本研究進行不同鏈段長酯/醚混合PU block copolymer之合成與物性探討。本研究先以4,4-Methylenebis(cyclohexyl isocyanate)（H12MDI）為硬鏈節、polytetramethylene glycol (PTMG1000)為軟鏈節及1,4 Butane diol（1,4 BD）合成末端含diol不同鏈段長之醚型軟鏈段；並以H12MDI及Polycaprolactone diol (PCL1000)合成不同鏈段長的酯型鏈段且末端含-NCO基團，接著再將兩者依所定比例進行不同鏈段長酯/醚混合型PU block copolymer之合成。探討酯/醚混合型PU block copolymer之熱性質與加工布織物物性，並與傳統的PU random copolymer作比較。
研究結果發現，就Tg,s方面，random型PU之Tg,s遠低於block型PU。同一醚型軟鏈長度下酯型軟鏈段增大時其Tgs大幅上升在下降。酯/醚軟鏈鏈段比相同時，軟鏈段愈長者其block型PU之Tg,s愈低。在PU之熱重量損失方面，PU之起始分解溫度以酯/醚混合軟鏈block型PU遠高於純PCL酯型PU(All C)與純PTMG醚型PU(All T) ；PU耐熱性均隨C/T莫耳比的提高而增加；在酯/醚軟鏈節莫耳比相同之下，軟鏈節鏈段長愈長耐熱性愈高。而在軟鏈斷裂解溫度下，random型PU遠低於block型PU；隨酯/醚軟鏈節C/T莫耳比的增加，軟鏈裂解溫度愈高；在酯/醚軟鏈節莫耳比相同之下，軟鏈節鏈段長愈長耐熱性愈高。在耐隆塗佈加工布方面，抗張強度以block型PU強度大於random型PU；另外抗張強度隨著酯/醚軟鏈節C/T莫耳比的增加而提高；在相同酯/醚軟鏈莫耳比下，軟鏈節鏈長愈長者抗張強度愈小。最後就透濕度而言，block型PU(B-1T1C)之透濕度小於random型PU (R-1T)；透濕度隨酯/醚軟鏈節C/T莫耳比愈大而下降；在相同酯/醚軟鏈莫耳比下，軟鏈節鏈長愈長者透濕度愈大。

In this study, first, we synthesized the hydroxyl-terminated ether segment and isocyanate-terminated ester segment with different chain length, respecility. The former procedures by using 4,4-methylenebis(cyclohexyl isocyanate, H12MDI), as hard chain , polytetramethylene glycol with molecule weight of 1000 as soft chain and 1,4-Butane diol. The later was synthesized by polycaprolactone with molecule weight of 1000 and H12MDI. The ether-soft segment and ester-soft segment proceed the polymerization of the polyurethane (PU) to from block copolymer of different length ester-ether segment. The thermal properties of regular PU(block PU) and random PU were compared. In addition, using polymer to coating on nylon fabric,and the tensile strength and the water vapor permeability (WVP) were investigated.
The result showed : The glass transition temperature (Tg,s) of block PUs are lower than random PUs, in the same composition. Within block PUs of low ester /ether molar ratio (C/T molar ratio), Tg,s enhance as decrease of ester-soft segment content. The PUs containing long ester/ether segment have low Tg,s . The block and random type of PUs have higher thermal decompose initiation (Tdi) than PU with single PCL or PTMG soft segment. In addition, block PUs have higher Tdi and thermal decompose of soft segment (Tds) than random PUs. The Tdi and Tds rise up as increase of C/T molar ratio. The PU containing long ester /ether segment has higher Tdi and Tds. Within the properties of coated fabric, tensile strength of fabric treated by the block PUs are higher then random PUs. Tensile strength increase following C/T molar ratio. The low tensile strength as showed while PUs contain short soft segment. The WVP of fabric treated by random PUs are higher then block PUs . The WVP decrease as increase of C/T molar ratio and decrease of long soft segment content.

1.C.H.M.Jacques,” polymer alloys , Blend , block , Craft , and interpenetrating network”, polymer science and technology,plenum press,New York（1997）
2.S.Abuzahr.G.L. Wilkes and Z.Ophir.,”Structure-property behavior of segmented polyether-MDI-butanediol based urethane: effect of composition ratio”.polymer,23,1077
3. D.Dieterich,prog.Org.Coat.,9,281（1981）
4. O.Lorenz and H. Huck,Angew,Makromol.Chem.,72,115（1978）
5.C.Hepburn,polyurethane Elastomer,2nd edition, Elsevier, London,（1991）,Chapter 3 and 10.
6. B.K.Kim and Y.M.Lee ,“Structure-property relationship of
polyurethane ionomer”,Vol.270,pp.956(1992)
7. D.Dieterich ,“Aqueous emulsions,dispersions and solutions of
polyurethanes；Synthesis and properties”,Progress in Organic Coatings”,
Vol.9,pp.281(1981)
8.渡邊昭夫,“水系PU樹酯在化學和纖維加工方面之應用”,Dyeing
Industry, Vol.35.No11,pp.534(1991)
