本論文針對含不同離子性之分散中心及軟鏈節進行各種水性聚胺基甲酸酯(polyurethane，PU)之合成及各項物性探討。首先固定軟鏈節種類變化不同離子性的分散中心合成各種離子型水性PU，探討分散中心種類及其離子性對合成水性PU之分散液性質、成型薄膜之熱性質、機械性質及應用於耐隆織物透濕防水加工之影響。其次，以末端為雙醇含甲氧基聚乙二醇的化合物為非離子分散中心，變化不同分子量的酯型或醚型的軟鏈節合成非離子型水性PU，探討水性PU之分散液性質、成型薄膜之熱性質及應用於耐隆織物透濕防水加工之影響。本論文進而固定N-甲基二乙醇胺為陽離子型分散中心，變化不同分子量的聚酯二醇(PCL)或聚醚二醇(PEG、PPG及PTMG )為軟鏈節，探討軟鏈節組成對合成PU分散液之溶液性質、成型薄膜之熱性質及其應用於耐隆織物透濕防水加工之影響。最後，為改善陽離子型及非離子型PU之缺點，將非離子PU依不同比例摻混到陽離子PU中，探討摻合物之各項性質。本論文之各章節結果歸納如下：
一、針對變化分散中心種類之合成PU方面，PU分散液之表面張力以非離子型PU > 陰離子型PU > 陽離子型PU。PU分散液與未處理耐隆織物間之接觸角以非離子型PU為最大，其次為陰離子型PU及陽離子型PU；陽離子型PU與陰離子PU接觸角之變化趨勢與其表面張力相同。除了非離子型PU的N-PDEA2000 PU及陰離子型的EES-200L PU具有兩個軟鏈節的熔點(Tms)外，其餘合成PU僅有一個Tms且差異不大，出現在22~25℃間。另外發現PU之軟鏈節熱焓受分散中心種類影響很大。加工織物之透濕度以非離子型PU最佳；陽離子PU加工織物則具有最佳的耐水壓。
二、針對不同軟鏈節組成之側鏈含甲基聚乙二醇非離子型水性PU之方面，PU分散液之表面張力大小依序為NPEG-PU > NPTMG-PU > NPPG-PU > NPCL-PU。PU分散液之粒徑以NPCL-PU為最大；粒徑則隨軟鏈節之分子量增大而變小。PU分散液對未處理的耐隆織物表面接觸角之趨勢與表面張力相同。PU薄膜之玻璃轉移溫度(Tgs)以NPCL-PU > NPEG-PU > NPPG-PU > NPTMG-PU；且隨軟鏈節分子量的增大而降低。其軟鏈節熔點(Tms)以NPEG-PU為最高，其次依序為NPCL-PU、NPTMG-PU，以NPPG-PU為最小；其Tms隨軟鏈節之分子量增大而提高。PU塗佈織物之透濕度為NPEG-PU > NPTMG-PU > NPPG-PU > NPCL-PU；且隨軟鏈節分子量增大而增加。另外，發現部分加工織物在進行耐水壓試驗後，其成型薄膜會從加工織物表面脫離的不良情況。
三、針對含不同軟鏈節組成N-甲基二乙醇胺系陽離子型水性PU之方面，PU分散液之表面張力為CPEG > CPTMG > CPPG > CPCL；且隨軟鏈節分子量增長而降低。分散液粒徑大小以軟鏈節為CPCL > CPPG > CPEG > CPTMG；且隨軟鏈節長度增長而提高。不論Tgs或Tms皆以CPEG最大，其次為CPCL、 CPTMG 、 CPPG最小。軟鏈節分子量需超過2000g mole-1後其domain才會有明顯的形成，而產生明顯的軟鏈節結晶。另外由DMA中發現，PU之微相分離程度以CPTMG > CPPG > CPCL，且隨軟鏈節分子量之增加而提高，PU薄膜之可撓性亦隨軟鏈節分子量之增加而增大。在軟鏈節對合成PU成型薄膜機械性質之影響方面，其抗張強度以PTMG者為最大，其次為PCL、PPG最小，且隨軟鏈節分子量之增加而下降，超過2000後又增大，伸度則相反。就塗佈加工織物之透濕度以軟鏈節CPEG > CPTMG > CPPG > CPCL，此數值遠低於前章的非離子PU。而耐水壓以CPTMG > CPCL > CPPG > CPEG；在軟鏈節分子量的影響方面，透濕度以軟鏈節分子量2000>3000>1000，而耐水壓以1000 > 3000 > 2000。另外發現加工織物之表觀性質會隨時間的增加而產生黃變。
四、針對非離子PU/陽離子PU摻合物方面，摻合物時成型薄膜之TgS 、硬鏈節的熱焓(△HH)隨N-PDEA PU摻含量增多而下降；軟鏈節熱焓(△Hs)則隨摻含量增加而上升；另外軟鏈節熔點與硬鏈節熔點在少量摻合時影響不大，但摻合量超過25%以上時開始下降。在機械性質方面，N-PDEA PU其成型薄膜強力較N-MDEA PU為低。就摻合物的機械性質而言，其強力隨N-PDEA PU摻合量之增加而降低，伸度則增大，惟少量的摻合N-PDEA PU (5%時)對成型薄膜強力影響不大且可有效的提升成型薄膜的伸度。在塗佈加工織物方面，摻合物加工織物透濕性遠及耐水壓均獲得提升且其表觀性已不會產生黃變。

