CN1708471A - Preparation method of lubricating oil cleaner - Google Patents
Preparation method of lubricating oil cleaner Download PDFInfo
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- CN1708471A CN1708471A CN 200380102560 CN200380102560A CN1708471A CN 1708471 A CN1708471 A CN 1708471A CN 200380102560 CN200380102560 CN 200380102560 CN 200380102560 A CN200380102560 A CN 200380102560A CN 1708471 A CN1708471 A CN 1708471A
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Abstract
The present invention relates to a process for preparing alkaline earth metal salicylates for use as lubricating oil detergents, and to compositions prepared by the process. The method comprises two steps. Step 1 is the application C14Or longer linear alpha-olefins, for salicylic acidAlkylation to produce alkylsalicylic acids in industrially acceptable yields. The alkylation conditions produce primarily oil-soluble mono-substituted para-alkylsalicylic acids. Step 2 is the subsequent neutralization of the oil-soluble acid and the application of CO in the presence of a promoter and a surfactant2The lime is made highly alkaline by carbonation. After overbasing, the reaction mixture was filtered and the solvent was removed by distillation. Alternatively, the alkyl salicylic acid may be reacted with a previously overbased alkaline earth metal sulfonate, such as calcium sulfonate, to produce an alkaline earth metal salicylate, the salt comprising a varying percentage of dispersed alkaline earth metal carbonate. In this method, there is no need to filter the final product, and therefore it is industrially preferable.
Description
Technical field
The present invention relates to the method that a kind of preparation is used for the high-alkaline base earth metals sanitising agent of lubricating oil.
Background technology
The additive that the alkaline earth salt of application organic carboxyl acid is made lubricating oil composition is known.These salt have dispersing agent performance, help to guarantee that engine cylinder inside keeps clean, and contain the deposition of carbon products on the elimination piston with in the piston groove, thereby prevent the piston ring bonding.
Alkalescence (or high alkalinity) alkaline earth salt for preparing these acid also is known.High alkalinity provides alkalescence to stock, and when using in lubricating oil composition, the acidic cpd reaction that it forms in operating process with the engine of using described composition also makes it neutralization.Therefore, issuable any sludge is owing to the dispersing agent performance of this salt disperses, and those acid that might strengthen sludge formation are neutralized.
High alkaline salicylate prepares by making corresponding alkylation Whitfield's ointment high alkalinityization.Alkyl is generally the chain alkyl greater than about 14 carbon atoms, thereby makes it have oil soluble.The salicylic preparation of alkylation by making the phenol alkylation to form alkylphenol, makes alkylphenol carboxylated so that the alkylation Whitfield's ointment to be provided by the Kolbe-Schmitt reaction usually then.The unfavorable economical effectiveness that produces except using high temperature and/or high pressure, the Kolbe-Schmitt route generates the alkylation Whitfield's ointment, and there are the following problems: when main application straight chained alkyl raw material, not every long chain alkylphenol can both be by carboxylated.Specifically, mainly utilize the conventional phenol alkylation of straight chained alkyl raw material that about 50: the 50 neighbour-alkylphenol and the mixture of right-alkylphenol are provided.Though Kolbe-Schmitt reaction is easy to carboxylated resulting long-chain right-alkylphenol, but resulting long-chain neighbour-alkylphenol but has lower reactivity, only has an appointment usually in the total amount of the alkylphenol that is obtained by main straight chain hydrocarbonylation raw material in this reaction 70% to be converted into the alkylation Whitfield's ointment.
A method that addresses this problem is to make alkyl salicylate (as wintergreen oil) alkylation, makes the hydrolysis of resulting alkylation alkyl salicylate so that the alkylation Whitfield's ointment to be provided then.The alkylation of alkyl salicylate is at US 5,434, and is open in 293.
DD-A-269619 and DD-A-293108 disclose the application acidic ion exchange resin or Tripyrophosphoric acid is made catalyzer and made the direct alkylating method of Whitfield's ointment with alkene.It is unfavorable (do not relate in the prior art with alkene acid is carried out in the alkylating method) as catalyzer that two documents all report using sulfated, because this has many shortcomings, if any etching problem and generation side reaction.
DE 689600 discloses application perchloric acid and has made catalyzer.
US 1,998, and 750 disclose in the presence of sulfuric acid, makes non-aromatic unit alcohol or any compound and Whitfield's ointment condensation that amyl group, hexyl, cyclohexyl or heptyl can be provided of any 5-7 of having carbon atom.
US 4,810,398 disclose a kind of basic alkaline earth metal salt of organic carboxyl acid blend, it prepares as follows: (a) a kind of mixture of preparation in hydrocarbon solvent, this mixture contain the organic carboxyl acid blend of monovalent and greater than the alkaline earth metal hydroxides and/or the alkaline earth metal oxide of monovalent; (b) in resulting mixture, add carbonic acid gas with amount whenever amount excess base earth metals at least 0.5 equivalent carbonic acid gas; (c) remove residual solid (if present) and waterbearing stratum (if present), thereby the organic carboxyl acid blend comprises a kind of C
8-30Alkyl salicylate and one or more alkanoic acids, the moieties of wherein said alkanoic acid is side chain and has 4-40 carbon atom.This salt has the dispersion agent characteristic, and allegedly is suitable for using in lubricating oil and fuel composition.
