CN105623789B - Lubricant oil composite and the method for improving its comprehensive performance - Google Patents
Lubricant oil composite and the method for improving its comprehensive performance Download PDFInfo
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Abstract
The present invention proposes a kind of lubricant oil composite and the method for improving lubricating oil comprehensive performance.The lubricant oil composite of the present invention, including：Alkyl sulfide phosphonic acid anhydrides, demulsifier, detersive, antioxidant, dispersant and major amount of lubricating base oil.The lubricant oil composite of the present invention has excellent high temperature detergency, oxidation stability, antiwear and antifriction, especially there is excellent high temperature detergency and demulsification performance, divide water quick, thorough, suitable for the lubrication of marine diesel engine, crankcase lubrication, the lubrication of middling speed piston type diesel engine especially suitable for two-stroke low speed cross head marine diesel machine.
Description
Technical field
The present invention relates to a kind of lubricant oil composite, more particularly to a kind of lubricating oil groups suitable for marine diesel engine
Close object.
Background technology
With China's economic development, sea transport industry rapidly develops, and the demand of large ship bunker oil is continuously increased, oil
Quality is continuously improved.These oil products mainly include two-stroke low speed cross-head type steam cylinder oil, system oil and four stroke middling speed cylinders
Shape piston diesel engine oil etc..Wherein, although system oil and four stroke diesel engine oil with medium speed are not so good as marine cylinder oil work
Make condition harshness, but the fuel being still related to is the higher diesel oil of sulfur content, has different areas of activity existing for water.Therefore, it is oily
Product there are certain requirements for base number, and in system oil in the range of 6~10mgKOH/g, middling speed machine oil requires base number 0 for general requirement
In the range of~40mgKOH/g.Generally speaking, it is desirable that system oil and middling speed machine oil have preferable high temperature detergency, inoxidizability,
Acid neutralize performance, it is point aqueous can and demulsification performance, wherein high temperature detergency and aqueous energy and demulsification performance be divided to be two weights
Want index.In recent years, also there are many research reports of middling speed machine oil and system oil.
CN 1203263《Crank axle for vessel case fluid composition containing demulsifier》A kind of crank axle for vessel case composition is described, is wrapped
Include substantial amounts of mineral oil base oil, a small amount of alkyl monosulfide phenates, salicylate, polyisobutene succinimide, dialkyl group two
Thiophosphate, epoxy second, propane block co-polyether, alcohols, dimethicone can modulate 3 according to requirement of the oil product to base number
The crank axle for vessel case oil of~40mgKOH/g, to meet low speed crosshead engine of boat and ship crankcase system and medium speed trunk piston
The lubricating requirement of engine.
CN 1253542《Lubricant oil composite》It describes one kind and lights ship hair for four stroke plunger type medium speed compressions
The lubricant oil composite of motivation, it includes a kind of mixtures of following substance：(A) a kind of oil of lubricant viscosity, accounts for more amount；
A kind of (B) oil-soluble overbased metal detergent additive, accounts for less amount, exists in the form of a kind of complex compound,
Stablize detergent base stock with more than one surfactant in the complex compound；Said composition is substantially free of scattered
Agent or the dispersant containing 1% based on composition quality or less than 1%, preferably less than 0.5%；And the TBN value of composition exists
3.5~100mgKOH/g, preferably in 8~100mgKOH/g.Said composition has excellent high temperature detergency and relatively low cost.
CN 1257255《Lubricant oil composite》, the lubricant oil composite of introduction is suitable for low speed, the work of 4 stroke cartridge type of middling speed
Plug either 2 stroke crosshead engines lubrication, lubricant oil composite, including：The major amount of oil with lubricant viscosity, wherein
Contain a small amount of fuel oil with slag fuel content；With mixed, a small amount of, at least one to have at least two be aromatics
Residue moiety or by the oil-soluble of doubly linked adjacent substitutable carbon atom or the ashless organic compound of oily dispersibility,
Described in carbon atom be respectively provided with oxygen-containing or oxygen-containing and nitrogen functional group, two kinds of groups are derived from carboxyl.Mainly solve cartridge type
Piston engine (TPEO), marine cylinder oil (MDCL), fuel are mixed into the scattering problem of lubricating oil.
CN 1257256《Lubricate the method for four stroke medium speed compression ignition engine of boat and ship》、CN 1322797《Lubricating oil
Composition》The lubricant oil composite of introduction includes, and the lubricating oil of (1) at least 60%, 100 dynamic viscosities are in 2~40mm2/s, (2)
2.55%~30% calcium salicylate, base number is in 100~450mgKOH/g, as unique overbased metal detersive,
(3) 0.1%~1.5% dihydrocarbyl dithiophosphate trbasic zinc phosphate, composition are free of dispersant, and base number is in 25~100mgKOH/g,
Said composition has excellent high temperature detergency.
CN 101570712《A kind of high-base-number ship cylinder lubricating oil》The lubricant oil composite of introduction, base oil are centre
Base base oil, metal detergent are the 40TBN high-base-number ship cylinder lubricating oils peculiar to vessel of calcium naphthenate.Be by weight percentage by
Calcium naphthenate 0.2%~25%, sulfurized alkylphenol calcium 0.2%~20%, succimide 0.2%~20%, tricresol phosphate
Fat or benzotriazole fatty amine salt 0.05%~15%, carbaminate 0.1%~18%, alkylnaphthalene 0.1%~16%, dimethyl
Silicon 0.0001%~0.1%, polyethers 0.01%~5% and base oil form for surplus, and there is excellent diffusivity, water resistant to divide water
Property, the performances such as corrosion and wear resistance and detergency, be in a leading position level at home, bunker oil production similar with foreign big oil companies
Quality is suitable, can meet the requirement of ocean and coastal waters large ship to bunker oil.
US 4358386《Crank axle for vessel case lubricating oil》Describe a kind of low speed bunker oil bent axle of base number in 3~10TBN
Case oil has preferable antiwear and antifriction, breaking, point aqueous, including high base number alkyl phenol calcium 1%~5%, dialkyl group
Dithiophosphates 0.1%~1%, oxiranylalkyl phenol 0.2%~0.4%, N alkyl glycines derivative 0.75%~
2%.
