CN112830904A - Purification method of diphenylamine sulfide - Google Patents
Purification method of diphenylamine sulfide Download PDFInfo
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- CN112830904A CN112830904A CN202110041607.4A CN202110041607A CN112830904A CN 112830904 A CN112830904 A CN 112830904A CN 202110041607 A CN202110041607 A CN 202110041607A CN 112830904 A CN112830904 A CN 112830904A
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- diphenylamine
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- sulfide
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- VXXOYZOZDIQRPL-UHFFFAOYSA-N n,n-diphenylthiohydroxylamine Chemical compound C=1C=CC=CC=1N(S)C1=CC=CC=C1 VXXOYZOZDIQRPL-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000000746 purification Methods 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 225
- 239000006185 dispersion Substances 0.000 claims abstract description 105
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000007788 liquid Substances 0.000 claims abstract description 61
- 239000013522 chelant Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims description 50
- 239000002904 solvent Substances 0.000 claims description 33
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 12
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 12
- LESFYQKBUCDEQP-UHFFFAOYSA-N tetraazanium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound N.N.N.N.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O LESFYQKBUCDEQP-UHFFFAOYSA-N 0.000 claims description 9
- QLBHNVFOQLIYTH-UHFFFAOYSA-L dipotassium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O QLBHNVFOQLIYTH-UHFFFAOYSA-L 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- ZUBZATZOEPUUQF-UHFFFAOYSA-N isononane Chemical compound CCCCCCC(C)C ZUBZATZOEPUUQF-UHFFFAOYSA-N 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 3
- AWNVVAMWLMUZOZ-UHFFFAOYSA-J magnesium;disodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical class [Na+].[Na+].[Mg+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O AWNVVAMWLMUZOZ-UHFFFAOYSA-J 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 55
- 239000012535 impurity Substances 0.000 abstract description 27
- 239000012043 crude product Substances 0.000 abstract description 17
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000011347 resin Substances 0.000 description 25
- 229920005989 resin Polymers 0.000 description 25
- 229910052751 metal Inorganic materials 0.000 description 23
- 239000002184 metal Substances 0.000 description 23
- 238000003756 stirring Methods 0.000 description 18
- 239000000178 monomer Substances 0.000 description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 12
- 229920002120 photoresistant polymer Polymers 0.000 description 12
- 238000001816 cooling Methods 0.000 description 9
- 238000001514 detection method Methods 0.000 description 9
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QGMGHALXLXKCBD-UHFFFAOYSA-N 4-amino-n-(2-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1C(=O)NC1=CC=CC=C1N QGMGHALXLXKCBD-UHFFFAOYSA-N 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- -1 thiazaanthracene Chemical compound 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- JCNRKGZAGGRTAL-UHFFFAOYSA-N triphenyl(sulfido)azanium Chemical compound C1(=CC=CC=C1)[N+](C1=CC=CC=C1)(C1=CC=CC=C1)[S-] JCNRKGZAGGRTAL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/20—[b, e]-condensed with two six-membered rings with hydrogen atoms directly attached to the ring nitrogen atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention is applicable to the technical field of semiconductors, and provides a method for purifying diphenylamine sulfide, which comprises the following steps: providing a first compound and a second compound, dissolving the first compound to form a first compound dispersion liquid, dissolving the second compound to form a second compound dispersion liquid, wherein the first compound comprises a crude product of diphenylamine sulfide, the second compound is a chelate, and then adding the second compound dispersion liquid into the first compound dispersion liquid to obtain a product compound, wherein the product compound is a pure product of diphenylamine sulfide, and the purity of the product compound is higher than that of the first compound. The method is adopted to purify the crude vulcanized diphenylamine product, so that the impurity content in the crude vulcanized diphenylamine product is reduced, the purity of the vulcanized diphenylamine is improved, and the cost is reduced.
Description
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to a method for purifying diphenylamine sulfide.
