CN105503535B - The preparation method and application of bis-phenol kind antioxidant based on mixed base catalyst - Google Patents
The preparation method and application of bis-phenol kind antioxidant based on mixed base catalyst Download PDFInfo
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Abstract
The invention discloses a kind of preparation method and application of the bis-phenol kind antioxidant based on mixed base catalyst.The preparation method includes：By dialkyl substituted phenol and aldehyde compound be placed in closed reactor and with the presence of mixing base catalyst and may be selected addition or without organic solvent under conditions of reacted, and bisphenol compound antioxidant product is obtained by post processing after the completion of reaction, the antioxidant product can be used for preparing lubricant oil composite, fuel composition or as plastics, age resister of rubber etc..The simple in production process operation of bisphenol compound antioxidant of the present invention, mild condition, wide material sources such as the raw material and catalyst of use and cheap and easy to get, reaction time is short, is easy to control, and technical process is safe, production process energy consumption is low, product yield and purity are high, and effectively can control and reduce pollutant emission, are a kind of energy-saving safe, the novel process of environmental protection.
Description
Technical field
It is more particularly to a kind of to be urged based on mixing base catalyst the present invention relates to a kind of antioxidant product and preparation method thereof
The preparation method and applications of the bis-phenol kind antioxidant of change.
Background technology
Lubricating oil refers to, to reduce friction, protection is mechanical and workpiece in various types of automobiles, plant equipment
Liquid or semisolid lubricants, mainly play lubrication, cooling, antirust, cleaning, sealing etc..Lubricating oil generally by base oil and
Additive two parts are constituted, and base oil is the main component of lubricating oil, decides the basic performance of lubricating oil；Additive then can be more
Mend and improve the deficiency of base oil aspect of performance.Additive on the one hand can assign base oil in itself without property or performance,
Such as anti-bubble, demulsification；On the other hand the original property of base oil or performance, such as antioxygen, wear-resistant, antirust can also be improved.
In recent years, with the increasingly harshness of lubricating condition, it is desirable to which lubricating oil possesses good high-temperature oxidation resistance.Accordingly
, also the performance to antioxidant proposes higher requirement.
Antioxidant conventional at present mainly has amine, phenols, sulfur-bearing class and containing Phosphorus etc..Wherein, Hinered phenols antioxidant
Have the advantages that antioxidant effect is good, toxicity is low, color and luster contaminative is small, compatibility is strong, be mainly used in synthetic rubber, polyolefin modeling
The oil product such as material, engineering plastics Polymer material and lubricating oil, fuel oil.And in strength Hinered phenols antioxidant, particularly
Typical product is bisphenol compound antioxidant product.
Most of method of existing bisphenol synthesis class compound antioxidant is in acid or base catalyst catalytic condition
Lower progress.
Such as CN102603491A and US3175010A are disclosed in base metal catalysts such as sodium hydroxide, solvent (a hydroxyl
Base alcohol, such as isopropanol) under existence condition, the dialkyl substituted phenol of 2,6- and formalin is occurred condensation reaction, and pass through again
A series of post processing is neutralized such as acid, distillation, washing, dry and obtain 4,4' methylene bis (2,6- be dialkyl substituted
Phenol).
And for example, US3211652A, US2807653A and US2944086A disclose in base catalyst such as sodium hydroxide or
Under potassium hydroxide, solvent existence condition, dialkyl substituted phenol and formalin or paraformaldehyde is set to carry out condensation reaction, and
Again bisphenol compound product is obtained through a series of post processing.
These foregoing technologies are to use the highly basic such as alkali metal compound such as sodium hydroxide to carry out being condensed instead for catalyst
Should, have the disadvantage catalyst corrosive equipment, post-process the pollution produced greatly, be unfavorable for environmental protection, and poor product quality.
CN103193602A discloses one kind with 2,6- DI-tert-butylphenol compounds, para-acetaldehyde for raw material, using organic base first
Sodium alkoxide is catalyst, and antioxidant 4,4'- ethylenes two (2,6- DI-tert-butylphenol compounds) are prepared under conditions of the presence of solvent petroleum ether
Method.The technique is after the completion of reaction, it is necessary to be washed, and collection organic phase separates organic phase solution and removed water, taken off
Color, obtained organic layer will carry out cooling down, crystallization, and filtering just can obtain required product.Although this technique product yield
Higher (91% can be reached), but it there is also some defects, such as reaction time is long, post processing complexity etc..
