Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
On the one hand, the present invention provides a kind of high-temperature chain oil compositions, on the basis of the weight of lubricant oil composite, profit
Sliding oil composition contains following components: the wear-resistant multiple-effect of antioxygen of the lube base oil of 85-99 weight %, 0.01-10 weight %
Additive, the thiophenols ester type antioxidant of 0.01-5 weight %, the Zinc oxide nanoparticle of 0.05-5 weight %, 0.01-5 weight
The demulsifier of % is measured, the wear-resistant multipurpose additive of antioxygen 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
Measure %;The content of the wear-resistant multipurpose additive of antioxygen is preferably 0.02-5 weight %, more preferably 0.1-4 weight %;Sulfophenates
The content of type antioxidant is preferably 0.05-3 weight %;The content of Zinc oxide nanoparticle is preferably 0.1-4 weight %, more preferably
For 0.1-3 weight %;The content of demulsifier is preferably 0.02-4 weight %, more preferably 0.05-3 weight %.
The present invention is directed to tie by the compound containing structure shown in formula (I) in lubricant oil composite, and shown in formula (I)
The compound of structure and thiophenols ester type antioxidant are combined and realize goal of the invention, though lubricant oil composite have it is excellent wear-resistant
With the performances such as anti-oxidant.Therefore, it for the selection of conventional constituents each in lubricant oil composite, does not limit specifically.
In the present invention, lube base oil can be lube base oil commonly used in the art, such as can be mine
Object lubricating oil and/or synthetic lubricant fluid.
Mineral lubricating oil in viscosity can from light fraction mineral oil to heavy distillat mineral oil, including saxol and plus
That hydrogen refines, the processed alkane of solvent, cycloalkanes and mixing par-affinic-naphthenic types mineral lubricating oil, are generally divided into I, II, Group III
Base oil, common trade names include I class 150SN, 600SN, II class 100N, 150N, 350N etc..
Synthetic lubricant fluid may include polymerization hydrocarbon ils, alkyl benzene and its derivative, polymerization hydrocarbon ils specific example include but
It is not limited to polybutene, polypropylene, propylene-isobutylene copolymers, the polybutene of chlorination, poly- (1- hexene), poly- (1- octene), gathers
(1- decene), common trade names include PAO4, PAO6, PAO8, PAO10 etc., alkyl benzene and its derivative specific example
Including but not limited to detergent alkylate, Tetradecylbenzene, dinonyl benzene, two (2- ethylhexyl) benzene, alkyl benzene derivate packet
Include alkylated diphenyl ether and alkylated diphenyl sulfide and its derivative, analog and homologue etc..
Another suitable type of synthetic lubricant fluid can be Esters oil, including dicarboxylic acids (such as phthalic acid, succinic acid, alkane
Base succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, decanedioic acid, fumaric acid, adipic acid, linoleic acid dimerization
Object, malonic acid, alkyl malonic acid, alkenyl malonic) with various alcohol (such as butanol, hexanol, dodecyl alcohol, 2- ethylhexyl alcohol,
Ethylene glycol, propylene glycol) ester or complex ester that condensation reaction generates occurs.The specific example of these esters includes but is not limited to adipic acid
Dibutyl ester, decanedioic acid two (2- ethylhexyl) ester, the just own ester of fumaric acid acid two, dioctyl sebacate, azelaic acid two are different pungent
Ester, two different decayl esters of azelaic acid, dioctyl phthalate, didecyl phthalate, decanedioic acid two (larane base) ester, linoleic acid
2- ethylhexyl diester of dimer etc..
Another suitable type of synthetic lubricant fluid can be for fischer tropsch process synthetic hydrocarbon oil and to this synthetic hydrocarbon oil by adding
Hydrogen isomery such as is hydrocracked, dewaxes at the lube base oil that process obtain.
In the present invention, lube base oil preferred viscosities index is greater than 80, saturated hydrocarbon content and is greater than 90 weight %, sulfur content
Less than the lube base oil of 0.03 weight %.
In the present invention, thiophenols ester type antioxidant can be thiophenols ester type antioxidant commonly used in the art, such as can be with
It is raw for 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate], such as Sichuan Yong Ye Chemical Co., Ltd.
The antioxidant 1035 of production, the IRGANOX L115 of BASF Aktiengesellschaft's production.
In the present invention, Zinc oxide nanoparticle is the single or composite nanoparticle of the ingredient containing Zinc oxide nanoparticle.Add
Adding the high-temperature chain lubricating oil of Zinc oxide nanoparticle has preferable high temperature wear resistance, and the abrasion resistance of oil product obtains after addition
To improvement.The partial size of nanoparticle is 3-150nm.
In the present invention, demulsifier can be propylene glycol block polyether, nonylphenol polyoxyethylene ether, ethylenediamine polyoxypropylene-
At least one of polyoxyethylene ether and propane diamine polyoxypropylene polyoxyethylene ether.
