Hard segment polyurethane elastomers

There are two important types of polymer in which an elastomeric and a glassy or non-crystalline rigid component are copolymerised. The simpler thermoplastic elastomers are usually triblock ABA copolymers with B as the elastomeric component and A as the glassy component, whereas the segmented polyurethane elastomers are multiblock copolymers in which alternate blocks are hard , i.e. relatively inflexible, and soft , i.e. relatively flexible. 

Based on various experimental studies, one can schematically represent the morphology of segmented polyurethane (elastomer or flexible foam polymer) on the nano- and micro-scale as shown in Figm-e 2.1. For the range of hard segments volume fraction less than 50%, much of the space is occupied by the soft phase matrix. Microphase-separated nano-domains of the hard phase are dispersed in this matrix they can be individual islands or can form percolated networks. Finally, there could also be some larger (micron-sized) macrophase-separated domains of hard phase, where hard phase domains are ordered at the macro-scale (this is especially true in the case of flexible foams). The relative amounts of all these elements depend on the formulation and processing history. 

The melt temperature of a polyurethane is important for processibiUty. Melting should occur well below the decomposition temperature. Below the glass-transition temperature the molecular motion is frozen, and the material is only able to undergo small-scale elastic deformations. For amorphous polyurethane elastomers, the T of the soft segment is ca —50 to —60 " C, whereas for the amorphous hard segment, T is in the 20—100°C range. The T and T of the mote common macrodiols used in the manufacture of TPU are Hsted in Table 2. 

Multiblock systems. A somewhat similar approach is involved in the production of thermoplastic polyurethane elastomers. In this case the chain contains soft segments that are largely aliphatic polyether in nature and also hard segments that are primarily polyurea (see Chapter 27). 

One partieular form of thermoplastic polyurethane elastomers is the elastic fibre known as spandex fibre. Like the usual thermoplastic rubbers these materials consist of hard and soft segments but to qualify for the term spandex by the US Federal Trade Commission the polymer used should contain at least 85% of segmented polyurethane. The first commercial material of this type was introduced by Du Pont in 1958 (Lycra). Several other similar materials have since been introduced including Dorlastan (Bayer), Spanzelle (Courtaulds) and Vyrene (US Rubber). 

Thermoplastic polyurethane elastomers are normally based on polyester prepolymers. The properties of these polymers can be systematically varied by tailoring the nature and ratio of the hard and soft segments. The stiffness of a polyurethane elastomer increases as the proportion of hard blocks increases. As the stiffness increases, the extensibility of the material decreases. 

While Table 3.3 deals with elastomers, it is important to mention that the effect of MDI illustrated in the table applies to MDI foams as well. Figure 3.7 shows the effect on the tensile strength of the polyurethane of increasing amounts of MDI. The increase in hard segments increases the brittleness but does not improve the strength of the polymer, as reflected in the elongation figures. The increase also exerts positive effects on the compression of the foam as noted in the next section. 

Soft blocks are composed of linear, dihydroxy poly ethers or polyesters with molecular weights between 600 and 3000. In a typical polymerization of a thermoplastic polyurethane elastomer, the macroglycol is end capped with the full amount of aromatic diisocyanate required in the final composition. Subsequently, the end-capped prepolymer and excess diisocyanate mixture reacts further with the required stoichiometric amount of monomeric diol to complete the reaction. The diol links the prepolymer segments together while excess diol and diisocyanate form short hard-block sements, leading to the (AB)n structure illustrated in Figure 1. Block lengths in (AB)n polymers are frequently much shorter than those in anionically synthesized ABA block copolymers. 

The presence of hard and soft domains in segmented polyurethanes also has been confirmed by experimental results using pulsed NMR and low-frequency dielectric measurements. Assink (55) recently has shown that the nuclear-magnetic, free-induction decay of these thermoplastic elastomers consists of a fast Gaussian component attributable to the glassy hard domains and a slow exponential component associated with the rubbery domains. Furthermore, the NMR technique also can be used to determine the relative amounts of material in each domain. 

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. 

Going up somewhat in hard segment content to the 50-60% range affords ( at least in polyurethane or urea-urethane RIM) the elastomers and elastoplastics, or perhaps a better word than elastoplastics would be toughened plastics. 

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