CN111100044B - Preparation method of alkyl zinc sulfinate series compounds - Google Patents
Preparation method of alkyl zinc sulfinate series compounds Download PDFInfo
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- CN111100044B CN111100044B CN201911382959.5A CN201911382959A CN111100044B CN 111100044 B CN111100044 B CN 111100044B CN 201911382959 A CN201911382959 A CN 201911382959A CN 111100044 B CN111100044 B CN 111100044B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C313/02—Sulfinic acids; Derivatives thereof
- C07C313/04—Sulfinic acids; Esters thereof
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/16—Salts of dithiocarbamic acids
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Abstract
The invention relates to a preparation method of alkyl zinc sulfinate series compounds, which comprises the steps of adding alkyl sulfonyl chloride into a mixed system of sodium sulfite, zinc oxide and water, obtaining alkyl zinc sulfinate series products by a one-pot method, and providing a zinc source for dialkyl zinc dithiocarbamate by a salt-containing mother liquor. The method can be carried out on conventional equipment, does not use an organic solvent, is simple and convenient to operate and has high safety; the hydrolysis of the alkyl sulfonyl chloride is effectively controlled, and the product yield is obviously improved; the by-products are recycled.
Description
Technical Field
The invention relates to a method for synthesizing alkyl zinc sulfinate compounds, which is mainly used for pesticide intermediates, plastics, rubber and lubricating oil auxiliaries.
Background
Currently, in the production technology of zinc alkyl sulfinate, there are mainly the following two routes:
one route is to use alkyl sulfonyl chloride, sodium sulfite and sodium hydroxide to react in water to produce alkyl sodium sulfinate, which then reacts with zinc chloride to produce alkyl zinc sulfinate. The method is rapid in reaction and is one of the most common production routes of the zinc benzenesulfinate. The defects are as follows: the benzene sulfonyl chloride is easy to hydrolyze under alkaline condition, the yield of the product is only 85 percent, and the quality is poor; the large amount of hydrolysis and inorganic salt by-products are difficult to separate and process, and are more difficult to be recycled. ② the route belongs to multi-step reaction, the used equipment is more, and the operation steps are complicated.
The literature reports another route: reducing 4-methylbenzenesulfonyl chloride by zinc powder to obtain 4-methylbenzenesulfinic acid zinc. The route is simple and no additional inorganic salt is introduced. The reduction activity of zinc powder is low, and the excess is more than 50%, so that the cost of raw materials is high. Secondly, excessive zinc powder is difficult to separate from the product, and the quality of the product is affected. And thirdly, a solvent medium is also used in the route, and obviously, the zinc powder and the organic solvent have larger safety risk when coexisting.
In order to overcome the defects of the prior art, the invention provides an innovative technical scheme. Namely, the alkyl sulfonyl chloride, sodium sulfite and zinc oxide are used for obtaining the alkyl zinc sulfinate product in a one-pot method in water. The reaction is carried out in a system from alkalescence to acidity, the hydrolysis of the alkyl sulfonyl chloride is effectively controlled, and the product yield can reach more than 99%. The salt-containing mother liquor is further recycled, and a zinc source is provided for the zinc dimethyldithiocarbamate. When the product is applied in specific fields such as rubber and plastic foaming product industry, the zinc alkyl sulfonate can be used together with the zinc dimethyldithiocarbamate and respectively used as a foaming active agent and a vulcanization accelerator.
Disclosure of Invention
The invention provides a preparation method of alkyl zinc sulfinate series compounds, which comprises the steps of adding alkyl sulfonyl chloride into a mixed system of sodium sulfite, zinc oxide and water, obtaining alkyl zinc sulfinate series products by a one-pot method, and providing a zinc source for dimethyl dithiocarbamate by a salt-containing mother liquor.
The alkyl sulfonyl chloride in the invention refers to alkyl sulfonyl chloride, benzene sulfonyl chloride and alkyl benzene sulfonyl chloride.
