CN1037616C - Multifunctional additive for lubricating oil - Google Patents

Multifunctional additive for lubricating oil Download PDF

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CN1037616C
CN1037616C CN93108557A CN93108557A CN1037616C CN 1037616 C CN1037616 C CN 1037616C CN 93108557 A CN93108557 A CN 93108557A CN 93108557 A CN93108557 A CN 93108557A CN 1037616 C CN1037616 C CN 1037616C
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formula
lubricating oil
methyl
benzotriazole
multifunctional additive
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CN1097461A (en
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任天辉
金芝珊
刘维民
薛群基
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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Abstract

The present invention relates to a novel compound, namely S-(1H-benzotriazole-1-group) methyl, N, N-dialkyl dithiocarbamate used as a multifunctional additive for lubricant grease. The present invention enables lubricant grease to have the advantages of favorable wear resistance, favorable extreme pressure resistance, favorable corrosion resistance and high heat stability, and to have the characteristics of no zinc, no phosphorus and multiple function.

Description

Multifunctional additive for lubricating oil
A kind of no zinc, without phosphorus multifunctional additive for lubricating oil and its production and use have been the present invention relates to.
The most frequently used antioxygen, the corrosion inhibitor of engine oil is zinc dialkyl dithiophosphate (200P).It can bring into play antioxygen, anticorrosive effect below 160 ℃, and has the extreme-pressure anti-wear effect concurrently.But temperature is higher than 160 ℃, and its effect descends greatly, even corroding metal.To the Hyundai Motor engine of waste gas conversion system is housed, element phosphor can make the poisoning of catalyst in this device especially.So, for the harsh day by day requirement in environment aspect and the consideration of poisoning aspect, seek not have zinc, multifunctional additive for lubricating oil without phosphorus and that can replace 200P is present pressing for.
Thiocarbamic acid derivatives has become a purposes class additive very widely.They are as oxidation inhibitor, and metal passivator and extreme pressure anti-wear additives successfully are applied to rubber, plastics and lubricating grease.
Benzotriazole and derivative thereof also are the lubricating oil and grease additives of using always, have good anticorrosively, antirust, anti-oxidant, and metal causes blunt and multiple function such as resistance to wear.
The object of the present invention is to provide thiocarbamate that contains benzotriazole functional group of a kind of novelty and its production and use.
The present invention realizes by following measure:
The novel S-with general formula (I) (1H-benzotriazole-1-yl) methyl, N, the N-dialkyl dithio amino formate is found:
R in the formula (I) 1, R 2Be C identical or inequality 2～C 10Alkyl, perhaps R 1R 2For-(CH 2) n-(n=4～6).
The concrete grammar of preparation formula (I) comprising:
A) the 1-chloromethyl benzo triazole of the dialkylamine dithio formate of use formula (II) and formula (III).
Figure C9310855700062
M is Na in the formula (II) +, K +, NH 4 +Or R 1R 2HH 2 +
B) in the presence of reaction medium;
C) normal temperature-100 ℃ following reaction is 1～10 hour.
Reaction medium is fed dimethyl sulfoxide, 1,4-dioxane or dimethyl formamide for the tetrahydrochysene furan in the method for preparation formula (I).
In the method for preparation formula (I), formula (II) compound (mol): reaction medium (ml) is 1: 500～2000.
The synthetic of the thiocarbamate that contains benzotriazole functional group involved in the present invention can be represented with following chemical equation:
Figure C9310855700063
The S-of general formula (I) (1H-benzotriazole-1-yl) methyl, N, N-dialkyl dithio amino formate can be used as a kind of multifunctional lubricant fat additives and use.
Formula of the present invention (I) compound can use separately, adds in mineral oil, synthetic oil, the lubricating grease, can obtain good anti-extreme pressure, and antiwear and friction reduction property also has good anti-oxidant, anticorrosive and high thermal stability simultaneously.
