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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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Cationic Chain-Growth Polymerization: Mechanism00:57

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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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Characteristics and Nomenclature of Copolymers01:24

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Copolymers are the products obtained from the polymerization of multiple monomer species. So, in a polymer chain itself, there can be multiple repeating units that come from different monomers. The process of synthesizing a polymer from different monomer species is called copolymerization. When two monomers are involved, the polymer is known as a bipolymer. Polymers with three and four monomers are termed terpolymers and quaterpolymers, respectively. Figure 1 depicts the copolymerization of...
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Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)01:16

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Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
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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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Olefin Metathesis Polymerization: Overview01:13

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Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
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Block Copolymer Sequence Inversion through Photoiniferter Polymerization.

Charles P Easterling1,2, Yening Xia1,3, Junpeng Zhao3

  • 1George & Josephine Butler Polymer Research Laboratory, Center for Macromolecular Science & Engineering, Department of Chemistry, University of Florida, P.O. Box 117200, Gainesville, Florida 32611-7200, United States.

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Researchers developed a new method for creating "inverted" block copolymers using photoiniferter-mediated radical polymerization. This technique overcomes limitations of reversible addition-fragmentation chain transfer polymerization for synthesizing complex polymer sequences.

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3D Printing and In Situ Surface Modification via Type I Photoinitiated Reversible Addition-Fragmentation Chain Transfer Polymerization
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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Organic Synthesis

Background:

  • Reversible addition-fragmentation chain transfer (RAFT) polymerization typically dictates block copolymer sequences based on radical stability and leaving group ability.
  • Existing RAFT methods limit access to specific, synthetically challenging comonomer sequences.
  • Alternative reinitiation pathways for thiocarbonylthio-terminated polymers are needed to expand block copolymer synthesis.

Purpose of the Study:

  • To develop a novel method for preparing block copolymers with reversed monomer addition sequences, termed 'inverted' block copolymers.
  • To overcome the inherent limitations of traditional RAFT polymerization in accessing specific block copolymer architectures.
  • To enable the synthesis of multiblock copolymers with synthetically challenging comonomer sequences.

Main Methods:

  • Employed photoiniferter-mediated radical polymerization.
  • Utilized thiocarbonylthio photolysis of xanthate- and dithiocarbamate-functional macromolecular chain transfer agents (macro-CTAs).
  • Generated leaving group macroradicals directly, bypassing the typical addition-fragmentation mechanism.

Main Results:

  • Successfully prepared 'inverted' block copolymers by reversing the conventional monomer addition order.
  • Demonstrated a method to directly form macroradicals via thiocarbonylthio photolysis, which is not achievable through standard RAFT.
  • Provided a viable route to synthesize block copolymers with previously inaccessible comonomer sequences.

Conclusions:

  • The developed photoiniferter-mediated approach offers a powerful alternative to RAFT polymerization for block copolymer synthesis.
  • This method significantly expands the scope of accessible block copolymer sequences, particularly for challenging monomer combinations.
  • The technique holds promise for the synthesis of advanced multiblock copolymers with tailored properties.