CN102365353A

CN102365353A - Marine engine lubrication

Info

Publication number: CN102365353A
Application number: CN2010800154936A
Authority: CN
Inventors: T·加纳; L·格雷戈里; J·哈特利; P·瓦茨
Original assignee: Infineum International Ltd
Current assignee: Infineum International Ltd
Priority date: 2009-04-07
Filing date: 2010-03-31
Publication date: 2012-02-29
Also published as: JP2012522879A; ES2428237T3; EP2417234A1; US20120028521A1; CA2755815A1; ES2425957T3; WO2010115594A1; KR101654397B1; WO2010115595A1; CN102365352A; SG174925A1; CA2755815C; AU2010234299B2; SG175117A1; KR20120006995A; US20120028522A1; CA2755308A1; AU2010234300A1; CA2755308C; JP2012522878A

Abstract

Trunk piston marine engine lubrication, when the engine is fueled by heavy fuel oil, is effected by a composition comprising a major amount of an oil of lubricating viscosity containing at least 50 mass % of a Group II basestock, and respective minor amounts of an overbased metal hydrocarbyl-substituted hydroxybenzoate detergent other than such a detergent having a basicity index of less than two and a degree of carbonation of 80% or greater and at least 1 mass % of a hydrocarbyl-substituted carboxylic acid, anhydride, ester or amide thereof. Asphaltene precipitation in the lubricant, caused by the presence of contaminant heavy fuel oil, is prevented or inhibited.

Description

Marine engine is lubricated

Technical field

The present invention relates to a kind of trunk piston marine engine lubricating composition of (oil motor) marine engine and lubricating of this mover that is used for the ignition of middling speed four-stroke.

Background of invention

The boats and ships trunkengine uses HFO (" HFO ") to carry out sea trip usually.HFO is that the heavy duty of petroleum distillate divides and comprise each molecule complex mixture of (comprising 15% bituminous matter at the most), and it is defined as and is insoluble in excessive aliphatic hydrocrbon (for example heptane) but dissolves in the petroleum distillate level branch in the aromatic solvent (for example toluene).Bituminous matter can be as pollutent via cylinder or petrolift and syringe entering engine lubricant, and bituminous matter can precipitate then, in mover, shows as " black paint " or " black sludge ".On piston face, exist such carbon-containing sediment to can be used as insulation layer and work, this can cause forming then the crack along the piston expansion.If piston is passed in the crack, then hot combustion gas can get into crankcase, possibly cause crankcase explosion.

Therefore hope highly that trunkengine oil (" TPEO ") prevents or suppresses asphaltene precipitation.Description of the Prior Art the method for doing like this.

WO96/26995 discloses and in diesel engine, has used hydrocarbyl substituted phenol to reduce " black paint ".WO96/26996 discloses in diesel engine demulsifying compound has been used for water-in-oil emulsion, and for example polyoxyalkylene polyol is to reduce " black paint ".US-B2-7,053,027 has described the combination of in non-dispersant TPEO, using one or more high alkalinity metal carboxylate salt purification agents and anti-wear additive.

The problem of asphaltene precipitation is more serious under higher basic raw material saturated level.WO2008/128656 described a kind of through in boats and ships trunkengine lubricant, use index of basicity less than 2 and the carbonation degree be 80% or the scheme of bigger high alkalinity metal hydrocarbyl substituted hydroxy benzoate purification agent to reduce the deposition of bituminous matter in this lubricant.Instance is the lubricant that comprises II group basic raw material, and the basic raw material saturated level that it has is higher than I group basic raw material.

Yet such scheme is limited to the purification agent of particular types.Have now found that in the present invention through in II group basic raw material, using the high alkalinity metal carboxylate salt purification agent of different range to solve the problem among the WO2008/128656 with carboxylic acid, acid anhydride, ester or the acid amides of hydrocarbyl substituted with its combined.

Summary of the invention

First aspect present invention be a kind of be used for improving use in bituminous matter; The trunk piston marine engine lubricating oil composition that bituminous matter in operating the mover of making fuel with HFO is handled; Said composition comprises the oil and the following component of minor amount respectively of the lubricant viscosity that contains 50 quality % or more II group basic raw material of main amount, or contain by this of main amount 50 quality % or more II group basic raw material lubricant viscosity oil and minor amount respectively this following component mixing and prepare:

(A) high alkalinity metal hydrocarbyl substituted hydroxy benzoate purification agent; Rather than index of basicity less than 2 and the carbonation degree be 80% or bigger the sort of purification agent, wherein the carbonation degree is the percentage ratio of the carbonate that exists in the high alkalinity metal hydrocarbyl substituted hydroxy benzoate purification agent of representing with molecular fraction with respect to the total excess base in this purification agent; With

(B) hydrocarbyl replaces carboxylic acid or its acid anhydride, ester or acid amides, wherein said or at least one alkyl contains at least 8 carbon atoms, and said acid, acid anhydride, ester or acid amides account at least 1 quality % of lubricating oil composition.

Second aspect present invention is the defined purification agent of first aspect present invention (A) and carboxylic acid, acid anhydride, ester or acid amides (B) purposes in the middling speed ignition marine engine that is combined in the said amount of first aspect present invention in the trunk piston boats and ships lubricating oil composition; That said composition comprises lubricant viscosity with main amount and the oil that contains 50 quality % or more II group basic raw material is handled to improve the bituminous matter of doing with HFO in the mover process of fuel in operation, and said composition and lubricating of under similar operations, in the presence of not having (B), comparing during use same amount purification agent (A).

Third aspect present invention is a kind of method of operating trunk piston middling speed ignition marine engine, and this method comprises the steps:

(i) with HFO supply engine fuel; With

(ii) use the crankcase of the defined compsn lubricating engine of first aspect present invention.

Fourth aspect present invention is the method that in the process of a kind of combustor surface at its lubricated middling speed ignition marine engine and operation mover bituminous matter is scattered in the trunk piston boats and ships lubricating oil composition, and this method comprises the steps:

(i) provide first aspect present invention defined compsn;

Said composition (ii) is provided in the combustion chamber;

HFO (iii) is provided in the combustion chamber; With

(iv) heavy fuel fired oil in the combustion chamber.

