CN106831351A - The preparation method of the ˊ propylidene of bisphenol compound antioxidant 4,4 double (tert-butyl phenols of 3 methyl 6) - Google Patents
The preparation method of the ˊ propylidene of bisphenol compound antioxidant 4,4 double (tert-butyl phenols of 3 methyl 6) Download PDFInfo
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- CN106831351A CN106831351A CN201610991152.1A CN201610991152A CN106831351A CN 106831351 A CN106831351 A CN 106831351A CN 201610991152 A CN201610991152 A CN 201610991152A CN 106831351 A CN106831351 A CN 106831351A
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- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
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Abstract
The invention discloses a kind of preparation method of the ˊ propylidene of bisphenol compound antioxidant 4,4 double (tert-butyl phenols of 3 methyl 6), specific building-up process is：With closed reactor as reaction vessel, ethanol is solvent, 6 tert-butyl-m-cresols and propionic aldehyde are reaction raw materials, the ethanol solution of saturation hydrogen chloride is catalyst, it is complete to TLC detection reactions in room temperature reaction, the pH value for adjusting reaction system with saturated sodium bicarbonate solution is 7, and to addition petroleum ether and mixture of ice and water in reaction system, stand, divide liquid, lower ethanol is mutually filtered, and it is double (tert-butyl phenol of 3 methyl 6) that filter cake vacuum drying obtains the ˊ propylidene of target product bisphenol compound antioxidant 4,4.Reaction of the invention is carried out at room temperature, effectively prevent high temperature, reduces energy consumption and danger coefficient, and post-processing operation is simple, it is only necessary to is filtered ethanol and mutually be can be obtained by purity target product higher, and reaction yield is higher, reaches more than 90%.
Description
Technical field
The invention belongs to the synthesis technical field of bisphenol compound antioxidant, and in particular to a kind of bisphenol compound antioxidant
The preparation method of 4,4 ˊ-propylidene double (3 methy 6 tert butyl phenols).
Background technology
Antioxidant is various in style, conventional more than over one hundred kind.By classification of chemical structure, following a few classes can be divided into：Hindered phenol
Antioxidant, suffocated amine antioxidant, phosphite ester kind antioxidant, sulphur ester antioxidant and metallic ion passivation agent etc..All
Antioxidant in, hindered phenol antioxygen is consumption maximum, uses a most wide kind antioxidant.Although its thermo oxidative aging effect is not
Such as suffocated amine antioxidant, but due to the toxicity of arylamine（It is carcinogenic, it is infertile）, color stain and the compatibility poor to polyolefin,
It will be replaced by hindered phenol antioxygen more effective, nontoxic, without color stain, therefore, usually in plastic products and light color
Used in rubber.At present, arylamine is only limitted to be applied in the tire industry for less considering toxicity and color stain, and can not
For druggist rubber sundrier, plastics and fiber aspect.Nontoxic antioxidant is that recent antioxidant develops instead of poisonous antioxidant
An important tendency.Hinered phenols antioxidant refers to the compound that substituted base is connected on aromatic ring, and common substitution base is main
It is the tert-butyl group or methyl.Symmetric form hindered bisphenol antioxidant refers to that alkylidene or sulfide linkage are directly connected to two hindered phenol structure units
Phenolic antioxidant.The volatility of bis-phenol and extraction loss are smaller, and heat endurance is high, thus anti-aging efficiency is preferable.Have
Representational bis-phenolic antioxidants have antioxidant 2,2'- methylene bis（Methyl tertbutyl phenol）（2246）, 2,2'- thiobis（Methyl
Tert-butyl phenol）（2246S）, 4,4'- sulphur di-s（Tertbutyl methyl phenol）（736）, 4,4'- thiobis（Methyl tert-butylbenzene
Phenol）（300）With 1,1'- bis-（Methylhydroxy tert-butyl-phenyl）Butane（BBM）Deng.
