KR100475399B1 - Overbased metal-containing detergents - Google Patents

Abstract

Phenate overbased detergents and salicylate overbased detergents with a TBN:% surfactant ratio of at least 11 are useful marine diesel lubricating additives.

Description

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

The present invention relates in particular to compositions suitable as lubricant additives, in particular calcium overbased detergents, and more particularly to materials suitable for use as lubricant additives for use in marine engines.

To meet the strong pressures on capital, maintainability and running costs, marine engine manufacturers are very keen to offer their suppliers to manufacture new engines designed to minimize fuel and lubricant consumption and provide lubricants that reduce wear and extend overhaul. Making a request. There is a continuing need for lubricating oil additives that provide washability, antioxidant and corrosion protection and that neutralize corrosive acids from sulfur containing fuels. Overbased detergents can uniquely play all of these necessary roles.

As a result of requirements imposed by engine manufacturers and users, lubricant formulators seek higher total base number (TBN) overbased detergents to maintain effectiveness while reducing processing speed (in this specification, over-salt) The TBN of the vaporized detergent is TBN in mg KOH / g, as measured by ASTM D2896). There is also a need for a product that is very effective as an additive, cheaper than existing products, and 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 oil, for example by a surfactant system comprising phenate, salicylate, sulfonate or naphthenate anions.

Overbased detergents initially contained, for example, a single form of a member or members of a phenate group or sulfonate group, but recently added two or more overbased detergents with different forms of anions or hybrid materials (where, Compositions containing anions of two or more phenate groups or sulfonate groups obtained by the preparation of two or more different groups of anions are mixed during the overbased process are available. As the basic substance, compounds of members of alkali and alkaline earth metal groups are used, and calcium compounds are most often used.

In lubricating oils for many applications, for example for use in marine engines, for maximum effectiveness it may be desirable in some cases for the overbased detergent to contain a relatively high proportion of phenate and salicylate anions. Such overbased detergents may also be useful in other applications.

The present invention provides that at least one of the surfactants is a sulfinated or unsulfurized phenol or derivatives thereof, the other or at least one of the surfactants is a surfactant different from the phenolic surfactant, and (a) a general formula R ^a -CH ( An acid of R ^b ) -COOH, wherein R ^a represents an alkyl or alkenyl group containing 10 to 24 carbon atoms, and R ^b represents hydrogen, an alkyl group having 1 to 4 carbon atoms or a CH ₂ COOH group ) Or acid anhydrides, acid chlorides or esters thereof, and (b) dicarboxylic acids or polycarboxylic acids containing 36 to 100 carbon atoms or acid anhydrides, acid chlorides or esters thereof, and are preferably derived from two or more surfactants. Preferably a surfactant system derived from said surfactant; When measured as described herein, a calcium overbased detergent having a ratio of said phenol in the surfactant system of at least about 35 mass% and having a TBN:% surfactant ratio of 15 or greater (as defined herein) To provide.

Regardless of the TBN:% surfactant ratio, the above ratio of phenol in the surfactant system is advantageously at least 45 mass%, preferably at least 55 mass%, in particular at least 70 mass%. Regardless of the ratio of phenol, the TBN:% surfactant ratio is advantageously at least 16, preferably at least 18, more preferably at least 20, in particular at least 21. Preferably the phenol ratio and TBN:% surfactant ratio are both as given. Advantageously the ratio and the ratio are at least 40 mass% and at least 18, preferably at least 45 mass% and at least 20, respectively.

The invention also provides that at least one of the surfactants is a salicylic acid or a derivative of salicylic acid or a derivative thereof, the other or at least one of the surfactants is a non-salicylic acid surfactant, and (a) a general formula R ^a -CH ( An acid of R ^b ) -COOH, wherein R ^a represents an alkyl or alkenyl group containing 10 to 24 carbon atoms, and R ^b represents hydrogen, an alkyl group having 1 to 4 carbon atoms or a CH ₂ COOH group ) Or acid anhydrides, acid chlorides or esters thereof, and (b) dicarboxylic acids or polycarboxylic acids containing 36 to 100 carbon atoms or acid anhydrides, acid chlorides or esters thereof, and are preferably derived from two or more surfactants. Preferably a surfactant system derived from said surfactant; When measured as described herein, a calcium overbased detergent having a ratio of said salicylic acid in the surfactant system of at least about 10 mass% and having a TBN:% surfactant ratio of 11 or more (as defined herein) To provide.

Regardless of the TBN:% surfactant ratio, the proportion of salicylic acid in the surfactant system is advantageously at least 15% by mass, preferably at least 25% by mass, more preferably at least 35% by mass, in particular at least 45% by mass, more In particular, it is 55 mass% or more, especially 70 mass% or more. Regardless of the ratio of salicylic acid, the TBN:% surfactant ratio is advantageously at least 12, more advantageously at least 13, preferably at least 14, more preferably at least 16, in particular at least 19, in particular at least 21. Preferably the salicylic acid ratio and said ratio are as given. Advantageously the ratio and the ratio are 25 mass% and 12, preferably 30 mass% and 13, respectively.

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%, for example at least 95 mol%, of the cations in the basic metal containing material are potassium ions. A cation other than calcium can be derived from using, for example, an overbased detergent of a surfactant salt whose cation is a metal other than calcium.

The proportion of surfactant in the overbased detergent and the proportion of individual surfactants (eg, phenol) in the surfactant system are the ratios measured by the method shown below, which also refers to the "standardized TBN" of the overbased detergent. The measuring method is shown.

