CN105418386B - A kind of method for synthesizing 2,3,4,5,6 Pentafluorophenols - Google Patents
A kind of method for synthesizing 2,3,4,5,6 Pentafluorophenols Download PDFInfo
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Abstract
The present invention relates to one kind synthesis 2,3,4,5, the method of 6 Pentafluorophenols, with 2,3,4, the halogeno-benzene of 5,6 five fluorine 1 hydrolyzes in the presence of catalyst and alkali and obtains 2,3,4,5,6 Pentafluorophenol sodium salts, then processing obtains 2,3 in the presence of zeolite catalyst, 4,5,6 Pentafluorophenols, catalyst can still keep high catalytic efficiency after reclaiming, save production cost, reduce environmental pollution.
Description
The application is the divisional application of the application for a patent for invention of Application No. 201510080203.0, and original application day is 2015
15 days 02 month year, publication date is on 06 10th, 2015, the entitled " side of one kind 2,3,4,5,6- Pentafluorophenols of synthesis
Method ".
Technical field
Phosphorus tungsten is loaded the present invention relates to a kind of method of 2,3,4,5,6- Pentafluorophenols of synthesis, more particularly to a kind of use
Acid/ZrO2Zeolite magnetic coupling carried catalyst synthesize 2,3,4,5,6- Pentafluorophenols method.
Background technology
Pentafluorophenol (Pentafluorophenol) molecular formula is C6HF5O, molecular weight is that 184.07, CAS is 771-61-
9, it is a kind of white crystalline body, hygroscopic, and fusing point is 34~36 DEG C.
Pentafluorophenol is a kind of important chemical intermediate, due to there is the fluorine atom of substitution hydrogen atom in its structure, no
The ordered arrangement of liquid crystal can be influenceed because of its steric effect, while fluorine atom has higher electronegativity, ensure that fluorinated liquid crystal
Structure has certain dipole moment, fluorine fat-soluble and can cause end and the fluorine-containing compound of side chain in mixed liquid crystal formula
Substantially increase the dissolubility of other liquid crystal compositions, become a kind of liquid-crystal compounds of function admirable.As liquid crystal intermediates,
2,3,4,5,6- Pentafluorophenols are particularly suitable for use in the preparation of many fluorine class monomeric liquid crystal materials, and many fluorine class monomeric liquid crystal materials glue with low
After degree and high dielectric anisotropy nematic liquid crystalline material are used in mixed way, the dipole moment of molecule can be increased, the response time is reduced,
Improve the display performance of liquid crystal material, improve definition, have great importance to production high-performance liquid crystal material.
Pentafluorophenol can activated carboxyl, promote peptide bond formed, can be used for Peptide systhesis.Pentafluorophenol or important
Medicine, pesticide intermediate, and can be used in the preparation of some high-molecular compounds.In recent years, Albemarle Corporation of the U.S. is used
In preparing catalyst activator (CN 101490102A, CN 101516927A).
Due to a variety of application fields of Pentafluorophenol, a variety of synthesis routes have been developed in recent years.Wherein
Be related to a kind of fluorophenol derivative in JP2005082548 A, it discloses the preparation of Pentafluorophenol, using pentafluorophenyl boric acid as
Initiation material is oxidized to obtain the Pentafluorophenol of target compound 2,3,4,5,6-, but initiation material price is high, be difficult to prepare, and should
Method inconvenient operation.
Chinese patent application CN103420801 A and the (Publication No. of applicant's earlier application CN 200510050211.7
CN187210 A) a kind of method for preparing Pentafluorophenol is individually disclosed, but the preparation process of both approaches all refers to lattice
Formula is reacted, and is unfavorable for industrialized production.
A kind of synthesis is disclosed in applicant's earlier application CN201210333409.6 (Publication No. CN102887817 A)
The method of 2,3,4,5,6- Pentafluorophenols, hydrolyzes in the presence of catalyst and alkali by initiation material of five fluorine halogeno-benzenes and obtains 2,
The sodium salt of 3,4,5,6- Pentafluorophenols, it is then acidified to obtain the Pentafluorophenol of target compound 2,3,4,5,6-, wherein using sulphur
Acidifying is hydrolyzed in the strong acid such as acid, nitric acid, hydrochloric acid.Wherein the use of strong acid proposes higher requirement to reactor, and receives
Rate is up to 82%, and minimum as little as 65.2%.
A kind of synthesis is disclosed in applicant's earlier application CN201210173668.7 (Publication No. CN102718635 A)
The method of 2,3,4,5,6- Pentafluorophenols, wherein using 2,3,4,5,6- five fluoro- 1- substituents benzene be raw material, by with lithiumation agent
Reaction obtains five fluorine lithium benzene, and five fluorine lithium benzene obtain penta phenyl fluoride boron with being hydrolyzed in acid condition after trialkyl borate esterification
Acid, last pentafluorophenyl boric acid aoxidizes in the presence of oxidant and obtains Pentafluorophenol.The n-BuLi wherein used meets water, air
Easily, there is potential safety hazard in burn, and yield is up to 78.5%, and minimum as little as 65.76%.