For the existing substantial amounts of report of the synthesis of such bis-phenolic antioxidants in document.Publication No. CN101704728 A's
Patent report with water as solvent, with the mixing that the organic solvents such as long-chain liquid organic benzene sulfonic acid and aliphatic hydrocarbon or toluene are constituted
Thing in closed container, reacts 4-7h and synthesizes some row bisphenol compound antioxidants as acidic catalyst in 60-95 DEG C.To the greatest extent
Tube reaction catalyst instead of inorganic acid such as sulfuric acid, hydrochloric acid etc. with organic acid, and to consersion unit corrosion, but reaction needs
Carry out, and filter gained filter cake needing wash with ethanol water at high temperature, cause the waste of substantial amounts of organic solvent and
The manpower and financial resources for needing consumption extra in industrial production.The patent report of Publication No. CN101638356A is with water as molten
Agent, inorganic acid is catalyst, and anion surfactant is emulsifying agent, the double dodecyls two of anionic Anionic Gemini Surfactant
Phenylate disulfonic acid sodium enables water miscible acid catalyst, fatty aldehyde and oil-soluble alkyl phenol fully emulsified to help emulsion, obtains
Product yield it is higher.However, the additive that the process system is added is more, operation religion is cumbersome, and increased production
Cost.The patent of Publication No. CN101693662A is also to employ similar industrial to have synthesized intermediate antioxidant 2246.
In sum, water is used as reaction medium, have the advantages that it is non-combustible, nontoxic, many using safety, low cost, to have
The machine solvent advantage to be replaced, thus enjoy the attention of people.In addition, reaction can also produce substantial amounts of sewage, right
Environment causes harm, and ultimately results in that production cost is high, and economic benefit is low.
The content of the invention
Present invention solves the technical problem that there is provided a kind of process is simple and bis-phenol chemical combination that yield and purity are higher
The preparation method of 4,4 ˊ of thing antioxidant-propylidene double (3 methy 6 tert butyl phenols).
The present invention is to solve above-mentioned technical problem to adopt the following technical scheme that, bisphenol compound antioxidant 4,4 ˊ-propylidene
The preparation method of double (3 methy 6 tert butyl phenols), it is characterised in that specifically building-up process is：It is anti-with closed reactor
Container is answered, ethanol is solvent, and 6- tert-butyl-m-cresols and propionic aldehyde are reaction raw materials, and the ethanol solution of saturation hydrogen chloride is catalysis
Agent, complete to TLC detection reactions in room temperature reaction, the pH value for adjusting reaction system with saturated sodium bicarbonate solution is 7, and to anti-
Addition petroleum ether and mixture of ice and water in system are answered, is stood, point liquid, lower ethanol is mutually filtered, filter cake vacuum drying obtains target
4,4 ˊ of product bisphenol compound antioxidant-propylidene is double (3 methy 6 tert butyl phenol).
The preparation of 4,4 ˊ of bisphenol compound antioxidant-propylidene of the present invention double (3 methy 6 tert butyl phenols)
Method, it is characterised in that concretely comprise the following steps：Ethanol and 6- tert-butyl-m-cresols are added in closed reactor, stirring makes 6-
Tert-butyl-m-cresol is dissolved completely in ethanol, and ice salt bath is cooled to after 10 DEG C the ethanol solution for adding saturation hydrogen chloride, then
Propionic aldehyde is added dropwise over, the air gone out in reactor with nitrogen displacement makes its inside in anaerobic state, is warming up to room temperature reaction 7h,
TLC detection reactions are complete, and the pH value for adjusting reaction system with saturated sodium bicarbonate solution is 7, and to adding stone in reaction system
Oily ether and mixture of ice and water, stand, and point liquid, lower ethanol phase suction filtration, filter cake is vacuum dried after being cleaned through saturated aqueous common salt and obtains
4,4 ˊ of target product bisphenol compound antioxidant-propylidene is double (3 methy 6 tert butyl phenol).
Further preferably, described 6- tert-butyl-m-cresols are 1 with the molar ratio of propionic aldehyde:1-2.
