CN110156706A - A kind of synthesis technology of antioxidant 3114 - Google Patents
A kind of synthesis technology of antioxidant 3114 Download PDFInfo
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- CN110156706A CN110156706A CN201910466175.4A CN201910466175A CN110156706A CN 110156706 A CN110156706 A CN 110156706A CN 201910466175 A CN201910466175 A CN 201910466175A CN 110156706 A CN110156706 A CN 110156706A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a kind of synthesis technologies of antioxidant 3114, and carry out stepwise reaction by control reaction temperature and be prepared: the first step, control is at 90~100 DEG C of temperature by raw material 2,3~4h of 6- DI-tert-butylphenol compounds and polyformaldehyde reaction；The product of the first step is reacted 2~3h with raw material cyanuric acid at 120~125 DEG C of temperature by second step, control；Two-step reaction is solvent by catalyst, dimethyl formamide solution of ionic liquid.The present invention is environmentally protective using the ionic liquid that easily recycles and can be recycled as catalyst, and reaction is efficient.
Description
Technical field
The present invention relates to a kind of synthesis technologies of antioxidant 3114, belong to antioxidant synthesis technical field.
Background technique
The oxidation that antioxidant can delay or prevent organic material such as plastics, rubber, fiber, adhesive, food and feed etc.
Process extends the service life of material, and the dosage of antioxidant is typically small, influences after addition on the performance of polymer smaller.
Antioxidant 3114 chemical name is 1,3,5- tri--(3,5- di-tert-butyl-4-hydroxyl benzyl) chlorinated isocyanurates, is one
The polynary Hinered phenols antioxidant of kind, is slightly soluble in water, is dissolved in acetone, benzene, chloroform, n,N-Dimethylformamide, ethyl alcohol, methanol, no
It pollutes, is not colored, since relative molecular mass is big and fusing point is high, therefore volatility is minimum, and migration is small, and water-extraction resistance is good, can
It assigns plastics excellent heatproof oxidation performance and photooxidation resistant, is suitable for polyethylene, polypropylene, polystyrene, ABS resin, gathers
Ester, nylon, polyvinyl chloride, polyurethane, cellulosic plastics and synthetic rubber, effect is especially pronounced in polyolefin.
Chinese patent CN104418814 A discloses a kind of synthetic method of Hinered phenols antioxidant 3114: using two steps
Solvent method synthesis technology, first with 2,6- DI-tert-butylphenol compounds and paraformaldehyde for raw material, methanol aqueous solution is solvent, in dimethylamine
Under the action of, it is heated to reflux progress addition reaction 5~8 hours, intermediate (3,5- DI-tert-butylphenol compounds -4- hydroxyl) benzyl is made
Methyl ether；Again with intermediate (3,5- DI-tert-butylphenol compounds -4- hydroxyl) methyl benzyl ether and isocyanuric acid for raw material, in methenamine or
Under triethylamine effect, using dimethylformamide as reaction dissolvent, it is heated to reflux at 120~140 DEG C 4~5 hours, negative pressure is continuous
It removes by-product carbinol and obtains target product through filtering, decrease temperature crystalline, centrifugation etc..In the invention, two-step reaction used catalyst
It is organic amine catalyst, can not recycles for subsequent experimental, and organic amine compound has high toxicity, persistently mostly
The features such as property, migration and bioconcentration, can have an adverse effect to environment and publilc health when dealing with improperly, in addition, two
Step response procedures are more, and total used time is longer.
" chemistry world " the 3rd phase in 2010 disclose " non-pressure process synthesize three-(3,5- di-tert-butyl-4-hydroxyl benzyls) it is different
Cyanurate (antioxidant 3114) ": be added in three-necked flask appropriate 2,6 di t butyl phenol, paraformaldehyde, cyanuric acid,
HMTA and DMF solvent, 4h is reacted at 120 DEG C, and ice bath crystallisation by cooling, suction filtration, methanol washing, drying obtain product.In the paper,
Single step reaction used catalyst is HMTA, can not also recycle, also can cause adverse effect to environment when dealing with improperly,
And the temperature of single step reaction is fixed, more by-product easily generated.