This study is focus on the synthesis, characteristic of aqueous polyurethane containing different dispersing center and soft segment and its application on coatings. In chapter 2, a series of waterborne polyurethane (WBPU) with different dispersing center of ionicity were synthesized by using 4,4-methylene bis(isocyanatocyclohexane, H12MDI), polytetramethylene glycol with molecular weight of 2000 (PTMG2000), and a series of ionic compound as hard segment, soft segment and dispersing center, respectively. The solution properties of the WBPU dispersion and thermal properties, mechanical properties and coated fabric were investigated.
In chapter 3, a series of nonionic aquesou PU(NAPU) containing side chain poly(ethylene glycol) monomethyl ether (PEGME) were synthesized using 4,4-methylene bis(isocyanatocyclohexane), the nonionic dispersing center produced by isophorone diisocyanate, N-diethanol amine and PEGME and a series of soft segments (PEG, PPG, PTMG and PCL) with a different molecular weight. The solution properties of the WBPU dispersion and thermal properties, mechanical properties and coated fabric were investigated.
In chapter 4, cationic aqueous polyurethane (CAPU) were prepared by the acetone process using H12MDI, N-methyldiethyolamine (N-MDEA) and a series of various polydiols (polyethylene glycol (PEG), polypropylene glycol (PPG) and polytetramethylene glycol (PTMG) for ester-type polyols and polycaprolactone (PCL) for ester-type polyol) with a different molecular weight (Mn=1000, 2000 and 3000g/mole). The solution properties of the WBPU dispersion and thermal properties, mechanical properties and coated fabric were investigated.
In chapter 5, in order to improve the water vapor permeability (WVP) of CAPU and waterproof of NAPU, The PU blend of CAPU and NAPU with different weight ratio was studied. The results are summed in the following observations:
1. Synthesis, physical properties of aqueous polyurethane with different dispersing center and its application on coating.
