KR102160538B1 - Marine engine lubrication - Google Patents

Abstract

The present invention
(A) is an oil-soluble ester basestock; Or greater than 0.1% to less than 90% by mass of an oil-soluble ester basestock, and at least 50% by mass of the residue of the lubricating viscosity oil, comprising a high saturation basestock;
(B) a small amount of metal alkyl salicylate detergent; And
(C) greater than 0.1% to less than 10% by mass of oil-soluble polyalkenyl-substituted carboxylic anhydride, wherein at least one polyalkenyl group is derived from a polyalkene having a number average molecular weight of 200 to 3000.
It relates to a trunk piston marine engine lubricant comprising a. Asphaltene precipitation in the lubricating oil composition caused by the presence of contaminant heavy fuel oil is prevented or suppressed.

Description

Marine engine lubrication {MARINE ENGINE LUBRICATION}

The present invention relates to a trunk piston marine engine lubrication composition for a medium-speed four-stroke compression-ignition (diesel) marine engine and to lubrication of the engine.

Ship trunk piston engines generally use heavy fuel oil (HFO) for offshore operations. Heavy fuel oil is the heaviest fraction of petroleum distillates and contains 15% or less asphaltene, defined as the fraction of petroleum distillates, which is insoluble in excess aliphatic hydrocarbons (e.g., heptane) but soluble in aromatic solvents (e.g. toluene) It contains a complex mixture of molecules. Asphaltene can enter the engine lubricant as a contaminant via a cylinder or fuel pump and injector, which can then produce asphaltene deposits that appear as "black paint" or "black sludge" in the engine. The presence of such carbonaceous deposits on the piston surface may act as an insulating layer, which may later form cracks that propagate through the piston. If the crack travels through the piston, hot combustion gases can enter the crankcase, causing a crankcase explosion.

Therefore, it is highly desirable that the trunk piston engine oil (TPEO) prevents or inhibits asphaltene precipitation. TPEO using Group 1 basestock may have the ability to dissolve asphaltenes. However, TPEO using a high saturated basestock (eg, Group II or III) requires a booster to achieve similar performance steps in this respect.

International Patent Application Publication No. WO 2010/115594 (hereinafter referred to as "594") and International Patent Application Publication No. WO 2010/115595 (hereinafter referred to as "595") include a Group II basestock of 50% by mass or more. , And a trunk piston marine engine lubricating oil composition each containing a small amount of a calcium salicylate cleaner and a polyalkenyl-substituted carboxylic anhydride. Data in "594" and "595" show that the combination provides improved asphaltene dispersibility.

US 2011/0319304 A1 ('304) describes the use of ester basestocks in high saturated basestock TPEO to improve the ability to disperse asphaltenes.

A problem in the art is still to further improve the asphaltene dispersibility of TPEO using a high saturated basestock.

The present invention satisfies the above problem by using anhydrides and esters in TPEO: a synergistic effect is observed as demonstrated in the data herein.

A first aspect of the present invention is a trunk piston marine engine lubricating oil composition for improving handling of asphaltenes during use when an engine is operated when heavy fuel oil is supplied as fuel, the composition comprising:

(A) is an oil-soluble ester basestock (A1);

Or from more than 0.1% to less than 90% by mass, preferably from 1 to 80% by mass, of an oil-soluble ester basestock (A1), and a lubricating viscosity of at least 50% by mass of the remainder of the oil, at least 90% of saturates and at most 0.03% Comprising a base stock (A2) comprising sulfur or a mixture thereof of,

Large amounts of lubricating viscosity oil;

(B) a small amount of oil-soluble metal cleaner; And

(C) a small amount of oil-soluble polyalkenyl-substituted carboxylic anhydride of greater than 0.1% to less than 10% by mass, preferably greater than 1% to less than 8% by mass, wherein at least one polyalkenyl group is 200 Derived from polyalkenes having a number average molecular weight of from 3000 to)

It is prepared by including, or mixing them.

The second aspect of the present invention

(i) replenishing the engine with heavy fuel oil as fuel; And

(ii) lubricating the crankcase of the engine with the composition according to the first aspect of the present invention.

It is a method of operating a trunk piston medium speed compression-ignition ship engine comprising a.

The third aspect of the present invention

(i) providing a composition according to the first aspect of the invention;

(ii) providing the composition to a combustion chamber;

(iii) providing heavy fuel oil to the combustion chamber; And

(iv) burning the heavy fuel oil in the combustion chamber

It is a method of dispersing asphaltenes in a trunk piston ship lubricating oil composition during operation of the engine and lubricating the surface of the combustion chamber of a medium speed compression-ignition ship engine comprising a

A fourth aspect of the invention is a cleaning agent (C) in combination with component (C) in an amount defined in the first aspect of the invention and given in this first aspect, in a trunk piston marine lubricating oil composition for a medium speed compression-ignition marine engine ( As the use of B), the composition comprises a large amount of the lubricating viscosity oil (A) as defined in the first aspect of the present invention, so that the handling of asphaltene during operation of the engine fueled by heavy fuel oil and the composition Engine lubrication.

