本研究以PEG、PDMS軟鏈或PEG/PDMS混合軟鏈為軟鏈節合成水性PU，探討以PU摻合方式及共聚合方式依不同PDMS含量比將疏水性PDMS導入於親水性PU中，其成形薄膜之熱性質、表面結構及物性。另外亦合成酯型(polycaprolactone glycol, PCL 1250)和醚型(polyethylene glycol, PEG 600, 1000 2000; Polypropylene glycol, PPG 1000,和 polytetramethylene glycol, PTMG 1000)水性PU，進而將不同含量PDMS-PU分別摻合於各類酯或醚型水性PU中，探討其成型薄膜之結晶性、熱性質與物性探討各種單獨與摻和PU水溶液與成型薄膜之結晶性、熱性質與物性與表面性質分析。最後，本研究探討個別及摻和水性PU prepolymer之水溶液性質及其對Nylon 織物表面性質之影響。結果發現摻和方式下PU中少量導入PDMS-PU成份，在成型時因PDMS會往PU表面遷徙，改變PU結晶性而造成PU熱性質及模數的大幅提升；但共聚合方式下導入PDMS其薄膜物性只能得到微幅的提升。X-ray構造分析結果發現，醚型PU P1000與E2000於PDMS-PU摻合比5%時結晶性提升，而酯型PU則於摻合比5%結晶性下降。DSC熱性質方面，除C1250以外其餘PU均在PDMS-PU摻合比 5~10%時Tg,s有最大值出現。醚型水性PU摻合PDMS-PU其Tm,h均提升且出現最高值，酯型水性PU摻合PDMS-PU其Tm,h大幅度降低。另外，E2000之吸收熱焓為最高。機械強力方面，於低PDMS-PU摻合比時以T1000之應力提升最大，約提升20~30 Mpa。而酯型PU C1250摻合PDMS-PU其應力值降抵。整體來說E1000具有最佳應力與應變之物性平衡。就摻和物分散液之粒徑分佈方面，醚型WBPU摻和物不論何者軟鏈節，隨PDMS-PU含量增大WBPU之粒徑與粒徑分散度均提高，其中酯型者(C1250)隨PDMS-PU摻和量增大粒徑急增且均大於單獨PDMS-PU。WBPU水溶液表面張力方面，WBPU摻和PDMS-PU其表面張力均下降，其中除了酯型系列外，於摻和5% PDMS-PU之WBPU水溶液表面張力均微幅提升，隨後降低趨近至PDMS-PU值附近。接觸角方面，水溶液對Nylon織物接觸角隨PDMS-PU摻和比增加，其接觸角隨之降低；成型薄膜對水之接觸角在少量PDMS-PU摻和時，接觸角大幅增大。摻和物成型薄膜以ATR-FTIR分析表面構造，發現除了酯型系列外，在低PDMS-PU含量下Si含量即遽然增大且趨近於單獨PDMS-PU之Si含量。除疏水性的pC1250外水滴消失時間隨PDMS-PU prepolymer摻和量增加而增大，且在低含量(5~10%)PDMS摻和時水滴消失時間即大幅提升，而水滴消失時間與加工液對Nylon織物之接觸角有關。5% PDMS-PU prepolymer摻和物對Nylon壓吸織物之乾燥速率均較原布增快，於15分鐘時水分率達10%左右。

First, the surface structure and physical properties of polyethylene glycol series polyurethane (PEG-PU) membranes, in which were introduced hydrophobic polydimethylsiloxane (PDMS) component by the procedure of PU blending or of soft-segment copolymerization, were studied in this investigation. Second, this research utilized different types of soft segments such as ester type Polyol (polycaprolactone glycol, PCL 1250), and ether type Polyol (polyethylene glycol, PEG 600, 1000, 2000; Polypropylene glycol, PPG 1000; polytetramethylene glycol, PTMG 1000) to synthesize various ester and ether types of waterborne polyurethanes (WBPUs). Furthermore, we used PDMS as a soft segment to synthesize PDMS-PU, which in different amounts was blended with various kinds of WBPU to study the neat WBPU and the blended WBPU solution properties and the crystallization, thermal, physical properties and surface structures of the membrane formations. Finally, we used PDMS as a soft segment to synthesize PDMS-PU prepolymer, which in different amounts was blended with various kinds of waterborne polyurethane prepolymers to demonstrate the solution properties of single and blended waterborne polyurethane prepolymer and its surface properties of nylon-treated fabrics. We have discovered that under the blending method of adding a small amount of PDMS-PU into PU, while forming a membrane, PDMS will migrate towards the PU membrane surface, changing the PU’s crystallizing property. This greatly increases PU’s thermal properties and modulus. However, under the method of copolymerization by introducing PDMS soft segment, the physical properties of the membrane are improved slightly. According to X-ray analysis, the ether-based PUs, synthesized from soft segment of PPG 1000 or PEG 2000, were found a maximum crystallinity at 5% blending ratio of PDMS-PU, but ester-based PUs, synthesized from soft segment of PCL 1250, had a declined crystallinity at 5% blending ratio. The analysis of the differential scanning calorimetric (DSC) revealed that Tg,s of PUs were the highest as the blending ratio of PDMS-PU was at a 5%~10%, except in the case of PU from PCL 1250. Moreover, Tm,h of ether-based PUs had maximum values, but Tm,h of ester-based PU greatly reduced when PU with PCL 1250 was blended with PDMS-PU. In addition, the PU from PEG2000 had the highest enthalpy. In terms of the mechanical property analysis, the stress of ether-based PUs would be elevated as PUs were blended with a small amount of PDMS-PU, and stress of PU from PTMG 1000, had increased the greatest value (20-30 Mpa). On the other hand, ester-based PU from PCL 1250 blended with PDMS-PU would reduce its stress. On the whole, the stress and strain of PU from PEG 1000 had the excellent balance. In PDMS-PU blending with WBPUs, no matter which kinds of WBPU are, the particle sizes of solution still increase with the increase of the blending amount of PDMS-PU. Among the various WBPUs, the ester type PCL 1250 series, its particle sizes is increased with the increase