Thermoplastic polyurethane polyester-based

In addition, polyester polyols are made by the reaction of caprolactone with diols. Poly(caprolactone diols) are used in the manufacture of thermoplastic polyurethane elastomers with improved hydrolytic stabiHty (22). The hydrolytic stabiHty of the poly(caprolactone diol)-derived TPUs is comparable to TPUs based on the more expensive long-chain diol adipates (23). Polyether/polyester polyol hybrids are synthesized from low molecular weight polyester diols, which are extended with propylene oxide. 

Among the polyurethane, polyester, and polyamide thermoplastic elastomers, those with polyether-based elastomer segments have better hydrolytic stabihty and low temperature flexibiUty, whereas polyester-based analogues are tougher and have the best oil resistance (43). Polycaprolactones and aUphatic polycarbonates, two special types of polyesters, are used to produce premium-grade polyurethanes (12). 

Polyester-based thermoplastic polyurethane elastomers (Section 27.4). 

Thermoplastic polyurethane elastomers have now been available for many years (and were described in the first edition of this book). The adipate polyester-based materials have outstanding abrasion and tear resistance as well as very good resistance to oils and oxidative degradation. The polyether-based materials are more noted for their resistance to hydrolysis and fungal attack. Rather specialised polymers based on polycaprolactone (Section 25.11) may be considered as premium grade materials with good all round properties. 

The thermoplastic polyurethane (TPU) adhesives must, of necessity, contain low gel content because they must be processable in an extruder. Most adhesives are relatively linear, with a functionality of 2.0, although small amounts of branching may be introduced, usually at the expense of a lower melt flow. Good physical properties of TPU s are obtained when the thermoplastic urethanes have molecular weights of 100,000 or higher (see p. 56 in [63]). Most TPU adhesives are based on symmetrical polyesters with a fast crystallizing backbone or a backbone slightly modified to increase the open time. 

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. 

The tensile properties of polyester-based thermoplastic polyurethanes were studied as a function of the time of exposure of the plastics to water, methanol, methanol-water, methanol-Isooctane, and methanol-water-lsooctane. The resulting decrease In the tensile properties of the plastics was attributed to reaction of the plastics with water and methanol. As Indicated by the decrease In properties, reaction with methanol Is Initially faster, but the reaction rate with water Increases with time — presumably because of the autocatalytic nature of the reaction. Nuclear magnetic resonance spectroscopy Indicated that the reaction mechanisms with methanol and water were transesterification and hydrolysis, respectively. 

Extensive degradation of polyester based thermoplastic polyurethane samples occurs due to hydrolysis In the presence of water and transesterification In the presence of methanol. 

Comparison of Polymers 14 and 15 in Figure 9 shows fairly similar polymerizations up to the point of shortstop addition. The control, Polymer 5, was slower but alive and growing at 18 minutes of polymerization time, reaching a final torque value of 660 meter-grams. Its steady intermediate polymerizarion rate is seen to be characteristic of uncatalyzed thermoplastic polyurethane elastomer polymerizations based on low acid number PTAd while Polymers 14 and 15 formed faster than usual from such a low acid number polyester glycol component. 

It also has been shown that azelate esters can also be used in place of adipate polyesters in thermoplastic polyurethanes, which also indicated improved hydrolytic stability as well as somewhat improved low-temperature properties as compared to those of the corresponding adipate polyester based urethanes (90). The tendency of polyester-based urethanes to hydrolyze, particularly at high humidities and elevated temperatures, can partly be reduced by incorporation of small amounts of polymeric carbodiimides (91). Alternately, the use of diisocyanate-containing carbodiimide groups helps to confer greater hydrolytic stability to polyester urethanes (92). 

Polymeric compounds are specific sealing materials intended to line or impregnate conducting hardware as well as electric radio circuits for electric insulation. They are based on epoxy and unsaturated polyester resins, liquid organosilicon rubbers and monomers (initial products for S3mthesizing pol3Tnethacrylates and polyurethanes). Compounds based on thermoplastic materials (tar, rosin, cerezin) in the form of solid or wax-like masses, heated for transformation into the liquid state, are confined to this application. 

The more viscous, mastic-type cements include some of the epoxies, urethanes and sflicones. Epoxies adhere well to both thermosets and thermoplastics. But epoxies are not recommended for most polyolefin bonding. Urethane adhesives have made inroads into flexible packaging, the shoe industry, and vinyl bonding. Polyester-based polyurethanes are often preferred over polyether systems because of their higher cohesive and adhesive properties. Sflicones are especially recommended where both bonding and sealing are desired. 

PROPERTIES OF THERMOPLASTIC POLYURETHANES BASED ON POLYCAPROLACTONE (POLYESTER) OF 2000 MOLECULAR WEIGHT... 

Besides the thermoplastic elastomers based on poly(styrene-6-elastomer- -styrene) block copolymers, five others are of commercial importance polyurethane/elastomer block copolymers, polyester/elastomer block copolymers, polyamide/elastomer block copolymers, polyolefin block copolymers, and polyetherimide/polysiloxane block copolymers. All five have the multiblock A-B-A-B. structure. The morphology of the polyurethane, polyester,... 

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