US 5753598《Lubricant oil composite with improved point of aqueous energy》Describe a kind of point of water performance improvement
Lubricant oil composite, demulsifier uses epoxyalkane and heterocyclic compound, such as dimercaptothiodiazole, with 0.1：1~0.5：1
Ratio is added in lubricating oil, is shown the demulsification effect of consonance and is preferably divided aqueous energy.
More than achievement in research can provide the ship lubricant oil of better performances or be four-stroke piston middling speed machine oil,
It can meet the job requirement of engine in most of occasion.With the reduction of petroleum resources, diesel oil sulphur that bunker fuel oil uses
Content is more and more, and this requires the high temperature detergency of oil product further improves.Meanwhile with the increase of engine power, oil
The extension of product drain period, it is desirable that the properties of original oil product will also further improve, wherein dividing water and demulsibility
It is required that it is also higher and higher, and divide water and demulsibility that cannot meet the requirements sometimes in existing formula, therefore, it is necessary to further
It improves.
The content of the invention
The present invention proposes a kind of lubricant oil composite and the method for improving lubricating oil comprehensive performance.
The lubricant oil composite of the present invention, including：Alkyl sulfide phosphonic acid anhydrides, demulsifier, detersive, antioxidant, dispersant and
Major amount of lubricating base oil.
The alkyl sulfide phosphonic acid anhydrides are the alpha-olefin and P of C5~C502S5The product of phosphine sulfideization reaction, preferably C10 occurs
The alpha-olefin and P of~C402S5The product of phosphine sulfideization reaction, the most preferably alpha-olefin of C10~C30 and P occurs2S5Generation phosphine sulfide
The product of reaction.When preparing the alkyl sulfide phosphonic acid anhydrides, the alpha-olefin and P of the C5~C502S5Molar ratio preferably 1：
1.5~2.5, reaction temperature is 100~250 DEG C, when the reaction time is 2~6 small, is preferably added to be catalyzed when the two reacts
Agent, the addition of the catalyst is the 0.1%~1% of the two material gross mass, the catalyst optimizing alkyl phenol, sulphur.
The alpha-olefin and P of the C5~C502S5The reaction equation that phosphine sulfideization is reacted, which occurs, is：
Wherein R " is the alkyl of C5~C50.
The alkyl sulfide phosphonic acid anhydrides account for the 0.01%~2% of lubricant oil composite gross mass, preferably 0.05%~1%,
Most preferably 0.05%~0.5%.
The demulsifier is non-polyether class demulsifier and/or polyethers demulsifier.
The non-polyether class demulsifier is acrylate and the copolymer of α-olefin sulfonic acid.
The structure of the copolymer of the acrylate and α-olefin sulfonic acid is：
Wherein R is C4~C18 alkyl or its mixed alkyl, preferably C4~C15 alkyl or its mixed alkyl, most preferably C5~
C10 alkyl or its mixed alkyl；Wherein A1 is hydrogen or methyl, and A2 is hydrogen or C1~C4 alkyl, preferably hydrogen, methyl, ethyl or third
Base, most preferably hydrogen, methyl or ethyl, x be 0~4 integer, preferably 0~3 integer, most preferably 0~2 integer；When A2 is hydrogen
When, x is positive integer；M be 1~50 integer, preferably 5~50, most preferably 10~30, n be 1~50 integer, preferably 5~50,
Most preferably 10~20.
The molecular weight of the copolymer of the acrylate and α-olefin sulfonic acid between 1000~15000, preferably 1500~
10000, most preferably 2000~8000.
The preparation method of the copolymer of the acrylate and α-olefin sulfonic acid is by alkyl acrylate and α-alkenyl sulphur
Acid is copolymerized, and collects product.
The structure of the alkyl acrylate is：
Wherein R is C4~C18 alkyl or its mixed alkyl, preferably C4~C15 alkyl or its mixed alkyl, most preferably C5~
C10 alkyl or its mixed alkyl；A1 is hydrogen or methyl.
The alkyl acrylate is to be obtained by methacrylic acid or acrylic acid with alkylol by esterification, and esterification is anti-
It is the acidic catalysts such as the concentrated sulfuric acid, acid-exchange resin to answer common catalyst.
The structure of the α-olefin sulfonic acid is：
Wherein A2 is hydrogen or C1~C4 alkyl, and preferably hydrogen, methyl, ethyl or propyl, most preferably hydrogen, methyl or ethyl, x is
0~4 integer, preferably 0~3 integer, most preferably 0~2 integer；When A2 is hydrogen, x is positive integer.
α-the olefin sulfonic acid is that alpha-olefin and sulfonating agent sulfonating reaction occur and obtains.The alpha-olefin is C3~C10
Alkene, such as the one or more in propylene, butylene, amylene, hexene, heptene, octene, nonene and decene can be selected, preferably
C3~C8 alkene, most preferably C3~C6 alkene.The sulfonating agent can select oleum and/or sulfur trioxide.
When sulfonating reaction occurs for alpha-olefin and sulfonating agent, solvent, preferably varsol, the varsol can be added in
It is preferred that C5~C10 alkane or its mixture.The 20%~200% of the preferred alpha-olefin quality of addition of the solvent, in sulfonation
Solvent is removed after reaction.
The reaction pressure of sulfonating reaction occurs for the alpha-olefin and sulfonating agent preferably between 0.1~4MPa, and most preferably 0.3
~3.0MPa, reaction temperature is preferably between 0~30 DEG C, and most preferably between 0~20 DEG C, the reaction time preferably 0.1~8 is small
When, most preferably 0.3~5 it is small when.
The molar ratio of the alpha-olefin and sulfonating agent preferably 1：1~1.5, more preferable 1：1~1.2.
In the product of the sulfonating reaction alkyl acrylate is cannot participate in containing α-olefin sulfonic acid, sultone, sultone
With the copolyreaction of α-olefin sulfonic acid.
Molar ratio between the alkyl acrylate and α-olefin sulfonic acid is 1~50：50~1, preferably 1~10：10~
1, most preferably 1~3：2~1.
The copolyreaction of the alkyl acrylate and α-olefin sulfonic acid preferably carries out in a solvent, and the solvent is preferably fragrant
One or more in hydrocarbon solvent, such as benzene, toluene and dimethylbenzene；Preferably 20~200 DEG C of reaction temperature, more preferable 30~150
DEG C, most preferably 40~120 DEG C, when the time preferably 1~20 of polymerization is small, it is more preferable 2~15 it is small when, most preferably 3~10 it is small when.
