CN109651161A - A kind of preparation method of styrenated diphenylamine - Google Patents
A kind of preparation method of styrenated diphenylamine Download PDFInfo
- Publication number
- CN109651161A CN109651161A CN201910121960.6A CN201910121960A CN109651161A CN 109651161 A CN109651161 A CN 109651161A CN 201910121960 A CN201910121960 A CN 201910121960A CN 109651161 A CN109651161 A CN 109651161A
- Authority
- CN
- China
- Prior art keywords
- reaction
- styrenated diphenylamine
- preparation
- kettle
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
- C10M135/10—Sulfonic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/52—Base number [TBN]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation methods of styrenated diphenylamine, it mainly comprises the steps that and diphenylamines is added in a kettle, polymerization inhibitor and catalyst, then air in nitrogen displacement kettle is passed through into reaction kettle, it heats and opens vacuum system, when temperature is increased to certain temperature, stop vacuum system after held for some time, gas reactor is replaced with nitrogen to normal pressure, styrene is added into reaction kettle, start alkylated reaction, after the completion of alkylated reaction, temperature of reaction system is down to room temperature, it releases product in reaction kettle and is filtered distillation, obtain styrenated diphenylamine product.This method is alkylated reaction using atlapulgite composite catalyst, reduce reaction temperature, shorten the reaction time, make generate styrenated diphenylamine in diphenylamines residual it is low, product appearance is of light color, it post-processes no three wastes to generate, is a kind of green synthesis process.
Description
Technical field
The invention belongs to lube oil additive technical field, specially a kind of liquid amine antioxidants ----styrol two
The preparation method of aniline.
Background technique
Lubricating oil can be inevitably oxidized during use, generate some acidic materials, influence the longevity of oil product
Life and service performance.Therefore it is very necessary some antioxidant to be added.Oil product antioxidant mainly has amine antioxidants, phenolic antioxidant
This several class with alkyl zinc dithiophosphate.ZDDP is common engine oil oxidation and corrosion inhibitor, but with development, cannot
Meet environmental protection and the requirement of high-temperature antioxidant.The inoxidizability and thermal stability of phenol type antioxidant are poor, can not reuse temperature
It is used in higher esters syntholube.And amine antioxidants are using more and more extensive, because of its good high temperature antioxidant
And thermal stability
United States Patent (USP) US4263456 discloses a kind of method for preparing styrene diphenylamines, but this method reaction temperature is high,
Condition is harsh, and diphenylamines residual is high in the product of generation, and contraposition styrenated diphenylamine is selectively low, triphenylethylene diphenylamines
Content it is generally higher, properties of product are adversely affected.
Chinese patent 201510134900.X discloses a kind of preparation method of styrenated diphenylamine antioxidant, the preparation
Method has the following steps composition: the atlapulgite crossed using acidic treatment is taken diphenylamines and styrene to react and generates benzene as catalyst
The mixture of ethylene diphenylamines.Unreacted styrene and diphenylamines is removed by distillation, products therefrom is styrol
Diphenylamines antioxidant.It is remaining that certain diphenylamines is had in reactor product, is influenced properties of product, be joined solvent in reaction process
Toluene pollutes so that reaction is cumbersome, while also will increase the discharge of industrial wastewater and sewage.It prepares according to the method
Product colour it is deeper, diphenylamines residual it is more, influence the appearance and performance of product.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of new styrenated diphenylamine, the products benzene second of preparation
Alkylene diphenylamines belongs to amine antioxidants, it has high temperature antioxidant and thermal stability, can be used for oil product, is also applied for black
The rubber product of color and light color, instead of the toxic antioxidant for having pollution, also can be used as anti-aging agent to the resist oxygen aging of vulcanizate and
Atmospheric aging has certain protective action, is alternatively arranged as stabilizer for synthetic rubber articles.Preparation method of the invention makes
Technique simplification, stable reaction, post-processing be simple and meanwhile products obtained therefrom in unhindered amina content it is lower.
The present invention provides a kind of preparation methods of styrenated diphenylamine, under the effect of the catalyst, by styrene and
Diphenylamines is alkylated reaction, generates styrenated diphenylamine.Specially following steps:
Step 1: being added diphenylamines and catalyst in a kettle, is then passed through into reaction kettle in nitrogen displacement kettle empty
Gas；
Step 2: heating and opens vacuum system；
Step 3: when temperature is increased to certain temperature, stops vacuum system after held for some time, gas reactor is used
Nitrogen is replaced to normal pressure；
Step 4: styrene being added into reaction kettle, starts alkylated reaction；
Step 5: after the completion of alkylated reaction, being down to room temperature for temperature of reaction system, releases product in reaction kettle and carried out
Filter, obtains styrenated diphenylamine product.