When the following terms and expressions are used herein, they have the following meanings.

The term "active ingredient" or "a.i." refers to an additive that is not a diluent or solvent.

The term “comprising” or similar terms specifically specifies the presence of a given feature, step, integer, or component, but does not exclude the presence or addition of one or more other features, steps, integers, components, or groups thereof. The term “consisting of” or “consisting essentially of” or similar terms may be included in the category of “comprising” or similar terms, wherein “consisting of essentially” substantially affects the characteristics of the composition to which the term applies. Allows the incorporation of substances that do not give.

The term "large amount" means at least 50% by mass, preferably at least 60% by mass, more preferably at least 70% by mass, even more preferably at least 80% by mass of the composition.

The term “minor amount” means less than 50% by mass, preferably less than 40% by mass, more preferably less than 30% by mass, even more preferably less than 20% by mass of the composition.

The term “TBN” refers to the total base number as measured by ASTM D2896.

Additionally, when used herein,

"Calcium content" is measured by ASTM 4951,

"Phosphorous content" is measured by ASTM D5185,

"Sulfated ash content" is measured by ASTM D874,

"Sulfur Content" is measured by ASTM D2622,

“KV100” means the kinematic viscosity at 100° C. as measured by ASTM D445.

In addition, the various components that are not only essential but also optimally and commonly used can react under conditions of combination, storage or use, and the present invention also provides a product obtainable or obtained by any such reaction Of course.

In addition, it is understood that any upper and lower quantities, ranges, and ratios described herein may be independently combined.

In the following, the features of the present invention will be discussed in more detail.

Lubrication viscosity oil (A)

Ester Base stock (A1)

The ester basestock (A1) is an organic ester basestock including, but not limited to, monoesters, diesters and polyolesters, and also polymer esters. It is generally considered a Group V basestock and is typically derived from animal or vegetable sources. Natural organic esters can be found in animal fats or vegetable oils. Organic esters can be synthesized by reacting organic acids with alcohols.

Monoesters can be prepared by reacting a monohydric alcohol with a monobasic fatty acid to produce a molecule having a single ester bond and a linear or branched alkyl group.

Diesters include monohydric alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol) and polybasic acids (e.g., phthalic acid, succinic acid). , Alkyl succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acid, alkenyl malonic acid) It can be prepared by creating a molecule that can be either topographic or aromatic with two ester groups. Specific examples of such esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, Didecyl phthalate, dieicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, and complex ester formed by reaction of 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid. I can.

Polyol esters may be prepared by esterifying one or more polyols such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol with one or more organic acids such as C ₅ to C ₁₂ monocarboxylic acids. I can. See, for example, US-A-6,462,001. Examples of the polyol ester include trimethylolpropane (TMP) ester.

Tricarboxylic acid esters are also preferred. The tricarboxylic acid ester is preferably a benzene tricarboxylic acid. Preferred benzene tricarboxylic acid esters are 1,2,4-benzenetricarboxylic acids having an alkyl chain length in the range of 5 to 10, preferably 7 to 9. A preferred 1,2,4-benzenetricarboxylic acid ester is trioctyl trimellitate.

The ester base stocks used in the present invention are those having a kinematic viscosity of 2 to 10 mm ² s ^-1 at 100°C, or those having a kinematic viscosity of 10 to 100 mm ² s ^-1 at 100°C. A specific example of a suitable polyol ester is Priolube (registered trademark) 3970, which is a neopentyl polyol, suitably an ester of TMP and one or more aliphatic saturated monocarboxylic acids, 6 to 12 carbon atoms and 100° C. It has a kinematic viscosity of 4.4 mm ² s ^-1 at.

The ester base stock may be present in an amount ranging from 2 to 85% by mass, preferably 5 to 50% by mass, more preferably 8 to 40% by mass.

Base stock (A2)

The base stock (A2) may have a viscosity range from light distillate inorganic oil to heavy lubricating oil. In general, the viscosity of the lubricating oil reaches 2 to 40 mm ² s ^-1 when measured at 100°C.

Natural oils include animal oils and vegetable oils (eg castor oil, lard oil); Liquid petroleum oils and hydropurified, solvent-treated, or acid-treated paraffinic, naphthenic and mixed paraffin-naphthenic types of inorganic oils. In addition, lubricating viscosity oils derived from coal or shale are provided as useful base oils.

Synthetic lubricants include hydrocarbon oils and halo-substituted hydrocarbon oils, such as polymerized and interpolymerized olefins (e.g. polybutylene, polypropylene, propylene-isobutylene copolymer, chlorinated polybutylene, poly(1- Hexene), poly(1-octene), poly(1-decene)); Alkylbenzene (eg, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene); Polyphenyls (eg, biphenyl, terphenyl, alkylated polyphenols); And alkylated diphenyl ethers and alkylated diphenyl sulfides, and derivatives, analogs and analogs thereof.

