CN101844963A - Method for preparing perfluoroalkyl iodide - Google Patents
Method for preparing perfluoroalkyl iodide Download PDFInfo
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- CN101844963A CN101844963A CN201010120783A CN201010120783A CN101844963A CN 101844963 A CN101844963 A CN 101844963A CN 201010120783 A CN201010120783 A CN 201010120783A CN 201010120783 A CN201010120783 A CN 201010120783A CN 101844963 A CN101844963 A CN 101844963A
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Abstract
The invention discloses a method for preparing perfluoroalkyl iodide, which is a telomerization method and a preparation method of a catalyst and a preparation method of a carrier of a load catalyst and a carrier which are used by the preparation method. The method for preparing the perfluoroalkyl iodide comprises the following steps of: adding fluoro olefin, a telomerization agent RfI and a copper catalyst into a kettle-type reactor, wherein in the copper catalyst, copper is loaded on a magnetic carrier, and the dose of the copper catalyst is in an amount of 0.5 to 5 percent based on the mass of the telomerization agent RfI; performing a reaction in the reactor at the reaction temperature of between 80 and 150 DEG C and under the pressure of the autogenous pressure of a system to synthesize perfluoroalkyl iodide; and after the reaction is finished, arranging the reaction system in an external magnetic field, and separating the copper catalyst loaded on the magnetic carrier from a reaction product under the action of the external magnetic field.
Description
Technical field
The present invention relates to a kind of preparation method of perfluoroalkyl iodide, this preparation method is a telomerization method, and the preparation method of the employed Preparation of catalysts method of this preparation method, catalyst-supporting support and carrier.
Background technology
Perfluoroalkyl iodide is a key intermediate of producing fluorine-contained finishing agent, fluorochemical surfactant and other fluorine-containing fine chemicals.Perfluoroalkyl iodide also can be converted into lubricating oil, lubricating grease and wax; Perfluor iodo octane can be converted into the perfluoro capryl bromine that has critical role in medicine.
Telomerization method is a kind of method of producing perfluoroalkyl iodide.Telomerization method is produced perfluoroalkyl iodide shown in reaction formula 1:
R
fI+nCF
2＝CF
2→R
f(CF
2CF
2)
nI
Formula 1
R in the formula
fI is a telogen, is the low carbon number perfluoroalkyl iodide thing that contains the 1-6 carbon atom, R
f(CF
2CF
2)
nI is a higher carbon number perfluoroalkyl iodide thing, and n is the 1-12 integer.
Reported first Cu powder such as the Chen Qingyun of the organic institute in Chinese Academy of Sciences Shanghai were as this telomerization catalyzer (Journal of Fluorine Chemistry in 1987,1987,36,483-489), the telomerization of PFEI and tetrafluoroethylene can be carried out at 80～100 ℃, finishes the reaction times weak point under this temperature; But, produce more high carbon number perfluoroalkyl iodide thing impurity when the mol ratio of tetrafluoroethylene and PFEI during 1: 2 to 2: 1 scope.
United States Patent (USP) (U.S.Pat.5,639,923) a kind of improving one's methods disclosed, in the telomerization process of Cu as catalyst low carbon number perfluoroalkyl iodide thing and tetrafluoroethylene, add a kind of transition metal such as Zn, Mn, V, Rh, or Ag, can improve the selectivity of copper catalyst, but still there is following problem in these catalyzer: as telogen, catalyzer is 4 or less than 4 perfluoroalkyl iodide thing CF to the synthetic n value of catalysis with PFEI
3CF
2(CF
2CF
2)
nI, selectivity is not ideal enough.
Chinese patent (CN1927788A) discloses under lower temperature of reaction with active palladium, niobium, tantalum and their alloy catalyst, effectively control the product of high carbon number, improve the selectivity of target product, improved the speed of reaction after catalyzer is activated greatly, reduce the reaction times.
It is Primary Catalysts that Chinese patent (CN101219924A) discloses with copper, glass putty and copper-tin mixture, and cuprous chloride and tin protochloride are auxiliary agent, has obtained result preferably.
It is Primary Catalysts that Chinese patent application 2009100003144.1 disclosed methods have adopted with copper, with Sn, and Ni, Fe, Zn, Mn, V, Rh, Ce, any two the elementary composition promotors at least in Y or the Ag element.
Having a common deficiency in the prior art is that the reaction after product is very difficult with separating of catalyzer.
