Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that this place is retouched
The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
On the one hand, the invention provides a kind of compressor oil composition, using the weight of lubricant oil composite as
Benchmark, lubricant oil composite contains following components:85-99 weight % lube base oil, 0.01-10
Weight % antioxygen multipurpose additive, 0.01-5 quality %2,2 '-thiobis [3- (3,5- di-t-butyl -4- hydroxyls
Base phenyl) ethyl propionate, 0.02-5 weight % Zinc oxide nanoparticle, 0.01-5 mass % pour-point depressant,
Antioxygen multipurpose additive is the compound of structure shown in formula (I):
In the present invention, on the basis of the weight of lubricant oil composite, the content of lube base oil is preferably
90-99 weight %;The content of antioxygen multipurpose additive is preferably 0.02-5 weight %, more preferably 0.1-4
Weight %;[content of 3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionate antioxidant is excellent for 2,2 '-thiobis
Elect 0.1-3 weight % as;The content of Zinc oxide nanoparticle is preferably 0.05-4 weight %, more preferably
0.05-3 weight %;The content of pour-point depressant is preferably 0.01-4 weight %, more preferably 0.05-2 weight %.
It is contemplated that the compound by containing structure shown in formula (I) in lubricant oil composite, and
The compound of structure shown in formula (I) and 2,2 '-thiobis [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic acid second
Ester type antioxidant is combined and realizes goal of the invention, even if lubricant oil composite has excellent wear-resistant and antioxygen
The performances such as change.Therefore, for the selection of each conventional constituents in lubricant oil composite, do not limit specifically
System.
In the present invention, lube base oil can be lube base oil commonly used in the art, for example
Can be mineral lubricating oil and/or synthetic lubricant fluid.
Mineral lubricating oil can be from light fraction mineral oil to heavy distillat mineral oil in viscosity, including liquid stone
Wax oil and hydrofinishing, the alkane that solvent is treated, cycloalkanes and mixing par-affinic-naphthenic types mineral lubricant
Oil, is generally divided into I, II, Group III base oil, and common trade names include I classes 150SN, 600SN,
II classes 100N, 150N, 350N etc..
Synthetic lubricant fluid can include polymerization hydrocarbon ils, alkyl benzene and its derivative, polymerize the specific example of hydrocarbon ils
Son includes but is not limited to polybutene, polypropylene, propylene-isobutylene copolymers, the polybutene of chlorination, poly- (1-
Hexene), poly- (1- octenes), poly- (1- decene), common trade names include PAO4, PAO6, PAO8,
PAO10 etc., alkyl benzene and its derivative specific example includes but is not limited to detergent alkylate, the tetradecane
Base benzene, dinonyl benzene, two (2- ethylhexyls) benzene, alkyl benzene derivate include the diphenyl ether of alkylation
Diphenyl sulfide and its derivative, analog and homologue with alkylation etc..
Another suitable type of synthetic lubricant fluid can be Esters oil, including dicarboxylic acids (such as phthalic acid,
It is butanedioic acid, alkyl succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, decanedioic acid, anti-
Butene dioic acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic) with
Various alcohol (such as butanol, hexanol, dodecyl alcohol, 2- ethylhexyl alcohols, ethylene glycol, propane diols) hairs
The ester or complex ester of raw condensation reaction generation.The specific example of these esters includes but is not limited to the fourth of adipic acid two
Ester, decanedioic acid two (2- ethylhexyls) ester, the just own ester of fumaric acid acid two, di-n-octyl sebacate, nonyl
Diacid di-isooctyl, two different decayl esters of azelaic acid, dioctyl phthalate, didecyl phthalate,
Decanedioic acid two (larane base) ester, 2- ethylhexyl diester of linoleic acid dimer etc..
Another suitable type of synthetic lubricant fluid can be for fischer tropsch process synthetic hydrocarbon oil and to this synthesis hydrocarbon
Oil by hydroisomerizing, be hydrocracked, the lube base oil that the PROCESS FOR TREATMENT such as dewax is obtained.
In the present invention, lube base oil preferred viscosities index is more than 80, saturated hydrocarbon content and is more than 90 weights
Measure the lube base oil that %, sulfur content are less than 0.03 weight %.
In the present invention, Zinc oxide nanoparticle is the single or composite Nano of the composition containing Zinc oxide nanoparticle
Particle.The high-temperature chain lubricating oil of addition Zinc oxide nanoparticle has preferable high temperature wear resistance, adds
Plus the abrasion resistance of rear oil product is improved.The particle diameter of nano-particle is 3-150nm.