Further preferably, the ethanol solution of described saturation hydrogen chloride is with the mass ratio that feeds intake of 6- tert-butyl-m-cresols
1.8-4.5:1。
Further preferably, the consumption of the petroleum ether is that the volume of 1g 6- tert-butyl-m-cresols correspondence petroleum ether is 4mL,
The consumption of the mixture of ice and water is that the quality of 1g 6- tert-butyl-m-cresols correspondence mixture of ice and water is 4g.
The structure of 4,4 ˊ of bisphenol compound antioxidant-propylidene of the present invention double (3 methy 6 tert butyl phenols)
Formula is：
。
The present invention has advantages below compared with prior art：
1st, the closed reactor of present invention selection effectively prevent first between reaction raw materials propionic aldehyde and the 6- tert-butyl groups as reaction vessel
Phenol contacts with oxygen in reaction system and to form oxide and deepen product colour, so as to avoid the aftertreatment technology of complexity；
2nd, the present invention to clean, the ethanol of green is used as solvent, it is ensured that whole reaction is carried out in homogeneous, it is to avoid surface work
Property the emulsifying agent such as agent use, simplify operation, save cost, while reduce the total amount of pollutant in post processing waste liquid,
Reduce the pollution to environment；
3rd, reaction of the invention is carried out at room temperature, effectively prevent high temperature, reduces energy consumption and danger coefficient, is conducive to
Production cost is reduced, and effect is preferably, and efficiency is improved；
4th, post-processing operation of the invention is simple, it is to avoid the step such as distillation, refined, accessory substance is in petroleum ether phase, it is only necessary to mistake
Filter ethanol mutually can be obtained by purity target product higher, and reaction yield is higher, reaches more than 90%.
Specific embodiment
The above of the invention is described in further details by the following examples, but this should not be interpreted as this
The scope for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair
Bright scope.
Embodiment 1
During ethanol 200mL, 6- tert-butyl-m-cresol 50g and methanesulfonic acid 27g put into closed reactor first, it is slowly added dropwise
Propionic aldehyde 27.8g, the air gone out in reactor with nitrogen displacement reacts 7h in 95 DEG C, and TLC detection reactions are complete, add saturation
NaHCO3The pH value of solution regulation reaction system is 7, takes 200g mixture of ice and water and 200mL petroleum ethers are added in container tank,
Start stirring, reaction solution is slowly dropped in container tank, completion of dropping, stand 3h, point liquid, lower ethanol phase suction filtration is used in combination
Appropriate saturated aqueous common salt washes away inorganic salts, is vacuum dried, and is weighed as 38.9g, and yield is 77.8%.
Embodiment 2
During ethanol 200mL, 6- tert-butyl-m-cresol 50g and p-methyl benzenesulfonic acid 27g put into closed reactor first, delay
Slow that propionic aldehyde 27.8g is added dropwise, the air gone out in reactor with nitrogen displacement reacts 7h in 95 DEG C, and TLC detection reactions are complete, add
Saturation NaHCO3The pH value of solution regulation reaction system is 7, takes 200g mixture of ice and water and 200mL petroleum ethers are added to container
Tank, starts stirring, reaction solution is slowly dropped in container tank, completion of dropping, stands 3h, point liquid, lower ethanol phase suction filtration, and
Inorganic salts are washed away with appropriate saturated aqueous common salt, is vacuum dried, be weighed as 36.3g, yield is 72.6%.
Embodiment 3
During ethanol 200mL and 6- tert-butyl-m-cresol 50g put into closed reactor first, opening stirring makes the 6- tert-butyl groups
Metacresol is completely dissolved in ethanol, and ice salt bath is cooled to 10 DEG C, is subsequently adding the ethanol solution of 100g saturation hydrogen chloride, slow drop
Plus propionic aldehyde 27.8g, the air gone out in reactor with nitrogen displacement, anaerobic state is at, it is warmed to room temperature reaction 7h, TLC inspection
Survey reaction complete, add saturation NaHCO3The pH value of solution regulation reaction system is 7, takes 200g mixture of ice and water and 200mL stones
Oily ether is added to container tank, starts stirring, reaction solution is slowly dropped in container tank, completion of dropping, stands 3h, point liquid, under
Layer ethanol phase suction filtration, and inorganic salts are washed away with appropriate saturated aqueous common salt, it is vacuum dried, 46.2g is weighed as, yield is 92.4%.
