CN103772157B - Method for preparing 1-alkoxy-1,1,2,2-tetrafluoroethane - Google Patents
Method for preparing 1-alkoxy-1,1,2,2-tetrafluoroethane Download PDFInfo
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Abstract
The invention discloses a method for preparing 1-alkoxy-1,1,2,2-tetrafluoroethane. The method comprises the following steps of (1) carrying out reaction on an alkali compound, [bmim]BF4 ionic liquid and fluorine intercalation hydrotalcite according to the mass ratio of 1:(0.05-0.2):(0.4-1), wherein the reaction temperature is 80-200 DEG C, the reaction time is 5-20 hours; after reaction, obtaining fluorine intercalation hydrotalcite loaded alkali compound and compound catalyst of [bmim]BF4 ionic liquid, and reserving for later use; (2) adding alcohol and the compound catalyst prepared in step (1)10-50% the mass of alcohol into a reaction kettle, sealing the reaction kettle, replacing the air in the reaction kettle with nitrogen, then aerating tetrafluoroethylene monomer, rising the temperature and beginning to react, wherein the reaction temperature is controlled to be 30-70 DEG C; finishing the reaction when tetrafluoroethylene monomer 100-400% mass of the alcohol is aerated, filtering and recycling the compound catalyst, washing and rectifying the filtrate so as to obtain the 1-alkoxy-1,1,2,2-tetrafluoroethane. The method has the advantages that the catalyst has good activity and can be recycled, few three wastes are generated, and the method is environmentally friendly.
Description
Technical field
The present invention relates to a kind of preparation method of fluorine-containing ether compounds, particularly a kind of preparation method of 1-alkoxyl group-1,1,2,2-Tetrafluoroethane.
Background technology
1-alkoxyl group-1,1,2,2-Tetrafluoroethane has excellent characteristic as hypotoxicity, low global warming potential and low Greenhouse effect, relative to the all-fluoroalkyl compound of Long carbon chain, there is less fluorine atom, there is price low, the feature such as extended residual rate is low in the environment, can be used as the refrigeration agent that cleaning performance is excellent, whipping agent, clean-out system, aerosol and waterproof dry solvent use, also can be used for the whipping agent of production polyurethane foam or polyisocyanurate foam, its performance just under development, have an optimistic view of by market outlook.
The syntheti c route of 1-alkoxyl group-1,1,2,2-Tetrafluoroethane has and mainly contains: the hydrogen alkoxylation of unsaturated hydrocarbons and alcohol, the alkylated reaction of acyl fluorides (carbonyl compound).Wherein the hydrogen alkoxylation of unsaturated hydrocarbons and alcohol is because raw material is easy to get, and reaction process is simple, and Application comparison is many.Wherein 1-methoxyl group-1,1,2,2-Tetrafluoroethane is usually by using methyl alcohol and tetrafluoroethylene to be obtained by reacting (J.Am.Chem.Soc., 73,1329 (1951)) under alkali metal compound (as potassium hydroxide or sodium hydroxide) exists
As China Patent Publication No. CN1651378A, denomination of invention: new hydrofluoro ether and preparation method thereof.This invention relates to new hydrofluoro ether and preparation method thereof, in dimethyl formamide DMF or dimethyl sulfoxide (DMSO) DMSO organic solvent, potassium hydroxide or sodium hydroxide is used to be catalyzer, prepare new hydrofluoro ether, raw material is trifluoro-ethylene, tetrafluoroethylene, vinylidene, R 1216, trifluorochloroethylene and trifluoroethanol, trifluoropropanol, methyl alcohol, ethanol, propyl alcohol, butanols, 20 ~ 90 DEG C of reactions, 1 ~ 10hrs, obtained hydrogen fluorine ether.
And for example China Patent Publication No. CN102115428A, denomination of invention: a kind of synthetic method of hydrogen fluorine ether.This application case provides a kind of synthetic method of hydrogen fluorine ether, according to ratio of weight and number with 20 ~ 100 parts of alcohol for raw material, described alcohols is a kind of in methyl alcohol, ethanol, propyl alcohol, trifluoro methyl alcohol, C3-Fluoroalcohol and octafluoropentanol, under 1 ~ 6 part of alkali catalyst exists, add 34 ~ 108 parts of Fluorine containing olefines continuously, react at 110 ~ 180 DEG C, reaction pressure is 0.6 ~ 1.2MPa, reaction times is 1 ~ 5h, after rectifying separation, obtain target product.
