Low-density polyethylene , manufacture

What differences would be observed between linear low density polyethylenes manufactured with a Ziegler-Natta catalyst versus a single site catalyst, such as a metallocene ... 

In 1989, the NDF Company opened a facility in Georgetown, South Carolina to produce low density polyethylene. Manufacturing of the polyethylene is done in two 50-ton reactors that are encased individually within their own 8-story-high process unit. The main raw materials for the manufacturing operations include ethylene, hexane, and hutene. The polymerization is completed in the presence of a catalyst. The hase chemicals for the catalyst are aluminum alkyl and isopentane. The reactor and catalyst preparation areas are on a distributed control system (DCS). A simplihed process flow diagram is attached. 

Random ethylene copolymers with small amounts (4-10 wt-%) of 7-olefins, e.g. 1-butene, 1-hexene, 1-octene and 4-methyl- 1-pentene, are referred to as linear low-density polyethylene, which is a commercially relevant class of polyolefins. Such copolymers are prepared by essentially the same catalysts used for the synthesis of high-density polyethylene [241]. Small amounts of a-olefin units incorporated in an ethylene copolymer have the effect of producing side chains at points where the 7-olefin is inserted into the linear polyethylene backbone. Thus, the copolymerisation produces short alkyl branches, which disrupt the crystallinity of high-density polyethylene and lower the density of the polymer so that it simulates many of the properties of low-density polyethylene manufactured by high-pressure radical polymerisation of ethylene [448] (Figure 2.3). 

Nonetheless, during the time when biodegradability was perceived as a potent selling attribute for products such as merchandise sacks and garbage bags, a number of products were introduced which were composed of a mixture of starch, usually about 6% by weight, and low-density polyethylene. Manufacturers of these materials claimed they were biodegradable, based on the fact that the starch component... 

Table 6 shows the sales estimates for principal film and sheet products for the year 1990 (14). Low density polyethylene films dominate the market in volume, followed by polystyrene and the vinyls. High density polyethylene, poly(ethylene terephthalate), and polypropylene are close in market share and complete the primary products. A number of specialty resins are used to produce 25,000—100,000 t of film or sheet, and then there are a large number of high priced, high performance materials that serve niche markets. The original clear film product, ceUophane, has faUen to about 25,000 t in the United States, with only one domestic producer. Table 7 Hsts some of the principal film and sheet material manufacturers in the United States.

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. 

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). 

Use the information given in Table 2.1 (Prices of Materials) and in Table 2.4 (Energy Content of Materials) to calculate the approximate cost of (a) aluminium, (b) low-density polyethylene, (c) mild steel and (d) cement in 2004, assuming that oil increases in price by a factor of 1.6 and that labour and other manufacturing costs increase by a factor of 1.3 between 1994 and 2004. 

At the end of the 1970s considerable interest developed in what became known as linear low density polyethylenes (LLDPE) which are intermediate in properties and structure to the high pressure and low pressure materials. While strictly speaking these are copolymers it is most convenient to consider them alongside the homopolymers. The LLDPE materials were rapidly accepted by industry particularly in the manufacture of film. The very low density polyethylenes (VLDPE) introduced by Union Carbide in 1985 were closely related. 

Polybut-1-ene became available in the early 1960s as Vestolen BT produced by Chemische Werke Hiils in Germany. Today it is manufactured by Shell in the United States. It is produced by a Ziegler-Natta system and the commercial materials have very high molecular weights of 770 000 to 3 000 000, that is about ten times that of the normal low-density polyethylenes. 

Dimerization of ethylene to butene-1 has been developed recently by using a selective titanium-based catalyst. Butene-1 is finding new markets as a comonomer with ethylene in the manufacture of linear low-density polyethylene (LLDPE). 

Polyethylene-based membranes are manufactured for use in hazardous waste landfills, lagoons, and similar applications. Two of these products have been tested to determine their effectiveness as barriers against radon diffusion. (In most cases, diffusive flow is considered of little or no significance as a mechanism of radon entry compared with convective flow). A 20-mil high-density polyethylene tested 99.9% effective in blocking radon diffusion under neutral pressure conditions. A 30-mil low-density polyethylene tested 98% effective in blocking radon diffusion under neutral pressure conditions. 

