Urethane solids

Major structural Felted fiber with High-porosity Solid urethane Solid polymer sheet... 

Forsyth, M., Meakin, P., MacFarlane, D.R., Hill, A.J. (1993) Free volume and conductivity of plasticized polyether-urethane solid polymer electrolytes . J. Phys. Condens. Matter 7, 7601. 

The water reaction evolves carbon dioxide and is to be avoided with solid elastomers but is important in the manufacture of foams. These reactions cause chain extension and by the formation of urea and urethane linkages they provide sites for cross-linking, since these groups can react with free isocyanate or terminal isocyanate groups to form biuret or allophanate linkages respectively (Figure 27.5). 

The most commonly used isocyanate in urethane adhesives is MDI. The pure material methylene diphenyl-isocyanate is a solid that melts around 37°C. Many variations of MDI are commercially available, and these variations fall into three major classes monomeric MDI, modified MDI s, and polymeric MDI s. 

The specialty class of polyols includes poly(butadiene) and polycarbonate polyols. The poly(butadiene) polyols most commonly used in urethane adhesives have functionalities from 1.8 to 2.3 and contain the three isomers (x, y and z) shown in Table 2. Newer variants of poly(butadiene) polyols include a 90% 1,2 product, as well as hydrogenated versions, which produce a saturated hydrocarbon chain [28]. Poly(butadiene) polyols have an all-hydrocarbon backbone, producing a relatively low surface energy material, outstanding moisture resistance, and low vapor transmission values. Aromatic polycarbonate polyols are solids at room temperature. Aliphatic polycarbonate polyols are viscous liquids and are used to obtain adhesion to polar substrates, yet these polyols have better hydrolysis properties than do most polyesters. 

Ceramic materials have found acceptance as cyclone liners for the apex orifice as well as other areas which exhibit severe abrasion. These include areas such as the lower cone liner and vortex finder. Nihard has also proven to be an acceptable wear material, especially for vortex finders and other areas which require strength as well as abrasion resistance. Other elastomer materials such as neoprene and nitrite are also utilized when hydrocarbons are present or when the temperature exceeds 60 °C. Urethane has found acceptance, especially in areas where the solids are relatively fine,... 

Another family of polyols is the filled polyols.llb There are several types, but die polymer polyols are die most common. These are standard polyether polyols in which have been polymerized styrene, acrylonitrile, or a copolymer thereof. The resultant colloidal dispersions of micrometer-size particles are phase stable and usually contain 20-50% solids by weight. The primary application for these polyols is in dexible foams where the polymer filler serves to increase foam hardness and load-bearing capacity. Other filled polyol types diat have been developed and used commercially (mainly to compete with die preeminent polymer polyols) include the polyurea-based PEID (polyhamstoff dispersion) polyols and the urethane-based PIPA (poly isocyanate polyaddition) polyols. 

Almost all urethane materials are synthesized without the use of solvents or water as diluents or earners and are referred to as being 100% solids. This is true of all foams and elastomers. There are many products, however, which do utilize solvents or water, and these are known as solvent-borne and waterborne systems, respectively. In the past, many coatings, adhesives, and binders were formulated using a solvent to reduce viscosity and/or ease application. However, the use of volatile solvents has been dramatically curtailed in favor of more environmentally friendly water (see Section 4.1.3), and now there are many aqueous coatings, adhesives, and associated raw materials. Hydrophilic raw materials capable of being dispersed in water are called water reducible (or water dispersible), meaning they are sufficiently hydrophilic so as to be readily emulsified in water to form stable colloidal dispersions. 

A solid suspended in a solid is called a solid suspension. Pigmented plastic - particles of dye suspended in a solid polymer - is a simple example. Freezing a liquid-liquid emulsion, such as milk, also yields a solid suspension. A layer of partially set paint, in which the urethane monomer has been consumed but the polymer has yet to form long chains, can also be thought of as representing a solid suspension. 

E Atherton, NL Benoiton, E Brown, RC Sheppard, B Williams. Racemisation of activated, urethane-protected amino-acids by jp-dimethylaminopyridine. Significance in solid-phase synthesis. J Chem Soc Chem Commun 336, 1981. 

The major side reaction associated with the use of mixed anhydrides is aminolysis at the carbonyl of the carbonate moiety (Figure 7.4, path B). The product is a urethane that resembles the desired protected peptide in properties, except that the amino-terminal substituent is not cleaved by the usual deprotecting reagents. Hence, its removal from the target product is not straightforward. The problem is serious when the residues activated are hindered (Val, lie, MeXaa), where the amounts can be as high as 10%. Other residues generate much less, but the reaction cannot be avoided completely, with the possible exception of activated proline (see Section 7.22). This is one reason why mixed anhydrides are not employed for solid-phase synthesis. 

RB Merrifield, AR Mitchell, JE Clarke. Detection and prevention of urethane acylation during solid-phase peptide synthesis by anhydride methods. J Org Chem 39, 660, 1974. 

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