The technical problems to be solved by the invention are to provide a kind of new method for being suitable for industrialized production Pentafluorophenol.
Therefore, a kind of technical scheme that the present invention is used is：Its depositing in copper catalyst and alkali with the fluoro- 1- halogeno-benzenes of 2,3,4,5,6- five
2,3,4,5,6- Pentafluorophenol sodium salts are obtained in lower hydrolysis, are then acidified in the presence of composite zeolite solid super acid catalyst
Processing obtains 2,3,4,5,6- Pentafluorophenols.As the invention is actually directed to entering for applicant earlier application CN102887817 A
One step is improved, and can further improve product yield, and avoid the use of the strong acid such as sulfuric acid, nitric acid, hydrochloric acid.
According to one embodiment of the invention, the invention provides a kind of side of 2,3,4,5,6- Pentafluorophenols of synthesis
Method, the described method comprises the following steps：
(A) the fluoro- 1- halogeno-benzenes of 2,3,4,5,6- five are hydrolyzed in the presence of catalyst and alkali and obtains 2,3,4,5,6- five
Fluorobenzene sodium phenolate；
(B) 2,3,4,5,6- Pentafluorophenols sodium is carried out at acidifying in the presence of composite zeolite solid super acid catalyst
Reason obtains 2,3,4,5,6- Pentafluorophenols.
According to one embodiment of the invention, the halogenic substituent in 2,3,4,5,6- five fluoro- 1- halogeno-benzenes is selected from Cl-
And Br-, preferably Br-。
The copper catalyst used in step (A) be selected from cupric oxide, cuprous oxide, copper powder, cupric sulfate pentahydrate, stannous chloride and
Copper chloride, preferably cuprous oxide.The mol ratio of the fluoro- 1- halogeno-benzenes of 2,3,4,5,6- five and copper catalyst is 1：(0.01~0.2),
It is preferred that 1：(0.05~0.1).
The alkali used in step (A) be one kind in sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate or it is a kind of with
On mixture, preferably use sodium hydroxide and sodium carbonate mixture.The alkali makes in 10%~30%w/w aqueous solution form
With preferably being used in 20%~25%w/w aqueous solution form.Particularly preferred sodium hydroxide and sodium carbonate are using total concentration as 20%
~25%w/w aqueous solution form is used.
The mol ratio of the fluoro- 1- halogeno-benzenes of 2,3,4,5,6- five and sodium hydroxide, sodium carbonate is 1 in reaction：(0.5~3.0)：
(0.5-2.0), preferably 1：(1.0~1.8)：(0.8-1.5).
The temperature of the hydrolysis of step (A) is 100~180 DEG C, preferably 130~160 DEG C.
According to one embodiment of the invention, composite zeolite solid super acid catalyst used in this application passes through as follows
It is prepared by step：Step 1：Natural Zeolite Support is pre-processed；Step 2：Synthesizing porous level zeolite；Step 3：The magnetic modification of zeolite；
Step 4：Prepare load phosphotungstic acid/ZrO2Zeolite magnetic coupling carried catalyst.
Step 1 carries out the pretreatment of Natural Zeolite Support, including following operation：
(1.1) to Natural Zeolite Support after 450 DEG C of -650 DEG C of calcination process, with containing ammonium concentration be 0.05~
The ammonium salt solution of 1.0mol/L ammonium nitrate, ammonium carbonate or ammonium sulfate swaps the liquid solid of processing, ammonium salt solution and zeolite
Product is than being 3:1~5:1；Swap time is 30 minutes to 60 hours, the zeolite after exchanging is washed with deionized, then be dried
And in 450 DEG C -650 DEG C calcination process again；
(1.2) carrier reaming：The zeolite that step (1.1) is obtained is put into HCl, HNO that concentration is 0.05~6mol/L3、
H2SO4Or the solution of citric acid；Immersion 6-10 hours, is washed with deionized to neutrality, dries, is calcined at 450 DEG C -650 DEG C
To pretreated carrier.
According to one embodiment of the invention, wherein the natural zeolite is modenite, sodalite, chabasie, eight
Face zeolite, preferably modenite.