The alkyl acrylate and α-olefin sulfonic acid add in initiator when being copolymerized, addition is alkyl acrylate
The 0.05%~5% of base ester and α-olefin sulfonic acid gross mass, preferably 0.1%~3%；The preferred azo compound of the initiator
And/or peroxide, such as azodiisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, peroxidating bay can be selected
Acyl, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, di-t-butyl peroxide, cumyl peroxide, perbenzoic acid uncle
Butyl ester, peroxidating trimethylacetic acid tertiary butyl ester, methyl ethyl ketone peroxide, cyclohexanone peroxide, di-isopropyl peroxydicarbonate and mistake
Aoxidize the one or more in two dicyclohexyl carbonates, preferably azo diisobutyl and/or benzoyl peroxide, most preferably azo
Bis-isobutyronitrile.
Material is washed with water after copolyreaction between the alkyl acrylate and α-olefin sulfonic acid, is removed not
The sultone and initiator of reaction；If adding solvent when being copolymerized, removing solvent is needed.
Neutral oil, the neutrality can be added in copolyreaction between the alkyl acrylate and α-olefin sulfonic acid
The addition of oil is the 20%~100% of the polymer quality.The neutral oil preferred solvent refined oil and/or poly- α-alkene
Hydrocarbon synthetic oil, such as HVI150, No. 6 hydrogenated oils, PAO4, PAO6 can be selected, 100 DEG C of dynamic viscosities of the neutral oil are 1
~8mm2Between/s.
The polyethers demulsifier is four (4- hydroxy phenyls) porphyrins and propylene oxide, the polymerizate of ethylene oxide,
Structure is：
Wherein j be 5~50 between integer, preferably 10~40, most preferably 10~30；K is the integer between 5~40, excellent
Select 5~30, most preferably 5~20.
Described four (4- hydroxy phenyls) porphyrin, structure are：
Described four (4- hydroxy phenyls) porphyrin is to be obtained by the reaction by parahydroxyben-zaldehyde and pyrroles using Adler methods, that is, is used
Directly synthesis obtains in propionic acid medium by parahydroxyben-zaldehyde and pyrroles, and dimethyl sulfoxide may be employed as solvent, can also use
The mixed solvent of propionic acid and dimethyl sulfoxide, to improve the yield of four (4- hydroxy phenyls) porphyrins.Specific reaction equation is as follows：
Preparing the described four more preferred methods of (4- hydroxy phenyls) porphyrin is：Para hydroxybenzene first is added in reaction vessel
Aldehyde, solvent in 125 DEG C~130 DEG C reflux, are added dropwise to the pyrroles of molal quantity identical with parahydroxyben-zaldehyde, back flow reaction 1h, cold
But；It is recrystallized by crystalline solid propionic acid wash, then with absolute ethyl alcohol, by 100 mesh silica gel post separations, obtains purple section, steam
Solvent, and crystallized with absolute ethyl alcohol to obtain purple four (4- hydroxy phenyls) porphyrin.
The preparation method of four (4- hydroxy phenyls) porphyrin and propylene oxide, the polymerizate of ethylene oxide, including：It will
With propylene oxide polymerisation first occurs for four (4- hydroxy phenyls) porphyrins, then polymerisation occurs with ethylene oxide, collects product.
The molar ratio of four (4- hydroxy phenyls) porphyrin and propylene oxide is 1：20~200, preferably 1：40~160, most
It is preferred that 1：40~120.
Pressure when polymerisation occurs with propylene oxide for four (4- hydroxy phenyls) porphyrin is 0.1~1MPa, preferably
0.1~0.8MPa, most preferably 0.2~0.6MPa；Reaction temperature be 80 DEG C~200 DEG C, preferably 100 DEG C~160 DEG C, most preferably
120 DEG C~140 DEG C；Reaction time for 1~10 it is small when, preferably 2~8 it is small when, most preferably 2~4 it is small when.
The molar ratio of four (4- hydroxy phenyls) porphyrin and ethylene oxide is 1：20~160, preferably 1：20~120, most
It is preferred that 1：20~80.
After with propylene oxide polymerisation occurs for four (4- hydroxy phenyls) porphyrin, polymerisation occurs with ethylene oxide
Pressure be 0.1~1MPa, most preferably preferably 0.1~0.8MPa, 0.2~0.6MPa；Reaction temperature is 80 DEG C~200 DEG C, excellent
Select 100 DEG C~160 DEG C, most preferably 120 DEG C~140 DEG C；Reaction time for 1~10 it is small when, preferably 2~8 it is small when, most preferably 2~4
Hour.
Molar ratio preferably 1~5 between the propylene oxide and ethylene oxide：1, most preferably 1~2.5：1.
Alkali metal hydroxide, most preferably potassium hydroxide and/or sodium hydroxide are preferably added in the polymerisation.
The molar ratio of the alkali metal hydroxide and four (4- hydroxy phenyls) porphyrins is 1~20：1, preferably 1~10：1,
Most preferably 1~4：1.
When adding alkali metal hydroxide in the polymerisation, nothing is added in into reaction product after the completion of reaction
Machine acid, neutralization reaction product to neutrality, the sulfuric acid solution of the inorganic acid preferably 10%~20%.
Solvent is preferably added to after the polymerisation, is preferably added to the inert organic solvents that boiling range is 100 DEG C~160 DEG C,
For example, toluene, dimethylbenzene, petroleum ether, steam solvent after pickling, the polymer of the present invention is obtained.
The copolymer of the acrylate and α-olefin sulfonic acid, four (4- hydroxy phenyls) porphyrin propylene oxide ethylene oxide are total to
Polymers can be used alone, and can also be used in combination；During compound use, mass ratio preferably 1~3 therebetween：3~1.
The demulsifier preferably accounts for the 0.001%~0.1% of lubricant oil composite gross mass, most preferably 0.01%~
0.1%.
