CN105601551A - Sulfur-containing hindered phenolic compound as well as preparation and application thereof - Google Patents
Sulfur-containing hindered phenolic compound as well as preparation and application thereof Download PDFInfo
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Abstract
The invention provides a sulfur-containing hindered phenolic compound as well as a preparation and an application thereof. The compound comprises the following structure as shown in the specification, wherein R1 is H or C1-C3 alkyl, R2 is C3-C18 aliphatic hydrocarbon group, and R3 and R4 are C1-C12 alkyl. The compound has the advantages of good oil solubility, antioxidation performance and abrasion resistance; the compound can be applied to lubricating oil as a multipurpose additive, wherein the addition is 0.1-3%; and the compound can be applied to grease as a multipurpose additive, wherein the addition is 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 subject to the many factors such as environment temperature, oxygen and catalytic action of metal ionImpact, easily oxidized rotten generation low molecular compound, further the polymer of condensation formation HMW is alsoDeposition is got off. This oxidation has not only promoted the formation of corrosive oxidation product and residue in oil, can alsoCause lubricating oil viscosity increase even to cause curing, make product greasy property variation, reduction of service life, evenCan etching mechanism equipment. Therefore lubricant grease in use uses antioxidant to a certain degree conventionallyThis oxidizing process of upper inhibition, in the service life of prolongation grease, ensures that oil quality is stable.
The known additive that can effectively play antioxidation mainly comprises phenols and aminated compounds at present. PhenolCompounds contains one or more hindered phenol functional group, and aminated compounds contains one or more nitrogen-atoms,These special functional groups can play and catch the free radical compounds that oxidizing process generates, thereby have stoped oxidationThe continuation of process occurs. Because the condition of work of current plant equipment is tending towards strongly, tending to accelerated oxidation speed,Shortened the service life of grease, therefore the efficiency to antioxidant and economy are had higher requirement. The U.S.Patent US4824601 has reported diphenylamine and the diisobutylene native catalyst (earthcatalyst) in acid activationThe lower alkylated amines mixture forming of effect, its oxidation resistance performance in lubricating oil and other functional fluid is excellentDifferent; US Patent No. 2005230664A1 reported a kind of following general formula antioxidant 9,10 ?acridanSynthetic method, it is to use the condensation under acidic catalyst effect of alkylation diphenylamine and aldehydes or ketones to prepare.
Patent CN1453347C adopts be obstructed tert-butyl group phenols, aldehyde, carbon disulfide and dialkylamine generation condensationThe compound of preparation has the ability of stronger Mulberry Extract and decompose hydroperoxide, can be stable to oil oxidationProperty provides more effective protection, also can play wear-resistant effect. Patent US4225450 has reported a kind of by being obstructedTert-butyl group phenols reacts the polysulfide phenolic antioxidant of preparation with Diethyldithiocarbamate, have betterAntioxidation and wear-resistant effect.
Summary of the invention
The invention provides a kind of sulfur-bearing hindered phenol compound, this compound has good oil-soluble, antioxidantAnd wear resistence, can be used as additive application in lubricating oil and grease product.
The present invention also provides the preparation method of above-claimed cpd.
The present invention also provides the application of this compound in lubricating oil and lubricating grease.
Compound provided by the invention has following structure:
Wherein R1For H or C1 ?the alkyl of C3; R2For C3～C18 aliphatic group, the preferably alkane of C3～C8Base; R3、R4For C1～C12 alkyl, preferably C1～C6 alkyl, R3、R4Can be the same or different.
The preparation method of compound provided by the invention comprises the following steps:
1) in organic solvent and under acid catalyst action, make fatty amine and aldehyde and 2,6 ?DI-tert-butylphenol compoundsThere is addition reaction, separate solvent and catalyst, obtain intermediate product.
2) make intermediate product and carbon disulfide, 4 ?(halogenated methyl) ?N, N ?dialkyl benzene formamide mix,Under base catalyst effect, react, after post processing, obtain product.
Step 1) in, said catalyst can be acidic catalyst, can be also base catalyst, acidityCatalyst can be organic proton acid compounds such as p-methyl benzenesulfonic acid, camphorsulfonic acid. Base catalyst can be for havingMachine alkali cpd, preferably nitrogenous organic base, can be triethylamine, pyridine etc. The consumption of catalyst is aldehyde mole20～150%, preferably 50～80% of amount.
Said fatty amine is selected from C3～C18 fatty amine, preferably one or more in C3～C8 alkylamine,Preferably propylamine, butylamine etc. The structure of described fatty amine is R2NH2; Wherein R2For C3～C18 aliphatic group,The preferably alkyl of C3～C8.
