CN103408475A - Preparation method of liquid antioxidant 4,6-di(octylsulfanylmethyl) o-cresol - Google Patents
Preparation method of liquid antioxidant 4,6-di(octylsulfanylmethyl) o-cresol Download PDFInfo
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Abstract
The invention relates to a preparation method of a liquid antioxidant 4,6-di(octylsulfanylmethyl) o-cresol. The preparation method comprises the following steps of: casting o-cresol, n-octyl mercaptan and paraformaldehyde in specified amount to a reaction kettle; adding a reaction solvent or then adding into water; casting a solid catalyst strong alkali and weak acid salt; then, starting stirring; continuously introducing or dropping an organic amine catalyst with a certain time; then, heating to reflux and performing reaction; after reaction, treating to obtain a product with high purity, less smell and low content of formaldehyde. The process is simple in industrial operation, low in cost and easy to realize. The yield based on o-cresol is greater than or equal to 98.0%, and the product obtained is approximately colorless. APHA is less than or equal to 10, and the product is transparent and the product purity is greater than or equal to 98.0%.
Description
Technical field
The present invention is about liquid antioxidant 4, the preparation method of 6-bis-(hot thiomethyl) ortho-cresol.It is raw material that the method adopts ortho-cresol, octyl mercaptan, paraformaldehyde, reacts under catalyzer of the present invention exists, and obtains high purity, almost colourless product with high yield of shorter reaction times.
Background technology
Liquid antioxidant 4,6-bis-(hot thiomethyl) ortho-cresol is the interior synergistic antioxidant kind of molecule that contains simultaneously hindered phenol and thioether in molecule, be applied in plastics and synthetic rubber, it is easy to emulsified, good with the phased soln of polymerization solvent, can safety, health, efficiently be used equably.In some application scenarios, can substitute the at present kinds such as the existing antioxidant BHT that causes environmental pollution, TNPP, be environmental type antioxidant kind.
Chinese invention patent CN102491925A adopts hollow nano level Al
2O
3Load H
3PO
4Synthetic 4,6-bis-(hot thiomethyl) ortho-cresol of catalyst, catalyzer prepares by pickling process, hollow Al
2O
3The diameter of nanometer ball is about 400-600nm, and aperture is 10nm, and hole is apart from 30nm, 80-90%H
3PO
4Soak.Catalyzer is realized reclaiming by again soaking.This patent adopts the solid catalyst of acid load, and its preparation and catalytic activity are difficult to guarantee.
The patent JP2009114160A of Japan Kawaguchi chemistry application is with the 1.81mol octyl mercaptan, 0.90mol ortho-cresol, the paraformaldehyde of 2.16mol86% are under the catalysis of tetramethyleneimine, 100 ℃ of reactions obtain near milk-toast 4,6-bis-(hot thiomethyl) ortho-cresol, reaction yield is 98.8%.This patented method adopts tetramethyleneimine high as solvent and catalyzer price, reclaims difficulty, causes cost high.
In the patent KR2009038270A of Korea S's brocade lake petroleum chemistry application, 6.8g ortho-cresol, 4g paraformaldehyde, 18.5g octyl mercaptan, the dimethylamine of 0.2 equivalent, the water of 5 equivalents, 0.15 the acetic acid of equivalent stirs 2h and obtains 4,6-bis-(hot thiomethyl) ortho-cresol under 120 ℃, reaction yield is 97%.In the method, use simultaneously dimethylamine and acetic acid to be catalyzer, reduced the alkalescence of dimethylamine, make speed of response and product reaction preference deteriorated.
In the patent US20080081929 of Korea S's brocade lake petroleum chemistry application, with ortho-cresol, paraformaldehyde, octyl mercaptan are raw material, and the piperidines aqueous solution is catalyzer, and reaction obtains 4,6-bis-(hot thiomethyl) ortho-cresol, and reaction yield is 97%.This patent method is used piperidines to be catalyzer, exists equally cost high, reclaims difficult problem.
Nanjing University of Technology 2007 is at chemistry world 48(2) the 107-109 page delivers the method for synthetic 4,6-bis-(hot thiomethyl) ortho-cresol, and the method be take dimethylamine and is catalyzer, and reaction yield is 90%.The method only be take dimethylamine and is catalyzer, and reaction yield is low, and product quality is difficult to reach high-quality, especially desirable appearance color.