Background
Diphenylamine sulfide, also known as phenothiazine, thiazaanthracene, thiodiphenylamine and PTZ, is an organic compound, is a yellow to greenish-gray powder or a flaky crystal, is generally used as a highly efficient polymerization inhibitor for acrylic acid, acrylic esters, methacrylic esters and ester monomers, and since the methacrylic acid monomer is an important component of a photoresist resin, the impurity content of diphenylamine sulfide is required to be low, and particularly, the content of each metal impurity is required to be less than 10 ppb. However, the vulcanized diphenylamine produced by the methods adopted in the prior art generally has a metal impurity content of more than 1ppm, that is, the content of metal impurities in the resulting vulcanized diphenylamine produced is usually 1000ppb or more, and when the vulcanized diphenylamine is used as a polymerization inhibitor for resins such as methacrylic monomers, because the impurity content in the vulcanized diphenylamine is more than 1000ppb, electronic-grade resin can not be prepared, that is, the resin prepared by using diphenylamine sulfide as polymerization inhibitor can not reach the high-purity standard required by the semiconductor industry, and further the resin can not be applied to photoresist resin, even if the metal impurity is applied to the photoresist resin, the photoresist resin may be high in content, which may cause the photoresist resin to fail, which may increase the cost, further, there is no method for reducing the content of metal impurities in the diphenylamine sulfide to 10ppb or less.
Therefore, a method for purifying the vulcanized diphenylamine is urgently needed at present, and the purity of the vulcanized diphenylamine is improved.
Disclosure of Invention
The embodiment of the invention provides a purification method of vulcanized diphenylamine, aiming at solving the technical problem of low purity of the vulcanized diphenylamine.
The embodiment of the invention is realized by providing a first compound and a second compound, dissolving the first compound to form a first compound dispersion liquid and dissolving the second compound to form a second compound dispersion liquid, wherein the first compound comprises a crude product of diphenylamine sulfide, and the second compound is a chelate;
and adding the second compound dispersion liquid into the first compound dispersion liquid to obtain a product compound, wherein the product compound is a pure vulcanized diphenylamine product, and the purity of the product compound is higher than that of the first compound.
Furthermore, the chelate comprises one or more of disodium ethylene diamine tetraacetate, tetrasodium ethylene diamine tetraacetate, dipotassium ethylene diamine tetraacetate, ammonium ethylene diamine tetraacetate and disodium ethylene diamine tetraacetate magnesium salt.
Still further, the first compound is dissolved in a first solvent to form the first compound dispersion, and the first solvent includes one or a combination of several of cyclohexanone, tetrahydrofuran, butanone, propylene glycol methyl ether acetate, toluene, n-octane, n-heptane and 2-methyloctane.
Further, after the steps of providing the first compound and the second compound, dissolving the first compound to form the first compound dispersion, and dissolving the second compound to form the second compound dispersion, before the step of adding the second compound dispersion to the first compound dispersion to obtain the product compound, the method further includes:
the first compound dispersion liquid is subjected to a first heat treatment.
Further, the temperature of the first heat treatment is 30-130 ℃.
Still further, the time of the first heat treatment is 1 hour to 5 hours.
Further, the second compound is dissolved in a second solvent to form the second compound dispersion, and the second solvent is water.
Further, the second compound is dissolved in the second solvent to form the second compound dispersion liquid, and the corresponding relationship between the mass ratio of the second solvent and the mass ratio of the second compound is 1: 1-5.
Further, after the steps of providing the first compound and the second compound, dissolving the first compound to form the first compound dispersion, and dissolving the second compound to form the second compound dispersion, before the step of adding the second compound dispersion to the first compound dispersion to obtain the product compound, the method further includes:
and carrying out second heat treatment on the second compound dispersion liquid, wherein the temperature of the second heat treatment is 30-90 ℃.
Further, the step of adding the second compound dispersion to the first compound dispersion to obtain a product compound comprises:
and removing the second compound dispersion liquid to obtain a product compound.
