CN109734603A - A kind of preparation method of liquid amine antioxidants - Google Patents
A kind of preparation method of liquid amine antioxidants Download PDFInfo
- Publication number
- CN109734603A CN109734603A CN201811495781.0A CN201811495781A CN109734603A CN 109734603 A CN109734603 A CN 109734603A CN 201811495781 A CN201811495781 A CN 201811495781A CN 109734603 A CN109734603 A CN 109734603A
- Authority
- CN
- China
- Prior art keywords
- reaction
- amine antioxidants
- liquid amine
- preparation
- 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
Landscapes
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Lubricants (AREA)
Abstract
The invention discloses a kind of preparation methods of liquid amine antioxidants, comprising the following steps: diphenylamines, atlapulgite composite catalyst, polymerization inhibitor are proportionally added into reaction kettle；Heating is alkylated reaction after being proportionally added into diisobutylene into reaction kettle；Reaction product after step (2) reaction is cooled down and is filtered, the mother liquor filtered out carries out vacuum distillation and removes unreacted alkene, obtains liquid amine antioxidants finished product.Method of the invention is alkylated reaction using atlapulgite composite catalyst, reduce reaction temperature, shorten the reaction time, make generate alkyl diphenylamine RF5057 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, mainly a kind of synthetic method of antioxidant for lubricant oil, specifically
For the preparation method of liquid amine antioxidants.
Background technique
Antioxidant is the compound for referring to prevent or organic material is delayed to aoxidize.Organic material all have in air
The property that oxygen reacts, although substance can change the industrial side for preventing oxidation operation its original attribute after oxidation reaction
There are many method, but it is still most easy most efficient method that antioxidant, which is added,.Lubricating oil in use also inevitably with oxygen
Chemical action and oxidation deterioration occur for contact, generate acidic materials, equipment is caused to be corroded.
Amine antioxidants are using earliest one of antioxidant, are a kind of efficient high-temperature antioxidants.RF5057 is a kind of
Main component is the liquid amine antioxidants of fourth octyl diphenylamine, has the characteristics that low volatility and good compatibility, is added
In the process without dilution, dust pollution is avoided, operating environment has been purified, can be widely applied to lubricating oil, polymer, rubber etc.
Industry can improve the compatibility of detersive, dispersing agent and other lube oil additives, oil-soluble and compatibility, enhance each addition
Synergistic effect between agent, improves the service efficiency of additive, to reach the class for improving lubricating oil and reduce other additives
The purpose of dosage.
CN103408431A discloses a kind of preparation method of aromatic liquid amine antioxidants；By diphenylamines and perfluorinated sulfonic acid
Resin mixing is heated to dropwise addition diisobutylene at 150 DEG C -180 DEG C and is alkylated reaction；, perfluor sulphur is recovered by filtration in product
Acid resin just obtains liquid after active carbon decolorization after filtrate removes unreacted diphenylamines by vacuum distillation
Aromatic amine antioxidant 5057.This method process is more many and diverse, is taken off again using active carbon with vacuum distillation removing diphenylamines
Color generates a large amount of solid waste, causes to environment potentially hazardous.This method preparation product colour it is deeper, diphenylamines residual compared with
It is more, influence the appearance and performance of product.
Summary of the invention
It is an object of the invention to overcome above-mentioned the shortcomings of the prior art, a kind of liquid amine antioxidants are provided ----
The preparation method of alkyl diphenylamine RF5057, the method overcome when reaction present in previous synthesis technology and other catalyst
Between it is long, condition is harsh, diphenylamines residual is high, product appearance color is deep, post-processing generates a large amount of waste water the disadvantages of.
Technical solution provided by the invention are as follows:
A kind of preparation method of liquid amine antioxidants RF5057, comprising the following steps:
(1) diphenylamines, atlapulgite composite catalyst, polymerization inhibitor are added in reaction kettle, are started after being replaced with nitrogen
Heat temperature raising is warming up to 50-70 DEG C (preferably 70 DEG C) and opens stirring afterwards, under vacuum conditions the water in elimination reaction system
Point.90~105 DEG C (preferably 100 DEG C) 100 DEG C are gradually heated to, heat preservation 10~60min (preferably 30 DEG C) stops vacuum afterwards
System is replaced with nitrogen to normal pressure.
The atlapulgite composite catalyst is compounded by atlapulgite, p-methyl benzenesulfonic acid, activated alumina mixing.
