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폴리아크릴로니트릴에 關한 硏究 (第 2 報) 폴리아크릴로니트릴의 熱分解에 關하여
노익삼,ICK SAM NOH 대한화학회 1967 대한화학회지 Vol.11 No.2
Structural changes attending polyacrylonitrile(PAN) upon heating and treating with nucleophilic reagents have been studied for some time and a few authors have studied on the thermal degradation, particularly on the characterization of degradation products in PAN. It is the purpose of this paper to report the kinetic study on the thermal degradation above $250^{\circ}C$ and make some suggestions as to the degradation process and mechanism in PAN. The degradation process in PAN is considered that three reactions are combined in two steps. Random chain scission accompanying the naphthylidine-type ring formation is the first step and the degradation of naphthylidine-type ring occurred as the next step. The reactions in the first step are competitive so that the maximum weight loss on pyrolysis of PAN, under such a condition that the degradation of naphthylidine-type ring is negligible, is depended on the relative reaction rate of these two competitive reactions.
노익삼 한국화학공학회 1974 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.12 No.6
高分子필름內에서의 物質의 移動現象은 從來 Gas, Vapor의 Diffusion에 對해 많은 硏究가 行해져 왔고 物質의 分離를 目的으로 Osmosis, Reverse osmosis, Dialysis, Electrodialysis, Ion exchange membrane, Ultrafiltration 등에서 여러지가 高分子膜이 利用되어 왔다. 特히 Dialysis는 Collodion, Cellophane膜을 主로 使用하여 이온 또는 極性化合物의 分離에 利用되고 있다. 本硏究는 Dialysis와 비슷한 機構로 여러 有機化合物을 分離할 수 있는 Plasticized PVC film을 利用하여 Plasticizer의 種類, 含量 등을 變化시킴으로서 特定物質을 選擇的으로 透過시킬 수 있다는 可能性을 나타냈으며 앞으로 特定成分의 分離, 除去 등을 目的으로 開發할 여지가 있음을 보여주고 있다.
Kinetics and Statistics of Structural Changes in Polyacrylonitrile
노익삼,Noh, Ick-Sam Korean Chemical Society 1966 대한화학회지 Vol.10 No.1
폴리아크릴로니트릴을 加熱할 때 着色과 同時에 構造變化가 있다는 것은 잘 알려진 事實이며 이것은 部分水素化나프틸리딘型環을 形成함에 基因하는 것으로 알려지고 있다. 本硏究는 이와 같은 構造變化의 反應을 動力學的 및 統計學的으로 取扱하여 지금까지 알려지지 않았던 새로운 事實들을 發見하였다. 첫째로 폴리아크릴로니트릴을 加熱할 때의 니트릴基의 減少는 一次反應이라는 것이며 이는 環形成反應이 긴連鎖反應으로 이루어지지 않는다는 것을 말해 주는 것이다. 다시 말하면 環形成時의 kinetic chain length는 極히 짧다는 것이다. 또 本 構造變化는 반드시 分子間反應(架橋結合)이 아니드라도, 일어날 수 있다는 것을 證明했다. 둘째로 環形成으로 니트릴基가 減少할 때 19~22%의 니트릴基가 殘存한다는 것이며 이를 統計學的으로 解析해본 結果 19.2%라는 計算値를 얻었으며 이는 實驗値와 잘 맞는 數値이다. It is well known that the coloration and structural changes in thermal treatment of polyacrylonitrile are due to the formation of partly hydrogenated naphthylidine-type ring involving the pendant nitrile groups. Any quantitative study of the reaction, in the sense of kinetics and/or statistics, however, has never been reported. This paper presents that, at first, the disappearance of the nitrile groups follows the first order kinetics, which indicates clearly that nitrile groups do not disappear by a long chain reaction-the kinetic chain length is very short. This observation rules out the long intramolecular and intermolecular propagation chain through which most of the nitrile groups disappear. From the evidence that a similar reaction occurs in propylene carbonate solutions without gel formation, one may conclude that the coloration and structural changes are not necessarily intermolecular reaction. Secondly, a finite amount of nitrile groups remains unreacted at the extrem of reaction-not contributed to the formation of naphthylidine-type ring. The concentration of this unreacted nitrile groups is 19∼22% which is good agreement with the statistically calculated value of 19.2%.
폴리아크릴로니트릴에 關한 硏究 (第 3 報) 폴리아크릴로니트릴에 對한 放射線照射에 關하여
노익삼,ICK SAM NOH 대한화학회 1967 대한화학회지 Vol.11 No.2
Radiolysis of polyacrylonitrile(PAN) has been studied. Parameters for crosslinking and scission induced by gamma-ray irradiation were obtained by means of sol-gel partitioning method. G-value of crosslinking in PAN ($\bar{M}n=6{\times}10^5$) was 0.038 and the gel dose 21.6 Mrad. The effects of irradiation on the thermal degradation rate in PAN was also studied. No appreciable changes in thermal degradation rate observed up to 81.8 Mrad of irradiation dose.