CN106318555B - A kind of Metalworking lubricating oil composition and preparation method thereof - Google Patents
A kind of Metalworking lubricating oil composition and preparation method thereof Download PDFInfo
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- CN106318555B CN106318555B CN201510332936.9A CN201510332936A CN106318555B CN 106318555 B CN106318555 B CN 106318555B CN 201510332936 A CN201510332936 A CN 201510332936A CN 106318555 B CN106318555 B CN 106318555B
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Abstract
The invention discloses a kind of Metalworking lubricating oil compositions, on the basis of the weight of lubricant oil composite, lubricant oil composite contains following components: the lube base oil of 85-98 weight %, the wear-resistant multipurpose additive of antioxygen of 0.01-10 weight %, the thiophenols ester type antioxidant of 0.01-5 weight %, the dinonylnaphthalene sulfonic acid salt of 0.01-5 weight % and organic anti-friction agent of 0.01-5 weight %, and the wear-resistant multipurpose additive of antioxygen is the compound of structure shown in formula (I).The present invention also provides the preparation methods of Metalworking lubricating oil composition.Metalworking lubricating oil composition of the invention has excellent abrasion resistance and antioxygenic property, can be used as metal working fluid and is widely used in the field of metal processing.
Description
Technical field
The present invention relates to lubricating oil fields, and in particular, to a kind of Metalworking lubricating oil group containing special additive
Close object and preparation method thereof.
Background technique
Intermetallic composite coating includes rolling, forging, stamping, drawing, molding, cutting and grinding.Intermetallic composite coating will use various
Types of metals working fluid can be divided into metal cutting process liquid, metal plastic forming working fluid two major classes.In these two types of process
In, biggish friction and high temperature are all generated among cutter, mold and processed metal works, thus metal working fluid is to lubrication
There is very high requirement with high-temperature oxidation resistance.Metal working fluid is generally lubricant oil composite.
Metal cutting process is generally divided into two stages: i.e. the timely removing of chip generation and chip, the two stages deposit
Very big friction between cutter and workpiece (chip generates the stage), cutter and chip (stage is eliminated in chip), this friction
Power consumption largely can and be changed into heat, to influence processing efficiency and workpiece quality, or even damage cutter and equipment.Add in grinding
In work, grinding speed is up to 1000 ms/min or more, and temperature is up to 1000 DEG C, for cooling and lubrication cutter and workpiece, it is necessary to make
With metal working fluid, generated heat when cutting is taken away in time, reduces the temperature of cutter and workpiece and plays lubrication and wear-resistant work
With reducing the roughness of workpiece surface, tool life.As energy-saving and environment-friendly requirement is continuously improved, and to gold
Belong to the continuous improvement of the requirement of processing quality, the stage of replacement that metal working fluid uses is increasingly longer, exploitation have it is preferably wear-resistant and
The metal working fluid of antioxygen property is the lasting R&D target of this field researcher.
It mainly includes phenols and aminated compounds that the lube oil additive of antioxidation can be effectively played by, which being currently known,.
Phenolic compound contains one or more and is obstructed phenol functional group, and aminated compounds then contains one or more nitrogen-atoms, these are special
Different functional group can capture the free radical compounds of oxidation process generation, so that oxidation process be prevented to continue to occur.Due to
The operating condition of Current mechanical equipment tends to strongly, often accelerated oxidation rate, shortens the service life of lubricating oil, therefore right
More stringent requirements are proposed for the efficiency and economy of antioxidant.
United States Patent (USP) US4824601A reports diphenylamine and diisobutylene in the alkaline-earth metal catalyst of acid activation
The lower alkylated amines mixture formed of (earth catalyst) effect, its anti-oxidant energy in lubricating oil and other functional fluids
Power is excellent in.
United States Patent (USP) US2005230664A1 reports a kind of antioxidant 9 of following general formula, the synthesis of 10- acridan
Method, it is to be condensed preparation under acidic catalyst effect using alkylated diphenylamine and aldehydes or ketones.
