CN103965139A - Thiadiazole derivative containing thiocarbamate and preparation and application thereof - Google Patents
Thiadiazole derivative containing thiocarbamate and preparation and application thereof Download PDFInfo
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- CN103965139A CN103965139A CN201310034059.8A CN201310034059A CN103965139A CN 103965139 A CN103965139 A CN 103965139A CN 201310034059 A CN201310034059 A CN 201310034059A CN 103965139 A CN103965139 A CN 103965139A
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- Prior art keywords
- thiocarbamate
- thiadiazole
- reaction medium
- thiadiazoles
- derivative
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- Granted
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- 150000004867 thiadiazoles Chemical class 0.000 title claims abstract description 30
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000010687 lubricating oil Substances 0.000 claims abstract description 19
- 239000012429 reaction media Substances 0.000 claims abstract description 16
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 dithiocarbamic acid alkyl chloride Chemical class 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 150000001348 alkyl chlorides Chemical class 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000007866 anti-wear additive Substances 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000002199 base oil Substances 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000012990 dithiocarbamate Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000654 additive Substances 0.000 description 14
- 230000000996 additive effect Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000010025 steaming Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 0 *N(C(S[N+])=S)I Chemical compound *N(C(S[N+])=S)I 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 231100000241 scar Toxicity 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 238000007445 Chromatographic isolation Methods 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- WDSONCXAIMMWHG-UHFFFAOYSA-N sulfocarbamic acid Chemical group OC(=O)NS(O)(=O)=O WDSONCXAIMMWHG-UHFFFAOYSA-N 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
- C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
- C10M135/36—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or oxygen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
- C10M2219/106—Thiadiazoles
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
Abstract
The invention relates to a thiadiazole derivative containing thiocarbamate, which is 2, 5-di-N, N' -dialkyl dithiocarbamate alkyl thioether-1, 3, 4-thiadiazole and has the following structural formula:
Description
Technical field
The present invention relates to a kind of additive for wear resistance of lubricating oil, particularly a kind of thiadiazoles derivative and preparation and application containing thiocarbamate.
Background technology
At present, 2,5-dimercapto-1,3,4-thiadiazole (DMTD) derivative has a wide range of applications in lubricating oil additive field, and it can well suppress the corrosion of metal such as copper and stainless steel, also has certain antioxygenation.And the most important application of DMTD derivative is as additive for wear resistance of lubricating oil.The element such as S, N is the active element that increases lubricating oil extreme pressure, abrasion resistance, and DMTD derivative is the heterogeneous ring compound that contains S, N element, and it is a class mild lubricating oil additive, and to be used in conjunction with effect fine with other functional additive.
It is 00801801.4 Thiadizole dimer additive and the lubricating oil composition that comprises this additive that Chinese invention patent discloses a kind of application number, by 2, the reaction product of 5-dimercapto-1,3,4-thiadiazole dipolymer-poly-(ether) glycol and adducts are as extreme-pressure additive.
It is 200480029627.4 the lubricating oil composition containing synthetic ester base oil, molybdenum compound and the compound based on thiadiazoles that Chinese invention patent discloses a kind of application number; can provide good wear-resistant protection to corrosion resistant material; the anti-wear agent of lubricating oil is 1; 3; 4-thiadiazoles derivative, 2,5-dimercapto-1; 3,4-Thiadizole dimer and the reaction product of gathering (ether) glycols.
US Patent No. 3980573 discloses the structure of multiple oil soluble DMTD derivative,
and study their extreme pressure and antiwear behavior by four ball frictional experiments.
US Patent No. 5514189 discloses dialkyl dithio amino formate derivative as multifunctional additive for lubricating oil, and the process of reaction is shown below:
The dialkyl dithio amino formate derivative of disclosed this structure not only has extreme pressure anti-wear, can in four ball frictional experiments, effectively reduce wear scar diameter, also has significant anti-oxidant function, improves the oxidation-resistance of lubricating oil.
