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Polyolefin Resins AccessScience from McGraw-Hill Education Page 1 of 10 www.accessscience.com Polyolefin resins Contributed by: Bruce Bersted, Steven A. Cohen Publication year: 2014 Polymers derived from hydrocarbon molecules that possess one or more alkenyl (or olefinic) groups. The term polyolefin typically is applied to polymers derived from ethylene, propylene, and other alpha-olefins, and from isobutylene, cyclic olefins, and butadiene and other diolefins. Polymers produced from other olefinic monomers, such as styrene, vinyl chloride, and tetrafluoroethylene, generally are considered separately. See also: ALKENE . Polyethylene The term polyethylene generally refers to any homopolymer or copolymer in which ethylene is the major component monomer. Polyethylene is a semicrystalline polymer of low to moderate strength and high toughness. ◦ ◦ The melting point varies from approximately 105 to 125 C (220 to 257 F), depending on the degree of crystallinity. The density of polyethylene reflects the degree of crystallinity, and is generally used in classifying 3 commercial grades. Low-density polyethylene, having densities ranging from 0.905 to 0.936 g ∕ cm, , can be subdivided into high-pressure low-density polyethylene (LDPE), and low-pressure low-density polyethylene copolymers, referred to as linear low-density polyethylene (LLDPE). This last term denotes a copolymer of polyethylene that is produced by the low-pressure polymerization process, as opposed to low-density polyethylene (or conventional polyethylene), which is produced by an older high-pressure polymerization process. In a typical linear low-density polyethylene, the percentage of comonomer would be on the order of 2–3 3 mol %, typically butene. High-density polyethylene (HDPE) covers the density range from 0.941 to 0.967 g ∕ cm, . See also: COPOLYMER . The various types of polyethylene are characterized by differences in structure ( Fig. 1 ). High-density polyethylene generally consists of a polymethylene (CH, 2 ), n chain with no, or very few, side chains to disrupt crystallization, while linear low-density polyethylene contains side chains whose length depends on the comonomer used. The spacing and uniformity of the incorporation of the comonomer in linear low-density polyethylene depends on both the process and the type of comonomer, but the incorporation of comonomer is generally nonuniform. To some extent, the uniformity tends to decrease with the size of the comonomer. Polyethylene with structures different from those produced with previous-generation catalysts are being produced with metallocene catalysts. Metallocene materials can cover the density range of both the high-density polyethylene and the linear low-density polyethylene, with the important distinction that the structures are very uniform in both molecular weight and comonomer incorporation. See also: METALLOCENES . AccessScience from McGraw-Hill Education Page 2 of 10 www.accessscience.com WIDTH:BFig. 1 Polyethylene structures. ( a ) Conventional low-density polyethylene. ( b ) Linear low-density polyethylene and high-density polyethylene with alpha-olefin comonomer. ( c ) Linear high-density polyethylene with no comonomer [a polymethylene chain]. ( d ) Metallocene low-density polyethylene. Polymerization The monomer for polyethylene is produced by cracking aliphatic hydrocarbons separated in the refining process. 2 Low-density polyethylene is formed by the polymerization of ethylene at high pressures (15,000–50,000 lb ∕ in., ◦ ◦ or 100–350 megapascals) and at temperatures of 150–300 C (300–570 F) in the presence of a small amount of organic peroxide or oxygen. The density is controlled by regulating the temperature, where lower temperatures lead to higher densities. Linear low-density polyethylene is produced commercially by the copolymerization of ◦ ◦ ethylene with alpha-olefins ranging from C, 3 to C, 8 at temperatures up to 250 C (480 F) at low pressure 2 (300–1100 lb ∕ in., or 2–7.6 MPa) in the presence of a chromium catalyst or titanium-based Ziegler-Natta catalyst. See also: CATALYSIS ; SINGLE-SITE CATALYSTS (POLYMER SCIENCE) . High-density polyethylene is formed at temperatures similar to those for linear low-density polyethylene and at 2 pressures of generally less than 1000 lb ∕ in., (7 MPa) by using either chromium or Ziegler catalysts. The molecular-weight distribution of high-density polyethylene is largely controlled by the type of catalyst, while the molecular weight is most often controlled with hydrogen level. Metallocene, or more generally single-site, catalysts have a transition metal sandwiched between organic ring compounds. They allow molecular weight and comonomer distributions to be closely controlled, such that each polymer molecule closely resembles the others. Additionally, these