Urethane markets

The late 80s will find the urethane market affected by the rougher problems of managing more severe open-flame fire situations. The institutional market size involved will be small, but will have a subtle effect on the residential market for urethane foams. 

Mobay Chemical Corp., "Urethane Market Report... 

Polyols. Several important polyhydric alcohols or polyols are made from formaldehyde. The principal ones include pentaerythritol, made from acetaldehyde and formaldehyde trimethylolpropane, made from -butyraldehyde and formaldehyde and neopentyl glycol, made from isobutyraldehyde and formaldehyde. These polyols find use in the alkyd resin (qv) and synthetic lubricants markets. Pentaerythritol [115-77-5] is also used to produce rosin/tall oil esters and explosives (pentaerythritol tetranitrate). Trimethylolpropane [77-99-6] is also used in urethane coatings, polyurethane foams, and multiftmctional monomers. Neopentyl glycol [126-30-7] finds use in plastics produced from unsaturated polyester resins and in coatings based on saturated polyesters. 

Leather-like materials now important in the market are of three main classes (/) vinyl-coated fabrics, (2) urethane-coated (synthetic) fabrics, and (J) man-made leathers. To appreciate their leather-replacement capabiUties it is necessary to know the stmcture of natural leather. 

Monofunctional, cyclohexylamine is used as a polyamide polymerization chain terminator to control polymer molecular weight. 3,3,5-Trimethylcyclohexylamines ate usehil fuel additives, corrosion inhibitors, and biocides (50). Dicyclohexylamine has direct uses as a solvent for cephalosporin antibiotic production, as a corrosion inhibitor, and as a fuel oil additive, in addition to serving as an organic intermediate. Cycloahphatic tertiary amines are used as urethane catalysts (72). Dimethylcyclohexylarnine (DMCHA) is marketed by Air Products as POLYCAT 8 for pour-in-place rigid insulating foam. Methyldicyclohexylamine is POLYCAT 12 used for flexible slabstock and molded foam. DM CHA is also sold as a fuel oil additive, which acts as an antioxidant. StericaHy hindered secondary cycloahphatic amines, specifically dicyclohexylamine, effectively catalyze polycarbonate polymerization (73). 

The polyamide copolymer of dodecanoic acid with methylenedi(cyclohexylamine) (MDCHA, PACM) was sold as continuous filament yam fiber under the tradename QIANA. As late as 1981, over 145,000 t was produced using high percentages, typically 80%, of trans, trans MDCHA isomer. The low melting raffinate coproduct left after t,t isomer separation by fractional crystallisation was phosgenated to produce a Hquid aUphatic diisocyanate marketed by Du Pont as Hylene W. Upon terrnination of their QIANA commitment, Du Pont sold the urethane intermediate product rights to Mobay, who now markets the 20% trans, trans—50% cis, trans—30% cis, cis diisocyanate isomer mixture as Desmodur W. In addition to its use in polyamides and as an isocyanate precursor, methylenedi (cyclohexyl amine) is used directiy as an epoxy curative. The Hquid diamine mixture identified historically as PACM-20 is marketed as AMICURE PACM by Anchor Chemical for performance epoxies. 

Almost all IDA derived chain extenders are made through ortho-alkylation. Diethyltoluenediamine (DE I DA) (C H gN2) (53), with a market of about 33,000 t, is the most common. Many uses for /-B I DA have been cited (1,12). Both DE I DA and /-B I DA are especially useful in RIM appHcations (49,53—55). Di(methylthio)-TDA, made by dithioalkylation of TDA, is used in cast urethanes and with other TDI prepolymers (56). Styrenic alkylation products of TDA are said to be useful, eg, as in the formation of novel polyurethane—polyurea polymers (57,58). Progress in understanding aromatic diamine stmcture—activity relationships for polyurethane chain extenders should allow progress in developing new materials (59). Chlorinated IDA is used in polyurethane—polyurea polymers of low hysteresis (48) and in reinforced polyurethane tires (60). The chloro-TDA is made by hydrolysis of chloro-TDI, derived from TDA (61). 

Urethane Industry Digest, Part B Marketing Guide, C. J. Swanson, Pubhshei, Hobday, Fla., June 1988. 

