Polymers urethane

The addition polymerization of diisocyanates with macroglycols to produce urethane polymers was pioneered in 1937 (1). The rapid formation of high molecular weight urethane polymers from Hquid monomers, which occurs even at ambient temperature, is a unique feature of the polyaddition process, yielding products that range from cross-linked networks to linear fibers and elastomers. The enormous versatility of the polyaddition process allowed the manufacture of a myriad of products for a wide variety of appHcations. 

Urethane network polymers are also formed by trimerization of part of the isocyanate groups. This approach is used in the formation of rigid polyurethane-modified isocyanurate (PUIR) foams (3). 

The late 1950s saw the emergence of cast elastomers, which led to the development of reaction injection mol ding (RIM) at Bayer AG in Leverkusen, Germany, in 1964 (see Plastics processing). Also, thermoplastic polyurethane elastomers (TPUs) and Spandex fibers (see Fibers, elastomeric) were introduced during this time. In addition, urethane-based synthetic leather (see Leather-LIKEmaterials) was introduced by Du Pont under the trade name Corfam in 1963. 

The late 1950s also witnessed the emergence of a new polymeric isocyanate (PMDI) based on the condensation of aniline with formaldehyde. This 

Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 

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Urethane grouts Urethane industry Urethane linkages Urethane plastisol Urethane polyesters Urethane polymers... 

The reaction of uiea with alcohols yields caibamic acid esters, commonly called urethanes (see Urethane polymers) ... 

Heating butanediol with acetylene in the presence of an acidic mercuric salt gives the cycHc acetal expected from butanediol and acetaldehyde (128). A commercially important reaction is with diisocyanates to form polyurethanes (129) (see Urethane POLYMERS). 

Stabilizers, pigments, and other additives are milled in spinning solvent, normally along with small amounts of the urethane polymer to improve dispersion stabiUty this dispersion is then blended to the desired concentration with polymer solution after chain extension. Most producers combine prepolymerization, chain extension, and additive addition and blending into a single integrated continuous production line. 

Polyurethane. SmaU quantities of polyurethane film are produced as a tough mbber-like film. Polyurethane is more commonly used to produce foamed sheet, both flexible and rigid. The flexible foam is used as cushioning in furniture and bedding the rigid foam is widely used for architectural insulation because of its outstanding thermal insulation efficiency (see Urethane POLYMERS). 

The amount and physical character of the char from rigid urethane foams is found to be affected by the retardant (20—23) (see Foams Urethane polymers). The presence of a phosphoms-containing flame retardant causes a rigid urethane foam to form a more coherent char, possibly serving as a physical barrier to the combustion process. There is evidence that a substantial fraction of the phosphoms may be retained in the char. Chars from phenohc resins (qv) were shown to be much better barriers to pyrolysate vapors and air when ammonium phosphate was present in the original resin (24). This barrier action may at least partly explain the inhibition of glowing combustion of char by phosphoms compounds. 

Urethane Polymers. An important use for glycerol is as the fundamental building block ia polyethers for urethane polymers (qv). In this use it is the initiator to which propylene oxide, alone or with ethylene oxide, is added to produce ttifunctional polymers which, on reaction with diisocyanates, produce flexible urethane foams. Glycerol-based polyethers (qv) have found some use, too, ia rigid urethane foams. 

Uses. Neopentyl glycol is used extensively as a chemical intermediate in the manufacture of polyester resins (see Alkyd resins), polyurethane polyols (see Urethane polymers), synthetic lubricants, polymeric plasticizers (qv), and other polymers. It imparts a combination of desirable properties to properly formulated esterification products, including low color, good weathering and chemical resistance, and improved thermal and hydrolytic stabiUty. 

This simple reaction is the bedrock of the polyurethane iadustry (see Urethane polymers). Detailed descriptions of the chemistry and process have been published (65—67). Certain carbamates are known to reversibly yield the isocyanate and polyol upon heating. This fact has been commercially used to synthesize a number of blocked isocyanates for elastomer and coating appHcations. 

In the second step, a papermaking method is also used for the fine fibers, less than 0.1 tex (1 den). This process is usually followed by a high pressure water jet process instead of the third step. In the fourth step, to obtain the required properties in specific appHcations, a polyurethane is selected out of the segmented polyurethanes, which comprises a polymer diol, a diisocyanate, and a chain extender (see Urethane polymers). A DMF—water bath for coagulation is also controlled to create the adequate pore stmcture in combination with fibers. 

Malonates can also be used as blocking agents in the formulation of one-part urethanes. These systems, curable by moisture, are used, for example, for automotive windshield gla2ing (53) (see Urethane polymers). 

Polymers. AH nitro alcohols are sources of formaldehyde for cross-linking in polymers of urea, melamine, phenols, resorcinol, etc (see Amino RESINS AND PLASTICS). Nitrodiols and 2-hydroxymethyl-2-nitro-l,3-propanediol can be used as polyols to form polyester or polyurethane products (see Polyesters Urethane polymers). 2-Methyl-2-nitro-l-propanol is used in tires to promote the adhesion of mbber to tire cord (qv). Nitro alcohols are used as hardening agents in photographic processes, and 2-hydroxymethyl-2-nitro-l,3-propanediol is a cross-linking agent for starch adhesives, polyamides, urea resins, or wool, and in tanning operations (17—25). Wrinkle-resistant fabric with reduced free formaldehyde content is obtained by treatment with... 

Sihcones (qv) have an advantage over organic resias ia their superior thermal stabiUty and low dielectric constants. Polyurethanes, when cured, are tough and possess outstanding abrasion and thermal shock resistance. They also have favorable electrical properties and good adhesion to most surfaces. However, polyurethanes are extremely sensitive to and can degrade after prolonged contact with moisture as a result, they are not as commonly used as epoxies and sihcones (see Urethane polymers). 

The most important tetrahydrofuran polymers are the hydroxy-terrninated polymers, that is, the a,C0-poly(tetramethylene ether) glycols used commercially to manufacture polyurethanes and polyesters (see Urethane polymers Polyesters, thermoplastic). 

Almost all TDA use is as a chemical intermediate, mosdy in polyurethanes. Toluenediamine derivatives are found as all three components of urethanes isocyanates, chain extenders, and polyols (see Isocyanates, organic Urethane polymers). 

Two of the more recendy developed polysulftde polymers are the mercaptan-terminated polyoxypropylene urethane polymer and the polythioether polymer. The urethane-backbone-based polymer is used in many sealant formulations for insulating glass appHcations. The thioether backbone contains sulfur, but no S—S bonds, which are the weakest part of the conventional polysulftde polymer. This polymer improves the thermal stabiHty and reduces the gas—Hquid permeabiHty. 

Glean-Up Solvent. Dimethyl sulfoxide is used to remove urethane polymers and other difficult-to-solvate materials from processing equipment. 

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