WO1995016011A1 - Concentres de phenates d'hydrocarbyle de metaux alcalino-terreux a indice de base totale eleve, leur production et compositions d'huile lubrifiantes terminees les contenant - Google Patents

Concentres de phenates d'hydrocarbyle de metaux alcalino-terreux a indice de base totale eleve, leur production et compositions d'huile lubrifiantes terminees les contenant Download PDF

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Publication number
WO1995016011A1
WO1995016011A1 PCT/GB1994/002602 GB9402602W WO9516011A1 WO 1995016011 A1 WO1995016011 A1 WO 1995016011A1 GB 9402602 W GB9402602 W GB 9402602W WO 9516011 A1 WO9516011 A1 WO 9516011A1
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Prior art keywords
lubricating oil
alkaline earth
earth metal
weight
additive concentrate
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PCT/GB1994/002602
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English (en)
Inventor
Stephen James Cook
Paul Kristian Robinson
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Bp Chemicals (Additives) Limited
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Application filed by Bp Chemicals (Additives) Limited filed Critical Bp Chemicals (Additives) Limited
Priority to EP95902851A priority Critical patent/EP0682688A1/fr
Priority to JP7516022A priority patent/JPH08506617A/ja
Publication of WO1995016011A1 publication Critical patent/WO1995016011A1/fr

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    • 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals

