CN101333179B - Method for preparing sulfur-containing bisphenol compounds anti-oxidant - Google Patents
Method for preparing sulfur-containing bisphenol compounds anti-oxidant Download PDFInfo
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- CN101333179B CN101333179B CN2008100208822A CN200810020882A CN101333179B CN 101333179 B CN101333179 B CN 101333179B CN 2008100208822 A CN2008100208822 A CN 2008100208822A CN 200810020882 A CN200810020882 A CN 200810020882A CN 101333179 B CN101333179 B CN 101333179B
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Abstract
The invention discloses a preparation method for sulfur-containing bisphenol compound antioxidant, which uses ethanol or methanol-water solution as reaction solvent, alkali metal hydroxide as catalyst, 2,6-2t-butyl phenol, formaldehyde, hydrogen sulfide as reaction materials to join a thiosulfate condensation reaction in a sealed reactor so as to generate bi-(3,5- di-tert-butyl -4 - hydroxy-benzyl) sulfide. The technical conditions of the synthesis are as follows: 2,6 - t-butyl phenol and formaldehyde are in a molar ratio of 1:1.85-2.0, while 2,6 - t-butyl phenol and hydrogen sulfide are in a molar ratio of 1:0.75-1.0; 2,6 - t-butyl phenol and alkali metal hydroxide are in a molar ratio of 1: 0.8-1.0; the mass fraction of ethanol or methanol-water solution is 55-65% or 70-85%; the reaction temperature is 50-65 DEG C and the reaction time is 20-30 minutes. Through crystallization separation, the product with granular pure white crystals can be directly obtained. The product of the invention has simple production process, high yield, low production costs and good quality.
Description
Technical field
The present invention relates to a kind of method for preparing sulfur-containing bisphenol compounds anti-oxidant, the sulfur-containing bisphenol compounds anti-oxidant product refers in particular to following formula (I).
Chemical name: two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) thioether, (the abbreviation methene-4426-S)
Background technology
Described formula (I) sulfur-containing bisphenol compounds is a kind of antioxidant product, is mainly used in the oxidation inhibitor of macromolecular materials such as synthetic rubber, polyolefin plastics and lubricating oil, fuel wet goods oil product.
Do not see the synthetic method of domestic and foreign literature report methene-4426-S product in recent years.
Prior art, with 2,6-t-butyl phenol, 36% formalin, sodium sulphite are raw material, carry out the sulfo-condensation reaction in methyl alcohol or aqueous ethanolic solution, obtain formula (I) product.
U.S.P:260609000 report 3,5-di-tert-butyl-4-hydroxyl chlorobenzene is a method for preparing raw material.
1978, the synthetic method of the report methene 4426-S of Guangzhou synthesis material aging institute product.Up to now, this method is always as the method for suitability for industrialized production.
As: in the reactor that has reflux exchanger, agitator, add formalin, sodium sulfide solution, 2 in proportion, 6-di-tert-butylphenol, solvent (methyl alcohol or ethanol).Heat up.(when being solvent with methyl alcohol 71-73 ℃, then be 80-82 ℃ when ethanol is solvent) picked up counting after reaction mass reached reflux temperature under this solvent strength, and back flow reaction carries out finishing in 30-40 minute, obtains the solid-liquid reaction mixture.Be cooled to 30-35 ℃, the solids crude product is separated from reaction solvent, thick product water repeatedly washed to neutral (product is alkalescence flavescence in storage process easily), the dry then product that gets.
The quality index of product is as shown in table 1.
The quality index of table 1. methene 4426-S product
This technological method is produced the subject matter that exists in methene-4426-S process.
1, industrial sodium sulfide content＞60% is orange-red translucent block crystallization, contains a spot of water-soluble inorganic salt and water-fast material.Impurity is sneaked in the product, and its ash content is increased.If the crystallization Na that separates out in the use saturated aqueous solution
2S9H
2O is a raw material, because price is higher, then can increase the raw materials cost in the production process greatly.
2, by proportioning raw materials, Na
2S9H
2O about excessive 30%.The concentration of sodium ion is higher in the reaction soln, and alkalescence is very strong.Temperature of reaction higher (80-82 ℃) in addition, 2, the 6-di-tert-butylphenol is oxidized easily, and both by product increases, and the reaction solution color that finally obtains is dark-brown.In addition, isolated thick product particle is very fine and smooth, and is adsorbed with the darker reaction mother liquor of color, makes that thick product appearance is a deep yellow, therefore needs a large amount of water repeatedly to wash, and could make the thick product that obtains meet the quality index of above-mentioned table 1.