Lubricant oil composite of the invention can also contain at least one of antirust agent and anti-foaming agent.Antirust agent can select
From imidazoles and/or alkenyl succinic acid esters, preferably 4,5- glyoxalidine, alkenyl imidazoline succinate and alkenyl succinic acid
At least one of ester, such as T746, T703, T747 that Jinzhou Kangtai Lube Additive Co., Ltd. can be selected to produce.
Anti-foaming agent can select polysiloxane type anti-foaming agent, such as can be dimethyl silicone polymer.For antirust agent, pour-point depressant and resist
The content of infusion can be the content of this field routine, this is known to those skilled in the art, herein no longer without particular/special requirement
It repeats.
In the present invention, the preparation method of the compound of structure shown in formula (I) is preferably included:
(a) aniline, sulfur chloride and 4- chloroaniline are reacted, generate intermediate M shown in formula (II),
(b) the intermediate M and dimercapto -1,3,4- thiadiazoles that step (a) obtains nucleophilic is carried out under alkaline condition to take
Generation reaction, generates multipurpose additive shown in formula (I),
In step (a) of the present invention, the concrete mode that aniline, sulfur chloride and 4- chloroaniline react is preferably included:
(i) under an inert atmosphere, in the first solvent, aniline is sufficiently reacted at -20-0 DEG C with sulfur chloride;
(ii) 4- chloroaniline is added in the reaction system of step (i), reacts 1-3h at 15-30 DEG C.
In the present invention, inert atmosphere can be the inert atmosphere of this field routine, such as can be by gases such as nitrogen, argon gas
It provides.
In step (i) of the present invention, the first solvent is preferably selected from methylene chloride, tetrahydrofuran, toluene, dimethylbenzene and dioxy six
At least one of ring, more preferably methylene chloride and/or tetrahydrofuran are still more preferably methylene chloride.
It in the present invention in step (i), is sufficiently reacted and refers to fully reacting, is i.e. reaction raw materials are reacted completely.
Reaction can be monitored using method commonly used in the art, to confirm fully reacting, such as thin layer chromatography can be used
(TLC) or the methods of gas-chromatography is monitored.
In step (ii) of the present invention, 1-3h is reacted at 15-30 DEG C, preferably after step (i) sufficiently reaction, by reactant
The temperature of system is gradually increased to 15-30 DEG C, adds 4- chloroaniline and carries out reaction 1-3h.It, can be further under the preferable case
Improve reaction yield.
In step (ii) of the present invention, the adding manner of 4- chloroaniline is preferably to be added by several times, such as can divide 3-4 times and add
Enter.Under the preferable case, reaction yield can be further improved.When gradation is added, each additional amount can be identical,
It can also be different, in order to easy to operate, preferably each additional amount is identical.
In step (ii) of the present invention, react 1-3h, stop reaction mode can for those skilled in the art it is contemplated that
Various modes, be quenched for example, quencher can be added, quencher can be quencher commonly used in the art, such as can
Think saturated salt solution.
In the present invention, the dosage of aniline, sulfur chloride and 4- chloroaniline is substantially equimolar amounts, but aniline and sulfur chloride can
With appropriate excessive.The molar ratio of aniline, sulfur chloride and 4- chloroaniline is preferably 0.9-1.5:0.9-1.5:0.8-1.2.
It will be understood by those skilled in the art that purer intermediate M, goes back in order to obtain in step (a) of the present invention
It needing to post-process the system after reaction, the mode of post-processing may include washing, drying, solvent be removed under reduced pressure, for example,
Reaction system after being quenched is used into distilled water and saturated common salt water washing respectively, anhydrous calcium chloride then is added at 15-30 DEG C
Or the desiccant such as anhydrous sodium sulfate, keep 10-60min.After being filtered to remove desiccant, at 0.01-0.05MPa, 40-60 DEG C
Solvent is removed, to obtain intermediate M.
In step (a) of the present invention, the reaction equation that aniline, sulfur chloride and 4- chloroaniline are reacted is as shown in Figure 1, figure
In 1, the first solvent is using methylene chloride, and purpose by way of example only is not construed as limiting the scope of the present invention.
In step (b) of the present invention, the condition of nucleophilic substitution is preferably included: under an inert atmosphere, in the second solvent,
Dimercapto-1,3,4-thiadiazole, alkaline reagent and catalyst are mixed into 10-30min at 15-30 DEG C, intermediate is then added
M is sufficiently reacted.I.e. alkaline condition is provided by alkaline reagent.
" inert atmosphere ", " sufficiently being reacted " are as previously mentioned, details are not described herein.
In the present invention, intermediate M is preferably slowly added to, such as can be added by several times, and 3-4 addition can be generally divided.?
