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    • 专利摘要:
    1523054 Overbased materials; lubricants LIQUICHIMICA ROBASSOMERO SpA and VSES INST PO PERERAB NEFTI VNIIINP 7 July 1976 [14 July 1975] 28340/76 Headings C4X and CSF In a process for the preparation of detergent additives for lubricating oils of the type in which an alkylphenol sulphide is reacted with an alkaline earth and carbonated, the water produced being distilled out and the product filtered and separated, the reaction is carried out in a hydrocarbon solvent containing 6 to 12 carbon atoms, in the presence of a promoter that comprises a primary or secondary alkylamine having no more than 20 carbon atoms, a polyalkyleneamine in which there are 2 to 6 nitrogen atoms and the alkylene radical has no more than 5 carbon atoms, an amino acid of 2 to 12 carbon atoms, an amino-alcohol or polyalkanolamine of 2 to 12 carbon atoms or a mono- or polyamide or imide with alkyl radicals of no more than 100 carbon atoms. The alkaline earth may be calcium oxide or hydroxide. Methanol may be used as co-promoter.
    公开号:SU644811A1
    申请号:SU762331672
    申请日:1975-07-14
    公开日:1980-02-05
    发明作者:Педитто Андреа；Фоссати Франко；А.Я. Левин；Петрилло Винченцо；Пери Паоло；Е.А. Иванова；А.А. Фуфаев；В.М. Школьников
    申请人:Всесоюзный научно-исследовательский институт по переработке нефти；А/О Ликуикимика Робассомеро(Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the field of petrochemistry, and in particular to methods for producing oil additives.
    Among the additives used g to improve the washing and antioxidant properties of lubricating oils, products based on alkyl phenols, in particular alkaline earth metal phenolates, are used. The best jq results are achieved when sulfur contains atoms in the additive molecule, i.e. the additive is an alkaline earth metal sulfide alkyl phenolate.
    A known method of producing additives of this type, consisting of the following: 'alkyl phenol with an alkyl radical C4-C ^ o , alkaline earth metal sulfonate and 20 Cg- monohydric alcohol (^ is heated, then elemental sulfur, alkaline earth metal oxide or hydroxide, ethylene glycol are charged and, after removal of reaction water, carbonate, 25 passing through the reaction mass of СО2., after which ethylene glycol and monohydric alcohol are removed.
    However, for this method, it is necessary to use another additive in the process - sulfonate, and also use high-boiling reagents - ethylene glycol and С 0 - Cjg alcohols, distillation of which makes the process more expensive and complicates its technology [1].
    Closest to the proposed method is a method for producing sulfidylphenolate additives [2J. According to this method, the additive is prepared by treating alkyl phenol sulfide with an alkaline earth metal oxide or hydroxide in the presence of a promoter, Cj.-C 6 dihydric alcohol (preferably ethylene glycol) and C d - C ^ monohydric alcohol (preferably C 9 - C, in at 110,200 ° C. Then removal of the reaction water and the dihydric alcohol mixture is held at 200 ° C. The residue was flushed with CO 2 at temperatures up to 200 ° C in the presences of a higher alcohol, wherein the amount of the latter should be at least 10-fold (by weight) with respect to the take in protses alkylphenols.
    The product obtained by this method contains up to 9.2% calcium, i.e. is highly alkaline, but does not have high enough detergents
    Gh UGGZHG and antioxidant properties. This can be explained by the fact that the process in the presence of ethylene glycol and higher alcohol at relatively high temperatures does not provide the optimal colloidal structure of the additive. It is also possible the deterioration of the properties of the additive due to contamination with its products of partial oxidation during the synthesis of insufficiently thermally stable higher alcohol, which are not removed from the additive during normal cleaning. In addition, the use of ethylene glycol and higher alcohol, boiling off at 200 ° C and above, which must be removed at the end of the synthesis, which significantly complicates the process technology and increases its cost.
    The purpose of the invention is the simplification of the technology of the process of obtaining additives and improving the washing and antioxidant properties of the additive.
    This is achieved in that the QUALITY · v'e promoter ispolechyut alkanolamines C 2 - C 5 fatty acids or amides with ~ 1b with 2a and polyamines with 2-6 nitrogen atoms and / or methanol and the process is carried out at 30-105 ° C.
    .................................................................................. An initial product of the / proposed method uses alkyl phenol sulfide of the general formula to be added to an alkyl 10 extender, filter the product and remove the solvent. Example 1. 445.5 g of nonane, 182, 5 phenol sulfide of the above general formula (R - dodecyl, x - * / 1.2 (average), I-1), 8.9 g of diethanolamine, 8, 5 g of H ^ O, 146.7 g of Ca (O.CH) 2 , 40.8 g of CO 2 are blown through the mixture at 95 ° C, then 167 g of lubricating oil are added and the mass is filtered. After removal of water and solvent, a product is obtained containing 8.9% Ca and 3.6% S and having a viscosity at 98.9 ° C. of 150 cSt.
