CN111559986A - Purification method of 1, 2-benzisothiazolin-3-ketone - Google Patents
Purification method of 1, 2-benzisothiazolin-3-ketone Download PDFInfo
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- CN111559986A CN111559986A CN202010571430.4A CN202010571430A CN111559986A CN 111559986 A CN111559986 A CN 111559986A CN 202010571430 A CN202010571430 A CN 202010571430A CN 111559986 A CN111559986 A CN 111559986A
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- benzisothiazolin
- sodium salt
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- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000000746 purification Methods 0.000 title abstract description 12
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 claims abstract description 68
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 29
- 239000000047 product Substances 0.000 claims abstract description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000008139 complexing agent Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012043 crude product Substances 0.000 claims abstract description 16
- 230000020477 pH reduction Effects 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000002386 leaching Methods 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000004321 preservation Methods 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- FMSKPKSLSVKPIP-UHFFFAOYSA-N 1,2-benzothiazol-3-one;sodium Chemical compound [Na].C1=CC=C2C(=O)NSC2=C1 FMSKPKSLSVKPIP-UHFFFAOYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 229940120146 EDTMP Drugs 0.000 claims description 3
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 claims description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 2
- RNMCCPMYXUKHAZ-UHFFFAOYSA-N 2-[3,3-diamino-1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound NC1(N)CCCC(CC(O)=O)(CC(O)=O)C1(CC(O)=O)CC(O)=O RNMCCPMYXUKHAZ-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 2
- VYTBPJNGNGMRFH-UHFFFAOYSA-N acetic acid;azane Chemical compound N.N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O VYTBPJNGNGMRFH-UHFFFAOYSA-N 0.000 claims description 2
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 2
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 229960003330 pentetic acid Drugs 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 9
- 239000002585 base Substances 0.000 abstract description 8
- 241001085205 Prenanthella exigua Species 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004042 decolorization Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000007791 liquid phase Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000001953 recrystallisation Methods 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- PXZSANDJGNKIIA-UHFFFAOYSA-N 2-methylsulfanylbenzonitrile Chemical compound CSC1=CC=CC=C1C#N PXZSANDJGNKIIA-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NHWQMJMIYICNBP-UHFFFAOYSA-N 2-chlorobenzonitrile Chemical compound ClC1=CC=CC=C1C#N NHWQMJMIYICNBP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GVVGQWPLZQAOSX-UHFFFAOYSA-N n'-(2-aminoethyl)ethane-1,2-diamine;sodium Chemical compound [Na].NCCNCCN GVVGQWPLZQAOSX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RMBAVIFYHOYIFM-UHFFFAOYSA-M sodium methanethiolate Chemical compound [Na+].[S-]C RMBAVIFYHOYIFM-UHFFFAOYSA-M 0.000 description 1
- ZAWGLAXBGYSUHN-UHFFFAOYSA-M sodium;2-[bis(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CC([O-])=O ZAWGLAXBGYSUHN-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
- C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Abstract
The invention discloses a purification method of 1, 2-benzisothiazolin-3-one, which is characterized in that a complexing agent is added in the purification process of an acid-base method to remove metal ions so as to control the content of a colored complex formed by the 1, 2-benzisothiazolin-3-one and the metal ions in a product and improve the quality of the product. The method comprises the following specific steps: 1) mixing the crude product of the 1, 2-benzisothiazolin-3-one with liquid alkali to prepare a sodium salt solution of the 1, 2-benzisothiazolin-3-one; 2) adding active carbon for decoloring and filtering; 3) adding hydrochloric acid into the aqueous alkali after the decolorization and filtration for acidification, and adding a complexing agent in the acidification process; 4) after acidification, the 1, 2-benzisothiazolin-3-one is obtained by solid-liquid separation and leaching. The purification method is simple to operate, and the obtained product is bright white in appearance, good in looseness, not easy to agglomerate, low in metal ion content, good in thermal stability after being prepared into thinner, and high in application value in industrial production.
Description
Technical Field
The invention relates to a purification method of 1, 2-benzisothiazolin-3-ketone, belonging to the field of fine chemical engineering.
