Research Of The Polyreaction Of Rosin Over Acidic Heteropoly Ionic Liquid Catalysts

Nineteen kinds of acidic heteropoly ionic liquid were designed and synthesized by adjustment the proportion of organic cations and heteropolyanions based on the designability of ionic liquids. The structure of optimized catalysts (H2[TEAPS]PW12O40, Smo.33[TEAPS]2PW12O40, Al0.66[MIMPS]PW12O40) were characterized by FT-IR and ’H-NMR. Potentiometric titration by butylamine was introduced to measure the acid character of catalysts and thermogravimetry-differential scanning calorimetry was applied to detect the thermal stability of the catalysts. The effects of temperature, reaction time, solvent type, the dosage of catalyst on rosin polymerization reaction have been investigated over the above catalysts, what’s more, the reused properties of these catalysts were also studied.1. FT-IR、1-NMR spectrums indicated that the free hydrogen in phosphotungstic acid was replaced by TEAPS+ or MIMPS+ to form the heteropoly ionic liquid.2. The results indicated that 15.0 g rosin,18.0 mL toluene and 5.0 g catalyst with 10 h at 110 ℃ were the optimum conditions for polymerization of rosin by using H2[TEAPS]PW12O40 as a catalyst. The softening point and acid value of polymerized rosin were 116.0 ℃ and 119.0 mg/g in this optimum conditions. In addition, the H2[TEAPS]PW12O40 catalyst could also keep good catalytic performance after 3 recycles and the softening point of polymerized rosin could been up to 117.9 ℃. The results showed that the designed and synthesized acidic heteropoly ionic liquid have been exhibited high catalytic activity and reusability in rosin polymerized reaction.3. The Bronsted-Lewis acidic heteropoly ionic liquid Smo.33[TEAPS]2PW12O40 exhibited more excellent catalytic performance. The results indicated that 15.0 g rosin, 18.0 mL toluene and 5.0 g catalyst with 10 h at 90 ℃ were the optimum conditions for rosin polymerized reaction over Smo.33[TEAPS]2PW12O40. The softening point and acid value of polymerized rosin were 120.1 ℃ and 111.8 mg/g in this optimum conditions. In addition, the Smo.33[TEAPS]2PW12O40 catalyst also could keep good catalytic performance after 5 recycles and the softening point of polymerized rosin could been up to 120.3 ℃.4. The optimum conditions of rosin polymerization reaction catalyzed by Al0.66[MIMPS]PW12O40 were obtained:m(rosin)=15.0 g, m(cat)=5.0 g, V(toluene)=18.0 mL, t=10 h, T=110 ℃. The softening point and acid value of polymerized rosin were 122.1 ℃ and 128.0 mg/g in this optimum conditions. In addition, the Alo.66[MIMPS]PW12O40 catalyst also could keep good catalytic performance after 3 recycles.