| 摘要: | 環境污染日益嚴重及立法的限制亦趨嚴格的情況下，原本由溶劑製程的ＰＵ樹酯已部分的被由低污染、低溶劑使用量的製程所取代。而基於溶劑的價格昂貴、對環境的高污染性及產物物性的比較下﹔水性ＰＵ系統的開發與應用已延續了４０年。 自1970年開始，水性ＰＵ的發展著重於工業生產價值，然而；公開文獻在軟、硬質兩相因離子基的導入；其熱性質的影響以及微相結構變化與物理性質之間的關係上，卻少有深入的探討。過去；不論是專利或文獻，大多都以極性式聚酯或聚醚類作為軟質段，對以非極性式軟質段的水性PU記載甚少。所以﹔本論文以分子量2500的聚烯類HTIP(Hydroxyl Terminated Polyisoprene)為軟質段，以預聚合混合法(pre- polymer mixing process)合成一系列以硬段含量(30wt.%、50 wt.%、70 wt.%)、離子基含量(1.0 wt.%〜3.0 wt.%不等)及中和劑種類(TEA、TPA、TBA)為變數的分散液，探討各分散液粒徑及黏度的變化，並以FTIR鑑定合成結構，以TGA及DSC探討其熱性質，以DMA探討其動態黏彈性質，以拉力測試探討應力應變的行為。 非極性式WPU會隨著硬段含量增加及離子基含量減少，粒徑隨之減小。FTIR的結果可知道以成功合成一系列分散液。由DSC與HTPB based WPU的TEM的結果，可以知道水性PU的微相結構為一立體網狀構造，隨著離子基及硬段含量增加，網狀密度增加且更為連續。而DMA的結果顯示硬質段的relaxation溫度隨著離子基含量增加而下降；隨著硬段含量增加而升高，而當中合劑種類改變，隨著烷基氨類碳數增加，硬質段的relaxation溫度隨之下降。由應力-應變的結果，斷裂強度與起始模數隨著離子基含量及硬段含量而增加，斷裂延伸則隨之下降，烷基氨類碳數增加，斷裂強度與起始模數隨之下降，斷裂延伸則上升。 Abstract Due to the need of environmental pollution control and strict legal limitation, conventional solvent-borned PU resin systems were replaced by low solvent or solvent-free aqueous PU dispersion.Water-borned PU use water as a solvent are less expensive,have excellent mechanical strengh and cause less pollution. So in the last 40 years,water-borned PU have generated interest. From 1970，since the fous on PU was mostly from industry,most of the literature was in the form of patents with emphasis only on synthesis and particle stability. The structure and property relationship, especially the effect of ionic group on the physical and morphological behaviors, has obtained very little attentions.In past,no matter patent or litrerature, polar polyester or polyether-polyol usually are the soft segment, but water-borned PU with nonpolar soft segment was received less attention. So,HTIP(Hydroxyl terminated Polyisoprene) as Mw 2500 was synthesized as soft segment in our series nonpolar water-borned PU dispersion by prepolymer mixing processes. The hard segment content was 30,50 and 70 wt.%). Ionic content was 1.0 - 3.0 wt.% and neutralizing agent were TEA,TPA and TBA. The variables were studied by ZetaSizer,Viscosity,FTIR,TGA,DSC,DMA and mechanical properties. The average diameter of dispersion particles become samaller with increasing hard segment content and decreasing ionic content. Successfully the series dispersion were synthesized and characterized by FTIR. The result of DSC and TEM of HTPB based WPU showed that the micro-structure of water-borned polyurethane was three-dimensional network and the density of network increased with increasing ionic content and hard segment content. The result of DMA showed that the relaxation temperature decreases with the increasing ionic content and increase with hard segment content. The relaxation temperature decreses with increasing number of carbons in various neutralizing agents. From the results of mechanical behavior,tensile strengh and initial modulus increase with increasing ionic content and hard segment content,elongation at break decrease with increasing ionic content and hard segment content. Tensile strengh and initial modulus decreases and elongation at break increases with increasing number of carbons in various neutralizing agents. |
