CN113816881B - Preparation method of rubber-plastic foaming accelerator zinc benzene sulfinate - Google Patents
Preparation method of rubber-plastic foaming accelerator zinc benzene sulfinate Download PDFInfo
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Abstract
The invention discloses a preparation method of zinc benzenesulfinate serving as a rubber and plastic foaming accelerant, which comprises the step of slowly adding benzenesulfonyl chloride into a mixed system of zinc powder, a phase transfer catalyst, an initiator and an organic solvent for reaction to obtain zinc benzenesulfinate ZBS. The method has the following advantages: (1) the process is simple and environment-friendly, and the only zinc chloride byproduct generated can be used as the raw material of other zinc thiocarbamate; (2) the reaction is completed in an inert organic solvent, so that the hydrolysis of benzene sulfonyl chloride is effectively avoided, and the product yield is high; (3) the generated zinc chloride has high solubility in water, is easier to wash by water than inorganic salt generated by the traditional process, and has better product quality; (4) the organic solvent is replaced by water in the post-reaction treatment stage, so that the problems of solvent recovery and safety are effectively avoided.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of zinc benzene sulfinate.
Background
Zinc Benzenesulfinate (ZBS) is a novel rubber plastic foaming accelerant. In the field of rubber and plastic heat insulation material processing, in order to make the heat insulation material porous and uniform, a foaming promoter, a foaming agent and other processing aids are required to be used in a matching way in the rubber and plastic heat insulation material processing process. The foaming accelerant Zinc Benzenesulfinate (ZBS) and Azodicarbonamide (AC) foaming agent are used together, so that the decomposition temperature can be greatly reduced, the processing process of the heat-insulating material can be optimized, the heat-insulating material is compact and porous, the pore size is uniform, and the heat-insulating performance of the product is greatly improved.
The production of zinc benzenesulfinate ZBS uses benzenesulfonyl chloride as a raw material, and there are mainly two preparation routes according to the difference of reducing agents. One is sodium sulfite as a reducing agent, and the other is zinc powder as a reducing agent.
CN 110652759A discloses a preparation method of zinc benzene sulfinate, which takes water as a medium and inorganic base as an acid-binding agent to cause benzene sulfonyl chloride and sodium sulfite to generate oxidation-reduction reaction; and adding a zinc chloride solution into the reaction liquid in the first step to perform double decomposition reaction to prepare the zinc benzenesulfinate. The method has a mature process, and has the main problems that about 1.5 tons of waste salt is produced in each ton of products, the waste salt is a mixture of sodium chloride and sodium sulfate, the waste salt belongs to solid hazardous waste, and the treatment difficulty and the cost are high.
CN 111100044B discloses a method for adding benzene sulfonyl chloride into a mixed system of sodium sulfite, zinc oxide and water to react to obtain benzene sulfinic acid zinc. Sodium sulfite is used as a reducing agent, zinc oxide is used as an acid-binding agent to neutralize acid generated in the reaction process, and is also used as a reactant to provide a zinc source for zinc benzenesulfinate, the generated solid waste salt is reduced, about 1.21 tons of mixed salt of zinc chloride and sodium sulfate is generated per ton of product, and the process does not have the result of avoiding generating a large amount of mixed salt.
Zinc chloride or zinc oxide is used as a zinc source, but as long as sodium sulfite is used as a reducing agent, a large amount of mixed salt is inevitably generated in the reaction mother liquor. The separation of chloride ions and sulfate ions is difficult and high in cost, so that the process has no market competitiveness. The national control on solid dangerous waste is more and more strict, and related processes cannot be approved by related national departments, so that the method belongs to the laggard process which is inevitably eliminated.
Another preparation method of the zinc benzenesulfinate is to directly reduce benzenesulfonyl chloride by using zinc powder to obtain the zinc benzenesulfinate and generate a byproduct zinc chloride. The mother liquor of the method only contains a byproduct of zinc chloride, and the three wastes are easy to treat. However, there are problems that (1) the difference in density between zinc powder and a solvent is large, and it is difficult to sufficiently mix the zinc powder and benzenesulfonyl chloride, which makes it difficult to carry out a reduction reaction. The process uses more zinc powder than the reaction quantity. Excessive zinc powder is difficult to separate from the product, and the quality of the product is affected. (2) The benzenesulfonyl chloride is easily hydrolyzed to generate benzenesulfonic acid as a byproduct, and the benzenesulfonic acid is also over-reduced to generate thiophenol, so that the yield is low. (3) The generated product zinc benzene sulfinate is separated out from the system and coated on the surface of the unreacted zinc powder, which hinders the complete reaction and seriously affects the product quality. Due to the problems, the process route for preparing the zinc benzenesulfinate by reducing the zinc powder does not realize industrial application.
