Effect of silanol content in silica support on catalytic performance of silica-anchored organotin catalyst for transesterification

ZHANG Yuanzhuo1,2 WANG Songlin3 XIAO Zhongliang1,2 CHEN Tong1 WANG Gongying1

(1.Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu, Sichuan, China 610041)
(2.University of Chinese Academy of Sciences, Beijing, China 100049)
(3.School of Chemistry and Chemical Engineering, Henan Institute of Science and Technology, Xinxiang, Henan, China 453003)

【Abstract】Silica-anchored organotin catalysts were synthesized by a new synthetic scheme. It involved the synthesis of organotin-silane during the preparation of organotin using inorganic SnCl4 as tin precursor, which was then anchored on the silicas for the transesterification of DMC with phenol to diphenyl carbonate. A series of silica supports containing different silanols were obtained by different preparations along with different treatments. The TG and ICP characterizations showed that the Sn loading of the catalyst had positive correlation with the silanol content of the silica support. The 29Si MAS NMR measurements indicated that the prepared catalysts possessed many T2 and T3 species, which was in favor of the stability. The more silanol the silica support contained, the more Sn the catalyst supported, and the more active the catalyst would be. Sn-MSiO2, the catalyst with the mesoporous silica support, exhibited the best catalytic performance: with a reaction temperature of 150 °C–180 °C for 9 h, and a catalyst amount of 1.0 g, the phenol conversion and the transesterification selectivity reached 50.4% and 99.9%, respectively; in recycle test with a catalyst amount of 0.5 g, the phenol conversion decreased from 41.2% to 35.0% after five runs. Sn leaching was the main reason for the decline of catalytic activity.

【Keywords】 organotin; anchor; silanol; diphenyl carbonate; phenol; transesterification;

【DOI】

【Funds】 National High Technology Research and Development Program of China (2013AA031703) Science and Technology Innovation Program for Youth Team of Sichuan Province (2013TD0010)

Download this article

(Translated by WANG YX)

    References

    [1] LI F S, YIN J Z, WEI D W, et al. Progress on the application and synthesis technology of polycarbonate [J]. Chemical Industry and Engineering Progress, 2002, 21 (6): 395–398 (in Chinese).

    [2] WANG Z, YANG X, LIU S, et al. One-pot synthesis of high-molecular-weight aliphatic polycarbonates via melt transesterification of diphenyl carbonate and diols using Zn(OAc)2 as a catalyst [J]. RSC Advances, 2015, 5 (106): 87311–873119.

    [3] WANG Z, YANG X, LIU S, et al. Magnesium acetate used as an effective catalyst for synthesizing aliphatic polycarbonates via melt transesterification process [J]. Chemical Research in Chinese Universities, 2016, 32 (3): 512–518.

    [4] FU Z H, ONO Y. Two-step synthesis of diphenyl carbonate from dimethyl carbonate and phenol using MoO3/SiO2 catalysts [J]. Journal of Molecular Catalysis A Chemical, 1997, 118 (3): 293–299

    [5] KIM W B, LEE J S. A new process for the synthesis of diphenyl carbonate from dimethyl carbonate and phenol over heterogeneous catalysts [J]. Catalysis Letters, 1999, 59 (1] ): 83–88.

    [6] NIU H Y, GUO H M, YAO J, et al. Transesterification of dimethyl carbonate and phenol to diphenyl carbonate catalyzed by titanocene complexes [J]. Acta Chimica Sinica, 2006, 64 (12): 1269–1272 (in Chinese).

    [7] GONG J, MA X, WANG S. Phosgene-free approaches to catalytic synthesis of diphenyl carbonate and its intermediates [J]. Applied Catalysis A General, 2007, 316 (1): 1–21.

    [8] TANG R Z, WANG S L, ZHANG Y Z, et al. Catalytic property of titanyl acetate in the transesterification reaction of dimethyl carbonate and phenol [J]. Chemical Journal of Chinese Universities, 2014, 35 (11): 2418–2424 (in Chinese).

    [9] MERCIER F A, BIESEMANS M, ALTMANN R, et al. Synthesis, characterization, and catalytic properties of diphenyl- and dichlorobutyltin functionalities grafted to insoluble polystyrene beads by a –(CH2)n– (n = 4, 6) spacer [J]. Organometallics, 2001, 20 (5): 958–962.

    [10] CAMACHO-CAMACHO C, BIESEMANS M, VAN POECK M, et al. Alkylchlorotins grafted to cross-linked polystyrene beads by a –(CH2)n– spacer (n = 4, 6, 11): selective, clean and recyclable catalysts for transesterification reactions [J]. Chemistry–A European Journal, 2005, 11 (8): 2455–2461.

    [11] PINOIE V, POELMANS K, MILTNER H E, et al. A polystyrene-supported tin trichloride catalyst with a C11-spacer catalysis monitoring using high-resolution magic angle spinning NMR [J]. Organometallics, 2007, 26 (27): 6718–6725.

