CN108675947B - Synthesis method of sodium allylsulfonate - Google Patents
Synthesis method of sodium allylsulfonate Download PDFInfo
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- CN108675947B CN108675947B CN201810705141.1A CN201810705141A CN108675947B CN 108675947 B CN108675947 B CN 108675947B CN 201810705141 A CN201810705141 A CN 201810705141A CN 108675947 B CN108675947 B CN 108675947B
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- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000001308 synthesis method Methods 0.000 title description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 58
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011780 sodium chloride Substances 0.000 claims abstract description 29
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims abstract description 24
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 23
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 23
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 229940101006 anhydrous sodium sulfite Drugs 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 18
- 239000006227 byproduct Substances 0.000 claims abstract description 16
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000003112 inhibitor Substances 0.000 claims abstract description 8
- 238000003408 phase transfer catalysis Methods 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 abstract description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 26
- 239000000047 product Substances 0.000 description 13
- 238000001291 vacuum drying Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920002972 Acrylic fiber Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229940001482 sodium sulfite Drugs 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 210000002268 wool Anatomy 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
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/14—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/22—Preparation in the form of granules, pieces, or other shaped products
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing sodium allylsulfonate, which takes anhydrous sodium sulfite and chloropropene as raw materials, takes polyethylene glycol and polyethylene glycol monomethyl ether as phase transfer agents, takes hydroquinone as a polymerization inhibitor, and adopts a liquid-solid three-system phase transfer catalysis principle to carry out sulfonation reaction synthesis. The invention adopts the phase transfer catalysis principle, and solves the problems that a large amount of water needs to be added when the anhydrous sodium sulfite is dissolved, the dropping time of the chloropropene is long, and the chloropropene and the anhydrous sodium sulfite are not easy to sulfonate; in the process of synthesizing the sodium allylsulfonate, the byproduct sodium chloride is recycled, purified and utilized, and the obtained byproduct sodium chloride can meet the requirement of industrial top grade.
Description
Technical Field
The invention relates to a method for synthesizing an alkene monomer, in particular to a method for synthesizing sodium allylsulfonate.
Background
Sodium allylsulfonate (Sodium allylsulfonate) of formula C3H5SO3Na, molecular weight 144.1. Sodium allylsulfonate is a white powdery crystal, very deliquescent, easily soluble in water, alcohol, insoluble in benzene. The aqueous solution is alkalescent and is easy to polymerize when heated for a long time. The dried product is stable to heat. Can be used as an artificial wool intermediate and widely applied to the industries of oil exploitation, water treatment, environmental protection and the like. If the acrylic fiber is used as a third monomer of the acrylic fiber, the dyeing property of the fiber can be improved, and the coloring is firm; the nickel plating brightener is used for electroplating nickel brightener to improve the metal distribution capability and ductility; used as water quality treating agent; use in oilfield drilling mud additives; it is used as building cement water reducing agent, early strength agent, etc.
As for the synthesis method of sodium allylsulfonate, the research of the prior art is rare, and a method for directly synthesizing sodium allylsulfonate by using allyl chloride and sodium sulfite is disclosed in journal of Natural industry of 5 th stage in 93 years, and the reaction is carried out under heterogeneous conditions, so that the reaction time is long, the reaction efficiency is low, the reaction is incomplete, and chloropropene is easy to polymerize. The product yield is too low to be suitable for industrial production. Chinese patent No. CN1085660C discloses a method for preparing sodium allylsulfonate monomer, which comprises adding a small amount of OP emulsifier into aqueous solution of sodium metabisulfite with a certain concentration, adding allyl chloride dropwise, controlling appropriate pH and temperature in a stirring and refluxing device, and reacting until no allyl chloride is refluxed. The reaction mixture is separated and purified to obtain the sodium allylsulfonate product with the purity of more than 98 percent. Although the method has the advantages of less equipment investment, short reaction time, low energy consumption, easy drying of products and low production cost, the OP emulsifier only plays a role in dispersing and dissolving the reaction, the reaction effect is poor, and the reaction yield is too low; and the OP emulsifier has cloud point and is not removed in the preparation process, so that a small amount of OP emulsifier is contained in the product, when the product is heated to a certain temperature, the cloud point changes turbid, the quality and the use of the product are influenced, and in the process of dropwise adding chloropropene and refluxing, chloropropene is easy to polymerize, and the reaction is influenced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a synthesis method of sodium allylsulfonate, which has the advantages of low production cost, safe operation, energy saving and environmental protection.
The purpose of the invention is realized by the following technical scheme: a process for synthesizing sodium allylsulfonate from anhydrous sodium sulfite and chloropropene, polyethylene glycol and polyethylene glycol monomethyl ether as phase transfer agent, hydroquinone as polymerization inhibitor, and liquid-solid three-system phase transfer catalysis.
