CN116987016B - Preparation method of high-purity high-stability lithium p-styrenesulfonate - Google Patents
Preparation method of high-purity high-stability lithium p-styrenesulfonate Download PDFInfo
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- YSKIQSYEHUCIFO-UHFFFAOYSA-M lithium;4-ethenylbenzenesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 YSKIQSYEHUCIFO-UHFFFAOYSA-M 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- TXGHAMMMKDELEQ-UHFFFAOYSA-L zinc 4-ethenylbenzenesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1.[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 TXGHAMMMKDELEQ-UHFFFAOYSA-L 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 12
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 claims abstract description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- 239000000243 solution Substances 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 20
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- WMPPDTMATNBGJN-UHFFFAOYSA-N 2-phenylethylbromide Chemical compound BrCCC1=CC=CC=C1 WMPPDTMATNBGJN-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- XRPCDXSRXPQUKT-UHFFFAOYSA-N 4-(2-bromoethyl)benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(CCBr)C=C1 XRPCDXSRXPQUKT-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 8
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 235000010288 sodium nitrite Nutrition 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- BHDBHKZESTYDAA-UHFFFAOYSA-N C(=C)OS(=O)(=O)C1=CC=CC=C1.[Li] Chemical compound C(=C)OS(=O)(=O)C1=CC=CC=C1.[Li] BHDBHKZESTYDAA-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000012047 saturated solution Substances 0.000 claims description 2
- CIBGZAYGXFGOFK-UHFFFAOYSA-L zinc;2-phenylethenesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C=CC1=CC=CC=C1.[O-]S(=O)(=O)C=CC1=CC=CC=C1 CIBGZAYGXFGOFK-UHFFFAOYSA-L 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 4
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 4
- 159000000002 lithium salts Chemical class 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 3
- SFYFPKNICQXSFE-UHFFFAOYSA-M lithium;4-ethylbenzenesulfonate Chemical compound [Li+].CCC1=CC=C(S([O-])(=O)=O)C=C1 SFYFPKNICQXSFE-UHFFFAOYSA-M 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000011780 sodium chloride Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 239000000203 mixture Substances 0.000 description 5
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 3
- BRIXOPDYGQCZFO-UHFFFAOYSA-N 4-ethylphenylsulfonic acid Chemical compound CCC1=CC=C(S(O)(=O)=O)C=C1 BRIXOPDYGQCZFO-UHFFFAOYSA-N 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- CBSIEJGODQIOKA-UHFFFAOYSA-N 2-bromoethyl benzenesulfonate Chemical compound BrCCOS(=O)(=O)C1=CC=CC=C1 CBSIEJGODQIOKA-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of high-purity high-stability lithium p-styrenesulfonate, which belongs to the field of chemical preparation, and can improve the dry content of the lithium p-styrenesulfonate to more than 98% and reduce the content of lithium salt to less than 0.5%. Firstly, the invention utilizes the characteristic that zinc p-styrenesulfonate is indissolvable in water, a large amount of water can be used for washing after synthesis, sodium chloride is fully washed, when lithium p-styrenesulfonate is synthesized, because zinc p-styrenesulfonate is indissolvable in water, excessive zinc p-styrenesulfonate is used for reacting with lithium carbonate, and after the lithium carbonate is completely reacted, the excessive zinc p-styrenesulfonate is filtered and recovered, and the inorganic salt content in the product is extremely low. Secondly, the problem that lithium p-ethylbenzenesulfonate is easy to polymerize in the concentration process is solved by adding seed crystals, and the purpose of long-term storage stability is achieved by adopting unconventional pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] as a polymerization inhibitor.
Description
Technical Field
The invention relates to a preparation method of chemicals, in particular to a preparation method of high-purity high-stability lithium p-styrenesulfonate.
