High-density polyethylene processing

High pressures are required for many commercial chemical processes. For example, the synthesis of ammonia is carried out at reactor pressures of up to 1000 bar, and high-density polyethylene processes operate up to 1500 bar. 

Sometimes a lower density polyethylene is made with both this type of catalysis or Ziegler-Natta. Branching is controlled by the addition of small amounts of 1-alkenes added to the ethylene. 1-Hexene would give a C4 branch, 1-octene a Ce branch, etc. If enough 1-alkene is used the polymer is called linear low-density polyethylene (LLDPE). It is made by a high-density polyethylene process but branching gives a lower density. 

Most high density polyethylene processing technologies require the melting of HDPE. Typical HDPE melt viscosities are between 1,000 and 100,000 Pa s( 10,000 10 P) the melt viscosity of HDPE strongly... 

Numerous industrial applications of applied thermodynamics have been reported in the literature for engineering analysis of wide varieties of chemical systems and processes. For example, Chen and Mathias reported examples of physical property modeling for the high-density polyethylene process and for sulfuric acid plants. Here, we present two recent examples that are illustrative of numerous applications of applied thermodynamics models in the industry for various process and product development studies. 

Keywords High density polyethylene Process control Process design Process modelling Product portfolio Super-active catalysts Ziegler slurry polymerization... 

The basic reason for this is the considerable reduction in fixed capital requirements for the new high-density polyethylene processes, since all of the HDPE processes shown in Table 4 use highly active catalysts and do not require removal of catalyst residues or non-crystalline polymer. Polypropylene, however, is still manufactured primarily by processes which require the removal of catalyst residues and atactic material, and this fact is reflected both in higher capital costs and higher product values, even though... 

Flashspun high density polyethylene fabrics have been commercial since the 1960s however, this is a proprietary and radically different process of manufacturing a spunbonded fabric, more technically challenging to produce, and highly capital intensive. 

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. 

Polypropylene polymers are typically modified with ethylene to obtain desirable properties for specific applications. Specifically, ethylene—propylene mbbers are introduced as a discrete phase in heterophasic copolymers to improve toughness and low temperature impact resistance (see Elastomers, ETHYLENE-PROPYLENE rubber). This is done by sequential polymerisation of homopolymer polypropylene and ethylene—propylene mbber in a multistage reactor process or by the extmsion compounding of ethylene—propylene mbber with a homopolymer. Addition of high density polyethylene, by polymerisation or compounding, is sometimes used to reduce stress whitening. In all cases, a superior balance of properties is obtained when the sise of the discrete mbber phase is approximately one micrometer. Examples of these polymers and their properties are shown in Table 2. Mineral fillers, such as talc or calcium carbonate, can be added to polypropylene to increase stiffness and high temperature properties, as shown in Table 3. 

Thermoplastics. The highest consumption of color concentrates is in thermoplastic resins, such as low and high density polyethylene, polypropylene, PVC, and polystyrene. Processing techniques for thermoplastics are usually based on dry color dispersion in a compatible resin (36). 

HDPE melts at about 135°C, is over 90% crystalline, and is quite linear, with more than 100 ethylene units per side chain. It is harder and more rigid than low density polyethylene and has a higher melting point, tensile strength, and heat-defiection temperature. The molecular weight distribution can be varied considerably with consequent changes in properties. Typically, polymers of high density polyethylene are more difficult to process than those of low density polyethylene. 

Blends of isobutylene polymers with thermoplastic resins are used for toughening these compounds. High density polyethylene and isotactic polypropylene are often modified with 5 to 30 wt % polyisobutylene. At higher elastomer concentration the blends of butyl-type polymers with polyolefins become more mbbery in nature, and these compositions are used as thermoplastic elastomers (98). In some cases, a halobutyl phase is cross-linked as it is dispersed in the polyolefin to produce a highly elastic compound that is processible in thermoplastic mol ding equipment (99) (see Elastomers, synthetic-thermoplastic). ... 

In the mid-1950s a number of new thermoplastics with some very valuable properties beeame available. High-density polyethylenes produced by the Phillips process and the Ziegler process were marketed and these were shortly followed by the discovery and rapid exploitation of polypropylene. These polyolefins soon became large tonnage thermoplastics. Somewhat more specialised materials were the acetal resins, first introduced by Du Pont, and the polycarbonates, developed simultaneously but independently in the United States and Germany. Further developments in high-impact polystyrenes led to the development of ABS polymers. 

The Phillips process for the manufacture of high-density polyethylene may be adapted to produce copolymers of ethylene with small amounts of propylene or but-l-ene and copolymers of this type have been available since 1958. These soon found application in blown containers and for injection moulding. Properties of two grades of such copolymers are compared with two grades of Phillips-type homopolymer in Table 11.11. 

By permission, Norton Chemical Process Products Corp., Bull. SI-72 and Bull. PTP-1 other manufacturer s data are equivalent, f Also available in polypropylene (including glass reinforced) high density polyethylene, rigid PVC, fluorinated vinyls. 

High-density polyethylene (HDPE) is produced by a low-pressure process in a fluid-bed reactor. Catalysts used for HDPE are either of the Zieglar-type (a complex of A1(C2H5)3 and a-TiCl4) or silica-alumina impregnated with a metal oxide such as chromium oxide or molybdenum oxide. 

High density polyethylene produced by a low-pressure low-temperature process involving Ziegler-Natta catalysts. This creates low levels of branching and hence a high degree of crystallinity. 

Cut Out Separations. This can produce significant savings regardless of the stage of the process to which it is applied, provided efficiency of other parts of the process can be maintained. Avoidance of treatments to feedstocks and intermediates is clearly advantageous as is the removal of the need to clean up catalyst residues in high density polyethylene. 

Gas phase olefin polymerizations are becoming important as manufacturing processes for high density polyethylene (HOPE) and polypropylene (PP). An understanding of the kinetics of these gas-powder polymerization reactions using a highly active TiCi s catalyst is vital to the careful operation of these processes. Well-proven models for both the hexane slurry process and the bulk process have been published. This article describes an extension of these models to gas phase polymerization in semibatch and continuous backmix reactors. 

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