It is added in atlapulgite and is equivalent to 0.1%~5% p-methyl benzenesulfonic acid of atlapulgite quality and is equivalent to atlapulgite matter
0.1%~5% activated alumina of amount is uniformly mixed in mixing device, has just obtained atlapulgite composite catalyst.
The atlapulgite composite catalyst additional amount is the 8%~36% of diphenylamines additional amount (quality).Atlapulgite
Composite catalyst is simple and easy to get, and reactivity is high, and post-processing is uncomplicated, generates without the three wastes, and can be recycled.
The polymerization inhibitor is hydroquinone, tert-butyl catechol, 2,6- dinitro-p-cresol or 2, bis- tertiary amyl of 5-
Hydroquinone.The additional amount of polymerization inhibitor described in reaction is mainly used for that diisobutylene is avoided to polymerize, and dosage is added with diisobutylene
On the basis of entering amount, the concentration of polymerization inhibitor is 30~150ppm.
(2) it heats up after addition diisobutylene and is alkylated reaction, 120~190 DEG C of reaction temperature, pressure 0.1~
0.45MPa, (analyze diphenylamine content by GC in laboratory is that can determine whether to have reacted to the fully reacting of 6~16 hours reaction time
Whether complete, from the reaction time generally at 6~16 hours).The additional amount of diisobutylene meets: the quality of diphenylamines and diisobutylene
Than for 100:96~100:130, diisobutylene can once be added, can also be added by several times.It is preferred that being first added at one time one
Point, (generally 1~3 hour) is slowly added to a part after reacting a period of time, after certain interval of time, is slow added into one
Point.The amount of addition is spaced time of addition not restriction.
(3) reaction product after step (2) reaction is cooled to (20~25 DEG C) of room temperature filterings, the mother liquor filtered out is subtracted
Unreacted alkene is distilled off to get liquid amine antioxidants RF5057 finished product is arrived in pressure.
The filter cake that step (3) is obtained by filtration can be used as catalyst circulation by collection processing and use (as in step (1)
Atlapulgite composite catalyst reuse)；Alkene (diisobutylene) through vacuum distillation recycling can continue to participate in reaction cycle benefit
Use (the reactant reuse as in step (2)).The vacuum degree control that mother liquor is evaporated under reduced pressure 0.08MPa~
0.095MPa。
The control of alkylated reaction temperature is preferably controlled in 140~180 DEG C at 120~190 DEG C in the above method.Reaction pressure
Power is in 0.1~0.45MPa, and pressure is higher when just starting to react, and with the progress of reaction, reaction pressure is gradually reduced.Reaction 6~
Fully reacting stops reaction after 16 hours.The distillate of distillation is recycling diisobutylene, can be used as raw material and continues cycling through use.Three
Faint yellow as clear as crystal liquid RF5057 product is obtained in mouth bottle.
Present invention has the advantage that:
The preparation method that the present invention provides a kind of liquid amine antioxidants (alkyl diphenylamine RF5057) has process
Simply, it post-processes uncomplicated and does not generate waste water.The product appearance color of preparation is shallower, and viscosity is high, and base number is high, hexichol in product
Amine residual content is lower, is greatly improved to the performance of product.
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.
Embodiment 1
The present embodiment provides the preparation methods of liquid amine antioxidants RF5057 a kind of, comprising the following steps:
(1) 200g atlapulgite is added in mixing device, 2g p-methyl benzenesulfonic acid and 5g activated alumina are compounded, opened
Dynamic mixing arrangement half an hour, the atlapulgite composite catalyst being just uniformly mixed are spare.
130g diphenylamines, 30g atlapulgite composite catalyst, 90ppm polymerization inhibitor are added in stainless steel cauldron to benzene
Diphenol is passed through nitrogen into reaction kettle, is sufficiently displaced from kettle after air, begins to warm up.Vacuum system, vacuum in kettle are opened simultaneously
Degree control is in 0.08MPa~0.095MPa.Start when temperature reaches 70 DEG C or so open stirring, stirring rate be 300 turns/
Divide, under vacuum conditions the moisture in elimination reaction system.Stop vacuum system after being gradually heated to 100 DEG C of heat preservation half an hours
System, is replaced with nitrogen to normal pressure.
(2) 165g diisobutylene is added, is gradually heated to start isothermal reaction at 175 DEG C, reacts 12 hours, stops anti-
It answers.