The detersive is high-base-number detergent and/or low alkali value detersive, wherein the high-base-number detergent is selected from
Base number is more than over base sulfosalt, high base number alkyl phenate and one kind or more in high base number salicylate of 300mgKOH/g
Kind, preferably alkyl benzene calcium sulfonate of the base number between 300~400mgKOH/g, SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER are most preferably high-alkali
It is worth sulfurized alkylphenol calcium, the alkyl of the sulfurized alkylphenol calcium is C10~C30, preferably C10~C20。
The low alkali value detersive includes low alkali value alkyl benzene calcium sulfonate, low alkali value of the base number in 20~150mgKOH/g
One or more in Sulfonic Lithium, low alkali value alkyl sodium salicylate and low alkali value sulfurized alkylphenol calcium, preferably low alkali value alkylbenzene
One or more in sulfoacid calcium, low alkali value Sulfonic Lithium and low alkali value alkyl sodium salicylate, most preferably low alkali value alkyl benzene sulphonate
Calcium and/or low alkali value Sulfonic Lithium.
The detersive preferably accounts for the 0.1%~20% of lubricant oil composite gross mass, and more preferable 0.2%~15%, most
It is preferred that 0.3%~10%.
The antioxidant is zinc dialkyl dithiophosphate, dialkyl dithiophosphoric acid copper, alkylated diphenylamine, two uncles
Butyl paracresol, di-tert-butylphenol, N phenyl-alpha-naphthylamines, sulfenyl phenolate, one kind in dialkyl dithio amino formate or
It is a variety of, preferably in zinc dialkyl dithiophosphate, alkylated diphenylamine, dialkyl dithio amino formate and sulfenyl phenolate
One or more, most preferably zinc dialkyl dithiophosphate and/or dialkyl dithio amino formate.The antioxidant accounts for
The 0.1%~5% of lubricant oil composite gross mass, preferably 0.2%~4%, most preferably 0.3%~2.5%.
The preferred polyisobutene succinimide ashless dispersant of the dispersant can select mono butonediimide, double
One or more in succimide and more succimides, the wherein number-average molecular weight of polyisobutene part 500~
Between 4000, preferably 1000~3000.The most preferably double succimides of the dispersant.The dispersant accounts for lubricant oil composite
The 0.1%~10% of gross mass, preferably 0.2%~8%, most preferably 0.3%~5%.
The lubricating base oil can select the one or more in API I, II, III, IV, V class lubricating base oil,
It is preferred that the one or more in API I, II, Group III oil.
The I class oil is the lubricating oil that fraction oil is obtained by clay-filtered, solvent refining, Viscosity Index 80~
Between 100,100 DEG C of dynamic viscosities are in 1~40mm2Between/s；The II class oil is distillate by lube oil hydrogenation
Reason obtains, and Viscosity Index is between 100~120, and 100 DEG C of dynamic viscosities are in 1~40mm2Between/s；The Group III oil
It is that distillate is obtained by hydroisomerizing, Viscosity Index is more than 120, and 100 DEG C of dynamic viscosities are in 1~40mm2Between/s；
The IV classes oil is the synthetic oil of alpha-olefine polymerizing, and Viscosity Index is between 120~150, and 100 DEG C of dynamic viscosities are 1
~40mm2Between/s；The V classes oil is Synthin oil or Esters oil, and Viscosity Index is between 120~150,100
DEG C dynamic viscosity is between 1~40mm2/s, such as adipic acid aliphatic ester, decanedioic acid aliphatic ester, pentaerythritol ester etc..
The present invention also provides a kind of methods for improving lubricating oil comprehensive performance, and this method is by above-mentioned alkyl sulfide phosphonic acids
Acid anhydride, demulsifier, detersive, antioxidant, dispersant are added in lubricating base oil.
The lubricant oil composite of the present invention has excellent high temperature detergency, oxidation stability, antiwear and antifriction, especially has
There are excellent high temperature detergency and demulsification performance, divide water quick, thoroughly, suitable for the lubrication of marine diesel engine, especially
Crankcase lubrication, the lubrication of middling speed piston type diesel engine suitable for two-stroke low speed cross head marine diesel machine.
Specific embodiment
It further illustrates the present invention rather than limits the invention by the following examples.
The preparation of 1 octadecyl phosphine sulfide acid anhydrides H-1 of embodiment
With motor agitators and reflux water-dividing, condense the 500mL three-necked flasks of facility, add in 100 grams of C18 α-
Alkene (0.4mol), 100 grams of HVI150 neutral oils, phosphorus pentasulfide 50 grams (0.23mol) then add in 0.75 gram of sulphur, control
Reaction temperature processed is 150 DEG C, there is hydrogen sulfide gas releasing at this time, absorbs hydrogen sulfide gas with 20% sodium hydroxide solution,
After when this thermotonus 5 is small, stop reaction, cooling, filtering separates unreacted phosphorus pentasulfide residue, obtains 236 grams of oil
Shape liquid, i.e. octadecyl phosphine sulfide acid anhydrides H-1, S contents 9.3%, P content 3.8%.
The preparation of 2 tetracosyl phosphine sulfide acid anhydrides H-2 of embodiment
With motor agitators and reflux water-dividing, condense the 500mL three-necked flasks of facility, add in 100 grams of C24 α-
Alkene (0.3mol), 80 grams of HVI150 neutral oils, phosphorus pentasulfide 36 grams (0.16mol) then add in 0.6 gram of nonyl phenol, control
Reaction temperature processed is 180 DEG C, there is hydrogen sulfide gas releasing at this time, absorbs hydrogen sulfide gas, control with 20% sodium hydroxide solution
System stops reaction, cooling when this thermotonus 6 is small, and filtering separates unreacted phosphorus pentasulfide residue, obtains 201 grams
Oily liquids, i.e. tetracosyl phosphine sulfide acid anhydrides H-2, S contents 7.7%, P content 2.9%.
