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Korean Chemical Engineering Research,
Vol.51, No.2, 279-284, 2013
Vol.51, No.2, 279-284, 2013
현탁중합을 이용한 레졸형 구형 페놀입자의 합성
Synthesis of Resole-type Phenolic Beads via Suspension Polymerization Technique
암모니아수 또는 트리에틸아민(TEA)을 촉매로 사용하여 페놀과 포름알데히드로부터 구형 페놀수지를 페놀:포름알데히드=1:1~1:4의 몰 비로 98 ℃에서 현탁중합을 통해 합성하였고, 이를 700 ℃의 질소 환경에서 탄화시켜 구형 탄소입자를 형성하였다. 현탁중합으로 형성된 구형 페놀수지의 열적 특성으로부터 후경화가 필요함을 확인하였다. 현탁중합의 최적조건을 결정하기 위하여 페놀/포름알데히드(P/F)의 몰 비, 촉매의 pH, 안정제의 분자량이 구형 페놀입자의 크기와 수율에 미치는 영향을 나머지 변수를 고정시킨 상태에서 조사하였다. P/F 몰 비에 따라 형성되는 입자 크기는 증가하는 반면 수득율은 감소하는 것을 확인하였고, 촉매의 pH가 클수록 큰 입자가 형성되며, 또한 안정제의 분자량은 입도분포보다는 수득율에 더 큰 영향을 미치는 것을 확인하였다. 또한 후경화를 거쳐 얻어진 구형 페놀수지의 열안정성을 TGA를 통하여 조사하였으며, P/F 몰 비가 높은 경우는 dibenzyl ether의 존재로 인하여 후경화 이후에도 220 ℃의 중량감소가 여전히 존재하며, 반면에 P/F 몰 비가 낮은 경우는 220 ℃ 이후 400 ℃에 걸쳐 꾸준한 중량감소가 일어나는 것으로부터 P/F 몰 비가 1:2인 경우가 열안정성이 가장 우수함을 확인하였다.
The phenolic beads in macrosize range were obtained by suspension polymerization at 98 ℃ from phenol and formaldehyde in the presence of basic catalyst with a phenol to formaldehyde (P/F) range of 1:1~1:4, and they were carbonized to spherical carbon beads under nitrogen at 700 ℃. Thermal analysis on spherical phenolic beads obtained by suspension polymerization showed that the postcuring process is essential. In order to optimize the suspension polymerization, the effects of the P/F molar ratio, the pH of catalyst, and the molecular weight of stabilizer on the size distribution and yield of spherical phenol beads were examined separatively. The particle size was increased whereas the yield was decreased with P/F molar ratio. The increasing basicity of catalyst made the particle size to increase, while the molecular weight of stabilizer had more effect on the yield rather than on the particle size distribution. The thermal stability of the spherical phenolic beads obtained through postcure was also examined by TGA. The phenol beads of high P/F ratio still showed the weight loss at 220 ℃ even after postcure due to the high possibility of dibenzyl ether, while those of low P/F ratio showed the steady decrease in weight during 220 ℃ to 400 ℃, which showed that the optimal P/F ratio was 1:2.
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