US 4,869,837 disclose a kind of method for preparing the basic alkaline earth metal salt of organic carboxyl acid blend, described method comprises: (a) a kind of mixture of preparation in hydrocarbon solvent, this mixture contain the organic carboxyl acid blend of monovalent and greater than the alkaline earth metal hydroxides and/or the alkaline earth metal oxide of monovalent; (b) in resulting mixture, add carbonic acid gas with amount whenever amount excess base earth metals at least 0.5 equivalent carbonic acid gas; (c) remove residual solid (if present) and waterbearing stratum (if present), thereby the organic carboxyl acid blend comprises the succsinic acid or the acid anhydrides of a kind of oil soluble alkyl salicylate and the replacement of one or more hydrocarbon, and wherein said alkyl has the number-average molecular weight of 120-5000.
US 4,876, and 020 discloses a kind of lubricating oil composition, and the molecular weight that described composition comprises lubricant base, one or more aromatic carboxylic acids' high-alkaline base earth metal salt and is selected from poly-alkoxylation alcohol is the stablizer of 150-1500.
US 5,049, and 685 disclose a kind of nuclear substituted Whitfield's ointment and salt of being represented by following general formula thereof:
R wherein
1Represent methylidene, sec.-propyl, the tertiary butyl, tert-pentyl, uncle's hexyl, uncle's octyl group, α, α-dialkyl benzene methyl or nuclear substituted α, α-dialkyl benzene methyl; And R
2Represent the tertiary butyl, tert-pentyl, uncle's hexyl, uncle's octyl group and α, α-dialkyl benzene methyl or nuclear substituted α, α-dialkyl benzene methyl.Nuclear substituted Whitfield's ointment and salt thereof allegedly all have solvability preferably in water, organic solvent or organic polyhydroxyl compound, and they are very favourable as sterilization and disinfectant, the stability of polymerizable compound or the developer of recording materials.
US 5,415, and 792 to disclose a kind of it is said to lubricating oil composition be the high alkalinity bigcatkin willow acid alkyl ester of useful additive.Especially, described composition is that lubricating oil composition is given cleaning and dispersing property, and provides alkalescence to stock.
US 5,434, and 293 disclose a kind of alkyl salicylate and raw material for alkylation of using solid acidic alkylation catalyst and about equimolar amount makes the alkylating method of alkyl salicylate.
US 5,451, and 331 disclose the method for a kind of TBN of preparation greater than 300 lubricating oil additive concentrate, and described method comprises at high temperature makes following component reaction: the salicyclic acid derivatives of component (A) through limiting; The alkali of component (B) alkaline-earth metal, it once adds in reaction process or repeatedly adds at intermediate point; At least a following compound of component (C): (i) water (ii) has the polyhydroxy-alcohol of 2-4 carbon atom, (iii) two-(C
3Or C
4) glycol, (iv) three-(C
2-C
4) glycol, (v) have general formula (I) R (OR
1)
xOR
2(I) list-or many-aklylene glycol alkyl oxide, wherein R is C
1-C
6Alkyl, R
1Be alkylidene group, R
2Be hydrogen or C
1-C
6Alkyl, and x is the integer of 1-6, (vi) C
1-C
20Single hydroxyl alcohol, (vii) C
1-C
20Ketone, (viii) C
1-C
10Carboxylicesters, or (ix) C
1-C
20Ether; Component (D) lubricating oil; Component (E) carbonic acid gas, it adds after component (B) adds back or each adding; Carboxylic acid or the derivative of component (F) through limiting; And at least a compound of component (G); its be (ii) paraffinic acid ammonium or single-, two-, three-or (i) inorganic halides of four-alkyl formate or paraffinic acid ammonium; prerequisite be when component (G) for (ii) the time; component (F) is not a chloride of acid, and the weight ratio of all components makes the TBN of the enriched material that is produced greater than 300.
US 5,734,078 disclose a kind of method for preparing alkyl salicylate, and wherein said alkyl substituent has 6 carbon atoms at least, described method comprise the steps: sulfuric acid as catalyzer in the presence of, at high temperature with containing the alkene and the salicylism reaction of at least 6 carbon atoms.The lubricating oil additive that comprises this alkylation salicylic acid metal salt and their preparation method are also disclosed simultaneously.
US 5,792,735 disclose a kind of lubricating oil composition of using in low or the medium speed diesel engines of allegedly being adapted at, described composition comprises the oil fuel with irreducible oil content, it is characterized in that phenates enriched material that described lubricating oil composition also comprises TBN and replace greater than 300 alkyl, and the sulfonate that replaces of the salicylate that replaces of alkyl and alkyl at least a.The phenates that alkyl replaces is preferably by adding has general formula R CH (R
1) CO
2The carboxylic acid of H such as stearic acid and the phenates of modification, wherein R is C
10-C
24Alkyl, R
1Be hydrogen or C
1-C
4Alkyl.
US 6,034, and 039 discloses the composite clean agent, it is said that it can provide improved deposition control and corrosion protection performance in crankcase oil.
Aforementioned publication here quotes in full as a reference.
Summary of the invention
The present invention relates to a kind of preparation as the alkaline-earth metal salicylate of lubricant detergents method, and the composition for preparing by described method.Described method comprised for two steps:
Step 1:
Use C
14Or longer linear alpha-olefin enforcement alkylation of salicylic acid, thereby prepare alkyl salicylate with industrial acceptable yields.Alkylation conditions mainly produce oil-soluble list-replacement to alkyl salicylate.