Step 2 carries out the synthesis of porous level zeolite, including following operation：
(2.1) under inert gas shielding, comonomer and initiator is added to dissolving in medium and obtain reaction solution, and
6~10h is reacted in 70~80 DEG C, the dispersion of polymer microballoon is obtained；
(2.2) mixed, then stirred by the mass ratio 1: 10~20: 0.5~3 of dispersion, Ludox, non-Ludox
Mix uniform, place naturally at room temperature, to complete its gel process；
(2.3) it is centrifuged again, is cooled to room temperature, washing, suction filtration, drying, 450 DEG C of -650 roasting and obtains the boiling of porous level
Stone；
Wherein, described comonomer is vinyl monomer, including maleic anhydride, styrene and vinyl acetate, copolymerization
The mol ratio of monomer is maleic anhydride：Styrene：Vinyl acetate is 1：1-2：The mass concentration of monomer is in 1-2, reaction solution
10%~30%；
Described initiator is organic peroxide or azo-compound, the preferred dialkyl group mistake of organic peroxide evocating agent
Oxide (such as di-t-butyl peroxide, cumyl peroxide), acyl class peroxide (such as dibenzoyl peroxide, mistake
Aoxidize lauroyl), hydroperoxides (such as isopropyl benzene hydroperoxide, TBHP), esters peroxide (such as mistake
Aoxidize t-butyl perbenzoate, the peroxidating trimethylacetic acid tert-butyl ester), two carbonic ester peroxide (such as dicetyl peroxydicarbonate diisopropyl
Ester, di-cyclohexylperoxy di-carbonate), the preferred azodiisobutyronitrile of azoic compound initiator (AIBN), ABVN,
The mass concentration of initiator is 0.1%~0.5% in reaction solution.
Described medium is C1-C12The mixed solution of alkylol and acetone, volume ratio is：1:1-1.5.Wherein described C1-
C12The preferred methanol of alkylol, ethanol, butanol, isopropanol, particularly preferred ethanol and isopropanol.
The Ludox is selected from tetraethyl orthosilicate, isopropyl titanate or zirconium-n-propylate, and the non-Ludox is selected from aluminic acid
Sodium, aluminum nitrate, aluminium secondary butylate, tert-butyl alcohol aluminium, aluminium ethylate and aluminium isopropoxide.
Or step 2 includes following operation：
(2.1) HNO is used3Solution and H2O2Solution is modified to carbon nano tube surface, obtains the carbon nanometer of surface modification
Pipe.
(2.2) by non-silicon precursor sol solution and cetyl trimethylammonium bromide (CTAB), absolute ethyl alcohol is dissolved in respectively
After remix together and stir 0.5-1.5 hours, obtain mixed system 1；By polyoxyethylene-poly-oxypropylene polyoxyethylene
Triblock copolymer (P123) and through above-mentioned modified carbon nano-tube add H2SO4In HCl mixed solutions, stir at room temperature straight
Melt completely to P123, addition is dissolved in the precursor aqueous solution that the Ludox of absolute ethyl alcohol is obtained, stir 2-3 hours, obtain mixture
It is 2；
(2.3) by mixed system 1 and it is 2-in-1 and and it is well mixed after, in Hydrothermal Synthesiss 40-50 hours at 95-105 DEG C, most
After take out, be cooled to room temperature, washing, suction filtration, drying, roasting obtain the Porous materials of two kinds of presomas with double-pore structure.
The Ludox is selected from tetraethyl orthosilicate, isopropyl titanate or zirconium-n-propylate, and non-Ludox is selected from sodium aluminate, nitre
Sour aluminium, aluminium secondary butylate, tert-butyl alcohol aluminium, aluminium ethylate and aluminium isopropoxide.
Step 3 is modified for magnetic, is comprised the following steps：It is n (Fe by mol ratio3+)：n(Fe2+) it is 1：0.7-0.5's
FeSO4·7H2O、Fe2(SO4)3, or n (Fe3+)：n(Fe2+) it is 1：0.7-0.5 FeCl3·6H2O、FeCl2It is dissolved in deionization
In water, cetyl trimethylammonium bromide is added, under an inert atmosphere, pH to 9-10 is adjusted；Add into the solution after regulation pH
Enter to derive from the zeolite of step 1 and step 2, be added dropwise after the completion of tetraethyl orthosilicate, stir 6 hours, add TiSO4, adjust pH extremely
13, while be added dropwise while stir, after the completion of standing, wash away impurity using Magnetic Isolation, and with acetone, afterwards, obtained magnetic consolidated
Body super acidic catalyst is put into baking oven, is dried at 105 DEG C.
According to one embodiment of the invention, the addition weight ratio of the zeolite of step 1 and step 2 is 1:4-1:1, preferably
The addition weight ratio of the zeolite of step 1 and step 2 is 2:3.
Step (4) is load phosphotungstic acid/ZrO2, comprise the following steps：By Zr (NO3)4It is dissolved in deionized water, prepares
Into the nitric acid aqueous zirconium that mass concentration is 30-40% (preferably 40%), the zeolite that abovementioned steps (3) are obtained is added to nitric acid
In aqueous zirconium, then strong agitation to even suspension instills ammoniacal liquor and causes Zr (OH)4Uniform deposition is on zeolite, and it is heavy to filter out
Starch and wash, 100-110 DEG C drying, then in air atmosphere 350-450 DEG C roasting；By it is foregoing in air atmosphere
Zeolite concentration after 350-450 DEG C of roasting impregnates 8 hours for 10 weight % Salkowski's solution, then evaporating water, 100-
110 DEG C of drying, then (preferably 300 DEG C) are calcined 200-400 DEG C in air atmosphere, obtain load phosphotungstic acid/ZrO2Zeolite.
