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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 generated carbocation,...
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A phase separable polycarbonate polymerization catalyst.

Chayanant Hongfa1, Jianhua Tian, Jeremy Andreatta

  • 1Chemistry Dept., Texas A&M Univ., College Station, TX 77842, USA.

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Polyisobutylene acts as a phase tag, separating a colored chromium(III) complex during CO2 and cyclohexene oxide copolymerization. This tag shows similar kinetics to low molecular weight complexes in polycarbonate formation.

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Area of Science:

  • Polymer Chemistry
  • Organometallic Chemistry
  • Catalysis

Background:

  • Chromium(III) complexes are effective catalysts for copolymerization reactions.
  • Polycarbonate synthesis via copolymerization of CO2 and epoxides is an important area of green chemistry.
  • Phase separation can aid in catalyst recovery and product purification.

Purpose of the Study:

  • To investigate the utility of polyisobutylene as a nonpolar phase tag for a salen chromium(III) catalyst.
  • To evaluate the kinetic impact of the polyisobutylene tag on catalyst performance in polycarbonate formation.
  • To compare the catalytic activity of the tagged complex with its low molecular weight counterpart.

Main Methods:

  • Synthesis of a salen chromium(III) complex.
  • Grafting of polyisobutylene to the salen ligand to create a phase tag.
  • Cr(III)-catalyzed copolymerization of CO2 and cyclohexene oxide.
  • Kinetic analysis of the polymerization process.

Main Results:

  • Polyisobutylene effectively acted as a nonpolar phase tag, enabling separation of the colored chromium(III) complex from the reaction products.
  • The presence of the polyisobutylene tag did not significantly alter the kinetics of the salen chromium(III) complex in the copolymerization reaction.
  • The catalytic performance was comparable to a similar low molecular weight salen chromium(III) complex.

Conclusions:

  • Polyisobutylene is a viable nonpolar phase tag for chromium(III) salen catalysts in CO2/epoxide copolymerization.
  • This tagging strategy facilitates catalyst separation without compromising catalytic activity.
  • The method offers potential for improved catalyst recovery and process efficiency in polycarbonate synthesis.