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CN1015642B - Alkaline earth metal hydrocarbyl phenates, their sulphurised derivates, their production and use thereof - Google Patents

Alkaline earth metal hydrocarbyl phenates, their sulphurised derivates, their production and use thereof

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Publication number
CN1015642B
CN1015642B CN87108239A CN87108239A CN1015642B CN 1015642 B CN1015642 B CN 1015642B CN 87108239 A CN87108239 A CN 87108239A CN 87108239 A CN87108239 A CN 87108239A CN 1015642 B CN1015642 B CN 1015642B
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Prior art keywords
acid
lubricating oils
multifunctional additive
alkyl
component
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CN87108239A
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CN87108239A (en
Inventor
查理斯·肯
约翰·克拉福德
希恩·帕特里克·奥康诺尔
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Rubrizzo Adi & Co Ltd (uk) Ltd
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BP Chemicals Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

An additive concentrate suitable for incorporation into a finished lubricating oil composition is disclosed. The additive concentrate comprises: (a) a lubricating oil; (b) a lubricating oil soluble sulphurized alkaline earth metal hydrocarbyl phenate modified by incorporation of from greater than 2 to 35% by weight based on the weight of the composition of either (i) at least one carboxylic acid having formula (I), wherein R is C10 to C24 alkyl or alkenyl group and R1 is either hydrogen, a C1 to C4 alkyl group or a -CH2-COOH group, or an anhydride, acid chloride or ester thereof or (ii) a di- or polycarboxylic acid containing from 36 to 100 carbon atoms or an anhydride, acid chloride or ester thereof, the composition having a TBN greater than 300.

Description

Alkaline earth metal hydrocarbyl phenates, their sulphurised derivates, their production and use thereof
The present invention relates generally to alkaline earth metal hydrocarbyl phenates and sulphurated derivatives thereof, their preparation and as the application of lubricating oil additive.The present invention be more particularly directed to have the alkaline earth metal hydrocarbyl phenates of high total basicnumber (TBN) and gratifying viscosity and the enrich additive composition of sulphurated derivatives thereof, their preparation and as the use of lubricating oil additive.
In internal combustion engine, often spill and mix with lubricating oil from the piston limit from the by product of combustion chamber.Many by products can form acidic substance in lubricating oil.There is kind of situation remarkable especially, promptly in diesel engine, can produces caustic acid by burning by high-sulphur low-grade fuel operation.Therefore, bonded acid comprises in the lubricating oil: the sulfur acid that the sulphur oxidation produces, the nitrogen acid that the oxidation of nitrogen produces in haloid acid that plumbous halogen scavenging agent derives in the fuel and the burning room air.These acid can cause sludgy deposits and bearing and the engine corrosion of parts in addition, cause the rapid wearing and early stage damage of engine.
Be commonly used to neutral lubrication oil inner acidic thing and disperseing have a class to belong to metal alkyl phenates and sulfurized metal alkyl phenates in the compound of sludge, metal wherein is an alkaline-earth metal, such as calcium, magnesium or barium." standard " and " overbasic " alkaline-earth metal alkyl phenate all can adopt.Such alkaline-earth metal alkyl phenate be used to describe in term " overbasic ": the equivalents of wherein alkaline-earth metal part and the ratio of the equivalents of phenol moieties be greater than 1, usually greater than 1.2, and also can be high to 4.5 or higher.By contrast, in " standard " alkaline-earth metal alkyl phenate, this equivalence ratio is 1.Therefore, " overbasic " material just contains than corresponding " standard " material and Duos alkaline-earth metal more than 20%.For this reason, " overbasic " alkaline-earth metal alkyl phenate than corresponding " standard " alkaline-earth metal alkyl phenate have higher in and the ability of acidic substance.