Background
1, 2-benzisothiazolin-3-one (BIT) is an important novel industrial bactericide. The organic fertilizer has the outstanding effect of inhibiting the breeding of microorganisms such as fungi, mildew, bacteria, algae and the like in an organic medium, has the advantages of high efficiency, broad spectrum, low toxicity, natural degradation in the environment and the like, and is considered to be one of safe and harmless green and environment-friendly products. At present, 1, 2-benzisothiazolin-3-one is used in the fields of emulsion paint, oil products, paper making, printing ink, leather products, water treatment and the like in developed countries such as Europe, America and Japan, and the application range is very wide.
The 1, 2-benzisothiazolin-3-one is usually produced by using o-chlorobenzonitrile as a raw material, the o-chlorobenzonitrile is condensed with sodium methyl mercaptide in a solvent to obtain o-methylthiobenzonitrile, chlorine is introduced into the o-methylthiobenzonitrile to chlorinate, a ring is closed, a crude product of the 1, 2-benzisothiazolin-3-one is obtained by filtration, and the crude product is usually purified by using an acid-base method. Patents CN103204823 and CN108794424 use an alcohol solvent or a mixed solvent of an alcohol and water to recrystallize 1, 2-benzisothiazolin-3-one, and although a solid with high purity is obtained, the recrystallization yield is low. Patent CN105801516 discloses a purification process of 1, 2-benzisothiazolin-3-one, which comprises adding solid metal salt into recrystallization solvent to obtain product with good crystal form at high yield, but because 1, 2-benzisothiazolin-3-one itself is easy to form complex with metal ion, new impurity is introduced into product. Patent CN105753805 recrystallizes 1, 2-benzisothiazolin-3-one using a nonpolar solvent, which requires a large amount of solvent due to the low solubility of 1, 2-benzisothiazolin-3-one in the nonpolar solvent. Patent CN109970677 discloses a purification method of 1, 2-benzisothiazolin-3-one by twice recrystallization, which uses two solvents with opposite polarities as recrystallization solvents respectively, and the method has the problems of low yield, large solvent consumption, difficult recovery of the secondary recrystallization solvent and the like, and is more suitable for preparing 1, 2-benzisothiazolin-3-one standard products in a small amount in a laboratory.
Common 1, 2-benzisothiazolin-3-one products in the market are white powdery solids with the water content of about 15 percent, in order to meet the market requirement, the products obtained by an organic solvent recrystallization method usually need to be rinsed with water after recrystallization or supplemented with water after drying to achieve the proper water content, the organic solvent residue is difficult to control or the products are agglomerated in the treatment process, the storage and the use of the products are troublesome, and the acid-base method directly uses water as the solvent, so that the related problems do not exist. Meanwhile, a large amount of hydrogen chloride gas is generated in the process of preparing the 1, 2-benzisothiazolin-3-one by chlorination of o-methylthiobenzonitrile and cyclization, part of the 1, 2-benzisothiazolin-3-one is salified with hydrogen chloride, and the residual hydrogen chloride in the solid can cause the crude product of the 1, 2-benzisothiazolin-3-one to be stronger in acidity, the acidity cannot be removed by an organic solvent recrystallization method, and the acidity of the product can be effectively reduced by an acid-base method.
In summary, the conventional acid-base method is still the preferred purification process for 1, 2-benzisothiazolin-3-one at present, and when the acid-base method is used for purifying the 1, 2-benzisothiazolin-3-one, the appearance of the product often shows the phenomena of purplish, reddish or yellowish color, poor looseness and the like. The reason is that N, S and O in the molecular structure of the 1, 2-benzisothiazolin-3-one are coordination sites with small steric hindrance, and are easy to form colored 1, 2-benzisothiazolin-3-one-metal complex impurities with metal ions in a system. The formation of the 1, 2-benzisothiazolin-3-one-metal complex seriously affects the purity, appearance and stability in the using process of the 1, 2-benzisothiazolin-3-one, so that metal ions introduced by equipment or raw materials are thoroughly removed in the acid-base method purification process, and the method has very important significance for improving the quality of the 1, 2-benzisothiazolin-3-one.
