CN107540559A - A kind of antioxidant 4,4 ' is double（α, α dimethyl benzyl）The preparation method of diphenylamines - Google Patents
A kind of antioxidant 4,4 ' is double（α, α dimethyl benzyl）The preparation method of diphenylamines Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of double (α, the α dimethyl benzyl) diphenylamines of antioxidant 4,4 '.Raw material diphenylamines is added in reaction vessel first, heating makes its thawing；Catalyst compounded continuation heating stirring is added after thawing；α-methylstyrene is added dropwise after stirring, heating response is carried out after dropwise addition；After reaction terminates, gained reaction solution is cooled, then adds petroleum ether and methanol mixed solvent, room temperature is down to and carries out cooling crystallization；Finally filtered successively, petroleum ether, washing and drying, antioxidant 4,4 ' double (α, α dimethyl benzyl) diphenylamines are obtained after drying.The present invention is only needed to filter after reaction, washs the age resistor product that can obtain high quality, needed not move through the complicated last handling processes such as acidifying, alkali neutralization, washing, produced without the three wastes, also eliminate many cumbersome steps using disposable synthesis age resistor.Therefore, the present invention has significant economic benefit and social benefit.
Description
First, technical field：
The invention belongs to the technical field of rubber antioxygen preparation method, and in particular to a kind of antioxidant 4,4 '-bis- (α, α-
Dimethyl benzyl) diphenylamines preparation method.
2nd, background technology：
China's rubber antioxygen yield is increased with the speed close to 40%, wherein with diphenylamine antioxidant rate of rise most
It hurry up, growth rate reaches 60%；Phenolic antioxidant is in the downslide impetus, but therefrom it has also been found that what is disabled abroad contains carcinogenic substance
The naphthylamines kind antioxidant of matter still slightly increases unexpectedly in Chinese market.Therefore, naphthylamines class antioxygen is substituted with non-toxic, environmental friendly antioxidant
Agent is very urgent.
It is found that diphenylamines is alkylated reaction with corresponding active olefin, a kind of the anti-of nonstaining property can be obtained
Oxygen agent, and there is good antioxygen property.Such as：Diphenylamines and styrene, α-methylstyrene, nonene, Diisobutylene
Reacted etc. being alkylated, generate corresponding alkylated diphenylamine class compound, i.e. antioxidant, the height of its existing amine antioxidants
Antioxygenic effect, there is the similar free of contamination feature of phenolic antioxidant again, be widely used in rubber tyre, various rubbers, lubrication
In oil, for the amines antioxidants for replacing having contaminative and toxicity；In addition, in synthetic rubber production process, traditional antioxygen
System is based on hindered phenol compound.However, from the point of view of the stable mechanism of phenolic antioxidant, hindered phenol compound capture peroxide
Coloured quinones is converted into after free radical；The presence of aldehydes matter so that easily go out when polymer contacts with gases such as NOx
Existing metachromatism, both produce color dirt, influence the presentation quality of polymeric articles in various degree, and have for product appearance color and luster
The synthetic material of high requirement, use a kind of effective measures for without phenolate antioxidant system being solution yellowing problems.Therefore, select
Alkylated diphenylamine kind antioxidant, with the pollution-free feature of its phenolic antioxidant having and efficient antioxygenic effect, with work(
Energy property antioxidant compounding, is made no phenolic age resistor, and substituted phenol antioxidant system uses in synthetic material, and it integrates anti-aging
Performance is good, cost is low, anti-oxidant efficiency high, easy to use, has potential development trend.