The invention provides a purification method of vulcanized diphenylamine, which comprises the following steps: providing a first compound and a second compound, dissolving the first compound to form a first compound dispersion liquid, dissolving the second compound to form a second compound dispersion liquid, wherein the first compound comprises a crude product of diphenylamine sulfide, the second compound is a chelate, and then adding the second compound dispersion liquid into the first compound dispersion liquid to obtain a product compound, wherein the product compound is diphenylamine sulfide, and the purity of the product compound is higher than that of the first compound. According to the invention, the second compound dispersion liquid is added into the first compound dispersion liquid, so that impurities in the crude product of the diphenylamine sulfide are reduced through the second compound dispersion liquid, the purity is further improved, and the cost is reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
At present, the content of impurities of vulcanized diphenylamine produced in the prior art is more, particularly the content of metal impurities reaches more than 10ppb, the vulcanized diphenylamine is used as a polymerization inhibitor to prepare methacrylic acid monomers, the methacrylic acid monomers are the composition of photoresist resin, and the content of the metal impurities in the vulcanized diphenylamine is high, so that the content of the metal impurities in the prepared resins such as the methacrylic acid monomers is high, and can not reach less than 10ppb required by the photoresist resin, and at present, a method for reducing the content of the metal impurities in the vulcanized diphenylamine to less than 10ppb does not exist, but the method can reduce the content of the metal impurities in the vulcanized diphenylamine to less than 10ppb, can prepare high-purity vulcanized diphenylamine, can prepare electronic-grade vulcanized diphenylamine, and can further adopt the electronic-grade vulcanized diphenylamine to prepare the electronic-grade resins such as the methacrylic acid monomers, further, the impurity content of resins such as electronic grade methacrylic acid monomer and the like can meet the requirements of the photoresist resin.
The invention provides a purification method of diphenylamine sulfide, which comprises the following steps:
step A, providing a first compound and a second compound, dissolving the first compound to form a first compound dispersion liquid, and dissolving the second compound to form a second compound dispersion liquid, wherein the first compound comprises a crude product of diphenylamine sulfide, and the second compound comprises a chelate.
In one embodiment, the chelate comprises one or a combination of disodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, dipotassium ethylenediaminetetraacetate, ammonium ethylenediaminetetraacetate, and disodium ethylenediaminetetraacetate magnesium salt.
In one embodiment, the first compound is dissolved in a first solvent to form the first compound dispersion, and the first solvent includes one or more of cyclohexanone, tetrahydrofuran, butanone, propylene glycol methyl ether acetate, toluene, n-octane, n-heptane, and 2-methyloctane.
In one embodiment, the mass ratio of the first compound to the first solvent is 1 to 1.5: 1-2. Specifically, the mass ratio of the first compound to the first solvent may be 1: 1. 1.1: 1.4, 1.4: 1.8 or 1:2, etc.
In one embodiment, after the steps of providing the first compound and the second compound, dissolving the first compound to form the first compound dispersion, and dissolving the second compound to form the second compound dispersion, the first compound dispersion is subjected to a first heat treatment before the step of adding the second compound dispersion to the first compound dispersion to obtain the product compound.
In one embodiment, the temperature of the first heat treatment is 30 degrees celsius to 130 degrees celsius. Specifically, the temperature of the first heat treatment may be 32 degrees celsius, 40 degrees celsius, 60 degrees celsius, 80 degrees celsius, 120 degrees celsius, 125 degrees celsius, or the like.
In one embodiment, the first heat treatment is performed for a period of time ranging from 1 hour to 5 hours. Specifically, the time of the first heat treatment may be 1.5 hours, 2 hours, 3.5 hours, 4.5 hours, or the like.
In one embodiment, the stirring speed of the first heat treatment is 80r/min to 140 r/min. Specifically, the stirring speed of the first heat treatment may be 82r/min, 90r/min, 100r/min, 112r/min, 130r/min, or the like.
In one embodiment, the second compound is dissolved in a second solvent to form the second compound dispersion, and the second solvent is water.
