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Step-Growth Polymerization: Overview01:03

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Step-growth or condensation polymerization is a stepwise reaction of bi or multifunctional monomers to form long-chain polymers. As all the monomers are reactive, most of the monomers are consumed at the early stages of the reaction to form small chains of reactive oligomers, which then combine to form long polymer chains in the late stages. Hence, the reaction has to proceed for a long time to achieve high molecular weight polymers.
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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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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: 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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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

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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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RAFT Polymerization for Advanced Morphological Control: From Individual Polymer Chains to Bulk Materials.

Karen Hakobyan1, Fumi Ishizuka1, Nathaniel Corrigan1

  • 1School of Chemical Engineering, University of New South Wales, Kensington, NSW, 2052, Australia.

Advanced Materials (Deerfield Beach, Fla.)
|November 6, 2024
PubMed
Summary
This summary is machine-generated.

Reversible-deactivation radical polymerization (RAFT) techniques precisely control polymer morphology at all scales. This enables the creation of custom nanostructures and macroscopic materials with detailed nanoscale and microscale features.

Keywords:
3D printingmicrophase separationmonomer sequence controlreversible addition‐fragmentation chain transfer (RAFT) polymerizationself‐assembly

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Area of Science:

  • Polymer Chemistry
  • Materials Science

Background:

  • Reversible-deactivation radical polymerization (RAFT) is crucial for controlling polymer synthesis.
  • Advanced RAFT techniques extend beyond "living" polymerization to enable morphological control across diverse length scales.

Purpose of the Study:

  • To explore the capability of RAFT techniques for precise morphological control of polymer systems.
  • To demonstrate the synthesis of sequence-defined polymers and polymerization-induced self-assembly (PISA) for nanostructure fabrication.
  • To investigate the production of macroscopic materials with nanoscale and microscale detail using polymerization-induced microphase separation (PIMS) and 3D printing.

Main Methods:

  • Utilizing advanced Reversible Addition-Fragmentation chain Transfer (RAFT) polymerization.
  • Employing single unit monomer insertion (SUMI) for sequence-defined polymer synthesis.
  • Leveraging polymerization-induced self-assembly (PISA) and polymerization-induced microphase separation (PIMS).

Main Results:

  • RAFT enables morphological control from the molecular level to macroscopic scales.
  • Sequence-defined polymers were synthesized, facilitating the creation of bespoke nanostructures via PISA.
  • Macroscopic materials with nanoscale and microscale features were produced using PIMS and 3D printing.

Conclusions:

  • RAFT polymerization provides comprehensive control over polymer morphology across all length scales.
  • The RAFT toolkit facilitates the design and fabrication of advanced materials with tailored structures.
  • This control spans from molecular-level precision to additive manufacturing applications.