A- -styrene

Chlorides are inert. However, the reaction ofp-chlorobenzophenone (9) with a styrene derivative proceeds satisfactorily at 150 C by u.sing dippb [l,4-bis(-diisopropylphosphino)butane] as a ligand to give the stilbene derivative 10. However, dippp [l,3-bis(diisopropylphosphino)propane] is an ineffective ligand[13]. On the other hand, the coupling of chlorobenzene with styrene proceeds in the presence of Zn under base-free conditions to afford the cis-stilbene 11 as a main product with evolution of H . As the ligand, dippp is... 

Structures of styrene, divinylbenzene, and a styrene-divinylbenzene co-polymer modified for use as an ion-exchange resin. The ion-exchange sites, indicated by R, are mostly in the para position and are not necessarily bound to all styrene units. 

Elastomers. Elastomers are polymers or copolymers of hydrocarbons (see Elastomers, synthetic Rubber, natural). Natural mbber is essentially polyisoprene, whereas the most common synthetic mbber is a styrene—butadiene copolymer. Moreover, nearly all synthetic mbber is reinforced with carbon black, itself produced by partial oxidation of heavy hydrocarbons. Table 10 gives U.S. elastomer production for 1991. The two most important elastomers, styrene—butadiene mbber (qv) and polybutadiene mbber, are used primarily in automobile tires. 

The organic and aqueous phases are prepared in separate tanks before transferring to the reaction ketde. In the manufacture of a styrenic copolymer, predeterrnined amounts of styrene (1) and divinylbenzene (2) are mixed together in the organic phase tank. Styrene is the principal constituent, and is usually about 90—95 wt % of the formulation. The other 5—10% is DVB. It is required to link chains of linear polystyrene together as polymerization proceeds. DVB is referred to as a cross-linker. Without it, functionalized polystyrene would be much too soluble to perform as an ion-exchange resin. Ethylene—methacrylate [97-90-5] and to a lesser degree trivinylbenzene [1322-23-2] are occasionally used as substitutes for DVB. 

MBS polymers are prepared by grafting methyl methacrylate and styrene onto a styrene—butadiene mbber in an emulsion process. The product is a two-phase polymer useful as an impact modifier for rigid poly(vinyl chloride). 

Fig. 5. Phase behavior of blends of a styrene—acrylonitrile copolymer containing 19 wt % of acrylonitrile with other SAN copolymers of varying AN content and as a function of the molecular weight of the two copolymers (° ) one-phase mixture ( ) two-phase mixtures as judged by optical clarity. Curve...

Fig. 2. Relationship between relative rate and monomer composition in the copolymerization of DAP with vinyl monomers A, styrene or methyl methacrylate B, methyl acrylate or acrylonitrile C, vinyl chloride D, vinyl acetate, and E, ethylene (41).

Depending on the concentration, the solvent, and the shear rate of measurement, concentrated polymer solutions may give wide ranges of viscosity and appear to be Newtonian or non-Newtonian. This is illustrated in Eigure 10, where solutions of a styrene—butadiene—styrene block copolymer are Newtonian and viscous at low shear rates, but become shear thinning at high shear rates, dropping to relatively low viscosities beyond 10 (42). The... 

Fig. 10. Viscosity vs shear rate for solutions of a styrene—butadiene—styrene block copolymer (42). A represents cyclohexanone, where c = 0.248 g/cm (9-xylene, where c = 0.246 g/cm C, toluene, where c = 0.248 g/cm. Courtesy of the Society of Plastics Engineers, Inc.

Fig. 44. Thermal mechanical behavior of a styrene—butadiene—styrene block copolymer in nitrogen at —180 to 150°C (280).

