KR100475390B1 - Overbased metal-containing detergents - Google Patents

Abstract

The present invention relates to useful marine diesel lubricant additives having a high proportion of phenate and salicylate surfactants in a surfactant system and having a TBN:% surfactant ratio of at least 11.

Description

Overbased Metal-Based Detergent {OVERBASED METAL-CONTAINING DETERGENTS}

The present invention relates, inter alia, to compositions suitable as lubricant additives, in particular to said water substances suitable for use as calcium overbased detergents, more particularly as lubricant additives for marine engines.

To meet the strong demands on capital, maintainability and performance prices, ship engine manufacturers build heavy new engines to minimize fuel and lubricant consumption, and supply suppliers with lubricants that reduce wear and extend overhaul. Making a request. There is a continuing need for lubricant additives that provide washability, oxidation resistance and corrosion protection and that neutralize acid corrosion from sulfur containing fuels. Overbased detergents can uniquely perform all these necessary functions.

As a result of the demands requested by engine manufacturers and users, lubricant formulators have been looking for high total base number (TBN) overbased detergents to reduce throughput while maintaining efficiency (in this specification, overbased detergents). Is the TBN (mgKOH / g) as measured by ASTM D2896). There is also a need for products that are highly effective as additives and are more cost effective than existing products and are relatively easy to manufacture and handle.

Overbased metal-containing detergents suitable for use as lubricant additives are typically prepared as a concentrate in oil. In such concentrates, the basic metal containing material is maintained in dispersion or solution in water, for example by a surfactant system comprising phenate, salicylate, sulfonate or naphthenate anions.

Overbased detergents initially contained a single type of anion, such as a group of phenate groups or sulfonate groups, but for several years add two or more overbased detergents having different different types of anions, or Compositions containing anions of two or more phenate groups or sulfonate groups obtained by the preparation of hybrid materials containing two or more different groups during the overbase process are used. As the basic substance, compounds of alkali and alkaline earth metal groups are used, and calcium compounds are most often used.

For example, in many applications for lubricating oils for marine engines, it may be desirable in some cases for the overbased detergent to contain relatively large amounts of phenate and salicylate anions for maximum efficiency. Such overbased detergents may also be useful in other applications.

The present invention is derivable (preferably derived) from two or more surfactants, at least one of which is a sulfinated or unsulfurized phenol or derivative thereof and the other or at least one is a non-phenolic surfactant. Calcium overbased detergent comprising a surfactant system, wherein the proportion of said phenol in the surfactant system measured as described herein is at least 15 mass%, and the overbased detergent is at least 21 TBN: % Surfactant ratio (as defined herein).

The term "calcium overbased detergent" means an overbased detergent wherein the metal cation of the basic metal containing material is essentially a calcium cation. Although small amounts of other cations may be present in the basic metal containing material, typically at least 80 mol%, more typically at least 90 mol%, such as at least 95 mol% of the cations in the basic metal containing material are calcium ions. Cations other than calcium can be derived from, for example, those used in the preparation of overbased detergents of surfactant salts, where the cations are metals other than calcium.

The percentage of surfactant in the overbased detergent and the percentage of individual surfactants (eg, phenol) in the surfactant system are measured by the method described below, which also shows how to measure the "standardized TBN" of the overbased detergent. It is a percentage.

1. Dialysis and Determination of Standardized TBN in Overbased Detergents

Known amounts (Ag, about 20 g) of liquid overbased detergents (almost free of other lubricant additives) are siphoned at a rate of 3 to 4 times per hour for 20 hours, with Soxhlet using n-hexane. Dialysis is carried out through the coating of an extruder (150 mm high x 75 mm inner diameter). The coating should contain substantially all metal containing materials and substantially all other samples. An example of a suitable coating is a gum rubber coating provided by Carters Products, Division of Carter Wallace Inc., Carters Products, 10105 New York, NY, under the trade name Trojans. The dialysate and residue obtained at the completion of the dialysis step are evaporated to dryness and any residual volatiles are removed in a vacuum oven (100 ° C. at less than 1 Torr or less than about 130 Pa). The mass (g) of dried residues is denoted by B. The percentage C of overbased detergent material in the liquid sample is represented by the following formula:

C = B / A × 100%

The “standardized TBN” of the overbased detergent (ie TBN is represented by a method independent of the content of the diluent) is TBN measured according to ASTM D2896 on the dried residue.

Background information on dialysis techniques can be found in Amos, R. and Albaugh, E.W. in "Chromatography in Petroleum Analysis", Altgelt, K.H. and Gouw, T.H., Eds, pages 417 to 422, Marcel Dekker, Inc., New York and Basel, 1979.

2.TBN: Determination of% Total Surfactant Ratio

A known amount of dry residue (Dg, about 10 g) is hydrolyzed as specified in sections 8.1 to 8.1.2 of ASTM D3712, with at least 200 ml of 25% by volume hydrochloric acid (specific gravity 1.18) in section 8.1.1 use. The amount of hydrochloric acid used should be sufficient to oxidize / hydrolyze the overbased detergent residue into organics (surfactants) and inorganics (calcium containing materials such as calcium chloride). The mixed ether extracts are dried by passing through anhydrous sodium sulfate. Sodium sulfate is rinsed with pure ether and the mixed ether solution is evaporated and dried (about 110 ° C.) to obtain a hydrolyzed residue. The mass (g) of dried hydrolysis residue is represented by E.

The percentage of total surfactant (Y) and TBN:% total surfactant ratio (X) in the original liquid overbased detergent is represented by the following formula:

Y = E / D × C

X = TBN / Y of liquid overbased detergent

It should be noted that in the measurement of X, the mass of the surfactant in free form (ie not in the form of salts or other derivatives) is used. For clarity, X will generally be referred to herein as "TBN:% surfactant ratio" and is the value of X as specified in the claims and elsewhere.

3. Determination of individual surfactants (in their glass form) in surfactant systems

The technique described below separates individual surfactants in hydrolyzed form from a hydrolyzed surfactant mixture derived from an overbased detergent. As shown below, the proportion of each individual surfactant is the mass proportion of the individual surfactants in hydrolyzed form in the hydrolyzed surfactant mixture. Thus, for example, if the overbased detergent contains a calcium phenate / sulfonate / salicylate surfactant system, the ratio of the individual surfactants in the surfactant system is represented as the ratio of phenol, sulfonic acid and salicylic acid, respectively.

The proportion of the individual surfactants can be measured by the following method.