Said aldehyde is selected from formaldehyde, acetaldehyde or propionic aldehyde etc.
Step 1) in organic solvent be polar organic solvent, the preferably larger organic solvent of polarity, Ke YishiA kind of or several in methyl alcohol, ethanol, DMSO (dimethyl sulfoxide (DMSO)), DMF (N, N ?dimethyl formamide) etc.The combination of planting.
Step 1) reaction temperature be 15 ?90 DEG C, preferably 30 ?60 DEG C; Reaction time be generally 1 ?6h, preferably2‐4h。
Step 2) in, said 4 ?(halogenated methyl) ?N, N ?in dialkyl benzene formamide, two alkyl R3,R4 can be identical or different, is selected from C1～C12 alkyl, preferably C1～C6 alkyl, can be for example methyl,Ethyl, propyl group etc. Halomethyl wherein can be chloromethyl, bromomethyl or iodomethyl, preferably bromomethyl.
Step 2) in said base catalyst can be organic base or inorganic alkali compound, organo-alkali compound is excellentSelect nitrogenous organic base, as triethylamine, pyridine etc.; Inorganic base can be NaOH, sodium methoxide, sodium carbonate etc.,Preferably nitrogenous organic base triethylamine. The consumption of catalyst is 50～200% of step 1 product mole, preferably80～150％。
Step 2) reaction temperature be 15 ?90 DEG C, preferably 30 ?60 DEG C, the reaction time is generally 1～8h, excellentSelect 2 ?4h.
Specifically, compound provided by the invention can be prepared by the following method:
1) in the reaction unit with electromagnetic agitation, (rotating speed can be 100 ?2000rpm, preferably200 ?800rpm), organic solvent, catalyst, fatty amine and aldehyde compound are mixed, after fully stirring, add2,6 ?DI-tert-butylphenol compounds. 15 ?react at 90 DEG C of temperature, the time generally continue 1 ?6h. Distillation is removed moltenAgent and catalyst, obtain intermediate product. Three kinds of reactants (fatty 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.
This step reaction equation is as follows:
2) intermediate product and base catalyst are mixed at 30 DEG C of 15 ?to (magnetic stirring apparatus rotating speed can be100 ?2000rpm, preferably 200 ?800rpm), then drip wherein carbon disulfide, then add wherein 4 ?(halogenated methyl) ?N, N ?dialkyl benzene formamide (halide). 15 ?react at 90 DEG C of temperature, when reactionBetween general continue 1 ?8h. The theoretical molar of three kinds of reactants (intermediate product M: carbon disulfide: halide)Ratio is 1:1:1, actual molar ratio can be 0.8 ?1.2:0.8 ?1.2:0.8 ?1.5.
This step reaction equation is as follows:
In equation, X is Cl, Br or I.
Characterize i.e. multipurpose additive of the present invention, the present invention's preparation in order to obtain purer end productThe method of multipurpose additive preferably also comprises reacted system carried out to post processing, and the mode of post processing can be wrappedDraw together washing, dry, removal of solvent under reduced pressure, for example, by abundant reacted system pour into 1 ?10 times of volumesIn ethyl acetate (or carrene), use respectively distilled water (or weakly acidic aqueous solution) and saturated common salt water washing,Then add the drier such as anhydrous calcium chloride or anhydrous sodium sulfate. Remove by filter after drier, decompression is removed moltenAgent, to obtain end product.
Compound provided by the invention has good oil-soluble, antioxygenic property and wear resistence, can be used as multiple-effect and addsAdd agent for lubricating oil, addition can be 0.1～3%, preferably 0.5～1.5%. Provided by the inventionizationCompound also can be used as multipurpose additive for lubricating grease, and addition can be 0.1～5%, and preferably 0.5～3%.
Brief description of the drawings
The intermediate M1 infrared spectrum of Fig. 1: embodiment 1.
Sample 1 high resolution mass spectrum prepared by Fig. 2: embodiment 1.
Sample 1 hydrogen spectrum prepared by Fig. 3: embodiment 1.
The intermediate M2 infrared spectrum of Fig. 4: embodiment 2.
Sample 2 high resolution mass spectrums prepared by Fig. 5: embodiment 2.
Sample 2 hydrogen spectrums prepared by Fig. 6: embodiment 2.
The intermediate M3 infrared spectrum of Fig. 7: embodiment 3.
Sample 3 high resolution mass spectrums prepared by Fig. 8: embodiment 3.
Sample 3 hydrogen spectrums prepared by Fig. 9: embodiment 3.
Detailed description of the invention
Below by embodiment, the present invention will be further described, but not thereby limiting the invention.