Summary of the invention
The invention provides a kind of prior art deficiency that overcomes, after reaction is finished, can relatively easily isolate the preparation method of the perfluoroalkyl iodide of product and catalyzer.
The preparation method of perfluoroalkyl iodide of the present invention adds fluoroolefin, telogen R in the still reaction still
fI and copper catalyst, used copper catalyst are that copper is carried on the magnetic carrier, and the copper magnetic catalyst consumption is telogen R
f0.5～5% of I quality under the condition of 80 ℃～150 ℃ of temperature of reaction and system autogenous pressure, is reacted in reactor, synthetic perfluoroalkyl iodide; After reaction is finished, reaction system is arranged in the foreign field, under the outside magnetic field effect, used copper magnetic catalyst is separated with reaction product.
The magnetic carrier of the copper-loading catalyst that the present invention is used can be a Z 250, also can be the composite oxides that are made of cobalt, nickel and iron, and its general formula is: A
xB
1-xFe
2O
4,
In the formula: x=0～1
A、B＝Co，Ni，Zn，Mn。
The preparation method of the magnetic carrier that the present invention is used is that the muriate of cobalt, nickel and iron is soluble in water respectively, mix post-heating to 70～80 ℃, add aqueous sodium hydroxide solution, through fully stirring after scouring, after handling, thorough drying obtains the composite oxides magnetic carrier that constitutes by cobalt, nickel and iron again to neutral.
The present invention with the method that copper is carried on the magnetic carrier is: Z 250 and mantoquita are placed distilled water, fully adding sodium hydroxide solution under the agitation condition, be warming up to 70～80 ℃, slowly be added dropwise to reductive agent, preserving heat after reaction ends at least 0.5 hour, carry out drying treatment after being washed with distilled water to neutrality, obtain copper catalyst Cu/Fe
3O
4
The used mantoquita of the present invention is: other mantoquita such as cupric nitrate, copper sulfate, neutralized verdigris, cupric chloride.The present invention with the method that copper catalyst is carried on the magnetic carrier can also be: will place water by composite oxides magnetic carrier and the mantoquita that cobalt, nickel and iron constitute, fully adding sodium hydroxide solution under the agitation condition, be warming up to 70～80 ℃, slowly drip reductive agent, preserving heat after reaction ends at least 0.5 hour, carry out drying treatment after being washed with distilled water to neutrality, obtain the magnetic copper catalyst.
The used reductive agent of the present invention can be: hydrazine hydrate, or sodium hypophosphite, or formaldehyde, or xitix, or sodium borohydride, or POTASSIUM BOROHYDRIDE, or S-WAT.
Perfluoroalkyl iodide telomer of the present invention has the general formula suc as formula 2:
R
f(CF
2CFY)
nI
Formula 2
Wherein, R
fBe C
1-6Perfluoroalkyl, n are 1～8 integer, and Y is selected from fluorine atom, chlorine atom, C
1～6Perfluoroalkyl.
Among the present invention since used catalyst cupport on magnetic carrier, product and catalyst separating are easy under the action of a magnetic field after reaction is finished, catalyzer reclaims easily.
Embodiment
Embodiment 1:Cu/Fe
3O
4Preparation of Catalyst
Take by weighing 10g Fe
3O
4, Cu (NO
3)
23H
2(4.30g 0.018mol), is dissolved in the 50ml distilled water stir about 10min to O.(0.9g, 0.018mol) solution 50ml are warmed up to 70～80 ℃, slowly drip 80%N to drip NaOH under stirring fast
2H
4H
2(2.3g, 0.036mol), preserving heat after reaction ends 0.5～4h is washed with distilled water to neutrality to O.80 ℃ of dry 16h obtain magnetic catalyst Cu/Fe
3O
4
Embodiment 2: magnetic Co
0.5Ni
0.5Fe
2O
4Preparing carriers
CoCl
24H
2O (12.02g, 0.05mol), NiCl
24H
2O (12.13g, 0.05mol), FeCl
3(16.40g 0.1mol), is mixed with 100ml respectively, 100ml, the solution of 200ml also mixes, warming-in-water to 70～80 ℃ are added dropwise to 3mol/l, the NaOH of 167ml continues to stir 1h, after the cooling, with distilled water and absolute ethanol washing to neutral; 80 ℃ of dry 16h.Obtain magnetic Co
0.5Ni
0.5Fe
2O
4Carrier.
