RAFT polymerization of methyl acrylate in carbon dioxide

Toshihiko Arita, Sabine Beuermann, Michael Buback, Philipp Vana

Research output: Contribution to journalArticlepeer-review

51 Citations (Scopus)


Reversible additon fragmentation chain transfer (RAFT) polymerizations of methyl acrylate (MA) in solution containing either 22 vol.-% CO2 or toluene were performed at 80°C and 300 bar using cumyl dithiobenzoate (CDB) at concentrations between 1.8 × 10-3 to 2.5 × 10 -2 mol · L-1 as the RAFT agent. Product molecular weight distributions and average molecular weight indicated the successful control of MA polymerization in CO2, even at low CDB concentrations. RAFT polymerization rates were strongly retarted by CDB and were lower in CO2 than in toluene solution. The enhanced fluidity associated with the addition of CO2 to the polymerizing system provided access to mechanistic details of RAFT polymerization. The data of the present study into MA, together with our recent results on RAFT polymerization of styrene in solution of CO2 and of toluene, suggest that self-termination of intermediate RAFT radicals is responsible for retardation in case of high concentrations of this intermediate and in case of enhanced fluidity, which may be achieved by polymerization in solution of CO2.

Original languageEnglish
Pages (from-to)283-293
Number of pages11
JournalMacromolecular Materials and Engineering
Issue number4
Publication statusPublished - 2005 Apr 19


  • High pressure
  • Kinetics (polymerization)
  • Living/controlled radical polymerization
  • Reversible addition fragmentation chain transfer (RAFT)
  • Supercritical carbon dioxide


Dive into the research topics of 'RAFT polymerization of methyl acrylate in carbon dioxide'. Together they form a unique fingerprint.

Cite this