Rheology of Thermoplastic Polyurethanes

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Abstract Thermoplastic polyurethane (TPU) has received considerable attention from both the scientific and industrial communities (Hepburn 1982; Oertel 1985; Saunders and Frish 1962). Applications for TPUs include automotive exterior body panels, medical implants such as the artificial heart, membranes, ski boots, and flexible tubing. Figure 10.1 gives a schematic that shows the architecture of TPU, consisting of hard and soft segments. Hard segments, which form a crystalline phase at service temperature, are composed of diisocyanate and short-chain diols as a chain extender, while soft segments, which control low-temperature properties, are composed of difunctional long-chain polydiols with molecular weights ranging from 500 to 5000. The soft segments form a flexible matrix between the hard domains. TPUs are synthesized by reacting difunctional long-chain diol with diisocyanate to form a prepolymer, which is then extended by a chain extender via one of two routes: (1) by a dihydric glycol chain extender or (2) by a diamine chain extender. The most commonly used diisocyanate is 4,4’-diphenylmethane diisocyanate (MDI), which reacts with a difunctional polyol forming soft segments, such as poly(tetramethylene adipate) (PTMA) or poly(oxytetramethylene) (POTM), to produce TPU, in which 1,4-butanediol (BDO) is used as a chain extender. There are two methods widely used to produce TPU: (1) one-shot reaction sequence and (2) two-stage reaction sequence. The reaction sequences for both methods are well documented in the literature (Hepburn 1982). It should be mentioned that MDI/BDO/PTMA produces ester-based TPU. One can also produce ether-based TPU when MDI reacts with POTM using BDO as a chain extender. TPUs are often referred to as “multiblock copolymers.” In order to have a better understanding of the rheological behavior of TPUs, one must first understand the relationships between the chemical structure and the morphology; thus, a complete characterization of the materials must be conducted. The rheological behavior of TPU depends, among many factors, on (1) the composition of the soft and hard segments, (2) the lengths of the soft and hard segments and the sequence length distribution, (3) anomalous linkages (branching, cross-linking), and (4) molecular weight.