According to one embodiment of the invention, the load capacity of zirconium oxide is the 5-10% of weight zeolite, phosphotungstic acid load
Measure the 5-10% for weight zeolite.
The catalyst prepared using this method is had the advantages that：
1. being mixed using natural zeolite with synthetic zeolite, use cost is reduced, while multistage pore-size distribution is avoided
Homogeneous narrow and small duct is unfavorable for macromolecular and participates in reaction in single molecular sieve, hinder product and reactant generation diffusion and
Generation carbon distribution.
2. due to having carried out expanding treatment to zeolite, both beneficial to the catalytic activity for improving zeolite, it is more beneficial in subsequent packet
Cover after magnetic material, still keep the diffusion rate in duct.
3. being prepared for zeolite molecular sieve using template original position, the alcohol for employing correspondence hydrolysate makees cosolvent, by molten
The regulation of agent has not only relaxed hydrolytic process during synthesis, and is conducive to the sedimentation of copolymer microsphere to grow, polymerization
Thing microspherulite diameter is homogeneous, and the single template of molecular weight distribution in order, by controlling reaction time and solvent ratio, can adjust vinyl and be total to
The size of polymers, can obtain various sizes of macropore template.
4. it is that template obtains mesoporous material using modified carbon nano-tube.
5. after coated magnetic material, after the reaction catalyst can be efficiently separated out from product by magnetic force, gram
Take the shortcoming that catalyst is not readily separated recovery.
6. magnetic material appearance coats matcoveredn, magnetic particle can be protected in reaction.
7. modified component in-situ preparation can be overlying on to zeolite surface by the inventive method, each component dispersion effect is good,
Be conducive to playing the effect of each component, synergy is more preferably.
8. load phosphotungstic acid/ZrO2The acidity of zeolite is further enhancing, can be effectively used for needing to use the chemistry of acid anti-
Ying Zhong, in the preparation process of 2,3,4,5,6- Pentafluorophenols, it is to avoid acid is hydrolyzed using strong acid such as sulfuric acid, nitric acid, hydrochloric acid
Change, conventional reactor can be used.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, present invention specific examples below
Illustrate, but the present invention is limited to absolutely not these examples.As described below is only the present invention preferably embodiment, is used only for explaining
The present invention, therefore can not be interpreted as the limitation to the scope of the claims of the present invention.It should be pointed out that all spirit in the present invention
With any modifications, equivalent substitutions and improvements done within principle etc., it should be included in the scope of the protection.
The test of zeolite catalyst acid strength of the present invention is carried out by Hammett indicator methods.Made using anhydrous cyclohexane
For solvent, compound concentration is 0.1%-0.5% indicator solutions.Indicator is dripped to dry catalyst surface and observe face during measure
Color change：Show that catalyst has reached the acid strength of the indicator used if color changes, now change acid stronger
Indicator be measured, until color no longer changes.The maximum acid strength that can be reached is that the acid of the catalyst is strong
Degree.
Illustrate preparation method of the present invention and its effect below by way of specific test examples.
The preparation of composite zeolite solid super acid catalyst
Step (1)：Zeolite is pre-processed
A1
To modenite carrier after 450 DEG C of calcination process, it is that 1.0mol/L ammonium nitrate is molten to add with containing ammonium concentration
Liquid swaps processing, and ammonium salt solution is 4 with the solid volume ratio of zeolite liquid:1, swap time is 6 hours, is repeated 4 times, uses deionization
Water washing exchange after modenite, then be dried and in 450 DEG C of calcination process again；
The zeolite of foregoing calcination process again is put into the H that concentration is 6mol/L2SO4In solution soak 6 hours, spend from
Sub- water washing re-dry, in 450 DEG C of roastings obtains pretreated carrier in 8 hours to neutrality.
A2
To modenite carrier after 650 DEG C of calcination process, it is that 0.05mol/L ammonium sulfate is molten to add with containing ammonium concentration
Liquid swaps processing, and ammonium salt solution is 3 with the solid volume ratio of zeolite liquid:1, swap time be 30 hours, be repeated 10 times, spend from
Sub- water washing exchange after modenite, then be dried and in 650 DEG C of calcination process again；
The zeolite of foregoing calcination process again is put into the salpeter solution that concentration is 0.05mol/L and soaked 12 hours, is used
Deionized water is washed to neutrality, re-dry, in 650 DEG C of roastings obtains pretreated carrier within 8 hours.
A3
To modenite carrier after 550 DEG C of calcination process, it is that 0.5mol/L ammonium carbonates are molten to add with containing ammonium concentration
Liquid swaps processing, and ammonium salt solution is 4 with the solid volume ratio of zeolite liquid:1, swap time is 60 hours, is washed with deionized
Modenite after exchange, then be dried and in 550 DEG C of calcination process again；
By the zeolite of foregoing calcination process again be put into concentration be 4mol/L hydrochloric acid solution in soak 10 hours, spend from
Sub- water washing re-dry, in 550 DEG C of roastings obtains pretreated carrier in 8 hours to neutrality.