The catalyst is a kind of atlapulgite composite catalyst, and atlapulgite composite catalyst refers to atlapulgite and right
Toluenesulfonic acid, activated alumina mixing compound.Atlapulgite composite catalyst additional amount be diphenylamines quality 2%~
25%.The p-methyl benzenesulfonic acid that quality is 0.1%~5% and the active oxidation that quality is 0.1%~5% are added in atlapulgite
It is uniformly mixed after aluminium compounding, obtains atlapulgite composite catalyst.Atlapulgite composite catalyst is simple and easy to get, reactivity
Height, post-processing is uncomplicated, generates without the three wastes, and can be recycled.
Polymerization inhibitor is added while diphenylamines and catalyst is added in the step 1 in a kettle, the polymerization inhibitor is
One of hydroquinone, bis- tertiary amyl hydroquinone of tert-butyl catechol, 2,6- dinitro-p-cresol and 2,5- are a variety of.
It is 30~150ppm that polymerization inhibitor additional amount, which meets mass concentration, in the step 1.
Vacuum degree is in 0.08MPa~0.095MPa in unlatching vacuum system control kettle in the step 2, in vacuum condition
Moisture in lower elimination reaction system.
Preferably, the certain temperature in the step 3 is 90-100 DEG C, certain time 30-40min.
Preferably, styrene is placed in Dropping feeder in the step 4, is divided by Dropping feeder into reaction kettle more
Secondary addition styrene, the temperature for controlling alkylated reaction is 110~180 DEG C, and the reaction time is 3~8 hours.
Preferably, in the step 4 styrene additional amount meet: the molar ratio of diphenylamines and styrene be 1:1.8~
2.8。
The filtered filter cake of step 5 is catalyst, be may be reused, and the mother liquor filtered out is evaporated under reduced pressure,
Distillate and styrenated diphenylamine product are obtained, wherein distillate is styrene, and recycling continues cycling through use as raw material.
What the present invention had is a little:
The preparation method of styrenated diphenylamine provided by the invention, optimizes synthetic route, it is determined that reaction is best
The appearance color of feed ratio and feeding sequence, the styrenated diphenylamine product made is light yellow, and viscosity is high, two in product
Aniline residue amount is 0.01wt%, is greatly improved to the performance of product.The preparation method also makes technique simplification, reaction steady
Fixed, unhindered amina in the simple oil product of gained simultaneously of post-processing content is lower.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
Technical solution of the present invention is clearly and completely described, it is clear that described embodiment is that a part of the invention is implemented
Example, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creativeness
Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of labour.
The present invention provides a kind of preparation method of styrenated diphenylamine, and the raw material used has: atlapulgite is compound to urge
Agent, styrene and diphenylamines.Atlapulgite composite catalyst refers to atlapulgite and p-methyl benzenesulfonic acid, activated alumina mixing
It compounds.Raw material is styrene and diphenylamines.The present invention does not have special limitation to their sources, using those skilled in the art
Known to member, its commercial goods can be such as used.
Present invention determine that the optimum condition of reaction, not only substantially improve the performance of product, yield reached 99% with
On, the content of unhindered amina is 0.01wt% in product；And optimize technique, experiment it is easy to operate；Make post-processing letter simultaneously
It is single, without the generation of waste water, exhaust gas and waste residue.
The present invention provides a kind of preparation methods of styrenated diphenylamine, comprising the following steps:
Step 1: diphenylamines, catalyst and polymerization inhibitor being added in reaction kettle, nitrogen is then passed through into reaction kettle,
With the air in nitrogen displacement kettle.
The atlapulgite composite catalyst additional amount is the 2%~25% of diphenylamines quality.Catalyst is atlapulgite
0.1%~5% p-methyl benzenesulfonic acid and 0.1%~5% activated alumina compounding is added in composite catalyst in atlapulgite
After be uniformly mixed, just obtained atlapulgite composite catalyst.
The polymerization inhibitor is hydroquinone, bis- tertiary amyl pair of tert-butyl catechol, 2,6- dinitro-p-cresol and 2,5-
One of benzenediol is a variety of；It is 30~150ppm that the polymerization inhibitor additional amount, which meets mass concentration,.