In embodiment, all raw materials are commercial goods. Unless stated otherwise, the reagent that uses is and analyzes pure ruleLattice.
Embodiment 1
In the flask with electromagnetic agitation, (rotating speed 300rpm) adds 100ml methyl alcohol and 50mlDMSO(dimethyl sulfoxide (DMSO)), then adds the propylamine of 0.1mol and the formaldehyde of 0.1mol wherein. At room temperature addEnter after the triethylamine of 0.05mol, by 0.1mol 2,6 ?DI-tert-butylphenol compounds add in reaction bulb. Feed in raw materialCheng Hou, is warming up to gradually 60 DEG C and reacts 3 hours again. Normal pressure steams except methyl alcohol and triethylamine, decompression (0.01～0.5Mpa, 60～100 DEG C) distill and remove DMSO, obtain intermediate product M1. Its infrared spectrum is shown in Fig. 1.
In the flask with electromagnetic agitation (rotating speed 400rpm) by the intermediate product M1 of 0.1mol andIn the mixture of 0.1mol triethylamine, drip the carbon disulfide of 0.1mol, after fully stirring, then add wherein0.12mol 4 ?(bromomethyl) ?N, N ?dimethyl benzamide, be then warming up to 50 DEG C reaction 2h, distillationRemove triethylamine, then reaction system is added to 200ml ethyl acetate, and proceed in separatory funnel. Use respectively100ml distilled water (twice) and the water washing of 50ml saturated common salt, and add 15g anhydrous sodium sulfate drying 15min.Filtrate after filtration is steamed and is desolventized under 40 DEG C, 0.03MPa, obtains end product sample 1.
The physico-chemical analysis data of sample 1 are as follows: sulfur content, 12.6%; Nitrogen content, 5.3%.
Hydrogen spectrum and the high resolution mass spectrum of sample 1 are shown in Fig. 2 and Fig. 3.
Embodiment 2
In the flask with electromagnetic agitation, (rotating speed 500rpm) adds 150ml ethanol and 50mlDMF(N, N ?dimethyl formamide), then adds the butylamine of 0.1mol and the acetaldehyde of 0.1mol wherein. In room temperatureUnder add after the p-methyl benzenesulfonic acid of 0.06mol, by 0.1mol 2,6 ?DI-tert-butylphenol compounds add in reaction bulb.After having fed in raw material, be warming up to gradually 45 DEG C and react again 4 hours. Normal pressure steams except ethanol equal solvent, (0.01～0.5Mpa, 60～100 DEG C) distill and remove DMF and pyridine, obtain intermediate product M2.
In the flask with electromagnetic agitation (rotating speed 400rpm) by the intermediate product M2 of 0.1mol andIn the mixture of 0.1mol pyridine, drip the carbon disulfide of 0.1mol, after fully stirring, then add wherein0.13mol 4 ?(chloromethyl) ?N, N ?diethylbenzene formamide, be then warming up to 60 DEG C reaction 3h. ReactionAfter finishing, with the dilution of 200ml ethyl acetate, wash with isopyknic citric acid water saturated solution, distilled water respectivelyAnd use 5g anhydrous sodium sulfate drying, after filtering, volatile component is removed in distillation, obtains sample 2.
The physico-chemical analysis data of sample 2 are as follows: sulfur content, 11.4%; Nitrogen content, 4.8%.
Hydrogen spectrum and the high resolution mass spectrum of sample 2 are shown in Fig. 5 and Fig. 6.
Embodiment 3
In the flask with electromagnetic agitation (rotating speed 550rpm) add 200mlDMF (N, N ?dimethylFormamide), then add wherein the hexylamine of 0.12mol and the acetaldehyde of 0.12mol. At room temperature addAfter the camphorsulfonic acid of 0.08mol, by 0.1mol 2,6 ?DI-tert-butylphenol compounds add in reaction bulb. Feed in raw materialCheng Hou, is warming up to gradually 60 DEG C and reacts 2 hours again. Decompression (0.01～0.5Mpa, 60～100 DEG C) distillationRemove DMF, obtain intermediate product M3.
In the flask with electromagnetic agitation (rotating speed 400rpm) by the intermediate product M3 of 0.1mol andIn the mixture of 0.1molNaOH, drip the carbon disulfide of 0.1mol, after fully stirring, then add wherein0.11mol 4 ?(bromomethyl) ?N, N ?dipropyl benzamide, be then warming up to 55 DEG C reaction 3.5h. ReactionAfter finishing, with the dilution of 150ml ethyl acetate, wash and use respectively 10g anhydrous calcium chloride with isopyknic distilled waterDry, after filtering, volatile component is removed in distillation, obtains sample 3.
