嫁接Al改性MCM-41介孔分子筛催化合成双酚F

doi:10.3724/SP.J.1095.2014.30235

摘要/Abstract

摘要： 以十六烷基三甲基溴化铵和正硅酸乙酯为原料，合成纯硅MCM-41介孔分子筛。再利用九水硝酸铝为改性剂来嫁接改性纯硅MCM-41介孔分子筛，NH3-TPD结果表明，嫁接后的AlMCM-41产生了中强酸。用改性后不同n(Si)/n(Al)的AlMCM-41催化合成双酚F，在n（苯酚）/n（甲醛）=30、反应时间5 h、反应温度90 ℃、m（甲醛）/m（AlMCM-41）=7的反应条件下，在一定范围内，双酚F的产率随Al含量增加而增加，但在n（Si）/n（Al）＜50时，双酚F的产率反而下降，当n（Si）/n（Al）=50时，双酚F的产率最高，为42.28%。

关键词: 硝酸铝, 嫁接, 双酚F, MCM-41分子筛

Abstract: Cetyltrimethylammonium bromide(CTAB) and tetraethylorthosilicate(TEOS) were selected as raw materials for the synthesis of pure silicon MCM-41. Using Al(NO3)3·9H2O as aluminum source to modify pure silicon MCM-41 by grafting method. The AlMCM-41 was characterized by NH3-TPD. The results show that AlMCM-41 produced mild acid after grafting. The synthesis of bisphenol F was catalyzed by AlMCM-41 with different silicon/aluminium. The optimized reaction conditions are:n(phenol)/n(formaldehyde)=30, reaction time of 5 h, reaction temperature of 90 ℃, m(formaldehyde)/m(AlMCM-41)=7. In a certain range, the yield of bisphenol F increases with the increase of Al. When the n(Si)/n(Al) is less than 50, the yield of bisphenol F tends to decrease. While n(Si)/n(Al)=50, the yield of bisphenol F can reach its highest value of 42.28%.

Key words: aluminum nitrate, grafting, bisphenol F, MCM-41 molecular sieve

中图分类号:

O643.3

谢铭宇, 李若飞, 贾雪, 田黎黎, 夏新年. 嫁接Al改性MCM-41介孔分子筛催化合成双酚F[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30235.

XIE Mingyu, LI Ruofei, JIA Xue, TIAN Lili, XIA Xiannian*. Synthesis of Bisphenol F Catalyzed by Aluminum-grafted MCM-41 Mesoporous Molecular Sieve[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30235.

参考文献

[1] SUN Qinliang. New Development of Epoxy Resin in Japan[J]. Thermosetting Resin,1995,(10):13-16(in Chinese).

孙勤良. 日本环氧树脂的最新发展概况[J]. 热固性树脂,1995,(10):13-16.

[2] WU Hong. Synthesis and Application of Bisphenol F[J]. Thermosetting Resin,1999,(3):32-34(in Chinese).

吴虹. 双酚F的合成和应用[J]. 热固性树脂,1999,(3):32-34.

[3] LIE Yanyun,YI Zhenyan,LU Jinhai. Synthesis of Bisphenol F[J]. J Petrochem Univ,2006,19(3):33-36(in Chinese).

李艳云,尹振晏,卢金海. 双酚F的合成[J]. 石油化工高等学校学报,2006,19(3):33-36.

[4] PAN Yi,HU Yun,NING Wei. The Synthesis and Characterizaton of Bi-phenolic Methane[J]. J Natl Univ Deffense Technol,2005,27(2):16-19(in Chinese).

盘毅,胡芸,宁威. 二酚基甲烷的合成与表征[J]. 国防科技大学学报,2005,27(2):16-19.

[5] WEN Qingru,JIANG Zhuojun. The Synthesis and Characterization of Bisphenol F[J]. Fujian Architecture Construct,2008,124(10):39-43(in Chinese).

温庆如,蒋卓君. 双酚F的合成与表征[J]. 福建建筑,2008,124(10):39-43.

[6] ZHANG Wenwen,LI Yunshan,HE Mingyang,et al. Synthesis of Bisphenol F by Using Modified Cation Exchange Resin[J]. Chem Ind Eng Prog,2007,26(7):1032-1035(in Chinese).

张文雯,李运山,何明阳,等. 改性阳离子交换树脂催化合成双酚F[J]. 化工进展,2007,26(7):1032-1035.

[7] ZHANG Wenwen,HE Mingyang,CHEN Qun. Analysis of 4,4′-Dihydroxypyridine-diphenylmethane in Bisphenol F Resultant by HPLC[J]. Chem Eng,2005,123(12):27-28(in Chinese).

张文雯,何明阳,陈群. 高效液相色谱法测定双酚F反应液中4,4′-二羟基二苯基甲烷的含量[J]. 化学工程师,2005,123(12):27-28.

[8] Garade A C,Kshirsagar V S,Rode C V. Selective Hydroxyalkylation of Phenol to Bisphenol Fover Dod-ecatungstophosphoric Acid(DTP) Impregnated on Fumed Silica[J]. Appl Catal A,2009,354:176-182.

[9] Garade A C,Kshirsagar V S,Mane R B,et al. Acidity Tuning of Montmorillonite K10 by Impregnation with Dodecatungstophosphoric Acid and Hydroxyalkylation of Phenol[J]. Appl Clay Sci,2010,48:164-170.

[10] Garade A C,Kshirsagar V S. Selective Synthesis of Bisphenol F Catalyzed by Microporous H-beta Zeolite[J]. Appl Catal A,2005,288:80.

[11] Kresge C T,Leonowicz M E,Roth W J,et al. Ordered Mesoporous Molecular Sieves Synthesized by a Liquid-crystal Template Mechanism[J]. Nature,1992,359:710.

[12] Beck J S,Vertuli J C,Roth W J,et al. A New Family of Mesoporous Molecular Sieves Prepared with Liquid Crystal Templates[J]. J Am Chem Soc,1992,114:10834.

[13] Suman K J,Tsuyoshi Kugita,Seitaro Namba. Bisphenol F Synthesis over Mesoporous Aluminosilicate MCM-41 Molecular Sieves[J]. Catal Lett,2003,90(3/4):143.

[14] Suman K J,Tsuyoshi Kugita,Seitaro Namba. Aluminum-grafted MCM-41 Molecular Sieve:an Active Catalyst for Bisphenol F Synthesis Process[J]. Appl Catal A,2004,266:245.

[15] Shen S C,Kawi S. Post-synthesis Alumination of MCM-41 by Al(NO3)3(Ⅰ):Improvement in Acidity for Purely Siliceous MCM-41[J]. Stud Surf Sci Catal,2000,129:219-226.

[16] Shen S C,Kawi S. Post-synthesis Alumination of Si-MCM-41 by Al(NO3)3(H):Enhancement of Hydrothermal, Mechanical and Chemical Stabilities[J]. Stud Surf Sci Catal,2000,129:227-235.

[17] JIN Lijie,ZHOU Ruiwen. Bisphenol F is Determined by HPLC[J]. Chinese J Anal Chem,2000,28(3):386(in Chinese).

景丽洁,周端文. 高效液相色谱法测定双酚F[J]. 分析化学,2000,28(3):386.