CN110054570A - A kind of recovery method of 1098 by-product of antioxidant - Google Patents
A kind of recovery method of 1098 by-product of antioxidant Download PDFInfo
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- CN110054570A CN110054570A CN201910469058.3A CN201910469058A CN110054570A CN 110054570 A CN110054570 A CN 110054570A CN 201910469058 A CN201910469058 A CN 201910469058A CN 110054570 A CN110054570 A CN 110054570A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
Abstract
The invention discloses a kind of recovery methods of 1098 by-product of antioxidant, the recovery method is by carrying out vacuum distillation processing to specific 1098 mother liquor of antioxidant, using heat filtering method in mother liquor 1098 by-product of antioxidant, 3,5- methyl esters is separated and recovered, and 1098 by-product of antioxidant of higher degree is obtained.Recovery method link linking of the invention is close, and collocation rationally, can be synergistic, reclaimer operation simplifies controllably, highly-safe, to 1098 by-product of antioxidant, 3, the rate of recovery of 5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters is high, realizes environmental benefit and economic benefit.
Description
Technical field
The present invention relates to a kind of recovery methods of 1098 by-product of antioxidant, belong to by-product recovery technology.
Background technique
Antioxidant 1098 (N, N'- bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine) is a kind of point
Complex type antioxidant in son has the double effects of hindered phenol and suffocated amine antioxidant, has good thermal stability, anti-precipitation
Property, anti-spoke steams tin and gives birth penetrating property and the compatibility with resin, be a kind of excellent high molecular material antioxidant and heat stabilizer, it is main
It is used for poly- phthalein amine and polyacetals, it can also be used to which polyolefin, poly-vinegar, natural or synthetic rubber and other pairs of thermal oxides are sensitive
High-molecular compound, general dosage be 0.3-1.0%, be used for poly- phthalein amine fiber when, the antioxygenic property of antioxidant 1098
Advantage it is especially bright, with the maturation of domestic technology, the application and production of antioxidant 1098, which continue to develop, to be expanded.
Nowadays, the reaction that antioxidant 1098 synthesizes is 3,5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters (referred to as 3,5- first
Ester) and the ammonolysis reaction that is carried out in xylene solution of hexamethylene diamine, it is found in 1098 production process of antioxidant, antioxidant 1098
Having content in mother liquor is 3~10% 1098 by-product of antioxidant.(Xiong Jieming, Lv Jiuzhuo, the Xu Yaxian .3,5- bis- such as Xiong Jieming
Tertiary butyl-4-hydroxy methyl phenylpropionate ammonolysis reaction mechanism and kinetics [J] Speciality Petrochemicals .2002 (5), 34-
37.) 3,5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters ([E]) and hexamethylene diamine ([DA]) ammonolysis in xylene solution are analyzed
React two kinds of mechanism that may be present, with di-n-octyl tin oxide (organotin) (SnO) be catalyst, 130~139 DEG C, urge
Agent concentration (1.386~5.545) × 10-3kmol/m3, in the excessive situation of hexamethylene diamine, system concentration in reaction process is become
Change data and be fitted analysis, discovery ammonolysis process is second order reaction to 3,5- methyl esters, and the generation of illustration purpose compound accounts for
Absolute predominance；Reaction process activation energy is 110.5kJ/mol, and reaction speed is directly proportional to catalyst concn, kinetics table
It is d [E]/dt=-2.568 × 10 up to formula16exp(-1.105×105/RT)[SnO][DA][E]2.By many experiments and survey
Examination, discovery 1098 by-product of antioxidant are N, N'- is bis--mistake of (3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine
Go the structure of a 3- (3,5- di-tert-butyl-hydroxy phenyl) propiono.
However, in currently available technology (such as to 1098 by-product of antioxidant of the residue of mother in synthesis antioxidant 1098
Shown in Fig. 1) recycling research it is seldom.Large-scale production for antioxidant 1098, if can be by antioxidant 1098 in mother liquor
The effective recycling of by-product, it will the cost for reducing production antioxidant 1098 is increased economic efficiency.
Summary of the invention
In view of the above existing problems in the prior art, the present invention provides a kind of recovery method of 1098 by-product of antioxidant,
The recovery method is simply controllable, and securely and reliably, the rate of recovery is high.
