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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: Mechanism01:09

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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...
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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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Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

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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...
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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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Thermal and Photochemical Electrocyclic Reactions: Overview01:26

Thermal and Photochemical Electrocyclic Reactions: Overview

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Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
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Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
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Tribochemically Controlled Atom Transfer Radical Polymerization Enabled by Contact Electrification.

Chen Wang1, Ruoqing Zhao1, Wenru Fan1

  • 1Frontiers Science Center for Flexible Electronics & Xi'an Institute of Biomedical Materials and Engineering (IBME), Northwestern Polytechnical University, Xi'an, 710072, China.

Angewandte Chemie (International Ed. in English)
|July 28, 2023
PubMed
Summary
This summary is machine-generated.

This study introduces tribochemically controlled atom transfer radical polymerization (tribo-ATRP) using contact-electro-catalysis (CEC) with titanium oxide. This method avoids high-energy stimuli, enabling controlled polymer synthesis with high precision.

Keywords:
Atom Transfer Radical PolymerizationContact ElectrificationFrictionMechanochemistryTitanium Oxide

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

  • Polymer Chemistry
  • Materials Science
  • Physical Chemistry

Background:

  • Traditional mechanochemical polymerization methods (RDRP) use high-energy ultrasound or ball milling.
  • These high-energy stimuli often lead to undesirable side reactions, limiting control over polymerization.
  • A need exists for gentler, more controlled polymerization techniques.

Purpose of the Study:

  • To develop a novel, low-energy approach for controlled radical polymerization.
  • To investigate the feasibility of tribochemically controlled atom transfer radical polymerization (tribo-ATRP) via contact-electro-catalysis (CEC).
  • To demonstrate the synthesis of polymers with controlled molecular weights and low dispersity using this new method.

Main Methods:

  • Utilized titanium oxide (TiO 2 ) particles and CuBr 2 /tris(2-pyridylmethylamine (TPMA) for contact-electro-catalysis (CEC).
  • Employed mechanical stirring to induce friction, generating electrical charges on TiO 2 particles.
  • Investigated the effect of friction frequency on electron transfer using theoretical simulations.

Main Results:

  • Successfully demonstrated tribo-ATRP enabled by CEC between TiO 2 and the catalyst system under stirring-induced friction.
  • Showcased the continuous regeneration of the active catalyst species (CuBr/TPMA) through electron transfer.
  • Achieved synthesis of various polymers with predetermined molecular weights, low dispersity, and high chain-end fidelity.

Conclusions:

  • Tribo-ATRP offers a facile and low-energy alternative to traditional mechanochemical polymerization.
  • CEC under mild friction conditions provides effective control over radical polymerization.
  • This approach opens new avenues for sustainable and precise polymer synthesis.