Non-phosgene synthesis of hexamethylene-1,6-diisocyanate from thermal decomposition of hexamethylene-1,6-dicarbamate over Zn–Co bimetallic supported ZSM-5 catalyst
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摘要
A non-phosgene route for the synthesis of hexamethylene-1,6-diisocyanate(HDI) was developed via catalytic decomposition of hexamethylene-1,6-dicarbamate(HDC) over Zn–Co bi-metallic supported ZSM-5 catalyst.The catalyst was characterized by FTIR and XRD analyses. Three solvents dioctyl sebacate(DOS), dibutyl sebacate(DBS) and 1-butyl-3-methylimidazolium tetrafluoroborate(BMIMBF_4) were investigated and compared; DOS gave better performance. The catalytic performances for thermal decomposition of HDC to HDI using DOS as solvent were then investigated, and the results showed that, under the optimized reaction conditions, i.e.,10 wt%concentration of HDC in DOS, 250 °C temperature, 60 min reaction time, 83.8% yield of HDI had been achieved over Zn–Co/ZSM-5. Decomposition of the intermediate hexamethylene-1-carbamate-6-isocyanate(HMI) over Zn–Co/ZSM-5 in DOS solvent was further studied and the results indicated that yield of HDI from HMI reached to 69.6%(98.6% HDI selectively) at 270 °C, which further increased the yield of the total HDI(HDI_(tol)) to as high as 95.0%. Recycling of catalyst showed that HDI and HMI yield slightly decreased, and by-product yield increased after the catalyst was reused for 4 times. At last possible reaction mechanism was proposed.
A non-phosgene route for the synthesis of hexamethylene-1,6-diisocyanate(HDI) was developed via catalytic decomposition of hexamethylene-1,6-dicarbamate(HDC) over Zn–Co bi-metallic supported ZSM-5 catalyst.The catalyst was characterized by FTIR and XRD analyses. Three solvents dioctyl sebacate(DOS), dibutyl sebacate(DBS) and 1-butyl-3-methylimidazolium tetrafluoroborate(BMIMBF_4) were investigated and compared; DOS gave better performance. The catalytic performances for thermal decomposition of HDC to HDI using DOS as solvent were then investigated, and the results showed that, under the optimized reaction conditions, i.e.,10 wt%concentration of HDC in DOS, 250 °C temperature, 60 min reaction time, 83.8% yield of HDI had been achieved over Zn–Co/ZSM-5. Decomposition of the intermediate hexamethylene-1-carbamate-6-isocyanate(HMI) over Zn–Co/ZSM-5 in DOS solvent was further studied and the results indicated that yield of HDI from HMI reached to 69.6%(98.6% HDI selectively) at 270 °C, which further increased the yield of the total HDI(HDI_(tol)) to as high as 95.0%. Recycling of catalyst showed that HDI and HMI yield slightly decreased, and by-product yield increased after the catalyst was reused for 4 times. At last possible reaction mechanism was proposed.
A non-phosgene route for the synthesis of hexamethylene-1,6-diisocyanate(HDI) was developed via catalytic decomposition of hexamethylene-1,6-dicarbamate(HDC) over Zn–Co bi-metallic supported ZSM-5 catalyst.The catalyst was characterized by FTIR and XRD analyses. Three solvents dioctyl sebacate(DOS), dibutyl sebacate(DBS) and 1-butyl-3-methylimidazolium tetrafluoroborate(BMIMBF_4) were investigated and compared; DOS gave better performance. The catalytic performances for thermal decomposition of HDC to HDI using DOS as solvent were then investigated, and the results showed that, under the optimized reaction conditions, i.e.,10 wt%concentration of HDC in DOS, 250 °C temperature, 60 min reaction time, 83.8% yield of HDI had been achieved over Zn–Co/ZSM-5. Decomposition of the intermediate hexamethylene-1-carbamate-6-isocyanate(HMI) over Zn–Co/ZSM-5 in DOS solvent was further studied and the results indicated that yield of HDI from HMI reached to 69.6%(98.6% HDI selectively) at 270 °C, which further increased the yield of the total HDI(HDI_(tol)) to as high as 95.0%. Recycling of catalyst showed that HDI and HMI yield slightly decreased, and by-product yield increased after the catalyst was reused for 4 times. At last possible reaction mechanism was proposed.
引文
[1] B.F. Arlas, L. Rueda, P.M. Stefani, K.D. Caba, I. Mondragon, A. Eceiza, Kinetic and thermodynamic studies of the formation of a polyurethane based on 1,6-hexamethylene diisocyanate and poly(carbonate-co-ester)diol, Thermochim. Acta 459(2007)94–103.