Above patent and catalyzer that technical literature uses are mainly alkali metal compound, and there is catalyst recovery difficulty, dregginess is high, and because solid particulate is thin, the shortcomings such as product and catalyst separating difficulty, simultaneously because use a large amount of solvent, easily cause environmental pollution.
Summary of the invention
Technical problem to be solved by this invention overcomes the deficiencies in the prior art, provides a kind of good catalyst activity, reusable edible; The three wastes are few, the preparation method of the 1-alkoxyl group of environmental protection-1,1,2,2-Tetrafluoroethane.
In order to solve above technical problem, present invention employs following technical scheme: a kind of preparation method of 1-alkoxyl group-1,1,2,2-Tetrafluoroethane, comprises the following steps:
(1) by basic cpd, [bmim] BF
4ionic liquid and fluorine intercalated houghite react 1:0.05 ~ 0.2:0.4 ~ 1 in mass ratio, and temperature of reaction is 80 ~ 200 DEG C, and the reaction times is 5 ~ 20h, obtain fluorine intercalated houghite load basic cpd and [bmim] BF after reaction terminates
4the composite catalyst of ionic liquid, for subsequent use;
(2) add the obtained composite catalyst of above-mentioned steps (1) of alcohol, alcohol quality 10 ~ 50% in a kettle., envelope still, with the air in nitrogen replacement still, then tetrafluoroethylene monomer is passed into, intensification starts reaction, and temperature of reaction controls at 30 ~ 70 DEG C, when terminating reaction after the tetrafluoroethylene monomer passing into alcohol quality 100 ~ 400%, filtered and recycled composite catalyst, filtrate is through washing, and rectifying obtains 1-alkoxyl group-1,1,2,2-Tetrafluoroethane.
Basic cpd described in step (1) is preferably sodium methylate or tetramethylammonium hydroxide.
Alcohol described in step (2) is preferably the one in methyl alcohol, ethanol, propyl alcohol, butanols.
Basic cpd described in step (1), [bmim] BF
4the mass ratio of ionic liquid and fluorine intercalated houghite is preferably 1:0.08 ~ 0.15:0.6 ~ 0.9, and temperature of reaction is preferably 100 ~ 150 DEG C, and the reaction times is preferably 7 ~ 15h.
The quality optimization of the composite catalyst described in step (2) is 20 ~ 40% of alcohol quality, and the quality optimization of tetrafluoroethylene monomer is 200 ~ 350% of alcohol quality, and temperature of reaction is preferably 30 ~ 50 DEG C.
The preparation method of 1-alkoxyl group-1,1,2,2-Tetrafluoroethane of the present invention, use tetrafluoroethylene and alkylol cpd to react for raw material, catalyzer uses fluorine intercalated houghite to be carrier, load basic cpd and [bmim] BF
4the composite catalyst that ionic liquid mixture generates, product is through washing, and rectifying obtains qualified product, has good catalyst activity, reusable edible; The three wastes are few, the advantage of environmental protection.
Fluorine intercalated houghite in the present invention can be prepared by method of the prior art, such as, and can with Ni (NO
3)
26H
2o, Mg (NO
3)
26H
2o and Al (NO
3)
39H
2o is raw material, selects NaOH and NaCO
3for compound precipitants, coprecipitation method is adopted to prepare ternary Ni/Mg/Al houghite, after pre-burning 2h under the air atmosphere of 723K roasting 4h, obtain corresponding composite oxides, again these composite oxides be impregnated in containing F-solution, utilize " memory effect " of hydrotalcite that F-is incorporated into hydrotalcite layers, namely obtaining fluorine intercalated houghite (can see Zhang Jun etc., what fluorine was modified contains the applied research of Ni houghite in methane portion oxidation synthesis gas [J]. chemistry of fuel journal, 2012, 40 (4): 424-429), wherein Ni, Mg, F and Al content is respectively 20-30%(wt%), 15-20%(wt%), 1-5%(wt%) and 50-65%(wt%).
The organic bases that basic cpd in the present invention can select this area conventional and inorganic alkali compound, preferred strong alkaline liquid compound (being abbreviated as SALC), more preferably sodium methylate or tetramethylammonium hydroxide.