The patent CN1990467A of Guangzhou Chemistry Inst., Chinese Academy of Sciences's application, ortho-cresol, paraformaldehyde, the reaction mol ratio of octyl mercaptan is 1:1-6:1-4, and reaction is by the catalyst reaction, and temperature of reaction is 50-250 ℃, reaction times 1-6h, wherein reaction solvent is methyl alcohol, ethanol etc., the carrier of catalyzer is silicon-dioxide, montmorillonite, gac, polyethylene, polypropylene, polyoxyethylene glycol etc., reaction yield are 98%.The catalyzer that the method adopts is solid catalyst, but still exists dissatisfactory problem on catalytic activity and products obtained therefrom quality.
The patent CN1515549A of Chemical Co. Ltd., Jilin Prov. Jiuxin Industry Group application, is characterized in that the 1mol ortho-cresol, and the 2-4mol paraformaldehyde is to add catalyst A l under the amount of ortho-cresol weight 0.5-5% at consumption
2O
3-H
3PO
4, reaction obtains 4,6-bis-(hot thiomethyl) ortho-cresol, and catalyzer also can replace with trisnonylphenyl phosphite, and reaction yield is 99%, purity 98%.It is restive that the method exists the activity of catalyzer equally, use simultaneously three nonyl benzene phosphorous acid esters can cause this catalyzer to be difficult to remove as catalyzer, although it also uses as antioxidant, but due to the meeting virose nonylphenol of hydrolysis tool in use, antioxidant kind for restriction use at present, cause antioxidant 4,6-bis-(hot thiomethyl) ortho-cresol Application Areas is restricted, and becomes the antioxidant of non-environmental protection.
In the patent EP275832A1 of Switzerland Ciba-Geigy company application, 16.22g ortho-cresol, 43.88g octyl mercaptan, 18.02g paraformaldehyde, 33% ethanolic soln, 4.1g dimethylamine, 21.4gDMF, backflow 2h obtains 61.8g4,6-bis-(hot thiomethyl) ortho-cresol, product purity 94.6%.The method has been used the high DMF of price, and it reclaims difficulty, causes cost high, and the purity of product is low simultaneously.
Summary of the invention
Method of the present invention and other prepare liquid antioxidant 4, the method of 6-bis-(hot thiomethyl) ortho-cresol, identical is, and all to adopt ortho-cresol, octyl mercaptan and paraformaldehyde be raw material, the present invention has overcome existing use solid supported catalyst in other preparation method and has been difficult for preparation, organic efficiency is low, and catalytic activity is restive; Use not environmental protection of catalytic organism agent, toxicity is high, and catalyst residue is difficult for removing in product; And long reaction time, product purity are low, the high and saturate problem of product appearance of monoadduct by-product and the novel method of establishing in reaction.Method of the present invention has adopted efficiently, has been easy to get, low-cost, the catalyzer of applying mechanically capable of circulation, has realized Reaction time shorten, improves product purity, and by product is few, and appearance color APHA value is≤10.
Liquid antioxidant 4, the preparation principle of 6-bis-(hot thiomethyl) ortho-cresol is as follows.When being reacted into product, produce single addition by product.
Ortho-cresol paraformaldehyde octyl mercaptan (NOM) 4,6-bis-(hot thiomethyl) ortho-cresol list addition by product
Of the present invention being characterized as, in reactor, measure in accordance with regulations input ortho-cresol, octyl mercaptan and paraformaldehyde, add reaction solvent, or add again water, drop into the solid catalyst strong base-weak acid salt, then open and stir, pass into continuously or drip into the organic amine catalyzer with certain hour, then be warming up under backflow and react.
Reaction solvent is alcohols, as dehydrated alcohol, aqueous ethanol or methyl alcohol, aqueous methanol.
This reaction completed reaction through 3～10 hours.
In above-mentioned preparation method, the mol ratio of raw material is ortho-cresol: octyl mercaptan: paraformaldehyde=1.0:1.95～2.05:2.20～3.60.