Prior art has been introduced the method for many preparations " standard " and " overbasic " metal alkyl phenates.A kind of method that is called " interpolation of single lime " prepared " overbasic " alkyl phenate usually comprises: with alkylphenol, under the condition that is with or without the sulphur existence, react with lubricating oil, oxy-compound, excessive alkaline earth metal hydroxides (in surpassing and the needed stoichiometric ratio of alkylphenol), generate an intermediate product, carry out carboxylation subsequently, distill overhead distillate (heading distillation) (so that removing unreacted oxy-compound) and filter then.The generation of intermediate product is accompanied by the remarkable increase of viscosity, and carboxylation thereupon is reduced to a corresponding low level with viscosity.The viscosity increase of following the generation of intermediate product and occurring is undesirable, is difficult to stir so that harm subsequent reactions because of it becomes reaction mixture.Increase by adding a spot of alkaline earth metal hydroxides in the reaction with viscosity is controlled on the acceptable level, and this " overbasic " alkyl phenate product must have the neutralising capacity of a reduction.For the product that obtains a kind of senior middle school and ability simultaneously the viscosity controller of intermediate product in the scope that suits, can add alkaline earth metal hydroxides respectively with two reactions steps (generally being called " two interpolation lime " technology) or three steps, carry out carboxylation subsequently.Therefore this method has the relatively long reinforced time.Another alternative method is to use viscosity depressant in the intermediate product generative process, such as tridecanol, and the hydroxylic solvent of 2-Ethylhexyl Alcohol or similar boiling range; But can increase the material cost of this technology in such event greatly.Though the TBN value of technology generally in 200～300 scopes, by the highest total basicnumber (TBN) that general prior art can obtain, was represented with milligram KOH/ gram in the past, was approximately 300; This value is consistent with the gratifying viscosity that has.Very clear, the target that we require to reach is to prepare a kind of have the alkaline-earth metal alkyl phenate of high TBN value or the multifunctional additive for lubricating oils that its sulphurated derivatives constitutes, and its TBN value should be greater than 300, more preferably greater than 350.So far do not find to obtain the possibility of this high TBN product as yet, because of the use of the alkaline earth metal alkali of higher concentration can be directed at the high viscosity product, even if in carboxylation is handled subsequently with excessive carbon dioxide " towards rare " this product but still can make it become insoluble thing.By in reaction mixture, mixing some the carboxylic acid or derivatives thereof that has 10 carbon atoms in into limited amount each molecule at least, we have just reached this purpose and have obtained its TBN value thus and have surpassed 300, can be under some situation greater than 350 product, this product is held suitable viscosity and has been avoided insoluble again.This viscosity in the time of 100 ℃ less than the 1000cSt(centistoke).
Both can in the preparation process of alkaline-earth metal alkyl phenate and sulphurated derivatives thereof, also can to this existing precedent, consult US-A-3,372,116 using carboxylic acid in the process with mixing into of lubricating oil composition, GB-A-1,440,261, US-A-4,049,560 and EP-A-0,094,814.
US-A-3,372,116 disclose a kind of improving one's methods of alkali metal phenolate that prepare, this method comprises: 25 ℃ between the cut point with (A), (B) He (C) react; (A) be the alkyl substituted phenol that contains 6 carbon atoms at least, said phenol with at the most one normally contain the mixture that 6 carbon atom alkyl replace succsinic acids or its acid anhydrides at least, or be neutral basic metal or alkaline earth salt substantially, in the above article any one; (B) be about 1～10 normal calcium or strontium alkali, corresponding to each normal (A); (C) be carbonic acid gas.This method improvement part is: corresponding to each normal calcium or strontium alkali, there is about 0.002～0.2 normal carboxylic acid or its basic metal, alkaline-earth metal, zinc or the plumbous salt that contains 100 carbon atoms at the most in reaction when carrying out.Preferred carboxylic acid is that those contain 10 carbon atoms at the most, preferably contains the monocarboxylic acid and the alkaline earth salt thereof of 10 carbon atoms at the most.All adopt water and carboxylate salt in many examples.We not only require to avoid the existence of water, but also discovery is insoluble because of carboxylate salt inherent in this system, and they can not be used for technology of the present invention.US-A-3,372,116 described technologies are not used to be enough to produce to be had above the ratio of the needed phenol of the phenates of 300TBN value to alkaline earth metal alkali.