1. Dialysis and Determination of Standardized TBN in Overbased Detergents

Soxhlet extruder (150 mm high) using a known amount (Ag, about 20 g) of liquid overbased detergent (almost no other lubricant additive) using n-hexane siphon at a rate of 3 to 4 times per hour for 20 hours Dialysis through a coating of 75 mm inner diameter). The coating should contain substantially all metal containing materials and pass substantially all of the remainder of the sample. Examples of suitable coatings are gum rubber coatings provided by Carter Products Division of Carter Wallace Inc., 10105 New York, NY under the trade name Trojans. Upon completion of the dialysis step the dialysate and residue obtained 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 ratio (C) of the 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 indicated by a method independent of the amount of diluent) is TBN measured according to ASTM D2896 on 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. Measurement of TBN:% Total Surfactant Ratio

A known amount of Dg (about 10 g) as defined in sections 8.1 to 8.1.2 of ASTM D3712, except that at least 200 ml (sp. Gr. 1.18) of 25% by volume hydrochloric acid was used in section 8.1.1. The dried residue is hydrolyzed. The amount of hydrochloric acid used should be sufficient to oxidize / hydrolyze the overbased detergent residues with 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 clean ether and the mixed ether solution is evaporated to dryness (about 110 ° C.) to obtain a hydrolyzed residue. The mass (g) of dried hydrolyzed residue is represented by E.

The ratio 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

In measuring X, it will be appreciated to use the mass of the surfactant in its free form (ie not in the form of a salt or other derivative). For clarity, X will generally mean “TBN:% surfactant ratio” herein, which is the value of X as defined in the claims and specification.

3. Determination of the individual surfactants (free form) in the surfactant system

The technique described below separates individual surfactants in hydrolyzed form from a mixture of hydrolyzed surfactants derived from overbased detergents. As shown below, the proportion of each individual surfactant is the proportion by mass of the individual surfactants in hydrolyzed form in the hydrolyzed surfactant mixture. Thus, for example, overbased detergents contain a calcium phenate / sulfonate / salicylate surfactant system, and 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.

A known amount of dried hydrolysis residue (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 columns were each 250 ml of 7 solvents with increasing polarity, i.e., heptane, cyclohexane, toluene, ethyl ether, acetone, methanol and 50% by volume of chloroform, 44% by volume of isopropanol and 6% by volume of ammonia solution (sp. elute with a mixture of gr.0.88). Each fraction is collected, evaporated to dryness, the resulting residue is weighed and analyzed to determine the amount (G ¹ , G ² , G ³ g) and properties of the surfactant (s) contained in the fraction.

Analysis of fractions (or hydrolyzed residues) can be performed by chromatography, spectroscopy and / or titration (color indicator or potentiometer) techniques 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 in any other case, where it is necessary to measure its proportion in a 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, H ¹ ) of a given surfactant in hydrolysis form is determined from the fraction (s) containing the surfactant, so that the proportion of surfactant in the surfactant system of the original overbased detergent is Is as follows:

H ¹ / F × 100%

The proportion (mass) of the individual surfactants (not in their free form, ie in the form of salts or other derivatives) based on the surfactant system can be expected from the proportion of surfactants used as starting materials, provided that the "reaction component" The ratio of must be known for each surfactant starting material (the term "reactive component" is defined in footnote 1 of Tables 1 and 2 in the Examples herein). The proportion of total surfactant (in its free form) in the liquid overbased product can then be estimated and the TBN:% surfactant ratio can be measured. Moreover, if the proportion of overbased detergent material in the liquid overbased product (ie, the ratio of liquid overbased product that is not oil or non-reactive surfactant material) is known, then standardized TBN can be expected.

As mentioned above, a good relationship has been found between estimates and measurements.

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 invention also

(a1) at least one of the surfactants is a sulfinated or unsulfated phenol or derivative thereof, the other or at least one of the surfactants is a surfactant which is not a phenolic surfactant, and (a) a general formula R ^a -CH (R ^b ) an acid of COOH, wherein R ^a represents an alkyl or alkenyl group containing 10 to 24 carbon atoms and R ^b represents hydrogen, an alkyl group having 1 to 4 carbon atoms or a CH ₂ COOH group Or acid anhydrides, acid chlorides or esters thereof, and (b) two or more surfactants which are not dicarboxylic or polycarboxylic acids containing 36 to 100 carbon atoms or acid anhydrides, acid chlorides or esters thereof;

(a2) at least one of the surfactants is a salicylic or unsulfated salicylic acid or derivative thereof, the other or at least one of the surfactants is a surfactant which is not a salicylic acid surfactant, and (a) the general formula R ^a -CH (R ^b ) an acid of COOH, wherein R ^a represents an alkyl or alkenyl group containing 10 to 24 carbon atoms and R ^b represents hydrogen, an alkyl group having 1 to 4 carbon atoms or a CH ₂ COOH group Or (a) at least two surfactants which are not acid anhydrides, acid chlorides or esters thereof, and (b) dicarboxylic acids or polycarboxylic acids containing 36 to 100 carbon atoms or acid anhydrides, acid chlorides or esters thereof,

(b) at least one basic calcium compound, and

(c) treating the mixture comprising oil with an overbased agent, wherein

If the starting material comprises (a1), when measured as described herein, the proportion of said phenol in the surfactant system is at least about 35 mass% and the overbased detergent has a TBN:% surfactant ratio of at least 15 ( As defined herein;

If the starting material comprises (a2), when measured as described herein, the ratio of the salicylic acid in the surfactant system is at least about 10 mass% and the overbased detergent has a TBN:% surfactant ratio of at least 11 ( And a calcium overbased detergent having the same as defined herein.

It will be understood that the mixture that is overbased contains free basic calcium compound (s), ie, basic calcium compound (s) capable of reacting with the overbased agent. The term “overbased agent” means a reagent or compound that can react with the basic calcium compound (s) (b) to form a basic calcium-containing material that can be maintained as a dispersion or solution in oil by a surfactant system. . If there is more than one overbased stage, other overbased agents may be used for other stages, if desired. In any individual overbased step, 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". In the context, it will be understood that carbonation includes treatment with other overbased agents unless specifically required otherwise.

Advantageously, upon completion of the carbonation step (s), some of the basic calcium compound (s) (b) are present in an unoxidized state. Advantageously, less than 15 mass%, in particular less than 11 mass%, of the basic calcium compound (s) remains in an unoxidized state.

