合成双酚F的工艺研究
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摘要
双酚F(BPF)是一种重要的有机化工原料,主要用于生产环氧树脂材料。由于其性能优异且用途广泛,已成为一种极具市场潜力的化工产品。世界上BPF主要采用路易斯酸催化法生产,磷酸催化法是一种很有发展潜力的工艺路线。
本文对以甲醛和苯酚为原料制备BPF的合成工艺过程进行了研究。
首先,研究了苯酚和甲醛合成BPF中使用的催化剂。与其他强酸型催化剂相比,磷酸催化剂具有更好的催化性能,有利于合成的进行。
其次,在磷酸催化条件下考察了反应时间、反应温度、催化剂加入量、原料配比对BPF收率和反应选择性的影响。确定了适宜反应条件:酚醛摩尔比10:1,催化剂用量为苯酚磷酸摩尔比10:1,反应温度60℃,反应时间4小时。在此条件下BPF收率能达到90%,过程选择性为100%。对催化剂的重复使用进行了考察,使用五次BPF收率仍然维持在70%以上,选择性大于85%。运用气相色谱对苯酚的含量进行检测,产品组成由高效液相色谱( HPLC)进行测试。
最后,研究了溶剂对产品异构体组成的影响,可用于合成不同品质要求的BPF。
Bisphenol-F (BPF) is an important organic chemical material, mainly used for the produce of epoxy resin. Because of its excellent properties and comprehensive application, BPF has huge market potential. BPF was mainly produced by the classical method of Lewis acid catalytic process in the world,the process of using phosphoric acid catalyst to BPF is a process with a great potential.
The synthesis process of BPF from formaldehyde and phenol was studied in this paper.
Firstly, the catalysts used for synthesis of BPF from formaldehyde and phenol were studied. Phosphoric acid catalyst was used, whose catalytic performance was excellent compared with the strong acid catalysts.
Secondly, the effects of reaction time, temperature, amount of catalyst, mole ratio of reagent on BPF yield rate and reaction selectivity were studied by using phosphoric acid catalyst. The optimal reaction conditions were: mole ratio of phenol to formaldehyde was 10/1, mole ratio of phenol to catalysts was 10/1, reaction temperature was 60℃and reaction time was 4 hours. Under the above conditions, the BPF yield reached more than 90%, the reaction process selectivity was 100%. Recycle of catalyst was also studied, BPF yield remains above 70% and the reaction process selectivity was also above 85% after the catalyst was used for five times. The amount of phenol was tested by GC and the content of product was test by HPLC.
Finally, the effect of solvent to the product content was studied, to synthesize different quality of BPF.
本文对以甲醛和苯酚为原料制备BPF的合成工艺过程进行了研究。
首先,研究了苯酚和甲醛合成BPF中使用的催化剂。与其他强酸型催化剂相比,磷酸催化剂具有更好的催化性能,有利于合成的进行。
其次,在磷酸催化条件下考察了反应时间、反应温度、催化剂加入量、原料配比对BPF收率和反应选择性的影响。确定了适宜反应条件:酚醛摩尔比10:1,催化剂用量为苯酚磷酸摩尔比10:1,反应温度60℃,反应时间4小时。在此条件下BPF收率能达到90%,过程选择性为100%。对催化剂的重复使用进行了考察,使用五次BPF收率仍然维持在70%以上,选择性大于85%。运用气相色谱对苯酚的含量进行检测,产品组成由高效液相色谱( HPLC)进行测试。
最后,研究了溶剂对产品异构体组成的影响,可用于合成不同品质要求的BPF。
Bisphenol-F (BPF) is an important organic chemical material, mainly used for the produce of epoxy resin. Because of its excellent properties and comprehensive application, BPF has huge market potential. BPF was mainly produced by the classical method of Lewis acid catalytic process in the world,the process of using phosphoric acid catalyst to BPF is a process with a great potential.
The synthesis process of BPF from formaldehyde and phenol was studied in this paper.
Firstly, the catalysts used for synthesis of BPF from formaldehyde and phenol were studied. Phosphoric acid catalyst was used, whose catalytic performance was excellent compared with the strong acid catalysts.