Alcohol in the present invention can select general formula to be the alcohol of ROH, and wherein R is a C
1-4alkyl group, as methyl alcohol, ethanol, propyl alcohol, isopropylcarbinol, butanols etc., be preferably the one in methyl alcohol, ethanol, propyl alcohol, butanols.
Fluorine intercalated houghite (LDH-F) load basic cpd of the present invention and [bmim] BF
4the schematic general formula of the composite catalyst that alkali ion liquid generates is shown in formula (1):
[LDH-F]
M.[[bmim]BF
4]
N.[SALC]
K（1）
(M=1，2，3，4；N,=1，2，3；K=1，2，3)
[bmim] BF in the present invention
4ionic liquid (1-butyl-3-Methylimidazole-tetrafluoride boron ionic liquid) has good thermostability, almost without vapour pressure, can dissolve many organic and inorganicss, be easy to and other separating substances, can recycle.[bmim] BF in the present invention
4ionic liquid can commercially availablely obtain, [bmim] BF produced as adopted Henan Lihua Pharmaceutical Co., Ltd.
4ionic liquid.
Compared with prior art, the present invention has following beneficial effect:
1, good catalyst activity, by product are few, fluorine intercalated houghite load basic cpd and [bmim] BF
4the composite catalyst of ionic liquid, has the function of catalyzer and compatilizer concurrently, because fluorine intercalated houghite and tetrafluoroethylene monomer have certain consistency, consistency between reactive fluorochemical monomer and composite catalyst is improved; Make fluorine intercalated houghite system alkalescence improve and specific surface area raising, the basic cpd of load on skeleton and [bmim] BF simultaneously
4the amount of ionic liquid increases, and the comprehensive alkalescence of composite catalyst is strengthened, and the catalytic activity of composite catalyst can be made stronger, have excellent low-temperature reactivity;
2, catalyzer reusable edible, fluorine intercalated houghite load basic cpd and [bmim] BF
4the composite catalyst of ionic liquid, is easy to and other separating substances, and the composite catalyst of recovery can recycle, and effectively can reduce the pollution of traditional volatile organic solvent to environment;
3, reaction yield is high, selectivity good, and reaction yield, more than 90%, reaches as high as 95%, and selectivity, more than 92%, reaches as high as 99%.
Embodiment
Below in conjunction with specific embodiment, illustrate the present invention further, but these embodiments are only for explaining the present invention, instead of for limiting the scope of the invention.
Raw materials usedly in embodiment all can commercially availablely obtain or prepare, part of compounds adopts following abbreviations also to explain:
Fluorine intercalated houghite (LDH-F): (preparation method is see Zhang Jun etc. in self-control, what fluorine was modified contains the applied research of Ni houghite in methane portion oxidation synthesis gas [J]. chemistry of fuel journal, 2012,40 (4): 424-429), wherein with Ni (NO
3)
26H
2o, Mg (NO
3)
26H
2o and Al (NO
3)
39H
2o is raw material, selects NaOH and NaCO
3for compound precipitants, coprecipitation method is adopted to prepare ternary Ni/Mg/Al houghite, after pre-burning 2h under the air atmosphere of 723K roasting 4h, obtain corresponding composite oxides, again these composite oxides be impregnated in containing F-solution, utilize " memory effect " of hydrotalcite that F-is incorporated into hydrotalcite layers, namely obtain fluorine intercalated houghite (LDH-F), in fluorine intercalated houghite, the mass percentage of Ni, Mg, F and Al is respectively 20-30%, 15-20%, 1-5% and 50-65%.
[bmim] BF
4ionic liquid: 1-butyl-3-Methylimidazole-tetrafluoride boron ionic liquid, purchased from Henan Lihua Pharmaceutical Co., Ltd..
Embodiment 1
A kind of preparation method of 1-methoxyl group-1,1,2,2-Tetrafluoroethane, comprises the following steps:
Step 1: add sodium methylate 100Kg, [bmim] BF in 300L reactor respectively
4ionic liquid 10Kg, stir 2h, then add the fluorine intercalated houghite (mass percentage of LDH-F, Ni, Mg, F and Al is respectively 23%, 16%, 3% and 58%) of 80Kg, at 120 DEG C, react 8h, after reaction terminates, obtain fluorine intercalated houghite load basic cpd and [bmim] BF
4the composite catalyst of ionic liquid.
