Polyethylene Polymerization Processes

Polyethylene is the simplest addition polymer, and we will briefly describe its polymerization process. Polyethylene, as discussed previously. Is made by opening the double bond in the ethylene molecule, and chemically bonding the monomers together in a reactor. That reactor can involve an autoclave (stirred tank) process or a tubular process. It can be done at low pressure (about 300 psi) or at pressures as high as 50,000 psi. Temperatures are controlled at some elevated level such as 125 to 250°C, but the temperature needed is very specific to the type of polymer structure desired. 

FIG. 23-23 Batch and continuous polymerizations, (a) Polyethylene in a tiihiilar flow reactor, up to 2 km long hy 6,4 cm ID, (h) Batch process for polystyrene, (c) Batch-continuous process for polystyrene, (d) Suspension (head) process for polyvinylchloride, (e) Emulsion process for polyvinylchloride, (Ray and Laurence, in Lapidus and Amundson, eds, Chemical Reactor Theory Review, Frentice-Hall, 1977. )... 

Polymerization processes are characterized by extremes. Industrial products are mixtures with molecular weights of lO" to 10. In a particular polymerization of styrene the viscosity increased by a fac tor of lO " as conversion went from 0 to 60 percent. The adiabatic reaction temperature for complete polymerization of ethylene is 1,800 K (3,240 R). Heat transfer coefficients in stirred tanks with high viscosities can be as low as 25 W/(m °C) (16.2 Btu/[h fH °F]). Reaction times for butadiene-styrene rubbers are 8 to 12 h polyethylene molecules continue to grow lor 30 min whereas ethyl acrylate in 20% emulsion reacts in less than 1 min, so monomer must be added gradually to keep the temperature within hmits. Initiators of the chain reactions have concentration of 10" g mol/L so they are highly sensitive to poisons and impurities. 

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

For composites with polymerization-modified filler it is typical that the physico-mechanical characteristics should increase symbatically with the quantity of polymer which becomes attached to the filler in the polymerization process. This effect has been observed for polyethylene [293, 321], poly(vinyl chloride) coats [316], and in [336, 337] for kaolin coated with poly(vinyl acetate) and introduced into the copolymer of ethylene and vinyl acetate. 

Structurally, plastomers straddle the property range between elastomers and plastics. Plastomers inherently contain some level of crystallinity due to the predominant monomer in a crystalline sequence within the polymer chains. The most common type of this residual crystallinity is ethylene (for ethylene-predominant plastomers or E-plastomers) or isotactic propylene in meso (or m) sequences (for propylene-predominant plastomers or P-plastomers). Uninterrupted sequences of these monomers crystallize into periodic strucmres, which form crystalline lamellae. Plastomers contain in addition at least one monomer, which interrupts this sequencing of crystalline mers. This may be a monomer too large to fit into the crystal lattice. An example is the incorporation of 1-octene into a polyethylene chain. The residual hexyl side chain provides a site for the dislocation of the periodic structure required for crystals to be formed. Another example would be the incorporation of a stereo error in the insertion of propylene. Thus, a propylene insertion with an r dyad leads similarly to a dislocation in the periodic structure required for the formation of an iPP crystal. In uniformly back-mixed polymerization processes, with a single discrete polymerization catalyst, the incorporation of these intermptions is statistical and controlled by the kinetics of the polymerization process. These statistics are known as reactivity ratios. 

Recycling polymers is one way to minimize the disposal problem, but not much recycling occurs at present. Only about 25% of the plastic made in the United States is recycled each year, compared with 55% of the aluminum and 40% of the paper. A major obstacle to recycling plastics is the great variation in the composition of polymeric material. Polyethylene and polystyrene have different properties, and a mixture of the two is inferior to either. Recyclers must either separate different types of plastics or process the recycled material for less specialized uses. Manufacturers label plastic containers with numbers that indicate their polymer type and make it easier to recycle these materials. Table 13-5 shows the recycling number scheme. 

The chemical and physical properties of the polymers obtained by these alternate methods are identical, except insofar as they are affected by differences in molecular weight. In order to avoid the confusion which would result if classification of the products were to be based on the method of synthesis actually employed in each case, it has been proposed that the substance be referred to as a condensation polymer in such instances, irrespective of whether a condensation or an addition polymerization process was used in its preparation. The cyclic compound is after all a condensation product of one or more bifunctional compounds, and in this sense the linear polymer obtained from the cyclic intermediate can be regarded as the polymeric derivative of the bifunctional monomer(s). Furthermore, each of the polymers listed in Table III may be degraded to bifunctional monomers differing in composition from the structural unit, although such degradation of polyethylene oxide and the polythioether may be difficult. Apart from the demands of any particular definition, it is clearly desirable to include all of these substances among the condensation... 

In principle, polymers equivalent to those obtained from vinyl and divinyl monomers may be synthesized by this method. The product in the above example possesses the same chain structure as polyethylene. The polymerization process, notwithstanding the likelihood of a metal alkyl intermediate, should conform satisfactorily to stepwise condensation. However, the product, and those obtained by Friedel-Crafts condensation as well, lack the recurrent functional groups which generally characterize condensation polymers. 

Polyethylene terephthalate also has the tendency, because it is produced by a condensation polymerization process, to depolymerize under high pressure and temperatures in the presence of water. Although this is usually a negative attribute, it can be utilized to regenerate pure monomers which can be repolymerized to make fresh polymer. This avoids the issues experienced by reprocessing resins, as the new resin has not experienced a previous heat history. A major drawback to this process is the requirement that the monomers used in polymerization processes must be highly pure, Unfortunately, this process is extremely costly and not performed on a commercial scale. 