Background
The current preparation of lithium p-styrenesulfonate adopts the following steps: the p-vinyl benzene sulfonic acid is synthesized by the reaction of beta-halogen ethyl benzene sulfonic acid and sodium hydroxide aqueous solution, then p-ethyl benzene sulfonic acid is prepared by acidification, and finally p-ethyl benzene sulfonic acid and lithium hydroxide are reacted to prepare the lithium p-styrene sulfonate.
However, the lithium p-styrenesulfonate prepared by the method has the following problems: firstly, the product content is 93-95% of the dry content, and the product content is low. Secondly, sodium bromide and sodium p-vinylbenzene sulfonate generated when beta-bromoethyl benzene sulfonate reacts with sodium hydroxide water are easy to dissolve in water, are simultaneously separated out when the temperature is reduced and crystallized, are not easy to separate, and when p-styrenesulfonic acid reacts with lithium hydroxide, the p-styrenesulfonic acid contains inorganic acid and reacts with lithium hydroxide to generate lithium salt (the general content is about 3.5 percent), so that the product content is influenced. In addition, when lithium products are produced, vacuum concentration is needed, the production cost is high, polymerization phenomenon can be generated in the concentration process, and the product quality is reduced. Finally, the produced sodium p-vinylbenzenesulfonate is also easy to polymerize in the storage process, and the existing polymerization inhibitor has poor effect.
Disclosure of Invention
In view of the above-mentioned series of problems, the present invention provides a novel method for producing lithium p-styrenesulfonate, which can raise the dry content of lithium p-styrenesulfonate to 98% or more and lower the content of lithium salt to 0.5% or less.
The invention provides a preparation method of a high-purity high-stability lithium p-styrenesulfonate product, which comprises the following steps of:
firstly, preparing p-bromoethyl benzene sulfonic acid by sulfonating beta-bromobenzene ethane with sulfur trioxide;
secondly, neutralizing and eliminating a p-bromoethyl benzene sulfonic acid solution and a sodium hydroxide solution to prepare sodium p-vinylbenzene sulfonate;
thirdly, reacting the sodium p-vinylbenzenesulfonate solution with zinc chloride to prepare zinc p-styrenesulfonate;
and fourthly, adding zinc p-styrenesulfonate into water to react with lithium carbonate to prepare lithium p-styrenesulfonate.
Preferably, in the first step, adding glacial acetic acid and methylene dichloride into a reaction kettle, stirring and cooling to below 10 ℃, slowly dropwise adding sulfur trioxide, controlling the reaction temperature to be 10-18 ℃, controlling the temperature to be 10-20 ℃ after dropwise adding, carrying out heat preservation reaction for 1-3 hours, adding water to react to remove excessive sulfur trioxide, standing for layering, and separating sulfuric acid, wherein the addition amount of the glacial acetic acid, the methylene dichloride and the sulfur trioxide is 0.5-5 times of the mass of the beta-bromophenyl ethane, the mass of the beta-bromophenyl ethane is 2-5 times, and the molar ratio of the beta-bromophenyl ethane to the beta-bromophenyl ethane is 1:1.05- - -1.3.
Preferably, the sodium p-vinylbenzenesulfonate solution prepared in the second step is directly subjected to the third reaction without any operation of concentration, crystallization and centrifugation.
Preferably, in the second step, after the first sodium hydroxide solution is dropwise added, the temperature slowly rises, dichloromethane is distilled and recovered, and the second sodium hydroxide solution is continuously dropwise added, the temperature is controlled between 95 ℃ and 105 ℃, wherein the adding amount ratio of the first sodium hydroxide to the second sodium hydroxide is 1:1-2, the molar ratio of the total sodium hydroxide added to the beta-bromophenylethane added in the first step is 1:1-1.6.
Preferably, the molar ratio of the added amount of zinc chloride in the third step to the beta-bromophenyl ethane added in the first step is 1 to 1.1:1, adding water into the prepared zinc p-styrenesulfonate to wash and remove residual inorganic salts in the materials, thereby obtaining a zinc p-styrenesulfonate intermediate with the dry purity of more than 99 percent.
