Polyether Based Thermoplastic Polyurethanes Effect of the Soft Segment Molecular Weight

A series of polyether-based thermoplastic polyure thanes, varying in soft segment molecular weight and hard seg ment content was prepared and studied. Poly(oxypropylene- oxyethylene) diols of Mn of 1000, 2000, 3000, and 4000 were the soft segment polyols. The hard segment, 4,4'-diphenyl methane diisocyanate (MDI) extended with 1,4-butanediol (BDO), and also the soft segment content were varied from 20 to 80 weight percent. Physical-mechanical, thermal (DSC) and dynamic-mechanical property data are used to elucidate the mechanical and morphological behavior of these polymers. Two distinct phases are detected in most of the polymers. The Tg of the amorphous soft phase decreases with increasing polyether molecular weight and is relatively unaffected by soft segment content except at very low levels (≤ 30%). Hard segments appar ently separate into ordered structures which melt between 150 and 220°C. The melting points and the heats of fusion generally increase with hard segment content and soft segment Mn. Soft segment molecular weight also has a significant influence on the mechanical properties of the polymers. In general, the ambient flexural moduli and the dynamic moduli (E') increase with in creasing soft segment Mn and the modulus/temperature curve is flattened.

[1]  P. Flory,et al.  Second‐Order Transition Temperatures and Related Properties of Polystyrene. I. Influence of Molecular Weight , 1950 .

[2]  T. Kajiyama,et al.  Differential Scanning Calorimetry of Polyurethanes , 1968 .

[3]  L. Morbitzer,et al.  Correlations between chemical structure, stress‐induced crystallization, and deformation behavior of polyurethane elastomers , 1972 .

[4]  H. Ono,et al.  Studies of the Structure of Polyurethane Elastomers. I. The Number-average MW Determination of the Hard-segment in the Poly(Ether)Urethane Elastomer by Means of Perchloric Acid Depolymerization , 1970 .

[5]  D. J. Massa Measuring the dynamic moduli of glassy polymers: analysis of the Rheovibron , 1973 .

[6]  F. E. Critchfield,et al.  Thermoplastic urethane elastomers. III. Effects of variations in isocyanate structure , 1975 .

[7]  Stuart L. Cooper,et al.  Effect of segment size and polydispersity on the properties of polyurethane block polymers , 1973 .

[8]  D. Lyman,et al.  Polyurethanes. IV. Effect of poly(propylene glycol) tacticity on the properties of block copolyether‐urethanes , 1977 .

[9]  S. Cooper,et al.  Some results on electron microscope investigations of polyether‐urethane and polyester‐urethane block copolymers , 1970 .

[10]  S. L. Hager A computer automated thermal analysis laboratory for polymer characterization , 1978 .

[11]  A. Sayigh,et al.  Microcellular Elastomers by Single-Stage Technology , 1969 .

[12]  K. Frisch,et al.  A One-Shot Method for Urethane and Urethane-Urea Elastomers , 1961 .

[13]  G. Wilkes,et al.  Superstructure in segmented polyether–urethanes , 1975 .

[14]  R. Fedors Dependence of the glass transition on molecular weight , 1979 .

[15]  T. Kajiyama,et al.  Thermal Properties of Polyurethanes. Enthalpies and Entropies of Fusion , 1970 .

[16]  C. S. Schollenberger,et al.  Thermoplastic Urethane Molecular Weight-Property Relations , 1973 .

[17]  E. Thomas,et al.  Morphological Studies of PCP/MDI/BDO-Based Segmented Polyurethanes , 1979 .

[18]  R. Aitken Thermoplastic urethane elastomers based on optically active poly(oxy-1,2-propylene)-α,ω-diol , 1979 .

[19]  R. M. Gerkin,et al.  Polyether‐based thermoplastic polyurethanes. I. Effect of the hard‐segment content , 1979 .

[20]  K. Gardner,et al.  Structure of the hard segments in polyurethane elastomers , 1979 .

[21]  F. E. Karasz,et al.  Low temperature dynamic mechanical properties of polyurethane-polyether block copolymers , 1972 .

[22]  Stuart L. Cooper,et al.  Properties of linear elastomeric polyurethanes , 1966 .

[23]  G. Corbett,et al.  Effect of formulation on properties and morphology of polyurethane elastomers , 1975 .

[24]  N. Schneider,et al.  Transition behavior and phase segregation in TDI polyurethanes , 1977 .