Accordingly, it is desirable to provide the antioxidant 3114 that a kind of catalyst can be recycled, is environmental-friendly, properties of product are excellent
Synthesis technology.
Summary of the invention
In view of the above existing problems in the prior art, the present invention provides a kind of synthesis technologies of antioxidant 3114, easily to return
The ionic liquid received and can be recycled is catalyst, and environmentally protective, reaction is efficient.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of synthesis technology of antioxidant 3114 carries out stepwise reaction by control reaction temperature and is prepared: the first step,
Control is at 90~100 DEG C of temperature by 3~4h of raw material 2,6 di t butyl phenol and polyformaldehyde reaction；Second step, control exist
The product of the first step is reacted into 2~3h with raw material cyanuric acid at 120~125 DEG C of temperature；Two-step reaction is with ionic liquid
Catalyst, dimethyl formamide solution are solvent.
As the further improvement of invention, the ionic liquid uses triethylamine cationic ion liquid.
As the further improvement of invention, the triethylamine cationic ion liquid is prepared in accordance with the following methods:
The phosphomolybdic acid of the amount of certain substance is dissolved in the single-necked flask containing 75~80% deionized waters, under lasting stirring
1~3 times of amount that accounts for phosphomolybdic acid substance of triethylamine ionic liquid is slowly added into phosphomolybdic acid aqueous solution, it is anti-at 40~60 DEG C
6h is answered, evaporation of solvent water is then rotated at 0.1MPa, 75 DEG C, obtains jade-green triethylamine cationic ion liquid.
As the further improvement of invention, the synthesis technology specifically includes the following steps:
(1) 2,6 di t butyl phenol, paraformaldehyde and ionic liquid of the amount of certain substance are added to containing 10~
In the reactor of 15% dimethyl formamide solution, nitrogen protection reacts 3~4h at 90~100 DEG C；The tertiary fourth of the 2,6- bis-
Base phenol, paraformaldehyde the mass ratio of the material are 1:1.1~1.2；The additional amount of the ionic liquid, with the amount of the substance of triethylamine
For 0.45~0.55% meter of the amount of 2,6 di t butyl phenol substance；
(2) temperature controlled in reactor rises to 120~125 DEG C, and the amount 25 for accounting for 2,6- DI-tert-butylphenol compounds substance is added
~28% cyanuric acid, the reaction was continued under nitrogen protection 2~3h；
(3) by-product carbinol is constantly removed under -0.05~0.07MPa after reaction, crystallisation by cooling is centrifuged to obtain crystallization
Crystallized product is washed with deionized in product, is then dried in vacuo at 60 DEG C, obtains target product；
(4) by centrifugate, dimethyl formamide solution is distilled off in oil pump at 10~100MPa, 30~50 DEG C, then will
Obtained product first continuously washs 2~3 remaining 2,6- DI-tert-butylphenol compounds of removal with ethyl alcohol, then with 20~30 DEG C of hot water
It continuously washs 2~3 times and removes remaining paraformaldehyde and cyanuric acid, ionic-liquid catalyst can be obtained after dry and recycle
It utilizes.
As the further improvement of invention, the triethylamine ionic liquid is N- fourth sulfonate radical triethylamine amphoteric ion liquid
SO3(CH2)4Et3N or N- protonates triethylamine ionic liquid Et3NH·HSO4。
As the further improvement of invention, the N- fourth sulfonate radical triethylamine amphoteric ion liquid SO3(CH2)4Et3N according to
Following methods preparation:
The ratio between amount by substance is that the triethylamine of 1:1 and Isosorbide-5-Nitrae-fourth sulfonic acid lactones are added in single-necked flask, 40~50 DEG C
Lower sufficiently reaction solidifies for 24 hours, washs solidfied material into cleaning solution without reactant with ether, vacuum drying obtains N- fourth sulfonate radical
Triethylamine amphoteric ion liquid SO3(CH2)4Et3N。
As the further improvement of invention, the N- protonates triethylamine ionic liquid Et3NH·HSO4In accordance with the following methods
Preparation:
A certain amount of triethylamine is added in single-necked flask, it is lasting to stir, by the sulphur of the amount with triethylamine same substance
Acid is prepared into the aqueous sulfuric acid that mass fraction is 4~4.5%, is then slowly dropped in triethylamine, anti-at 40~45 DEG C
It answers after 6h that rotary evaporation removes water at 0.1MPa, 75 DEG C, then washes 3~4 removing unreacted reactants with ether, be dried in vacuo
The N- of colorless viscous protonates triethylamine ionic liquid Et3NH·HSO4。
The present invention has the advantage that compared with prior art
1, the present invention using ionic liquid be catalyst be used for antioxidant 3114 synthesis, ionic liquid with it is non-volatile,
It is good chemical stability and thermal stability, can be recycled and environmentally friendly, referred to as " green " chemical solvent, thus just
Just the recycling and recycling for realizing catalyst in antioxidant 3114 synthesis process, reduce usually used homogeneous catalyst pair
The adverse effect of environment.
