CN111153778A - Method for purifying diethyl ether and method for improving purity of nitrogen-containing organic matter by using diethyl ether - Google Patents
Method for purifying diethyl ether and method for improving purity of nitrogen-containing organic matter by using diethyl ether Download PDFInfo
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- CN111153778A CN111153778A CN201811323287.6A CN201811323287A CN111153778A CN 111153778 A CN111153778 A CN 111153778A CN 201811323287 A CN201811323287 A CN 201811323287A CN 111153778 A CN111153778 A CN 111153778A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/46—Use of additives, e.g. for stabilisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/392—Separation; Purification; Stabilisation; Use of additives by crystallisation; Purification or separation of the crystals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
- C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
- C07C257/12—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to hydrogen atoms
Abstract
The invention relates to a method for purifying diethyl ether, which comprises the steps of adding a free radical scavenger and a hydroperoxide decomposer into diethyl ether, or adding a mixed solution of the free radical scavenger and the hydroperoxide decomposer into the diethyl ether to purify the diethyl ether, and then purifying the purified diethyl ether mixed solution after full reaction by adopting any one of a liquid separation extraction method, a filtration method or a re-evaporation method to obtain the purified diethyl ether. The invention also discloses a method for improving the purity of the nitrogenous organic matter by using the diethyl ether and application thereof, wherein the diethyl ether is purified by using the purification method. The purified diethyl ether or the purified diethyl ether is used for cleaning the nitrogen-containing organic matter, so that active free radicals and peroxy diethyl ether contained in the diethyl ether are removed, the generation of halogen simple substances in the nitrogen-containing organic halide is effectively reduced, and the high-purity nitrogen-containing organic matter is obtained. The method of the invention has the characteristics of simplicity, easy implementation, low cost and the like.
Description
Technical Field
The invention belongs to the technical field of ether and nitrogen-containing organic matter purification, and relates to a method for purifying ether, a method for improving the purity of nitrogen-containing organic matter by using ether and application thereof.
Background
Organic-inorganic hybrid perovskite (ABX)3) The solar cell has the advantages of simple preparation process, low cost, high photoelectric conversion efficiency and the like, and is expected to become a new generationMainstream photovoltaic technology replaces traditional silicon-based solar cells. The photosensitive material of perovskite solar cell is mainly prepared from nitrogen-containing organic halide precursor AX (A: nitrogen-containing organic substance such as methylamine and formamidine; X ═ Cl, Br, I) and lead halide (PbX)2) The precursors AX and PbX2Has a very important influence on the performance of the solar cell. Particularly, the precursor AX is very easy to be oxidized in the preparation process to generate a halogen simple substance, so that defects are caused in the perovskite thin film, and the device performance of the perovskite solar cell is reduced. Therefore, it is important to improve the purity of the precursor AX.
Generally, diethyl ether is adopted in the purification process of a precursor AX to precipitate the precursor AX from a solution to obtain high-purity crystals, and the long-standing diethyl ether generally contains high-activity radicals and peroxy diethyl ether, which tend to oxidize the precursor AX into a simple halogen substance, so that impurities of a crystalline material are caused, and finally, the performance of the perovskite solar cell device is deteriorated.
In the existing chinese patent (patent publication No. CN106866387A), a method of blocking ether from air by floating a layer of antioxidant magnetic nanoparticles on the distilled ether is disclosed, so as to inhibit the formation of oxygen radical and peroxide in ether, but this method cannot eliminate the active free radical and peroxy ether in ether. In the existing Chinese patent (patent publication No. CN107337607A), it is disclosed that under the protection of nitrogen, the crude product is purified by using alcoholic solution of organic amine which can provide alkaline environment, and the organic ammonium alcohol solution promotes I2The disproportionation reaction is carried out to generate iodide ions, thereby effectively reducing the content of free iodine in the product. However, this method cannot prevent the precursor AX from being oxidized, and cannot fundamentally prevent the generation of iodine as a simple substance, and also has a loss of raw materials.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for purifying diethyl ether and a method for improving the purity of nitrogen-containing organic matters by using diethyl ether.