As indicated above, carbonation is performed at less than 100 ° C. Typically the carbonation is carried out at 15 ° C. or higher, preferably at 25 ° C. or higher. Advantageously, the carbonation is carried out at 80 ° C. or lower, more advantageously at 60 ° C. or lower, preferably at 50 ° C. or lower, more preferably at 40 ° C. or lower, in particular at 35 ° C. or lower. Advantageously, the temperature is maintained almost constant during each carbonation step, with only minor fluctuations. If there is more than one carbonation step, two or all carbonation steps are preferably carried out at about the same temperature, but other temperatures may be used if desired, provided that each step is carried out below 100 ° C.

Carbonation can be carried out at atmospheric, superatmospheric or subatmospheric pressure. Preferably the carbonation is carried out at atmospheric pressure.

Advantageously, there is a "thermal immersion" step following the first carbonation step (and preferably the second or each subsequent carbonation step, if also used), wherein the mixture is at a selected temperature without the addition of any further chemical reagents. It is maintained in the range (or selected temperature), which is usually higher than the temperature at which carbonation is performed during the period before any further processing steps are performed. 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 thermal immersion temperature may typically be carried out in the range of 15 ° C. to below reflux, preferably 25 to 60 ° C .: The temperature is such that little material (eg, solvent) is removed from the system during the thermal immersion step. It is shown that thermal immersion has the effect of assisting product stabilization, dissolution of solids and filterability.

Preferably, after the first carbonation step (and heat soaking step, if used), an additional amount of basic calcium compound (component (b)) is added to the mixture, the mixture is carbonated again, advantageously after the second carbonation step Perform a thermal immersion step.

The reduced viscosity product can be obtained by using one or more additional additives of the basic calcium compound and by continuous carbonation, advantageously carrying out a thermal soaking step after each carbonation step. 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 convenient viscosity can be obtained by using the steps mentioned in this paragraph. In each case, a comparative is prepared with the product resulting from the treatment of the same amount of basic calcium compound and overbased agent in several steps.

Basic calcium compounds for use in the preparation of overbased detergents include calcium oxide, hydroxides, alkoxides and carboxylates. Calcium oxide and more particularly hydroxide are preferably used. If desired, mixtures of basic compounds may be used.

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 advantageously has a mass percentage of toluene of at least 1.5, preferably at least 15, more preferably at least 45, in particular at least 60, more particularly based on calcium overbased detergents (except oil) At least 90. For practical / economic reasons, the ratio of toluene is typically at most 1200, advantageously at most 600, preferably at most 500, in particular at most 150. The amount of methanol used is advantageously calcium detergents (excluding oils). ), So that the mass% of methanol is at least 1.5, preferably at least 15, more preferably at least 30, in particular at least 45, more particularly at least 50. For this reason, the proportion of methanol (as solvent) is typically at most 800, advantageously at most 400, preferably at most 200, in particular at most 100. The ratio is applied whether toluene and methanol are used together or separately.

Preferred promoters for use according to the invention are methanol and water. The amount of methanol used is advantageously the mass% of methanol based on the initial load of the basic calcium compound (s) (e.g. calcium hydroxide) (ie excluding any basic calcium compound (s) applied in the second or successive step). Is at least 6, preferably at least 60, more preferably at least 120, in particular at least 180, more particularly at least 210. For practical / economic reasons, the proportion of methanol (as promoter) is typically at most 3200, advantageously at most 1600, preferably at most 800, in particular at most 400. The amount of water in the initial reaction mixture (prior to treatment with the overbased agent) advantageously excludes basic calcium compound (s) (e.g. calcium hydroxide) (ie, excluding any basic calcium compound (s) added to the second or continuous stage). The mass% of water, based on the initial amount of, is at least 0.1, preferably at least 1, more preferably at least 3, in particular at least 6, more in particular at least 12, in particular at least 20. For practical / economic reasons, the proportion of water is typically at most 320, advantageously at most 160, preferably at most 80, in particular at most 40. If the reactants used are not anhydrides, the proportion 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, it should be allowed for any water present in the surfactant itself. Advantageously, the reaction medium comprises methanol, water (at least 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 carbonation, improve filterability or as viscous agents for overbased detergents. However, overbased detergents according to the invention can be prepared by processes that do not require the use of inorganic halide or ammonium salt catalysts (eg, ammonium salts of lower carboxylic acids or alcohols), preferably such halides or There are few 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). Furthermore, overbased detergents according to the present invention can be prepared by methods that do not require the use of reagents such as dihalogenated alcohols (eg ethylene glycol) used when operating at high temperatures: Formulated detergents are preferably free of halogenated alcohols or residues thereof.

The invention also relates to overbased detergents prepared by the process of the invention, concentrates comprising overbased detergents prepared according to or according to the invention and prepared according to the invention or according to the invention. Oily compositions comprising overbased detergents, in particular lubricants, in particular marine lubricants are provided.

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

The overbased detergents according to the invention advantageously have at least 300, more advantageously at least 330, preferably at least 350, more preferably at least 400, in particular at least 450 TBN. As will be seen later in this specification, an important aspect of the present invention is to provide a high TBN overbased detergent having an acceptable viscosity and containing a relatively high proportion of phenate and salicylate surfactants in the surfactant system.

The present invention also makes it possible to provide overbased detergents with high standardized TBNs (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 (relatively expensive) of surfactant required to prepare a defined overbased detergent of TBN. With suitable starting materials / reaction conditions, a ratio of at least 25, at least 30, for example at least 35 or at least 40, can be obtained.

Surfactants from surfactant systems of overbased detergents prepared according to or according to the invention contain, for example, one or more hydrocarbyl groups as substituents on the aromatic ring. The term " hydrocarbyl " as used herein refers to a group in which the group concerned consists mainly of hydrogen and carbon atoms but which does not exclude the presence of other atoms or groups in such a proportion that the groups are insufficient to deviate from the actual hydrocarbon characteristics. . Advantageously, the hydrocarbyl group in the surfactant for use according to the invention is an aliphatic group, preferably an alkyl or alkylene group, in particular an alkyl group, which can be linear or branched. The total carbon number in the surfactant should be sufficient to give the desired oil solubility.

