CN107501143A - A kind of preparation method of the methylphenol of antioxidant 2,4 2 (n-octylthiomethylene) 6 - Google Patents
A kind of preparation method of the methylphenol of antioxidant 2,4 2 (n-octylthiomethylene) 6 Download PDFInfo
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- CN107501143A CN107501143A CN201710833776.5A CN201710833776A CN107501143A CN 107501143 A CN107501143 A CN 107501143A CN 201710833776 A CN201710833776 A CN 201710833776A CN 107501143 A CN107501143 A CN 107501143A
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Abstract
The present invention relates to a kind of antioxidant 2, the preparation method of 4 two (n-octylthiomethylene) 6 methylphenol, it is characterized in that in closed reactor, in the presence of secondary amine catalyst, raw material ortho-methyl phenol, benzaldehyde compound, n-octyl mercaptan reaction generation antioxidant 2,4 two (n-octylthiomethylene) 6 methylphenol；Desolvation after reaction, water, the unreacting material of catalyst and excess, obtain product；Product can be purified further.This method catalyst and class raw materials of compound dosage are few, and easily removing is clean after reaction, and product will not change colour, transparent shape.
Description
Technical field
The present invention relates to a kind of preparation technology of a kind of preparation method of antioxidant, specifically phenolic antioxidant 1520,
It is a kind of in closed reactor, using secondary amine as catalyst, raw material ortho-methyl phenol, n-octyl mercaptan, benzaldehyde compound reaction
Afterwards, it is purified to obtain the method for the light colorless product of smell.
Background technology
Antioxidant 2, also referred to as 4- bis- (n-octylthiomethylene) -6- methylphenols, antioxidant 1520, its molecular formula are
C25H44OS2, structural formula is as follows：
2,4- bis- (n-octylthiomethylene) -6- methylphenols are a kind of Hinered phenols antioxidants of alkyl containing mercaptan,
There is thioether and hindered phenol Liang Zhong functional groups, this two class there is the group of cooperative effect to together provide antioxygen be turned into structure
With.2,4- bis- (n-octylthiomethylene) -6- methylphenols have the advantages that toxicity is low, color and luster contaminative is small, compatibility is strong；Its
Volatility is very low, has extremely low volatilization consumption in processing, dry and storage, therefore, it is using increasingly extensive.
At present, antioxidant 2, (the n-octylthiomethylene) -6- of 4- bis- methylphenols are mainly with ortho-methyl phenol, just pungent sulphur
Alcohol, paraformaldehyde are Material synthesis, and the reaction equation of synthetic route is as follows：
In the presence of a catalyst, antioxidant 2,4- bis- are prepared as raw material using ortho-methyl phenol, n-octyl mercaptan, paraformaldehyde
(n-octylthiomethylene) -6- methylphenols, by charging reaction order successively, the difference of operating method, " substep can be divided into
Method " and " one kettle way ".
" method of fractional steps " refers to that excessive formaldehyde (being decomposed by paraformaldehyde) and secondary amine occur with ortho-methyl phenol first
Mannich reactions generate amine-methylated intermediate；It is anti-at 150 DEG C or so with n-octyl mercaptan again after amine-methylated intermediate is purified
2,4- bis- (n-octylthiomethylene) -6- methylphenols should be generated, product is purified to obtain through post-processing approach such as distillations.The method is reacted
Process is relatively cumbersome, and the dosage of secondary amine is big, and the preparation purge process of intermediate is also required to more time, and yield is relatively low.
Such as method 1：Patent US3832328 in 1999 is reported first with ortho-methyl phenol and the paraformaldehyde and two of excess
Methylamine is prepared for Mannich base, and Mannich base removes volatile amine with thiol reactant, heating again, and generation sulfidomethyl phenol derives
Thing, the method that then separating-purifying obtains product.The method course of reaction is relatively cumbersome, and needs to use substantial amounts of dimethylamine, in
The preparation purge process of mesosome is also required to more time, and yield is relatively low, and is not suitable for industrialized production.
" one kettle way " is in the case of secondary amine makees catalyst, and ortho-methyl phenol, n-octyl mercaptan, formaldehyde are (by paraformaldehyde point
Solution) three kinds of raw materials are mixed together and carry out reaction and generate (the n-octylthiomethylene) -6- methylphenols of antioxidant 2,4- bis-.