Preferably, the molar ratio of zinc p-styrenesulfonate to lithium carbonate in the fourth step is 1:1-1.05; the concentration of the lithium p-styrenesulfonate aqueous solution prepared in the fourth step is 40wt%, and the concentration is the saturated solution concentration of the lithium p-styrenesulfonate at normal temperature.
Preferably, in the second step, sodium nitrite as a polymerization inhibitor is added into the p-bromoethyl benzene sulfonic acid solution before the p-bromoethyl benzene sulfonic acid solution reacts with sodium hydroxide, wherein the addition amount of the polymerization inhibitor and the mass percentage of beta-bromoethyl benzene are 0.1-0.5%.
Preferably, after the fourth step, there is also: fifthly, adding lithium p-styrenesulfonate crystals into the solution of the lithium p-styrenesulfonate prepared in the fourth step, wherein the addition amount of the lithium p-styrenesulfonate crystals is 25-35% of the mass of the solution of the lithium p-styrenesulfonate, the crystallization temperature is 2-10 ℃, and the crystallization time is 1-5 hours; the water content of the lithium p-styrenesulfonate prepared by high-speed centrifugation of the crystallized lithium p-styrenesulfonate for 1-3 hours is 5-12wt%.
Preferably, the lithium p-styrenesulfonate product comprises lithium vinylbenzenesulfonate and pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] serving as a polymerization inhibitor, wherein the pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] is prepared in the fourth step and then is fully mixed with the lithium p-styrenesulfonate through crushing, and the mixing mass ratio of the pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] serving as the polymerization inhibitor to the lithium p-styrenesulfonate is 0.001-0.1:1.
preferably, the lithium carbonate content in the prepared lithium p-styrenesulfonate is less than 0.5 weight percent, and the sodium bromide content is less than 0.1 weight percent.
Compared with the prior art, the invention provides a novel preparation method of lithium p-styrenesulfonate, which can increase the dry content of the lithium p-styrenesulfonate to more than 98 percent and reduce the content of lithium salt to less than 0.5 percent. Firstly, the invention utilizes the characteristic that zinc p-styrenesulfonate is indissolvable in water, a large amount of water can be used for washing after synthesis, sodium chloride is fully washed, when lithium p-styrenesulfonate is synthesized, because zinc p-styrenesulfonate is indissolvable in water, excessive zinc p-styrenesulfonate is used for reacting with lithium carbonate, and after the lithium carbonate is completely reacted, the excessive zinc p-styrenesulfonate is filtered and recovered, and the inorganic salt content in the product is extremely low. Secondly, the invention solves the problem that lithium p-ethyl benzene sulfonate is easy to polymerize in the concentration process by adding seed crystals. In addition, the invention adopts unconventional pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] as a polymerization inhibitor, thereby achieving the purpose of long-term storage stability.
Detailed Description
Example 1: the lithium p-styrenesulfonate of this example was prepared by the following steps:
sulfonation: beta-bromophenylethane (content) 37.37Kg, glacial acetic acid 0.5Kg and 180Kg of dichloromethane are added into a 300 liter glass lining reaction kettle, 17.6Kg of sulfur trioxide is slowly added dropwise under stirring and temperature reduction below 10 ℃, the dropwise adding time is controlled to be about 3 hours, and the reaction temperature is controlled to be below 15 ℃. After the dripping is finished, controlling the temperature to be 10-20 ℃, and preserving the heat for 2 hours. Adding water to react excessive sulfur trioxide, standing for layering, and separating sulfuric acid to obtain a p-bromoethyl benzene sulfonic acid solution.