Definitions

  • the present invention relates in general to lubricating oil additive concentrates having a total base number (TBN) greater than 300 containing an alkaline earth metal hydrocarbyl phenate, a process for their production and finished lubricating oil compositions containing the additive concentrate.
  • TBN total base number
  • metal alkyl phenates wherein the metal is an alkaline earth metal such as calcium, magnesium or barium. Both "normal” and “overbased” alkaline earth metal alkyl phenates have been employed.
  • overbased is used to describe those alkaline earth metal alkyl phenates in which the ratio of the number of equivalents of the alkaline earth metal moiety to the number of equivalents of the phenol moiety is greater than one, and is usually greater than 1.2 and may be as high as 4.5 or greater.
  • the equivalent ratio of alkaline earth metal moiety to phenol moiety in "normal” alkaline earth metal alkyl phenates is one.
  • the "overbased” material contains greater than 20% in excess of the alkaline earth metal present in the corresponding "normal” material. For this reason "overbased" alkaline earth metal alkyl phenates have a greater capability for neutralising acidic matter than do the corresponding "normal” alkaline earth metal alkyl phenates.
  • TBN total base number as measured in mg KOH/g by the method of ASTM D2896
  • Rl wherein R is a C ⁇ 0 to 24 alk y! or alkenyl group and R 1 is either hydrogen, a C- to C 4 alkyl group or a -CH2-COOH group, or an anhydride, acid chloride or ester thereof or (ii) a di- or polycarboxylic acid containing from 36 to 100 carbon atoms or an anhydride, acid chloride or ester thereof, the composition having a TBN greater than 300.
  • the additive concentrate can be prepared by reacting at elevated temperature (1) a hydrocarbyl phenol and sulphur, (2) an alkaline earth metal base, (3) a solvent such as a polyhydric alcohol, (4) a lubricating oil, (5) carbon dioxide, and (6) sufficient to provide from greater than 2 to less than 40% by weight based on the weight of the concentrate of either (i) a carboxylic acid having the formula (I) or an acid anhydride or ester thereof or (ii) a di- or polycarboxylic acid containing from 36 to 100 carbon atoms or an acid anhydride or ester thereof.
  • Our EP-A-273588 also discloses an alkaline earth metal sulphurised hydrocarbyl phenate- containing composition having a high TBN.
  • the composition can be prepared by reacting at elevated temperature (A) a sulphurised alkaline earth metal hydrocarbyl phenate having a TBN less than that of the final additive concentrate, (B) an alkaline earth metal base added in either a single addition or in a plurality of additions at intermediate points during the reaction, (C) either a polyhydric alcohol having from 2 to 4 carbon atoms, a di- or tri- (C2 to C4) glycol, an alkylene glycol alkyl ether or a polyalkylene glycol alkyl ether, (D) a lubricating oil, (E) carbon dioxide added subsequent to the, or each, addition or component (B), and (F) sufficient to provide from greater than 2 to 35% by weight based on the weight of the concentrate of either (i) a carboxylic acid having the formula (I) or an acid anhydride, or ester thereof or (ii) a di- or polycarboxylic acid containing from 36 to 100 carbon atoms or an acid an
  • EP-A-271262 is one for the production of a high TBN alkaline earth metal containing composition from the precursors of a sulphurised hydrocarbyl phenol ie a hydrocarbyl phenol and elemental sulphur (first-intent process)
  • the process of EP-A-273588 is a process for the production of a high TBN alkaline earth metal containing composition by upgrading a pre-formed alkaline earth metal sulphurised hydrocarbyl phenate (upgrade process) .
  • the high TBN phenate-containing concentrates described hereinbefore have one or more of the following properties:- capability of neutralising acidic materials, capability of dispersing sludge, antioxidancy and improved compatability with other lubricating oil additives, for example highly overbased sulphonates.
  • a problem to be overcome is that of extending the range of properties of the phenate containing concentrates by, for example, improving the anti-wear properties of the detergents.
  • a solution to the problem is to further modify the phenate with boron.
  • EP-B-0416757 discloses a process for producing an alkaline earth metal borate dispersion, comprising the steps of:
  • component (B) 10 to 20 parts by weight of an alkaline earth metal hydroxide or oxide, (C) 0.5 to 6.5 moles, per mole of component (B), of a boric acid or anhydride,
  • EP-B-0416757 is published in greater detail in the April 1983 issue of Lubrication Engineering, 4.9, 4, 263-268 in a paper entitled "Calcium Borate Overbased Metallic Detergent" by Kiyoshi Inone. It is apparent that the disclosure is only concerned with overbased detergents in which the alkaline reservoir is exclusively composed of alkaline earth metal borates in contrast to alkaline earth metal carbonates or mixed borates/carbonates. To this end their preparation begins with the neutral salts and there is no subsequent carbonation step. Moreover, there is no disclosure of materials having a high Total Base Number, the highest TBN mentioned being 207 mg KOH/g for the phenates and 200 mg KOH/g for the salicylate.
  • the present invention provides an overbased additive concentrate suitable for incorporation into a finished lubricating oil composition, the additive concentrate comprising:-
  • R is a C 10 to C 2 4 alkyl or alkenyl group and R 1 is hydrogen, a C j to C 4 alkyl group or a -CH2-COOH group, or an anhydride or ester thereof, or (ii) a di- or polycarboxylic acid containing from 36 to 100 carbon atoms or an anhydride or ester thereof,
