CASE polyurethanes

In any case, polyurethane dielectric elastomers have continued to be studied in the last decade, particularly with regard to the possibility of increasing their actuation performance. It is well known that both dielectric and mechanical properties are key parameters governing the electromechanical response of any dielectric elastomer, which can be in principle improved by an increase of the dielectric constant and by a decrease of the elastic modulus. In order to increase the dielectric permittivity of a polymer elastomeric matrix, various methods are available (Carpi et al. 2008), such as making composites or blends with highly polarizable phases. Table 1 constitutes a non-exhaustive list of works fi-om the literature, mostly relying on such methods for improving the performance of polyurethane dielectric elastomers. The studies are classified in terms of system complexity and component materials. 

Some of the advantages of moisture curable CASE polyurethanes are that there are no solvent emissions, and an improvement in properties due to the formation of urea groups. 

A novel polymer optical waveguide switch has been fabricated which uses total internal reflection from a thermally induced index barrier created by a silver stripe heater. In this case, polyurethane with An of -3.3 X 10 C" was used for the switching layer and PMMA was used for the substrate and buffer layers. A small part of the polyurethane film was left uncovered by the PMMA buffer to allow for injection of 632.8 nm He-Ne laser light into a single-mode waveguide by means of a prism-... 

Solvent-bome polychloroprene adhesives are excellent for bonding leather because of their high wettability and permanent tack (heat activation is not needed). However, these adhesives have poor performance with most of rubber soles and with several synthetic uppers. In these cases, polyurethane adhesives provide better performance. 

In situ techniques involve polymerization and sol-gel reactions. In the former case, polyurethanes are produced from suitable polyols and polyisocyanates in the presence of nanoparticles or their sources e.g., an organoclay with mean particle size initially in the range of a few micrometers). According to the sol-gel route, nanoparticles are produced in situ via suitable chemical reactions e.g., [10]). 

The thermal conductivity of a cellular polymer can change upon aging under ambient conditions if the gas composition is influenced by such aging. Such a case is evidenced when oxygen or nitrogen diffuses into polyurethane foams that initially have only a fluorocarbon blowing agent in the cells (32,130,143,190,191,198-201). 

Another type of polyol often used in the manufacture of flexible polyurethane foams contains a dispersed soHd phase of organic chemical particles (234—236). The continuous phase is one of the polyols described above for either slab or molded foam as required. The dispersed phase reacts in the polyol using an addition reaction with styrene and acrylonitrile monomers in one type or a coupling reaction with an amine such as hydrazine and isocyanate in another. The soHds content ranges from about 21% with either system to nearly 40% in the styrene—acrylonitrile system. The dispersed soHds confer increased load bearing and in the case of flexible molded foams also act as a ceU opener. 

Polyurethane, PVC, and extruded polystyrene provide the bulk of the cellular plastics used for low and cryogenic temperature appHcations. In some cases, eg, the insulation of Hquid hydrogen tanks on space systems, foams have been reinforced with continuous glass fibers throughout the matrix. This improves strength without affecting thermal performance significantly. 

For other recreational surfaces, such as mnning tracks, the installation techniques are quite different. Most are poured-in-place. An interlocking tile technique may be employed for tennis courts. In all cases, adequate provision for weathering and water drainage is essential. In general, the resiHent surfaces are installed over a hard base (see Fig. 4) that contains the necessary curbs to provide the finished level. Outdoors, asphalt is the most common base, and indoors, concrete. A poured-in-place polyurethane surface (14) is mixed on-site and cast from at least two components, an isocyanate and a filled... 

The largest segment of the CASE family of polyurethanes are elastomers. Cast polyurethane elastomers reached a new dimension when high pressure impingement mixing led to reaction injection molding (RIM). This technology is used widely in the automotive industry, and reinforced versions (RRIM) and stmctural molded parts (SRIM) have been added in more recent years. 