Figure 5 illustrates a typical distillation train in a styrene plant. Benzene and toluene by-products are recovered in the overhead of the benzene—toluene column. The bottoms from the benzene—toluene column are distilled in the ethylbenzene recycle column, where the separation of ethylbenzene and styrene is effected. The ethylbenzene, containing up to 3% styrene, is taken overhead and recycled to the dehydrogenation section. The bottoms, which contain styrene, by-products heavier than styrene, polymers, inhibitor, and up to 1000 ppm ethylbenzene, are pumped to the styrene finishing column. The overhead product from this column is purified styrene. The bottoms are further processed in a residue-finishing system to recover additional styrene from the residue, which consists of heavy by-products, polymers, and inhibitor. The residue is used as fuel. The residue-finishing system can be a flash evaporator or a small distillation column. This distillation sequence is used in the Fina-Badger process and the Dow process. 

OC-Methylstyrene. This compound is not a styrenic monomer in the strict sense. The methyl substitution on the side chain, rather than the aromatic ring, moderates its reactivity in polymerization. It is used as a specialty monomer in ABS resins, coatings, polyester resins, and hot-melt adhesives. As a copolymer in ABS and polystyrene, it increases the heat-distortion resistance of the product. In coatings and resins, it moderates reaction rates and improves clarity. Physical properties of a-methylstyrene [98-83-9] are shown in Table 12. 

Other developments in chelating resins include fibers made from poly(ethylene glycol) and poly(vinyl alcohol) to which EDA was attached with epichl orohydrin (281) and a styrene—divinylbenzene resin with pendant EDTA or DETPA groups (282). 

Butadiene and styrene may be polymerised in any proportion. The Tfs of the copolymers vary in an almost linear manner with the proportion of styrene present. Whereas SBR has a styrene content of about 23.5% and is rubbery, copolymers containing about 50% styrene are leatherlike whilst with 70% styrene the materials are more like rigid thermoplastics but with low softening points. Both of these copolymers are known in the rubber industry as high-styrene resins and are usually used blended with a hydrocarbon rubber such as NR or SBR. Such blends have found use in shoe soles, car wash brushes and other mouldings but in recent times have suffered increasing competition from conventional thermoplastics and to a less extent the thermoplastic rubbers. 

Somewhat less well known are the styrene-isoprene-styrene (SIS) triblocks. The commercial grade (Cariflex TR-1107) is stated to have a styrene-isoprene... 

A number of thermosetting acrylic resins for use as surface coatings have appeared during recent years. These are generally complex copolymers and terpolymers such as a styrene-ethyl acrylate-alkoxy methyl acrylamide... 

BRIGHTON, c. A., PRITCHARD, G., and SKINNER, G. A., Styrene Polymers Technology and Environmental Aspects, Applied Science, London (1979)... 

Blends of PPO with a styrenic material, usually, but not always, high-impact polystyrene. (Referred to below as Styrenic PPOs.)... 

The higher water absorption (typically 3.5% compared with about 0.3% at saturation for a styrenic PPO). 

Figure 32.1. Polar diagrams for three thermoplastic materials, CYCOLOY (a PC/ABS blend), ULTEM (polyetherimide) and NORYL (a styrenic PPO). The shaded area indicates the range...

Polymer-polymer fractal interfaces may result from the interdiffusion of monomers or of polymers themselves. Koizumi et al. [31] annealed the interface between polystyrene and a styrene-isoprene diblock polymer at 150 C and showed extensive roughening of the interface by mutual interdiffusion on a micron scale (Fig. 8). 

Fig. 8. Electron micrograph.s showing the interface between polystyrene (top) and a styrene-isoprene diblock polymer (bottom), annealed at I50°C for the times shown. Isoprene units are stained and appear black) (reproduced from [31], copyright American Chemical Society).

An 800-gal reaetor eontaining a styrene mixture with a speeifie heat of 0.6 eal/gm °C has a 10-in. rupture disk and a vent line with equivalent length = 400. The vessel MAWP is 100 psig and the rupture disk set pressure is 20 psig. The styrene mixture had a self-heat rate of 60°C/min at 170°C as it is tempered in a DIERS venting test. Determine the allowable reaetor mixture eharge to limit the overpressure to 10% over the set pressure. 

Figure 6.7 Schematic flowsheet of a styrene plant (Stanley and El-Halwagi, 1995, reproduced with peimission of the McGraw Hill Companies).

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