The dried hydrolysis residue of known amount (Fg, about 1 g) obtained as described above is placed on top of a 450 × 25 mm (inner diameter) frit glass column filled with 60-100 US mesh florisil. Florisil is a magnesium silicate having a CAS number of 8014-97-9. The column was subjected to 250 ml of 7 solvents each, namely heptane, cyclohexane, toluene, ethyl ether, acetone, methanol and 50 vol% chloroform, 44 vol% isopropanol and 6 vol% ammonia solution, in increasing order of polarity. Elution with a mixture of (specific gravity 0.88). Each fraction was collected, evaporated to dryness, the resulting residue weighed and analyzed to determine the amount (G ¹ , G ² , G ³ ... g) and properties of the surfactant (s) contained in the fraction. Measure

Fractions (or hydrolyzed residues) can be analyzed by chromatography, spectroscopy and / or titration (color indicator or potentiometer) methods known to those skilled in the art. If the overbased detergent contains a sulfonate surfactant and salicylate surfactant, the sulfonic acid and salicylic acid obtained by hydrolysis of these surfactants will usually elute from the column together. In this case and when it is necessary to measure its proportion in the sulfonic acid containing mixture, the proportion of sulfonic acid in the mixture is described in Epton in Trans. Far. Soc. April 1948, 226 can be measured by the method described.

In this method, the mass (g, designated H ¹ ) of a given surfactant in hydrolyzed form is determined from the fraction (s) containing the surfactant and thus the interface in the surfactant system of the original overbased detergent. The proportion of active agent is as follows:

H ¹ / F × 100%

The percentage (mass%) of an individual surfactant (in its free form, ie not in the form of a salt or other derivative), based on the surfactant system, can be predicted from the proportion of surfactant used as starting material, provided that the "reaction component The percentage of "is known for the starting material of each surfactant (the term" reactive component "is defined in Note 1 of Tables 1 and 2 in the Examples herein). Thus, the percentage of total surfactant (in its free form) in the liquid overbased product can be predicted and the TBN:% surfactant ratio can be measured. Moreover, standardized TBNs can be predicted, but the proportion of overbased detergent material in the liquid overbased product (ie, the ratio of liquid overbased products that are non-oil or non-reactive surfactant materials) is known.

There is a good correlation between the predicted value and the measurement as described above.

The overbased detergent according to the invention is preferably a hybrid overbased detergent, ie an overbased detergent obtained by overbased a mixture containing two or more surfactants. One or more surfactants in the overbased mixture may be present in the already prepared overbased detergent.

The present invention also provides a process for the preparation of calcium overbased detergents having a surfactant system derived from two or more surfactants, the process comprising: (a) two or more surfactants (one or more of which are sulfurized or unsulfurized phenols or Derivatives thereof, the other or one or more of which is a surfactant other than a phenolic surfactant); (b) one or more basic calcium compounds; And (c) treating the mixture comprising the oil with an overbased agent (as defined later), wherein the treating with the overbased agent is carried out in one or more steps, preferably in two or more steps at a temperature of less than 100 ° C. The total proportion of phenol in the surfactant system of the overbased detergent, as measured herein, is at least 15 mass% and the overbased detergent has a TBN:% surfactant ratio of at least 21.

It will be understood that the mixture to be overbased contains free basic calcium compound (s), ie basic calcium compound (s) capable of reacting with the overbase. The term "overbased" means a reagent or compound that can react with basic calcium compound (s) (b) to form a basic calcium containing material that can be maintained in oil as a dispersion or solution by a surfactant system. If more than one overbased stage is used, other overbased agents may be used for other stages if necessary. In any individual overbased stage, a mixture of other overbased agents may be used if desired.

Examples of suitable overbased agents are carbon dioxide, a source of boron (eg boric acid), sulfur dioxide, hydrogen sulfide and ammonia. Preferred overbased agents are carbon dioxide or boric acid or mixtures thereof. The most preferred overbased agent is carbon dioxide, and for convenience treatment with the overbased agent will generally be referred to as "carbonation". Unless expressly stated otherwise herein, reference to carbonization herein is to be understood to include references to treatment with other overbased agents.

It is advantageous that some of the basic calcium compound (s) (b) are inelastic at the completion of the carbonization step (s). It is advantageous that the basic calcium compound (s) of up to 15% by mass, in particular up to 11% by mass, are non-elasticized.

As mentioned above, carbonization is carried out at less than 100 ° C. Typically, the carbonization is carried out at 15 ° C. or higher, preferably at 25 ° C. or higher. Advantageously, the carbonization is carried out below 80 ° C, more advantageously below 60 ° C, preferably below 50 ° C, more preferably below 40 ° C, in particular below 35 ° C. Advantageously, the temperature remains almost constant during each carbonization step, with only minor fluctuations. In the case where there is more than one carbonization step, two or all carbonization steps are preferably carried out at about the same temperature, but other temperatures may be used if necessary, with each step having to be carried out below 100 ° C.

Carbonization can be carried out at atmospheric, superatmospheric or subatmospheric pressure. Preferably the carbonization is carried out at atmospheric pressure.

Advantageously, a "heat-soaking" step is carried out after the first carbonization step (and preferably also the second or each subsequent carbonization step), wherein the mixture is added without the addition of any further chemical reagents. The selected temperature range (or selected temperature) (usually higher than the temperature at which carbonization is carried out) is maintained for a period before any further processing steps are carried out. The mixture is usually stirred during thermal dipping. Typically, the thermal immersion can be carried out for a period of at least 30 minutes, advantageously at least 45 minutes, preferably at least 60 minutes, in particular at least 90 minutes. The temperature at which the thermal immersion is carried out can typically be carried out in the range from 15 ° C. to below the reflux temperature of the reaction mixture, preferably from 25 to 60 ° C. The temperature is such that It is the temperature that almost does not have. Thermal immersion has the effect of stabilizing the product, dissociating solids and filtering.

Preferably, after the first carbonization step (and the heat dipping step, if used), an additional amount of basic calcium compound (component (b)) is added to the mixture, the mixture is carbonized again and the heat dipping step after the second carbonization step It is advantageous to carry out.

Products with reduced viscosity can be obtained using one or more additional additions of the basic calcium compound and subsequent carbonization, preferably after each carbonization step, a thermal soaking step is carried out. This is an important aspect of the present invention. Moreover, it has been found that products of high TBN and high TBN:% surfactant ratios with easy viscosity can be obtained by using the steps mentioned in this paragraph. In each case, the same amount of basic calcium compound and overbased agent can be used to compare the resulting product with fewer steps.

Basic calcium compounds for use in the preparation of overbased detergents include calcium oxide, calcium hydroxide, calcium alkoxide and calcium carboxylate. Calcium oxide and more particularly calcium hydroxide are preferably used. Mixtures of basic compounds can be used as needed.

Mixtures that become overbased by an overbased agent should usually contain water and may also contain one or more solvents, accelerators or other materials commonly used in overbased processes.

