CN103736503A - Solid acid catalyst with high-efficiency ring-opening reaction catalysis performance - Google Patents

Solid acid catalyst with high-efficiency ring-opening reaction catalysis performance Download PDF

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CN103736503A
CN103736503A CN201410021055.0A CN201410021055A CN103736503A CN 103736503 A CN103736503 A CN 103736503A CN 201410021055 A CN201410021055 A CN 201410021055A CN 103736503 A CN103736503 A CN 103736503A
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reaction
catalyst
ring
tio
opening reaction
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陈静
杨惠
侯文华
胡晨晖
张丽宏
张�荣
梅伟钢
黄前进
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Nanjing Tech University
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Nanjing Tech University
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Abstract

The invention discloses a solid acid catalyst. Commercial TiO2 (titanium dioxide) serving as a matrix is immersed by using an ammonium persulfate solution and roasted at a high temperature, so that S2O8<2->/TiO2 is prepared. The catalyst has a certain acid content, has high-efficiency performance for catalyzing alcoholysis ring-opening reaction styrene oxide at a room temperature; the solid acid catalyst is simple in preparation, and has reusability; a raw material is easily available. The solid acid catalyst belongs to one kind of ring-opening reaction catalysts which is environment-friendly and easy to industrialize.

Description

A kind of solid acid catalyst with efficient ring-opening reaction catalytic performance
Technical field
The invention belongs to inorganic functional material field, relate to a kind of acid catalyst for ring-opening reaction.Specifically, be a kind ofly to take commercial titanium dioxide as matrix, the solid super-strong acid (S of over cure acid group modification 2o 8 2-/ TiO 2) preparation and the application of ring-opening reaction catalyst.
Background technology
β-alkoxyl alcohol occupies critical role in fine chemistry industry and medication chemistry, and its preparation is all conventionally under the condition of acid or alkali, by epoxide and alcohols generation ring-opening reaction and generate.Some typical lewis acid are (as BF 3oEt 2, SnCl 4, FeCl 3) and
Figure BSA0000100447190000011
acid is (as H 2sO 4, HCl etc.) can be used to the alcoholysis catalysts of epoxide, but these catalyst system and catalyzings are all the catalyst that uses disposable consumption,, there is the problems such as contaminated environment in difficult separating, washing, has greatly limited their practical application.Therefore, development and application efficient, capable of circulation, environmental protection epoxide alcoholysis ring-opening reaction catalyst becomes current research direction.
There are some researches show, some loaded catalysts are developed, for the ring-opening reaction of epoxide, as: CuO-SiO 2(F.Zaccheria, F.Santoro, R.Psaro and N.Ravasio, Green Chem., 2011,13,545-548), D-72 sulfonate resin (synthetic chemistry, 2006,14 (2): 181-183), mesoporous silicon load Fe (III) (S.Das and T.Asefa, ACS Catal., 2011,1,502-510) etc., their easy and product separations, reusable.But reaction all need be in certain temperature, or carries out under counterflow condition, exists certain energy consumption problem.
Recently, the marquis of Nanjing University Wenhua etc. (Chem.Commun., 2013,49, publish an article on 7507-7509), utilize [the TiNbO of S, Fe codope 5] -nanometer sheet, has obtained having the ring-opening reaction catalyst of lewis acid structure, usings multiple alcohol as substrate, can catalyze and synthesize at ambient temperature β-alkoxyl alcohol, and post catalyst reaction is treated, reusable.The Chinese invention patent of publication number CN103333049A in 2013, has announced three kinds of phosphotungstic acid ionic-liquid catalysts, under normal temperature, normal pressure, the alcoholysis reaction of energy efficient catalytic Styryl oxide, after reaction finishes, catalyst is easy to separation, has good reusability.But, [the TiNbO of S, Fe codope no matter 5] -nanometer sheet, or all there is the complexity of preparation in phosphotungstic acid ionic-liquid catalyst.
Summary of the invention
