CN102320983A - A kind of preparation method of liquid octylated diphenylamine oxidation inhibitor - Google Patents
A kind of preparation method of liquid octylated diphenylamine oxidation inhibitor Download PDFInfo
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- CN102320983A CN102320983A CN201110158159A CN201110158159A CN102320983A CN 102320983 A CN102320983 A CN 102320983A CN 201110158159 A CN201110158159 A CN 201110158159A CN 201110158159 A CN201110158159 A CN 201110158159A CN 102320983 A CN102320983 A CN 102320983A
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- octylated diphenylamine
- pentanoic
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Abstract
A kind of preparation method of liquid octylated diphenylamine oxidation inhibitor the invention belongs to the field of chemical synthesis, particularly a kind of method of synthesis of high content list octyl diphenylamine.Under the effect of catalyzer, pentanoic and diisobutylene are reacted, generate the octylated diphenylamine mixture, and then feed isobutene reaction, through promptly getting liquid octylated diphenylamine oxidation inhibitor after the distillation; The atlapulgite of said catalyzer for crossing through processed.The liquid octylated diphenylamine oxidation inhibitor normal temperature of processing is down light yellow viscous liquid, and the kinematic viscosity under 40 ℃ is 50～300mm
2/ s.Liquid octylated diphenylamine oxidation inhibitor can be effective to oil product, the lubricant of various application under turbo, aircraft and the High Operating Temperature, also can be used in the polymer rubber goods, and it is aging to prevent that rubber thermooxidizing and elasticity from deflecting.
Description
Technical field
The invention belongs to the field of chemical synthesis, particularly a kind of method of synthesis of high content list octyl diphenylamine.
Background technology
At present, no matter be the aerospace lubricating oil, or engine oil, and industrial lubricant (like high-temperature chain oil, compressor oil, heat conduction wet goods), all high performance oxidation inhibitor has been proposed requirement, and this requirement is more and more harsher.Oxidation inhibitor zinc dialkyl dithiophosphate (ZDDP) in the general engine oil can not satisfy the requirement of environmental protection and high-temperature behavior, needs the new high-temperature antioxidant of development.
The demand can be satisfied by the oxidation inhibitor alkylated diphenylamine.Alkylated diphenylamine can be effective to oil product, the lubricant of various application under turbo, aircraft and the High Operating Temperature, also can be used in the polymer rubber goods, and it is aging to prevent that rubber thermooxidizing and elasticity from deflecting.
Octylated diphenylamine oxidation inhibitor belongs to a kind of typical alkylated diphenylamine kind antioxidant.Octylated diphenylamine is synthetic by pentanoic and diisobutylene usually; If the synthetic technological condition condition is different; Then the substituted group of alkylation, substituted position can be different to some extent, forms and also can distinguish to some extent so obtain the structure of product, has solid-state and liquid two kinds under the normal temperature.Provided by the present invention be the liquid octylated diphenylamine with and preparation method thereof.
CN1882651A discloses a kind of preparation method of octylated diphenylamine antioxidant composition.The obtained product of this method comprises 65-98 weight % dioctyl diphenylamine, the single octyl diphenylamine of 29 weight % at the most, and 5 weight % octyl group butyl pentanoic at the most, 1.5 weight % trioctylphosphine pentanoic at the most, 1 weight % pentanoic at the most, said composition at room temperature is a solid.But because the solid octylated diphenylamine do not have liquid octylated diphenylamine oil soluble good, be prone to advantages such as allotment, thus in the actual production consumption much smaller than the liquid octylated diphenylamine.