[2] R.M. Versteegen, R.P. Sijbesma, E.W. Maijer, Polyurethanes:Synthesis and characterization, Angew. Chem. Int. Ed. 38(2010)2917–2919.
[3] D.L. Sun, S.J. Xie, J.R. Deng, Z.S. Chao, Progress in clean synthesis of hexamethylene-1,6-diisocyanate, Chem. Ind. Eng. 27(2010)271–277.
[4] O. Kreye, H. Mutlu, M.A.R. Meier, Sustainable routes to polyurethane precursors,Green Chem. 15(2013)1431–1455.
[5] J.S. Nowick, D.L. Holmes, G. Noronha, E.M. Smith, T.M. Nguyen, S.L. Huang, Synthesis of peptide isocyanates and isothiocyanates, J. Org. Chem. 61(1996)3929–3934.
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[7] W.H. Lin, Y.S. Guo, S.A. Dai, An ef?cient one-pot synthesis of aliphatic diisocyanate from diamine and aiphenyl carbonate, J. Taiwan Inst. Chem. Eng. 50(2015)322–327.
[8] Y. Cao, X.T. Li, H.Q. Li, L.G. Wang, G.Y. Zhu, Q. Tang, Heterogeneous synthesis of dimethylhexane-1,6-dicarbamate from 1,6-hexanediamine and methyl carbonate by two-step variable temperature technology in methanol over CeO2catalyst,Chin. J. Chem. Eng. 23(2)(2014)446–450.
[9] H.Q. Li, Y. Cao, X.T. Li, L.G. Wang, F.J. Li, G.Y. Zhu, Heterogeneous catalytic methoxycarbonylation of 1,6-hexanediamine by dimethyl carbonate to dimethylhexane-1,6-dicarbamate, Ind. Eng. Chem. Res. 53(2)(2014)626–634.
[10] L.Y. Zhao, P. He, L.G. Wang, A. Muhammad, Y. Cao, H.Q. Li, Catalysts screening, optimization and mechanism studies of dimethylhexane-1,6-dicarbamate synthesis from 1,6-hexanediamine and dimethyl carbonate over Mn(OAc)2catalyst, Catal.Today 281(2017)392–401.
[11] A. Muhammad, Y. Cao, L.G. Wang, P. He, H.Q. Li, Synthesis of hexamethylene-1,6-dicarbamate by methoxycarbonylation of 1,6-hexamethylene diamine with dimethyl carbonate over bulk and hybrid heteropoly acid catalyst, Res. Chem.Intermed. 43(2017)6951–6972.
[12] T. Masuda, D. Saylik, L. Diebele. Production of aliphatic isocyanate:Japan Pat,6239826, 1994.
[13] S.C. Miranda, C.C. Cabrero, E.F. Gutierrez, P.S. Carnero, M.S. Queralt, P.U. Sola, Isocyanate production procedure, US Pat, 6639101, 2003.
[14] D.L. Sun, J.Y. Luo, R.Y. Wen, J.R. Deng, Z.S. Chao, Phosgene-free synthesis of hexamethylene-1, 6-diisocyanate by the catalytic decomposition of dimethylhexane-1, 6-dicarbamate over zinc-incorporated berlinite(ZnAlPO4), J.Hazard. Mater. 266(2014)167–173.
[15] M.J. Hyun, M. Shin, Y.J. Kim, Y.W. Suh, Phosgene-free decomposition of dimethylhexane-1,6-dicarbamate over ZnO, Res. Chem. Intermed. 42(2016)57–70.
[16] C. Jeong, M.J. Hyun, Y.W. Suh, Activity of coprecipitated CuO/ZnO catalysts in the decomposition of dimethylhexane-1,6-dicarbamate, Catal. Commun. 70(2015)34–39.
[17] Y. Cao, H. Li, N. Qin, G. Zhu, Kinetics of the decomposition of dimethylhexane-1,6-dicarbamate to 1,6-hexamethylene diisocyanate, Chin. J. Chem. Eng. 23(2015)775–779.
[18] C.T. Hung, K.C. Lin, C.B. Wang, S.H. Begum, X. Han, S.B. Liu, Zeolite ZSM-5 supported bimetallic Fe-based catalysts for selective catalytic reduction of NO:effects of acidity and metal loading, Adv. Porous Mater. 4(2016)189–199.
[19] N. Rahimi, R. Karimzadeh, Catalytic cracking of hydrocarbons over modi?ed ZSM-5zeolites to produce light ole?ns:a review, Appl. Catal. A Gen. 398(2011)1–17.