The preparation of 3 propene sulfonic acid mixture of embodiment
With stirring, heating, cryostat the corrosion-resistant autoclaves of 500mL in add in 80 grams of 30 DEG C~60 DEG C petroleum ethers, so
Rear enclosed reaction kettle opens stirring, and is passed through cryostat and carries out temperature control, then squeezes into 40 grams of propylene into kettle with high-pressure pump
(0.952mol), and be passed through high pure nitrogen, control reactor pressure between 0.8~1MPa, control the temperature of reaction kettle 0~
10 DEG C, the steel cylinder for storing sulfur trioxide is heated, and as being measured on electronic scale, then heating temperature is controlled to cause three oxidations
Sulphur steel cylinder pressure is more than autoclave pressure, and opens sulfur trioxide steel cylinder outlet valve, and gas is passed through to the snorkel of autoclave
In, it then passes to and sulfonating reaction is carried out in the liquid phase of autoclave, sulfur trioxide intake is 77.7 grams (0.971mol), at this time
Pressure in reaction kettle is controlled between 0.8~1.2MPa, when the reaction time is 3.2 small, after reaction, to continuously decrease reactor
Pressure, after pressure reaches normal pressure, stop stirring, then solvent distillation, obtains 115.8 grams of propene sulfonic acid mixture, analysis
It was found that；Containing 54% propene sulfonic acid in the product, 46% propene sultone, the acid value of mixture is 260.8mgKOH/g.
The preparation of 4 butylene azochlorosulfonate acid mixture of embodiment
With stirring, heating, 70 grams of n-hexanes of addition in the 500mL autoclaves of cryostat, then capping kettle, is opened
Stirring, and be passed through cryostat and carry out temperature control, butylene 38 grams (0.679mol) is then squeezed into kettle with high-pressure pump, and is passed through High Purity Nitrogen
Gas, control reactor pressure control the temperature of reaction kettle that will store sulfur trioxide at 0~10 DEG C between 0.8~1MPa
Steel cylinder heats, and is placed in measuring on electronic scale, then controls heating temperature that sulfur trioxide steel cylinder pressure is caused to be more than autoclave pressure
Power, and sulfur trioxide steel cylinder outlet valve is opened, gas is passed through in the snorkel of autoclave, then passes to the liquid of autoclave
Sulfonating reaction is carried out in phase, sulfur trioxide intake is 54.88 grams (0.686mol), at this time control reaction kettle in pressure 0.8
Between~1.2MPa, when the reaction time is 2.8 small, after reaction, the pressure of reactor is continuously decreased, when pressure reaches normal pressure
Afterwards, stirring is stopped, then solvent distillation obtains 91.3 grams of butylene azochlorosulfonate acid mixture, containing 53% butylene sulfonic acid in the product,
47% butene sultone, the acid value of mixture is 225.3mgKOH/g.
The synthesis of embodiment 5 four (4- hydroxy phenyls) porphyrin
With reflux and stirring, temperature control device three-necked flask in add in 10 grams of parahydroxyben-zaldehyde (M=122.12,
0.0819mol), propionic acid 160ml and dimethyl sulfoxide (DMSO) 10ml mixed solvents, are warming up to 125~130 DEG C and flow back, then drip
Add 5.5 grams of pyrroles (M=67.09,0.0819mol), reflux time is 140 minutes, and material then is imported beaker, is put into
Refrigerator is cooled to 2~4 DEG C, place 10 it is small when after filter, obtain blue colored crystal, then by this crystalline solid propionic acid wash, then use
Absolute ethyl alcohol recrystallizes, and by 100 mesh silica gel post separations, obtains bluish violet section, steams solvent, and crystallize to obtain with absolute ethyl alcohol
4.5 grams of bluish violet four (4- hydroxy phenyls) porphyrin.
Structural characterization is carried out to product：From its ultraviolet spectrogram as can be seen that at 422nm (Soret bands), 517,553,
There is absworption peak at 594,651nm (Q bands)；1H NMR analysis shows, chemical shift infrared analysis the result shows that, 3398cm-1It is corresponding
In the phenolic hydroxyl group stretching vibration absworption peak on phenyl ring, 3370cm-1Corresponding is pyrroles's N-H stretching vibration peaks on the big ring of porphyrin,
1100~1200cm-1Between there is the vibration absorption peak of porphyrin ring, 1249cm-1It is the stretching vibration peak of phenyl ring C-O, l608cm-1、l 508cm-1、l 473cm-1It is phenyl ring skeleton stretching vibration peak, more than analysis result shows that the product of synthesis is really four
(4- hydroxy phenyls) porphyrin.
The synthesis of 6 acrylic acid C5 ester butylene sulfonic acid copolymers P1 of embodiment
In the 500mL three-necked flasks with motor agitators and condenser pipe, 110 grams of toluene, 63.9 grams of propylene are added in
Sour C5 esters (0.45mol, M=142) add in 0.08 gram of azodiisobutyronitrile, introduce nitrogen protection, open and stir and be warming up to 70
DEG C, observing response object has apparent heat release at this time, and controlling reaction temperature is 90 DEG C, when polymerisation 1 is small, adds embodiment 4
64 grams of the butylene azochlorosulfonate acid mixture (containing 53% butylene sulfonic acid, 0.25mol, M=136) of preparation, 0.05 gram of two isobutyl of azo
Nitrile, be gradually heating to 105 DEG C carry out copolyreaction 4 it is small when.Twice, then reaction product is washed respectively with 200 grams of distilled water
60 grams and HVI150 (production of Sinopec Yanshan Petrochemical branch company) are added in, material is warming up to 125 DEG C and is evaporated under reduced pressure, is obtained
To acrylic acid C5 ester butylene sulfonic acid copolymer 157.6 grams (P1).Infrared analysis the result shows that：In 1721cm-1、1160cm-1Near
There is strong absworption peak, and illustrate to contain ester type compound in product, 1184cm-1、1053cm-1、3650cm-1The spike at place shows have
Sulfonic acid group exists, 1640cm-1Locate non-telescope vibration peak to occur, there is no double bond presence in compound, it is third to illustrate the compound
Olefin(e) acid C5 ester butylene sulfonic acid copolymers；Gpc analysis shows the number-average molecular weight of copolymer for 5130, and wherein copolymer contains
It measures as 61.92%, the content of flux oil is 38.02%, and the content of acrylic acid C5 esters is 65.47% in copolymer, butylene sulfonic acid
Content be 34.53%.