To achieve the goals above, the present invention adopts the following technical scheme: a kind of recycling side of 1098 by-product of antioxidant
Method, comprising the following steps:
(1) mother liquor after taking antioxidant 1098 to prepare is spare；
(2) mother liquor pre-processes: mother liquor being depressurized removal solvent, obtains particle I, solvent I is then added and is dissolved, is centrifuged
Filtering carries out 2~3 times, and obtained filtrate is solution II；The solvent I selects benzene or toluene；
(3) solution II is handled: the decompression of solution II is steamed into solvent I, particle II is obtained, particle II is put into pure water, into
Row ultrasonication disperses particle II in water, obtains suspension；
(4) suspension is heat-treated: being heated while stirring to suspension, when suspension temperature is heated to 70 DEG C, particle II goes out
It now melts, keeps suspension temperature at 70~72 DEG C, make the fusing of particle II until not increasing temperature after re-melting again to 75 DEG C of guarantors
5~10min is held, until the not re-melting of particle II, continues to heat suspension, suspension solution temperature is heated to boiling, boiling 3~
Then 4min carries out solution being cooled to 75~80 DEG C, obtains hot suspension until particle II is unchanged in the solution；
(5) heat filtering: it is that heat filtering is carried out at 75~80 DEG C that hot suspension, which is maintained at temperature, with 75~80 in heat filtering
DEG C hot water wash 2~3 times, the white crystal being dried to obtain be 1098 by-product of antioxidant, residual liquid III be 3,5- bis-
Tertiary butyl-4-hydroxy methyl phenylpropionate organic layer and hot water layer；
(6) crystallisation by cooling: being cooled to 72 DEG C for the standing of residual liquid III, lower layer 3,5- di-t-butyl -4- hydroxy phenylpropionic acid
Methyl esters organic layer gradually crystallizes, and is then cooled to 65 DEG C and keeps, filters while hot, obtains white crystal 3,5- di-t-butyl -4-
Hydroxy phenylpropionic acid methyl esters and hot water.
Further, in the step (1), the mother liquor after prepared by antioxidant 1098 passes through following steps acquisition: with 3,
5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters, 1,6- hexamethylene diamine are raw material, react in dimethylbenzene, are first passed through the N of 5min2, then
Basic catalyst sodium methoxide is added, in N2Under protection, pressure is under -0.075MPa, and heating reaction, temperature is controlled 167~170
DEG C, after reacting 6~8h, ethyl alcohol dissolution, recrystallization, 1~2h of ageing is added, centrifugal filtration carries out 2~3 times, and what is be dried to obtain is white
Color crystal is antioxidant 1098, and remaining solution is 1098 mother liquor of antioxidant；3,5- di-t-butyl -4- the hydroxy benzenes third
Sour methyl esters and 1, the molar ratio of 6- hexamethylene diamine are 2:1~1.05, and basic catalyst sodium methoxide dosage is 3,5- di-t-butyl -4- hydroxyl
The 0.4~1.0% of base methyl phenylpropionate.
Further, the concentration of alcohol is 70~100%.
Further, in the step (3), the mass ratio of the particle II and pure water is 1:2~3.
Further, in the step (3), the supersonic frequency of the ultrasonication is 20~25kHz, and ultrasonic time is
20~30min.
Further, oil bath heating is selected in the heat treatment in the step (4).
Further, in the step (5), the heat filtering selects decompression heat to filter.
Further, in the step (5), washing hot water amount used is the 0.5~0.8 of II mass of particle every time
Times.
Beneficial effects of the present invention:
1, the present invention separates and recovers 1098 by-product of antioxidant using heat filtering from solution II and echos relative to resin
Rectification process reduces cost recovery, and easy to operate controllable, and the rate of recovery is high.
2, the recovery method recycles 1098 by-product recovery of antioxidant in mother liquor, can be with the tertiary fourth of 3,5- bis-
The reaction of base -4- hydroxy phenylpropionic acid methyl esters generates antioxidant 1098, reduces the pollution to environment, increases economic efficiency.
3, the present invention can also be former by 3,5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters remaining in mother liquor by heat filtering
Expect recycling and reusing, improves the utilization rate of raw material.
4, in the recovery method, hot water used can be recycled, and be economized on resources, and production cost is reduced, and be improved economical
Benefit.
