CN1760180A - Method for synthesizing modified-antioxidant 300 - Google Patents
Method for synthesizing modified-antioxidant 300 Download PDFInfo
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- CN1760180A CN1760180A CN 200510045113 CN200510045113A CN1760180A CN 1760180 A CN1760180 A CN 1760180A CN 200510045113 CN200510045113 CN 200510045113 CN 200510045113 A CN200510045113 A CN 200510045113A CN 1760180 A CN1760180 A CN 1760180A
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Abstract
An improved process for preparing the antioxidizing agent 300 includes such steps as the thio-reaction between SCl2 and 5-methyl-2-tert-butyl phenol existence of petroleum ether while filling N2 at final reaction phase for regulating pH value and promoting reaction, water washing the coarse product for removing by-product and impurities, filtering and drying. Its advantages are high purity and quality of product and no environmental pollution.
Description
Technical field
The present invention relates to a kind of improved antioxidant 300 synthetic method, belong to organic synthetic technology.
Background technology
Antioxidant 300 promptly refers to 4, and 4 '-thiobis (5-methyl-2-tert.-butyl phenol) oxidation inhibitor is a kind of extraordinary thiobisphenol kind antioxidant, adds to reach the effect that prevents the alkene degraded, delays variable color on a small quantity in polyolefine.Its route of synthesis is under the condition of non-polar solvent (such as sherwood oil), carry out thio reaction by sulfur dichloride and 5-methyl-2-tert.-butyl phenol under relatively low temperature and make crude product, but yield often is not very high.Once relevant for the report of making reaction solvent with tetracol phenixin, though it is can improve reaction yield, tetracol phenixin is poisonous, big especially to the injury of human body, and find that also its solubleness for 300 products is bigger with respect to sherwood oil in the experiment, also influential to the complexity of obtaining product.Therefore, from the technology that present domestic production producer is adopted, what generally adopt is under 5 ℃ to 15 ℃ condition, and sulfur dichloride and 5-methyl-2-tert.-butyl phenol react in sherwood oil is made boundary's matter of solvent, obtain the antioxidant 300 crude product, obtain elaboration by recrystallization then.
As everyone knows, nearly all organic reaction all is a quite complicated process, wherein is mingled with a lot of side reactions, and Fan Ying balanced degree also relatively is difficult to grasp simultaneously.The building-up process of antioxidant 300 is no exception, we find in experiment, because there is bigger dissolving in the hydrogen chloride gas that reaction process generates in solution, have stoped forward reaction further to carry out, make the thio reaction can not be thorough as we are desirable, cause the crude reaction yield low.More traditional way is in the latter stage of thio reaction reaction system to be led to N at present
2, drive a certain amount of hydrogen chloride gas away, prolong the reaction times simultaneously, but effect not very desirable.Can see that from relevant report the yield for preparing the antioxidant 300 crude product by this method is greatly about about 85%, and is still lower, needs further improvement.
Summary of the invention
The object of the present invention is to provide a kind of improved antioxidant 300 synthetic method, crude reaction yield height and purity height, color and luster are good.
Improved antioxidant 300 synthetic method of the present invention, under sherwood oil non-polar solvent condition, carry out thio reaction by sulfur dichloride and 5-methyl-2-tert.-butyl phenol and make crude product, it is characterized in that in reaction system, feeding ammonia in the latter stage of thio reaction, dissolved hydrogen chloride gas in the neutralization solution is adjusted the reaction soln pH value, promotes reaction to carry out to the positive reaction direction, improve the crude product yield, the crude product yield reaches more than 90%.
It is 6～9 suitable to feed behind the ammonia pH value of control reaction soln and be, the best is 7～8.
The feeding situation visual response situation of ammonia determines, sees influence factors such as the size of solution amount and speed of response, determines that by the control pH value total amount gets final product.In the experiment that we carry out, NH
3Gas flow rate generally is controlled to be 10ml/min-80ml/min, preferably 20ml/min-50ml/min; Logical NH
3The time of gas generally is controlled at 30min-90min, preferably 45min-60min.
The reaction batching is determined to get final product according to reaction equation.
After thio reaction finishes, wash product with water, remove byproduct of reaction and impurity after, filter again, dry subsequent disposal, can obtain highly purified crude product, and make the color color and luster of crude product obtain very big change, improve the crude product quality.
Synthetic method of the present invention is the latter stage at original thio reaction, changes over to lead to N
2Method, adopt logical NH
3Gas is protected reaction system, NH
3The hydrogenchloride that generates with reaction can neutralize completely, and dissolved hydrogenchloride is still less remaining in the reaction system that makes, and promotes balance to carry out to the positive reaction direction, and the organic reaction degree is more thorough.Take WATER-WASHING METHOD to remove the ammonium chloride of reaction generation and by product and the impurity that reaction process generates simultaneously, the purity of crude reaction, color also obtain bigger change.