Using the tert-butyl phenols that is obstructed, aldehyde, carbon disulfide and dialkylamine condensation preparationization occurs for patent CN1191340C
Object is closed, which has the stronger ability for capturing free radical and peroxynitrite decomposition compound, can provide to oil oxidation stability
More effectively protection, may also function as wear-resistant effect.
Patent US4225450 reports one kind and reacts preparation with Diethyldithiocarbamate by the tert-butyl phenols that is obstructed
Polysulfide phenolic antioxidant, have preferable antioxidation and wear-resistant effect.
Summary of the invention
The purpose of the invention is to meet wear-resistant and antioxygen property the high request to Metalworking lubricating oil, one is provided
Kind Metalworking lubricating oil composition and preparation method thereof.
The present inventor has found that lubricant oil composite contains the compound of structure shown in formula (I) under study for action:
And the compound and thiophenols ester type antioxidant are combined, and Metalworking lubricating oil composition can be made to have excellent
The performances such as wear-resistant and anti-oxidant.
Therefore, to achieve the goals above, on the one hand, the present invention provides a kind of Metalworking lubricating oil composition, with
On the basis of the weight of lubricant oil composite, the lubricant oil composite contains following components: the lube base of 85-98 weight %
Oil, the wear-resistant multipurpose additive of antioxygen of 0.01-10 weight %, the thiophenols ester type antioxidant of 0.01-5 weight %, 0.01-5 weight
The dinonylnaphthalene sulfonic acid salt of % and organic anti-friction agent of 0.01-5 weight % are measured, the wear-resistant multipurpose additive of antioxygen is formula (I)
The compound of shown structure:
Preferably, on the basis of the weight of lubricant oil composite, the lubricant oil composite contains following components: 90-98
The thiophenols ester type of the lube base oil of weight %, the wear-resistant multipurpose additive of antioxygen of 0.1-4 weight %, 0.1-3 weight %
Organic anti-friction agent of antioxidant, the dinonylnaphthalene sulfonic acid salt of 0.2-3 weight % and 0.2-3 weight %.
On the other hand, the present invention provides a kind of preparation methods of Metalworking lubricating oil composition, which comprises
Containing lube base oil, the wear-resistant multipurpose additive of antioxygen, thiophenols ester type antioxidant, dinonylnaphthalene sulfonic acid salt and organic it will subtract
Rub agent raw material be uniformly mixed obtain lubricant oil composite, wherein on the basis of the weight of lubricant oil composite, lube base
The dosage of oil is 85-98 weight %, the dosage of the wear-resistant multipurpose additive of antioxygen is 0.01-10 weight %, thiophenols ester type antioxygen
The dosage of agent is 0.01-5 weight %, the dosage of dinonylnaphthalene sulfonic acid salt is 0.01-5 weight %, and the dosage of organic anti-friction agent is
0.01-5 weight %, the wear-resistant multipurpose additive of antioxygen are the compound of structure shown in formula (I):
Preferably, on the basis of the weight of lubricant oil composite, the dosage of lube base oil is 90-98 weight %, resists
The dosage of the wear-resistant multipurpose additive of oxygen is 0.1-4 weight %, the dosage of thiophenols ester type antioxidant is 0.1-3 weight %, two nonyls
The dosage of base naphthalene sulfonate is 0.2-3 weight %, and the dosage of organic anti-friction agent is 0.2-3 weight %.
Metalworking lubricating oil composition of the invention has excellent abrasion resistance and antioxygenic property, can be used as gold
Belong to working fluid and is widely used in the field of metal processing.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is the reaction equation of (a) the step of preparing antioxygen wear-resistant multipurpose additive.
Fig. 2 is the reaction equation of (b) the step of preparing antioxygen wear-resistant multipurpose additive.
Fig. 3 is the hydrogen spectrum spectrogram of the wear-resistant multipurpose additive of antioxygen of preparation example preparation.
Fig. 4 is the carbon spectrum spectrogram of the wear-resistant multipurpose additive of antioxygen of preparation example preparation.
Fig. 5 is the mass spectrogram of the wear-resistant multipurpose additive of antioxygen of preparation example preparation.