Many documents on diphenylamine age resistor are had been disclosed for now.Such as：CN1195661A discloses one kind
The method that the cumenyl -4- cumenyl diphenylamines of age resistor 4,4 ' -2 is prepared by diphenylamines and 2-methyl styrene.This method
A large amount of solvents are used during the course of the reaction, and are acidified in post processing with hydrochloric acid, then are washed after being neutralized with alkali, and work is strong
Degree is big and serious to equipment corrosion；CN101538208 B disclose one kind and prepare 4- (alpha, alpha-dimethylbenzyl) diphenylamines and 4,
The method of 4 '-bis- (alpha, alpha-dimethylbenzyl) diphenylamine compounds, under the effect of catalyst activity carclazyte, in 120~175 DEG C of temperature
Under the conditions of degree, alkylated reaction is occurred into for diphenylamines and excessive α-methylstyrene, is evaporated under reduced pressure, passed through again after filtering
It is granulated or crushes, obtain 4- (alpha, alpha-dimethylbenzyl) diphenylamines and 4,4 '-bis- (alpha, alpha-dimethylbenzyl) diphenylamines mixes
Compound.This method atlapulgite addition is the 8~30% of diphenylamines weight, and dosage is big, possible bumping in course of reaction, and instead
Should obtain for mixture.
3rd, the content of the invention：
The technical problem to be solved in the present invention is：According to existing using diphenylamines and α-methylstyrene as Material synthesis antioxygen
Weak point existing for agent, the present invention provide a kind of freshly prepared side of antioxidant 4,4 '-bis- (alpha, alpha-dimethylbenzyls) diphenylamines
Method.Technical solution of the present invention uses diphenylamines and a- methyl styrenes as reactant, and addition inorganic salts are catalyst compounded, carries out
Catalytic alkylation reaction, double (alpha, alpha-dimethylbenzyl) diphenylamines of 4,4- are prepared, through organic solvent recrystallizing and refining, obtain
The higher product of purity.
In order to solve the above problems, the present invention adopts the technical scheme that：
The present invention provides a kind of preparation method of antioxidant 4,4 '-bis- (alpha, alpha-dimethylbenzyls) diphenylamines, the preparation
Method comprises the following steps：
A, raw material diphenylamines is added in reaction vessel first, heating is melted the diphenylamines of addition；Melt completely
After add it is catalyst compounded, continue heating stirring mixed；
B, after step a is well mixed, α-methylstyrene is added dropwise, time for adding is 0.5~2h；After completion of dropwise addition, control
Reaction temperature is 120~160 DEG C, and 1~2h is reacted under this temperature conditions, and reaction terminates；
C, after reaction terminates, gained reaction solution is cooled, petroleum ether and methanol mixed solvent is then added, is down to room
Temperature carries out cooling crystallization；
D, after crystallization terminates, filtered successively, petroleum ether, washing and drying, obtained after drying antioxidant 4,4 '-
Double (bis (alpha, alpha-dimethylbenzyl) base) diphenylamines.
It is multiple described in step a according to the preparation method of above-mentioned antioxidant 4,4 '-bis- (alpha, alpha-dimethylbenzyls) diphenylamines
Dosage with catalyst is the 0.3~6% of diphenylamines weight.
It is multiple described in step a according to the preparation method of above-mentioned antioxidant 4,4 '-bis- (alpha, alpha-dimethylbenzyls) diphenylamines
With catalyst be by sodium chloride, potassium chloride, frerrous chloride, magnesium chloride, aluminium chloride, anhydrous stannous chloride and zinc chloride at least
Two kinds of mixing compoundings form.
According to the preparation method of above-mentioned antioxidant 4,4 '-bis- (alpha, alpha-dimethylbenzyls) diphenylamines, Alpha-Methyl in step b
The mol ratio of addition is 1.9~2.5 between styrene and diphenylamines：1.
According to the preparation method of above-mentioned antioxidant 4,4 '-bis- (alpha, alpha-dimethylbenzyls) diphenylamines, stone described in step c
Oily ether is 60# petroleum ethers or 120# petroleum ethers.
According to the preparation method of above-mentioned antioxidant 4,4 '-bis- (alpha, alpha-dimethylbenzyls) diphenylamines, stone described in step c
The dosage of oily ether is 2~4 times of diphenylamines weight；The dosage of the methanol is 0.1~1 times of diphenylamines weight.
According to the preparation method of above-mentioned antioxidant 4,4 '-bis- (alpha, alpha-dimethylbenzyls) diphenylamines, dried described in step d
Temperature is 40~60 DEG C when dry, and drying time is 10~15h.
