• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    This invention relates to lubricating oils. The lubricating composition includes mineral oil containing 0.1-3.0 wt.% Of the additive - compounds of total f-ly 1 or P @, where R 1 is H, C 1-4 -alkoxycarbonyl, NO 2 R 2 and R 3 - independent and equal to H, C 1-18 - alkyl C 12-18 - alkenyl, phenyl, dodecylphenyl, benzyl 2-methoxyethyl C 1-4 - alkoxycarbonylmethyl R 4 - C 18 - alkyl or alkenyl. This additive improves the anti-corrosion, anti-oxidation and anti-wear properties of lubricating oil. 4 tab.
    公开号:SU1498394A3
    申请号:SU864027563
    申请日:1986-05-22
    公开日:1989-07-30
    发明作者:Каменцинд Хуго；Филлипс Емайр
    申请人:Циба - Гейги Аг (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to a composition of lubricating oils containing additives based on oil-soluble derivatives of benzothiazolin-2-thione.
    The mineral oil-based lubricant composition according to the invention contains as an additive 0.1 to 3% by weight of a compound as used;
     i-fl 1
    C-S (j) l: l J
    f
    Q
    CHj-N (R2) (R3)
    S X-CHj-.V-OIj-N S (II)
    ) t
    ..nrl
    where R is hydrogen, C —C-alkoxycarbonyl or nitro;
    R
    j
    Rjindependently from each other hydrogen, s;, - C, -al to il.
    avu pods for growing
    Q
    NS (II)
    rl
    icar-;
    ug
    R, -alkenip, phenyl, dodecylphenyl, benzyl, 2-methoxyethyl or C, -C-alkoxycarbonylmethyl; C, -alkyl or alkenyl.
    Lubricant dosap obtained by mixing the additive with the base oil.
    You can also predissolve the additives in a small amount of oil and mix this concentrate into the lubricant.
    In addition to the additives of formulas I, II, the lubricant composition may also contain other additives that are common for lubricating oils, for example, antioxidants, metal passivators, corrosion inhibitors, and in4 improving agents.
    WITH
    00
    with
    QD 4
     C / 1
    deck, equipment, equipment (its freezing point, sprinklers, detergents or other additives to protect against wear.
    As antioxidants can be used:
    a) Alkylated and non-alkylated aromatic amines and their mixtures, for example dioctyldiphenylamine, mono-tert-ox t ylphenyl-o (- α-naphty. - butyl-p-phenylenediamine;
    b) alkylated phenols, for example 2,6-di-tert-butyl-p-cresol, 4,4 bis- (2,6-diisopropylphenol), 2,4,6-triisopropylphenol, 2,2-thio-bis- (4- methyl 6-tert-butylphenol), 4,4 - methyl oil bis (2,6-di-tert-butylphenol);
    c) esters of thiodipropionic acid or thiodiocetic acid, for example, dnapurylthiodipropionate or dioctnlthiodiacetate;
    d) salts of carbamic and dithiophosphoric acid, for example, antimony diamylditi carbamate, diamyldithiophosphate
    .)
    Examples of additives that improve the viscosity index: polymethacrylates, copolymers of vinylpyrrolidone / methacrylate, polybuttons, copolymers of olefins, copolymers of styrene / acrylate.
    Examples of lowering point agents: alkylated naphthalenes, alkylated phenols, polymethacrylates.
    Examples of detergents and dispersing agents: amides of polyalkenyl succinic acid, oil-soluble metallic soap, such as Ca-, Ba-, Mg- and Ai carboxylates, -phenols or -sulfonat
    Sulfur and / or phosphorus and / or halogen containing compounds, such as sulfonated vegetable oils, dialkyl dithiophosphates of zinc, tritolyl phosphate, chlorinated paraffins, alkyl and aryl disulfides can also be used as additives to reduce wear.