[20] A. Muhammad, Y. Cao, P. He, L.G. Wang, J.Q. Chen, H.Q. Li, An ef?cient green route for hexamethylene-1,6-diisocyanate synthesis by thermal decomposition of hexamethylene-1,6-dicarbamate over Co3O4/ZSM-5 catalyst:An indirect utilization of CO2, Chin. J. Chem. Eng. 25(2017)1760–1770.
[21] L.F. Isernia, FTIR study of the relation, between extra-framework aluminum species and the adsorbed molecular water, and its effect on the acidity in ZSM-5 steamed zeolite, Mater. Res. 16(2013)792–802.
[22] X.H. Zhao, L. Wei, J. Julson, J.Z. Gu, Y.H. Cao, Catalytic cracking of inedible camelina oils to hydrocarbon fuels over bifunctional Zn/ZSM-5 catalysts, Korean J. Chem.Eng. 32(2015)1528–1541.
[23] S.H. Zhang, Z.X. Gao, S.J. Qing, S.Y. Liu, Y. Qiao, Effect of zinc introduction on catalytic performance of ZSM-5 in conversion of methanol to light ole?ns, Chem. Pap. 68(2014)1187–1193.
[24] Z.J. Wang, H.M. Zhang, L.G. Zhang, J.S. Yuan, S.G. Yan, C.Y. Wang, Low-temperature synthesis of Zn O nanoparticles by solid-state pyrolytic reaction, Nanotechnology 14(2003)11–15.
[25] C.W. Tang, C.B. Wang, S.H. Chien, Characterization of cobalt oxides studied by FT-IR,Raman, TPR and TG-MS, Thermochim. Acta 473(2008)68–73.
[26] A. Fisher, P. Goodall, M.W. Hinds, S.N. Nelms, D.M. Penny, Atomic spectrometry update. Industrial analysis:Metals, chemicals and advanced materials, J. Anal. At.Spectrom. 19(2004)1567–1595.
[27] P.C. Roy, W.H. Doh, S.K. Jo, C.M. Kim, Interaction of methanol and hydrogen on a ZnO(0001)single crystal surface, J. Phys. Chem. C 117(2013)15116–15121.
[2] R.M. Versteegen, R.P. Sijbesma, E.W. Maijer, Polyurethanes:Synthesis and characterization, Angew. Chem. Int. Ed. 38(2010)2917–2919.
[3] D.L. Sun, S.J. Xie, J.R. Deng, Z.S. Chao, Progress in clean synthesis of hexamethylene-1,6-diisocyanate, Chem. Ind. Eng. 27(2010)271–277.
[4] O. Kreye, H. Mutlu, M.A.R. Meier, Sustainable routes to polyurethane precursors,Green Chem. 15(2013)1431–1455.
[5] J.S. Nowick, D.L. Holmes, G. Noronha, E.M. Smith, T.M. Nguyen, S.L. Huang, Synthesis of peptide isocyanates and isothiocyanates, J. Org. Chem. 61(1996)3929–3934.
[6] E. Delebecq, J.P. Pascault, B. Boutevin, F. Ganachaud, On the versatility of urethane/urea bonds:Reversibility, blocked isocyanate, and non-isocyanate polyurethane,Chem. Rev. 113(2012)80–118.
[7] W.H. Lin, Y.S. Guo, S.A. Dai, An ef?cient one-pot synthesis of aliphatic diisocyanate from diamine and aiphenyl carbonate, J. Taiwan Inst. Chem. Eng. 50(2015)322–327.
[8] Y. Cao, X.T. Li, H.Q. Li, L.G. Wang, G.Y. Zhu, Q. Tang, Heterogeneous synthesis of dimethylhexane-1,6-dicarbamate from 1,6-hexanediamine and methyl carbonate by two-step variable temperature technology in methanol over CeO2catalyst,Chin. J. Chem. Eng. 23(2)(2014)446–450.
[9] H.Q. Li, Y. Cao, X.T. Li, L.G. Wang, F.J. Li, G.Y. Zhu, Heterogeneous catalytic methoxycarbonylation of 1,6-hexanediamine by dimethyl carbonate to dimethylhexane-1,6-dicarbamate, Ind. Eng. Chem. Res. 53(2)(2014)626–634.
[10] L.Y. Zhao, P. He, L.G. Wang, A. Muhammad, Y. Cao, H.Q. Li, Catalysts screening, optimization and mechanism studies of dimethylhexane-1,6-dicarbamate synthesis from 1,6-hexanediamine and dimethyl carbonate over Mn(OAc)2catalyst, Catal.Today 281(2017)392–401.