Further, the reaction temperature of the sulfonation reaction is 55-65 ℃, the reaction time is 1.5-2.5 hours, and the pH value of the reaction solution is 7-9.
Further, the polyethylene glycol is polyethylene glycol 600.
Further, the weight ratio of the anhydrous sodium sulfite to the chloropropene is 1: 0.60-0.70. .
Further, the weight ratio of the polyethylene glycol, the polyethylene glycol monomethyl ether and the hydroquinone is 1: 1.1-1.5: 0.1 to 0.2.
Further, the method also comprises the steps of cooling, filtering, distilling and drying, and specifically comprises the following steps: cooling the solution after the sulfonation reaction to room temperature, carrying out suction filtration, wherein the obtained solid is a byproduct sodium chloride, and collecting the filtrate for later use; and distilling the filtrate under the conditions of-0.06 MPa of pressure and 30-98 ℃, cooling and crystallizing after distillation, and drying the obtained crystals in vacuum.
The method comprises the following steps of by-product purification: dissolving the byproduct sodium chloride in pure water, adding hydrogen peroxide, adjusting the pH value of the solution to 10 by using sodium hydroxide after reaction, standing for 1.5-2.5 h after stirring, filtering to remove impurities, adjusting the pH value of the solution to 6-7 by using hydrochloric acid, and evaporating, crystallizing and drying to obtain the industrial-grade sodium chloride.
Further, the vacuum drying conditions are as follows: the drying temperature is 75-85 ℃, the vacuum pressure is-0.06 MPa, and the drying time is 2.5-3.5 h.
The invention has the following advantages:
(1) the invention takes chloropropene and anhydrous sodium sulfite as raw materials, polyethylene glycol and polyethylene glycol monomethyl ether as phase transfer agents and hydroquinone as polymerization inhibitors, and adopts a method of adding chloropropene once to carry out liquid-solid three-phase transfer system reaction. The invention adopts the phase transfer catalysis principle, and solves the problems that a large amount of water needs to be added when the anhydrous sodium sulfite is dissolved, the dropping time of the chloropropene is long, and the chloropropene and the anhydrous sodium sulfite are not easy to sulfonate, so the method has the characteristics of less water addition, high reaction speed, simple reaction operation, high product yield and low cost;
(2) in the process of synthesizing sodium allylsulfonate, the byproduct sodium chloride is recycled, purified and utilized, and the obtained byproduct sodium chloride can meet the requirement of industrial high-grade;
(3) in the synthesis process, a trace amount of hydroquinone is added as a polymerization inhibitor, and the addition of the hydroquinone is favorable for preventing the polymerization of chloropropene and the self-polymerization of sodium allylsulfonate in the reaction process, so that the product quality of the sodium allylsulfonate product is obviously improved; the purity of the sodium allylsulfonate prepared by the method is more than 98.5%, and the yield is more than 95%.
(4) The synthesis method disclosed by the invention is low in production cost, safe to operate, simple in preparation method, energy-saving and environment-friendly, and is suitable for industrial large-scale production.
Detailed Description
The invention is further described below with reference to examples, without limiting the scope of the invention to the following:
example 1:
a process for synthesizing sodium allylsulfonate from anhydrous sodium sulfite and chloropropene, polyethylene glycol 600 and methoxypolyethylene glycol as phase transfer agent, hydroquinone as polymerization inhibitor, and liquid-solid three-system phase transfer catalysis. Wherein the weight ratio of the anhydrous sodium sulfite to the chloropropene is 1: 0.60; the weight ratio of the polyethylene glycol, the polyethylene glycol monomethyl ether and the hydroquinone is 1: 1.1: 0.1. the reaction temperature of the sulfonation reaction is 55 ℃, the reaction time is 1.5h, and the pH value of the reaction solution is 7.
Cooling the solution after the sulfonation reaction to room temperature, carrying out suction filtration, wherein the obtained solid is a byproduct sodium chloride, and collecting the filtrate for later use; dissolving the by-product sodium chloride in pure water, adding hydrogen peroxide, adjusting the pH value of the solution to 10 by using sodium hydroxide after reaction, standing for 1.5h after stirring, filtering to remove impurities, adjusting the pH value of the solution to 6 by using hydrochloric acid, and evaporating, crystallizing and drying to obtain industrial-grade sodium chloride;
distilling the filtrate, wherein the distillation conditions are-0.06 MPa and 30-98 ℃, cooling and crystallizing after distillation, and vacuum drying the obtained crystal, wherein the vacuum drying conditions are as follows: the drying temperature is 75 ℃, the vacuum pressure is-0.06 MPa, and the drying time is 2.5 h.