The molar ratio of the alkyl sulfonyl chloride to the sodium sulfite to the zinc oxide is 1.0: 1.0-1.5: 0.98-1.2.
The adding mode of the alkyl sulfonyl chloride is as follows: slowly adding the mixture at the temperature of 20-80 ℃, completely heating the mixture until the mixture flows back, and keeping the mixture for 3-10 hours.
The mother liquor is treated in a mode of a zinc source for synthesizing the zinc dimethyldithiocarbamate by a two-step method.
The alkyl zinc sulfinate series products obtained by the invention are used for pesticide intermediates, plastics, rubber and lubricating oil auxiliaries.
The invention also claims a method for recycling zinc alkyl sulfinate and zinc dimethyl dithiocarbamate, which comprises the following steps:
(1) adding alkyl sulfonyl chloride into a mixed system of sodium sulfite, zinc oxide and water, and obtaining a series of alkyl zinc sulfinate products by a one-pot method;
(2) collecting salt-containing mother liquor, and providing a zinc source for producing the zinc dimethyldithiocarbamate;
(3) and (3) mixing the mother liquor collected in the step (2), a dimethylamine aqueous solution and a sodium hydroxide solution, dropwise adding carbon disulfide, and reacting to obtain a white powdery product, namely zinc dimethyldithiocarbamate.
Wherein, the yield of the series products of the alkyl zinc sulfinate exceeds 99 percent, and the yield of the zinc dimethyldithiocarbamate exceeds 98.5 percent calculated by dimethylamine.
The invention has the beneficial effects that:
(1) the process is simple; the alkyl sulfenyl zinc product is obtained by using alkyl sulfonyl chloride, sodium sulfite and zinc oxide in water through a one-pot method.
(2) The by-products can be recycled, the salt-containing mother liquor is further recycled, and a zinc source is provided for the zinc dialkyl dithiocarbamate. The chemical oxygen demand in the mother liquor is obviously reduced.
(3) The method is carried out in a system from alkalescence to acidity, so that the hydrolysis of the alkyl sulfonyl chloride is effectively controlled, and the product yield is improved to over 99 percent.
Detailed Description
Detailed embodiments of the present invention will be disclosed in this section. The embodiments disclosed herein are examples of the present invention, which may be embodied in various forms. Therefore, specific details disclosed, including specific structural and functional details, are not intended to be limiting, but merely serve as a basis for the claims. The present invention will now be described with reference to examples and comparative examples.
Example 1
100mL of water, 44.4g of anhydrous sodium sulfite, and 22.8g of zinc oxide were put into a 500mL flask at room temperature, stirred, and 50.0g of benzenesulfonyl chloride was added dropwise at room temperature, and the mixture was heated to reflux and held for 3 hours. Separating and collecting mother liquor, washing filter cake with water, and drying to obtain zinc benzene sulfinate. The yield is 99.8 percent, and the purity is 99.21 percent by liquid chromatography detection.
And at normal temperature, adding 31.41g of the collected mother liquor, 31.41g of 40% dimethylamine aqueous solution and 34.85g of 32% sodium hydroxide solution into a 1L flask, uniformly mixing, continuously dropwise adding 21.78g of carbon disulfide, finishing adding 2-3 h, and keeping the temperature for 2 h. Heating to 60-70 ℃ until the reaction is finished. Separating, washing and drying to obtain a white powdery product. The yield was 98.5% based on dimethylamine.
Example 2
2000kg of water, 296.0kg of anhydrous sodium sulfite and 182.4kg of zinc oxide were put into a container of 5m at room temperature3And (3) stirring the mixture in a reaction kettle, dripping 400.0kg of benzene sulfonyl chloride at the temperature of 35-40 ℃, and heating to reflux and keeping for 10 hours. Separating and collecting mother liquor, washing and drying filter cakes to obtain the zinc benzene sulfinate with the yield of 99.2 percent and the purity of 98.9 percent by liquid chromatography detection.
