Styrene-acrylonitrile copolymer production process

Acrylonitrile—Butadiene—Styrene. ABS is an important commercial polymer, with numerous apphcations. In the late 1950s, ABS was produced by emulsion grafting of styrene-acrylonitrile copolymers onto polybutadiene latex particles. This method continues to be the basis for a considerable volume of ABS manufacture. More recently, ABS has also been produced by continuous mass and mass-suspension processes (237). The various products may be mechanically blended for optimizing properties and cost. Brittle SAN, toughened by SAN-grafted ethylene—propylene and acrylate mbbets, is used in outdoor apphcations. Flame retardancy of ABS is improved by chlorinated PE and other flame-retarding additives (237). 

In the early 1980s, workers at Shell could demonstrate melt processability of polyketone produeed by palladium cyanide catalysts, after extensive extraction of catalyst residues from the polymers and blending these with other polymers such as styrene/acrylonitrile copolymer. From these studies, it was suggested that thermoplastic properties were possible in principle, and that the polyketone backbone was not inherently unstable in the melt as previously concluded. However, catalyst extraction did not offer a viable production option from a technical and economic viewpoint. 

Acrylonitrile is also commonly found in impact modifiers, such as the acrylonitrile-butadiene-styrene (ABS) type, produced by emulsion polymerisation. Polybutadiene seed latex particles are grafted onto styrene and acrylonitrile in a seeded emulsion polymerisation process. As the styrene-acrylonitrile copolymer shell forms, polybutadiene domains are spontaneously separated within. The resulting impact modifier particles are subsequently compounded with polystyrene to product high impact polystyrene (HIPS). The impact modification properties of the latex particles may be optimised through varying the butadiene content, the particle size and structure, and the shell molecular weight. A basic formulation for an ABS impact modifier is given in Table 6. 

Many important polymers are made commerdally via suspension polymerization of vinyl monomers. These include poly(vinyl chloride), poly(methyl methacrylate), expandable polystyrene, styrene-acrylonitrile copolymers and a variety of ion-exchange resins and specialist materials. The annual polymer production from suspension processes is very high. 

Rubber-Modified Copolymers. Acrylonitrile—butadiene—styrene polymers have become important commercial products since the mid-1950s. The development and properties of ABS polymers have been discussed in detail (76) (see Acrylonitrile polymers). ABS polymers, like HIPS, are two-phase systems in which the elastomer component is dispersed in the rigid SAN copolymer matrix. The electron photomicrographs in Figure 6 show the difference in morphology of mass vs emulsion ABS polymers. The differences in stmcture of the dispersed phases are primarily a result of differences in production processes, types of mbber used, and variation in mbber concentrations. 

Buna [Butadien natrium] The name has been used for the product, the process, and the company VEB Chemische Werke Buna. A process for making a range of synthetic rubbers from butadiene, developed by IG Farbenindustrie in Leverkusen, Germany, in the late 1920s. Sodium was used initially as the polymerization catalyst, hence the name. Buna S was a copolymer of butadiene with styrene Buna N a copolymer with acrylonitrile. The product was first introduced to the pubhc at the Berlin Motor Show in 1936. Today, the trade name Buna CB is used for a polybutadiene rubber made by Bunawerke Hiils using a Ziegler-Natta type process. German Patent 570, 980. 

The most important commercial processes for polyacrylonitrile (XLIII) are solution and suspension polymerizations. Almost all the products containing acrylonitrile are copolymers. Styrene-acrylonitrile (SAN) copolymers are useful as plastics (Sec. 6-8a). 

Copolymerization allows the synthesis of an almost unlimited number of different products by variations in the nature and relative amounts of the two monomer units in the copolymer product. A prime example of the versatility of the copolymerization process is the case of polystyrene. More than 11 billion pounds per year of polystyrene products are produced annually in the United States. Only about one-third of the total is styrene homopolymer. Polystyrene is a brittle plastic with low impact strength and low solvent resistance (Sec. 3-14b). Copolymerization as well as blending greatly increase the usefulness of polystyrene. Styrene copolymers and blends of copolymers are useful not only as plastics but also as elastomers. Thus copolymerization of styrene with acrylonitrile leads to increased impact and solvent resistance, while copolymerization with 1,3-butadiene leads to elastomeric properties. Combinations of styrene, acrylonitrile, and 1,3-butadiene improve all three properties simultaneously. This and other technological applications of copolymerization are discussed further in Sec. 6-8. 