Step 2:
Make the oil-soluble acid neutralization subsequently, and in the presence of promotor such as methyl alcohol and tensio-active agent such as alkyl salicylate, use CO
2Carbonation high alkalinityization by lime.High alkalinity after-filtration reaction mixture, and remove solvent by distillation.
Alternatively, alkyl salicylate can react with the sanitising agent that is selected from following high alkalinityization in advance: the sulfonate of overbasic basic metal or alkaline-earth metal, phenates or carboxylate salt, thereby produce the salicylate of basic metal or alkaline-earth metal, described salt comprises the dispersive basic metal that changes per-cent or the carbonate of alkaline-earth metal.In this method, do not need to filter the finished product, therefore industrial be preferred.Further preferably over-based detergent is the alkaline earth metal sulfonate such as the calcium sulphonate of high alkalinityization in advance in addition.
Show that compositions of olefines works in the following areas in the performance of the finished product: the consistency and the oil soluble of pressure reduction scanning calorimetry (PDSC) and detergent additive.Concerning the PDSC of optimum, preferred chain length is C
16-C
18, and higher C
18Content can cause additive compatibility and deliquescent raising.
More specifically, the present invention relates to a kind of prepare the alkaline-earth metal salicylate method, described method comprises the steps:
A) in the presence of strong acid catalyst, make the Whitfield's ointment alkylation, form oil-soluble alkylation Whitfield's ointment with the linear alpha-olefin that comprises at least 14 carbon atoms;
B) the described oil-soluble alkylation Whitfield's ointment of neutralization;
C) in the presence of promotor and tensio-active agent, use CO
2Carbonation by lime makes described oil-soluble alkylation Whitfield's ointment high alkalinityization;
D) product filtration C); With
E) remove solvent by distillation.
On the other hand, the present invention relates to a kind of prepare the alkaline-earth metal salicylate method, described method comprises the steps:
A) in the presence of strong acid catalyst, make the Whitfield's ointment alkylation, form oil-soluble alkylation Whitfield's ointment with the linear alpha-olefin that comprises at least 14 carbon atoms;
B) make described oil-soluble alkylation Whitfield's ointment and the sanitising agent reaction that is selected from following high alkalinityization in advance: the sulfonate of overbasic basic metal or alkaline-earth metal, phenates or carboxylate salt, as calcium sulphonate, thereby produce the salicylate of basic metal or alkaline-earth metal, described salt comprises the dispersive basic metal that changes per-cent or the carbonate of alkaline-earth metal.
On the other hand, the present invention relates to a kind of alkaline-earth metal salicylate for preparing by the method that comprises following steps:
A) in the presence of strong acid catalyst, make the Whitfield's ointment alkylation, form oil-soluble alkylation Whitfield's ointment with the linear alpha-olefin that comprises at least 14 carbon atoms;
B) the described oil-soluble alkylation Whitfield's ointment of neutralization;
C) in the presence of promotor and tensio-active agent, use CO
2Carbonation by lime makes described oil-soluble alkylation Whitfield's ointment high alkalinityization;
D) product filtration C); With
E) remove solvent by distillation.
On the other hand, the present invention relates to a kind of alkaline-earth metal salicylate for preparing by the method that comprises following steps:
A) in the presence of strong acid catalyst, make the Whitfield's ointment alkylation, form oil-soluble alkylation Whitfield's ointment with the linear alpha-olefin that comprises at least 14 carbon atoms;
B) make described oil-soluble alkylation Whitfield's ointment and the sanitising agent reaction that is selected from following high alkalinityization in advance: the sulfonate of overbasic basic metal or alkaline-earth metal, phenates or carboxylate salt, as calcium sulphonate, thereby produce the salicylate of basic metal or alkaline-earth metal, described salt comprises the dispersive basic metal that changes per-cent or the carbonate of alkaline-earth metal.
Embodiment
By above as can be known, in the method for the invention, the first step comprises uses C
14Or longer linear alpha-olefin makes the Whitfield's ointment alkylation, thereby produces alkyl salicylate with industrial acceptable yields.Alkylation conditions mainly produce oil-soluble mono-substituted right-alkyl salicylate.
Alkyl salicylate uses strong acid, be preferably anhydrous methylsulfonic acid makes catalyzer and is prepared by Whitfield's ointment and linear alpha-olefin.Other adaptable strong acid comprises sulfuric acid, hydrochloric acid, nitric acid, trifluoroacetic acid, perchloric acid etc.Described condition makes the Whitfield's ointment that suspends in the alkene be about 120-150 ℃ internal reaction in temperature range.Product is adjacent and to monoalkylation Whitfield's ointment and some dialkyl groupization and the salicylic mixture of trialkylization.With respect to for the synthetic product that obtains of Kolbe-Schmitt, the content of alkylphenol is very low, and the color of product is very good.The alkylation salicylate has the acid number that is about theoretical value 85-95%.The PDSC of the corresponding high alkaline calcium salt of these Whitfield's ointments and panel coker value (panel coker value) and contrast sublimed salicylic acid sanitising agent are quite or more excellent.
