| Budget Amount *help |
¥3,300,000 (Direct Cost: ¥3,300,000)
Fiscal Year 2002: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 2001: ¥2,000,000 (Direct Cost: ¥2,000,000)
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| Research Abstract |
Synthesis and solid phase ring-opening polymerization of macrocyclic S-aryl thioesters, macrocyclic sulfides containing s-triazine structure were studied. The macrocyclic sulfides were prepared by the reaction of 1-dibutylamino-3, 5-dimercapto-s-triazine (BADMT) with (o-, m-, p-) xylylene dibromide using bases at a dilute condition (0.01 mol/L) in various solvents. The obtained products were worked up using recycle preparative HPLC to isolate macrocyclic dimmers [(o-, m-, p-) CS-2], trimers [(o-, m-, p-) CS-3], tetramers [(o-, m-, p-) CS-4], with moderate yields, respectively.
The ring-opening polymerizations of the obtained macrocyclic sulfides in bulk were examined under N_2 atmosphere. Although the ring-opening polymerization of each macrocyclic sulfide without catalysts proceeded over 300℃, the molecular weights of the resulted polymers were not relatively high. On the other hand, the polymerizations were enhanced efficiently by using catalysts such as quaternary onium halides. When the polymerization of o-CS-2 was conducted with tetraphenyphosphonium chloride at 250℃ for 10min, a poly (sulfide) with Mw of 180000 was obtained at a conv. of 23%. The behavior of the solvent free ring-opening polymerization of the macrocyclic sulfides was investigated to found that the ring-opening polymerization occurred rapidly to produce high molecular weight polymers.
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