According to the preparation method of above-mentioned antioxidant 4,4 '-bis- (alpha, alpha-dimethylbenzyls) diphenylamines, gained produces in step d
Moisture content≤0.50% in product antioxidant 4,4 '-bis- (bis (alpha, alpha-dimethylbenzyl) base) diphenylamines.
The chemical equation being related in preparation method of the present invention is as follows：
The related raw material being related in technical solution of the present invention：
Diphenylamines：White monocline flaky crystal, 53~54 DEG C of fusing point, 302 DEG C of boiling point, density 1.160g/mL, it is soluble in third
Ketone, benzene, carbon tetrachloride and ethyl acetate, ethanol, ether, glacial acetic acid and petroleum ether are dissolved in, it is not soluble in water.
A- methyl styrenes：Colourless liquid, there is pungent odour, it is heated to polymerize, it is inflammable.Fusing point -23.21, boiling
Point 165.38, density 0.9106g/ml, refractive index 1.5386 can be common with styrene, acrylonitrile, butylene and divinylbenzene etc.
It is poly-.It is inflammable, explosion limit 0.7~3.4% (volume fraction) in air.
The positive beneficial effect of the present invention：
1st, the present invention is using disposable synthesis 4,4 '-bis- (alpha, alpha-dimethylbenzyl) diphenylamine compound age resistor, reaction
Only it need to be filtered after end, wash the age resistor product that can obtain high quality, needing not move through acidifying, alkali neutralization, washing etc.
Complicated last handling process, produced without the three wastes, also eliminate many cumbersome steps.Therefore, the present invention has significant warp
Benefit of helping and social benefit.
2nd, catalyst amount is few in preparation method of the present invention, active height, can be removed by washing from product, not influence to produce
Quality.
3rd, crystallize product using mixed solvent in preparation process of the present invention, it is not necessary to product is directly obtained by distillation,
Eliminate many cumbersome steps.
In a word, 4, the 4 ' of present invention process preparation-bis- (alpha, alpha-dimethylbenzyl) diphenylamines are that a kind of efficient amine is prevented
Old agent product, its is heat-resisting, fast light, ageing resistace is notable.Compared with other general amines antioxidants, have it is nontoxic, tasteless,
The advantages that color is shallow.Product prepared by the present invention be as age resister be commonly used to BR, NR, CR, EPDM, nitrile, butyronitrile, SBR and
All kinds of rubber such as ethylene propylene diene rubber and its compound；It can provide long-acting anti-oxidant, heat resistanceheat resistant and anti-interferenceization effect；Meanwhile
Also there is preferable antitoxic effect to rubber.Product of the present invention can be widely applied in various elastomers, applied to polyethylene,
The plastic color master grain such as polypropylene and polyvinyl chloride；And polyurethane foam plastics and India-rubber wire, cable, food can be used as
The antioxidant of packaging material, adhesive is heat-resisting, fast light especially in neoprene colour cable cover(ing), ageing resistace is notable.
Make fast light anti-aging antioxidant in polyethers and its foamed plastics, can also be used as lubrication oil antioxidant.
4th, illustrate：
The liquid chromatogram of the products obtained therefrom of Fig. 1 embodiment of the present invention 1；
The liquid chromatogram of the products obtained therefrom of Fig. 2 embodiment of the present invention 2；
The liquid chromatogram of the products obtained therefrom of Fig. 3 embodiment of the present invention 3；
The liquid chromatogram of the products obtained therefrom of Fig. 4 embodiment of the present invention 4；
The liquid chromatogram of the products obtained therefrom of Fig. 5 embodiment of the present invention 5；
The infrared spectrogram of the products obtained therefrom of Fig. 6 embodiment of the present invention 1.
5th, embodiment：
The present invention is expanded on further with reference to embodiments, but is not intended to limit the content of technical solution of the present invention protection.