One or more surfactants may be used in the form of derivatives thereof, if desired, in the preparation of the overbased detergent according to the invention, provided that derivatives other than metal salts react with basic calcium compound (s) (b) to It should be able to form salts. Unless expressly inappropriate in the context of the specification, the surfactants in the "free" (non-salt) form as discussed below for individual surfactants or elsewhere in the specification include suitable derivatives of 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 (eg alkyl catechol) or fused aromatic rings (eg alkyl naphthol) and phenols modified by chemical reactions (eg , Alkylene crosslinked phenols and manic base condensation phenols); And salgenin-type phenols (generated by the reaction of phenols with aldehydes under basic conditions).

Preferred phenols from which the overbased detergent according to the invention can be derived are of the formula:

In the above formula,

R is a hydrocarbyl group,

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

In lubricating oil overbased detergents, phenol is 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, which advantageously contains 5 to 100 carbon atoms, preferably 5 to 40 carbon atoms, in particular 9 to 12 carbon atoms, and the average carbon number among all R groups is appropriate in the oil. It is about 9 or more to ensure solubility. 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 for use in the preparation of sulfided phenols or phenates is any compound or element which introduces-(S) _x- (where x is generally from 1 to about 4) crosslinking groups between alkyl phenol monomer groups. to be. Thus, it is possible to carry out the reaction 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. The use of elemental sulfur will typically yield a mixture of crosslinking groups-(S) _x -as described above. 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 run 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.

When 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.

Regardless of the technique for preparing it, sulfided alkyl phenols useful for the preparation of overbased detergents include diluents and unreacted alkyl phenols, and generally from 2 to 20 mass%, preferably based on the mass of sulfided alkyl phenols Preferably 4 to 14 mass%, most preferably 6 to 12 mass%.

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

Aldehydes which can modify the phenols used according to 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 Patent Application No. 5 259 967.

Mannich base-condensed phenols are prepared by the reaction of phenols, aldehydes and amines. Examples of suitable 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 such substituents significantly degrade the surfactant properties of the phenol. Examples of such substituents are methoxy groups and halogen atoms.

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. Methods 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 the carboxylation of phenoxide, by the Kolbe-Schmitt method, in which case it will be obtained in a mixture with the non-carboxylated phenol (generally in a diluent).

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

One or more surfactants from which the overbased detergent can be derived may be sulfonic acid or derivatives thereof. The sulfonic acids used according to the invention are typically sulfonated, or aromatic hydrocarbons of those obtained from fractionation by hydrocarbyl-substituted, especially alkyl-substituted aromatic hydrocarbons, for example by distillation and / or extraction of petroleum. Obtained by alkylation. Examples include those obtained by alkylation of benzene, toluene, xylene, naphthalene, biphenyl or halogen derivatives thereof such as chlorobenzene, chlorotoluene or chloronaphthalene. Alkylation of aromatics is carried out using alkylating agents having at least about 3 to 100 carbon atoms such as, for example, haloparaffins, olefins obtainable by dehydrogenation of paraffins, and polymers of polyolefins such as ethylene, propylene and / or butenes. It can be carried out in the presence of a catalyst. Alkylaryl sulfonic acids generally contain 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 source from which they are obtained.

When neutralizing these alkylaryl sulfonic acids to provide sulfonates, hydrocarbon solvents and / or diluent oils as well as accelerators and viscosity modifiers may also be included in the reaction mixture.

Another type of sulfonic acid that may be used in accordance with the present invention includes alkyl phenol sulfonic acids. These sulfonic acids can be sulfided. Whether sulfided or unsulfurized, these sulfonic acids are believed to have surfactant properties comparable to sulfonic acids rather than surfactant properties comparable to phenols.

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

If desired, the at least one surfactant from which the surfactant system in the overbased detergent is derived may be a carboxylic acid, not the acid mentioned above.

Carboxylic acids that can be used according to the invention include monocarboxylic acids and dicarboxylic acids. (If this specification indicates the number of carbon atoms in the carboxylic acid, the carbon atom (s) in the carboxylic acid are included in the number.) One example of a monocarboxylic acid is iso-octanoic acid. Iso-octanoic acid can optionally be used in the form of a mixture of C ₈ acid isomers marketed by Exxon Chemical under the trade name “Cekanoic”. Other suitable acids are dicarboxylic acids having two or more carbon atoms dividing carboxyl groups and those which are tertiary substituted at α-carbon atoms. 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 another group of surfactant and not a carboxylic acid surfactant. (Or they contain hydroxyl groups but are not considered phenolic surfactants.)

If a carboxylic acid / derivative is used, it represents (a) an acid of the general formula R ^a -CH (R ^b ) -COOH, wherein R ^a represents an alkyl or alkenyl group containing 10 to 24 carbon atoms, and R ^b is Hydrogen, alkyl group having 1 to 4 carbon atoms or CH ₂ COOH group) or acid anhydride, acid chloride or ester thereof, or (b) dicarboxylic or polycarboxylic acid or acid anhydride thereof containing 36 to 100 carbon atoms No acid chlorides or esters.

In another aspect of the invention, the carboxylic acid / derivative, if used, has 8 to 11 carbon atoms in the carboxyl-containing moiety.

In a further aspect of the invention, if 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 at least 11 carbon atoms in the carboxyl-containing moiety. In another embodiment, the carboxylic acid surfactant is not hydrocarbyl-substituted succinic acid or derivatives thereof.

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 the surfactant is used in the form of a salt, any suitable cation may be present, for example quaternary nitrogen ions or preferably metal ions. Suitable metal ions include those of alkali metals, alkaline earth metals (including magnesium) and transition metals. 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 desired, mixtures of two or more members of any one group of surfactants may be used to prepare overbased detergents according to the invention, provided that one or more surfactants from other groups are also present. Thus, for example, many methods of introducing substituents into aromatic rings produce a mixture of compounds and it is generally convenient to use such mixtures without separating the components from each other.