Step (2)：The synthesis 1 of porous level zeolite
B1
Under inert gas shielding, by mol ratio 1:1:1 maleic anhydride, styrene and vinyl acetate and diphenyl peroxide
It is 1 that formyl, which is added to ethanol with acetone volume ratio,:1 in the mixed solvent dissolving obtains the matter of initiator in reaction solution, reaction solution
It is 0.1% to measure concentration, and is reacted 6 hours in 70 DEG C, obtains the dispersion of polymer microballoon；
Dispersion, tetraethyl orthosilicate Ludox and aluminum nitrate are mixed according to 1: 10: 0.5 mass ratio, then
Stir, place naturally at room temperature, to complete gel process；
It is centrifuged again, is cooled to room temperature, washing, suction filtration, drying, 450 DEG C of roastings and obtains within 6 hours porous level zeolite.
B2
Under inert gas shielding, by mol ratio 1:2:2 maleic anhydride, styrene and vinyl acetate and diphenyl peroxide
It is 1 that formyl, which is added to ethanol with acetone volume ratio,:1.5 in the mixed solvent dissolving obtains initiator in reaction solution, reaction solution
Mass concentration is 0.5%, and is reacted 10 hours in 80 DEG C, obtains the dispersion of polymer microballoon；
Dispersion, tetraethyl orthosilicate Ludox and aluminum nitrate are mixed according to 1: 20: 3 mass ratio, then stirred
Mix uniform, place naturally at room temperature, to complete gel process；
It is centrifuged again, is cooled to room temperature, washing, suction filtration, drying, 650 DEG C of roastings and obtains within 5 hours porous level zeolite.
B3
Under inert gas shielding, by mol ratio 1:2:2 maleic anhydride, styrene and vinyl acetate and diphenyl peroxide
It is 1 that formyl, which is added to ethanol with acetone volume ratio,:1.5 in the mixed solvent dissolving obtains initiator in reaction solution, reaction solution
Mass concentration is 0.3%, and is reacted 8 hours in 80 DEG C, obtains the dispersion of polymer microballoon；
Dispersion, tetraethyl orthosilicate Ludox and aluminum nitrate are mixed according to 1: 15: 1.5 mass ratio, then
Stir, place naturally at room temperature, to complete gel process；
It is centrifuged again, is cooled to room temperature, washing, suction filtration, drying, 550 DEG C of roastings and obtains within 5 hours porous level zeolite.
Step (2)：The synthesis 2 of porous level zeolite
B'1
Use dense HNO3With 30% mass concentration H2O2Carbon nano tube surface (external diameter 6nm or so) is modified, surface is obtained
Modified CNT.
By aluminum nitrate be dissolved in after absolute ethyl alcohol and remixing respectively with cetyl trimethylammonium bromide (CTAB) together with simultaneously
Stirring 0.5 hour, obtains mixed system 1；By the triblock copolymer (P123) of polyoxyethylene-poly-oxypropylene polyoxyethylene and
Dense H is added through above-mentioned modified carbon nano-tube2SO4In HCl mixed solutions, stir until P123 melts completely, add at room temperature
The teos solution of absolute ethyl alcohol is dissolved in, stirs 3 hours, obtains mixed system 2；
By mixed system 1 and it is 2-in-1 and and it is well mixed after, be reloaded into reactor, in 95 DEG C of Hydrothermal Synthesiss 50 hours, finally
Take out, be cooled to room temperature, washing, suction filtration, drying, roasting obtain the zeolite of two kinds of presomas with double-pore structure,
Amount ratio is, CNT：Aluminum nitrate：CTAB：Triblock copolymer：Silester=2g：2g：3g：1g：2ml.
B'2
Use dense HNO3With 30% mass concentration H2O2Carbon nano tube surface (external diameter 6nm or so) is modified, surface is obtained
Modified CNT.
By aluminum nitrate be dissolved in after absolute ethyl alcohol and remixing respectively with cetyl trimethylammonium bromide (CTAB) together with simultaneously
Stirring 1.5 hours, obtains mixed system 1；By the triblock copolymer (P123) of polyoxyethylene-poly-oxypropylene polyoxyethylene and
Dense H is added through above-mentioned modified carbon nano-tube2SO4In HCl mixed solutions, stir until P123 melts completely, add at room temperature
The teos solution of absolute ethyl alcohol is dissolved in, stirs 2 hours, obtains mixed system 2；
By mixed system 1 and it is 2-in-1 and and it is well mixed after, be reloaded into reactor, in 105 DEG C of Hydrothermal Synthesiss 40 hours, most
After take out, be cooled to room temperature, washing, suction filtration, drying, roasting obtain the zeolite of two kinds of presomas with double-pore structure.
Amount ratio is, CNT：Aluminum nitrate：CTAB：Triblock copolymer：Silester=2g：2g：3g：1g：2ml.