9. C.Hepburn,“Polyurethane Elastomers”,Applied science publishers,
London and New York,pp.50
10. 郭淑琴、顏明雄，酯醚型混合軟鏈節水性PU樹脂之合成、構造與物性及其對耐隆織物之透濕防水加工研究
國立台灣科技大學纖維及高分子工程技術研究所
博士學位論文，中華民國八十七年
11.吳佳鴻、顏明雄，含PEG軟鏈親疏水鏈段block PU copolymer
之合成、物性及其對耐隆織物透濕防水加工之應用
國立台灣科技大學高分子所碩士學位論文，中華民國九十五年
12.蔡毓豪、顏明雄，含PEG-SIPM-PEG軟鏈節PU之合成、物性及
其對耐隆之物透濕防水加工之應用
國立台灣科技大學高分子所碩士學位論文，中華民國九十五年
13. B. Fu, and W. J. Macknight, Rubber Chenistry and Technol. Vol.59, pp896 (1986)
14. A. Lilanonitkul, S. L. Cooper, Adv. Urethane Sci. Technol. Vol.7, pp163(1979)
15. T. R. Hesketh., J. W, C, Van bogart, S. L. Cooper, Polymer Eng. and Sci., V.20, 190, (1980).
16. B. K. Kim, Y. M. Lee., Colloid & Polymer Science, 956-961（1994）
17. S. L. Cooper,”Diffusion of gases through polyurethane Block Polymer”, J. Appl. Poly. Sci., vol.23, pp201 (1978)
18. B. Zorn；“ Porous Polyurethane Film and Coatings” Journal of CoatedFabrics 13，166（1984）
19. S. P. Zoran, J. of Polym. Sci. ; Polym. Phys. Ed. .Vol.27,545 (1989)
20. R.A.Phillips, J.C.Stevenson,M.R. Nagarajan, and S.L.Cooper, “Structure-Property Relationships and Moisture Sensitivity of PDMS/PTMO Mixed Soft Segment Urethane Elastomers”,J. Macromol. Sci.-Phys., B27（2＆3）,pp.245 （1988）
21.R.W.Seymour., g.m.Estes and S.L.Cooper, “Infrared studieds of segmented polyurethane elestomers. I. Hydrogen bonding”, Macromolecules, Vol.3, pp.579（1970）
22. T.A. Speckhard, S.L. Cooper, Rubber Chem. Technol, Vol.59, pp405 (1986)
23. T. O. Ahn﹐S. U. Jung﹐H. M. Jeong S. W. Lee﹐”The properties of
polyurethanes with mixed chain extenders and mixed soft
segments”﹐J. Appl. Polym. Sci., Vol.51﹐P.43~49 (1994).
24. N. S. Schneider, C. S. P. Sung, R. W. Matton, J. L. Illinger,
Macromolecules, V.8, P.62 (1975)
25. R. W. Seymour., G. M. Estes and S. L. Cooper., “Infrared studies of
elastomer Ι, Hydrogen bonding”, Macromolecules, Vol.3, pp.579
(1970)
26. N. S. Schneider, C. S. P. Suns, R.W. Matton, and J. L. llinsger,
Macromolecules，Vol.8, 62. (1975)
27.Yen, M. S.; Cheng, K. L. J. Appl. Poly. Sci., 1994, 52, 1707.
28.Hye-Jin Yoo, Han-Do Kim, “Properties of Crosslinked Blends of Pellethene and Multiblock Polyurethane Containing Poly(ethylene oxide) for Biomaterials”, Journal of Applied Polymer Science, Vol.91,2348-2357(2004)
29.鄭琨琳、顏明雄，H12MDI系PU樹脂之合成、物性及其在織物
透濕防水加工上之應用
國立臺灣工業技術學院纖維及高分子工程技術研究所
博士學位論文，中華民國八十五年
30.Jae Whan Cho, Yong Chae Jung, Yong-Chan Chung, Byoung Chul Chun, “Improved Mechanical Properties of Shape-Memory Polyurethane Block Copolymers through the Control of the Solf-Segment Arrangement”, Journal of Applied Polymer Science, Vol.93,2410-2415(2004)
31.B.K.Kim,J.S.Lee,M.C.Lee,and K.S.Yoon,”Polyurethane – poly(methyl methacrylate) Block Copolymer Dispersions Through Polyurethane Macroiniferters, Journal of Polymer Applied Science,88,1971(2003)
32.B.S.Lee,B.C.Chun, Y.C.Chung,KyungIlSul,and J.W.Cho, ”Structure and Thermomechanical Properties of Polyurethane Block Copolymers with Shape Memory Effect”. American Chemical Society,34,6431(2001)
33.J.H.Lee,Y.M.Ju, and D.M.Kim,”Platelet adhesion onto segment polyurethane film surfaces modified by addition and crosslinking of PEO-containing block copolymer, Biomaterials ,21,683(2000).
34.J.H.Yang, B.C.Chun, Y.C.Chung, and J.H.Cho, ”Comparison of thermal/ mechanical properties and shape memory effect of polyurethane block-copolymer with planar or bent shape of hard segment”,polymer,44,3251(2003).
35.B. Gebben, “A Water Vapor-permeable membrane from block copolymers of poly(butylenes terephthalate) and polyethylene oxide”, Journal of Membrane Science 113 323-329(1996)
36.Daniel Cohn, Theodor Stern, M. Fernanda Gonzalesz, Julia Epstein, “Biodegradable poly(ethylene oxide)/poly(ε-caprolactone) multiblock coplymers”, John Wiley & Sons,Inc. 273-281 (2001)
37.On the study of polyurethane ionomer - Part I
38.蕭伯卓、顏明雄，非離子水性PU之合成,構造與物性及其對PET
織物親水加工之研究
國立台灣科技大學纖維及高分子研究所
碩士學位論文，中華民國八十七年