    [12] PINOIE V, BIESEMANS M, WILLEM R. Organotin catalysts grafted onto cross-linked polystyrene supports through polar spacers [J]. Applied Organometallic Chemistry, 2010, 24 (2): 135–141.

    [13] TOUPANCE T, RENARD L, JOUSSEAUME B, et al. Silica-anchored organotin trichloride: a recyclable and clean organotin catalyst for transesterification reactions [J]. Dalton Transactions, 2013, 42 (26): 9764–9770.

    [14] FU Q J, STEELE A M, TSANG S C. Novel inorganic oxide supported organotin hydrides for fine chemical catalysis [J]. Green Chemistry, 2001, 3 (2): 71–73.

    [15] MATLIN S A, GANDHAM P S. An immobilized organotin catalyst for reduction of ketones and aldehydes [J]. Journal of the Chemical Society, Chemical Communications, 1984, 12: 798–799.

    [16] SAYARI A, HAN B H, YANG Y. Simple synthesis route to monodispersed SBA-15 silica rods [J]. Journal of the American Chemical Society, 2004, 126 (44): 14348–14349.

    [17] CHO S B, NAKANISHI K, KOKUBO T, et al. Dependence of apatite formation on silica gel on its structure: effect of heat treatment [J]. Journal of the American Ceramic Society, 1995, 78 (7): 1769–1774.

    [18] RYCZKOWSKI J, GOWOREK J, GAC W, et al. Temperature removal of templating agent from MCM-41 silica materials [J]. Thermochimica Acta, 2005, 434 (1): 2–8.

    [19] KIM J M, CHANG S M, KONG S M, et al. Control of hydroxyl group content in silica particle synthesized by the sol-precipitation process [J]. Ceramics International, 2009, 35 (3): 1015–1019.

    [20] DE FARIAS R, AIROLDI C. Thermogravimetry as a reliable tool to estimate the density of silanols on a silica gel surface [J]. Journal of Thermal Analysis and Calorimetry, 1998, 53 (3): 751–756.

    [21] DUAN H M, GE Q J, XU D Y, et al. Effect of cobalt loading on performances of Co/SBA-15 catalysts for Fischer-Tropsch synthesis [J]. Petrochemical Technology, 2009, 38 (7): 716–722 (in Chinese).

    [22] KHODAKOV A Y, GRIBOVAL-CONSTANT A, BECHARA R, et al. Pore size effects in Fischer-Tropsch synthesis over cobalt-supported mesoporous silicas [J]. Journal of Catalysis, 2002, 206 (2): 230–241.

    [23] YU P, HE J, YANG L, et al. Stepwise fabrication and architecture of heterogeneous 9-thiourea epiquinine catalyst with excellent enantioselectivity in the asymmetric Friedel-Crafts reaction of indoles with imines [J]. Journal of Catalysis, 2008, 260 (1): 81–85.

    [24] KRÖCHER O, KÖPPEL R A, FRÖBA M, et al. Silica hybrid gel catalysts containing group (Ⅷ) transition metal complexes: preparation, structural, and catalytic properties in the synthesis of N,N-dimethylformamide and methyl formate from supercritical carbon dioxide [J]. Journal of Catalysis, 1998, 178 (1): 284–298.

    [25] AN Z, HE J, DAI Y, et al. Enhanced heterogeneous asymmetric catalysis via the acid-base cooperation between achiral silanols of mesoporous supports and immobilized chiral amines [J]. Journal of Catalysis, 2014, 317: 105–113.

    [26] FAN B, ZHANG J, LI R, et al. In situ preparation of functional heterogeneous organotin catalyst tethered on SBA-15 [J]. Catalysis Letters, 2008, 121 (3): 297–302.

    [27] WANG S, BAI R, MEI F, et al. Pyroaurite as an active, reusable and environmentally benign catalyst in synthesis of diphenyl carbonate by transesterification [J]. Catalysis Communications, 2009, 11 (3): 202–205.

    [28] ZHOU X, GE X, TANG R Z, et al. Preparation and catalytic property of modified multi-walled carbon nanotube-supported TiO2 for the transesterification of dimethyl carbonate with phenol [J]. Chinese Journal of Catalysis, 2014, 35 (4): 481–489 (in Chinese).

    [29] TANG R Z, CHEN T, CHEN Y, et al. Core-shell TiO2@SiO2 catalyst for transesterification of dimethyl carbonate and phenol to diphenyl carbonate [J]. Chinese Journal of Catalysis, 2014, 35 (4): 457–461 (in Chinese).

    [30] WANG S, TANG R, ZHANG Y, et al. 12-Molybdophosphoric acid supported on titania: a highly active and selective heterogeneous catalyst for the transesterification of dimethyl carbonate and phenol [J]. Chemical Engineering Science, 2015, 138: 93–98.

This Article

ISSN:0438-1157

CN: 11-1946/TQ

Vol 68, No. 05, Pages 1892-1898

May 2017

Downloads:0

Share
Article Outline

Abstract

  • Introduction
  • 1 Experimental materials and methods
  • 2 Experimental results and discussion
  • 3 Conclusion
  • References