B'3
Use dense HNO3With 30% mass concentration H2O2Carbon nano tube surface (external diameter 6nm or so) is modified, surface is obtained
Modified CNT.
By aluminum nitrate be dissolved in after absolute ethyl alcohol and remixing respectively with cetyl trimethylammonium bromide (CTAB) together with simultaneously
Stirring 1 hour, obtains mixed system 1；By the triblock copolymer (P123) of polyoxyethylene-poly-oxypropylene polyoxyethylene and warp
Above-mentioned modified carbon nano-tube adds dense H2SO4In HCl mixed solutions, stir until P123 melts completely, add molten at room temperature
In the teos solution of absolute ethyl alcohol, stir 2.5 hours, obtain mixed system 2；
By mixed system 1 and it is 2-in-1 and and it is well mixed after, be reloaded into reactor, in 100 DEG C of Hydrothermal Synthesiss 45 hours, most
After take out, be cooled to room temperature, washing, suction filtration, drying, roasting obtain the zeolite of two kinds of presomas with double-pore structure.
Amount ratio is, CNT：Aluminum nitrate：CTAB：Triblock copolymer：Silester=2g：2g：3g：1g：2ml.
Step (3)：Magnetic is modified
C1
It is n (Fe by mol ratio3+)：n(Fe2+) it is 1：0.7 FeSO4·7H2O and Fe2(SO4)3It is dissolved in deionized water
In, cetyl trimethylammonium bromide is added, under an inert atmosphere, pH to 9 is adjusted；Add and derive from into the solution after regulation pH
The zeolite of step 1 and step 2, is added dropwise after the completion of tetraethyl orthosilicate, stirs 6 hours, adds TiSO4, adjust pH to 13, side drop
Edged stir, after the completion of stand, impurity is washed away using Magnetic Isolation, and with acetone, afterwards, by obtained magnetic solid superacid
Catalyst is put into baking oven, is dried at 105 DEG C.
C2
It is n (Fe by mol ratio3+)：n(Fe2+) it is 1：0.5 FeSO4·7H2O and Fe2(SO4)3It is dissolved in deionized water
In, cetyl trimethylammonium bromide is added, under an inert atmosphere, pH to 10 is adjusted；Added into the solution after regulation pH
From the zeolite of step 1 and step 2, it is added dropwise after the completion of tetraethyl orthosilicate, stirs 6 hours, add TiSO4, adjust pH to 13, side
Be added dropwise side stirring, after the completion of stand, impurity is washed away using Magnetic Isolation, and with acetone, afterwards, by obtained magnetic solid super
Acid catalyst is put into baking oven, is dried at 100 DEG C.
C3
It is n (Fe by mol ratio3+)：n(Fe2+) it is 1：0.7 FeCl3·6H2O and FeCl2Dissolve in deionized water, plus
Enter cetyl trimethylammonium bromide, under an inert atmosphere, adjust pH to 9；Added into the solution after regulation pH and derive from step 1
With the zeolite of step 2, it is added dropwise after the completion of tetraethyl orthosilicate, stirs 6 hours, add TiSO4, pH to 13 is adjusted, when being added dropwise
Stirring, after the completion of stand, impurity is washed away using Magnetic Isolation, and with acetone, afterwards, by obtained catalyzed with solid magnetic super acid
Agent is put into baking oven, is dried at 110 DEG C.
Step (4)：Phosphotungstic acid/ZrO2Load
D1
By Zr (NO3)4It is dissolved in deionized water, the nitric acid aqueous zirconium that mass concentration is 30% is configured to, by foregoing step
Suddenly the zeolite that (3) are obtained is added in nitric acid aqueous zirconium, strong agitation to even suspension, is then instilled ammoniacal liquor and is caused Zr
(OH)4Uniform deposition on zeolite, filter out sediment and wash, 100 DEG C drying, then in air atmosphere 450 DEG C roasting.Will
The foregoing zeolite concentration in air atmosphere after 350 DEG C of roastings impregnates 8 hours for 10 weight % Salkowski's solution, Ran Houzheng
Solid carbon dioxide point, 100 DEG C of drying, then 300 DEG C of roastings in air atmosphere obtain load phosphotungstic acid/ZrO2Zeolite.
D2
By Zr (NO3)4It is dissolved in deionized water, the nitric acid aqueous zirconium that mass concentration is 40% is configured to, then by before
State the zeolite that step (3) obtains to be added in nitric acid aqueous zirconium, strong agitation to even suspension, then instill ammoniacal liquor and cause Zr
(OH)4Uniform deposition on zeolite, filter out sediment and wash, 105 DEG C drying, then in air atmosphere 350 DEG C roasting.Will
The foregoing zeolite concentration in air atmosphere after 350 DEG C of roastings impregnates 8 hours for 10 weight % Salkowski's solution, Ran Houzheng
Solid carbon dioxide point, 110 DEG C of drying, then 400 DEG C of roastings in air atmosphere obtain load phosphotungstic acid/ZrO2Zeolite.