It is oil-soluble by its contained alkyl substituent the alkyl salicylate of using in the inventive method to be become.Possible is that alkyl salicylate can contain more than one alkyl substituent, and for example two or three but preferably only contain such substituting group, and are positioned at contraposition.The number of carbon atom is preferably at least 14 in alkyl substituent, and is preferably 14-30.When alkyl salicylate mainly only contained an alkyl substituent, alkyl most preferably contained 14-26 carbon atom.Alkyl can be for straight or branched, but most preferably is straight chain.Suitable alkene comprises tetradecene, cetene, 1-vaccenic acid, 1-eicosylene, 1-two dodecylenes, 1-tetracosene, reaches the mixture of aforementioned substances etc., but is not limited to this.
Can use through or without the sublimed salicylic acid that is further purified.
The reaction implementation condition depends on the character of applied alkene.It will be recognized by one skilled in the art that the difference with alkene, changing the peak optimization reaction condition may wish.
The temperature of Whitfield's ointment and olefine reaction is preferably 50 ℃ or higher, and can be about 50-200 ℃ suitably.Optimal Temperature in this scope depends on the carbon chain lengths of alkene.C
14The Optimal Temperature of alkene is generally about 100-150 ℃, for example about 120 ℃.
Usually reaction duration is not very crucial.About 2-36 hour reaction times is normally gratifying.
If wish, reaction can be implemented in solvent, but solvent-applied not usually.
Can from reaction mixture, reclaim alkyl salicylate by using method as known in the art.To C
14High-grade alkyl salicylate more, solvent-applied extraction usually.
In second step of the inventive method, oil-soluble acid is neutralized, and in the presence of promotor such as methyl alcohol and tensio-active agent such as alkyl salicylate, uses CO
2Carbonation high alkalinityization by lime.High alkalinity after-filtration reaction mixture, and remove solvent by distillation.
Alternatively, alkyl salicylate can react with the alkaline earth metal sulfonate such as the calcium sulphonate of high alkalinityization in advance, thereby produces the alkaline-earth metal salicylate, and described salt includes the dispersive alkaline earth metal carbonate that changes per-cent.In this method, do not need to filter the finished product, therefore industrial be preferred.
Alkaline-earth metal salicylate sanitising agent by the inventive method preparation suitably comprises calcium salicylate sanitising agent, magnesium salicylate sanitising agent or its mixture.
Added alkali number should be enough to provide high alkalinity salt, and promptly wherein the ratio of the equivalents of metal part and the equivalents of alkylated salicylamide acid moieties and can be at the most 4.5 or higher usually greater than about 1.2.
High-alkaline base earth metals salicylate can obtain to produce alkaline earth metal carbonate such as lime carbonate and magnesiumcarbonate or alkaline earth metal borate such as magnesium borate by making neutral alkaline-earth metal salicylate high alkalinityization.
The base number of salicylic acid metal salt sanitising agent does not limit particularly; But this base number in the about 60-350mgKOH/g of scope, is preferably about 150-350mgKOH/g usually.
Metal base can once add in reaction process or repeatedly add at intermediate point.
The reaction mixture of high alkalinityization also suitably contains promotor, is preferably to contain oxygen organic solvent and optional water.Suitable promotor comprises C
1-6Alcohol, polyhydroxy-alcohol such as ethylene glycol, propylene glycol, glycerol or 1, the C of 3-dihydroxypropane, ether such as ethylene glycol or propylene glycol
1-4Monoether, Di Iso Propyl Ether, 1,3-or 1,4-diox or 1,3-dioxolane.This promotor is preferably C
1-6Alcohol, particularly methyl alcohol.
Be used for alkyl salicylate and metal base reaction solvent can for
(1) has the polyhydroxy-alcohol of 2-4 carbon atom;
(2) two-(C
2-C
4) glycol;
(3) three-(C
2-C
4) glycol;
(4) have the list of following general formula-or multi alkylidene diol alkyl oxide:
R
1(OR
2)
xOR
3, R wherein
1Be C
1-C
6Alkyl, R
2Be alkylidene group, R
3Be hydrogen or C
1-C
6Alkyl, x are the integer of 1-6;
(5) has the single hydroxyl alcohol of 20 carbon atoms at the most;
(6) has the ketone of 20 carbon atoms at the most;
(7) has the carboxylicesters of 10 carbon atoms at the most;
(8) volatile liquid hydrocarbon; Or
(9) has the ether of 20 carbon atoms at the most.
Preferred solvent is unreactive hydrocarbons, and it can be aliphatic hydrocrbon or aromatic hydrocarbons.Suitable example comprises toluene, dimethylbenzene, petroleum naphtha and aliphatic paraffin such as hexane, reaches alicyclic paraffin.
The combination of methyl alcohol and petroleum naphtha is preferred especially, and wherein methyl alcohol is used as promotor in reaction.
Consider as the purpose purposes angle of lubricating oil additive from the high alkalinity product, preferably add the base oil of thinner as a supplement.Base oil can be animal oil, vegetables oil or mineral oil.It is preferably the lubricating oil of petroleum derivation, for example cycloalkanes base oil, alkane base oil or mixed base oil.Alternatively, lubricating oil can be synthetic oil, for example synthetic ester or polymeric hydrocarbon lubricating oil.
In the production of high alkalinity metal salt, can use carbonic acid gas with gas or solid form, the advantageous applications gas form, it can air blast pass through reaction mixture.Usually after adding, metal base adds carbonic acid gas.
