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。
本實驗室過去在非極性PU的研究，發現由MDI-BD及cis-HTPB，且硬質段含量為55%所合成出相分離的非極性PU，由TEM觀察發現其型態為長圓柱狀(cylinder)或是平板狀(lamellar)。由此結果本實驗在硬質段中導入在側邊帶有巨大基團的分子去破壞其硬質段的平板結構。巨大基團能使主鏈的側邊產生具有1 nm的空間去影響硬質相的區域。PU的組成是由MDI、PolyIP、BD、bulky group進行兩階段溶液聚合法導入此巨大基團進行硬質段部份的改質，藉由添加不同量的巨大基團與硬質段含量的改變、搭配FT-IR、DSC、DMA及機械性質的分析，探討巨大基團對PU結構與性質的影響。

Segmented Polyurethane are linear block copolymers of the -(HS)n- type. Segmented polyurethane possesses enormous amount of chemical
structures and its Micro-phase structure could react to form a variety of
properties, hence it complicates its own as well. In order to probe into the
mutual actions between its properties and compositions, we synthesize the nonpolar PU elastomer into a complete whole.
Our previous research on nonpolar polyurethane, the experiment utilized better-performed phase-separated nonpolar-based PU, synthesized by MDI- BD, cis-HTPB and hard segment content 55%, direct observation the morphology by TEM, discover its shape was a long cylinder or lamellar form, which it’s in a regular state. With this in mind, add bulky group into Hard-segment, studying for the hard-segment of structure and properties.
The structure-property relationships of a series of nonpolar segmented polyurethane(PU) with bulky side group were investigated. The bulky group is a molecule that can make a space about 1nm beside the backbone to interfere the hard segment domain. The PU based on 4,4-Diphenylmethane diisocyanate (MDI), polyisoprene(Poly-IP,MW 2500), 1,4-Butanediol (BD) and bulky group are synthesized by two-step solution polymerization. Hard-segment content (35,45,55,65 wt%) and bulky group contents (0,4,8,12 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.

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. 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
3. 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
4. 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
5. 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
6. 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
7. 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
8. 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
9. C. Arnold and J.R. , “Development and Characterization of En-7: a Ferric Acetylacetonate Catalyzed Polybutadiene-Based Elastomer.” ,
J. Elast. Plast. , v6 , p238 , 1974
10. 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
11. J. W. C. Van Bogart , P. E. Gibson , S. L. Cooper , “Structure-property relationships in polycaprolactone-polyurethanes. ” , J. Appl. Polym. Sci. Phys. Ed. , v21 , p65 , 1983
12. 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
13. C. Li , S. L. Goodman , R. M. Albrecht , and S. L. Cooper , “Morphology of segmented polybutadiene-polyurethane elastomers.” , Macromolecules , v21 , p2367 , 1988
14. 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
15. 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
16. N. S. Schneider , R. W. Matton , “Thermal transition behavior of polybutadiene containing polyurethanes.” ,
Polym. Eng. Sci. , v19 , p1122 , 1979
17. 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
18. 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
19. 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
20. 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
21. P. W. Ryan , “Polyurethane based on hydroxyl- terminated polybutadienes.” , Brit. Polym. J. , v3, p415 , 1971
22. 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
23. R. Bonart , “Thermoplastic elastomers”, Polymer , v20 , p1389 , 1979
24. J. Blackwell and K. H. Gardner , “Structure of the hard segments in polyurethane elastomers.” , Polymer , v20 , p13 , 1979
25.J.Blackwell , M.R. Nagarajan ,“Conformational analysis of poly(MDI-butandiol) hard segment in polyurethane elastomers” , Polymer , v22 , p202 , 1981
26. J. Blackwell, M. R. Nagarajan , T. B. Hoitink , “Structure of polyurethane elastomers effect of chain extender length on the structure of MDI-diol hard segments.” , Polymer , v23 , p950 , 1982
27. J. Blackwell, M. R. Nagarajan , 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
28. R. W. Seymour, Stuart L. Cooper ,“Thermal Analysis of Polyurethane Block Polymers”, Macromolecules , v6 , p48 , 1973
29. J. T. Koberstein, T. P. Russell ,“Simultaneous SAXS-DSC study of multiple endothermic behavior in polyether-based polyurethane block copolymers”, Macromolecules , v19 , p714 , 1986
30. T. R. Hesketh, J. W. C. Van Bogart, S. L. Cooper ,“Differential scanning calorimetry analysis of morphological changes in segmented elastomers ” , Polymer Engineering and Science , v20 , p190 , 1980
31. L. M. Leung, J. T. Koberstein ,“Small-angle scattering analysis of hard-microdomain structure and microphase mixing in polyurethane elastomers ”, J. Appl. Polym. Sci. Phys. Ed. , v23 , p1883 , 1985