The addition of formula of the present invention (I) compound is 0.1wt%～20wt%.
Formula of the present invention (I) compound also can with the compound use of other lubricating oil and grease additive, can reach synergy synergy or obtain and can be fit to the no zinc of present internal combustion (IC) engine lubricating oil demand for development, without phosphorus engine lubrication oil production.
Formula of the present invention (I) compound is the very effective no zinc of a class, without phosphorus multifunctional lubricant fat additives, and concrete synthetic has: S-(1H-basis and triazole-1-yl) methyl, N, N-diethyldithiocarbamate.S-(1H-basis and triazole-1-yl) methyl, N, N-second, n-butyl dithiocarbamate ester.S-(1H-basis and triazole-1-yl) methyl, N, N-di-n-octyl dithiocarbamate.S-(1H-basis and triazole-1-yl) methyl, N, N-two positive decyl dithiocarbamates.S-(1H-basis and triazole-1-yl) methyl, the piperidines dithio formate.
In order to understand the present invention better, describe by example.Example 1:
In the 20ml dimethyl sulfoxide (DMSO), add 3.34g (0.02mol) 1-chloromethyl benzo triazole, after stirring at room is molten extremely entirely, add 4.44g (0.02mol) diethylamide dithio formic acid diethyl ammonium salt, 50 ℃ of constant temperature, stirring reaction 6 hours.The reaction mixture extracted with diethyl ether, washing then, anhydrous MgSO 4Drying is filtered, and filtrate steaming is removed ether solvent, promptly gets white solid product: S-(1H-benzotriazole-1-yl) methyl, N, N-diethyldithiocarbamate.Example 2:
Under the ice-water bath cooling,, under agitation drop in the 100ml tetrahydrofuran solution of 0.1mol (12.9g) Di-n-Butyl Amine the 50ml tetrahydrofuran solution of 0.05mol (3.8g) dithiocarbonic anhydride.Behind the room temperature reaction 2 hours, add 0.05mol (8.35g) 1-chloromethyl benzo triazole, back flow reaction 4 hours.Filter, filtrate steaming gets light yellow solid after removing tetrahydrofuran solvent, promptly gets white powdered solid product: S-(1H-benzotriazole-1-yl) methyl, N, N-second, n-butyl dithiocarbamate ester with sherwood oil (60～90 ℃) washing.Example 3:
Under the ice-water bath cooling, the 50ml tetrahydrochysene furan of 0.05mol (3.8g) dithiocarbonic anhydride is fed solution, drop in the 200ml tetrahydrofuran solution of 0.1mol (24.1g) two n-octyl amine under stirring.Reaction added 0.05mol (8.35g) 1-chloromethyl benzo triazole, back flow reaction 8 hours after 2 hours under the room temperature.Filter, filtrate steaming is used the ether dissolution residue after removing tetrahydrofuran solvent, washing, anhydrous MgSO 4Drying is filtered, and steams except that getting light yellow viscous liquid product: S-(1H-benzotriazole-1-yl) methyl, N, N-di-n-octyl dithiocarbamate behind the ether.Example 4:
In the 200ml tetrahydrofuran (THF), add 0.05mol (8.35g) 1-chloromethyl benzo triazole, be stirred to the two n-Decylamine base dithio formic acid sylvite that complete molten back adds 0.05mol under the room temperature, back flow reaction 10 hours.Filter, remove the tetrahydrofuran solvent in the filtrate after, add ether dissolution, after the washing, anhydrous MgSO 4Drying is filtered, and steams and removes ether, gets light yellow viscous liquid product: S-(1H-benzotriazole-1-yl) methyl, N, N-two positive decyl dithiocarbamates.Example 5:
At 100ml 1, add 0.05mol (8.25g) 1-chloromethyl benzo triazole in the 4-dioxane, be stirred to complete molten after, add 0.05mol) (9.2g) piperidines dithio formic acid sodium salt, 50 ℃ of reactions of constant temperature 2 hours.Steam and remove 1, behind the 4-dioxane solvent, use the chloroform dissolution residual substance, washing, anhydrous MgSO 4Drying is filtered, and steaming removes chloroform and promptly gets white solid product: S-(1H-benzotriazole-1-yl) methyl, piperidines dithio formate.
The product that obtains in the above-mentioned example is through C, H, N ultimate analysis, 1HNNR, 13CNNR and 1R spectroscopic analysis conclusive evidence are the compounds that will obtain.
Table 1 results of elemental analyses
Example %C %H %N