    Compounds of formula 1 are prepared by reacting 2-mercaptobenzothiazole (III) with monoamine R -NTi-R and aldehyde R 2 - CHO.
    shshka
    Examples of metal metal passivators:
    a) for copper, benzotriazole, tett ragidrobenzotriazole, 2-mercaptobenzotriazole, 2,5-dimercaptothiadiazole, salicylidenepropylene diamine, salicylaminoguanidine salts;
    b) for lead, derivatives of sebicinic acid, quinizarin, propyl gallate.
    Examples of pickling inhibitors are: a) organic acids, their esters, metal salts, and hydrogen subrides, for example, N-oleyl-sarcosine, sorbinate-mono-oleate, lead naphthenate, dodecyl-sodium anhydride;
    b) nitrogen-containing compounds, for example, primary, secondary or tertiary aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids, for example, oil soluble alkyl ammonium carboxylates; heterocyclic compounds, for example, substituted imidazolines and oxazolines;
    c) sulfur-containing compounds, for example barium dinoniphaphthalene sulfonates, petroleum sulfonates.
    (w) -RZ-CHO + E -NH-R - I
    The amine can be primary or secondary monoamino. In this case, it works well with an equimolar ratio or with a slight excess of aldehyde. Non-polar solvents, especially toluene, c-cyclohexane or ligroin are preferred as the reaction medium. But polar solvents can also be used, especially alcohols, such as ethanol or methanol. You can also first form the corresponding amine salt III, which is soluble in water, and then convert the salt with the aldehyde in an aqueous medium.
    Compounds of formula II are prepared by reacting 2-mercaptobenzothiazole with. RI is CHO and primary monoamine Rj-NH in a molar ratio of 2: 2:
    2 III + 2 R ,, - CHO + R, - NH - II
    The following examples illustrate the preparation of the additive. Temperatures are indicated in ° C.
    N
    N
    five
    Example 1. Mannich reactions
    in methanol / water.
    To a suspension of 250.8 g (1.5 mol) of 2-mercaptobenzothiazole in 1500 ml of methanol is added 112.8 ml of a 37% aqueous formaldehyde solution (1.5 mol) and put under stirring 362, А MP (1.5) mol) 3-bis- (2-ethyl-hexyl) -amine. The mixture is stirred for 15 hours and then evaporated in vacuo. 618 g of cumulative 3-Gbis- (2-ethyl-hexyl) -amine of tyl-benzothiazolin-2-thione remain (as a brown-brown oil).
    Calculated,%: C 68.52; H 9.58; N 6.66; S 15.24.
    Found,%: C 68.36; H 9.57; N 6.69; S 15.29.
    Example 2. The mannich reaction in ethanol / water,
    In suspension 33, D5 g (0.2 mol) of 2-mercaptobenzothiazole in 120 ml of ethnol, 18.63 g (0.2 mol) of aniline are added with stirring, and the temperature is reduced to 30 ° C. 16.4 g of a 37% formaldehyde aqueous solution (0.2 mol) are then added for another 30 minutes. The precipitate formed is filtered off and washed with cold ethanol and hexano. 47 g of 3- (phenylaminomethyl) benzothiazolin-2-thione are obtained, which has a melting point of 102-103 ° C.
    Calculated,%: C, 61.74; H 4.44; 10.29; S 23,54o
    Found,%: C 61.53; H 4.43; 10.10; S 23.79.
    Similarly, using technical dodecylaniline (mixture of isomers), 3- (dodecylphenyl aminomethyl) -benzothiazolin-2-tion (as a brown oil) is obtained.
    Example 3. Mannich reaction in toluene / water.
    To a suspension of 16.7 g (0.1 mol) of 2-mercaptobenzothiazole in 40 ml of toluene, 10.12 g (13.7 ml; 0.01 mol) of dipropylamine and 8.3 g (7.6 MP, 0.1 mol) of a 36% aqueous formaldehyde solution. Mixture of in




    vigorously stirred for 5 hours at 30 s. The small aqueous phase is then separated and the toluene phase is introduced into the vacuum :. 26.5 g of a yellow-orange crystallized 3- (dipropylaminomethyl) benzothiazolin-2-thione, which has a melting point of 60-62 ° C, remains.
