Rigid Polyurethanes

Diester/Ether Diol of Tetrabromophthalic Anhydride. This material [77098-07-8] is prepared from TBPA in a two-step reaction. First TBPA reacts with diethylene glycol to produce an acid ester. The acid ester and propylene oxide then react to give a diester. The final product, a triol having two primary and one secondary hydroxyl group, is used exclusively as a flame retardant for rigid polyurethane foam (53,54). 

J. S. Newman, "Smoke Characteri2ation of Rigid Polyurethane/Isocyanurate Foams," 34th SPl Annual Polyurethane Technical Marketing Conference, New Orleans, La., Oct. 21—24, 1992, pp. 307—311. 

Miscellaneous chemicals are used to modify the final properties of rigid polyurethane foams. Eor example, halogenated materials are used for flammabihty reduction, diols may be added for toughness or flexibiUty, and terephthalate-based polyester polyols may be used for decreased flammabiUty and smoke generation. Measurements of flammabihty and smoke characteristics are made with laboratory tests and do not necessarily reflect the effects of foams in actual fire situations. 

Process and Equipment. Rigid polyurethane foam processes use the same high or low pressure pumping, metering, and mixing equipment as earher described for flexible foams. Subsequent handling of the mixture is deterrnined by the end product desired. 

Applications. The principal use for rigid polyurethane foams is for iasulation ia various forms utilized by a variety of iadustries. Lamiaates for resideatial sheatiag (1.2 to 2.5 cm thick with aluminum skins) and roofing board (2.5 to 10.0 cm thick with roofing paper skins) are the leading products with about 45 metric tons of Hquid spray systems also ia use. Metal doors iasulated by a pour-ia-place process coastitute another substantial use. 

Aromatic Isocyanates. In North America, aromatic isocyanates ate heavily used as monomers for addition and condensation polymers. The principal appflcafions include both flexible and rigid polyurethane foam and nonceUulat appflcations, such as coatings, adhesives, elastomers, and fibers. 

The major uses of aniline are in the manufacture of polymers, mbber, agricultural chemicals, dyes and pigments, pharmaceuticals, and photographic chemicals. Approximately 67% of the wodd production of aniline is used in the manufacture of rigid polyurethanes and reaction-injection-molded (RIM) parts for the constmction, automotive, and durable goods industries. 

TDA-derived polyols are made by alkoxylation. Polypropylene oxide adducts of I DA (14) and TDA-initiated polyether polyols (13,15) are used in rigid polyurethane foams and continue to be included in new formulations (62) as well as older appHcations. 

The plastic sandwich roof is made from rigid polyurethane foam panels sandwiched inside a plastic coating. 

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 avadabihty of PMDI also led to the development of polyurethane-modified isocyanurate (PUIR) foams by 1967. The PUIR foams have superior thermal stabiUty and combustibiUty characteristics, which extend the use temperature of insulation foams well above 150°C. The PUIR foams are used in pipe, vessel, and solar panel insulation glass-fiber-reinforced PUIR roofing panels having superior dimensional stabiUty have also been developed. More recently, inexpensive polyester polyols based on residues obtained in the production of dimethyl terephthalate (DMT) have been used in the formulation of rigid polyurethane and PUIR foams. 

Most low density rigid polyurethane foams have a closed-ceU content of >90%. Above 0.032 g/cm, closed-ceU content increases rapidly and is generally >99% above 0.192 g/cm. Bun foam, produced under controlled conditions, has a very fine-cell stmcture, with cell sizes of 150—200 lm. 

Polymeric isocyanates or PMDI ate cmde products that vary in exact composition. The main constituents are 40—60% 4,4 -MDI the remainder is the other isomers of MDI, trimeric species, and higher molecular weight oligomers. Important product variables are functionaHty and acidity. Rigid polyurethane foams are mainly manufactured from PMDI. The so-called pure MDI is a low melting soHd that is used for high performance polyurethane elastomers and spandex fibers. Liquid MDI products are used in RIM polyurethane elastomers. 

Table 5. Typical Rigid Polyurethane Panel Formulation ...

More than 50% of the rigid polyurethane foams manufactured in the United States in 1994 are used in the constmction industry (Table 10). About... 

The polyurethane industry is dominated by the multinational isocyanate producers. Several of the principal isocyanate producers, including BASF, Bayer, Dow, ICI, and Olin, also manufacture polyols, the other significant building block for polyurethanes. Annual production capacities of the global aromatic isocyanate producers are Hsted in Table 11. Polyols, mainly used for flexible foam production, account for 65 wt % in a flexible foam formulation, 35% in rigid polyurethane foams, and even less in PUIR foams. 

Table 27.4 Typical applications of cellular rigid polyurethanes and polyisocyanurates...

These materials not only have a good resistance to burning and flame spread but are also able to withstand service temperatures of up to 150°C. At the same time polyisocyanurate foams have the very good hydrolytic stability and low thermal conductivity associated with rigid polyurethane foams. 

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. 

Rigid polyurethane foams used in refrigerators and freezers - Alternatives include hydrocarbons (pentane) and HCFC-141b long-term alternatives include HFCs (134a, -245, -356, -365). Vacuum panels may be used in the future. 

Rigid polyurethane for other appliances. Alternatives include HCFC-141b, HCFC-22, blends of -22 and HCFC-142b, pentane, and carbon dioxide/water blowing. In the long term, the alternatives include HFCs. 

Rigid polyurethane used for boardstock andflexible-faced laminations - Alternatives include HCFC-141b and pentane in the long term, the use of HFCs should be developed. 

Spray applications of rigid polyurethane - Alternatives currently in use for spray applications include carbon dioxide/water and HCFC-14 lb. Long-term alternatives will be HFCs. 

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