水性聚醯胺酸之製備與應用

A Study on Synthesis and Application of Waterborne Polyamic acid

王千榕(Chien-Jung Wang)

指導教授 ： 鄭如忠

國立臺灣大學/工學院/高分子科學與工程學研究所/碩士(2022年)

https://doi.org/10.6342/NTU202203405

摘要

聚醯亞胺（Polyimide, PI）由於具優異的熱、電氣和機械性質，被廣泛受到高科技領域的應用，為當今重要的工程塑膠之一。本研究利用二胺（Diamine）與二酸酐（Dianhydride），以二步法先經加成反應（Addition Reaction）聚合成聚醯胺酸高分子（Polyamic Acid, PAA），接著，利用不同種類的有機鹼（Organic Base）與羧基（Carboxyl Group）反應，藉由離子化的過程使其具親水性，形成水性聚醯胺酸高分子（Polyamic Acid Salt, PAAS），最後，再經高溫環化（Imidization）形成聚醯亞胺高分子。後續將其應用在碳纖維上漿製程中，以上漿步驟將碳纖維表面改質成含有PI之界面層，來增強與碳纖維和後續耐高溫樹脂（PPS、PA6、PEEK、PEAK）之結合性，並利用界面剪切強度（IFSS）檢測方法評估，結果顯示以本研究之PI改質之碳纖維與耐高溫樹脂（PPS、PA6）的介面性能增加 50% 左右。除此之外，利用穩定性加速測試儀（LUMiSizer）測試水性漿液的性質，結果顯示出本研究之水性聚醯胺酸漿料有良好的安定性。藉由傅立葉式紅外線光譜儀（Fourier Transform Infrared Spectrometer, FT-IR）、核磁共振儀（Nuclear Magnetic Resonance Spectrometer, NMR）、熱重損失分析儀（Thermogravimetric Analyzer, TGA）、示差掃描熱量分析儀（Differential Scanning Calorimeter, DSC）、動態光散射粒徑分析儀（Dynamic Light Scattering Particle Size Distribution, DLS）、界面電位分析儀（Zeta Potential Analyzer, Zeta）和酸鹼度計（pH Meter）來鑑定聚合物之結構、熱性質和乳液性質。綜上所述，本實驗成功地藉由使用離子化試劑進行簡單的處理，製備出貯存穩定性高的耐熱水性漿液，可以與多種高階工程塑膠匹配，而且，此聚醯胺酸水性上漿劑製備過程簡單、生產效率高，方便實現工業化的製備與應用。

關鍵字

離子化 ； 水性聚醯胺酸 ； 表面改質劑 ； 複合材料界面剪切強度

並列摘要

Polyimide (PI) is widely used in high-technology fields owing to its excellent thermal, electrical, and mechanical properties and is one of the most important engineering plastics nowadays. In this study, polyamic acid (PAA) solution was synthesized based on diamine and dianhydride monomers via addition reaction. The water dispersible PAA was achieved by using ionization process to obtain polyamic acid salt (PAAS) with the addition of different organic bases. In order to improve the interface properties of carbon fiber composites, water dispersible PAA was utilized as a coating layer on the carbon fiber surface. After modification with PAA, the interfacial shear strength (IFSS) of carbon fiber composites was significantly increased. In conclusion, this research has successfully developed a water-dispersible slurry with high temperature resistance and storage stability via the ionization process, making it a potential industrial application prospect in improving the interface performance of carbon fiber composites.

並列關鍵字

Ionization ； Waterborne polyamic acid ； Sizing agent ； Interfacial shear strength

參考文獻

1. Yuan, H.; Zhang, S.; Lu, C.; He, S.; An, F., Improved interfacial adhesion in carbon fiber/polyether sulfone composites through an organic solvent-free polyamic acid sizing. Applied Surface Science 2013, 279, 279-284.

2. Hao, R.; Jiao, X.; Zhang, X.; Tian, Y., Fe3O4/graphene modified waterborne polyimide sizing agent for high modulus carbon fiber. Applied Surface Science 2019, 485, 304-313.

3. Jung, H.; Bae, K. J.; Jin, J.-u.; Oh, Y.; Hong, H.; Youn, S. J.; You, N.-H.; Yu, J., The effect of aqueous polyimide sizing agent on PEEK based carbon fiber composites using experimental techniques and molecular dynamics simulations. Functional Composites and Structures 2020, 2 (2).

4. Yuan, C.; Li, D.; Yuan, X.; Liu, L.; Huang, Y., Preparation of semi-aliphatic polyimide for organic-solvent-free sizing agent in CF/PEEK composites. Composites Science and Technology 2021, 201.

5. Ding, Y.; Bikson, B.; Nelson, J. K., Polyimide Membranes Derived from Poly(amic acid) Salt Precursor Polymers. 1. Synthesis and Characterization. Macromolecules 2002, 35 (3), 905-911.