Method 2：CIBA companies of Switzerland in 1998 are disclosed with neighbour in patent US4874885A and European patent EP 1116714
Methylphenol, n-octyl mercaptan, excessive poly methanol are raw material, are with dimethylamine agueous solution, dimethylformamide (DMF) respectively
Catalysts and solvents, the method for preparing 2,4- bis- (n-octylthiomethylene) -6- methylphenols.The method produces more waste water, production
Product are weak yellow liquid, and purity and yield are all relatively low.Need to use sodium borohydride, thus production cost during purifying products
Height, purification step are complicated.
Method 3：At home, Zhou Qin et al. have studied using ortho-methyl phenol, n-octyl mercaptan, excess paraformaldehyde as original
Material, decil alcoholic solution is catalyst, and DMF is solvent, synthesizes the side of 2,4- bis- (n-octylthiomethylene) -6- methylphenols
Method, because water contained in dimethylamine solution can suppress the generation of reaction, and formaldehyde generation imines ion intermediate is not easy to, led
Yield is caused to reduce；And excessive paraformaldehyde removing is difficult.
Compared to " method of fractional steps ", " one kettle way " is simple to operate, and yield is also high, and secondary amine dosage is few.
But either " method of fractional steps ", still " one kettle way ", what is used at present is all atmospheric pressure reflux reaction, and reactant formaldehyde exists
It is easy for vaporing away under reaction temperature, so while participate in reaction is formaldehyde, but can only be made of the high paraformaldehyde of boiling point
Raw material, low boiling site catalyst such as dimethylamine can only also use the aqueous solution, or make catalyst with of a relatively high piperidines of boiling point etc., but i.e.
Make be so, dimethylamine, piperidines, paraformaldehyde decompose caused by formaldehyde can also have partial loss during the course of the reaction, institute was in the past
It is past significantly excessive.Paraformaldehyde, piperidines removing are clean difficult after so reacting, and dimethylamine agueous solution can cause many waste water to produce
It is raw, also there is substantial amounts of organic exhaust gas.And due to being opening reaction, product is easily partly oxidized, with color.
The content of the invention
The invention aims to overcome existing atmospheric pressure reflux preparation method to exist because raw material easily runs mistake, often make
With the high raw material of boiling point, and the excess raw material removing that dosage is brought more is clean difficult, and the organic exhaust gas that equipment opening band is come is more,
The bad deficiency of product colour, there is provided a kind of simple to operate, formaldehydes raw material, catalyst amount are few, and it is easy to be removed after reaction,
High, of light color, smell the is light preparation side of obtained antioxidant 2,4- bis- (n-octylthiomethylene) -6- methylphenol product purities
Method.
The realization of the object of the invention, comprises the following steps：
(1) in the presence of a catalyst, raw material ortho-methyl phenol, formaldehydes raw material, n-octyl mercaptan react conjunction in closed kettle
Into 2,4- bis- (n-octylthiomethylene) -6- methylphenols, i.e. antioxidant 1520.
(2) after reacting, desolvation, water, catalyst and excessive response raw material, product is obtained.
In the step (1) added catalyst be dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine,
One or more of mixtures in di-iso-butylmanice, two tert-butylamines, piperidines.
Added formaldehydes raw material is paraformaldehyde, metaformaldehyde, formaldehyde gas, formalin in the step (1)
In one kind, or several mixture.
In the step (1) reaction can not solubilizer, can also solubilizer.Added solvent can be N, N- dimethyl
Formamide, N, N- diethylformamides, DMA, N, N- diethyl acetamides, DMA, N, N-
Diethylaniline, N, N- dimethyl benzylamines, N, one or more of mixtures in N- diethyl benzylamines.
Preferably, in above-mentioned preparation process, added formaldehydes raw material is metaformaldehyde or formaldehyde in the step (1)
Gas, solvent are DMF, and secondary amine catalyst is dimethylamine gas, piperidines.
Raw material formaldehyde (or paraformaldehyde decompose caused by formaldehyde) in the step (1) is with o-cresol mole ratio
2.00~3.00, raw material n-octyl mercaptan is 2.00~2.20 with o-cresol mole ratio；Reaction temperature is 70~180 DEG C, instead
It is 3~9h between seasonable.
Preferably, in above-mentioned preparation process, raw material formaldehyde in the step (1) (or caused by paraformaldehyde resolution
Formaldehyde) with o-cresol mole ratio it is 2.02~2.10, raw material n-octyl mercaptan and o-cresol mole ratio be 2.00~
2.02；Reaction temperature is 120~150 DEG C, and the reaction time is 3~4h.
The crude product that the step (2) obtains can be purified further, and method of purification can be washing, crystallization, or cooling
The method of washing.