Embodiment 4
During ethanol 200mL and 6- tert-butyl-m-cresol 50g put into closed reactor first, opening stirring makes the 6- tert-butyl groups
Metacresol is completely dissolved in ethanol, and ice salt bath is cooled to 10 DEG C, is subsequently adding the ethanol solution of 100g saturation hydrogen chloride, slow drop
Plus propionic aldehyde 27.8g, the air gone out in reactor with nitrogen displacement, anaerobic state is at, it is warming up to 95 DEG C of reactions 7h, TLC
Detection reaction is complete, adds saturation NaHCO3The pH value of solution regulation reaction system is 7, takes 200g mixture of ice and water and 200mL
Petroleum ether is added to container tank, starts stirring, reaction solution is slowly dropped in container tank, completion of dropping, stands 3h, point liquid,
Lower ethanol phase suction filtration, and inorganic salts are washed away with appropriate saturated aqueous common salt, it is vacuum dried, 43.1g is weighed as, yield is 86.2%.
Embodiment 5
During ethanol 200mL and 6- tert-butyl-m-cresol 50g put into closed reactor first, opening stirring makes the 6- tert-butyl groups
Metacresol is completely dissolved in ethanol, and ice salt bath is cooled to 10 DEG C, is subsequently adding the ethanol solution of 100g saturation hydrogen chloride, slow drop
Plus propionic aldehyde 36.0g, the air gone out in reactor with nitrogen displacement, anaerobic state is at, it is warming up to room temperature reaction 7h, TLC
Detection reaction is complete, adds saturation NaHCO3The pH value of solution regulation reaction system is 7, takes 200g mixture of ice and water and 200mL
Petroleum ether is added to container tank, starts stirring, reaction solution is slowly dropped in container tank, completion of dropping, stands 3h, point liquid,
Lower ethanol phase suction filtration, and inorganic salts are washed away with appropriate saturated aqueous common salt, it is vacuum dried, 44.2g is weighed as, yield is 90.4%.
Embodiment 6
During ethanol 200mL and 6- tert-butyl-m-cresol 50g put into closed reactor first, opening stirring makes the 6- tert-butyl groups
Metacresol is completely dissolved in ethanol, and ice salt bath is cooled to 10 DEG C, is subsequently adding the ethanol solution of 150g saturation hydrogen chloride, slow drop
Plus propionic aldehyde 27.8g, the air gone out in reactor with nitrogen displacement, anaerobic state is at, it is warming up to room temperature reaction 7h, TLC
Detection reaction is complete, adds saturation NaHCO3The pH value of solution regulation reaction system is 7, takes 200g mixture of ice and water and 200mL
Petroleum ether is added to container tank, starts stirring, reaction solution is slowly dropped in container tank, completion of dropping, stands 3h, point liquid,
Lower ethanol phase suction filtration, and inorganic salts are washed away with appropriate saturated aqueous common salt, it is vacuum dried, 44.75g is weighed as, yield is
91.5%。
Embodiment above describes general principle of the invention, principal character and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, simply original of the invention is illustrated described in above-described embodiment and specification
Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, and these changes and improvements each fall within
In the scope of protection of the invention.
Claims (5)
1. bisphenol compound antioxidant 4, the preparation method of 4 ˊ-propylidene double (3 methy 6 tert butyl phenols), it is characterised in that
Specifically building-up process is：With closed reactor as reaction vessel, ethanol is solvent, and 6- tert-butyl-m-cresols and propionic aldehyde are reaction
Raw material, the ethanol solution of saturation hydrogen chloride is catalyst, complete to TLC detection reactions in room temperature reaction, uses saturated sodium bicarbonate
The pH value of solution regulation reaction system is 7, and to petroleum ether and mixture of ice and water is added in reaction system, is stood, point liquid, lower floor
Ethanol is mutually filtered, and filter cake vacuum drying obtains target product bisphenol compound antioxidant 4, double (the 3- methyl-6-terts of 4 ˊ-propylidene
Butylphenol).
