CN105601551B - A kind of sulfur-bearing hindered phenol compound and its preparation method and application - Google Patents
A kind of sulfur-bearing hindered phenol compound and its preparation method and application Download PDFInfo
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- CN105601551B CN105601551B CN201410680162.4A CN201410680162A CN105601551B CN 105601551 B CN105601551 B CN 105601551B CN 201410680162 A CN201410680162 A CN 201410680162A CN 105601551 B CN105601551 B CN 105601551B
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Abstract
The present invention provides a kind of sulfur-bearing hindered phenol compound and extremely prepares and apply.The compound has following structure:Wherein R1For H or C1-C3 alkyl, R2For C3~C18 aliphatic groups, R3、R4For C1~C12 alkyl.The compound that the present invention is provided has good oil-soluble, antioxygenic property and wear resistence, can be used for as multipurpose additive in lubricating oil, and addition can be 0.1~3%, can also be used for as multipurpose additive in lubricating grease, and addition can be 0.1~5%.
Description
Technical field
The present invention relates to a kind of novel sulfurized hindered phenol compound and its preparation method and application.
Background technology
Lubricant grease is in use by the shadow of many factors such as environment temperature, oxygen and catalytic action of metal ion
Ring, be oxidized easily rotten generation low molecular compound, the polymer and deposition that further condensation forms HMW get off.This
Plant the formation that oxidation not only promotes corrosive oxidation products and residue in oil, additionally it is possible to cause lubricating oil viscosity increase very
To solidification is caused, product greasy property is set to be deteriorated, reduction of service life, or even can corrosion of mechanical equipment.Therefore lubricant grease exists
Suppress this oxidizing process to a certain extent usually using antioxidant during use, extend the use longevity of grease
Life, it is ensured that oil quality is stable.
The additive that can effectively play antioxidation is currently known mainly including phenols and aminated compounds.Phenol generalization
Compound contains one or more phenol functional groups that are obstructed, and aminated compounds then contains one or more nitrogen-atoms, these special officials
Can roll into a ball can play the free radical compounds for catching oxidizing process generation, so as to prevent the continuation of oxidizing process to occur.Due to
The condition of work of Current mechanical equipment tends to be strong, often accelerated oxidation speed, shortens the service life of grease, therefore right
The efficiency and economy of antioxidant propose higher requirement.United States Patent (USP) US4824601 reports diphenylamine and two isobutyls
The alkylated amines mixture that alkene is formed under native catalyst (earth catalyst) effect of acid activation, it is in lubricating oil and its
Oxidation resistance performance is excellent in its functional fluid;United States Patent (USP) US2005230664A1 reports a kind of antioxygen of below general formula
Agent 9, the synthetic method of 10- acridans, it is to use alkylated diphenylamine with aldehydes or ketones under acidic catalyst effect
It is prepared by condensation.
Patent CN1453347C occurs prepared by condensation using the tert-butyl group phenols that is obstructed, aldehyde, carbon disulfide and dialkylamine
Compound has the stronger ability for catching free radical and peroxynitrite decomposition compound, can provide more effective to oil oxidation stability
Protection, may also function as wear-resistant effect.Patent US4225450 reports a kind of by tert-butyl group phenols and the alkyl dithiocarbamates of being obstructed
Polysulfide phenolic antioxidant prepared by formic acid reactant salt, with preferable antioxidation and wear-resistant effect.
The content of the invention
The invention provides a kind of sulfur-bearing hindered phenol compound, the compound has good oil-soluble, antioxidant and resisted
Mill property, can be as additive application in lubricating oil and grease product.
Present invention also offers the preparation method of above-claimed cpd.
Present invention also offers application of the compound in lubricating oil and lubricating grease.
The compound that the present invention is provided has following structure:
Wherein R1For H or C1-C3 alkyl;R2For C3~C18 aliphatic groups, preferably C3~C8 alkyl;R3、R4For
C1~C12 alkyl, preferably C1~C6 alkyl, R3、R4It can be the same or different.
The preparation method for the compound that the present invention is provided comprises the following steps:
1) in organic solvent with acidic catalyst effect, make fatty amine and aldehyde and 2,6- DI-tert-butylphenol compounds occur plus
Into reaction, separation solvent and catalyst obtain intermediate product.
