Soft segment polyurethanes

Merrill and Salzman have developed PEO soft segment polyurethanes and indeed have demonstrated minimal adsorption of blood proteins and minimal platelet adhesion on such surfaces121). Nagaoka et al. have studied various methacrylate copolymers with PEO side-chains of varying lengths and showed a direct correlation between minimization of platelet adhesion with increased PEO side-chain length and surface... 

Characterization. Film samples about 0.25-mm thick were prepared by compression molding the polyurethanes under dry nitrogen at 180°C and 3 MPa pressure. After molding for 20 min, the samples were allowed to cool slowly in the press under dry nitrogen flow. Figure 2 shows the thermal history of the 180°C-molded films. No discoloration was observed when the samples were removed from the mold. The two soft-segment polyurethanes were compression molded at 120°C. The films were allowed to stand at least one week at room temperature in a dessicator before being evaluated with the Rheovibron DDV-IIB Dynamic Visco-... 

The sensitivity to hydrolysis is a key issue in many applications. The ester bond in 4GT-PTMO copolymers is sensitive to hydrolysis however, it is fairly protected since most of the ester is contained in a crystalline structure. The addition of a small amount (1-2%) of a hindered aromatic polycarbodiimide substantially increases the lifetime of this material in the presence of hot water or steam (Brown et al., 1974). Polyurethanes are susceptible to hydrolytic attack, especially those with polyester soft segments. However, polyester soft segment polyurethanes are generally more resistant to oils, organic solvents, and thermal degradation. lonomers will swell when exposed to water in fact, a commercial hydrated perfluorosulfonic ionomer (Nation) is used as a membrane separator in chlor-alkali cells. Styrene-diene copolymers and polyolefin TPEs are insensitive to water. 

The behavior of soft-segment polyurethanes (SPU) may be used to clarify the above question. The polymers used in ref. 63 were bicomponent polymers with a polyurethane hard segment and an aliphatic polyether soft segment. The surface energy of the soft... 

Camposa E, Cordeiroa R, Santosb AC, Gil MH, et al. Design and characterization of bi-soft segmented polyurethane microparticles for biomedical application. Colloids Surf B Biointerfaces July 2011 88 477-82. 

The hydroxyl groups can be esterified normally the interesting diacrylate monomer (80) and the biologicaky active haloacetates (81) have been prepared in this manner. Reactions with dibasic acids have given polymers capable of being cross-linked (82) or suitable for use as soft segments in polyurethanes (83). Polycarbamic esters are obtained by treatment with a diisocyanate (84) or via the bischloroformate (85). 

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. 

Flexible foams are three-dimensional agglomerations of gas bubbles separated from each other by thin sections of polyurethanes and polyureas. The microstmetures observed in TDI- and MDI-based flexible foams are different. In TDI foams monodentate urea segments form after 40% conversion, foUowed by a bidentate urea phase, which is insoluble in the soft segment. As the foam cures, annealing of the precipitated discontinuous urea phase... 

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). 

Given the versatility of polyurethanes, for instance by manipulating the nature of the soft segment or the chain extender, the introduction of a hydrolytically... 

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. 

In an NMR analysis of the effects of /-irradiation induced degradation on a specific polyurethane (PU) elastomer system, Maxwell and co-workers [87] used a combination of both H and 13C NMR techniques, and correlated these with mechanical properties derived from dynamic mechanical analysis (DMA). 1H NMR was used to determine spin-echo decay curves for three samples, which consisted of a control and two samples exposed to different levels of /-irradiation in air. These results were deconvoluted into three T2 components that represented T2 values which could be attributed to an interfacial domain between hard and soft segments of the PU, the PU soft segment, and the sol... 

These materials are segmented copolyether esters formed by the melt transesterification of dimethyl terephthalate, poly(tetramethylene ether) glycol and 1,4-butane diol. As with the thermoplastic polyurethanes, one can describe a hard segment and a soft segment, the hard segments forming crystalline areas which act as pseudocrosslinks . 

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