Secondly, the effects of reaction time, temperature, amount of catalyst, mole ratio of reagent on BPF yield rate and reaction selectivity were studied by using phosphoric acid catalyst. The optimal reaction conditions were: mole ratio of phenol to formaldehyde was 10/1, mole ratio of phenol to catalysts was 10/1, reaction temperature was 60℃and reaction time was 4 hours. Under the above conditions, the BPF yield reached more than 90%, the reaction process selectivity was 100%. Recycle of catalyst was also studied, BPF yield remains above 70% and the reaction process selectivity was also above 85% after the catalyst was used for five times. The amount of phenol was tested by GC and the content of product was test by HPLC.
Finally, the effect of solvent to the product content was studied, to synthesize different quality of BPF.
引文
[1]王克智,双酚化合物及其应用[J],塑料科技,1996,2:47~54
[2]颜茵,等.中国化工产品大会上卷[M].北京:化学工业出版社,1994,(7):124~128
[3]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.
[4] Pan Y., Yun H. ,et a1. Synthesis and characterization of bisphenol-F. [J]. College of Aerospace and Material Engineering,2005,27(2):15-19.
[5] Kuratomi. I.,Kenichiro A. ,et a1. Method for simultaneous manufacture of high-purity 4,4'-bisphenol-F and general-purpose bisphenol-F:JP2005-77090 [P].2005-03-17.
[6]黄文清,等.世界精细化工产品手册(续篇),化工部科技情报所(1986):16~19
[7]黄恩奖,BPF及BPF型环氧树脂[J],环氧树脂应用技术,1997,(4):45~48
[8]卢传政,环氧树脂发展概况[J],中国塑料,1999,(2);50~57
[9]J.A布赖德林,塑性材料,北京:化学工业出版社, 2002,(3);12~21
[10]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):
[11] Iimuro S. ,Ito S. ,Takashima T. ,et a1.Method for simultaneous preparation of bisphenol F and novolak phenol resins: US,5395915 [P].1995-03-07
[12]Robet Granjon R. ,Michel Fournier L. Solid bisphenol-F particulates:US,4338470[P].1982-06-06
[13]储伟,催化剂工程,成都:四川大学出版社,2006,9
[14]唐齐超,吴虹,双酚F的合成工艺:中国,96115169.2[P].1997-10-01
[15]Chen M. Y. Ike M. ,Fujita M. ,Acute toxicity,mutagenicity and estrogenicity of bisphenol-A and other bisphenols [J].Environ Toxico, 2002,17: 80~86
[16]Morris R. O. ,Wilbraham M. , Process for making basic hydroxyphenyl methanes: US 4400554 [P]. 1983-05-18
[17]李鹏飞,庞先柴,在离子交换树脂上负载AlCl3的固体超强酸催化剂的研制[J],精细石油化工,1993(1):17~19
[18]张宏涛,吴虹,热同性树脂,北京:化学工业出版社, 1996,43~48
[19]黄仲涛,工业催化剂手册,北京:化学工业出版社,2004,10
[20]张宏涛,吴虹,唐齐超,双酚F的合成及其应用研究综述[J],热固性树脂,1996(4):
[21]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
[22] Carvill B. ,Glasgow K. ,Roland M. ,et a1.Process for the synthesis of Bisphenol-F:US,20050004406[P].2005-01-06.
[24]秦金来,张文雯,何明阳,陈群,双酚F催化剂技术进展[J],化工进展,2004,23(7):710~717.