Therefore, the zinc benzenesulfinate is prepared by directly reducing benzenesulfonyl chloride with zinc powder, the mixed salt is avoided, the problem of the method can be solved, and the process route for preparing the zinc benzenesulfinate by reducing the zinc powder is industrially applied and becomes the research and development purpose of the invention.
Disclosure of Invention
In order to solve various problems in the prior art, an environment-friendly, efficient and low-cost synthesis method is developed, a zinc powder reduction route is still used, the defects of the original zinc powder reduction process are overcome through a series of innovative means, namely benzenesulfonyl chloride is slowly added into a mixed system of zinc powder, an organic solvent, an initiator and a surfactant to react to obtain the zinc benzenesulfinate. The surfactant is added into the system, so that uniform mixing of the benzene sulfonyl chloride and the zinc powder can be promoted, the reaction efficiency is improved, the reduction of the benzene sulfonyl chloride can be completed by adopting the zinc powder with the reaction amount close to that in the system, and the zinc powder residue in the product caused by excessive zinc powder is effectively avoided. The inert solvent can prevent the generated ZBS from adhering to the surface of the zinc powder, so that the reaction is smoothly and completely carried out. In order to overcome the problem that the reduction reaction can not be smoothly carried out in an organic solvent, the invention screens out a proper initiator to enable the benzenesulfonyl chloride to be reduced by zinc powder in the organic solvent, thereby not only preventing ZBS precipitated in a system from being attached to the surface of the zinc powder, but also reducing the hydrolysis of benzenesulfonyl chloride and improving the reaction yield. After the reaction is finished, the zinc chloride and the product zinc benzenesulfinate are separated out from the system together, a proper amount of water is added into the system to dissolve the zinc chloride, then the organic solvent is recovered, the solvent can be recycled, and the zinc chloride can be used for synthesizing other products.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of Zinc Benzenesulfinate (ZBS) as a rubber and plastic foaming promoter comprises the following steps:
s1, sequentially adding an organic solvent, zinc powder, a surfactant and an initiator into a reaction kettle, and stirring and mixing;
s2, slowly adding benzenesulfonyl chloride into the suspension obtained in the step S1 for reaction, and after the dripping is finished, keeping the temperature and reacting for about 2 hours;
s3, after the reaction is finished, adding a proper amount of water, and fully stirring to dissolve zinc chloride in the system in the water; slowly raising the temperature and recovering the organic solvent in the system.
And S4, cooling, filtering, washing and drying to obtain the product zinc benzene sulfinate.
The molar ratio of the benzenesulfonyl chloride to the zinc powder to the surfactant to the initiator is 1.0-0.95-1.0; preferably, the molar ratio of the benzenesulfonyl chloride to the zinc powder to the surfactant to the initiator is 1.0;
the used commercial zinc powder has the mesh number of 80 meshes, 120 meshes, 200 meshes, 300 meshes, 400 meshes, 600 meshes and 800 meshes; preferably, the commercial zinc powder used has a mesh size of 400 mesh, 600 mesh;
the used surfactants are triethyl benzyl ammonium chloride, tetrabutyl ammonium bromide, hexadecyl ammonium bromide, OP-10 and Tween-20; preferably, the surfactant used is cetyl ammonium bromide;
the reaction initiator is hydrochloric acid solution, sulfuric acid, acetic acid and zinc chloride solution; preferably, the reaction initiator used is an aqueous solution of zinc chloride;
the organic solvent is toluene, chloroform, dichloroethane or dichloromethane; preferably, the organic solvent used is dichloromethane;
in the step S2, the dripping temperature of the selected benzenesulfonyl chloride is 20-55 ℃, and the dripping time is 1.5-3 h; more preferably, the dripping temperature of the benzene sulfonyl chloride is 30-35 ℃, and the dripping time is 1.5-2.0 h.
Preferably, in the step S5, the selected temperature reduction is that the temperature of the reaction system is reduced to 15-50 ℃ after the reaction is finished; more preferably, the temperature is reduced to 20-30 ℃ after the reaction is finished.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the process is simple and environment-friendly, and the only zinc chloride byproduct generated can be used as the raw material of other zinc thiocarbamate; the reaction is finished in an inert organic solvent, so that the hydrolysis of benzene sulfonyl chloride is effectively avoided, and the product yield is high; the generated zinc chloride has high solubility in water, is easier to wash by water than inorganic salt generated by the traditional process, and has better product quality; the organic solvent is replaced by water in the post-reaction treatment stage, so that the problems of solvent recovery and safety are effectively avoided. Specifically, the method comprises the following steps:
1. the surfactant is added into the system, so that uniform mixing of the benzene sulfonyl chloride and the zinc powder can be promoted, the reaction efficiency is improved, the reduction of the benzene sulfonyl chloride can be completed by adopting the zinc powder with the reaction amount close to that in the system, and the zinc powder residue in the product caused by excessive zinc powder is effectively avoided.