Disclosure of Invention
Aiming at the problems in the existing 1, 2-benzisothiazolin-3-keto acid alkaline purification process, the invention provides a purification method for effectively reducing impurities in a product and improving the appearance of the product, so that the quality of the 1, 2-benzisothiazolin-3-one purified by the method is obviously improved.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for purifying 1, 2-benzisothiazolin-3-one, comprising the steps of:
1) mixing the crude product of the 1, 2-benzisothiazolin-3-one with liquid alkali, heating, keeping the temperature and stirring to prepare a sodium salt solution of the 1, 2-benzisothiazolin-3-one;
2) adding active carbon for decoloring and filtering;
3) adding hydrochloric acid into the decolored and filtered alkali solution for acidification, and adding a complexing agent in the acidification process;
4) and cooling the solid-liquid mixture obtained after acidification, performing solid-liquid separation, leaching the obtained solid with deionized water, and performing suction filtration to obtain the finished product of the 1, 2-benzisothiazolin-3-one.
Further, the temperature for heat preservation and stirring in the step 1) is 70-75 ℃.
Further, the adding amount of the activated carbon in the step 2) is 0.5-2% of the weight of the crude product of the 1, 2-benzisothiazolin-3-one, and the preferable adding amount of the activated carbon is 1%.
Further, the temperature of solid-liquid separation in the step 3) is 45-50 ℃.
Further, the pH value of acidification in the step 3) is 3-14, and the optimal acidification pH value is 6-9.
Further, in the step 3), the complexing agent is one or more of nitrilotriacetic acid and sodium salt thereof, ethylene diamine tetraacetic acid and sodium salt thereof, ethylene glycol diethyl ether diamine tetraacetic acid and sodium salt thereof, cyclohexanediamine tetraacetic acid and sodium salt thereof, diethylenetriamine pentaacetic acid and sodium salt thereof, hydroxyethyl ethylenediamine triacetic acid and sodium salt thereof, ethylene diamine tetramethylene phosphonic acid and sodium salt thereof, diethylenetriamine pentamethylene phosphonic acid and sodium salt thereof, aminotrimethylene phosphonic acid and sodium salt thereof, hydroxyethylene diphosphonic acid and sodium salt thereof, oxalic acid and sodium salt thereof, tartaric acid and sodium salt thereof, and citric acid and sodium salt thereof.
Further, in the step 3), the addition amount of the complexing agent is 0.005-0.5% of the weight of the 1, 2-benzisothiazolin-3-one sodium salt solution, and the preferable addition amount of the complexing agent is 0.01-0.1% of the weight of the 1, 2-benzisothiazolin-3-one sodium salt solution.
Further, adding a complexing agent in the step 3), and then keeping the temperature and stirring for 0.5 hour.
Further, the water content of the finished product 1, 2-benzisothiazolin-3-one in the step 4) is 14-16%.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a novel method for purifying 1, 2-benzisothiazolin-3-one, which adopts an acid-base method to purify the 1, 2-benzisothiazolin-3-one, and a complexing agent is added in the acidification process to remove metal ions introduced in equipment and raw materials, so that the 1, 2-benzisothiazolin-3-one is prevented from being influenced by the metal ions, and a coordination compound influencing the product quality is generated.
Meanwhile, the 1, 2-benzisothiazolin-3-one purified by the method has bright white appearance, good looseness, difficult caking, low metal ion content, good thermal stability after preparing thinner, simple operation and high application value in industrial production.
Drawings
The invention is further illustrated in the following description with reference to the drawings.
FIG. 1 is a typical HPLC chromatogram of 1, 2-benzisothiazolin-3-one obtained by adding a complexing agent in example 1;
FIG. 2 is a typical HPLC chromatogram of 1, 2-benzisothiazolin-3-one obtained in example 1 without addition of a complexing agent, wherein the absorption peaks at retention times of 24.270min and 25.686min are absorption peaks of complexes formed by different coordination of 1, 2-benzisothiazolin-3-one and iron.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are not intended to limit the scope of the invention.