Embodiment 1：
The preparation method of antioxidant 4,4 ' of the present invention-bis- (alpha, alpha-dimethylbenzyls) diphenylamines, the preparation method it is detailed
Step is as follows：
A, raw material diphenylamines 50.0g is added first and be equipped with the reaction vessel of agitator, reflux condenser, heating makes to add
The diphenylamines entered is melted；Addition is prepared catalyst compounded by 1.0g zinc chloride and 1.0g iron chloride after melting completely, after
Continuous heating stirring is mixed；
B, after step a is well mixed, α-methylstyrene 70.8g, time for adding 0.5h is added dropwise；After completion of dropwise addition, control
Reaction temperature processed is 130~140 DEG C, 1h is reacted under this temperature conditions, reaction terminates；
C, after reaction terminates, gained reaction solution is cooled, 60# petroleum ethers 140g and methanol 10g is then added and prepares
Mixed solvent, be down to 25 ± 2 DEG C progress cooling crystallizations；
D, after crystallization terminates, filtered successively, petroleum ether and washing, then dry 15h under the conditions of 40 DEG C, dry
After obtain antioxidant 4,4 '-bis- (bis (alpha, alpha-dimethylbenzyl) bases) diphenylamines.
The present embodiment products obtained therefrom outward appearance is white crystal, yield 82%, and purity 98.67% (refers to accompanying drawing 1).
Embodiment 2：
The preparation method of antioxidant 4,4 ' of the present invention-bis- (alpha, alpha-dimethylbenzyls) diphenylamines, the preparation method it is detailed
Step is as follows：
A, raw material diphenylamines 100.0g is added first and be equipped with the reaction vessel of agitator, reflux condenser, heating makes
The diphenylamines of addition is melted；The compounding prepared by 1.0g zinc chloride and 1.0g anhydrous stannous chlorides is added after completely melting to urge
Agent, continue heating stirring and mixed；
B, after step a is well mixed, α-methylstyrene 150g, time for adding 2.0h is added dropwise；After completion of dropwise addition, control
Reaction temperature is 135~145 DEG C, 2h is reacted under this temperature conditions, reaction terminates；
C, after reaction terminates, gained reaction solution is cooled, 60# petroleum ethers 320g and methanol 10g is then added and prepares
Mixed solvent, be down to 25 ± 2 DEG C progress cooling crystallizations；
D, after crystallization terminates, filtered successively, petroleum ether and washing, then dry 10h under the conditions of 60 DEG C, dry
After obtain antioxidant 4,4 '-bis- (bis (alpha, alpha-dimethylbenzyl) bases) diphenylamines.
The present embodiment products obtained therefrom outward appearance is white crystal, yield 84%, and purity 98.31% (refers to accompanying drawing 2).
Embodiment 3：
The preparation method of antioxidant 4,4 ' of the present invention-bis- (alpha, alpha-dimethylbenzyls) diphenylamines, the preparation method it is detailed
Step is as follows：
A, raw material diphenylamines 50.0g is added first and be equipped with the reaction vessel of agitator, reflux condenser, heating makes to add
The diphenylamines entered is melted；The compounding prepared by 0.5g aluminium chloride and 0.5g anhydrous stannous chlorides is added after completely melting to be catalyzed
Agent, continue heating stirring and mixed；
B, after step a is well mixed, α-methylstyrene 80.5g, time for adding 0.5h is added dropwise；After completion of dropwise addition, control
Reaction temperature processed is 120~130 DEG C, 1h is reacted under this temperature conditions, reaction terminates；
C, after reaction terminates, gained reaction solution is cooled, 120# petroleum ethers 120g and methanol 10g is then added and prepares
Mixed solvent, be down to 25 ± 2 DEG C progress cooling crystallizations；
D, after crystallization terminates, filtered successively, petroleum ether and washing, then dry 13h under the conditions of 50 DEG C, dry
After obtain antioxidant 4,4 '-bis- (bis (alpha, alpha-dimethylbenzyl) bases) diphenylamines.
The present embodiment products obtained therefrom outward appearance is white crystal, yield 84%, and purity 98.40% (refers to accompanying drawing 3).