Examples of suitable solvents are aromatic solvents (eg benzene, alkyl substituted benzenes (eg toluene or xylene), halogen substituted benzenes) and lower alcohols (less than 8 carbon atoms), preferably aliphatic lower alcohols. Preferred solvents are toluene and / or methanol. The amount of toluene used is advantageously at least 1.5% by mass, preferably at least 15% by mass, more preferably at least 45% by mass, in particular at least 60% by mass, based on calcium overbased detergents (except oil) In particular, the amount is 90 mass% or more. For practical / economic reasons, the amount of toluene is typically less than 1200% by mass, advantageously less than 600% by mass, preferably less than 500% by mass, in particular less than 150% by mass. The amount of methanol used is advantageously at least 1.5% by mass, preferably at least 15% by mass, more preferably at least 30% by mass, in particular at least 45% by mass, more particularly based on calcium overbased detergents (except oil) It is the quantity which will be 50 mass% or more. For practical / economic reasons, the amount of methanol (as solvent) is typically less than 800 mass%, advantageously less than 400 mass%, preferably less than 200 mass%, in particular less than 100 mass%.

The percentage may be used together or applied separately or toluene and methanol.

Preferred promoters for use according to the invention are methanol and water. The amount of methanol used is advantageously based on the initial amount of basic calcium compound (s) (e.g. calcium hydroxide) (i.e. excluding any basic calcium compound (s) added in the second or subsequent steps). It is the quantity used as the mass% or more, Preferably it is 60 mass% or more, More preferably, it is 120 mass% or more, Especially 180 mass% or more, More especially, 210 mass% or more. For practical / economic reasons, the amount of methanol (as promoter) is typically less than 3200 mass%, advantageously less than 1600 mass%, preferably less than 800 mass%, in particular less than 400 mass%. The amount of water in the initial reaction mixture (prior to base treatment) advantageously excludes basic calcium compound (s) (eg calcium hydroxide) (ie any basic calcium compound (s) added to the second or subsequent steps). An amount such that water is at least 0.1% by mass, preferably at least 1% by mass, more preferably at least 3% by mass, in particular at least 6% by mass, more particularly at least 12% by mass, in particular at least 20% by mass, to be. For practical / economic reasons, the amount of water is typically less than 320 mass%, advantageously less than 160 mass%, preferably less than 80 mass%, in particular less than 40 mass%. If the reactants used are not anhydrides, the amount of water in the reaction mixture should take into account any water in the components and also water formed by neutralization of the surfactant. In particular, consideration should be given to any water present in the surfactant itself.

Advantageously, the reaction medium comprises methanol, water (some of which may be produced during salt formation) and toluene.

If desired, low molecular weight carboxylic acids (from 1 to about 7 carbon atoms) (eg, formic acid, inorganic halides or ammonium compounds) can be used to promote carbonization, improve filterability, or as viscous agents for overbased detergents. However, overbased detergents according to the invention can be prepared by processes which do not require the use of inorganic halide or ammonium salt catalysts (e.g., ammonium salts of lower carboxylic acids or alcohols), preferably such halides or There are no groups derived from ammonium catalysts (when inorganic halides or ammonium salts are used in the overbased process, the catalyst will usually be present in the final overbased detergent). In addition, the overbased detergents according to the invention can be prepared by processes that do not require the use of reagents such as dihydric alcohols (eg ethylene glycol) used when operating at high temperatures. The detergent is preferably free of dihydric alcohol or residues thereof.

The invention also provides an overbased detergent prepared by the process of the invention, a concentrate comprising an overbased detergent prepared according to or according to the invention, and a preparation according to or according to the invention. Oil-based compositions, in particular lubricating oils, in particular marine lubricating oils, comprising the overbased detergent.

For ease of handling, the follow KV to the present invention or a vaporized overbased detergent prepared according to the invention is advantageously 20,000mm ² / s is less than (preferably 10,000mm ² / s or less, particularly 5,000mm ² / under s) KV ₁₀₀ of less than ₄₀ and 2,000 mm ² / s (preferably less than 1,000 mm ² / s, in particular less than 500 mm ² / s). Throughout this specification, the viscosity is measured according to ASTM D445.

The overbased detergent according to the invention advantageously has a TBN of at least 300, more advantageously at least 330, preferably at least 350, more preferably at least 400, in particular at least 450. As described herein below, an important aspect of the present invention relates to the provision of TBN overbased detergents having an acceptable viscosity and relatively high ratios of phenate and salicylate surfactants in surfactant systems.

The present invention also makes it possible to provide overbased detergents having a high standardized TBN (as defined herein). Thus, for example, overbased detergents may have a standardized TBN of at least 450, in particular at least 460, advantageously at least 500, more advantageously at least 550, preferably at least 600, more preferably at least 650.

The TBN:% surfactant ratio is a measure of the amount of surfactant (comparatively expensive) required to make an overbased detergent of a particular TBN. The overbased detergent according to the invention has a TBN:% surfactant ratio of at least 21. With suitable starting materials / reaction conditions, a ratio of at least 25, at least 30, such as at least 35 or at least 40, can be obtained. Independently of the TBN:% surfactant ratio, the phenol ratio in the surfactant system is advantageously at least 25% by mass, more advantageously at least 35% by mass, preferably at least 45% by mass, more preferably at least 55% by mass, in particular It is 70 mass% or more.

Surfactant systems which can be derived from, or are derived from, overbased detergents prepared according to the invention or according to the invention, preferably contain one or more hydrocarbyl groups as substituents on, for example, aromatic rings. As used herein, the term "hydrocarbyl" does not exclude the presence of other atoms or groups in an amount in which the group concerned consists primarily of hydrogen and carbon atoms but does not deviate from the substantial hydrocarbon characteristics of the group. Advantageously, the hydrocarbyl groups in the surfactants used according to the invention are aliphatic groups, preferably alkyl or alkylene groups, in particular alkyl groups, which can be linear or branched. The total carbon number in the surfactant should be sufficient to give the desired oil solubility.

In the preparation of the overbased detergent according to the invention, if desired, one or more surfactants may be used in the form of derivatives thereof as needed, provided that the derivatives are not reacted with basic calcium compound (s) (b) if they are not metal salts. Calcium salts of the surfactant can be formed. If this is not clearly inadequate herein, the following discussion of each surfactant, and in other cases herein, of surfactants in the form of “free” (non-salt), also applies to appropriate derivatives of such surfactants. Examples of suitable derivatives of any preferred surfactants include ammonium salts, metal salts or esters of phenols; Ammonium salts, metal salts, esters, anhydrides, acid chlorides or amides of salicylic acid; Ammonium salts, metal salts, esters, anhydrides, acid chlorides or amides of carboxylic acids; Ammonium salts, metal salts, esters or anhydrides of sulfonic acids.

The phenols used according to the invention may be unsulfurized or preferably sulfurized. Moreover, the term "phenol" as used herein refers to phenols containing one or more hydroxyl groups (e.g. alkyl catechol), phenols containing molten aromatic rings (e.g. alkyl naphthol), phenols modified by chemical reactions. (Eg, alkylene crosslinked phenols and Mannich base condensed phenols); And salgenin-type phenols (generated by the reaction of phenols with aldehydes under basic conditions).