Chinese invention patent discloses the thiadiazoles derivative N that a kind of application number is 201010128335.3 hydroxyls, N '-dialkyldithiocarbamacompositions-2-hydroxyl-3-(5-methylthio group-1,3,4-thiadiazoles-2 thioether group) preparation method of-propyl diester, and as the application of wear preventive additive.From the four ball frictional experiment data of announcing, the extreme pressure and antiwear behavior of this analog derivative is better than the extreme-pressure anti-friction additive of other structure.
New through looking into, have no relevant to 2,5-dimercapto-1,3,4 thiadiazoles and thiocarbamate are the domestic and foreign literature report of the synthetic wear preventive additive of raw material.
Summary of the invention
The object of this invention is to provide a kind of thiadiazoles derivative containing thiocarbamate and preparation method thereof, such material has good extreme pressure and antiwear behavior as lubricating oil additive.
A kind of thiadiazoles derivative containing thiocarbamate of the present invention, is characterized in that this derivative is 2,5-, bis-N, N '-dialkyldithiocarbamacompositions alkyl sulfide ether-1, and 3,4-thiadiazoles, has following structural formula:
In formula, R1, R2, R3 and R4 are the straight or branched alkyl of identical or different C1～C28, and n is 1～4.
The preparation method of a kind of thiadiazoles derivative containing thiocarbamate provided by the invention:
A, 2,5-dimercapto-1,3,4-thiadiazole and N, N '-dialkyldithiocarbamacompositions alkyl chloride (or bromine) is 1:2.0～1 for ester in molar ratio: 2.3 proportionings;
B, by 2,5-dimercapto-1,3,4-thiadiazoles and N, N '-dialkyldithiocarbamacompositions alkyl chloride (or bromine) joins in reaction medium for ester, adds catalyzer in reaction medium simultaneously, under 10～160 DEG C of temperature condition, react 1～10 hour, obtain reactant;
C, reactant is filtered, washs, removes reaction medium, vacuum-drying must be containing the thiadiazoles derivative product of thiocarbamate;
Described N, N '-dialkyldithiocarbamacompositions alkyl chloride (or bromine) for the structural formula of ester is:
In formula, R1, R2, R3 and R4 are the straight or branched alkyl of identical or different C1～C28, and n is 1～4.
Described reaction medium is acetone or tetrahydrofuran (THF) or benzene or toluene or methyl alcohol or ethanol or Virahol or N, N '-dimethyl formamide.
Described 2,5-dimercapto-1,3,4-thiadiazole (mol) is 1:500～1:1800 with the ratio of reaction medium (mL).
Described catalyzer is sodium bicarbonate or sodium carbonate or pyridine or diethylamine or triethylamine or sodium hydroxide or potassium hydroxide.
Described 2, the mol ratio of 5-dimercapto-1,3,4-thiadiazole and catalyzer is 1:0.1～1:2.
Containing the thiadiazoles derivative of thiocarbamate, as extreme pressure anti-wear additives, the addition in lubricating oil is 0.05wt%～10wt%.
The present invention can represent with chemical equation below containing the preparation method of the thiadiazoles derivative of thiocarbamate:
Feature of the present invention is: in thiadiazoles, having introduced containing sulfo-carbamate groups oil-soluble group is extreme-pressure anti-wear group, and this thiadiazoles derivative can be dissolved in lubricating oil, makes it have splendid extreme pressure and antiwear behavior.Can add to separately in lubricating oil as extreme-pressure anti-friction additive, also can with other lubricating oil additive compound use, play wear-resistant synergy.
Embodiment
Below by specific preparation with should be used for illustrating containing the synthetic of the thiadiazoles derivative of thiocarbamate and in application aspect extreme pressure and antiwear behavior, but be not limited to following examples.