5, recovery process link of the invention linking is close, and collocation rationally, can be synergistic, and reclaimer operation simplification can
Control, it is highly-safe, it is high to the rate of recovery of 1098 by-product of antioxidant, 3,5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters, reach
The purpose of recycling, economizes on resources, and realizes environmental benefit and economic benefit.
Detailed description of the invention
Fig. 1 is that antioxidant 1098 synthesizes equation.
Specific embodiment
The present invention is further elaborated with reference to embodiments.These embodiments be only for illustrative purposes,
And do not limit the scope of the invention and essence.For those of ordinary skill in the art to which the present invention belongs, it is not departing from
Under the premise of inventive concept, a number of simple deductions or replacements can also be made, is regarded as belonging to the scope of protection of the present invention.
Embodiment 1
A kind of recovery method of 1098 by-product of antioxidant, steps are as follows:
(1) acquisition of 1098 mother liquor of antioxidant: in the reaction flask equipped with mechanical agitator, thermometer and reflux condensing tube
Middle addition 5.84g (0.02mol) 3,5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters, 1.174g (0.0101mol) 1,6- hexamethylene diamine
To be first passed through the N of 5min in raw material and 40ml dimethylbenzene2, 0.0033g basic catalyst sodium methoxide is added, in N2Under protection,
Pressure is under -0.075MPa, and heating reaction, temperature is controlled at 167~170 DEG C, and after reacting 6~8h, 100% second of 20ml is added
Alcohol dissolution, recrystallization, 1~2h of ageing, centrifugal filtration carry out 2~3 times, and the white crystal being dried to obtain is antioxidant 1098,
It is weighed as 5.739g, remaining solution is 1098 mother liquor of antioxidant；
(2) mother liquor pre-processes: mother liquor being depressurized removal solvent, 6ml toluene is then added and is dissolved, carries out in centrifuge
Centrifugal filtration carries out 2~3 times, and obtained filtrate is solution II, and obtains sodium methoxide；
(3) solution II is handled: the decompression of solution II being steamed toluene, obtains particle II, weighs it for 0.6630g, by particle
II is put into 8ml pure water, carries out ultrasonication in Vltrasonic device, supersonic frequency be 20~25kHz ultrasonic time be 20~
30min disperses particle II in water, obtains suspension；
(4) suspension is heat-treated: suspension is put into oil bath pan, is heated while stirring to suspension, suspension temperature
When being heated to 70 DEG C, particle II melts, and keeps suspension temperature at 70~72 DEG C, makes the fusing of particle II until not re-melting
Temperature is increased again afterwards to 75 DEG C of 5~10min of holding, until the not re-melting of particle II, continues to heat suspension, suspended liquor temperature
Degree is heated to boiling, then 3~4min of boiling carries out solution being cooled to 75~80 DEG C until particle II is unchanged in the solution,
Obtain hot suspension；
(5) heat filtering: it is to carry out depressurizing hot suction filtration at 75~80 DEG C that hot suspension, which is put into baking oven, and is maintained at temperature, heat
It is washed 2~3 times, each 4ml in filtering with 75~80 DEG C of hot water, the white crystal being dried to obtain is 1098 by-product of antioxidant
Object weighs it as 0.4022g, and residual liquid III is 3,5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters organic layer and hot water layer；
(6) crystallisation by cooling: being cooled to 72 DEG C for the standing of residual liquid III, lower organic layer 3,5- di-t-butyl -4- hydroxyl
Methyl phenylpropionate organic layer gradually crystallizes, and then cooling keeps to 65 DEG C and keeps, and filters while hot, obtains white crystal 3,5- bis-
Tertiary butyl-4-hydroxy methyl phenylpropionate and hot water, dry, weighing 3,5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters quality is
0.2501g, using infrared spectrum measurement 3,5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters, wavelength 3613.9cm-1O-H is analyzed,
Wavelength 3072,2956,872cm-1Analyze C-H, 1720cm-1Analyze C=O, 11438.5cm-1Analyze C=C.
It is tested, obtained 1098 yield of antioxidant is 90.23%, the white crystal 3 recycled, the tertiary fourth of 5- bis-
The rate of recovery 97.33% of base -4- hydroxy phenylpropionic acid methyl esters, the white crystal recycled are returning for 1098 by-product of antioxidant
Yield 99.04%.