The polymers described above have been chemically pure, although physically helerodisperse. It is oflen possible lo combine two or more of these monomers in the same molecule to form a copolymer. This process produces still further modification of molecular properties and, in turn, modification of the physical properties of file product. Many commercial polymers are copolymers because of the blending of properties achieved in this way. For example, one of the important new polymers of the past ten years has been the family of copolymers of acrylonitrile, butadiene and styrene, commonly called ABS resins. The production of these materials has grown rapidly in a short period of time because of their combination of dimensional stability and high impact resistance. These properties are related to the impact resistance of acrylonitrile-butadiene rubber and the dimensional stability of polystyrene, which are joined in the same molecule. 

Styrenic copolymers are materials capable of thermoplastic processing which, in addition to styrene (S), also contain at least one other monomer in the main polymer chain. Styrene-acrylonitrile (SAN) copolymers are the most important representative and basic building blocks of the entire class of products. By adding rubbers to SAN either ABS (acrylonitrile-butadiene-styrene) or ASA (acrylate-styrene-acrylonitrile) polymers are obtained depending on the type of rubber component employed. These two classes of products yield blends composed of ASA and polycarbonate (ASA -f PC) or ABS and polyamide (ABS -(- PA). 

Butadiene (bpI o13= — 4-413°C, d4°=0.621 l)(l> has become a major petrochemical product thanks to the development of its copolymers with styrene and acrylonitrile. The earliest processes for manufacturing butadiene started with acetylene and formaldehyde (Germany, the Reppe process), or produced it by the aldolization of acetaldehyde (Germany), or by the dehydration and dehydrogenation of ethanol (USSR, United States Union Carbide),... 

Several other common industrial polymers are also used in biomedical applications [51]. Because of its low cost and easy processibility, polyethylene is frequently used in the production of catheters. High-density polyethylene is used to produce hip prostheses, where durability of the polymer is critical. Polypropylene, which has a low density and high chemical resistance, is frequently employed in syringe bodies, external prostheses, and other non-implanted medical applications. Polystyrene is used routinely in the production of tissue culture dishes, where dimensional stability and transparency are important. Styrene-butadiene copolymers or acrylonitrile-butadiene-styrene copolymers are used to produce opaque, molded items for perfusion, dialysis, syringe connections, and catheters. 

Unplasticized PVC present some processing difficulties due to its high melt viscosity in addition, the finished product is too brittle for some applications. To overcome these problems and to produce toughening, certain polymeric additives are usually added to the PVC. These materials, known as impact modifiers, are generally semicompatible and often some what rubbery in nature [14]. Among the most important impact modifiers in use today are butadiene-acrylonitrile copolymers (nitrile rubber), acrylonitrile-butadiene-styrene (ABS) graft terpolymers, methacrylate-butadiene-styrene (MBS) terpo-lymers, chlorinated polyethylene, and some polyacrylates. 

Looking at the historical development of the emulsion pol)nnerization, it is seen that the trigger factor in this development was the necessity for synthetic rubber in the wartime. The production of styrene/butadiene rubber (SBR) satisfied this requirement. Today, millions of tons of S)mthetic latexes are produced by the emulsion pol3merization process for use in wide variety of applications. In the S)mthetic latexes, the most important groups are styrene/butadiene copolymers, vinyl acetate homopol)rmers and copol)nners, and polyacrylates. Other synthetic latexes contain copolymers of ethylene, styrene, vinyl esters, vinyl chloride, vinylidene chloride, acrylonitrile, cloroprene and polyurethane. 

In the production of reactor blends or copolymers a small variation of the reactor feed or process variables, like temperature and pressure, may easily lead to demixing of the copolymer solution or the blend in the reactor. In figure 4. some recent measurements on the blend Poly(Methyl Methacrylate/Poly (Styrene Acrylonitrile) (PMMA/SAN)[46] are summarized. The latter data were collected in a laser light scattering autoclave (as described under 3.1.3)... 

Copolymers of acrylonitrile with other monomers are widely used. Copolymers of vinylidene chloride and acrylonitrile hnd application as low-gas-permeability films. Styrene-acrylonitrile (SAN polymers) copolymers have also been used in packaging applications. A number of acrylonitrile copolymers were developed for beverage containers, but the requirement of very low levels of residual acrylonitrile monomer in this application led to many of these products being removed from the market. One copolymer currently available is Barex (BP Chemicals). Acrylonitrile is also used with butadiene and styrene to form ABS polymers. Unlike the homopolymer, copolymers of acrylonitrile can be processed by many methods including extra-sion, blow molding, and injection molding. BP Chemicals is a major supplier of these copolymers. 

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