Step 2: add 100Kg methyl alcohol in 500L stainless steel autoclave, the composite catalyst that the above-mentioned steps (1) of 30Kg is obtained, closes charging opening, with the air in nitrogen replacement still, then pass into tetrafluoroethylene monomer, heat up and start reaction, temperature of reaction controls at 40 DEG C, and metering passes into the tetrafluoroethylene of reactor, when terminating reaction after the tetrafluoroethylene monomer passing into 300Kg, filtered and recycled composite catalyst, filtrate is through washing, and rectifying obtains 1-methoxyl group-1,1,2,2-Tetrafluoroethane.Yield and selectivity are in table 1.
Embodiment 2
A kind of preparation method of 1-methoxyl group-1,1,2,2-Tetrafluoroethane, comprises the following steps:
Step 1: add sodium methylate 100Kg, [bmim] BF in 300L reactor respectively
4ionic liquid 10Kg, stir 2h, then add the fluorine intercalated houghite (mass percentage of LDH-F, Ni, Mg, F and Al is respectively 30%, 15%, 1% and 54%) of 40Kg, at 200 DEG C, react 5h, after reaction terminates, obtain fluorine intercalated houghite load basic cpd and [bmim] BF
4the composite catalyst of ionic liquid.
Step 2: add 100Kg methyl alcohol in 500L stainless steel autoclave, the composite catalyst that the above-mentioned steps (1) of 30Kg is obtained, closes charging opening, with the air in nitrogen replacement still, then pass into tetrafluoroethylene monomer, heat up and start reaction, temperature of reaction controls at 70 DEG C, and metering passes into the tetrafluoroethylene of reactor, when terminating reaction after the tetrafluoroethylene monomer passing into 300Kg, filtered and recycled composite catalyst, filtrate is through washing, and rectifying obtains 1-methoxyl group-1,1,2,2-Tetrafluoroethane.Yield and selectivity are in table 1.
Embodiment 3
A kind of preparation method of 1-methoxyl group-1,1,2,2-Tetrafluoroethane, comprises the following steps:
Step 1: add sodium methylate 100Kg, [bmim] BF in 300L reactor respectively
4ionic liquid 10Kg, stir 2h, then add the fluorine intercalated houghite (mass percentage of LDH-F, Ni, Mg, F and Al is respectively 20%, 20%, 5% and 55%) of 100Kg, at 80 DEG C, react 20h, after reaction terminates, obtain fluorine intercalated houghite load basic cpd and [bmim] BF
4the composite catalyst of ionic liquid.
Step 2: add 100Kg methyl alcohol in 500L stainless steel autoclave, the composite catalyst that the above-mentioned steps (1) of 30Kg is obtained, closes charging opening, with the air in nitrogen replacement still, then pass into tetrafluoroethylene monomer, heat up and start reaction, temperature of reaction controls at 30 DEG C, and metering passes into the tetrafluoroethylene of reactor, when terminating reaction after the tetrafluoroethylene monomer passing into 300Kg, filtered and recycled composite catalyst, filtrate is through washing, and rectifying obtains 1-methoxyl group-1,1,2,2-Tetrafluoroethane.Yield and selectivity are in table 1.
Embodiment 4
10Kg composite catalyst is added in a kettle., the other the same as in Example 1 in step 2.Obtain 1-methoxyl group-1,1,2,2-Tetrafluoroethane product, yield and selectivity are in table 1.
Embodiment 5
50Kg composite catalyst is added in a kettle., the other the same as in Example 1 in step 2.Obtain 1-methoxyl group-1,1,2,2-Tetrafluoroethane product, yield and selectivity are in table 1.
Embodiment 6
Add 100Kg tetrafluoroethylene monomer in step 2, the other the same as in Example 1, obtain 1-methoxyl group-1,1,2,2-Tetrafluoroethane product, yield and selectivity are in table 1.
Embodiment 7
[bmim] BF added in step 1
4ionic liquid is 15Kg, fluorine intercalated houghite is 60Kg; The composite catalyst added in step 2 is 40Kg, and tetrafluoroethylene monomer is 400Kg, the other the same as in Example 1, and obtain 1-methoxyl group-1,1,2,2-Tetrafluoroethane product, yield and selectivity are in table 1.