The synthesis of 7 methacrylic acid C8 ester propene sulfonic acids copolymer p 2 of embodiment
In the 500mL three-necked flasks with motor agitators and condenser pipe, 100 grams of dimethylbenzene, 73.6 grams of first are added in
Base acrylic acid C8 esters (0.38mol, M=196) add in 0.07 gram of azodiisobutyronitrile, introduce nitrogen protection, open and stir and rise
Temperature is to 75 DEG C, and observing response object has apparent heat release at this time, and controlling reaction temperature is 95 DEG C, when polymerisation 1.5 is small, is added
90.37 grams of propene sulfonic acid mixture (containing 54% propene sulfonic acid, 0.4mol, M=122) prepared by embodiment 3,0.06 gram of idol
Nitrogen bis-isobutyronitrile, be gradually heating to 108 DEG C carry out copolyreaction 5 it is small when.Two are washed with 200 grams of distilled water respectively to reaction product
It is secondary, 80 grams of 6# oil (production of Sinopec Shanghai Gaoqiao petrochemical industry branch company) are then added in, material is warming up to 125 DEG C and is depressurized
Distillation, obtains methacrylic acid C8 ester propene sulfonic acids copolymer 201 grams (P2).Infrared analysis the result shows that：In 1721cm-1、
1160cm-1Nearby there is strong absworption peak, and illustrate to contain ester type compound in product, 1184cm-1、1053cm-1、3650cm-1Place
Spike shows with the presence of sulfonic acid group, 1640cm-1Locate non-telescope vibration peak to occur, there is no double bond presence in compound, illustrate this
Compound is methacrylic acid C8 ester propene sulfonic acid copolymers；Gpc analysis shows that the number-average molecular weight of copolymer is 3860,
The content of middle copolymer is 60.2%, and the content of flux oil is 39.8%, and the content of methacrylic acid C8 esters is in copolymer
60.83%, the content of propene sulfonic acid is 39.17%.
The synthesis of embodiment 8 four (4- hydroxy phenyls) porphyrin propylene oxide ethylene oxide copolymer N1
In 250 milliliters of autoclaves with motor agitators and condensation, heating mantle, four (4- hydroxy benzenes are added in
Base) porphyrin 4.5 grams (M=678.7,0.0066mol), 1.5 grams of potassium hydroxide (0.027mol) are added in, then three after nitrogen displacement
90 DEG C are warming up to after secondary；Start that 30 grams of propylene oxide (0.52mol) are added dropwise into autoclave, control reaction pressure 0.6MPa, instead
Temperature is answered as 125 DEG C, when reaction 3 is small；Ethylene oxide 14 grams (0.32mol) is added dropwise into autoclave, controls reaction pressure
0.5MPa, reaction temperature is 125 DEG C, when reaction 2 is small；10 grams of toluene is added in after reaction, transfers the material into 200ml beakers
In, remaining potassium hydroxide in 10% 50 milliliters of neutralization reaction products of sulfuric acid solution is added in, and be washed with deionized twice,
Until reaction product is in neutrality；Oil reservoir in material is put into vacuum distillation apparatus, product 47.8 is obtained after steaming solvent toluene
Gram, ultra-violet analysis the result shows that：There is absworption peak at 424nm (Soret bands), 521,561,599,659 (Q bands) nm.Copolymerization
Object infrared analysis the result shows that：3350cm-1Neighbouring peak corresponds to the hydroxyl on polyethers, 3370cm-1Corresponding neighbouring peak is porphyrin
Pyrroles's N-H stretching vibration peaks on big ring, 1100~1200cm-1Nearby there is the vibration absorption peak of porphyrin ring, 1249cm-1Near
Peak is the stretching vibration peak of phenyl ring C-O, 1608cm-1、1508cm-1、l 473cm-1Neighbouring peak is phenyl ring skeleton stretching vibration peak,
Show the presence of the big ring of porphyrin and tetraphenyl substituent group structure, in addition in 1060~1150cm-1Between there is alkyl ehter bond
Stretching vibration peak, in 2900cm-1Nearby there is methyl and methylene stretching vibration peak, show polyethers occur on the big ring of porphyrin
Structure by thinking that synthesized is four (4- hydroxy phenyls) porphyrin propylene oxide ethylene oxide polyether compounds, passes through
Its equal molecular mass of number of gpc analysis is 7353.
The synthesis of embodiment 9 four (4- hydroxy phenyls) porphyrin propylene oxide ethylene oxide copolymer N2
In 250 milliliters of autoclaves with motor agitators and condensation, heating mantle, four (4- hydroxy phenyls) porphins are added in
Quinoline 5 grams (M=678.7,0.0074mol), 1.25 grams of sodium hydroxides (0.031mol), then with heating up afterwards three times after nitrogen displacement
To 90 DEG C；20 grams of propylene oxide (0.34mol) are added dropwise into autoclave, control reaction pressure 0.6MPa, reaction temperature 122
DEG C, when reaction 2.5 is small；Ethylene oxide 10.5 grams (0.24mol) is added dropwise into autoclave, controls reaction pressure 0.5MPa, reaction
Temperature is 125 DEG C, when reaction 2 is small；20 grams of dimethylbenzene are added in after reaction, are transferred the material into 200ml beakers, are added in
Remaining sodium hydroxide in 10% 50 milliliters of neutralization reaction products of sulfuric acid solution, and be washed with deionized twice, until anti-
Product is answered to be in neutrality；Oil reservoir in material is put into vacuum distillation apparatus, 34.69 grams of product is obtained after steaming solvent xylene.
Ultra-violet analysis the result shows that：There is absworption peak at 426nm (Soret bands), 522,564,599,661 (Q bands) nm.Infrared analysis knot
Fruit shows：3350cm-1Neighbouring peak corresponds to the hydroxyl on polyethers, 3370cm-1Corresponding neighbouring peak is pyrroles N- on the big ring of porphyrin
H stretching vibration peaks, 1100~1200cm-1Nearby there is the vibration absorption peak of porphyrin ring, 1249cm-1Neighbouring peak is phenyl ring C-O
Stretching vibration peak, 1608cm-1、1508cm-1、l473cm-1It is phenyl ring skeleton stretching vibration peak, shows the big ring of porphyrin and tetraphenyl
The presence of substituent group structure, in addition in 1060~1150cm-1Between there is the stretching vibration peak of alkyl ehter bond, in 2900cm-1
Nearby there is methyl and methylene stretching vibration peak, show polyether structure occur on the big ring of porphyrin, by thinking
Synthesis is four (4- hydroxy phenyls) porphyrin propylene oxide ethylene oxide polyether compounds, and by gpc analysis, it counts equal molecule matter
It measures as 4810.