(3) it after temperature of reaction system is down to room temperature, releases product in reaction kettle and is filtered, filter cake is that catalyst can weigh
It is multiple to use.The mother liquor that will filter out is added in there-necked flask and carries out decompression steaming under the conditions of vacuum degree 0.095MPa or so, 190 DEG C
It evaporates, distillate is recycling diisobutylene, can be used as raw material and continues cycling through use.Faint yellow as clear as crystal liquid is obtained in there-necked flask
Body alkyl diphenylamine RF5057 product is 0.13% according to diphenylamine content in chromatography product, dioctyl diphenylamine content
It is 13.46%, base number is by being measured as 175.1mgKOH/g.
Embodiment 2
The present embodiment provides the preparation methods of liquid amine antioxidants RF5057 a kind of, comprising the following steps:
(1) 200g atlapulgite is added in mixing device, 1g p-methyl benzenesulfonic acid and 3g activated alumina are compounded, opened
Dynamic mixing arrangement half an hour, the atlapulgite composite catalyst being just uniformly mixed are spare.
130g diphenylamines, 40g atlapulgite composite catalyst, 90ppm polymerization inhibitor are added in stainless steel cauldron to benzene
Diphenol is passed through nitrogen into reaction kettle, is sufficiently displaced from kettle after air, begins to warm up.Vacuum system, vacuum in kettle are opened simultaneously
Degree control is in 0.08MPa~0.095MPa.Start when temperature reaches 70 DEG C or so open stirring, stirring rate be 300 turns/
Divide, under vacuum conditions the moisture in elimination reaction system.Stop vacuum system after being gradually heated to 100 DEG C of heat preservation half an hours
System, is replaced with nitrogen to normal pressure.
(2) 60g diisobutylene is added, is gradually heated to start isothermal reaction at 160 DEG C, starts timing, after reaction 3 hours
It is slowly added into 50g diisobutylene again, the reaction was continued at 170 DEG C for temperature control, and it is different that reaction was slowly added into 50g bis- after the 7th hour again
Butylene, temperature, which controls after at 170 DEG C, the reaction was continued 5 hours, stops reaction.
(3) it after temperature of reaction system is down to room temperature, releases product in reaction kettle and is filtered, filter cake is that catalyst can weigh
It is multiple to use.The mother liquor that will filter out is added in there-necked flask and carries out decompression steaming under the conditions of vacuum degree 0.095MPa or so, 190 DEG C
It evaporates, distillate is recycling diisobutylene, can be used as raw material and continues cycling through use.Faint yellow as clear as crystal liquid is obtained in there-necked flask
Body alkyl diphenylamine RF5057 product is 0.27% according to diphenylamine content in chromatography product, dioctyl diphenylamine content
It is 17.66%, base number is by being measured as 173.6mgKOH/g.
Embodiment 3
The present embodiment provides the preparation methods of liquid amine antioxidants RF5057 a kind of, comprising the following steps:
(1) 200g atlapulgite is added in mixing device, 3g p-methyl benzenesulfonic acid and 1g activated alumina are compounded, opened
Dynamic mixing arrangement half an hour, the atlapulgite composite catalyst being just uniformly mixed are spare.
130g diphenylamines, 25g atlapulgite composite catalyst, 75ppm polymerization inhibitor 2,6- are added in stainless steel cauldron
Dinitro-p-cresol is passed through nitrogen into reaction kettle, is sufficiently displaced from kettle after air, begins to warm up.Vacuum system is opened simultaneously,
Vacuum degree control starts to open stirring when temperature reaches 70 DEG C or so in 0.08MPa~0.095MPa. in kettle, and stirring rate is
300 revs/min, the moisture in elimination reaction system under vacuum conditions.Stop very after being gradually heated to 100 DEG C of heat preservation half an hours
Empty set system, is replaced with nitrogen to normal pressure
(2) 130g diisobutylene is added, is gradually heated to start isothermal reaction at 170 DEG C.Reaction 12 hours stops anti-
It answers.
(3) it after temperature of reaction system is down to room temperature, releases product in reaction kettle and is filtered, filter cake is that catalyst can weigh
It is multiple to use.The mother liquor that will filter out is added in there-necked flask and carries out decompression steaming under the conditions of vacuum degree 0.095MPa or so, 190 DEG C
It evaporates, distillate is recycling diisobutylene, can be used as raw material and continues cycling through use.Faint yellow as clear as crystal liquid is obtained in there-necked flask
Body alkyl diphenylamine RF5057 product is 0.50% according to diphenylamine content in chromatography product, dioctyl diphenylamine content
It is 15.41%, base number is by being measured as 174.7mgKOH/g.