In the preparation method of the above, catalyzer is the mixture of organic amine and strong base-weak acid salt, organic amine such as dimethylamine, diethylamine, dimethylamine agueous solution; Strong base-weak acid salt such as sodium carbonate, salt of wormwood.
In the preparation method of the above, the mol ratio of organic amine and ortho-cresol is 1:0.10～0.40, and the mol ratio of strong base-weak acid salt and ortho-cresol is 1:0.005～0.02.
Question response is complete, reaction solution is cooled to 40～45 ℃, then the water that adds 2～4 times of quality of alcoholic solvent quality, under stirring, be warming up to 40～45 ℃, at this temperature, stirred 30～60 minutes, then be incubated standing approximately 30～60 minutes, separate upper organic phase 1 and lower floor's water (water 1).In organic phase 1, add formic acid or acetic acid, under 40～45 ℃, stirred 30～40 minutes; Use the water of the same volume of step washing and wash once, the phase (water 2) of anhydrating obtained organic phase 2 in standing rear minute.
The ratio of octyl mercaptan molar weight and ortho-cresol molar weight, adopt following treatment process A or treatment process B to process to organic phase 2 and obtain product 4,6-bis-(hot thiomethyl) ortho-cresol when feeding intake.
If following treatment process A is adopted in ratio≤2.0 of octyl mercaptan molar weight and ortho-cresol molar weight while feeding intake: by organic phase 2 through siccative, as the anhydrous magnesium sulfate dehydration, filter and namely obtain product.
As ratio>2.0 of octyl mercaptan molar weight and ortho-cresol molar weight while feeding intake, adopt following treatment process B: organic phase 2 is under agitation heated up, 100～105 ℃ of lower underpressure distillation 1～2 hour, to be with cut odorous to distillate to only, then be cooled to 40～45 ℃, add anhydrous magnesium sulfate to carry out drying, after filtering sal epsom, namely obtain product.
Merge water 1 and water 2 that twice washing separates, add sheet alkali, the pH value that makes water is 10～12, carries out normal pressure or rectification under vacuum, reclaims and obtains alcoholic solvent and dimethylamine agueous solution.This regenerant is capable of circulation to be applied mechanically.
Effect of the present invention is: reaction finishes aftertreatment and obtains high purity, and smell is little, low formaldehyde content, and the product of low colourity, this process industrial is simple to operate, and cost is low and be easy to realize.
Yield >=the 98.0%(of present method is in ortho-cresol).
The product appearance that the inventive method obtains is similar to colourless APHA≤10, is transparence, product purity >=98.0%.
Embodiment
Embodiment 1:
Extremely qualified with the air in the reactor of nitrogen replacement 2000 liters.In reactor, add ortho-cresol 400kg(3.699kmol, mol ratio is in 1.0), octyl mercaptan 1055kg(7.212kmol, mol ratio 1.95) and paraformaldehyde 278kg(9.257kmol, mol ratio 2.50), then squeeze into 95% ethanol 50kg, drop into industrial sodium carbonate solid 7.8kg(0.074kmol, mol ratio 0.02).Open to stir and condenser cooling water, at normal temperatures with adding 33% dimethylamine agueous solution 50kg(0.366kmol, mol ratio 0.10 in 30 minutes).Material is under agitation heated up, be warming up to reflux temperature, reaction is 5 hours under this reflux temperature.
In the gained reaction solution, add deionized water 100kg, under stirring, thing liquid is cooled to 42 ℃, then stopped stirring standing 30 minutes, then separate carefully lower floor's water 1, obtain organic phase 1.In organic phase 1, add formic acid 1kg, then add deionized water 100kg, under stirring, be warming up to 40～45 ℃, at this temperature, kept approximately 30 minutes.Then stratification is 30 minutes, and minute sub-cloud water 2, obtain upper organic phase 2.Gained upper organic phase 2 is added to industrial anhydrous magnesium sulfate 15kg under 40～45 ℃, stir about 30 minutes, then standing approximately 2 hours, in this temperature range, remove by filter sal epsom, obtain product, yield is 98.5%.
Water 1 and water 2 that two secondary clearings are obtained merge, and adding appropriate sheet alkali to make the pH value is 10～12, then carries out normal pressure or rectification under vacuum, reclaim alcoholic solvent and organic amine, carry out recycled.
