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Polymers02:34

Polymers

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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...
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Radical Chain-Growth Polymerization: Overview01:10

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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: Mechanism01:09

Radical Chain-Growth Polymerization: Mechanism

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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

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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.
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Radical Chain-Growth Polymerization: Chain Branching01:17

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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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Aldol Condensation vs Claisen Condensation01:33

Aldol Condensation vs Claisen Condensation

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Aldol condensation is an acid or base-catalyzed condensation between aldehydes or ketones to give an α,ꞵ-unsaturated carbonyl compound. A base-promoted condensation between ester molecules to produce a ꞵ-ketoester is known as the Claisen condensation. In the presence of a base, both reactions involve deprotonation of the acidic α hydrogen to produce the corresponding enolates. The nucleophilic enolates attack their respective nonenolized carbonyl compound forming a tetrahedral...
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Updated: Jan 26, 2026

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
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Recent Progress on Hyperbranched Polymers Synthesized via Radical-Based Self-Condensing Vinyl Polymerization.

Xiaofeng Wang1, Haifeng Gao2

  • 1Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556, USA. xwang26@nd.edu.

Polymers
|April 12, 2019
PubMed
Summary

Controlled radical polymerization (CRP) of inimers and transmers enables the synthesis of hyperbranched polymers. These polymers offer tunable properties and diverse applications in nanomedicine and catalysis.

Keywords:
controlled radical polymerizationhyperbranched polymerinimerself-condensing vinyl polymerizationtransmer

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Area of Science:

  • Polymer Chemistry
  • Materials Science

Background:

  • Hyperbranched polymers are complex macromolecules with unique properties.
  • Controlled radical polymerization (CRP) offers precise control over polymer architecture.

Purpose of the Study:

  • To review recent advancements in synthesizing hyperbranched polymers using CRP techniques.
  • To highlight the versatility of inimers and transmers in polymer synthesis.

Main Methods:

  • Utilizing controlled radical polymerization (CRP) methods such as atom transfer radical polymerization (ATRP), nitroxide-mediated polymerization (NMP), and reversible addition fragmentation chain transfer (RAFT).
  • Employing inimers and transmers for self-condensing vinyl polymerization and copolymerization with monovinyl monomers.

Main Results:

  • Successful synthesis of hyperbranched and hyperstar polymers with controlled molecular weights, compositions, and degree of branching.
  • Demonstrated strategies for regulating polymer-polymer reactions, leading to well-defined structures and low dispersity.
  • Explored applications of CRP-produced hyperbranched polymers in various fields.

Conclusions:

  • CRP of inimers and transmers is a powerful strategy for creating advanced hyperbranched polymers.
  • These polymers show significant potential in areas like encapsulation, nanomedicine, diagnostic imaging, and catalysis.