    Example 2. 324.6 g of toluene, 175 g of alkyl phenol sulphide, the same as in Example 1, 8.7 g of diethanolamine, 183 g of CX ^ OD, 105 g of Ca (0H) s, were charged into the reactor, 28 g of CO ^ was blown at 55 ° C, then add 175 g of lubricating oil and heated to remove methanol and water. The mass is filtered and after removal of the solvent, a product is obtained containing 8.22% Ca and 3.71% S and having a viscosity of 160 cSt at 9.8.9 ° C.
    Example 3. 445.5 g of cumene, 182.5 g of alkyl phenol sulfide of the above formula (R-80% dodecyl and 20% nonyl, X-1, p-0), 8.9 g olea acid and tetraethylene pentamine, 8.5 g of H 2 0, 146.7 g of Ca (OH) I, the mixture was purged with 40.8 g of CO 2 at 95 ° C, then 167 g of lubricating oil was added and the mass was filtered. After removal of water and solvent, a product is obtained containing 8.65% Ca 3,34%, S, with a viscosity of 145 cSt at 98.9 ° C.
    Example 4. 445.5 g of cumene, 182.5 g of alkyl phenol sulfide, the same as in example 3.4 g of diethanolamine, 8.5 g of H 2 O, 146.7 g of Ca (OH) 4 , were charged into the reactor; the mixture was purged with 40 , 8 g of CO and at 95 ° C, then add 167 g of lubricating oil and the mass is filtered.
    After removal of water and solvent, the product contains 8.25% Sai 3.39% S and has a viscosity of 95 cSt at 5098.9 ° C.
    Example 5-Synthesis lead like this. the same as described in Example 1, but using the alkyl phenol sulfide of the following general formula (R-80% dodecyl and 20% nonyl, X-1). Received a product with a viscosity of 110 cSt at 98.9 ° C, 1 containing 8.4% Ca and 3.2% S.
    • where R is the alkyl radical C ’X = 1-2, and = 0-1.
    Alkylphenol sulfide is subjected to treatment with an alkaline earth metal oxide or hydroxide in a stream of carbon dioxide, followed by distillation of water, filtration and distillation of the solvent. The process is carried out in the presence of water, using methanol and / or oxygen-containing derivatives of organic amines as promoters, such as alkanols ·, C 2 - or fatty acid amides C <5 ~ C 2 о and polyamine with 4-6 atoms, nitrogen, in the hydrocarbon an aromatic solvent, paraffinic or naphthenic type with 6-10 carbon atoms y ^ perODa, such as cumene, nonane,; toluene or xylene.
    The process temperature is 30-105 ° C, in the case of methanol, preferably 50-60 ° C, in other cases 95-98 ° C. Duration ( reactions 1-20 hours, in the case of methanol, preferably 2-5 hours, in ~ other cases, 4-10 hours
    Then water and methanol are distilled off at a return temperature of the solution45 • Example 6, The synthesis is carried out as described in example 1, but using alkylphenol sulfide of the following general formula, (x-1.5 on average). A product with a viscosity of 87 cSt at 98.9 ° C was obtained, containing 8.4% Ca and 3.4% S., 'ί
    Example 7. 100 g of alkyl phenol sulfide of the general formula, in which P is Cg-alkyl, 100 g of lubricating oil, 300 g of xylene, 5 g of monoethanolamine, 3.9 g of water, 105 g of Ca (0H), are charged into the reactor. ) 2 , purge 7.4 g of CO Z at 80 ° C, then rake to remove water, filter and distill xylene. A product is obtained containing 4.3% Ca and 3.25% S, with a viscosity of 39 cSt at 100 ° C.
    An example. 100 g of benzene, 31.2 g of CaO and 25.7 g of CH, OH are loaded into the reactor, the mixture is stirred for 1 h at 2 ° C – 25 ° C, then 62.1 g of a mixture of alkyl phenol sulfide similar to that used in Example 7 are loaded with oil and at 60 s purge 4.3 g of CO ^ g. A product is obtained containing 7.3% Ca and 3.4% S, with a viscosity of 92.8 cSt at 100 a C.