Sohd rocket propellants represent a very special case of a particulate composite ia which inorganic propellant particles, about 75% by volume, are bound ia an organic matrix such as polyurethane. An essential requirement is that the composite be uniform to promote a steady burning reaction (1). Further examples of particulate composites are those with metal matrices and iaclude cermets, which consist of ceramic particles ia a metal matrix, and dispersion hardened alloys, ia which the particles may be metal oxides or intermetallic compounds with smaller diameters and lower volume fractions than those ia cermets (1). The general nature of particulate reinforcement is such that the resulting composite material is macroscopicaHy isotropic. 

Most thermoplastic elastomers are stable materials and decompose only slowly under normal processing conditions. If decomposition does occur, the products are usuaHy not particularly ha2ardous and should not present a problem if good ventilation is provided. Extra caution should be exercised when processing polyurethanes, especiaHy those containing polycaprolactone segments. In these cases the decomposition products may include isocyanates and caprolactam, both of which are potential carcinogens. 

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). 

For materials of equivalent density water-blown polyurethanes and the hydrocarbon-blown polystyrene foams have similar thermal conductivities. This is because the controlling factor determining the conductivity is the nature of the gas present in the cavities. In both of the above cases air, to all intents and purposes, normally replaces any residual blowing gas either during manufacture or soon after. Polyurethane foams produced using fluorocarbons have a lower thermal conductivity (0.12-0.15 Btu in fr h °F ) (0.017-0.022 W/mK) because of the lower conductivity of the gas. The comparative thermal conductivities for air, carbon dioxide and monofluorotrichloromethane are given in Table 27.3. 

There is also growing interest in multi-phase systems in which hard phase materials are dispersed in softer polyether diols. Such hard phase materials include polyureas, rigid polyurethanes and urea melamine formaldehyde condensates. Some of these materials yield high-resilience foams with load deflection characteristics claimed to be more satisfactory for cushioning as well as in some cases improving heat resistance and flame retardancy. 

The first urethane reaction in Fig. 1 is used in two major ways in adhesives. In one case, a two-component adhesive usually employs a polyol and polyisocyanate with catalyst. This can react at room temperature to form the polyurethane. The second use of this reaction is to make an isocyanate-terminated prepolymer. Reacting a stoichiometric excess of isocyanate with polyol can produce an isocyanate-terminated prepolymer. A prepolymer is often made with an NCO/OH ratio of 2.0, as shown below, but the isocyanate ratio can range from 1.4 to over 8.0, depending upon the application ... 

Hydrolysis studies compared a polycarbonate urethane with a poly(tetramethyl-ene adipate) urethane and a polyether urethane based on PTMEG. After 2 weeks in 80°C water, the polycarbonate urethane had the best retention of tensile properties [92], Polycarbonates can hydrolyze, although the mechanism of hydrolysis is not acid-catalyzed, as in the case of the polyesters. Polycarbonate polyurethanes have better hydrolysis resistance than do standard adipate polyurethanes, by virtue of the highest retention of tensile properties. It is interesting to note in the study that the PTMEG-based urethanes, renowned for excellent hydrolysis resistance, had lower retention of physical properties than did the polycarbonate urethanes. 

The R s of a fibrous or cellular insulation like those in Table 2 generally decrease as the temperature increases. In the case of closed-cell polymeric foams like polyurethane nr pnlyisncyanurate board, the R may decrease if the insulation temperature drops below the condensation temperature of the blowing agent in the cells. This is because of changes in the gas- phase composition and therefore the gas-phase thermal conductivity. The R of insulations also depends on density when all other factors are constant. The relationship bett een R and density... 

In the case of some tanks used to carry wine or chlorinated solvents the final coat applied over an epoxy coating is sometimes an oil-free polyurethane enamel because this paint resists chlorinated solvents better than do epoxies, does not taint wines and is not stained by red wines. 

In the special case of pipelines operating at relatively high temperatures such as for the transmission of heavy fuel oil at up to 85°C, heat insulation and electrical insulation are provided by up to 50 mm of foam-expanded polyurethane. As a further insurance against penetration of water, and to prevent mechanical damage, outer coatings of polyethylene (5 mm), butyl laminate tape (0-8 mm) or coal-tar enamel reinforced with glass fibre (2-5 mm) have been used. 

---