Abstract
Effect of organo nanoclay (Cloisite 30B) on the polyesterification of adipic acid (AA) with diethylene glycol(DEG) was investigated with p-toluene sulfonic acid (p-TSA) (Br${\phi}$nsted acid) and butylchlorotin dihydroxide (Lewis acid) catalyst at 383 and 423 K. The initial [OH]/[COOH] molar ratio was two and the concentration of the catalysts in the reactants was 0.14 mol% based on the total reactants. The kinetics of the polyesterification was interpreted with the conversion data that was calculated from the acid values of the reactant-product mixture. The reaction rate of the polyesterification, which was catalyzed with p-TSA, exhibited the second-order dependency on AA concentration. When Butylchlorotin dihydroxide was used, the reaction rate revealed the first-order dependency on AA concentration. The activation energy of the reactions catalyzed with p-TSA and Butylchlorotin dihydroxide were calculated at 42.2 and 63.8 kJ/mol, respectively. Addition of 5 wt% Cloisite 30B to the reactant significantly diminished the activity of p-TSA, so the reaction rate decreased and the activation energy was calculated at 72.9 kJ/mol. Butylchlorotin dihydroxide catalyst maintained its activity regardless of the addition of Cloisite 30B to the reactant and the activation energy was calculated to 61.8 kJ/mol. Lewis acid catalyst, butylchlorotin dihydroxide, was more effective than Br${\phi}$nsted acid catalyst for the esterification of AA with DEG.
Adipic acid(AA)와 diethylene glycol(DEG) 사이에서 일어나는 반응의 속도에 대한 유기나노점토(Cloisite 30B)의 영향을 규명하기 위하여 383K와 423 K에서 Br${\phi}$nsted acid인 p-toluene sulfonic acid(p-TSA)와 Lewis acid인 butylchlorotin dihydroxide를 촉매로 사용하여 에스테르 반응을 수행하였다. 촉매의 양은 전체반응물의 0.14 mol%만큼 사용하였다. 반응 생성물의 산가로부터 계산된 전환율 vs. 시간의 자료를 사용하여 반응속도를 해석하였다. [OH]/[COOH] 초기 몰비가 2인 상태에서 수행되는 polyester-diol 합성반응의 속도는 p-TSA 촉매하에서는 AA에 대하여 2차 반응으로, butylchlorotin dihydroxide 촉매하에서는 AA에 대하여 1차 반응으로 잘 해석되었으며 두 반응의 활성화 에너지는 각각 42.2 kJ/mol, 63.8 kJ/mol이었다. AA와 DEG에 Cloisite 30B를 5 wt% 첨가시키면 p-TSA 촉매는 활성이 크게 줄어 반응속도가 매우 느려졌으며, 이 때 활성화 에너지는 72.9 kJ/mol로 높게 계산되었다. Butylchlorotin dihydroxide 촉매는 Cloisite 30B의 첨가에 관계없이 거의 일정한 활성을 유지하였다. Butylchlorotin dihydroxide 촉매하에서 Cloisite 30B를 첨가한 반응의 활성화 에너지는 61.8 kJ/mol로 Cloisite 30B를 첨가하지 않은 반응의 활성화 에너지보다 약간 낮았다.