The synthesis of 1 acrylic acid C5 ester acrylic copolymers D1 of comparative example
In the 500mL three-necked flasks with motor agitators and condenser pipe, 110 grams of toluene, 63.9 grams of propylene are added in
Sour C5 esters (0.45mol, M=142) add in 0.08 gram of azodiisobutyronitrile, introduce nitrogen protection, open and stir and be warming up to 70
DEG C, observing response object has apparent heat release at this time, and controlling reaction temperature is 90 DEG C, when polymerisation 1 is small, adds acrylic acid 18
Gram (0.25mol, M=72), 0.05 gram of azodiisobutyronitrile, be gradually heating to 105 DEG C carry out copolyreaction 4 it is small when.To reaction
Product is washed twice respectively with 200 grams of distilled water, then adds in 52 grams of HVI150 (production of Sinopec Yanshan Petrochemical branch company),
Material is warming up to 125 DEG C to be evaporated under reduced pressure, obtains acrylic acid C5 esters acrylic copolymer 135 grams (D1).Analysis result table
It is bright：The number-average molecular weight of copolymer is 4938, and wherein the content of copolymer is 61.48%, and the content of flux oil is 38.52%,
The content of acrylic acid C5 esters is 78.02% in copolymer, and the content of acrylic acid is 21.98%.
The synthesis of 2 ethylene glycol SYNPERONIC PE/F68 D2 of comparative example
In 250 milliliters of autoclaves with motor agitators and condensation, heating mantle, 0.5 gram of solid hydrogen is added in
Sodium oxide molybdena (0.0125mol), ethylene glycol 0.4 gram (0.0067mol), is then warming up to 90 DEG C afterwards three times after nitrogen displacement；Start
30 grams of propylene oxide (0.52mol) are added dropwise into autoclave, control reaction pressure 0.6MPa, reaction temperature is 125 DEG C, reaction 3
Hour；Ethylene oxide 14 grams (0.32mol) is added dropwise into autoclave, controls reaction pressure 0.5MPa, reaction temperature is 125 DEG C,
React 2 it is small when；Reaction pressure 0.5MPa is controlled, reaction temperature is 125 DEG C, when reaction 2 is small；It transfers the material into after reaction
In 200ml beakers, remaining sodium hydroxide in 10% 50 milliliters of neutralization reaction products of sulfuric acid solution is added in, and uses deionized water
Twice of washing, until reaction product is in neutrality；Oil reservoir in material is put into vacuum distillation apparatus, product is obtained after steaming solvent
44.89 grams, infrared analysis the result shows that：3350cm-1Neighbouring peak corresponds to the hydroxyl on polyethers, in 1060~1150cm-1Between
There is the stretching vibration peak of alkyl ehter bond, in 2900cm-1Nearby there is methyl and methylene stretching vibration peak, show to exist poly-
Ether structure is ethylene glycol propylene oxide ethylene oxide polyether compound, and it is 6629 that by gpc analysis, it, which counts equal molecular mass,.
Test method and experiment raw material
Test method used by 1.
GB/T265 oil product kinematic viscosity measuring methods and dynamic viscosity calculating method
GB/T2541 oil products viscosity index (VI) calculates table
GB/T3535 petroleum products pour point measuring methods
GB/T7305 oil and Synthesis liquid resistance to emulsion pipette method
GB/T11143 inhibitings mineral oil test for rust preventing ability method in the presence of water
GB/T12579 lubricating oil spumescence measuring methods
GB/T3142 load carrying capacity of lubricant measuring method four ball methods
SH/T0251 oil product base numbers measuring method (perchloric acid potentiometric titration)
SH/T0619 oil-water separativeness measuring methods peculiar to vessel
SH/T0649 marine lubricant etching tests
High temperature detergency measuring method
The method for evaluating high temperature detergency is lacquering and QZX experiment, which carries out on L-1 plate-type coking devices.
Coke test condition is：Plate temperature/oil temperature=320 DEG C/100 DEG C, time 2 h stop/ETAD expected time of arrival and departure=45 second/15 second, into lacquer test
Condition is：Plate temperature/oil temperature=300 DEG C/150 DEG C, time 2 h are carried out continuously.
Inoxidizability measuring method
The method of evaluation anti-oxidative stability is PDSC experiments, which is on 5000 DSC of TA, 2910 thermal analyzers
It carries out, experimental condition：Heating rate is 100 DEG C/min, constant temperature 60min, 3.5MPa.
2. base oil used in experiment
The base oil of 1 experiment of table
3. test additive therefor
The additive of 2 experiment of table
According to tetra- stroke medium speed trunk piston machine oil of API40 viscosity level modulations 12TBN and No. 40 ship lubricant oils, wherein
It is total to using alkyl sulfide phosphonic acid anhydrides, acrylate butylene sulfonic acid copolymer, four (4- hydroxy phenyls) porphyrin propylene oxide ethylene oxide
Polymers and other additives form embodiment 10~19, using other additives, common demulsifier T1001, DL-32, commercially available
TBN12 middling speeds machine oil and No. 40 ship lubricant oils be contrasted example 3~14 together, formula composition is shown in Table 3,4,7,8, test knot
Fruit is shown in Table 5,6,9,10.
The embodiment of 3 12TBN of table, tetra- stroke medium speed trunk piston machine oil
The comparative example of 4 12TBN of table, tetra- stroke medium speed trunk piston machine oil
The performance test of 5 12TBN of table, tetra- stroke middling speed piston oil embodiments
The performance test of 6 12TBN of table, tetra- stroke middling speed piston oil comparative examples
The embodiment of 7 No. 40 ship lubricant oils of table
The comparative example of 8 No. 40 ship lubricant oils of table
The performance test of 9 No. 40 ship lubricant oil embodiments of table
The performance test of 10 No. 40 ship lubricant oil comparative examples of table
It can be seen from the above result that in the case where other additives are identical, using alkyl sulfide phosphonic acid anhydrides, acrylate alkenyl
Sulfonic acid copolymer and/or the TBN12 tetra- that four (4- hydroxy phenyls) porphyrin propylene oxide ethylene oxide copolymers are demulsifier allotment
Stroke medium speed trunk piston oil and No. 40 system oils have preferable wear resistence, inoxidizability, divide water and demulsibility, resist
Bubble property.Using oiliness improver, acrylic acid C5 ester acrylic copolymers D1, alkyl phenol propylene oxide ethylene oxide polymer D2, T1001
With the tetra- stroke medium speed trunk piston oils of TBN12 of DL32 demulsifiers allotment and the wear resistences of No. 40 system oils, inoxidizability, demulsification
Property, anti-foaming property be not so good as embodiment.Therefore, marine lubricant composition of the invention has excellent high temperature detergency, anti-oxidant
Property, antiwear and antifriction divide water and breaking, anti-foaming property.