The invention is realized in such a way that a method for purifying diethyl ether is provided, which comprises the following steps: adding a free radical scavenger and a hydroperoxide decomposer into ether for purification reaction, or adding a mixed solution of the free radical scavenger and the hydroperoxide decomposer into the ether for purification reaction, obtaining a purified ether mixed solution after full purification reaction, and then purifying the purified ether mixed solution after full reaction by adopting any one of a liquid-separating extraction method, a filtering method or a re-steaming method to obtain purified ether; wherein the content of the first and second substances,
the free radical scavenger comprises at least one of hindered phenol compounds, amine compounds and quinone compounds, the hydroperoxide decomposer comprises phosphite esters or thioester compounds, and the dosage of the free radical scavenger and the dosage of the hydroperoxide decomposer are respectively 0.01-5%.
Further, the radical scavenger is any one of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) N-octadecyl propionate, pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, 2, 6-di-tert-butyl-p-cresol, methylene-bis (di-tert-butylcresol), isooctyl-3- (3, 5-di-tert-butyl-hydroxyphenyl) propionate, p-diisooctyldiphenylamine and butyloctyl-substituted diphenylamine, and the hydroperoxide decomposer is tris (2, 4-di-tert-butylphenyl) phosphite, dilauryl thiodipropionate, and a mixture thereof, Zinc dialkyl dithiophosphate, zinc dialkyl dithiocarbamate, 3-thiodipropionate, and methylene bis (tetramethylene) dithiocarbamic acid ester.
Further, the free radical scavenger and the hydroperoxide decomposer are directly mixed with ether for reaction, or are firstly dissolved in other solvents and then are mixed with ether for reaction, and the other solvents comprise alcohol solvents, benzene, toluene, chlorobenzene, acetone, carbon tetrachloride, chloroform, cyclohexane, ester organic solvents and ether organic solvents.
Further, the conditions of the sufficient purification reaction are: sealing or under the protection of inert gas, stopping light, stirring, oscillating or standing for more than one day at the temperature of 0-30 ℃.
Further, the method for purifying the diethyl ether comprises the following steps:
a1, dissolving 0.05mol of a radical scavenger pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate in 50mL of chloroform, dissolving 0.05mol of a hydroperoxide decomposer tris (2, 4-di-tert-butylphenyl) phosphite in 50mL of acetone, and mixing the two solutions;
a2, adding 100mL of the mixed solution into 2L of diethyl ether, oscillating, fully mixing, placing at room temperature in a sealed and light-proof manner for more than one week, and completely purifying to remove free radicals and peroxy diethyl ether in the diethyl ether to obtain a purified diethyl ether mixed solution;
and A3, or purifying the diethyl ether mixed solution after full purification reaction by adopting a re-steaming method to obtain purified diethyl ether.
Further, the method for purifying the diethyl ether comprises the following steps:
b1, respectively adding 0.1mol of a free radical scavenger, namely n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and 0.1mol of a hydroperoxide decomposer, namely didodecyl thiodipropionate, into 10L of diethyl ether, fully mixing, oscillating, standing at room temperature in a closed and light-proof manner for more than one week, and completely purifying to remove free radicals and peroxy diethyl ether in the diethyl ether to obtain a purified diethyl ether mixed solution;
and B2, then, purifying the diethyl ether mixed solution after the full purification reaction by adopting a filtration method to obtain purified diethyl ether.