If the overbased detergents are prepared from any of the specified surfactants in the above specification, the total proportion of these surfactants (in free form) in the surfactant system of the overbased detergents is advantageously at least 75 mass%, preferably 85 It is more than mass%, especially 95 mass%.

In one embodiment of the invention, the surfactant system is derived from one or more sulfed phenols or derivatives thereof and one or more sulfonic acids or derivatives thereof and the ratio of phenol to sulfonic acids in the surfactant system measured as described herein. Is in the range of 15:85 to 95: 5 mass%, preferably 30:70 to 70:30 mass%, in particular 40:60 to 60:40 mass%.

In another aspect of the invention, 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 in a surfactant system measured as described herein. The ratio of phenol to sulfonic acid to carboxylic acid is 5 to 90: 5 to 90: 5 to 90 mass%, preferably 20 to 80: 10 to 50:10 to 50 mass%, in particular 30 to 70:10 to 30:10 To 30% by mass.

In an embodiment of the present invention, the surfactant system is derived from at least one sulfurized phenol or derivative thereof, at least one salicylic acid or derivative thereof and at least one sulfonic acid or derivative thereof and measured as described herein. The ratio of salicylic acid to sulfonic acid is 5 to 90% by mass: 5 to 90% by mass: 20 to 80% by mass, preferably 20 to 80% by mass: 20 to 80% by mass: 10 to 50% by mass, in particular 30 To 50 mass%: 25 to 45 mass%: 15 to 35 mass%.

In any embodiment of the invention, if the minimum percentage of phenol or salicylic acid is optionally higher than the lowest of any range specified in the preceding three paragraphs with respect to the ratio of phenol or salicylic acid, the lowest of the range given above for this embodiment. Should be replaced by the minimum% above. Thus, in one embodiment of the present invention the minimum percentage of phenol in the surfactant system is 35% by mass, while in another embodiment of the present invention the minimum percentage of salicylic acid in the surfactant system is 10% by mass.

The present invention makes it possible to obtain high TBN overbased phenate and / or salicylate detergents while minimizing the amount of (relatively expensive) surfactant components of the overbased detergent: the present invention thus provides a relatively high TBN: It is possible to obtain phenates or salicylate overbased detergents with a% surfactant ratio. This is especially advantageous for marine lubricants, since marine engines require relatively large amounts of lubricants containing high TBN overbased detergents (eg marine diesel cylinder lubricant (MDCL) is a "one-pass" lubricant). However, it is also advantageous in the case of other lubricants, for example crankcase lubricants. In addition, the present invention makes it possible to provide very effective overbased detergents having a relatively low viscosity even when the surfactant system contains a relatively high proportion of phenate and / or salicylate.

High TBN calcium overbased sulfonates and carboxylates with low viscosity are previously known. It can contain relatively high proportions of phenates and / or salicylates in some cases while minimizing the amount of relatively expensive surfactants required (thus providing good levels of performance in many applications, eg marine lubricants). The provision of calcium overbased detergents that can have high TBN and low viscosity represents a significant technical advance.

In addition, previously proposed methods of preparing overbased phenates and / or salicylate detergents used relatively high carbonation temperatures, for example temperatures of 100 ° C. or higher, and many conventional proposals have carbon numbers of 12 or more. The use of surfactants such as any carboxylic acid has been described as essential to obtaining a satisfactory product. 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 indicated 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 hybrid detergents have the advantage of providing an overbased detergent system having properties due to two or more surfactants without the need to prepare or blend two or more respective overbased detergents. In addition, eliminating the need to blend each overbased detergent provides more flexibility with regard to the final TBN, surfactant ratio, and TBN:% surfactant ratio, and also in the preparation of the blend containing each overbased detergent. Overcome problems of immiscibility or stability that you may experience.

More particularly, the hybrid overbased detergents of the present invention have been found to improve stability when used to formulate, for example, lubricants for trunk piston marine diesel engines, ie medium-speed marine diesel engines. In particular, blending such oils to contain phenate, sulfonate and salicylate surfactant anions results in an oil in which two or more of these anions are in the form of the complex detergent of the present invention, as measured by the% volume precipitate reduction in the stored oil. Greater stability when provided by. This compares to this oil, in which three anions are provided separately in the oil.

For example, each of the inventive phenate: sulfonate hybrid overbased detergents and oils formulated separately with salicylates provided, and the phenate: sulfonate: salicylate hybrid overbased detergents of the invention Oils have greater stability than comparative oils combined with phenates, sulfonates and salicylates, each 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 to the compositions, for example lubricants or greases, 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% by mass of overbased detergent based on the active ingredient based on the final lubricant. And automotive crankcase lubricants typically contain from 0.01 to 6% by mass of overbased detergents based on the active ingredient based on the final lubricant.

The overbased detergents according to or according to the present invention are fat soluble, or are materials that are soluble in oil or stably dispersible with the aid of a suitable solvent (with any other additives referred to below). The term fat soluble, soluble or stably dispersible as used herein does not necessarily indicate that the additive is soluble, soluble, miscible, or suspended in oil at all ratios. This means that the additives are, for example, soluble or stably dispersible in the oil to an extent sufficient to achieve the desired effect in the environment in which the oil is used. Moreover, incorporation of other additives into the oil-based composition may optionally incorporate higher levels of special additives.

Overbased detergents may be incorporated into the base oil in any convenient way. Thus, they may optionally be added directly to the oil by, for example, dispersing or dissolving them in the oil at a 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 can 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 indicated above, overbased detergents are particularly useful for lubricating oils 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, depending on their raw materials, are for example paraffinic, naphthenic, mixed or paraffinic-naphthenic as well as the methods used in the preparation, for example the distillation range, and whether they are passed directly, decomposition Inorganic lubricating oils, which can vary widely depending on whether they have been used, hydrorefined or solvent extracted.

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

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

The overbased detergents according to or according to the invention can be used in lubricating oil compositions which typically comprise a large proportion of lubricating oil and typically a small proportion of overbased detergent. Additional additives may be incorporated into the compositions to meet particular needs. 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 further antioxidants, antifoam agents and / or rust inhibitors. The additional optional additives specified below are more suitable for use in lubricants for automotive engines than in lubricants for marine engines.