Example 1 51.20 (51.40) 5.65 (5.75) 20.21 (19.93)
Example 2 56.89 (57.14) 7.14 (7.14) 16.85 (16.67)
Example 3 63.95 (64.24) 9.01 (8.99) 12.48 (12.49)
Example 4 66.45 (66.67) 9.50 (9.52) 11.20 (11.11)
In example 5 53.11 (53.40) 5.35 (5.40) 19.07 (19.18) its brackets is calculated value.
Table 2 1The HNNR analytical results
Example fragrance-H N-CH2-S fat-H
Example 1 8.04 (d, 1H) 7.94 (d, 1H) 6.80 (S, 2H) 4.05 (q, and 2H) 3.69 (q, 2H)
7.50(t，1H)7.38(t，1H) 1.29(t，3H)1.23(q，3H)
Example 2 8.05 (d, 1H) 7.94 (d, 1H) 6.01 (S, 2H) 3.97 (t, and 2H) 3.61 (t, 2H)
7.50(t，1H)7.38(t，1H) 1.71(m，2H)1.62(m，2H)
1.37(m，2H)1.30(m，2H)
0.97(t，3H)0.90(t，3H)
Example 3 8.04 (d, 1H) 7.94 (d, 1H) 6.81 (S, 2H) 3.96 (t, and 2H) 3.60 (t, 2H)
7.50(t，1H)7.38(t，1H) 1.70(m，2H)1.63(m，2H)
1.30(m，20H)
0.90(t，3H)0.86(t，3H)
Example 4 8.04 (d, 1H) 7.94 (d, 1H) 6.01 (S, 2H) 3.96 (t, and 2H) 3.60 (t, 2H)
7.50(t，1H)7.08(t，1H) 1.70(m，2H)1.63(m，2H)
1.30(m，28H)
0.88(m，6H)
Example 5 0.04 (d, 1H) 7.94 (d, 1H) 6.82 (S, 2H) 4.30 (t, and 2H) 3.83 (t, 2H)
7.50 (t, 1H) 7.38 (t, 1H) 1.71 (m, 4H) 1.61 (m, 2H) chemical shift (8) unit is ppm.Above result is on Brucker AN-400 type superconduction nuclear-magnetism filter spectrometer, is interior mark with TMS, and deuterochloroform is to obtain under the condition of solvent.
Table 3 13The CNNR analytical results
Example C-3a C-4 C-5 C-6 C-7 C-72 C-8 C9 other-C
Example 1 146.0 119.8 124.2 127.6 111.2 132.4 53.8 191.4 50.3 47.0
12.6 11.4
Example 2 146.1 119.8 124.2 127.7 111.3 132.5 54.0 191.8 55.8 52.7
29.4 28.2
20.6 19.9
13.3 13.6
Example 3 146.0 119.8 124.2 127.6 111.2 132.4 53.9 191.7 56.0 52.9
31.7 31.6
29.1 28.9
27.4 26.7
26.6 26.0
22.6 22.5
14.0
Example 4 146.0 119.3 124.2 127.6 111.2 132.4 53.9 191.7 56.0 52.9
31.7 31.6
29.1 28.9
27.4 26.7
26.6 26.0
24.5 23.2
22.6 22.5
14.0
Example 5 146.0 119.7 124.2 127.6 111.2 132.4 53.9 191.1 53.7 51.6
26.0 25.3
24.0 above data are with OCCL on Brucker AN-400 superconduction magnetic resonance spectroscopy instrument 3Chemical shift be 77.0 to obtain.The evaluation of product:
According to the GB3142-82 standard, to commodity 200P and example 2, example 3, the product that obtains in the example 4 are dispersed in the last non seizure load (P in the chemical pure whiteruss 8Value) carried out measuring (addition is 1wt%).Testing used four-ball tester is English home-made Seta-Shell type four ball EP lubricant test machines.Testing used steel ball is the secondary standard steel ball (φ 12.7mm, GCr15 bearing steel, HRc are 59-61) that Lanzhou Berings Factory produces.Experiment is at room temperature carried out, and rotating speed is 1480 rev/mins.The results are shown in Table 4.
Table 4 last non seizure load (P 6Value) evaluation result
Additive concentration (wt%) PB value (kg)
White oil 100 38
200P 1 70
Example 21 70
Example 31 65
Example 41 65
Measured the product that obtains in example 2, example 3, the example 4 with above-mentioned four-ball tester simultaneously and be dispersed in the white oil, under different load, addition is 1wt%, and rotating speed is 1480 rev/mins, and experimental period is 30 minutes wear scar diameters (WSD) under the condition.The result is plotted among Fig. 1.The result of table 4 and Fig. 1 shows that this series benzotriazole derivative has the performance better than 200P aspect the supporting capacity and the effect of resistance to wearing.
In addition, investigated the thermal stability of this series compound on thermal analyzer, the result shows that this series compound has good thermostability, and decomposition temperature is in 250～280 ℃ of scopes.And measured the product that obtains in example 2, example 3, the example 4 according to the G85096-85 standard method and be dispersed in corrosion resistance in the liquid stone film.The oil sample of each product 1wt% as can be known is respectively 1a level, 2b level, 2b level at 3 hours corrosion levels to copper sheet of 100 ℃ of following constant temperature after measured.Illustrate that this series compound has good corrosion resistance.
Fig. 2 is example 2 products: 10The CHNR spectrogram
Fig. 3 is example 2 products 1The HNNR spectrogram
Fig. 4 is example 2 products 1HNNR amplifies collection of illustrative plates

