嵌段式聚氨基甲酸酯(Segmented Polyurethane，SPU)是由軟質段與硬質段交替相連之的-(HS)n-型多團聯嵌段式共聚合物。PU因軟、硬質段可選擇之結構種類多，所擁有的化學結構種類相當多，加上其內部特殊的微相型態，反應出相當多變的性質；但也因此使得PU的型態、結構與性質間的關係複雜化。因此，我們藉由合成完全相分離的PU來探討此微區型態及型態變化的關係。
本實驗室過去曾探討自行合成的水性PU(Waterbone Polyurethane，WPU)型態及結構，在結構變化與物性間的關係有重要發現，搭配用穿透式電子顯微鏡對於微相結構的觀察結果，建立了三個水性PU的模式；而此水性PU特有之雙連續相網狀結構(Phase separated bicontinuous network structure)也使此種水性PU具有高透明性、高拉伸剛性、高堅韌性、耐高溫且易加工等特性。本研究將原本水性PU具水溶性的離子基部份改質為不具水溶性的基團，利用兩階段溶液聚合法合成非離子型PU，希望維持其材料特性並期望能將此高分子實用化。
本研究自行合成兩種醯胺-雙醇類作為取代水性PU離子基(DMPA)的巨大基團(Bulky group)，搭配FT-IR、H-NMR及MS進行結構鑑定。而後將以兩階段溶液聚合法分別導入此兩種巨大基團進行硬質段部份的改質，由不同巨大基團添加量與不同硬質段含量，再搭配FT-IR、DSC、DMA及拉力機的分析，探討巨大基團對PUU結構與性質的影響。

A series of nonpolar segmented polyurethaneurea(PUU) with bulky side group have been synthesized and their structure-property relationship have been investigated. The bulky group is a molecule that can make a space about 1nm beside the backbone to interfere the hard segment domain. The PUU based on 4,4’-dicyclohexylmethane diisocyanate (H12MDI), polyisoprene(Poly-IP,MW 2500),ethylenediamine(EDA) and two kinds of bulky groups are synthesized by two-step solution polymerization. Hard-segment content (35,45,55,70 wt%) and bulky group contents (0,4.5,8,10,15 wt%) are varied and their effect on the properties are studied. Properties are studied by Fourier-Transform Infrared(FT-IR),Differential Scanning Calorimetry(DSC),Dynamic Mechanical Analysis(DMA) and tensile-strain testing.
The bulky groups (I and II) are two kinds of self-synthesized amide-diol that are reacted by trimethylacetic acid(TMAA) and dipropylacetic acid (DPAA) separately with 2-Amino-2-methyl-1,3-propanediol(AMPD). Chemical structures of bulky groups are characterized by FT-IR, Nuclear Magnetic Resonance(NMR) and Mass Spectroscopy (MS).The yields of bulky I and II are about 42.5% and 40.7%.
The introduction of bulky group result in the C=O stretching of urea and urethane both shift to higher wavenumbers means that the hydrogen bonding strength is reduced. The storage modulus, Young’s modulus and tensile strength are increasing with increasing hard-segment content, but elongation at break is decreasing on the contrary. As the bulky group exists in PUU, the hard-segment domain may become loosely that is to say intermolecular force (cohesive energy) between hard segments is weakening. So the mechanical properties are reduced including Young’s modulus, tensile strength and elongation at break.