The surface tension followed the order: NAPU > AAPU > CAPU. For the surface tension of the nonionic WBPU increased as a longer PEGME side chain length. The surface tension of AAPU with sulphonic acid sodium salt (EES-L200 PU) was higher than that of AAPU with carboxylic acid group, and the carboxylic group-based anionic WBPU decreased with increasing the length of methylene side chains; in addition, the surface tension of CAPU were found to be N-butyldiethanolamine-based PU > N-ethyldiethanolamine-based PU > N-methyldiethylamine-based PU. For the contact angle of WBPU dispersion on untreated nylon fabric, the sequence followed the order: NAPU > AAPU > CAPU. Expecting for NAPU, the effect of dispersing center on the contact angle was the same as CAPU and AAPU. As for the thermal properties, the melting point of soft segment (Tms) of WBPU was almost not affected by the ionicity of dispersing center, but the heat of fusion of the soft segment (ΔHs) was greatly affected. Expecting for the NAPU with side chain length of 2000g/mole (N-PDEA2000 PU) and EES-L200 PU having two obviously Tms, the other WBPUs only had a Tms at 22~27 C. For dynamic mechanical analysis, the glass transition temperature of the soft segment followed the order: N-BDEA PU > N-EDEA PU > N-MDEA PU for CAPU; EES-L200 PU > DMBA PU > DMPA PU for AAPU; NAPU with side chain length of 750g/mole > NAPU with side chain length of 550g/mole > nonionic WBPU with side chain length of 2000g/mole. The tensile strength of WBPU film showed as AAPU > CAPU > NAPU, however the elongation showed the opposite trend.
2. Synthesis, physical properties of nonionic aqueous polyurethane with different soft segment composition and its application on coating.
The surface tension of PU dispersion and its contact angle to untreated nylon fabric are higher for the ether-based PU dispersion than for the ester-based PU dispersion, with a sequence of NPEG-PU > NPTMG-PU > NPPG-PU > NPCL-PU. Both the surface tension and the contact angle between PU dispersion and nylon fabric increase upon increasing the Mw of the soft segment. As for the thermal property of PU film, the Tgs of NPCL-PU is the highest, followed by NPEG-PU, NPTMG-PU and NPPG-PU, and the Tgs decreases with the increase in the length of the soft segment. The Tms follows the order: NPEG-PU > NPCL-PU > NPPG-PU > NPTMG-PU, and the Tms increases upon increasing the soft segment length. As regard to PU coated fabric, the trend of WVP is NPEG-PU > NPTMG-PU > NPPG-PU > NPCL-PU, which increases with the increasing the soft segment length. With regarding to application for the coating, the coated-PU with PEG-PU has an excellent WVP.
3. Synthesis, physical properties of MDEA series cationic aqueous polyurethane with different soft segment composition and its application on coating.
The results showed the ether-based PU showed a higher surface tension value, contact angle and WVP with a sequence of CPEG-PU > CPTMG-PU > CPPG-PU > CPCL-PU, and it increases with increasing Mn of the soft segment. As for the thermal properties, the PEG-PU has the highest glass transition temperatures of the soft segment (Tgs) and its melting point (Tms) than those of CPCL-PU, CPTMG-PU and CPPG-PU. For the thermal stability of CAPUs casting film, the PEG-PU has ideal thermal stability, followed by PTMG-PU and PCL-PU, and the CAPU with a larger Mn of the soft segment having better thermal stability. Besides, the PTMG-PU has excellent tensile strength, followed by PCL-PU and PPG-PU. For coated fabric, the trend of WVP followed the order: CPEG-PU > CPTMG-PU > CPPG-PU > CPCL-PU, while the WP followed the order: CPTMG-PU > CPCL-PU > CPPG-PU > CPEG-PU. Finally, the CAPU-coated fabric has an excellent performance after washing and its wash-durability was still 80%.
4. The Physical Properties of Aqueous Nonionic Polyurethane Blend with Aqueous Cationic Polyurethane
The NAPU has a lower Tgs, Tms, TmH and ΔHH and tensile strength than CAPU. The tensile strength of PU blends decreases as the content of N-PDEA 750 PU increases. When the low blend ratio of N-PDEA 750 PU (e.g. 5%), the tensile strength of casting film only shows less influence that can improve the elongation effectively. In terms of coating treated fabrics, NAPU coated fabrics show lower waterproof than those treated by cationic PU. However, the WVP and anti-yellowing of the NAPU coated fabrics are significantly better than the one treated by CAPU.

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