2. The inert solvent can prevent the generated ZBS from adhering to the surface of the zinc powder, so that the reaction is smoothly and completely carried out.
3. The appropriate initiator is adopted to ensure that the benzenesulfonyl chloride is reduced by using zinc powder in an organic solvent, so that ZBS precipitated in the system is prevented from being attached to the surface of the zinc powder, the hydrolysis of benzenesulfonyl chloride is reduced, and the reaction yield is improved.
After the reaction is finished, the zinc chloride and the product zinc benzenesulfinate are separated out from the system together, a proper amount of water is added into the system to dissolve the zinc chloride, and then the organic solvent is recovered, the solvent can be recycled, the zinc chloride can be used for synthesizing other products, the three wastes are reduced, and the resource utilization rate is improved.
Detailed Description
The zinc powder used in the examples of the present invention was a commercially available zinc powder having a mesh size of 400.
Example 1
120mL of methylene chloride, 15.12g of zinc powder, 0.2g of hexadecylammonium bromide, 0.2g of zinc chloride and 20mL of water were sequentially added to a 500mL flask at normal temperature, and stirring was started. Slowly adding 40g of benzene sulfonyl chloride into the system at the temperature of between 30 and 35 ℃, and preserving the temperature for about 2 hours after the addition is finished. 120ml of water is added, and the temperature is raised to 41 to 55 ℃ to recover the dichloromethane. Cooling to 25-30 ℃, filtering, washing and drying to obtain the benzene sulfinic acid zinc white solid with the yield of 98.2 percent and the purity of 96.5 percent.
Comparative example 2
120mL of water, 15.12g of zinc powder, 0.2g of hexadecylammonium bromide and 0.2g of zinc chloride were sequentially added to a 500mL flask at normal temperature, and stirring was started. Slowly adding 40g of benzene sulfonyl chloride into the system at the temperature of between 30 and 35 ℃, and preserving the temperature for about 2 hours after the addition is finished. Cooling to 25-30 ℃, filtering, washing and drying to obtain the zinc benzenesulfinate gray solid with the yield of 78.5% and the purity of 73.2%.
Example 3
120mL of toluene, 15.12g of zinc powder, 0.2g of hexadecylammonium bromide, 0.2g of zinc chloride and 20mL of water were sequentially added to a 500mL flask at normal temperature, and stirring was started. Slowly adding 40g of benzene sulfonyl chloride into the system at the temperature of between 30 and 35 ℃, and preserving the temperature for about 2 hours after the addition is finished. 120g of water is added, and the temperature is raised to 41 to 55 ℃ to recover the dichloromethane. Cooling to 25-30 ℃, filtering, washing and drying to obtain the zinc benzene sulfinate white solid with the yield of 95.4 percent and the purity of 94.5 percent.
Example 4
120mL of methylene chloride, 15.12g of zinc powder, 0.2g of hexadecylammonium bromide, 0.2g of concentrated hydrochloric acid and 20mL of water were sequentially added to a 500mL flask at normal temperature, and stirring was started. Slowly adding 40g of benzene sulfonyl chloride into the system at the temperature of between 30 and 35 ℃, and preserving the temperature for about 2 hours after the addition is finished. 120g of water is added, and the temperature is raised to 41 to 55 ℃ to recover the dichloromethane. Cooling to 25-30 ℃, filtering, washing and drying to obtain the zinc benzene sulfinate white solid with the yield of 96.5 percent and the purity of 95.6 percent.
Comparative example 5
120mL of methylene chloride, 15.12g of zinc powder, 0.2g of hexadecylammonium bromide and 20mL of water were sequentially added to a 500mL flask at normal temperature, and stirring was started. Slowly adding 40g of benzene sulfonyl chloride into the system at the temperature of between 30 and 35 ℃, and preserving the temperature for about 2 hours after the addition is finished. The zinc powder settled to the bottom of the flask and agglomerated into a mass, and the reaction did not proceed.
Comparative example 6
120mL of methylene chloride, 15.12g of zinc powder, 0.2g of zinc chloride and 20mL of water were sequentially added to a 500mL flask at room temperature, and stirring was started. Slowly adding 40g of benzene sulfonyl chloride into the system at the temperature of between 30 and 35 ℃, and preserving the temperature for about 2 hours after the addition is finished. Adding 120g of water, heating to 41-55 ℃, recovering dichloromethane, ensuring that the product is not uniformly dispersed in a system, is extremely easy to explode and boil, and leaving a small amount of zinc powder particles at the bottom. Cooling to 25-30 ℃, carrying out suction filtration and washing, picking out a small amount of zinc particles, and drying to obtain the white zinc benzene sulfinate solid with the yield of 88% and the purity of 92.6%.