In the present invention, pour-point depressant can be selected from poly alpha olefin, vinyl acetate copolymer and alkyl
At least one of C8-C18 dialkyl fumarate, poly- alkylmethacrylate, alkylnaphthalene,
Such as can be from the V385 of T803, Run Yinglian company of the southern petroleum additive company in Wuxi.
The lubricant oil composite of the present invention can also contain at least one of antirust agent and anti-foaming agent.Antirust
Agent can be selected from imidazoles and/or alkenyl succinic acid esters, preferably 4,5- glyoxalidine, alkenyl imidazoline
At least one of succinate and alkenyl succinic acid ester, for example can be from the safe lubricating oil addition in Jinzhou
T746, T703, T747 of agent Co., Ltd production.Anti-foaming agent can select polysiloxane type anti-foaming agent,
For example can be silicone oil and/or dimethyl silicone polymer.Content for antirust agent and anti-foaming agent is wanted without special
Ask, can be the conventional content in this area, this is known to those skilled in the art, will not be repeated here.
In the present invention, the preparation method of the compound of structure is preferably included shown in formula (I):
(a) by 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene carry out condensation reaction, shown in generation formula (II)
Intermediate M,
(b) the intermediate M that step (a) is obtained is contacted into progress bromo-reaction with bromide reagent, it is raw
Into the bromination product shown in formula (III),
(c) bromination product that step (b) is obtained is made to contact progress with the compound shown in formula (IV) even
Connection reaction, the antioxidant shown in generation formula (I),
In step (a) of the present invention, the condition of condensation reaction is preferably included:Under an inert atmosphere,
In one solvent, in the presence of the first catalyst, by 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene at -20-0 DEG C
15-30 DEG C is risen to after lower reaction 0.5-1.5h, 70-80 DEG C of reaction 1-3h is then heated to.
In the present invention, inert atmosphere can be the conventional inert atmosphere in this area, for example can by nitrogen,
The gases such as argon gas are provided.
It will be understood by those skilled in the art that in order that stable reaction progress, reacts at -20-0 DEG C
15-30 DEG C is risen to after 0.5-1.5h, it should be to slowly warm up to 15-30 DEG C, for example, can be by -20-0 DEG C
System after lower reaction 0.5-1.5h is placed under 15-30 DEG C of environment temperature, makes reaction system itself slow
It is warming up to 15-30 DEG C.
In the present invention, the first solvent is preferably selected from methanol, ethanol, DMF and acetonitrile
At least one, more preferably methanol and/or acetonitrile are still more preferably methanol.
In the present invention, the first catalyst can be inorganic acid or organic acid, be preferably selected from acetic acid, to methyl
At least one of benzoic acid and benzene sulfonic acid, more preferably acetic acid.
In the present invention, the consumption of 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene is substantially equimolar amounts, but
Formaldehyde and benzene can be suitably excessive.The mol ratio of 2,6 di t butyl phenol, formaldehyde and benzene is preferably
0.9-1.5:0.9-10:0.9-10。
In step (a) of the present invention, the consumption of the first catalyst can be catalytic amount, with the tertiary fourths of 2,6- bis-
On the basis of the molal quantity of base phenol, the consumption of the first catalyst is preferably 5-100 moles of %, more preferably
10-30 moles of %.
It will be understood by those skilled in the art that in step (a) of the present invention, it is purer in order to obtain
Intermediate M, in addition it is also necessary to reacted system is post-processed, the mode of post processing can include subtracting
Pressure removes solvent, then dilutes, washs through solvent, drying, depressurize and remove solvent again, for example, general is instead
Should after system remove solvent at 0.01-0.05MPa, 40-60 DEG C, be subsequently poured into 1-10 times of volume
In ethyl acetate (or dichloromethane), respectively with distilled water and saturated common salt water washing, then at 15-30 DEG C
The lower addition drier such as anhydrous calcium chloride or anhydrous sodium sulfate, keeps 10-60min.It is filtered to remove drying
After agent, solvent is removed at 0.01-0.05MPa, 40-60 DEG C, to obtain intermediate M.