Use the Agilent high performance liquid chromatography of Hyper 0DS2C18 in mobile phase methanol: water ratio is 0.85:0.15 (v/
V) flow velocity is to measure under 0.9mL/min, UV Detection wavelength are 254nm, retention time 6.14917min, the antioxygen measured
1098 by-product purity of agent be 98.54%, 109.3~112.5 DEG C of fusing point.
Embodiment 2
A kind of recovery method of 1098 by-product of antioxidant, steps are as follows:
(1) acquisition of 1098 mother liquor of antioxidant: in the reaction flask equipped with mechanical agitator, thermometer and reflux condensing tube
Middle addition 5.84g (0.02mol) 3,5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters, 1.195g (0.0103mol) 1,6- hexamethylene diamine
To be first passed through the N of 5min in raw material and 40ml dimethylbenzene2, 0.0033g basic catalyst sodium methoxide is added, in N2Under protection,
Pressure is under -0.075MPa, and heating reaction, temperature is controlled at 167~170 DEG C, and after reacting 6~8h, 100% second of 20ml is added
Alcohol dissolution, recrystallization, 1~2h of ageing, centrifugal filtration carry out 2~3 times, and the white crystal being dried to obtain is antioxidant 1098,
It is weighed as 5.782g, remaining solution is 1098 mother liquor of antioxidant；
(2) mother liquor pre-processes: mother liquor being depressurized removal solvent, 6ml toluene is then added and is dissolved, carries out in centrifuge
Centrifugal filtration carries out 2~3 times, and obtained filtrate is solution II, and obtains sodium methoxide；
(3) solution II is handled: the decompression of solution II being steamed toluene, obtains particle II, weighs it for 0.6329g, by particle
II is put into 8ml pure water, carries out ultrasonication in Vltrasonic device, supersonic frequency be 20~25kHz ultrasonic time be 20~
30min disperses particle II in water, obtains suspension；
(4) suspension is heat-treated: suspension is put into oil bath pan, is heated while stirring to suspension, suspension temperature
When being heated to 70 DEG C, particle II melts, and keeps suspension temperature at 70~72 DEG C, makes the fusing of particle II until not re-melting
Temperature is increased again afterwards to 75 DEG C of 5~10min of holding, until the not re-melting of particle II, continues to heat suspension, suspended liquor temperature
Degree is heated to boiling, then 3~4min of boiling carries out solution being cooled to 75~80 DEG C until particle II is unchanged in the solution,
Obtain hot suspension；
(5) heat filtering: it is to carry out depressurizing hot suction filtration at 75~80 DEG C that hot suspension, which is put into baking oven, and is maintained at temperature, heat
It is washed 2~3 times, each 4ml in filtering with 75~80 DEG C of hot water, the white crystal being dried to obtain is 1098 by-product of antioxidant
Object weighs it as 0.4535g, and residual liquid III is 3,5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters organic layer and hot water layer；
(6) crystallisation by cooling: being cooled to 72 DEG C for the standing of residual liquid III, lower organic layer 3,5- di-t-butyl -4- hydroxyl
Methyl phenylpropionate organic layer gradually crystallizes, and is then cooled to 65 DEG C and keeps, and filtering obtains white crystal 3,5- di-t-butyl-
4- hydroxy phenylpropionic acid methyl esters and hot water, dry, weighing 3,5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters quality is 0.1762g.
It is tested, obtained 1098 yield of antioxidant is 90.91%, the white crystal 3 recycled, the tertiary fourth of 5- bis-
The rate of recovery 98.93% of base -4- hydroxy phenylpropionic acid methyl esters, the white crystal recycled are returning for 1098 by-product of antioxidant
Yield 99.67%.
Use the Agilent high performance liquid chromatography of Hyper 0DS2C18 in mobile phase methanol: water ratio is 0.85:0.15 (v/
V) flow velocity is to measure under 0.9mL/min, UV Detection wavelength are 254nm, retention time 6.14917min, the antioxygen measured
1098 by-product purity of agent be 98.92%, 109.5~112.3 DEG C of fusing point.