3, because this producing and manufacturing technique washs in the thick product process, exist in a large number by dark-brown, produce a product and approximately produce washes 12-15 ton to deep yellow to flaxen washes, yellow and muddy, wherein contain a small amount of phenolic compound, Na
2S, formaldehyde, ethanol etc., directly discharging causes severe contamination to environment usually.Washes enters ground water regime, run into after the acid can the release portion severe toxicity hydrogen sulfide, carelessly slightly will cause toxicity damage among the personnel.If it is huge this part waste water being carried out the economic cost of harmless treatment cost.Therefore at present methene-4426-S products production producer has no option, direct waste discharge, and the sight of sewage discharge makes us startling.
4, separate the reaction mother liquor that obtains behind the thick product, be aqueous ethanolic solution, wherein contain approximately excessive 60% formaldehyde, 30%Na
2S, a spot of 2,6-di-tert-butylphenol and product.The distillation reaction mother liquor reclaims in ethanol, the formaldehyde process, under 80-100 ℃ condition, and Na
2S, formaldehyde, a spot of 2,6-di-tert-butylphenol and product section polycondensation form new organism residue, are a kind of not only water insoluble but also the sulfur-bearing that is insoluble to alcohol is determined material, outward appearance is a Vandyke brown, can not carry out harmless treatment with simple incinerating method.Solid slag abandon the another big source of pollution that become this producing and manufacturing technique.
5, poor product quality.The thick product in reaction back is washed with water to neutrality, but the alkaline matter of crystallite-cladded inside can't be removed therefore easily flavescence in storage process.Usually flavescence in three time-of-weeks, product appearance index: little yellowy crystalline powder.The appearance index of product can influence its use properties in polymkeric substance, even can cause the appearance color flavescence of white polymer.
If 6 expect fusing point＞141 ℃, have the product of particulate state white crystals, then must carry out recrystallizing and refining with dehydrated alcohol.Because methene-4426-S is less to the solubleness of aqueous ethanolic solution, when the ethanol massfraction less than 96% the time, recrystallization process is difficult to carry out, and must use industry anhydrous ethanol.Therefore before recrystallization, need the thick product of methene-4426-S is removed wherein moisture through drying process, just can carry out recrystallizing and refining then.Because thick product particle is very fine and smooth, the massfraction of water is very high again in the wet product, is generally 10～12%, thus in drying process energy consumption bigger.
Summary of the invention
The objective of the invention is to obtain a kind of method for preparing sulfur-containing bisphenol compounds anti-oxidant.Wherein:
1, adopting low carbon fat alcohol such as first, aqueous ethanolic solution is reaction solvent, 2,6-di-tert-butylphenol, formaldehyde, hydrogen sulfide are reaction raw materials, alkali metal hydroxide is a catalyzer, in closed reaction kettle, carry out the sulfo-condensation reaction, after reaction finishes, the solidliquid mixture that production (I) sulfur-containing bisphenol compounds anti-oxidant product and reaction solvent form.
2, with the alkali metal hydroxide catalyzer in the mineral acid neutralization reaction mixture.
3, the hydrogen sulfide raw material that is unbound state is removed in separation from reaction mixture, and collects, and recycles.
4, from reaction mixture, remove the low carbon fat alcohol reaction solvent.Add aliphatic solvents, dissolving methene-4426-S solids crude product.Wash with water, remove the impurity such as inorganic salt that are dissolved in the oil reservoir.Formula (I) sulfur-containing bisphenol compounds anti-oxidant methene-4426-S product Crystallization Separation with being contained in the oil reservoir directly obtains having particulate state pure white crystalline product of the present invention.
5, the aliphatic solvents behind separation methene-4426-S product can be recycled.
Perhaps the another program of Cai Yonging is: with 2,6-t-butyl phenol, 36% formalin, sodium sulphite are raw material, carry out the sulfo-condensation reaction in methyl alcohol or aqueous ethanolic solution, obtain formula (I) product.With excessive sodium sulphite in the mineral acid neutralization reaction mixture, from reaction mixture, separate simultaneously and remove the hydrogen sulfide raw material that is unbound state.From reaction mixture, remove methyl alcohol or ethanol.Add aliphatic solvents, dissolving methene-4426-S solids crude product.Wash with water, remove the impurity such as inorganic salt in the oil reservoir first.Methene-4426-S the antioxidant product that is contained in the oil reservoir is separated.Aliphatic solvents behind the product separation is collected and is recycled.
Methyl alcohol or ethanol that the present invention uses, specification is the commercial industrial product.