Example 7
120mL of methylene chloride, 15.12g of zinc powder, 0.2g of benzyltriethylammonium chloride, 0.2g of zinc chloride and 20mL of water were sequentially added to a 500mL flask at room temperature, and stirring was started. Slowly adding 40g of benzene sulfonyl chloride into the system at the temperature of between 30 and 35 ℃, and preserving the temperature for about 2 hours after the addition is finished. 120g of water is added, and the temperature is raised to 41 to 55 ℃ to recover dichloromethane. Cooling to 25-30 ℃, filtering, washing and drying to obtain the zinc benzene sulfinate white solid with the yield of 97.5 percent and the purity of 95.6 percent.
Example 8
360mL of methylene chloride, 45.3g of zinc powder, 0.5g of hexadecylammonium bromide, 0.5g of zinc chloride and 60mL of water are sequentially added into a 1000mL flask at normal temperature, and stirring is started. At 30-35 ℃, 120g of benzene sulfonyl chloride is slowly added into the system, and after the addition, the temperature is kept for about 2h. 360ml of water is added, and the temperature is raised to 41 to 55 ℃ to recover the dichloromethane. Cooling to 25-30 ℃, filtering, washing and drying to obtain the benzene sulfinic acid zinc white solid with the yield of 98.8 percent and the purity of 96.7 percent.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention will still fall within the protection scope of the technical solution of the present invention.
Claims (12)
1. The preparation method of zinc benzenesulfinate is characterized by comprising the following steps of:
s1, sequentially adding an organic solvent, zinc powder, a surfactant and an initiator into a reaction kettle, and stirring and mixing;
s2, slowly adding benzenesulfonyl chloride into the suspension obtained in the step S1 for reaction, and after the dripping is finished, carrying out heat preservation reaction for 2 hours;
s3, after the reaction is finished, adding a proper amount of water, fully stirring to dissolve zinc chloride in the system into the water, slowly heating, and recovering the organic solvent in the system;
s4, cooling, filtering, washing and drying to obtain a product zinc benzene sulfinate;
the initiator is a zinc chloride solution; the organic solvent is toluene or dichloromethane, the surfactant is one or more of triethylbenzylammonium chloride, tetrabutylammonium bromide, hexadecylammonium bromide, OP-10 and tween 20, and the molar ratio of the benzenesulfonyl chloride to the zinc powder to the surfactant to the initiator is 1.0 to 0.95 to 1.0 to 0.001 to 0.01; in the step S2, the dripping temperature of the benzenesulfonyl chloride is 20 to 55 ℃.
2. The method of claim 1, wherein the mole ratio of the benzenesulfonyl chloride, zinc powder, surfactant and initiator is 1.0.
3. The method as defined in claim 1, characterized in that said zinc powder has a mesh number of 80 mesh, 120 mesh, 200 mesh, 300 mesh, 400 mesh, 600 mesh or 800 mesh.
4. The method as defined in claim 1, characterized in that said zinc powder has a mesh size of 400 or 600.
5. The method of claim 1, wherein the surfactant is cetyl ammonium bromide.
6. The method of claim 1, wherein the initiator is an aqueous solution of zinc chloride.
7. The method of claim 1, wherein the solvent is methylene chloride.
8. The method of claim 1, wherein the selected benzenesulfonyl chloride is added dropwise at step S2 for 1.5 to 3 hours.
9. The method according to claim 1, wherein in step S2, the dripping temperature of the benzenesulfonyl chloride is 30-35 ℃ and the dripping time is 1.5-2.0 h.
10. The method according to claim 1, wherein in the step S4, the temperature is reduced to 15 to 50 ℃ after the reaction is finished.
11. The method as claimed in claim 10, wherein the temperature is reduced to 20 to 30 ℃ after the reaction is finished.
12. The method according to claim 1, wherein the product zinc benzenesulfinate is obtained as a rubber and plastic foaming promoter.
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| CN110642759A (en) * | 2019-09-05 | 2020-01-03 | 浙江杰上杰新材料有限公司 | Synthesis method of zinc benzenesulfinate |
| CN111100044B (en) * | 2019-12-27 | 2020-10-16 | 鹤壁元昊化工有限公司 | Preparation method of alkyl zinc sulfinate series compounds |
| CN112062698A (en) * | 2020-09-12 | 2020-12-11 | 嘉兴市金利化工有限责任公司 | Automatic continuous production process of zinc benzene sulfinate |
| CN112592299A (en) * | 2020-12-18 | 2021-04-02 | 鹤壁中昊新材料科技有限公司 | Preparation method of benzene sulfinic acid zinc compound |
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