Unrefined, refined and re-refined oils can be used in the lubricants of the present invention. Unrefined oils are those obtained directly from natural or synthetic sources without further purification treatment. For example, shale oil obtained directly from a retorting operation, petroleum oil obtained directly from distillation are unrefined oils. Refined oil is similar to unrefined oil, except that the oil is further processed in one or more purification steps to improve one or more characteristics. A number of such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and permeation, are known to those skilled in the art. Re-refined oil is obtained by a process similar to that used to provide refined oil, but is undertaken with the used oil already in service. Such re-refined oils are also known as recycled oils or reprocessed oils, and are often further processed using techniques to remove waste additives and oil breakdown products.

The American Petroleum Institute (API) publication ["Engine Oil Licensing and Certification System", Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998] classifies basestock as follows:

Group I basestocks contain less than 90% saturates and/or more than 0.03% sulfur and have a viscosity index of at least 80 and less than 120 when using the test methods specified in Table E-1.

Group II basestocks contain more than 90% saturation and less than 0.03% sulfur and have a viscosity index of 80 or more and less than 120 when using the test methods specified in Table E-1.

Group III basestocks contain at least 90% saturation and less than 0.03% sulfur and have a viscosity index of 120 or more when using the test methods specified in Table E-1.

Group IV basestock is polyalphaolefin (PAO).

Group V basestocks include all other basestocks not included in Group I, II, III, or IV.

The analysis methods for the basestock are shown in the table below:

( Table E-1)

As an example, the base stock (A2) includes a group II, group III and group IV base stock, and a base stock derived from a hydrocarbon may be synthesized by a Fischer-Tropsch process. In the Fischer-Tropsch process, synthesis gas (Synthsis gas or'syngas') containing carbon monoxide and hydrogen is first generated and then converted to hydrocarbons by the Fischer-Tropsch process. These hydrocarbons typically require additional processing to be useful as base oils. For example, they are hydroisomerized by techniques known in the art; Hydrocracking, hydroisomerization; Dewaxed; Or hydrogen isomerization reaction and dewaxing. The synthesis gas can be, for example, from a gas, eg natural gas or other gaseous hydrocarbons, by steam reforming where the basestock can be referred to as a liquefaction process ("GTL") base oil; Or from vaporization of biomass if the basestock can be referred to as a biomass liquefied (“BTL” or “BMTL”) base oil; Or it can be produced from the vaporization of coal if the basestock can be referred to as a liquefied coal ("CTL") base oil.

As described, when used in the present invention, the base stock (A2) contains 50% by mass or more of the above-defined base stock or a mixture thereof. Preferably, it contains at least 60% by mass, such as at least 70%, 80% or 90% by mass, of the above-defined basestock or mixtures thereof. (A2) may comprise substantially all of the above-defined basestocks or mixtures thereof.

Overbased ( overbased ) Metal cleaner (B)

Metal cleaners are additives based on so-called metal "soap", ie metal salts of acidic organic compounds, sometimes referred to as surfactants. They generally contain a polar head with a long hydrophobic tail. Metal base (e.g., carbonate) An overbased metal cleaner comprising a neutralized metal cleaner as the outer layer of micelles is provided by reacting an excess metal base such as oxide or hydroxide with an acidic gas such as carbon dioxide to contain a large amount of metal base Can be. Examples of cleaning agents include metal salicylate, phenate, salicylate, and combinations thereof.

In the present invention, the overbased metal cleaner (B) is preferably an overbased metal hydrocarbyl-substituted hydroxybenzoate, more preferably a hydrocarbyl-substituted salicylate cleaner. The metal may be an alkali metal (eg, Li, Na, K) or an alkaline earth metal (eg, Mg, Ca).

"Hydrocarbyl" means a group or radical that contains carbon and hydrogen atoms and is bonded to the moiety of the molecule through a carbon atom. Under conditions that do not change the fundamental hydrocarbon properties and properties of the group, it may contain heteroatoms such as atoms other than carbon and hydrogen. As examples of hydrocarbyl, alkyl and alkenyl may be mentioned. A preferred overbased metal hydrocarbonyl-substituted hydroxybenzoate is a calcium alkyl-substituted salicylate and has the structure shown below:

In the above formula, R is a linear alkyl group. There may be more than one R group attached to the benzene ring. The COO ^- group may be in the ortho, meta or para position with respect to the hydroxyl group, with the ortho position being preferred. The R group may be in the ortho, meta or para position with respect to the hydroxyl group.

Salicylic acid is typically prepared by carboxylation of phenoxide by the Kolbe-Schmitt process, in which case it will generally be obtained in the form of a mixture (usually as a diluent) with non-carboxylated phenols. The salicylic acid can be non-sulfided or sulfided, chemically modified and/or contain additional substituents. Processes for sulfiding alkyl salicylic acids are known to those skilled in the art and are described, for example, in US 2007/0027057.

The alkyl groups advantageously contain 5 to 100, preferably 9 to 30, in particular 14 to 24 carbon atoms.

The term “overbasic” is generally used to describe a metal cleaner in which the ratio of the number of equivalents of metal moieties to the number of equivalents of acid moieties exceeds one. The term “low-basic” is used to describe a metal cleaner having an equivalent ratio of metal moieties to acid moieties greater than 1 and less than or equal to about 2.

