Urethane foams, rigid

Introduction. Rigid urethane foams are hard (high ratio of load bearing/density) foams having very low flexibility. They show permanent deformation, i.e., no complete recovery after compression. In other words, the compression deflection curves of rigid urethane foams exhibit yield points. 

As opposed to flexible urethane foams, rigid urethane foams have a highly cross-linked chemical structure and a high percent of closed cells, e.g., over 90%. Rigid urethane foams can be classified as follows unmodified (or pure) rigid urethane foams and modified rigid urethane foams, which include isocyanurate-modified, epoxy-modified, amide-modified and oxazolidone-modified rigid urethane foams. 

Preparation. The polyisocyanates utilized in rigid urethane foams include TDl-prepolymers, crude TDl (undistilled TDl), modified MDl 

In principle, both the one-shot process and semi-prepolymer processes have been used for rigid-urethane-foam manufacturing. However, the monomeric TDI-based one-shot process was used only in the initial stage of the rigid-urethane-foam industry because of the toxicity problems of TDI and difficulties in controlling reactivity due to the high NCO percent. For these reasons TDI-prepolymers, blends of TDI prepolymers and polymeric isocyanates, and 100% polymeric isocyanate are most widely used. 

In the household-refrigerator industry, however, the one-shot process employing crude TDI (which has a lower percent NCO and contains oligomeric compounds, such as isocyanurate- and carbodiimide-types of oligomers) is still widely employed because of its low cost. 

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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. 

Triphenyl phosphate [115-86-6] C gH O P, is a colorless soHd, mp 48—49°C, usually produced in the form of flakes or shipped in heated vessels as a hquid. An early appHcation was as a flame retardant for cellulose acetate safety film. It is also used in cellulose nitrate, various coatings, triacetate film and sheet, and rigid urethane foam. It has been used as a flame-retardant additive for engineering thermoplastics such as polyphenylene oxide—high impact polystyrene and ABS—polycarbonate blends. 

Phosphorus-Containing Diols and Polyols. The commercial development of several phosphoms-contaiuing diols occurred in response to the need to flame retard rigid urethane foam insulation used in transportation and constmction. There are a large number of references to phosphoms polyols (111) but only a few of these have been used commercially. 

One noteworthy neurotoxic response was demonstrated in laboratory pyrolysis studies using various types of phosphoms flame retardants in rigid urethane foam, but the response was traced to a highly specific interaction of trimethylolpropane polyols, producing a toxic bicycHc trimethylolpropane phosphate [1005-93-2] (152). Formulations with the same phosphoms flame retardants but other polyols avoided this neurotoxic effect completely. 

Methylenebis(4-phenyl isocyanate). This compound is also known as methyl diisocyanate [101-68-8] (MDI) and is produced by the condensation of aniline and formaldehyde with subsequent phosgenation. Its principal end use is rigid urethane foams other end uses include elastic fibers and elastomers. Total formaldehyde use is 5% of production (115). 

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. 

This reaction is catalyzed by hydrogen chloride and yields can be essentially quantitative when using either free phosphonic acid or its diesters. The flame retardant, Eyrol 6, produced by Akzo Chemicals, Inc. and used for rigid urethane foams, is synthesized as follows (24). 

Over 4 billion PETP bottles will be available for colleetion across Europe in 1999. PUR Products has introduced technology into the UK which involves glycolysis of postconsumer PETP into materials for the manufacture of rigid urethane foams for building insulation. This application offers a substantial new market for aromatic polyester polyols derived from glycolised PETP recyclate. PUR(PRODUCTS)LTD. 

Temperature dependence of the elastic modulus of the rigid urethane foam. 

L.D. Booth and L.M. Huber, "Bimetallic Bow of Rigid Urethane Foam Composites", Proc. SPI 6th International Conf.. 1983, pp 85-99. 

Kalspray Rigid urethane foam Baxenden Chemical... 

The structural semi-flexible and rigid urethane foams, combining high strength with low density and low cost, have found wide interest and early acceptance in divergent markets although this development is still quite new. The semi-flexible foams are used primarily in the transportation industry. At medium densities,... 

The rigid urethane foam concept with integral skins has also found considerable interest in the automotive industry for exterior body parts, such as engine or trunk compartment lids, fenders and even full roofs. These parts can be reinforced with metal inserts where necessary or hinges and fasteners can be molded in for ready mounting. 

Rigid urethane foam lamination Allows composites of rigid urethanes... 

Rigid urethane foam is recognised as an outstanding material for insulation application. It has desirable properties, such as (Kaplan, 1969) ... 

There are three general methods of applying rigid urethane foam ... 

Foams may be prepared by either one of two fundamental methods. In one method, a gas such as air or nitrogen is dispersed in a continuous liquid phase (e.g. an aqueous latex) to yield a colloidal system with the gas as the dispersed phase. In the second method, the gas is generated within the liquid phase and appears as separate bubbles dispersed in the liquid phase. The gas can be the result of a specific gasgenerating reaction such as the formation of carbon dioxide when isocyanate reacts with water in the formation of water-blown flexible or rigid urethane foams. Gas can also be generated by volatilization of a low-boiling solvent (e.g. trichlorofluoromethane, F-11, or methylene chloride) in the dispersed phase when an exothermic reaction takes places, (e.g. the formation of F-11 or methylene chloride-blown foams). 

CFCs. Table 6 shows major CFCs. CFC-11 has been the representative blowing agent for both flexible and rigid urethane foams (155). The use of CFCs brought significant advantages to both flexible and rigid polyurethane foams. However, ozone-depletion potential (ODP) in the stratosphere have led to the worldwide ban of the production and use of CFCs by 1995. 

Chloropropane as blowing agent for rigid urethane foams has been developed by Recticel (240). 

Flame Retardants. Among the isocyanate-based foams, polyurethane foams, both flexible and rigid, are flammable. Due to serious fire hazards of polyurethane foams, strict fire regulations have come out on the use of foams in the areas of furniture and public transportation. In addition, the use of rigid urethane foams in building insulation have resulted in stricter fire regulations. 

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