In summary, all there are severe reaction conditions in the synthesis technique of existing bisphenol compound antioxidant substantially, behaviour
Make difficult, while post-processing difficulty, environmental pollution is serious, is unfavorable for the defects such as industrialized production.
The content of the invention
It is a primary object of the present invention to provide a kind of preparation of the bis-phenol kind antioxidant based on mixed base catalyst
Methods and applications, to overcome deficiency of the prior art.
To achieve the above object, the technical solution adopted by the present invention includes：
A kind of bis-phenol kind antioxidant based on mixed base catalyst provided among the embodiment of the present invention
Preparation method includes：Dialkyl substituted phenol and aldehyde compound are placed in closed reactor and having mixing base catalyst
(as follows also can referred to as " mixed base " or " catalyst ") and may be selected addition or without organic solvent exist under conditions of
Reacted, and obtain bisphenol compound antioxidant product by post processing after the completion of reaction.
Further, shown in the structure such as following formula (I) or (II) of the bisphenol compound antioxidant：
R in formula1、R2、R4、R5At least it is selected from C1-C10Straight chained alkyl or the alkyl with side chain, R3At least it is selected from H or C1-
C5Straight chained alkyl or the alkyl with side chain, R1、R2、R4、R5Can be with identical or difference.
Further, the present invention only need to by aforementioned base materials, catalyst and may be selected addition or without organic solvent exist
Reacted in enclosed environment, without addition other materials, particularly water, surfactant etc..
Further, the dialkyl substituted phenol may be selected from but be not limited to lower formula (III) or (IV) represented by structure
Any one compound or their mixture：
Wherein R1、R2、R3、R4At least it is selected from C1-C10Straight chained alkyl or the alkyl with side chain；R1、R2、R3、R4Can phase
It is same or different.
It is further preferred that described dialkyl substituted phenol can be 2- tert-butyl-4-methyl-Phenols and/or 2,6- bis-
Tert-butyl phenol.
Further, the formula of the mixing base catalyst is MxB(OR6)4, wherein M includes alkali metal and/or alkaline earth is golden
Belong to element, such as Na, K, Li, Ca, Mg, R6At least it is selected from C1-C22Straight chained alkyl or alkyl with side chain, cycloalkyl,
Alkylaryl, x is 0.5 or 1, but not limited to this.
Further, it is described mixing base catalyst can be by alkali metal and/or alkaline-earth metal hydroboron with
R6OH is made by back flow reaction.
It is further preferred that the mol ratio of the catalyst and dialkyl substituted phenol is 0.05-0.6:1, further
It is preferred that, the mol ratio of the catalyst and dialkyl substituted phenol is 0.1-0.3:1.
It is preferred that, the formula of the aldehyde compound is R7CHO, R7Preferably from H or C1-C5Straight chained alkyl is carried
The alkyl of side chain, but not limited to this.
It is further preferred that the aldehyde compound may be selected from but be not limited to formaldehyde, acetaldehyde, dimethoxym ethane, paraformaldehyde, three
One kind or their mixture in metacetaldehyde.Most preferably, the aldehyde compound is paraformaldehyde.During the course of the reaction,
The formaldehyde that paraformaldehyde is decomposited participates in reaction.
It is further preferred that the mol ratio of the aldehyde compound and dialkyl substituted phenol is 1-7:1.It is further excellent
Choosing, the mol ratio of the aldehyde compound and dialkyl substituted phenol is 2-5:1.
It is preferred that, the reaction temperature used in the preparation method is 20-150 DEG C, and the reaction time is 0.5-10h.
It is further preferred that the reaction temperature used in the preparation method is 40-130 DEG C, the reaction time is 1-8h.
Further, in the preparation method, after the reaction of dialkyl substituted phenol and aldehyde compound terminates, also to anti-
Addition acid in mixture is answered to be neutralized, and adding deionized water separates out product, is afterwards divided product using modes such as filterings
Separate out, obtain target product.
Wherein, the acid includes inorganic acid and/or organic acid.The inorganic acid includes hydrochloric acid, phosphoric acid, polyphosphoric acids, phosphorus
Wolframic acid, perchloric acid, boric acid, bromic acid, carbonic acid, hypochlorous acid, sulfurous acid etc. or their mixture, the organic acid include first
Acid, oxalic acid, acetic acid, propionic acid, trifluoroacetic acid, benzoic acid, methanesulfonic acid, p-methyl benzenesulfonic acid, trimethylacetic acid, alkyl benzene sulphonate etc. or it
Mixture.Further, the alkyl of the alkyl benzene sulphonate can be selected from C1-C28Straight chained alkyl or the alkane with side chain
Base, alkyl can be distributed in contraposition, meta or ortho position, and not limited to this.Described acid particularly preferably uses organic acid.