The term “overbased calcium salt of surfactant” refers to an overbased detergent in which the metal cation of the oil-insoluble metal salt is essentially a calcium cation. Small amounts of other cations may be present in the oil-insoluble metal salt, but typically at least 80 mol%, more typically at least 90 mol%, such as at least 95 mol% cations in the oil-insoluble metal salt are calcium ions. Cations other than calcium can be derived, for example, by use in the preparation of overbased detergents of surfactant salts in which the cation is a metal other than calcium. Preferably, the metal salt of the surfactant is calcium.

Carbonated overbased metal cleaners typically include amorphous nanoparticles. In addition, nanoparticulate materials including carbonates in the form of crystalline calcite and vaterite are disclosed in the art.

The basicity of a detergent can be expressed as the total base number (TBN) (sometimes called the base number (BN)). The total base number is the amount of acid required to neutralize all of the basicity of the overbased material. TBN can be measured using ASTM standard D2896 or a procedure equivalent thereto. The cleaning agent may have a low TBN (ie, a TBN of less than 50), a medium TBN (ie a TBN of 50 to 150) or a high TBN (ie, a TBN of greater than 150, such as 150 to 500). The basicity may also be expressed as a basicity index (BI), which is the molar ratio of total base to total soap in the overbased detergent.

Polyalkenyl -Substituted Carboxylic acid Anhydride (C)

The anhydride may account for at least 1 to 7% by weight, such as 2 to 6% by weight, of the lubricating oil composition. Preferably, the anhydride accounts for 3 to 5% by mass, such as 4 to 5% by mass.

The anhydride may be a mono or polycarboxylic anhydride, preferably a dicarboxylic anhydride. The polyalkenyl group preferably has 8 to 400, such as 8 to 100 carbon atoms.

The general formula of exemplary anhydrides can be shown as follows:

In the above formula,

R ¹ represents a C ₈ to C ₁₀₀ branched or linear polyalkenyl group.

The polyalkenyl residue may have a number average molecular weight of 200 to 3000, preferably 350 to 950.

Suitable hydrocarbons or polymers that are used in the formation of the anhydrides of the present invention to produce polyalkenyl moieties include homopolymers, interpolymers or low molecular weight hydrocarbons. One class of such polymers are polymers of C ₃ to C ₂₈ alpha-olefins of ethylene and/or one or more of the formula H ₂ C=CHR ¹ , wherein R ¹ is a straight or branched chain alkyl radical having 1 to 26 carbon atoms. Wherein the polymer has a carbon-carbon unsaturated bond, preferably a high terminal ethenilidene unsaturation. Preferably, the polymer is ethylene and at least one alpha-olefin of the above formula (wherein R ¹ is an alkyl having 1 to 18 carbon atoms, more preferably an alkyl having 1 to 8 carbon atoms, even more preferably an alkyl having 1 or 2 carbon atoms. ) Of interpolymers. Thus, useful alpha-olefin monomers and comonomers are, for example, propylene, butene-1, hexene-1, octene-1, 4-methylpentene-1, decene-1, dodecene-1, tridecene-1, Tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1, and mixtures thereof (eg, a mixture of propylene and butene-1). Examples of such polymers are propylene homopolymer, butene-1 homopolymer, ethylene-propylene copolymer, ethylene-butene-1 copolymer, propylene-butene copolymer, etc., wherein the polymer has at least some terminal and/or internal unsaturated bonds. Contains. Preferred polymers are ethylene and propylene, and unsaturated copolymers of ethylene and butene-1. The interpolymer may contain small amounts, such as 0.5 to 5 mole percent, of C ₄ to C ₁₈ non-conjugated diolefin comonomers. However, it is preferred that the polymer comprises only alpha-olefin homopolymers, interpolymers of alpha-olefin comonomers, and interpolymers of ethylene and alpha-olefin comonomers. The ethylene content in the polymer used is preferably in the range of 0 to 80%, more preferably 0 to 60% on a molar basis. When propylene and/or butene-1 is used with ethylene and comonomer(s), the ethylene content of the copolymer is most preferably 15 to 50%, although higher or lower ethylene content may be present.

These polymers are alpha-olefin monomers, or mixtures of alpha-olefin monomers, or one with ethylene in the presence of a catalyst system comprising at least one metallocene (e.g., cyclopentadienyl-transition metal compound) and an alumoxane compound. It can be prepared by polymerizing a mixture containing the above C ₃ to C ₂₈ alpha-olefin monomer. Using this process, it is possible to provide a polymer in which 95% or more of the polymer chains have terminal ethylidene-type unsaturated bonds. The proportion of polymer chains exhibiting terminal ethnylidene unsaturation can be determined by FTIR spectroscopy analysis, titration or C ¹³ NMR. This latter type of interpolymer may be characterized by the formula POLY-C(R ¹ )=CH ₂ , wherein R ¹ is C ₁ to C ₂₆ alkyl, preferably C ₁ to C ₁₈ alkyl, more preferably C ₁ to C ₈ alkyl, most preferably C ₁ to C ₂ alkyl (eg methyl or ethyl), and POLY represents a polymer chain. The chain length of the R ¹ alkyl group will depend on the comonomer(s) selected to be used in the polymerization. A small amount of the polymer chain may contain terminal ethenyl (i.e. vinyl) unsaturation, i.e. POLY-CH=CH ₂ , and some of the polymer may contain internal monounsaturation, e.g. POLY-CH=CH(R ¹ ), where , R ¹ is as defined above). These terminally unsaturated interpolymers can be prepared by known metallocene chemistry and are also prepared as described in U.S. Patents 5,498,809, 5,663,130, 5,705,577, 5,814,715, 6,022,929 and 6,030,930. It could be.