  • the TBN of the concentrate is greater than 300, preferably greater than 350, more preferably greater than 400.
  • the concentrate has a viscosity of less than lOOOcSt, preferably less than 750cSt, more preferably less than 500cSt.
  • the lubricating oil [component (A)] is suitably an animal oil, a vegetable oil or a mineral oil, such as a naphthenic base, paraffin base or mixed base oil.
  • the lubricating oil is a petroleum- derived lubricating oil. Solvent neutral oils are particularly suitable.
  • the lubricating oil may be a synthetic lubricating oil.
  • Suitable synthetic lubricating oils include synthetic ester lubricating oils, which oils include diesters such as di-octyl adipate, di-octyl sebacate and tridecyladipate,or polymeric hydrocarbon lubricating oils, for example liquid polyisobutenes and poly-alpha olefins.
  • the lubricating oil may suitably comprise from 10 to 90%, typically from 10 to 70%, by weight of the composition.
  • Component (B) is a lubricating oil soluble alkaline earth metal hydrocarbyl phenate modified by reaction to incorporate (a), (b) and (c).
  • the alkaline earth metal hydrocarbyl phenates may be sulphurised or non-sulphurised, preferably sulphurised.
  • the alkaline earth metal may be strontium, barium, calcium or magnesium, preferably calcium or barium, more preferably calcium.
  • the alkaline earth metal may be present in an amount in the range from 10 to 20% by weight based on the weight of the composition.
  • the hydrocarbyl phenate moiety of the alkaline earth metal hydrocarbyl phenate is preferably derived from at least one alkyl phenol.
  • the alkyl group of the alkyl phenol may be straight-chain or branched- chain or a mixture thereof. Suitable alkyl groups contain from 4 to 50, preferably from 9 to 28 carbon atoms.
  • a particularly suitable alkyl phenol is the C 12 - alkyl phenol obtained by alkylating phenol with propylene tetramer.
  • the phenol may be mono- or poly- alkylated.
  • the alkaline earth metal phenate is modified by incorporation of (a),(b) and (c). As regards (a) this may be either (i) or (ii). As regards (i) this is at least one carboxylic acid having the formula (I), or an anhydride or ester thereof.
  • R in the formula (I) is an unbranched alkyl or alkenyl group.
  • Preferred acids of formula (I) are those wherein R is a C ⁇ Q to C24, more preferably C 18 to C 2 4 straight-chain alkyl group and R 1 is hydrogen.
  • suitable saturated carboxylic acids of formula (I) include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and lignoceric acid.
  • suitable unsaturated acids of formula (I) include lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, gadoleic acid, erucic acid, ricinoleic acid, linoleic acid and linolenic acid.
  • Mixtures of acids may also be employed, for example rape top fatty acid.
  • Particularly suitable mixtures of acids are those commercial grades containing a range of acids, including both saturated and unsaturated acids.
  • Such mixtures may be obtained synthetically or may be derived from natural products, for example cotton oil, ground nut oil, coconut oil, linseed oil, palm kernel oil, olive oil, corn oil, palm oil, castor oil, soyabean oil, sunflower oil, herring oil, sardine oil and tallow.
  • Sulphurised acids and acid mixtures may also be employed.
  • the carboxylic acid there may be used the acid anhydride, or the ester derivatives of the acid, preferably the acid anhydride. It is preferred however to use a carboxylic acid or a mixture of carboxylic acids.
  • a preferred carboxylic acid of formula (I) is stearic acid.
  • the alkaline earth metal hydrocarbyl phenate may be modified by incorporation of (ii), which is a di- or polycarboxylic acid containing from 36 to 100 carbon atoms or an acid anhydride or ester derivative thereof, preferably an acid anhydride thereof.
  • (ii) is a polyisobutene succinic acid or a polyisobutene succinic anhydride.
  • component (B) (a) and in particular stearic acid are preferred to incorporate component (B) (a) and in particular stearic acid.
  • the carboxylic acid(s) having the formula (I), the di-or polycarboxylic acid, or the acid anhydride or ester therof is incorporated in an amount from greater than 10% to 35%, more preferably from 12 to 20%, for example about 16% by weight based on the weight of the concentrate.
  • An advantage of incorporating greater than 10% of the carboxylic acid or derivative thereof is generally a relatively lower concentrate viscosity.
  • sulphur may be present in the composition in an amount in the range from 1 to 6, preferably from 1.5 to 3% by weight based on the weight of the composition.
  • the phenate is modified by incorporation of boron (b) . This may suitably be present in the form of the borate salt. Boron is present in an amount in the range from 0.01 to 10% by weight, preferably from 0.25 to 5% by weight based on the weight of the concentrate composition.
  • the phenate is further modified by incorporating carbon dioxide (c).
  • carbon dioxide may be present in the composition in an amount in the range from 5 to 20, preferably from 9 to 15% by weight based on the weight of the composition.
  • the present invention provides an overbased additive concentrate suitable for incorporation into a finished lubricating oil composition, the additive concentrate comprising:-
  • R is a C- ⁇ Q to C24 alkyl or alkenyl group and R ⁇ is hydrogen, a C ⁇ to C4 alkyl group or a -CH2-COOH group, or an anhydride or ester thereof, or (ii) a di- or polycarboxylic acid containing from 36 to 100 carbon atoms or an anhydride or ester thereof,