In one embodiment, the second compound is dissolved in the second solvent to form the second compound dispersion, and the mass ratio of the second solvent to the mass ratio of the second compound is in a relationship of 1: 1-5. Specifically, the correspondence relationship between the mass ratio of the second solvent and the mass ratio of the second compound may be 1: 2. 1: 3 or 1: 4, etc.
In one embodiment, after the steps of providing the first compound and the second compound, dissolving the first compound to form the first compound dispersion, and dissolving the second compound to form the second compound dispersion, the second compound dispersion is subjected to a second heat treatment before the step of adding the second compound dispersion to the first compound dispersion to obtain the product compound.
In one embodiment, the temperature of the second heat treatment is 30 to 90 degrees celsius. Specifically, the temperature of the second heat treatment may be 35 degrees celsius, 40 degrees celsius, 50 degrees celsius, 70 degrees celsius, or 80 degrees celsius, or the like.
In one embodiment, the second heat treatment stirring speed is 80r/min to 140 r/min. The stirring speed of the second heat treatment is 80r/min-140 r/min. Specifically, the stirring speed of the second heat treatment may be 82r/min, 90r/min, 100r/min, 112r/min, 130r/min or the like.
And B, adding the second compound dispersion liquid into the first compound dispersion liquid to obtain a product compound, wherein the product compound is a pure vulcanized diphenylamine product, and the purity of the product compound is higher than that of the first compound.
In one embodiment, the step of adding the second compound dispersion to the first compound dispersion to obtain the product compound comprises:
and removing the second compound dispersion liquid to obtain a product compound.
The detailed description is as follows:
example one
Adding 100 g of the first compound into a first four-neck flask, wherein the first compound is a crude product of diphenylamine sulfide, the content of metal impurities in the crude product of diphenylamine sulfide is more than 10ppb, adding 100 g of a first solvent into the first four-neck flask to form a first compound dispersion liquid, the first solvent is tetrahydrofuran, the purity of tetrahydrofuran is 99.99999% or more, and carrying out first heat treatment on the first compound dispersion liquid, wherein the temperature of the first heat treatment is 60 ℃, the stirring speed of the first heat treatment is 100r/min, and the time of the first heat treatment is 2 hours.
5 grams of the second compound, which includes a chelate, in this example, disodium ethylenediaminetetraacetate, was added to the second four-necked flask. And then, adding 95 g of the second solvent into the second four-mouth flask to form a second compound dispersion liquid, namely, a disodium ethylene diamine tetraacetate dispersion liquid, wherein the second solvent is water, and carrying out second heat treatment on the disodium ethylene diamine tetraacetate dispersion liquid, the temperature of the second heat treatment is 60 ℃, and the stirring speed of the second heat treatment is 90 r/min.
Then, the heated disodium ethylene diamine tetraacetate dispersion liquid in the second four-neck flask is added into the first four-neck flask, and the first four-neck flask is continuously heated and stirred for 1 hour to 4 hours, wherein the heating and stirring time is 1 hour in the embodiment. And after heating and stirring, standing and layering, leading out the disodium ethylene diamine tetraacetate dispersion liquid, and repeating the operation for 3 times until the disodium ethylene diamine tetraacetate dispersion liquid is completely led out to obtain a product compound, wherein the product compound is a pure vulcanized diphenylamine product, and the purity of the pure vulcanized diphenylamine product is higher than that of the crude vulcanized diphenylamine product.
And cooling, crystallizing, collecting and drying the first four-neck flask to obtain a 71.3 g purified product of the vulcanized diphenylamine, detecting the purified product of the vulcanized diphenylamine, and recovering tetrahydrofuran. And cooling the first four-neck flask to 0-20 ℃, and in the embodiment, cooling the first four-neck flask to 0 ℃. The crystallization time is 10 hours to 24 hours, and in the present example, the crystallization time is set to 10 hours.
And carrying out ICP-MS detection on the dried diphenylamine sulfide pure product to obtain the data in the table 1, wherein the ICP-MS is an inductively coupled plasma mass spectrometer. In table 1, ND represents that ND is out of the lowest detection range of the instrument because the element content is low.