Embodiment 3
A kind of recovery method of 1098 by-product of antioxidant, steps are as follows:
(1) acquisition of 1098 mother liquor of antioxidant: in the reaction flask equipped with mechanical agitator, thermometer and reflux condensing tube
Middle addition 5.84g (0.02mol) 3,5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters, 1.195g (0.0103mol) 1,6- hexamethylene diamine
To be first passed through the N of 5min in raw material and 40ml dimethylbenzene2, 0.0033g basic catalyst sodium methoxide is added, in N2Under protection,
Pressure is under -0.075MPa, and heating reaction, temperature is controlled at 167~170 DEG C, and after reacting 6~8h, 100% second of 20ml is added
Alcohol dissolution, recrystallization, 1~2h of ageing, centrifugal filtration carry out 2~3 times, and the white crystal being dried to obtain is antioxidant 1098,
It is weighed as 5.781g, remaining solution is 1098 mother liquor of antioxidant；
(2) mother liquor pre-processes: mother liquor decompression being steamed ethyl alcohol, 6ml toluene is then added and is dissolved, carries out in centrifuge
Centrifugal filtration carries out 2~3 times, and obtained filtrate is solution II, and obtains sodium methoxide；
(3) processing of solution II and heat treatment: the decompression of solution II is steamed into toluene, obtains particle II, weighing it is
0.6328g carries out ultrasonication in Vltrasonic device, and supersonic frequency is that 20~25kHz ultrasonic time is 20~30min, so
After be put into oil bath pan, heat while stirring, when particle temperature is heated to 69.5 DEG C, particle II melts, keep particle II
Temperature makes the fusing of particle II after not re-melting at 70~75 DEG C, then 75~80 DEG C of 5~10min of holding of temperature, until particle II
Not re-melting continues to be heated to particle II 100 DEG C, and particle II is unchanged in the solution, obtains hot suspension；
(4) heat filtering: it is to carry out depressurizing hot suction filtration at 75~80 DEG C that hot suspension, which is put into baking oven, and is maintained at temperature, heat
It is washed 2~3 times, each 4ml in filtering with 75~80 DEG C of hot water, the white crystal being dried to obtain is 1098 by-product of antioxidant
Object weighs it as 0.4537g, and residual liquid III is 3,5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters organic layer and hot water layer；
(5) crystallisation by cooling: being cooled to 72 DEG C for the standing of residual liquid III, lower organic layer 3,5- di-t-butyl -4- hydroxyl
Methyl phenylpropionate organic layer gradually crystallizes, and then cooling keeps to 65 DEG C and keeps, and filters while hot, obtains white crystal 3,5- bis-
Tertiary butyl-4-hydroxy methyl phenylpropionate and hot water, dry, weighing 3,5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters quality is
0.1753g。
It is tested, obtained 1098 yield of antioxidant is 90.91%, the white crystal 3 recycled, the tertiary fourth of 5- bis-
The rate of recovery 98.42% of base -4- hydroxy phenylpropionic acid methyl esters, the white crystal recycled are returning for 1098 by-product of antioxidant
Yield 99.72%.
Use the Agilent high performance liquid chromatography of Hyper 0DS2C18 in mobile phase methanol: water ratio is 0.85:0.15 (v/
V) flow velocity is to measure under 0.9mL/min, UV Detection wavelength are 254nm, retention time 6.14917min, the antioxygen measured
1098 by-product purity of agent be 96.12%, 107.2~112.8 DEG C of fusing point.
It is found through experimental implementation process, during heat treatment, compared with Example 2, particle II directly adds the present embodiment
The temperature of heat fusing is not easy to, and operational stability is poor, and the temperature-controllable degree that particle II directly heats fusing is put into than particle II
The temperature-controllable degree that fusing is heated in pure water is low；The antioxidant 1098 of melt processed recycling is directly heated through particle II simultaneously
By-product purity is lower than the 1098 by-product purity of antioxidant for being put into through particle II and heating melt processed recycling in pure water.
Embodiment 4
The present embodiment is that different solvents I is respectively adopted in the pretreatment of step (2) mother liquor to carry out dissolution filter, and different is molten
Influence of the agent I to product by-product recovery effect.