[11] A. Muhammad, Y. Cao, L.G. Wang, P. He, H.Q. Li, Synthesis of hexamethylene-1,6-dicarbamate by methoxycarbonylation of 1,6-hexamethylene diamine with dimethyl carbonate over bulk and hybrid heteropoly acid catalyst, Res. Chem.Intermed. 43(2017)6951–6972.
[12] T. Masuda, D. Saylik, L. Diebele. Production of aliphatic isocyanate:Japan Pat,6239826, 1994.
[13] S.C. Miranda, C.C. Cabrero, E.F. Gutierrez, P.S. Carnero, M.S. Queralt, P.U. Sola, Isocyanate production procedure, US Pat, 6639101, 2003.
[14] D.L. Sun, J.Y. Luo, R.Y. Wen, J.R. Deng, Z.S. Chao, Phosgene-free synthesis of hexamethylene-1, 6-diisocyanate by the catalytic decomposition of dimethylhexane-1, 6-dicarbamate over zinc-incorporated berlinite(ZnAlPO4), J.Hazard. Mater. 266(2014)167–173.
[15] M.J. Hyun, M. Shin, Y.J. Kim, Y.W. Suh, Phosgene-free decomposition of dimethylhexane-1,6-dicarbamate over ZnO, Res. Chem. Intermed. 42(2016)57–70.
[16] C. Jeong, M.J. Hyun, Y.W. Suh, Activity of coprecipitated CuO/ZnO catalysts in the decomposition of dimethylhexane-1,6-dicarbamate, Catal. Commun. 70(2015)34–39.
[17] Y. Cao, H. Li, N. Qin, G. Zhu, Kinetics of the decomposition of dimethylhexane-1,6-dicarbamate to 1,6-hexamethylene diisocyanate, Chin. J. Chem. Eng. 23(2015)775–779.
[18] C.T. Hung, K.C. Lin, C.B. Wang, S.H. Begum, X. Han, S.B. Liu, Zeolite ZSM-5 supported bimetallic Fe-based catalysts for selective catalytic reduction of NO:effects of acidity and metal loading, Adv. Porous Mater. 4(2016)189–199.
[19] N. Rahimi, R. Karimzadeh, Catalytic cracking of hydrocarbons over modi?ed ZSM-5zeolites to produce light ole?ns:a review, Appl. Catal. A Gen. 398(2011)1–17.
[20] A. Muhammad, Y. Cao, P. He, L.G. Wang, J.Q. Chen, H.Q. Li, An ef?cient green route for hexamethylene-1,6-diisocyanate synthesis by thermal decomposition of hexamethylene-1,6-dicarbamate over Co3O4/ZSM-5 catalyst:An indirect utilization of CO2, Chin. J. Chem. Eng. 25(2017)1760–1770.
[21] L.F. Isernia, FTIR study of the relation, between extra-framework aluminum species and the adsorbed molecular water, and its effect on the acidity in ZSM-5 steamed zeolite, Mater. Res. 16(2013)792–802.
[22] X.H. Zhao, L. Wei, J. Julson, J.Z. Gu, Y.H. Cao, Catalytic cracking of inedible camelina oils to hydrocarbon fuels over bifunctional Zn/ZSM-5 catalysts, Korean J. Chem.Eng. 32(2015)1528–1541.
[23] S.H. Zhang, Z.X. Gao, S.J. Qing, S.Y. Liu, Y. Qiao, Effect of zinc introduction on catalytic performance of ZSM-5 in conversion of methanol to light ole?ns, Chem. Pap. 68(2014)1187–1193.
[24] Z.J. Wang, H.M. Zhang, L.G. Zhang, J.S. Yuan, S.G. Yan, C.Y. Wang, Low-temperature synthesis of Zn O nanoparticles by solid-state pyrolytic reaction, Nanotechnology 14(2003)11–15.
[25] C.W. Tang, C.B. Wang, S.H. Chien, Characterization of cobalt oxides studied by FT-IR,Raman, TPR and TG-MS, Thermochim. Acta 473(2008)68–73.
[26] A. Fisher, P. Goodall, M.W. Hinds, S.N. Nelms, D.M. Penny, Atomic spectrometry update. Industrial analysis:Metals, chemicals and advanced materials, J. Anal. At.Spectrom. 19(2004)1567–1595.
[27] P.C. Roy, W.H. Doh, S.K. Jo, C.M. Kim, Interaction of methanol and hydrogen on a ZnO(0001)single crystal surface, J. Phys. Chem. C 117(2013)15116–15121.