In conjunction with latest Progress, for the deficiency of existing catalyst.The invention provides a kind of S 2o 8 2-the TiO of modification 2open loop, catalytic reaction material (S 2o 8 2-/ TiO 2) preparation method, as catalyst, substitute the tradition of generally using at present
Figure BSA0000100447190000012
acid and Lewis acid, for the ring-opening reaction of Styryl oxide.Gained catalyst has good room temperature catalysis ring-opening reaction performance, can be applicable to the preparation of β-alkoxyl alcohol compounds.
S of the present invention 2o 8 2-/ TiO 2the advantages such as ring-opening reaction catalyst has simple, the used synthesis material of preparation method and is easy to get, and post processing is simple, and reusability is good.There is good prospects for commercial application.
S of the present invention 2o 8 2-/ TiO 2ring-opening reaction catalyst, the alcoholysis ring-opening reaction of catalysis Styryl oxide.Catalyst amount is few, and reaction condition is gentle, efficient, and reusability, environmental friendliness.
The present invention's alcohol compound consumption used is 1~10mL, and Styryl oxide consumption is 0.1~0.5mL (1.2~4mmol), and catalyst amount is 0.4~5% of Styryl oxide molal quantity, and reaction temperature is room temperature, normal pressure, and the reaction time is 10~180min.Reaction progress adopts gas-chromatography to follow the tracks of and detects analysis.
Alcohol compound of the present invention can be the unit alcohol of different carbon numbers, and alcohol compound is as reaction substrate, simultaneously also as the solvent of reaction system.
The specific embodiment
Embodiment 1:
Solid acid catalyst S 2o 8 2-/ TiO 2synthetic: by 1g commodity TiO 2(titanium dioxide) joins 15mL0.5mol/L (NH 4) 2s 2o 8in solution, dipping evaporates solution rotating 60 ℃ of oven dry after stirring 5h.Finally at 500 ℃, roasting 5h can obtain catalyst S 2o 8 2-/ TiO 2, gained catalyst acid amount is 1.8mmol/g.
The present invention is described in detail in detail by the following examples, and these embodiment are only for clear open the present invention, not as limitation of the present invention.
Embodiment 2:
Methyl alcohol is the ring-opening reaction of the Styryl oxide of substrate: in the round-bottomed flask of 25mL, add successively 0.04g S 2o 8 2-/ TiO 2, 5mL methyl alcohol.After stirring at room is even, drip 0.11mL Styryl oxide, start reaction.After reaction a period of time, get a certain amount of reactant liquor, adopt the ring-opening reaction process of gas-chromatography monitoring Styryl oxide.Catalytic reaction the results are shown in Table 1.
Embodiment 3:
Other alcohol is the ring-opening reaction of the Styryl oxide of substrate: use respectively ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol replace the methyl alcohol in example 2, as solvent.Investigate the experiment of catalytic activity as embodiment 2, catalytic reaction the results are shown in Table 1
Table 1 catalyst activity evaluation result
Figure BSA0000100447190000021
Embodiment 4:
Catalyst repeat performance: the experiment of investigating catalytic activity with fresh catalyst is as embodiment 2.After reaction finishes, by suction filtration, isolate solid catalyst, after washing and dry simple process, continue on for catalytic reaction.After 4 times are reused, under similarity condition, room temperature, 10 minutes, the yield of open-loop products was still up to more than 80%.If with 0.5mol/L (NH 4) 2s 2o 8solution is the used catalyst of impregnation process again, through rotary evaporation, dries, and after roasting 5h, is used further to react at 500 ℃ next time.After 5 times are reused, under similarity condition, room temperature, 10 minutes, the yield of open-loop products was up to more than 99%, with fresh catalyst without essential distinction.
Although with preferred embodiment in detail the present invention has been described in detail, yet it is not intended to limit the present invention.Any those skilled in the art, without departing from the spirit and scope of the present invention, should make various modifications and change.Therefore protection scope of the present invention should be considered as appending claims limited range.