Embodiment 4
The present embodiment provides the preparation methods of liquid amine antioxidants RF5057 a kind of, comprising the following steps:
(1) 200g atlapulgite is added in mixing device, 3g p-methyl benzenesulfonic acid and 1g activated alumina are compounded, opened
Dynamic mixing arrangement half an hour, the atlapulgite composite catalyst being just uniformly mixed are spare.
130g diphenylamines, 30g atlapulgite composite catalyst, 80ppm polymerization inhibitor 2,5- are added in stainless steel cauldron
Two tertiary amyl hydroquinones, nitrogen is passed through into reaction kettle, is sufficiently displaced from kettle after air, is begun to warm up.Vacuum is opened simultaneously
System, vacuum degree control starts to open stirring, stirring when temperature reaches 70 DEG C or so in 0.08MPa~0.095MPa. in kettle
Rate is 300 revs/min, under vacuum conditions the moisture in elimination reaction system.After being gradually heated to 100 DEG C of heat preservation half an hours
Stop vacuum system, is replaced with nitrogen to normal pressure.
(2) 146g diisobutylene is added, is gradually heated to start isothermal reaction at 165 DEG C.Reaction 12 hours stops anti-
It answers.
(3) it after temperature of reaction system is down to room temperature, releases product in reaction kettle and is filtered, filter cake is that catalyst can be with
It reuses.The mother liquor that will filter out is added in there-necked flask and carries out decompression steaming under the conditions of vacuum degree 0.095MPa or so, 190 DEG C
It evaporates, distillate is recycling diisobutylene, can be used as raw material and continues cycling through use.Faint yellow as clear as crystal liquid is obtained in there-necked flask
Body alkyl diphenylamine RF5057 product is 0.45% according to diphenylamine content in chromatography product, dioctyl diphenylamine content
It is 17.64%, base number is by being measured as 173.4mgKOH/g.
Embodiment 5
The present embodiment provides the preparation methods of liquid amine antioxidants RF5057 a kind of, comprising the following steps:
(1) 200g atlapulgite is added in mixing device, 5g p-methyl benzenesulfonic acid and 6g activated alumina are compounded, opened
Dynamic mixing arrangement half an hour, the atlapulgite composite catalyst being just uniformly mixed are spare.
130g diphenylamines, 30g atlapulgite composite catalyst, the tertiary fourth of 70ppm polymerization inhibitor are added in stainless steel cauldron
Base catechol, nitrogen is passed through into reaction kettle, is sufficiently displaced from kettle after air, is begun to warm up.Vacuum system, kettle are opened simultaneously
Interior vacuum degree control starts to open stirring when temperature reaches 70 DEG C or so in 0.08MPa~0.095MPa., and stirring rate is
300 revs/min, the moisture in elimination reaction system under vacuum conditions.Stop very after being gradually heated to 100 DEG C of heat preservation half an hours
Empty set system, is replaced with nitrogen to normal pressure.
(2) 155g diisobutylene is added, is gradually heated to start isothermal reaction at 170 DEG C.Reaction 15 hours stops anti-
It answers.
(3) it after temperature of reaction system is down to room temperature, releases product in reaction kettle and is filtered, filter cake is that catalyst can be with
It reuses.The mother liquor that will filter out is added in there-necked flask and carries out decompression steaming under the conditions of vacuum degree 0.095MPa or so, 190 DEG C
It evaporates, distillate is recycling diisobutylene, can be used as raw material and continues cycling through use.Faint yellow as clear as crystal liquid is obtained in there-necked flask
Body alkyl diphenylamine RF5057 product is 0.44% according to diphenylamine content in chromatography product, dioctyl diphenylamine content
It is 14.72%, base number is by being measured as 177.3mgKOH/g.
Embodiment 6
The present embodiment provides the preparation methods of liquid amine antioxidants RF5057 a kind of, comprising the following steps:
(1) 200g atlapulgite is added in mixing device, 1g p-methyl benzenesulfonic acid and 6g activated alumina are compounded, opened
Dynamic mixing arrangement half an hour, the atlapulgite composite catalyst being just uniformly mixed are spare.
130g diphenylamines, 30g atlapulgite composite catalyst, the tertiary fourth of 50ppm polymerization inhibitor are added in stainless steel cauldron
Base catechol, nitrogen is passed through into reaction kettle, is sufficiently displaced from kettle after air, is begun to warm up.Vacuum system, kettle are opened simultaneously
Interior vacuum degree control starts to open stirring when temperature reaches 70 DEG C or so in 0.08MPa~0.095MPa., and stirring rate is
300 revs/min, the moisture in elimination reaction system under vacuum conditions.Stop very after being gradually heated to 100 DEG C of heat preservation half an hours
Empty set system, is replaced with nitrogen to normal pressure.