Embodiment 4：
The preparation method of antioxidant 4,4 ' of the present invention-bis- (alpha, alpha-dimethylbenzyls) diphenylamines, the preparation method it is detailed
Step is as follows：
A, raw material diphenylamines 50.0g is added first and be equipped with the reaction vessel of agitator, reflux condenser, heating makes to add
The diphenylamines entered is melted；The compounding prepared by 1.5g magnesium chlorides and 1.5g anhydrous stannous chlorides is added after completely melting to be catalyzed
Agent, continue heating stirring and mixed；
B, after step a is well mixed, α-methylstyrene 80.5g, time for adding 0.5h is added dropwise；After completion of dropwise addition, control
Reaction temperature processed is 130~140 DEG C, 1h is reacted under this temperature conditions, reaction terminates；
C, after reaction terminates, gained reaction solution is cooled, then adds what 60# petroleum ethers 140g and methanol 5g was prepared
Mixed solvent, it is down to 25 ± 2 DEG C of progress cooling crystallizations；
D, after crystallization terminates, filtered successively, petroleum ether and washing, then dry 14h under the conditions of 45 DEG C, dry
After obtain antioxidant 4,4 '-bis- (bis (alpha, alpha-dimethylbenzyl) bases) diphenylamines.
The present embodiment products obtained therefrom outward appearance is white crystal, yield 85%, and purity 98.24% (refers to accompanying drawing 4).
Embodiment 5：
The preparation method of antioxidant 4,4 ' of the present invention-bis- (alpha, alpha-dimethylbenzyls) diphenylamines, the preparation method it is detailed
Step is as follows：
A, raw material diphenylamines 100.0g is added first and be equipped with the reaction vessel of agitator, reflux condenser, heating makes
The diphenylamines of addition is melted；Addition is prepared catalyst compounded by 0.6g magnesium chlorides and 0.6g aluminium chloride after melting completely,
Continue heating stirring to be mixed；
B, after step a is well mixed, α-methylstyrene 160.5g, time for adding 1.0h is added dropwise；After completion of dropwise addition, control
Reaction temperature processed is 130~140 DEG C, 1h is reacted under this temperature conditions, reaction terminates；
C, after reaction terminates, gained reaction solution is cooled, 60# petroleum ethers 300g and methanol 10g is then added and prepares
Mixed solvent, be down to 25 ± 2 DEG C progress cooling crystallizations；
D, after crystallization terminates, filtered successively, petroleum ether and washing, then dry 12h under the conditions of 55 DEG C, dry
After obtain antioxidant 4,4 '-bis- (bis (alpha, alpha-dimethylbenzyl) bases) diphenylamines.
The present embodiment products obtained therefrom outward appearance is white crystal, yield 83%, and purity 98.44% (refers to accompanying drawing 5).
Claims (8)
- A kind of 1. preparation method of antioxidant 4,4 '-bis- (alpha, alpha-dimethylbenzyls) diphenylamines, it is characterised in that the preparation side Method comprises the following steps：A, raw material diphenylamines is added in reaction vessel first, heating is melted the diphenylamines of addition；Add after melting completely Enter it is catalyst compounded, continue heating stirring mixed；B, after step a is well mixed, α-methylstyrene is added dropwise, time for adding is 0.5~2h；After completion of dropwise addition, control reaction Temperature is 120~160 DEG C, and 1~2h is reacted under this temperature conditions, and reaction terminates；C, after reaction terminates, gained reaction solution is cooled, petroleum ether and methanol mixed solvent is then added, is down to room temperature and enters Row cooling crystallization；D, after crystallization terminates, filtered successively, petroleum ether, washing and drying, antioxidant 4,4 '-bis- is obtained after drying (bis (alpha, alpha-dimethylbenzyl) base) diphenylamines.
- 2. the preparation method of antioxidant 4,4 ' according to claim 1-bis- (alpha, alpha-dimethylbenzyls) diphenylamines, its feature It is：Catalyst compounded dosage described in step a is the 0.3~6% of diphenylamines weight.