Collecting mother liquor 2m at normal temperature363.44kg of 40% dimethylamine aqueous solution and 70.36kg of 32% sodium hydroxide solution are uniformly mixed, 43.96kg of carbon disulfide is continuously dripped, the addition is completed within 4-5 hours, and the temperature is kept for 2 hours. Heating to 60-70 ℃ until the reaction is finished. Separating, washing and drying to obtain a white powdery product. The yield was 98.9% based on dimethylamine.
Example 3
2000kg of water, 444.0kg of anhydrous sodium sulfite and 202.8kg of zinc oxide were put into a container of 5m at room temperature3Stirring the mixture in a reaction kettle, slowly adding 431.76kg of p-toluenesulfonyl chloride at 40-50 ℃, and heating to reflux and keeping the temperature for 10 hours. Separating and collecting mother liquor, washing filter cake with water, and drying to obtain white powder of zinc p-toluenesulfinate with a yield of 99.9% and a purity of 99.4% by liquid chromatography detection.
Collecting mother liquor 2m at normal temperature370.54kg of 40% dimethylamine aqueous solution and 79.02kg of 32% sodium hydroxide solution are uniformly mixed, 49.37kg of carbon disulfide is continuously dripped, the addition is completed within 4-5 hours, and the temperature is kept for 2 hours. Heating to 60-70 ℃ until the reaction is finished. Separating, washing and drying to obtain a white powdery product. The yield was 99.0% based on dimethylamine.
Example 4
2000kg of water, 444.0kg of anhydrous sodium sulfite and 221.2kg of zinc oxide were put into a container of 5m at room temperature3Stirring the mixture in a reaction kettle, adding 431.76kg of p-toluenesulfonyl chloride at 50-60 ℃, and heating to reflux and keeping for 5 hours. Separating and collecting mother liquor, washing filter cake with water, and drying to obtain zinc p-toluenesulfinate with yield of 99.4% and liquid-phase colorThe purity of the spectrum detection is 99.01%.
At normal temperature, 2000kg of collected mother liquor, 76.94kg of water containing 40% of dimethylamine aqueous solution and 86.19kg of 32% of sodium hydroxide solution are uniformly mixed, 53.85kg of carbon disulfide is continuously dripped, the addition is completed within 4-5 hours, and the temperature is kept for 2 hours. Heating to 60-70 ℃ until the reaction is finished. Separating, washing and drying to obtain a white powdery product. The yield was 99.2% based on dimethylamine.
Example 5
150mL of water, 38.0g of anhydrous sodium sulfite and 22.8g of zinc oxide are put into a 500mL flask at normal temperature, stirred and heated to 70-80 ℃, 76.11g of dodecyl sulfonyl chloride is slowly added, and the mixture is heated to reflux and kept for 5 hours. Separating and collecting mother liquor, washing filter cake with water, and drying to obtain the zinc dodecylbenzene sulfinate. The yield is 99.7%, and the purity is 98.4% by liquid chromatography detection.
And at normal temperature, adding 31.41g of the collected mother liquor, 31.41g of 40% dimethylamine aqueous solution and 34.85g of 32% sodium hydroxide solution into a 1L flask, uniformly mixing, continuously dropwise adding 21.78g of carbon disulfide, finishing adding 2-3 h, and keeping the temperature for 2 h. Heating to 60-70 ℃ until the reaction is finished. Separating, washing and drying to obtain a white powdery product. The yield was 98.8% based on dimethylamine.
Example 6
150mL of water, 44.4g of anhydrous sodium sulfite and 22.8g of zinc oxide are put into a 500mL flask at normal temperature, stirred and heated to 60-70 ℃, 65.89g of 3-tert-butylbenzene sulfonyl chloride is slowly added, and the mixture is heated to reflux and kept for 4 hours. Separating and collecting mother liquor, washing filter cake with water, and drying to obtain 3-tert-butyl benzene sulfinic acid zinc with the purity of 98.5% by liquid chromatography detection.