This product quality is: outward appearance is colourless transparent liquid; APHA value≤10; 4,6-bis-(hot thiomethyl) o-cresol content 98.5%; Water-content≤0.1%; Formaldehyde content≤10ppm; Octyl mercaptan content: do not detect.
Embodiment 2:
Extremely qualified with the air in the reactor of nitrogen replacement 2000 liters.In reactor, add ortho-cresol 400kg(3.699kmol, mol ratio is in 1.0), octyl mercaptan 1080kg(7.383kmol, mol ratio 2.00) and paraformaldehyde 278kg(9.257kmol, mol ratio 2.50), then squeeze into methyl alcohol 80kg and deionized water 5kg, drop into industrial magnesium phosphate solid 2.6kg(0.019kmol, mol ratio 0.005).Open to stir and condenser cooling water, at normal temperatures with adding 33% dimethylamine agueous solution 222kg(1.477kmol, mol ratio 0.40 in 30 minutes).Material is under agitation heated up, be warming up to reflux temperature, reaction is 10 hours under this reflux temperature.
In the gained reaction solution, add deionized water 320kg, under stirring, thing liquid is cooled to 40 ℃, then stopped stirring standing 60 minutes, then separate carefully lower floor's water 1, obtain organic phase 1.In upper organic phase 1, add formic acid 13kg, then add deionized water 320kg, under stirring, be warming up to 40～45 ℃, at this temperature, kept approximately 30 minutes.Then after standing 60 minutes, carry out layering, minute sub-cloud water 2, obtain upper organic phase 2.Gained upper organic phase 2 is added to industrial anhydrous magnesium sulfate 16kg under 40～45 ℃, stir about 30 minutes, then standing approximately 2 hours, in this temperature range, remove by filter sal epsom, obtain product.Yield is 98.5%.
Water 1 and water 2 that two secondary clearings are obtained merge, and add appropriate sheet alkali to make pH value 10～12, then carry out normal pressure or rectification under vacuum, reclaim alcoholic solvent and organic amine, carry out recycled.
This product quality is: outward appearance is colourless transparent liquid; APHA value≤10; 4,6-bis-(hot thiomethyl) o-cresol content 98.5%; Water-content≤0.1%; Formaldehyde content≤10ppm; Octyl mercaptan content: do not detect.
Embodiment 3:
Extremely qualified with the air in the reactor of nitrogen replacement 2000 liters.In reactor, add ortho-cresol 400kg(3.699kmol, mol ratio is in 1.0), octyl mercaptan 1110kg(7.588kmol, 2.05) and paraformaldehyde 400kg(13.320kmol, mol ratio 3.60), then squeeze into 95% ethanol 40kg and deionized water 4kg, drop into industrial magnesium phosphate solid 5.1kg(0.037kmol, mol ratio 0.010).Open to stir and condenser cooling water, at normal temperatures with adding 30% dimethylamine agueous solution 100kg(0.665kmol, mol ratio 0.18 in 30 minutes).Material is under agitation heated up, be warming up to reflux temperature, reaction is 3 hours under this reflux temperature.
In the gained reaction solution, add deionized water 80kg, under stirring, thing liquid is cooled to 40 ℃, then stopped stirring standing 40 minutes, then separate carefully lower floor's water 1, obtain organic phase 1.In this organic phase 1, add formic acid 12kg, then add deionized water 80kg, under stirring, be warming up to 40～45 ℃, at this temperature, kept approximately 30 minutes, then stratification is 30 minutes.Divide sub-cloud water 2, obtain upper organic phase 2.
The gained organic phase is squeezed into and is carried out in vacuum still with infusion pump, open to stir and vacuum, in 100～110 ℃/10～15mmHg(absolute pressure) lower vacuum distilling 1 hour, to without till being with cut odorous to distillate.
Thing liquid after vacuum distilling is cooled to 40～45 ℃, then adds industrial anhydrous magnesium sulfate 5kg, stir about 30 minutes, then standing approximately 2 hours, in this temperature range, remove by filter sal epsom, obtain product.Yield is 98.3%.