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 Metalworking lubricating oil compositions, using the weight of lubricant oil composite as base
Standard, lubricant oil composite contain following components: lube base oil, the antioxygen of 0.01-10 weight % of 85-98 weight % is wear-resistant
The dinonylnaphthalene sulfonic acid salt and 0.01- of multipurpose additive, the thiophenols ester type antioxidant of 0.01-5 weight %, 0.01-5 weight %
Organic anti-friction agent of 5 weight %, the wear-resistant multipurpose additive of antioxygen are 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 90-98 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 0.1-3 weight %；The content of dinonylnaphthalene sulfonic acid salt is preferably 0.1-4 weight %, more preferably
For 0.2-3 weight %；The content of organic anti-friction agent is preferably 0.1-4 weight %, more preferably 0.2-3 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 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
For thiodipropionic acid bis-dodecanol ester (DLTDP), thio-2 acid double octadecyl esters (DSTDP), 2,5- dimercapto -1,3,4- thiophene two
Azoles (DMTD) and 2, at least one of 2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate], preferably
2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate], such as the production of Sichuan Yong Ye Chemical Co., Ltd.
Antioxidant 1035, BASF Aktiengesellschaft production IRGANOX L115.
In the present invention, dinonylnaphthalene sulfonic acid salt can be dinonyl naphthalene sulfonate barium, dinonylnaphthalene sulfonic acid zinc, dinonyl naphthalene sulphur
At least one of sour calcium and dinonylnaphthalene sulfonic acid ammonium, preferably dinonyl naphthalene sulfonate barium, such as Suzhou specialty oil factory
T705、T705A。
In the present invention, organic anti-friction agent can in polyol esters of fatty acids, aliphatic amine and aliphatic amide at least
It is a kind of.Wherein, aliphatic alkyl is preferably saturation or unsaturated alkyl of the carbon atom number between 6-60, and more preferably carbon is former
Saturation or unsaturated alkyl of the subnumber between 10-50.Polyol esters of fatty acids for example may include fatty glyceride, fat
Sour pentaerythritol ester, ethylene glycol fatty acid, fatty acid succinate, fatty acid ethanolamide amine ester, fatty acid diethanolamine ester, rouge
Monoesters, dibasic acid esters or the polyester of the compounds such as fat triethylenetetraminehexaacetic acid alkanolamine ester, such as monoolein, oleic acid diglyceride, stearic acid list
Pentaerythritol ester, lauric acid/dodecanoic acid diethylene glycol dilaurate, oleic acid diethanol amine monoesters, triethanolamine oleate monoesters etc.；Aliphatic amine is for example
It may include that alkyl replaces monoamine or polyamine, alkoxylated alkyl to replace monoamine or polyamine and alkyl ether amine etc.,
Such as the tallow amine of ethoxylation and the butter fat ether amines of ethoxylation；Aliphatic amide for example may include oleic acid acyl
Amine, coconut oleoyl amine, oleic acid diethyl amide etc..Organic anti-friction agent can select F10, F20 etc. of BASF Aktiengesellschaft.
Lubricant oil composite of the invention can also contain antirust agent and/or anti-foaming agent.Antirust agent can be selected from imidazoles
And/or alkenyl succinic acid esters, such as can be in 4,5- glyoxalidine, alkenyl imidazoline succinate and alkenyl succinic acid ester
At least one, such as can select Jinzhou Kangtai Lube Additive Co., Ltd. produce T746, T703, T747.Anti- bubble
Agent can select polysiloxane type anti-foaming agent, such as can be silicone oil and/or dimethyl silicone polymer.For antirust agent and anti-bubble
The content of agent can be the content of this field routine without particular/special requirement, this is known to those skilled in the art, no longer superfluous herein
It states.
