Chain Branching01:17

Radical Chain-Growth Polymerization: Chain Branching

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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...
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Radical Chain-Growth Polymerization: Mechanism01:09

Radical Chain-Growth Polymerization: Mechanism

3.8K
The radical chain-growth polymerization mechanism consists of three steps: initiation, propagation, and termination of polymerization. The polymerization initiates when a free radical generated from the radical initiator adds to the unsaturated bond in the monomer. The unpaired electron of the free radical and one π electron in the unsaturated bond creates a σ bond between the free radical and the monomer. As a result, the other π electron in the unsaturated bond converts this species into...
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Free-Radical Chain Reaction and Polymerization of Alkenes02:35

Free-Radical Chain Reaction and Polymerization of Alkenes

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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.
10.2K
Radical Reactivity: Electrophilic Radicals01:02

Radical Reactivity: Electrophilic Radicals

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Radicals adjacent to electron‐withdrawing groups are called electrophilic radicals. These radicals readily react with nucleophilic alkenes. For example, the malonate radical, in which the radical center is flanked by two electron‐withdrawing groups, reacts readily with butyl vinyl ether, which consists of an electron‐donating oxygen substituent. The reaction between electrophilic malonate radical and nucleophilic vinyl ether is favored because the radical has a...
2.6K
Radical Formation: Overview01:03

Radical Formation: Overview

2.7K
A bond can be broken either by heterolytic bond cleavage to form ions or homolytic bond cleavage to yield radicals. A fishhook arrow is used to represent the motion of a single electron in homolytic bond cleavage. There are two main sources from which radicals can be formed:
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the...
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Free-Radical-Induced Grafting from Plasma Polymer Surfaces.

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Plasma technologies offer advanced methods for polymer surface modification. This review highlights how plasma-enhanced chemical vapor deposition (PECVD) and free-radical chemistry enable precise tuning of polymer properties.

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Surface Science

Background:

  • Plasma technologies have advanced significantly, finding broad applications in polymer chemistry.
  • These technologies are used for surface functionalization of polymer substrates or synthesis of novel plasma polymers.
  • Plasma polymer films (PPFs) deposited via plasma-enhanced chemical vapor deposition (PECVD) are of significant interest.

Purpose of the Study:

  • To review the growing applications of plasma-based technologies in modifying polymer surface properties.
  • To emphasize the role of free-radical chemistry in controllable surface functionalization.
  • To illustrate how plasma treatments can tune polymer characteristics without altering bulk properties.

Main Methods:

  • Surface functionalization of polymer substrates using reactive or inert gases.
  • Synthesis of plasma polymers from organic or mixed precursors.
  • Deposition of plasma polymer films (PPFs) using plasma-enhanced chemical vapor deposition (PECVD).

Main Results:

  • Plasma-treated and synthesized polymers exhibit highly reactive surfaces rich in free radicals.
  • These reactive sites allow for controlled surface functionalization.
  • Plasma polymer films demonstrate excellent adhesion and highly cross-linked structures.

Conclusions:

  • Plasma-based technologies, particularly PECVD, are effective for tailoring polymer surface properties.
  • Free-radical chemistry is a key mechanism for precise surface modification.
  • Careful handling of plasma-generated radicals enables advanced material functionalization.