Low-density polyethylene processing

Several commercial processes are used to produce high-density polyethylene. All employ more moderate pressures and most also use lower temperatures than the low-density polyethylene processes. The Ziegler-developed process uses the mildest conditions, 200-400 kPa (2 atm) and 50-75°C, to polymerize a solution of ethylene in a hydrocarbon solvent using a titanium tetrachloride/aluminum alkyl-based coordination catalyst. After quenching the polymerized mixture with a simple alcohol, the catalyst residues may be removed by extraction with dilute hydrochloric acid or may be rendered inert by a proprietary additive. The product is almost insoluble in the hydrocarbon solvent, so is recovered by centrifuging and drying. The final product is extruded into uniform pellets and cooled for shipping to fabricators. 

Orbey, H., Bokis, C.P., and Chen, C.-C., Equation of state modeling of phase equilibrium in the low-density polyethylene process the Sanchez-Lacombe, Statistical Associating Fluid Theory, and the polymer-SRK equation of state, Ind. Eng. Chem. Res., 37, 4481, 1998. 

Linear Low Density Polyethylene Linear polyethylenes with density 0.91-0.94 g/cm. Has better tensile, tear, and impact strength, and crack-resistance properties, but poorer haze and gloss than branched low-density polyethylene. Processed by extrusion at increased pressure and higher melt temperatures compared to branched low-density polyefliylene, and by molding. Used to manu-faeture film, sheet, pipe, electrical insulation, liners, bags, and food wraps. Also called LLDPE. 

FIGURE 12.3 Tubular low-density polyethylene process. Reprinted with permission from CHEMTECH 13(4), 223 (1983). Copyright 1983 American Chemical Society. 

The second type of solution polymerization concept uses mixtures of supercritical ethylene and molten PE as the medium for ethylene polymerization. Some reactors previously used for free-radical ethylene polymerization in supercritical ethylene at high pressure (see Olefin POLYMERS,LOW DENSITY polyethylene) were converted for the catalytic synthesis of LLDPE. Both stirred and tubular autoclaves operating at 30—200 MPa (4,500—30,000 psig) and 170—350°C can also be used for this purpose. Residence times in these reactors are short, from 1 to 5 minutes. Three types of catalysts are used in these processes. The first type includes pseudo-homogeneous Ziegler catalysts. In this case, all catalyst components are introduced into a reactor as hquids or solutions but form soHd catalysts when combined in the reactor. Examples of such catalysts include titanium tetrachloride as well as its mixtures with vanadium oxytrichloride and a trialkyl aluminum compound (53,54). The second type of catalysts are soHd Ziegler catalysts (55). Both of these catalysts produce compositionaHy nonuniform LLDPE resins. Exxon Chemical Company uses a third type of catalysts, metallocene catalysts, in a similar solution process to produce uniformly branched ethylene copolymers with 1-butene and 1-hexene called Exact resins (56). 

The low vinyl acetate ethylene—vinyl acetate copolymers, ie, those containing 10—40 wt % vinyl acetate, are made by processes similar to those used to make low density polyethylene for which pressures are usually > 103 MPa (15,000 psi). A medium, ie, 45 wt % vinyl acetate copolymer with mbber-like properties is made by solution polymerisation in /-butyl alcohol at 34.5 MPa (5000 psi). The 70—95 wt % vinyl acetate emulsion copolymers are made in emulsion processes under ethylene pressures of 2.07—10.4 MPa (300—1500 psi). 

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. 

In the Institut Fransais du Petrc le process (62), ethylene is dimerized into polymer-grade 1-butene (99.5% purity) suitable for the manufacture of linear low density polyethylene. It uses a homogeneous catalyst system that eliminates some of the drawbacks of heterogeneous catalysts. It also inhibits the isomerization of 1-butene to 2-butene, thus eliminating the need for superfractionation of the product (63,64). The process also uses low operating temperatures, 50—60°C, and pressures (65). 

Union Carbide Corp. also uses a siUca-supported chromium catalyst in their extremely low cost Unipol gas-phase linear low density ethylene copolymer process, which revolutionized the industry when it was introduced in 1977 (86—88). The productivity of this catalyst is 10 —10 kg polymer/kg transition metal contained in the catalyst. By 1990, the capacity of Unipol linear low density polyethylene reactors was sufficient to supply 25% of the world s total demand for polyethylene. 

The cooling requirements will be discussed further in Section 8.2.6. What is particularly noteworthy is the considerable difference in heating requirements between polymers. For example, the data in Table 8.1 assume similar melt temperatures for polystyrene and low-density polyethylene, yet the heat requirement per cm is only 295 J for polystyrene but 543 J for LDPE. It is also noteworthy that in spite of their high processing temperatures the heat requirements per unit volume for FEP (see Chapter 13) and polyethersulphone are, on the data supplied, the lowest for the polymers listed. 

Processes for Making Linear Low-density Polyethylene and Metallocene Polyethylene... 

There has been interest, particularly in Japan, in the production of cross-linked low-density polyethylene foam. Some processes, such as the Furukawa process and the Hitachi process, use chemical cross-linking techniques whilst others, such as the Sekisui process, involve radiation cross-linking. 

Fluidised-bed techniques, pioneered with low-density polyethylene, have been applied to PVC powders. These powders can be produced by grinding of conventional granules, either at ambient or sub-zero temperatures or by the use of dry blends (plasticised powders). The fluidised bed process is somewhat competitive with some well-established paste techniques, and has the advantage of a considerable flexibility in compound design. 

The three isomers constituting n-hutenes are 1-hutene, cis-2-hutene, and trans-2-hutene. This gas mixture is usually obtained from the olefinic C4 fraction of catalytic cracking and steam cracking processes after separation of isobutene (Chapter 2). The mixture of isomers may be used directly for reactions that are common for the three isomers and produce the same intermediates and hence the same products. Alternatively, the mixture may be separated into two streams, one constituted of 1-butene and the other of cis-and trans-2-butene mixture. Each stream produces specific chemicals. Approximately 70% of 1-butene is used as a comonomer with ethylene to produce linear low-density polyethylene (LLDPE). Another use of 1-butene is for the synthesis of butylene oxide. The rest is used with the 2-butenes to produce other chemicals. n-Butene could also be isomerized to isobutene. ... 

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