  • the ratio of the weight of the additive concentrate (Yg) to the weight of the hydrocarbyl phenate or its precursors, from which the modified alkaline earth metal hydrocarbyl phenate is derived (Xg) may be regarded as 'the scale up factor'. It is an advantage of the concentrate of the preferred embodiment that it can have a ' scale up factor' of at least 3, for example at least 5, and as high as at least 10. This is an advantage because the higher the 'scale up factor" the higher is the proportion of lubricating oil in the concentrate relative to hydrocarbyl phenol at a given high TBN and since lubricating oil is very much cheaper than hydrocarbyl phenol, the cost of the product is reduced proportionately.
  • Component (A*) is a lubricating oil. Suitable lubricating oils are as hereinbefore described.
  • Component (B') of the preferred embodiment is an alkaline earth metal hydrocarbyl phenate modified before overbasing by reaction with an aldehyde and further modified by reaction to incorporate (a) from greater than 2 to less than 40% by weight based on the weight of the concentrate of either (i) at least one carboxylic acid having the formula (I) or an anhydride or ester thereof, or (ii) a di- or polycarboxylic acid containing from 36 to 100 carbon atoms or an anhydride or ester thereof, (b) boron in an amount of from 0.01 to 10% by weight, and (c) carbon dioxide.
  • any aldehyde may be employed. Suitable aldehydes include formaldehyde, propionaldehyde and butyraldehyde for example.
  • a preferred aldehyde is formaldehyde in one or other of its physical forms. It is believed, though we do not wish to be bound in any way by the theory, that reaction with the aldehyde, for example formaldehyde, by condensation with the elimination of water results in the bridging of two or more phenate molecules.
  • the present invention provides a process for the production of an additive concentrate as hereinbefore described which process comprises reacting at elevated temperature:- (A") at least one compound which is (A")(i) an alkaline earth metal hydrocarbyl phenate, (A")(ii) an alkaline earth metal sulphurised hydrocarbyl phenate, (A")(iii) an alkaline earth metal hydrocarbyl phenate and a source of sulphur, (A")(iv) a hydrocarbyl phenol,
  • a mono- or poly-alkylene glycol alkyl ether of the formula:- fOR ⁇ -JxOR 2 (II) wherein in the formula (II) R is a C ⁇ to C 6 alkyl group, R 1 is an alkylene group, R 2 is hydrogen or a C to C 6 alkyl group and x is an integer of from 1 to 6, either alone or in combination with either (2) a hydrocarbon solvent or (3) either (a) water, (b) a C to C 2Q monohydric alcohol, (c) a ketone containing up to 20 carbon atoms, (d) a carboxylic acid ester containing up to 10 carbon atoms or (e) an aliphatic, alicyclic or aromatic ether containing up to 20 carbon atoms or, (4) a C to C 4 monohydric alcohol in combination with a hydrocarbon solvent (2), (E”) a lubricating oil,
  • Rl wherein R is a to C 2 4 alkyl or alkenyl group and R is hydrogen, a C ⁇ to C alkyl group or a -CH2COOH group, or an anhydride or ester of either (i) or (ii) and optionally (H") a catalyst for the reaction with (F"), and (I") a source of boron.
  • the hydrocarbyl substituent or substituents of the compounds (A")(i) - (vi) may suitably be an alkyl or alkenyl group, preferably a C- ⁇ -C ⁇ alkyl group.
  • the hydrocarbyl group is a dodecyl group derived from propylene tetramer.
  • the alkaline earth metal is preferably either strontium, calcium, magnesium or barium, more preferably calcium or barium, most preferably calcium.
  • the amount of sulphur in (A")(ii) and (A")(v), is suitably greater than 1%, preferably at least 4% by weight, typically in the range from 4 to 12% by weight
  • a prefered component (A") is an overbased alkaline earth metal sulphurised hydrocarbyl phenate, for example one having a TBN in the range from about 50 to about 250, typically from about 100 to about 200.
  • the compounds (A")(i) - (vi) and their preparation are well known in the art. Many are commercially available.
  • the aldehyde there may be used formaldehyde, butyraldehyde, propionaldehyde, dodecylaldehydes and higher alkyl aldehydes. It is preferred to use formaldehyde.
  • Formaldehyde may be added in any of its physical forms but it is preferred to use either paraformaldehyde or aqueous formaldehyde (formalin), of which formalin is more preferred.
  • the aldehyde may suitably be added in an amount sufficient to react with any alkyl phenol present in (A")(i) - (vi) on at least a 1:1 basis.
  • reaction of (A") with (B") may suitably be accomplished at elevated temperature, suitably in the range from 30 to 120°C, typically from 50 to 100°C.
  • elevated temperature suitably in the range from 30 to 120°C, typically from 50 to 100°C.
  • component (B) be present in the reaction mixture.
  • participation of (B) is unnecessary.
  • Component (C") is an alkaline earth metal base added either in a single addition or in a plurality of additions at intermediate points during the reaction.
  • the alkaline earth metal is preferably strontium, calcium, magnesium or barium, more preferably calcium or barium, most preferably calcium.
  • the base moiety may suitably be an oxide or a hydroxide, preferably the hydroxide.
  • a calcium base may be added, for example, in the form of quick lime (CaO) or in the form of slaked lime (Ca(OH>2) / preferably in the form of slaked lime. As regards the amount of component (C") to be added, this should be sufficient to achieve the desired TBN.
  • the amount will be greater starting with components (A") (iv) - (A") (vi) than it will be starting with components (A") (i)-(A") (iii) by the amount required to convert (A") (iv)-(A") (vi) to (A") (i)-(A") (iii).
