高剛性可溶聚醯亞胺合成與架橋特性研究

Studies on the synthesis of high modulus/solvent soluble Polyimide and their cross-linking prophttp://etds.ntut.edu.tw/images/correct.giferties

楊偉志(Wei-Chih Yang)

指導教授 ： 廖義田

國立臺北科技大學/工程學院/有機高分子研究所/碩士(2014年)

https://doi.org/10.6841/NTUT.2014.00134

摘要

可溶性聚醯亞胺具有易加工、高儲存安定性的製程優點，但由於傳統一步法合成的可溶性聚醯亞胺，其軟化溫度較低，本研究藉由添加熱固性雙馬來醯亞胺(bismaleimide, BMI)於可溶性聚醯亞胺中，經熱烘烤硬化後，形成具有半穿繞結構(semi-interpenetrating polymer network (SIPN))的高分子結構，提升高分子耐熱特性以及尺寸安定性。本研究中利用4,4'-oxydianiline(ODA) 和3,3'-diaminodiphenylsulfone(3,3'-DDS)兩種二胺，分別以五種不同比例(1:0, 0.7:0.3, 0.5:0.5, 0.3:0.7, 0:1)和4,4'-oxydiphthalic anhydride(ODPA)二酸酐，利用一步法合成出芳香族聚醯亞胺(PI)，之後再將合成出的聚醯亞胺，分別添加不同比例的N,N'-bismaleimido-4,4'-diphenylmethane(BMI)，探討最終結構物性。經由實驗結果發現，所合成的可溶性聚醯亞胺其固有黏度(inherent viscisity)約為0.33~0.74dL/g(0.5g/dL, NMP, 30℃)。聚醯亞胺在常溫下可溶於NMP、DMAc、m-cresol中，展現了極佳的溶解特性，隨著BMI的增加，交聯度隨之提高。而藉由BMI的增加也可提升在鉛筆硬度的特性，使之從2H上升到4H。另外經由熱機械分析儀(TMA)、熱重分析儀(TGA)和動態機械分析儀(DMA)也可得知，增加BMI的添加量，有略提升熱變形溫度(HDT)，降低玻璃轉移溫度(Tg)和熱膨脹係數(CTE)，這些結果也顯示，添加BMI增加部分交聯特性，可提升聚醯亞胺的熱穩定性。但也由於BMI( - CH2 -)的增加，造成熱裂解溫度(Td)下降。但仍與傳統兩步法合成全芳香聚醯亞胺相當(450℃以下並沒有明顯的重量損失產生，甚至有些組合達500℃以上)。

關鍵字

聚醯亞胺 ； 雙馬來醯亞胺 ； 溶解度 ； 熱硬度

並列摘要

Soluble polyimides with ease of processing, high storage stability of the advantages. However, due to the traditional one-step synthesis of soluble polyimides, its softening temperature is low, the study by adding thermosetting bismaleimide (BMI) in the soluble polyimide, and curing by heat , to form a semi-wear around the structure (semi-interpenetrating polymer network (SIPN)) of the polymer structure, enhance the heat resistance and dimensional stability of the polymer. In this study, the use of 4,4'-oxydianiline (ODA) and 3,3'-diamino diphenyl sulfone (3,3'-DDS) two kinds of diamine, respectively, in five different ratios (1:0, 0.7:0.3, 0.5:0.5, 0.3:0.7, 0:1) and 4,4'-oxydiphthalic anhydride (ODPA), the use of one-step synthesis of aromatic polyimide (PI) were then added different proportions of N, N'-bismaleimido-4,4'-diphenylmethane (BMI), investigate the properties of the final structure. The experimental results showed that the synthesis of soluble polyimides its intrinsic viscosity (inherent viscisity) is about 0.33 ~ 0.74dL / g (0.5g/dL, NMP, 30 ℃). Polyimide is soluble at room temperature, NMP, DMAc, m-cresol, and show the excellent solubility characteristics of the BMI increases, the degree of crosslinking increases. With the increase in BMI may also enhance the properties of the pencil hardness of from 2H to make up to 4H. Also via Thermal Mechanical Analysis (TMA), Thermal Gravimetric Analysis (TGA) and Dynamic Mechanical Analysis (DMA) we can see that, added to increase the amount of BMI, there are slightly enhance the heat distortion temperature (HDT), lowering the glass transition temperature (Tg) and thermal expansion coefficient (CTE), these results also show that adding BMI increased crosslinking properties section, you can enhance the thermal stability of the polyimides. But due to the BMI (- CH2 -) is increased, resulting in thermal decomposition temperature (Td) decreased. But still with the traditional two-step synthesis of wholly aromatic polyimides fairly (no significant weight loss results in the following 450 ℃, and even some combination of more than 500 ℃).

並列關鍵字

Polyimide ； bismaleimide ； solubility ； Hot hardness

參考文獻

29. Yang, C. P.; Hsiao, S. H.; Chen, K. H. Polymer 2002, 43, 5095.

2. Li, F.; Harris, F. W.; Cheng, S. Z. D. Polymer 1996, 37, 5321.

42. Chern, Y. T.; Twu, J. T.; Chen, J. C. Eur. Polym. J. 2009.

45. Li, F.; Fang, G., J. J.; Honigfort, P. S.; Chen, J.-C.; Harris, F. W.; Cheng, S. Z. D. Polymer 1999, 40, 4571.

46. Li, F.; Ge, J. J.; Honigfort, P. S.; Fang, S.; Chen, J. C.; Harris, F. W.; Cheng, S. Z. D. Polymer 1999, 40, 4987.