Another useful class of polymers are those prepared by cationic polymerization such as isobutene, styrene, and the like. Conventional polymers of this class are by polymerization of C ₄ rectified streams having a butene content of 35 to 75% by mass and an isobutene content of 30 to 60% by mass in the presence of Lewis acid catalysts such as aluminum trichloride or boron trifluoride. And the obtained polyisobutene. A preferred source of monomers for making poly-n-butene is a petroleum feedstream such as Raffinate II. Such feedstocks are disclosed in the art, such as in US Pat. No. 4,952,739. Polyisobutylene is the most preferred skeleton of the present invention because it can be readily obtained by cationic polymerization from a butene stream (eg, using an AlCl ₃ or BF ₃ catalyst). Such polyisobutylenes generally contain unsaturated residues along the polymer chain in the amount of about 1 ethylenic double bond per polymer chain. A preferred embodiment uses a pure isobutylene stream or a polyisobutylene prepared from a raffinate I stream to produce a reactive isobutylene polymer having a terminal vinylidene olefin. Preferably, these polymers, referred to as highly reactive polyisobutylene (HR-PIB), have a terminal vinylidene content of 65% or more, such as 70% or more, more preferably 80% or more, most preferably 85% or more. . The preparation of such polymers is described, for example, in US Pat. No. 4,152,499. HR-PIB is known and commercially available under the trade names of Glissopal (trade name) (BASF) and Ultravis (trade name) (BP-Amoco). Available.

The polyisobutylene polymers that can be used are generally based on 400 to 3000 hydrocarbon chains. Methods for producing polyisobutylene are known. Polyisobutylene can be functionalized by halogenation (eg, chloride), terminal “ene” reaction, or free radical grafting with a catalyst, as described below.

In order to prepare (C), the hydrocarbon or polymer backbone is selectively functionalized with a carboxylic anhydride-producing moiety at the carbon-carbon unsaturated site on the polymer or hydrocarbon chain, or any one of the three processes described above, or Combinations of these can be used in any order and functionalized randomly along the chain.

Processes for reacting polymeric hydrocarbons with unsaturated carboxylic anhydrides and preparation of derivatives derived from these compounds are described in US 3,087,936; US 3,172,892; US 3,215,707; US 3,231,587; US 3,272,746; US 3,275,554; US 3,381,022; US 3,442,808; US 3,565,804; US 3,912,764; US 4,110,349; US 4,234,435; US 5,777,025; US 5,891,953; And EP 0 382 450 B1; CA-1,335,895 and GB-A-1,440,219. The polymer or hydrocarbon is a functional group on the polymer or hydrocarbon chain mainly at the site of carbon-carbon unsaturation (also referred to as ethylene or olefin unsaturation) using a halogen auxiliary functionalization (e.g., chlorination) process or a terminal "ene" reaction. Or it can be functionalized by reacting the polymer or hydrocarbon with a carboxylic acid anhydride moiety under conditions to add an agent, ie an acid anhydride.

Selective functionalization is performed by adding chlorine or bromine to the unsaturated α-olefin polymer for about 0.5 to 10 hours, preferably 1 to 7 hours at a temperature of 60 to 250°C, preferably 110 to 160°C, such as 120 to 140°C. By passing through, the unsaturated α-olefin polymer can be achieved by halogenation, such as chlorination or bromination, with about 1 to 8% by weight, preferably 3 to 7% by weight of chlorine or bromine, based on the weight of the polymer or hydrocarbon. The halogenated polymer or hydrocarbon (hereinafter referred to as a skeleton) is then, at 100 to 250°C, typically about 180 to 235°C, for about 0.5 to 10 hours, such as 3 to 8 hours, as a number of functional groups required for the skeleton. It reacts sufficiently with a monounsaturated reactant, such as a monounsaturated carboxylic acid reactant, which can be added, so that the obtained product contains the desired number of moles of the monounsaturated carboxylic acid reactant per mole of the halogenated skeleton. Alternatively, the skeleton and the monounsaturated carboxylic acid reactant are mixed and heated while adding chlorine to the hot material.