In the manufacture of highly resident flexible foams and thermoset RIM elastomers, graft or polymer polyols are used. Graft polyols are dispersions of free-radical-polymerized mixtures of acrylonitrile and styrene partially grafted to a polyol. Polymer polyols are available from BASF, Dow, and Union Carbide. In situ polyaddition reaction of isocyanates with amines in a polyol substrate produces PHD (polyhamstoff dispersion) polyols, which are marketed by Bayer (21). In addition, blending of polyether polyols with diethanolamine, followed by reaction with TDI, also affords a urethane/urea dispersion. The polymer or PHD-type polyols increase the load bearing properties and stiffness of flexible foams. Interreactive dispersion polyols are also used in RIM appHcations where elastomers of high modulus, low thermal coefficient of expansion, and improved paintabiUty are needed. 

Trimethylolpropane (TMP), the reduced crossed aldol condensation product of //-butyraldehyde and formaldehyde, competes in many of the same markets as glycerol (qv) and pentaerythritol. The largest market for TMP is as a precursor in unsaturated polyester resins, short-oil alkyds, and urethanes for surface coatings (see Alkyd resins). 

The distribution of powder coating sales by resin type for various geographical areas is given in Table 5. The polyester—epoxy hybrids account for 50% of the European market, yet have only market share <25% in the rest of the world. Similarly, the polyester urethanes, which account for only a small market share in Europe, find significant usage in the United States andjapan. AcryUcs hold a significant share only in the Japanese market. 

In the adhesives market growth has been slower than in other segments. Increasing competition from other materials, most notably polyurethanes and acryhcs, is affecting the market (see Acrylic ester polymers Urethane polymers). 

The vast majority of reactive hot melts are moisture-curing urethane adhesives. Radiation (UV/EB) curable adhesives have been explored in the laboratory since the mid-1970s, but are only recently beginning to gain significant market penetration, particularly for PSA applications. The formulation and properties of these two classes of adhesives are discussed below. 

To improve on penetration and heat resistance (properties normally in opposition when formulating hot melts), reactive hot melt systems are being developed. Moisture curing urethanes have already gained wide acceptance in a number of wood and automotive applications. UV cure is slowly gaining acceptance in PSA, labeling, and other markets. 

Moisture-curing hot melts are a small but fast growing segment of the urethane adhesive market. They are used mostly in construction and furniture assembly applications. Recent applications include RV sidewall assembly and other OEM automotive applications. Smaller applications include bookbinding and footwear. A typical adhesive is shown below ... 

Solvent-home urethanes are still widely used to bond leather and athletic shoes. The OEM automotive market uses some solvent-home urethanes together with chlorosulfonated polyethylene as a primer. Some urethane solvent-home packaging adhesives are used for cap liners and for paper and foil lamination. Some textile laminating applications are still based on solvent-home urethanes. 

Two-component waterborne urethanes are the preferred choice to replace solvent-borne urethane adhesives, especially in the packaging and shoe industries. At this time, the packaging area is the largest application of two-part waterborne urethanes. Good strides have been made by the two-part waterborne urethanes in the shoe industry, especially in the athletic shoe market. Waterborne urethanes are also replacing the solvent-borne products in the OEM door panels. 

Several coats of resin are applied to the prepared substrate at approximately 4- to 6-hour intervals, with one or more coats being dressed with colored paint flakes which are sealed in by the next coat and then lightly sanded. This type of flooring was widely marketed about ten years ago but, in the main, they were considered unsatisfactory due to rapid discoloration of the floor because of the lack of ultraviolet stability of the urethane resins used, which rapidly turned yellow-brown and looked dirty. However, ultraviolet-stable urethane resins that do not suffer this discoloration are now available, and this type of durable decorative flooring is gaining re-acceptance (for example, for kitchens, toilets and reception areas). 

Flexible foams are used in applications where a high degree of resiliency is required with moderate load-bearing capacity. Essentially all foam seating is urethane based, including the furniture and automotive markets. Other examples are packaging, textiles, filters, sports equipment, and recreational items. 

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. 

Since the introduction of the first polysulfide sealants in the 1950s, the sealant market had grown by 1992 into a 1.4 billion industry. Sealant use is generally divided into four categories transportation, construction, consumer, and industrial. Table 9 lists the market segment value of each use as of 1992 and Table 10 the market share of the various material types. Continued growth is expected, especially for silicones, urethanes, and acrylics. Table 11 lists suppliers of sealants. 

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,... 

Commonly used adhesives include epoxy, rubber, acrylic or vinyl emulsions, and urethanes. Epoxies are high-priced, but they have better chemical resistance and durability than the others, and they have dominated the market in outdoor applications. Significant advantages of the epoxy-based adhesives are that they have no solvents and, therefore, exhibit little shrinkage. They cure relatively fast and, therefore, are not as exposed to inclement... 

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