In this specification sheets, if use and in use, following wording and statement have following implication:

" activeconstituents " or " (a.i.) " refer to not to be the additive materials of thinner or solvent;

" comprise " or any cognate regulation exists said characteristic, step or integral body or component, have or add one or more other characteristics, step, integral body, component or its combination but do not get rid of; Statement " by ... constitute " or " basically by ... constitute " or cognate can be included in " comprising " or the cognate, wherein " basically by ... constitute " allow to comprise the material of the compsn characteristic that this material of materially affect is not used;

" main amount " refers to surpass 50 quality % of compsn;

" minor amount " refers to 50 quality % less than compsn;

" TBN " refers to the total basicnumber according to ASTM D2896 measurement.

" calcium contents " measured according to ASTM 4951 in this external this specification sheets; " phosphorus content " measured according to ASTM D5185; " sulfate ash content " measured according to ASTM D874; " sulphur content " measured according to ASTM D2622; " KV100 " refers to according to ASTM D445 100 ℃ of following measured motion viscosity.

Will also be understood that each component used, basic and best and routine can be reacted and product that the present invention also provides the product that can be obtained by this reaction arbitrarily or obtained by this reaction arbitrarily under preparation, storage or working conditions.

In addition, amount, scope and the ratio that should understand any upper and lower bound as herein described can independently make up.

Detailed Description Of The Invention

To discuss characteristic of the present invention hereinafter in more detail at present.

The oil of lubricant viscosity

The lubricating oil viscosity scope can be from lightweight overhead product MO to heavy grease.Usually the range of viscosities that should oil under 100 ℃, records is 2-40mm ²/ sec.

Natural oil comprises animal oil and vegetables oil (for example Viscotrol C, lard); The MO of kerosene and unifining, solvent treatment or acid-treated paraffinic hydrocarbons, naphthenic hydrocarbon and blended paraffinic hydrocarbons-naphthenic hydrocarbon type.The oil of the lubricant viscosity that is obtained by coal or shale also can be used as base oil.

Ucon oil comprises the alkene (for example polybutylenes, Vestolen PP 7052, propylene-isobutylene copolymers, chlorinated polybutylenes, gather the 1-hexene, gather the 1-octene, gather 1-decene) of hydrocarbon ils and the substituted hydrocarbon ils of halogen such as polymerization or copolymerization; Korenyl (for example dodecylbenzene, tetradecyl benzene, dinonyl benzene, two (2-ethylhexyl) benzene); Polyphenyl (for example biphenyl, terphenyl, alkylation gather phenol); With alkylation phenyl ether and alkylation diphenyl sulfide and verivate, analogue and homologue.

Wherein the oxyalkylene polymer through modifications such as esterification, etherificates and interpolymer and verivate thereof constitute another kind of known ucon oil to terminal hydroxy group.The polyoxyalkylene polymers that these instance prepares for the polymerization through ethylene oxide or propylene oxide and the alkyl of polyoxyalkylene polymers and aryl ethers (for example molecular weight is that 1000 methyl gathers Isopropanediol ether or molecular weight is the phenyl ether of the polyoxyethylene glycol of 1000-1500); And monocarboxylate and polycarboxylate, the for example acetic ester of Tetraglycol 99, blended C ₃-C ₈Fatty ester and C ₁₃The oxygen acid diester.

Another kind of suitable ucon oil comprises the ester of dicarboxylicacid (for example phthalic acid, succsinic acid, alkyl succinic acid and alkenyl succinic, toxilic acid, nonane diacid, suberic acid, sebacic acid, fumaric acid, hexanodioic acid, linoleic acid dimer, propanedioic acid, alkyl propanedioic acid, alkenyl propanedioic acid) and various alcohol (for example butanols, hexanol, dodecyl alcohol, 2-ethylhexyl alcohol, terepthaloyl moietie, monoalkyl ethers of diethylene glycol, Ucar 35).The specific examples of such ester comprises the 2-ethylhexyl diester of the two eicosyl esters of hexanodioic acid dibutyl ester, sebacic acid two (2-ethylhexyl) ester, fumaric acid di-n-hexyl ester, sebacic acid dioctyl ester, nonane diacid diisooctyl ester, nonane diacid diiso decyl ester, phthalic acid dioctyl ester, phthalic acid didecyl ester, sebacic acid, linoleic acid dimer and through making 1 mole of sebacic acid and 2 moles of Tetraglycol 99s and 2 moles of 2 ethyl hexanoic acids react the complex ester that form.

The ester that can be used as synthetic oil also comprises by C ₅-C ₁₂Those of monocarboxylic acid and polyvalent alcohol and polyol ester preparation are like NSC 6366, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol and tripentaerythritol.

Based on the oil of silicon as gather alkyl-, gather aryl-, gather alkoxyl group-or gather the aryloxy silicone oil and silicic acid ester oil comprises another kind of available synthetic lubricant; Such oil comprises silicic acid tetraethyl ester, silicic acid tetra isopropyl ester, silicic acid four (2-ethylhexyl) ester, silicic acid four (4-methyl-2-ethylhexyl) ester, silicic acid four (to tert-butyl-phenyl) ester, six (4-methyl-2-ethylhexyl) sily oxide, gathers (methyl) siloxanes and gathers (aminomethyl phenyl) siloxanes.Other ucon oils comprise the liquid ester (for example Tritolyl Phosphate, tricresyl phosphate octyl group ester, decylphosphonic acid diethyl ester) and the polymerizing tetrahydrofuran of phosphorated acid.

