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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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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,...
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Polymerization generates chiral centers along the entire backbone of a polymer chain. Accordingly, the stereochemistry of the substituent group has a significant effect on polymer properties. Polymers formed from monosubstituted alkene monomers feature chiral carbons at every alternate position in the polymer backbone. Relative to the predominant orientation of substituents at the adjacent chiral carbons, the polymer can exist in three different configurations: isotactic, syndiotactic, and...
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The word polymer is derived from the Greek words “poly” which means “many” and “mer” which means “parts”. Polymers are long chains of molecules composed of repeating units of smaller molecules, known as monomers. They either occur naturally, such as DNA and proteins, or can be constructed synthetically, like plastics. They have varied structural characteristics, such as linear chains, branched chains, or complex networks, that contribute to the...
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Copolymers are the products obtained from the polymerization of multiple monomer species. So, in a polymer chain itself, there can be multiple repeating units that come from different monomers. The process of synthesizing a polymer from different monomer species is called copolymerization. When two monomers are involved, the polymer is known as a bipolymer. Polymers with three and four monomers are termed terpolymers and quaterpolymers, respectively. Figure 1 depicts the copolymerization of...
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Access to Hydroxy-Functionalized Polypropylene through Coordination Polymerization.

Yuanhao Zhong1,2, Iskander Douair3, Tiantian Wang1,4

  • 1State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China.

Angewandte Chemie (International Ed. in English)
|December 31, 2019
PubMed
Summary

Researchers developed a new method to create hydroxy-functionalized polypropylene, a challenging polymer. This breakthrough involves the copolymerization of allenes and propylene, opening new avenues in polymer science.

Keywords:
allenescopolymerizationhydroxylated polypropylenespolar monomersrare-earth metals

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Area of Science:

  • Polymer Chemistry
  • Organic Synthesis

Background:

  • Industrial production of hydroxy-functionalized polyethylene exists via radical copolymerization and alcoholysis.
  • Synthesizing hydroxy-functionalized polypropylene is difficult due to propylene's inability to undergo radical polymerization and catalyst poisoning in coordination copolymerization with polar monomers.

Purpose of the Study:

  • To develop a novel strategy for synthesizing hydroxy-functionalized polypropylene.
  • To explore the coordination polymerization of allenes and their subsequent modification.

Main Methods:

  • Coordination polymerization of allenes using rare-earth-metal precursors to form 1,2-regulated polyallenes.
  • Post-polymerization modification of polyallenes via hydroboration/oxidation to yield poly(allyl alcohol) analogues.
  • Copolymerization of allenes and propylene, followed by modification to produce hydroxy-functionalized polypropylene.

Main Results:

  • Achieved pure 1,2-regulated polyallenes through coordination polymerization of allenes.
  • Successfully synthesized poly(allyl alcohol) analogues from polyallenes.
  • For the first time, produced hydroxy-functionalized polypropylene through copolymerization of allenes and propylene, followed by modification.
  • DFT simulations indicated kinetic control governs the reaction mechanism.

Conclusions:

  • A novel and effective strategy for producing hydroxy-functionalized polypropylene has been established.
  • The developed method overcomes previous limitations in synthesizing this important functionalized polymer.
  • The findings suggest potential for new functional polyolefins through controlled polymerization and modification techniques.