The alkali metal hydroxide that the present invention uses specifically refers to: sodium hydroxide or potassium hydroxide.Specification is the commercial industrial product.Can replace in addition yellow soda ash, the sodium bicarbonate of alkali metal hydroxide as catalyzer; Salt of wormwood, saleratus.
The mineral acid that the present invention uses specifically refers to: sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid.Specification is the commercial industrial product.
The aliphatic solvents that the present invention uses specifically refers to: benzene,toluene,xylene; C
6～C
9Straight-chain paraffin or branched paraffin.Specification is the commercial industrial product.
The raw material that uses among the present invention: hydrogen sulfide, Na
2S9H
2The O specification is the commercial industrial product.
The raw material that uses among the present invention: 2,6-t-butyl phenol, 36% formalin are the commercial industrial product.Can replace 36% formalin with Paraformaldehyde 96.
Of the present invention 2, the mol ratio of 6-t-butyl phenol and formaldehyde raw material is 1: 1.85～2.0.Formaldehyde is excessive to help 2, and 6-t-butyl phenol feed stock conversion and product yield improve.
Of the present invention 2, the mol ratio of 6-t-butyl phenol and hydrogen sulfide raw material is 1: 0.75～1.0.The hydrogen sulfide raw material is excessive to help 2, and 6-t-butyl phenol feed stock conversion and product yield improve.After the reaction, excessive hydrogen sulfide obtains reclaiming.
It is catalyzer that the present invention selects alkali metal hydroxide, and catalyst consumption increases, and helps improving 2, and the condensation reaction speed of 6-t-butyl phenol and formaldehyde and hydrogen sulfide shortens the reaction times.If but alkalimetal ion concentration is higher in the reaction system, oxidisability improves, and by product increases, the jaundice of product appearance color, target product downgrade.Suit 2, the mol ratio of 6-t-butyl phenol and alkali metal hydroxide catalyzer is 1: 0.8～1.0.
The present invention selects ethanol, methanol aqueous solution as reaction solvent.When using ethanol as reaction solvent, suitable alcoholic acid massfraction is 55-65%; When using methyl alcohol as reaction solvent, the massfraction of its methyl alcohol in the aqueous solution is 70-85%.
The present invention is chosen in and carries out condensation reaction in the enclosed autoclave, and temperature of reaction is 45-70 ℃, and suitable temperature of reaction is 50-65 ℃.Reaction times is 15-50 minute, and the suitable reaction times is 20-30 minute.
With mineral acid of the present invention methene-4426-S the solid phase prod that contains that reaction generates is formed solidliquid mixture with reaction solvent and neutralizes, the usage quantity of mineral acid raw material by with the chemical reaction stoichiometric number adding of alkali metal hydroxide catalyzer.After neutralization reaction finishes, separate from reaction mixture and remove the hydrogen sulfide raw material that is unbound state, collecting the new work of laying equal stress on is that reaction raw materials uses.Add aliphatic solvents, fully dissolving remains in the methene-4426-S solids crude product in the reactor, washes with water, removes the impurity such as small amounts of inorganic salt that are dissolved in the oil reservoir.Standing demix is removed water layer and distillation is handled, and water is collected, and recycles again after treatment, contains the stillage residue discharging of impurity such as inorganic salt or further does harmless treatment.Methene-4426-S product Crystallization Separation with being contained in the oil reservoir obtains having particulate state pure white crystalline product of the present invention.Aliphatic solvents behind separation methene-4426-S product is collected and is recycled.
Methene-4426-S the product of new process preparation of the present invention has the crystallization of particulate state pure white, and the product fusing point is 142-144 ℃.
Advantage of the present invention:
1, the methene-4426-S product of new process of the present invention preparation has that production process is simple, product yield is high, production cost is low, the measured characteristics of matter.The molar product yield is 91-95%; Fusing point: 142-144 ℃; The liquid chromatography massfraction is greater than 98.5%.
2, temperature of reaction is low, 50-65 ℃; Reaction times is short, 20-30 minute; Reduce the higher thick product drying process of water content, greatly reduce the consumption of the energy.
3, the hydrogen sulfide raw material can be recycled, and cuts down the consumption of raw materials.
4, the most important is that the discharging that has solved a large amount of waste water in the production process causes the serious environmental pollution problem.
5, the present invention's technological process of preparing methene-4426-S product is convenient to suitability for industrialized production.
Embodiment
Be embodiments of the invention below, the various raw materials that adopted among the embodiment all are commercially available industrial goods.