Embodiment 3: magnetic Cu/Co
0.5Ni
0.5Fe
2O
4Preparation of Catalyst
Get the Co after the processing
0.5Ni
0.5Fe
2O
4Carrier 10g, CuSO
45H
2(4.50g 0.018mol), is dissolved in the 50ml distilled water stir about 10min to O.(0.9g, 0.018mol) solution 50ml are warmed up to 70～80 ℃, slowly drip 80%N to drip NaOH under stirring fast
2H
4H
2(1.7g, 0.027mol), preserving heat after reaction ends 0.5～4h is washed with distilled water to neutrality to O.80 ℃ of dry 16h obtain magnetic catalyst Cu/Co
0.5Ni
0.5Fe
2O
4
The present invention had once used hydrazine hydrate, sodium hypophosphite, formaldehyde, xitix, sodium borohydride, POTASSIUM BOROHYDRIDE or S-WAT, be equipped with catalyzer etc. different reductive agent reduction coppers, test shows that to adopt the effect of hydrazine hydrate best, hydrazine hydrate reducing power under a small amount of alkaline condition is strong, its oxidation products is clean nitrogen, also plays to make the reductive copper powder be not easy the effect of oxidation in air.The employing of other reductive agent is for example: in the Cu powder Preparation of Catalyst, with Cu (NO
3)
23H
2(4.30g 0.018mol), is dissolved in the 50ml distilled water O, is in the vigorous stirring state.Under the normal temperature with reduction system 50mlNaBH
4(0.68g, 0.018mol)-(0.144mol, 6g) mixing solutions slowly splashes into NaOH, rapidly vigorous reaction.Reaction finishes the back and respectively washs three times with distilled water and dehydrated alcohol.80 ℃ of dry 16h obtain the Catalysts Cu powder.
Adopt similar method can obtain the magnetic cu ferrite catalyzer that other metals are formed
Below each embodiment be the preparation of perfluoroalkyl iodide
Comparison example
At 2L stainless steel vertical response still, add copper powder 2.5 grams of using sodium borohydride reduction in the comparison example 1.Reactor with the nitrogen leak test, vacuumize.Add 2020 gram C
2F
5I, 30 restrains TFE, is warming up to begin reaction, and when to 140 ℃, the about 2.20MPa of pressure when waiting to be reduced to a certain degree, replenishes TFE, repeatedly several times, and until C
2F
5The mol ratio of I and TFE equals 2: 1, and pressure no longer descends, and unreacted C is reclaimed in cooling
2F
5I treats the copper catalyst natural sedimentation then, surperficial catalyst-free partly product extract out, last 100ml copper catalyst and product mixture reclaim copper catalyst after with filter paper filtering 1h, but filtering recovering catalyst is comparatively difficult, resultant telomer C
2F
5(CF
2CF
2)
nI is 924g altogether.Ratio with each component in the gas chromatographic analysis product sees Table 1
Table 1 products distribution table
| Chain number (n) | ??1 | ??2 | ??3 | ??4 | ??≥5 |
| Ratio (%wt) | ??24.97 | ??32.98 | ??22.71 | ??11.7 | ??7.64 |
Embodiment 4:
At 2L stainless steel vertical response still, add Cu/Fe, 4.06 grams.Reactor with the nitrogen leak test, vacuumize.Add 1768 gram C
2F
5I, 30 restrains TFE, is warming up to begin reaction, and when to 140 ℃, the about 2.20MPa of pressure when waiting to be reduced to a certain degree, replenishes TFE, repeatedly several times, and until C
2F
5The mol ratio of I and TFE equals 4: 1, and pressure no longer descends, and unreacted C is reclaimed in cooling
2F
5I reclaims copper catalyst then under the action of a magnetic field, obtain telomer C
2F
5(CF
2CF
2)
nI is 427g altogether.Ratio with each component in the gas chromatographic analysis product sees Table 2:
Table 2 products distribution table
| Chain number (n) | ??1 | ??2 | ??3 | ??4 | ??≥5 |
| Ratio (%wt) | ??31.59 | ??35.78 | ??19.05 | ??7.25 | ??3.53 |
Embodiment 5:
At 2L stainless steel vertical response still, add Cu/Fe
3O
4, 11.28 grams.Reactor with the nitrogen leak test, vacuumize.Add 2035 gram C
2F