of blending amount of PDMS-PU, and is further larger than the particle size of neat WBPU. Except C1250 (polycaprolactone glycol) series, the WBPU solution blended with 5% PDMS-PU has a slight increase of surface tension, and subsequently declines following 5%. With an increase of PDMS-PU content, the contact angle of various WBPU to nylon fabrics decreases. With an increase of molecular weight of PEG soft segment, the contact angle of WBPU solution was larger. The C1250 of ester type WBPU has the largest a drop of extent for the contact angle. In addition, the contact angle of water to the waterborne PU membrane is increased greatly and immediately, when there is small amount of PDMS-PU blending. In the surface structure of ATR-FTIR analysis, except the ester type C1250 series, the Si content on the membrane surface suddenly increases, getting close to the Si value of single PDMS-PU. On the other hand, except the hydrophobic pC1250 series, the drop absorption time of treated fabrics were increased with an increase of PDMS-PU content. And it increased greatly and immediately when the content of PDMS-PU blending was low (5~10%). The result of drop absorption time was related to the contact angle of PU preoplymer solution to nylon fabric. For the blended treated fabrics, the drying time was faster than untreated fabric, and moisture ratio reached to about 10% in 15 minutes.

Scheme A Synthesis of waterborne polyurethane 16
Scheme B Synthesis of waterborne polyurethane 49
Scheme C Synthesis of WBPU prepolymer. 111

Table 1 Thermal properties of WBPU with PEG and PDMS mixture soft segment by the procedure of PU blending and by soft segment copolymerization. 26
Table 2 Dynamic Mechanical Thermal Analysis of WBPU with PEG and PDMS mixture soft segment by the procedure of PU blending and by soft segment copolymerization. 31
Table 3 Element Composition Data Measured form the Surface of WBPU with PEG and PDMS mixture soft segment by the procedure of PU blending and by soft segment copolymerization. 33
Table 4 The synthetic constitutions of WBPU polymers. 50
Table 5 The physical properties of WBPUs measured by blending WBPUs of various soft segment types with PDMS-PU. 66
Table 6 The physical properties of WBPUs measured by blending WBPUs of molecular weight of different PEG soft segments with PDMS-PU. 67
Table 7 The solution properties and surface properties of membrane for different soft segment types of WBPU. 84
Table 8 The solution properties and surface properties of membrane for different molecular weight of PEG soft segment of WBPU by blended with PDMS-PU. 89
Table 9 The solution properties and surface properties of membrane for different soft segment types of WBPU by blended with PDMS-PU. 90
Table 10 Atomic compositions of surface from ATR-FTIR for different soft segment types of WBPU membranes by blending with PDMS-PU. 102
Table 11 The symbols and compositions of WBPU prepolymers. 112
Table 12 The solution properties and surface properties of WBPU prepolymers from different soft segments. 119

Figure 1 NCO(%) residual value of PU prepolymer for different reaction times in the prepolymerization step. 21
Figure 2 FTIR analyses of WBPU membranes formed by blending different weight ratios of PDMS-PU with PEG-PU or from the mixed PEG and PDMS soft segments copolymerized PU with various PDMS content weight ratios. 22
Figure 3 DSC analysis of WBPU of PEG and PDMS mixture soft segment with blending method (A:PEG2000, B:B2000-5%, C:B2000-10%, D:BE2000-15%, E:BE2000-25%, F:BE2000-50%, G:BE2000-75%, H:PDMS2000) and copolymer method (a:PEG2000, b:C2000-5%, c:C2000-10%, d:C2000-15%, e:C2000-25%, f:C2000-50%, g:C2000-75%, h:PDMS2000). 25
Figure 4 Thermal property of WBPU with PEG and PDMS mixture soft segment by the procedure of PU blending ( ) and by soft segment copolymerization ( ). 27
Figure 5 DMA analysis of WBPU with PEG and PDMS mixture soft segment by the procedure of PU blending (upper) and by soft segment copolymerization (lower). 30
Figure 6 Surface element analysis of WBPU with PEG and PDMS mixture soft segment by the procedure of PU blending and by soft segment copolymerization. 34
Figure 7 Water vapor permeability (WVP) and water resistance versus PDMS content of coated nylon fabrics with WBPU 37