    0
    five
    0
    Calculated,%: C 50.96; H 7.19; N 9.99; S 22.86.
    Found,%: C 59.82; H 7.20; N 9.89; S 22.86.
    The remaining examples, similar to examples 1-3, are given in table. 1-3, with the following notation: Method A - analogously to Example 1; method B - analogously to example 2; method C is analogous to example 3.
    In the Analysis column, the first line contains the calculated values, and the second - the values found (in%).
    Example 16. Test to reduce wear
    In a suitability test for hsHoca, the standard American Society for Testing Materials Method D 2783-81 using Shell’s four-ball device is used. The main oil is Katenek R 941 Shell. Determine: a) load 5 welding WL as load (in kg) at which 4 balls are welded for 10 seconds, and b) average diameter
    0
    five
    0
    five
    0
    five
    WSD wear at 40 kg load for 1 hour (in mm).
    Example 17. Test for passivating copper.
    A brilliantly polished copper sheet with a size of 100 mm is immersed in turbine oil, which contains 50 rrg of dissolved sulfur and 0.05% Cs-bis (2-ethylhexyl) aminomethyl-benzothiazolin-2-thion. The comparative test does not contain a thiazoline derivative. Samples are heated for 2 hours to 100 C. Then the copper sheet is washed with petroleum ether, dried, and its color is assessed according to ABTASH 130, comparing with the standard color table. The evaluation was carried out in four steps: 1 - no. 2 - moderate fade; 3 - severe fading; 4 - corrosion,
    Example 18. Test for antioxidant properties.
    This method is a modified version of the Oxidation Test in a rotational bomb for mineral oils (ASTM D 2272). The test oil is a motor oil based on a multi-oil oil, which contains half the usual amount of zinc dithiophosphate (0.75%; zinc content is 0.06% based on motor oil). Amendment made |
    to show the potential effect of the subject stabilizer.
    Additives are tested in engine oil in the presence of 2% water, liquid discharged nitrated fraction of motor gasoline as a catalyst (4% of the initial concentration), liquid metal naphthenate as the second catalyst (4% of the initial concentration). The test is completed with a distinct bending of the pressure / time diagram. Listed in table. The 4 results indicate the time (in minutes) before the pressure / time curve bends.
    The test results of the oil with additives are given in Table 4c.
    The results of the comparative tests will show that in comparable concentrations the additive according to the invention is superior to the known compounds.
    The known compounds are less soluble in oil than those described, so that the former are less suitable for use in high concentrations due to the fact that they can precipitate at these concentrations and block the lubricating system, forgetting it.
    Due to the fact that with increasing concentration of the additive in the oil increases
    N (-СНг-СН- (СНг) з-СНз) г
    I SNgSNz
    -N - (- CH, CH, CHj),
    A / C 98/97
    9A
    Mixture:
    ,
    - «™, 1И1
    -IN CiiH25
    mixture of isoners
    -N- (SI jCH jCH, CH,),
    e 1D9839D
    and the effectiveness of stabilization against oxidation, the described compounds are more beneficial than the known ones.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    A lubricant composition containing mineral oil and an additive based on a benzothiazole derivative, characterized in that, in order to study the antiwear, anticorrh ionic and antioxidant properties, the composition as a benzothiazole derivative contains 0.1-3% by weight of a compound formulas
    0
    ".
    c-s
    CH, -K (Ng) (Bz)
    Q
    S N-CH, -N-SI, -to S
    Y y
    S r
    five
    0
    S
    where R is hydrogen, C, -C-alkoxycarbonyl or nitro;
    Rj and RJ are independently of each other hydrogen, alkyl, C ,, - C ,, - alkenyl, phenyl, dodecylphenyl, benzyl, 2-methoxyethyl or C, alkoxycarbonylmethyl; R is C-alkyl or alkenyl.