Water 1 and water 2 that two secondary clearings are obtained merge, and add appropriate sheet alkali to make pH value 10～12, then carry out normal pressure or rectification under vacuum, reclaim alcoholic solvent and organic amine, carry out recycled.
This product quality is: outward appearance is colourless transparent liquid; APHA value≤10; 4,6-bis-(hot thiomethyl) o-cresol content 98.3%; Water-content≤0.1%; Octyl mercaptan content: do not detect.
Example 4:
Extremely qualified with the air in the reactor of nitrogen replacement 2000 liters.In reactor, add ortho-cresol 400kg(3.699kmol, mol ratio is in 1.0), octyl mercaptan 1071kg(7.321kmol, mol ratio 1.98), paraformaldehyde 311kg(10.356kmol, mol ratio 2.80), then squeeze into methyl alcohol 70kg and deionized water 8kg, drop into industrial sodium carbonate solid 7.8kg(0.074kmol, mol ratio 0.02).Open to stir and condenser cooling water, at normal temperatures with adding 35% dimethylamine agueous solution 119kg(0.924kmol, mol ratio 0.25 in 20 minutes).Material is under agitation heated up, be warming up to reflux temperature, reaction is 3.5 hours under this reflux temperature.
In the gained reaction solution, add deionized water 160kg, under stirring, thing liquid is cooled to 40 ℃, then stopped stirring standing 40 minutes, then separate carefully lower floor's water 1, obtain organic phase 1.In this organic phase 1, add acetic acid 10kg, then add deionized water 160kg, under stirring, be warming up to 40～45 ℃, at this temperature, kept approximately 30 minutes.Then stratification is 30 minutes, and minute sub-cloud water 2, obtain upper organic phase 2.Gained upper organic phase 2 is added to industrial anhydrous magnesium sulfate 10kg under 40～45 ℃, stir about 30 minutes, then standing approximately 2 hours, in this temperature range, remove by filter sal epsom, obtain product.Yield is 98.6%.
Water 1 and water 2 that two secondary clearings are obtained merge, and add appropriate sheet alkali to make pH value 10～12, then carry out normal pressure or rectification under vacuum, reclaim alcoholic solvent and organic amine, carry out recycled.
This product quality is: outward appearance is colourless transparent liquid; APHA value≤10; 4,6-bis-(hot thiomethyl) o-cresol content 98.6%; Water-content≤0.1%; Formaldehyde content≤10ppm; Octyl mercaptan content: do not detect.
Example 5:
Extremely qualified with the air in the reactor of nitrogen replacement 2000 liters.In reactor, add ortho-cresol 400kg(3.699kmol, mol ratio is in 1.0), octyl mercaptan 1083kg(7.403kmol, mol ratio 2.00), paraformaldehyde 278kg(9.257kmol, mol ratio 2.50), then squeeze into ethanol 90kg and deionized water 15kg, drop into industrial sodium carbonate solid 6.0kg(0.057kmol, mol ratio 0.015).Open to stir and condenser cooling water, at normal temperatures with adding diethylamine 54.0kg(0.738kmol, mol ratio 0.20 in 30 minutes).Material is under agitation heated up, be warming up to reflux temperature, reaction is 3 hours under this reflux temperature.
In the gained reaction solution, add deionized water 150kg, under stirring, thing liquid is cooled to 40 ℃, then stopped stirring standing 60 minutes, then separate carefully lower floor's water 1, obtain organic phase 1.In upper organic phase 1, add acetic acid 7kg, then add deionized water 150kg, under stirring, be warming up to 40～45 ℃, at this temperature, kept approximately 30 minutes, then stratification is 30 minutes.Divide sub-cloud water 2, obtain upper organic phase 2.Gained upper organic phase 2 is added to industrial anhydrous magnesium sulfate 15kg under 40～45 ℃, stir about 30 minutes, then standing approximately 2 hours, in this temperature range, remove by filter sal epsom, obtain product.Yield is 98.6%.
Water 1 and water 2 that two secondary clearings are obtained merge, and add appropriate sheet alkali to make pH value 10～12, then carry out normal pressure or rectification under vacuum, reclaim alcoholic solvent and organic amine, carry out recycled.