Embodiment 1
By 30.0g2,5-dimercapto-1,3,4-thiadiazoles joins in 100mL reaction medium toluene, under stirring, add 8.0g sodium hydroxide catalyst, be heated to after 60 DEG C, slowly drip 152.0gN, N '-diisooctyl dithiocarbamic acid ethyl chloride, for ester toluene solution, is warmed up to 90 DEG C after dropwising, react 5 hours, to be cooled to room temperature, filter out a small amount of insoluble substance, be then washed till neutrality with distilled water, steaming desolventizes, and vacuum-drying obtains the thiadiazoles derivative product that yellow oily liquid contain thiocarbamate.
Embodiment 2
By 15.0g2,5-dimercapto-1,3,4-thiadiazoles joins in 100mL reaction medium ethanol, under stirring, add 10.1g Triethylamine catalyst, be heated to after 60 DEG C, slowly drip 59.7gN, N '-second, n-butyl dithiocarbamate methyl brominated esters benzole soln, after dropwising, be warmed up to 75 DEG C, react 4 hours, to be cooled to room temperature, filter out a small amount of insoluble substance, then be washed with distilled water to neutrality, steaming desolventizes, and vacuum-drying obtains the thiadiazoles derivative product that weak yellow liquid contains thiocarbamate.
Embodiment 3
By 15.0g2, 5-dimercapto-1, 3, 4-thiadiazoles joins 150mL N, in N '-dimethyl formamide, under stirring, add 8.4g sodium bicarbonate catalyzer, be heated to after 90 DEG C, slowly drip 81.6gN, N '-dioctyl dithiocarbamic acid Butyryl Chloride is for ester N, N '-dimethyl formamide solution, after dropwising, be warmed up to 155 DEG C, react 6 hours, to be cooled to room temperature, filter out a small amount of insoluble substance, then be washed with distilled water to neutrality, steaming desolventizes, vacuum-drying, obtain the thiadiazoles derivative product that yellow liquid contains thiocarbamate.
Embodiment 4
By 15.0g2,5-dimercapto-1,3,4-thiadiazoles joins in 180mL reaction medium acetone, adds 7.9g pyridine catalyst under stirring, slowly drips 45.2gN, N '-dipropyl disulfide, for carboxylamine ethyl chloro ester acetone soln, is warmed up to 45 DEG C after dropwising, react 4 hours, to be cooled to room temperature, filter out a small amount of insoluble substance, be then washed with distilled water to neutrality, steaming desolventizes, vacuum-drying, obtains the thiadiazoles derivative product that weak yellow liquid contains thiocarbamate.
The thiadiazoles derivative product containing thiocarbamate respectively embodiment 1-4 being obtained carries out column chromatographic isolation and purification, warp is to C, H, N, S ultimate analysis, draw table 1 result, from results of elemental analyses, C, the H of product, N, S element all conform to substantially with theoretical value, and absolute error is in allowed band.
Table 1: results of elemental analyses (being calculated value in bracket)
| Embodiment | C（％） | H（％） | N（％） | S（％） |
| 1 | 46.25（46.99） | 7.13（7.44） | 5.29（5.48） | 21.97（21.93） |
| 2 | 40.56（40.74） | 6.05（6.17） | 8.72（8.64） | 34.28（34.57） |
| 3 | 46.54（46.38） | 7.44（7.37） | 4.89（4.92） | 19.57（19.68） |
| 4 | 38.51（38.42） | 5.82（5.69） | 9.88（9.96） | 38.93（39.85） |
Performance evaluation to the thiadiazoles derivative product containing thiocarbamate:
Test oil is that the product that embodiment 1 and 2 is obtained is dissolved in hydrogenated base oil, and addition is 1.0wt%.
Experiment is used lever four-ball friction and wear test machine, steel ball is II level GCr15 bearing steel ball (φ 12.7mm), at ambient temperature, rotating speed is to move under 1450r/min, according to GB/T3142-1982(1990) standard, carry out last non seizure load (PB value) mensuration to testing oil, the results are shown in Table 2.
