Polyurethane thermoplastic rubbers

Epichlorohydrin rubber Thermoplastic polyurethanes Nitrile rubber... 

It is generally more convenient to use the thermoplastic polyurethane rubbers discussed in Section 27.4.4 for those applications where a cast process is not appropriate. 

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). 

If polypropylene is too hard for the purpose envisaged, then the user should consider, progressively, polyethylene, ethylene-vinyl acetate and plasticised PVC. If more rubberiness is required, then a vulcanising rubber such as natural rubber or SBR or a thermoplastic polyolefin elastomer may be considered. If the material requires to be rubbery and oil and/or heat resistant, vulcanising rubbers such as the polychloroprenes, nitrile rubbers, acrylic rubbers or hydrin rubbers or a thermoplastic elastomer such as a thermoplastic polyester elastomer, thermoplastic polyurethane elastomer or thermoplastic polyamide elastomer may be considered. Where it is important that the elastomer remain rubbery at very low temperatures, then NR, SBR, BR or TPO rubbers may be considered where oil resistance is not a consideration. If, however, oil resistance is important, a polypropylene oxide or hydrin rubber may be preferred. Where a wide temperature service range is paramount, a silicone rubber may be indicated. The selection of rubbery materials has been dealt with by the author elsewhere. ... 

Thermoplastic polyurethane (TPU) is a type of synthetic polymer that has properties between the characteristics of plastics and rubber. It belongs to the thermoplastic elastomer group. The typical procedure of vulcanization in rubber processing generally is not needed for TPU instead, the processing procedure for normal plastics is used. With a similar hardness to other elastomers, TPU has better elasticity, resistance to oil, and resistance to impact at low temperatures. TPU is a rapidly developing polymeric material. 

Kumar G., Neelakantan N.R., and Subramanian N., Mechanical behaviour of polyacetal and thermoplastic polyurethane elastomer toughened polyacetal, Polym. Plastics TechnoL Eng., 32, 33, 1993. Newmann W. et al.. Preprints, 4th Rubber Technology Conference, London, May 22-25, 1962. Farrissey W.J. and Shah T.M., Handbook of Thermoplastic Elastomers (Walker B.M. and Rader C.P., eds.). Van Nostrand Reinhold, New York, 1988. 

The elasticity of thermoplastic polyurethane rubbers (which are also known as thermoplastic urethanes or TPUs) is a function of their morphology which comprises hard and soft phases. The hard phases consist of hydrogen bonded clusters of chain segments, which are linked by flexible chain segments that make up the soft phase. The hard blocks, which are the minor phase, exist as separate domains within a continuous matrix of the majority soft phase, as shown schematically in Fig. 25.9. 

When a thermoplastic polyurethane elastomer is heated above the melting point of its hard blocks, the chains can flow and the polymer can be molded to a new shape. When the polymer cools, new hard blocks form, recreating the physical crosslinks. We take advantage of these properties to mold elastomeric items that do not need to be cured like conventional rubbers. Scrap moldings, sprues, etc. can be recycled directly back to the extruder, which increases the efficiency of this process. In contrast, chemically crosslinked elastomers, which are thermosetting polymers, cannot be reprocessed after they have been cured. 

Thermoplastic polyurethanes do not require compounding as do the conventional rubbers, and exhibit the same general properties as the cast and millable types. 

Polyurethane multiblock copolymers of the type described by Eqs. 2-197 and 2-198 constitute an important segment of the commercial polyurethane market. The annual global production is about 250 million pounds. These polyurethanes are referred to as thermoplastic polyurethanes (TPUs) (trade names Estane, Texin). They are among a broader group of elastomeric block copolymers referred to as thermoplastic elastomers (TPEs). Crosslinking is a requirement to obtain the resilience associated with a rubber. The presence of a crosslinked network prevents polymer chains from irreversibly slipping past one another on deformation and allows for rapid and complete recovery from deformation. 

Global consumption of thermoplastic rubbers of all types is estimated at about 600,000 t/yr (51). Of this, 42% was estimated to be consumed in the United States, 39% in Western Europe, and 19% in Japan. At present, the worldwide market is estimated to be divided as follows styrenic block copolymers, 48% hard polymer/elastomer combinations, 26% thermoplastic polyurethanes, 12% thermoplastic polyesters, 4% and others, 9%. The three largest end uses were transportation, 23% footwear, 18% and adhesives, coatings, etc, 16%. The ranges of the hardness values, prices, and specific gravities of commercially available materials are given in Table 4. 

Santra RN et al. (1995) In-situ compatibilization of thermoplastic polyurethane and polydimethyl siloxane rubber by using ethylene methyl acrylate copolymer as a reactive polymeric compatibilizer. Adv Poly Technol 14(l) 59-66... 

PVC is the most commonly calendered plastic, especially in plasticized flexible form. Other materials commonly calendered are rubber, ABS, polyurethane, and thermoplastic elastomers. 

Thermoplastic polyurethanes Acetals copolymers only Thermoplastic rubbers some only Thermoplastic olefins some only Cellulosics only certain dyes... 

U.S. Pat. No. 7,022,751 [111] describes a fiber-reinforced composite plastic material comprising thermoplastic polymers such as HDPE, LDPE, polypropylene, PVC, and polystyrene a high melting point waste polymer fiber material such as polyethylene terephthalate and nylon, an inorganic filler, such as glass and other material, and an organic filler such as wood or particles of a thermoset plastic, such as rubber and polyurethane foam. 

Blends of the commodity polymers with more specialty polymers are limited although many specific examples exist in the patent/open literature. In the design of polymer blends for specific application needs, countless opportunities can be envisioned. Examples may include PE/poly(s-caprolactone) (PCL) blends for biodegradable applications (proposed), polyolefin (PO)/poly(vinyl alcohol) (PVAL) blends for antistatic films, PO/silicone rubber blends for biomedical applications, PO/thermoplastic polyurethane TPU (or other thermoplastic elastomers) for applications similar to plasticized PVC, functionalized PO/thermoset blends. 

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