2) intermediate product is made to be mixed with carbon disulfide, 4- (halogenated methyl)-N, N- dialkyl benzene formamide, in base catalysis
Agent effect under react, it is post-treated after obtain product.
Step 1) in, described catalyst can be acidic catalyst or base catalyst, and acidic catalyst can
Think the organic proton acid compound such as p-methyl benzenesulfonic acid, camphorsulfonic acid.Base catalyst can be organo-alkali compound, preferably contain
Nitrogen organic base, can be triethylamine, pyridine etc..The consumption of catalyst is 20~150%, preferably the 50~80% of aldehyde mole.
Described fatty amine is selected from C3~C18 fatty amines, the preferably one or more in C3~C8 alkylamines, preferably third
Amine, butylamine etc..The structure of the fatty amine is R2NH2;Wherein R2For C3~C18 aliphatic groups, preferably C3~C8 alkyl.
Described aldehyde is selected from formaldehyde, acetaldehyde or propionic aldehyde etc..
Step 1) in organic solvent be polar organic solvent, the preferred larger organic solvent of polarity can be methanol, second
One or more of combinations in alcohol, DMSO (dimethyl sulfoxide (DMSO)), DMF (N,N-dimethylformamide) etc..
Step 1) reaction temperature be 15-90 DEG C, preferably 30-60 DEG C;Reaction time is generally 1-6h, preferably 2-4h.
Step 2) in, in described 4- (halogenated methyl)-N, N- dialkyl benzene formamide, two alkyl R3, R4 can phases
It is same or different, selected from C1~C12 alkyl, preferably C1~C6 alkyl, such as can be methyl, ethyl, propyl group.Halogen first therein
Base can be chloromethyl, bromomethyl or iodomethyl, preferably bromomethyl.
Step 2) in described base catalyst can be organic base or inorganic alkali compound, organo-alkali compound is preferably nitrogenous
Organic base, such as triethylamine, pyridine;Inorganic base can be sodium hydroxide, sodium methoxide, sodium carbonate etc., preferably nitrogenous organic base three
Ethamine.The consumption of catalyst is 50~200%, preferably the 80~150% of step 1 product molar amount.
Step 2) reaction temperature be 15-90 DEG C, preferably 30-60 DEG C, the reaction time is generally 1~8h, preferably 2-4h.
Specifically, the compound that the present invention is provided can be prepared by the following method:
1) in the reaction unit with electromagnetic agitation (rotating speed can be 100-2000rpm, preferably 200-800rpm), will
Organic solvent, catalyst, fatty amine and aldehyde compound mixing, add 2,6- DI-tert-butylphenol compounds after being sufficiently stirred for.At 15-90 DEG C
At a temperature of react, the time typically continue 1-6h.Solvent and catalyst is distilled off, intermediate product is obtained.Three kinds of reactant (fat
Amine:Aldehyde:2,6- DI-tert-butylphenol compounds) theoretical molar ratio be 1:1:1, actual molar ratio can be 0.8-1.3:0.8‐
1.3:0.8‐1.2.
The step reaction equation is as follows:
2) intermediate product and base catalyst mix to (magnetic stirring apparatus rotating speed can be 100- at 15-30 DEG C
2000rpm, preferably 200-800rpm), carbon disulfide is then added dropwise thereto, then add 4- (halogenated methyl)-N, N- thereto
Dialkyl benzene formamide (halide).Reacted at a temperature of 15-90 DEG C, the reaction time typically continues 1-8h.Three kinds of reactants (in
Between product M:Carbon disulfide:Halide) theoretical molar ratio be 1:1:1, actual molar ratio can be 0.8-1.2:0.8‐
1.2:0.8‐1.5.
The step reaction equation is as follows:
In equation, X is Cl, Br or I.
In order to which the final product for obtaining purer is characterized, i.e. multipurpose additive of the invention, the present invention prepares multiple-effect
The method of additive preferably also includes post-processing reacted system, the mode of post processing can include washing, drying,
Removal of solvent under reduced pressure, for example, abundant reacted system is poured into the ethyl acetate (or dichloromethane) of 1-10 times of volume, point
Not Yong distilled water (or weakly acidic aqueous solution) and saturated common salt water washing, then add anhydrous calcium chloride or anhydrous sodium sulfate etc. do
Drying prescription.It is filtered to remove after drier, removal of solvent under reduced pressure, to obtain final product.
