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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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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.
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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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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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Supramolecularly Catalyzed Polymerization: From Consecutive Dimerization to Polymerization.

Xiaoyan Tang1, Zehuan Huang1, Hao Chen1

  • 1Key Lab of Organic Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing, 100084, China.

Angewandte Chemie (International Ed. in English)
|May 15, 2018
PubMed
Summary
This summary is machine-generated.

This study introduces supramolecular catalysis for polymerization using cucurbit[8]uril (CB[8]) to create polyelectrolytes via enhanced photodimerization. This novel method offers tunable molecular weights and advances supramolecular polymer chemistry.

Keywords:
cucurbiturilhost-guest systemspolymer chemistrysupramolecular catalysissupramolecular chemistry

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Area of Science:

  • Polymer Chemistry
  • Supramolecular Chemistry
  • Catalysis

Background:

  • Covalent polymerization typically requires specific conditions and catalysts.
  • Supramolecular chemistry offers unique non-covalent interactions for molecular assembly.
  • Developing efficient catalytic systems for polymerization in aqueous solutions remains a challenge.

Purpose of the Study:

  • To develop a novel method for promoting covalent polymerization using supramolecular catalysts.
  • To prepare polyelectrolytes in aqueous solution through a CB[8]-enhanced photodimerization process.
  • To explore the tunability of polymer properties via supramolecular catalysis.

Main Methods:

  • Utilized cucurbit[8]uril (CB[8]) as a supramolecular catalyst.
  • Employed the photodimerization of Brooker merocyanine moieties in aqueous solution.
  • Investigated the effect of CB[8] concentration and irradiation time on polymerization.

Main Results:

  • Successfully synthesized polyelectrolytes in water using CB[8] as a catalyst.
  • Demonstrated that 10 mol% CB[8] is sufficient for effective catalysis due to spontaneous replacement.
  • Showed that polymer molecular weights can be controlled by adjusting irradiation time or monomer concentration.

Conclusions:

  • Supramolecular catalysis with CB[8] provides an efficient route for aqueous polyelectrolyte synthesis.
  • This approach combines supramolecular chemistry principles with polymer synthesis methodologies.
  • The findings open new avenues for supramolecular polymer chemistry and polymerization techniques.