Claims (10)

1, a kind of multifunctional additive for lubricating oil is characterized in that S-(1H-benzotriazole-1-yl) methyl by general formula (I), N, and the N-dialkyl dithio amino formate is formed, R in the formula 1, R 2Be alkyl identical or inequality, perhaps R 1R 2For-(CH 2) n-, n=4～6.
2, multifunctional additive for lubricating oil as claimed in claim 1, the compound that it is characterized in that formula (I) are S-(1H-benzotriazole-1-yl) methyl, N, N-diethyldithiocarbamate.
3, multifunctional additive for lubricating oil as claimed in claim 1, the compound that it is characterized in that formula (I) are S-(1H-benzotriazole-1-yl) methyl, N, N-second, n-butyl dithiocarbamate ester.
4, multifunctional additive for lubricating oil as claimed in claim 1, the compound that it is characterized in that formula (I) are S-(1H-benzotriazole-1-yl) methyl, N, N-di-n-octyl dithiocarbamate.
5, multifunctional additive for lubricating oil as claimed in claim 1, the compound that it is characterized in that formula (I) are S-(1H-benzotriazole-1-yl) methyl, N, N-two positive certain herbaceous plants with big flowers base dithiocarbamates.
6, multifunctional additive for lubricating oil as claimed in claim 1, the compound that it is characterized in that formula (I) are S-(1H-benzotriazole-1-yl) methyl, the piperidines dithio formate
7, the preparation method of the multifunctional additive for lubricating oil of general formula (I) is characterized in that
Figure C9310855700031
A) M is Na in the 1-chloromethyl benzo triazole of the dialkyl dithiocarbamate of use formula (II) and formula (III), formula (II) +, K +, NH 4 +Or R 1R 2NH 2 +, formula (II) is 1: 0.9～1.1 with the mol ratio of formula (III);
B) in the presence of reaction medium, formula (II) compound (mol): reaction medium (ml) is 1: 500～2000;
C) normal temperature-100 ℃ following reaction is 2～10 hours.
8, the preparation method of multifunctional additive for lubricating oil as claimed in claim 7 is characterized in that reaction medium is a tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), 1,4-dioxane or dimethyl formamide.
9, the S-of formula (I) (1H-benzotriazole-1-yl) methyl, N, the method for N-dialkyl dithio amino formate multifunctional additive for lubricating oil is characterized in that R in the formula Chinese style 1, R 2Be alkyl identical or inequality, perhaps R 1R 2For-(CH 2) n-, n=4～6.
10, method as claimed in claim 9 is characterized in that S-(1H-benzotriazole-1-yl) methyl of formula (I), N, the N-dialkyl dithio amino formate can with the compound use of other lubricating oil additive.
CN93108557A 1993-07-15 1993-07-15 Multifunctional additive for lubricating oil Expired - Fee Related CN1037616C (en)