Preferred phenols leading to overbased detergents according to the invention can be represented by the formula

In the above formula,

R is a hydrocarbyl group,

y is 1 to 4: wherein when y is 1 or more, the hydrocarbyl groups may be the same or different.

In lubricating oil overbased detergents, phenols are often used in sulfided form. Sulfated hydrocarbyl phenols are typically represented by Formula 2:

In the above formula,

x is generally 1-4. In some cases, two or more phenol molecules may be joined by S _x crosslinking.

In the above formula, the hydrocarbyl group represented by R is advantageously an alkyl group having 5 to 100 carbon atoms, preferably 5 to 40 carbon atoms, in particular 9 to 12 carbon atoms, wherein the average carbon number in all R groups provides adequate solubility in oil. Is about 9 or more. Preferred alkyl groups are nonyl (tripropylene) groups.

In the following discussion, hydrocarbyl-substituted phenols will be referred to as alkyl phenols for convenience.

The sulfiding agent used in the production of sulfided phenols or phenates is any compound or element with a-(S) _x- (where x is generally 1 to about 4) crosslinking groups introduced between the alkyl phenol monomer groups. . Thus, the reaction can be carried out with elemental sulfur or halides thereof, for example sulfur dichloride, more preferably sulfur monochloride. Using the elemental sulfur, the sulfidation reaction can be carried out by heating the alkyl phenol compound at 50 to 250 ° C, preferably at 100 ° C or more. With elemental sulfur, a mixture of the aforementioned crosslinking groups-(S) _x -is typically obtained. Using sulfur halides, the sulfidation reaction can be carried out by heating the alkyl phenol at -10 to 120 ° C, preferably at 60 ° C or more. The reaction can be carried out in the presence of a suitable diluent. Diluents advantageously comprise organic diluents which are substantially inert, for example mineral oil or alkanes. In any case, the reaction is conducted for a time sufficient to effect the actual reaction. It is generally preferred to use 0.1 to 5 moles of alkyl phenolic material per equivalent of sulfiding agent.

If elemental sulfur is used as the sulfiding agent, it may be preferable to use a basic catalyst such as sodium hydroxide or an organic amine, preferably a heterocyclic amine (eg morpholine).

Details of the sulfiding method are known to those skilled in the art.

Sulfurized alkyl phenols useful in the preparation of overbased detergents include diluents and unreacted alkyl phenols, regardless of the method of making them, generally from 2 to 20 mass%, based on the mass of sulfided alkyl phenol, Preferably it contains 4-14 mass%, Most preferably, 6-12 mass%.

As mentioned above, the term "phenol" as used herein includes phenols and Mannich base-condensed phenols modified by, for example, chemical reaction with aldehydes.

Aldehydes which can modify the phenols used in accordance with the invention include, for example, formaldehyde, propionaldehyde and butyraldehyde. Preferred aldehydes are formaldehyde. Aldehyde-modified phenols suitable for use in accordance with the present invention are described, for example, in US Pat. No. 5,259 967.

Mannich base-condensed phenols are prepared by the reaction of phenols, aldehydes and amines. Examples of suitable Mannich base-condensed phenols are described in British Patent Application No. 2 121 432.

In general, phenols may include substituents other than those mentioned above unless the substituents significantly impair the surfactant properties of the phenol. Examples of such substituents are methoxy groups and halogen atoms.

In a preferred embodiment of the invention, at least one surfactant capable of inducing the surfactant system is salicylic acid or a derivative thereof.

Salicylic acid used according to the invention may be unsulfurized or sulfided, and may be chemically modified and / or contain further substituents such as those discussed above for phenols, for example. Processes similar to those described above can also be used to sulfide hydrocarbyl-substituted salicylic acid and are known in the art. Salicylic acid is typically prepared by carboxylation of phenoxide by the Kolbe-Schmitt process, in which case it will be obtained in a mixture with the non-carboxylated phenol (generally in a diluent).

Preferred substituents on the fat-soluble salicylic acid from which the overbased detergent according to the invention can be derived are those substituents defined as R in the above discussion of phenols. In alkyl-substituted salicylic acids, the alkyl groups are advantageously 5 to 100 carbon atoms, preferably 9 to 30, in particular 14 to 20 carbon atoms.

In another aspect of the invention, the one or more surfactants capable of inducing the surfactant system are sulfonic acids or derivatives thereof.

The sulfonic acids used according to the invention are typically hydrocarbyl-substituted, especially alkyl-substituted aromatic hydrocarbons, for example by sulfonation of those obtained from petroleum fractionation by distillation and / or extraction, or by aromatic hydrocarbons Obtained by alkylation of. Such examples include those obtained by alkylation of benzene, toluene, xylene, naphthalene, biphenyl or halogen derivatives thereof such as chlorobenzene, chlorotoluene or chloronaphthalene. Alkylation of aromatic hydrocarbons includes, for example, alkylating agents having at least about 3 to 100 carbon atoms, such as haloparaffins, olefins obtainable by dehydrogenation of paraffins, and polymers of polyolefins such as ethylene, propylene and / or butene. Can be carried out in the presence of a catalyst. Alkylaryl sulfonic acids generally contain from about 7 to about 100 carbon atoms or more. They preferably contain about 16 to about 80 carbon atoms, or 12 to 40 carbon atoms per alkyl-substituted aromatic moiety depending on the raw material from which they are obtained.

When neutralizing the alkylaryl sulfonic acid to make sulfonates sulfonates, not only accelerators and viscosity modifiers but also hydrocarbon solvents and / or diluent oils may also be included in the reaction mixture.

Another type of sulfonic acid that can be used according to the invention includes alkyl phenol sulfonic acids. Such sulfonic acids can be sulfided. Whether sulfided or unsulfurized, these sulfonic acids are thought to have surfactant properties similar to sulfonic acids rather than surfactant properties similar to phenolic properties.

Sulphonic acids suitable for use according to the invention also include alkyl sulfonic acids. In such compounds, the alkyl group suitably contains 9 to 100 carbon atoms, advantageously 12 to 80 carbon atoms, in particular 16 to 60 carbon atoms.

In one aspect of the invention, the surfactant system may be derived from one or more sulfided phenols or derivatives thereof and one or more sulfonic acids or derivatives thereof. In this case, the ratio of phenol to sulfonic acid as measured herein is 15:85 to 95: 5 mass%, preferably 30:70 to 70:30 mass%, especially 40:60 to 60:40 mass It is preferable that it is%.

In another aspect of the invention, the surfactant system may be derived from one or more sulfided phenols or derivatives thereof, one or more salicylic acids or derivatives thereof and one or more sulfonic acids or derivatives thereof. In such cases, the ratio of phenol to salicylic acid to sulfonic acid in the surfactant system measured as described herein is advantageously 15 to 90 mass%: 5 to 90 mass%: 20 to 80 mass%; Preferably it is 20-80 mass%: 20-80 mass%: 10-50 mass%; Especially 30-50 mass%: 25-45 mass%: 15-35 mass%.