The invention is realized in such a way, and provides a method for improving the purity of nitrogenous organic matters by using ether, which comprises the following steps:
c1, dissolving the nitrogen-containing organic matter powder in an alcohol solution, wherein the alcohol solution comprises at least one of methanol, ethanol, isopropanol and n-butanol;
c2, under the condition of continuous stirring, gradually adding the purified diethyl ether mixed solution or the purified diethyl ether obtained by the diethyl ether purification method into the fully dissolved nitrogenous organic matter alcohol solution, and stopping adding the purified diethyl ether mixed solution or the purified diethyl ether when no nitrogenous organic matter crystal is separated out;
c3, removing the solution by adopting a filtering method or a centrifugal method to obtain a recrystallized crystal of the nitrogenous organic matter;
c4, repeating the steps C1, C2 and C3 at least once in sequence, and recrystallizing the recrystallized crystal obtained for the first time until a pure-color nitrogen-containing organic crystal with high purity is obtained;
c5, dispersing the high-purity pure-color nitrogen-containing organic crystal obtained in the step C4 in the purified diethyl ether mixed solution or the purified diethyl ether obtained by the diethyl ether purification method, fully stirring and dispersing, and then obtaining the nitrogen-containing organic crystal solid after washing the diethyl ether by a centrifugal method or a filtering method;
c6, repeating the process of the step C5 at least once, and then washing the obtained nitrogen-containing organic crystal solid for a plurality of times by diethyl ether;
and C7, placing the nitrogen-containing organic crystal solid obtained in the step C6 in a vacuum oven, vacuumizing, heating to 50-80 ℃, keeping for more than 10 hours until the solvent mixed in the nitrogen-containing organic crystal solid is completely removed, cooling to room temperature, and taking out for later use.
Further, the nitrogen-containing organic substance includes any one of formamidine halide, methyl halide, and guanidine halide.
Further, in step C1, the method for promoting the dissolution of the nitrogen-containing organic powder material in the alcohol solution includes at least one of heating, ultrasonic, stirring and shaking.
The invention is realized by providing the application of the nitrogen-containing organic matter, wherein the nitrogen-containing organic matter is obtained by the method for improving the purity of the nitrogen-containing organic matter by utilizing the diethyl ether, and the nitrogen-containing organic matter is applied to the preparation of perovskite solar cells or is respectively applied to the preparation of semiconductors, diodes, detectors and nano materials.
Compared with the prior art, the method for purifying the diethyl ether and the method for improving the purity of the nitrogenous organic matter by using the diethyl ether have the advantages that the free radical scavenger and the hydroperoxide decomposer are added into the diethyl ether, or the mixed solution of the free radical scavenger and the hydroperoxide decomposer is added into the diethyl ether to purify the diethyl ether, and then the mixed solution of the purified diethyl ether after the full reaction is purified by any one of a liquid separation extraction method, a filtration method or a re-evaporation method to obtain the purified diethyl ether. And the purified diethyl ether or the purified diethyl ether is used for cleaning the nitrogen-containing organic matter, so that active free radicals and peroxy ethyl ether contained in the diethyl ether are removed, the problems of impure products and raw material loss of oxidized and recrystallized nitrogen-containing organic matter are solved, and the generation of a halogen simple substance in the nitrogen-containing organic halide is effectively reduced, so that the purified diethyl ether material and the high-purity nitrogen-containing organic matter are obtained, and the method is very suitable for preparing high-performance perovskite photovoltaic devices. Meanwhile, the method has the characteristics of simplicity, feasibility, low cost and the like.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. And are not intended to limit the invention. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
It is known that ether forms radicals and peroxy ether (CH) by the action of light, heat, etc. after storage for a long period of time3CH2OCHOOHCH3) The chain reaction is initiated as follows:
(1) initiation phase
(2) Growth phase
CH3CH2OCHCH3·+O2→CH3CH2OCHOOCH3·
CH3CH2OCHOOCH3·+CH3CH2OCH2CH3→CH3CH2OCHOOHCH3+CH3CH2OCHCH3·
(3) Branching reaction
(4) Termination phase
The free radical in the ether solution comprises peroxy ether radical (CH)3CH2OCHOOCH3Cnidium fruit, Ether oxy radical (CH)3CH2OCHOCH3·), ether radical (CH)3CH2OCHCH3HO), which rapidly abstract a hydrogen atom from the polymer chain to form an ether radical, due to the short lifetime and high reactivity of ether and hydroxyl radicals. Under the condition of oxygen enrichment, the ether radical is quickly converted into peroxy ether radical. Therefore, the ether solution mainly contains peroxyether radical free radical.
