| Popis: |
Relative concentrations of catalysts, sulfide catalyst structure, and organic phase monomer concentration were studied for the bimechanistic phase transfer catalyzed (BPTC) polymerization of aqueous sodium sulfide with 1,8-dibromooctane (DBO). BPTC is a new phase transfer mechanism which combines the effects of normal phase transfer with “inverse” phase transfer catalyzed reactions. Two catalysts are used: an ammonium salt and a cyclic or acyclic sulfide. With hexadecyltrimethylammonium chloride (CTMAC) and tetrahydrothiophene (THT), the optimum catalyst concentrations were found to be 10 mol-% and 5 mol-%, respectively, per DBO, but each was independent of the other. Diluting the monomer with o-dichlorobenzene did not significantly alter the mechanism's profile, but expectedly lowered obtainable molecular weight. Of five sulfide catalysts examined, pentamethylene sulfide and dimethyl sulfide were the best, producing the highest molecular weight polyaliphatic sulfides with polydispersities Mw/Mn of ca. 1,3. |
Plný text