Example 2:
a process for synthesizing sodium allylsulfonate from anhydrous sodium sulfite and chloropropene, polyethylene glycol 600 and methoxypolyethylene glycol as phase transfer agent, hydroquinone as polymerization inhibitor, and liquid-solid three-system phase transfer catalysis. Wherein the weight ratio of the anhydrous sodium sulfite to the chloropropene is 1: 0.65; the weight ratio of the polyethylene glycol, the polyethylene glycol monomethyl ether and the hydroquinone is 1: 1.2: 0.12. the reaction temperature of the sulfonation reaction is 65 ℃, the reaction time is 2.5h, and the pH value of the reaction solution is 9.
Cooling the solution after the sulfonation reaction to room temperature, carrying out suction filtration, wherein the obtained solid is a byproduct sodium chloride, and collecting the filtrate for later use; dissolving the byproduct sodium chloride in pure water, adding hydrogen peroxide, adjusting the pH value of the solution to 10 by using sodium hydroxide after reaction, standing for 2.5h after stirring, filtering to remove impurities, adjusting the pH value of the solution to 7 by using hydrochloric acid, and evaporating, crystallizing and drying to obtain industrial-grade sodium chloride;
distilling the filtrate, wherein the distillation conditions are-0.06 MPa and 30-98 ℃, cooling and crystallizing after distillation, and vacuum drying the obtained crystal, wherein the vacuum drying conditions are as follows: the drying temperature is 85 ℃, the vacuum pressure is-0.06 MPa, and the drying time is 3.5 h.
Example 3:
a process for synthesizing sodium allylsulfonate from anhydrous sodium sulfite and chloropropene, polyethylene glycol 600 and methoxypolyethylene glycol as phase transfer agent, hydroquinone as polymerization inhibitor, and liquid-solid three-system phase transfer catalysis. Wherein the weight ratio of the anhydrous sodium sulfite to the chloropropene is 1: 0.7; the weight ratio of the polyethylene glycol, the polyethylene glycol monomethyl ether and the hydroquinone is 1: 1.5: 0.2. the reaction temperature of the sulfonation reaction is 60 ℃, the reaction time is 2 hours, and the pH value of the reaction solution is 8.
Cooling the solution after the sulfonation reaction to room temperature, carrying out suction filtration, wherein the obtained solid is a byproduct sodium chloride, and collecting the filtrate for later use; dissolving the byproduct sodium chloride in pure water, adding hydrogen peroxide, adjusting the pH value of the solution to 10 by using sodium hydroxide after reaction, standing for 2 hours after stirring, filtering to remove impurities, adjusting the pH value of the solution to 6.5 by using hydrochloric acid, and evaporating, crystallizing and drying to obtain industrial-grade sodium chloride;
distilling the filtrate, wherein the distillation conditions are-0.06 MPa and 30-98 ℃, cooling and crystallizing after distillation, and vacuum drying the obtained crystal, wherein the vacuum drying conditions are as follows: the drying temperature is 80 ℃, the vacuum pressure is-0.06 MPa, and the drying time is 3 h.
Experimental example 1: synthesis method of sodium allylsulfonate
160kg of anhydrous sodium sulfite was slowly added to a reactor to which 290kg of pure water was added with stirring. 0.8kg of polyethylene glycol 600 and 0.8kg of polyethylene glycol monomethyl ether, 0.09kg of hydroquinone and 96kg of chloropropene were added. Controlling the pH value of the reaction solution to be 7-9, keeping the reaction temperature to be 56-61 ℃, and reacting for 2 hours;
cooling the solution to room temperature, carrying out suction filtration to obtain 74kg of solid sodium chloride, and collecting filtrate;
dissolving 74kg of solid sodium chloride subjected to suction filtration in 250kg of pure water, adding 0.003% hydrogen peroxide, adjusting the pH value to 10 by using a sodium hydroxide solution after reaction, standing for 2 hours after stirring, filtering to remove impurities such as iron, calcium, magnesium and the like, adjusting the pH value to 6-7 by using hydrochloric acid, and evaporating, crystallizing and drying to obtain 72kg of industrial-grade sodium chloride;
distilling the filtrate under negative pressure of-0.06 MPa at 30-98 deg.C, distilling to remove 95kg of water, cooling for crystallization, vacuum drying at 80 deg.C under-0.06 MPa for 3 hr to obtain 178kg of product.
