Epoxy resins markets

Currendy, epoxy resins (qv) constitute over 90% of the matrix resin material used in advanced composites. The total usage of advanced composites is expected to grow to around 45,500 t by the year 2000, with the total resin usage around 18,000 t in 2000. Epoxy resins are expected to stiH constitute about 80% of the total matrix-resin-systems market in 2000. The largest share of the remaining market will be divided between bismaleimides and polyimide systems (12 to 15%) and what are classified as other polymers, including thermoplastics and thermoset resins other than epoxies, bismaleimides, cyanate esters, and polyimide systems (see Composites,polymer-matrix-thermoplastics). 

The commercial possibiUties for epoxy resins were first recognized by DeTrey Emres in Switzerland and DeVoe and Raynolds in the United States (1,2). In 1936, DeTrey Emres produced a low melting bisphenol A-based epoxy resin that gave a thermoset composition with phthaUc anhydride. Apphcation of the hardened composition was foreseen in dental products, but initial attempts to market the resin were unsuccessful. The patents were hcensed to CIBA AG of Basel, Switzerland (now CIBA-GEIGY), and in 1946 the first epoxy adhesive was shown at the Swiss Industries Eair and samples of casting resin were offered to the electrical industry. 

There is, quite clearly, scope or a very wide range of epoxy resins. The nonepoxy part of the molecule may be aliphatic, cycloaliphatic or highly aromatic hydrocarbon or it may be non-hydrocarbon and possibly polar. It may contain unsaturation. Similar remarks also apply to the chain extension/cross-linking agents, so that cross-linked products of great diversity may be obtained. In practice, however, the commercial scene is dominated by the reaction products of bis-phenol A and epichlorohydrin, which have some 80-90% of the market shtu"e. 

PEN applications in the wire and cable market include printer cable and insulated wire wraps. PEN has a higher Tg and melting point, as well as higher flame resistance than PET. PEN him coated with a dispersion consisting of epoxy resin and Al(OH3) gave a semi-cured insulating him. When applied on copper wire, wound, and heated, a coil with good flame retardance and adhesion between the wire and the him was obtained [65],... 

The two major uses of phenol in 1995 were the production of bisphenol-A (35%) and the production of phenolic resins (34%) (CMR 1996). The largest use for bisphenol-A is as an intermediate in the production of epoxy resins (Thurman 1982). Phenol-formaldehyde resins comprise over 95% of this market (Thurman 1982). The plywood adhesive industry required 26% of the total production of phenolic resins in 1977. These low-cost, versatile, thermoset resins have other major uses in the construction, automotive, and appliance industries (Thurman 1982). 

E. HSlmes, J. Bakker and J. Ahimosata, Epoxy Resins Marketing Research Report, Chemical Economics Handbook (1984). 

Nylons 6/6 and 6 comprise more than 90% of the polyamide market. The two have similar properties but nylon 6 has a lower Tm (223°C). Small amounts of nylons 6/9, 6/10, 6/12, 11, 12, 12/12, and 4/6 are produced as specialty materials. Those with more methylene groups than nylons 6/6 and 6 have better moisture resistance, dimensional stability, and electrical properties, but the degree of crystallinity, Tm, and mechanical properties are lower. Specialty nylons made from dimerized fatty acids find applications as hot-melt adhesives, crosslinking agents for epoxy resins, and thermographic inks. 

From W. F. Stahl, Chemical Economics Handbook, Marketing Research Report on Epoxy Resins, p. 580.0600A, August, 1994. 

Addition poly(imide) oligomers are used as matrix resins for high performance composites based on glass-, carbon- and aramide fibers. The world wide market for advanced composites and adhesives was about 70 million in 1990. This amounted to approximately 30-40 million in resin sales. Currently, epoxy resins constitute over 90% of the matrix resin materials in advanced composites. The remaining 10% are unsaturated polyester and vinylester for the low temperature applications and cyanate esters and addition poly(imides) for high temperatures. More recently thermoplastics have become important and materials such as polyimides and poly(arylene ether) are becoming more competitive with addition polyimides. 

A modified BMI-epoxy resin system has been introduced by Shell Chemical Company. The system is a highly reactive blend of a bismaleimide, COM-PIMIDE 1206 (55-60% by weight solution of BMI in DMF), and EPON Resin 1151, a polyfunctional epoxy resin (60). In contrast to many polyimide resins on the market, no free MDA is present in the product. This is an important feature, since MDA has been identified as an animal carcinogen and possibly a human carcinogen. This resin system has been fully evaluated for use in multilayer PCB boards (61). 2-Methylimidazole is recommended as a catalyst. However, if required, the processing window can be widened by using 2-phenylimidazole... 

Boron Trichloride. Approximately 75-95% of the BC13 consumed in the United States is used to prepare boron filaments by CVD (7). These high performance fibers are used to reinforce composite materials (qv) made from epoxy resins and metals (Al, Ti). The principal markets for such composites are aerospace industries and sports equipment manufacturers. 

The major commercial alternative to DOPO and its derivatives for reactively flame retarding epoxy resins, especially for electronic applications, is an oligo(l,3-phenylene methylphosphonate) (Structure 5.18) marketed by Supresta under the tradename Fyrol PMP. Fyrol PMP has a functionality higher than that of DOPO and can be used either as a hardener (curing agent) or be precondensed with an epoxy. 

Adhesive markets represent only a small percentage of the total consumption of epoxy resins. However, epoxy adhesives provide significant value added, so that their prices and profit margins are generally higher than those for other adhesive types. Globahy in the year 2002, epoxy adhesives represented about 31 percent (or about 0.7 billion lb) of the total liquid epoxy demand (Fig. 1.2). The U.S. market is estimated to be just less than 200 million lb.10... 

A majority of the world s epoxy resin market consists of the DGEBA type. The liquid DGEBA resins are typically used where low viscosity, high reactivity, and high crosslink density are required. The low viscosity allows them to be conveniently and easily compounded with fdlers and other additives. The relatively high functionality allows them to... 

Market penetration is expected to increase further due to stricter environmental regulations and the availability of a greater variety of products. The first radiation curable adhesives were limited to acrylate and epoxy resins. Today, many different types of radiation curable adhesive systems are commercially available. 

Epoxy acrylates are dominant oligomers in the radiation curable adhesives market. A bisphenol A epoxy resin is reacted with acrylic acid or methacrylate acid to provide unsaturated terminal reactive groups. The acrylic acid-epoxy reaction to make bisphenol A diacrylate destroys any free ingredients such as epichlorohydrin used to make the DGEBA epoxy starting raw material. 

The role of the epoxy resin manufacturer depends on the nature of the product and the markets. It is often more convenient for the resin manufacturer to modify a base resin, such as providing an adduct, a graft polymer, or a blend. In this case the modified resin would likely be shipped to a formulator for incorporation of other fillers and modifiers and... 

The traditional cross-linking technologies utilized in the coatings market range from hydroxyl functional binders (acrylics or polyesters) cross-linked with melamines (IK) or isocyanates (2K) to drying oils that cure through oxidation of unsaturation in the backbone, to epoxy resins cross-linked with amino resins (amido amines, amines, etc.). 

---