5I, 30 restrains TFE, is warming up to begin reaction, and when to 140 ℃, the about 2.24MPa of pressure when waiting to be reduced to a certain degree, replenishes TFE, repeatedly several times, and until C
2F
5The mol ratio of I and TFE equals 4: 1, and pressure no longer descends, and unreacted C is reclaimed in cooling
2F
5I reclaims copper catalyst then under the action of a magnetic field, obtain telomer C
2F
5(CF
2CF
2)
nI is 530.5g altogether.Ratio with each component in the gas chromatographic analysis product sees Table 3:
Table 3 products distribution table
| Chain number (n) | ??1 | ??2 | ??3 | ??4 | ??≥5 |
| Ratio (%wt) | ??29.73 | ??38.47 | ??18.96 | ??7.32 | ??3.56 |
Embodiment 6:
At 2L stainless steel vertical response still, add Cu/Co
0.5Ni
0.5Fe
2O
4Catalyzer 7.30 grams.Reactor with the nitrogen leak test, vacuumize.Add 2020 gram C
2F
5I, 30 restrains TFE, is warming up to begin reaction, and when to 140 ℃, the about 2.26MPa of pressure when waiting to be reduced to a certain degree, replenishes TFE, repeatedly several times, and until C
2F
5The mol ratio of I and TFE equals 4: 1, and pressure no longer descends, and unreacted C is reclaimed in cooling
2F
5I reclaims copper magnetic catalyst then under the action of a magnetic field, obtain telomer C
2F
5(CF
2CF
2)
nI is 579g altogether.Ratio with each component in the gas chromatographic analysis product sees Table 4:
Table 4 products distribution table
| Chain number (n) | ??1 | ??2 | ??3 | ??4 | ??≥5 |
| Ratio (%wt) | ??30.53 | ??39.21 | ??20.07 | ??6.7 | ??2.47 |
Embodiment 7:
At 2L stainless steel vertical response still, add Cu/CoFe
2O
4Catalyzer 11.35 grams.Reactor with the nitrogen leak test, vacuumize.Add 2020 gram C
2F
5I, 30 restrains TFE, is warming up to begin reaction, and when to 140 ℃, the about 2.09MPa of pressure when waiting to be reduced to a certain degree, replenishes TFE, repeatedly several times, and until C
2F
5The mol ratio of I and TFE equals 4: 1, and pressure no longer descends, and unreacted C is reclaimed in cooling
2F
5I reclaims copper catalyst then under the action of a magnetic field, obtain telomer C
2F
5(CF
2CF
2)
nI is 496g altogether.Ratio with each component in the gas chromatographic analysis product sees Table 5:
Table 5 products distribution table
| Chain number (n) | ??1 | ??2 | ??3 | ??4 | ??≥5 |
| Ratio (%wt) | ??30.53 | ??39.21 | ??20.07 | ??6.7 | ??2.59 |
Embodiment 8:
At 2L stainless steel vertical response still, add Cu/Co
0.5Zn
0.5Fe
2O
4Catalyzer 9.51 grams.Reactor with the nitrogen leak test, vacuumize.Add 2020 gram C
2F
5I, 30 restrains TFE, is warming up to begin reaction, and when to 140 ℃, the about 2.55MPa of pressure when waiting to be reduced to a certain degree, replenishes TFE, repeatedly several times, and until C
2F
5The mol ratio of I and TFE equals 2: 1, and pressure no longer descends, and unreacted C is reclaimed in cooling
2F
5I reclaims copper catalyst then under the action of a magnetic field, obtain telomer C
2F
5(CF
2CF
2)
nI is 548g altogether.Ratio with each component in the gas chromatographic analysis product sees Table 6:
Table 6 products distribution table
| Chain number (n) | ??1 | ??2 | ??3 | ??4 | ??≥5 |
| Ratio (%wt) | ??33.48 | ??36.32 | ??18.54 | ??6.66 | ??2.70 |
Embodiment 9:
At 2L stainless steel vertical response still, add Cu/ZnFe
2O
4Catalyzer 11 grams.Reactor with the nitrogen leak test, vacuumize.Add 2023 gram C
2F
5I, 30 restrains TFE, is warming up to begin reaction, and 140 ℃ of temperature of reaction, the about 2.29MPa of pressure when waiting to be reduced to a certain degree, replenishes TFE, repeatedly several times, until C
2F
5The mol ratio of I and TFE equals 4: 1.Unreacted C is reclaimed in cooling
2F
5I reclaims copper catalyst then under the action of a magnetic field, obtain telomer C
2F
5(CF
2CF
2)
nI is 483.5g altogether.Ratio with each component in the gas chromatographic analysis product sees Table 7:
Table 7 products distribution table