Chlorination usually contributes to an increase in the reactivity of the starting olefin polymer by the monounsaturated functionalization reactants, but this is necessary in some polymers or hydrocarbons contemplated for their use in the present invention, especially preferred polymers or hydrocarbons with high end bond content and reactivity. Not. Thus, preferably, the backbone and monounsaturated functional reactants (carboxylic acid reactants) are brought into contact at elevated temperature to cause an initial thermal “ene” reaction. Yen reactions are known.

The hydrocarbon or polymer backbone can be functionalized by random bonding of functional groups along the polymer chain by various methods. For example, the polymer in solution or solid form can be grafted with a monounsaturated carboxylic acid reactant, as described above, in the presence of a free radical initiator. When carried out in solution, the grafting takes place at an elevated temperature in the range of 100 to 260°C, preferably 120 to 240°C. Preferably, grafting with a free-radical initiator is achieved in an inorganic lubricating oil solution containing for example 1 to 50% by weight, preferably 5 to 30% by weight of polymer, based on the initial total oil solution.

Free-radical initiators that may be used are peroxides, hydroperoxides and azo compounds, preferably compounds having a boiling point above about 100° C. and thermally decomposed in the above grafting temperature range to give free-radicals. Representative examples of such free-radical initiators are azobutyronitrile, 2,5-dimethylhex-3-ene-2, 5-bis-tert-butyl peroxide and dicumene peroxide. Initiator, when used, is typically used in an amount of 0.005 to 1% by weight, based on the weight of the reaction mixture solution. Typically, the monounsaturated carboxylic acid reactant and free-radical initiator are used in a weight ratio range of about 1.0:1 to 30:1, preferably 3:1 to 6:1. The grafting is preferably carried out in an inert atmosphere such as under nitrogen blanketing. The resulting grafted polymer is characterized by having carboxylic acid (or derivative) moieties randomly bound along the polymer chain, of course it is understood that some of the polymer chains remain ungrafted. The free radical grafting described above can also be used for other polymers and hydrocarbons used in the present invention.

Preferred monounsaturated reactants used to functionalize the backbone are mono- and dicarboxylic acid materials, i.e. acid or acid derivative materials, such as (i) monounsaturated C ₄ to C ₁₀ dicarboxylic acids, wherein (a) carboxyl Groups are contiguous (ie located on adjacent carbon atoms) and (b) at least one, preferably both of said adjacent carbon atoms are part of said monounsaturation; (ii) derivatives of (i), such as anhydrides of (i) or C ₁ to C ₅ alcohol derived mono- or diesters; (iii) monounsaturated C ₃ to C ₁₀ monocarboxylic acid (here, the carbon-carbon double bond is conjugated with a carboxyl group, that is, a carboxyl group of the structure -C=C-CO-); And (iv) a derivative of (iii), such as the C ₁ to C ₅ alcohol derived mono- or diester of (iii). Mixtures of monounsaturated carboxylic acid substances (i) to (iv) can also be used. Upon reaction with the skeleton, the monounsaturation of the monounsaturated carboxylic acid reactant becomes saturated. Thus, for example, maleic anhydride becomes a skeleton-substituted succinic anhydride, and acrylic acid becomes a skeleton-substituted propionic acid. Examples of such monounsaturated carboxylic acid reactants include fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and lower alkyls thereof (e.g., C ₁ to C ₄ alkyl) acid esters such as methyl maleate, ethyl fumarate and methyl fumarate.

In order to provide the required functionality, the monounsaturated carboxylic acid reactant, preferably maleic anhydride, is typically in an approximately equivalent molar amount to about 100% by mass excess, preferably 5 to 50% by mass excess, based on the moles of polymer or hydrocarbon. It will be used in a range amount. Unreacted excess monounsaturated carboxylic acid reactant can be removed from the final dispersant product, if necessary, usually under vacuum, for example by stripping.

Ball-additive

The lubricating oil composition of the present invention may further contain additional additives different from (B) and (C). Such additional additives may include, for example, ashless dispersants, other metal cleaners, antiwear agents such as zinc dihydrocarbyl dithiophosphate, antioxidants and demulsifiers. In some cases, it is not necessary to provide an ashless dispersant.

Although not required, it may be desirable to prepare one or more additive packages or concentrates comprising additives, wherein additives (B) and (C) can be added to the base oil at the same time to form a lubricating oil composition. Dissolution of the additive package into the lubricating oil can be facilitated by the solvent and by mixing with gentle heating, but this is not essential. When an additive package is combined with an amount of base oil, such an additive package is typically formulated to contain an appropriate amount of the additive(s) to provide the desired concentration and/or to perform the intended function in the final composition. Thus, according to the present invention, additives (B) and (C) are mixed with a small amount of base oil or other compatible solvent together with other preferred additives, based on the additive package, for example, 2.5 to 90% by mass of the additive in an appropriate proportion. It is possible to form an additive package containing the active ingredient in an amount of, preferably 5 to 75% by mass, most preferably 8 to 60% by mass, and the balance being a base oil.

The final composition as a trunk piston engine oil may typically contain 30% by mass, preferably 10 to 28% by mass, more preferably 12 to 24% by mass of the additive package, the balance being the base oil. The trunk piston engine oil may have a composition TBN (using ASTM D2896) of 20 to 60, such as 30 to 55. For example, TBN may be 40 to 55, or 35 to 50.