Oil not refining, refining and that re-refine can be used in the lubricant of the present invention.Unrefined oil is for directly being obtained by natural or synthetic source and not carrying out those of further purification processes.The shale oil that for example directly obtains by the destructive distillation operation; The oil that directly obtains by distillation; Or the ester oil that directly obtains by esterification and further do not handle and use be unrefined oil.Treated oil is similar to unrefined oil, and different is that this oil is further handled to improve one or more performances in one or more purification step.Many such purification techniquess such as distillation, SX, acid or alkali extraction, filtration and diafiltration all are that those skilled in the art are known.The oil of re-refining is used to provide those methods of treated oil to obtain through being similar to, but by used oil beginning.Such oil of re-refining is also known as the oils that reclaims or reprocess and uses the technology of removing useless additive and oil decomposition product to carry out other processing usually.

Among the present invention to the definition of basic raw material and base oil with at API (API) publication " Engine Oil Licensing and Certification System "; Industry Services Department; The 4th edition; In December, 1996, appendix find in 1,1998 year 12 months those are identical.Said publication with basic raw material according to following classification:

A) I group basic raw material contains less than 90% full compound and/or greater than 0.03% sulphur, and viscosity index is more than or equal to 80 and less than 120 (using specified test among the table E-1).

B) II group basic raw material contains more than or equal to 90% saturates and is less than or equal to 0.03% sulphur, and viscosity index is more than or equal to 80 and less than 120 (using specified test among the table E-1).

C) III group basic raw material contains more than or equal to 90% saturates and is less than or equal to 0.03% sulphur, and viscosity index is more than or equal to 120 (using specified test among the table E-1).

D) IV group basic raw material is poly-alpha olefins (PAO).

E) V group basic raw material comprises the every other basic raw material that is not included in I, II, III or the IV group.

The analytical procedure of basic raw material is that following table is listed:

Character	Testing method
		Saturates	ASTM?D?2007
Viscosity index	ASTM?D?2270
		Sulphur	ASTM?D?2622
	ASTM?D?4294
			ASTM?D?4927
	ASTM?D?3120

As described, the oil of lubricant viscosity contains 50 quality % or more II group basic raw materials among the present invention.Preferably, it contains just like 60 quality % or more; For example 70,80 or 90 quality % or more II organize basic raw material.The oil of lubricant viscosity can be all II group basic raw materials basically.High alkaline metal detergent (A)

Metal detergent is the additive based on so-called metal " soap ", and promptly the metal-salt of acidic organic compound is called tensio-active agent sometimes.They comprise polar head and long hydrophobic tail usually.Comprising the neutral metal detergent can be through making excess metal alkali such as oxide compound or oxyhydroxide and sour gas such as carbon dioxide reaction through comprising that a large amount of metal base provide as the outer field high alkaline metal detergent of metal base (for example carbonate) micella.

In the present invention, high alkaline metal detergent (A) is a high alkalinity metal hydrocarbyl substituted hydroxy benzoate, preferred alkyl substituted salicylic acid salt purification agent.

" alkyl " refers to contain carbon and Wasserstoffatoms and via the group of the rest part bonding of carbon atom and molecule.It can contain heteroatoms, promptly except carbon and the atom the hydrogen, as long as they do not change the basic hydrocarbon character and the characteristic of group.The alkyl instance that can mention is alkyl and alkenyl.Structure shown in high alkalinity metal hydrocarbyl substituted hydroxy benzoate has usually:

Wherein R is linearity or branched aliphatic alkyl, and more preferably alkyl comprises straight chain or branched-alkyl.Can have greater than a radicals R and be connected on the phenyl ring.M is basic metal (for example lithium, sodium or potassium) or earth alkali metal (for example calcium, magnesium, barium or strontium).Preferred calcium or magnesium; Especially preferred calcium.Group COOM can be positioned at ortho position, a position or the contraposition for hydroxyl, preferred ortho position.Radicals R can be positioned at ortho position, a position or the contraposition for hydroxyl.

Hydroxy-benzoic acid is carboxylated by Kolbe-Schmitt method preparation through phenates usually, and this moment usually (being in the thinner usually) obtain with mixture with not carboxylated phenol.Hydroxy-benzoic acid can be not sulfuration or sulfurized, but and chemical modification and/or contain other substituting group.The method of the hydroxy-benzoic acid of sulfuration hydrocarbyl substituted is known for those skilled in the art, and for example is described among the US2007/0027057.

In the hydrocarbyl substituted hydroxy-benzoic acid, alkyl preferred alkyl (comprise straight chain-or branched-alkyl), and alkyl advantageously contains 5-100, preferred 9-30,14-24 carbon atom especially.

The ratio that term " high alkalinity " is generally used for being described in wherein metal construction part equivalents and sour structure division equivalents is greater than 1 metal detergent.The equivalence ratio that term " low alkalinity " is used to be described in the part of metal construction wherein and sour structure division is greater than 1 and about at the most 2 metal detergent.

The metallic cation that " calcium salt of overbased surfactants " refers to be insoluble in therein the metal-salt of oil is the cationic high alkaline detergent of calcium basically.A spot of other positively charged ions can be present in the metal-salt that is insoluble in oil, but are insoluble at least 80 moles of % in the metal-salt of oil usually, at least 90 moles of % more generally, and for example the positively charged ion of at least 95 moles of % is a calcium ion.Positively charged ion beyond the calcium can be for example obtained by the use in being manufactured on the high alkaline detergent that positively charged ion wherein is the metallic surface promoting agent salt beyond the calcium.The metal-salt of preferred surfactant also is a calcium.

The carbonating high alkaline metal detergent comprises unbodied nano particle usually.In addition, the Nanoparticulate material that comprises the carbonate that is corn spar and vaterite (vaterite) form is disclosed.

The alkalescence of purification agent can be represented with total basicnumber (TBN).Total basicnumber be in required acid amounts of all alkalescence of overbased material.The program measurement that TBN can use ASTM standard D2896 or be equal to.Purification agent can have low TBN (being that TBN is less than 50), medium TBN (being that TBN is 50-150) or high TBN (be TBN greater than 150 like 150-500).In the present invention, can use index of basicity and carbonation degree.Index of basicity is all an alkali and all mol ratio of soaps in the high alkaline detergent.The carbonation degree is the percentage ratio that is present in the carbonate in the high alkaline detergent to represent with molecular fraction with respect to the total excess base in the purification agent.