2. 4,4 ˊ of bisphenol compound antioxidant-propylidene according to claim 1 double (3 methy 6 tert butyl phenol)
Preparation method, it is characterised in that concretely comprise the following steps：Ethanol and 6- tert-butyl-m-cresols are added in closed reactor, are stirred
6- tert-butyl-m-cresols are made to be dissolved completely in ethanol, ice salt bath is cooled to after 10 DEG C the ethanol solution for adding saturation hydrogen chloride,
Then propionic aldehyde is added dropwise over, the air gone out in reactor with nitrogen displacement makes it internal in anaerobic state, is warming up to room temperature anti-
7h, TLC is answered to detect that reaction is complete, the pH value for adjusting reaction system with saturated sodium bicarbonate solution is 7, and is added in reaction system
Enter petroleum ether and mixture of ice and water, stand, point liquid, lower ethanol phase suction filtration, filter cake is vacuum dried after being cleaned through saturated aqueous common salt
Obtain 4,4 ˊ of target product bisphenol compound antioxidant-propylidene double (3 methy 6 tert butyl phenol).
3. double (3- methyl-6-tert butyl benzene of 4,4 ˊ of bisphenol compound antioxidant-propylidene according to claim 1 and 2
Phenol) preparation method, it is characterised in that：Described 6- tert-butyl-m-cresols are 1 with the molar ratio of propionic aldehyde:1-2.
4. double (3- methyl-6-tert butyl benzene of 4,4 ˊ of bisphenol compound antioxidant-propylidene according to claim 1 and 2
Phenol) preparation method, it is characterised in that：The ethanol solution of described saturation hydrogen chloride and the quality that feeds intake of 6- tert-butyl-m-cresols
Than being 1.8-4.5:1.
5. double (3- methyl-6-tert butyl benzene of 4,4 ˊ of bisphenol compound antioxidant-propylidene according to claim 1 and 2
Phenol) preparation method, it is characterised in that：The consumption of the petroleum ether is the volume of 1g 6- tert-butyl-m-cresols correspondence petroleum ether
It is 4mL, the consumption of the mixture of ice and water is that the quality that 1g 6- tert-butyl-m-cresols correspond to mixture of ice and water is 4g.
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| CN201610991152.1A CN106831351B (en) | 2016-11-11 | 2016-11-11 | Preparation method of bisphenol compound antioxidant 4,4' -propylene bis (3-methyl-6-tert-butylphenol) |
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| CN201610991152.1A CN106831351B (en) | 2016-11-11 | 2016-11-11 | Preparation method of bisphenol compound antioxidant 4,4' -propylene bis (3-methyl-6-tert-butylphenol) |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110133122A (en) * | 2019-04-24 | 2019-08-16 | 广东省医疗器械质量监督检验所 | The method for detecting the 3,5- di-t-butyl -4- hydroxy phenylpropionic acid and 2,4- DI-tert-butylphenol compounds in sodium chloride injection |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1526690A (en) * | 2003-09-23 | 2004-09-08 | 上海大学 | High-temperature antioxidant and its prepn |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1526690A (en) * | 2003-09-23 | 2004-09-08 | 上海大学 | High-temperature antioxidant and its prepn |
Non-Patent Citations (1)
| Title |
|---|
| GORODETSKII, E. T. ET AL: "An extraction method for phenol-aldehyde condensation", 《UKRAINSKII KHIMICHESKII ZHURNAL》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110133122A (en) * | 2019-04-24 | 2019-08-16 | 广东省医疗器械质量监督检验所 | The method for detecting the 3,5- di-t-butyl -4- hydroxy phenylpropionic acid and 2,4- DI-tert-butylphenol compounds in sodium chloride injection |
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