1. D. J. Hourston , G. Williams , R. Satguru , J. D. Padget , D. Pears ,
“Structure-property study of polyurethane anionomers based on
various polyols and diisocyanates.” ,
J. Appl. Polym. Sci., v66 , p2035 , 1997
2. N. S. Schneider , C. R. Desper , J. L. Illinger , A. O. King , D. Barr ,
“Structural studies of crystalline MDI-based polyurethanes.” ,
J. Macromol. Sci. Phys. , B11 , p527 , 1975
3. M. Xu, W. J. MacKnight, C. H. Y. Chen, E. L. Thomas ,
“Structure and morphology of segmented polyurethanes: 1. Influence
of incompatability on hard-segment sequence length.” ,
Polymer , v24 , p1327 , 1983
4. C. Arnold and J.R. , “Development and Characterization of En-7: a
Ferric Acetylacetonate Catalyzed Polybutadiene-Based Elastomer.” ,
J. Elast. Plast. , v6 , p238 , 1974
5. C. Li , X. Yu , T. A. Speckhard , S. L. Cooper , “Synthesis and
properties of polycyanoethylmethylsiloxane polyurea urethane
elastomers: A study of segmental compatibility.” ,
J. Polym. Sci. Polym. Phys. Ed. , v26 , p315 , 1988
6. J. W. C. Van Bogart , P. E. Gibson , S. L. Cooper , “Structure-property
relationships in polycaprolactone-polyurethanes. ” ,
J. Polym. Sci. Polym. Phys. Ed. , v21 , p65 , 1983
7. D. B. Klinedinst , E. Yilgör , I. Yilgör , F. L. Beyer , G. L. Wilkes ,
“Structure–property behavior of segmented polyurethaneurea
copolymers based on an ethylene–butylene soft segment.” ,
Polymer , v46 , p10191 , 2005
8. T. A. Speckhard , P. E. Gibson , S. L. Cooper , V. S. C. Chang , J. P.
Kennedy , “Properties of polyisobutylene polyurethane block
copolymers: 2. Macroglycols produced by the ‘inifer’ technique”,
Polymer , v26, p55 , 1985
9. K. Ono , H. Shimada , T. Nishimura , S. Yamashita , H. Okamoto , Y.
Minoura , “Effects of number-average molecular weight of liquid
Hydroxy-terminated polybutadiene on physical properties of the
elastomers.” , J. Appl. Polym. Sci. , v21, p3223 , 1977
10. N. S. Schneider , R. W. Matton , “Thermal transition behavior of
polybutadiene containing polyurethanes.” ,
Polym. Eng. Sci. , v19 , p1122 , 1979
70
11. C. M. Brunette , S. L. Hsu , W. J. Macknight , N. S. Schneider ,
“Structural and mechanical properties of polybutadiene-containing
polyurethanes.” , Polym. Eng. Sci. , v21, p163 , 1981
12. B. Bengtson , C. Feger , W. J. MacKnight , N. S. Schneider ,
“Thermal and mechanical properties of solution polymerized
segmented polyurethanes with butadiene soft segments.” ,
Polymer , v26, p895 , 1985
13. C. Li , S. L. Goodman , R. M. Albrecht , and S. L. Cooper ,
“Morphology of segmented polybutadiene-polyurethane elastomers.” ,
Macromolecules , v21 , p2367 , 1988
14. T. K. Chen , C. J. Hwung , C. C. Hou , “Effects of number-average
molecular weight of network chain on physical properties of
cis-polybutadiene-containing polyurethane” ,
Polym. Eng. Sci. , v32 , p115 , 1992
15. X. H. Yu , M. R. Nagarajan , T. G. Grasel , P. E. Gibson , S. L. Cooper ,
“Polydimethylsiloxane-polyurethane elastomers: Synthesis and
properties of segmented copolymers and related zwitterionomers. ” ,
J. Polym. Sci. Polym. Phys. Edn. , v23 , p2319 , 1985
16. R. A. Phillips; J. Castles Stevenson; M. R. Nagarajan; S. L. Cooper ,
“Structure-property relationships and moisture sensitivity of
PDMS/PTMO mixed soft segment urethane elastomers.” ,
J. Macromol. Sci. Phys. , v27, p245 , 1988
17. T. A. Speckhard and S. L. Cooper , “Ultimate tensile properties of
segmented polyurethane elastomers: factors leading to reduced
properties for polyurethanes based on nonpolar soft segments.” ,
Rubber Chem. Technol. , v59 , p405 , 1986
18. P. W. Ryan , “Polyurethane based on hydroxyl- terminated
polybutadienes.” , Brit. Polym. J. , v3, p415 , 1971
19. G. N. Petrov, A. S. Lykin , “Synthesis of oligomers with reactive end
groups and elastomers derived from them. Review.” ,
Polym. Sci. U.S.S.R. , v20 , p1351 , 1977
20. D. K. Lee , H. B. Tsai , “Properties of segmented polyurethanes
derived from different diisocyanates.” ,
J. Appl. Polym. Sci. , v75 , p167 , 2000
21. J. Blackwell and K. H. Gardner , “Structure of the hard segments in
polyurethane elastomers.” , Polymer , v20 , p13 , 1979
71
22. J. Blackwell, M. R. Nagarajan and T. B. Hoitink , “Structure of
polyurethane elastomers. X-ray diffraction and conformational
analysis of MDI-propandiol and MDI-ethylene glycol hard
segments.” , Polymer , v22 , p1534 , 1981
23. J. Blackwell, M. R. Nagarajan and T. B. Hoitink , “Structure of
polyurethane elastomers effect of chain extender length on the
