Synthesis of polyetherols with isocyanuric ring. Kinetics and mechanisms of reactions, part 2: Consecutive reaction of ethylene carbonate with isocyanuric acid

Abstract

The kinetics and mechanism of the reaction between isocyanuric acid and ethylene carbonate was studied. The multistep reaction in the presence of potassium carbonate as catalyst leads to polyetherols. The imide and hydroxyl groups of intermediates react with ethylene carbonate by slightly different mechanism and kinetics. The rate constants for these elementary processes were established, and based on these experimental data the mechanism of reaction was proposed. Using the isocyanuric acid and 1,3,5-tris(2-hydroxyethyl)isocyanurate, it has been found that the reaction of ethylene carbonate with intermediates occurs via a mixed

Synthesis of polyetherols with isocyanuric ring. Kinetics and mechanisms of reactions, part 1: Reaction between isocyanuric acid and ethylene carbonate

“…Elemental analysis of the separated product, which was purified by recrystallization from water, corroborates well with the conclusion (see part 2 10).…”

“…Tetrabutyl ammonium hydroxide, potassium carbonate, or 1,4‐diazabicyclo[2.2.2]octane were used as catalysts. Here we have undertaken detailed kinetic and mechanistic studies on the reaction in the presence of a variable amount of EC focusing on the initial step and a consecutive reaction between EC and oligoetherols (see part 2, in this issue 10) formed initially. The literature data do not describe the kinetics and mechanisms of the reactions between alkylene carbonates and IA, but some mechanistic details are known for the reactions between alkylene carbonates with other organic compounds 11–15.…”

New method of synthesis of oligoetherols with carbazole ring

“…Their decom-position starts already at 130 °C. The lower thermal resistance on these cases in probably related to the presen-Lubczak: New Method of Synthesis of Oligoetherols ... ce of ethylene or propylene glycols formed during reaction with trace water present in substrates, and also as a result other processes as described in 26 . These glycols are in quantities of a few percent by weight and were isolated from oligoetherols upon distillation under reduced pressure and identified by their IR spectra.…”

Synthesis of polyetherols with isocyanuric ring: Kinetics and mechanisms of reactions in the presence of DABCO as catalyst

“…Detailed analysis and a description of particular stages of the reactions (1)–(7) are included in 9. Also, the kinetics and mechanisms of the reaction between semiproduct of reaction IA with EC, i.e., THEI and EC, were studied 10. Similar relationships were found as for the reaction between IA with EC, except for the inhibition by reactive groups of THEI.…”

“…The literature data do not describe the kinetics and mechanisms of the reactions between alkylene carbonates and IA. In 9,10, the kinetics and mechanism of reaction between EC and IA or 1,3,5‐tris(2‐hydroxyetyl) isocyanurate (THEI, I, where x = y = z =1) in DMSO solvent in the presence of K 2 CO 3 have been presented. The following kinetic law describes the reaction between IA and EC in the presence of this catalyst: V = k 0 ′′ · c K 1/3 · c AH −1 , where c K and c AH are the concentration of catalyst and imide groups of IA, respectively, in mol/kg DMSO.…”