This product quality is: outward appearance is colourless transparent liquid; APHA value≤10; 4,6-bis-(hot thiomethyl) o-cresol content 98.6%; Water-content≤0.1%; Formaldehyde content≤10ppm; Octyl mercaptan content: do not detect.
Example 6:
Extremely qualified with the air in the reactor of nitrogen replacement 2000 liters.In reactor, add ortho-cresol 400kg(3.699kmol, mol ratio is in 1.0), octyl mercaptan 1087kg(7.430kmol, mol ratio 2.01), paraformaldehyde 244kg(8.125kmol, mol ratio 2.20), then squeeze into ethanol 75kg and deionized water 5kg, drop into industrial magnesium phosphate solid 6.0kg(0.057kmol, mol ratio 0.015).Open to stir and condenser cooling water, at normal temperatures with passing into dimethylamine gas 33.5kg(0.743kmol, mol ratio 0.20 in 30 minutes).Material is under agitation heated up, be warming up to reflux temperature, reaction is 3 hours under this reflux temperature.
In the gained reaction solution, add deionized water 200kg, under stirring, thing liquid is cooled to 40 ℃, then stopped stirring standing 40 minutes, then separate carefully lower floor's water 1, obtain organic phase 1.In this organic phase 1, add acetic acid 10kg, then add deionized water 200kg, under stirring, be warming up to 40～45 ℃, at this temperature, kept approximately 30 minutes, then stratification is 30 minutes.Divide sub-cloud water 2, obtain upper organic phase 2.Gained upper organic phase 2 is added to industrial anhydrous magnesium sulfate 10kg under 40～45 ℃, stir about 30 minutes, then standing approximately 2 hours, in this temperature range, remove by filter sal epsom, obtain product.Yield is 98.7%.
Water 1 and water 2 that two secondary clearings are obtained merge, and add appropriate sheet alkali to make pH value 10～12, then carry out normal pressure or rectification under vacuum, reclaim alcoholic solvent and organic amine, carry out recycled.
This product quality is: outward appearance is colourless transparent liquid; APHA value≤10; 4,6-bis-(hot thiomethyl) o-cresol content 98.7%; Water-content≤0.1%; Formaldehyde content≤10ppm; Octyl mercaptan content: do not detect.
Comparative Examples:
Extremely qualified with the air in the reactor of nitrogen replacement 2000 liters.In reactor, add ortho-cresol 400kg(3.699kmol, mol ratio is in 1.0), octyl mercaptan 1080kg(7.383kmol, mol ratio 2.00), paraformaldehyde 311kg(10.356kmol, mol ratio 2.80) and, then squeeze into methyl alcohol 50kg.Open to stir and condenser cooling water, at normal temperatures with adding 35% dimethylamine agueous solution 191kg(1.483kmol, mol ratio 0.40 in 20 minutes).Material is under agitation heated up, be warming up to reflux temperature, reaction is 11.5 hours under this reflux temperature.
In the gained reaction solution, add deionized water 200kg, under stirring, thing liquid is cooled to 40 ℃, then stopped stirring standing 40 minutes, then separate carefully lower floor 1, obtain organic phase 1.In upper organic phase 1, add acetic acid 10kg, then add deionized water 200kg, under stirring, be warming up to 40～45 ℃, at this temperature, kept approximately 30 minutes, then stratification is 30 minutes.Divide sub-cloud water 2, obtain upper organic phase 2.Gained upper organic phase 2 is added to industrial anhydrous magnesium sulfate 18kg under 40～45 ℃, stir about 30 minutes, then standing approximately 2 hours, in this temperature range, remove by filter sal epsom, obtain product.Yield is 96.2%.
This product quality is: outward appearance is colourless transparent liquid; The APHA value is 30-50; 4,6-bis-(hot thiomethyl) o-cresol content 96.2%; Water-content≤0.1%; Formaldehyde content≤10ppm; Octyl mercaptan content: do not detect.
Claims (10)
1. liquid antioxidant 4, the preparation method of 6-bis-(hot thiomethyl) ortho-cresol, it is characterized in that, in reactor, drop into ortho-cresol, octyl mercaptan and paraformaldehyde, add reaction solvent, drop into the solid catalyst strong base-weak acid salt, then open and stir, add continuously the organic amine catalyzer, then be warming up under backflow and react.