Example 1
Adding 180g of 1, 2-benzisothiazolin-3-one crude product (the liquid phase normalized purity is 97.6 percent), 200g of crude product and 20 percent caustic soda liquid into a four-mouth bottle with a mechanical stirrer and a thermometer, heating to 70-75 ℃ until the crude product and the 20 percent caustic soda liquid are completely dissolved, adding 2g of activated carbon, continuously stirring for 1 hour, then carrying out heat filtration, cooling the filtrate to 45-50 ℃, adding 31 percent hydrochloric acid containing 200ppm of ferric chloride to adjust the pH value to 8.0-8.5, adding 100mg of complexometric agent disodium ethylenediamine tetraacetate, keeping the temperature and stirring for 0.5 hour, continuously adding 31 percent hydrochloric acid containing 200ppm of ferric chloride to adjust the pH value to 3.0-4.0, keeping the temperature and stirring for 0.5 hour, filtering, and eluting with deionized water to obtain 172g of bright white powdery 1, 2-benzisothiazolin-3-one with water content of 14.62 percent and liquid phase normalized purity of more than 99.5 percent, wherein the quality of the obtained product and the color number of the prepared 20 percent solution after thermal stability are as follows:
TABLE 1, 2-Benzisothiazolin-3-one product solutions Heat stability number and Metal content
As can be seen from FIGS. 1 and 2, the absorption peaks with retention times of 24.270min and 25.686min in the liquid chromatogram disappeared after the crude 1, 2-benzisothiazolin-3-one was purified by the method disclosed in this application. Therefore, the method disclosed by the application is used for purifying the 1, 2-benzisothiazolin-3-one, so that complex impurities formed by the benzisothiazolin-3-one and iron in different coordination modes can be effectively avoided, the product purity is further improved, and the product quality is ensured.
Example 2
Adding 180g of 1, 2-benzisothiazolin-3-one crude product (the liquid phase normalized purity is 97.6%) and 200g of 20% caustic soda liquid into a four-mouth bottle with a mechanical stirrer and a thermometer, heating to 70-75 ℃ until the crude product and the 20% caustic soda liquid are completely dissolved, adding 2g of activated carbon, continuously stirring for 1 hour, then carrying out heat filtration, cooling the filtrate to 45-50 ℃, adding 50mg of complexing agent ethylenediamine tetramethylene phosphonic acid, carrying out heat preservation stirring for 0.5 hour, adjusting the pH value to 3.0-4.0 by using 31% hydrochloric acid, carrying out heat preservation stirring for 0.5 hour, carrying out suction filtration, and carrying out deionized water leaching to obtain 174g of bright white powdery 1, 2-benzisothiazolin-3-one, containing 14.13% of water and the liquid phase normalized purity being more than 99.
Example 3
Adding 180g of 1, 2-benzisothiazolin-3-one crude product (the liquid phase normalized purity is 97.6%) and 200g of 20% caustic soda liquid into a four-mouth bottle with a mechanical stirrer and a thermometer, heating to 70-75 ℃ to be completely dissolved, adding 2g of activated carbon, continuously stirring for 1 hour, then carrying out heat filtration, cooling the filtrate to 45-50 ℃, adding 31% hydrochloric acid to adjust the pH value to 6.0-7.0, adding 200mg of complexing agent citric acid, stirring for 0.5 hour under heat preservation, continuously adding 31% hydrochloric acid to adjust the pH value to 3.0-4.0, stirring for 0.5 hour under heat preservation, carrying out suction filtration, and carrying out rinsing with deionized water to obtain 175g of bright white powdery 1, 2-benzisothiazolin-3-one, containing 15.18% of water and having the liquid phase normalized purity of more than 99.5%.
Example 4
Adding 180g of 1, 2-benzisothiazolin-3-one crude product (the liquid phase normalized purity is 97.6%) and 200g of 20% liquid alkali into a four-mouth bottle with a mechanical stirrer and a thermometer, heating to 70-75 ℃ to be completely dissolved, adding 2g of activated carbon, continuously stirring for 1 hour, then carrying out heat filtration, cooling the filtrate to 45-50 ℃, adding 100mg of complexing agent sodium aminotriacetate and hydroxyethylidene diphosphonic acid respectively, carrying out heat preservation stirring for 0.5 hour, adjusting the pH value to 3.0-4.0 by using 31% hydrochloric acid, carrying out heat preservation stirring for 0.5 hour, carrying out suction filtration and deionized water leaching to obtain 170g of bright white powdery 1, 2-benzisothiazolin-3-one, containing 14.56% of water and having the liquid phase normalized purity of more than 99.5%.
