Polyethylene Phillips petroleum

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. 

Countries produciug commodity LLDPE and their capacities, as well as production volumes of some U.S. companies, are Hsted iu Table 5. Iu most cases, an accurate estimate of the total LLDPE production capacity is compHcated by the fact that a large number of plants are used, iu turn, for the manufacture of either HDPE or LLDPE iu the same reactors. VLDPE and LLDPE resius with a uniform branching distribution were initially produced in the United States by Exxon Chemical Company and Dow Chemical Company. However, since several other companies around the world have also aimounced their entry into this market, the worldwide capacity of uniformly branched LLDPE resins in 1995 is expected to reach a million tons. Special grades of LLDPE resins with broad MWD are produced by Phillips Petroleum Co. under the trade name Low Density Linear Polyethylenes or LDLPE. 

Low Pressure Linear (Low Density) Polyethylene" in ECT3rd ed., under "Olefin Polymers," Vol. 16, pp. 385—401, byj. N. Short, Phillips Petroleum Co. 

Fig. 21. A low density polyethylene tubular reactor used by Phillips Petroleum (85).

In 1951 Robert Banks and Paul Hogan of Phillips Petroleum discovered that ethylene could be polymerized under rather mild conditions of temperature and pressure to afford high molecular weight polyethylene using chromium trioxide as the catalyst. This invention laid the foundation for both the Phillips and Union Carbide processes for ethylene polymerization (both use heterogeneous chromium catalysts). 

Phillips (1) A process for polymerizing ethylene and other linear olefins and di-olefins to make linear polymers. This is a liquid-phase process, operated in a hydrocarbon solvent at an intermediate pressure, using a heterogeneous oxide catalyst such as chromia on silica/ alumina. Developed in the 1950s by the Phillips Petroleum Company, Bartlesville, OK, and first commercialized at its plant in Pasadena, TX. In 1991, 77 reaction fines were either operating or under construction worldwide, accounting for 34 percent of worldwide capacity for linear polyethylene. 

High-density polyethylene (HDPE) is a commodity chemical that is produced on a very large scale in one of two catalytic processes the Ziegler-Natta and the Phillips process. The latter accounts for about one third of all polyethylene. It uses a catalyst consisting of small amounts of chromium (0.2-1.0 wt% Cr) on a silica support, developed by Hogan and Banks at the Phillips Petroleum Company in the early 1950s [84,85]. 

In 1953, Ziegler in Germany, Phillips Petroleum Co. (USA) and Standard Oil Co. (USA) were able to discover the process of manufacturing polyethylene by avoiding the use of high pressure. The polyethylene so obtained is termed as the high density polyethylene. 

Thanks are due to Lloyd M. Cooke, Union Carbide Corp., and James A. Reid, Phillips Petroleum Co., for gifts of polyethylene samples. 

Materials. Marlex 5003 polyethylene (PE) was supplied by the Phillips Petroleum Company, Bartlesville, Oklahoma. 

Even Phillips Petroleum, badly affected by Boone Pickens takeover attempt, managed to make substantial profits from its petrochemicals because of drastic restructuring. New prospects were also opening up for the United States chemicals industry as needs grew for butene and hexene comonomers used to produce linear low-density polyethylene (LLDPE), also as consumption of higher olefins to prepare detergent alcohols increased and as demand for MTBE used as a gasoline additive soared. 

Application Produce linear polyethylene (LPE) using the Phillips Petroleum Co., LPE process. 

Phillips Petroleum Co. Polyethylene, LLDPE-HDPE Ethylene Energy efficient loop-reactor technology polymerizes slurry with catalyst 20 1998... 

Barriers to entry into the pseudocommodity business include all the barriers for commodities plus the all-important customer know-how. Lack of technical expertise and patent protection can be formidable barriers to potential producers of a pseudocommodity. Du Pont was the sole producer of nylon from 1939 to 1951. Barriers to entry were removed under threat of government antitrust action in 1951, with the licensing of Chemstrand, which later became part of Monsanto. Since then a number of companies have entered the nylon business. Technical know-how and patent protection played a major role in both high- and low-pressure polyethylene manufacture in the years shortly after World War II. ICI developed polyethylene, but Union Carbide had a superior high-pressure process. Ziegler, Du Pont, and Phillips Petroleum all developed low-pressure processes, which they subsequently licensed to other manufacturers. Many pseudocommodities eventually become commodities by the diffusion of technology, standardization of the product, and the entry of many firms into the business. 

High-density polyethylenes are formed from metal oxide initiation. These poly-ethylenes are stiffer, with much less branching. HDPE is used more in automotive applications due to this property. Phillips Petroleum uses a chromic oxide catalyst and Standard Oil of Indiana has developed a molybdenum oxide catalyst [5], These catalysts are not flammable, which presents an advantage over Ziegler-Natta. 