    Products obtained by the methods specified in the examples • are compared in terms of detergent and antioxidant properties to a product obtained in a known manner • with a content of 9.2% Ca and 3.7% S at a viscosity of 2.35 cSt at 98.9 ° FROM. Washing properties are determined by an indicator characterizing the ability of an oil with an additive to wash off soot deposits from a metal surface, and antioxidant properties are determined by the amount of sediment formed in an oil with an additive after its oxidation for 5 hours at 200 ° C in the presence of metal6
    Oil with 3%additives according to the examples of the proposed /5 inventions:one 322 .403 24.4 10 four 37,45 46.56 58.8
    about
    0.6 about
    oh oh
    The data indicate a high efficiency of additives obtained by the proposed method.
    oxidation catalyst. The evaluation results are shown below.
    Sediment
    Oil without additives
    Oil with .3% detergent after oxidation,%
    12 additives according to the known method
    10.8 g
    0.9
    权利要求:
    Claims (2)
    [1]
    (54) METHOD FOR OBTAINING SULFIDALKYLPENOLATIC ADDITIVE TO LUBRICATING OILS and antioxidant properties. This can be explained by the fact that carrying out the process in the presence of ethylene glycol and higher alcohol at relatively high temperatures does not provide an optimal colloidal structure of the additive. It is also possible for the additive properties to deteriorate due to contamination by its partial oxidation products during the synthesis process of insufficiently thermally stable higher alcohol, which are not removed from the additive during normal cleaning. In addition, the use of ethylene glycol and higher alcohol boiling at and above, which must be removed at the end of the synthesis, which significantly complicates the process technology and increases its cost. The purpose of the invention is to preempt the process of obtaining additives and improve the detergent and antioxidant properties of the additive. This is achieved by using L5 C5 alkanolamines or fatty acid amides of до прИ prlyamines with 2–6 atoms1 of nitrogen and / or methanol as a promoter, and the phenol sulfide sulfide of the general formula is used as the promoter. where R is an alkyl radical With, .- With f X 1-2,. The alkylphenol sulfide is treated with an oxide or hydroxide of alkaline earth metal in a stream of carbon dioxide with the subsequent distillation of water, filtration and distillation of the solvent. The process is carried out by the presence of water, using as promoters methanol and / or oxygen-containing derivatives of amines, such as Cr – C alkanols or 4-6 atoms of prlyamine fatty acid, nitrogen, in an aromatic, paraffinic or naphthenic hydrocarbon solvent with 6-10 atoms V1 feather a, for example, cumene, nonane toluene or xylene. The temperature of the SO-SW process, in the case of using methanol, is preferably SO-BS With, in other cases EB-EV C. The reaction time is 1-20 hours, in the case of using methanol, preferably 2-5 hours, in other cases - 4- 10 hours. Then water and methanol are distilled off at the temperature of the reverse flow of the solvent, the product is filtered and the solvent is distilled off. Example. Charged to the reactor 445.5 g of nonane, 182, 5 g of alkylphenol sulfide of the above general formula (R - dodedil, x - .1,2 (average), hl), 8.9 g of diethanolamine, 8.5 g, 146, 7 g of Ca (PM) 2, 40.8 g of COg are blown through the mixture at 95 ° C, then 167 g of lubricating oil is added and the mass is filtered. After removing the water and solvent, a product is obtained containing 8.9% Ca and 3.6% S and having a viscosity at 98.9 s 150 cSt. Example2. 324.6 g of toluene, 175 g of alkylphenol sulfide, the same as in Example 1, 8.7 g of diethanolamine, 183 g, 105 g of Ca (OH) 2, are charged to the reactor, the mixture is purged with 28 g of CO at, then 175 are added g of lubricating oil and heated to remove methanol and water. After the removal of the solvent, a mass filter is used to obtain a product containing 8.22% Ca and 3.71% S and having a viscosity of 160 cSt at 98.9 ° C. 445.5 g of cumene, 182.5 g of alkylphenolsulfide of the above formula (1g-80% dodecyl and 20% nonyl, X-1, and-0), 8.9 g of oleic acid amide and tetraethylenepentamine, 8.5 g of HjjO, 146.7 g of Ca (OH) 2, the mixture was blown at 40.8 g of CO, at 95 ° C, then 167 g of lubricating oil and a filter mass of 5 tons were added. After removing the water and solvent, get the product containing 8.65% Ca and 3.34% S, with a viscosity of 145 cSt at 98.9 ° C. ,, Example 4. 