If desired, one or more surfactants capable of inducing surfactant systems in overbased detergents may be carboxylic acids.

Carboxylic acids that can be used according to the invention include monocarboxylic acids and dicarboxylic acids. Preferred monocarboxylic acids are those containing from 1 to 30 carbon atoms, in particular from 8 to 24 carbon atoms. (When the specification indicates the number of carbon atoms in the carboxylic acid, the carbon atom (s) in the carboxyl group are encompassed by that number.) Examples of monocarboxylic acids are iso-octanoic acid, stearic acid, oleic acid, palmitic acid. And behenic acid. Iso-octanoic acid can be used, if necessary, in the form of a mixture of C ₈ acid isomers marketed by Exxon Chemical under the trade name “Cekanoic”. Other suitable acids are those having tertiary substitution at di-acids and α-carbon atoms with two or more carbon atoms dividing the carboxyl group. Also suitable are dicarboxylic acids having 35 or more carbon atoms, for example 36 to 100 carbon atoms. Unsaturated carboxylic acids can be sulfided. Although salicylic acid contains a carboxyl group, for the purposes of the present specification salicylic acid is considered a separate group of surfactant and not a carboxylic acid surfactant. (Or they contain hydroxyl groups, but they are not considered phenolic surfactants.)

In one embodiment of the invention, when a carboxylic acid / derivative is used, it is (a) an acid of the general formula R ^a -CH (R ^b ) -COOH, wherein R ^a is alkyl containing from 10 to 24 carbon atoms or An alkenyl group, R ^b represents hydrogen, an alkyl group having 1 to 4 carbon atoms or a CH ₂ COOH group or an acid anhydride, acid chloride or ester thereof), or (b) a carbon atom of 36 to 100 It does not contain dicarboxylic acids or polycarboxylic acids or acid anhydrides, acid chlorides or esters thereof. In another embodiment of the invention, if a carboxylic acid / derivative is used it has 8 to 11 carbon atoms in the carboxyl-containing moiety.

In a further aspect of the invention, when a carboxylic acid / derivative is used, it is not a monocarboxylic acid / derivative having 11 or more carbon atoms in the carboxyl-containing moiety. In another embodiment, the carboxylic acid / derivative is not a dicarboxylic acid / derivative having 11 or more carbon atoms in the carboxyl-containing moiety. In further embodiments, the carboxylic acid / derivative is not a polycarboxylic acid / derivative having 11 or more carbon atoms in the carboxyl-containing moiety. In another embodiment, the carboxylic acid surfactant is not hydrocarbyl-substituted succinic acid or derivatives thereof.

In another aspect of the present invention, the surfactant system may be derived from one or more sulfurized phenols or derivatives thereof, one or more sulfonic acids or derivatives thereof and one or more carboxylic acids or derivatives thereof. In such cases, the ratio of phenol to sulfonic acid to carboxylic acid, as measured herein, may range from 15 to 90 mass%: 5 to 90 mass%: 5 to 90 mass%; Preferably it is 20-80 mass%: 10-50 mass%: 10-50 mass%; In particular, it is 30-70 mass%: 10-30 mass%: 10-30 mass%.

Examples of other surfactants that can be used according to the invention include the following compounds and derivatives thereof: naphthenic acid, in particular naphthenic acid, dialkylphosphonic acid, dialkylthiophosphonic acid and dialkyl containing one or more alkyl groups Dithiophosphoric acid, high molecular weight (preferably ethoxylated) alcohols, dithiocarbamic acid, thiophosphine and dispersants. These types of surfactants are known to those skilled in the art.

If a surfactant is used in the form of a salt, any suitable cation, for example quaternary nitrogen ions or preferably metal ions, may be present. Suitable metal ions include alkali metals, alkaline earth metals (including magnesium) and transition metal ions. Examples of suitable metals are lithium, potassium, sodium, magnesium, calcium, barium, copper, zinc and molybdenum. Preferred metals are lithium, potassium, sodium, magnesium and calcium, more preferably lithium, sodium, magnesium and calcium, in particular calcium. Neutralization of the surfactant may be carried out before the addition of the basic calcium compound (s) (b) used in the overbased step or by the basic calcium compound.

If necessary, mixtures of two or more members of any one group of surfactants can be used to prepare the overbased detergent according to the invention, provided that at least one surfactant from another group is also present. Thus, for example, a mixture of compounds is produced by many processes of introducing a substituent into an aromatic ring, and it is generally convenient to use such mixture without separation of the components from each other.

The overbased detergents used herein are any particular surfactant, such as phenolic surfactants and sulfonic acid surfactants, or phenolic surfactants, sulfonic acid surfactants and carboxylic acid surfactants, or phenolic surfactants, salicylic acid surfactants and sulfides. When prepared from phonic acid surfactants, the total proportion of these surfactants (free form) in the surfactant system of overbased detergents is advantageously at least 75% by mass, preferably at least 85% by mass, in particular at least 95% by mass. .

It is possible according to the invention to obtain high TBN overbased phenate detergents while minimizing the amount of (relatively expensive) surfactant components of the overbased detergents; The present invention thus yields a phenate overbased detergent having a relatively high TBN:% surfactant ratio. Thus, especially for marine lubricants, since marine engines require a relatively large amount of lubricant (e.g. marine diesel cylinder lubricant (MDCL) is a "one-pass" lubricant) containing high TBN overbased detergents. However, it is also advantageous in the case of other lubricants, for example crankcase lubricants. In addition, very effective overbased detergents having a relatively low viscosity can be provided by the present invention even when the surfactant system contains a relatively high content of phenate / salicylate.

High TBN calcium overbased sulfonates and carboxylates with low viscosity are previously known. Surfactant systems that can contain relatively high amounts of phenates while minimizing the need for relatively expensive surfactants, providing excellent levels of performance in many applications (eg marine lubricants) and can also have high TBN and low viscosity The provision of calcium overbased detergents, including the above, shows considerable technical progress.

In addition, the previously proposed method of preparing overbased phenate detergents used a relatively high carbonization temperature, for example a temperature of 100 ° C. or higher, and many conventional proposed methods require 12 or more carbon atoms to obtain satisfactory products. It has been disclosed that the use of a surfactant such as any carboxylic acid having is essential. According to the invention, it can be carried out at low temperatures and without reagents such as glycols required for operation at high temperatures. In addition, satisfactory products can be obtained without using any carboxylic acid having 12 or more carbon atoms previously disclosed as essential.

As mentioned above, the overbased detergent according to the invention is preferably a hybrid overbased detergent, ie an overbased detergent obtained by overbased a mixture containing two or more surfactants. Such a hybrid detergent has the advantage that it can provide an overbased detergent system having properties by two or more surfactants without the need to prepare or blend two or more separate overbased detergents. It also eliminates the need to blend separate overbased detergents, providing more flexibility with regard to the final TBN, surfactant ratio, and TBN:% surfactant ratio, and also preparing blends containing separate overbased detergents. It can overcome the problems of incompatibility or stability that can be experienced.