Table 1:
as can be seen from Table 1, the method of the present invention is adopted to purify the crude product of diphenylamine sulfide, so that the content of metal impurities in the obtained pure product of diphenylamine sulfide is less than 10ppb, namely, the metal impurities of Ag, Al, Ca, Cu, Fe, K, Li, Mg, Mn, Na, Ni, Zn and the like are all less than 10ppb, the preparation method of the invention can be used for preparing electronic-grade vulcanized diphenylamine, further, electronic-grade vulcanized diphenylamine can be used as a polymerization inhibitor to prepare electronic-grade resins such as methacrylic acid monomers and the like, further, the resin such as electronic grade methacrylic acid monomer and the like meets the requirement that the metal content of the photoresist resin is less than 10ppb, particularly the content of Al, K, Mn and Na is far lower than the detection range of ICP-MS, moreover, the method for purifying the crude product of the diphenylamine sulfide is simple to operate, high in efficiency, short in period and low in cost.
The electronic grade is high purity.
In the invention, when the disodium ethylene diamine tetraacetate dispersion liquid in the second four-neck flask is heated to the same temperature as the first compound dispersion liquid in the first four-neck flask, the disodium ethylene diamine tetraacetate dispersion liquid is added into the first four-neck flask, so that the yield of the pure vulcanized diphenylamine is improved, and the production cost is reduced.
Example two
Adding 100 g of the first compound into a first four-neck flask, wherein the first compound is a crude product of vulcanized diphenylamine, the content of metal impurities in the crude product of vulcanized diphenylamine reaches more than 10ppb, adding 200 g of a first solvent into the first four-neck flask to form a first compound dispersion liquid, wherein the first solvent is toluene, the purity of the toluene reaches 99.99999% or more, performing first heat treatment on the first compound dispersion liquid to form the first compound dispersion liquid, the temperature of the first heat treatment is 80 ℃, the stirring speed of the first heat treatment is 100r/min, and the time of the first heat treatment is 1 hour.
Adding 10 grams of the second compound into a second four-neck flask, wherein the second compound comprises a chelate, in this embodiment, the chelate is dipotassium ethylenediamine tetraacetate, then adding 90 grams of the second solvent into the second four-neck flask to form dipotassium ethylenediamine tetraacetate dispersion, wherein the second solvent is water, performing second heat treatment on the dipotassium ethylenediamine tetraacetate dispersion, the temperature of the second heat treatment is 80 ℃, and the stirring speed of the second heat treatment is 100 r/min.
Then, adding the heated dipotassium ethylenediamine tetraacetate dispersion liquid in the second four-neck flask into the first four-neck flask, continuing to heat and stir the first four-neck flask for 1 hour to 4 hours, in the embodiment, the heating and stirring time is 1 hour, standing and layering, taking out the second compound dispersion liquid, repeating the operation for 3 times until the dipotassium ethylenediamine tetraacetate dispersion liquid is completely led out to obtain a product compound, wherein the product compound is a pure diphenylamine sulfide product, and the purity of the product compound is higher than that of the first compound, that is, the purity of the pure diphenylamine sulfide product is higher than that of the crude diphenylamine sulfide product.
And cooling, crystallizing, collecting and drying the first four-neck flask to obtain 70.1 g of a pure vulcanized diphenylamine product, detecting the pure vulcanized diphenylamine product, and recovering the toluene. And cooling the first four-neck flask to 0-20 ℃, and in the embodiment, cooling the first four-neck flask to 0 ℃. The crystallization time is 10 hours to 24 hours, and in the present example, the crystallization time is set to 10 hours.
And carrying out ICP-MS detection on the dried product compound to obtain data in the table 2, wherein the ICP-MS is an inductively coupled plasma mass spectrometer. In table 2, ND indicates that the element content is low and exceeds the detection range of the instrument.