And at normal temperature, adding 31.41g of the collected mother liquor, 31.41g of 40% dimethylamine aqueous solution and 34.85g of 32% sodium hydroxide solution into a 1L flask, uniformly mixing, continuously dropwise adding 21.78g of carbon disulfide, finishing adding 2-3 h, and keeping the temperature for 2 h. Heating to 60-70 ℃ until the reaction is finished. Separating, washing and drying to obtain a white powdery product. The yield was 98.2% based on dimethylamine.
Example 7
200mL of water, 44.4g of anhydrous sodium sulfite and 22.8g of zinc oxide are put into a 500mL flask at normal temperature, stirred and heated to 60-70 ℃, 58.51g of 3-tert-butylbenzene sulfonyl chloride is slowly added, and the mixture is heated to reflux and kept for 6 hours. Separating and collecting mother liquor, washing filter cake with water, and drying to obtain 3-tert-butyl benzene sulfinic acid zinc with the purity of 98.3% by liquid chromatography detection.
And at normal temperature, adding 31.41g of the collected mother liquor, 31.41g of 40% dimethylamine aqueous solution and 34.85g of 32% sodium hydroxide solution into a 1L flask, uniformly mixing, continuously dropwise adding 21.78g of carbon disulfide, finishing adding 2-3 h, and keeping the temperature for 2 h. Heating to 60-70 ℃ until the reaction is finished. Separating, washing and drying to obtain a white powdery product. The yield was 98.3% based on dimethylamine.
Example 8
100mL of water, 44.4g of anhydrous sodium sulfite, and 22.8g of zinc oxide were put into a 500mL flask at room temperature, stirred, and 58.5g of 2-methoxybenzenesulfonyl chloride was added dropwise at room temperature, and the mixture was heated to reflux and held for 3 hours. Separating and collecting mother liquor, washing filter cake with water, and drying to obtain 2-methoxy benzene sulfinic acid zinc. The yield is 99.6%, and the purity is 98.8% by liquid chromatography detection.
And at normal temperature, adding 31.41g of the collected mother liquor, 31.41g of 40% dimethylamine aqueous solution and 34.85g of 32% sodium hydroxide solution into a 1L flask, uniformly mixing, continuously dropwise adding 21.78g of carbon disulfide, finishing adding 2-3 h, and keeping the temperature for 2 h. Heating to 60-70 ℃ until the reaction is finished. Separating, washing and drying to obtain a white powdery product. The yield was 98.5% based on dimethylamine.
Example 9
150mL of water, 44.4g of anhydrous sodium sulfite, and 22.8g of zinc oxide were put into a 500mL flask at room temperature, stirred and heated to 50-60 ℃, 70.41g of 4-butoxyphenylsulfonyl chloride was slowly added thereto, and the mixture was heated to reflux and held for 6 hours. Separating and collecting mother liquor, washing filter cake with water, and drying to obtain the zinc 4-butoxybenzene sulfinate. The yield is 99.3 percent, and the purity is 99.12 percent by liquid chromatography detection.
And at normal temperature, adding 31.41g of the collected mother liquor, 31.41g of 40% dimethylamine aqueous solution and 34.85g of 32% sodium hydroxide solution into a 1L flask, uniformly mixing, continuously dropwise adding 21.78g of carbon disulfide, finishing adding 2-3 h, and keeping the temperature for 2 h. Heating to 60-70 ℃ until the reaction is finished. Separating, washing with water for 2 times, and drying to obtain white powder product. The yield was 98.9% based on dimethylamine.
Comparative example 1
Adding 13.74g of anhydrous sodium sulfite and 200mL of water into a 500mL flask, stirring, heating to 55-60 ℃, dropwise adding a dichloromethane solution dissolved with 19.05g of p-toluenesulfonyl chloride, and simultaneously dropwise adding a 10% sodium hydroxide solution to control the pH of the system to 7-8. After the completion, the temperature is raised to 85 ℃, 28.6g of 28.2 percent zinc sulfate is dripped, the temperature is kept for 3 hours, and the zinc p-toluenesulfinate is obtained by cooling and separation. Yield 85%, melting point 151.7 ℃.