  • Component (D") is a solvent for the reactants.
  • the solvent (D") may be either (D") (1) alone or in combination with either
  • (D")(l) is either (i) a polyhydric alcohol having 2 to 4 carbon atoms, (ii) a di-(C 3 or C ) glycol, (iii) a tri- (C 2 to C 4 ) glycol or (iv) a mono- or poly-alkylene glycol alkyl ether of the formula:-
  • R(OR 1 )xOR 2 (II) wherein in the formula (II) R is a C j , to C 6 alkyl group, R 1 is hydrogen or a C ⁇ to Cg alkyl group and x is an integer from 1 to 6.
  • Suitable compounds having the formula (I) include the monomethyl or dimethyl ethers of (a) ethylene glycol, (b) diethylene glycol, (c) triethylene glycol or (d) tetraethylene glycol.
  • a suitable compound is methyl diglycol (CH3OCH2CH2OCH2CH2OH) .
  • Mixtures of glycol ethers of formula (V) and glycols may also be employed.
  • the polyhydric alcohol may suitably be either a dihydric alcohol, for example ethylene glycol or propylene glycol, or a trihydric alcohol, for example glycerol.
  • the di-(C3 or C 4 ) glycol may suitably be dipropylene glycol, the tri- (C 2 to C 4 ) glycol may suitably be triethylene glycol.
  • the component (D")(l) is either ethylene glycol or methyl diglycol.
  • (D")(2) is a hydrocarbon solvent which may be aliphatic or aromatic. Examples of suitable hydrocarbons include toluene, xylene, naphtha and aliphatic paraffins, for example hexane, and cycloaliphatic paraffins.
  • (D")(3) may be either (i) water, (ii) a C to C 2 Q monohydric alcohol, (iii) a ketone having up to 20 carbon atoms, (iv) a carboxylic acid ester having up to 10 carbon atoms or (v) an aliphatic, alicyclic or aromatic ether having up to 20 carbon atoms. Examples are methanol, 2-ethyl hexanol, cyclohexanol, cyclohexanone, benzyl alcohol, ethyl acetate and acetophenone.
  • (D")(4) may be a C j _ to C 4 monohydric alcohol, preferably methanol.
  • Preferred solvents (D") comprise ethylene glycol, a mixture of ethylene glycol and 2-ethyl hexanol and a mixture of methanol and toluene.
  • Component (E) is a lubricating oil. Suitable lubricating oils are described hereinbefore with reference to the concentrate composition. For the production of additive concentrates having a high 'scale up factor' the amount of lubricating oil must be such that a 'scale up factor' as hereinbefore defined of at least 3.0 is achieved.
  • Component (F) is carbon dioxide added subsequent to each addition of component (C").
  • Carbon dioxide may be added in the form of a gas or a solid, preferably in the form of a gas. In gaseous form it may suitably be blown through the reaction.
  • Component (G") is either (i) a di- or polycarboxylic acid containing from 36 to 100 carbon atoms or (ii) a carboxylic acid of the formula (I), or an acid anhydride or ester of either (i) or (ii). Suitable components (G") are described hereinbefore with reference to components (B)(a)(i) and (ii) of the concentrate composition.
  • a preferred carboxylic acid of formula (I) is stearic acid.
  • Optional component (H") is a catalyst. It is preferred that a catalyst be present for the achievement of higher TBN concentrates, for example TBNs greater than 350, and for the production of the higher 'scale-up factor' concentrates.
  • the catalyst may be either an inorganic compound or an organic compound, preferably an inorganic compound. Suitable inorganic compounds include hydrogen halides, metal halides, ammonium halides, metal alkanoates, ammonium alkanoates or a mono-, di-, tri- or tetra-alkyl ammonium formate or alkanoate.
  • the metal moiety of metal halides or metal alkanoates this is suitably either zinc, aluminium, or an alkaline earth metal, for example calcium.
  • a preferred metal moiety is calcium.
  • the chloride is preferred.
  • the alkanoate moiety is suitably a C2 to C ⁇ g alkanoate, preferably a C to C alkanoate, for example an acetate or propionate.
  • a substituted ammonium compound is used, it is preferably a tetra- (C to C alkyl) ammonium compound, especially a tetramethylammonium compound such as tetramethylammonium acetate.
  • suitable catalysts include calcium chloride, ammonium chloride, calcium acetate, ammonium acetate, zinc acetate, and tetramethylammonium acetate.
  • Component (I) is a source of boron.
  • the source of boron there may suitably be used either a boric acid or an anhydride thereof. Examples thereof include orthoboric acid, metaboric acid, tetraboric acid and boric anhydride. Generally orthoboric acid is preferred. Borate salts and esters of boric acid may also be employed.
  • the molar ratio of the source of boron to the alkaline earth metal base (Component (C")) may suitably be in the range from 0.1 to 10, for example 0.5 to 6.
  • component (C) must be added before component (F") and when component (H") is employed it must be present during the reaction of component (F").
  • component (B) is present during the production of high 'scale up factor' concentrates. In this event component (A") should be reacted with (B") before reaction with the remaining components.
  • a catalyst include both organic and inorganic bases. It will usually be found most convenient to use as the catalyst in the reaction of (A") with (B") an alkaline earth metal base identical with the base used as component (C").
  • component D both a polyhydric alcohol having 2 to 4 carbon atoms [(D")(l)(i)] eg ethylene glycol, and a C to C 2Q monohydric alcohol [(D")(3)(b) eg 2-ethyl hexanol it is very much preferred to add component [(D")(l)(i) after all the other components have been reacted and before addition of component (F").