Example

The invention is illustrated by the following examples, but is not limited to these in any way.

ingredient

The following ingredients were used:

Ester Base stock (A1)

Polyol ester (PRIOLUBE (registered trademark) 3970), a trimethylolpropane ester with a C8-10 fatty acid having a viscosity of 4.4 mm ² s ^-1 at 100° C., for example Croda( Croda) lubricants;

Polymer esters in the form of copolymers of alpha-olefins (KETJENLUBE (registered trademark) 115), and dicarboxylic acid dibutyl esters with an average molecular weight of approximately 1400.

Base stock (A2)

Group I oil (XOMAPE 600) (for comparison)

Group II oil (RLOP 600)

Group III oil (YUBASE 8)

Commercial name in parentheses.

Detergent (B)

Calcium alkyl salicylate (BI 8.0)

Calcium alkyl salicylate (BI 3.0)

Basicity index in parentheses.

PIBSA (C)

Polyisobutene succinic anhydride, derived from polyisobutene with a number average molecular weight of 950

HFO

Heavy fuel oil (ISO-F-RMK 380)

Trunk Piston Marine Engine Lubricant ( TPEO )

The above ingredients were selected and blended to provide a range of TPEO. Some are examples of the invention, others are control examples for comparison purposes. When each HFO was contained, the composition of the tested TPEO was described in the table under the subheading "Results" below (mass%).

exam

Light scattering

Test trunk piston marine engine lubricating oil (TPEO) for asphaltene dispersibility using light scattering according to the focused beam reflectance method (“Focused Beam Reflectance Method” (FBRM)) that predicts asphaltene agglomeration and consequently “black sludge” formation. Evaluated.

The FBRM test method was published at the 7th International Symposium on Ship Engineering in Tokyo, Japan from October 24 to 28, 2005, and as a journal of the Society [The Benifits of Salicylate Detergents in TPEO Applications with a Variety of Base Stocks] Was published. More details were presented at the CIMAC meeting held in Vienna, Austria from 21 to 24 May 2007, as a conference bulletin [Meeting the Challenge of New Base Fluids for the Lubrication of Medium Speed Marine Engines-An Additive Approach]. Was published. In the latter paper, the FBRM method is used to predict the performance of a basestock-based lubricant system containing more than or less than 90% saturates and more than or less than 0.03% sulfur, a quantitative analysis of asphaltene dispersibility. It has been disclosed that results can be obtained. The prediction of the relative performance obtained from the FBRM was confirmed by engine tests in marine diesel engines.

The FBRM probe contains a fiber optic cable that moves to allow the laser light to reach the probe tip. At the tip, the lens focuses the laser light to a small point. The lens is rotated to scan the circular path between the probe window and the sample with a focused beam. As the particles flow through the window, they cross the scanning path and provide backscattered light from the individual particles.

The scanning laser beam travels much faster than the particles, which means that the particles are effectively stationary. As the focused beam reaches one edge of the particle, the amount of backscattered light increases, and the amount will decrease when the focused beam reaches the other edge of the particle.

The instrument measures the time of increased backscatter. The time of backscattering from a particle multiplied by the scan speed is the distance or chord length. The chord length is a straight line between any two points on the edge of the particle. It is represented as a chord length distribution, ie as a graph of the number of chord lengths (particles) measured as a function of chord length dimension in microns. As measurements are made in real time, distribution statistics can be calculated and tracked. Typically, FBRM measures tens of thousands of chords per second, creating a strong [several times chord length] distribution. This method provides an absolute measure of the particle size distribution of asphaltene particles.

The focused beam reflectance probe (FBRM), model Lasentec D600L, is supplied by Mettler Toledo, Leicester, UK. This equipment was configured to provide a particle size resolution of 1 μm to 1 mm. Data from FBRM can be presented in several ways. Studies have suggested that the average count per second can be used as a quantitative determinant of the asphaltene dispersibility. This value is a function of both the average size and level of agglomerates. Herein, the average count rate (over the entire size range) was monitored using a measurement time of 1 second per sample.

The test TPEO was heated to 60° C. and stirred at 400 rpm. When the temperature reached 60° C., an FBRM probe was put into the sample and measured for 15 minutes. An aliquot (10% w/w) of heavy fuel oil was introduced into TPEO under stirring using a four-winged stirrer (400 rpm). When the count rate reached the equilibrium value (typically overnight) the average count value per second was taken.

result

Light scattering

The FBRM test results are summarized in the table below, with lower particle counts indicating better performance.

Reference examples are indicated by "reference".

Each tested TPEO has a BN of 40 and contains 1.23% by mass (relative to calcium) of calcium salicylate at BI 8.0 and 0.24% by mass (relative to calcium), calcium salicylate at BI 3.0, and the same Includes positive Zn and silicone antifoam. The residue of the finished oil component is given in the table below:

[Table 1]

Reference 3 and reference 4 are illustrated in US Patent Application Publication No. 2011/0319304 A1 ('304).