Viscosity index improvers (or viscosity modifiers) provide lubricating oil 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 Patent Application 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 in use, and 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 in an oil or additive package under normal blending conditions. For example, copper may be in the form of copper dihydrocarbyl thio or dithio-phosphate. Alternatively, copper is added as a copper salt of synthetic or natural carboxylic acids, for example 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 lubricant 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 and 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 improving dispersants act as both viscosity index improving agents and dispersants. Examples of viscosity index improving dispersants suitable for use in lubricating oil compositions include hydrocarbyl-substituted mono- or amines such as polyamines and hydrocarbyl substituents comprising chains of length sufficient to provide the compound with viscosity index improving properties. Reaction products of dicarboxylic acids.

Examples of dispersants and viscosity index improving dispersants may be 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 methods for their preparation are given 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 have 1 to 18 carbon atoms, preferably 2 to 12 carbon atoms. It contains).

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 a polysiloxane antifoaming agent, for example silicone oil or polydimethyl siloxane.

Some of the aforementioned additives can provide several effects: Thus, for example, a single additive can act as a dispersant-oxidation inhibitor. This method is known and does not need to be studied further herein.

If the lubricating oil composition contains one or more of the aforementioned additives, each additive is typically blended into the base oil in an amount such that the additive can provide its desired function. When used in crankcase lubricants, representative effective amounts of these additives are:

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

Typical ratios for additives for MDCL (Ship Diesel Cylinder Lubricant) are:

If multiple additives are used, it may be desirable to prepare one or more additive packages including, but not necessarily, multiple additives simultaneously added to the base oil to form a lubricating oil composition. Dissolving the additive package (s) in the lubricating oil can be facilitated by the solvent and by mixing with mild heating, but this is not necessary. The additive package (s) will typically be formulated to contain the additive (s) in an appropriate amount to provide the desired concentration in the final blend when the additive package is mixed with a predetermined amount of base lubricant. Thus, at least one overbased detergent according to the invention is 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 by weight, based on the additive package. Can form an additive package containing the active ingredient in an amount of about 5 to about 75% by mass, most preferably about 8 to about 60% by mass, the appropriate proportion of the additive and the remainder of the base oil.

The final blend may typically contain about 5-40 mass% of the additive package (s) (the rest is base oil).

The following examples illustrate the invention.

Example 1

540 g of toluene, 276 g of methanol and 22 g of diluent oil (150 N) were introduced into the reactor and mixed while maintaining the temperature at about 20 ° C. Calcium hydroxide (Ca (OH) ₂ ) (145 g) was added and the mixture was heated to 40 ° C with stirring. To the slurry obtained by the above method, a mixture of the phenol and sulfonic acid surfactants shown in Table 1 and 100 g of toluene was added and maintained at 40 ° C., followed by the addition of an additional amount (50 g) of toluene and water (22 g). did.

After neutralizing the surfactant with calcium hydroxide, the temperature of the mixture is reduced to about 28 ° C. and carbon dioxide (62 g) is injected into the mixture at a rate such that substantially all carbon dioxide is absorbed into the reaction mixture to form a basic substance. While maintaining at about 28 ℃. The temperature was then raised to 60 ° C. for 60 minutes and then the mixture was cooled to a temperature of 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 loaded. After this second carbonation step, the temperature was raised to 60 ° C. for 90 minutes.

The volatiles were then distilled off, a second load of diluent oil (209 g) was introduced and the product was filtered to remove the precipitate.

Details of starting materials used in all examples are given in Table 1 and footnotes therein. The amount of diluent oil (SN150) in Table 1 is the total amount loaded. Table 2 shows TBN,% total surfactant (Y, measured as described herein) and TBN:% total surfactant ratio (X, with viscosity data and filtration rate (kg / m ² / hour) and filtration gradient Measured as described herein), standardized TBN, and the proportion of each surfactant in the surfactant system of the overbased detergent (see footnote 2 for Tables 1 and 2).

Example 2

540 g of toluene, 276 g of methanol, 22 g of water and 22 g of diluent oil (150 N) were introduced into the reactor and mixed while maintaining the temperature at about 20 ° C. Calcium hydroxide (Ca (OH) ₂ ) (54 g) was added and the mixture was heated to 40 ° C with stirring. To the slurry obtained by the above method, a mixture of the sulfonic acid surfactant shown in Table 1 and 100 g of toluene was added, and an additional amount (50 g) of toluene was added after maintaining at 40 ° C. The salicylic acid surfactants shown in Table 1 were then introduced into the reactor.

After neutralizing the surfactant with calcium hydroxide, the temperature of the mixture is reduced to about 28 ° C. and carbon dioxide (24 g) is injected into the mixture at a rate at which substantially all carbon dioxide is absorbed into the reaction mixture to form a basic substance. While maintaining at about 28 ℃. The temperature was then raised to 60 ° C. for 60 minutes and then the mixture was cooled to a temperature of about 28 ° C. for 30 minutes. At 28 ° C., an additional amount of calcium hydroxide (50 g) was added and loaded with carbon dioxide (25 g). The temperature was then raised to 60 ° C. again for 60 minutes and then the mixture was cooled to a temperature of about 28 ° C. for 30 minutes. The order of calcium hydroxide (50 g each time), carbonation (25 g each time) and thermal immersion was performed three times under the conditions shown in the second time, except that the temperature was raised to 60 ° C. for 90 minutes after the fifth carbonation step. Repeated over.

The volatiles were then distilled off, a second load of diluent oil (98 g) was introduced and the product was filtered to remove the precipitate.

Examples 3 to 60

The procedure shown in Example 1 was repeated with the following ranges of toluene, methanol and water and the starting materials and proportions of starting materials shown in Table 1 and the footnotes relating thereto, except as follows: toluene 500 to 690 g ; 270 to 330 g of methanol; And 15-25 g of water. The properties of the overbased detergent obtained are shown in Table 2.