Synthetic method of the present invention is ingenious rationally, crude reaction yield height, and the purity height, color and luster is good, quality is good, is convenient to operation again, implements easily, and non-environmental-pollution is beneficial to and applies.
Embodiment
The invention will be further described below in conjunction with the foregoing description.
Embodiment 1
In the four-hole boiling flask of the 500ml that agitator, thermometer and constant pressure funnel are housed, add the 5-methyl-2-tert.-butyl phenol of 100g and the sherwood oil of 300ml, solution is cooled to 12 ℃ under the whipped state, sherwood oil (100ml) solution of solvent sulfur dichloride (31.4g) moves into constant pressure funnel, and in 2.5 hours time, slowly be added drop-wise in the reaction flask, keep the temperature in the four-hole bottle to be no more than 12 ℃ simultaneously, drip the back and continue to stir insulation, with the logical NH of flow velocity of 30ml/min
3Gas 50min detects pH value of solution value 7.3, stops ventilatory response solution and slowly rises to room temperature, and byproduct and ammonium chloride are removed in washing, reaction soln pressure filtration, and filter cake gets crude product 101g after washing cryodrying with petroleum ether solvent, and yield is 92.6%.The product fusing point is determined as 157-159 ℃ with capillary tube technique.
Original method compares:
In the four-hole boiling flask of the 500ml that agitator, thermometer and constant pressure funnel are housed, add the 5-methyl-2-tert.-butyl phenol of 100g and the sherwood oil of 300ml, under whipped state, make reaction soln be cooled to 12 ℃, the ready prepd mixed solution that is dissolved with sulfur dichloride (31.4g) sherwood oil (100ml) is moved into constant pressure funnel, keep the temperature in the reaction flask to be no more than 12 ℃, in 2.5 hours time, the mixed solution in the constant pressure funnel slowly is added drop-wise to reaction flask, continue to stir and insulation, with flow velocity logical N in reaction flask of 30ml/min
2Gas 50min slowly rises to room temperature then, reaction system pressure filtration, and filter cake gets crude product 92g with petroleum ether solvent washing cryodrying, and yield is 84.4%.The product fusing point is determined as 156.5-158 ℃ with capillary tube technique.
Embodiment 2
In being housed, the 1000ml four-hole reaction flask of agitator, thermometer and constant pressure funnel adds the 5-methyl-2-tert.-butyl phenol of 200g and the sherwood oil of 550ml, solution is cooled to 12 ℃ under the whipped state, pour solvent sulfur dichloride (63g)+sherwood oil (200ml) solution into constant pressure funnel, in 3 hours the solution in the constant pressure funnel slowly is added dropwise to reaction flask, keep the temperature in the reaction flask to be no more than 12 ℃ simultaneously, drip and continue to stir insulation, with the logical NH of flow of 50ml/min
3Gas 40min detects pH value of solution value 7.5, stops ventilatory response solution and slowly rises to room temperature, the method of washing with water is removed less byproduct and ammonium chloride, solution pressure filtration, filter cake washs cryodrying then with petroleum ether solvent and gets antioxidant 300 crude product 102g, amounts to yield and is about 93.5%.The product fusing point is sent out with kapillary and is determined as 156.5-159 ℃.
Embodiment 3
In the four-hole reaction flask of the 1000ml that agitator, thermometer and constant pressure funnel are housed, add the 5-methyl-2-tert.-butyl phenol of 200g and the sherwood oil of 550ml, make solution reduce to 10 ℃ under the whipped state, sherwood oil (200ml) solution that will be dissolved with sulfur dichloride (63g) moves into constant pressure funnel, in 3 hours, slowly be added dropwise in the reaction flask, keep solution temperature to be no more than 10 ℃, we lead to NH with the speed of 50ml/min in reaction flask under whipped state to drip off the back
3Gas 30min detects pH value of solution value 7.8, stops ventilation and slowly rises to room temperature, and byproduct and ammonium chloride are removed in washing, and filter cake gets antioxidant 300 crude product 98g with petroleum ether solvent washing back cryodrying after the reaction soln pressure filtration, and yield is 90%.The product fusing point is determined as 157-159 ℃ with the kapillary assay method.
Embodiment 4
In the four-hole reaction flask of the 1000ml that agitator, thermometer and constant pressure funnel are housed, add the 5-methyl-2-tert.-butyl phenol of 200g and the sherwood oil of 600ml, make solution reduce to 10 ℃ under the whipped state, solvent sulfur dichloride (63g)+sherwood oil (200ml) solution is moved into constant pressure funnel, and in 3 hours, slowly be added dropwise in the reaction flask, keep the temperature in the reaction flask to be no more than 10 ℃, drip off and continue to stir, with the logical NH of flow velocity of 40ml/min
3Gas 60min detects pH value of solution value 8.0, and the solution that stops to ventilate slowly rises to room temperature, and byproduct and ammonium chloride are removed in washing, and filter cake gets antioxidant 300 crude product 101.7g with petroleum ether solvent washing cryodrying after the reaction soln pressure filtration, and yield is 93.3%.The product fusing point is determined as 157-159.5 ℃ with the kapillary rule.