Step 2: beginning to warm up, and the vacuum system of reaction kettle is opened while beginning to warm up, and removing is anti-under vacuum conditions
The moisture in system is answered, vacuum degree is preferably 0.08MPa~0.095MPa.The present invention is opened after being preferably heated to 55~75 DEG C and is stirred
It mixes, the rate of the stirring is preferably 280~350rpm.
Step 3: in heating up process, melting completely after system, is generally being warming up to 100~120 DEG C or so, after
System is kept the temperature again after melting completely, and the time of the heat preservation is preferably 25~35min, more preferably 30min.After heat preservation,
Reaction system stops vacuum system, is replaced using nitrogen to normal pressure.
Step 4: after displacement to normal pressure, temperature continues to be raised to a certain temperature (generally alkylated reaction temperature), by benzene second
Alkene point, which is added to be alkylated in reaction kettle with diphenylamines, to react.The molar ratio of the diphenylamines and styrene is preferably 1:
1.8~2.8.The styrene can be added at one time, and can also be added by several times；It is preferred that being added by several times；Of the invention certain
In embodiment, a part can be first added in styrene, and a part is added after reacting a period of time, adds after certain interval of time
A part.In the present invention, the temperature of the alkylated reaction is preferably 110~180 DEG C, and more preferably 130~150 DEG C；Institute
The time for stating alkylated reaction is preferably 3~8 hours.
Step 5: after the completion of alkylated reaction, being down to room temperature for temperature of reaction system, releases product in reaction kettle and carried out
Filter, the filter cake being obtained by filtration are catalyst, be may be reused, and the mother liquor filtered out is evaporated under reduced pressure, will be not anti-in filtrate
The styrene answered removes, and the styrene recycled can be used as raw material and continue to use, and the vacuum degree of vacuum distillation is preferably
0.08MPa~0.095MPa, obtaining faint yellow as clear as crystal thick liquid is styrenated diphenylamine product.
The preparation method of styrenated diphenylamine provided by the invention, simple process are post-processed uncomplicated and are not generated useless
Water.
The present invention mainly optimizes synthetic route, it is determined that reaction optimum charging ratio and feeding sequence, experimental result table
It is bright: to be light yellow, viscosity height, diphenylamines residual quantity in product the invention enables the styrenated diphenylamine product appearance color arrived
For 0.01wt%, kinematic viscosity is 20~40mm2/s(100℃)；Base number is 85~110mgKOH/g.
In order to further illustrate the present invention, the antioxidant styrene new to one kind provided by the invention below with reference to embodiment
The preparation method of diphenylamines is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
The preparation method of styrenated diphenylamine provided in this embodiment, comprising:
Step 1: 200g atlapulgite is added in mixing device, 2g p-methyl benzenesulfonic acid and 5g activated alumina are answered
Match, start mixing arrangement half an hour, the atlapulgite composite catalyst being just uniformly mixed is spare.
Step 2: 130g diphenylamines, 13g atlapulgite composite catalyst, 50ppm polymerization inhibitor are added in stainless steel cauldron
Agent hydroquinone, nitrogen is passed through into reaction kettle, is sufficiently displaced from air in kettle；
Step 3: it is begun to warm up after replacing air, while opening vacuum system, vacuum degree control is in 0.08MPa in kettle
~0.095MPa；
Step 4: start to open stirring when temperature reaches 65 DEG C or so, stirring rate is 350 revs/min, in vacuum condition
Moisture in lower elimination reaction system.Stop vacuum system after being gradually heated to 100 DEG C of heat preservation half an hours, with nitrogen replace to
Normal pressure；
Step 5: 200g styrene is added in Dropping feeder, styrene is slowly added dropwise at 135 DEG C and starts to react, instead
It answers 5 hours, stops reaction；
Step 6: after the completion of alkylated reaction, being down to room temperature for temperature of reaction system, releases product in reaction kettle and carried out
Filter, filter cake may be reused for catalyst；The mother liquor that will filter out is added in there-necked flask in vacuum degree 0.095MPa or so,
It is evaporated under reduced pressure under the conditions of 155 DEG C, distillate is recycling styrene, can be used as raw material and continues cycling through use.In there-necked flask
To faint yellow as clear as crystal thick liquid styrenated diphenylamine product.
Appearance Visual, chromatography, the survey of viscosity and base number are carried out to styrenated diphenylamine product prepared by embodiment 1
Fixed, diphenylamine content is 0.01% in styrenated diphenylamine product made from embodiment 1, and 100 DEG C of kinematic viscosity are
25.62mm2/ s, base number 100.32mgKOH/g, the refraction index at 25 DEG C is 1.6361.