The physico-chemical analysis data of sample 3 are as follows: sulfur content, 10.2%; Nitrogen content, 4.5%.
Hydrogen spectrum and the high resolution mass spectrum of sample 3 are shown in Fig. 8 and Fig. 9.
Embodiment 4
Prepare by the following method complex lithium grease:
By 6kg500SN base oil, (100 DEG C of viscosity are 10mm2/ s, lower with) with 0.68kg12 ?hydroxyl tristearinAcid, 0.38kg decanedioic acid mix and blend be heated to 80 DEG C add lithium hydroxide aqueous solution (0.34kg lithium hydroxide,1.5kg water), reaction is warmed up to 210 DEG C of high temperature refining 10min after 1h, is chilled to chamber after adding 2.8kg base oilTemperature is carried out triple-roller mill milled processed, obtains basic fat.
Sample 1,2,3 prepared by embodiment adds compound lithium base with the ratio of 2% (part by weight) respectivelyThe sample that lubricating grease is made, and basic fat and 2,6 ?DI-tert-butylphenol compounds (reaching purchased from Jin Zhourun), T323 (ammoniaBase monothioester, purchased from Yongtai, Jinan) the sample assessment of data prepared is as shown in table 1.
Table 1 lubricating grease properties of sample data
Sample 1,2,3 has good oxidation resistance and extreme pressure and antiwear behavior as can be seen from Table 1.
Claims (18)
1. a sulfur-bearing hindered phenol compound, has following structure:
Wherein R1For H or C1 ?the alkyl of C3, R2For C3～C18 aliphatic group, R3、R4For C1～C12Alkyl.
2. according to the said compound of claim 1, wherein, R2For the alkyl of C3～C8, R3、R4ForC1～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, make C3～C18 fatty amine and aldehyde and 2,6 ?twoTert-butyl phenol generation addition reaction, separates solvent and catalyst, obtains intermediate product.
2) make intermediate product and carbon disulfide, 4 ?(halogenated methyl) ?N, N ?dialkyl benzene formamide mix,Under base catalyst effect, react, after post processing, obtain product.
4. according to the said method of claim 3, wherein step 1) in, said catalyst is that acidity is urgedAgent or base catalyst, acidic catalyst is selected from organic proton acid compound, and base catalyst is selected from nitrogenously to be hadMachine alkali.
5. according to the said method of claim 4, wherein step 1) in, said acidic catalyst is selected fromP-methyl benzenesulfonic acid or camphorsulfonic acid, base catalyst is selected from triethylamine or pyridine.
6. according to the said method of claim 3, wherein step 1) in, the consumption of catalyst is aldehyde mole20～150% of amount.
7. according to the said method of claim 3, wherein step 1) in, said fatty amine be selected from C3～One or more in C8 alkylamine.
8. according to the said method of claim 3, wherein step 1) in, said aldehyde is selected from formaldehyde, secondAldehyde or propionic aldehyde etc.
9. according to the said method of claim 3, wherein step 1) in, organic solvent is selected from methyl alcohol, secondAlcohol, dimethyl sulfoxide (DMSO), N, N ?one or more in dimethyl formamide.
10. according to the said method of claim 3, wherein step 1) reaction temperature be 15 ?90 DEG C, anti-Between seasonable, be 1 ?6h.
11. according to the said method of claim 3, wherein step 2) in, said 4 ?(halogenated methyl)?N, N ?in dialkyl benzene formamide, two alkyl are selected from C1～C12 alkyl, halogenated methyl is wherein selected from chlorineMethyl, bromomethyl or iodomethyl.
12. according to the said method of claim 3 or 11, wherein step 2) in, said 4 ?(haloMethyl) ?N, N ?in dialkyl benzene formamide, two alkyl are selected from C1～C6 alkyl, halomethyl is wherein bromineMethyl.
13. according to the said method of claim 3, wherein step 2) in said base catalyst be organicAlkali or inorganic alkali compound, organo-alkali compound is selected from triethylamine or pyridine; Inorganic base is selected from NaOH, firstSodium alkoxide or sodium carbonate.
14. according to the said method of claim 3 or 13, wherein step 2) consumption of catalyst is step 150～200% of product mole.
15. according to the said method of claim 3, wherein step 2) reaction temperature be 15 ?90 DEG C, anti-Between seasonable, be 1～8h.
Described in 16. claims 1, compound is as the application of lubricating oil and grease additive.
The application of compound in lubricating grease described in 17. claims 1, addition is 0.1～5%.
The application of compound in lubricating oil described in 18. claims 1, addition is 0.1～3%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
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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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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| 溫晓葵 等: "硫代受阻酚类抗氧剂的应用发展情况分析", 《化工管理》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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