Table 2:
as can be seen from Table 2, the method of the present invention is adopted to purify the crude product of diphenylamine sulfide, so that the content of metal impurities in the obtained pure product of diphenylamine sulfide is less than 10ppb, namely, the metal impurities of Ag, Al, Ca, Cu, Fe, K, Li, Mg, Mn, Na, Ni, Zn and the like are all less than 10ppb, the preparation method of the invention can be used for preparing electronic-grade vulcanized diphenylamine, further, electronic-grade vulcanized diphenylamine can be used as a polymerization inhibitor to prepare electronic-grade resins such as methacrylic acid monomers and the like, further, the resin such as electronic grade methacrylic acid monomer and the like meets the requirement that the metal content of the photoresist resin is less than 10ppb, especially the content of Ca, K, Mn and Na is far lower than the detection range of ICP-MS, moreover, the method for purifying the crude product of the diphenylamine sulfide is simple to operate, high in efficiency, short in period and low in cost.
EXAMPLE III
Adding 20000 g of the first compound into a first reaction kettle of 100 liters, wherein the first compound is a crude vulcanized diphenylamine, the content of metal impurities in the crude vulcanized diphenylamine is more than 10ppb, adding 40000 g of a first solvent into the first reaction kettle to form a first compound dispersion, the first solvent is n-heptane, the purity of the n-heptane is more than or equal to 99.99999%, and performing first heat treatment on the formed first compound dispersion, wherein the temperature of the first heat treatment is 70 ℃, the stirring speed of the first heat treatment is 100r/min, and the time of the first heat treatment is 2 hours.
Adding 4000 g of the second compound including a chelate compound into a 100 l reaction kettle II, wherein the chelate compound is ammonium ethylene diamine tetraacetate, then adding 36000 g of the second solvent into the reaction kettle II to form a second compound dispersion liquid, namely, an ammonium ethylene diamine tetraacetate dispersion liquid, wherein the second solvent is water, performing a second heat treatment on the ammonium ethylene diamine tetraacetate dispersion liquid, the temperature of the second heat treatment is 70 ℃, the stirring speed of the second heat treatment is 80r/min-140r/min, and in the embodiment, the stirring speed of the second heat treatment is 130 r/min.
And then adding the heated ammonium ethylene diamine tetraacetate dispersion liquid in the second reaction kettle into the first reaction kettle, continuously heating and stirring the first reaction kettle for 1-4 hours, wherein in the embodiment, the heating and stirring time is 2 hours, standing and layering, leading out the ammonium ethylene diamine tetraacetate dispersion liquid, and repeating the operation for 3 times until the ammonium ethylene diamine tetraacetate dispersion liquid is completely led out to obtain a product compound, wherein the product compound is a pure vulcanized diphenylamine product, and the purity of the product compound is higher than that of the first compound, namely, the purity of the pure vulcanized diphenylamine product is higher than that of the crude vulcanized diphenylamine product.
And cooling, crystallizing, collecting and drying the first reaction kettle to obtain 141200 g of a pure vulcanized dianiline product, detecting the pure vulcanized dianiline product, and recovering the n-heptane. And cooling the first four-neck flask to 0-20 ℃, and in the embodiment, cooling the first four-neck flask to 0 ℃. The crystallization time is 10 hours to 24 hours, and in the present example, the crystallization time is set to 10 hours.
And carrying out ICP-MS detection on the dried product compound to obtain data in the table 3, wherein the ICP-MS is an inductively coupled plasma mass spectrometer. In table 3, ND indicates that the detected element content is low and exceeds the detection range of the instrument.
Table 3:
as can be seen from Table 3, the method of the present invention is adopted to purify the crude product of diphenylamine sulfide, so that the content of metal impurities in the obtained pure product of diphenylamine sulfide is less than 10ppb, namely, the metal impurities of Ag, Al, Ca, Cu, Fe, K, Li, Mg, Mn, Na, Ni, Zn and the like are all less than 10ppb, the preparation method of the invention can be used for preparing electronic-grade vulcanized diphenylamine, further, electronic-grade vulcanized diphenylamine can be used as a polymerization inhibitor to prepare electronic-grade resins such as methacrylic acid monomers and the like, further, the resin such as electronic grade methacrylic acid monomer is applied to the photoresist resin, the requirement that the metal content of the photoresist resin is less than 10ppb can be met, particularly, Cu, Mn and Na are far less than the ICP-MS detection range, in addition, the method for purifying the crude product of the diphenylaniline sulfide is simple to operate, high in efficiency, short in period and low in cost.