2, the present invention by by N- fourth sulfonate radical triethylamine amphoteric ion liquid or N- protonate triethylamine ionic liquid with
Phosphomolybdic acid is compound to prepare triethylamine cationic ion liquid, and method is simple, efficient, and the catalyst effect of preparation is good, can
Reusability is high.
3, the present invention reacts molten using identical in the same reactor using the method for a step solvent, two-step reaction
Agent and catalyst, the reaction for first carrying out 2,6- DI-tert-butylphenol compounds and paraformaldehyde at a lower temperature generate intermediate, so
Heating carries out the reaction of intermediate and cyanuric acid afterwards, and not only total reaction time is shorter for the reaction process of two step temperature, while can
The generation for reducing by-product, improves the yield and purity of product.
4, for the present invention with deionized water wash crystallization product, antioxidant 3114 has certain dissolution in methanol solution
Property, but be practically insoluble in aqueous solution, thus reduce toward loss caused by when being often used methanol wash crystallization product, improve production
The yield of object.
Specific embodiment
Below with reference to embodiment, the present invention will be described in detail, it is to be understood that protection scope of the present invention is not had
The limitation of body embodiment.
Embodiment 1
(1) 2,6 di t butyl phenol and paraformaldehyde are added to according to the ratio of the amount of the substance of 1:1.1~1.2 containing 10
It in the reactor of~15% dimethyl formamide solution, and is 2,6- DI-tert-butylphenol compounds substance with the amount of the substance of triethylamine
0.45~0.55% meter of amount, is added triethylamine-fourth sulfonic group cationic ion liquid, nitrogen protection, at 90~100 DEG C
React 3~4h；
(2) temperature controlled in reactor rises to 120~125 DEG C, and the amount 25 for accounting for 2,6- DI-tert-butylphenol compounds substance is added
~28% cyanuric acid, the reaction was continued under nitrogen protection 2~3h；
(3) by-product carbinol is constantly removed under -0.05~0.07MPa after reaction, crystallisation by cooling is centrifuged to obtain crystallization
Crystallized product is washed with deionized in product, is then dried in vacuo at 60 DEG C, obtains target product；
(4) by centrifugate, dimethyl formamide solution is distilled off in oil pump at 10~100MPa, 30~50 DEG C, then will
Obtained product first continuously washs 2~3 remaining 2,6- DI-tert-butylphenol compounds of removal with ethyl alcohol, then with 20~30 DEG C of hot water
It continuously washs 2~3 times and removes remaining paraformaldehyde and cyanuric acid, ionic-liquid catalyst can be obtained after dry and recycle
It utilizes.