More particularly, it has been found that the hybrid overbased detergent of the present invention results in improved stability when used to formulate lubricants for example for trunk piston marine diesel engines, ie for medium-speed marine diesel engines. In particular, when formulating the oil to contain phenate, sulfonate and salicylate surfactant anions, greater stability is achieved when two or more of these anions are provided to the oil in the form of the complex detergent of the invention (stored As measured by volume percent reduction of sediment in oil). This is compared to the oil when three anions are provided to the oil each separately.

For example, oils in combination with phenate: sulfonate hybrid overbased detergents of the invention and salicylates provided separately, and oils in combination with phenates: sulfonate: salicylate hybrid overbased detergents of the invention Has greater stability than the comparative oils, each combined with phenates, sulfonates and salicylates provided separately.

For example, overbased detergents prepared according to the invention or prepared according to the invention which are generally prepared as concentrates in oils containing 50 to 70 mass% of overbased detergents based on the mass of the concentrate are oil-based. Useful as additives (such as lubricants or greases) to the compositions, the present invention therefore also provides such compositions containing overbased detergents and concentrates for use in the preparation of such compositions. The amount of overbased detergent included in the oil-based composition depends on the type of composition and its proposed use: marine lubricants typically range from 0.5 to 18 mass% of overbased detergents based on the active ingredient Automotive crankcase lubricant typically contains 0.01 to 6% by mass of overbased detergent (based on the active ingredient based on the final lubricant).

The overbased detergents according to or according to the invention are substances which are either fat soluble or dissolved in oil (with any other additives described below) with the aid of a suitable solvent, or are stably dispersible. The term fat soluble, soluble or stable dispersibility, as used herein, does not necessarily indicate that the additive may be soluble, soluble, miscible, or suspended in the oil in all proportions. However, additives mean, for example, that they are soluble or stably dispersible in the oil to an extent sufficient to achieve their desired effect in the environment in which the oil is used. Moreover, when other additives are incorporated into the oil-based composition, higher levels of special additives may be incorporated as needed.

The overbased detergent can be incorporated into the base oil in any convenient way. Thus, they may optionally be added directly to the oil by dispersing or dissolving them in the oil at the desired level of concentration with the aid of a suitable solvent such as toluene or cyclohexane. Such blending can occur at room or elevated temperatures.

Overbased detergents according to or according to the invention are particularly useful in lubricating oil compositions using base oils in which the mixture is dissolved or dispersed. Base oils that may be used with the overbased detergents include those suitable for use as spark-ignition and compression-ignition internal combustion engines, such as crankcase lubricants for automotive and truck engines, and marine diesel engines. As mentioned above, overbased detergents are particularly useful for lubricants for use in marine engines.

Synthetic base oils include alkyl esters of dicarboxylic acids, polyglycols and alcohols; Poly-α-olefins including polybutene; Alkyl benzenes; Organic esters of phosphoric acid, and polysilicon oils.

Natural base oils are not only their raw materials, for example paraffinic, naphthenic, mixed or paraffinic-naphthenic, but also the methods used in the preparation, such as their distillation range, and directly carried out or degraded, Inorganic lubricants that can vary widely depending on whether they are hydropurified or solvent extracted.

Lubricant base stocks suitable for use in crankcase lubricants conveniently have a viscosity of about 2.5 to about 12 cSt or mm ² / s at 100 ° C., but base stocks having other viscosities, such as bright stock, may be used. .

Lubricant base stocks suitable for use in marine lubricants conveniently have a viscosity of about 3 to about 15 cSt or mm ² / s at 100 ° C., but base stocks having other viscosities may also be used. Thus, bright raw materials having a viscosity of about 30 to 35 cSt or mm ² / s at 100 ° C. can be used, for example.

The overbased detergents according to or according to the invention can be used in lubricating oil compositions which typically comprise large amounts of lubricating oil and typically small amounts of overbased detergents. Additional additives may be incorporated into the compositions to conform to particular regulations. Examples of additional additives that may be included in the lubricating oil composition containing the overbased detergent according to the invention include viscosity index improvers, abrasion inhibitors, other antioxidants or antioxidants, friction modifiers, dispersants, other detergents, metal rust inhibitors, Abrasives, pour point inhibitors and foam inhibitors. Lubricants suitable for use in marine engines advantageously include dispersants and antiwear agents as further additives, and may also include other additives such as additional antioxidants, antifoam agents and / or rust inhibitors. The additional optional additives described below are more suitable for use in automotive engine lubricants than in lubricants for marine engines.

Viscosity index improvers (or viscosity modifiers) provide lubricating oils with high and low temperature operability, maintain shear stability at elevated temperatures and exhibit acceptable viscosity or flowability at low temperatures. Compounds suitable for use as viscosity modifiers are generally high molecular weight hydrocarbon polymers including polyesters, and viscosity index improving dispersants that act as dispersants as well as viscosity index improvers. The fat soluble viscosity modified polymers generally have a weight average molecular weight of about 10,000 to 1,000,000, preferably 20,000 to 500,000 as measured by gel permeation chromatography or light dispersion methods.

Abrasion inhibitors reduce degradation of metal parts in contact with the lubricating oil composition. Thiadiazoles, for example those disclosed in US Pat. Nos. 2 719 125, 2 719 126 and 3 087 932, are examples of wear inhibitors for lubricating oils.

Antioxidants or antioxidants reduce the tendency of mineral oils to damage when used, evidence of such damage is, for example, the production of varnish-like deposits and sludge on metal surfaces and an increase in viscosity. Suitable oxidation inhibitors include sulfided alkyl phenols and their alkali or alkaline earth metal salts; Diphenylamine; Phenyl-naphthylamine; And sulfurized or sulfurized hydrocarbons.

Other antioxidants or antioxidants that may be used in the lubricating oil composition include fat-soluble copper compounds. Copper may be blended into the oil as any suitable fat-soluble copper compound. Fat soluble means that the compound is fat soluble under normal blending conditions in an oil or additive package. For example, copper may be in the form of copper dihydrocarbyl thio- or dithio-phosphate. Alternatively, copper can be added as a copper salt of synthetic or natural carboxylic acids, such as C ₈ to C ₁₈ fatty acids, unsaturated acids or branched carboxylic acids. Also useful are fat soluble copper dithiocarbamates, sulfonates, phenates and acetylacetonates. Examples of particularly useful copper compounds are basic, neutral or acidic copper Cu ^I and / or Cu ^II salts derived from alkenyl succinic acids or anhydrides.

Copper antioxidants may generally be used in amounts of about 5 to 500 ppm per weight of copper in the final lubricating composition.

Friction modifiers and fuel savers that are miscible with other components of the final oil may also be included. Examples of such materials are glyceryl monoesters of higher fatty acids, esters of long-chain polycarboxylic acids and diols, oxazoline compounds and fat-soluble molybdenum compounds.