On the other hand, the peroxyethyl ether is unstable, and because the activation energy of radical homolysis is low, at room temperature, the peroxyethyl ether is homolyzed in a radical mode and then undergoes a branching reaction with the ethyl ether, thereby accelerating the oxidation reaction.
CH3CH2OCHOOHCH3→HO·+CH3CH2OCHOCH3- (Ether decomposing, free radical mode)
The free radicals in the ether react with a nitrogen-containing organic halide precursor AX of the perovskite solar cell to generate a halogen simple substance, namely methylamine iodide (CH)3NH3I) The reaction with the peroxyethyl ether radical is exemplified by the following procedure:
2CH3NH3I+2CH3CH2OCHOOCH3·→2CH3NH2+I2+2CH3CH2OCHOOHCH3
the preferred embodiment of the method for purifying diethyl ether of the present invention comprises the following steps: adding a free radical scavenger and a hydroperoxide decomposer into the ether for purification reaction, or adding a mixed solution of the free radical scavenger and the hydroperoxide decomposer into the ether for purification reaction, and fully purifying to obtain a purified ether mixed solution.
And then, purifying the purified diethyl ether mixed solution after full reaction by adopting any one of a liquid separation extraction method, a filtration method or a re-evaporation method to obtain the purified diethyl ether.
The free radical scavenger comprises at least one of hindered phenol compounds, amine compounds and quinone compounds, the hydroperoxide decomposer comprises phosphite esters or thioester compounds, and the dosage of the free radical scavenger and the dosage of the hydroperoxide decomposer are respectively 0.01-5%. The free radical scavenger is capable of reacting with free radicals in diethyl ether to form a stable compound. The hydroperoxide decomposer can react with the peroxy ether to generate a stable product without free radicals, and prevent or slow branching reaction.
The free radical scavenger is any one of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) N-octadecyl propionate, tetra (3, 5-di-tert-butyl-4-hydroxy) pentaerythritol phenylpropionate, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, 2, 6-di-tert-butyl-p-cresol, methylene-bis (di-tert-butyl-cresol), isooctyl-3- (3, 5-di-tert-butyl-hydroxyphenyl) propionate, p-diisooctyldiphenylamine and butyloctyl substituted diphenylamine, and the hydroperoxide decomposer is tri- (2, 4-di-tert-butylphenyl) phosphite, dilauryl thiodipropionate, zinc dialkyldithiophosphate, Any one of zinc dialkyldithiocarbamate, 3-thiodipropionate and methylene bis (tetramethylene) dithiocarbamate.
The free radical scavenger and the hydroperoxide decomposer are directly mixed with ether for reaction, or are dissolved in other solvents and then are mixed with ether for reaction, and the other solvents comprise alcohol solvents, benzene, toluene, chlorobenzene, acetone, carbon tetrachloride, chloroform, cyclohexane, ester organic solvents and ether organic solvents.
The conditions of the intensive purification reaction are: sealing or under the protection of inert gas, stopping lighting, stirring, oscillating or standing for more than one day at the temperature of 0-30 ℃.
Specifically, as an embodiment, a method for purifying diethyl ether comprises the following steps:
a1, 0.05mol of a radical scavenger pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate was dissolved in 50mL of chloroform, and 0.05mol of a hydroperoxide decomposer tris (2, 4-di-tert-butylphenyl) phosphite was dissolved in 50mL of acetone, and the two solutions were mixed.
A2, adding 100mL of the mixed solution into 2L of diethyl ether, oscillating, fully mixing, sealing at room temperature and keeping out of the sun for more than one week, and completely purifying to remove free radicals and peroxy diethyl ether in the diethyl ether to obtain the purified diethyl ether mixed solution.