GB-A-1,440,261 disclose a kind of lubricating oil composition.Comprise lubricating oil, washing agent or dispersion agent additive and a kind of mixture that constitutes by two kinds of carboxylic acids at least, wherein a kind of fusing point of carboxylic acid is at least in each molecule of 20 ℃ and it no more than 30 carbon atom, the fusing point that other plants carboxylic acid is lower than 20 ℃, the low melting point carboxylic acid to the weight ratio of high-melting-point carboxylic acid between 1.5: 5～8: 1.But washing agent high alkalinity phenates, it has suitable TBN value is between 50～100.In this lubricating oil composition, the miscellany amount of acid is 0.05～2.0Wt%.(Wt refers to weight ratio)
US-A-4,049,560 has described a kind of preparation of high alkalinity magnesium washing agent, and the technology of employing comprises for carbonic acid gas is introduced in the reaction mixture:
(a) phenol red or the thiophenol that contain one or more alkyl replacements of 15～40Wt%, or contain phenol or the thiophenol that one or more alkyl replace, or have the said one or more alkyl substituted phenols or the thiophenol of containing of sulphur,
(b) organic sulfonic acid of 5～15Wt%, organic sulfonic acid ester (salt) or organo-sulfate (salt);
(c) glycol of 5～15Wt%, C 1-C 5Monohydroxy-alcohol or C 2-C 4Alkoxyl alcohol,
(d) magnesium hydroxide of 2～15Wt% or activated magnesia,
(e) C of 0.1Wt% at least 1-C 18Carboxylic acid, its acid anhydride, or its ammonium, amine salt, said C 1-C 18The I family of carboxylic acid or II family metal-salt reach,
(f) at least the thinning oil of 10Wt% (comprise be present in component (a) and (b) in).
The quantity of carboxylic acid (in the component (e)) be preferably in 0.5～2.0Wt%.Zhi Bei product it is said that its TBN is approximately 200～250 by this method, for example 225.
EP-A-0,094,814 discloses a kind of into multifunctional additive for lubricating oils of lubricating oil composition of mixing, and this enriched material comprises lubricating oil, and the high alkalinity alkaline earth metal hydrocarbyl of 10～90Wt% sulfuration phenates; This phenates, during high alkaline purification or thereafter, with 0.1～10Wt% preferably 2～6Wt%(based on multifunctional additive for lubricating oils weight) carboxylic acid handle, said carboxylic acid has following structural formula:
Figure 87108239_IMG3
(the R here is C 10-C 24Unprotected side chain alkyl or alkenyl, R 1Be H, C 1-C 4Alkyl or-CH 2-COOH); Or this sour acid anhydride or salt replace this carboxylic acid.EP-A-0,094814 goal of the invention is to solve the problem that multifunctional additive for lubricating oils ran into that many usefulness contain high alkalinity additive, promptly deficient in stability causes the problem that precipitation increases and foams.EP-A-0,094,814 problem is not that preparation has a problem of the phenates multifunctional additive for lubricating oils that is higher than 300TBN value, during in fact with the phenates multifunctional additive for lubricating oils of the prepared of this invention, although confirmed to have overcome stability and its TBN value of problem of foaming less than 300.
Can reach a conclusion thus: the prior art of all employing carboxylic acids does not propose the preparation problem of the multifunctional additive for lubricating oils that is made of the high alkalinity alkaline earth metal hydrocarbyl phenates that has greater than 300TBN value and appropriate viscosity.
In view of the above, the invention provides a kind of suiting on the one hand and mix the into multifunctional additive for lubricating oils of finished lube composition, this multifunctional additive for lubricating oils comprises:
(a) lubricating oil
(b) dissolve in the improved sulfuration or the unvulcanised alkaline earth metal hydrocarbyl phenates of lubricating oil, improvements are by mixing into greater than 2% mode less than one of following composition of 40%, based on composition total weight, (ⅰ) at least a carboxylic acid with following structural formula:
Wherein R is C 10-C 24Alkyl or alkenyl and R 1Be H or C 1-C 4Alkyl or-CH-COOH, or the acid anhydride of this carboxylic acid, acyl chlorides or ester; (ⅱ) contain binary or polycarboxylic acid or its acid anhydride, acyl chlorides or its ester of 36～100 carbon atoms, said composition has the TBN value greater than 300.
