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Related Concept Videos

Step-Growth Polymerization: Overview01:03

Step-Growth Polymerization: Overview

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.
Many natural and synthetic polymers are produced by...
Ziegler–Natta Chain-Growth Polymerization: Overview01:17

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Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta catalyst, high molecular...
Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

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 generated carbocation,...
Anionic Chain-Growth Polymerization: Mechanism01:04

Anionic Chain-Growth Polymerization: Mechanism

The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael acceptor.
Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)00:53

Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)

Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
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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 the...

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Updated: Jul 1, 2026

Microwave-assisted Functionalization of Poly(ethylene glycol) and On-resin Peptides for Use in Chain Polymerizations and Hydrogel Formation
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Functional and Network PHAs via Stereoselective Polymerization and Tailored Post-Transformation.

Ruirui Li1, Yingluo Zhao1, Jun-Jie Tian1

  • 1Department of Chemistry, Colorado State University, Fort Collins, Colorado, USA.

Angewandte Chemie (International Ed. in English)
|June 30, 2026
PubMed
Summary

This study introduces a new method for creating functionalized polyhydroxyalkanoates (PHAs) with tunable properties. These advanced PHA materials can be transformed into various forms, including robust thermosets and dynamic networks.

Keywords:
PHAcrosslinked polymerfunctionalized PHApost‐functionalizationstereoselective polymerization

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

Published on: February 18, 2022

Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Organic Synthesis

Background:

  • Functionalization of poly(3-hydroxyalkanoate)s (PHAs) is key for tailored material properties.
  • Current methods for PHA functionalization and the range of achievable functional groups are limited.
  • Further exploration is needed to expand PHA material capabilities.

Purpose of the Study:

  • To develop a novel method for synthesizing vinyl-, allyl-, and propargyl-functionalized PHAs.
  • To explore the transformation of these functionalized PHAs into advanced materials.
  • To investigate the formation of PHA supramolecular stereocomplexes.

Main Methods:

  • Catalyst-controlled stereoselective ring-opening polymerization of functionalized propiolactones.
  • Copolymerization with β-butyrolactone.
  • Post-polymerization modification strategies including crosslinking, network formation, and grafting.

Main Results:

  • Synthesis of vinyl-, allyl-, and propargyl-functionalized PHAs with high syndiotacticity (Pr up to 0.95).
  • Achieved a broad glass and melting transition window (Tg down to -31°C, Tm up to 126°C).
  • Developed three methods to create crosslinked thermosets, dynamic elastomeric networks, and grafted PHAs.
  • Demonstrated PHA supramolecular stereocomplexes from blending enantiomeric vinyl-functionalized PHAs.

Conclusions:

  • The developed method offers a versatile platform for creating functionalized PHAs with precisely controlled properties.
  • The resulting PHA materials exhibit enhanced thermal robustness, mechanical toughness, and resistance to creep and solvents.
  • This work expands the scope of PHA functionalization and opens new avenues for advanced polymer applications.