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Related Concept Videos

Anionic Chain-Growth Polymerization: Overview01:20

Anionic Chain-Growth Polymerization: Overview

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,...
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.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
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,...
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...
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.
Radical Chain-Growth Polymerization: Mechanism01:09

Radical Chain-Growth Polymerization: Mechanism

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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Synthesis of Programmable Main-chain Liquid-crystalline Elastomers Using a Two-stage Thiol-acrylate Reaction
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Published on: January 19, 2016

Insertion polymerization of acrylate.

Damien Guironnet1, Philipp Roesle, Thomas Rünzi

  • 1University of Konstanz, Department of Chemistry, D-78457 Konstanz, Germany.

Journal of the American Chemical Society
|January 1, 2009
PubMed
Summary
This summary is machine-generated.

Researchers discovered multiple acrylate insertions during ethylene copolymerization and methyl acrylate homo-oligomerization for the first time. Labile-substituted complexes were key to these novel polymerization findings and mechanistic insights.

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Area of Science:

  • Polymer Chemistry
  • Organometallic Chemistry

Background:

  • Ethylene copolymerization is a significant industrial process.
  • Controlling acrylate insertion into polymer chains remains a challenge.

Purpose of the Study:

  • To report the first observation of multiple acrylate insertions in ethylene copolymerization.
  • To describe the insertion homo-oligomerization of methyl acrylate.
  • To elucidate the mechanistic role of catalyst precursors.

Main Methods:

  • Utilized labile-substituted complexes as catalyst precursors.
  • Investigated copolymerization of ethylene with acrylate monomers.
  • Studied homo-oligomerization of methyl acrylate.

Main Results:

  • Observed multiple insertions of acrylate in ethylene copolymerization for the first time.
  • Achieved insertion homo-oligomerization of methyl acrylate.
  • Provided mechanistic insights attributed to the catalyst precursors.

Conclusions:

  • Labile-substituted complexes are crucial for novel acrylate polymerization behaviors.
  • These findings open new avenues for designing advanced polymer architectures.