High-impact polystyrene process

Polystyrene. Polystyrene [9003-53-6] is a thermoplastic prepared by the polymerization of styrene, primarily the suspension or bulk processes. Polystyrene is a linear polymer that is atactic, amorphous, inert to acids and alkahes, but attacked by aromatic solvents and chlorinated hydrocarbons such as dry cleaning fluids. It is clear but yellows and crazes on outdoor exposure when attacked by uv light. It is britde and does not accept plasticizers, though mbber can be compounded with it to raise the impact strength, ie, high impact polystyrene (HIPS). Its principal use in building products is as a foamed plastic (see Eoamed plastics). The foams are used for interior trim, door and window frames, cabinetry, and, in the low density expanded form, for insulation (see Styrene plastics). 

In the mid-1950s a number of new thermoplastics with some very valuable properties beeame available. High-density polyethylenes produced by the Phillips process and the Ziegler process were marketed and these were shortly followed by the discovery and rapid exploitation of polypropylene. These polyolefins soon became large tonnage thermoplastics. Somewhat more specialised materials were the acetal resins, first introduced by Du Pont, and the polycarbonates, developed simultaneously but independently in the United States and Germany. Further developments in high-impact polystyrenes led to the development of ABS polymers. 

The main reason for extruding polystyrene is to prepare high-impact polystyrene sheet. Such sheet can be formed without difficulty by vacuum forming techniques. In principle the process consists of clamping the sheet above the mould, heating it so that it softens and becomes rubbery and then applying a vacuum to draw out the air between the mould and the sheet so that the sheet takes up the contours of the mould. 

As mentioned earlier, unmodified polystyrene first found application where rigidity and low cost were important prerequisites. Other useful properties were the transparency and high refractive index, freedom from taste, odour and toxicity, good electrical insulation characteristics, low water absorption and comparatively easy processability. Carefully designed and well-made articles from polystyrene were often found to be perfectly suitable for the end-use intended. On the other hand the extensive use of the polymers in badly designed and badly made products which broke only too easily caused a reaction away from the homopolymer. This resulted, first of all, in the development of the high-impact polystyrene and today this is more important than the unmodified polymer (60% of Western European market). 

The process was originally developed in the 1940s for use with vinyl plas-tisols in liquid form. It was not until the 1950s that polyethylene powders were successfully moulded in this way. Nowadays a range of materials such as nylon, polycarbonate, ABS, high impact polystyrene and polypropylene can be moulded but by far the most common material is polyethylene. 

In the late 1940s, the demand for styrene homopolymers (PS) and styrene-acrylonitrile copolymers (SAN) was drastically reduced due to their inherent brittleness. Thus, the interest was shifted to multiphase high-impact polystyrene (HIPS) and rubber-modified SAN (ABS). In principle, both HIPS and ABS can be manufactured by either bulk or emulsion techniques. However, in actual practice, HIPS is made only by the bulk process, whereas ABS is produced by both methods [132,133]. 

Polystyrene One of the high volume plastics, is relatively low in cost, easy to process, has sparkling clarity, and low water absorption. But basic form (crystal PS) is brittle, with low heat and chemical resistance, poor weather resistance. High impact polystyrene is made with butadiene modifiers provides significant improvements in impact strength and elongation over crystal polystyrene, accompanied by a loss of transparency and little other property improvement. PS is used in many different formulations. 

The styrenic thermoplastic elastomers are the only type which are fully compounded in the manner of conventional elastomers. In this case, however, the addition of carbon black, or other fillers, does not give reinforcement. Additions of polystyrene, or high impact polystyrene, and oil are used to vary hardness and tear strength, and fillers can be used to cheapen the material. Other added polymers, e g., EVA, can be used to increase ozone resistance. These materials also require antioxidants for protection during processing and service life, and the poor UV stability restricts their use in outdoor applications. 

Figure 2. Continuous mass process (40) for crystal and high impact polystyrene.

Polycarbonate is blended with a number of polymers including PET, PBT, acrylonitrile-butadiene-styrene terpolymer (ABS) rubber, and styrene-maleic anhydride (SMA) copolymer. The blends have lower costs compared to polycarbonate and, in addition, show some property improvement. PET and PBT impart better chemical resistance and processability, ABS imparts improved processability, and SMA imparts better retention of properties on aging at high temperature. Poly(phenylene oxide) blended with high-impact polystyrene (HIPS) (polybutadiene-gra/f-polystyrene) has improved toughness and processability. The impact strength of polyamides is improved by blending with an ethylene copolymer or ABS rubber. 

High impact polystyrene can be made by prepolymerization in a w/o emulsion with ensuing suspension polymerization. The processes which... 

The phase relationships of two-phase polymer systems also have been of considerable interest in recent years. In an important series of papers, Molau and co-workers (19-24) studied systems, which were denoted POO emulsions (polymeric oil-in-oil), prepared by dissolving a given polymer in monomer and then polymerizing the monomer. During polymerizations of this type the composition of the respective phases reverses, and a phase inversion process was proposed to explain this. A similar process has been suggested as the mechanism by which poly-butadiene forms the dispersed phase in the manufacture of high-impact polystyrenes (22,25). Recently, Kruse has pointed out that this phase-inversion point may correspond to that point on a ternary phase diagram at which the reaction line bisects a tie line (26), and we have advanced a similar point of view in our earlier reports (17,18, 27). 

Application To produce a wide range of general purpose and high-impact polystyrenes (PS) via the bulk continuous process using the BP Chemicals/ABB Lummus Global technology. 

In the early 1940s, researchers at Dow produced interpolymer blends of styrene and butadiene by an emulsion process. The polymer, called Styralloy 22, was used as insulation for radar cables until it was displaced by low-density polyethylene produced by ICI. Later, Dow experimented with soluble GRS copolymerized with styrene to make high-impact polystyrene. 

In 1954, Dow finally perfected a can process to make high-impact polystyrene (HIPS). The secret was that the traditional can process could not simply be used since the product would be full of gel particles of rubber ( fish-eyes ) instead, the styrene-rubber mixture was first carried out to 30% conversion with shearing agitation. Then the mixture was transferred to 10 gallon cans where the reaction was completed. This process was documented in the now famous Amos patent [18]. 

Other chemical companies have also designed their own continuous process to produce high-impact polystyrene (HIPS), such as the Dow process, which consists of three elongated reactors in series (US Patent 2727 884, 1955) the BASF process, which consists of a prepolymerization CSTR followed by cascade of three CSTRs (US Patent 3 658 946, 1972) the Shell process, which consists of three CSTRs followed by a plug flow reactor (US Patent 4011 284, 1977) and the Monsanto process, which consists of a CSTR followed by a horizontal plug flow reactor (US Patent 3 903 202, 1975). 

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