The invention provides a purification method of vulcanized diphenylamine, which comprises the following steps: providing a first compound and a second compound, dissolving the first compound to form a first compound dispersion liquid, dissolving the second compound to form a second compound dispersion liquid, wherein the first compound comprises a crude product of diphenylamine sulfide, the second compound is a chelate, and then adding the second compound dispersion liquid into the first compound dispersion liquid to obtain a product compound, wherein the product compound is diphenylamine sulfide, and the purity of the product compound is higher than that of the first compound. According to the invention, the second compound dispersion liquid is added into the first compound dispersion liquid, and impurities, namely metal impurities, in the crude product of the diphenylamine sulfide are reduced through the second compound dispersion liquid, so that the purity of the diphenylamine sulfide is improved, and the cost is reduced.
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 principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A method for purifying vulcanized diphenylamine, which is characterized by comprising the following steps:
providing a first compound and a second compound, dissolving the first compound to form a first compound dispersion liquid and dissolving the second compound to form a second compound dispersion liquid, wherein the first compound comprises a crude diphenylamine sulfide product, and the second compound comprises a chelate;
and adding the second compound dispersion liquid into the first compound dispersion liquid to obtain a product compound, wherein the product compound is a pure vulcanized diphenylamine product, and the purity of the product compound is higher than that of the first compound.
2. The method for purifying diphenylamine sulfide of claim 1, wherein the chelate compound comprises one or more of disodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, dipotassium ethylenediaminetetraacetate, ammonium ethylenediaminetetraacetate, and disodium magnesium ethylenediaminetetraacetate salts.
3. The method for purifying vulcanized diphenylamine according to claim 1, wherein the first compound is dissolved in a first solvent to form the first compound dispersion, and the first solvent includes one or a combination of cyclohexanone, tetrahydrofuran, butanone, propylene glycol methyl ether acetate, toluene, n-octane, n-heptane, and 2-methyloctane.
4. The method for purifying diphenylamine sulfide of claim 1, wherein after the steps of providing the first compound and the second compound, dissolving the first compound to form the first compound dispersion, and dissolving the second compound to form the second compound dispersion, and before the step of adding the second compound dispersion to the first compound dispersion to obtain the product compound, the method further comprises:
the first compound dispersion liquid is subjected to a first heat treatment.
5. The purification method of diphenylamine sulfide claim 4, wherein the temperature of the first heat treatment is 30-130 ℃.
6. The purification method of diphenylamine sulfide claim 4, wherein the time for the first heat treatment is 1-5 hours.
7. The method for purifying vulcanized diphenylamine according to claim 1, wherein the second compound is dissolved in a second solvent to form the second compound dispersion, and the second solvent is water.
8. The method for purifying vulcanized diphenylamine according to claim 7, wherein the second compound is dissolved in the second solvent to form the second compound dispersion, and the mass ratio of the second solvent to the mass ratio of the second compound has a correspondence relationship of 1: 1-5.
9. The method for purifying diphenylamine sulfide of claim 1, wherein after the steps of providing the first compound and the second compound, dissolving the first compound to form the first compound dispersion, and dissolving the second compound to form the second compound dispersion, and before the step of adding the second compound dispersion to the first compound dispersion to obtain the product compound, the method further comprises:
and carrying out second heat treatment on the second compound dispersion liquid, wherein the temperature of the second heat treatment is 30-90 ℃.
10. The method for purifying diphenylamine sulfide of claim 1, wherein the step of adding the second compound dispersion to the first compound dispersion to obtain the product compound comprises:
and removing the second compound dispersion liquid to obtain a product compound.
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