Polymerization of acrylates and bulky methacrylates with the use of zirconocene precursors: Block copolymers with methyl methacrylate

Konstantinos Kostakis*, Stylianos Mourmouris, Marinos Pitsikalis, Nikolaos Hadjichristidis

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

16 Scopus citations

Abstract

The polymerization behavior of cyclohexyl methacrylate and trimethyl-silyloxyethyl methacrylate with the catalytic system Cp 2ZrMe2/B(C6F5)3/ZnEt 2 was examined. Block copolymers of these bulky methacrylates with methyl methacrylate (MMA), having high molecular weights and relatively narrow molecular weight distributions, were prepared. n-Butyl acrylate and tert-butyl acrylate were polymerized with various catalytic systems based on zirconocene complexes. These polymerizations seemed to proceed to a nonquantitative yield, producing polymers with high molecular weights and relatively low polydispersities. This behavior indicated the presence of termination reactions in the initiation step, which appeared to be faster than the propagation step. Block copolymers of these acrylates with MMA were synthesized with the catalytic system rac-Et(Ind)2ZrMe2/[B(C6F 5)4]-[Me2NHPh]+/ZnEt 2, starting from the polymerization of MMA. The block copolymers produced were well defined in most cases, as indicated by size exclusion chromatography, NMR, and differential scanning calorimetry measurements.

Original languageEnglish (US)
Pages (from-to)3337-3348
Number of pages12
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume43
Issue number15
DOIs
StatePublished - Aug 1 2005

Keywords

  • Block copolymers
  • GPC
  • Gel permeation chromatography
  • Glass transition
  • Metallocene catalysts
  • NMR
  • Poly(methacrylates)

ASJC Scopus subject areas

  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry

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