Cast polyurethanes Hard segments

In cross-linked polyurethanes, there are actual chemical bonds formed in a three-dimensional manner. The main difference is that with the cast-able polyurethanes the actual chemical structure consists of two major zones, a hard zone and a soft zone. This is not as pronounced in the cross-linked polyurethanes. A typical example is the addition of TMP (trimethy-lol propane) to polyurethane to make it softer. This curative will make the material much softer as it breaks the hard segment zoning up to a certain degree. They do, however, give a material with improved compression set properties. 

Solutions of Biomer were obtained from Ethicon Inc. Biomer is poly (ether polyurethane) which contains urea linkage in the hard segment according to our IR analysis (19). Films of Biomer were cast on clean glass plates by diluting the polymer solution in dimethyl acetyl-amide. The films were dried in a vacuum oven at 50°C for 24 hr. The final film thickness was around 125/a. GPC analysis showed that the content of oligomers in Biomer was also negligible. Kel-F82, which is a copolymer composed of chlorotrifluoroethylene (97%) and vinylidene fluoride (3% ), was obtained from the 3M Company. 

Both series of polyurethanes were prepared using a prepolymer technique in which reactants were mixed at 70 °C/1 hour, cast into molds at 105 °C/2 hours, and cured at 80 °C/14 hours. The BD/MDI hard segment contents ranged from 0% (transparent, colorless homopolyurethanes) to 30% w/w (opaque, white copolyurethanes). All elastomers were characterized using DSC, dynamic mechanical, and tensile stress-strain measurements. 

Polyurethane. [This polymer was supplied by R. A. Auerbach, Lord Corporation.] The polyurethane was composed of a soft segment of poly(tetramethylene glycol) with a molecular weight of 1000 and a hard segment of p-diphenylmethane 4,4 -diisocyanate (MDI), and was chain extended with ethylenediamine (7). A solution of 7 wt % polyurethane in N,N-dimethylacetamide was used to cast the films. The phase-separated samples (ANN) were prepared by annealing the film at 135°C for 90 min in a helium atmosphere, and the mixed, nonphase-separated samples (NEQ)... 

Table 8.4 Distribution of hard and soft segments in cast polyurethanes ... 

In order to understand the effect of high MW diols on the formation of amorphous hard segments and their interaction with the crystalline hard segments, FT-IR analysis of the cast polyurethanes was performed. Samples were cast as films on a NaCl plate from a hot dimethyl sulphoxide (DMSO) solution. 

Proton spin-temperature equilibration between the hard- and soft-segment-rich domains of the polyurethane elastomer on the order of 10-100 ms might be considered fast relative to a macroscopically phase-separated blend [26] or copolymer, but slow relative to a strongly interacting mixture [25]. This is reasonable for a microphase-separated material whose solid state morphology has been the subject of considerable theoretical and experimental research. Under fortuitous circumstances, intimate (near-neighbor) contact between dissimilar molecules in a mixture can be studied via direct measurement of proton spin diffusion in a two-dimensional application of the 1H-CRAM PS experiment (Combined Rotation And Multiple Pulse Spectroscopy). Belfiore et al. [17,25,31] have detected intermolecular dipolar communication in a hydrogen-bonded cocrystallized solid solution of poly(ethylene oxide) and resorcinol on the f00-/xs time scale, whereas Ernst and coworkers [26] report the absence of proton spin diffusion on the 100-ms time scale for an immiscible blend of polystyrene and poly(vinyl methyl ether), cast from chloroform. 

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