(2) 150g diisobutylene is added, is gradually heated to start isothermal reaction at 173 DEG C.Reaction 12 hours stops anti-
It answers.
(3) it after temperature of reaction system is down to room temperature, releases product in reaction kettle and is filtered, filter cake is that catalyst can be with
It reuses.The mother liquor that will filter out is added in there-necked flask and carries out decompression steaming under the conditions of vacuum degree 0.095MPa or so, 190 DEG C
It evaporates, distillate is recycling diisobutylene, can be used as raw material and continues cycling through use.Faint yellow as clear as crystal liquid is obtained in there-necked flask
Body alkyl diphenylamine RF5057 product is 0.32% according to diphenylamine content in chromatography product, dioctyl diphenylamine content
It is 12.86%, base number is by being measured as 173.8mgKOH/g.
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.
Embodiment 7
Table 1: the high-temperature oxidation resistant experimental result of embodiment 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 alkyl diphenylamine RF5057 oxidation induction period longest of technical solution preparation, antioxygen property are preferable.According to
The liquid amine antioxidants product appearance color of technical solution preparation provided by the invention is shallower, and viscosity is high, and base number is high, in product
Diphenylamines residual content is lower, is greatly improved to product antioxygen property.
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 (9)
1. a kind of preparation method of liquid amine antioxidants, which comprises the following steps:
(1) diphenylamines, atlapulgite composite catalyst, polymerization inhibitor are proportionally added into reaction kettle；
(2) heating is alkylated reaction after being proportionally added into diisobutylene into reaction kettle；
(3) reaction product after step (2) reaction is cooled down and is filtered, the mother liquor filtered out carries out vacuum distillation and removes unreacted alkene
Hydrocarbon obtains liquid amine antioxidants finished product.
2. the preparation method of liquid amine antioxidants according to claim 1, which is characterized in that the atlapulgite is compound
Catalyst is compounded by atlapulgite, p-methyl benzenesulfonic acid, activated alumina mixing, is added in atlapulgite and is equivalent to work
Property carclazyte quality 0.1%~5% p-methyl benzenesulfonic acid and be equivalent to 0.1%~5% active oxidation of atlapulgite quality
Aluminium is uniformly mixed in mixing device, obtains atlapulgite composite catalyst.
3. the preparation method of liquid amine antioxidants according to claim 1, which is characterized in that the polymerization inhibitor is pair
Benzenediol, tert-butyl catechol, 2,6- dinitro-p-cresol or 2, bis- tertiary amyl hydroquinone of 5-.
4. the preparation method of liquid amine antioxidants according to claim 1, which is characterized in that activity is white in step (1)
Native composite catalyst additional amount is that diphenylamines is added the 8%~36% of quality；The additional amount of the polymerization inhibitor is added with diisobutylene
On the basis of entering amount, the concentration of polymerization inhibitor is 30~150ppm；The additional amount of diisobutylene described in step (2) meets: diphenylamines
Mass ratio with diisobutylene is 100:96~100:130.
5. the preparation method of liquid amine antioxidants according to claim 1, which is characterized in that by hexichol in step (1)
It after amine, atlapulgite composite catalyst, polymerization inhibitor are proportionally added into reaction kettle, is first replaced with nitrogen, then begins to warm up liter
Temperature opens stirring, under vacuum conditions the moisture in elimination reaction system, then is gradually heated to 90~105 after being warming up to 70 DEG C
DEG C, stop vacuum system after keeping the temperature 10~60min, is replaced with nitrogen to normal pressure, then carried out again subsequent step (2).
6. the preparation method of liquid amine antioxidants according to claim 1, which is characterized in that alkane described in step (2)
The reaction temperature of glycosylation reaction is 120~190 DEG C, and reaction pressure is 0.1~0.45MPa, and the reaction time is 6~16 hours.
7. the preparation method of liquid amine antioxidants according to claim 1, which is characterized in that two described in step (2)
Reaction kettle once can be all added in isobutene, and reaction kettle can also be added several times.
8. the preparation method of liquid amine antioxidants according to claim 1, which is characterized in that step filters in (3)
The filter cake arrived is used as catalyst circulation use by collecting processing；Alkene through vacuum distillation recycling continues to participate in reaction cycle benefit
With.