Figure 8 The relationship between water vapor permeability (WVP) and water resistance versus PDMS content of coated nylon fabrics with WBPU 38
Figure 9 SEM diagrams of Nylon fabrics coated with PEG and PDMS mixture soft segment by the procedure of WBPU blending and by soft segment copolymerization. The B% and C% show the PDMS content ratio in WBPU from mixture method. (B: blending and C: copolymerization) 40
Figure 10 The relation between moisture and time for various mixture method at 90℃. 41
Figure 11 FTIR spectrum of WBPUs of different soft segment types. 53
Figure 12 FTIR analysis of WBPUs analyzed by blending WBPUs of different soft segment types with PDMS-PU. 55
Figure 13 FTIR analysis of WBPUs analyzed by blending WBPUs of molecular weight of different PEG soft segments with PDMS-PU. 56
Figure 14 X-ray analysis of WBPU membranes of different soft segment types. 58
Figure 15 X-ray analysis of WBPU membranes analyzed by blending WBPUs of different soft segment types with PDMS-PU. 59
Figure 16 X-ray analysis of WBPU membranes analyzed by blending WBPUs of molecular weight of different PEG soft segments with PDMS-PU. 61
Figure 17 DSC analysis of WBPUs of various soft segment types and PDMS-PU blends. 63
Figure 18 Thermal properties of WBPU membranes measured by blending WBPUs of different soft segments with PDMS-PU at various blending ratios. 68
Figure 19 Stress-strain curves of WBPU membranes measured by blending WBPUs of different soft segment types with PDMS-PU. 70
Figure 20 Stress-strain curves of WBPU membranes measured by blending WBPUs of molecular weight of different PEG soft segment with PDMS-PU. 71
Figure 21 Stress of WBPU membranes measured by blending WBPUs of different soft segments with PDMS-PU at various blending ratios. 73
Figure 22 Strain of WBPU membranes measured by blending WBPUs of different soft segments with PDMS-PU at various blending ratios. 74
Figure 23 Dispersion of Particle size in distribution of the different soft segment types of WBPUs. 83
Figure 24 Surface tension of WBPU dispersions. 87
Figure 25 Dispersion of particle size in distribution for PEG1000 soft segment of WBPUs by blended with PDMS-PU. 91
Figure 26 Dispersion of particle size in distribution for PCL1250 soft segment of WBPUs by blended with PDMS-PU. 92
Figure 27 Comparison of dispersion of average particle size of WBPU dispersion blended with various soft segment types and different blend ratio of PDMS-PU. 95
Figure 28 Comparison of variance particle size of WBPU dispersion blended with various soft segment types and different blend ratio of PDMS-PU. 96
Figure 29 Comparison of critical surface tension of WBPU dispersion blended with various soft segment types and different blend ratio of PDMS-PU. 97
Figure 30 Comparison of contact angle of WBPU dispersion blended with various soft segment types and different blend ratio of PDMS-PU to Nylon fabrics. 100
Figure 31 Comparison of contact angle of water to WBPU dispersion blended with various soft segment types and different blend ratio of PDMS-PU. 101
Figure 32 Atomic compositions of surface from ATR-FTIR for different soft segment types of WBPU membranes by blended with PDMS-PU on the blend ratio. 103
Figure 33 FTIR spectrum of WBPU prepolymer from different soft segment types. 115
Figure 34 The particle size distribution of WBPU prepolymer dispersions from different soft segments. 118
Figure 35 The surface tension of WBPU prepolymer dispersions. 121
Figure 36 Comparison of average particle size (a) and variance particle size (b) of PDMS-WBPU prepolymer blends. 124
Figure 37 Comparison of critical surface tension of PDMS-WBPU prepolymer dispersion blends from different soft segments. 125
Figure 38 Comparison of contact angle of PDMS-WBPU prepolymer dispersion blends from different soft segments to nylon fabrics. 126
Figure 39 The add-on before washing (a) and add-on after washing (b) for blending different PDMS content ratios of WBPU prepolymers on treated nylon fabrics. 129
Figure 40 The vertical wicking height and PDMS content ratio for treated nylon fabrics. 132
Figure 41 The drop absorption time and PDMS content ratio for treated nylon fabrics. 133
Figure 42 The drop absorption time and contact angle of PDMS-PU prepolymer blends. 134
Figure 43 The moisture ratio and drying time at 90℃ for treated nylon fabrics with single WBPU prepolymers (a) and PDMS-WBPU blends (b). 136