Embodiment 2
The preparation method of styrenated diphenylamine provided in this embodiment, comprising:
Step 1: 200g atlapulgite is added in mixing device, 5g p-methyl benzenesulfonic acid and 1g activated alumina are answered
Match, start mixing arrangement half an hour, the atlapulgite composite catalyst being just uniformly mixed is spare.
Step 2: 130g diphenylamines, 20g atlapulgite composite catalyst, 40ppm polymerization inhibitor are added in stainless steel cauldron
Agent hydroquinone, nitrogen is passed through into reaction kettle, is sufficiently displaced from air in kettle；
Step 3: beginning to warm up, while opening vacuum system, and vacuum degree control is in 0.08MPa~0.095MPa in kettle；When
Temperature starts to open stirring when reaching 65 DEG C or so, and stirring rate is 350 revs/min, under vacuum conditions in elimination reaction system
Moisture.
Step 4: stop vacuum system after being gradually heated to 100 DEG C of heat preservation half an hours, replaced with nitrogen to normal pressure；
Step 5: being added 180g styrene in Dropping feeder, and reaction kettle 60g styrene is first added, is gradually heated to 145
Start to react at DEG C；Remaining styrene is slowly added dropwise in reaction after 1 hour, stop reaction after reaction 5 hours
Step 6: starting to cool down after the completion of alkylated reaction, and temperature of reaction system is down to room temperature, releases in reaction kettle and produces
Object is filtered, and filter cake may be reused for catalyst；The mother liquor that will filter out is added in there-necked flask in vacuum degree
0.095MPa or so is evaporated under reduced pressure under the conditions of 155 DEG C, and distillate is recycling styrene, and can be used as raw material and continue cycling through makes
With.Faint yellow as clear as crystal thick liquid styrenated diphenylamine product is obtained in there-necked flask.
The present invention carries out Appearance Visual, chromatography, viscosity and alkali to styrenated diphenylamine product prepared by embodiment 2
The measurement of value, diphenylamine content is 0.01% in styrenated diphenylamine product made from embodiment 2, and 100 DEG C of kinematic viscosity are
27.32mm2/s, base number 96.54mgKOH/g, the refraction index at 25 DEG C is 1.6371.
Embodiment 3
The preparation method of styrenated diphenylamine provided in this embodiment, comprising:
Step 1: 200g atlapulgite is added in mixing device, 1g p-methyl benzenesulfonic acid and 6g activated alumina are answered
Match, start mixing arrangement half an hour, the atlapulgite composite catalyst being just uniformly mixed is spare.
Step 2: 130g diphenylamines, 10g atlapulgite composite catalyst, 60ppm polymerization inhibitor are added in stainless steel cauldron
Agent tert-butyl catechol, nitrogen is passed through into reaction kettle, is sufficiently displaced from air in kettle；
Step 3: beginning to warm up, while opening vacuum system, and vacuum degree control is in 0.08MPa~0.095MPa in kettle；When
Temperature starts to open stirring when reaching 65 DEG C or so, and stirring rate is 350 revs/min, under vacuum conditions in elimination reaction system
Moisture.
Step 4: stop vacuum system after being gradually heated to 100 DEG C of heat preservation half an hours, replaced with nitrogen to normal pressure；
Step 5: 185g styrene is added in Dropping feeder, styrene is slowly added dropwise at 140 DEG C and starts to react；Instead
It answers 5 hours, stops reaction；
Step 6: after the completion of alkylated reaction, being down to room temperature for temperature of reaction system, releases product in reaction kettle and carried out
Filter, filter cake may be reused for catalyst；The mother liquor that will filter out is added in there-necked flask in vacuum degree 0.095MPa or so,
It is evaporated under reduced pressure under the conditions of 155 DEG C, distillate is recycling styrene, can be used as raw material and continues cycling through use.In there-necked flask
To faint yellow as clear as crystal thick liquid styrenated diphenylamine product.
The present invention carries out Appearance Visual, chromatography, viscosity and alkali to styrenated diphenylamine product prepared by embodiment 3
The measurement of value, diphenylamine content is 0.01% in styrenated diphenylamine product made from embodiment 3, and 100 DEG C of kinematic viscosity are
23.74mm2/s, base number 95.37mgKOH/g, the refraction index at 25 DEG C is 1.6366.
Embodiment 4
The preparation method of styrenated diphenylamine provided in this embodiment, comprising:
Step 1: 200g atlapulgite is added in mixing device, 2g p-methyl benzenesulfonic acid and 5g activated alumina are answered
Match, start mixing arrangement half an hour, the atlapulgite composite catalyst being just uniformly mixed is spare.