Embodiment 5
As embodiment 3, after sulfur dichloride has dropwised, control NH
3Gas feeds reaction flask with the flow velocity of 30ml/min, time lengthening is to 90min, detect pH value of solution value 8.7, the solution that stops to ventilate slowly rises to room temperature, the method of washing with water is removed by product and ammonium chloride, solution pressure filtration, filter cake gets oxidation inhibitor crude product 97.3g with petroleum ether solvent washing back cryodrying, and yield is 89.3%.The product fusing point is determined as 157-159 ℃ by capillary tube technique.
Embodiment 6
As embodiment 3, after sulfur dichloride has dropwised, NH
3Gas feeds reaction flask 70min in the flow velocity with 40ml/min, detect pH value of solution value 7.6, the solution that stops to ventilate slowly rises to room temperature, WATER-WASHING METHOD is removed by product and ammonium chloride, solution is through the washing of pressure filtration petroleum ether solvent, cryodrying obtains antioxidant 300 crude product 99.8g then, and yield is 91.6%.The product fusing point is determined as 157.5-159.5 ℃ by capillary tube technique.
Embodiment 7
As embodiment 3, after sulfur dichloride has dropwised, NH
3Gas feeds reaction flask 75min in the flow velocity with 45ml/min, detect pH value of solution value 8.5, the solution that stops to ventilate slowly rises to room temperature, and WATER-WASHING METHOD is removed by product and ammonium chloride, solution is through the washing of pressure filtration petroleum ether solvent, and cryodrying obtains the antioxidant 300 crude product then.
Embodiment 8
As embodiment 3, after sulfur dichloride has dropwised, NH
3Gas feeds reaction flask 35min in the flow velocity with 70ml/min, detect pH value of solution value 6.6, the solution that stops to ventilate slowly rises to room temperature, and WATER-WASHING METHOD is removed by product and ammonium chloride, solution is through the washing of pressure filtration petroleum ether solvent, and cryodrying obtains the antioxidant 300 crude product then.
Embodiment 9
As embodiment 1, after sulfur dichloride has dropwised, NH
3Gas feeds reaction flask 40min in the flow velocity with 60ml/min, detect pH value of solution value 7.2, the solution that stops to ventilate slowly rises to room temperature, and WATER-WASHING METHOD is removed by product and ammonium chloride, solution is through the washing of pressure filtration petroleum ether solvent, and cryodrying obtains the antioxidant 300 crude product then.
Embodiment 10
As embodiment 2, after sulfur dichloride has dropwised, NH
3Gas feeds reaction flask 60min in the flow velocity with 50ml/min, detect pH value of solution value 7, the solution that stops to ventilate slowly rises to room temperature, and WATER-WASHING METHOD is removed by product and ammonium chloride, solution is through the washing of pressure filtration petroleum ether solvent, and cryodrying obtains the antioxidant 300 crude product then.
Claims (3)
1, a kind of improved antioxidant 300 synthetic method, under sherwood oil non-polar solvent condition, carry out thio reaction by sulfur dichloride and 5-methyl-2-tert.-butyl phenol and make crude product, it is characterized in that in reaction system, feeding ammonia in the latter stage of thio reaction, adjust the reaction soln pH value, promote reaction to carry out.
2, improved antioxidant 300 synthetic method according to claim 1 is characterized in that feeding that the pH value of control reaction soln is 6～9 behind the ammonia.
3, improved antioxidant 300 synthetic method according to claim 1 and 2, it is characterized in that thio reaction finishes after, wash product with water, remove byproduct of reaction and impurity after, filter again, dry subsequent disposal.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100451134A CN1318401C (en) | 2005-11-10 | 2005-11-10 | Method for synthesizing modified-antioxidant 300 |
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| CN1318401C CN1318401C (en) | 2007-05-30 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651213A (en) * | 2019-01-31 | 2019-04-19 | 淄博万科化工有限公司 | The production method of antioxidant 300 |
| CN115073334A (en) * | 2022-07-01 | 2022-09-20 | 江苏极易新材料有限公司 | Synthesis method of 4,4' -thiobis (6-tert-butyl-m-cresol) |
-
2005
- 2005-11-10 CN CNB2005100451134A patent/CN1318401C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651213A (en) * | 2019-01-31 | 2019-04-19 | 淄博万科化工有限公司 | The production method of antioxidant 300 |
| CN115073334A (en) * | 2022-07-01 | 2022-09-20 | 江苏极易新材料有限公司 | Synthesis method of 4,4' -thiobis (6-tert-butyl-m-cresol) |
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| CN1318401C (en) | 2007-05-30 |
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