Commercial linear polyethylene, the most commonly used type of plastic, was bom more than half a century ago with the accidental discovery at Phillips Petroleum Company that chromium oxide supported on silica can polymerize a-olefins.1 The same catalyst system, modified and evolved, is used even today by dozens of companies throughout the world, and it accounts for a large share of the world s high-density polyethylene (HDPE) supply, as well as some low-density polymers. The catalyst is now more active and has been tailored in numerous ways for many specialized modem applications. This chapter provides a review of our understanding of the complex chemistry associated with this catalyst system, and it also provides examples of how the chemistry has been exploited commercially. It is written from an industrial perspective, drawing especially on the commercial experience and the research of numerous scientists working at Phillips Petroleum... 

Cyclohexane. Pure grade cyclohexane (Phillips Petroleum Co.) was passed through activated Linde 3A molecular sieves under argon into a stainless steel oxygen bomb (9 gal). It was dispensed under pressure through a valve connected to polyethylene tubing with a syringe needle attached. 

This reasearch was supported by the U. S. Atomic Energy Commission, Document No. AEC COO-1088-29, and by the Advanced Research Projects Agency of the Department of Defense through the Northwestern University Materials Research Center. We wish to thank Lloyd Cooke of the Union Carbide Corp. and James Reid of the Phillips Petroleum Co. for the gift of polyethylene samples. 

Phillips Petroleum had difficulty maintaining quality control in the early years of making polyethylene. As a result, it produced large quantities of the product that could not be sold for commercial, industrial, or household use. The company faced financial ruin. Fortu nately, a new toy came into existence in the mid 1950s, the hula hoop. A hula hoop is simply a ring of plastic that... 

Polyethylene (Marlex 5003, Phillips Petroleum Co., Bartlesville, Okla.) was formed from powder into 0.009-inch-thick sheets between specularly smooth Mylar sheets in a metal mold at a temperature of 150°C. and pressure of 1000 p.s.i. for approximately 5 minutes. The polymer has a density of 0.95 and a melt index of 0.3. 

Other kinds of coordination catalytic systems developed few years before the Ziegler-Natta catalysts were based on chromium and molybdenum oxides supported on SiOj AI2O3 and other supports. The catalysts were patented by Phillips Petroleum and Standard Oil companies of Indiana for the synthesis of polyolefins. Although Phillips catalysts were the first to produce a fraction of crystalline polypropylene, these systems were more useful for the production of polyethylene. In fact, the Phillips and the Ziegler-Natta catalysts are currently the two commercial systems that dominate the production of HDPE [2]. 

As we saw previously, polypropylene was first made in June 1951, unintentionally as a solid polymer, by Phillips Petroleum, who were at that time seeking to convert excess refinery gases, ethylene and propylene, to high-octane fuel. Phillips developed their chromium olefin polymerization catalyst for linear polyethylene, but in fact, Phillips never entered the polypropylene manufacturing business. Paul Hogan and Robert Banks recorded the invention of the process by which they produced crystalline polypropylene about an hour after their discovery. As we shall see in more detail below, their January 1953 patent application was issued in March 1983 (32 years after their discovery) [11]. 

By recognizable name , only two of the early players in the polyolefin industry are listed ExxonMobil— formerly Exxon, previously Esso, previously Standard Oil (S.O.)—at the head of the list and Chevron Phillips, which was formed 1 July 2000 by merging the chemical operations of Phillips Petroleum Company and Chevron Corporation. Dow Chemical purchased Union Carbide Corporation for 9.3bn in 2001 and through that acquisition can claim to have been an early participant in this polyolefin industry (recalling that Union Carbide was rapidly developing ICI low-density polyethylene plants during WWH under sub-licence from DuPont). 

Hogan, J. P. Norwood, D. D. Ayres, C. A., Phillips Petroleum Company loop reactor polyethylene technology. J. Appl. Polym. ScL Appl Polym. Symp. 1981, 56,49-60. 

The loop reactors, which are recycled tubular reactors, are used by the Phillips Petroleum Co. and Solvay et Cie. The Phillips process is characterized by the use of a light hydrocarbon diluent such as isopentane or isobutane in loop reactors which consist of four jacketed vertical pipes. Figure 1 shows the schematic flow diagram for the loop reactor polyethylene process. The use of high-activity supported chromium oxide catalyst eliminates the need to deash the product. This reactor is operated at about 35 atm and 85-110° C with an average polymer residence time of 1.5 hr. Solid concentrations in the reactor and effluent are reported as 18 and 50 wt %, respectively. The reactor diameter is 30 in. (O.D.) and the length of the reactor loop is about 450 ft. 

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