A3, and then, purifying the diethyl ether mixed solution after full purification reaction by adopting a re-steaming method to obtain purified diethyl ether.
Specifically, as another embodiment, a method for purifying diethyl ether comprises the steps of:
b1, respectively adding 0.1mol of a free radical scavenger, namely n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and 0.1mol of a hydroperoxide decomposer, namely didodecyl thiodipropionate, into 10L of diethyl ether, fully mixing, oscillating, standing at room temperature in a sealed and light-proof manner for more than one week, and completely purifying to remove free radicals and peroxy diethyl ether in the diethyl ether to obtain a purified diethyl ether mixed solution.
And B2, then, purifying the diethyl ether mixed solution after the full purification reaction by adopting a filtration method to obtain purified diethyl ether.
The invention also discloses a method for improving the purity of the nitrogenous organic compound by using the ether, which comprises the following steps:
and C1, dissolving the nitrogen-containing organic matter powder in an alcohol solution, wherein the alcohol solution comprises at least one of methanol, ethanol, isopropanol and n-butanol.
C2, under the condition of continuous stirring, gradually adding the purified diethyl ether mixed solution or the purified diethyl ether obtained by the diethyl ether purification method into the fully dissolved nitrogenous organic matter alcohol solution, and stopping adding the purified diethyl ether mixed solution or the purified diethyl ether when no nitrogenous organic matter crystal is separated out.
And C3, removing the solution by adopting a filtering method or a centrifugal method to obtain recrystallized crystals of the nitrogen-containing organic matters.
C4, repeating the steps C1, C2 and C3 at least once in sequence, and recrystallizing the recrystallized crystal obtained for the first time until obtaining the pure-color nitrogen-containing organic crystal with high purity.
C5, dispersing the pure color nitrogen-containing organic crystal obtained in the step C4 in the purified diethyl ether mixed solution or the purified diethyl ether obtained by the diethyl ether purification method, fully stirring and dispersing, and then obtaining the nitrogen-containing organic crystal solid after washing by diethyl ether through a centrifugation or filtration method.
C6, repeating the process of the step C5 at least once, and then washing the obtained nitrogen-containing organic crystal solid for a plurality of times by diethyl ether.
And C7, placing the nitrogen-containing organic crystal solid obtained in the step C6 in a vacuum oven, vacuumizing, heating to 50-80 ℃, keeping for more than 10 hours until the solvent mixed in the nitrogen-containing organic crystal solid is completely removed, cooling to room temperature, and taking out for later use.
The nitrogen-containing organic matter comprises any one of formamidine halide, methyl halide and guanidine halide.
In step C1, the method for promoting dissolution of the nitrogen-containing organic powder material in the alcohol solution includes at least one of heating, sonication, stirring, and shaking.
Specifically, as an embodiment, a method for improving the purity of nitrogen-containing organic substances by using diethyl ether comprises the following steps:
d1, putting 10g of methyl amine iodide powder into a beaker, pouring 100mL of absolute ethyl alcohol, and stirring until the methyl amine iodide powder is completely dissolved.
D2, adding the ether mixed solution into the beaker by using a separating funnel, stopping the injection of the ether until the methyl ammonium iodide crystal is not separated out, and stirring for 15 minutes.
D3, removing the solution by suction filtration by using a Buchner funnel to obtain a recrystallized ammonium methyliodide crystal.
D4, repeating the steps D1, D2 and D3 twice in sequence, and repeatedly recrystallizing the first obtained recrystallized methyl ammonium iodide crystal to obtain a pure color methyl ammonium iodide crystal with high purity.
D5, dispersing the pure color methyl ammonium iodide crystal with high purity obtained in the step D4 in 100ml of the ether mixed solution after purification obtained by the ether purification method, fully stirring and dispersing, and obtaining the methyl ammonium iodide crystal solid after ether cleaning by a centrifugal method.