Steps are as follows:
(1) acquisition of 1098 mother liquor of antioxidant: in the reaction flask equipped with mechanical agitator, thermometer and reflux condensing tube
Middle addition 5.84g (0.02mol) 3,5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters, 1.195g (0.0103mol) 1,6- hexamethylene diamine
To be first passed through the N of 5min in raw material and 40ml dimethylbenzene2, 0.0033g basic catalyst sodium methoxide is added, in N2Under protection,
Pressure is under -0.075MPa, and heating reaction, temperature is controlled at 167~170 DEG C, and after reacting 6~8h, 100% second of 20ml is added
Alcohol dissolution, recrystallization, 1~2h of ageing, centrifugal filtration carry out 2~3 times, and the white crystal being dried to obtain is antioxidant 1098,
Remaining solution is 1098 mother liquor of antioxidant；
(2) mother liquor pre-process: by mother liquor depressurize removal solvent, then be added solvent I dissolved, carried out in centrifuge from
Heart filtering, carries out 2~3 times, and obtained filtrate is solution II；
(3) solution II is handled: the decompression of solution II is steamed into solvent I, particle II is obtained, particle II is put into 8ml pure water,
Ultrasonication is carried out in Vltrasonic device, supersonic frequency is that 20~25kHz ultrasonic time is 20~30min, and particle II is made to exist
Disperse in water, obtains suspension；
(4) suspension is heat-treated: suspension is put into oil bath pan, is heated while stirring to suspension, suspension temperature
When being heated to 70 DEG C, particle II melts, and keeps suspension temperature at 70~72 DEG C, makes the fusing of particle II until not re-melting
Temperature is increased again afterwards to 75 DEG C of 5~10min of holding, until the not re-melting of particle II, continues to heat suspension, suspended liquor temperature
Degree is heated to boiling, then 3~4min of boiling carries out solution being cooled to 75~80 DEG C until particle II is unchanged in the solution,
Obtain hot suspension；
(5) heat filtering: it is to carry out depressurizing hot suction filtration at 75~80 DEG C that hot suspension, which is put into baking oven, and is maintained at temperature, heat
It is washed 2~3 times, each 4ml in filtering with 75~80 DEG C of hot water, the white crystal being dried to obtain is 1098 by-product of antioxidant
Object, III residual liquid III of residual liquid are 3,5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters organic layer and hot water layer；
(6) crystallisation by cooling: being cooled to 72 DEG C for the standing of residual liquid III, lower organic layer 3,5- di-t-butyl -4- hydroxyl
Methyl phenylpropionate organic layer gradually crystallizes, and then cooling keeps to 65 DEG C and keeps, and filters while hot, obtains white crystal 3,5- bis-
Tertiary butyl-4-hydroxy methyl phenylpropionate and hot water, it is dry.
The present embodiment is that benzene, toluene, methanol, pure water are respectively adopted in step (2) as solvent I, carries out dissolution filter, no
Influence of the same solvent I to product by-product recovery effect, the results are shown in Table 1.
Table 1
It is found from above-mentioned table 1, solvent I selects the mixed liquor dissolution filter of benzene, toluene or benzene and toluene, antioxidant
The purity of 1098 by-products is higher.
Embodiment 5
Experimental procedure in this implementation is same as Example 2, difference be the present embodiment using different catalyst point into
Row catalysis reaction, observes influence of the catalyst to product yield, product by-product recovery rate effect.
The present embodiment in example 2 the step of (1) be separately added into basic catalyst sodium methoxide, potassium methoxide, sodium ethoxide, second
Potassium alcoholate carries out catalysis reaction, is tested, and the rate of recovery and purity of measurement product yield, product by-product, the results are shown in Table 2.
Table 2
It is found from above-mentioned table 2, sodium methoxide catalyzed effect is best, and 1098 yield of antioxidant is higher, sodium methoxide, methanol
Potassium, sodium ethoxide, potassium ethoxide catalysis influence very little to the rate of recovery of 3,5 methyl esters, 1098 by-product of antioxidant.
Embodiment 6
Experimental procedure in this implementation is same as Example 2, and difference is the present embodiment using different catalyst amounts
Divide and carry out catalysis reaction, observes influence of the different catalyst amounts to product yield, product by-product recovery rate effect.
The present embodiment in example 2 the step of (1) respectively 0.35%, 0.45%, 0.55%, 0.92%, 1%, 1.1%
Different amounts of sodium methoxide carries out catalysis reaction, is tested, the recovering effect of measurement product yield, product by-product, as a result such as table 3
It is shown.
Table 3
It is found from above-mentioned table 3, the dosage of sodium methoxide is the 0.4~1% of 3,5 methyl esters quality, and 1098 yield of oxidant reaches
90% or more, high income, the dosage of sodium methoxide to the rate of recovery of 3,5 methyl esters, 1098 by-product of antioxidant, impurities affect very
It is small.
