Репозиторий Университета

© 2019 Elsevier Ltd The effect of different initiators (tert-butyl chloride (t-BuCl) and 2-chloro-2-phenylpropane (CumCl) on the cationic polymerization of isobutylene co-initiated by acidic chloroferrate imidazole-based ionic liquid emimCl-FeCl3 (emimCl: 1-ethyl-3-methylimidazolium chloride, molar fraction of FeCl3 (χ(FeCl3)) ≥ 0.6) in the presence of diisopropyl ether at 0 °C and [IB] = 5.2 M has been investigated. Generally, the use of all above-mentioned initiators results in increase of the monomer conversion from 30% to 60% as well as in decrease of molecular weight from 2500 g mol−1 to 1100 g mol−1 and polydispersity from 2.6 to 1.7, respectively, but does not influence the content of exo-olefin end group. It was demonstrated that CumCl does not initiated directly the polymerization at 0 °C or −20 °C, rather, it decomposed with the formation of the proton, a true initiator of the polymerization. It was also found that addition of small amounts (1% by volume) of benzene or its derivatives into the polymerization system leads to further increase of the monomer conversion (>90%). The rate of isobutylene polymerization depends on basicity of aromatic compounds added and increases in the following order: benzene < toluene ≈ mesitylene.

© 2019, Chinese Chemical Society Institute of Chemistry, Chinese Academy of Sciences Springer-Verlag GmbH Germany, part of Springer Nature. The cationic polymerization of C4 mixed feed and isobutylene co-initiated by AlCl3×OiPt2, iBuAlCl2×nOiPr2, and [emim]Cl-FeCl3×nOiPr2 ([emim]Cl: 1-ethyl-3-methylimidazolium chloride) has been investigated. AlCl3×OiPr2 co-initiated cationic polymerization of C4 mixed feed proceeds at a lower rate than polymerization of isobutylene affording polymers with higher molecular weight. Complexes of iBuAlCl2 with diisopropyl ether of different compositions are more suitable co-initiators than AlCl3×OiPr2 for the synthesis of highly reactive polyisobutylene (HR PIB) from C4 mixed feed due to their higher activity in the polymerization as well as possibility to prepare polyisobutylenes with lower molecular weight and higher content of exo-olefin end groups. However, iBuAlCl2 needs activating via addition of external water (initiator) and/or interaction with salts hydrates in order to increase the reaction rate and the saturated monomer conversion. [Emim]Cl-FeCl3/iPr2O is a quite promising catalyst for the preparation of HR PIB with high exo-olefin end group content (> 80%) and relatively low polydispersity (Mw/Mn < 2.8) via cationic polymerization of C4 mixed feed. The sonication of reaction mixture in case of using [emim]Cl-FeCl3 allowed increasing the reaction rate and decreasing the molecular weight.

© 2018 Elsevier Ltd A number of imidazole-based acidic (χ(LA)≥0.6) ionic liquids (RmimCl-LA, where R = Et or Bu, LA = AlCl3, AlBr3, iBuAlCl2, FeCl3, GaCl3, and BBr3) has been synthesized and their activity in cationic polymerization of isobutylene has been assessed. Among different ionic liquids tested here, emimCl-AlCl3, emimCl-FeCl3 and emimCl-GaCl3 showed the best results in terms of monomer conversion, exo-olefin end group content and polydispersity. It was shown that reaction rate depended strongly on the rate of partial hydrolysis of corresponding ionic liquid and increased in the following order: emimCl-FeCl3<emimCl-GaCl3<emimCl-AlCl3. It was demonstrated that emimCl-FeCl3 is the most promising catalyst for the synthesis of HR PIB with desired low molecular weight (Mn < 2500 g mol−1) and polydispersity (Mw/Mn < 2.5) and high content of exo-olefin end groups (>85%). However, due to poor dispergation of emimCl-FeCl3 in n-hexane as well as its high stability toward hydrolysis, the catalyst aging and/or sonication of reaction mixture is required in order to provide acceptable polymerization rate.