Hydrolysis: the p-bromoethyl benzene sulfonic acid solution is added into a 300 liter reaction kettle, 74.5g of sodium nitrite is added, sodium hydroxide solution with 40 percent of the total mass of sodium hydroxide is dropwise added under stirring (sodium hydroxide is dropwise added for the first time), the temperature is slowly increased during the dropwise adding process, and methylene dichloride is distilled off and recovered. After the solvent is distilled out, the temperature is controlled between 95 ℃ and 105 ℃, the rest sodium hydroxide solution is continuously dripped (sodium hydroxide is dripped for the second time), the temperature is controlled between 95 ℃ and 105 ℃, 8kg of sodium hydroxide is added, the mixture is dripped to weak alkalinity, and the reaction is continuously carried out for 0.5 to 1 hour under the heat preservation.
Salt formation: cooling, adding 60kg of zinc chloride solution (48 wt%) and stirring at normal temperature to make reaction for 3 hr, filtering, adding 50kg of water into filter cake to make washing twice, fully washing to remove inorganic salt in the material so as to obtain the invented zinc p-styrenesulfonate intermediate product with a dry purity of 99.6%.
Conversion: 19kg of washed zinc p-styrenesulfonate is added into a 100 liter reaction kettle, 50kg of water is added, the mixture is stirred uniformly, 6kg of lithium carbonate is added, the mixture is stirred at normal temperature for reaction for 4 hours, and the mixture is filtered. The filtrate was weighed 75.1kg and tested for lithium p-styrenesulfonate content: 38.8wt% and a yield of 76.67%. The filter cake is washed by adding 50kg of water and is used as the water for the next batch of reaction.
And (3) crystallization: 42 kg of lithium p-styrenesulfonate solution is added into a 100 liter glass reaction kettle, stirred and cooled to about 5 ℃, 12.4 kg of lithium p-styrenesulfonate crystal is added, and stirred and crystallized for 3 hours. Centrifuging, centrifuging at a high speed for 1.5 hours, weighing the materials, wherein the total weight of the materials is 40.8kg, the detected moisture is 10.5%, the dry content is 98.87%, and the lithium carbonate content is as follows: 0.11wt% sodium bromide content: 0.05wt% yield of finished product: 64.99%. 26.7kg of mother liquor was recovered, and the content of lithium p-styrenesulfonate was 18.99wt%. And recycling mother liquor. The total yield was 76.59%.
Example 2: polymerization inhibitor experiment:
5 batches of lithium p-styrenesulfonate products (content 98.87%) are weighed, 100g of each batch are added with 0.2g of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (number 01), hydroquinone (number 02), tert-butylcatechol (number 03), diethylhydroxylamine (number 04), p-hydroxyanisole (number 05) and sodium nitrite (number 06) respectively, and the mixture is added into a pulverizer to be pulverized uniformly. Sealing, and storing in a constant temperature drying oven at 40 ℃. Samples were taken every 5 days for testing and the results are shown in table 1.
TABLE 1 polymerization inhibiting effect of different polymerization inhibitors
As can be seen from Table 1, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] was used as a polymerization inhibitor, and the dry matter content after 20 days of storage was still above 98%.
The foregoing is merely exemplary embodiments of the present invention and is not intended to limit the scope of the invention, which is defined by the appended claims.
Claims (10)
1. The preparation method of the high-purity high-stability lithium p-styrenesulfonate product is characterized by comprising the following steps of:
firstly, preparing p-bromoethyl benzene sulfonic acid by sulfonating beta-bromobenzene ethane with sulfur trioxide;
secondly, neutralizing and eliminating a p-bromoethyl benzene sulfonic acid solution and a sodium hydroxide solution to prepare sodium p-vinylbenzene sulfonate;
thirdly, reacting the sodium p-vinylbenzenesulfonate solution with zinc chloride to prepare zinc p-styrenesulfonate;
and fourthly, adding zinc p-styrenesulfonate into water to react with lithium carbonate to prepare lithium p-styrenesulfonate.