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 preparations of Metalworking lubricating oil composition
Method, this method comprises: lube base oil, the wear-resistant multipurpose additive of antioxygen, thiophenols ester type antioxidant, dinonyl will be contained
The raw material of naphthalene sulfonate and organic anti-friction agent is uniformly mixed and obtains lubricant oil composite, wherein with the weight of lubricant oil composite
On the basis of, the dosage of lube base oil is 85-98 weight %, the dosage of the wear-resistant multipurpose additive of antioxygen is 0.01-10 weight
Measure %, thiophenols ester type antioxidant dosage be 0.01-5 weight %, the dosage of dinonylnaphthalene sulfonic acid salt is 0.01-5 weight %,
The dosage of organic anti-friction agent is 0.01-5 weight %, and the wear-resistant multipurpose additive of antioxygen is the compound of structure shown in formula (I):
In the method for the present invention, it is preferable that on the basis of the weight of lubricant oil composite, the dosage of lube base oil is
90-98 weight %, the wear-resistant multipurpose additive of antioxygen dosage be 0.1-4 weight %, the dosage of thiophenols ester type antioxidant is
0.1-3 weight %, dinonylnaphthalene sulfonic acid salt dosage be 0.2-3 weight %, the dosage of organic anti-friction agent is 0.2-3 weight %.
As previously mentioned, raw material can also contain antirust agent and/or anti-foaming agent in the method for the present invention.
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.
It is the wear-resistant multipurpose additive of lube base oil, antioxygen, thiophenols ester type antioxidant, dinonylnaphthalene sulfonic acid salt, organic
Anti-friction agent, antirust agent and anti-foaming agent are as previously mentioned, details are not described herein.
Embodiment
The present invention is further illustrated for embodiment below, but is not intended to limit the present invention.
In the following Examples and Comparative Examples:
The method for monitoring fully reacting: thin-layer chromatography chromatography (TLC) fluorescence developing method.
Gross production rate=final product mole/aniline moles × 100%
The physico-chemical analysis method of product: constituent content is measured by inductively coupled plasma body ion emission spectroscopy method.
Structure characterization methods: nuclear magnetic resonance method (1H hydrogen spectrum,13C carbon spectrum), high resolution mass spectrum.
Preparation example
It is filled with nitrogen protection in the 500ml flask with electromagnetic agitation sub (mixing speed 300rpm), 150ml is added
Methylene chloride, then be added 0.2mol sulfur chloride, after being fully cooled in ice-water bath, the aniline of 0.2mol is added.Monitoring
Ice-water bath is moved back to fully reacting, is placed in 25 DEG C at room temperature, after reaction system is gradually increased to 25 DEG C, is added three times 4- chlorine
Aniline is reacted, and each additional amount is identical, and 4- chloroaniline 0.15mol is added altogether.30ml saturation is added after sustained response 2 hours
Reaction system, is then transferred in separatory funnel by saline solution quenching reaction, uses 50ml distilled water and 50ml saturated salt solution respectively
Washing, and 10g anhydrous sodium sulfate dry 20min at 25 DEG C is added.Filtered filtrate is evaporated off molten under 40 DEG C, 0.05MPa
Agent obtains intermediate M1.
It is filled with nitrogen protection in the 500ml flask with electromagnetic agitation sub (mixing speed 400rpm), 150ml is added
DMF (n,N-Dimethylformamide), be then added 0.2mol dimercapto-1,3,4-thiadiazole and 0.2mol potassium carbonate,
The potassium sulfate of 0.05mol stirs 20 minutes at 25 DEG C, is added three times above-mentioned intermediate M1, and each additional amount is identical, is added altogether
Intermediate M10.12mol.Then to fully reacting 250ml ethyl acetate is added in reaction system by monitoring, and be transferred to separatory funnel
In, 100ml distilled water (twice) and 50ml saturated common salt water washing are used respectively, and 15g anhydrous sodium sulfate is added and does at 25 DEG C
Dry 20min.Solvent is evaporated off at 40 DEG C, 0.03MPa in filtered filtrate, obtains final product S1.Calculating gross production rate is 76%.
The physico-chemical analysis data of product are as follows: sulfur content, and 41.3%；Nitrogen content, 13.9%.
S1 is subjected to structural characterization, respectively obtain hydrogen spectrum, carbon spectrum and high resolution mass spec spectrogram, see respectively Fig. 3, Fig. 4 and
Fig. 5.
It can be seen that S1 with knot shown in formula (I) from the physico-chemical analysis data of above-mentioned preparation example, Fig. 3, Fig. 4 and Fig. 5
Structure.
Embodiment 1
The present embodiment is for illustrating lubricant oil composite and preparation method thereof of the invention.