Ref. 4 (using ester alone) confirms the teaching of '304.

Reference 5 (used by PIBSA alone) confirms the teaching of '594.

Examples 1-3 confirm the synergistic effect of PIBSA and esters.

Each tested TPEO has a BN of 40 and contains 0.75% by mass (relative to calcium) of calcium salicylate at BI 8.0 and 0.68% by mass (relative to calcium), calcium salicylate at BI 3.0, and the same Contains positive Zn. The residue of the finished oil component is given in the table below:

[Table 2]

The results show that changing the processing rate of PIBSA and ester affects the result: In Examples 4 to 8, the PIBSA processing rate was kept constant, and the ester processing rate continued to increase; In Examples 9 to 13, the ester processing rate was kept constant, and the PIBSA processing rate continued to increase. Example 14 shows the applicability of the invention to Group III base oils, greater than Reference 6 (Group I oil), and Example 15 shows the applicability of the invention to esters other than Priolube 3970. .

Each tested TPEO has a BN of 30 and contains 0.56% by mass (relative to calcium) of calcium salicylate of BI 8.0, and 0.51% by mass (relative to calcium) of calcium salicylate BI 3.0, It contains the same amount of Zn. The residues of the finished oil component are given in the table below.

[Table 3]

The above results show that the effect of the present invention appears in TPEO with lower BN.

Claims (20)

As a trunk piston marine engine lubricating oil composition for improving asphaltene handling during use when the heavy fuel oil is supplied as fuel,
(A) is an oil-soluble ester basestock (A1); or
0.1% to 90% by mass of an oil-soluble ester basestock (A1), and a basestock comprising at least 50% by mass of the residue of oil with a lubricating viscosity of at least 90% of saturates and at most 0.03% of sulfur or mixtures thereof ) Containing,
A lubricating viscosity oil of at least 50% by mass of the composition;
(B) small amounts of oil-soluble overbased metal hydrocarbyl-substituted hydroxybenzoate detergents; And
(C) a small amount of oil-soluble polyalkenyl-substituted carboxylic acid anhydride of greater than 0.1% to less than 10% by mass of the composition, wherein at least one polyalkenyl group is a polyalkene having a number average molecular weight of 200 to 3000. Derived from)
Containing, or prepared by mixing them, a lubricating oil composition. The method of claim 1,
A lubricating oil composition, wherein the basestock (A2), if present, comprises more than 60% by mass of a basestock containing at least 90% saturates and at most 0.03% sulfur or mixtures thereof. The method of claim 1,
The lubricating oil composition, wherein the basestock (A2), if present, is a group II, group III or group IV basestock. The method of claim 1,
A lubricating oil composition, wherein the metal hydrocarbyl-substituted hydroxybenzoate detergent (B) is a calcium alkyl salicylate detergent. The method of claim 4,
The lubricating oil composition, wherein the metal hydrocarbyl-substituted hydroxybenzoate detergent (B) is C ₉ to C ₃₀ alkyl-substituted. The method of claim 4,
The lubricating oil composition, wherein the metal hydrocarbyl-substituted hydroxybenzoate detergent (B) is C ₂₀ or higher alkyl-substituted. The method of claim 1,
The lubricating oil composition, wherein the polyalkenyl substituent in the anhydride (C) has 8 to 400 carbon atoms. The method of claim 1,
The lubricating oil composition wherein the polyalkenyl substituent in anhydride (C) has a number average molecular weight of 350 to 1000. The method of claim 1,
The lubricating oil composition, wherein the polyalkenyl-substituted carboxylic anhydride (C) is succinic anhydride. The method of claim 9,
The lubricating oil composition, wherein the succinic anhydride (C) is polybutene succinic anhydride. The method of claim 1,
The lubricating oil composition, wherein the ester basestock (A1) is present in an amount of 10 to 90% by mass. The method of claim 1,
The lubricating oil composition, wherein the ester base stock (A1) has a kinematic viscosity of 2 to 10 mm ² s ^-1 at 100°C. The method of claim 1,
The ester base stock (A1) is a polyol ester base stock, a lubricant composition. The method of claim 1,
Lubricating oil composition further comprising a heavy fuel oil component. A method of operating a trunk piston medium-speed compression-ignition marine engine, comprising:
(i) replenishing the engine with heavy fuel oil as fuel; And
(ii) lubricating the crankcase of the engine with a composition according to any one of claims 1 to 14.
How it works, including. A method of dispersing asphaltenes in a trunk piston ship lubricating oil composition during operation of the engine and during operation of the combustion chamber surface of a medium speed compression-ignition ship engine,
(i) providing a composition according to any one of claims 1 to 14;
(ii) providing the composition in the combustion chamber;
(iii) providing heavy fuel oil in the combustion chamber; And
(iv) burning the heavy fuel oil in the combustion chamber
Dispersion method comprising a. The method of claim 16,
A dispersion method in which the dispersion of asphaltenes is measured using a focused beam reflectance method ("Focussed Beam Reflectance Method", FBRM). delete delete delete