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Method for preparing sulfur-containing bisphenol compound antioxidant by means of recycling mother liquor

A kind of technology of sulfur-containing bisphenol, cyclic preparation

Inactive Publication Date: 2012-08-01
佛山市顺德区荷叶化工有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008]2. Due to the fact that there is a large amount of washing wastewater from dark brown to dark yellow to light yellow in the process of washing crude products in this production process, the production of one ton of products produces approximately 12-15 tons of waste water, yellow and turbid, containing a small amount of phenolic compounds, Na2S, formaldehyde, ethanol, etc., usually discharged directly, causing serious pollution to the environment
Washing waste water is discharged into the groundwater system, and some highly toxic hydrogen sulfide gas will be released after encountering acid, which will cause poisoning and injury to personnel if you are not careful
[0009]3. Poor product quality
After the reaction, the crude product is washed with water or ethanol aqueous solution to neutrality, but the alkaline substance wrapped inside the crystal grains cannot be removed, so the product is easy to turn yellow during storage, usually within three weeks, forming a yellowish powder Bulk products, affect its performance in polymers, and even cause the appearance of white polymers to turn yellow
[0010]4. If you want to obtain a product with a melting point > 140°C and granular white crystals, you must use absolute ethanol for recrystallization and refinement
[0012] 1. While neutralizing the alkali metal hydroxide catalyst in the reaction mixture with inorganic acid, the excess hydrogen sulfide raw material in the reaction mixture becomes a free gas again, during production It needs to be completely absorbed with lye and recycled. After absorption, the by-product composed of lye and Na2S needs to be further processed to obtain Na without alkali metal hydroxide 2S aqueous solution can be recycled, the process in production is longer, and the investment in equipment is larger;
[0013]2. Use excessive formaldehyde to increase the conversion rate of 2,6-phenol raw material and product yield. The molar ratio of 2,6-phenol to formaldehyde raw material is 1:1.85 ~2.0, the excess formaldehyde is nearly 50%, therefore, after removing the methanol or ethanol reaction solvent from the reaction mixture, add an aliphatic hydrocarbon solvent to dissolve the solid crude product of methylene-4426-S, let it stand for stratification, and separate the lower water layer ;Washing with water, combining the washing water and the lower water layer separated by standing, which contains the excessive amount of formaldehyde and sodium sulfate fed, which needs to be distilled, which consumes a lot of energy, and it is difficult for enterprises to bear such high Therefore, the accumulation of formaldehyde still causes serious environmental pollution and waste of formaldehyde raw materials.

Method used

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  • Method for preparing sulfur-containing bisphenol compound antioxidant by means of recycling mother liquor
  • Method for preparing sulfur-containing bisphenol compound antioxidant by means of recycling mother liquor

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0050] In the GST-2 type stainless steel autoclave with magnetic stirring, 103g (0.5mol) of raw materials 2,6-di-tert-butylphenol, 28.0g of paraformaldehyde, 1236g of 80% ethanol aqueous solution, 20g of sodium hydroxide, After nitrogen replacement, 25 g of hydrogen sulfide was added. Start stirring and heating, and fully mix the reaction raw materials in the kettle. When the temperature rises to 50~53°C, stop heating, keep the temperature for 70 minutes, and the reaction ends. Cool down to 3~6°C, filter, separate the reaction mother liquor, and collect; the separated methylene-4426-S solid product is washed with 70~80% ethanol aqueous solution to obtain methylene-4426-S with granular pure white crystals Antioxidant product, HPLC purity: 98.7%, melting point: 142.1~143.6℃, ​​yield 94.5%

Embodiment 2

[0052] In the GST-2 type stainless steel autoclave with magnetic stirring, 103g (0.5mol) of raw materials 2,6-di-tert-butylphenol, 32.0g of paraformaldehyde, 1030g of 83% ethanol aqueous solution, 20g of sodium hydroxide, After nitrogen substitution, 18 g of hydrogen sulfide was added. Start stirring and heating, and fully mix the reaction raw materials in the kettle. When the temperature rises to 54~56°C, stop heating, keep warm for 50 minutes, and the reaction ends. Cool down to 3~6°C, filter, separate the reaction mother liquor, and collect; the separated methylene-4426-S solid product is washed with 70~80% ethanol aqueous solution to obtain methylene-4426-S with granular pure white crystals Antioxidant product, HPLC purity: 99.0%, melting point: 142.6~143.5℃, yield 95.2%

Embodiment 3

[0054] In the GST-2 type stainless steel autoclave with magnetic stirring, 103g (0.5mol) of raw materials 2,6-di-tert-butylphenol, 34.0g of paraformaldehyde, 825g of 85% ethanol aqueous solution, 16g of sodium hydroxide, After nitrogen substitution, 15 g of hydrogen sulfide was added. Start stirring and heating, and fully mix the reaction raw materials in the kettle. When the temperature rises to 58~60°C, stop heating, keep warm for 40 minutes, and the reaction ends. Cool down to 3~6°C, filter, separate the reaction mother liquor, and collect; the separated methylene-4426-S solid product is washed with 70~80% ethanol aqueous solution to obtain methylene-4426-S with granular pure white crystals Antioxidant product, HPLC purity: 98.5%, melting point: 142.3~143.8℃, yield 92.8%

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Abstract

The invention relates to a method for preparing sulfur-containing bisphenol compound antioxidant by means of recycling mother liquor, which belongs to the field of synthetic rubber, polyolefin plastics and lubricating oil. Ethanol water is used as a reaction solvent, 2, 6-di-tert-buty phenol, paraformaldehyde and hydrogen sulfide or sodium hydrosulfide are used as raw materials, sodium hydroxide is used as a catalyst, and reaction is performed in a closed reactor to prepare a methylene-4426-S product. The product is separated by means of filtration and washed by the ethanol water to obtain a white crystal product. Residual reaction mother liquor mainly includes ethanol water and contains organic matters such as formaldehyde, the sodium hydroxide, Na2S, the methylene-4426-S product and the like. The reaction mother liquor is collected to serve as the reaction solvent, and condensation reaction is continued to prepare the methylene-4426-S product. The reaction mother liquor is recycled, consumption of paraformaldehyde and hydrogen sulfide or sodium hydrosulfide is reduced, and 2,6-phenol raw material conversion rate, target product yield and target product quality can be kept.

Description

technical field [0001] The invention belongs to the field of synthetic rubber, polyolefin plastic and lubricating oil. It relates to a method for preparing a sulfur-containing bisphenol compound antioxidant by circulating mother liquor. The product of the sulfur-containing bisphenol compound antioxidant specifically refers to the following formula (I), (referred to as methylene-4426-S). [0002] [0003] (I) [0004] (I) Chemical name: bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide. Background technique [0005] Methylidene-4426-S is a sulfur-containing bisphenol compound antioxidant product, which is mainly used as an antioxidant for synthetic rubber, polyolefin plastics and other polymer materials, as well as oil products such as lubricating oil and fuel oil. [0006] The Guangzhou Synthetic Materials Aging Research Institute has disclosed the synthesis method of methylene-4426-S products, using 2,6-tert-butylphenol (referred to as 2,6-phenol), 36% formaldehyde aqueo...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C323/16C07C319/14
Inventor 杜飞陆网军叶涛马得森蒋鹏俊
Owner 佛山市顺德区荷叶化工有限公司
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