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 PDFInfo
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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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- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 238000007142 ring opening reaction Methods 0.000 title claims abstract description 25
- 238000006555 catalytic reaction Methods 0.000 title claims description 12
- 239000011973 solid acid Substances 0.000 title abstract description 6
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 8
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- -1 alcohol compound Chemical class 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- 238000004817 gas chromatography Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 239000011949 solid catalyst Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 3
- 238000006424 Flood reaction Methods 0.000 claims 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000005245 sintering Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000002924 oxiranes Chemical class 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229940074869 marquis Drugs 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- VBUNOIXRZNJNAD-UHFFFAOYSA-N ponazuril Chemical compound CC1=CC(N2C(N(C)C(=O)NC2=O)=O)=CC=C1OC1=CC=C(S(=O)(=O)C(F)(F)F)C=C1 VBUNOIXRZNJNAD-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
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
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
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
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
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.
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|---|---|---|---|
| CN201410021055.0A CN103736503A (en) | 2014-01-17 | 2014-01-17 | Solid acid catalyst with high-efficiency ring-opening reaction catalysis performance |
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Cited By (2)
| 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 |
-
2014
- 2014-01-17 CN CN201410021055.0A patent/CN103736503A/en active Pending
Patent Citations (3)
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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 |
Non-Patent Citations (4)
| Title |
|---|
| 杨惠等: "MCM-41负载S2O82-/TiO2催化合成β-烷氧基醇", 《中国化学会第十四届胶体与界面化学会议论文摘要集-第1分会：表面界面与纳米结构材料》 * |
| 杨惠等: "MCM-41负载S2O82-/TiO2催化合成β-烷氧基醇", 《中国化学会第十四届胶体与界面化学会议论文摘要集-第1分会：表面界面与纳米结构材料》, 21 July 2013 (2013-07-21), pages 288 - 289 * |
| 陈静等: "MCM-41负载 S2O82-/TiO2固体超强酸的制备和酯化性能研究", 《无机化学学报》 * |
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Cited By (3)
| 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 |