Plastics early

By 1900 the only plastics materials available were shellac, gutta percha, ebonite and celluloid (and the bitumens and amber if they are considered as plastics). Early experiments leading to other materials had, however, been carried out. The... 

Phenol was first isolated m the early nineteenth century from coal tar and a small por tion of the more than 4 billion lb of phenol produced m the United States each year comes from this source Although significant quantities of phenol are used to prepare aspirin and dyes most of it is converted to phenolic resins used m adhesives and plastics... 

Because of projected nylon-6,6 growth of 4—10% (167) per year in the Far East, several companies have announced plans for that area. A Rhc ne-Poulenc/Oriental Chemical Industry joint venture (Kofran) announced a 1991 startup for a 50,000-t/yr plant in Onsan, South Korea (168,169). Asahi announced plans for a 15,000-t/yr expansion of adipic acid capacity at their Nobeoka complex in late 1989, accompanied by a 60,000-t/yr cyclohexanol plant at Mizushima based on their new cyclohexene hydration technology (170). In early 1990 the Du Pont Company announced plans for a major nylon-6,6 complex for Singapore, including a 90,000-t/yr adipic acid plant due to start up in 1993 (167). Plans or negotiations for other adipic acid capacity in the area include Formosa Plastics (Taiwan) (171) and BASF-Hyundai Petrochemical (South Korea) (167). Adipic acid is a truly worldwide... 

Aryl Phosphates. Aryl phosphates were introduced into commercial use early in the twentieth century for flammable plastics such as cellulose nitrate and later for cellulose acetate. CeUulosics are a significant area of use but are exceeded now by plastici2ed vinyls (93—95). Principal appHcations are in wire and cable insulation, coimectors, automotive interiors, vinyl moisture barriers, plastic greenhouses (Japan), furniture upholstery, conveyer belts (especially in mining), and vinyl foams. 

The first cellular synthetic plastic was an unwanted cellular phenol—formaldehyde resin produced by early workers in this field. The elimination of cell formation in these resins, as given by Baekeland in his 1909 heat and pressure patent (2), is generally considered the birth of the plastics industry. The first commercial cellular polymer was sponge mbber, introduced between 1910 and 1920 (3). 

Cellular Ebonite. CeUular ebonite is the oldest rigid ceUular plastic. It was produced in the early 1920s by a process similar to the processes described for making ceUular mbber. The formulation of mbber and vulcani2ing agent is changed to produce an ebonite rather than mbber matrix (114). 

As early as 1966, natural gas was available to all of the lower 48 states in the United States. During the period 1967—1990, the U.S. transmission system grew from 362,700 km to 450,800 km. Over this same time period, the distribution mains increased from 867,800 km to 1,347,000 km. As plastic pipe and reUable joining technology became available, the use of plastic pipe expanded to include the distribution of gas in low pressure systems. By 1990, approximately 24% of the U.S. distribution system was based on plastic pipe (1). 

Applications. The applications sought for these polymers include composites, stmctural plastics, electronics/circuit boards, aircraft/spacecraft coatings, seals, dental and medical prosthetics, and laser window adhesives. However, other than the early commercialization by Du Pont of the NR-150 B material, Httie development has occurred. These polymers are quite expensive ( 110 to 2200 per kg for monomers alone). 

Urea—Formaldehyde and Urea-Based. In the 1970s and early 1980s, urea materials were in general use particularly for direct field retrofitting of cavity wall constmction of wood frame and masonry. However, because of formaldehyde odor and excess shrinkage under specific conditions, this ceUular plastic has limited use as an insulation. 

The volatile content of the treated paper is important because moisture acts as a temporary plasticizer to promote resin flow during early stages of pressing (9). Dynamic mechanical analysis of the treated paper is a very useful means to study the initial flow stages of a resin and the cure time required to complete cross-linking (10). 

Second, in the early 1950s, Hogan and Bank at Phillips Petroleum Company, discovered (3,4) that ethylene could be catalyticaHy polymerized into a sohd plastic under more moderate conditions at a pressure of 3—4 MPa (435—580 psi) and temperature of 70—100°C, with a catalyst containing chromium oxide supported on siUca (Phillips catalysts). PE resins prepared with these catalysts are linear, highly crystalline polymers of a much higher density of 0.960—0.970 g/cnr (as opposed to 0.920—0.930 g/cnf for LDPE). These resins, or HDPE, are currentiy produced on a large scale, (see Olefin polymers, HIGH DENSITY POLYETHYLENE). 

High density polyethylene (HDPE) is defined by ASTM D1248-84 as a product of ethylene polymerisation with a density of 0.940 g/cm or higher. This range includes both homopolymers of ethylene and its copolymers with small amounts of a-olefins. The first commercial processes for HDPE manufacture were developed in the early 1950s and utilised a variety of transition-metal polymerisation catalysts based on molybdenum (1), chromium (2,3), and titanium (4). Commercial production of HDPE was started in 1956 in the United States by Phillips Petroleum Company and in Europe by Hoechst (5). HDPE is one of the largest volume commodity plastics produced in the world, with a worldwide capacity in 1994 of over 14 x 10 t/yr and a 32% share of the total polyethylene production. 

As a family of resins originally developed in the early twentieth century, the nature and potential of phenoHc resins have been explored thoroughly to produce an extensive body of technical Hterature (1 8). A symposium sponsored by the American Chemical Society commemorated 75 years of phenoHc resin chemistry in 1983 (9), and in 1987 the PhenoHc Mol ding Division of the Society of the Plastics Industry (SPI) sponsored a conference on phenoHcs in the twenty-first century (1). 

Interaction Parameters. Early attempts to describe PVC—plasticizer compatibiHty were based on the same principles as used to describe solvation, ie, like dissolves like (2). To obtain a quantitative measure of PVC—plasticizer compatibihty a number of different parameters have been used. More recently these methods have been assessed and extended by many workers (7—9). In all cases it is not possible to adequately predict the behavior of polymeric plasticizers. 

Environmental Effects of Plasticizers. Measurement of the effect of phthalates on environmental species is difficult because standard test methods are not designed to deal with poorly water-soluble substances. Eor this reason a number of early studies are flawed and their results should be disregarded in favor of more recent investigations where these difficulties have been overcome. 

Bayer marketed PPS compounds in the United States under the trade name Tedur, but the company has exited the PPS business. PPS is also marketed in the United States by GE Plastics, whose source of neat resin is Tosoh Corporation of Japan. GE Plastics markets PPS under the trade name Supec PPS. Patent activity by Tennessee Eastman describes an alternative process for the production of poly(phenylene sulfide/disulfide), although samples of such product have not appeared as of early 1996. Both Phillips and Hoechst Celanese have aimounced plans to debotdeneck their existing U.S. faciUties in order to meet anticipated market growth. 

---