在環保意識抬頭的驅使下，工業與學術界開始朝向水性高分子來發展，當中受到矚目的水性樹脂之一，即水性聚胺基甲酸酯-脲酯(waterborne polyurethane-ureas，WPUUs)。雖到目前為止對其物性已有ㄧ定程度的了解，但物性與結構、型態間的關係卻尚未確立，甚至連真實的結構、型態究竟為何都還沒有被清楚地窺探過。這是因為一般以極性polyol所合成的WPUUs (極性式WPUUs) 其軟、硬質段間存在著氫鍵作用力，以致無法達到完全的相分離而複雜了結構與物性間的關係。反觀若以非極性式polyol來合成WPUUs (非極性式WPUUs)，便可排除軟、硬質段間氫鍵的影響，預期能夠達到近乎完全的相分離，而有助於了解並釐清結構與物性間的關係。 本研究為了能完整的探討，於是自行合成出700、2050與3400等不同分子量之非極性且可染色的HTPB為polyol，而選用的diisocyanates有H12MDI、HDI與IPDI等三種，離子基為DMPA，中和劑(neutralizer)有TEA、TPA與NaOH等三種，以及EDA作為鏈延長劑(chain extender)，進行搭配組合製作出包含不同軟質段分子量、離子基與硬質段含量等眾多的WPUU樣品來。從合成、分散液性質、造膜與熱裂解，以及WAXD、TEM、FTIR、DSC、DMA與Tensile等方面進行測試，針對結構與物性做一嚴謹的研究。 眾多的證據均清楚地指出WPUUs的型態是由節點(nodes)與分支(cords)所組成的連續網狀結構，尺寸僅~ 2 nm寬，明顯不同於過去文獻所認為WPUUs是偏向於離子體(Ionomers)具有離子團簇聚集的型態；而所謂的離子團簇，像是分散且不連續的multiplets與clusters等微域。此一確實存在的連續網狀結構足以完整地說明為何非極性式HTPB-based WPUUs能表現出比非極性式HTPB-based PUs優異許多的機械性質，甚至不輸於傳統極性式PUs；以及能製作出硬質段含量(可達70 wt%)高於傳統PUs而不會脆裂的特殊性質來。 Waterborne poly(urethane-urea)s, WPUUs, based on nonpolar hydroxyl-terminated polybutadiene (HTPB) as the soft segment were successfully synthesized. The influences of the COOH group content and soft-segment molecular weight (Mns) on the dispersion, morphology, tensile and pyrolysis properties were investigated. The variations of the particle size and viscosity with increasing the COOH group content and decreasing the Mns were predominated by the hydrophilicity of the polymer chain first and then by the effect of the water swelling. The measurements of Fourier transfer infrared (FT-IR) and differential scanning calorimetry (DSC) indicated that the phase-separation degree decreased as the COOH group content increased and Mns decreased. It was worthy to note that the hydrogen bonding and phase mixing between the soft and hard segments in this study could not be occurred. Therefore, it implied that the hard segments tended to form the looser packing and smaller domains in the soft phases. In this case, the increases of the interface area and contact opportunity between the soft and hard segments resulted in the present behaviors resembled the phase mixing. Besides, HTPB-based WPUUs exhibited the higher tensile stress, the elongation at break and modulus with decreasing the COOH group content and Mns. In thermal degradation, the introduction of HTPB polyol improved the thermal stability.