  • a preferred order of addition for the production of high 'scale up factor' concentrates comprises in a first step reacting component (A") (i), (ii) or (iv) with component (B") in the presence of components (D") and (G") and a catalytic amount of component (C") and thereafter in a subsequent step or steps reacting the phenate with components (C") (I"), and finally (F").
  • Component (E") the lubricating oil, may suitably be added with components (A") and (B”).
  • the catalyst for the carbonation (component H” ) may be added at any point, suitably after completion of the first step.
  • the elevated temperature at which the process is operated may be a temperature in the range from 15 to 200°C, preferably from 50 to 175°C.
  • the selection of the optimum temperature within the aforesaid range will depend to a large extent on the nature of the solvent employed.
  • it is preferred to recover the concentrate as a solution in lubricating oil by separating off the solvent (D"), for example by distillation at subatmospheric pressure.
  • a finished lubricating oil composition which composition comprises a major proportion of a lubricating oil and a minor proportion of an additive concentrate as hereinbefore described.
  • the amount of additive concentrate present in the finished lubricating oil will depend on the nature of the final use. Thus, for marine lubricating oils the amount of additive concentrate present may suitably be sufficient to provide a TBN of 9 to 100 and for automobile engine lubricating oils the amount may suitably be 5 sufficient to provide a TBN of 4 to 20.
  • the finished lubricating oil may also contain effective amounts of one or more other types of conventional lubricating oil additives, for example viscosity index improvers, anti-wear agents, antioxidants, dispersants, rust inhibitors, pour-point depressants, - Q or the like, which may be incorporated into the finished lubricating oil composition either directly or through the intermediacy of the concentrate composition.
  • viscosity index improvers for example viscosity index improvers, anti-wear agents, antioxidants, dispersants, rust inhibitors, pour-point depressants, - Q or the like, which may be incorporated into the finished lubricating oil composition either directly or through the intermediacy of the concentrate composition.
  • Step 1 A mixture of the following ingredients (A) - (G) was reacted at 1452c/ll"Hg:-
  • Step 2 The resultant reaction mixture was held for 5 minutes prior to addition of ingredient (H):- (H) 42g ethylene glycol Step 3
  • the resultant reaction mixture was cooled to 1302C/ll"Hg 35 prior to addition of ingredient (I):- (I) 72g carbon dioxide at (1 bar)
  • Step 4 The resultant reaction mixture was heated to 2102C/28"Hg to remove the 2-ethyl hexanol and the ethylene glyol Step 5
  • the product was filtered. Analysis of product Ca 13.99% S 1.81% AV 385 mgKOH/g VIOO 1443 cSt B 0.8%
  • Step 1 A mixture of the following ingredients (A) - (G) was reacted at 1302C/ll"Hg:- (A) 189g of an oil soluble 150TBN calcium C 12 -alkyl phenate,
  • Step 3 The resultant reaction mixture was cooled to 1302C/ll"Hg prior to addition of ingredient (I):- (I) 94g carbon dioxide 1 bar
  • Step 4 The resultant reaction mixture was heated to 2102C/28"Hg to remove the 2-ethyl hexanol and ethylene glycol.
  • Step 5 The product was filtered. Analysis of product Ca 13.60% S 1.84% AV 387 mgKOH/g V100 606 CSt B 0.8%
  • Step 2 The resultant reaction was held for 5 minutes at 130°/ll inches Hg and subsequently cooled to 100°C/1 bar prior to the addition of ingredients (E) - (H):-
  • Step 3 The resultant reaction mixture was heated to 130°C/11 inches Hg and held for 5 minutes prior to the addition of component
  • Step 4 The resultant reaction mixture was held for 5 minutes at
  • Step 6 The product was filtered.
  • the product weight was 478g and the distillate weight was
  • Example 3 The procedure of Example 3 was repeated except that in step 1 the amount of boric acid added was 16.5g. The product weight was 460g and the distillate weight was 212g. The filtration rate was good and the crude sediment was 3.6%. The 'scale-up factor' was 1:2.4. Analysis of product Ca 13.70% AV 381mg KOH/g S 1.80 B 0.50% v 100 72 cSt - Example 5 Step 1 A mixture of the following ingredients (A) to (F) was heated to 145°C/21 inches Hg:-
  • Step 2 The resultant reaction mixture was held at 145°C/21 inches Hg for 15 minutes and subsequently cooled to 100°c prior to the addition of ingredients (G) - (I):-
  • Step 3 The resultant reaction mixture was held at 130°C/11 inches Hg for 10 minutes prior to the addition of ingredient
  • Step 4 The resultant reaction mixture was heated at 210°C/10 mm
  • Step 5 The product was filtered.
  • the product weight was 422g and the distillation weight was 211g.
  • the filtration rate was good and the crude sediment was
  • Examples 3 and 4 exhibited significantly improved antioxidant properties as compared with a similar non-boronated product.
  • Example 8 The products of Examples 3, 4 and 6 were tested in the Shell Four Ball Test (ASTM D4172). Also tested by way of comparison was the boron-free calcium sulphurised hydrocarbyl phenate as described in Example 7. The scar depth in mm recorded after one hour at 40 kg load at 1200 rpm is recorded in Table 2.
  • Example 9 From an examination of the Table it can be seen that the products of Examples 3 and 6 are better and the product of Example 4 is comparable in terms of anti-wear as compared with a similar non- boronated product.
  • Example 9 From an examination of the Table it can be seen that the products of Examples 3 and 6 are better and the product of Example 4 is comparable in terms of anti-wear as compared with a similar non- boronated product.