Can use carbonation catalyst to produce the metal-salt of height high alkalinityization.Catalyzer can be preferably mineral compound for mineral compound or organic compound.Suitable mineral compound comprise hydrogen halide, metal halide, ammonium halide, paraffinic acid metal-salt, paraffinic acid ammonium or single-, two-, three-or four-alkyl formate ammonium or paraffinic acid ammonium.The example of suitable catalyst comprises calcium chloride, ammonium chloride, lime acetate, ammonium acetate, zinc acetate and tetramethyl-(ammonium acetate).Catalyzer is usually with the concentration application of about 2wt% at the most.Can in EP-A-0351052, find producing the highly more comprehensive description of the alkylated salicylamide acid metal salt of high alkalinityization.
The suitable high temperature of using in the above-mentioned reaction can be about 100-500 °F (about 38-260 ℃).
The enriched material of metal-salt can reclaim as the distillation type stripping by conventional method in the solvent.If desired, finally can the filtering and concentrating thing.
In a word, the method for preparing overbased calcium salicylate is included in and makes alkylation Whitfield's ointment and the calcium sulphonate of choosing wantonly or vitriolic solution in the oil (for convenience, following description is being incited somebody to action and is being retell calcium cpd, but those skilled in the art will understand at an easy rate, by analogizing, present method can be used magnesium compound, and the mixture of calcium and magnesium) with calcium oxide or calcium hydroxide slurry reaction, and make carbonic acid gas Peng Pao pass through reaction mixture, thereby in calcium salicylate, add excessive lime carbonate, and the calcium sulphonate that may exist, the latter gives the basicity of stocking that product wishes.In the method, found to add low-molecular-weight alcohol such as first alcohol and water and promoted that the formation of lime carbonate micellar dispersion is favourable.
In order to obtain the TBN high product, during as unique storage alkaline agent, calcium hydroxide is a large amount of excessive application in reaction mixture when industrial.
Dispersion agent is the production method of over-based detergent and an optional components in the product.A kind of useful dispersion agent is hydrocarbyl substituted succinic or acid anhydrides and the reactor product that contains the amine of at least one uncle or secondary amino nitrogen atom, and for example the polyalkylene polyamine of polyalkylene polyamine, replacement and ammoniacal liquor can satisfy this requirement.Two-succinimide also can be used as optional dispersion agent.Two-succinimide prepares by hydrocarbyl substituted succinic or acid anhydrides and the amine reaction that contains two uncles and/or secondary nitrogen-atoms at least.This two-succinimide has polyisobutenyl two-succinimide, diethylenetriamine or Triethylenetetramine (TETA) or (as the US 3,438,899 of Benoit) such as tetren or N-methyl dipropylenetriamines of ethylene diamine.Above-mentioned various dispersion agent can be used separately also and can use with the form of mixture.
Overbased calcium salicylate product of the present invention has unbodied micellar structure.Overbased calcium salicylate or similar over-based detergent are the stabilising dispersions of amorphous calcium carbonate.
Overbased calcium salicylate sanitising agent of the present invention can or more clean dosage with about 0.1-25wt% and add in engine or the lubricating oil.
The present invention goes for multiple lubricating oil.Lubricating oil can be made up of one or more natural oils, one or more synthetic oils or its mixture.Natural oil comprises the mineral lubricating oils of paraffinic hydrocarbons, naphthenic hydrocarbon or hydrocarbon mixture after animal oil and vegetables oil (as Viscotrol C, lard), liquid petroleum and hydrofining, solvent treatment or the acid treatment.The oil with lubricant viscosity that is obtained by coal or shale also is useful base oil.
Ucon oil comprises hydrocarbon ils and halo hydrocarbon ils, for example the alkene of polymeric and copolymerization (as polybutene, polypropylene, propylene-isobutylene copolymers, chloro polybutene, poly-(1-hexene), poly-(1-octene), poly-(1-decene)); Alkylbenzene (as dodecylbenzene, tetradecyl benzene, dinonyl benzene, two (2-ethylhexyl) benzene); Polyphenyl (as biphenyl, terphenyl, alkylating polyphenol); Alkylating biphenyl ether and alkylating diphenyl sulfide and derivative, analogue and homolog.
Epoxy alkane polymkeric substance and multipolymer with and the derivative of institute's modifications such as terminal hydroxyl groups is esterified, etherificate constituted another kind of known ucon oil.Their example has the polyoxyalkylene polymers for preparing by oxyethane or propylene oxide polymerization, the alkyl or aryl ether (is that 1000 the poly-Isopropanediol ether of methyl, biphenyl ether, the molecular weight that molecular weight is the polyoxyethylene glycol of 500-1000 are the Anaesthetie Ether of the polypropylene glycol of 1000-1500 as molecular-weight average) of these polyoxyalkylene polymers; With and single-and many carboxyl ester, for example acetic ester, blended C
3-C
8The C of fatty acid ester and TEG
13The oxygen acid diester.
Another kind of suitable ucon oil comprises the ester of dicarboxylic acid (as phthalic acid, succsinic acid, alkyl succinic acid and alkenyl succinic acid, toxilic acid, nonane diacid, suberic acid, sebacic acid, fumaric acid, hexanodioic acid, linoleic acid dimer, propanedioic acid, alkyl propanedioic acid, thiazolinyl propanedioic acid) and multiple alcohol (as butanols, hexanol, dodecanol, 2-ethylhexyl alcohol, ethylene glycol, Diethylene Glycol monoether, propylene glycol).The object lesson of these esters comprises the 2-ethylhexyl diester of the two eicosane esters of Polycizer W 260, sebacic acid two-(2-ethylhexyl) ester, fumaric acid two-just own ester, dioctyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, dioctyl phthalate (DOP), didecyl phthalate, sebacic acid, linoleic acid dimer, and by making one mole of sebacic acid and two moles of TEGs and two moles of 2 ethyl hexanoic acids react the complex ester that form.