catalyst systems permit the incorporation of comonomers once thought incompatible with previous catalyst generations. See also: POLYMERIZATION ; SINGLE-SITE CATALYSTS (POLYMER SCIENCE) . Properties The physical properties of polyethylene, regardless of process, are primarily dependent on the degree of crystallinity, which is related to the density and the molecular weight. Uniformity in both molecular weight and comonomer can also affect the observed properties. The stiffness, yield strength, and thermal and mechanical AccessScience from McGraw-Hill Education Page 3 of 10 www.accessscience.com properties increase with the crystallinity, which can be systematically reduced by the addition of comonomer. Failure properties, such as toughness and ultimate tensile strength, increase with molecular weight, while to a lesser extent failure properties tend to decrease with broadening of the molecular-weight distribution for a given peak molecular weight. Polyethylene generally shows excellent toughness at low temperatures, because of the ◦ ◦ low glass transition temperature (generally believed to be between − 80 and − 120 C or − 112 and − 184 F). Environmental stress cracking, in the presence of detergents, is reduced for polyethylene copolymers as the size of the alpha-olefin comonomer is increased and as the density is decreased. Clarity is generally increased with decreasing crystallinity, although the morphology of the crystalline phase can also affect clarity. The melt flow properties are affected by molecular weight and long-chain branching. Choice of fabrication technique to produce items of commerce from polyethylene generally determines the melt flow properties needed and therefore the type of polyethylene used. Among commodity polymers, polyethylene is unique with respect to the ease of formation of long-chain branching, the presence of which can dramatically affect melt fabrication options. Generally, the ease of flow for both extrusion and injection molding increases with molecular-weight distribution and long-chain branching, but decreases with molecular weight. Consequently, low-molecular-weight resins are favored for injection-molding applications. Processes requiring melt strength and strain hardening of the molten polymer, such as blown film and foam, favor high molecular weight, the presence of long-chain branching, and to a lesser extent broadening of the molecular-weight distribution. For a given molecular weight, long-chain branching can either enhance or diminish the melt viscosity at low shear rates (melt strength), with the high levels in most low-density polyethylenes yielding lower viscosity at a given molecular weight. See also: PLASTICS PROCESSING . Use and fabrication Polyethylene is used in greater volume worldwide than any other plastic, because it is relatively inexpensive, extremely versatile, and adaptable to a large array of fabrication techniques. Its advantages are chemical inertness (resistance to solvents, acids, and alkalis) and good dielectric and barrier properties. Major uses include packaging films, plastic containers, molded articles, foam, pipe, cable sheathing, and coatings. Because of its broad melting range, low-density polyethylene can be used in heat-seal operations. Film applications include food packaging bags, shrink wrap, and garment bags. Blow-molded containers are used in milk and other household containers, while injection-molded items include housewares, pails, and toys. Because of its low degree of crystallinity, low-density polyethylene is limited for applications requiring high stiffness, temperature resistance, tensile strength, and good barrier properties. Linear low-density polyethylene is a versatile material that finds wide application in plastic films. Films produced by extrusion, blown, and cast film processes are widely used as garbage bags, stretch cling films, and other items that require the properties of flexibility, tear and puncture resistance, and toughness. The toughness of linear low-density polyethylene is generally superior to low-density polyethylene and increases with the size of the AccessScience from McGraw-Hill Education Page 4 of 10 www.accessscience.com comonomer. The very low density formulations of linear low-density polyethylene are also used for heat-seal applications, and are stronger than those using low-density polyethylene. While the relatively narrow molecular-weight distribution makes extrusion-coating applications somewhat difficult, specific resin grades are commercially available for this purpose. The molded items made from linear low-density polyethylene are similar to those made from low-density polyethylene, such as trash cans, food containers, and closures. Sheathing and flexible pipe are applications that take advantage of the flexibility
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