The compound that the present invention is provided has good oil-soluble, antioxygenic property and wear resistence, can be used as multipurpose additive
For in lubricating oil, addition can be 0.1~3%, preferably 0.5~1.5%.The compound that the present invention is provided can also be used as many
Imitating additive is used in lubricating grease, and addition can be 0.1~5%, preferably 0.5~3%.
Brief description of the drawings
Fig. 1:The intermediate M1 infrared spectrums of embodiment 1.
Fig. 2:The high resolution mass spectrum of sample 1 prepared by embodiment 1.
Fig. 3:The hydrogen of sample 1 spectrum prepared by embodiment 1.
Fig. 4:The intermediate M2 infrared spectrums of embodiment 2.
Fig. 5:The high resolution mass spectrum of sample 2 prepared by embodiment 2.
Fig. 6:The hydrogen of sample 2 spectrum prepared by embodiment 2.
Fig. 7:The intermediate M3 infrared spectrums of embodiment 3.
Fig. 8:The high resolution mass spectrum of sample 3 prepared by embodiment 3.
Fig. 9:The hydrogen of sample 3 spectrum prepared by embodiment 3.
Embodiment
Below by embodiment, the present invention will be further described, but not thereby limiting the invention.
All raw materials are commercial goods in embodiment.Unless stated otherwise, institute is the pure specification of analysis using reagent.
Embodiment 1
(rotating speed 300rpm) adds 100ml methanol and 50ml DMSO (dimethyl Asias in the flask with electromagnetic agitation
Sulfone), 0.1mol propylamine and 0.1mol formaldehyde are then added thereto.Add at room temperature after 0.05mol triethylamine, will
0.1mol 2,6- DI-tert-butylphenol compounds are added in reaction bulb.After the completion of charging, it is gradually heating to 60 DEG C and reacts again 3 hours.Often
Methanol and triethylamine is evaporated off in pressure, and decompression (0.01~0.5Mpa, 60~100 DEG C) is distilled off DMSO, obtains intermediate product M1.Its
Infrared spectrum is shown in Fig. 1.
(rotating speed 400rpm) is by the 0.1mol second of intermediate product M1 and 0.1mol tri- in the flask with electromagnetic agitation
In the mixture of amine be added dropwise 0.1mol carbon disulfide, after being sufficiently stirred for, then thereto add 0.12mol 4- (bromomethyl)-
N, N- dimethyl benzamide, then heat to 50 DEG C of reaction 2h, triethylamine are distilled off, then reaction system is added
200ml ethyl acetate, and be transferred in separatory funnel.100ml distilled water (twice) and 50ml saturated common salt water washings are used respectively, and
Add 15g anhydrous sodium sulfate dryings 15min.Solvent is evaporated off under 40 DEG C, 0.03MPa in filtrate after filtering, obtains final product
Sample 1.
The physico-chemical analysis data of sample 1 are as follows:Sulfur content, 12.6%;Nitrogen content, 5.3%.
The hydrogen spectrum and high resolution mass spectrum of sample 1 are shown in Fig. 2 and Fig. 3.
Embodiment 2
(rotating speed 500rpm) adds 150ml ethanol and 50ml DMF (N, N- diformazans in the flask with electromagnetic agitation
Base formamide), 0.1mol butylamine and 0.1mol acetaldehyde are then added thereto.At room temperature add 0.06mol to first
After benzene sulfonic acid, 0.1mol 2,6- DI-tert-butylphenol compounds are added in reaction bulb.After the completion of charging, be gradually heating to 45 DEG C it is anti-again
Answer 4 hours.Ethanol equal solvent is evaporated off in normal pressure, and DMF and pyridine is distilled off in (0.01~0.5Mpa, 60~100 DEG C), obtains centre
Product M2.