On the long mill of mechanical type four balls wearing resistance test machine, according to SH/T0189-1992(392N) standard carried out the test of long mill to testing oil, and steel ball is II level GCr15 bearing steel ball (φ 12.7mm), and test conditions is rotating speed 1200r/min, 75.1 DEG C of temperature, the time is 60min.Wear scar diameter (WSD) the results are shown in Table 2.
Test-results shows, the thiadiazoles derivative product containing thiocarbamate of the present invention adds in lubricating oil, makes lubricating oil have good extreme pressure and antiwear behavior.
Table 2: the wear-resistant data comparison of various materials
| Additive | Concentration (wt%) | P BValue (N) | WSD（mm） |
| Hydrogenated base oil | 100 | 588 | 0.715 |
| Embodiment 1 | 1.0 | 980 | 0.492 |
| Embodiment 2 | 1.0 | 921 | 0.537 |
In addition, according to GB/T5096-1985(1991) standard method, carry out anti-copper corrosion performance measurement to testing oil, at 100 DEG C, constant temperature 3 hours, is all chosen as 2A level to the corrosion of copper sheet.
Claims (3)
1. containing a thiadiazoles derivative for thiocarbamate, it is characterized in that: this derivative is 2,5-, bis-N, N '-dialkyldithiocarbamacompositions alkyl sulfide ether-1,3,4-thiadiazoles, has following structural formula:
In formula, R1, R2, R3 and R4 are the straight or branched alkyl of identical or different C1～C28, and n is 1～4.
2. a preparation method for the thiadiazoles derivative containing thiocarbamate claimed in claim 1, is characterized in that:
A, 2,5-dimercapto-1,3,4-thiadiazole and N, N '-dialkyldithiocarbamacompositions alkyl chloride or brominated esters are 1:2.0～1 in molar ratio: 2.3 proportionings;
B, by 2,5-dimercapto-1,3,4-thiadiazoles and N, N '-dialkyldithiocarbamacompositions alkyl chloride or brominated esters join in reaction medium, add catalyzer in reaction medium simultaneously, under 10～160 DEG C of temperature condition, react 1～10 hour, obtain reactant;
C, reactant is filtered, washs, removes reaction medium, vacuum-drying must be containing the thiadiazoles derivative product of thiocarbamate;
Described N, the structural formula of N '-dialkyldithiocarbamacompositions alkyl chloride or brominated esters is:
In formula, R1, R2, R3 and R4 are the straight or branched alkyl of identical or different C1～C28, and n is 1～4;
Described reaction medium is acetone or tetrahydrofuran (THF) or benzene or toluene or methyl alcohol or ethanol or Virahol or N, N '-dimethyl formamide;
Described 2,5-dimercapto-1,3,4-thiadiazole (mol) is 1:500～1:1800 with the ratio of reaction medium (mL);
Described catalyzer is sodium bicarbonate or sodium carbonate or pyridine or diethylamine or triethylamine or sodium hydroxide or potassium hydroxide;
Described 2, the mol ratio of 5-dimercapto-1,3,4-thiadiazole and catalyzer is 1:0.1～1:2.
