Synthesis of Polyester-diol and Exfoliation of Nanoclay through Esterification between Adipic Acid and Diethylene Glycol

We synthesized polyester-diol containing Cloisite 30B which is exfoliated during the synthesis. First, esterification was conducted with excess adipic acids and two 2-hydroxyethyl groups of the tertiary ammonium tethered to Cloisite 30B silicate layer. Due to the small molecular size of adipic acid ($d{\approx}3.0\;{\AA}$, $L{\approx}9.3\;{\AA}$), it penetrated into the interlayer of Cloisite 30B, reacted with the 2-hydroxyethyl groups, and produced the tertiary ammonium that has the two ethyl-ester adipic acid groups, one methyl group, and one hydrogenated alkyl group. Through the esterification, the molecular size of the tertiary ammonium increased and as the result, the basal space of Cloisite 30B increased from $18.4\;{\AA}$ to more than $58.3\;{\AA}$. The produced ethyl-ester adipic acid and unreacted adipic acid reacted with excess diethylene glycol ([COOH]/[OH]${\approx}0.6$) to be polyester-diol. The COOH conversion calculated from the acid value of the reactant mixture was 94%. The number average molecular weight and PDI of the produced polyester-diol were 830 g/mol and 1.2, respectively.

Adipic Acid와 Diethylene Glycol의 에스테르 반응을 통한 나노점토의 박리와 폴리에스테르형 디올의 합성

Cloisite 30B가 박리, 분산된 폴리에스테르형 디올을 제조하였다. 먼저, Cloisite 30B에 치환된 2-hydroxyethyl기를 가진 4급 암모늄염을 과량의 adipic acid와 혼합하여 $130^{\circ}C$에서 반응시켜, 에스테르기로 연결하고 양말단에 카르복실기를 가지는 ethyl-ester adipic acid 암모늄염으로 만들었다. 이 과정에서 Cloisite 30B의 실리케이트 층간 간격이 $18.4\;{\AA}$ ($2{\theta}=4.9^{\circ}$)에서 $58.3\;{\AA}$ ($2{\theta}=1.5^{\circ}$)보다 넓게 확장되었다. 층간 간격의 확장은 분자크기가 작은 adipic acid($d{\approx}3.0\;{\AA}$, $L{\approx}9.3\;{\AA}$)가 Cloisite 30B의 층간에서 Cloisite 30B의 2-hydroxyethyl기와 반응하여 분자크기가 커졌기 때문이다. Cloisite 30B가 박리/분산된 adipic acid를 과량의 diethylene glycol([COOH]/[OH]${\approx}0.6$)와 혼합하여 $140^{\circ}C$ 에서 반응시킴으로써 diol을 합성하였다. Acid value로 측정한 전환율은 94%였다. 합성한 diol은 수평균분자량이 830 g/mol, PDI가 1.2로, 평균중합도가 약 7.8인 polyester-diol 형태이다.