Preparation Of Dicyclopentadiene Dioxide By Tri-Phase Phase Transfer Catalysis

Because in practicality the catalyst cann't be recovered completely to effect the quality of product which is existing in the preparation of dicyclopentadiene dioxide (DCPDDO in short), we find a epoxidation method that is green and suitable for industrial production which uses 50% industrial hydrogen peroxide as oxidant and PS grafted quaternary ammonium phosphor tungsten heterpoly acid salts as tri-phase phase transfer catalyst. The catalyst we used was inexpensive, gained easily, low toxicity and recovered easily through simple filtration.In this paper, we adopted PS grafted N-benzyl-N,N-dimethyl-N-dodecyl quaternary ammonium phosphor tungsten heterpoly peracid salt (PS-12N-PW=O in short) as tri-phase phase transfer catalyst and 50% industrial hydrogen peroxide as oxidant in the epoxidation of dicyclopentadiene (DCPD in short) through compareing the advantages and disadvantages of the synthesis methods of alicyclic epoxy compound. The catalyst's structure was characterized by IR. Its content of W was determined by ICP (w (W)=25.48%). Effects of the particle size of catalyst, adding method of hydrogen peroxide, volume of solvent, molar ratio of reactants, reaction temperature, amount of catalyst, reaction time, kinds of solvent and concertration of hydrogen peroxide on the reaction have been studied. The optimal reaction conditions obtained by orthogonal test were (based on 0.05 mol DCPD):dichloroethane 18 mL, catalyst 2.25 g, n(DCPD):n(H2O2)=1:2.75, reaction temperature 60℃, reaction time 12 h. Under the conditions, the yield of DCPDDO can reach 89% and the catalyst's recovery rate is above 95%. Under the conditions, an appropriate equal parts amplification reaction was applied in this reaction. The result showed that the yield of DCPDDO can reach 92.73% which was a little higher than the small reaction and the catalyst's recovery rate is above 95%. There is no significant decrease interms of catalytic activity after seven recycles.We have prepared a series of PS grafted quaternary ammonium phosphor tungsten heterpoly acid salts as tri-phase phase transfer catalyst in order to investigate their effects on the epoxidation of DCPD. On the one hand, we find that the activity of PS grafted quaternary ammonium phosphor tungsten heterpoly peracid salts are higher than the corresponding of PS grafted quaternary ammonium 12 phosphotungstic acid salts. The reason maybe that the activity of gel-type's phosphotungstic peracid higher than 12 phosphotungstic acid. On the other hand, we find the highest activity catalyst which was PS grafted N-benzyl-N,N-dimethyl-N-octyl quaternary ammonium phosphor tungsten heterpoly peracid salt (PS-8N-PW=O in short). And its structure was characterized by IR. Its content of W was detemined by ICP (w (W)=24.90%). Effects of the particle size of catalyst, preparation methods of catalyst, adding methods of hydrogen peroxide, volume of solvent, molar ratio of reactants, reaction temperature, amount of catalyst, reaction time, kinds of solvent and concertration of hydrogen peroxide on the reaction have been studied. The optimal reaction conditions obtained by orthogonal test were (based on 0.05 mol DCPD):dichloroethane 13 mL, catalyst 2.75 g, n(DCPD):n(H2O2)=1:2.50, reaction temperature 60℃, reaction time 3.5 h. Under the conditions, the yield of DCPDDO can reach 96.61% and the catalyst's recovery rate is above 95%. Under the conditions, an appropriate equal parts amplification reaction was applied in this reaction. The result showed that the yield of DCPDDO can reach 97.64% which was a little higher than the small reaction and the catalyst's recovery rate is above 95%. There is no significant decrease interms of catalytic activity after six recycles. But its stability was a little lower than PS-12N-PW=O's.Although PS-8N-PW=O had lower stability in the reusable catalyst compared to PS-12N-PW=O, it had lower reaction time, higher yield in the epoxidation of DCPD. So it was preferable in the continuous production of industry. And this method is not reported in the epoxidation of DCPD.We have got the solubility of DCPDDO in a series of common used solvent using synthesis method. It gives a basic data for separating and purifying DCPDDO and addresses the gap of the solubility of DCPDDO. We can give conclusion as follow through comparison and analysis these data:The sequence of DCPDDO's solubility under the similar number of C:amides>ketones>tri-halohydrocarbon> alcohol>arene>aryl halide>di-halohydrocarbon>esters>tetra-halohydrocarbon >cyclane>n-paraffin>branched paraffin.We find in this paper's epoxidation system, the best re-crystallization solvent that used to purify DCPDDO is alcohol. And its purity can reach 99% by GC after re-crystallized for three times.We have demonstrated that the purity product was DCPDDO by the analysis of melting point,IR spectrum,13C-NMR,DEPT135 and 1H-NMR.