Can be used as the useful ester of synthetic oil and comprise that also those are by C
5-C
12Monocarboxylic acid and polyhydroxy-alcohol and polyhydroxy ethers such as neopentyl glycol, TriMethylolPropane(TMP), season penta methyl alcohol, dipentaerythritol and the ester of tripentaerythritol preparation.
Silicon-based oil as poly-alkyl-, poly-aryl-, poly-alkoxyl group-and poly-aryloxy silicone oil and silicic acid ester oil formed another kind of useful ucon oil; They comprise tetraethyl orthosilicate, silicic acid four isopropyl esters, four-(2-ethylhexyl) silicon ester, four-4-methyl-(2-ethylhexyl) silicon ester, four-(right-tert-butyl-phenyl) silicon ester, six-(4-methyl-2-pentoxy) sily oxide, poly-(methyl) siloxanes and poly-(aminomethyl phenyl) siloxanes.Other ucon oil comprises the liquid ester (as the diethyl ester of tricresyl phosphate (o-toluene ester), trioctyl phosphate, decylphosphonic acid) and the polymeric tetrahydrofuran (THF) of phosphoric acid.
Not refining, that refined all can be used in the lubricating oil of the present invention with oil refining.Lian Zhi oil is not for handling directly by those oil natural or that synthetic source obtains without being further purified.For example directly operate the shale oil that obtains, the oil or the direct ester oil that is obtained by esterification process that are directly obtained by distillation by destructive distillation, these oil are used without further processing, are called not refining oil.The oil of refining with do not refine oils seemingly, just their are further handled in one or more purification steps, to improve one or more characteristics.Multiple this class purification technique such as distillation, solvent extraction, acid or alkali extract, filter and soak into, and all are known concerning those skilled in the art.Refining oil by with obtain refining the similar method of oily institute's application method and obtain, but its application to as if already used oil.This refining oil is also referred to as recovered oil or handling oil again, and often carries out additional processing to remove useless additive and oil decomposition product by technology.
Especially, the present invention relates to engine oil formulation and additive thereof.As using here, term " engine oil " refers to the lubricating oil that can use in engine oil, and for example it comprises automotive oil or diesel engine oil.Lubricating oil composition of the present invention also is suitable for the lubricated ship engine that includes four-stroke trunk-piston engine and two stroke crosshead engines.
Making up oil have the interior viscosity of lubricant viscosity scope, is generally about 45-6000SUS under 100 (about 38 ℃).Lubricating oil also can contain one or more high-alkaline base earth metals sanitising agents, its at least a metallic neutrality and high alkaline salicylate that is as described herein based on alkyl salicylate.Detergent components accounts for significant quantity generally, and its scope is generally 0.01-25wt%, is preferably 0.1-10wt%, more preferably 0.1-5.0wt%.If not indicated otherwise, all weight percent is all in the weight of whole lubricating oil composition.
The amount of the multifunctional additive for lubricating oils that is comprised in final lubricating oil will depend on the character of final application.Concerning marine lubricant, making TBN usually is that 9-100 is just enough; Concerning automobile engine lubricating oil, making TBN is that 4-20 is just enough.
As using here, term " total basicnumber " or " TBN " refer in 1 gram additive, the equivalent amount of alkali with respect to milligram KOH.Therefore, the TBN number is high more, reflects that it is the stronger product of alkalescence, and therefore has higher alkalescence and stock.The total basicnumber of compositions of additives can be determined at an easy rate by ASTM methods of test D2896 or other equivalent processes.
Final lubricating oil also can contain the traditional lubrication oil additive of one or more other types of significant quantity, for example viscosity index improver, anti-wear agent, antioxidant, dispersion agent, rust-preventive agent, pour point depressor, and analogue.
To become more obvious by following embodiment advantage of the present invention and key character.
Embodiment
Embodiment 1
Alkylation of salicylic acid
In 3 liters of Glass Containerss being furnished with agitator, thermometer and heating jacket, add Whitfield's ointment (215.0 gram).Next add blended C
14-C
18Alkene (367.7 gram) adds alkylation catalyst then as 45.1 gram methylsulfonic acids.Heated mixt to 120 ℃ also kept 24 hours under this temperature.Add some VM﹠amp then; P petroleum naphtha (582.6 gram), and make limpid solution sedimentation to remove spent catalyst.The product that is reclaimed is by the limpid little yellow alkyl salicylate that petroleum naphtha dilutes, be suitable for direct high alkalinityization or with the sanitising agent reaction of high alkalinityization in advance.
Embodiment 2
The preparation of calcium salicylate
To containing 20 gram VM﹠amp; The calcium sulphonate that adds 35 gram 500TBN in the reaction vessel of P petroleum naphtha, 15 gram base oils and 20 gram methyl alcohol.In case behind the thorough mixing, slowly add 100 gram embodiment, 1 described alkyl salicylate, in ensuing two hours, elevate the temperature to 420 °F (about 216 ℃).Steam stripped calcium salicylate be bright and limpid, viscosity is 45 centistokes, TBN is 170, and the per-cent of calcium is 6.1%.
