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Related Concept Videos

Olefin Metathesis Polymerization: Overview01:13

Olefin Metathesis Polymerization: Overview

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Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
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Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)01:16

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Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
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Free-Radical Chain Reaction and Polymerization of Alkenes02:35

Free-Radical Chain Reaction and Polymerization of Alkenes

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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.
8.2K
Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)00:53

Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)

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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...
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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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Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

2.4K
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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Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes
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Modulating Polyolefin Copolymer Composition via Redox-Active Olefin Polymerization Catalysts.

W Curtis Anderson1, Brian K Long1

  • 1Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996, United States.

ACS Macro Letters
|May 26, 2022
PubMed
Summary
This summary is machine-generated.

Redox-active catalysts precisely control polyolefin comonomer levels during ethylene copolymerization. Catalyst reduction predictably decreases alpha-olefin incorporation, enhancing polymer architecture control.

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Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization
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Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization
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Area of Science:

  • Polymer Chemistry
  • Catalysis
  • Materials Science

Background:

  • Precise control over polymer architecture and composition is crucial in polymer synthesis.
  • Tailoring polyolefin properties requires effective methods for controlling comonomer incorporation.

Purpose of the Study:

  • To demonstrate the use of redox-active olefin polymerization catalysts for predictable control of comonomer incorporation.
  • To investigate the effect of catalyst reduction on alpha-olefin incorporation in ethylene copolymerization.

Main Methods:

  • Utilized redox-active olefin polymerization catalysts.
  • Performed in situ reduction of the catalyst using a chemical reductant.
  • Conducted copolymerization of ethylene with higher alpha-olefins.
  • Analyzed polymer properties using Gel Permeation Chromatography (GPC), Differential Scanning Calorimetry (DSC), Gas Chromatography (GC), and Nuclear Magnetic Resonance (NMR) spectroscopy.

Main Results:

  • Catalyst reduction via in situ reductant addition led to a significant decrease in alpha-olefin incorporation.
  • The observed decrease in alpha-olefin incorporation is attributed to the catalyst's increased electron density and reduced consumption rate of alpha-olefins.
  • Homopolymerizations of propylene and 1-hexene were investigated to support the findings.

Conclusions:

  • Redox-active catalysts offer a predictable method for modulating comonomer incorporation in polyolefin synthesis.
  • Catalyst redox state directly influences alpha-olefin consumption, providing a handle for controlling copolymer composition.
  • This approach advances the precise synthesis of tailored polyolefin materials.