Figure 24.3 Two-step polymerization process for the manufacture of polyethylene terephthalate ...

Linear combination of atomic orbitals (LCAO) method, 16 736 Linear condensation, in silanol polycondensation, 22 557-558 Linear congruential generator (LCG), 26 1002-1003 Linear copolymers, 7 610t Linear density, 19 742 of fibers, 11 166, 182 Linear dielectrics, 11 91 Linear elastic fracture mechanics (LEFM), 1 509-510 16 184 20 350 Linear ethoxylates, 23 537 Linear ethylene copolymers, 20 179-180 Linear-flow reactor (LFR) polymerization process, 23 394, 395, 396 Linear free energy relationship (LFER) methods, 16 753, 754 Linear higher a-olefins, 20 429 Linear internal olefins (LIOs), 17 724 Linear ion traps, 15 662 Linear kinetics, 9 612 Linear low density polyethylene (LLDPE), 10 596 17 724-725 20 179-211 24 267, 268. See also LLDPE entries a-olefin content in, 20 185-186 analytical and test methods for,... 

Solution polymerization process, for aromatic polyamides, 19 718—720 Solution polymerization, 20 408 acrylamide polymers, 1 321 acrylic ester monomers, 1 381—383 for linear low density polyethylene, 20 196-197... 

Macromolecules are found in nature. Cellulose, wool, starch, and DNA are but a few of the macromolecules that occur naturally. Carbons ability to form these large, complex molecules is necessary to provide the diversity of compounds needed to make up a tree or a human being. But many of the useful macromolecules that we use every day are created in the lab and industrial complex by chemists. Nylon, rayon, polyethylene, and polyvinyl chloride are all synthetic macromolecules. They differ by which repeating units (monomers) are joined together in the polymerization process. Our society has grown to depend on these plastics, these synthetic fabrics. The complexity of carbon compounds is reflected in the complexity of our modern society. 

Albeit having a simple chemical formula, — (CH2— CH2) —, polyethylene is a broad family with versatile properties that depend on which of the three main polymerization processes is used ... 

So you can see why branching in the polymerization process can be a problem—the symmetry is affected. And you can get a hint why PP was commercialized long after polyethylene. The chemistry and catalysis are a lot more demanding. Thats why Giulio Natra won the Nobel Prize for his contribution to the field of stereo-catalysis, the discovery of the effects of titanium chloride and organo-aluminum compounds. 

For most step polymerizations, for example, in the synthesis of polyl hexamethylene adipa-mide) or polyethylene terephthalate), two reactants or monomers are used in the process, and the polymer obtained contains two different kinds of structures in the chain. This is not the case for chain polymerizations, where only one monomer need be used to produce a polymer. However, chain polymerizations can be carried out with mixtures of two monomers to form polymeric products wiht two different structures in the polymer chain. This type of chain polymerization process in which two monomers are simultaneously polymerized is termed a copolymerization, and the product is a copolymer. It is important to stress that the copolymer is not an alloy of two homopolymers hut contains units of both monomers incorporated into each copolymer molecule. The process can be depicted as... 

Coordination copolymerization of ethylene with small amounts of an a-olefin such as 1-butene, 1-hexene, or 1-octene results in the equivalent of the branched, low-density polyethylene produced by radical polymerization. The polyethylene, referred to as linear low-density polyethylene (LLDPE), has controlled amounts of ethyl, n-butyl, and n-hexyl branches, respectively. Copolymerization with propene, 4-methyl-1-pentene, and cycloalk-enes is also practiced. There was little effort to commercialize linear low-density polyethylene (LLDPE) until 1978, when gas-phase technology made the economics of the process very competitive with the high-pressure radical polymerization process [James, 1986]. The expansion of this technology was rapid. The utility of the LLDPE process Emits the need to build new high-pressure plants. New capacity for LDPE has usually involved new plants for the low-pressure gas-phase process, which allows the production of HDPE and LLDPE as well as polypropene. The production of LLDPE in the United States in 2001 was about 8 billion pounds, the same as the production of LDPE. Overall, HDPE and LLDPE, produced by coordination polymerization, comprise two-thirds of all polyethylenes. 

Polymerization of esters to produce polyesters is an important commercial process. Polyethylene terephthalate or PET is one of the most common plastics used in food containers (Table 15.4). This ester is formed by the reaction of ethylene glycol and terephthalic acid (Figure 15.17). PET and other polyesters consist of esters linked together. Notice that both terephthalic acid and ethylene glycol have two carboxyls and two hydroxyls, respectively. When a polyester such as PET is formed, a monomer con-... 

Polyethylene. The most straightforward process for the production of polymers from ethylene is that of the direct polymerization of the olefin. The polymerization process usually requires pressures and temperatures of 15,000 to 30,000 pounds per square inch and 200° to 300° C., and may be effected in either gas or liquid phase reactions (9). The polymer of molecular weight above 20,000 is the white, translucent plastic, polyethylene, widely used in electrical insulation, packaging material for foods, cosmetics and pharmaceuticals, liners for paper bags, etc. Articles molded from polyethylene are semirigid or rigid, depending on their thickness, but in thin films the material has excellent flexibility, even at relatively low temperatures. 

Characteristics of the Graft Polymerization Process. Under certain polymerization conditions such as when the vinyl chloride/polyethylene ratio is high, heterogeneous products are obtained in the sense that, beside the polyethylene grains gorged with PVC, independent suspension PVC particles are formed. Since the optimum conditions for production of PVC and graft copolymers are not necessarily identical, it is advantageous to avoid the formation of these independent PVC particles. 

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