Beneficial effect：Preparation method of the present invention can use the lower boiling raw materials such as formaldehyde, dimethylamine, and dosage
It is few, it can be removed after reaction clean；Product colour is light.And it is technical scheme concise in technology, simple to operate, easily realize industrial metaplasia
Production.
Specific implementation method
It is illustrative to the application and further understand below in conjunction with specific embodiment, but embodiment is only used as example
Son provides, and is not intended as whole technical schemes of the present invention, is not limited overall technical solution.It is all have it is identical or
Similar technique feature, simple change or replacement, belong to the scope of the present invention.
Embodiment 1
In the pressure-resistant reactor equipped with temperature sensor and mechanical agitator add metaformaldehyde (112.32g,
1.25mol), ortho-methyl phenol (64.88g, 0.60mol), n-octyl mercaptan (176.99g, 1.21mol), solvent DMF
(120.5mL), first-class reactor.The air in reactor is discharged with nitrogen, adds dimethylamine (3.40g, about 0.076mol).Add
Heat is to 130 DEG C, reaction 3h or so.Reaction solution is put into nitrogen in the transposed four-hole boiling flask of air after reaction.Decompression is steamed
The raw material of desolventizing, water, catalyst and excess is evaporated, cooling obtains product 250.82g.
Embodiment 2
In the pressure-resistant reactor equipped with temperature sensor and mechanical agitator add metaformaldehyde (17.14g,
0.57mol), ortho-methyl phenol (32.27g, 0.28mol), n-octyl mercaptan (81.92g, 0.56mol), solvent DMF (62.0mL),
First-class reactor.The air in reactor is discharged with nitrogen, adds dimethylamine (3.21g, about 0.070mol).130 DEG C are heated to,
React 3h or so.Reaction solution is put into nitrogen in the transposed four-hole boiling flask of air after reaction.Vacuum distillation desolventizing,
The raw material of water, catalyst and excess, cooling obtain crude product 124.30g.Into crude product add 85.0mL absolute methanols and
The mixed solution of 40.0mL toluene, shakes up, and carries out low temperature crystallization purification.Filtered at low temperature after product precipitation, filter cake
Washed with low-temperature anhydrous methanol, collect solid product.Filtrate continues low temperature crystallization, filters, so circulation 3 times, and product is most of
Separate out.Merge 3 obtained crystalline products, melt, pour into separatory funnel, stand；Lower floor's product is separated, is added thereto about
35.10g anhydrous sodium sulfates and a small amount of sodium pyrosulfite, fully rock, and place.Revolving sloughs residual solvent, cools down, finally filters
Obtain product 101.89g.There is portioned product in methanol filtrate.
Embodiment 3
In the pressure-resistant reactor equipped with temperature sensor and mechanical agitator add metaformaldehyde (36.90g,
1.23mol), ortho-methyl phenol (64.60g, 0.60mol), n-octyl mercaptan (175.54g, 1.20mol), solvent DMF
(93.3mL), first-class reactor.The air in reactor is discharged with nitrogen, adds dimethylamine (3.57g, about 0.079mol).Add
Heat is to 130 DEG C, reaction 3h or so.Reaction solution is put into nitrogen in the transposed four-hole boiling flask of air after reaction.Decompression is steamed
The raw material of desolventizing, water, catalyst and excess is evaporated, cooling obtains crude product 258.68g.Into crude product add 190.0mL without
The mixed solution of water methanol and 85.0mL toluene, shakes up, and carries out low temperature crystallization purification.Taken out at low temperature after product precipitation
Filter, filter cake are washed with low-temperature anhydrous methanol, collect solid product.Filtrate continues low temperature crystallization, filters, so circulation 3 times, product
It is most of to separate out.Merge 3 obtained crystalline products, melt, pour into separatory funnel, stand；Lower floor's product is separated, thereto
About 55.23g anhydrous sodium sulfates and a small amount of sodium pyrosulfite are added, is fully rocked, is placed.Revolving sloughs residual solvent, cools down, most
Filter afterwards and obtain end-product 208.50g.There is portioned product in methanol filtrate.