Claims (16)
1. a kind of lubricant oil composite, including：Alkyl sulfide phosphonic acid anhydrides, demulsifier, detersive, antioxidant, dispersant and primary amount
Lubricating base oil；The demulsifier is non-polyether class demulsifier and/or polyethers demulsifier；The non-polyether class demulsifier
For acrylate and the copolymer of α-olefin sulfonic acid；The polyethers demulsifier is four (4- hydroxy phenyls) porphyrins and epoxy third
The polymerizate of alkane, ethylene oxide；
The structure of the copolymer of the acrylate and α-olefin sulfonic acid is：
Wherein R is C4~C18 alkyl or its mixed alkyl；A1 is hydrogen or methyl, and A2 is hydrogen or C1~C4 alkyl, and x is 0~4
Integer；When A2 is hydrogen, x is positive integer；M is 1~50 integer, and n is 1~50 integer；
The structure of described four (4- hydroxy phenyls) porphyrins and propylene oxide, the polymerizate of ethylene oxide is：
Wherein j is the integer between 5~50；K is the integer between 5~40.
2. composition described in accordance with the claim 1, which is characterized in that the alkyl sulfide phosphonic acid anhydrides are α-alkene of C5~C50
Hydrocarbon and P2S5The product of phosphine sulfideization reaction occurs.
3. composition described in accordance with the claim 1, which is characterized in that it is total that the alkyl sulfide phosphonic acid anhydrides account for lubricant oil composite
The 0.01%~2% of quality.
4. composition described in accordance with the claim 1, which is characterized in that the copolymer of the acrylate and α-olefin sulfonic acid
Molecular weight is between 1000~15000.
5. composition described in accordance with the claim 1, which is characterized in that the copolymer of the acrylate and α-olefin sulfonic acid
Preparation method is to be copolymerized alkyl acrylate and α-olefin sulfonic acid, collects product；The alkyl acrylate
Structure is：
Wherein R is C4~C18 alkyl or its mixed alkyl；A1 is hydrogen or methyl；
The structure of the α-olefin sulfonic acid is：
Wherein A2 is hydrogen or C1~C4 alkyl, and x is 0~4 integer；When A2 is hydrogen, x is positive integer；
Molar ratio between the alkyl acrylate and α-olefin sulfonic acid is 1~50：50~1；
The alkyl acrylate and α-olefin sulfonic acid add in initiator when being copolymerized.
6. according to the composition described in claim 5, which is characterized in that the alkyl acrylate and α-olefin sulfonic acid occur altogether
The temperature of poly- reaction is 20~200 DEG C, when the time of polymerization is 1~20 small.
7. composition described in accordance with the claim 1, which is characterized in that the structure of described four (4- hydroxy phenyls) porphyrin is：
8. composition described in accordance with the claim 1, which is characterized in that four (4- hydroxy phenyls) porphyrin and propylene oxide,
The preparation method of ethylene oxide polymerization product is that four (4- hydroxy phenyls) porphyrins and propylene oxide first that polymerisation occur, then with
Polymerisation occurs for ethylene oxide, collects product.
9. according to the composition described in claim 8, which is characterized in that described four (4- hydroxy phenyls) porphyrin rubs with propylene oxide
You are than being 1：20~200, pressure when polymerisation occurs for four (4- hydroxy phenyls) porphyrin and propylene oxide for 0.1~
1MPa, reaction temperature are 80 DEG C~200 DEG C, when the reaction time is 1~10 small；Four (4- hydroxy phenyls) porphyrin and epoxy second
The molar ratio of alkane is 1：20~160；After with propylene oxide polymerisation occurs for four (4- hydroxy phenyls) porphyrin, with epoxy second
The pressure of polymerisation occurs for alkane for 0.1~1MPa, and reaction temperature is 80 DEG C~200 DEG C, when the reaction time is 1~10 small；Institute
It is 1~5 to state the molar ratio between propylene oxide and ethylene oxide：1.
10. composition described in accordance with the claim 1, which is characterized in that the demulsifier accounts for lubricant oil composite gross mass
0.001%~0.1%.
11. composition described in accordance with the claim 1, which is characterized in that the detersive is high-base-number detergent and/or low
Base number detersive；Wherein described high-base-number detergent is selected from over base sulfosalt, the high base number alkane that base number is more than 300mgKOH/g
One or more in base phenates and high base number salicylate；The low alkali value detersive include base number 20~
Low alkali value alkyl benzene calcium sulfonate, low alkali value Sulfonic Lithium, low alkali value alkyl sodium salicylate and the low alkali value vulcanization alkane of 150mgKOH/g
One or more in base phenol calcium.
12. composition described in accordance with the claim 1, which is characterized in that the detersive accounts for lubricant oil composite gross mass
0.1%~20%.
13. composition described in accordance with the claim 1, which is characterized in that the antioxidant for zinc dialkyl dithiophosphate,
Dialkyl dithiophosphoric acid copper, alkylated diphenylamine, di-tert-butyl p-cresol, di-tert-butylphenol, N phenyl-alpha-naphthylamines, vulcanization alkane
One or more in base phenol, dialkyl dithio amino formate account for the 0.1%~5% of lubricant oil composite gross mass.
14. composition described in accordance with the claim 1, which is characterized in that the dispersant is polyisobutene succinimide
Ashless dispersant accounts for the 0.1%~10% of lubricant oil composite gross mass.
15. composition described in accordance with the claim 1, which is characterized in that the lubricating base oil be selected from API I, II, III,
One or more in IV, V class lubricating base oil.
16. it is by the alkyl sulfide phosphonic acid anhydrides, broken described in one of claim 1-15 a kind of method for improving lubricating oil comprehensive performance
Emulsion, detersive, antioxidant, dispersant are added in lubricating base oil.
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