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_ob=ArticleURL&_udi=B6TXS4FNTH9P3&_user=2512477&_coverDate=08%2F31%2F2005&_rdoc=1&_fmt=high&_ orig=search&_origin=search&_sort=d&_docanchor=&view=c&_searchStrId= 1643422958&_rerunOrigin=google&_acct=C000027478&_version=1&_urlVer sion=0&_userid=2512477&md5=215b0bc0e89ae9ffec51764e7caecd90&searcht ype=a#sch1 Reaction mechanism

The thermal degradation of polystyrene is a typical radical chain mechanism, where initiation, propagation and termination ((6) and (7)) are the relevant reaction classes. The initiation is the formation of polymeric radicals (Scheme 1). Once the polymeric radical is formed, the bond energies of CC and CH bonds adjacent to the radicals decrease from 346.9 and 409.6 kJ/mol to 122.8 kJ/mol and 167.2 kJ/mol, respectively, so a series of unzipping reactions (Scheme 2) proceeds and styrene monomer is obtained. Besides the unzipping reaction, the propagation step consists of H-abstraction ((3) and (4)) and -decomposition (Scheme 5). Termination consists of recombination (Scheme 6) and disproportionation reactions (Scheme 7). (1) (2) (3) (4) (5) (6) (7) In contrast to solvent-less thermal degradation, solvents probably affect the reaction mechanism, because of the distribution of products is quite different from thermal degradation without solvent. Products were obtained from polystyrene degradation or/and secondary reaction, so benzene, toluene, ethylbenzene and p-xylene probably had different effects on these two different processes. As to investigating the effect of benzene, toluene, ethylbenzene and p-xylene on the secondary reaction, the above solvents reacted with styrene directly in the same operating conditions. The analytical results of feeds and products are listed in Table 5. As expected, more side-products were obtained in accordance with the sequence of benzene, toluene, p-xylene and ethylbenzene used as supercritical solvents. The results showed that styrene in supercritical benzene and toluene produced less side-products, and only 2.4% and 4.0% of styrene converted into other products, respectively, while 35% and 42% of styrene in p-xylene and ethylbenzene, respectively, converted into side-products. According to the above analysis, it can be concluded that benzene and toluene have little effect on the secondary reactions, while p-xylene and ethylbenzene affect them substantially. As can be seen from Table 5, toluene used as supercritical solvent gave the most styrene due to its little effect on

the degradation and secondary reactions. However, benzene used as supercritical solvent to depolymerise polystyrene gave more side-products than toluene, though benzene had less effect on the secondary reaction, which implied that benzene changed the process of degradation. Furthermore, more secondary reactions occurred at the expense of the primary products using ethylbenzene and p-xylene as supercritical solvents. Table 5. The decomposition products obtained from the reaction of styrene in different supercritical solvents at 370 C
Compositio ns (wt.%) Benzene + styre ne Toluene + styre ne pXylene + styre ne Feed 0 0 0 83.2 16.3 0 Product 1.75 0.55 0.49 86.0 10.6 0.11 Ethylbenzene + styre ne

Feed Benzene Toluene Ethylbenzen e Xylene Styrene methylstyren e 78.9 0 0 0 20.9 0

Product 76.7 2.45 0.20 0.03 20.4 0.17

Feed 0 82.2 0 0 17.7 0

Product 2.0 78.5 0.34 0.19 17.0 0.18

Feed 0 0 81.1 0 18.8 0

Product 0.13 1.06 84.3 0.31 10.9 2.28

The pressure of PS degradation in supercritical benzene, toluene, ethylbenzene and p-xylene was 4.9 MPa, 3.8 MPa, 3.5 MPa and 3.4 MPa, respectively.

In summary, the use of supercritical solvents changed the reaction mechanism of polystyrene degradation due to the closed system. All the supercritical solvents increased the rate of polystyrene degradation while affecting the reaction mechanism differently. Moreover, among the solvents used in our work, toluene was founded to be the most effective to recover styrene from polystyrene.