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  • Lubricants (AREA)

Abstract

Un concentré pour additif convenant pour être incorporé dans une huile lubrifiante terminée comprend: (A) une huile lubrifiante, et (B) un phénate d'hydrocarbyle de métal alcalino-terreux, soluble dans une huile lubrifiante et modifié par une réaction pour comprendre: a) de plus de 2 à moins de 40 % en poids du concentré de soit 1): au moins un acide carboxylique de formule (I) où R représente un groupe C10-24 alkyle ou alkényle et R1 représente hydrogène, un groupe C¿1-4? alkyle ou un groupe -CH2COOH, ou un de leurs anhydrides ou esters, soit 2) un acide di- ou polycarboxylique contenant 36 à 100 atomes de carbone, ou un de leurs anhydrides ou esters; b) 0,01 à 10 % en poids de bore et c) du dioxyde de carbone. Ce concentré présente un indice de base totale supérieur à 300.
PCT/GB1994/002602 1993-12-08 1994-11-29 Concentres de phenates d'hydrocarbyle de metaux alcalino-terreux a indice de base totale eleve, leur production et compositions d'huile lubrifiantes terminees les contenant WO1995016011A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP95902851A EP0682688A1 (fr) 1993-12-08 1994-11-29 Concentres de phenates d'hydrocarbyle de metaux alcalino-terreux a indice de base totale eleve, leur production et compositions d'huile lubrifiantes terminees les contenant
JP7516022A JPH08506617A (ja) 1993-12-08 1994-11-29 高いｔｂｎアルカリ土類金属ヒドロカルビルフェネート濃縮物、これらの製造およびこれらを含有する完成潤滑油組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9325132.0 1993-12-08
GB939325132A GB9325132D0 (en) 1993-12-08 1993-12-08 Lubricating oil additives

Publications (1)

Publication Number Publication Date
WO1995016011A1 true WO1995016011A1 (fr) 1995-06-15

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PCT/GB1994/002602 WO1995016011A1 (fr) 1993-12-08 1994-11-29 Concentres de phenates d'hydrocarbyle de metaux alcalino-terreux a indice de base totale eleve, leur production et compositions d'huile lubrifiantes terminees les contenant

Country Status (4)

Country Link
EP (1) EP0682688A1 (fr)
JP (1) JPH08506617A (fr)
GB (1) GB9325132D0 (fr)
WO (1) WO1995016011A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997046646A1 (fr) * 1996-05-31 1997-12-11 Exxon Chemical Patents Inc. Detergents surbasiques contenant des metaux
WO1997046647A1 (fr) * 1996-05-31 1997-12-11 Exxon Chemical Patents Inc. Detergents surbasiques contenant des metaux
JP2000514473A (ja) * 1996-05-31 2000-10-31 エクソン ケミカル パテンツ インコーポレイテッド 金属含有過塩基性清浄剤
WO2004044109A2 (fr) * 2002-11-06 2004-05-27 The Lubrizol Corporation Des calixarates et lubrifiants en sus de la base contenant du bore et methodes s'y rapportant