Embodiment 8
Sodium methylate is replaced with 100Kg tetramethylammonium hydroxide in step 1, and [bmim] BF added
4ionic liquid is 10Kg, fluorine intercalated houghite is 90Kg; The composite catalyst added in step 2 is 20Kg, the other the same as in Example 1.Obtain 1-methoxyl group-1,1,2,2-Tetrafluoroethane product, yield and selectivity are in table 1.
Embodiment 9
Sodium methylate is replaced, the other the same as in Example 2 with 100Kg tetramethylammonium hydroxide in step 1.Obtain 1-methoxyl group-1,1,2,2-Tetrafluoroethane product, yield and selectivity are in table 1.
Embodiment 10
Sodium methylate is replaced, the other the same as in Example 3 with 100Kg tetramethylammonium hydroxide in step 1.Obtain 1-methoxyl group-1,1,2,2-Tetrafluoroethane product, yield and selectivity are in table 1.
Embodiment 11
Sodium methylate is replaced, the other the same as in Example 4 with 100Kg tetramethylammonium hydroxide in step 1.Obtain 1-methoxyl group-1,1,2,2-Tetrafluoroethane product, yield and selectivity are in table 1.
Embodiment 12
Replace sodium methylate with 100Kg tetramethylammonium hydroxide in step 1, the other the same as in Example 5, obtain 1-methoxyl group-1,1,2,2-Tetrafluoroethane product, yield and selectivity are in table 1.
Embodiment 13
Replace sodium methylate with 100Kg tetramethylammonium hydroxide in step 1, other is with embodiment 6, and obtain 1-methoxyl group-1,1,2,2-Tetrafluoroethane product, yield and selectivity are in table 1.
Embodiment 14
[bmim] BF added in step 1
4ionic liquid is 8Kg, and fluorine intercalated houghite is 70Kg; Replace methyl alcohol with ethanol in step 2, and the tetrafluoroethylene monomer added is 200Kg, temperature of reaction controls at 50 DEG C, the other the same as in Example 1, and obtain fluoro-1,1,2, the 2-Tetrafluoroethane of 1-oxyethyl group-1-, yield and selectivity are in table 1.
Embodiment 15
[bmim] BF added in step 1
4ionic liquid is 5Kg, and fluorine intercalated houghite is 50Kg; With propanol instead of methanol in step 2, and the tetrafluoroethylene monomer added is 350Kg, and temperature of reaction controls at 60 DEG C, and the other the same as in Example 1 obtains 1-(positive propoxy)-1,1,2,2-Tetrafluoroethane, yield and selectivity are in table 1.
Embodiment 16
At 100 DEG C, 15h is reacted in step 1; Replace methyl alcohol with butanols in step 2, the other the same as in Example 1, obtain product 1-(n-butoxy) product such as-1,1,2,2-Tetrafluoroethane, yield and selectivity are in table 1.
Embodiment 17
At 150 DEG C, 7h is reacted in step 1; The composite catalyst added in step 2 is reclaim the catalyzer obtained, the other the same as in Example 1 by the preparation method of embodiment 1.Obtain 1-alkoxyl group-1,1,2,2-Tetrafluoroethane product, yield and selectivity are in table 1.
Comparative example 1
Step 1 does not add fluorine intercalated houghite (LDH-F), the other the same as in Example 1.Obtain 1-methoxyl group-1,1,2,2-Tetrafluoroethane product, yield and selectivity are in table 1.
Comparative example 2
Step 1 does not add [bmim] BF
4ionic liquid, the other the same as in Example 1.Obtain 1-methoxyl group-1,1,2,2-Tetrafluoroethane product, yield and selectivity are in table 1.
Comparative example 3
The sodium methylate adding methanol quality 15% in step 2 replaces composite catalyst, the other the same as in Example 1.Obtain 1-methoxyl group-1,1,2,2-Tetrafluoroethane product, yield and selectivity are in table 1.
Comparative example 4
The tetramethylammonium hydroxide adding 15% of methanol quality in step 2 replaces composite catalyst, and other is with embodiment 8.Obtain 1-methoxyl group-1,1,2,2-Tetrafluoroethane product, yield and selectivity are in table 1.