It is further preferred that the acid is 1-5 with the mol ratio for mixing base catalyst:1, especially preferably 1-2:1.
Further, in the preparation method, it also may be selected to use solvent, and the solvent is mixed with raw material, catalyst
After be placed in enclosed environment react.
The solvent is organic solvent, for example：Pentane, hexane, octane, heptane, hexamethylene, dichloromethane, methanol, second
Alcohol, isopropanol, the tert-butyl alcohol, ether, expoxy propane, tetrahydrofuran, DMF, dimethyl sulfoxide (DMSO), toluene, diformazan
Benzene, petroleum ether, acetonitrile etc., but not limited to this.
It is further preferred that the consumption of the solvent be 5-100ml/mmol (relative to mole of dialkyl substituted phenol
Amount), especially preferably 10-50ml/mmol (relative to the mole of dialkyl substituted phenol).
In some cases, solvent is also dispensed, if for example, some reaction raw materials of composition hybrid reaction system
It is liquid, it is liquid at the reaction temperatures to be particularly, and its consumption is enough to make whole hybrid reaction system be in flow-like, simultaneously
Being smoothed out for reaction is not influenceed also.
The purposes of the bisphenol compound antioxidant is additionally provided among one embodiment of the invention.For example, carrying
A kind of lubricant oil composite is supplied, it includes described bisphenol compound antioxidant.In another example there is provided a kind of plastics or rubber
Glue, wherein including the bisphenol compound antioxidant as antiager active component.
Compared with prior art, advantages of the present invention includes：
(1) the invention provides a kind of new, highway route design more scientific and reasonable bisphenol compound antioxidant
Production technology, and process conditions are gentle, reaction time is short, is easy to operational control, and technical process is safe, production process energy consumption
It is low；
(2) technique of the invention uses the foregoing mixing base catalyst with good stability, one side high catalytic efficiency,
Product yield and purity are high (both of which reaches more than 95%), and another aspect post-reaction treatment is greatly simplified, and will not be to equipment
Cause corrosion；
(3) it is preferred to use heavy wall pressure vessel as reactor in technique of the invention, reaction system can be made in closing
In the state of carry out condensation reaction, the oxidation of paraformaldehyde in the basic conditions and alkyl phenol raw material can be effectively prevented from and double
The oxidation of phenolic compound product；
(4) technique of the invention can control and reduce significantly pollutant emission, be a kind of technique of environmental protection.
Embodiment
Technical scheme will be described in detail with reference to some embodiments as follows, but these embodiments should not be by
Think that any limitation can be constituted to protection scope of the present invention.
The present invention mainly provides a kind of novel preparation process of bisphenol compound antioxidant, and it is mainly with mixing
Alkali is as catalyst, using dialkyl substituted phenol and aldehyde compound as raw material, by raw material, catalyst and selectable addition
Or without organic solvent in enclosed environment, it is particularly anti-in the heavy wall voltage-resistant reactor for can be formed insulation and obturation environment
Should, after reaction terminates, reaction product adds deionized water after being neutralized through acid, then separate obtain separate out such as (I) or (II) formula
Shown target product.The technical process is with short production cycle, and product purity is high, and high income, process is easily controllable.By the preparation
Method can improve the technology of product, economic indicator, and be conducive to controlling and reducing environmental pollution.In addition, present invention process can
Using mixed base that is cheap and being easily obtained as catalyst, not only excellent catalytic effect, catalyst stability height, can be carried
High feed stock conversion, simultaneous reactions post processing is greatly simplified, and product yield is high, and quality is good, to equipment almost without any corrosion.
In the technique of the present invention, the raw material such as dialkyl substituted phenol, aldehyde compound and mixing base catalyst, You Jirong
The selection range and reaction condition of agent, including the scope such as reaction temperature, time can as indicated earlier, here is omitted.
In the preparation process in accordance with the present invention, reaction is carried out in closed reactors, and reaction system is in the state of closing
Lower carry out condensation reaction, can be prevented effectively from oxidation and the oxygen of bisphenol compound product of alkyl phenol raw material and aldehyde compound
Change, the bisphenol compound product finally obtained is off-white color crystalline solid.
