| 摘要: | 本研究主要分為兩部分，其一是將硬鏈段1,6-己二異氰酸酯 (hexamethylene diisocyanate, HDI)與軟鏈段四氫呋喃均聚醚(Poly
-tetramethylene-ether-glycol, PTMG)和鏈延長劑2,6-吡啶二甲醇(2,6-Pyridinedimethanol, 2,6-PDM)與雙羥乙基苯基磷酸酯防燃劑(bis(2-hydroxyethyl)phenylphosphonate, BHPP)進行共聚合反應製作防燃形狀記憶型聚氨基甲酸酯(Flame resistant shape memory polyurethane,
簡稱FRSMPU)其二則是單獨合成形狀記憶聚氨基甲酸酯(Shape Memory Polyurethane, SMPU)反應完成後再混摻芳香族磷酸酯防燃劑(Aromatic phosphate)，簡稱BFSMPU(Blend flame resistant SMPU)，並與共聚合型之防燃形狀記憶型聚氨基甲酸酯相比較，以探討二者防燃性、形狀記憶功能、合成性、機械性質、熱性質及防皺加工性之差異性。由結果發現，形狀記憶聚氨基甲酸酯與雙羥乙基苯基磷酸酯防燃劑共聚合後，分子量會上升，且分子鏈長短較為平均，但隨著防燃劑含量上升，而分子量會下降。且在傅立葉紅外線光譜中發現出具有聚氨基甲酸酯官能基團；X光繞射中SMPU在2θ=20°地方均出現繞射峰，其可能為非晶相結構或是微小結晶結構；而混摻磷系防燃劑中發現因相容性問題，當添加量增加，會在約2θ=16.8°及18.9°出現兩個防燃添加劑的特殊主峰，在共聚合防燃劑X光繞射圖中，可以發現共聚單體BHPP愈多，將減少鬆散的軟鏈段且增加應鏈段含量，其XRD繞射圖產生第二主峰d=0.3734 nm與約2θ=23.8°(PU-04)。由能量散佈光譜圖中可以發現到，隨著磷系防燃劑增加，其磷元素也會上升；磷系防燃劑含量增加，防燃性與玻璃轉位溫度會上升，但熱裂解溫度、機械性質下降及形狀回復率皆呈下降現象。
至於，混摻型防燃形狀記憶聚氨基甲酸酯雖具有較佳的防燃效果，但其機械性質有明顯的下降，當添加量到達PU-FR20時，已不具有彈性體之延伸量特性。共聚合及混摻型防燃形狀記憶聚氨基甲酸酯皆具良好防燃性能，但機械性質與形狀記憶效果共聚合明顯較混摻方法佳。當加工於棉織物進行物性測試時，發現共聚合防燃聚氨酯樹酯其織物柔軟度與抗縐回復角相對更佳，且可以發現抗縐回復角性質可與形狀記憶效果相互對照。
In this study, the synthesis and characterization of flame resistant shape memory polyurethane had been researched. This article mainly included two studied parts. One of the flame resistant shape memory polyurethane was synthesized based on 1,6-hexamethlene diisocyanate (HDI), poly-tetramethylene-ether-glycol(PTMG), 2,6-Pyridinedimethanol (2,6-PDM) and bis(2-hydroxyethyl)Phenylphosphonate(BHPP) in various molar ratios, called here FRSMPU. The other part only synthesized SMPU was blended with aromatic phosphate as flame resistant, called BFSMPU. From results show the FRSMPU and BFSMPU contain phosphorus composition were characterized by FT-IR and energy dispersive spectroscopy(EDS). The weight-average and number-average molecular weights of FRSMPU were decreased with increasing molar ratios of bis(2-hydroxyethyl)phenylphosphonate .
The morphological characteristics and mechanical properties were investigated using X-ray diffraction(XRD), dynamic mechanical analysis(DMA) and thermal gravimetric analysis(TGA). XRD results indicated phase separation for the aromatic phosphate as flame resistant additive blended with SMPU due to both poor compatibility. Too much additive was added into SMPU, the BFSMPU exhibited two prominent peak around 16.8° and 18.9° because of diffraction of aromatic phosphate material. Moreover, the XRD diffraction on patterns of neat SMPU exhibited one broad diffraction peak at 2θ of 20° with weak intensity compared to FRSMPU. Such a broad peak is attributed to the amorphous structure of polymer. However, BHPP could be susceptible to be crystallized in the segmented SMPU. As the presence of such small crystallite or even some ordering of soft segment chains. The second diffraction prominent peak 2θ of FRSMPU(PU-04) increased with an increase in BHPP around 23.8°. The results also indicated that the thermal and mechanical properties and shape-memory behavior decreased with increasing aromatic phosphate additive or BHPP copolymer in SMPU. The flame resistant, mechanical properties, shape-memory and wrinkle free of fabrics for copolymer SMPU(FRSMPU) were better than blended polymer (BFSMPU). |