Table 1: the yield of embodiment 1 ~ 17 and comparative example 1 ~ 4 and selectivity.
| Yield % | Selectivity .% | |
| 1 | 93 | 99 |
| 2 | 93 | 98 |
| 3 | 95 | 99 |
| 4 | 91 | 96 |
| 5 | 94 | 99 |
| 6 | 92 | 96 |
| 7 | 99 | 98 |
| 8 | 90 | 96 |
| 9 | 95 | 99 |
| 10 | 91 | 92 |
| 11 | 92 | 98 |
| 12 | 90 | 93 |
| 13 | 92 | 95 |
| 14 | 92 | 95 |
| 15 | 93 | 96 |
| 16 | 93 | 98 |
| 17 | 91 | 97 |
| Comparative example 1 | 76 | 87 |
| Comparative example 2 | 79 | 83 |
| Comparative example 3 | 58 | 77 |
| Comparative example 4 | 55 | 79 |
From comparative example 1, singly add [bmim] BF
4ionic liquid and basic cpd, do not carry out load and can reduce catalytic effect; From comparative example 2, do not add [bmim] BF
4alkali ion liquid also can reduce catalytic effect; From comparative example 3 and ratio 4, use alkaline matter as catalyzer, catalytic effect is poor; From embodiment 17, when catalyzer of the present invention is reused, still there is good catalytic effect, can reuse.
Claims (4)
1. the preparation method of 1-alkoxyl group-1,1,2, a 2-Tetrafluoroethane, is characterized in that comprising the following steps:
(1) by basic cpd, [bmim] BF
4ionic liquid and fluorine intercalated houghite react 1:0.05 ~ 0.2:0.4 ~ 1 in mass ratio, and temperature of reaction is 80 ~ 200 DEG C, and the reaction times is 5 ~ 20h, obtain fluorine intercalated houghite load basic cpd and [bmim] BF after reaction terminates
4the composite catalyst of ionic liquid is for subsequent use, and described basic cpd is sodium methylate or tetramethylammonium hydroxide;
(2) add the obtained composite catalyst of above-mentioned steps (1) of alcohol, alcohol quality 10 ~ 50% in a kettle., envelope still, with the air in nitrogen replacement still, then tetrafluoroethylene monomer is passed into, intensification starts reaction, and temperature of reaction controls at 30 ~ 70 DEG C, when terminating reaction after the tetrafluoroethylene monomer passing into alcohol quality 100 ~ 400%, filtered and recycled composite catalyst, filtrate is through washing, and rectifying obtains 1-alkoxyl group-1,1,2,2-Tetrafluoroethane.
2. the preparation method of 1-alkoxyl group-1,1,2,2-Tetrafluoroethane according to claim 1, the alcohol that it is characterized in that described in step (2) is the one in methyl alcohol, ethanol, propyl alcohol, butanols.
3. the preparation method of 1-alkoxyl group-1,1,2,2-Tetrafluoroethane according to claim 1, is characterized in that the basic cpd described in step (1), [bmim] BF
4the mass ratio of ionic liquid and fluorine intercalated houghite is 1:0.08 ~ 0.15:0.6 ~ 0.9, and temperature of reaction is 100 ~ 150 DEG C, and the reaction times is 7 ~ 15h.
4. 1-alkoxyl group-1 according to claim 1,1,2, the preparation method of 2-Tetrafluoroethane, it is characterized in that the quality of the composite catalyst described in step (2) is 20 ~ 40% of alcohol quality, the quality of tetrafluoroethylene monomer is 200 ~ 350% of alcohol quality, and temperature of reaction is 30 ~ 50 DEG C.
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| CN103254041A (en) * | 2013-05-03 | 2013-08-21 | 巨化集团技术中心 | Preparation method of hydrofluoroether |
| CN103394328A (en) * | 2013-08-20 | 2013-11-20 | 青岛科技大学 | Hydroxyl functionalized ionic liquid/hydrotalcite-like compound composite material, and preparation method and application thereof |
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| CN103254041A (en) * | 2013-05-03 | 2013-08-21 | 巨化集团技术中心 | Preparation method of hydrofluoroether |
| CN103394328A (en) * | 2013-08-20 | 2013-11-20 | 青岛科技大学 | Hydroxyl functionalized ionic liquid/hydrotalcite-like compound composite material, and preparation method and application thereof |
| CN103412021A (en) * | 2013-08-29 | 2013-11-27 | 青岛科技大学 | Functionalized ionic liquid-hydrotalcite-like composite material fixed protein modified electrode as well as preparation method and application thereof |
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