In step (a) of the present invention, 2,6- DI-tert-butylphenol compounds, formaldehyde and benzene carry out the reaction of condensation reaction
Equation is as shown in figure 1, in Fig. 1, the first solvent uses methanol, and the first catalyst is used
Acetic acid, purpose by way of example only, is not construed as limiting to the scope of the present invention.
In step (b) of the present invention, the condition of bromo-reaction is preferably included:Under an inert atmosphere,
In two solvents, in the presence of the second catalyst, under the conditions of lucifuge, during step (a) is obtained
Mesosome M reacts 1-2h with bromide reagent at 15-30 DEG C, is then quenched with quencher.
" inert atmosphere " is as it was previously stated, will not be repeated here.
It will be understood by those skilled in the art that more stably being carried out to react, preferably to intermediate
Brominated reagent is slowly added in M.
In the present invention, the second solvent is preferably selected from tetrahydrofuran, dichloromethane, chloroform and ether extremely
Few one kind, more preferably tetrahydrofuran.
In the present invention, the second catalyst is preferably selected from ammonium nitrate, benzoyl peroxide (BPO) and azo
At least one of bis-isobutyronitrile (AIBN).
In the present invention, bromide reagent is preferably N-bromosuccinimide (NBS) and/or Br2, it is more excellent
Elect NBS as.
In step (b) of the present invention, it is quenched with quencher, quencher can be commonly used in the art
Quencher, for example, can be saturated aqueous common salt.
In step (b) of the present invention, the consumption of intermediate M and bromide reagent is substantially equimolar amounts,
But bromide reagent typically can be suitably excessive, reaches 1.1-3 times of equivalent of reaction substrate.Intermediate M with
Bromide reagent mol ratio is preferably 0.9-1.2:0.9-3.0.
In step (b) of the present invention, the consumption of the second catalyst can be catalytic amount, with intermediate M's
On the basis of molal quantity, the consumption of the second catalyst is preferably 10-100 moles of %, and more preferably 40-60 rubs
You are %.
In the inventive method step (b), intermediate M is contacted with bromide reagent carries out the anti-of bromo-reaction
Equation is answered as shown in Fig. 2 in Fig. 2, bromide reagent uses NBS, mesh by way of example only
, the scope of the present invention is not construed as limiting.
It is also micro in addition to the bromination product shown in generation formula (III) in step (b) of the present invention
The amount of the bromination product generation at ortho position, the bromination product generation without meta, but the bromination product at ortho position is very
Subsequent reactions are not had materially affect by pettiness, can be ignored.
It will be understood by those skilled in the art that in step (b) of the present invention, it is purer in order to obtain
Bromination product, in addition it is also necessary to the system after to being quenched is post-processed, and the mode of post processing can include water
Wash, dry, removal of solvent under reduced pressure, for example, system after being quenched distillation water washing, then at 15-30 DEG C
The lower addition drier such as anhydrous calcium chloride or anhydrous sodium sulfate, keeps 10-60min.It is filtered to remove drying
After agent, solvent is removed at 0.01-0.05MPa, 40-60 DEG C, to obtain bromination product.
In step (c) of the present invention, the condition of coupling reaction is preferably included:Under an inert atmosphere,
In three solvents, in the presence of the 3rd catalyst, the bromination product that step (b) is obtained and formula (IV)
Shown compound reacts 4-8h at 80-100 DEG C.
" inert atmosphere " is as it was previously stated, will not be repeated here.
In the present invention, in order that stable reaction is carried out, 80-100 DEG C, Ran Hou are preferably gradually heating to
4-8h is reacted at 80-100 DEG C.
In the present invention, the 3rd solvent is preferably selected from dichloromethane, chloroform, toluene and tetrahydrofuran extremely
Few one kind, more preferably dichloromethane.
In the present invention, the 3rd catalyst preferably includes palladium salt, part and alkali.Palladium salt is preferably selected from palladium
And/or palladium-dibenzalacetone complex compound [Pd2(dba)3];Part is preferably selected from tri-tert phosphorus, dinaphthol
And at least one of double (diphenylphosphino) ferrocene (dppf) (BINAP);Alkali is preferably selected from uncle
At least one of sodium butoxide, potassium tert-butoxide, cesium carbonate and sodium carbonate.
In step (c) of the present invention, the bromination product that step (b) is obtained and the chemical combination shown in formula (IV)
The consumption of thing is substantially equimolar amounts, but the compound shown in formula (IV) can be suitably excessive.Step
(b) mol ratio of the compound shown in bromination product and formula (IV) obtained is preferably 0.9-1.5:0.9-2.5.