D6, repeating the process of the step D5 once, and then washing the obtained methyl ammonium iodide crystal solid twice by diethyl ether.
D7, putting the methyl ammonium iodide crystal solid obtained in the step D6 into a vacuum oven, vacuumizing, heating to 50-60 ℃, keeping for 24 hours until the solvent mixed in the methyl ammonium iodide crystal solid is completely removed, cooling to room temperature, and taking out for later use.
Specifically, as another embodiment, a method for improving the purity of nitrogen-containing organic substances by using diethyl ether comprises the following steps:
e1, 10g of formamidine ammonium iodide powder is put into a beaker, 100mL of absolute ethanol is poured into the beaker, and the beaker is stirred until the powder is completely dissolved.
E2, adding the ether mixture solution into the beaker gradually by using a separating funnel until formamidine ammonium iodide crystal is not separated out, stopping ether injection, and stirring for 15 minutes.
E3, removing the solution by suction filtration by using a Buchner funnel to obtain the recrystallized ammonium formamidine iodide crystal.
E4, repeating the steps E1, E2 and E3 for three times in sequence, and repeatedly recrystallizing the firstly obtained recrystallized ammonium formamidine iodide crystal to obtain the high-purity pure formamidine ammonium iodide crystal.
E5, dispersing the high-purity pure formamidine ammonium iodide crystal obtained in the step E4 in 100ml of purified diethyl ether mixed solution obtained by the diethyl ether purification method, fully stirring and dispersing, and then obtaining a diethyl ether-washed ammonium formamidine ammonium iodide crystal solid by a centrifugal method.
E6, repeating the procedure of step E5 twice, and then washing the obtained ammonium formamidine iodide crystal solid with diethyl ether three times.
E7, putting the solid ammonium iodide formamidine crystal obtained in the step E6 into a vacuum oven, vacuumizing and heating to 70-80 ℃, keeping for 24 hours until the solvent mixed in the solid ammonium iodide formamidine crystal is completely removed, cooling to room temperature and taking out for later use.
The invention also discloses application of the nitrogen-containing organic matter, wherein the nitrogen-containing organic matter is obtained by the method for improving the purity of the nitrogen-containing organic matter by utilizing the diethyl ether, and the nitrogen-containing organic matter is applied to preparation of perovskite solar cells or is respectively applied to preparation of semiconductors, diodes, detectors and nano materials.
The process of the present invention is illustrated below with reference to specific examples.
The first embodiment is as follows:
11) 0.05mol of the radical scavenger pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate was weighed out and dissolved in 50mL of chloroform.
12) 0.05mol of tris (2, 4-di-tert-butylphenyl) phosphite, which is a hydroperoxide decomposer, was weighed out and dissolved in 50mL of acetone.
13) Mixing the two solutions, adding 100mL of the mixed solution into 2L of diethyl ether, oscillating, fully mixing, sealing at room temperature and keeping out of the sun for more than one week, completely reacting, and removing free radicals and peroxy diethyl ether in the diethyl ether to obtain a purified diethyl ether mixed solution.
14) 10g of methyl amine iodide powder was weighed into a beaker, poured into 100mL of anhydrous ethanol, and stirred until completely dissolved. And adding the purified ether mixed solution into the beaker by using a separating funnel gradually, stopping injecting the ether until the methyl amine iodide crystals are not separated out, and fully stirring for 15 minutes. And (4) performing suction filtration by using a Buchner funnel to obtain a methyl ammonium iodide solid.
15) Repeating the step 14) twice in sequence to obtain high-quality methyl ammonium iodide crystals.
16) Dispersing the obtained product into 100mL of purified ether mixed solution, fully stirring and dispersing the obtained product, and then centrifuging the obtained product to obtain a methyl ammonium iodide solid.
17) Repeating the step 16) once to obtain high-quality methyl ammonium iodide crystals.