By the S1 of 0.1 parts by weight, 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid of 3 parts by weight
Ethyl ester], the dinonyl naphthalene sulfonate barium of 3 parts by weight, the stearic acid monopentaerythritol ester of 1.5 parts by weight, 0.01 parts by weight poly- two
Methylsiloxane and the sorbitol monooleate of 0.3 parts by weight are added to the mixed lubrication oil base oil of PAO10 and PAO40
In (PAO10 is 76 parts by weight, and PAO40 is 16.09 parts by weight), 3h is stirred at 60 DEG C, is uniformly mixed and obtains lubricating oil composition
Object A1.
Embodiment 2
The present embodiment is for illustrating lubricant oil composite and preparation method thereof of the invention.
By the S1 of 1.4 parts by weight, the 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) third of 1.4 parts by weight
Acetoacetic ester], the dinonyl naphthalene sulfonate barium of 0.2 parts by weight, the triethanolamine oleate monoesters of 3 parts by weight, 0.01 parts by weight poly- two
Methylsiloxane and the sorbitol monooleate of 0.3 parts by weight are added to the 600SN lube base oil of 93.69 parts by weight
In (viscosity index (VI) 87, saturated hydrocarbon content are 92 weight %, and sulfur content is 0.02 weight %), 6h is stirred at 40 DEG C, is mixed
Uniformly obtain lubricant oil composite A2.
Embodiment 3
The present embodiment is for illustrating lubricant oil composite and preparation method thereof of the invention.
By the S1 of 4 parts by weight, 2,2'- thiobis [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid of 0.1 parts by weight
Ethyl ester], the dinonyl naphthalene sulfonate barium of 1.5 parts by weight, the oleic acid diethyl amide of 0.2 parts by weight, 0.01 parts by weight poly- diformazan
Radical siloxane and the sorbitol monooleate of 0.3 parts by weight are added in the dibutyl adipate of 93.89 parts by weight, at 90 DEG C
Lower stirring 1h is uniformly mixed and obtains lubricant oil composite 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: using TA5000-DSC2910 differential thermal analysis
The measurement of instrument progress initial oxidation temperature；The measurement of oxidation induction period is carried out using high pressure differential scanning amount method (PDSC)；Using
Tetra-ball machine test method, measures PB, PD value by GB/T3142, measures wear scar diameter by SH/T 0189.It the results are shown in Table 1.
Table 1
| A1 | A2 | A3 | D1 | D2 | D3 | D4 | D5 | |
| Initial oxidation temperature, DEG C | 204 | 225 | 251 | 203 | 213 | 205 | 191 | 192 |
| Oxidation induction period, min | 26.5 | 49.3 | 61.8 | 33.4 | 42.7 | 32.1 | 23.6 | 24.5 |
| PB, kgf | 80 | 90 | 130 | 50 | 80 | 45 | 75 | 70 |
| PD, kgf | 245 | 285 | 320 | 210 | 250 | 205 | 245 | 240 |
| Wear scar diameter d60 40, mm | 0.60 | 0.54 | 0.48 | 0.68 | 0.61 | 0.67 | 0.63 | 0.64 |
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.
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.
Metalworking lubricating oil composition of the invention has excellent abrasion resistance and antioxygenic property, can be used as gold
Belong to working fluid and is widely used in the field of metal processing.
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.
Claims (11)
1. a kind of Metalworking lubricating oil composition, which is characterized in that on the basis of the weight of lubricant oil composite, the lubrication
Fluid composition contains following components: the lube base oil of 85-98 weight %, the wear-resistant multiple-effect of antioxygen of 0.01-10 weight % add
Add agent, the thiophenols ester type antioxidant of 0.01-5 weight %, the dinonylnaphthalene sulfonic acid salt of 0.01-5 weight % and 0.01-5 weight
Organic anti-friction agent of % is measured, the wear-resistant multipurpose additive of antioxygen is the compound of structure shown in formula (I):
2. lubricant oil composite according to claim 1, wherein on the basis of the weight of lubricant oil composite, the profit
Sliding oil composition contains following components: the lube base oil of 90-98 weight %, the wear-resistant multiple-effect of antioxygen of 0.1-4 weight % add
Add agent, the thiophenols ester type antioxidant of 0.1-3 weight %, the dinonylnaphthalene sulfonic acid salt of 0.2-3 weight % and 0.2-3 weight %
Organic anti-friction agent.