Wherein, triethylamine-fourth sulfonic group cationic ion liquid is prepared in accordance with the following methods:
(1) triethylamine and Isosorbide-5-Nitrae-fourth sulfonic acid lactones that the ratio between amount of substance is 1:1 are added in single-necked flask, 40~50
It sufficiently reacts at DEG C and solidifies for 24 hours, wash solidfied material into cleaning solution without reactant with ether, vacuum drying obtains N- fourth sulfonic acid
Root triethylamine amphoteric ion liquid SO3(CH2)4Et3N；
(2) phosphomolybdic acid of the amount of certain substance is dissolved in the single-necked flask containing 75~80% deionized waters, is persistently stirred
Mix lower 1 times of amount of the N- fourth sulfonate radical triethylamine amphoteric ion liquid SO that will account for phosphomolybdic acid substance3(CH2)4Et3N is slowly added into
In phosphomolybdic acid aqueous solution, 6h is reacted at 40~60 DEG C, and evaporation of solvent water is then rotated at 0.1MPa, 75 DEG C, is obtained light green
The triethylamine of color-fourth sulfonic group cationic ion liquid [HSO3(CH2)4Et3N]·H2PMo12O40。
Embodiment 2
(1) 2,6 di t butyl phenol and paraformaldehyde are added to according to the ratio of the amount of the substance of 1:1.1~1.2 containing 10
It in the reactor of~15% dimethyl formamide solution, and is 2,6- DI-tert-butylphenol compounds substance with the amount of the substance of triethylamine
0.45~0.55% meter of amount, is added triethylamine-fourth sulfonic group cationic ion liquid, nitrogen protection, at 90~100 DEG C
React 3~4h；
(2) temperature controlled in reactor rises to 120~125 DEG C, and the amount 25 for accounting for 2,6- DI-tert-butylphenol compounds substance is added
~28% cyanuric acid, the reaction was continued under nitrogen protection 2~3h；
(3) by-product carbinol is constantly removed under -0.05~0.07MPa after reaction, crystallisation by cooling is centrifuged to obtain crystallization
Crystallized product is washed with deionized in product, is then dried in vacuo at 60 DEG C, obtains target product；
(4) by centrifugate, dimethyl formamide solution is distilled off in oil pump at 10~100MPa, 30~50 DEG C, then will
Obtained product first continuously washs 2~3 remaining 2,6- DI-tert-butylphenol compounds of removal with ethyl alcohol, then with 20~30 DEG C of hot water
It continuously washs 2~3 times and removes remaining paraformaldehyde and cyanuric acid, ionic-liquid catalyst can be obtained after dry and recycle
It utilizes.
Wherein, triethylamine-fourth sulfonic group cationic ion liquid is prepared in accordance with the following methods:
(1) triethylamine and Isosorbide-5-Nitrae-fourth sulfonic acid lactones that the ratio between amount of substance is 1:1 are added in single-necked flask, 40~50
It sufficiently reacts at DEG C and solidifies for 24 hours, wash solidfied material into cleaning solution without reactant with ether, vacuum drying obtains N- fourth sulfonic acid
Root triethylamine amphoteric ion liquid SO3(CH2)4Et3N；
(2) phosphomolybdic acid of the amount of certain substance is dissolved in the single-necked flask containing 75~80% deionized waters, is persistently stirred
Mix lower 2 times of amount of the N- fourth sulfonate radical triethylamine amphoteric ion liquid SO that will account for phosphomolybdic acid substance3(CH2)4Et3N is slowly added into
In phosphomolybdic acid aqueous solution, 6h is reacted at 40~60 DEG C, and evaporation of solvent water is then rotated at 0.1MPa, 75 DEG C, is obtained light green
The triethylamine of color-fourth sulfonic group cationic ion liquid [HSO3(CH2)4Et3N]2·HPMo12O40。
Embodiment 3
(1) 2,6 di t butyl phenol and paraformaldehyde are added to according to the ratio of the amount of the substance of 1:1.1~1.2 containing 10
It in the reactor of~15% dimethyl formamide solution, and is 2,6- DI-tert-butylphenol compounds substance with the amount of the substance of triethylamine
0.45~0.55% meter of amount, is added triethylamine-fourth sulfonic group cationic ion liquid, nitrogen protection, at 90~100 DEG C
React 3~4h；
(2) temperature controlled in reactor rises to 120~125 DEG C, and the amount 25 for accounting for 2,6- DI-tert-butylphenol compounds substance is added
~28% cyanuric acid, the reaction was continued under nitrogen protection 2~3h；
(3) by-product carbinol is constantly removed under -0.05~0.07MPa after reaction, crystallisation by cooling is centrifuged to obtain crystallization
Crystallized product is washed with deionized in product, is then dried in vacuo at 60 DEG C, obtains target product；
(4) by centrifugate, dimethyl formamide solution is distilled off in oil pump at 10~100MPa, 30~50 DEG C, then will
Obtained product first continuously washs 2~3 remaining 2,6- DI-tert-butylphenol compounds of removal with ethyl alcohol, then with 20~30 DEG C of hot water
It continuously washs 2~3 times and removes remaining paraformaldehyde and cyanuric acid, ionic-liquid catalyst can be obtained after dry and recycle
It utilizes.