D3
By Zr (NO3)4It is dissolved in deionized water, the nitric acid aqueous zirconium that mass concentration is 35% is configured to, then by before
State the zeolite that step (3) obtains to be added in nitric acid aqueous zirconium, strong agitation to even suspension, then instill ammoniacal liquor and cause Zr
(OH)4Uniform deposition on zeolite, filter out sediment and wash, 110 DEG C drying, then in air atmosphere 400 DEG C roasting.Will
The foregoing zeolite concentration in air atmosphere after 350 DEG C of roastings impregnates 8 hours for 10 weight % Salkowski's solution, Ran Houzheng
Solid carbon dioxide point, 105 DEG C of drying, then 200 DEG C of roastings in air atmosphere obtain load phosphotungstic acid/ZrO2Zeolite.
Table 1：Catalyst characterization
Wherein, preparation process refers to the step of catalyst preparation is used, and such as A1B1C1D1 is referred to before use respectively
Step A1, B1, C1 and D1 preparation are stated, natural zeolite and synthetic zeolite ratio are referred to by selecting asynchronous in step (3)
Rapid 1 and the obtained natural zeolite of zeolite ratio and synthetic zeolite ratio of step 2.
The preparation of 2,3,4,5,6- Pentafluorophenols
Embodiment 1
Water 620g, sodium hydroxide 50.6g (1.26mol), sodium carbonate 105.2g are added inside 2L autoclave
(0.99mol), cuprous oxide 11g (0.076mol), five bromofluorobenzene 222.3g (0.9mol) enclosed high pressure kettles are warming up to 140 DEG C,
And room temperature is cooled to after being reacted 5 hours at 140 DEG C, 2,3,4,5,6- Pentafluorophenol sodium materials are poured out, filters, filtrate is used
Invent the catalyst 2 in foregoing table 1 to be acidified at 40-60 DEG C, after acidifying, extracted with methyl tertiary butyl ether(MTBE), merged organic
Phase, is distilled to recover solvent, then by tower rectifying on product, obtain 2,3,4,5,6- Pentafluorophenol 145.8g, content 99.6%, yield
88.0%.
Mass spectral analysis and elementary analysis are carried out to products therefrom, acquired results are as follows：
Mass spectrum：m/z:183.99 (100.0%), 185.00 (6.5%).
Elementary analysis result：C,39.15；H,0.55；F,51.61；O,8.69.Molecular weight of product is：184.07.
Embodiment 2
Embodiment 1 is repeated, difference is that final reaction obtains 2,3,4 using 10 later catalyst 2 are reused,
5,6- Pentafluorophenol 137.5g, content 99.5%, yield 83.0%.
Embodiment 3
Embodiment 1 is repeated, difference is to use the catalyst 17 in foregoing table 1, and final reaction obtains 2,3,4,5,6- five
Fluorophenol 147.8g, content 99.7%, yield 89.0%.
Embodiment 4
Embodiment 1 is repeated, difference is that final reaction obtains 2,3,4 using 10 later catalyst 17 are reused,
5,6- Pentafluorophenol 139.2g, content 99.6%, yield 84.0%.
Embodiment 5
Embodiment 1 is repeated, difference is the bromofluorobenzene of raw material five replacing with five fluorochlorobenzenes, and inventory is 182.3g
(0.9mol), final reaction obtains 2,3,4,5,6- Pentafluorophenol 140.8g, content 99.4%, yield 85.0%.
Embodiment 6
Embodiment 5 is repeated, difference is that final reaction obtains 2,3,4 using 10 later catalyst 2 are reused,
5,6- Pentafluorophenol 132.5g, content 99.4%, yield 80.0%.
These are only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Any modifications, equivalent substitutions and improvements made within principle etc., should be included in the scope of the protection.