2. The method of manufacturing according to claim 1, characterized in that: adding the beta-bromophenyl ethane into a reaction kettle, continuously adding glacial acetic acid and dichloromethane, stirring and cooling to below 10 ℃, slowly dropwise adding sulfur trioxide, controlling the reaction temperature to be 10-18 ℃, controlling the temperature to be 10-20 ℃ after dropwise adding, carrying out heat preservation reaction for 1-3 hours, adding water to react to remove excessive sulfur trioxide, standing for layering, and separating sulfuric acid, wherein the addition amount of the glacial acetic acid, the dichloromethane and the sulfur trioxide is 0.5-5 times of the mass of the beta-bromophenyl ethane, 2-5 times of the mass of the beta-bromophenyl ethane, and the molar ratio of the beta-bromophenyl ethane to the beta-bromophenyl ethane is 1:1.05-1.3.
3. The method of manufacturing according to claim 1, characterized in that: the sodium p-vinylbenzenesulfonate solution prepared in the second step is directly subjected to the third step reaction without any operation of concentration, crystallization and centrifugation.
4. The preparation method according to claim 2, characterized in that: in the second step, after the first sodium hydroxide solution is dropwise added, the temperature slowly rises, methylene dichloride is distilled out and recovered, and the second sodium hydroxide solution is continuously dropwise added, the temperature is controlled between 95 ℃ and 105 ℃, wherein the adding amount ratio of the first sodium hydroxide to the second sodium hydroxide is 1:1-2, the molar ratio of the total sodium hydroxide added to the beta-bromophenylethane added in the first step is 1:1-1.6.
5. The method of manufacturing according to claim 1, characterized in that: the molar ratio of the added amount of zinc chloride in the third step to the beta-bromophenylethane added in the first step is 1-1.1:1, adding water into the prepared zinc p-styrenesulfonate to wash and remove residual inorganic salts in the materials, thereby obtaining a zinc p-styrenesulfonate intermediate with the dry purity of more than 99 percent.
6. The method of manufacturing according to claim 1, characterized in that: in the fourth step, the molar ratio of the zinc styrene sulfonate to the lithium carbonate is 1:1-1.05; the concentration of the lithium p-styrenesulfonate aqueous solution prepared in the fourth step is 40wt%, and the concentration is the saturated solution concentration of the lithium p-styrenesulfonate at normal temperature.
7. The method of manufacturing according to claim 1, characterized in that: and in the second step, adding a polymerization inhibitor sodium nitrite into the p-bromoethyl benzene sulfonic acid solution before reacting with sodium hydroxide, wherein the addition amount of the polymerization inhibitor and the mass percentage of beta-bromoethyl benzene are 0.1-0.5%.
8. The method of manufacturing according to claim 1, characterized in that: after the fourth step, the method further comprises: fifthly, adding lithium p-styrenesulfonate crystals into the solution of the lithium p-styrenesulfonate prepared in the fourth step, wherein the addition amount of the lithium p-styrenesulfonate crystals is 25-35% of the mass of the solution of the lithium p-styrenesulfonate, the crystallization temperature is 2-10 ℃, and the crystallization time is 1-5 hours; and (3) centrifuging the crystallized lithium p-styrenesulfonate at a high speed for 1-3 hours to obtain the lithium p-styrenesulfonate with the water content of 5-12wt%.
9. The preparation method according to claim 1, wherein the lithium p-styrenesulfonate product comprises lithium vinylbenzenesulfonate and pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] serving as a polymerization inhibitor, wherein the pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] serving as the polymerization inhibitor is prepared in the fourth step, and the lithium p-styrenesulfonate product and the lithium p-styrenesulfonate are fully mixed by crushing, and the mixing mass ratio of the pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] serving as the polymerization inhibitor to the lithium p-styrenesulfonate is 0.001-0.1:1.
10. the method of manufacturing according to claim 1, characterized in that: the lithium carbonate content in the prepared lithium p-styrenesulfonate is less than 0.5 weight percent, and the sodium bromide content is less than 0.1 weight percent.
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