| Chain number (n) | ??1 | ??2 | ??3 | ??4 | ??≥5 |
| Ratio (%wt) | ??32.5 | ??37.50 | ??18.22 | ??6.56 | ??3.16 |
Embodiment 10:
At 2L stainless steel vertical response still, add Cu/Co
0.5Mn
0.5Fe
2O
4Type molecular sieve catalyst 10g, reactor with the nitrogen leak test, vacuumize.Add 2020 gram C
2F
5I, 30 restrains TFE, is warming up to begin reaction, and 140 ℃ of temperature of reaction, the about 2.40MPa of pressure when waiting to be reduced to a certain degree, replenishes TFE, repeatedly several times, until C
2F
5The mol ratio of I and TFE equals 4: 1.Unreacted C is reclaimed in cooling
2F
5I reclaims copper catalyst then under the action of a magnetic field, obtain telomer C
2F
5(CF
2CF
2)
nI is 513g altogether.Ratio with each component in the gas chromatographic analysis product sees Table 8:
Table 8 products distribution table
| Link number (n) | ??1 | ??2 | ??3 | ??4 | ??≥5 |
| Ratio (%wt) | ??36.20 | ??35.55 | ??16.93 | ??6.09 | ??2.52 |
Embodiment 11:
At 2L stainless steel vertical response still, add Cu/MnFe
2O
4Type molecular sieve catalyst 10g, reactor with the nitrogen leak test, vacuumize.Add 2025 gram C
2F
5I, 30 restrains TFE, is warming up to begin reaction, and 140 ℃ of temperature of reaction, the about 2.37MPa of pressure when waiting to be reduced to a certain degree, replenishes TFE, repeatedly several times, until C
2F
5The mol ratio of I and TFE equals 4: 1.Unreacted C is reclaimed in cooling
2F
5I reclaims copper catalyst then under the action of a magnetic field, obtain telomer C
2F
5(CF
2CF
2)
nI is 446g altogether.Ratio with each component in the gas chromatographic analysis product sees Table 9:
Table 9 products distribution table
| Chain number (n) | ??1 | ??2 | ??3 | ??4 | ??≥5 |
| Ratio (%wt) | ??30.31 | ??40.45 | ??19.79 | ??6.51 | ??2.33 |
The method that reclaims copper catalyst among the above embodiment 4 to 11 is after copper catalyst is participated in telomerization perfluoroalkyl iodide (liquid) to be poured in the Plastic Bottle, with an about 10cm
2Square common magnet is observed visible copper catalyst and promptly is adsorbed on bottle wall outside the Plastic Bottle wall is positioned over the Plastic Bottle wall, and the liquid in the bottle is poured out, and repeats this operation 2～3 times, and all copper catalysts are separable clean.
Claims (11)
1. the preparation method of a perfluoroalkyl iodide adds fluoroolefin, telogen R in the still reaction still
fI, copper catalyst under the condition of 80 ℃～150 ℃ of temperature of reaction and system autogenous pressure, react in reactor, and synthetic perfluoroalkyl iodide is characterized in that used copper magnetic catalyst is that copper is carried on the magnetic carrier, and the copper catalyst consumption is telogen R
f0.5～5% of I quality makes reaction system place under the foreign field after reaction is finished, and catalyzer can separate with reaction product.
2. the magnetic carrier of the used load copper of the preparation method of the described perfluoroalkyl iodide of claim 1 is characterized in that Z 250.
3. the magnetic carrier of the used load copper of the preparation method of the described perfluoroalkyl iodide of claim 1 is characterized in that the composite oxides that are made of cobalt, nickel and iron, and its general formula is: A
xB
1-xFe
2O
4,
In the formula: x=0～1
A、B＝Co，Ni，Zn，Mn。
4. the preparation method of the described magnetic carrier of claim 3, it is characterized in that adopting coprecipitation method to prepare general formula is A
xB
1-xFe
2O
4Carrier.
5. the preparation method of the described magnetic carrier of claim 4, it is characterized in that: the salt of cobalt, nickel and iron is soluble in water respectively, mix post-heating to 70～80 ℃, add sodium hydroxide solution, through the abundant extremely neutrality of after scouring that stirs, after handling, thorough drying gets magnetic carrier again.