3. lubricant oil composite according to claim 1, wherein the lube base oil be mineral lubricating oil and/or
Synthetic lubricant fluid.
4. lubricant oil composite according to claim 1, wherein the thiophenols ester type antioxidant is 2,2'- thiobis
[3- (3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate].
5. lubricant oil composite according to claim 1, wherein the dinonylnaphthalene sulfonic acid salt is dinonylnaphthalene sulfonic acid
At least one of barium, dinonylnaphthalene sulfonic acid zinc, dinonylnaphthalene sulfonic acid calcium and dinonylnaphthalene sulfonic acid ammonium.
6. lubricant oil composite according to claim 1, wherein organic anti-friction agent is polyol esters of fatty acids, rouge
At least one of fat race amine and aliphatic amide.
7. lubricant oil composite according to claim 1, wherein the lubricant oil composite also contain antirust agent and/or
Anti-foaming agent, the antirust agent are at least one of 4,5- glyoxalidine, alkenyl imidazoline succinate and alkenyl succinic acid ester；
The anti-foaming agent is silicone oil.
8. lubricant oil composite according to claim 7, wherein the anti-foaming agent is dimethyl silicone polymer.
9. a kind of preparation method of Metalworking lubricating oil composition, which is characterized in that the described method includes: lubricating oil will be contained
The wear-resistant multipurpose additive of base oil, antioxygen, thiophenols ester type antioxidant, the raw material of dinonylnaphthalene sulfonic acid salt and organic anti-friction agent are mixed
It closes and uniformly obtains lubricant oil composite, wherein on the basis of the weight of lubricant oil composite, the dosage of lube base oil is
85-98 weight %, the wear-resistant multipurpose additive of antioxygen dosage be 0.01-10 weight %, the dosage of thiophenols ester type antioxidant is
0.01-5 weight %, dinonylnaphthalene sulfonic acid salt dosage be 0.01-5 weight %, the dosage of organic anti-friction agent is that 0.01-5 is weighed
% is measured, the wear-resistant multipurpose additive of antioxygen is the compound of structure shown in formula (I):
10. according to the method described in claim 9, wherein, on the basis of the weight of lubricant oil composite, lube base oil
The use that dosage is 90-98 weight %, the dosage of the wear-resistant multipurpose additive of antioxygen is 0.1-4 weight %, thiophenols ester type antioxidant
Amount is 0.1-3 weight %, the dosage of dinonylnaphthalene sulfonic acid salt is 0.2-3 weight %, and the dosage of organic anti-friction agent is 0.2-3 weight
Measure %.
11. according to the method described in claim 9, wherein, the mixed condition includes: that temperature is 40-90 DEG C, time 1-
6h。
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| CN112410103A (en) * | 2020-09-18 | 2021-02-26 | 江苏上阳金属新材料有限公司 | Lubricant for processing metal products and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186107A (en) * | 1996-12-11 | 1998-07-01 | 出光兴产株式会社 | metalworking oil composition |
| CN1356382A (en) * | 2001-12-27 | 2002-07-03 | 上海交通大学 | Dithioamino acid triazine derivative as additive for antioxidizing extreme pressure lubricating oil |
| CN1453347A (en) * | 2002-04-26 | 2003-11-05 | 中国石油化工股份有限公司 | Prepn of antioxidant for lubricant oil |
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2015
- 2015-06-16 CN CN201510332936.9A patent/CN106318555B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186107A (en) * | 1996-12-11 | 1998-07-01 | 出光兴产株式会社 | metalworking oil composition |
| CN1356382A (en) * | 2001-12-27 | 2002-07-03 | 上海交通大学 | Dithioamino acid triazine derivative as additive for antioxidizing extreme pressure lubricating oil |
| CN1453347A (en) * | 2002-04-26 | 2003-11-05 | 中国石油化工股份有限公司 | Prepn of antioxidant for lubricant oil |
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