High alkalinity metal hydrocarbyl substituted hydroxy benzoate can be through any technology preparation of using in this area.Universal method is following:

In the solvent mixture that constitutes by volatile hydrocarbon, alcohol and water with in the metal base of molar excess and the hydrocarbyl substituted hydroxy-benzoic acid to produce high alkalinity metal hydrocarbyl substituted hydroxy-benzoic acid salt complex slightly;

2. carbonating to be to produce colloidal dispersion metal carbonate, subsequently afterreaction for some time;

3. remove and do not have colloidal dispersion residual solid; With

4. stripping is to remove process solvent.

High alkalinity metal hydrocarbyl substituted hydroxy benzoate can prepare through high alkalinity method in batches or continuously.

Metal base (for example metal hydroxides, MOX or metal alkoxide), preferred lime (calcium hydroxide) can add in one or more steps.Feeding in raw material can be identical or different, because can add carbonic acid gas thereafter.When adding calcium hydroxide again when reinforced, the carbon dioxide treatment in stage does not need fully before.Along with carbonating is carried out, make dissolved oxyhydroxide be converted into the colloidal state carbonate particle in the mixture that is scattered in volatile hydrocarbon solvent and non-volatile hydrocarbon oil.

Carbonating can be through carrying out in the TR of the reflux temperature of pure promotor at the most in one or more steps.Adding temperature can be similar or different, or can add in the step at each and change.Temperature raises therein and the optional stage of reducing then can be before another carbonation step.

The volatile hydrocarbon solvent of reaction mixture is preferably boiling point and is not more than about 150 ℃ aromatic hydrocarbon that is generally liquid.Found that aromatic hydrocarbon provides some benefit, the filtration velocity of for example improving, and the instance of suitable solvent is toluene, YLENE and ethylbenzene.

The alkanol particular methanol, but other alcohols such as ethanol can be used.The correct selection of the ratio of alkanol and hydrocarbon solvent and the water-content of initial action mixture has importance to obtaining required product.

Oil can add in this reaction mixture; If add, suitable oil comprises hydrocarbon ils, particularly those of mineral source.Most suitable is 38 ℃ of following viscosity is 15-30mm ²The oil of/sec.

After carrying out last processing with carbonic acid gas, usually reaction mixture is heated to the temperature of rising, for example more than 130 ℃ to remove volatile matter (water and any residual alkanol and hydrocarbon solvent).When synthetic the completion, owing to exist the sediment that suspends to make that crude product is muddy.It is for example through filtering or centrifugal the clarification.These measurements can be used before intermediate point or at intermediate point or after solvent is removed.

Usually this product is used as oil solution.If reaction mixture contains the oil that is not enough to keep oil solution after removing volatile matter, then should add other oil.This can carry out before intermediate point or at intermediate point or after solvent is removed.

In the present invention, (A) can have following character:

(A1) index of basicity be 2 or bigger and carbonation degree be 80% or bigger; Or

(A2) index of basicity be 2 or bigger and carbonation degree less than 80%; Or

(A3) index of basicity less than 2 and the carbonation degree less than 80%.

Carboxylic acid and acid anhydride thereof, ester or acid amides (B)

As described, acid and acid anhydride thereof, ester or acid amides constitute at least 1 quality % of lubricating oil composition.Preferred it constitute 1.5 quality % like 10 quality % at the most, like 2-10 quality %, for example 3-6 quality %.(B) can be mixture.

Acid can be monocarboxylic acid or poly carboxylic acid, preferred dicarboxylic.Alkyl preferably has 8-400, like 8-100 carbon atom.

The acid anhydride of preferred dicarboxylic is as (B).

When acid was dicarboxylicacid, ester can be half ester or diester.Ester group can comprise alkyl, aryl or aralkyl, and amide group can be and do not replace or have one or more alkyl, aryl or aralkyl.

The general formula of exemplary monocarboxylic acid and dicarboxylicacid and acid anhydride thereof, ester or acid amides is as follows:

R wherein ¹Be C ₈-C ₁₀₀Branching or linear alkyl such as polyalkenyl, alkyl or alkaryl;

X and Y are OR independently of one another ²And OR ³, R wherein ²And R ³Be Wasserstoffatoms or alkyl, aryl or aralkyl independently of one another, or X and Y be-O-together, and/or as follows:

R ¹CH ₂COR ⁴(II)，

R wherein ⁴Be OR ⁵Or NR ⁶R ⁷, R wherein ⁵, R ⁶And R ⁷Be Wasserstoffatoms or alkyl independently of one another.

Preferred alkyl is a polyalkenyl.The number-average molecular weight that this polyalkenyl structure division can have is 200-3000, preferred 350-950.

The suitable hydrocarbons or the polymkeric substance that in forming acid/verivate of the present invention, use comprise homopolymer, interpolymer or lower molecular weight hydro carbons.A kind of in this base polymer comprises that ethene and/or at least a has formula H ₂C=CHR ¹C ₃-C ₂₈The polymkeric substance of terminal olefin, wherein R ¹For the straight chain that comprises 1-26 carbon atom or branched-alkyl and wherein polymkeric substance contain carbon carbon unsaturated link(age), the end vinylidene of preferred heights is unsaturated.Preferred this base polymer comprises ethene and at least a interpolymer with terminal olefin of following formula, wherein R ¹For having the alkyl of 1-18 carbon atom, more preferably have the alkyl of 1-8 carbon atom, also more preferably have the alkyl of 1-2 carbon atom.Therefore available 'alpha '-olefin monomers and comonomer for example comprise propylene, 1-butylene, 1-hexene, 1-octene, 4-methyl-1-pentene, 1-decene, 1-dodecylene, 1-tridecylene, tetradecene, 1-15 carbenes, cetene, 1-heptadecene, 1-vaccenic acid, 1-19 carbenes and composition thereof (for example the mixture of propylene and 1-butylene etc.).The instance of this base polymer is alfon, 1-butylene homopolymer, ethylene-propylene copolymer, ethene-butene-1 copolymer, propene-1-butene copolymer etc., and wherein this polymkeric substance contains part end and/or inner unsaturated at least.Preferred polymkeric substance is the unsaturated copolymer of ethene and propylene and ethene and 1-butylene.Interpolymer of the present invention can contain minor amount, for example 0.5-5 mole %C ₄-C ₁₈Unconjugated diolefine comonomer.Yet preferred polymkeric substance of the present invention only comprises the interpolymer of alpha-olefin homo, alpha-olefin comonomer and the interpolymer of ethene and alpha-olefin comonomer.The ethene molar content of the polymkeric substance that uses in the present invention is preferably 0-80%, more preferably 0-60%.When with propylene and/or 1-butylene as with the comonomer of ethene the time, the ethylene content of this base polymer most preferably is 15-50%, but can have higher or lower ethylene content.