Step 2: 130g diphenylamines, 30g atlapulgite composite catalyst, 100ppm resistance are added in stainless steel cauldron
Poly- agent 2,6- dinitro-p-cresol are passed through nitrogen into reaction kettle, are sufficiently displaced from air in kettle；
Step 3: beginning to warm up, while opening vacuum system, and vacuum degree control is in 0.08MPa~0.095MPa in kettle；When
Temperature starts to open stirring when reaching 65 DEG C or so, and stirring rate is 350 revs/min, under vacuum conditions in elimination reaction system
Moisture.
Step 4: stop vacuum system after being gradually heated to 100 DEG C of heat preservation half an hours, replaced with nitrogen to normal pressure；
Step 5: 150g styrene is added in Dropping feeder, styrene is slowly added dropwise at 160 DEG C and starts to react；Instead
It answers 5 hours, stops reaction；
Step 6: after the completion of alkylated reaction, being down to room temperature for temperature of reaction system, releases product in reaction kettle and carried out
Filter, filter cake may be reused for catalyst；The mother liquor that will filter out is added in there-necked flask in vacuum degree 0.095MPa or so,
It is evaporated under reduced pressure under the conditions of 155 DEG C, distillate is recycling styrene, can be used as raw material and continues cycling through use.In there-necked flask
To faint yellow as clear as crystal thick liquid styrenated diphenylamine product.
The present invention carries out Appearance Visual, chromatography, viscosity and alkali to styrenated diphenylamine product prepared by embodiment 4
The measurement of value, diphenylamine content is 0.01% in styrenated diphenylamine product made from embodiment 4, and 100 DEG C of kinematic viscosity are
22.56mm2/s, base number 98.52mgKOH/g, the refraction index at 25 DEG C is 1.6350.
Embodiment 5
The preparation method of styrenated diphenylamine provided in this embodiment, comprising:
Step 1: 200g atlapulgite is added in mixing device, 2g p-methyl benzenesulfonic acid and 5g activated alumina are answered
Match, start mixing arrangement half an hour, the atlapulgite composite catalyst being just uniformly mixed is spare.
Step 2: 130g diphenylamines, 18g atlapulgite composite catalyst, 35ppm polymerization inhibitor are added in stainless steel cauldron
Agent 2, bis- tertiary amyl hydroquinone of 5-, nitrogen is passed through into reaction kettle, is sufficiently displaced from air in kettle；
Step 3: beginning to warm up, while opening vacuum system, and vacuum degree control is in 0.08MPa~0.095MPa in kettle；When
Temperature starts to open stirring when reaching 65 DEG C or so, and stirring rate is 350 revs/min, under vacuum conditions in elimination reaction system
Moisture.
Step 4: stop vacuum system after being gradually heated to 100 DEG C of heat preservation half an hours, replaced with nitrogen to normal pressure；
Step 5: 220g styrene is added in Dropping feeder, styrene is slowly added dropwise at 140 DEG C and starts to react；Instead
It answers 5 hours, stops reaction；
Step 6: after the completion of alkylated reaction, being down to room temperature for temperature of reaction system, releases product in reaction kettle and carried out
Filter, filter cake may be reused for catalyst；The mother liquor that will filter out is added in there-necked flask in vacuum degree 0.095MPa or so,
It is evaporated under reduced pressure under the conditions of 155 DEG C, distillate is recycling styrene, can be used as raw material and continues cycling through use.In there-necked flask
To faint yellow as clear as crystal thick liquid styrenated diphenylamine product.
The present invention carries out Appearance Visual, chromatography, viscosity and alkali to styrenated diphenylamine product prepared by embodiment 5
The measurement of value, diphenylamine content is 0.01% in styrenated diphenylamine product made from embodiment 5, and 100 DEG C of kinematic viscosity are
28.83mm2/s, base number 93.76mgKOH/g, the refraction index at 25 DEG C is 1.6337.
Embodiment 6
The preparation method of styrenated diphenylamine provided in this embodiment, comprising:
Step 1: 200g atlapulgite is added in mixing device, 2g p-methyl benzenesulfonic acid and 5g activated alumina are answered
Match, start mixing arrangement half an hour, the atlapulgite composite catalyst being just uniformly mixed is spare.