Wherein, triethylamine-fourth sulfonic group cationic ion liquid is prepared in accordance with the following methods:
(1) triethylamine and Isosorbide-5-Nitrae-fourth sulfonic acid lactones that the ratio between amount of substance is 1:1 are added in single-necked flask, 40~50
It sufficiently reacts at DEG C and solidifies for 24 hours, wash solidfied material into cleaning solution without reactant with ether, vacuum drying obtains N- fourth sulfonic acid
Root triethylamine amphoteric ion liquid SO3(CH2)4Et3N；
(2) phosphomolybdic acid of the amount of certain substance is dissolved in the single-necked flask containing 75~80% deionized waters, is persistently stirred
Mix lower 3 times of amount of the N- fourth sulfonate radical triethylamine amphoteric ion liquid SO that will account for phosphomolybdic acid substance3(CH2)4Et3N is slowly added into
In phosphomolybdic acid aqueous solution, 6h is reacted at 40~60 DEG C, and evaporation of solvent water is then rotated at 0.1MPa, 75 DEG C, is obtained light green
The triethylamine of color-fourth sulfonic group cationic ion liquid [HSO3(CH2)4Et3N]3·PMo12O40。
Embodiment 4
(1) 2,6 di t butyl phenol and paraformaldehyde are added to according to the ratio of the amount of the substance of 1:1.1~1.2 containing 10
It in the reactor of~15% dimethyl formamide solution, and is 2,6- DI-tert-butylphenol compounds substance with the amount of the substance of triethylamine
0.45~0.55% meter of amount, is added N- and protonates triethylamine cationic ion liquid, nitrogen protection, at 90~100 DEG C
React 3~4h；
(2) temperature controlled in reactor rises to 120~125 DEG C, and the amount 25 for accounting for 2,6- DI-tert-butylphenol compounds substance is added
~28% cyanuric acid, the reaction was continued under nitrogen protection 2~3h；
(3) by-product carbinol is constantly removed under -0.05~0.07MPa after reaction, crystallisation by cooling is centrifuged to obtain crystallization
Crystallized product is washed with deionized in product, is then dried in vacuo at 60 DEG C, obtains target product；
(4) by centrifugate, dimethyl formamide solution is distilled off in oil pump at 10~100MPa, 30~50 DEG C, then will
Obtained product first continuously washs 2~3 remaining 2,6- DI-tert-butylphenol compounds of removal with ethyl alcohol, then with 20~30 DEG C of hot water
It continuously washs 2~3 times and removes remaining paraformaldehyde and cyanuric acid, ionic-liquid catalyst can be obtained after dry and recycle
It utilizes.
Wherein, N- protonates triethylamine cationic ion liquid and prepares in accordance with the following methods:
(1) a certain amount of triethylamine is added in single-necked flask, it is lasting to stir, by the amount with triethylamine same substance
Sulfuric acid is prepared into the aqueous sulfuric acid that mass fraction is 4~4.5%, is then slowly dropped in triethylamine, at 40~45 DEG C
Rotary evaporation removes water at 0.1MPa, 75 DEG C after reaction 6h, then washes 3~4 removing unreacted reactants with ether, is dried in vacuo
The N- for obtaining colorless viscous protonates triethylamine ionic liquid Et3NH·HSO4；
(2) phosphomolybdic acid of the amount of certain substance is dissolved in the single-necked flask containing 75~80% deionized waters, is persistently stirred
Mix lower 1 times of amount of the N- protonation triethylamine ionic liquid Et that will account for phosphomolybdic acid substance3NH·HSO4It is slowly added into phosphomolybdic acid water
In solution, 6h is reacted at 40~60 DEG C, and evaporation of solvent water is then rotated at 0.1MPa, 75 DEG C, obtains jade-green N- matter
Sonization triethylamine cationic ion liquid (Et3NH)H2PMo12O40。
Embodiment 5
(1) 2,6 di t butyl phenol and paraformaldehyde are added to according to the ratio of the amount of the substance of 1:1.1~1.2 containing 10
