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Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

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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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Radical Chain-Growth Polymerization: Overview01:10

Radical Chain-Growth Polymerization: Overview

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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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Anionic Chain-Growth Polymerization: Mechanism01:04

Anionic Chain-Growth Polymerization: Mechanism

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

Ziegler–Natta Chain-Growth Polymerization: Overview

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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...
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Anionic Chain-Growth Polymerization: Overview01:20

Anionic Chain-Growth Polymerization: Overview

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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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Controlling the Size, Shape and Stability of Supramolecular Polymers in Water
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Controlled supramolecular polymerization of π-systems.

Goutam Ghosh1, Pradip Dey1, Suhrit Ghosh1

  • 1School of Applied and Interdisciplinary Sciences, Indian Association for the Cultivation Science, 2A and 2B Raja S. C. Mullick Road, Kolkata, 700032, India. psusg2@iacs.res.in.

Chemical Communications (Cambridge, England)
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Controlled supramolecular polymerization (CSP) enables precise synthesis of supramolecular polymers. This kinetic control approach overcomes thermodynamic limitations, yielding polymers with tailored lengths and structures.

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Supramolecular Chemistry

Background:

  • Supramolecular polymers typically lack mesoscopic precision due to thermodynamic control via spontaneous self-assembly.
  • Controlling nucleation and isolating dormant states are key to achieving controlled polymerization.
  • Kinetic control offers a pathway to overcome thermodynamic limitations in supramolecular polymerization.

Purpose of the Study:

  • To describe recent advancements in controlled supramolecular polymerization (CSP) primarily under kinetic control.
  • To highlight the synthesis of π-conjugated supramolecular polymers with enhanced precision.
  • To explore the potential of CSP for creating complex polymer architectures.

Main Methods:

  • Retarding spontaneous nucleation by manipulating experimental parameters (e.g., cooling rate, solvent composition, H-bonding).
  • Utilizing a dormant kinetically controlled monomer pool.
  • Employing aggregated/molecular initiators (seeds) or external stimuli (e.g., light) to initiate chain-growth polymerization.

Main Results:

  • Achieved supramolecular polymers with narrow dispersity and predictable length.
  • Demonstrated stereo-selective synthesis through CSP.
  • Enabled chain extension via batch-wise monomer addition, leading to supramolecular block copolymers.

Conclusions:

  • Controlled supramolecular polymerization under kinetic control offers precise synthesis of well-defined supramolecular polymers.
  • CSP facilitates the creation of complex architectures like block copolymers.
  • This approach significantly advances the field of supramolecular polymer synthesis.