Step 2: 130g diphenylamines, 20g atlapulgite composite catalyst, 70ppm polymerization inhibitor are added in stainless steel cauldron
Agent hydroquinone, nitrogen is passed through into reaction kettle, is sufficiently displaced from air in kettle；
Step 3: it begins to warm up.Vacuum system is opened simultaneously, vacuum degree control is in 0.08MPa~0.095MPa in kettle；When
Temperature starts to open stirring when reaching 65 DEG C or so, and stirring rate is 350 revs/min, under vacuum conditions in elimination reaction system
Moisture；
Step 4: stop vacuum system after being gradually heated to 100 DEG C of heat preservation half an hours, replaced with nitrogen to normal pressure；
Step 5: 190g styrene is added in Dropping feeder, styrene is slowly added dropwise at 150 DEG C and starts to react；Instead
It answers 5 hours, stops reaction；
Step 6: after the completion of alkylated reaction, being down to room temperature for temperature of reaction system, releases product in reaction kettle and carried out
Filter, filter cake may be reused for catalyst；The mother liquor that will filter out is added in there-necked flask in vacuum degree 0.095MPa or so,
It is evaporated under reduced pressure under the conditions of 155 DEG C, distillate is recycling styrene, can be used as raw material and continues cycling through use.In there-necked flask
To faint yellow as clear as crystal thick liquid styrenated diphenylamine product.
The present invention carries out Appearance Visual, chromatography, viscosity and alkali to styrenated diphenylamine product prepared by embodiment 6
The measurement of value, diphenylamine content is 0.01% in styrenated diphenylamine product made from embodiment 6, and 100 DEG C of kinematic viscosity are
26.38mm2/s, base number 97.32mgKOH/g, the refraction index at 25 DEG C is 1.6356.
Embodiment 7
The preparation method of styrenated diphenylamine provided in this embodiment, comprising:
Step 1: 200g atlapulgite is added in mixing device, 5g p-methyl benzenesulfonic acid and 5g activated alumina are answered
Match, start mixing arrangement half an hour, the atlapulgite composite catalyst being just uniformly mixed is spare.
Step 2: 130g diphenylamines, 25g atlapulgite composite catalyst, 80ppm polymerization inhibitor are added in stainless steel cauldron
Agent tert-butyl catechol, nitrogen is passed through into reaction kettle, is sufficiently displaced from air in kettle；
Step 3: beginning to warm up, while opening vacuum system, and vacuum degree control is in 0.08MPa~0.095MPa in kettle；When
Temperature starts to open stirring when reaching 65 DEG C or so, and stirring rate is 350 revs/min, under vacuum conditions in elimination reaction system
Moisture.
Step 4: stop vacuum system after being gradually heated to 100 DEG C of heat preservation half an hours, replaced with nitrogen to normal pressure；
Step 5: 160g styrene is added in Dropping feeder, styrene is slowly added dropwise at 140 DEG C and starts to react；Instead
It answers 5 hours, stops reaction；
Step 6: after the completion of alkylated reaction, being down to room temperature for temperature of reaction system, releases product in reaction kettle and carried out
Filter, filter cake may be reused for catalyst；The mother liquor that will filter out is added in there-necked flask in vacuum degree 0.095MPa or so,
It is evaporated under reduced pressure under the conditions of 155 DEG C, distillate is recycling styrene, can be used as raw material and continues cycling through use.In there-necked flask
To faint yellow as clear as crystal thick liquid styrenated diphenylamine product.
The present invention carries out Appearance Visual, chromatography, viscosity and alkali to styrenated diphenylamine product prepared by embodiment 7
The measurement of value, diphenylamine content is 0.01% in styrenated diphenylamine product made from embodiment 7, and 100 DEG C of kinematic viscosity are
24.63mm2/s, base number 99.76mgKOH/g, the refraction index at 25 DEG C is 1.6355.
High-temperature oxidation resistant experiment is carried out to sample of the invention using Pressurized Differential Scanning Calorimeter, measures the oxidation of oil product
Induction period, base oil select the 150N of Longyan Shang Lian lubricating oil Co., Ltd, and production of the invention is added according to 0.4% ratio
Product, and be compared with reference substance, oxidation induction period is longer, and antioxygen property is better.Experimental result is as shown in table 1.
Reference substance is available alkyl diphenylamine commodity in the market, as it can be seen from table 1 according to provided by the invention
The liquid amine antioxidants styrenated diphenylamine oxidation induction period longest of technical solution preparation, antioxygen property are preferable.According to this
The liquid amine antioxidants product appearance color for the technical solution preparation that invention provides is shallower, and viscosity is high, and base number is high, two in product
Aniline residue content is lower, is greatly improved to product antioxygen property.