32.D. J. Meier , “Network statistics of block copolymers and filled elastomers : Swelling equilibria.” , Appl. Polym. Symp. , v2 , p67 , 1974
33. C. Li , S. L. Cooper , “Direct observation of the micromorphology of polyether polyurethanes using high-voltage electron microscopy.” ,
Polymer , v31, p3 , 1990
34. S. Mitsuhiro, S. Masakatsu , S. Shinichi , Y. Tomoyuki , N. Shunji , “Structure characterization of polyurethane containing
poly(dimethylsiloxane).” , Macromolecules , v24 , p6254 , 1991
35. Robert M. Briber, Edwin L. Thomas, “The structure of MDI/BDO-based polyurethanes: Diffraction studies on model compounds and oriented thin films. ”, J. Polym. Sci., Polym. Phys. Ed. , v23 , p1915 , 1985
36. J.A. Miller, G. Pruckmeyer, J.E. Epperson, and S.L. Cooper, “The thermal response of the polyether soft segment chain conformation in a polyurethane block copolymer measured by small-angle neutron scattering.”, Polymer, v26, p1915 , 1985
37. J.A. Miller, S.L. Cooper, C.C. Han, and G. Pruckmeyer, “Small-angle neutron scattering from a polyurethane block copolymer.” , Macromolecules, v17, p1063 , 1984
38. 王啓蒼，「巨大基團的合成及巨大基團對Polyurethane urea結構與性質的影響」，國立中央大學，碩士論文，民國97年
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.J.F. Rabek, “Experimental Methods in Polymer Chemistry”, Wiley New York, p562 , 1980
44.Takayuki Murayama, “Dynamic mechanical analysis of polymeric material”, Elsevier Scientific Publishing, 1978
45. 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
46. 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
47. 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
48. C.S. Wang and D. J. Kenney , “Effect of hard segments on morphology and properties of thermoplastic polyurethanes.” ,
J. Elast. Plast. , v27 , p182 , 1995
49. S. L. Cooper, and G. M. Estes, “Multiphase Polymer”, Adv. Chem. Ser.176, American Chemical Society,Washington D. C., 1979.
50. M. Serrano, W. J. Macknight, E. L. Thomas, J. M. Ottno, “Transport-morphology relationships in segmented polybutadiene polyurethanes: 2. Analysis .” , Polymer , v28 , p1674 , 1987
51. J. T. Koberstein, A. F. Galambos, L. M. Leung, “Compression-molded polyurethane block copolymers. 1. Microdomain morphology and thermomechanical properties .” , Macromolecules , v25 , p6195 , 1992
52. C. Z. Yang, K. K. S. and S. L. Cooper, “Morphology and properties of polybutadiene- and polyether-polyurethane zwitterionomers .” , Macromol. Chem. , v184 , p651 , 1983
53. T. A. Speckhard, K. K. S. Hwang, C. Z. Yang, W. R. Laupan and S. L. Cooper, “Properties of segmented polyurethane zwitterionomer elastomers .” , J. Macromol. Sci-Phys. , v23 , p175 , 1984
54. J. T. Koberstein, L. M. Leung, “Compression-molded polyurethane block copolymers. 2. Evaluation of microphase compositions .” , Macromolecules. , v25 , p6205 , 1992
55. Y. Camberlin, J. P. Pascault, M. Letoffe and 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
56. I. Yilgor, J. S. Rifle, G. L. Wilkes, J. E. McGrath, “Siloxane-urea segmented copolymers .” , Polym. Bull. , v8 , p535 , 1982
57. Y. Camberlin, J. P. Pascault, M. Letoffe and P. Claudy, “Synthesis and DSC study of model hard segments from diphenyl methane diisocyanate and butane diol .” , J. Polym. Sci. Polym. Chem. Ed. , v20 , p383 , 1982
58. Y. Li, T. Gao, J. Liu, K. Linliu, C. R. Desper and B. Chu, “Multiphase structure of a segmented polyurethane: effects of temperature and annealing .” , Macromolecules. , v25 , p7365 , 1992
59. J. W. C. Van Bogart, P. A.Bluemke and S. L. Cooper, “Annealing-induced morphological changes in segmented elastomers .” , Polymer , v22 , p1428 , 1981
60. L. Cuve’, J. P. Pascualt and G. Boiteux, “Synthesis and properties of polyurethanes based on polyolefin: 2. Semicrystalline segmented polyurethanes prepared under heterogeneous or homogeneous synthesis conditions .” , Polymer , v33 , p3957 , 1992
61. W. Hu and J. T. Koberstein, “The effect of thermal annealing on the thermal properties and molecular weight of a segmented polyurethane copolymer .” , J. Polym. Sci. Polym. Phys. Ed. , v32 , p437 , 1994
62. Z. S. Petrovi , Z. Zavargo, J. H. Flyn, and W, J. Macknight, “Thermal degradation of segmented polyurethanes .” , J. Appl. Polym. Sci. , v51 , p1087 , 1994
63. Michael L. Matuszak, and K. C. Frisch, “Thermal degradation of linear polyurethanes and model biscarbamates .” , J. Polym. Sci. Chem. Ed. , v11 , p637 , 1973
64. Tzong-Liu Wang, and Tar-Hwa Hsieh, “Effect of polyol structure and molecular weight on the thermal stability of segmented poly(urethaneureas) .” , Polym. degradation stab. , v55 , p95 , 1997
65. 廖家陽，「巨大基團對Polyurethane urea結構與性質的影響」，國立中央大學，碩士論文，民國96年
66. 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