Embodiment 7
Experimental procedure in this implementation is same as Example 2, and difference is that the present embodiment uses the second of different quality containing
Alcohol dissolution, filtering, recrystallization, observe shadow of the ethyl alcohol to product yield, product by-product recovery rate effect of different quality containing
It rings.
The present embodiment in example 2 the step of (1) respectively with 70%, 75%, 80%, 85%, 95%, 100% difference
The ethanol washing of mass fraction, filtering, recrystallization are tested, and product purity, the rate of recovery effect of product by-product, knot are measured
Fruit is as shown in 4 institute of table.
Table 4
It finds from above-mentioned table 4, mass fraction the ethanol washing greater than 75%, the antioxidant 1098 that is recrystallized to give
Purity is up to 99% or more, and to the rate of recovery of 3,5 methyl esters, 1098 by-product of antioxidant, impurities affect very little.
Technical solution of the present invention, process procedure linking is close, and collocation rationally, can be synergistic, composition it is anti-oxidant
The recovery method of 1098 by-product of agent.
Finally it should be noted that the above embodiments are only used to illustrate and not limit the technical solutions of the present invention, although reference
Above-described embodiment describes the invention in detail, it will be appreciated by those skilled in the art that can still carry out to the present invention
Modification or equivalent replacement should all cover without departing from the spirit or scope of the invention, or any substitutions
In scope of the presently claimed invention.
Claims (8)
1. a kind of recovery method of 1098 by-product of antioxidant, which comprises the following steps:
(1) mother liquor after taking antioxidant 1098 to prepare is spare；
(2) mother liquor pre-processes: mother liquor being depressurized removal solvent, obtains particle I, solvent I is then added and is dissolved, was centrifuged
Filter carries out 2~3 times, and obtained filtrate is solution II；The solvent I selects benzene or toluene；
(3) solution II is handled: the decompression of solution II being steamed solvent I, particle II is obtained, particle II is put into pure water, is surpassed
Sonicated disperses particle II in water, obtains suspension；
(4) suspension is heat-treated: being heated while stirring to suspension, when suspension temperature is heated to 70 DEG C, particle II melts
Change, keep suspension temperature at 70~72 DEG C, make the fusing of particle II until do not increased after re-melting again temperature keep 5 to 75 DEG C~
10min, until the not re-melting of particle II, continues to heat suspension, suspension solution temperature is heated to boiling, and boil 3~4min,
It is unchanged in the solution to particle II, then solution is carried out to be cooled to 75~80 DEG C, obtains hot suspension；
(5) heat filtering: it is that heat filtering is carried out at 75~80 DEG C that hot suspension, which is maintained at temperature, with 75~80 DEG C in heat filtering
Hot water washs 2~3 times, and the white crystal being dried to obtain is 1098 by-product of antioxidant, and residual liquid III is the tertiary fourth of 3,5- bis-
Base -4- hydroxy phenylpropionic acid methyl esters organic layer and hot water layer；
(6) crystallisation by cooling: being cooled to 72 DEG C for the standing of residual liquid III, lower layer 3,5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters
Organic layer gradually crystallizes, and is then cooled to 65 DEG C and keeps, filters while hot, obtains white crystal 3,5- di-t-butyl -4- hydroxyl
Methyl phenylpropionate and hot water.
2. a kind of recovery method of 1098 by-product of antioxidant according to claim 1, which is characterized in that the step
(1) in, the mother liquor after prepared by antioxidant 1098 is obtained by following steps: with 3,5- di-t-butyl -4- hydroxy phenylpropionic acid first
Ester, 1,6- hexamethylene diamine are raw material, react in dimethylbenzene, are first passed through the N of 5min2, basic catalyst sodium methoxide is added, in N2
Under protection, pressure is under -0.075MPa, and heating reaction, temperature is controlled at 167~170 DEG C, and after reacting 6~8h, it is molten that ethyl alcohol is added
Solution, recrystallization, 1~2h of ageing, centrifugal filtration carry out 2~3 times, and the white crystal being dried to obtain is antioxidant 1098, remaining
Solution be 1098 mother liquor of antioxidant；Mole of 3,5- the di-t-butyl -4- hydroxy phenylpropionic acid methyl esters and 1,6- hexamethylene diamine
Than for 2:1~1.05, basic catalyst sodium methoxide dosage be 3,5- di-t-butyl -4- hydroxy phenylpropionic acid methyl esters 0.4~
1.0%.