US4824601 discloses a kind of method for preparing liquid octylated diphenylamine oxidation inhibitor.Its preparation method is that pentanoic, diisobutylene, catalyzer are reacted being higher than under 160 ℃ of temperature; Make it to generate earlier high-load dioctyl diphenylamine mixture; And then elevated temperature; Make the dioctyl diphenylamine cracking, dioctyl diphenylamine can be cracked into single octyl diphenylamine, butyl pentanoic, butyl octyl pentanoic even have part and be cracked into pentanoic.Sampling analysis, the content of dioctyl diphenylamine is lower than at 25% o'clock in reaction solution, stopped reaction.This method has following shortcoming:
1, temperature of reaction is higher, and temperature of reaction is all more than 160 ℃ usually, and cracking temperature reaches 200 ℃ especially, and reaction conditions is violent, also is prone to generate the multidigit substituent of pentanoic under the high temperature, and like the trioctylphosphine pentanoic, this product is that we are not conceivable.
2, reaction process is wayward, needs the content of sampling analysis dioctyl diphenylamine midway, if error in judgement or take a sample inaccurately causes in the finished product content of final dioctyl diphenylamine to be higher than at 25% o'clock, product at room temperature will become solid.
3, contain pentanoic and trioctylphosphine pentanoic in the obtained product.Pentanoic has pungency to skin, and in oil product, is prone to flavescence; The trioctylphosphine pentanoic is that our institute is unwanted.Want to isolate this two kinds of components, just must carry out the negative pressure rectification and purification product.This will waste mass energy, and prolong entire reaction period.
CN1288000A also discloses the method that a kind of and US4824601 similarly prepare liquid octylated diphenylamine oxidation inhibitor.Its preparation method is in the presence of activated bauxite catalyst, 170～230 ℃ with make under the pressure that diisobutylene is in a liquid state, make diisobutylene and pentanoic contact reacts, when dioctyl diphenylamine content in the product less than 20% the time, stopped reaction is also collected product.Reaction times needs 20～25 hours.In its reaction product, the butyl pentanoic accounts for 15～25%, octyl diphenylamine 25～30%, and the butyl octyl pentanoic accounts for 25～30%, and dioctyl diphenylamine accounts for 10～20%, and pentanoic accounts for 2～4%.There is long reaction time equally in this method, reaches 20～25 hours; Temperature of reaction is high, reaches 170～230 ℃; Pentanoic content residual in the product is higher, reaches shortcomings such as 2～4%.The prepared product trade mark at home is T534, and effect is lower than external trade mark IRGANOX 5057.
US2943112 proposition monoalkyl pentanoic in alkylated reaction is active stronger than diphenylamine reaction, is reacted more easily.That is to say that in alkylated reaction, in case generate the monoalkyl pentanoic, the group that just has an alkene reacts the generation dialkyl diphenylamine with it, make that the content of monoalkyl pentanoic is very low in the entire reaction thing at once.So be difficult to prepare the high alkyl diphenyl amine composition of monoalkyl pentanoic content.
Summary of the invention
In order to overcome above prior art defective, the invention provides a kind of preparation method of new liquid octylated diphenylamine oxidation inhibitor.
Technical scheme of the present invention is: under the effect of catalyzer, pentanoic and diisobutylene are reacted, generate the octylated diphenylamine mixture, and then feed isobutene reaction, through promptly getting liquid octylated diphenylamine oxidation inhibitor after the distillation; The atlapulgite of said catalyzer for crossing through processed.
It is raw material that the present invention adopts pentanoic and diisobutylene; Alkylated reaction takes place under the effect of atlapulgite catalytic alkylation; And then feed iso-butylene in the reaction solution and unreacted pentanoic carries out the secondary alkylated reaction; Pass through simple distillation at last, remove not the diisobutylene of complete reaction and the isobutylene oligomer that possibly exist, promptly get liquid octylated diphenylamine oxidation inhibitor.
Each components contents comprises the pentanoic of 1 % (mass percent) at the most in the liquid octylated diphenylamine of processing, 5～15 % butyl pentanoic, 50～80 % single octyl diphenylamine, 5～15 % butyl octyl pentanoic and 5～15 % dioctyl diphenylamines.Liquid octylated diphenylamine oxidation inhibitor normal temperature is down light yellow viscous liquid, and the kinematic viscosity under 40 ℃ is 50～300mm
2/ s.Liquid octylated diphenylamine oxidation inhibitor can be effective to oil product, the lubricant of various application under turbo, aircraft and the High Operating Temperature, also can be used in the polymer rubber goods, and it is aging to prevent that rubber thermooxidizing and elasticity from deflecting.