One typical use system of the bisphenol compound antioxidant of the present invention is as additive application in lubricating oil composition
Thing, but it is also possible to applied to other purposes.Further, a kind of lubricating oil group is disclosed among some embodiments of the present invention
Compound, it contains described bisphenol compound antioxidant, can also include the one or more in following component, such as lubricating oil
Base oil, detergent-dispersant additive, antiwear additive, zinc dialkyl dithiophosphate, alkylated diphenylamine, viscosity index improver, pour point
Depressant, corrosion inhibitor, antirust agent, anti-foaming agent, supplement friction improver or its mixture.In some embodiments of the present invention
Among disclose a kind of plastics or rubber, it includes described bisphenol compound antioxidant, and can also include plastics or rubber
Basic components, these basic components can be various suitable types known in the art.
To make the object, technical solutions and advantages of the present invention clearer, the embodiment to the present invention is entered below
Row is described in detail.
The mixing base catalyst used in following examples is mainly prepared by following technique, including：It is by mol ratio
4-7:1-3 sodium borohydride and R6OH mixing and back flow reaction, are made mixing base catalyst tetraalkoxy Boratex, such as tetramethyl
Epoxide Boratex, tetraethoxy Boratex etc..Wherein, sodium borohydride can also use other alkali metal and/or the boron of alkaline-earth metal
Hydrogen compound, for example, potassium borohydride, lithium borohydride, calcium borohydride, magnesium borohydride etc. are substituted.
Embodiment 1
By paraformaldehyde 14.63g, 2- t-butyl-p-methylphenol 20g, (mol ratio is 4:1) base catalyst tetramethyl, is mixed
Epoxide Boratex 1.92g and dimethyl sulfoxide (DMSO) (DMSO) 360ml are added in the heavy wall glass bomb with magneton, setting temperature
Spend for 150 DEG C, be warming up to design temperature, stirring reaction 0.5 hour.After reaction terminates, added into flask foregoing any one
Plant organic acid (such as acetic acid) to neutralize, have product precipitation after adding deionized water, filter to obtain product 2,2 '-methylene-bis- (4- first
Base -6- tert-butyl phenols).Product yield is more than 95%, and product purity is more than 98%.
Embodiment 2
By paraformaldehyde 23.2g, 2- t-butyl-p-methylphenol 25.5g, (mol ratio is 5:1) base catalyst tetramethyl, is mixed
Epoxide lithium borate 1.10g and DMSO 310ml are added in the heavy wall glass bomb with magneton, and design temperature is 100 DEG C,
It is warming up to design temperature, stirring reaction 2 hours.After reaction terminates, the post processing be the same as Example 1 of reaction product.Product yield
More than 95%, product purity is more than 98%.
Embodiment 3
By paraformaldehyde 13.53g, 2- t-butyl-p-methylphenol 37g, (mol ratio is 2:1) base catalyst tetrem, is mixed
Epoxide Boratex 9.64g and toluene 225ml are added in the heavy wall glass bomb with magneton, and design temperature is 20 DEG C, is risen
Temperature is to design temperature, stirring reaction 10 hours.After reaction terminates, the post processing be the same as Example 1 of reaction product.Product yield is big
In 95%, product purity is more than 98%.
Embodiment 4
By paraformaldehyde 15.28g, 2,6 di t butyl phenol 15g, (mol ratio is 7:1) base catalyst tetramethyl oxygen, is mixed
Ylboronic acid potassium 3.79g is added in the heavy wall glass bomb with magneton, and design temperature is 130 DEG C, is warming up to design temperature,
Stirring reaction 8 hours.After reaction terminates, the post processing be the same as Example 1 of reaction product.Product yield is more than 95%, and product is pure
Degree is more than 98%.
Embodiment 5
By paraformaldehyde 3.64g, 2,6 di t butyl phenol 25g, (mol ratio is 1:1) propoxyl group of base catalyst four, is mixed
Boratex 3.27g is added in the heavy wall glass bomb with magneton, and design temperature is 130 DEG C, is warming up to design temperature, stirs
Mix reaction 1 hour.After reaction terminates, the post processing be the same as Example 1 of reaction product.Product yield is more than 95%, product purity
More than 98%.
