Styrene handling

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. 

Ethjlben ne Synthesis. The synthesis of ethylbenzene for styrene production is another process in which ZSM-5 catalysts are employed. Although some ethylbenzene is obtained direcdy from petroleum, about 90% is synthetic. In earlier processes, benzene was alkylated with high purity ethylene in liquid-phase slurry reactors with promoted AlCl catalysts or the vapor-phase reaction of benzene with a dilute ethylene-containing feedstock with a BF catalyst supported on alumina. Both of these catalysts are corrosive and their handling presents problems. 

Styrene is mildly toxic, flammable, and can be made to polymerize violently under certain conditions. However, handled according to proper procedures, it is a relatively safe organic chemical. Styrene vapor has an odor threshold of 50—150 ppm (72,73). 

Storage and Handling of Styrene-Tjpe Monomers, Eorm No. 115-575-79, Organic Chemicals Dept., Dow Chemical USA, Midland, Mich., 1979. 

There are two problems in the manufacture of PS removal of the heat of polymeriza tion (ca 700 kj /kg (300 Btu/lb)) of styrene polymerized and the simultaneous handling of a partially converted polymer symp with a viscosity of ca 10 mPa(=cP). The latter problem strongly aggravates the former. A wide variety of solutions to these problems have been reported for the four mechanisms described earlier, ie, free radical, anionic, cationic, and Ziegler, several processes can be used. Table 6 summarizes the processes which have been used to implement each mechanism for Hquid-phase systems. Free-radical polymerization of styrenic systems, primarily in solution, is of principal commercial interest. Details of suspension processes, which are declining in importance, are available (208,209), as are descriptions of emulsion processes (210) and summaries of the historical development of styrene polymerization processes (208,211,212). 

Vinyl acetate is a colorless, flammable Hquid having an initially pleasant odor which quickly becomes sharp and irritating. Table 1 Hsts the physical properties of the monomer. Information on properties, safety, and handling of vinyl acetate has been pubUshed (5—9). The vapor pressure, heat of vaporization, vapor heat capacity, Hquid heat capacity, Hquid density, vapor viscosity, Hquid viscosity, surface tension, vapor thermal conductivity, and Hquid thermal conductivity profile over temperature ranges have also been pubHshed (10). Table 2 (11) Hsts the solubiHty information for vinyl acetate. Unlike monomers such as styrene, vinyl acetate has a significant level of solubiHty in water which contributes to unique polymerization behavior. Vinyl acetate forms azeotropic mixtures (Table 3) (12). 

Because of analogy of radical formation by iron(II) ion from either peroxides or oxaziridines, the latter were proposed repeatedly as initiators of radical chains, e.g. in styrene polymerization and in treatment of unsaturated polyesters. Oxaziridines appear to be easier to prepare than peroxides and to be less hazardous in handling (76MI50801). 

More recently, Carreira reported a [Fe(TPP)Cl]-catalyzed diastereoselective synthesis of trifluoromethyl-substituted cyclopropane in aqueous media [56]. The carbene precursor trifluoromethyl diazomethane is difficult to be handled, generated in situ from trifluoroethyl amine hydrochloride, and reacts with styrene in the presence of [Fe(TPP)Cl] to give the corresponding cyclopropanes in high yields and with excellent diastereoselectivities (Scheme 12). 

So the handling of hydrocarbons presents serious fire hazards. There are many accidents linked to this in the industrial sector. For instance, a serious accident happened when polyethylene was stored. It appeared to be caused by the diffusion of monomer through the mass of polymer, which created an inflammable atmosphere in the storage container. Incorporating a mixture of oxygen and styrene in a reactor cause spontaneous ignition. 

The additive feed tank must be large enough to handle all additives plus a carrier solution of styrene. The pounds of dodecylbenzene sulfonate, tricalcium phosphate, and benzoyl peroxide (50% water) used per batch are... 

The syn-isomer decomposed exothermically to styrene when handled in a nitrogen... 

Using insights contributed to by Mark, his laboratory group was steadily concocting new polymers, turning them over to the development department. Toward the end of 1929, word was rushed about the plant that one of these showed great promise. This polymer was formed from the common liquid styrene and could be transformed into a clear plastic from which cigar holders, toys, handles, etc. could be constructed. About a month later the first order for polystyrene was placed. The crisis was past. 

Progress in Polystyrene Research. As so often happens, practical applications have a stimulating effect on investigations of the underlying fundamentals. This is true of polystyrene, too. Styrene is a particularly versatile monomer, as it is copolymerizable with numerous other monomers, may be copolymerized by any known method, and is also easy to handle. 

The bioconversion was carried out in a two-liquid phase system (Figure 15.12), which was developed at the 2-L level, and scaled up to the 30-L level to produce almost 400 g of product. Several apolar phases were used, of which bis(2-ethylhexyl)phthalate (BEHP) was preferred because it showed a better partitioning of epoxystyrene toward the apolar phase and away from the aqueous phase than did hexadecane. This was important because the product was quite toxic to the recombinant biocatalyst when it appeared in the aqueous phase. This bioconversion illustrates that apolar compounds like styrene and its epoxide, which are quite toxic to microorganisms, can be handled successfully in two-liquid-phase cultures. The toxicity of the substrate and product are not significant issues here. 

Handling. Styrene is a colorless liquid but tends toward a yellowish cast as it ages. It feels oily to the touch and smells like the aromatics compounds. Left alone at room temperature, styrene will eventually polymerize with itself to a clear glassy solid. 

Technical grade styrene is 99% minimum purity. It is shipped, with a polymerization inhibitor in it, in standard tank cars or trucks. However, it has none of the severe handling precautions that benzene does. 

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