Polyethylene a-process

Spherilene [Spherical polyethylene] A process for making polyethylene in the form of granules. The catalyst combines a Ziegler-Natta catalyst with a silane. Developed by Montecatini, Italy. The first plant was due for startup by Himont, in Lake Charles, LA, in 1993. 

Dimerization in concentrated sulfuric acid occurs mainly with those alkenes that form tertiary carbocations In some cases reaction conditions can be developed that favor the formation of higher molecular weight polymers Because these reactions proceed by way of carbocation intermediates the process is referred to as cationic polymerization We made special mention m Section 5 1 of the enormous volume of ethylene and propene production in the petrochemical industry The accompanying box summarizes the principal uses of these alkenes Most of the ethylene is converted to polyethylene, a high molecular weight polymer of ethylene Polyethylene cannot be prepared by cationic polymerization but is the simplest example of a polymer that is produced on a large scale by free radical polymerization... 

It is estimated that 27,000 t/yr of CSM have been commercially used in the United States. However, due to environmental problems in the manufacturing process, it has been necessary to develop a process that is much mote expensive. As a result many companies using CSM ate trying to replace the CSM with CPE or other elastomers. The result is a decline in the usage of this polymer. Chlorosulfonated polyethylene is sold under the trade name Hypalon (DuPont—Dow Company). 

Calendering operations are done routinely, and warm roUs (40—90°C) are recommended for optimum sheet smoothness. A process aid, such as low molecular weight polyethylene wax, is often used. Sheet thicknesses of 0.5—1.3 mm (20—50 mils) can normally be produced. 

As a result of the work of Ziegler in Germany, Natta in Italy and Pease and Roedel in the United States, the process of co-ordination polymerisation, a process related to ionic polymerisation, became of significance in the late 1950s. This process is today used in the commercial manufacture of polypropylene and polyethylene and has also been used in the laboratory for the manufacture of many novel polymers. In principle the catalyst system used governs the way in which a monomer and a growing chain approach each other and because of this it is possible to produce stereoregular polymers. 

Polyethylene is processed by a wide variety of techniques, most of which were outlined briefly in Chapter 8. There is insufficient space here to deal adequately with the principles and practice of these processes or even with the particular characteristics of polyethylene being fabricated by these processes. For this reason a list of books giving further details Is given at the end of Chapter 8. 

Very high molecular weight polyethylenes (A/ in the range 1-6 X 10 ) prepared by the Ziegler process have also become available. As might be expected from consideration of Figure 3.1 these polymers cannot be processed easily in the molten state without decomposition and it is therefore often necessary to process in the rubbery phase. 

Polycarbonate melts adhere strongly to metals and if allowed to cool in an injection cylinder or extrusion barrel may, on shrinkage, pull pieces of metal away from the wall. It is therefore necessary to purge all equipment free of the resin, with a polymer such as polyethylene, after processing. 

Corrective Action Application At a Navy facility in Guam, approximately 25 tons of PCB contaminated soil was treated using the KPEG (potassium polyethylene glycol) process. PCB concentrations were reduced from 3000 ppm to less than 5 ppm. Upon completion of treatment using the KPEG process, the soil was neutralized from a pH of 14 to 7. A full-scale system for this process is currently under development. 

Perhaps the most familiar addition polymer is polyethylene, a solid derived from the monomer ethylene. We might represent the polymerization process as... 

Addition polymers are formed by the reaction of the monomeric units without the elimination of atoms. The monomer is usually an unsaturated organic compound such as ethylene, H2C=CHs, which in the presence of a suitable catalyst will undergo an addition reaction to form a long chain molecule such as polyethylene. A general equation for the first stage of such a process is... 

As a final example of the application of gas-liquid-particle operation to a process involving a gaseous reactant and a solid catalyst, the possibility of polymerizing ethylene in, for example, a slurry operation employing a metal or metal oxide catalyst can be cited. It has been suggested that the good control of reaction conditions obtained in a slurry-type operation may be of importance in the production of certain types of polyethylene (Rl). 