From above embodiment as can be seen that the invention optimizes synthetic route, it is determined that reaction optimum charging ratio and throwing
Material sequence.The styrenated diphenylamine product appearance color made is light yellow, and viscosity is high, and diphenylamines residual quantity is in product
0wt% is greatly improved to the performance of product.The results showed that product appearance is light yellow viscous liquid；Diphenylamines is remaining
Content is 0.01t%；Kinematic viscosity is 20~40mm2/s (100 DEG C)；Base number is 85~110mgKOH/g.
These are only the preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of styrenated diphenylamine, which comprises the following steps:
Step 1: diphenylamines and catalyst are added in a kettle, air in nitrogen displacement kettle is then passed through into reaction kettle；
Step 2: heating and opens vacuum system；
Step 3: when temperature is increased to certain temperature, stopping vacuum system after held for some time, by gas reactor nitrogen
It replaces to normal pressure；
Step 4: styrene being added into reaction kettle, starts alkylated reaction；
Step 5: after the completion of alkylated reaction, being down to room temperature for temperature of reaction system, releases product in reaction kettle and is filtered steaming
It evaporates, obtains styrenated diphenylamine product.
2. the preparation method of styrenated diphenylamine according to claim 1, which is characterized in that urging in the step 1
Agent is atlapulgite composite catalyst；The atlapulgite composite catalyst includes atlapulgite, p-methyl benzenesulfonic acid and activity
Aluminium oxide mixing；The p-methyl benzenesulfonic acid, activated alumina quality be atlapulgite quality 0.1%~5% 0.1%~
5%.
3. the preparation method of styrenated diphenylamine according to claim 1 or 2, which is characterized in that in the step 1
The additional amount of catalyst is the 2%~25% of diphenylamines quality.
4. the preparation method of styrenated diphenylamine according to claim 2, which is characterized in that the catalyst by with
The preparation of lower section method:
Atlapulgite, p-methyl benzenesulfonic acid and activated alumina are added in mixing device to be compounded, starting mixing arrangement carries out
Mixing, obtains atlapulgite composite catalyst after mixing.
5. the preparation method of styrenated diphenylamine according to claim 1, which is characterized in that anti-in the step 1
Answer and be added diphenylamines in kettle and catalyst while is added polymerization inhibitor, the polymerization inhibitor be hydroquinone, tert-butyl catechol,
One of bis- tertiary amyl hydroquinone of 2,6- dinitro-p-cresol and 2,5- is a variety of；The polymerization inhibitor additional amount meets quality
Concentration is 30~150ppm.
6. the preparation method of styrenated diphenylamine according to claim 1, which is characterized in that opened in the step 2
Vacuum system controls in kettle vacuum degree in 0.08MPa~0.095MPa, under vacuum conditions the moisture in elimination reaction system.
7. the preparation method of styrenated diphenylamine according to claim 1, which is characterized in that one in the step 3
Determining temperature is 90-100 DEG C, certain time 30-40min.
8. the preparation method of styrenated diphenylamine according to claim 1, which is characterized in that by benzene in the step 4
Ethylene is placed in Dropping feeder, and styrene is added several times into reaction kettle by Dropping feeder, controls the temperature of alkylated reaction
Degree is 110~180 DEG C, and the reaction time is 3~8 hours.
9. the preparation method of styrenated diphenylamine according to claim 1, which is characterized in that benzene second in the step 4
The additional amount of alkene meets: the molar ratio of diphenylamines and styrene is 1:1.8~2.8.