These polymkeric substance can be through polymerization of Alpha-olefin monomer in the presence of the catalyst system that comprises at least a metallocenes (for example cyclopentadienyl moiety-transistion metal compound) and aikyiaiurnirsoxan beta (alumoxane) compound; Or the mixture of 'alpha '-olefin monomers, or comprise ethene and at least a C ₃-C ₂₈The mixture of 'alpha '-olefin monomers and preparing.Use this method can be provided at wherein 95% or more polymer chain have terminal vinylidene type unsaturated polymer.The percentage ratio that shows terminal vinylidene unsaturated polymer chain can be by FTIR spectroscopic analysis, titration or C ¹³NMR measures.This interpolymer of back one type can be characterised in that to have formula POLY-C (R ¹)=CH ₂, R wherein ¹Be C ₁-C ₂₆Alkyl, preferred C ₁-C ₁₈Alkyl, more preferably C ₁-C ₈Alkyl, most preferably C ₁-C ₂Alkyl (for example methyl or ethyl) and wherein POLY be polymer chain.Alkyl R ¹Chain length depend on and selectedly be used for the polymeric comonomer and change.The polymer chain of minor amount can contain terminal ethylenyl groups, and promptly vinyl is unsaturated, i.e. POLY-CH=CH ₂, and a part of polymkeric substance can contain inner single unsaturated, POLY-CH=CH (R for example ¹), R wherein ¹As above define.The interpolymer of these terminal unsaturations can be through the luxuriant chemical preparation of known metal and also can be like United States Patent(USP) Nos. 5,498,809; 5,663,130; 5,705,577; 5,814,715; 6,022,929 and 6,030,930 is said and prepare.

The polymkeric substance that another kind of usable polymers prepares for the cationoid polymerisation through iso-butylene, vinylbenzene etc.This common base polymer comprise through butene content be about 35 quality % to about 75 quality % and iso-butylene content be the Cs of about 30 quality % to about 60 quality % ₄Refinery materials flow polymerization and polyisobutene of obtaining in the presence of lewis acid catalyst such as aluminum chloride or boron trifluoride.The monomeric preferred source that is used to prepare poly-n-butene is petroleum feeding materials flow such as Raffinate II.These raw materials are disclosed in like United States Patent(USP) No. 4,952 in the art, in 739.Polyisobutene is the most preferred skeleton of the present invention, because it is easy to (for example use AlCl through cationoid polymerisation by butene stream ₃Or BF ₃Catalyzer) obtains.This type polyisobutene contains position residual unsaturated along this chain with the amount of about 1 olefinic double bond/polymer chain usually.The embodiment preferred utilization prepares the reactive isobutene polymer with vinylidene end group alkene by the polyisobutene of pure iso-butylene materials flow or Raffinate I materials flow preparation.The vinylidene endgroup content that preferred these polymkeric substance (being called highly reactive polyisobutene (HR-PIB)) have is at least 65%, for example 70%, more preferably at least 80%, most preferably at least 85%.The preparation of this base polymer for example is described in the United States Patent(USP) No. 4,152,499.HR-PIB be known and HR-PIB with trade(brand)name Glissopal ^TM(from BASF) and Ultravis ^TM(from BP-Amoco) is commercially available.

Spendable polyisobutene polymkeric substance is usually based on the hydrocarbon chain of 400-3000.The known method for preparing polyisobutene.Polyisobutene can be through halogenation (for example chlorination), heat " alkene " reaction, or through the be described below free radical grafting of catalyzer (for example superoxide) and functionalized of use.

For produce (B) hydrocarbon or polymer backbone can use in above-mentioned three kinds of methods any or its with the carbon carbon unsaturated regioselectivity ground that is combined in polymkeric substance or hydrocarbon chain of random order or randomly functionalized with the structure division (acid or anhydride structure division) that produces carboxylic acid along chain.

Make the method for polymer hydrocarbon and unsaturated carboxylic acid, acid anhydride or ester reaction and be disclosed in United States Patent(USP) Nos. 3,087,936 by such compound verivate; 3,172,892; 3,215,707; 3,231,587; 3,272,746; 3,275,554; 3,381,022; 3,442,808; 3,565,804; 3,912,764; 4,110,349; 4,234,435; 5,777,025; 5,891,953; And EP0382450B1; CA-1,335,895 and GB-A-1,440,219.This polymkeric substance or hydrocarbon can use the reaction of auxiliary functionalized (for example chlorination) method of halogen or heat " alkene " cause functional structure's part or reagent through making polymkeric substance or hydrocarbon, i.e. acid, acid anhydride, ester structure part etc. mainly add to reaction under the condition on polymkeric substance or the hydrocarbon chain in carbon carbon unsaturated (also be called olefinic or ethylenic is unsaturated) position and functionalized with the structure division (acid or anhydride) of generation carboxylic acid.