Embodiment 6
By paraformaldehyde 17.45g, 2,6 di t butyl phenol 30g, (mol ratio is 4:1) base catalyst tetramethyl oxygen, is mixed
Ylboronic acid calcium 13.78g and toluene 145ml are added in the heavy wall glass bomb with magneton, and design temperature is 40 DEG C, heating
To design temperature, stirring reaction 3 hours.After reaction terminates, the post processing be the same as Example 1 of reaction product.Product yield is more than
95%, product purity is more than 98%.
In addition, inventor is also using listed other raw materials above, such as dimethoxym ethane, Metaldehyde, other
Paraformaldehyde, You Jirong in the alternate embodiment 1-6 such as organic solvent, other mixing base catalysts and other process conditions
Agent, catalyst and corresponding process conditions have carried out synthetic test, and it is also ideal to obtain yield, the purity of product etc., exists substantially
More than 95%.
It should be noted that disclosed is a variety of of preferred embodiment, every local change or modification
And come from the technological thought of the present invention and be that the people for being familiar with this technology is easy to what is deduced, the patent right of the present invention is not departed from all
Scope.
Claims (22)
1. a kind of preparation method of the bis-phenol kind antioxidant based on mixed base catalyst, it is characterised in that including：By dioxane
Base fortified phenol and aldehyde compound are placed in closed reactor and are having mixing base catalyst and may be selected to add or do not add
Plus organic solvent exist under conditions of reacted, and after the completion of reaction by post processing acquisition bisphenol compound antioxygen
Agent product；The formula of the mixing base catalyst is MxB(OR6)4, wherein M include alkali metal and/or alkali earth metal, R6Extremely
C is selected from less1‐C22Straight chained alkyl or alkyl, cycloalkyl or alkylaryl with side chain, x are 0.5 or 1.
2. the preparation method of the bis-phenol kind antioxidant based on mixed base catalyst according to claim 1, its feature exists
In：The dialkyl substituted phenol includes having any one compound of structure shown in lower formula (III) or (IV) or two kinds
The combination of above compound：
Wherein R1、R2、R3、R4At least it is selected from C1-C10Straight chained alkyl or the alkyl with side chain, R1、R2、R3、R4It is identical or not
Together.
3. the preparation method of the bis-phenol kind antioxidant based on mixed base catalyst according to claim 2, its feature exists
In：The dialkyl substituted phenol includes 2- tert-butyl-4-methyl-Phenols and/or 2,6 di t butyl phenol.
4. the preparation method of the bis-phenol kind antioxidant based on mixed base catalyst according to claim 1, its feature exists
In：The mixing base catalyst is main by alkali metal and/or the hydroboron and R of alkaline-earth metal6OH passes through back flow reaction system
.
5. the preparation method of the bis-phenol kind antioxidant based on mixed base catalyst according to claim 1, its feature exists
In：The mol ratio of the mixing base catalyst and dialkyl substituted phenol is 0.05-0.6:1.
6. the preparation method of the bis-phenol kind antioxidant based on mixed base catalyst according to claim 5, its feature exists
In：The mol ratio of the mixing base catalyst and dialkyl substituted phenol is 0.1-0.3:1.
7. the preparation method of the bis-phenol kind antioxidant based on mixed base catalyst according to claim 1, its feature exists
In：The formula of the aldehyde compound is R7CHO, wherein R7At least it is selected from H, C1-C5Straight chained alkyl or the alkane with side chain
Base.
8. the preparation method of the bis-phenol kind antioxidant based on mixed base catalyst according to claim 1, its feature exists
In：The aldehyde compound includes any one in formaldehyde, acetaldehyde, dimethoxym ethane, paraformaldehyde, para-acetaldehyde or two or more
Combination.
9. the preparation method of the bis-phenol kind antioxidant based on mixed base catalyst according to claim 8, its feature exists
In：The aldehyde compound is paraformaldehyde.
10. the preparation method of the bis-phenol kind antioxidant based on mixed base catalyst according to claim 9, its feature exists
In：The mol ratio of the aldehyde compound and dialkyl substituted phenol is 1-7:1.
11. the preparation method of the bis-phenol kind antioxidant based on mixed base catalyst, its feature according to claim 10
It is：The mol ratio of the aldehyde compound and dialkyl substituted phenol is 2-5:1.