Under the preferable case, reaction yield can be further improved.When gradation is added, each additional amount can be identical, can also
With difference, in order to easy to operate, preferably each additional amount is identical.
In the present invention, the second solvent is preferably selected from methylene chloride, tetrahydrofuran, toluene, dimethylbenzene, N, N- dimethyl formyl
At least one of amine, more preferably methylene chloride and/or n,N-Dimethylformamide are still more preferably N, N- dimethyl
Formamide.
In the present invention, alkaline reagent is preferably selected from least one of inorganic bases such as potassium carbonate, sodium carbonate, sodium methoxide.
In the present invention, catalyst is preferably potassium sulfate.
In step (b) of the present invention, the dosage of dimercapto-1,3,4-thiadiazole, alkaline reagent and intermediate M is substantially etc.
Mole, but dimercapto-1,3,4-thiadiazole and alkaline reagent can be suitably excessive.Dimercapto -1,3,4- thiadiazoles, alkalinity examination
The molar ratio of agent and intermediate M are preferably 0.9-3.0:0.9-5.0:0.8-1.5.
In step (b) of the present invention, the dosage of catalyst can be catalytic amount, with mole of dimercapto-1,3,4-thiadiazole
On the basis of number, the dosage of catalyst is preferably 5-100 moles of %, more preferably 10-50 moles of %.
In step (b) of the present invention, reaction equation such as Fig. 2 that dimercapto-1,3,4-thiadiazole and intermediate M are reacted
Shown, in Fig. 2, alkaline reagent is using potassium carbonate, purpose by way of example only, does not constitute and limits to the scope of the present invention
System.
It will be understood by those skilled in the art that purer final product, i.e., multiple-effect of the invention add in order to obtain
Add agent, the present invention prepares the method for multipurpose additive it is also preferable to include post-processing to the system after reaction, the side of post-processing
Formula may include washing, drying, solvent be removed under reduced pressure, for example, the system after abundant reaction to be poured into the acetic acid of 1-10 times of volume
In ethyl ester (or methylene chloride), distilled water and saturated common salt water washing are used respectively, anhydrous calcium chloride then is added at 15-30 DEG C
Or the desiccant such as anhydrous sodium sulfate, keep 10-60min.After being filtered to remove desiccant, at 0.01-0.05MPa, 40-60 DEG C
Solvent is removed, to obtain final product.
Each step that the method for the compound of structure shown in formula (I) is prepared in the present invention preferably carries out under stiring, for
Mixing speed can be the mixing speed of this field routine, for example, mixing speed can be 100-800rpm without particular/special requirement.
In the present invention, for the first solvent and the second solvent amount without particular/special requirement, can be the solvent of this field routine
Dosage, this is known to those skilled in the art, and details are not described herein.
As described above, the present invention is directed to the compound by containing structure shown in formula (I) in lubricant oil composite, and formula
(I) compound and thiophenols ester type antioxidant of structure shown in are combined and realize goal of the invention, even if lubricant oil composite has
The excellent performances such as wear-resistant and anti-oxidant.It therefore, can be using this for the preparation method of lubricant oil composite without particular/special requirement
The conventional use of method in field, for example, second aspect, the present invention also provides a kind of preparation sides of high-temperature chain oil composition
Method, this method comprises: lube base oil, the wear-resistant multipurpose additive of antioxygen, thiophenols ester type antioxidant, optional oxygen will be contained
Change zinc nanoparticles, the raw material of optional demulsifier is uniformly mixed and obtains lubricant oil composite, wherein with lubricant oil composite
On the basis of weight, the dosage of lube base oil is 85-99 weight %, the dosage of the wear-resistant multipurpose additive of antioxygen is 0.01-10
Weight %, thiophenols ester type antioxidant dosage be 0.01-5 weight %, the dosage of Zinc oxide nanoparticle be 0.05-5 weight
% is measured, the dosage of demulsifier is 0.01-5 weight %, and the wear-resistant multipurpose additive of antioxygen is the chemical combination of structure shown in formula (I)
Object:
In the method for the present invention, on the basis of the weight of lubricant oil composite, the dosage of lube base oil is preferably 90-99
The dosage of the wear-resistant multipurpose additive of weight %, antioxygen is preferably 0.02-5 weight %, more preferably 0.1-4 weight %, thiophenols
The dosage of ester type antioxidant be preferably 0.05-3 weight %, Zinc oxide nanoparticle dosage be preferably 0.1-4 weight %, it is more excellent
It is selected as 0.1-3 weight %, the dosage of demulsifier is preferably 0.05-4 weight %, more preferably 0.05-3 weight %.
As previously mentioned, raw material can also contain at least one in antirust agent, pour-point depressant and anti-foaming agent in the method for the present invention
Kind.