3. an application for the thiadiazoles derivative containing thiocarbamate claimed in claim 1, is characterized in that: containing the thiadiazoles derivative of thiocarbamate, as extreme pressure anti-wear additives, the addition in lubricating oil is 005wt%～10wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310034059.8A CN103965139B (en) | 2013-01-30 | 2013-01-30 | Thiadiazole derivative containing thiocarbamate and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310034059.8A CN103965139B (en) | 2013-01-30 | 2013-01-30 | Thiadiazole derivative containing thiocarbamate and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103965139A true CN103965139A (en) | 2014-08-06 |
| CN103965139B CN103965139B (en) | 2016-03-09 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543099A (en) * | 2016-10-30 | 2017-03-29 | 湖南工程学院 | A kind of Biodegradable lube oil additive 2,5 dialkyl acetamides, 1,3,4 thiadiazoles and preparation method thereof |
| CN110156719A (en) * | 2019-05-31 | 2019-08-23 | 长沙望城石油化工有限公司 | A kind of thiadiazole compound and its preparation method and application containing waste propylhomoserin ester |
| CN111892629A (en) * | 2020-08-18 | 2020-11-06 | 洛阳太平洋联合石油化工有限公司 | Thiadiazole derivative containing molybdenum and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3663561A (en) * | 1969-12-29 | 1972-05-16 | Standard Oil Co | 2-hydrocarbyldithio - 5 - mercapto-1,3,4-thiadiazoles and their preparation |
| US5026865A (en) * | 1985-07-26 | 1991-06-25 | R. T. Vanderbilt Company, Inc. | Substituted 2,5-dimercapto-1,3,4-thiadiazoles and lubricating compositions containing same |
| US20020058594A1 (en) * | 1999-10-20 | 2002-05-16 | R.T. Vanderbilt Company, Inc. | Thiadiazole dimer additives and lubricating compositions containing the same |
| CN101787322A (en) * | 2010-03-18 | 2010-07-28 | 上海交通大学 | Extreme pressure antiwear agent containing ester-based thiadiazole derivative and preparation method thereof |
| CN101857580A (en) * | 2010-04-27 | 2010-10-13 | 华东交通大学 | A kind of thiadiazole derivative containing hydroxyl and xanthic acid and its preparation method and application |
-
2013
- 2013-01-30 CN CN201310034059.8A patent/CN103965139B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3663561A (en) * | 1969-12-29 | 1972-05-16 | Standard Oil Co | 2-hydrocarbyldithio - 5 - mercapto-1,3,4-thiadiazoles and their preparation |
| US5026865A (en) * | 1985-07-26 | 1991-06-25 | R. T. Vanderbilt Company, Inc. | Substituted 2,5-dimercapto-1,3,4-thiadiazoles and lubricating compositions containing same |
| US20020058594A1 (en) * | 1999-10-20 | 2002-05-16 | R.T. Vanderbilt Company, Inc. | Thiadiazole dimer additives and lubricating compositions containing the same |
| US6620771B2 (en) * | 1999-10-20 | 2003-09-16 | R. T. Vanderbilt Company, Inc. | Thiadiazole dimer additives and lubricating compositions containing the same |
| CN101787322A (en) * | 2010-03-18 | 2010-07-28 | 上海交通大学 | Extreme pressure antiwear agent containing ester-based thiadiazole derivative and preparation method thereof |
| CN101857580A (en) * | 2010-04-27 | 2010-10-13 | 华东交通大学 | A kind of thiadiazole derivative containing hydroxyl and xanthic acid and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 姚俊兵等: "润滑油脂抗磨极压添加剂研究进展", 《润滑油》, vol. 21, no. 3, 30 June 2006 (2006-06-30), pages 29 - 37 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543099A (en) * | 2016-10-30 | 2017-03-29 | 湖南工程学院 | A kind of Biodegradable lube oil additive 2,5 dialkyl acetamides, 1,3,4 thiadiazoles and preparation method thereof |
| CN110156719A (en) * | 2019-05-31 | 2019-08-23 | 长沙望城石油化工有限公司 | A kind of thiadiazole compound and its preparation method and application containing waste propylhomoserin ester |
| CN111892629A (en) * | 2020-08-18 | 2020-11-06 | 洛阳太平洋联合石油化工有限公司 | Thiadiazole derivative containing molybdenum and preparation method and application thereof |
| CN111892629B (en) * | 2020-08-18 | 2023-08-22 | 洛阳太平洋联合石油化工有限公司 | Molybdenum-containing thiadiazole derivative, and preparation method and application thereof |
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