In Examples 3 and 13-16, 15 g of formic acid was also introduced into the reactor.

In Example 21, SN600 oil was used instead of SN150 oil.

In Examples 4, 12, 17, 19, 29-41, 43, and 54, the product was filtered off of the solvent after removal of the polar solvent. The final product was separated by removing the remaining volatiles and introducing the desired amount of diluent oil. (Diluent oil may be introduced at any stage of the process, for example, before or after distilling off the nonpolar solvent.)

In Examples 55 and 56, further (third) addition of calcium hydroxide, carbon dioxide under the conditions shown in Example 1 for this second sequence, except that each thermal immersion step was carried out as in the first sequence. Addition and thermal immersion. In Example 57, the procedure of Example 2 was performed.

In Example 27, carbonation was carried out at 30 ° C.

In Example 58, carbonation was carried out at 55 ° C. The product was separated by distilling off the polar solvent, adding toluene, centrifuging to remove the precipitate, and then distilling out the volatiles.

The preparation of the overbased detergent according to the invention is particularly advantageous for hydrogen reasons when the detergent is kept at elevated temperature, e. Sulfur compounds such as sulfides and mercaptans.

This occurrence is undesirable because it interferes with safe and hygienic plant operation. One way to prevent or ameliorate this occurrence is to treat the olefin at any stage in the preparation of the detergent. For example, the olefin can be incorporated at any stage in the raw material preparation, neutralization, overbased, distillation of volatiles, or at elevated temperatures, i.e. at any stage in the preparation of the detergent. Incorporation during solvent distillation, for example at about 130 ° C., is preferred.

Any olefin may be used that may remain in solution or dispersion in the detergent at elevated temperature. Examples of such olefins are those having a high or low degree of substitution having from 18 to 60 carbon atoms or more. Specific examples of such olefins are n-octadecene; Olefin mixtures having, on average, 24 carbon atoms; And multimers of butenes. Suitable treatment rates for the olefins are at least 0.1-5 mass%, preferably 0.1-2 mass%, based on the finished detergent.

Footnotes of Tables 1 and 2

1. Sources of phenol, sulfonic acid and salicylic acid surfactants (see Table 1) are given in Table 3 below. In this table:

a.i. = Mass% of surfactant-containing material loaded into the reaction vessel other than diluent oil.

r.i. =% By mass of the "reactive component", ie, the percentage of surfactant loaded into the reaction vessel in connection with calcium in the liquid overbased detergent.

(The term "active ingredient" has its general meaning and will be construed to refer to the proportion of surfactant-containing material comprising molecules different from the diluent oil molecules. The interface for preparing the overbased detergent according to the invention When using active agents it has been found that in some cases some of the surfactant molecules do not react with the basic calcium compound (s), but remain in unreacted non-base form in liquid overbased detergents. % Is lower than% of "active ingredient."

2. In Table 2, Ph%, Sulph%, Sal% and Carbox% are the phenolic surfactants, sulfonic acids based on the mass of the total surfactant (hydrolyzed form) associated with the basic calcium compound in the overbased detergent, respectively. % By mass of surfactant and salicylic acid surfactant (hydrolyzed form).

Claims (39)