Embodiment 1
In the GST-2 type, have in the magnetic agitation stainless steel autoclave, add raw material 2 successively, 6-DI-tert-butylphenol compounds 206.0g (1.0mol), 36.0% formalin 163.0g (1.956mol), dehydrated alcohol 475.0g, water 212.0g, sodium hydroxide 32.0g (0.80mol), hydrogen sulfide 27.2g (0.80mol).Start stirring, the reaction raw materials in the thorough mixing still.When temperature rises to 62-65 ℃, stop heating, insulation reaction 30 minutes, reaction finishes.Be cooled to 25-30 ℃, add 50% sulfuric acid 78.4g neutralization reaction mixture, separate from reaction mixes and remove the hydrogen sulfide raw material that is unbound state, collecting the new work of laying equal stress on is that reaction raw materials uses.From reaction mixes, separate and remove the ethanol synthesis solvent.Add 390g toluene, fully dissolving remains in the methene-4426-S solids crude product in the reactor, uses 150g water washing twice respectively, removes in the oil reservoir impurity such as a spot of inorganic salt.Merge bath water twice, distillation is handled, and water is collected and reused, and contains the stillage residue discharging of impurity such as inorganic salt on a small quantity or further does harmless treatment.With the oxidation inhibitor methene-4426-S Crystallization Separation that is contained in the oil reservoir, obtain having particulate state pure white crystalline 220g of the present invention, fusing point: 142.3-143.5 ℃, yield 93.6%.
Embodiment 2
In the GST-2 type, have in the magnetic agitation stainless steel autoclave, add raw material 2 successively, 6-DI-tert-butylphenol compounds 206.0g (1.0mol), 36.0% formalin 173.0g (2.08mol), dehydrated alcohol 475.0g, water 145.0g, sodium hydroxide 40.0g (1.0mol), hydrogen sulfide 27.2g (0.80mol).Start stirring, the reaction raw materials in the thorough mixing still.When temperature rises to 50-52 ℃, stop heating, insulation reaction 20 minutes, reaction finishes.Be cooled to 25-30 ℃, add 50% sulfuric acid 98.0g neutralization reaction mixture, carry out aftertreatment, obtain having particulate state pure white crystalline 223g of the present invention by the same procedure of embodiment 1.Fusing point: 142.1-143.8 ℃, yield 94.9%.
Embodiment 3
In the GST-2 type, have in the magnetic agitation stainless steel autoclave, add raw material 2 successively, 6-DI-tert-butylphenol compounds 206.0g (1.0mol), 36.0% formalin 154.0g (1.85mol), dehydrated alcohol 475.0g, water 290.0g, potassium hydroxide 32.0g (0.80mol),, hydrogen sulfide 25.5g (0.75mol).Start stirring, the reaction raw materials in the thorough mixing still.When temperature rises to 55-58 ℃, stop heating, insulation reaction 25 minutes, reaction finishes.Be cooled to 25-30 ℃, add 50% sulfuric acid 78.4g neutralization reaction mixture, carry out aftertreatment, obtain having particulate state pure white crystalline 217g of the present invention by the same procedure of embodiment 1.Fusing point: 142.5-143.9 ℃.Yield 92.3%.
Embodiment 4
In the GST-2 type, have in the magnetic agitation stainless steel autoclave, add raw material 2 successively, 6-DI-tert-butylphenol compounds 103.0g (0.5mol), 36.0% formalin 86.7g (1.04mol), anhydrous methanol 520.0g, water 116.0g, sodium hydroxide 20.0g (0.5mol), hydrogen sulfide 12.9g (0.38mol).Start stirring, the reaction raw materials in the thorough mixing still.When temperature rises to 55-58 ℃, stop heating, insulation reaction 30 minutes, reaction finishes.Be cooled to 25-30 ℃, add 20% hydrochloric acid 90.0g neutralization reaction mixture, separate from reaction mixture and remove the hydrogen sulfide raw material that is unbound state, collecting the new work of laying equal stress on is that reaction raw materials uses.From reaction mixes, separate and remove the methyl alcohol reaction solvent.Add the 230g normal hexane, fully dissolving remains in the methene-4426-S solids crude product in the reactor, uses 80g water washing twice respectively, removes in the oil reservoir impurity such as a spot of inorganic salt.Merge bath water twice, distillation is handled, and water is collected and reused, and contains the stillage residue discharging of impurity such as inorganic salt on a small quantity or further does harmless treatment.With the oxidation inhibitor methene-4426-S Crystallization Separation that is contained in the oil reservoir, obtain having particulate state pure white crystalline 108g of the present invention.Fusing point: 142.0-143.6 ℃, yield 91.9%.