Claims (9)
1. the method for one kind 2,3,4,5,6- Pentafluorophenols of synthesis, the described method comprises the following steps：
(A) the fluoro- 1- halogeno-benzenes of 2,3,4,5,6- five are hydrolyzed in the presence of copper catalyst and alkali and obtains the fluorine of 2,3,4,5,6- five
Phenol sodium salt；
(B) 2,3,4,5,6- Pentafluorophenols sodium is carried out into acidification in the presence of composite zeolite solid super acid catalyst to obtain
To 2,3,4,5,6- Pentafluorophenols,
Wherein described composite zeolite solid super acid catalyst is prepared by following steps：
(1) Zeolite support is pre-processed, including following operation：
(1.1) it is 0.05~1.0mol/L with containing ammonium concentration to Natural Zeolite Support after 450 DEG C of -650 DEG C of calcination process
Ammonium nitrate, the ammonium salt solution of ammonium carbonate or ammonium sulfate swap processing, the solid volume ratio of the liquid of ammonium salt solution and zeolite is 3:1
~5:1；Swap time is 30 minutes to 60 hours, the zeolite after exchanging is washed with deionized, then be dried and 450
DEG C of -650 DEG C calcination process again；The natural zeolite is modenite；
(1.2) carrier reaming：The zeolite that step (1.1) is obtained is put into HCl, HNO that concentration is 0.05~6mol/L3、H2SO4
Or soaked 6-10 hours in citric acid, it is washed with deionized to neutrality, dries, pre-processed in 450 DEG C of -650 DEG C of roastings
Carrier afterwards；
(2) synthesis of porous level zeolite, including following operation：
(2.1) HNO is used3And H2O2Carbon nano tube surface is modified, the CNT of surface modification is obtained,
(2.2) together with non-Ludox being dissolved in after absolute ethyl alcohol and remixed with cetyl trimethylammonium bromide (CTAB) respectively
And stir 0.5-1.5 hours, obtain mixed system 1；By the triblock copolymer of polyoxyethylene-poly-oxypropylene polyoxyethylene
(P123) CNT and through above-mentioned surface being modified is added to H2SO4In HCl mixed solutions, stir at room temperature until
P123 melts completely, and addition is dissolved in the precursor aqueous solution that the Ludox of absolute ethyl alcohol is obtained, and stirs 2-3 hours, obtains mixed system
2；
(2.3) by mixed system 1 and it is 2-in-1 and and it is well mixed after, in Hydrothermal Synthesiss 40-50 hours at 95-105 DEG C, finally take
Go out, be cooled to room temperature, washing, suction filtration, drying, roasting obtain the zeolite of two kinds of presomas with double-pore structure,
The Ludox is tetraethyl orthosilicate, and non-Ludox is selected from sodium aluminate, aluminum nitrate, aluminium secondary butylate, tert-butyl alcohol aluminium, aluminium ethylate
And aluminium isopropoxide；
(3) magnetic is modified, and is comprised the following steps：
It is n (Fe by mol ratio3+)：n(Fe2+) it is 1：0.7-0.5 FeSO4·7H2O、Fe2(SO4)3, or n (Fe3+)：n(Fe2+)
For 1：0.7-0.5 FeCl3·6H2O、FeCl2Dissolving in deionized water, adds cetyl trimethylammonium bromide, in inertia
Under atmosphere, pH to 9-10 is adjusted；The zeolite derived from step 1 and step 2 is added into the solution after regulation pH, positive silicic acid four is added dropwise
After the completion of ethyl ester, stir 6 hours, add TiSO4, adjust pH to 13, while be added dropwise while stir, after the completion of stand, utilize magnetic divide
From, and impurity is washed away with acetone, afterwards, obtained magnetic solid super acidic catalyst is put into baking oven, dried at 105 DEG C
It is dry；Wherein the addition weight ratio of the zeolite of step 1 and step 2 is 1:4-1:1；
(4) phosphotungstic acid/ZrO2Load, comprise the following steps：
By Zr (NO3)4It is dissolved in deionized water, the nitric acid aqueous zirconium that mass concentration is 30-40% is configured to, by foregoing step
Suddenly the zeolite that (3) are obtained is added in nitric acid aqueous zirconium, strong agitation to even suspension, is then instilled ammoniacal liquor and is caused Zr
(OH)4Uniform deposition on zeolite, filter out sediment and wash, 100-110 DEG C drying, then in 350- in air atmosphere
450 DEG C of roastings；
The foregoing zeolite concentration in air atmosphere after 350-450 DEG C of roasting is impregnated for 10 weight % Salkowski's solution
8 hours, then evaporating water, 100-110 DEG C of drying, then the 200-400 DEG C of roasting in air atmosphere, obtained loading phosphorus tungsten
Acid/ZrO2Zeolite.
2. the copper catalyst according to the method described in claim 1, used in step (A) is selected from cupric oxide, cuprous oxide, copper
Powder, cupric sulfate pentahydrate, stannous chloride and copper chloride.
3. according to the method described in claim 1, it is characterised in that the load capacity of zirconium oxide is the 5-10% of weight zeolite, phosphorus tungsten
Sour load capacity is the 5-10% of weight zeolite.
4. according to the method described in claim 1, it is characterised in that in step (3), the addition weight of the zeolite of step 1 and step 2
Amount is than being 2:3.
5. according to the method described in claim 1,2,3,4,5,6- five fluoro- 1- halogeno-benzenes and copper catalyst rub in step (A)
You are than being 1：(0.01~0.2).
6. according to the method described in claim 1, it is characterised in that the alkali used in step (A) be sodium hydroxide, potassium hydroxide,
One or more kinds of mixtures in calcium hydroxide, sodium carbonate.
7. method according to claim 6, it is characterised in that the alkali used in step (A) is with 10%~30%w/w water
Solution form is used.
8. according to the method described in claim 1, it is characterised in that the hydrolysising reacting temperature of step (A) is 100~180 DEG C.
9. according to the method described in claim 1, it is characterised in that 2,3,4,5, the 6- five fluoro- 1- halos used in step (A)
Halogenic substituent in benzene is selected from Cl and Br.
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