(rotating speed 400rpm) is by 0.1mol intermediate product M2 and 0.1mol pyridine in the flask with electromagnetic agitation
Mixture in be added dropwise 0.1mol carbon disulfide, after being sufficiently stirred for, then thereto add 0.13mol 4- (chloromethyl)-N,
N- diethyl-benzamides, then heat to 60 DEG C of reaction 3h.Reaction terminate after with 200ml ethyl acetate dilute, respectively with etc.
Simultaneously volatile component is distilled off after using 5g anhydrous sodium sulfate dryings, filtering in the citric acid water saturated solution of volume, distillation water washing,
Obtain sample 2.
The physico-chemical analysis data of sample 2 are as follows:Sulfur content, 11.4%;Nitrogen content, 4.8%.
The hydrogen spectrum and high resolution mass spectrum of sample 2 are shown in Fig. 5 and Fig. 6.
Embodiment 3
(rotating speed 550rpm) adds 200ml DMF (DMF) in the flask with electromagnetic agitation,
Then 0.12mol hexylamine and 0.12mol acetaldehyde are added thereto.Add at room temperature after 0.08mol camphorsulfonic acid, will
0.1mol 2,6- DI-tert-butylphenol compounds are added in reaction bulb.After the completion of charging, it is gradually heating to 60 DEG C and reacts again 2 hours.Subtract
DMF is distilled off in pressure (0.01~0.5Mpa, 60~100 DEG C), obtains intermediate product M3.
(rotating speed 400rpm) is by 0.1mol intermediate product M3 and 0.1molNaOH in the flask with electromagnetic agitation
Mixture in be added dropwise 0.1mol carbon disulfide, after being sufficiently stirred for, then thereto add 0.11mol 4- (bromomethyl)-N,
N- dipropyl yl-benzamides, then heat to 55 DEG C of reaction 3.5h.Reaction is diluted after terminating with 150ml ethyl acetate, is used respectively
Isometric distillation water washing is simultaneously dried with 10g anhydrous calcium chlorides, and volatile component is distilled off after filtering, that is, obtains sample 3.
The physico-chemical analysis data of sample 3 are as follows:Sulfur content, 10.2%;Nitrogen content, 4.5%.
The hydrogen spectrum and high resolution mass spectrum of sample 3 are shown in Fig. 8 and Fig. 9.
Embodiment 4
Complex lithium grease is prepared as follows:
By 6kg 500SN base oils, (100 DEG C of viscosity are 10mm2/ s, similarly hereinafter) and 0.68kg 12- hydroxy stearic acids,
0.38kg decanedioic acid, which is mixed, is heated to 80 DEG C of addition lithium hydroxide aqueous solutions (0.34kg lithium hydroxides, 1.5kg water), reaction
210 DEG C of high temperature refining 10min are warming up to after 1h, adds and is cooled to room temperature progress triple-roller mill milled processed after 2.8kg base oils, obtain
Basic fat.
Sample 1,2,3 prepared by embodiment adds complex lithium grease system with the ratio of 2% (part by weight) respectively
Into sample, and basic fat (moistens purchased from Jinzhou and reaches) with 2,6- DI-tert-butylphenol compounds, T323 (aminothio esters, purchased from Jinan
Yongtai) prepare sample assessment of data it is as shown in table 1.
The lubricating grease properties of sample data of table 1
Sample 1,2,3 has good oxidation resistance and extreme pressure and antiwear behavior as can be seen from Table 1.
Claims (17)
1. a kind of sulfur-bearing hindered phenol compound, with following structure:
Wherein R1For H or C1-C3 alkyl, R2For C3~C18 aliphatic groups, R3、R4For C1~C12 alkyl.
2. according to the compound described in claim 1, wherein, R2For C3~C8 alkyl, R3、R4For C1~C6 alkyl.
3. the preparation method of compound described in claim 1, comprises the following steps:
1) under the effect of polar organic solvent catalyst neutralisation, send out C3~C18 fatty amines and aldehyde and 2,6- DI-tert-butylphenol compounds
Raw addition reaction, separation solvent and catalyst, obtain intermediate product, described catalyst is acidic catalyst or base catalysis
Agent, acidic catalyst is selected from organic proton acid compound, and base catalyst is selected from nitrogenous organic base;
2) intermediate product is mixed with carbon disulfide, 4- (halogenated methyl)-N, N- dialkyl benzene formamide, make in base catalyst
Reacted under, it is post-treated after obtain product.