Selective functionalization can be realized through halogenation; For example pass through at 60-250 ℃; Preferred 110-160 ℃; Chlorine or bromine was passed through the about 0.5-10 of polymkeric substance hour, and preferred 1-7 hour and the unsaturated alpha-olefinic polymer of chlorination or bromination be to be about 1-8 quality % based on polymkeric substance or hydrocarbon weight, preferably 3-7 quality % chlorine or bromine.Make halogenated polymer or hydrocarbon (skeleton hereinafter referred to as) and enough can required functional structure's part number be added to the single unsaturated reactant on the skeleton then; For example single unsaturated carboxylic acid reactant is at 100-250 ℃; Usually about 180 ℃-235 ℃ were reacted about 0.5-10 hour down; For example 3-8 hour, make the every mole of halogenation skeleton of product that obtains contain single unsaturated carboxylic acid reactant of required mole number.Perhaps, skeleton and single unsaturated carboxylic acid reactant are mixed when chlorine is added hot material and heat.

Although chlorination helps to make the reactivity of starting olefin polymkeric substance to increase along with single unsaturated functionalization thing usually; But some can be used for polymkeric substance of the present invention or hydro carbons, particularly have high-end linkage content and reactive those preferred polymkeric substance or hydro carbons not necessarily.Therefore preferably make skeleton and single unsaturated functional response's thing, for example the carboxylic acid reaction thing contacts to cause that initial heat " alkene " reaction takes place at elevated temperatures.Known alkene reaction (ene reaction).

Hydrocarbon or polymer backbone can be through being made functional structure part along the random connection of polymer chain and functionalized by the whole bag of tricks.For example, being the polymkeric substance of solution or solid form can be as stated with the grafting in the presence of radical initiator of single unsaturated carboxylic acid reactant.When carrying out with solution, be grafted on about 100-260 ℃, carry out under the temperature of preferred 120-240 ℃ rising.Preferably, radical causes is grafted on that to contain be 1-50 quality % based on initial total oil solution for example, carries out in the mineral lubricating oils solution of preferred 5-30 quality % polymkeric substance.

Spendable radical initiator is superoxide, hydroperoxide and azo cpd, and preferred boiling point is greater than about 100 ℃ and thermolysis and those of radical are provided in the grafting TR.These radical initiators be represented as azo butyronitrile, peroxo-2, the 5-dimethyl-oneself-3-alkene-2,5-di-t-butyl and peroxo-two cumenes.In use, initiator is the amount use of 0.005-1 weight % usually with the weight based on reaction mixture solution.Usually, aforementioned single unsaturated carboxylic acid reactant materials and radical initiator are with about 1.0: 1-30: 1, preferred 3: 1-6: 1 weight ratio is used.Grafting is preferably in inert atmosphere as under nitrogen protection, carry out.The gained graftomer is characterised in that carboxylic acid (or verivate) structure division that has along the random connection of polymer chain: will of course be appreciated that the grafting not yet of partial polymer chain.Above-mentioned free radical grafting can be used for other polymkeric substance of the present invention and hydro carbons.

That the single unsaturated reactant that preferably is used for functionalized skeleton comprises is single-with the dicarboxylicacid material, i.e. acid or acid derivative material comprise (i) single unsaturated C ₄-C ₁₀Dicarboxylicacid, wherein (a) carboxyl be ortho position base (promptly being positioned on the adjacent carbons) and (b) said adjacent carbons at least one, preferred two are a said monounsaturated part; (ii) the verivate of (i) is like the acid anhydride or the C of (i) ₁-C ₅Alcohol deutero-list-or diester; (iii) single unsaturated C ₃-C ₁₀Monocarboxylic acid, wherein carbon-carbon double bond and carboxyl conjugation, promptly structure is-C=C-CO-; (iv) (iii) verivate is like (iii) C ₁-C ₅Alcohol deutero-list-or diester.Can also use the mixture of single unsaturated carboxylic acid material (i)-(iv).When reacting with skeleton, the list of single unsaturated carboxylic acid reactant is unsaturated become saturated.Therefore, for example toxilic anhydride becomes the substituted succinyl oxide of skeleton, and vinylformic acid becomes the substituted propionic acid of skeleton.The instance of the single unsaturated carboxylic acid reactant of this type is the low alkyl group (C for example of fumaric acid, methylene-succinic acid, toxilic acid, toxilic anhydride, chlorine toxilic acid, chlorine toxilic anhydride, vinylformic acid, methylacrylic acid, Ba Dousuan, styracin and above-mentioned acid ₁-C ₄Alkyl) ester, for example toxilic acid methyl esters, ethyl fumarate and fumarate dimethyl.

For required functionality is provided, single unsaturated carboxylic acid reactant, preferred toxilic anhydride serves as that about equimolar amount is excessive to about 100 quality % with the mole number based on polymkeric substance or hydrocarbon usually, the amount use that preferred 5-50 quality % is excessive.Unreacted excessive single unsaturated carboxylic acid reactant can be through for example stripping and from final dispersion product, removing under vacuum if desired usually.

The additive (A) and the processing speed (B) that are contained in the lubricating oil composition can for example be 1-2.5, preferred 2-20, more preferably 5-18 quality %.

Be total to additive

Lubricating oil composition of the present invention can comprise with (A) and (B) different and (A) with (B) additional in addition other additives.The additional additive of this type can for example comprise ashless dispersant, other metal detergents, anti-wear agent such as dialkyl zinc dithiophosphate, inhibitor and demulsifying compound.

Although not necessarily, possibly hope to prepare a kind of or more kinds of additive-package or enriched material that comprises additive, can be with additive (A) and (B) add simultaneously in the base oil through it to form lubricating oil composition.The dissolving of additive-package in lubricating oil can promote through solvent and through following mild heat to mix, but this not necessarily.When the base lubricant of additive-package and predetermined amount merged, additive-package was configured to contain an amount of additive usually desired concn to be provided and/or to realize expectation function in final preparaton.Therefore; Additive of the present invention (A) and (B) can be mixed together and form based on additive-package with the additive of a small amount of base oil or other compatible solvent and other hope with a certain amount of additive-package that contains activeconstituents; The 2.5-90 quality % of proper ratio for example; Preferred 5-75 quality %, the additive of 8-60 quality % most preferably, surplus is a base oil.