It in the reactor of~15% dimethyl formamide solution, and is 2,6- DI-tert-butylphenol compounds substance with the amount of the substance of triethylamine
0.45~0.55% meter of amount, is added N- and protonates triethylamine cationic ion liquid, nitrogen protection, at 90~100 DEG C
React 3~4h；
(2) temperature controlled in reactor rises to 120~125 DEG C, and the amount 25 for accounting for 2,6- DI-tert-butylphenol compounds substance is added
~28% cyanuric acid, the reaction was continued under nitrogen protection 2~3h；
(3) by-product carbinol is constantly removed under -0.05~0.07MPa after reaction, crystallisation by cooling is centrifuged to obtain crystallization
Crystallized product is washed with deionized in product, is then dried in vacuo at 60 DEG C, obtains target product；
(4) by centrifugate, dimethyl formamide solution is distilled off in oil pump at 10~100MPa, 30~50 DEG C, then will
Obtained product first continuously washs 2~3 remaining 2,6- DI-tert-butylphenol compounds of removal with ethyl alcohol, then with 20~30 DEG C of hot water
It continuously washs 2~3 times and removes remaining paraformaldehyde and cyanuric acid, ionic-liquid catalyst can be obtained after dry and recycle
It utilizes.
Wherein, N- protonates triethylamine cationic ion liquid and prepares in accordance with the following methods:
(1) a certain amount of triethylamine is added in single-necked flask, it is lasting to stir, by the amount with triethylamine same substance
Sulfuric acid is prepared into the aqueous sulfuric acid that mass fraction is 4~4.5%, is then slowly dropped in triethylamine, at 40~45 DEG C
Rotary evaporation removes water at 0.1MPa, 75 DEG C after reaction 6h, then washes 3~4 removing unreacted reactants with ether, is dried in vacuo
The N- for obtaining colorless viscous protonates triethylamine ionic liquid Et3NH·HSO4；
(2) phosphomolybdic acid of the amount of certain substance is dissolved in the single-necked flask containing 75~80% deionized waters, is persistently stirred
Mix lower 2 times of amount of the N- protonation triethylamine ionic liquid Et that will account for phosphomolybdic acid substance3NH·HSO4It is slowly added into phosphomolybdic acid water
In solution, 6h is reacted at 40~60 DEG C, and evaporation of solvent water is then rotated at 0.1MPa, 75 DEG C, obtains jade-green N- matter
Sonization triethylamine cationic ion liquid (Et3NH)2HPMo12O40。
Embodiment 6
(1) 2,6 di t butyl phenol and paraformaldehyde are added to according to the ratio of the amount of the substance of 1:1.1~1.2 containing 10
It in the reactor of~15% dimethyl formamide solution, and is 2,6- DI-tert-butylphenol compounds substance with the amount of the substance of triethylamine
0.45~0.55% meter of amount, is added N- and protonates triethylamine cationic ion liquid, nitrogen protection, at 90~100 DEG C
React 3~4h；
(2) temperature controlled in reactor rises to 120~125 DEG C, and the amount 25 for accounting for 2,6- DI-tert-butylphenol compounds substance is added
~28% cyanuric acid, the reaction was continued under nitrogen protection 2~3h；
(3) by-product carbinol is constantly removed under -0.05~0.07MPa after reaction, crystallisation by cooling is centrifuged to obtain crystallization
Crystallized product is washed with deionized in product, is then dried in vacuo at 60 DEG C, obtains target product；
(4) by centrifugate, dimethyl formamide solution is distilled off in oil pump at 10~100MPa, 30~50 DEG C, then will
Obtained product first continuously washs 2~3 remaining 2,6- DI-tert-butylphenol compounds of removal with ethyl alcohol, then with 20~30 DEG C of hot water
It continuously washs 2~3 times and removes remaining paraformaldehyde and cyanuric acid, ionic-liquid catalyst can be obtained after dry and recycle
It utilizes.
