PAN/MA及PAN/MA/DMI共聚物之低溫環化動力學研究

The study of low temperature cyclization kinetic in PAN/MA and PAN/MA/DMI copolymers

許元熏(Yuan-Hsun Hsu)

指導教授 ： 芮祥鵬

國立臺北科技大學/工程學院/有機高分子研究所/碩士(2012年)

摘要

本研究是將以PAN為基材的共聚物比較於不同恆溫環環化溫度與不同升溫速率來進行熱氧化(環化)處理，再經由恆溫與非恆溫動力學方程式來驗證此環化反應。實驗中，當同樣在低溫的時候，PAN為基材的聚丙烯腈/丙烯酸甲酯/二甲酯衣康酸(AN/MA/DMI)三共聚物會比以PAN為基材的聚丙烯腈/丙烯酸甲酯(AN/MA)二共聚物還要來的提早環化反應。
經由avrami動力學方程式分析得知，溫度越高，環化速率(k)也隨著增加。因此，我們可以發現到，隨著PAN為基材的DMI成分加入的越多，環化反應的時間就越少，環化速率也跟著增加。
根據上述，我們把DMI視為一種對於PAN的環化催化劑。儀器驗證共聚物部分之分子量可由GPC測量，共聚物之組成分可由NMR光譜計算得知。

關鍵字

恆溫動力學 ； 聚丙烯腈環化微差掃描熱卡計 ； 碳纖維

並列摘要

Isothermal kintic and non-isothermal analysis of thermo-oxidative stabilzation (cyclization) process in polyacrylonitrile (PAN)-based copolymers was studied with use of the differential scanning calorimetry (DSC) data.The exothermic peaks of PAN-based copolymers made of acrylonitrile/methyl acrylate/dimethyl itaconate (AN/MA/DMI) terpolymers is much earlier cyclization reaction starts at lower temperature than PAN-based copolymers made of acrylonitrile/methyl acrylate(PAN/MA) dipolymers.
By avrami equation analysis the cyclization rate (k) increased when the temperature increased.However, we can observe that the more consists of dimethyl itaconate, the better decrease the cyclization reaction time and increase the cyclization rate (k) in PAN-based.
Based on the above results,we can regard dimethyl itaconate as a cyclization catalyst to PAN-based.In this paper, these observation were confirmed by structural characterization by FT-IR, measured molecular weigh using GPC, calculated consist of PAN-based copolymer by NMR.

並列關鍵字

isothermal kinetic ； polyacrylonitrile ； cyclization ； DSC ； carbon fiber

參考文獻

[9] Zhu Y, Wilding M. A., Mukhopadhyay S. K.J Mater Sci, Vol. 31, 1996.

[11] Gupta, A. K., Chand, N. J Polym Sci Polym Phys Ed , Vol. 18, 1980.

[12] Hinrichsen, G. J Polym Sci C: Polym Symp,Vol.38, 1972.

[13] K. I. Suresh, K. Saji Thomas, B. S. Rao. and C. P. Reghunadhan Nair, Polym. Adv. Technol, Vol.19, 2008.

[17] Burlant, W. J., Parson, J. J Polym Sci, Vol.22, 1956.