Final preparaton as trunkengine oil can contain 30 quality % usually, preferred 10-28 quality %, and the more preferably additive-package of 12-24 quality %, surplus is a base oil.The compound TBN (using ASTM D2896) that preferred tubular piston engine has is 20-60 such as 25-55.

Embodiment

The present invention explains through following instance, but is limited to the following example never in any form.

Component

Use following component:

Component (A):

(A1) TBN is that 350 (index of basicity is 2 or bigger; The carbonation degree is 80% or bigger) the SAP 002 purification agent

(A2) TBN is that 225 (index of basicity is 2 or bigger; The carbonation degree is less than 80%) the SAP 002 purification agent

(A3) TBN is that 65 (index of basicity is less than 2; The carbonation degree is less than 80%) the SAP 002 purification agent

Component (B):

(B1) oleic acid

(B2) derived from number average weight be the polyisobutylene succinic acid of 450 polyisobutene

(B3) derived from number-average molecular weight be the polyisobutene succinyl oxide (" PIBSA ") of the polyisobutene of 950 (72%ai)

(B4) derived from number-average molecular weight be the polyisobutene succinyl oxide (" PIBSA ") of the polyisobutene of 450 (75%ai)

(B5) isooctadecane base succinyl oxide

(B6) succsinic acid two (2-hydroxypropyl) 2-dodecyl ester

(B7) oleylamide

(B8) tetren, two isooctadecane base acid amides.

Base oil I:API I organizes base oil, is known as XOMAPE600

Base oil II:API II organizes base oil, is known as CHEV600R

HFO: HFO, ISO-F-RMK 380

Phenolate: TBN is 255 calcium phenylate purification agent

Sulphonate: TBN is 425 calcium sulfonate detergents

Lubricant

The above component blend that makes selection is to obtain a series of trunk piston marine engine lubricants.Some lubricants are the embodiment of the invention; Other are correlated with reference to embodiment for being used for.When containing HFO separately, the composition of the lubricant of test is shown in the table under the title as a result.

Test

Panel coking test

Panel coking test is used for the performance of evaluation test lubricant.Testing method comprises that oil through spraying test at the pond internal rotation metal pectination equipment that contains oil is to the metal sheet of heating.When the test duration finished, the settling of formation can be assessed through weight with through the visually inspect of plate outward appearance.

Use panel coker (model is PK-S, is provided by the Yoshida Kagaku Kikai Co. of Japanese Osaka) to test.Clean test panel fully, before being inserted into device, weigh then.Test oil is mixed with 2.5%HFO, and in the pond with 225g gained mixture adding apparatus.When this oily temperature is 100 ℃ and test panel when being 320 ℃, with metal combs equipment automatically rotation so that this oil injection to test panel.

Testing sequence continues 120 circulations, and each circulation constitutes by oil being ejected into therein 15 seconds on the plate and 45 seconds of not spraying.

When EOT, with this plate of normal heptane washing, drying is weighed and visually inspect again.Record settling weight.

Scattering of light

Test lubricant also uses scattering of light to estimate bitum dispersiveness according to focused beam reflection method (" FBRM "), and its prediction bituminous matter agglomeration forms with " black sludge " therefore.

The FBRM testing method also is disclosed in Tokyo, and the 7th time of 24-28 day in October, 2005 about being published among the Conference Proceedings in the international symposium of marine engine and with " The Benefits of Salicylate Detergents in TPEO Applications with a Variety of Base Stocks ".Other details are disclosed in CIMAC Congress; Vienna, 21-24 day in May, 2007 and be published among the Conference Proceedings with " Meeting the Challenge of New Base Fluids for the Lubrication of Medium Speed Marine Engines-An Additive Approach ".After disclose through using the FBRM method to obtain in the document mentioned and predicted the dispersed quantitative result of bituminous matter that is greater than or less than 90% saturates and the performance of the lubricant system of the basic raw material that is greater than or less than 0.03% sulphur based on containing.The prediction of the relative performance that is obtained by FBRM confirms through the Engine Block Test in the boat diesel engine mover.

The FBRM probe contains fiber optic cable, and laser propagation arrives probe tips through it.In the end, it is point that eyeglass makes laser focusing.The rotation eyeglass makes the circular path of light beam between the scope of probe and sample that focuses on scan.Along with particle flow is passed through this scope, they and scan path intersect, and obtain back-scattered light by each particle.

Scan laser beam ratio particle is propagated much fast; This means that particle is effectively fixing.Along with the light beam that focuses on arrives particulate on one side, the amount of back-scattered light increases; When the light beam that focuses on arrived the particulate the other side, this measured reduction.

This apparatus measures the backscattered time that increases.Multiply by sweep velocity by a backscattered time of particle, the result is distance or chord length.Chord length is at the straight line between any 2 on the particle limit.This representes that with chord length distribution chord length (particle) the number conduct of promptly measuring is in the graph of function of the chord length size of micron.As real-time is measured, and can calculate the statistics that distributes with tracking.FBRM has measured tens thousand of string/seconds usually, causes the relevant distribution with chord length of sane number (robust number-by-chord length distribution).This method obtains the absolute measurement of bituminous matter particulate size-grade distribution.

Focused beam reflective probe (FBRM), model are Lasentec D600L, by Mettler Toledo, and Leicester, UK supply.In structure, use this instrument to obtain the granularity of the resolving power of 1 μ m to 1mm.The data of FBRM can exist in every way.Research shows the quantitatively determined that can be used as the bituminous matter dispersiveness average counter/second.This value is the function of the mean sizes of agglomerate and level.In this application, use 1 second Measuring Time of each sample monitoring average counter speed (in the whole dimension scope).

The test lubricant preparaton is heated to 60 ℃ and stir with 400rpm; When temperature reaches 60 ℃, the FBRM probe is inserted in the sample and measured 15 minutes.One aliquot HFO (10%w/w) is being used introducing lubricant formulation agent under quaterfoil formula whisking appliance (with the 400rpm) stirring.When counting rate reaches equilibrium value (spending the night usually), read the value of average counter/second.