structure of MDI-diol hard segments.” , Polymer , v23 , p950 , 1982
24. Y. Camberlin , J. P. Pascault , J. M. Letoffé , P. Claudy , “Model hard
segments from diphenyl methane diisocyanate and different chain
extenders, and corresponding linear block polyurethanes. ” ,
J. Polym. Sci. Polym. Chem. Ed. , v20, p1445 , 1982
25. M. V. Pandya; D. D. Deshpande; D. G. Hundiwale; U. R. Kapadi ,
“Cast Polyurethanes: Effect of Chain Extenders on Thermal
Mechanical and Dynamic Mechanical Properties.” ,
J. Macromol. Sci. Chem. , v24 , p527 , 1987
26. R. Sandén , N. Wingborg , “Bonding a HTPB liner to modern rocket
case materials.” , J. Appl. Polym. Sci. , v37, p167 , 1989
27. S. Vlad , S. Oprea , “Chain extender and diisocyanate amount effects
on the thermal, mechanical and wettability properties of some
polyurethane elastomers.” , e-Polymer , No.027 , p1 , 2008
28. Z. S. Petrovi , I. Javni , “The effect of soft-segment length and
concentration on phase separation in segmented polyurethanes. ” ,
J. Polym. Sci. , B , Polym. Phys. , v27 , p545 , 1989
29. D. J. Martin , G. F. Meijs , G. M. Renwick , P. A. Gunatillake and
S. J. McCarthy , “Effect of soft-segment CH2/O ratio on morphology
and properties of a series of polyurethane elastomers.” ,
J. Appl. Polym. Sci. , v60 , p557 , 1996
30. H.D. Kim , T.J. Lee , J.H. Huh , D.J. Lee , “Preparation and properties
of segmented thermoplastic polyurethane elastomers with two
different soft segments.” , J. Appl. Polym. Sci. , v73 , p345 , 1996
31. D. J. Meier , “Network statistics of block copolymers and filled
elastomers : Swelling equilibria.” ,
Appl. Polym. Symp. , N.2 , p67 , 1974
32. C. Li , S. L. Cooper , “Direct observation of the micromorphology of
polyether polyurethanes using high-voltage electron microscopy.” ,
Polymer , v31, p3 , 1990
72
33. S. Mitsuhiro, S. Masakatsu , S. Shinichi , Y. Tomoyuki , N. Shunji ,
“Structure characterization of polyurethane containing
poly(dimethylsiloxane).” , Macromolecules , v24 , p6254 , 1991
34. L. M. Leung , J. T. Koberstein , “Small-angle scattering analysis of
hard-microdomain structure and microphase mixing in polyurethane
elastomers.” , J. Polym. Sci., Polym. Phys. Ed. , v23 , p1883 , 1985
35. 陳柏宏，「完全相分離PU 之完整形態硏究」，國立中央大學，碩
士論文，民國89 年
36. 邱家永，「嵌段式PU 的結構與性質(I)」，國立中央大學，博士論
文，民國86 年
37. 謝添壽，「嵌段式PU 的結構與性質(II)」，國立中央大學，博士論
文，民國87 年
38. D. Dieterich , “Aqueous emulsions, dispersions and solutions of
polyurethanes; synthesis and properties.” ,
Prog. Org. Coat. , v9 , p281 , 1981
39. H. Takizawa , Y. Yoshioka , M. Morigaki , “Silver halide
photographic material.” , European Patent , EP0706086A1
40. E. Sobol , M. Bialer and B. Yagen , “Tetramethylcyclopropyl
Analogue of a Leading Antiepileptic Drug, Valproic Acid. Synthesis
and Evaluation of Anticonvulsant Activity of Its Amide Derivatives.” ,
J. Med. Chem. , v47 , p4316 , 2004
41. M. Levi , B. Yagen and M. Bialer , “Pharmacokinetics and
Antiepileptic Activity of Valproyl Hydroxamic Acid Derivatives.” ,
Pharm. Res. , v14 , p213 , 1997
42. Pavia , Lampman , Kriz , 3rd Ed. , Introduction to SPECTROSCOPY
43. Yong-Cheng Ning , Structural Identification of Organic Compounds
with Spectroscopic Techniques
44. K.Downard , Mass Spectrometry A Foundation Course
45. Skoog , Holle , Nieman , Principles of Instrumental Analysis
46. H. Ishihara; I. Kimura; K. Saito; H. Ono , “Infrared studies on
segmented polyurethane-urea elastomers” ,
J. Macromol. Sci. , Phys. , v10 , p591 , 1974
73
47. T. A. Speckhard , G. Ver Strate , P. E. Gibson , S. L. Cooper ,
“Properties of polyisobutylene-polyurethane block copolymers: I.
Macroglycols from ozonolysis of isobutylene-isoprene copolymer.” ,
Polym. Eng. Sci. , v23, p337 , 1983
48. T. A. Speckhard , K. K. S. Hwang and S. L. Cooper , “Properties of
polyisobutylene polyurethane bloch copolymers - 3.Hard segments
based on 4,4’-dicyclohexylmethane diisocyanate (H12MDI) and
butane diol.” , Polymer , v26, p70 , 1985
49. S. W. Wong , G. J. Cormier and K. C. Frisch , “Structure-Property
relationships of transparent cycloaliphatic polyurethane elastomers .” ,
Polym. Mater. Sci. Eng. , v49 , p63 , 1983
50. C.S. Wang and D. J. Kenney , “Effect of Hard Segments on
Morphology and Properties of Thermoplastic Polyurethanes.” ,
J. Elast. Plast. , v27 , p182 , 1995
51. C. S. Paik Sung , T. W. Smith , and N. H. Sung , “Properties of
Segmented Polyether Poly(urethaneureas) Based of 2,4-Toluene
Diisocyanate. 2.Infrared and Mechanical Studies.” ,
Macromolecules , v13 , p117 , 1980