10. the preparation method of styrenated diphenylamine according to claim 1, which is characterized in that the step 5 filtering
Filter cake afterwards is catalyst, be may be reused, the mother liquor filtered out is evaporated under reduced pressure, and distillate and styrol are obtained
Hexichol amine product, wherein distillate is styrene, and recycling continues cycling through use as raw material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910121960.6A CN109651161A (en) | 2019-02-18 | 2019-02-18 | A kind of preparation method of styrenated diphenylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910121960.6A CN109651161A (en) | 2019-02-18 | 2019-02-18 | A kind of preparation method of styrenated diphenylamine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109651161A true CN109651161A (en) | 2019-04-19 |
Family
ID=66123145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910121960.6A Pending CN109651161A (en) | 2019-02-18 | 2019-02-18 | A kind of preparation method of styrenated diphenylamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109651161A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759523A (en) * | 2021-02-19 | 2021-05-07 | 李俊乐 | Styryl diphenylamine antioxidant and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725237A (en) * | 2015-03-25 | 2015-06-24 | 江苏飞亚化学工业有限责任公司 | Preparation method of styrenated diphenylamine antiager |
| CN104744264A (en) * | 2015-03-25 | 2015-07-01 | 江苏飞亚化学工业有限责任公司 | Preparation method for styrenated diphenylamine antioxidant |
| CN105541638A (en) * | 2016-01-28 | 2016-05-04 | 江苏飞亚化学工业有限责任公司 | Preparation method of styrenated diphenylamine antioxidizer |
| CN106944142A (en) * | 2017-03-22 | 2017-07-14 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation method of composite catalyst and nonyl diphenylamine |
| CN108329215A (en) * | 2018-04-10 | 2018-07-27 | 李新君 | A kind of preparation method of styrenated diphenylamine anti-aging agent |
-
2019
- 2019-02-18 CN CN201910121960.6A patent/CN109651161A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725237A (en) * | 2015-03-25 | 2015-06-24 | 江苏飞亚化学工业有限责任公司 | Preparation method of styrenated diphenylamine antiager |
| CN104744264A (en) * | 2015-03-25 | 2015-07-01 | 江苏飞亚化学工业有限责任公司 | Preparation method for styrenated diphenylamine antioxidant |
| CN105541638A (en) * | 2016-01-28 | 2016-05-04 | 江苏飞亚化学工业有限责任公司 | Preparation method of styrenated diphenylamine antioxidizer |
| CN106944142A (en) * | 2017-03-22 | 2017-07-14 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation method of composite catalyst and nonyl diphenylamine |
| CN108329215A (en) * | 2018-04-10 | 2018-07-27 | 李新君 | A kind of preparation method of styrenated diphenylamine anti-aging agent |
Non-Patent Citations (1)
| Title |
|---|
| 李博仑: "液态抗氧剂烷基二苯胺的合成", 《天津科技大学研究生学位论文》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759523A (en) * | 2021-02-19 | 2021-05-07 | 李俊乐 | Styryl diphenylamine antioxidant and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN87103140A (en) | Yi Bingchunan is as the deactivators of the catalyzer of alpha-olefin solution polymerization process | |
| TWI436975B (en) | Production of ethylenically unsaturated acids or esters thereof | |
| CN117888377A (en) | Method for producing decolorized polyester, and decolorizer | |
| CN109651161A (en) | A kind of preparation method of styrenated diphenylamine | |
| CN1727320A (en) | reactive benzophenone photoinitiator and preparation method thereof | |
| TWI308574B (en) | A process for producing polycarbonates | |
| WO2007074750A1 (en) | Process for producing (meth)acrylic ester | |
| CN105418469A (en) | Preparation method for antioxidant 2,4-bi(n-octyl sulfur methylene)-6-methylphenol | |
| CN106944142B (en) | A kind of preparation method of composite catalyst and nonyl diphenylamine | |
| CN106317382A (en) | Preparation method of anti-aging agent | |
| CN107501143A (en) | A kind of preparation method of the methylphenol of antioxidant 2,4 2 (n-octylthiomethylene) 6 | |
| CN101423483A (en) | High basic value (TBN400) sulfurized calcium alkyl and preparation method thereof | |
| KR960008491B1 (en) | Autosynergistic phenolic antioxidant reaction product | |
| CA1142966A (en) | Alkylation of 2,6-di-tert-alkylphenols with alkanediols | |
| CN114058002A (en) | Method for producing copolycarbonates with improved thermal degradation resistance, copolycarbonates and use thereof | |
| CN106432799B (en) | A kind of reclaimed rubber activator, preparation method and application | |
| CN1481347A (en) | Method of depolymerizing aromatic polycarbonate | |
| CN109734603A (en) | A kind of preparation method of liquid amine antioxidants | |
| KR100686367B1 (en) | Improved process for the preparation of mercaptomethylphenols | |
| CN110590702B (en) | Novel method for preparing 2-mercaptobenzothiazole | |
| CN108863728A (en) | A kind of preparation method of 9,9- bis- (4- hydroxyaryl) compound of fluorene class | |
| CN101063002A (en) | Anthraquinone type solvent dye and preparation and application thereof | |
| CN111517962A (en) | Preparation method of amine anti-aging agent | |
| JP2005263717A (en) | Method for producing cyanoalkoxy compound | |
| CN105001836B (en) | A kind of anti-coking synthesis aromatic hydrocarbons conduction oil and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190419 |
|
| RJ01 | Rejection of invention patent application after publication |