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Step-Growth Polymerization: Overview01:03

Step-Growth Polymerization: Overview

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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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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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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...
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Molecular Weight of Step-Growth Polymers01:08

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Step growth polymerization involves bi or multifunctional monomers. Bifunctional monomers react to form linear step growth polymers, whereas multifunctional monomers react to form non-linear or branched polymers.
As the step-growth polymerization involves step-wise condensation of monomers, the molecular weight also builds up eventually. Consequently, high molecular weight polymers are obtained at the late stages of the polymerization, where 99% of monomers have been consumed.
The extent of the...
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Anionic Chain-Growth Polymerization: Overview01:20

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The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
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Polymers02:34

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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Updated: Oct 21, 2025

Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers
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Overcoming the Low Driving Force in Forming Depolymerizable Polymers through Monomer Isomerization.

Hanlin Chen1, Zhen Shi1, Tze-Gang Hsu1

  • 1School of Polymer Science and Polymer Engineering, University of Akron, 170 University Ave., Akron, OH, 44325, USA.

Angewandte Chemie (International Ed. in English)
|September 9, 2021
PubMed
Summary
This summary is machine-generated.

This study introduces a novel cyclooctene-based system for high-driving-force living polymerization, enabling the creation of chemically recyclable polymers with diverse architectures. The system facilitates efficient depolymerization back to monomers, enhancing polymer sustainability.

Keywords:
cis-to-trans isomerizationdepolymerizationdriving forcering-opening metathesis polymerization

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Sustainable Chemistry

Background:

  • Polymer sustainability is a major challenge.
  • Existing depolymerization systems often lack a sufficient driving force for polymerization.
  • This limits the ability to create polymers with diverse functionalities and architectures.

Purpose of the Study:

  • To develop a depolymerizable polymer system with a high driving force for polymerization.
  • To enable living ring-opening metathesis polymerization (ROMP) for creating complex polymer architectures.
  • To achieve efficient chemical recycling of polymers.

Main Methods:

  • Utilized a cyclooctene-based monomer with a fused trans-cyclobutane ring.
  • Employed cis-to-trans alkene isomerization to increase ring strain energy.
  • Optimized reaction conditions, including the use of excess triphenylphosphine, to suppress side reactions.

Main Results:

  • Achieved living ROMP at monomer concentrations as low as 0.025 M.
  • Demonstrated efficient depolymerization of the resulting polymers back to cis-cyclooctene monomers.
  • Successfully suppressed secondary metathesis and depolymerization using excess triphenylphosphine.

Conclusions:

  • The developed trans-cyclobutane fused trans-cyclooctene system provides a high driving force for living polymerization.
  • This system is promising for the development of chemically recyclable polymers with tunable architectures.
  • It addresses key limitations in current depolymerizable polymer research, advancing polymer sustainability.