Wherein, N- protonates triethylamine cationic ion liquid and prepares in accordance with the following methods:
(1) a certain amount of triethylamine is added in single-necked flask, it is lasting to stir, by the amount with triethylamine same substance
Sulfuric acid is prepared into the aqueous sulfuric acid that mass fraction is 4~4.5%, is then slowly dropped in triethylamine, at 40~45 DEG C
Rotary evaporation removes water at 0.1MPa, 75 DEG C after reaction 6h, then washes 3~4 removing unreacted reactants with ether, is dried in vacuo
The N- for obtaining colorless viscous protonates triethylamine ionic liquid Et3NH·HSO4；
(2) phosphomolybdic acid of the amount of certain substance is dissolved in the single-necked flask containing 75~80% deionized waters, is persistently stirred
Mix lower 3 times of amount of the N- protonation triethylamine ionic liquid Et that will account for phosphomolybdic acid substance3NH·HSO4It is slowly added into phosphomolybdic acid water
In solution, 6h is reacted at 40~60 DEG C, and evaporation of solvent water is then rotated at 0.1MPa, 75 DEG C, obtains jade-green N- matter
Sonization triethylamine cationic ion liquid (Et3NH)3PMo12O40。
Method synthesis antioxidant 3114 of the embodiment 1 into embodiment 6 is respectively adopted, calculates the receipts of product in each embodiment
Rate measures the fusing point of each product, and the purity of each product is measured by high performance liquid chromatography (HPLC), and the results are shown in Table 1；
The performance in embodiment 1 after catalyst circulation use has also been investigated simultaneously, and the results are shown in Table 2.
The yield and purity of product in 1 embodiment of table
The recycling of catalyst in 2 embodiment 2 of table
If data can be seen that the antioxidant 3114 synthesized using the embodiment of the present invention 1 to embodiment 6 in table 1, yield is equal
In 95.15% or more, purity 99.28% or more, and fusing point meets specified in 3974~3975-2007 of national standard HG/T
Range.In addition, by it can be seen from the data in table 2 embodiment of the present invention prepare catalyst continuously repeat use after, yield and
Though purity decrease to some degree, but still it is maintained at higher level, while fusing point also still conforms to the range of national regulations.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit and essential characteristics of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.In addition, it should be understood that although this specification is described in terms of embodiments, but it is not each
Embodiment only contains an independent technical solution, this narrating mode of specification only for clarity, this field skill
Art personnel should consider the specification as a whole, and the technical solutions in the various embodiments may also be suitably combined, form ability
The other embodiments that field technique personnel are understood that.
Claims (7)
1. a kind of synthesis technology of antioxidant 3114, which is characterized in that the synthesis technology carries out substep by control reaction temperature
Reaction is prepared: the first step, and control is at 90~100 DEG C of temperature by raw material 2,6- DI-tert-butylphenol compounds and polyformaldehyde reaction
3~4h；The product of the first step is reacted 2~3h with raw material cyanuric acid at 120~125 DEG C of temperature by second step, control；Two steps
Reaction is solvent by catalyst, dimethyl formamide solution of ionic liquid.
2. synthesis technology according to claim 1, which is characterized in that the ionic liquid using triethylamine cationic from
Sub- liquid.
3. a kind of synthesis technology of antioxidant 3114 according to claim 2, which is characterized in that the triethylamine cation
Type ionic liquid is prepared in accordance with the following methods:
The phosphomolybdic acid of the amount of certain substance is dissolved in the single-necked flask containing 75~80% deionized waters, will be accounted under lasting stirring
1~3 times of amount of triethylamine ionic liquid of phosphomolybdic acid substance is slowly added into phosphomolybdic acid aqueous solution, is reacted at 40~60 DEG C
Then 6h rotates evaporation of solvent water at 0.1MPa, 75 DEG C, obtains jade-green triethylamine cationic ion liquid.
