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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.
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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.
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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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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...
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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.
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Radical Chain-Growth Polymerization: Mechanism01:09

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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...
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Continuous Additive Manufacturing using Olefin Metathesis.

Jeffrey C Foster1, Adam W Cook1, Nicolas T Monk1

  • 1Sandia National Laboratories, Albuquerque, NM, 87185, USA.

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|March 11, 2022
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Summary
This summary is machine-generated.

This study introduces dual-wavelength olefin metathesis polymerization for additive manufacturing. This chemistry enables precise control over polymerization using different light wavelengths for advanced 3D printing applications.

Keywords:
additive manufacturingdual-wavelengtholefin metathesisphotosensitizerstereolithography

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Additive Manufacturing

Background:

  • Olefin metathesis polymerization offers unique advantages for polymer synthesis.
  • Additive manufacturing (AM) requires precise control over polymerization kinetics.
  • Developing selective polymerization methods is crucial for advanced AM techniques.

Purpose of the Study:

  • To develop a selective dual-wavelength olefin metathesis polymerization process for continuous additive manufacturing.
  • To enable precise control over initiation and deactivation using distinct light wavelengths.
  • To adapt the process for both 2D stereolithography (SLA) and 3D continuous AM.

Main Methods:

  • Formulation of a dicyclopentadiene-based resin with a latent olefin metathesis catalyst.
  • Incorporation of photosensitizers (PSs) and photobase generators (PBGs) for wavelength-specific activation and deactivation.
  • Utilizing dual-wavelength light (e.g., blue and UV) to control polymerization initiation and termination.
  • Application in 2D SLA printing with photomasks or patterned light, and 3D continuous AM.

Main Results:

  • Successful implementation of selective dual-wavelength olefin metathesis polymerization.
  • Efficient initiation achieved with one wavelength (e.g., blue light).
  • Rapid catalyst decomposition and polymerization deactivation achieved with a second wavelength (e.g., UV light).
  • Demonstrated 2D SLA printing capabilities.
  • Achieved 3D continuous AM printing rates of 36 mm/h with patterned light and up to 180 mm/h with high-intensity, un-patterned light.

Conclusions:

  • The developed dual-wavelength olefin metathesis polymerization is a versatile technique for additive manufacturing.
  • This method allows for precise spatiotemporal control over polymerization, crucial for complex 3D structures.
  • The process demonstrates high printing speeds, making it suitable for efficient continuous additive manufacturing.