2. the method for claim 1, is characterized in that described reaction solvent is methyl alcohol or ethanol.
3. the method for claim 1, add water again while it is characterized in that in described reaction solvent not containing water.
4. the method for claim 1, is characterized in that ortho-cresol: octyl mercaptan: paraformaldehyde=1.0:1.95～2.05:2.20～3.60 mol ratios.
5. the method for claim 1, is characterized in that catalyzer is the mixture of organic amine and strong base-weak acid salt, and organic amine is dimethylamine, diethylamine or dimethylamine agueous solution; Strong base-weak acid salt is sodium carbonate or salt of wormwood.
6. the method for claim 1, the mol ratio that it is characterized in that organic amine and ortho-cresol is 1:0.10～0.40, the mol ratio of strong base-weak acid salt and ortho-cresol is 1:0.005～0.02.
7. method claimed in claim 1 is described, it is characterized in that after being warming up under backflow and having reacted, reaction solution is cooled to 40～45 ℃, then the water that adds 2～4 times of quality of alcoholic solvent quality, under stirring, be warming up to 40～45 ℃, at this temperature, stirred 30～60 minutes, and then be incubated standing approximately 30～60 minutes, separate upper organic phase 1 and lower floor's water 1; In organic phase 1, add formic acid or acetic acid, under 40～45 ℃, stirred 30～40 minutes; Use the water of the same volume of step washing and wash once, the standing rear minute phase 2 of anhydrating, obtain organic phase 2.
8. method as claimed in claim 7, is characterized in that if ratio≤2.0 of octyl mercaptan molar weight and ortho-cresol molar weight while feeding intake, by organic phase 2 through desiccant dehydrations, filter and namely obtain product.
9. method as claimed in claim 6, ratio>2.0 that it is characterized in that octyl mercaptan molar weight and ortho-cresol molar weight when feeding intake, organic phase 2 is under agitation heated up, 100～105 ℃ of lower underpressure distillation 1～2 hour, to be with cut odorous to distillate to only, then be cooled to 40～45 ℃, add anhydrous magnesium sulfate to carry out drying, after filtering sal epsom, namely obtain product.
10. method as claimed in claim 6, is characterized in that merging water 1 and the water 2 that twice washing separates, and adds sheet alkali, and the pH value that makes water is 10～12, carries out normal pressure or rectification under vacuum, reclaims and obtain alcoholic solvent and dimethylamine agueous solution.
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| CN104478771A (en) * | 2014-11-26 | 2015-04-01 | 东南大学 | Purification method of hindered-phenol efficient antioxidant |
| CN104974064A (en) * | 2015-06-15 | 2015-10-14 | 江苏常州酞青新材料科技有限公司 | Preparation method of anti-oxidant 2,4-(dioctylthiol-6-methyl)phenol |
| CN106905206A (en) * | 2017-03-03 | 2017-06-30 | 湘潭大学 | The preparation of 2 methyl 4,6 pairs (n-octyl sulfidomethyl) phenol |
| CN113045462A (en) * | 2021-03-24 | 2021-06-29 | 江苏极易新材料有限公司 | Synthesis method of antioxidant 1520 |
| CN114031530A (en) * | 2021-11-10 | 2022-02-11 | 枣阳市福星化工有限公司 | Preparation method of 2, 4-di (n-octylthiomethylene) -6-methylbenzene-phenol |
| WO2022092655A1 (en) * | 2020-10-30 | 2022-05-05 | 금호석유화학 주식회사 | Method for preparing thiomethylphenol derivative |
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| CN115151528A (en) * | 2020-10-30 | 2022-10-04 | 锦湖石油化学株式会社 | Process for preparing thiomethylphenol derivatives |
| CN113045462A (en) * | 2021-03-24 | 2021-06-29 | 江苏极易新材料有限公司 | Synthesis method of antioxidant 1520 |
| CN114031530A (en) * | 2021-11-10 | 2022-02-11 | 枣阳市福星化工有限公司 | Preparation method of 2, 4-di (n-octylthiomethylene) -6-methylbenzene-phenol |
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