12. the preparation method of the bis-phenol kind antioxidant based on mixed base catalyst according to claim 1, its feature exists
In described post processing includes：In the reactant mixture formed after dialkyl substituted phenol and aldehyde compound reaction terminate
Acid is added to be neutralized, and adding deionized water separates out product, afterwards isolates product, obtains target product；
Wherein, it is described acid include inorganic acid and/or organic acid, the inorganic acid include hydrochloric acid, phosphoric acid, polyphosphoric acids, phosphotungstic acid,
Any one in perchloric acid, boric acid, bromic acid, carbonic acid, hypochlorous acid, sulfurous acid or two or more combinations, the organic acid bag
Include in formic acid, oxalic acid, acetic acid, propionic acid, trifluoroacetic acid, benzoic acid, methanesulfonic acid, p-methyl benzenesulfonic acid, trimethylacetic acid, alkyl benzene sulphonate
Any one or two or more combinations, the alkyl of the alkyl benzene sulphonate are selected from C1-C28Straight chained alkyl or with side chain
Alkyl, wherein alkyl are distributed in contraposition, meta or ortho position.
13. the preparation method of the bis-phenol kind antioxidant based on mixed base catalyst, its feature according to claim 12
It is：The acid is selected from organic acid.
14. the preparation method of the bis-phenol kind antioxidant based on mixed base catalyst according to claim 12 or 13, its
It is characterised by, the acid is 1-5 with the mol ratio for mixing base catalyst:1.
15. the preparation method of the bis-phenol kind antioxidant based on mixed base catalyst, its feature according to claim 14
It is, the acid is 1-2 with the mol ratio for mixing base catalyst:1.
16. the preparation method of the bis-phenol kind antioxidant based on mixed base catalyst according to claim 1, its feature exists
In：The organic solvent includes pentane, hexane, octane, heptane, hexamethylene, dichloromethane, methanol, ethanol, isopropanol, tertiary fourth
Alcohol, ether, expoxy propane, tetrahydrofuran, DMF, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene, petroleum ether, acetonitrile
In any one or two or more combinations.
17. the preparation method of the bis-phenol kind antioxidant based on mixed base catalyst according to claim 1 or 16, it is special
Levy and be：Relative to the mole of dialkyl substituted phenol, the consumption of the organic solvent is 5-100ml/mmol.
18. the preparation method of the bis-phenol kind antioxidant based on mixed base catalyst, its feature according to claim 17
It is：Relative to the mole of dialkyl substituted phenol, the consumption of the organic solvent is 10~50ml/mmol.
19. the preparation method of the bis-phenol kind antioxidant based on mixed base catalyst according to claim 1, its feature exists
In：The reaction temperature used in the preparation method is 20-150 DEG C, and the reaction time is 0.5-10h.
20. the preparation method of the bis-phenol kind antioxidant based on mixed base catalyst, its feature according to claim 19
It is：The reaction temperature used in the preparation method is 40-130 DEG C, and the reaction time is 1-8h.
21. the preparation method of the bis-phenol kind antioxidant based on mixed base catalyst according to claim 1, its feature exists
In：The bisphenol compound antioxidant has structure shown in lower formula (I) or (II)：
R in formula1、R2、R4、R5At least it is selected from C1-C10Straight chained alkyl or the alkyl with side chain, R3At least it is selected from H or C1-C5Directly
Alkyl group or the alkyl with side chain, R1、R2、R4、R5Identical or difference.
22. a kind of preparation method of composition, it is characterised in that including：
Bisphenol compound antioxidant is prepared using the method any one of claim 1-21,
And, the bisphenol compound antioxidant is mixed with other components of the composition, the composition is formed；
The composition includes lubricant oil composite, fuel composition, plastics composite or rubber composition.
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| CN111088095B (en) * | 2018-10-23 | 2022-10-21 | 中国石油化工股份有限公司 | Air compressor oil composition and preparation method thereof |
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| US2944086A (en) * | 1955-09-23 | 1960-07-05 | Ethyl Corp | 1, 1-bis(3, 5-dialkyl-4-hydroxyphenyl) methanes |
| US4107137A (en) * | 1974-03-12 | 1978-08-15 | Societe Francaise D'organo Synthese | Phenolic antioxidants for synthetic polymers |
| US4927553A (en) * | 1983-05-06 | 1990-05-22 | Ethyl Corporation | Haze-free boronated antioxidant |
| US4707300A (en) * | 1987-03-09 | 1987-11-17 | The Goodyear Tire & Rubber Company | Autosynergistic phenolic antioxidant reaction product |
| CN103193602A (en) * | 2013-04-08 | 2013-07-10 | 南通惠康国际企业有限公司 | Method for preparing antioxidant 4,4'-ethylene bi(2,6-di-tert-butylphenol) |
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