    Table I
    ArtknHS (ZV
    Jn "read K, K (in conjunction with
    I, / R
    , SYZ
    (csn) 2
    ten
    eleven
    wasp
    I,
    -lI- (CH2-C-0-C4H9) lV
    -at-(
    CBj-ca, -o-e-Cr "(" .- (St.), with
    CH, CH, -CB-ci ,, /, -il
    i ..
    -to
    15
    0:
    SI, (sn, b-sn,
    ) I - (- CH, -CH-CH, CH,) i
    Continued table.
    Output, (g)
    View
    Float point
    Analysis (X)
    one
    Cr stallnzat
    beige colour
    102 106
    62.29 7.84 9.08 62.89 7.66 9.07
    30.78 21.05
    97
    99
    95
    90
    99
    93
    96
    Brown yellow
    Yellow crystal lieat
    Brown to light oil
    Yellow crystal leaat
    Orange oil
    Crystalkzat
    Oexfogo
    colors
    Cornflower yellow oil
    65
    72.80 10.78 4, E9 72.60 10.73 i, 88
    75.36 11.50 3.99 75.56 I, 54 3.98
    63.97 5.37. 9.3g 63.93 5.42, 9.13
    9670.1B 5.35 7.44
    9870.05 5.43 7.37
    65,826,149; 53
    65,906,308,23
    54-57 56,586,656,60
    56,446,706,54
    53.82 6.45 8.97 53.93 6.51 8.75
    IV, 43 11.43
    9.14 9.16
    21.34 21.10
    7.03 17.22
    19.52 19.51
    15.10 15.30
    20.52 19.91
    table 2
    Brown oil
    65.81 9.00 65.95 9.22
    5.68 5.59
    13.01 12.90
    Orange red oil
    61.90 8.44 9.02 13.77 62.12 8.56 8.97 13.55
    U9839A
    12
    Table 3
    T | blot it

    98
    119,174
    117 144

    97 MO
    137 9B 120 J57

    137 I4t 101 114 128
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    同族专利:
    公开号 | 公开日
    BR8602353A|1987-01-21|
    EP0203033A2|1986-11-26|
    US4810399A|1989-03-07|
    EP0203033A3|1989-05-03|
    JPH0784599B2|1995-09-13|
    JPS61271283A|1986-12-01|
    US4737302A|1988-04-12|
    CA1261836A|1989-09-26|
    EP0203033B1|1992-03-11|
    DE3684173D1|1992-04-16|
    US4803001A|1989-02-07|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB1028924A|1962-03-13|1966-05-11|Castrol Ltd|Lubricating compositions containing heterocyclic thio-ethers of saturated carboxylic acids|
    DE3684173D1|1985-05-23|1992-04-16|Ciba Geigy Ag|AMINOMETHYL DERIVATIVES FROM BENZOTHIAZOLINTHION AS A LUBRICANT ADDITIVE.|DE3684173D1|1985-05-23|1992-04-16|Ciba Geigy Ag|AMINOMETHYL DERIVATIVES FROM BENZOTHIAZOLINTHION AS A LUBRICANT ADDITIVE.|
    US4917809A|1986-11-11|1990-04-17|Ciba-Geigy Corporation|High-temperature lubricants|
    US4965005A|1987-09-17|1990-10-23|Ciba-Geigy Corporation|Aminomethyl derivatives of monothiocarbamates and dithiocarbamates as additives for lubricants|
    EP0595771B1|1992-10-30|1996-11-27|Ciba-Geigy Ag|Phosphorfree lubricant-additives|
    CA2160679A1|1993-04-16|1994-10-27|Akzo Nobel N.V.|Liquid stabilizer comprising metal soap and solubilized metal perchlorate|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CH219985|1985-05-23|
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