Dispersants keep the water-soluble material produced by oxidation during use in suspension in the fluid to prevent sludge agglomeration and precipitation or deposition on metal parts. So-called ashless dispersants are organic materials that do not substantially form ash upon combustion as compared to metal-containing (and thus ash-forming) detergents. Boronated metal-free dispersants are also considered herein as ashless dispersants. Suitable dispersants include, for example, derivatives of long-chain hydrocarbon-substituted carboxylic acids in which the hydrocarbon group contains 50 to 400 carbon atoms, examples of which are derivatives of high molecular weight hydrocarbyl-substituted succinic acid. Such hydrocarbyl-substituted carboxylic acids can, for example, react with nitrogen-containing compounds, advantageously polyalkylene polyamines, or esters. Particularly preferred dispersants are the reaction products of polyalkylene amines with alkenyl succinic anhydrides.

Viscosity index improvement dispersants act as both viscosity index improvers and dispersants. Examples of viscosity index improving dispersants suitable for use in lubricating compositions include hydrocarbyl-substituted mono- amines (such as polyamines) and hydrocarbyl substituents comprising chains of length sufficient to provide the compound with viscosity index improving properties. Or reaction products with dicarboxylic acids.

Examples of dispersants and viscosity index improving dispersants are disclosed in European Patent Application No. 24146.

Additional detergents and metal rust inhibitors include metal salts of sulfonic acids, alkyl phenols, sulfided alkyl phenols, alkyl salicylic acids, thiophosphonic acids, naphthenic acids and other fat-soluble mono- and dicarboxylic acids, which may be overbased. Representative examples of detergent / rust inhibitors and their preparation are described in European Patent Application No. 208 560.

Anti-wear agents, as their name implies, reduce the wear of metal parts. Zinc dihydrocarbyl dithiophosphate (ZDDP) is very widely used as an antiwear agent. Particularly preferred ZDDPs for use in oil-based compositions are those of the general formula Zn [SP (S) (OR ¹ ) (OR ² )] ₂ , wherein R ¹ and R ² are from 1 to 18, preferably from 2 to 12 carbon sources. It is a compound of).

Pour point inhibitors, otherwise known as lubricating oil flow improvers, lower the minimum temperature at which the fluid may or may flow. Such additives are known. Foaming control can be provided by anti-foaming agents of the polysiloxane type, for example silicone oil or polydimethyl siloxane.

Some of the above mentioned additives can provide multiple effects; Thus, for example, a single additive can act as a dispersant-oxidation inhibitor. This method is known and need not be discussed further herein.

If the lubricating composition contains one or more of the additives described above, each additive is typically blended into the base oil in an amount in which the additive can provide the desired function. Typical amounts of these additives when used in crankcase lubricants are:

Typical ratios for additives for TPEO (trunk piston engine oil) are:

Typical ratios for additives for MDCL (shipping diesel cylinder lubricant) are as follows:

When multiple additives are used, it may be desirable to prepare one or more additive packages including, but not necessarily, additives to form a lubricating oil composition by adding multiple additives simultaneously to the base oil. Dissolving the additive package (s) in the lubricating oil may be facilitated by the solvent and by mixing with mild heating, but this is not necessary. When the additive package is mixed with a predetermined amount of base lubricant, the additive package (s) will be formulated containing the appropriate amount of additive (s) to provide the desired concentration in the final blend. Thus, the at least one overbased detergent according to the invention can be added to a small amount of base oil or other miscible solvent together with other preferred additives, for example from about 2.5 to about 90 mass%, preferably based on the additive package. An additive package is formed that contains about 5 to about 75 mass%, most preferably about 8 to about 60 mass% of the active ingredient and the balance in the appropriate amount of base oil.

The final blend typically contains about 5-40 mass% of the additive package (s), with the remainder being the base oil.

The following examples illustrate the invention.

Example 1

540 g of toluene, 276 g of methanol, and 22 g of diluted oil (150N) were introduced into the reactor and maintained at about 20 ° C. while mixing. Calcium hydroxide (Ca (OH) ₂ ) (145 g) was added and the mixture was heated to 40 ° C with stirring. To the slurry obtained in this way, a mixture of the phenol and sulfonic acid surfactants specified in Table 1 maintained at 40 ° C. and 100 g of toluene were added followed by an additional amount (50 g) of toluene.

After neutralizing the surfactant with calcium hydroxide, the temperature of the mixture is reduced to about 28 ° C. and maintained at this temperature of 28 ° C. while carbon dioxide is added to the mixture at a rate such that almost all carbon dioxide is absorbed into the reaction mixture to form a basic substance. Injected. The temperature was then raised to 60 ° C. for 60 minutes and then the mixture was cooled to about 28 ° C. for 30 minutes. At 28 ° C., an additional amount of calcium hydroxide (127 g) was added and carbon dioxide (62 g) was charged. After the second carbonization step the temperature was raised to 60 ° C. for 90 minutes.

Subsequently, the volatiles were distilled off, another fill of diluent oil (267 g) was introduced and the product was filtered to remove the precipitate.

Details of the starting materials used in all the examples are given in Table 1 and the accompanying notes. In Table 1, the amount of diluted oil SN150 is the total amount filled. Table 2 shows TBN,% total surfactant (Y, measured as described herein) and TBN:% total surfactant ratio (X, measured as described herein), standardized TBN and overbased detergents. The proportion of individual surfactants in the surfactant system (see note 2 in Table 1 and Table 2) is shown along with the viscosity data, filtration rate (kg / m ² / h) and filtration gradient.

Examples 2 to 23

500 to 690 g of toluene, using the starting materials and starting material proportions shown in Table 1 and the accompanying notes; 270 to 330 g methanol; The method shown in Example 1 was repeated using 15-25 g of water. The characteristics of the overbased detergent obtained are shown in Table 2.

In Examples 5-8, 15 g of formic acid was added to the reactor.

In Example 12, SN600 oil was used in place of SN150 oil.

In Examples 2, 4, 9, 10 and 18 to 22, the product was filtered off in the solvent after removal of the polar solvent.

In Example 17 carbonization was carried out at 30 ° C.

In Example 23, the addition (third) calcium hydroxide addition, carbon dioxide addition, and thermal immersion sequence were performed under the conditions shown in Example 1 for the second sequence, except that each thermal immersion step was performed as the first sequence. It was.

Hydrogen sulfide and when in the production of an overbased detergent according to the invention, in particular after the distillation of volatiles and before filtration to remove deposits, the detergent needs to be maintained at elevated temperatures such as 130 ° C. for extended periods of time, for reasons of operation. There may be release of sulfur compounds such as mercaptans.

Such releases are undesirable because they are safe and impede the operation of sanitary installations. A way to prevent or improve this release is to treat olefins at any stage of the preparation of the detergent. For example, the olefins may be mixed in the period of time spent in the preparation of raw materials, neutralization, overbased, distillation of volatiles or elevated temperatures (ie, any stage of detergent preparation). Mixing during solvent distillation is preferred (eg, about 130 ° C.).

