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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...
Olefin Metathesis Polymerization: Overview01:13

Olefin Metathesis Polymerization: Overview

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 of a...
Free-Radical Chain Reaction and Polymerization of Alkenes02:35

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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.
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...
Cycloaddition Reactions: MO Requirements for Photochemical Activation01:12

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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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Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization
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Published on: November 27, 2015

Tailoring iron complexes for ethylene oligomerization and/or polymerization.

Wenjuan Zhang1, Wen-Hua Sun, Carl Redshaw

  • 1Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.

Dalton Transactions (Cambridge, England : 2003)
|December 25, 2012
PubMed
Summary
This summary is machine-generated.

Iron-based catalysts show promise for ethylene oligomerization and polymerization, overcoming issues like deactivation and low molecular weight products. Modified iron complexes offer high activity and linear polyethylene production, with successful pilot plant trials.

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Area of Science:

  • Catalysis
  • Organometallic Chemistry
  • Polymer Science

Background:

  • Late transition metal catalysts for ethylene reactivity often suffer from deactivation and low molecular weight product formation at higher temperatures.
  • Iron-based complex pre-catalysts offer a potential solution to these industrial challenges.
  • Ligand design and modification are key to improving catalyst performance.

Purpose of the Study:

  • To review recent advancements in iron-based complex pre-catalysts for ethylene reactivity.
  • To highlight their potential for selective ethylene oligomerization or polymerization.
  • To discuss strategies for overcoming limitations of traditional catalysts.

Main Methods:

  • Fine-tuning substituents on existing ligands for iron complexes.
  • Designing novel ligand sets for iron pre-catalysts.
  • Investigating the performance of modified bis(imino)pyridyliron dichlorides and 2-iminophenanthrolyliron pre-catalysts.

Main Results:

  • Modified bis(imino)pyridyliron dichlorides demonstrate high-temperature operation and produce highly linear polyethylene.
  • New iron complex models exhibit high activity in ethylene oligomerization and/or polymerization.
  • The 2-iminophenanthrolyliron pre-catalyst has been successfully implemented in a 500-tonne pilot plant.

Conclusions:

  • Iron-based complex pre-catalysts are effective alternatives to late transition metal catalysts for ethylene conversion.
  • Ligand modification is crucial for achieving high activity, selectivity, and thermal stability.
  • Successful pilot-scale application indicates the industrial viability of these iron-based systems.