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Publication number Priority date Publication date Assignee Title
CN102746279A (en) * 2011-04-19 2012-10-24 中国科学院兰州化学物理研究所 Benzotriazole group-containing ionic liquid and its preparation method and use
CN102321262B (en) * 2011-07-14 2013-01-23 厦门欧德力汽车用品有限公司 Automobile rubber and plastic protective agent and preparation method thereof
CN108048163B (en) * 2018-01-19 2021-02-26 东莞理工学院 Dithiocarbamic acid group s-triazine derivative multifunctional lubricating oil additive and preparation method and application thereof
CN111363602B (en) * 2020-03-17 2022-03-29 派默(苏州)新材料有限公司 Multifunctional oil additive and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4789747A (en) * 1980-11-05 1988-12-06 Basf Aktiengesellschaft Control of unwanted plant growth with 2-aryloxy-2-azolylalkanecarboxamides, herbicides containing them, and the manufacture thereof
EP0433842A2 (en) * 1989-12-21 1991-06-26 ZAMBON GROUP S.p.A. 1,2,3-Triazole derivatives active as inhibitors of the enzyme HMG-COA reductase and pharmaceutical compositions containing them
US5133900A (en) * 1987-03-16 1992-07-28 King Industries, Inc. Thermooxidatively stable compositions
US5219478A (en) * 1991-12-12 1993-06-15 Exxon Research And Engineering Co. Lubricating oil containing O-alkyl-N-alkoxycarbonylthionocarbamate salts of dithiobenzoic acid
EP0546829A1 (en) * 1991-12-12 1993-06-16 Exxon Research And Engineering Company Lubricating oil containing antiwear/antioxidant additive

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4789747A (en) * 1980-11-05 1988-12-06 Basf Aktiengesellschaft Control of unwanted plant growth with 2-aryloxy-2-azolylalkanecarboxamides, herbicides containing them, and the manufacture thereof
US5133900A (en) * 1987-03-16 1992-07-28 King Industries, Inc. Thermooxidatively stable compositions
EP0433842A2 (en) * 1989-12-21 1991-06-26 ZAMBON GROUP S.p.A. 1,2,3-Triazole derivatives active as inhibitors of the enzyme HMG-COA reductase and pharmaceutical compositions containing them
US5219478A (en) * 1991-12-12 1993-06-15 Exxon Research And Engineering Co. Lubricating oil containing O-alkyl-N-alkoxycarbonylthionocarbamate salts of dithiobenzoic acid
EP0546829A1 (en) * 1991-12-12 1993-06-16 Exxon Research And Engineering Company Lubricating oil containing antiwear/antioxidant additive

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