- 3. the preparation method of antioxidant 4,4 ' according to claim 1-bis- (alpha, alpha-dimethylbenzyls) diphenylamines, its feature It is：Catalyst compounded described in step a is by sodium chloride, potassium chloride, frerrous chloride, magnesium chloride, aluminium chloride, anhydrous protochloride At least two mixing compoundings in tin and zinc chloride form.
- 4. the preparation method of antioxidant 4,4 ' according to claim 1-bis- (alpha, alpha-dimethylbenzyls) diphenylamines, its feature It is：The mol ratio of addition is 1.9~2.5 between α-methylstyrene and diphenylamines in step b：1.
- 5. the preparation method of antioxidant 4,4 ' according to claim 1-bis- (alpha, alpha-dimethylbenzyls) diphenylamines, its feature It is：Petroleum ether described in step c is 60# petroleum ethers or 120# petroleum ethers.
- 6. the preparation method of antioxidant 4,4 ' according to claim 1-bis- (alpha, alpha-dimethylbenzyls) diphenylamines, its feature It is：The dosage of petroleum ether described in step c is 2~4 times of diphenylamines weight；The dosage of the methanol is diphenylamines weight 0.1~1 times.
- 7. the preparation method of antioxidant 4,4 ' according to claim 1-bis- (alpha, alpha-dimethylbenzyls) diphenylamines, its feature It is：Temperature is 40~60 DEG C when being dried described in step d, and drying time is 10~15h.
- 8. the preparation method of antioxidant 4,4 ' according to claim 1-bis- (alpha, alpha-dimethylbenzyls) diphenylamines, its feature It is：Moisture content≤0.50% in products obtained therefrom antioxidant 4,4 '-bis- (bis (alpha, alpha-dimethylbenzyl) bases) diphenylamines in step d.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111517962A (en) * | 2020-06-11 | 2020-08-11 | 新乡市瑞丰新材料股份有限公司 | Preparation method of amine anti-aging agent |
| CN113773205A (en) * | 2021-09-24 | 2021-12-10 | 天津利安隆新材料股份有限公司 | Preparation method of 4,4' -di (phenylisopropyl) diphenylamine |
| CN113912500A (en) * | 2020-07-10 | 2022-01-11 | 华东理工大学 | Method for preparing amine compound by using microchannel reactor |
| WO2023209042A1 (en) | 2022-04-27 | 2023-11-02 | Nyco | Use of an antioxidant for reducing and/or preventing the toxicity of a rubber composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3452056A (en) * | 1966-04-07 | 1969-06-24 | Uniroyal Inc | Substituted diphenylamines |
| CN105732400A (en) * | 2014-12-12 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method for (para, para)-diisopropylphenyl diphenylamine product |
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2017
- 2017-08-29 CN CN201710754050.2A patent/CN107540559A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3452056A (en) * | 1966-04-07 | 1969-06-24 | Uniroyal Inc | Substituted diphenylamines |
| CN105732400A (en) * | 2014-12-12 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method for (para, para)-diisopropylphenyl diphenylamine product |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111517962A (en) * | 2020-06-11 | 2020-08-11 | 新乡市瑞丰新材料股份有限公司 | Preparation method of amine anti-aging agent |
| CN111517962B (en) * | 2020-06-11 | 2023-08-15 | 新乡市瑞丰新材料股份有限公司 | Preparation method of amine anti-aging agent |
| CN113912500A (en) * | 2020-07-10 | 2022-01-11 | 华东理工大学 | Method for preparing amine compound by using microchannel reactor |
| CN113773205A (en) * | 2021-09-24 | 2021-12-10 | 天津利安隆新材料股份有限公司 | Preparation method of 4,4' -di (phenylisopropyl) diphenylamine |
| WO2023209042A1 (en) | 2022-04-27 | 2023-11-02 | Nyco | Use of an antioxidant for reducing and/or preventing the toxicity of a rubber composition |
| FR3135084A1 (en) * | 2022-04-27 | 2023-11-03 | Nyco | Use of an antioxidant to reduce and/or prevent the toxicity of a rubber composition |
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