18) Putting the obtained methyl ammonium iodide crystal into a vacuum oven, vacuumizing, heating to 60 ℃, keeping for 24 hours, cooling to room temperature, and taking out for later use.
Example two:
21) respectively weighing 0.1mol of n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate as a free radical scavenger and 0.1mol of didodecyl thiodipropionate as a hydroperoxide decomposer, adding the n-octadecyl and the didodecyl thiodipropionate into 10L of diethyl ether, oscillating, fully mixing, sealing at room temperature and keeping out of the sun for more than one week, and completely reacting to remove free radicals and peroxy diethyl ether in the diethyl ether.
22) 10g of formamidine ammonium iodide powder was added to the beaker, and 100mL of anhydrous methanol was poured and stirred until completely dissolved. And adding the purified ether mixed solution into the beaker by using a separating funnel gradually, stopping the injection of ether until the formamidine ammonium iodide crystal is not separated out any more, and fully stirring for 15 minutes. And (4) performing suction filtration by using a Buchner funnel to obtain solid formamidine ammonium iodide.
23) Repeating the step 22) for three times to obtain high-quality formamidine ammonium iodide crystals.
24) Dispersing the solid into 100mL of purified ether mixed solution, fully stirring and dispersing, and then centrifuging to obtain the formamidine ammonium iodide solid.
25) Repeating the step 24) twice to obtain high-quality formamidine ammonium iodide crystals.
26) Putting the obtained methyl ammonium iodide crystal into a vacuum oven, vacuumizing, heating to 60 ℃, keeping for 24 hours, cooling to room temperature, and taking out for later use.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principles of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A method for purifying diethyl ether is characterized by comprising the following steps: adding a free radical scavenger and a hydroperoxide decomposer into ether for purification reaction, or adding a mixed solution of the free radical scavenger and the hydroperoxide decomposer into the ether for purification reaction to obtain a purified ether mixed solution after full purification reaction, and then purifying the purified ether mixed solution after full reaction by adopting any one of a liquid-separating extraction method, a filtering method or a re-steaming method to obtain purified ether; wherein the content of the first and second substances,
the free radical scavenger comprises at least one of hindered phenol compounds, amine compounds and quinone compounds, the hydroperoxide decomposer comprises phosphite esters or thioester compounds, and the dosage of the free radical scavenger and the dosage of the hydroperoxide decomposer are respectively 0.01-5%.
2. The method for purifying diethyl ether of claim 1, wherein the radical scavenger is any one of N-octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis (3, 5-di-t-butyl-4-hydroxy) phenylpropionate, N' -bis- (3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl) hexanediamine, 2, 6-di-t-butyl-p-cresol, methylene-bis (di-t-butylcresol), isooctyl-3- (3, 5-di-t-butyl-hydroxyphenyl) propionate, p-diisooctyldiphenylamine, and butyloctyldiphenylamine, and the hydroperoxide decomposer is any one of tris (2, 4-di-t-butylphenyl) phosphite, t-butylphenyl phosphite, N-octadecyl-propionate, N-octadecyl-tetrakis (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, N-butyl-octyldiphenylamine, one of dilauryl thiodipropionate, zinc dialkyldithiophosphate, zinc dialkyldithiocarbamate, 3-thiodipropionate and methylenebisbutanedithiocarbamate.
3. The method for purifying diethyl ether of claim 1, wherein the radical scavenger and the hydroperoxide decomposer are directly mixed with diethyl ether for reaction, or dissolved in other solvents and then mixed with diethyl ether for reaction, wherein the other solvents include alcohol solvents, benzene, toluene, chlorobenzene, acetone, carbon tetrachloride, chloroform, cyclohexane, ester organic solvents, and ether organic solvents.
4. The method of purifying diethyl ether of claim 1, wherein the conditions for the sufficient purification reaction are: sealing or under the protection of inert gas, stopping light, stirring, oscillating or standing for more than one day at the temperature of 0-30 ℃.