Example 5
Adding 180g of 1, 2-benzisothiazolin-3-one crude product (with liquid phase normalized purity of 97.6%) and 200g of 20% caustic soda liquid into a four-necked bottle with a mechanical stirrer and a thermometer, heating to 70-75 ℃ until the crude product and the 20% caustic soda liquid are completely dissolved, adding 2g of activated carbon, continuously stirring for 1 hour, then carrying out heat filtration, cooling the filtrate to 45-50 ℃, adding 31% hydrochloric acid to adjust the pH value to be 8.5-9.0, adding 100mg of complexing agent disodium ethylenediamine tetraacetic acid, 50mg of oxalic acid and 100mg of sodium diethylenetriamine pentamethylenephosphonate, carrying out heat preservation stirring for 0.5 hour, continuously adding 31% hydrochloric acid to adjust the pH value to be 3.0-4.0, carrying out heat preservation stirring for 0.5 hour, carrying out suction filtration and carrying out deionized water leaching to obtain 168g of bright white powdery 1, 2-benzisothiazolin-3-one, wherein the water content is 14.16.
The present invention is not limited to the above-described embodiments, and the above-described examples and descriptions are only illustrative of the principle of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the present invention, which fall within the scope of the claimed invention.
Claims (10)
1. A method for purifying 1, 2-benzisothiazolin-3-one, comprising the steps of:
1) mixing the crude product of the 1, 2-benzisothiazolin-3-one with liquid alkali, heating, keeping the temperature and stirring to prepare a sodium salt solution of the 1, 2-benzisothiazolin-3-one;
2) adding active carbon for decoloring and filtering;
3) adding hydrochloric acid into the decolored and filtered alkali solution for acidification, and adding a complexing agent in the acidification process;
4) and (3) carrying out solid-liquid separation on the solid-liquid mixture obtained after acidification, leaching the obtained solid with deionized water, and carrying out suction filtration after leaching to obtain the finished product of the 1, 2-benzisothiazolin-3-one.
2. The method of purifying 1, 2-benzisothiazolin-3-one according to claim 1, characterized in that: the temperature of the heat preservation stirring in the step 1) is 70-75 ℃.
3. The method of purifying 1, 2-benzisothiazolin-3-one according to claim 1, characterized in that: the temperature of solid-liquid separation in the step 3) is 45-50 ℃.
4. The method of purifying 1, 2-benzisothiazolin-3-one according to claim 1, characterized in that: the pH value of acidification in the step 3) is 3-14.
5. The method of purifying 1, 2-benzisothiazolin-3-one according to claim 4, characterized in that: the pH value of acidification in the step 3) is 6-9.
6. The method of purifying 1, 2-benzisothiazolin-3-one according to claim 1, characterized in that: in the step 3), the complexing agent is one or more of nitrilotriacetic acid and sodium salt thereof, ethylene diamine tetraacetic acid and sodium salt thereof, ethylene glycol diethyl ether diamine tetraacetic acid and sodium salt thereof, cyclohexanediamine tetraacetic acid and sodium salt thereof, diethylenetriamine pentaacetic acid and sodium salt thereof, hydroxyethyl ethylenediamine triacetic acid and sodium salt thereof, ethylene diamine tetramethylene phosphonic acid and sodium salt thereof, diethylenetriamine pentamethylene phosphonic acid and sodium salt thereof, aminotrimethylene phosphonic acid and sodium salt thereof, hydroxyethylene diphosphonic acid and sodium salt thereof, oxalic acid and sodium salt thereof, tartaric acid and sodium salt thereof, and citric acid and sodium salt thereof.
7. The method of purifying 1, 2-benzisothiazolin-3-one according to claim 1, characterized in that: the addition amount of the complexing agent in the step 3) is 0.005-0.5 percent of the weight of the 1, 2-benzisothiazolin-3-one sodium salt solution.
8. The method of purifying 1, 2-benzisothiazolin-3-one according to claim 7, characterized in that: in the step 3), the addition amount of the complexing agent is 0.01-0.1% of the weight of the 1, 2-benzisothiazolin-3-one sodium salt solution.
9. The method of purifying 1, 2-benzisothiazolin-3-one according to claim 1, characterized in that: adding a complexing agent in the step 3), and then keeping the temperature and stirring for 0.5 hour.
10. The method of purifying 1, 2-benzisothiazolin-3-one according to claim 1, characterized in that: the water content of the finished product 1, 2-benzisothiazolin-3-one in the step 4) is 14-16%.
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