At least one of the surfactants is a sulfinated or unsulfated phenol or derivative thereof, the other or at least one of the surfactants is a surfactant which is not a phenolic surfactant, and (a) the general formula R ^a -CH (R ^b )- An acid of COOH, wherein R ^a represents an alkyl or alkenyl group having 10 to 24 carbon atoms and 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 Esters, and (b) surfactant systems derived from at least two surfactants which are not dicarboxylic acids or polycarboxylic acids having 36 to 100 carbon atoms or acid anhydrides, acid chlorides or esters thereof; The proportion of said phenol in the surfactant system is at least 35 mass% and has a TBN:% surfactant ratio of at least 15, wherein the% surfactant is the mass% of the total surfactant in free form in the liquid overbased product; Inorganic halide or ammonium salt, and calcium overbased detergent, wherein there are substantially no groups or compounds derived from said compounds and no groups derived from dihydric alcohols and dihydric alcohols. The method of claim 1, Overbased detergents having a proportion of phenol of at least 45 mass% in the surfactant system. The method of claim 1, An overbased detergent with a TBN:% surfactant ratio of 16 or greater. The method of claim 1, An overbased detergent having said proportions and ratios of at least 40 mass% and at least 18, respectively. The method of claim 1, An overbased detergent wherein the phenol is a hydrocarbyl-substituted phenol. The method of claim 1, An overbased detergent wherein at least one surfactant from which the surfactant system is derived is sulfonic acid or a derivative thereof. The method of claim 6, Overbased detergent wherein the sulfonic acid is a hydrocarbyl-substituted aryl sulfonic acid. The method according to any one of claims 5 to 7, Overbased detergent with a total proportion of phenol and sulfonic acid of at least 75% by mass in the surfactant system. The method according to any one of claims 5 to 7, Overbased detergents in which the surfactant system is derived from one or more sulfurized 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 ranges from 15:85 to 95: 5 mass% . The method of claim 1, An overbased detergent wherein the at least one surfactant from which the surfactant system is derived is a carboxylic acid or derivative thereof that is not a carboxylic acid / derivative as defined in claim 1. The method of claim 10, An overbased detergent wherein the carboxylic acid has from 8 to 11 carbon atoms in the carboxyl-containing moiety. The method of claim 10 or 11, Overbased detergents 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 10 or 11, Surfactant systems are derived from one or more sulfurized phenols or derivatives thereof and one or more sulfonic acids or derivatives thereof and one or more carboxylic acids or derivatives thereof, wherein the ratio of phenol to sulfonic acids to carboxylic acids is from 35 to 90: 5 to 90: 5 to Overbased detergents in the range of 90% by mass. The method of claim 1, An overbased detergent wherein the one or more surfactants from which the surfactant system is derived are sulfided or unsulfated salicylic acid or derivatives thereof. The method of claim 14, An overbased detergent wherein salicylic acid is a hydrocarbyl-substituted salicylic acid. At least one of the surfactants is a sulfided or unsulfated salicylic acid or derivative thereof, the other or at least one of the surfactants is a surfactant that is not a salicylic acid surfactant, and (a) is a general formula R ^a -CH (R ^b )- An acid of COOH, wherein R ^a represents an alkyl or alkenyl group having 10 to 24 carbon atoms and 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 Esters, and (b) surfactant systems derived from at least two surfactants which are not dicarboxylic acids or polycarboxylic acids having 36 to 100 carbon atoms or acid anhydrides, acid chlorides or esters thereof; The proportion of salicylic acid in the surfactant system is at least 10 mass% and has a TBN:% surfactant ratio of at least 11, wherein the% surfactant is the mass% of the total surfactant in free form in the liquid overbased product; Inorganic halide or ammonium salt, and calcium overbased detergent, wherein there are substantially no groups or compounds derived from said compounds and no groups derived from dihydric alcohols and dihydric alcohols. The method of claim 16, An overbased detergent with a proportion of salicylic acid in the surfactant system of at least 15% by mass. The method according to claim 16 or 17, An overbased detergent with a TBN:% surfactant ratio of at least 12. The method according to claim 16 or 17, And overbased detergents having said ratios and ratios of 25% by mass and 12, respectively. The method according to claim 16 or 17, An overbased detergent wherein salicylic acid is a hydrocarbyl-substituted salicylic acid. The method according to claim 16 or 17, An overbased detergent wherein the at least one surfactant from which the surfactant system is derived is a sulphated or unsulfurized phenol or derivative thereof. The method of claim 21, An overbased detergent wherein the phenol is a hydrocarbyl-substituted phenol. The method of claim 16, An overbased detergent wherein at least one surfactant from which the surfactant system is derived is sulfonic acid or a derivative thereof. The method of claim 23, Overbased detergent wherein the sulfonic acid is a hydrocarbyl-substituted aryl sulfonic acid. The method according to claim 14 or 15 or 23 or 24, Overbased detergents having a total proportion of phenol, salicylic acid and sulfonic acid in the surfactant system of at least 75 mass%. The method according to claim 14 or 15 or 23 or 24, The surfactant is derived from at least one sulfurized phenol or derivative thereof, at least one salicylic acid or derivative thereof and at least one sulfonic acid or derivative thereof; Calcium overbased detergent with a ratio of phenol to salicylic acid to sulfonic acid in the surfactant system ranging from 5 to 90 mass%: 10 to 90 mass%: 20 to 80 mass%. The method according to claim 16 or 17, An overbased detergent wherein the at least one surfactant from which the surfactant system is derived is a carboxylic acid or derivative thereof that is not a carboxylic acid / derivative as defined in claim 1. The method of claim 27, An overbased detergent wherein the carboxylic acid has from 8 to 11 carbon atoms in the carboxyl-containing moiety. The method according to claim 1 or 16, Overbased detergent with a TBN of at least 300. The method according to claim 1 or 16, Overbased detergent with a standardized TBN of 450 or more. The method according to claim 1 or 16, Overbased detergents having a viscosity of up to 20,000 mm ² / s at 40 ° C. The method according to claim 1 or 16, Overbased detergent having a viscosity of at most 100 ° C. up to 2000 mm ² / s. The method according to claim 1 or 16, Overbased detergent, a hybrid detergent. As a method of preparing a calcium overbased detergent, In less than 100 ℃ in one step or more, (a) at least one of the surfactants is a sulfinated or unsulfurized phenol or derivative thereof, the other or at least one of the surfactants is a surfactant other than a phenolic surfactant, and (a) is a general formula R ^a- Acids of CH (R ^b ) -COOH, wherein R ^a represents an alkyl or alkenyl group having 10 to 24 carbon atoms and R ^b represents hydrogen, an alkyl group having 1 to 4 carbon atoms or a CH ₂ COOH group At least two surfactants which are not acid anhydrides, acid chlorides or esters, and (b) dicarboxylic acids or polycarboxylic acids having 36 to 100 carbon atoms or acid anhydrides, acid chlorides or esters thereof; (a2) at least one of the surfactants is a salicylic or unsulfated salicylic acid or derivative thereof, the other or at least one of the surfactants is a surfactant which is not a salicylic acid surfactant, and (a) the general formula R ^a -CH (R ^b ) an acid of COOH, wherein R ^a represents an alkyl or alkenyl group having 10 to 24 carbon atoms and R ^b represents hydrogen, an alkyl group having 1 to 4 carbon atoms or a CH ₂ COOH group, or an acid anhydride thereof, At least two surfactants, which are not acid chlorides or esters, and (b) dicarboxylic acids or polycarboxylic acids having 36 to 100 carbon atoms or acid anhydrides, acid chlorides or esters thereof, (b) at least one basic calcium compound, and (c) treating the mixture comprising the oil with an overbased agent as defined above at less than 100 ° C. in at least one step, wherein If the starting material comprises (a1), the proportion of said phenol in the surfactant system of the overbased detergent is at least 35 mass% and the overbased detergent has a TBN:% surfactant ratio of at least 15; If the starting material comprises (a2), when measured as described herein, the proportion of said salicylic acid in the surfactant system of the overbased detergent is at least 10 mass% and the overbased detergent is at least 11 TBN:% Having a surfactant ratio, where% surfactant is the mass percent of the total surfactant in free form in the liquid overbased product; A process for the preparation of calcium overbased detergents, which is carried out without using inorganic halides or ammonium salts, and groups or compounds derived from said compounds and groups derived from dihydric alcohols and dihydric alcohols. An oil-based composition comprising the overbased detergent of claim 1. 36. The method of claim 35 wherein A composition in the form of a concentrate. A lubricant comprising the overbased detergent of claim 1. The method of claim 37, Lubricating oil, wherein the lubricant is used in marine engines. A lubrication method for a marine engine comprising supplying the lubricating oil of claim 37 to the engine.