Reactions of living polytetrahydrofuran with amines: 3. Secondary amines

Real-time monitoring of living cationic ring-opening polymerization of THF and direct prediction of equilibrium molecular weight of polyTHF

“…The equilibrium living cationic ring-opening polymerization of THF initiated with MeOTf has been achieved at various initial initiator concentrations from 0.9 mmol⋅L −1 to 123.2 mmol⋅L −1 at 0 °C in CH 2 Cl 2 , toluene and CH 3 CN. An effective real-time monitoring of monomer consumption during THF polymerization via ATR-FTIR spectroscopy has been successfully developed for kinetic investigation and determination of equilibrium monomer concentration ([M] e ), equilibrium polymerization time (t e ), equilibrium monomer conversion (c e ).…”

“…The cationic ring-opening polymerizations of tetrahydrofuran (THF) initiated with methyl triflate (MeOTf) were carried out at 0 °C at [THF] 0 = 6.16 mol·L −1 in toluene, CH 2 Cl 2 and CH 3 Fig. 1, the living cationic ring-opening polymerization of THF initiated by MeOTf could be achieved and the polymers with theoretical molecular weight and narrow molecular weight distribution could be obtained in large scale of [I] 0 from 0.9 mmol⋅L −1 to 123.2 mmol⋅L −1 at 0 °C in toluene, CH 2 Cl 2 and CH 3 CN before the polymerization reached equilibrium.…”

“…To examine the effect of polymerization temperature, the cationic ring-opening polymerizations of THF initiated by MeOTf were conducted at various temperatures ranging from 0 °C to 20 °C in toluene, CH 2 Cl 2 and CH3 CN respectively. The representative semilogarithmic kinetic plots of ln([M] 0 −[M] e )/([M]−[M] e ) versus time for THF polymerization in CH 3 CN at various temperatures are shown in…”

Reactions of Living Polytetrahydrofuran with Amines V ‐ Tertiary Amine Terminated Polybutadienes; The Synthesis of Novel Ionically Linked Block Copolymers

“…Thus, secondary amine terminal groups are formed with primary amines,' tertiary amine groups with secondary amines,? and quaternary ammonium salts with tertiary a m i n e~; "~ the last two reactions are illustrated in Eqns (1) and (2). In particular, reaction of living polyTHF with triethylamine has been shown to be complete within five minutes under ambient conditions, and its rapidity and exclusivity to result solely in a terminally quaternised product of low disperity.…”

“…The reaction rate should be enhanced if the electrophilic polymer reagent were more reactive than the benzyl bromide derivatives tested hitherto and therefore it seemed logical to consider reactions analogous to Eqn (2) in which a tertiary amine terminated polymer was allowed to react directly with living polyTHF (Eqn (3)).…”