9. the preparation method of liquid amine antioxidants according to claim 1, which is characterized in that in step (3) mother liquor into
The vacuum degree control of row vacuum distillation is in 0.08MPa~0.095MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811495781.0A CN109734603A (en) | 2018-12-07 | 2018-12-07 | A kind of preparation method of liquid amine antioxidants |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811495781.0A CN109734603A (en) | 2018-12-07 | 2018-12-07 | A kind of preparation method of liquid amine antioxidants |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109734603A true CN109734603A (en) | 2019-05-10 |
Family
ID=66358564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811495781.0A Pending CN109734603A (en) | 2018-12-07 | 2018-12-07 | A kind of preparation method of liquid amine antioxidants |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109734603A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113045429A (en) * | 2019-12-27 | 2021-06-29 | 中国石油天然气股份有限公司 | Method for simultaneously preparing antioxidant of butyl octyl diphenylamine and dioctyl diphenylamine and obtained product |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503617A (en) * | 2015-07-30 | 2016-04-20 | 中国科学院宁波材料技术与工程研究所 | High-selectivity alkylated diphenylamine and its preparation method and use |
| 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 |
-
2018
- 2018-12-07 CN CN201811495781.0A patent/CN109734603A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503617A (en) * | 2015-07-30 | 2016-04-20 | 中国科学院宁波材料技术与工程研究所 | High-selectivity alkylated diphenylamine and its preparation method and use |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113045429A (en) * | 2019-12-27 | 2021-06-29 | 中国石油天然气股份有限公司 | Method for simultaneously preparing antioxidant of butyl octyl diphenylamine and dioctyl diphenylamine and obtained product |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| NO171630B (en) | APPLICATION OF CALCINATED HYDROTALKITES AS CATALYSTS FOR ETHOXYLING BY PROPOXYLING OF COMPOUNDS WITH ACTIVE H ATOMS | |
| CN108586522B (en) | Novel bio-based phosphite antioxidant and preparation method thereof | |
| CN1844071A (en) | Phenol ortho alkylation method with high-conversion and high-selectivity | |
| CN109734603A (en) | A kind of preparation method of liquid amine antioxidants | |
| CN106944142B (en) | A kind of preparation method of composite catalyst and nonyl diphenylamine | |
| CN105038904B (en) | A kind of lubricating oil high-temperature anti-oxidant and preparation method thereof | |
| CN107501143A (en) | A kind of preparation method of the methylphenol of antioxidant 2,4 2 (n-octylthiomethylene) 6 | |
| CN101538208B (en) | Method for preparing mixture of 4-(alpha, alpha-dimethylbenzyl) diphenylamine and 4,4-bis (alpha, alpha-dimethylbenzyl) diphenylamine | |
| CN113956135A (en) | Preparation method of high-yield 4, 4' -biphenol | |
| CN102659606A (en) | Preparation method of alkylated diphenylamine antioxidant with high color stability | |
| CN112320766B (en) | Preparation method and application of hollow mesoporous inorganic oxide nanosphere solid alkali | |
| CN102826961A (en) | Cycling treatment method for waste acid produced in production of hydroquinone | |
| CN102476995B (en) | Preparation method of liquid hindered phenol carboxylic ester antioxidant | |
| CN109651161A (en) | A kind of preparation method of styrenated diphenylamine | |
| CN104560407B (en) | A kind of preparation method of epoxy plasticiser | |
| CN104379545A (en) | Method for producing 4,4''-dihydroxy-m-terphenyls | |
| US2671117A (en) | Hydroxy aromatic hydrocarbonolefin polymer alkylation with alcl2 hso4 catalyst | |
| CN103159625A (en) | Method of producing trimethylolpropane oleate with single kettle | |
| CN108929239B (en) | Preparation method of sodium polysulfide | |
| CN108913325A (en) | The method of solvent extraction combination composite metal oxide adsorbent regeneration waste lubricating oil | |
| RU2279466C1 (en) | Method of selectively purifying lubricating oil fraction for removing polycyclic aromatics | |
| CN1203572A (en) | Method for c-alkylating hydroxylated aromatic compounds | |
| CN102976901A (en) | Synthetic method for hybrid tertiary butyl phenol | |
| CN113528236A (en) | Method for removing colloid in hogwash oil | |
| CN102766030A (en) | Method for preparing 3-bromine-4-hydroxy benzaldehyde |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190510 |