6. the preparation method who is carried on the copper catalyst on the magnetic carrier that the preparation method of the described perfluoroalkyl iodide of claim 1 is used is characterized in that adopting the liquid phase chemical reduction method that copper is carried on the carrier.
7. the preparation method who is carried on the copper catalyst on the magnetic carrier that the preparation method of the described perfluoroalkyl iodide of claim 1 is used, it is characterized in that: Z 250 and mantoquita are placed distilled water, fully adding aqueous sodium hydroxide solution under the agitation condition, be warming up to 70～80 ℃, slowly drip reductive agent, preserving heat after reaction ends at least 0.5 hour is carried out drying treatment after being washed with distilled water to neutrality, obtains magnetic catalyst Cu/Fe
3O
4
8. the preparation method of the described copper catalyst of claim 7 is characterized in that used mantoquita is cupric nitrate or copper sulfate or neutralized verdigris or cupric chloride.
9. the preparation method who is carried on the copper catalyst on the magnetic carrier that the preparation method of the described perfluoroalkyl iodide of claim 1 is used is characterized in that adopting the liquid phase chemical reduction method that copper is carried on the carrier.
10. the preparation method who is carried on the copper catalyst on the magnetic carrier that the preparation method of the described perfluoroalkyl iodide of claim 1 is used, it is characterized in that resulting magnetic carrier of claim 4 and mantoquita are placed water, fully adding aqueous sodium hydroxide solution under the agitation condition, be warming up to 70～80 ℃, slowly drip reductive agent, preserving heat after reaction ends at least 0.5 hour is carried out drying treatment after being washed with distilled water to neutrality, obtains being carried on the copper catalyst on the magnetic carrier.
11. the preparation method of claim 7 or 8 or 9 or 10 described copper catalysts is characterized in that employed reductive agent is hydrazine hydrate or sodium hypophosphite or formaldehyde or xitix or sodium borohydride or POTASSIUM BOROHYDRIDE or S-WAT.
Priority Applications (1)
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|---|---|---|---|
| CN201010120783A CN101844963A (en) | 2010-02-04 | 2010-02-04 | Method for preparing perfluoroalkyl iodide |
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|---|---|---|---|
| CN201010120783A CN101844963A (en) | 2010-02-04 | 2010-02-04 | Method for preparing perfluoroalkyl iodide |
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|---|---|
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Family
ID=42769800
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109647413A (en) * | 2018-11-12 | 2019-04-19 | 华中科技大学 | It is catalyzed load type metal catalyst and its preparation of organic wastewater treatment through persulfate |
| CN110205095A (en) * | 2019-06-10 | 2019-09-06 | 南京航空航天大学 | One kind being directed to the efficient wave absorbing agent and preparation method thereof of 2 ~ 18GHz frequency range |
| CN110240733A (en) * | 2019-06-17 | 2019-09-17 | 湖北工业大学 | Copper-loaded nanoparticle of ferroso-ferric oxide and preparation method thereof and preparation root resistance material in apply |
| CN115181004A (en) * | 2022-09-09 | 2022-10-14 | 天津绿菱气体有限公司 | Preparation method of trifluoroiodomethane |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109647413A (en) * | 2018-11-12 | 2019-04-19 | 华中科技大学 | It is catalyzed load type metal catalyst and its preparation of organic wastewater treatment through persulfate |
| CN109647413B (en) * | 2018-11-12 | 2020-10-16 | 华中科技大学 | Supported metal catalyst for catalyzing persulfate to treat organic wastewater and preparation method thereof |
| CN110205095A (en) * | 2019-06-10 | 2019-09-06 | 南京航空航天大学 | One kind being directed to the efficient wave absorbing agent and preparation method thereof of 2 ~ 18GHz frequency range |
| CN110205095B (en) * | 2019-06-10 | 2020-10-16 | 南京航空航天大学 | Efficient wave absorbing agent for 2-18 GHz frequency band and preparation method thereof |
| CN110240733A (en) * | 2019-06-17 | 2019-09-17 | 湖北工业大学 | Copper-loaded nanoparticle of ferroso-ferric oxide and preparation method thereof and preparation root resistance material in apply |
| CN110240733B (en) * | 2019-06-17 | 2021-11-12 | 湖北工业大学 | Ferroferric oxide copper-loaded nano particle, preparation method thereof and application thereof in preparing root-resisting material |
| CN115181004A (en) * | 2022-09-09 | 2022-10-14 | 天津绿菱气体有限公司 | Preparation method of trifluoroiodomethane |
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