Embodiment 4
In the pressure-resistant reactor equipped with temperature sensor and mechanical agitator add metaformaldehyde (31.50g,
0.35mol), ortho-methyl phenol (18.28g, 0.17mol), n-octyl mercaptan (49.74g, 0.34mol), solvent DMF (28.0mL),
First-class reactor.The air in reactor is discharged with nitrogen, adds dimethylamine (1.24g, about 0.028mol).130 DEG C are heated to,
React 3h or so.Reaction solution is put into nitrogen in the transposed four-hole boiling flask of air after reaction.Vacuum distillation desolventizing,
The raw material of water, catalyst and excess, cooling obtain crude product 56.89g.All passages communicated with air of molecular distillation apparatus
Close.Open corresponding power supply, and the cooling water of cold plate and cold well condenser.Vacuum system is opened, the temperature of heating plate is set
Degree, it is respectively 200 DEG C, 120 DEG C that charging, which fills material preheating temperature, and the rotating speed of rotating scraped film device is 380r/min.Maintain vacuum
In the case of 125Pa or so, raw material is added dropwise, has colorless product to be flowed out from light fraction outlet after 3 minutes, maintains stable dropwise addition
Speed.Material is dripped after 45 minutes.Molecular distillation apparatus continues to start 15 minutes.Close and heat successively, rotary scraping, very
Sky, cooling water, power supply.Colorless product 44.25g is collected into altogether.Restructuring sub-export has the 2.13 grams of outflows of red thick thing, vacuum
Cold Jing Chu has 0.51 gram of liquid frowzy.With ethanol wash mill.
Claims (7)
1. a kind of preparation method of antioxidant 1520, it is characterised in that this method includes following preparation process：
(1) in the presence of a catalyst, raw material ortho-methyl phenol, formaldehydes raw material, n-octyl mercaptan react synthesis 2 in closed kettle,
4- bis- (n-octylthiomethylene) -6- methylphenols, i.e. antioxidant 1520；
(2) after reacting, desolvation, water, catalyst and excessive response raw material, product is obtained.
2. a kind of preparation method of antioxidant 1520 according to claim 1, it is characterized in that：It is added in the step (1)
Catalyst be dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-iso-butylmanice, two tert-butylamines, in piperidines
One kind, or several mixtures.
3. a kind of preparation method of antioxidant 1520 according to claim 1, it is characterized in that：It is added in the step (1)
Formaldehydes raw material can be one kind in paraformaldehyde, metaformaldehyde, formaldehyde gas, formalin, or several mixing
Thing.
4. a kind of preparation method of antioxidant 1520 according to claim 2, it is characterized in that：It is added in the step (1)
Catalyst be dimethylamine, the mixture of one or both of piperidines.
5. a kind of novel preparation method of antioxidant 1520 according to claim 3, it is characterized in that：Institute in the step (1)
The formaldehydes raw material added is metaformaldehyde or formaldehyde gas.
6. a kind of novel preparation method of antioxidant 1520 according to claim 1, it is characterized in that：In the step (1)
Raw material formaldehyde (or formaldehyde caused by paraformaldehyde resolution) is 2.00~3.00 with o-cresol mole ratio, the just pungent sulphur of raw material
Alcohol is 2.00~2.20 with o-cresol mole ratio；Reaction temperature is 70~180 DEG C, and the reaction time is 3~9h.
7. a kind of novel preparation method of antioxidant 1520 according to claim 6, it is characterized in that：In the step (1)
Raw material formaldehyde (or formaldehyde caused by paraformaldehyde resolution) is 2.02~2.10 with o-cresol mole ratio, the just pungent sulphur of raw material
Alcohol is 2.00~2.02 with o-cresol mole ratio；Reaction temperature is 120~150 DEG C, and the reaction time is 3~4h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111116983A (en) * | 2019-12-05 | 2020-05-08 | 梁山新翔新材料有限公司 | Synthetic method for emulsion type antioxidant |
| 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 |
| CN114195979A (en) * | 2021-11-18 | 2022-03-18 | 周佳男 | High-resilience antibacterial sponge and preparation method thereof |
| CN114940741A (en) * | 2022-07-11 | 2022-08-26 | 安徽冠泓塑业有限公司 | High-toughness anti-aging fire-fighting boot and production method thereof |
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| CN106905206A (en) * | 2017-03-03 | 2017-06-30 | 湘潭大学 | The preparation of 2 methyl 4,6 pairs (n-octyl sulfidomethyl) phenol |
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| CN106905206A (en) * | 2017-03-03 | 2017-06-30 | 湘潭大学 | The preparation of 2 methyl 4,6 pairs (n-octyl sulfidomethyl) phenol |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111116983A (en) * | 2019-12-05 | 2020-05-08 | 梁山新翔新材料有限公司 | Synthetic method for emulsion type antioxidant |
| 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 |
| CN114195979A (en) * | 2021-11-18 | 2022-03-18 | 周佳男 | High-resilience antibacterial sponge and preparation method thereof |
| CN114940741A (en) * | 2022-07-11 | 2022-08-26 | 安徽冠泓塑业有限公司 | High-toughness anti-aging fire-fighting boot and production method thereof |
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