445.5 g of cumene, 182.5 g of alkylphenol sulfide, the same as in example 3.4 g of 4 ethanethyl amine 8.5 g of HjO, 146.7 g of Ca (OH) / j., the mixture is purged with 40.8 g of SO when with, then 167 g of lubricating oil is added and the mass is filtered. After removal of water and solvent, the product contains 8.25% Ca and 3.39% S and has a viscosity of 95 cSt poi 98 ,. Example 5. Synthesis of conduct. same as described in Example 1, but alkyl phenol sulfand of the above general formula is used (B-80% dodecyl and 20% nonyl, x-1). A product with a viscosity of 110 cSt at 98, 1 containing 8.4% Ca and 3.2% S was obtained. EXAMPLE 6 Synthesis is carried out as. described in example 1, but using alkylphenol sulfide of the general formula given (x-1.5 on average). A product was obtained with a viscosity of 87 cSt at 98.9 ° C, containing 8.4% Ca and 3.4% S .. Example. Charged to the reactor is 100 g of alkylphenol sulfide of the above general formula, in which P is Cg alkyl of lubricating oil, 300 g of xylene, 5 g of ethanolamine, 3.9 g of water, 105 g of Ca (OH) 2., Is blown., 4 g The COi is then heated to remove the water, filtered and the xi lol is distilled off. A product is obtained containing 4.3% Ca and 3.25% S, with a viscosity of 39 cSt at 100 ° C. For example 8. 100 g of benzene, 31.2 g of CaO and 25, g are charged to the reactor, the mixture is stirred for 1 hour at 2 ° –25 ° C, then 62.1 g of the mixture, an alkylphenol sulfide, is used which is similar to that used in , with oil and with rinsing 4.3 g COf f A product containing 3% Ca and 3.4% S is obtained, with a sulfur content of 92.8 cSt at. The products obtained by the methods indicated in the examples given are compared in detergent and anti-oxidative properties with the product obtained in a known manner with a content of 9.2% Ca and 3,% S at a viscosity of 2.35 cSt at 98 ,. The washing properties are determined by an indicator characterizing the ability of the oil with an additive to wash away soot deposits from the metal surface, and the antioxidant properties are determined by the amount of sediment formed in the oil with the additive after it has been oxidized for 5 hours at 200 ° C in the presence of a metallic oxidation catalyst. The results of the evaluation are shown below. Display - Sludge washing after oxidation,% properties Oil without additive Oil with .3% additive by a known method Oil with 3% additive according to examples of proposed / invention: 1 The data indicate high efficiency of additives obtained by the proposed method. The invention method of producing sulfidalkylphenolate additives to lubricating oils by treating alkylphenol sulfide with an oxide or hydroxide of alkaline earth metal in a stream of carbon dioxide when heated in the presence of promoters and solvents, followed by improving the product, in order to improve the antioxidants with antioxidants, who have antioxidants with antioxidants. of the process, alkanolamines Cj. - Cg or amides of fatty acids and polyamines of nitrogen and / or a month of 2 to 6 atomic processes are used as a promoter. carried out at 30-105 C. Sources of information, taken into account in the examination 1. US patent 317836B, l. 252-33.4 publ. 1965.
    [2]
    2. The patent CIOA 3725381, p, 60-137, published. 1973.
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    同族专利:
    公开号 | 公开日
    IN145347B|1978-09-30|
    AU508645B2|1980-03-27|
    BR7604604A|1977-08-02|
    JPS6137316B2|1986-08-22|
    DE2631675A1|1977-01-20|
    DE2631675C2|1987-06-04|
    FR2318219A1|1977-02-11|
    ES450050A1|1977-08-16|
    IT1044574B|1980-03-31|
    BE844089A|1976-11-03|
    AU1579976A|1978-01-12|
    ZA764090B|1977-06-29|
    JPS5230803A|1977-03-08|
    US4212752A|1980-07-15|
    GB1523054A|1978-08-31|
    CA1084800A|1980-09-02|
    FR2318219B1|1980-07-18|
    引用文献:
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    KR101706903B1|2009-06-16|2017-02-14|셰브론 필립스 케미컬 컴퍼니 엘피|Oligomerization of alpha olefins using metallocene-ssa catalyst systems and use of the resultant polyalphaolefins to prepare lubricant blends|
    KR101643801B1|2010-02-19|2016-07-28|인피늄 인터내셔날 리미티드|Wet friction clutch-lubricant systems providing high dynamic coefficients of friction through the use of sodium detergents|
    KR101681355B1|2010-02-19|2016-11-30|인피늄 인터내셔날 리미티드|Wet friction clutch-lubricant systems providing high dynamic coefficients of friction through the use of borated detergents|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT25386/75A|IT1044574B|1975-07-14|1975-07-14|DETERGENT ADDITIVE FOR ITS PREPARATION|DD19375976A| DD125278A1|1975-07-14|1976-07-08|
    RO7686964A| RO72555A|1975-07-14|1976-07-13|PROCEDURE FOR PREPARING LUBRICANTS ADDITIVES|
    BG7633733A| BG33815A1|1975-07-14|1976-07-13|Method for the production of washing and antioxydant additive to lubricant oils|
    YU173276A| YU39615B|1975-07-14|1976-07-13|Process for obtaining additives for lubricating oils|
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