Comparative example 2
100mL of water, 44.4g of anhydrous sodium sulfite and 35.38g of 32% sodium hydroxide are put into a 500mL flask at normal temperature, stirred, 50.0g of benzenesulfonyl chloride is dripped at normal temperature, heat is preserved for 1h after the addition, the temperature is raised to 60 ℃, 81g of 28.2% zinc sulfate is dripped, and the heat is kept for 3 h. Separating and collecting mother liquor, washing and drying to obtain white powder zinc benzene sulfinate. Yield 84.2%, melting point 222.1 ℃.
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 are within the protection scope of the technical solution of the present invention.
Claims (6)
1. A method for preparing a zinc alkylsulfinate compound, which is characterized by comprising the following steps: adding alkyl sulfonyl chloride into a mixed system of sodium sulfite, zinc oxide and water, and obtaining an alkyl zinc sulfinate product by a one-pot method; wherein the molar ratio of the alkyl sulfonyl chloride to the sodium sulfite to the zinc oxide is 1.0: 1.0-1.5: 0.98-1.2, and the alkyl sulfonyl chloride refers to dodecyl sulfonyl chloride, benzene sulfonyl chloride, p-methylbenzene sulfonyl chloride, 3-tert-butylbenzene sulfonyl chloride, 2-methoxybenzene sulfonyl chloride or 4-butoxybenzene sulfonyl chloride; the adding mode of the alkyl sulfonyl chloride is as follows: slowly adding the mixture at the temperature of 20-80 ℃, completely heating the mixture until the mixture flows back, and keeping the mixture for 3-10 hours.
2. The method according to claim 1, wherein the salt-containing mother liquor after separation of the zinc alkylsulfinate compound is collected and used as a zinc source for the two-step synthesis of zinc dialkyldithiocarbamate.
3. The method of claim 1, wherein the yield is greater than 99%.
4. The method of claim 1, wherein the product is used as an intermediate for agricultural chemicals, and as an adjuvant for plastics, rubbers, and lubricants.
5. A method for circularly producing zinc alkyl sulfinate and zinc dimethyl dithiocarbamate comprises the following steps:
(1) the preparation method of any one of claims 1 to 4, wherein alkyl sulfonyl chloride is added into a mixed system of sodium sulfite, zinc oxide and water, a one-pot method is adopted to obtain an alkyl zinc sulfinate product, and a salt-containing mother liquor after separation of an alkyl zinc sulfinate compound is collected;
(2) providing a zinc source for producing zinc dimethyldithiocarbamate with the salt-containing mother liquor collected in the step (1);
(3) and (3) mixing the mother liquor collected in the step (2), a dimethylamine aqueous solution and a sodium hydroxide solution, dropwise adding carbon disulfide, and reacting to obtain a white powdery product, namely zinc dimethyldithiocarbamate.
6. The process of claim 5 wherein the yield of zinc hydrocarbyl sulfinate product is greater than 99% and the yield of zinc dimethyldithiocarbamate is greater than 98.5% based on dimethylamine.
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| 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 |
| CN113816881B (en) * | 2021-10-21 | 2023-04-18 | 鹤壁中昊新材料科技有限公司 | Preparation method of rubber-plastic foaming accelerator zinc benzene sulfinate |
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| CN101786973B (en) * | 2010-03-11 | 2013-01-16 | 嘉兴学院 | Synthesizing process of 4-methyl sodium benzene sulphinate |
| CN102276509B (en) * | 2011-06-03 | 2014-05-21 | 鹤壁联昊化工股份有限公司 | One-step method for preparing rubber promoter zinc dibenzyl dithiocarbamate |
| CN102295592A (en) * | 2011-06-22 | 2011-12-28 | 濮阳蔚林化工股份有限公司 | Preparation method of rubber vulcanization accelerator zinc dimethyldithiocarbamate |
| JP2013114166A (en) * | 2011-11-30 | 2013-06-10 | Canon Inc | Charging roller, electrophotographic device, and manufacturing method of charging roller |
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