In the method for the present invention, for mixed mode without particular/special requirement, such as each original of lube base oil can will be removed
Material component is added separately in lube base oil, can also will be mixed and made into concentrate again except each component of lube base oil
It is added in lube base oil.
In the method for the present invention, mixed condition is preferably included: temperature is 40-90 DEG C, time 1-6h.
The wear-resistant multipurpose additive of lube base oil, antioxygen, thiophenols ester type antioxidant, Zinc oxide nanoparticle, demulsification
Agent, antirust agent and anti-foaming agent are as previously mentioned, details are not described herein.
Embodiment 3
The present embodiment is for illustrating lubricant oil composite and preparation method thereof of the invention.
By the S1 of 1.9 parts by weight, the 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) third of 0.1 parts by weight
Acetoacetic ester], the single Zinc oxide nanoparticle (Shandong Turner rice Materials Co., Ltd) of 0.25 parts by weight, 0.5 parts by weight second
Diamines polyoxypropylene polyoxyethylene ether, the dimethyl silicone polymer of 0.01 parts by weight are (limited purchased from the new four seas chemical industry share in Hubei
Company) it is added in the dibutyl adipate of 97.39 parts by weight, 1h is stirred at 90 DEG C, is uniformly mixed and obtains lubricating oil composition
Object A3.
Comparative example 1
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, S1 is replaced with etc. the 2,2'- of parts by weight
Thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate], obtains lubricant oil composite D1.
Comparative example 2
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by 2,2'- thiobis [3- (3,5- bis- uncles
Butyl -4- hydroxy phenyl) ethyl propionate] S1 that the parts by weight such as replaces with, obtain lubricant oil composite D2.
Comparative example 3
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by S1 and 2,2'- thiobis [3- (3,5-
Di-tert-butyl-hydroxy phenyl) ethyl propionate] zinc dibutyl dithiocarbamate that the parts by weight such as replaces with, it is lubricated
Fluid composition D3.
Comparative example 4
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by S1 and 2,2'- thiobis [3- (3,5-
Di-tert-butyl-hydroxy phenyl) ethyl propionate] the trimethylphenyl zinc phosphite that the parts by weight such as replaces with, obtain lubricating oil composition
Object D4.
Comparative example 5
Lubricant oil composite is prepared according to the method for embodiment 2, unlike, by S1 and 2,2'- thiobis [3- (3,5-
Di-tert-butyl-hydroxy phenyl) ethyl propionate] the fourth octyl diphenylamine that the parts by weight such as replaces with, obtain lubricant oil composite D5.
Test case
Lubricant oil composite A1-A3, D1-D5 are tested as follows respectively:
The measurement of initial oxidation temperature is carried out using TA5000-DSC2910 differential thermal analyzer;
The measurement 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 measured by GB/T3142;
Wear scar diameter is measured using SH/T 0189.
The sediment yield that oil product when using 250 DEG C of measurement of the test of inclined plate coking analog meter generates.
It the results are shown in Table 1.
Table 1
|
A1 |
A2 |
A3 |
D1 |
D2 |
D3 |
D4 |
D5 |
Initial oxidation temperature, DEG C |
204 |
211 |
219 |
192 |
190 |
198 |
191 |
192 |
Oxidation induction period, min |
43.7 |
50.7 |
58.2 |
32.6 |
37.8 |
33.1 |
29.4 |
31.5 |
PB, kgf |
90 |
100 |
105 |
50 |
65 |
55 |
65 |
50 |
PD, kgf |
295 |
305 |
310 |
225 |
265 |
220 |
240 |
230 |
Wear scar diameter d60 40, mm |
0.53 |
0.47 |
0.46 |
0.69 |
0.61 |
0.71 |
0.62 |
0.64 |
High temperature deposition object amount, mg |
6.9 |
5.5 |
5.1 |
10.2 |
9.6 |
9.2 |
10.3 |
9.7 |
It will be understood by those skilled in the art that initial oxidation temperature is higher, the thermal stability of lubricating oil is better;Oxidation
Induction period is longer, and the antioxygenic property of lubricating oil is better;PB, PD value are bigger, and the wear resistance of lubricating oil is better;Wear scar diameter
Smaller, the wear resistance of lubricating oil is better;Coking amount is higher, and the cokeability resistant to high temperatures for representing this test specimen is poorer.
A2 is compared with D1-D5 respectively as can be seen that lubricant oil composite of the invention is with preferably anti-oxidant
Property and abrasion resistance.
High-temperature chain oil composition of the invention has excellent abrasion resistance and antioxygenic property, can be widely applied to
High-temperature chain lubricating area.
It is described the prefered embodiments of the present invention in detail above in conjunction with attached drawing, still, the present invention is not limited to above-mentioned realities
The detail in mode is applied, within the scope of the technical concept of the present invention, a variety of letters can be carried out to technical solution of the present invention
Monotropic type, these simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.