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US4021419A (en) * 1973-05-02 1977-05-03 The Lubrizol Corporation Basic metal salts of sulfur- and methylene-bridged poly-phenol compositions, and epoxide-reacted derivatives thereof, and lubricants containing them
WO1987001723A1 (fr) * 1985-09-18 1987-03-26 The Lubrizol Corporation Usinage de metaux en utilisant des lubrifiants contenant des sels de metaux alcalino-terreux basiques
EP0273588A1 (fr) * 1986-11-29 1988-07-06 Bp Chemicals (Additives) Limited Alkylphénates de métaux alcalino-terreux sulfurés, leur préparation et leur utilisation
EP0354647A2 (fr) * 1988-06-14 1990-02-14 Bp Chemicals (Additives) Limited Procédé de préparation d'un concentré d'additifs pour des huiles lubrifiantes
EP0383359A2 (fr) * 1987-03-17 1990-08-22 Elf Antar France Procédé de préparation d'un additif suralcanisé renfermant un dérivé inorganique du bore, l'additif ainsi obtenu et compositions lubrifiantes renfermant ledit additif

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3070576A (en) * 1958-04-24 1962-12-25 Socony Mobil Oil Co Inc Complex metal salts of alkylphenolaldehyde condensation products and method for preparing same
US4021419A (en) * 1973-05-02 1977-05-03 The Lubrizol Corporation Basic metal salts of sulfur- and methylene-bridged poly-phenol compositions, and epoxide-reacted derivatives thereof, and lubricants containing them
WO1987001723A1 (fr) * 1985-09-18 1987-03-26 The Lubrizol Corporation Usinage de metaux en utilisant des lubrifiants contenant des sels de metaux alcalino-terreux basiques
EP0273588A1 (fr) * 1986-11-29 1988-07-06 Bp Chemicals (Additives) Limited Alkylphénates de métaux alcalino-terreux sulfurés, leur préparation et leur utilisation
EP0383359A2 (fr) * 1987-03-17 1990-08-22 Elf Antar France Procédé de préparation d'un additif suralcanisé renfermant un dérivé inorganique du bore, l'additif ainsi obtenu et compositions lubrifiantes renfermant ledit additif
EP0354647A2 (fr) * 1988-06-14 1990-02-14 Bp Chemicals (Additives) Limited Procédé de préparation d'un concentré d'additifs pour des huiles lubrifiantes

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997046646A1 (fr) * 1996-05-31 1997-12-11 Exxon Chemical Patents Inc. Detergents surbasiques contenant des metaux
WO1997046647A1 (fr) * 1996-05-31 1997-12-11 Exxon Chemical Patents Inc. Detergents surbasiques contenant des metaux
JP2000511577A (ja) * 1996-05-31 2000-09-05 エクソン ケミカル パテンツ インコーポレイテッド 金属含有過塩基性清浄剤
JP2000511953A (ja) * 1996-05-31 2000-09-12 エクソン ケミカル パテンツ インコーポレイテッド 金属含有過塩基性清浄剤
JP2000514473A (ja) * 1996-05-31 2000-10-31 エクソン ケミカル パテンツ インコーポレイテッド 金属含有過塩基性清浄剤
US6281179B1 (en) 1996-05-31 2001-08-28 Infineum Usa L.P. Process for preparing an overbased metal-containing detergents
CN1073148C (zh) * 1996-05-31 2001-10-17 埃克森美孚化学专利公司 高碱性含金属清净剂
US6417148B1 (en) 1996-05-31 2002-07-09 Infineum Usa L.P. Overbased metal-containing detergents
JP4763103B2 (ja) * 1996-05-31 2011-08-31 エクソンモービル ケミカル パテンツ インコーポレイテッド 金属含有過塩基性清浄剤
WO2004044109A2 (fr) * 2002-11-06 2004-05-27 The Lubrizol Corporation Des calixarates et lubrifiants en sus de la base contenant du bore et methodes s'y rapportant
WO2004044109A3 (fr) * 2002-11-06 2004-07-01 Lubrizol Corp Des calixarates et lubrifiants en sus de la base contenant du bore et methodes s'y rapportant

Also Published As

Publication number Publication date
EP0682688A1 (fr) 1995-11-22
GB9325132D0 (en) 1994-02-09
JPH08506617A (ja) 1996-07-16

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