In step (c) of the present invention, the consumption of catalyst can be catalytic amount, with mole of bromination product
On the basis of number, the consumption of palladium salt is preferably 5-50 moles of %, more preferably 5-20 moles %, more enters one
Step is preferably 5-10 moles of %;The consumption of part is preferably 5-50 moles of %, more preferably 10-30 moles %;
The consumption of alkali is preferably 5-50 moles of %, more preferably 10-30 moles %.
In step (c) of the present invention, the bromination product that step (b) is obtained and the chemical combination shown in formula (IV)
Thing contact carries out the reaction equation of coupling reaction as shown in figure 3, in Fig. 3, palladium salt uses acetic acid
Palladium, purpose by way of example only, is not construed as limiting to the scope of the present invention.
It will be understood by those skilled in the art that in order to obtain purer final product, i.e. formula (I)
Shown antioxidant, the inventive method preferably also includes post-processing reacted system, post-processes
Mode can include filtering, solvent dilution, washing, dry, removal of solvent under reduced pressure, for example, will be anti-
The filtrate after system filtering after answering is poured into the ethyl acetate (or dichloromethane) of 1-10 times of volume,
Then with distillation water washing, anhydrous calcium chloride or anhydrous sodium sulfate etc. is then added at 15-30 DEG C and is done
Drying prescription, keeps 10-60min.It is filtered to remove after drier, is removed at 0.01-0.05MPa, 40-60 DEG C
Solvent is removed, to obtain the antioxidant shown in formula (I).
Each step of the method for the compound of structure shown in formula (I) is prepared in the present invention preferably under agitation
Carry out, can be the conventional mixing speed in this area, for example, stirring for mixing speed without particular/special requirement
It can be 100-800rpm to mix speed.
The present invention is prepared in the method for the compound of structure shown in formula (I), for the first solvent, second
The amount of solvent and the 3rd solvent, without particular/special requirement, can be the conventional solvent load in this area, this is ability
Well known to field technique personnel, it will not be repeated here.
As described above, it is contemplated that passing through the change containing structure shown in formula (I) in lubricant oil composite
Compound, and the compound and 2 of structure shown in formula (I), 2 '-thiobis [3- (3,5- di-t-butyl -4- hydroxyls
Phenyl) ethyl propionate type antioxidant combination and realize goal of the invention, even if lubricant oil composite have it is excellent
The performance such as wear-resistant and anti-oxidant.Therefore, for lubricant oil composite preparation method without particular/special requirement,
Method commonly used in the art can be used, for example, second aspect, present invention also offers one kind pressure
The preparation method of contracting engine oil base oil, this method includes:It will add containing lube base oil, antioxygen multiple-effect
Plus agent, 2,2 '-thiobis are [3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionate types antioxidant, optional
Zinc oxide nanoparticle, the raw material of optional organic carboxyl acid class compound are well mixed and obtain lubricating oil composition
Thing, wherein, on the basis of the weight of lubricant oil composite, the consumption of lube base oil is 85-99 weights
Measure %, the consumption of antioxygen multipurpose additive is 0.01-10 weight %, 2,2 '-thiobis [3- (3,5- di-t-butyls
- 4- hydroxy phenyls) ethyl propionate type antioxidant consumption be 0.01-5 weight %, Zinc oxide nanoparticle
Consumption is 0.02-5 weight %, and the consumption of pour-point depressant is 0.01-5 weight %, the antioxygen multipurpose additive
The compound of structure shown in formula (I):
In the inventive method, on the basis of the weight of lubricant oil composite, the consumption of lube base oil is excellent
It is preferably 0.02-5 weight % to elect 90-99 weight %, the consumption of antioxygen multipurpose additive as, more preferably
0.1-4 weight %, 2,2 '-thiobis be [3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionate type antioxidant
Consumption is preferably that 0.1-3 weight %, the consumption of Zinc oxide nanoparticle are preferably 0.05-4 weight %, more
Preferably 0.05-3 weight %, the consumption of pour-point depressant is preferably 0.02-4 weight %, more preferably 0.05-2
Weight %.
As it was previously stated, in the inventive method, raw material can also contain in antirust agent, pour-point depressant and anti-foaming agent
At least one.
In the inventive method, for mixing mode without particular/special requirement, can will for example remove lube base
Each raw material components of oil are added separately in lube base oil, can also will be each except lube base oil
Component is mixed and made into concentrate and is then added in lube base oil.