5. A process for the purification of diethyl ether according to claim 1, comprising the steps of:
a1, dissolving 0.05mol of a radical scavenger pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate in 50mL of chloroform, dissolving 0.05mol of a hydroperoxide decomposer tris (2, 4-di-tert-butylphenyl) phosphite in 50mL of acetone, and mixing the two solutions;
a2, adding 100mL of the mixed solution into 2L of diethyl ether, oscillating, fully mixing, placing at room temperature in a sealed and light-proof manner for more than one week, and completely purifying to remove free radicals and peroxy diethyl ether in the diethyl ether to obtain a purified diethyl ether mixed solution;
a3, and then, purifying the diethyl ether mixed solution after full purification reaction by adopting a re-steaming method to obtain purified diethyl ether.
6. A process for the purification of diethyl ether according to claim 1, comprising the steps of:
b1, respectively adding 0.1mol of a free radical scavenger, namely n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and 0.1mol of a hydroperoxide decomposer, namely didodecyl thiodipropionate, into 10L of diethyl ether, fully mixing, oscillating, standing at room temperature in a closed and light-proof manner for more than one week, and completely purifying to remove free radicals and peroxy diethyl ether in the diethyl ether to obtain a purified diethyl ether mixed solution;
and B2, then, purifying the diethyl ether mixed solution after the full purification reaction by adopting a filtration method to obtain purified diethyl ether.
7. A method for improving the purity of nitrogen-containing organic matters by utilizing diethyl ether is characterized by comprising the following steps:
c1, dissolving the nitrogen-containing organic matter powder in an alcohol solution, wherein the alcohol solution comprises at least one of methanol, ethanol, isopropanol and n-butanol;
c2, under the condition of continuous stirring, gradually adding the purified diethyl ether mixed solution or the purified diethyl ether obtained by the diethyl ether purification method of any one of claims 1 to 6 into the fully dissolved nitrogenous organic matter alcohol solution, and stopping adding the purified diethyl ether mixed solution or the purified diethyl ether when no nitrogenous organic matter crystal is separated out;
c3, removing the solution by adopting a filtering method or a centrifugal method to obtain a recrystallized crystal of the nitrogenous organic matter;
c4, repeating the steps C1, C2 and C3 at least once in sequence, and recrystallizing the recrystallized crystal obtained for the first time until a pure-color nitrogen-containing organic crystal with high purity is obtained;
c5, dispersing the high-purity pure-color nitrogen-containing organic crystal obtained in the step C4 in the purified diethyl ether mixed solution or the purified diethyl ether obtained by the diethyl ether purification method of any one of claims 1 to 5, fully stirring and dispersing, and then obtaining the nitrogen-containing organic crystal solid after being washed by the diethyl ether through a centrifugation or filtration method;
c6, repeating the process of the step C5 at least once, and then washing the obtained nitrogen-containing organic crystal solid for a plurality of times by diethyl ether;
and C7, placing the nitrogen-containing organic crystal solid obtained in the step C6 in a vacuum oven, vacuumizing, heating to 50-80 ℃, keeping for more than 10 hours until the solvent mixed in the nitrogen-containing organic crystal solid is completely removed, cooling to room temperature, and taking out for later use.
8. The method of claim 7, wherein the nitrogen-containing organic compound comprises any one of formamidine halide, methyl halide, guanidine halide.
9. The method for improving the purity of nitrogen-containing organic substances by using diethyl ether as claimed in claim 7, wherein in step C1, the method for promoting the dissolution of the nitrogen-containing organic substance powder material in the alcohol solution comprises at least one of heating, ultrasonic treatment, stirring and shaking.
10. Use of a nitrogen-containing organic substance, wherein the nitrogen-containing organic substance is obtained by the method for improving the purity of the nitrogen-containing organic substance by using the ether according to any one of claims 7 to 9, and the nitrogen-containing organic substance is to be used in the preparation of perovskite solar cells or is to be used in the preparation of semiconductors, diodes, detectors and nano materials respectively.
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