Embodiment 5
In the GST-2 type, have in the magnetic agitation stainless steel autoclave, add raw material 2 successively, 6-DI-tert-butylphenol compounds 206.0g (1.0mol), 36.0% formalin 173.0g (2.08mol), dehydrated alcohol 475.0g, water 145.0g, sodium hydroxide 32.0g (0.8mol), hydrogen sulfide 34.0g (1.0mol).Start stirring, the reaction raw materials in the thorough mixing still.When temperature rises to 62-65 ℃, stop heating, insulation reaction 30 minutes, reaction finishes.Be cooled to 25-30 ℃, add 50% sulfuric acid 78.4g neutralization reaction mixture, carry out aftertreatment, obtain having particulate state pure white crystalline 219g of the present invention by the same procedure of embodiment 1.Fusing point: 142.1-143.8 ℃.Yield 93.2%.
Embodiment 6
In the GST-2 type, have in the magnetic agitation stainless steel autoclave, add raw material 2,6 di t butyl phenol 206.0g (1.0mol) successively, 36.0% formalin 163.0g (1.956mol), dehydrated alcohol 475.0g, water 91.0g, Na2S9H
2O180g (0.75mol).Start stirring, the reaction raw materials in the thorough mixing still.When temperature rises to 62-65 ℃, stop heating, insulation reaction 20 minutes, reaction finishes.Be cooled to 25-30 ℃, add 50% sulfuric acid 147g neutralization reaction mixture, below carry out aftertreatment, obtain having particulate state pure white crystalline 201g of the present invention, fusing point: 141.8-142.5 ℃ by the same procedure of embodiment 1.Yield 85.5%.
Claims (3)
1. method for preparing sulfur-containing bisphenol compounds anti-oxidant, it is characterized in that adopting ethanol or methanol aqueous solution is reaction solvent, alkali metal hydroxide is a catalyzer, 2,6-di-tert-butylphenol, formaldehyde, hydrogen sulfide are reaction raw materials, carry out the sulfo-condensation reaction in closed reaction kettle, generate sulfur-containing bisphenol compounds anti-oxidant, be two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) thioethers shown in the formula (I)
Wherein 2, the mol ratio of 6-t-butyl phenol and formaldehyde is 1: 1.85～2.0,2, the mol ratio of 6-t-butyl phenol and hydrogen sulfide is 1: 0.75～1.0,2, the mol ratio of 6-t-butyl phenol and alkali metal hydroxide is 1: 0.8～1.0, and the massfraction of ethanol in the aqueous solution is that 55-65% or the massfraction of methyl alcohol in the aqueous solution are 70-85%, temperature of reaction is 50-65 ℃, and the reaction times is 20-30 minute; Alkali metal hydroxide refers to sodium hydroxide or potassium hydroxide.
2. a kind of method for preparing sulfur-containing bisphenol compounds anti-oxidant according to claim 1 is characterized in that with the alkali metal hydroxide catalyzer in sulfuric acid or the hydrochloric acid neutralization reaction mixture, makes the hydrogen sulfide raw material in the reaction mixture be unbound state and separation.
3. a kind of method for preparing sulfur-containing bisphenol compounds anti-oxidant according to claim 1, after it is characterized in that from reaction mixture, removing ethanol or methyl alcohol, add aliphatic solvents, wash with water, with the described sulfur-containing bisphenol compounds anti-oxidant Crystallization Separation that is contained in the aliphatic solvents, directly obtain having particulate state pure white crystalline sulfur-containing bisphenol compounds anti-oxidant.
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| CN102617424B (en) * | 2012-02-23 | 2014-05-07 | 常州大学 | Method for preparing sulfur-containing bisphenol compound antioxidant by means of recycling mother liquor |
| CN103012225B (en) * | 2012-12-10 | 2014-10-29 | 常州大学 | Method for synthesizing sulfur-containing bisphenol compound antioxidant |
| CN107721891B (en) * | 2016-08-17 | 2019-05-14 | 宁波百思佳医药科技有限公司 | The environment-friendly preparation method thereof of BIHOBS a kind of and its application in anti-corrosive fresh-keeping field |
| CN110938239A (en) * | 2019-12-12 | 2020-03-31 | 梁山新翔新材料有限公司 | Hindered phenol antioxidant and synthesis method thereof |
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Non-Patent Citations (2)
| Title |
|---|
| A. E. Prosenko et al.Synthesis and Antioxidant Properties.《Russian Journal of Applied Chemistry》.2003,第76卷(第2期),256-260. * |
| 王加源.最优回归设计与逐步回归分析在抗氧剂甲叉4426-S合成中的应用.《合成材料老化与应用》.1980,1-3、6-7页. * |
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