In the inventive method, the condition of mixing is preferably included:Temperature is 40-90 DEG C, and the time is 1-6h.
Lube base oil, antioxygen multipurpose additive, 2,2 '-thiobis [3- (3,5- di-t-butyl -4- hydroxy benzenes
Base) for example preceding institute of ethyl propionate type antioxidant, Zinc oxide nanoparticle, pour-point depressant, antirust agent and anti-foaming agent
State, will not be repeated here.
Embodiment 3
The present embodiment is used to illustrate lubricant oil composite of the present invention and preparation method thereof.
By the S1 of 2 parts by weight, the 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyls) of 0.2 parts by weight
Ethyl propionate], the single Zinc oxide nanoparticle (Shandong Turner rice Materials Co., Ltd) of 0.35 parts by weight,
The T803 of the southern petroleum additive company in the Wuxi of 0.1 parts by weight and the polydimethylsiloxanes of 0.1 parts by weight
Alkane (being purchased from Hubei xinsihai Chemical Co., Ltd.) is added to the dibutyl adipate of 97.4 parts by weight
In, 1h is stirred at 90 DEG C, it is well mixed to obtain lubricant oil composite A3.
Comparative example 1
Method according to embodiment 2 prepares lubricant oil composite, unlike, by S1 replace with wait weigh
2, the 2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate] of part is measured, lubricating oil composition is obtained
Thing D1.
Comparative example 2
Method according to embodiment 2 prepares lubricant oil composite, unlike, by 2,2'- thiobis [3- (3,5-
Di-tert-butyl-hydroxy phenyl) ethyl propionate] S1 of parts by weight such as replace with, obtain lubricant oil composite
D2。
Comparative example 3
Method according to embodiment 2 prepares lubricant oil composite, unlike, by S1 and 2,2'- is thio
Double [3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionates] dibutyl dithio of parts by weight such as replace with
Carbaminate, obtains lubricant oil composite D3.
Comparative example 4
Method according to embodiment 2 prepares lubricant oil composite, unlike, by S1 and 2,2'- is thio
Double [3- (3,5- di-tert-butyl-hydroxy phenyls) ethyl propionates] the trimethylphenyl phosphorous of parts by weight such as replace with
Sour zinc, obtains lubricant oil composite D4.
Comparative example 5
Method according to embodiment 2 prepares lubricant oil composite, unlike, by S1 and 2,2'- is thio
Double [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionates] the fourth octyl diphenylamine of parts by weight such as replace with,
Obtain lubricant oil composite D5.
Test case
Lubricant oil composite A1-A3, D1-D5 are tested as follows respectively:
The measure of initial oxidation temperature is carried out using TA5000-DSC2910 differential thermal analyzers;
The measure of oxidation induction period is carried out using high pressure differential scanning amount method (PDSC);
Using tetra-ball machine test method, PB, PD value are determined by GB/T3142;
Wear scar diameter is determined using SH/T 0189;
The sediment yield that oil product when determining 250 DEG C is produced is tested using swash plate coking analog meter.
It the results are shown in Table 1.
Table 1
It will be understood by those skilled in the art that initial oxidation temperature is higher, the heat endurance of lubricating oil
Better;Oxidation induction period is longer, and the antioxygenic property of lubricating oil is better;PB, PD value are bigger, lubrication
The wear resistance of oil is better;Wear scar diameter is smaller, and the wear resistance of lubricating oil is better;Coking amount is got over
Height, the high temperature resistance cokeability for representing this test specimen is poorer..
A2 is compared with D1-D5 respectively as can be seen that the lubricant oil composite of the present invention has more
Good inoxidizability, abrasion resistance and the property of high temperature resistance deposit generation.
The compressor oil composition of the present invention has excellent abrasion resistance and antioxygenic property, can be extensive
Applied to compressor lubrication field.
The preferred embodiment of the present invention is described in detail above in association with accompanying drawing, still, the present invention is not limited
Detail in above-mentioned embodiment, can be to the present invention in the range of the technology design of the present invention
Technical scheme carry out a variety of simple variants, these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment,
In the case of reconcilable, it can be combined by any suitable means, in order to avoid unnecessary
Repeat, the present invention no longer separately illustrates to various possible combinations.
In addition, various embodiments of the present invention can be combined randomly, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.