The meliority of the inventive method:
The inventive method preparation be a kind of liquid octylated diphenylamine oxidation inhibitor, compare than the solid octylated diphenylamine, it is good to have an oil soluble, is prone to advantages such as allotment, so be widely used in the actual production.
Though US4824601, CN1288000A also disclose the preparation method of liquid octylated diphenylamine, pentanoic content is higher in the prepared product, influences quality product.And it has temperature of reaction, cracking temperature is high, is prone to generate by product; Reaction time is long, shortcoming such as reach 20～25 hours.And the inventive method is through reducing the dosage of diisobutylene; Control reaction temperature; The amount of less generation dioctyl diphenylamine, and then carry out the secondary alkylated reaction through iso-butylene, diphenylamine reaction unnecessary in the product has been generated active principle butyl pentanoic; And reaction conditions is gentle, only needs reaction between 120～155 ℃; Reaction time is short, only needs 3～6 hours.
The inventive method has also solved and has proposed the difficult technical barrier of preparing the high alkyl diphenyl amine composition of monoalkyl pentanoic content among the US2943112.Product efficacy is equal to the oxidation inhibitor that the external trade mark is IRGANOX L57.
Before using, atlapulgite of the present invention, can increase its catalytic activity through drying and dewatering.Catalyzer can recycle 5～8 times.
The present invention adds excessive pentanoic when preparation octylated diphenylamine mixture.The add-on of diisobutylene is slightly less than the purpose of the add-on of pentanoic and is in this reaction raw materials, reduces to generate dioctyl diphenylamine, makes that the content of dioctyl diphenylamine reduces in the finished product.
The mass ratio that feeds intake of preferred pentanoic and diisobutylene is 100 ︰ 60～98.Better ratio is 100 ︰ 80～98.
The consumption of catalyst activity carclazyte can change within the specific limits, but that consumption does not need is too big, in order to avoid waste, the mass ratio that feeds intake of general pentanoic and catalyzer is 100 ︰ 2～10, preferred 100 ︰ 3～8.
The condition that the present invention prepares the octylated diphenylamine mixture is: under 0.05～0.5MPa pressure, 100～160 ℃ of temperature condition.Preferred 0.2～0.25 MPa pressure, 130～135 ℃.
Under normal pressure with iso-butylene and octylated diphenylamine mixture reaction.
Embodiment
Atlapulgite in the reactor drum that whisking appliance, Dropping feeder and nitrogen replaceable equipment 1L are housed behind adding 200g pentanoic (purity 99.8%), the 9.8g drying and dewatering; Begin to be heated to 80 ℃ after opening nitrogen replacement 3 times; After treating that pentanoic melts fully, open stirring and be warming up to 130 ℃.160g～196g diisobutylene is slowly dropped in the above reactor drum through 1 hour through feeding device, and reaction mixture kept reacting about 3 hours again, and controlled temperature is at 130～135 ℃, and reaction pressure is at 0.2～0.25MPa.
After insulation finishes, in 1 hour, feed the 23g iso-butylene and continue reaction, after the reaction solution normal pressure filtered, the filter residue next batch continued to use, and promptly got liquid octylated diphenylamine oxidation inhibitor after the filtrating simple distillation.
Contain following each mass percent composition through analyzing liquid octylated diphenylamine oxidation inhibitor:
0.83% pentanoic, 9.74 % butyl pentanoic, the single octyl diphenylamine of 63.51 %, 10.41 % butyl octyl pentanoic, 13.56% dioctyl diphenylamine, surplus is made up of the isomer component.
The kinematic viscosity of liquid octylated diphenylamine oxidation inhibitor under 40 ℃ is 256mm2/s.