The result

Panel coking test

The result of panel coking test is summarised in the following table, and wherein except as otherwise noted, number is the mass percent of activeconstituents.

Table 1

Ex	SAP 002 (A1)	?PIBSA(B3)	Base oil I	Base oil II	Settling (g)
						1	8.57	?7.00	?-	84.43	?0.0221
X	8.57	?-		91.43	?0.0759
						Y	8.57	?-	?91.43		?0.0450

Each lubricant contains the 44.6mM soap and TBN is 30.Each lubricant also contains 0.5 quality %HFO.

The result shows that the embodiment of the invention (Ex1) produces with the corresponding embodiment (ExX) that lacks PIBSA and with lacking embodiment (ExY) in the I of PIBSA group base oil and compares much little settling that the bituminous matter of promptly improving is dispersed.

Table 2

Ex	Calcium phenylate	Calcium sulphonate	?PIBSA(B3)	Base oil II	Settling (g)
						P	4.40	4.40	?7.00	84.20	0.1489
Q	4.40	4.40	?-	91.20	0.1009

Each lubricant contains the 42mM soap and TBN is 30.Each lubricant also contains 0.5 quality %HFO.

The result is presented at when purification agent is the combination of phenates/sulphonate and exists PIBSA (ExP) to reduce the bituminous matter handling property.Discovery in this and the table 1 is suitable, in the time that purification agent is salicylate, and improved performance.

Scattering of light

The FBRM test result is summarised in the following table 3.

Table 3

The result shows in all cases, only (A)+(B) is superior to (A).

Other results by those FBRM that in calibration instrument, independently carry out of table 3 are summarised in the following table 4.

Table 4

The result shows that (A) that represented by each A1, A2 and A3 and (B3) combination only are superior to (A) and only (B3).

Claims

1. one kind is used for improving and uses in bituminous matter; The trunk piston marine engine lubricating oil composition that bituminous matter in operating the mover of making fuel with HFO is handled; Said composition comprises the oil and the following component of minor amount respectively of the lubricant viscosity that contains 50 quality % or more II group basic raw material of main amount, or contain by this of main amount 50 quality % or more II group basic raw material lubricant viscosity oil and minor amount respectively this following component mixing and prepare:

(A) high alkalinity metal hydrocarbyl substituted hydroxy benzoate purification agent rather than index of basicity less than 2 and the carbonation degree be 80% or bigger the sort of purification agent, wherein the carbonation degree is the percentage ratio of the carbonate that exists in the high alkalinity metal hydrocarbyl substituted hydroxy benzoate purification agent of representing with molecular fraction with respect to the total excess base in the purification agent; With

(B) hydrocarbyl replaces carboxylic acid or its acid anhydride, ester or acid amides, wherein said or at least one alkyl contains at least 8 carbon atoms, and said acid, acid anhydride, ester or amine account at least 1 quality % of lubricating oil composition, for example at least 1.5 quality %.

2. compsn as claimed in claim 1, wherein (A) has following character:

(A2) index of basicity be 2 or bigger and carbonation degree less than 80%; Or

(A3) index of basicity less than 2 and the carbonation degree less than 80%.

3. according to claim 1 or claim 2 compsn, wherein (B) is as follows:

R wherein ¹Be C ₈-C ₁₀₀Branching or linear alkyl are like polyalkenyl, alkyl or alkaryl; X and Y are OR independently of one another ²And OR ³, R wherein ²And R ³Be Wasserstoffatoms or alkyl, aryl or aralkyl independently of one another, or X and Y are-O-together; And/or as follows:

R ¹CH ₂COR ⁴(II)，

R wherein ¹As above define,

R ⁴Be OR ⁵Or NR ⁶R ⁷, R wherein ⁵, R ⁶And R ⁷Be Wasserstoffatoms or alkyl independently of one another.

4. like each described compsn among the claim 1-3, wherein the metal in (A) is a calcium.

5. like each described compsn among the claim 1-4, wherein the hydrocarbyl substituted hydroxy benzoate in (A) is a salicylate.

6. like each described compsn among the claim 1-5, wherein the oil of lubricant viscosity contains greater than 60 quality % II group basic raw material.

7. like each described compsn among the claim 1-6, it is individual as 12-100 that wherein the alkyl in (B) has 8-400, especially 16-64 carbon atom.

8. like each described compsn among the claim 1-7, wherein in acid or verivate (B), hydrocarbyl substituent is derived from polyolefine.

9. like each described compsn among the claim 1-8, wherein (B) is succsinic acid or succinyl oxide.

10. compsn as claimed in claim 9, wherein (B) is polyisobutylene succinic acid or acid anhydride.

11. like each described compsn among the claim 1-10, its TBN is 20-60, for example 25-55.

12. the defined purification agent of claim 1 (A) and the defined carboxylic acid of claim 1, acid anhydride, ester or acid amides (B); Combination with the defined amount of claim 1; The purposes that in trunk piston boats and ships lubricating oil composition, is used for middling speed ignition marine engine; Said composition comprises oil lubricant viscosity and that contain 50 quality % or more II group basic raw material of main amount; Handle to improve the bituminous matter of doing with HFO in the mover process of fuel in operation, with and with under similar operations, do not having (B) the lubricating of comparing during use same amount purification agent (A) down through said composition.

13. a method of operating trunk piston middling speed ignition marine engine comprises the steps:

(i) with HFO supply engine fuel; With

(ii) use the crankcase of each defined compsn lubricating engine of claim 1-11.

14. a method that in the process of the combustor surface of its lubricated middling speed ignition marine engine and operation mover, bituminous matter is scattered in the trunk piston boats and ships lubricating oil composition, it comprises the steps:

(i) claim 1-11 is provided each defined compsn;

Said compsn (ii) is provided in the combustion chamber;

HFO (iii) is provided in the combustion chamber; With

(iv) heavy fuel fired oil in the combustion chamber.