The main use of propylene is for polymerization to polypropylene, a process similar to the manufacture of high-density polyethylene (i.e., a low-pressure, catalytic process). Textile hhers made from polypropylene are relatively low-cost and have particularly good properties, such as high resistance to abrasion and soiling for use in furniture upholstery and indoor/outdoor carpeting. 

The use of polyethylene glycol ethers in a process in which a high viscosity emulsion is formed on contact with residual crude oil has also been tested as a means of plugging thief zones using surfactants (248-250). Precipitation of sodium pectate when fresh water solutions contact brine has been proposed as a method of plugging high permeability zones (251). 

In addition to the lengths of polymer molecules, the cross-sectional shapes have a major effect on their hardness and thermal stability. Aliphatics (paraffins, polyethylene, etc.) have the most simple cross-sectional shapes. Their simple and relatively symmetric shapes allow them to slide past on another readily via a process called reptation (de Gennes, 1990). As a result, linear polyethylene is relatively soft (Figure 13.1). 

The improvement of its activity and stability has been approach by the use of GE tools (see Refs. [398] and [399], respectively). A process drawback is the fact that the oxidation of hydrophobic compounds in an organic solvent becomes limited by substrate partition between the active site of the enzyme and the bulk solvent [398], To provide the biocatalyst soluble with a hydrophobic active site access, keeping its solubility in organic solvents, a double chemical modification on horse heart cytochrome c has been performed [400,401], First, to increase the active-site hydrophobicity, a methyl esterification on the heme propionates was performed. Then, polyethylene glycol (PEG) was used for a surface modification of the protein, yielding a protein-polymer conjugates that are soluble in organic solvents. 

CDP A process for destroying dioxins and polychlorinated biphenyls by treatment with a polyethylene glycol and sodium peroxide in a fixed catalyst bed. Developed by Sea Marconi Technologies, Turin, Italy. See also KPEG. 

KPEG [K (potassium) polyethylene glycol] A process for destroying polychlorinated bipheny ls in contaminated soil by heating to 150°C, under pressure, with potassium hydroxide,... 

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. 

Sclair A process for polymerizing ethylene. Depending on the co-monomer used, the product can be linear low-density polyethylene (LLDPE) or high-density polyethylene (HDPE). Developed by DuPont in 1960 and widely licensed. Engineered by Uhde under the name Sclairtech. Nova Chemicals (Alberta) acquired the technology in 1994. 

UNIPOL [Union Carbide Polymerization] A process for polymerizing ethylene to polyethylene, and propylene to polypropylene. It is a low-pressure, gas-phase, fluidized-bed process, in contrast to the Ziegler-Natta process, which is conducted in the liquid phase. The catalyst powder is continuously added to the bed and the granular product is continuously withdrawn. A co-monomer such as 1-butene is normally used. The polyethylene process was developed by F. J. Karol and his colleagues at Union Carbide Corporation the polypropylene process was developed jointly with the Shell Chemical Company. The development of the ethylene process started in the mid 1960s, the propylene process was first commercialized in 1983. It is currently used under license by 75 producers in 26 countries, in a total of 96 reactors with a combined capacity of over 12 million tonnes/y. It is now available through Univation, the joint licensing subsidiary of Union Carbide and Exxon Chemical. A supported metallocene catalyst is used today. 

Similarly large anisotropies were later reported for highly emissive blends of alkoxy-substituted bis(phenylethynyl)benzene derivatives and polyolefins such as linear low-density polyethylene (LLDPE) and isotactic polypropylene (z-PP) [8,9]. The latter systems reach high levels of anisotropy at very low draw ratios, which is advantageous from a processing point of view. 

Polymers such as PVC, polyethylene, polypropylene or polystyrene are synthesised by using a process known as polymerisation. 

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