Cationic polymerization of butadiene using alkyl aluminum compounds as co-initiators: an efficient approach toward solid polybutadienes. Issue 11 (28th February 2022)

• Record Type: Journal Article
• Authors: Rozentsvet, Victor A.; Ulyanova, Daria M.; Sablina, Nelly A.; Kostjuk, Sergei V.; Tolstoy, Peter M.; Novakov, Ivan A.
• Is Part Of: Polymer chemistry. Volume 13:Issue 11(2022)
• Page Start: 1596
• Page End: 1607
• Publication Date: 2022-02-28
• Subjects: Polymers -- Periodicals; Macromolecules -- Periodicals; Polymerization -- Periodicals; 547.705
• DOI: 10.1039/d1py01684a
• Languages: English
• ISSNs: 1759-9954

Abstract

Abstract : Solid, soluble in organic solvents polybutadienes with reduced unsaturation and high glass transition and softening points were synthesized for the first time. Abstract : The cationic polymerization of butadiene using secondary alkyl chlorides (isopropyl chloride, 2-chlorobutane) as initiators and alkylaluminum compounds (Et2 AlCl, EtAlCl2 and Et3 Al) as co-initiators has been investigated. It was shown that secondary alkyl chlorides in conjunction with alkylaluminum compounds are efficient initiating systems for the preparation of fully soluble solid polybutadienes with reduced unsaturation (40–46 mol%) and high glass transition (56–66 °C) and softening (138–184 °C) temperatures. The cationic polymerization of butadiene with i PrCl/Et3 Al and i PrCl/Et2 AlCl initiating systems is characterized by an induction period which is consistent with the in situ formation of EtAlCl2, a true co-initiator of the polymerization. According to 1D and 2D NMR spectroscopy, the synthesized polybutadienes possessed isopropyl or sec -butyl groups connected with trans -1, 4 structures as head groups.