[25]Ohko Y. I. ,Ando C.,Niwa T. ,et a1.Degradation of bisphen-F in water by acidic catalyst [J].Environ. Sci. Technol,2001,35:2365~2368
[26] Kishan G. ,Vetrivel R. ,Kukalyekar N. ,et a1.Functionalized silicone resins,methods for their preparation,and use as catalysts:US,20050033002 [P], 2005-02-10
[27]刘大壮,孙培勤,催化工艺开发,北京:气相出版社,2002,5
[28]Tagawa T.,Amemiya J.,Goto S. ,et a1. Halogen-free Friede-Crafts aeylation of toluene with benzoic anhydride over insoluble heteropoly acid catalyst,J. Jpa. Petroleum Inst,2003,46(2):105110 AppLCata1.A,2004,257(1):19~23
[29]田部浩日,新固体酸和碱及其催化作用,北京:化学工业出版社,1992,154~177
[30]Izumi Y. ,Ogawa M. , Urabe K. ,et a1. Alkali metal salts and ammonium salts of Keggin-type heteropolyacids as solid acid catalysts forliquid-phase FriedeI-Crafts reactions,Appl. Cata1. A,1995,132(1):127~ 140
[31] Ficher H. C. ,et a1.A Computer simulation study on acylation reactionof aromatic hydrocarbons over acidic zeolites [J].Plastics and Rubber Processing and Applications,1990,(14):103~107
[32]Suman K. ,Kugita T. ,et a1. Selective synthesis of bisphenol F catalyzed by microporous H-βzeolite[J]. Applied Catalysis,2005,(288): 1~2
[33] Wang Y. ,Zhou S. L. ,Xia J.R. ,et a1.Trapping and degradation of volatile nirtrosamines on cyclodextrin and zeolites [J].Micropor. Mesopor. Mat.,2004,75:247~254
[34]Chatterjee A. ,Bhattacharyan ,Iwasaki T. , A Computer simulation study on acylation reactionof aromatic hydrocarbons over acidic zeolites,J. Catal, 1999, 185(1):23~32
[35]Choudhary V. R. ,Jana S. K. ,et a1. Highly active SiMCM-41 supported Ga2O3 and In203 catalysts for Friedel-Crafts-Type benzylation and acylation reactions in the presence or absenceof moisture[J],J. Catal,2000,192(2):257~261
[36]胡拖平,秦张峰,王建国,SiO2负载杂多酸催化的甲苯与乙酸酐酰化反应,燃料化学学报,2005,33(5):622~625
[37]Kozhe V. ,Nikov I.,et al.Friedel Crafts aeylation and related reactions catalysedby heteropoly acids,Appl. Cata1. A,2003,256(1~2):3~18
[38]王槐平,王彪,周世新.SO42-/ZrO2固体超强酸催化剂上异丁烷与丁烯烷基化的研究,石油化工,2001,30(8) :597~601
[39]Arata K. ,Nakamura H. , Friedel Crafts acylation of toluene catalyzed by solid superacids,Appl . Cata1. A,2000,197(2):213~219
[40]Paul S.,Nanda P.,Gupta R .Zinc Mediated Friedel-Crafts acylation in solvent-free conditlons under microwave irradiation,Synthesis,2003,18:2877~2881
[41]Gawande M. B. , Deshpande S. S. et al. A novel solgel synthesized catalyst for Friedel-Crafts benzoylation reaction under solvent-free conditions,J.Mo1. Cata1. A,2005,241(1~2):155~156
[42] Finn S. R. ,et al. Epoxy resin[J],J See Chem Ind,London,1950,(2):69~74
[43]徐克勋,精细有机化工原料及中间体手册,北京:化学工业出版,2001,402~408
[44]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,2005,19(12):27~28
[2]颜茵,等.中国化工产品大会上卷[M].北京:化学工业出版社,1994,(7):124~128
[3]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.
[4] Pan Y., Yun H. ,et a1. Synthesis and characterization of bisphenol-F. [J]. College of Aerospace and Material Engineering,2005,27(2):15-19.
[5] Kuratomi. I.,Kenichiro A. ,et a1. Method for simultaneous manufacture of high-purity 4,4'-bisphenol-F and general-purpose bisphenol-F:JP2005-77090 [P].2005-03-17.
[6]黄文清,等.世界精细化工产品手册(续篇),化工部科技情报所(1986):16~19
[7]黄恩奖,BPF及BPF型环氧树脂[J],环氧树脂应用技术,1997,(4):45~48
[8]卢传政,环氧树脂发展概况[J],中国塑料,1999,(2);50~57
[9]J.A布赖德林,塑性材料,北京:化学工业出版社, 2002,(3);12~21
[10]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):
[11] Iimuro S. ,Ito S. ,Takashima T. ,et a1.Method for simultaneous preparation of bisphenol F and novolak phenol resins: US,5395915 [P].1995-03-07
[12]Robet Granjon R. ,Michel Fournier L. Solid bisphenol-F particulates:US,4338470[P].1982-06-06
[13]储伟,催化剂工程,成都:四川大学出版社,2006,9
[14]唐齐超,吴虹,双酚F的合成工艺:中国,96115169.2[P].1997-10-01
[15]Chen M. Y. Ike M. ,Fujita M. ,Acute toxicity,mutagenicity and estrogenicity of bisphenol-A and other bisphenols [J].Environ Toxico, 2002,17: 80~86
[16]Morris R. O. ,Wilbraham M. , Process for making basic hydroxyphenyl methanes: US 4400554 [P]. 1983-05-18
[17]李鹏飞,庞先柴,在离子交换树脂上负载AlCl3的固体超强酸催化剂的研制[J],精细石油化工,1993(1):17~19
[18]张宏涛,吴虹,热同性树脂,北京:化学工业出版社, 1996,43~48
[19]黄仲涛,工业催化剂手册,北京:化学工业出版社,2004,10
[20]张宏涛,吴虹,唐齐超,双酚F的合成及其应用研究综述[J],热固性树脂,1996(4):
[21]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
[22] Carvill B. ,Glasgow K. ,Roland M. ,et a1.Process for the synthesis of Bisphenol-F:US,20050004406[P].2005-01-06.