The product of embodiment 2 is tested in PDSC (pressure reduction scanning calorimetry), finds that its induction time is 109 minutes.The OIT of corresponding calcium sulphonate is lower than 30 minutes.
Use the panel coker test like products is carried out the high-temperature cleaning test, find the deposition that it has 3.5 milligrams.In above-mentioned reaction, be used as alkali source (CaCO
3) corresponding overbased sulfonate 75 milligrams deposition is arranged.
Panel coker test is the process of the tendency of oil formation solid decomposed product when determining at high temperature contact with the surface.This test can be implemented with Falex Panel Coking TestApparatus, designs this testing installation and is used for implementing federal touchstone (FederalTest Standard) 791 B, method 3462.
Embodiment 3
The preparation of calcium salicylate
The alkylsalicylate that adds preparation among the 140 gram embodiment 1 in reactor adds 50 gram base oils, 220 gram VM﹠amp then; P petroleum naphtha, 9 gram methyl alcohol, 7.5 gram neutral calcium sulfonates and 23 gram hydrated limes.Heated mixt to 140 (60 ℃), and add CO
2, all be converted into CaCO up to lime
3Filter reaction mixture, and distillation, thus produce bright and clear water poplar acid calcium sanitising agent fluid.
The PDSC test shows that OIT is 140 minutes, and the panel coker test shows that it has clean-up performance preferably, has 8.5 milligrams deposition.
Embodiment 4
The preparation of calcium salicylate
Comparative Examples
The accurate condition of the reaction needed of alkyl salicylate and overbased sulfonate, otherwise can form undesirable crystal calcium carbonate.Reaction conditions hereinafter described produces and mainly contains CaCO
3The final salicylate of vaterite form.
Condition is identical with embodiment 2, just except adding 20 gram methyl alcohol, also will add 20 gram water.Strengthen polarity and make tensio-active agent colloid instability, and make amorphous oil soluble CaCO
3Be converted into crystal vaterite.The finished product are very sticking, and are very muddy, are unsuitable for using.
Under the situation that does not depart from ultimate principle of the present invention, can carry out many changes and improvements, therefore should understand protection scope of the present invention with reference to appended claim.
Claims (12)
- One kind prepare the alkaline-earth metal salicylate method, it comprises the steps:A) in the presence of strong acid catalyst, make the Whitfield's ointment alkylation, form oil-soluble alkylation Whitfield's ointment with the linear alpha-olefin that comprises at least 14 carbon atoms;B) the described oil-soluble alkylation Whitfield's ointment of neutralization;C) in the presence of promotor and tensio-active agent, use CO 2Carbonation by lime makes described oil-soluble alkylation Whitfield's ointment high alkalinityization;D) product filtration C); WithE) remove solvent by distillation.
- 2. the process of claim 1 wherein that described strong acid catalyst is anhydrous methylsulfonic acid.
- 3. the process of claim 1 wherein that described alkylation step is about 50-200 ℃ of enforcement down in temperature range.
- 4. the process of claim 1 wherein that described linear alpha-olefin is selected from: tetradecene, cetene, 1-vaccenic acid, 1-eicosylene, 1-two dodecylenes, 1-tetracosene, and the mixture of aforementioned substances.
- 5. the process of claim 1 wherein that described high alkalinity step implements in the presence of promotor.
- One kind prepare the alkaline-earth metal salicylate method, it comprises the steps:A) in the presence of strong acid catalyst, make the Whitfield's ointment alkylation, form oil-soluble alkylation Whitfield's ointment with the linear alpha-olefin that comprises at least 14 carbon atoms;B) make described oil-soluble alkylation Whitfield's ointment and the sanitising agent reaction that is selected from following high alkalinityization in advance: the sulfonate of overbasic basic metal or alkaline-earth metal, phenates or carboxylate salt, thereby produce the salicylate of basic metal or alkaline-earth metal, described salt comprises the dispersive basic metal that changes per-cent or the carbonate of alkaline-earth metal.
- 7. the method for claim 6, wherein said strong acid catalyst is anhydrous methylsulfonic acid.
- 8. the method for claim 6, wherein said alkylation step is about 50-200 ℃ of enforcement down in temperature range.
- 9. the method for claim 6, wherein said linear alpha-olefin is selected from: tetradecene, cetene, 1-vaccenic acid, 1-eicosylene, 1-two dodecylenes, 1-tetracosene, and the mixture of aforementioned substances.
- 10. the method for claim 6, wherein said high alkalinity step is implemented in the presence of promotor.
- 11. alkaline-earth metal salicylate for preparing by the method that comprises following steps:A) in the presence of strong acid catalyst, make the Whitfield's ointment alkylation, form oil-soluble alkylation Whitfield's ointment with the linear alpha-olefin that comprises at least 14 carbon atoms;B) the described oil-soluble alkylation Whitfield's ointment of neutralization;C) in the presence of promotor and tensio-active agent, use CO 2Carbonation by lime makes described oil-soluble alkylation Whitfield's ointment high alkalinityization;D) product filtration C); WithE) remove solvent by distillation.