Any olefin may be used that may remain in solution or dispersion in detergents at elevated temperatures. Examples of such olefins are high or low substituted olefins having 18 to 60 carbon atoms or more. Specific examples of such olefins include n-octadecene; Olefin mixtures having an average carbon number of 24; And oligomers of butenes. Suitable treatment rates for the olefins are at least 0.1-5% by mass, preferably 0.1-2% by mass, based on the processed detergent.

Comments on Table 1 and Table 2

1. Sources of phenol, sulfonic acid, salicylic acid and carboxylic acid surfactants (see Table 1) are shown in Table 3 below.

In Table 3, a.i. = Mass% of the surfactant-containing substance filled in the reaction vessel, not diluent oil. r.i. = Mass% of "reactive component", ie, the percentage of surfactant filled in the reaction vessel associated with calcium in the liquid overbased detergent.

(The term "active ingredient" has its usual meaning and will be understood to refer to a portion of the surfactant containing material which comprises molecules other than diluent oil molecules. The interface for preparing an overbased detergent according to the invention When using an active agent, in some cases the surfactant molecule portion does not react with the basic calcium compound (s) and remains in unsalted form in the liquid overbased detergent.In this case, the percentage of "reactive component" is "active." Will be lower than the percentage of components ").

2. In Table 2,% phenol,% sulfonic acid,% salicylic acid and% carboxylic acid are based on the mass of the total surfactant (hydrolysis form) with respect to the basic calcium compound in the overbased detergent, respectively. Mass% (hydrolysis form) of surfactant, salicylic acid surfactant and carboxylic acid.

Claims (27)

A calcium overbased detergent comprising a surfactant system derived from two or more surfactants, At least one surfactant is a sulfurized or unsulfurized phenol or derivative thereof, and the other or at least one other surfactant is a surfactant that is not a phenolic surfactant, The proportion of said phenol in the surfactant system is at least 15% by mass and has a TBN:% surfactant ratio of at least 21, where% surfactant is the mass% of the total surfactant in the free form in the liquid overbased product. ; Inorganic halides or ammonium salts, and substantially free of groups or compounds derived from said compounds, free of dihydric alcohols and groups derived from dihydric alcohols, Calcium overbased detergent. The method of claim 1, An overbased detergent wherein the proportion of phenol in the surfactant system is at least 25% by mass. The method according to claim 1 or 2, An overbased detergent wherein the phenol is a hydrocarbyl substituted phenol. The method according to claim 1 or 2, An overbased detergent wherein the at least one surfactant derived from the surfactant system is sulfonic acid or a derivative thereof. The method of claim 4, wherein An overbased detergent wherein the sulfonic acid is a hydrocarbyl substituted aryl sulfonic acid. The method of claim 4, wherein An overbased detergent having a total proportion of phenol and sulfonic acid in the surfactant system of at least 75% by mass. The method of claim 4, wherein An overbased detergent wherein the surfactant system is derived from one or more sulfided phenols or derivatives thereof and one or more sulfonic acids or derivatives thereof, wherein the ratio of phenol to sulfonic acids in the surfactant system is from 15:85 to 95: 5 mass%. The method according to claim 1 or 2, An overbased detergent wherein the at least one surfactant derived from the surfactant system is a carboxylic acid or derivative thereof. The method of claim 8, The carboxylic acid / derivative is (a) an acid of formula R ^a -CH (R ^b ) -COOH, wherein R ^a is an alkyl or alkenyl group having 10 to 24 carbon atoms, and R ^b is hydrogen, an alkyl group having 1 to 4 carbon atoms , CH ₂ COOH group or an acid anhydride, acid chloride or ester thereof) and (b) an overbased detergent other than dicarboxylic acid, polycarboxylic acid, or acid anhydride, acid chloride or ester thereof. The method of claim 8, An overbased detergent wherein the carboxylic acid / derivative has 8 to 11 carbon atoms at the carboxyl residue. The method of claim 8, An overbased detergent having a total proportion of phenol, sulfonic acid and carboxylic acid in the surfactant system of at least 75% by mass. The method of claim 8, The surfactant system is derived from one or more sulfided phenols or derivatives thereof, one or more sulfonic acids or derivatives thereof and one or more carboxylic acids or derivatives thereof, and the ratio of phenol to sulfonic acid to carboxylic acid is 15 to 90: 5 to 90: 5 to 90 Overbased detergent by mass. The method according to claim 1 or 2, An overbased detergent wherein the one or more surfactants derived from the surfactant system are sulfurized or unsulfated salicylic acid or derivatives thereof. The method of claim 13, An overbased detergent wherein salicylic acid is a hydrocarbyl substituted salicylic acid. The method of claim 13, An overbased detergent having a total proportion of phenol, salicylic acid and sulfonic acid in the surfactant system of at least 75% by mass. The method of claim 13, The surfactant system is derived from at least one sulfided phenol or derivative thereof, at least one salicylic acid or derivative thereof and at least one sulfonic acid or derivative thereof, wherein the ratio of phenol to salicylic acid to sulfonic acid in the surfactant system is from 15 to 90% by mass: 5-90 mass%: overbased detergent which is 20-80 mass%. The method according to claim 1 or 2, Overbased detergent with a TBN of at least 300. The method according to claim 1 or 2, Overbased detergent with a standardized TBN of at least 450. The method according to claim 1 or 2, An overbased detergent having a viscosity of up to 20,000 mm ² / s at 40 ° C. The method according to claim 1 or 2, Overbased detergent having a viscosity of less than 2,000 mm ² / s at 100 ° C. The method according to claim 1 or 2, Overbased detergent, a hybrid detergent. A process for preparing calcium overbased detergents having a surfactant system derived from two or more surfactants, (a) two or more surfactants, one or more of which are sulfurized or unsulfurized phenols or derivatives thereof, and the other or one or more other surfactants, which are not phenolic surfactants; (b) one or more basic calcium compounds; And (c) treating the mixture comprising the oil in at least one step using an overbased agent at a temperature below 100 ° C., wherein The total proportion of phenols in the surfactant system of the overbased detergent is at least 15% by mass and the TBN:% surfactant ratio of at least 21 [wherein the% surfactant is the mass% of the total surfactant in free form in the liquid overbased product. Is; A process for the preparation of calcium overbased detergents, which is carried out without the use of inorganic halides or ammonium salts, and groups or compounds derived from said compounds and groups derived from dihydric and dihydric alcohols. An oil-based composition comprising an overbased detergent according to claim 1. The method of claim 23, A composition in the form of a concentrate. Lubricating oil comprising an overbased detergent according to claim 1. The method of claim 25, Lubricant, wherein the lubricant is used in marine engines. A lubrication treatment method of a marine engine comprising supplying a lubricating oil according to claim 25 to an engine.