Ethylene low density

Poly(ethylene), low density Poly(e-caprolactam) 1933 1938 1939 1939 Thermoplastics Fibers, thermoplastics Silicone 1901 Epoxy resins 1938 1942 1946 1956 Fluids, resins, elastomers Adhesives... 

Werner (1980) has studied devolatilization in corotating twin-screw extruders when the volatile component was stripped from the polymeric solution by applying a vacuum to the system. Rough estimates of the equilibrium partial pressure of the volatile component in the feedstream for each of the systems studied by Werner indicate that this pressure was less than the applied pressure, which means that bubbles could have been formed. Figure 17 shows the influence of the externally applied pressure on the exit concentration for a methyl methacrylate-poly(methyl methacrylate) system of fixed concentration. Note that the exit concentration decreases as the pressure is decreased, but seems to approach an asymptotic value at the lowest pressures studied. Werner also reported that at a fixed flow rate and feed concentration the exit concentration did not vary with screw speed (over the range 150-300 min" ), which also suggests that ky alay, is independent of screw speed. Figure 18 is a plot of data obtained by Werner on an ethylene-low-density poly(ethylene) system and also shows that decreases in the applied pressure result in decreases in the exit concentration, but here a lower asymptote is not observed. 

Fig. 18. Experimentally measured values of the exit concentration as a function of pressure and water content for the system ethylene-low-density polyfethylene). Data were obtained in a twin-screw extruder by Werner. (Reproduced with permission from Werner, 1980.)...

In Chapter 1, it was mentioned that highly branched low density polyethylene and copolymers made with polar comonomers are produced only by free radical polymerization at very high pressure and temperature. (All other forms of commercially available polyethylene are produced with transition metal catalysts under much milder conditions see Chapters 3, 5 and 6.) In this chapter we will review how initiators achieve free radical polymerization of ethylene. Low density polyethylene and copolymers made with polar comonomers are produced in autoclave and tubular processes, to be discussed in Chapter 7,... 

Fig. 5.11. Intrinsic viscosity [q] as a function of the molar mass M for linear poly(ethylene) (high density poly(ethyl-ene),HDPE) and longchain branched poly(ethylene) (low density poly(ethyl-ene), LDPE) in tetraline at 7=120 (data from [47,94]) as well as for a dendrimer with 3,5-dioxybenzylidene units in tetra-hydrofuran at 7=30 X (data from [47,95])...

Figure 8.32 Melt flow index variation with blend composition for high-density poly-ethylene/low-density polyethylene blend at 190°C and 2.16-kg test load condition for MFI using data from Ref. 87 (validity at all temperatures). (Reprinted from Ref. 78 with kind permission from Steinkopff Verlag Darmstadt.)...

Rejon A and Alvarez C (1987), Mechanical and flow properties of high density poly-ethylene/low density polyethylene . Polymer Engineering Science, 27,640-646. 

S. Khalili, M. Masoomi, and R. Bagheri, The effect of organo-modified montmorillonite on mechanical and barrier properties of linear low-density poly-ethylene/low-density polyethylene blend films, /. Plast. Film Sheeting 29 (1), 39-55 (January, 2013). 

One of the mam uses of the linear a olefins prepared by oligomerization of ethylene is in the preparation of linear low density polyethylene Linear low density polyethylene is a copoly mer produced when ethylene is polymerized in the presence of a linear a olefin such as 1 decene [H2C=CH(CH2)7CH3] 1 Decene replaces ethylene at random points in the growing polymer chain Can you deduce how the structure of linear low density polyethylene differs from a linear chain of CH2 units ... 

Low-density Medium-density High-density Ultra high-molecular-weight Glass-fiber- reinforced, high-density Ethylene-vinyl acetate copolymer... 

Low density polyethylene has been pyrolyzed at 800°C to produce ethylene, propylene, and other light olefins ia 75% yield (43). 

This type of adhesive is generally useful in the temperature range where the material is either leathery or mbbery, ie, between the glass-transition temperature and the melt temperature. Hot-melt adhesives are based on thermoplastic polymers that may be compounded or uncompounded ethylene—vinyl acetate copolymers, paraffin waxes, polypropylene, phenoxy resins, styrene—butadiene copolymers, ethylene—ethyl acrylate copolymers, and low, and low density polypropylene are used in the compounded state polyesters, polyamides, and polyurethanes are used in the mosdy uncompounded state. 

HDPE, high density polyethylene PP, polypropylene EVA, ethylene—vinyl alcohol SMC, sheet-molding compound ERP, fiber-reinforced plastic LDPE, low density polyethylene PE, polyethylene BMC, bulk mol ding compound TPE, thermoplastic elastomer. 

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.

An independent development of a high pressure polymerization technology has led to the use of molten polymer as a medium for catalytic ethylene polymerization. Some reactors previously used for free-radical ethylene polymerization at a high pressure (see Olefin polymers, low density polyethylene) have been converted to accommodate catalytic polymerization, both stirred-tank and tubular autoclaves operating at 30—200 MPa (4,500—30,000 psig) and 170—350°C (57,83,84). CdF Chimie uses a three-zone high pressure autoclave at zone temperatures of 215, 250, and 260°C (85). Residence times in all these reactors are short, typically less than one minute. 

AH higher a-olefins, in the presence of Ziegler-Natta catalysts, can easily copolymerise both with other a-olefins and with ethylene (51,59). In these reactions, higher a-olefins are all less reactive than ethylene and propylene (41). Their reactivities in the copolymerisation reactions depend on the sise and the branching degree of their alkyl groups (51) (see Olefin polya rs, linear low density polyethylene). 

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. 

In order to improve the physical properties of HDPE and LDPE, copolymers of ethylene and small amounts of other monomers such as higher olefins, ethyl acrylate, maleic anhydride, vinyl acetate, or acryUc acid are added to the polyethylene. Eor example, linear low density polyethylene (LLDPE), although linear, has a significant number of branches introduced by using comonomers such as 1-butene or 1-octene. The linearity provides strength, whereas branching provides toughness. 

Around Izod notch Low-density polyethylene Ethylene-propylene block copolymers Cellulose nitrate and propionate ABS and high-impact polystyrene Bis-phenol A polycarbonate... 

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