- 12. alkaline-earth metal salicylate for preparing by the method that comprises following steps:A) in the presence of strong acid catalyst, make the Whitfield's ointment alkylation, form oil-soluble alkylation Whitfield's ointment with the linear alpha-olefin that comprises at least 14 carbon atoms;B) make described oil-soluble alkylation Whitfield's ointment and the sanitising agent reaction that is selected from following high alkalinityization in advance: the sulfonate of overbasic basic metal or alkaline-earth metal, phenates or carboxylate salt, as calcium sulphonate, thereby produce the salicylate of basic metal or alkaline-earth metal, described salt comprises the dispersive basic metal that changes per-cent or the carbonate of alkaline-earth metal.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US42249302P | 2002-10-31 | 2002-10-31 | |
| US60/422,493 | 2002-10-31 | ||
| US10/674,896 | 2003-09-29 |
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| CN2007101996240A Division CN101219944B (en) | 2002-10-31 | 2003-10-15 | Method for producing lubricant detergents |
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| CN1708471A true CN1708471A (en) | 2005-12-14 |
| CN100400493C CN100400493C (en) | 2008-07-09 |
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| CNB2003801025608A Expired - Lifetime CN100400493C (en) | 2002-10-31 | 2003-10-15 | Preparation method of lubricating oil detergent |
| CN2007101996240A Expired - Lifetime CN101219944B (en) | 2002-10-31 | 2003-10-15 | Method for producing lubricant detergents |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276450A (en) * | 2011-05-16 | 2011-12-14 | 锦州康泰润滑油添加剂有限公司 | Preparation process for alkaline calcium alkylsalicylate |
| CN102597193A (en) * | 2009-12-02 | 2012-07-18 | 雪佛龙奥伦耐有限责任公司 | Low temperature performance lubricating oil detergents and method of making the same |
| WO2012167530A1 (en) * | 2011-06-09 | 2012-12-13 | 无锡南方石油添加剂有限公司 | Cleaning agent for lubricating oil and production process thereof |
| CN103508882A (en) * | 2012-06-21 | 2014-01-15 | 中国石油天然气股份有限公司 | A kind of preparation method of alkyl salicylic acid |
| CN106701252A (en) * | 2015-07-21 | 2017-05-24 | 中国科学院宁波材料技术与工程研究所 | Salicylate detergent, and preparation method and application thereof |
| CN109679729A (en) * | 2019-02-18 | 2019-04-26 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation process of high base number sulfurized alkylsalicylate |
| CN111170850A (en) * | 2019-12-26 | 2020-05-19 | 山东源根石油化工有限公司 | Additive, preparation method and lubricating oil using additive |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098466B (en) * | 2013-04-03 | 2016-01-20 | 中国石油天然气股份有限公司 | A kind of preparation method of alkyl salicylate |
| BR112018009402B1 (en) * | 2015-11-10 | 2021-05-11 | Basf Se | method for reprocessing alkanesulfonic acid |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8814008D0 (en) * | 1988-06-14 | 1988-07-20 | Bp Chemicals Additives | Lubricating oil additives |
| US5434293A (en) * | 1993-12-23 | 1995-07-18 | Chevron Chemical Company | Alkylation of alkyl salicylate using a long chain carbon feed |
| GB9522359D0 (en) * | 1995-11-01 | 1996-01-03 | Bp Chemicals Additives | Alkylation process |
-
2003
- 2003-10-15 CN CNB2003801025608A patent/CN100400493C/en not_active Expired - Lifetime
- 2003-10-15 CN CN2007101996240A patent/CN101219944B/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102597193A (en) * | 2009-12-02 | 2012-07-18 | 雪佛龙奥伦耐有限责任公司 | Low temperature performance lubricating oil detergents and method of making the same |
| US8778856B2 (en) | 2009-12-02 | 2014-07-15 | Chevron Oronite Company Llc | Low temperature performance lubricating oil detergents and method of making the same |
| CN102597193B (en) * | 2009-12-02 | 2014-09-17 | 雪佛龙奥伦耐有限责任公司 | Low temperature performance lubricating oil detergent and preparation method thereof |
| CN102276450A (en) * | 2011-05-16 | 2011-12-14 | 锦州康泰润滑油添加剂有限公司 | Preparation process for alkaline calcium alkylsalicylate |
| WO2012167530A1 (en) * | 2011-06-09 | 2012-12-13 | 无锡南方石油添加剂有限公司 | Cleaning agent for lubricating oil and production process thereof |
| US9102895B2 (en) | 2011-06-09 | 2015-08-11 | Wuxi South Petroleum Additive Co., Ltd. | Detergent for lubricant oil and production process thereof |
| CN103508882A (en) * | 2012-06-21 | 2014-01-15 | 中国石油天然气股份有限公司 | A kind of preparation method of alkyl salicylic acid |
| CN103508882B (en) * | 2012-06-21 | 2015-05-27 | 中国石油天然气股份有限公司 | A kind of preparation method of alkyl salicylic acid |
| CN106701252A (en) * | 2015-07-21 | 2017-05-24 | 中国科学院宁波材料技术与工程研究所 | Salicylate detergent, and preparation method and application thereof |
| CN106701252B (en) * | 2015-07-21 | 2020-02-04 | 中国科学院宁波材料技术与工程研究所 | Salicylate detergent, preparation method and application thereof |
| CN109679729A (en) * | 2019-02-18 | 2019-04-26 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation process of high base number sulfurized alkylsalicylate |
| CN111170850A (en) * | 2019-12-26 | 2020-05-19 | 山东源根石油化工有限公司 | Additive, preparation method and lubricating oil using additive |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101219944B (en) | 2012-02-22 |
| CN100400493C (en) | 2008-07-09 |
| CN101219944A (en) | 2008-07-16 |
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