HDPE manufacture

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. 

FIGURE 230 The swelling temperature of polymers in isobutane, plotted here against the polymer density, provides the operations guideline for HDPE manufacture with Cr/silica. 

Another important advantage of DRT dryer as a predryer in PP drying is its suitability in a corrosive environment. A persistent problem often seen in PP and high-density polyethylene (HDPE) manufacturing plants is the deterioration of the equipment due to free chlorides. The chlorides result from the deactivation of the activated catalysts with alcohol. Stress corrosion cracking is the most common corrosion... 

Phillips supported chromium (II) catalyst, the most commonly used for high density polyethylene (HDPE) manufacture, possibly behaves in a similar manner, but the olefin insertion reaction is faster by several orders of magnitude. In the original Zeigler catalyst systems for HDPE, an aluminium alkyl is used to reductively alkylate the primary component, most frequently a titanium compound, to give the true catalytic species. 

High-density polyethylene was produced commercially during these early years with both the Phillips Cr-based catalyst and the Ziegler Ti-based catalyst however, each catalyst type provided a different type of polymer structure that addressed different polyethylene markets and applications. For the most part, each product type was unique to these markets and consequently HDPE manufactured by each type of catalyst did not compete with each other. 

Commonly, nowadays, the active catalyst (based on chromium, titanium, or vanadium) used in HDPE manufacture is adsorbed onto a highly porous silica support. Determination of the silica catalyst support content of the final polymer gives an assessment of the economic productivity of the reactor, i.e., its output of PE... 

Plastic materials represent less than 10% by weight of all packagiag materials. They have a value of over 7 biUion including composite flexible packagiag about half is for film and half for botties, jars, cups, tubs, and trays. The principal materials used are high density polyethylene (HDPE) for botties, low density polyethylene for film, polypropylene (PP) for film, and polyester for both botties and films. Plastic resias are manufactured by petrochemical companies, eg. Union Carbide and Mobil Chemical for low density polyethylene (LDPE), Solvay for high density polyethylene, Himont for polypropylene, and Shell and Eastman for polyester. 

Orientation. Most articles made of HDPE, including film, fiber, pipes, and injection-molded articles, exhibit some degree of molecular and crystal orientation (21). In some cases, orientation develops spontaneously for example, during melt flow into a mold and its subsequent crystallisation. When blown HDPE film and fiber are manufactured, orientation can be introduced dehberately by stretching. 

AH technologies employed for catalytic polymerization processes in general are widely used for the manufacture of HDPE. The two most often used technologies are slurry polymerization and gas-phase polymerization. Catalysts are usuaHy fine-tuned for a particular process. 

Two modifications of the duidized-bed reactor technology have been developed. In the first, two gas-phase duidized-bed reactors coimected to one another have been used by Mobil Chemical Co. and Union Carbide to manufacture HDPE resins with broad MWD (74,75). In the second development, a combination of two different reactor types, a small slurry loop reactor followed by one or two gas-phase duidized-bed reactors (Sphetilene process), was used by Montedision to accommodate a Ziegler catalyst with a special particle morphology (76,77). This catalyst is able to produce PE resins in the form of dense spheres with a diameter of up to 4—5 mm such resins are ready for shipping without pelletization. 

Solution Polymerization. Two solution polymerization technologies ate practiced. Processes of the first type utilize heavy solvents those of the second use molten PE as the polymerization medium (57). Polyethylene becomes soluble ia saturated C —hydrocarbons above 120—130°C. Because the viscosity of HDPE solutions rapidly iacrease with molecular weight, solution polymerization is employed primarily for the production of low mol wt resias. Solution process plants were first constmcted for the low pressure manufacture of PE resias ia the late 1950s they were later exteasively modified to make their operatioa economically competitive. 

Extrusion. In general, extmsion is the process of forcing a polymer melt through a die (104,105). Typical extmsion appHcations include initial resin pelletization after manufacture and production of film, sheet, pipe, tubing, and insulated wire. The HDPE extmsion temperature is around 150°C, the pressure 40—50 MPa (5800—7250 psi). An extmsion production line usually consists of an extmder (mono- or twin-screw) with a die at the end, a cooling and shaping device, a pulling device (a roUer), and a cutter. 

HDPE is one of the largest commodity plastics manufactured worldwide. Dynamics of HDPE production is represented by the following data indicating both the existing and projected demand (t/yr) (114) ... 

The current and projected HDPE capacities are shown in Table 3, and producers of resins in Table 4. In most cases, an accurate estimation of the total HDPE volume is compHcated by the fact that a large number of plants also use the same reactors for manufacture of HDPE or LLDPE. UHMWPE is produced in the United States (Himont and American Hoechst), in Japan (Asahi), and in Germany (Hoechst) worldwide capacity is approximately 45,000 tons. The use of post-consumer (recycled) HDPE is gradually increasing in volume. The growth of recycling programs is driven principally by economics (110,114) it has increased from a mere 60,000 tons in 1989 to 350,000 tons in 1994 and is expected to increase to 1.4 million t in the year 2000 (115). 

The chemical iadustry manufactures a large variety of semicrystalline ethylene copolymers containing small amounts of a-olefins. These copolymers are produced ia catalytic polymerisation reactions and have densities lower than those of ethylene homopolymers known as high density polyethylene (HDPE). Ethylene copolymers produced ia catalytic polymerisation reactions are usually described as linear ethylene polymers, to distiaguish them from ethylene polymers containing long branches which are produced ia radical polymerisation reactions at high pressures (see Olefin POLYMERS, LOWDENSITY polyethylene). 

Chromium Oxide-Based Catalysts. Chromium oxide-based catalysts were originally developed by Phillips Petroleum Company for the manufacture of HDPE resins subsequendy, they have been modified for ethylene—a-olefin copolymerisation reactions (10). These catalysts use a mixed sihca—titania support containing from 2 to 20 wt % of Ti. After the deposition of chromium species onto the support, the catalyst is first oxidised by an oxygen—air mixture and then reduced at increased temperatures with carbon monoxide. The catalyst systems used for ethylene copolymerisation consist of sohd catalysts and co-catalysts, ie, triaLkylboron or trialkyl aluminum compounds. Ethylene—a-olefin copolymers produced with these catalysts have very broad molecular weight distributions, characterised by M.Jin the 12—35 and MER in the 80—200 range. 

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. 

Polyolefins are manufactured and used in much greater quantity than any other class of plastics. The principal polyolefins are polyethylenes of various densities (LDPE, LLDPE, HDPE) and polypropylene (PP) (see Olefin polymers). 

The head of the femoral component then articulates with an ion-bombarded, HDPE, high walled, acetabular liner which fits iato a screwed ia, machined, titanium, chromium—cobalt—molybdenum or vanadium—aluminum metallic alloy hydroxyapatite-coated acetabular shell/cup. Each of the separate parts of the modular system for total hip arthroplasty is manufactured ia several different sizes. 

Trade name Manufacturer ABS LDPE HDPE pp PS Concentration, %... 

Manufacture of milk containers using postconsumer HDPE has the potential to significantly lower the GHG emissions and energy due to the... 

Applications Radiotracer measurements, which combine high sensitivity and specificity with poor spatial resolution, have been used for migration testing. For example, studies have been made on HDPE, PP and HIPS to determine effects of manufacturing conditions on migration of AOs from plastic products into a test fat [443]. Labelled antioxidant was determined radio-analytically after 10 days at 40 °C. Acosta and Sas-tre [444] have used radioactive tracer methods for the determination of styrene ethyl acrylate in a styrene ethyl acrylate copolymer. 

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