화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Macromolecular Research, Vol.28, No.8, 751-761, July, 2020
DOI10.1007/s13233-020-8091-3  Export Citation
Copper-Catalysed “Activators Regenerated by Electron Transfer” “Atom Transfer Radical Polymerisation” of Styrene from a Bifunctional Initiator in Ethyl Acetate/Ethanol, Using Ascorbic Acid/Sodium Carbonate as Reducing System
Niccolò Braidi, Mirko Buffagni†, Franco Ghelfi†, Manuel Imperato, Alberto Menabue, Francesca Parenti, Armando Gennaro1, Abdirisak A. Isse1, †, Elena Bedogni2, Luisa Bonifaci2, Gianfranco Cavalca2, Angelo Ferrando2, Aldo Longo2, †, and Ida Morandini2
  • Department of Chemical and Geological Sciences, University of Modena and Reggio Emilia, Via Campi 103, 41125 Modena, Italy
  • 1Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131 Padova, Italy
  • 2“Claudio Buonerba” Research Centre, Plant of Mantova, Versalis (Eni) S.p.A., Via Taliercio 14, 46100 Mantova, Italy
E-mail:, , ,
A new copper(II) chloride/tris(2-piridylmethyl)amine (1/1) catalysed “Activators Regenerated by Electron Transfer” “Atom Transfer Radical Polymerisation” (ARGET ATRP) process for the polymerisation of styrene is described. The salient features of the method are the simultaneous use of ascorbic acid (reducing agent) and Na2CO3 (basic agent), the employment of a bifunctional initiator (ethyl 2,2-dichloropropionate) and the utilisation of a green solvent mixture composed of ethyl acetate and ethanol (AcOEt/EtOH). Na2CO3 plays a central role since not only preserves the ligand from protonation, but it can also activate the reducing agent. The quantity of monomer in the reaction mixture, the AcOEt/EtOH ratio and the load of ascorbic acid/carbonate are important factors for achieving a regular transformation. Working at 100 °C and with a metal load of only 0.025 mol%, an almost perfectly controlled telechelic polystyrene is produced, provided that conversion is kept below 50%. If conversion is higher, the control is gradually lost due superimposition of a step-growth process to the main chain polymerisation process. Two interesting phenomena, encountered during this study, are activation of the redox complex by using only Na2CO3 and gelation of polystyrene at 60 °C.
Keywords:styrene;ARGET ATRP;copper;ascorbic acid;sodium carbonate
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