PROPERTIES OF STYRENIC POLYMERS

Fracture Behavior of High-Impact Polystyrene and Acrylonitrile-Butadiene-Styrene 

Modern Styrenic Polymers Polystyrene and Styrenic Copolymers. Edited by J. Scheirs and D. B. Priddy 2003 John Wiley Sons Ltd 

This chapter presents recent results on quantitative analyses of the fracture behavior of HIPS and ABS. The emphasis is put on the prediction of fracture performance over a wide range of deformation rates and temperatures. Different approaches currently used to characterize fracture performance are applied to HIPS and ABS and recommendations on the use of these methods are presented. The fundamental mechanisms controlling the dependence of fracture performance and yield on deformation rate and temperature are discussed. 

With increasing temperature, the fracture mode changes from brittle to semi-ductile at about -50 °C and then becomes ductile at temperatures higher than 

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The effect of additives, others than plasticizers, on the dynamic mechanical properties of styrene polymers have attracted little attention from researchers. Flame retardants such as l,2-bis(tetrabromophthalimide)ethane, crystalline decabromodiphenyl oxide (DBDPO) and antimony trioxide (Sb203) do not affect the a relaxation of aPS [38,39]. 

J. Zhang, D. D. Jiang, D. Wang, and C. A. Wilkie, Mechanical and fire properties of styrenic polymer nanocomposites based on an oligomerically-modified clay. Polymers for Advanced Technologies, 16 (2005), 800-806. 

Zhang, J. Jiang, D.D. Wilkie, C.A. Fire properties of styrenics polymer-clay nanocomposites based on an oligomerically modified clay. Polym. Degrad. Stab. 2006, 91, 358-366. 

G-5—G-9 Aromatic Modified Aliphatic Petroleum Resins. Compatibihty with base polymers is an essential aspect of hydrocarbon resins in whatever appHcation they are used. As an example, piperylene—2-methyl-2-butene based resins are substantially inadequate in enhancing the tack of 1,3-butadiene—styrene based random and block copolymers in pressure sensitive adhesive appHcations. The copolymerization of a-methylstyrene with piperylenes effectively enhances the tack properties of styrene—butadiene copolymers and styrene—isoprene copolymers in adhesive appHcations (40,41). Introduction of aromaticity into hydrocarbon resins serves to increase the solubiHty parameter of resins, resulting in improved compatibiHty with base polymers. However, the nature of the aromatic monomer also serves as a handle for molecular weight and softening point control. 

Styrene is a colorless Hquid with an aromatic odor. Important physical properties of styrene are shown in Table 1 (1). Styrene is infinitely soluble in acetone, carbon tetrachloride, benzene, ether, / -heptane, and ethanol. Nearly all of the commercial styrene is consumed in polymerization and copolymerization processes. Common methods in plastics technology such as mass, suspension, solution, and emulsion polymerization can be used to manufacture polystyrene and styrene copolymers with different physical characteristics, but processes relating to the first two methods account for most of the styrene polymers currendy (ca 1996) being manufactured (2—8). Polymerization generally takes place by free-radical reactions initiated thermally or catalyticaHy. Polymerization occurs slowly even at ambient temperatures. It can be retarded by inhibitors. 

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. 

Vinyltoluene, comprising a mixture of ca 33% para- and 67% y /i7-methylstyrene, has been marketed for ca 45 yr by Dow Chemical Company and also by Cosden. However, the performance properties of the polymers prepared from the para isomer are not only superior to those of the polymer prepared from the typical mixed isomers, but are generally superior to those of polystyrene (60). This advantage, coupled with a raw material cost advantage over styrene, suggests that i ra-methylstyrene may displace significant amounts of styrene, currendy a 3.2 x 10 t/yr domestic market. 

Between the 1920s when the initial commercial development of mbbery elastomers based on 1,3-dienes began (5—7), and 1955 when transition metal catalysts were fkst used to prepare synthetic polyisoprene, researchers in the U.S. and Europe developed emulsion polybutadiene and styrene—butadiene copolymers as substitutes for natural mbber. However, the tire properties of these polymers were inferior to natural mbber compounds. In seeking to improve the synthetic material properties, research was conducted in many laboratories worldwide, especially in the U.S. under the Rubber Reserve Program. 

The properties of styrenic block copolymers are dependent on many factors besides the polymerization process. The styrene end block is typically atactic. Atactic polystyrene has a molecular weight between entanglements (Me) of about 18,000 g/mol. The typical end block molecular weight of styrenic block copolymers is less than Mg. Thus the softening point of these polymers is less than that of pure polystyrene. In fact many of the raw materials in hot melts are in the oligomeric region, where properties still depend on molecular weight (see Fig. 1). 

Table 7.1 shows the pore properties of several polymer monolithic columns prepared from styrene/DVB, methacrylates, and acrylamides along with the feed porosity and column efficiency, summarized from several recent publications. Some important points seem to be clearly shown in Table 7.1, especially by the comparison of the properties between methacrylate-based polymer monoliths and silica monoliths. 

Hivalloy A process for grafting styrenic polymers on to polyolefines, using a Ziegler-Natta catalyst. The products combine the physical properties of both polymer types. Developed by Montell and commercialized in the United States in 1997. See also Catalloy. Oxley, D. F., Chem. Ind. (London), 1998, (8), 307. 

In polymers that exhibit tacticity, the extent of the stereoregularity determines the crystallinity and the physical properties of the polymers. The placement of the monomer units in the polymer is controlled first by the steric and electronic characteristics of the monomer. However, the presence or absence of tacticity, as well as the type of tacticity, is controlled by the catalyst employed in the polymerization reaction. Some common polymers, which can be prepared in specific configuration, include poly(olefins), poly(styrene), poly(methyl methacrylate), and poly(butadiene). 

Figure 7. Physical properties of styrene-isoprene block polymers.

An outstanding property of these polymers is their shear stability. The sonic shear stability testsfci indicate that these polymers are superior to some of the currently used polymers of ethylene-propylene or methacrylate type. The excellent stability of the hydrogenated diene-styrene polymers is attributed to their relatively low molecular weight and narrow distribution consistent with the established theory of shear degradation of polymers. The most recent developments in this field are block polymer VI improvers with dispersancy properties, built into the molecule by chemical modification of the rubber block. 2... 

In this work, studies were made on the photochemistry of styrene copolymers containing minor amounts (2-7%) of MVK, MIPK and tBVK. The properties of these polymers are summarized in Table I. The low concentrations of carbonyl units present should minimize the effects of energy... 

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