4. according to the method described in claim 3, wherein step 1) in, described acidic catalyst is selected from p-methyl benzenesulfonic acid or camphor tree
Brain sulfonic acid, base catalyst is selected from triethylamine or pyridine.
5. according to the method described in claim 3, wherein step 1) in, the consumption of catalyst is the 20~150% of aldehyde mole.
6. according to the method described in claim 3, wherein step 1) in, described fatty amine in C3~C8 alkylamines one
Plant or several.
7. according to the method described in claim 3, wherein step 1) in, described aldehyde is selected from formaldehyde, acetaldehyde or propionic aldehyde.
8. according to the method described in claim 3, wherein step 1) in, organic solvent be selected from methanol, ethanol, dimethyl sulfoxide (DMSO),
One or more in N,N-dimethylformamide.
9. according to the method described in claim 3, wherein step 1) reaction temperature be 15-90 DEG C, the reaction time is 1-6h.
10. according to the method described in claim 3, wherein step 2) in, described 4- (halogenated methyl)-N, N- dialkyl benzene first
In acid amides, two alkyl are selected from C1~C12 alkyl, and halogenated methyl therein is selected from chloromethyl, bromomethyl or iodomethyl.
11. according to the method described in claim 3 or 10, wherein step 2) in, described 4- (halogenated methyl)-N, N- dialkyl group
In benzamide, two alkyl are selected from C1~C6 alkyl, and halomethyl therein is bromomethyl.
12. according to the method described in claim 3, wherein step 2) in described base catalyst be organic base or inorganic alkalization
Compound, organo-alkali compound is selected from triethylamine or pyridine;Inorganic base is selected from sodium hydroxide, sodium methoxide or sodium carbonate.
13. according to the method described in claim 3 or 12, wherein step 2) consumption of catalyst is step 1 product molar amount
50~200%.
14. according to the method described in claim 3, wherein step 2) reaction temperature be 15-90 DEG C, the reaction time is 1~8h.
15. compound described in claim 1 is used as the application of lubricating oil and grease additive.
16. application of the compound described in claim 1 in lubricating grease, addition is 0.1~5% (part by weight).
17. application of the compound described in claim 1 in lubricating oil, addition is 0.1~3% (part by weight).
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CN111057025A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Phenol derivative and preparation method and application thereof |
CN110283127A (en) * | 2019-03-22 | 2019-09-27 | 浙江农林大学暨阳学院 | A kind of method that nickel catalysis prepares 2- t-butyl carbamate benzimidazoles compound |
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GB1024651A (en) * | 1962-01-03 | 1966-03-30 | Us Rubber Co | Organic dithiocarbamate stabilizers for materials subject to oxidative deterioration |
US4225450A (en) * | 1977-07-21 | 1980-09-30 | Ciba-Geigy Corporation | Lubricant compositions containing dithiocarbamyl antioxidants |
US4824601A (en) * | 1983-12-08 | 1989-04-25 | Ciba-Geigy-Corporation | Liquid antioxidant produced by alkylating diphenylamine with a molar excess of diisobutylene |
WO1995034602A1 (en) * | 1994-06-10 | 1995-12-21 | Akzo Nobel N.V. | Secondary accelerators for the sulfur-vulcanization of rubber |
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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2014
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GB1024651A (en) * | 1962-01-03 | 1966-03-30 | Us Rubber Co | Organic dithiocarbamate stabilizers for materials subject to oxidative deterioration |
US4225450A (en) * | 1977-07-21 | 1980-09-30 | Ciba-Geigy Corporation | Lubricant compositions containing dithiocarbamyl antioxidants |
US4824601A (en) * | 1983-12-08 | 1989-04-25 | Ciba-Geigy-Corporation | Liquid antioxidant produced by alkylating diphenylamine with a molar excess of diisobutylene |
WO1995034602A1 (en) * | 1994-06-10 | 1995-12-21 | Akzo Nobel N.V. | Secondary accelerators for the sulfur-vulcanization of rubber |
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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