Why is Ziegler-Natta linear low density polyethylene used to manufacture cling films ... 

Van Vliet et al. (2004, 2006) investigated the formation of hot spots and reactor efficiency in various geometrical configurations of a tubular reactor for manufacturing Low-Density Polyethylene (LDPE) by means of the above... 

Polymerization inhibitors miscellaneous, 23 383 in styrene manufacture, 23 338 Polymerization initiators alkyllithiums as, 74 251 cerium application, 5 687 peroxydicarbonates as, 74 290 Polymerization kinetics, in PVC polymerization, 25 666-667 Polymerization mechanism, for low density polyethylene, 20 218 Polymerization methods, choice of,... 

A new propose for the manufacture of Low density polyethylene has been developed by Doro Chemical Co. This process uses much lower pressure in the presence of a catalyst system. Considerable reduction in plant cost is possible for this process. 

Mixed C4 olefins (primarily iC4) are isolated from a mixed C olefin and paraffin stream. Two different liquid adsorption high-purity C olefin processes exist the C4 Olex process for producing isobutylene (iCf ) and the Sorbutene process for producing butene-1. Isobutylene has been used in alcohol synthesis and the production of methyl tert-butyl ether (MTBE) and isooctane, both of which improve octane of gasoHne. Commercial 1-butene is used in the manufacture of both hnear low-density polyethylene (LLDPE) and high-density polyethylene (HDPE)., polypropylene, polybutene, butylene oxide and the C4 solvents secondary butyl alcohol (SBA) and methyl ethyl ketone (MEK). While the C4 Olex process has been commercially demonstrated, the Sorbutene process has only been demonstrated on a pilot scale. 

Aspinall JA, Duffy TD, Saunders MB, et al. The effect of low density polyethylene containers on some hospital-manufactured eye drop formulations. 1. Sorption of phenyl mercuric acetate. J Clin Hosp Pharm 1980 5 21-9. 

A polymeric composition for use in foam manufacture comprises a linear low density polyethylene and a resiliency modifier resin. The linear low density polyethylene is present in an amount of from about 1 to 90 weight percent of the polymeric composition and has a z-average molecular weight greater than about 700,000. The resiliency modifier resin is present in an amount of from 10 to about 99 weight percent of the polymeric composition and may be a low density polyethylene. 

Ethylene Polymers. Depending on the polymerization conditions, three major types of polyethylene are manufactured low-density polyethylene (LDPE) by free-radical polymerization, linear low-density polyethylene (LLDPE) by copolymerization of ethylene with terminal olefins, and high-density polyethylene (HDPE) by coordination polymerization. The processes yield polymers with different characteristics (molecular weight, molecular weight distribution, melt index, strength, crystallinity, density, processability). 

The first section of this chapter describes the most important high pressure process run under homogeneous conditions to manufacture Low Density PolyEthylene (LDPE). The radical polymerization of ethylene to LDPE is carried out in tubular reactors or in stirred autoclaves. Tubular reactors exhibit higher capacities than stirred autoclaves. The latter are preferred to produce ethylene copolymers having a higher comonomer content. 

It is expected that around 500,000 tons mPE will be manufactured in 2000 in Western Europe. Resins from high-pressure- as well as from low-pressure processes suffer more difficult processability. Their narrow molecular-weight distribution results in an unfavourable viscosity behaviour [8], As with linear low-density polyethylene (LLDPE), the viscosity of mPE is independent of the shear-rate over a wide range and reduces only at high shear-rates (Fig. 9.5-11). Therefore, energy consumption is high when mPE is processed with extruders which are designed for LDPE. 

The film thickness produced by film blowing ranges from 10 /mi to 100 pm and the rates of production are very high. The most common plastic films produced by this method are branched LDPE, linear low density polyethylene (LLDPE), and linear HDPE films. By using more than one extruder, multilayer films can also be manufactured. To appreciate the... 

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