Claims (10)

1.S 2o 8 2-/ TiO 2the preparation of ring-opening reaction catalyst, its preparation process is as follows:
Commodity TiO 2(titanium dioxide) stirs and floods a few hours in ammonium persulfate aqueous solution, revolves steaming, and after oven dry, under hot conditions, roasting obtains efficient ring-opening reaction catalyst (S 2o 8 2-/ TiO 2).
2. according to described in claim 1, it is characterized in that commodity TiO 2add in ammonium persulfate aqueous solution and stir, preferably temperature is 0~60 ℃, soak time 2~12h.
3. according to described in claim 1, it is characterized in that, the molar concentration of ammonium persulfate aqueous solution is 0.01~5mol/L.
4. according to described in claim 1, it is characterized in that, in step, roasting under hot conditions, sintering temperature is 400~700 ℃, heating rate is 1~10 ℃/min.
5. according to described in claim 1, it is characterized in that, the acid amount of catalyst is 0.5-2.5mmol/g.
6. according to described in claim 1, it is characterized in that, in catalyst, sulfate radical content is 10-60% (weight ratio).
7. S according to claim 1 2o 8 2-/ TiO 2the ring-opening reaction of catalysis Styryl oxide, it is characterized in that: alcohol compound consumption is 1~10mL, Styryl oxide consumption is that 0.1~0.5mL (1.2~4mmol) catalyst amount is 0.4~5% of Styryl oxide molal quantity, reaction temperature is room temperature, pressure is normal pressure, and the reaction time is 10~300min.Reaction progress adopts gas-chromatography to follow the tracks of and detects analysis.
8. according to the S described in claim 1 and 7 2o 8 2-/ TiO 2the ring-opening reaction of catalysis Styryl oxide, is characterized in that: the unit alcohol of different carbon numbers participates in reaction as nucleopilic reagent.Different alcohol is as reaction substrate, simultaneously also as the solvent of reaction system.
9. according to the S described in claim 1 and 7 2o 8 2-/ TiO 2the ring-opening reaction of catalysis Styryl oxide, is characterized in that: the ring-opening reaction of the catalysis Styryl oxide that is substrate for methyl alcohol, room temperature, normal pressure, reaction time is 10~20min, productive rate > 99%, and reaction adopts gas phase to follow the tracks of and detects analysis; Catalyst is reusable.
10. S according to claim 1 2o 8 2-/ TiO 2the ring-opening reaction of catalysis Styryl oxide, is characterized in that: after completion of the reaction, suction filtration goes out solid catalyst, through washing, dry.Again through (NH 4) 2s 2o 8solution floods again, and rotary evaporation is dried roasting.Its activity is equal to fresh catalyst, has good reusability.
CN201410021055.0A 2014-01-17 2014-01-17 Solid acid catalyst with high-efficiency ring-opening reaction catalysis performance Pending CN103736503A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104801331A (en) * 2015-04-24 2015-07-29 南京工业大学 Method for preparing catalyst with excellent performance in epoxyethylbenzene alcoholysis by use of methanol at room temperature
CN113083323A (en) * 2021-04-13 2021-07-09 中国科学技术大学 Copper-modified palladium-titanium dioxide nano composite material and preparation method and application thereof

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CN101020631A (en) * 2007-03-23 2007-08-22 上海工程技术大学 S2O8 2-/TiO2 Al2 O3 super solid acid catalyzed n-butyl acetate synthesizing process
JP2013140333A (en) * 2011-12-07 2013-07-18 Ricoh Co Ltd Toner, developer and image forming apparatus
CN103333049A (en) * 2013-05-27 2013-10-02 南京工业大学 Catalysis of styrene oxide alcoholysis ring-opening reaction by phosphotungstic acid ionic liquid

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CN101020631A (en) * 2007-03-23 2007-08-22 上海工程技术大学 S2O8 2-/TiO2 Al2 O3 super solid acid catalyzed n-butyl acetate synthesizing process
JP2013140333A (en) * 2011-12-07 2013-07-18 Ricoh Co Ltd Toner, developer and image forming apparatus
CN103333049A (en) * 2013-05-27 2013-10-02 南京工业大学 Catalysis of styrene oxide alcoholysis ring-opening reaction by phosphotungstic acid ionic liquid

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104801331A (en) * 2015-04-24 2015-07-29 南京工业大学 Method for preparing catalyst with excellent performance in epoxyethylbenzene alcoholysis by use of methanol at room temperature
CN104801331B (en) * 2015-04-24 2018-01-05 南京工业大学 A kind of preparation method of the catalyst with room temperature Methanolysis Styryl oxide performance
CN113083323A (en) * 2021-04-13 2021-07-09 中国科学技术大学 Copper-modified palladium-titanium dioxide nano composite material and preparation method and application thereof

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Application publication date: 20140423