[24]秦金来,张文雯,何明阳,陈群,双酚F催化剂技术进展[J],化工进展,2004,23(7):710~717.
[25]Ohko Y. I. ,Ando C.,Niwa T. ,et a1.Degradation of bisphen-F in water by acidic catalyst [J].Environ. Sci. Technol,2001,35:2365~2368
[26] Kishan G. ,Vetrivel R. ,Kukalyekar N. ,et a1.Functionalized silicone resins,methods for their preparation,and use as catalysts:US,20050033002 [P], 2005-02-10
[27]刘大壮,孙培勤,催化工艺开发,北京:气相出版社,2002,5
[28]Tagawa T.,Amemiya J.,Goto S. ,et a1. Halogen-free Friede-Crafts aeylation of toluene with benzoic anhydride over insoluble heteropoly acid catalyst,J. Jpa. Petroleum Inst,2003,46(2):105110 AppLCata1.A,2004,257(1):19~23
[29]田部浩日,新固体酸和碱及其催化作用,北京:化学工业出版社,1992,154~177
[30]Izumi Y. ,Ogawa M. , Urabe K. ,et a1. Alkali metal salts and ammonium salts of Keggin-type heteropolyacids as solid acid catalysts forliquid-phase FriedeI-Crafts reactions,Appl. Cata1. A,1995,132(1):127~ 140
[31] Ficher H. C. ,et a1.A Computer simulation study on acylation reactionof aromatic hydrocarbons over acidic zeolites [J].Plastics and Rubber Processing and Applications,1990,(14):103~107
[32]Suman K. ,Kugita T. ,et a1. Selective synthesis of bisphenol F catalyzed by microporous H-βzeolite[J]. Applied Catalysis,2005,(288): 1~2
[33] Wang Y. ,Zhou S. L. ,Xia J.R. ,et a1.Trapping and degradation of volatile nirtrosamines on cyclodextrin and zeolites [J].Micropor. Mesopor. Mat.,2004,75:247~254
[34]Chatterjee A. ,Bhattacharyan ,Iwasaki T. , A Computer simulation study on acylation reactionof aromatic hydrocarbons over acidic zeolites,J. Catal, 1999, 185(1):23~32
[35]Choudhary V. R. ,Jana S. K. ,et a1. Highly active SiMCM-41 supported Ga2O3 and In203 catalysts for Friedel-Crafts-Type benzylation and acylation reactions in the presence or absenceof moisture[J],J. Catal,2000,192(2):257~261
[36]胡拖平,秦张峰,王建国,SiO2负载杂多酸催化的甲苯与乙酸酐酰化反应,燃料化学学报,2005,33(5):622~625
[37]Kozhe V. ,Nikov I.,et al.Friedel Crafts aeylation and related reactions catalysedby heteropoly acids,Appl. Cata1. A,2003,256(1~2):3~18
[38]王槐平,王彪,周世新.SO42-/ZrO2固体超强酸催化剂上异丁烷与丁烯烷基化的研究,石油化工,2001,30(8) :597~601
[39]Arata K. ,Nakamura H. , Friedel Crafts acylation of toluene catalyzed by solid superacids,Appl . Cata1. A,2000,197(2):213~219
[40]Paul S.,Nanda P.,Gupta R .Zinc Mediated Friedel-Crafts acylation in solvent-free conditlons under microwave irradiation,Synthesis,2003,18:2877~2881
[41]Gawande M. B. , Deshpande S. S. et al. A novel solgel synthesized catalyst for Friedel-Crafts benzoylation reaction under solvent-free conditions,J.Mo1. Cata1. A,2005,241(1~2):155~156
[42] Finn S. R. ,et al. Epoxy resin[J],J See Chem Ind,London,1950,(2):69~74
[43]徐克勋,精细有机化工原料及中间体手册,北京:化学工业出版,2001,402~408
[44]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,2005,19(12):27~28