4. synthesis technology according to any one of claims 1 to 3, which is characterized in that the synthesis technology specifically includes following
Step:
(1) 2,6 di t butyl phenol, paraformaldehyde and ionic liquid of the amount of certain substance are added to containing 10~15%
In the reactor of dimethyl formamide solution, nitrogen protection reacts 3~4h at 90~100 DEG C；The 2,6- di-tert-butyl
Phenol, paraformaldehyde the mass ratio of the material are 1:1.1~1.2；The additional amount of the ionic liquid, with the amount of the substance of triethylamine for 2,
0.45~0.55% meter of the amount of 6- DI-tert-butylphenol compounds substance；
(2) temperature controlled in reactor rises to 120~125 DEG C, be added the amount 25 of 2,6- DI-tert-butylphenol compounds substance of accounting for~
28% cyanuric acid, the reaction was continued under nitrogen protection 2~3h；
(3) by-product carbinol is constantly removed under -0.05~0.07MPa after reaction, crystallisation by cooling is centrifuged to obtain crystallization production
Crystallized product is washed with deionized in object, is then dried in vacuo at 60 DEG C, obtains target product；
(4) by centrifugate, dimethyl formamide solution is distilled off in oil pump at 10~100MPa, 30~50 DEG C, then will be obtained
Product 2~3 remaining 2,6- DI-tert-butylphenol compounds of removal are first continuously washed with ethyl alcohol, then it is continuous with 20~30 DEG C of hot water
It washs 2~3 times and removes remaining paraformaldehyde and cyanuric acid, ionic-liquid catalyst can be obtained after dry and recycle benefit
With.
5. a kind of synthesis technology of antioxidant 3114 according to claim 4, which is characterized in that the triethylamine ionic liquid
Body is N- fourth sulfonate radical triethylamine amphoteric ion liquid SO3(CH2)4Et3N or N- protonates triethylamine ionic liquid Et3NH·
HSO4。
6. a kind of synthesis technology of antioxidant 3114 according to claim 5, which is characterized in that the N- fourth sulfonate radical three
Ethamine amphoteric ion liquid SO3(CH2)4Et3N is prepared in accordance with the following methods:
The ratio between amount by substance is that the triethylamine of 1:1 and Isosorbide-5-Nitrae-fourth sulfonic acid lactones are added in single-necked flask, is filled at 40~50 DEG C
Divide reaction to solidify for 24 hours, washs solidfied material into cleaning solution without reactant with ether, vacuum drying obtains three second of N- fourth sulfonate radical
Amine amphoteric ion liquid SO3(CH2)4Et3N。
7. a kind of synthesis technology of antioxidant 3114 according to claim 5, which is characterized in that the N- protonates three second
Amine ionic liquid Et3NH·HSO4It prepares in accordance with the following methods:
A certain amount of triethylamine is added in single-necked flask, it is lasting to stir, by the sulfuric acid system of the amount with triethylamine same substance
The standby aqueous sulfuric acid for being 4~4.5% at mass fraction, is then slowly dropped in triethylamine, reacts 6h at 40~45 DEG C
Rotary evaporation removes water at 0.1MPa, 75 DEG C afterwards, then washes 3~4 removing unreacted reactants with ether, is dried in vacuo colourless
Sticky N- protonates triethylamine ionic liquid Et3NH·HSO4。
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| CN111100083A (en) * | 2019-12-18 | 2020-05-05 | 利安隆（中卫）新材料有限公司 | Method for reducing solid waste in antioxidant 3114 production |
| WO2020238188A1 (en) * | 2019-05-31 | 2020-12-03 | 江苏极易新材料有限公司 | Process for synthesizing antioxidant 3114 |
| CN112898916A (en) * | 2021-01-28 | 2021-06-04 | 江苏极易新材料有限公司 | Preparation method of composite antioxidant |
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| WO2020238188A1 (en) * | 2019-05-31 | 2020-12-03 | 江苏极易新材料有限公司 | Process for synthesizing antioxidant 3114 |
| CN111100083A (en) * | 2019-12-18 | 2020-05-05 | 利安隆（中卫）新材料有限公司 | Method for reducing solid waste in antioxidant 3114 production |
| CN111100083B (en) * | 2019-12-18 | 2023-05-05 | 利安隆（中卫）新材料有限公司 | Method for reducing solid waste in production of antioxidant 3114 |
| CN112898916A (en) * | 2021-01-28 | 2021-06-04 | 江苏极易新材料有限公司 | Preparation method of composite antioxidant |
| CN112898916B (en) * | 2021-01-28 | 2021-11-02 | 江苏极易新材料有限公司 | Preparation method of composite antioxidant |
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