3. a kind of recovery method of 1098 by-product of antioxidant according to claim 2, which is characterized in that the ethyl alcohol is dense
Degree is 70~100%.
4. a kind of recovery method of 1098 by-product of antioxidant according to claim 1, which is characterized in that the step
(3) in, the mass ratio of the particle II and pure water is 1:10~15.
5. a kind of recovery method of 1098 by-product of antioxidant according to claim 1, which is characterized in that the step
(3) in, the supersonic frequency of the ultrasonication is 20~25kHz, and ultrasonic time is 20~30min.
6. a kind of recovery method of 1098 by-product of antioxidant according to claim 1, which is characterized in that the step
(4) oil bath heating is selected in the heat treatment in.
7. a kind of recovery method of 1098 by-product of antioxidant according to claim 1, which is characterized in that the step
(5) in, the heat filtering selects decompression heat to filter.
8. a kind of recovery method of 1098 by-product of antioxidant according to claim 1, which is characterized in that the step
(5) in, washing hot water amount used is 5~8 times of II mass of particle every time.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283095A (en) * | 2019-07-31 | 2019-09-27 | 江苏极易新材料有限公司 | A method of recycling 1024 intermediate of antioxidant |
| CN112574053A (en) * | 2020-12-11 | 2021-03-30 | 江苏极易新材料有限公司 | Synthesis process of antioxidant 1098 |
| CN114957007A (en) * | 2022-06-15 | 2022-08-30 | 江苏极易新材料有限公司 | Method for recycling 3,5 methyl ester through 1010 alcoholysis of antioxidant |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3584047A (en) * | 1967-12-29 | 1971-06-08 | Geigy Chem Corp | Alkylhydroxyphenyl polyamides |
| GB1299591A (en) * | 1968-12-18 | 1972-12-13 | Ici Ltd | Amides |
| CN104211616A (en) * | 2013-06-05 | 2014-12-17 | 中国石油化工股份有限公司 | Preparation method for antioxidant |
-
2019
- 2019-05-31 CN CN201910469058.3A patent/CN110054570B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3584047A (en) * | 1967-12-29 | 1971-06-08 | Geigy Chem Corp | Alkylhydroxyphenyl polyamides |
| GB1299591A (en) * | 1968-12-18 | 1972-12-13 | Ici Ltd | Amides |
| CN104211616A (en) * | 2013-06-05 | 2014-12-17 | 中国石油化工股份有限公司 | Preparation method for antioxidant |
Non-Patent Citations (4)
| Title |
|---|
| 吕九琢 等: "合成N,N’-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]六甲撑二胺的新工艺", 《精细化工》 * |
| 熊杰明 等: "3 , 5-二叔丁基-4-羟基苯丙酸甲酯氨解反应机理和反应动力学", 《精细石油化工》 * |
| 胡应喜 等: "N,N’-双[3-(3’,5’-二叔丁基-4’-羟基苯基)丙酰]六甲撑二胺的合成", 《天然气化工》 * |
| 陈赤阳 等: "N,N′-双[3-(3′,5′-二叔丁基-4′-羟基苯基)丙酰]己二胺的合成新工艺", 《河南化工》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283095A (en) * | 2019-07-31 | 2019-09-27 | 江苏极易新材料有限公司 | A method of recycling 1024 intermediate of antioxidant |
| CN110283095B (en) * | 2019-07-31 | 2021-02-09 | 江苏极易新材料有限公司 | Method for recovering antioxidant 1024 intermediate |
| CN112574053A (en) * | 2020-12-11 | 2021-03-30 | 江苏极易新材料有限公司 | Synthesis process of antioxidant 1098 |
| CN114957007A (en) * | 2022-06-15 | 2022-08-30 | 江苏极易新材料有限公司 | Method for recycling 3,5 methyl ester through 1010 alcoholysis of antioxidant |
| CN114957007B (en) * | 2022-06-15 | 2023-09-08 | 江苏极易新材料有限公司 | Method for recycling 3,5 methyl ester through alcoholysis of antioxidant 1010 |
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