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Related Concept Videos

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

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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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Thermal and Photochemical Electrocyclic Reactions: Overview01:26

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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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Cycloaddition Reactions: MO Requirements for Thermal Activation01:16

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Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
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Thermal Electrocyclic Reactions: Stereochemistry01:17

Thermal Electrocyclic Reactions: Stereochemistry

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The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
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Updated: May 25, 2025

3D Printing and In Situ Surface Modification via Type I Photoinitiated Reversible Addition-Fragmentation Chain Transfer Polymerization
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Random Copolymerization: An Efficient Strategy for Significantly Enhancing Photothermal Performance Through

Wenjin Xu1, Haoran Tan1, Yu Li1

  • 1School of Material Science and Engineering, Nanchang Hangkong University, 696 Fenghe South Avenue, Nanchang 330063, China.

Polymers
|February 26, 2025
PubMed
Summary
This summary is machine-generated.

Researchers developed high-performance photothermal (PT) polymers using donor-acceptor random copolymers. Tuning the ratios of benzothiadiazole (BT) and benzodithiadiazole (BBT) acceptors significantly enhanced PT performance for applications like water evaporation and therapy.

Keywords:
TICTphotothermal propertiesrandom copolymerization strategy

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Area of Science:

  • Materials Science
  • Polymer Chemistry
  • Photophysics

Background:

  • Photothermal (PT) polymers are crucial for applications like water evaporation, photocatalysis, and photothermal therapy.
  • High-performance PT polymers often face limitations due to structural requirements that can hinder optimal performance.
  • Developing general strategies for high-performance PT polymers remains a significant challenge.

Purpose of the Study:

  • To fabricate high-performance donor-acceptor (D-A) random copolymers for enhanced photothermal properties.
  • To investigate the effect of tuning benzothiadiazole (BT) and benzodithiadiazole (BBT) acceptor ratios on PT performance.
  • To explore the synergistic effects of open-shell radical and twisted intermolecular charge transfer (TICT) states.

Main Methods:

  • Synthesis of D-A random copolymers (PBT4T-BBT-x) by cross-mixing bithiophene donors with BT and BBT acceptors.
  • Fine-tuning the ratios of BT and BBT units within the polymer structure.
  • Characterization of photothermal conversion efficiency (PTCE) and photothermal temperature under laser irradiation.

Main Results:

  • The random copolymers exhibited controllable open-shell radical effects and TICT states upon tuning BT/BBT ratios.
  • Synergistic effects of radicals and TICT states significantly enhanced PT performance.
  • PTCE increased from 21.7% to 58.5%, and PT temperature rose from 150 °C to 232 °C with optimal BBT ratios.
  • The copolymers demonstrated good water evaporation rates.

Conclusions:

  • The developed D-A random copolymers offer a viable strategy for high-performance photothermal materials.
  • Tuning the ratios of specific acceptors (BT and BBT) is key to unlocking enhanced photothermal properties.
  • This approach provides a valuable pathway for creating advanced materials for photothermal therapy and water evaporation.