Experimental example 2: synthesis method of sodium allylsulfonate
160kg of anhydrous sodium sulfite was slowly added to a reactor to which 280kg of pure water was added with stirring. 0.7kg of polyethylene glycol 600 and 0.7kg of polyethylene glycol monomethyl ether, 0.08kg of hydroquinone and 102kg of chloropropene were added. Controlling the pH value of the reaction solution to be 7-9, keeping the reaction temperature to be 56-58 ℃ and the reaction time to be 1.6 hours;
cooling the solution to room temperature, performing suction filtration to obtain 73kg of solid sodium chloride, and collecting filtrate;
dissolving 73kg of solid sodium chloride subjected to suction filtration in 250kg of pure water, adding 0.002% of hydrogen peroxide, adjusting the pH value to 9.6 by using a sodium hydroxide solution after reaction, standing for 1.5 hours after stirring, filtering to remove impurities such as iron, calcium, magnesium and the like, adjusting the pH value to 6-7 by using hydrochloric acid, and obtaining 70kg of industrial-grade sodium chloride after evaporation, crystallization and drying;
distilling the filtrate under negative pressure of-0.06 MPa at 30-98 deg.C, distilling to remove water 100kg, cooling for crystallizing, vacuum drying at 80 deg.C under-0.06 MPa for 3 hr to obtain 176 kg.
Experimental example 3: synthesis method of sodium allylsulfonate
160kg of anhydrous sodium sulfite was slowly added to a reactor to which 300kg of pure water was added with stirring. 0.65kg of polyethylene glycol 600 and 0.65kg of polyethylene glycol monomethyl ether were added, 0.07kg of hydroquinone was added, and 109kg of chloropropene were added. Controlling the pH value of the reaction solution to be 7-9, keeping the reaction temperature to be 56-60 ℃, and reacting for 2.2 hours;
cooling the solution to room temperature, carrying out suction filtration to obtain 74kg of solid sodium chloride, and collecting filtrate;
dissolving 74kg of solid sodium chloride subjected to suction filtration in 250kg of pure water, adding 0.004% of hydrogen peroxide, adjusting the pH value to 11 by using a sodium hydroxide solution after reaction, standing for 2 hours after stirring, filtering to remove impurities such as iron, calcium, magnesium and the like, adjusting the pH value to 6-7 by using hydrochloric acid, and obtaining 71kg of industrial-grade sodium chloride after evaporation, crystallization and drying;
distilling the filtrate under negative pressure of-0.06 MPa at 30-98 deg.C, distilling to remove water 103kg, cooling for crystallizing, vacuum drying at 80 deg.C under-0.06 MPa for 3 hr to obtain 175 kg.
The following experiments illustrate the beneficial effects of the present invention:
the quality of the finished products prepared in experimental example 1, experimental example 2 and experimental example 3 of the present invention was measured, and the results are shown in table 1.
Table 1: the quality detection result of the sodium allylsulfonate product prepared by the method of the invention
| Detecting items | Experimental example 1 | Experimental example 2 | Experimental example 3 |
| Content (a) of | 99.0 | 99.2 | 99.1 |
| Chloride (in terms of NaCl)% | 0.3 | 0.2 | 0.2 |
| Sodium sulfite (Na)2SO3),％ | 0.1 | 0.1 | 0.1 |
| Iron (Fe)% | 0.00001 | 0.00002 | 0.00001 |
| Water content (H)2O),％ | 0.2 | 0.1 | 0.1 |
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution of the present invention and the inventive concept within the technical scope of the present invention.
Claims (1)
1. A synthetic method of sodium allylsulfonate is characterized in that anhydrous sodium sulfite and chloropropene are used as raw materials, polyethylene glycol and polyethylene glycol monomethyl ether are used as phase transfer agents, hydroquinone is used as a polymerization inhibitor, a liquid-solid three-system phase transfer catalysis principle is adopted to carry out sulfonation reaction synthesis, a solution after sulfonation reaction is cooled to room temperature for suction filtration, the obtained solid is a byproduct sodium chloride, and filtrate is collected for later use; distilling the filtrate under the conditions of-0.06 MPa of pressure and 30-98 ℃, cooling and crystallizing after distillation, and drying the obtained crystals in vacuum;
wherein the reaction temperature of the sulfonation reaction is 55-65 ℃, the reaction time is 1.5-2.5 h, and the pH value of the reaction solution is 7-9;
the polyethylene glycol is polyethylene glycol 600;
the weight ratio of the anhydrous sodium sulfite to the chloropropene is 1: 0.60-0.70;
the weight ratio of the polyethylene glycol, the polyethylene glycol monomethyl ether and the hydroquinone is 1: 1: 0.1 to 0.2;
the method also comprises a step of purifying the by-product, which comprises the following steps: dissolving the byproduct sodium chloride in pure water, adding hydrogen peroxide, adjusting the pH value of the solution to 10 by using sodium hydroxide after reaction, standing for 1.5-2.5 h after stirring, filtering to remove impurities, adjusting the pH value of the solution to 6-7 by using hydrochloric acid, and evaporating, crystallizing and drying to obtain the industrial-grade sodium chloride.
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Citations (7)
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