Claims (8)
1. the preparation method of a liquid octylated diphenylamine oxidation inhibitor; It is characterized in that under the effect of catalyzer, pentanoic and diisobutylene being reacted, generate the octylated diphenylamine mixture; And then the feeding isobutene reaction, through promptly getting liquid octylated diphenylamine oxidation inhibitor after the distillation; The atlapulgite of said catalyzer for crossing through processed.
2. method according to claim 2 is characterized in that: the mass ratio that feeds intake of pentanoic and diisobutylene is 100 ︰ 60～98.
3. method according to claim 3 is characterized in that: the mass ratio that feeds intake of pentanoic and diisobutylene is 100 ︰ 80～98.
4. according to claim 1 or 2 or 3 or 3 described methods, it is characterized in that: the mass ratio that feeds intake of pentanoic and catalyzer is 100 ︰ 2～10.
5. method according to claim 5 is characterized in that: the mass ratio that feeds intake of pentanoic and catalyzer is 100 ︰ 3～8.
6. method according to claim 1 is characterized in that: under 0.05～0.5MPa pressure, 100～160 ℃ of temperature condition, prepare the octylated diphenylamine mixture.
7. method according to claim 6 is characterized in that: under 0.2～0.25 MPa pressure, 130～135 ℃ of temperature condition, prepare the octylated diphenylamine mixture.
8. method according to claim 1 is characterized in that: under normal pressure with iso-butylene and octylated diphenylamine mixture reaction.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659606A (en) * | 2012-05-07 | 2012-09-12 | 常州大学 | Preparation method of alkylated diphenylamine antioxidant with high color stability |
| CN104628579A (en) * | 2013-11-08 | 2015-05-20 | 中国石油天然气股份有限公司 | Method for preparing liquidized butyl diphenylamine/octyl diphenylamine |
| CN109369418A (en) * | 2018-10-10 | 2019-02-22 | 河南师范大学 | A kind of continuous synthesis technology and synthesizer of energy saving and environment friendly alkyl benzene amine class I liquid I antioxidant |
| 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2943112A (en) * | 1957-11-06 | 1960-06-28 | Pennsalt Chemicals Corp | Alkylation of diphenylamine |
| CN1288000A (en) * | 1999-09-10 | 2001-03-21 | 中国石油化工集团公司 | Method for preparing liquid alkyl diphenylamine |
| CN101863774A (en) * | 2010-06-02 | 2010-10-20 | 江苏科技大学 | Method for preparing liquid alkylated diphenylamine compound by ionic liquid catalyst |
-
2011
- 2011-06-14 CN CN201110158159A patent/CN102320983A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2943112A (en) * | 1957-11-06 | 1960-06-28 | Pennsalt Chemicals Corp | Alkylation of diphenylamine |
| CN1288000A (en) * | 1999-09-10 | 2001-03-21 | 中国石油化工集团公司 | Method for preparing liquid alkyl diphenylamine |
| CN101863774A (en) * | 2010-06-02 | 2010-10-20 | 江苏科技大学 | Method for preparing liquid alkylated diphenylamine compound by ionic liquid catalyst |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659606A (en) * | 2012-05-07 | 2012-09-12 | 常州大学 | Preparation method of alkylated diphenylamine antioxidant with high color stability |
| CN104628579A (en) * | 2013-11-08 | 2015-05-20 | 中国石油天然气股份有限公司 | Method for preparing liquidized butyl diphenylamine/octyl diphenylamine |
| CN104628579B (en) * | 2013-11-08 | 2016-08-17 | 中国石油天然气股份有限公司 | A kind of method preparing fluidization fourth, octyl diphenylamine |
| CN109369418A (en) * | 2018-10-10 | 2019-02-22 | 河南师范大学 | A kind of continuous synthesis technology and synthesizer of energy saving and environment friendly alkyl benzene amine class I liquid I antioxidant |
| 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 |
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