(a) component of composition is a lubricating oil.Suitable lubricating oil is animal oil, vegetables oil and mineral oil.Suitable lubricating oil can be the lubricating oil of petroleum derivation, as cycloalkyl, paraffin base or mixed base oil.Dissolvent neutral oil particularly suitable.As an alternative, lubricating oil can be synthetic lubricating oil.Suitable ucon oil comprises synthetic ester oil grease, and it comprises diester such as Octyl adipate, dioctyl sebacate and hexanodioic acid tridecyl diester, or polymeric hydrocarbon lubricating oil such as liquid polyisobutene and poly-d alkene.The appropriate amount of lubricating oil is 10～90% of a composition weight, preferably 10～70%.
Component (b) is to dissolve in the improved sulfuration of lubricating oil or unvulcanised, and sulfurized alkaline earth metal hydrocarbyl phenates preferably, this phenates be by mixing into, with greater than 2% less than 40Wt%, and based on the amount of composition, (ⅰ) or (ⅱ) one and improve.Suitable alkaline-earth metal can be strontium, calcium, magnesium and barium, and wherein calcium, magnesium and barium are preferable, and the best is a calcium.The alkyl phenol moieties is preferably derived by at least a alkylphenol and is got in the alkaline earth metal hydrocarbyl phenates.Alkyl in the alkylphenol can be that side chain or unbranched is arranged.Suitable alkyl contains 4～50, preferably 9～28 carbon atoms.A kind of particularly suitable alkylphenol is the C that the tetramer by propylene gets the phenol alkylation 12-alkylphenol.
The alkaline earth metal hydrocarbyl phenates is by mixing into composition (ⅰ) or (ⅱ) being improved.As for (ⅰ), it is a kind of carboxylic acid or its acid anhydride, acyl chlorides or its ester with structure formula I at least.In the structure formula I, R preferentially selects the alkyl or the alkenyl of unprotected side chain for use.The acid of preferred construction formula I is that those R are C 10-C 24, C preferably 18-C 24Straight chained alkyl and R 1Be the acid of H.The suitable saturated carboxylic acid of structure formula I comprises capric acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, eicosanoic acid, docosoic and tetracosanoic acid for example.The suitable unsaturated carboxylic acid of structure formula I comprises lauroleic acid, Oleomyristic acid, Zoomeric acid, oleic acid, cis-9-20 carbon acid, erucic acid, ricinolic acid, linoleic acid plus linolenic acid for example.Also can adopt the mixture of acid, as rape head lipid acid.The mixture of the acid of particularly suitable is a series of commercial grade acid, comprises saturated and unsaturation acid.These mixtures can also can be by neutral products derive acquisition, for example cotton oil, peanut oil, Oleum Cocois, Toenol 1140, palm-kernel oil, sweet oil, Semen Maydis oil, plam oil, Viscotrol C, soya-bean oil, Trisun Oil R 80, menhaden fish oil, sardine fat and Tallow, beef by the synthetic method.Also can adopt the mixture of sulfurized acid and acid.Except carboxylic acid, the derivative of also available its acid anhydride, acyl chlorides or its ester, the most handy acid anhydrides.In any case top-priority is with carboxylic acid or mixed carboxylic acid.The optimization acid of a structure formula I is a stearic acid.
Except (ⅰ), or what replace that (ⅰ) improve the alkaline earth metal hydrocarbyl phenates is to mix into (ⅱ), is to contain the binary of 36～100 carbon atoms or the derivative of polycarboxylic acid or its acid anhydride, acyl chlorides or ester, preferably its sour acid anhydride (ⅱ).Preferably (ⅱ) is polyisobutylene succinic acid or polyisobutene succinyl oxide.
Carboxylic acid, binary or polycarboxylic acid, its acid anhydride, acyl chlorides or its ester that preferably has a structure formula I mixed weight shared in composition for greater than 10% to 35%, and preferably 12～20%, for example be approximately 16%.The input of mixing of carboxylic acid or derivatives thereof is a relatively low concentrated viscosity greater than the advantage of 10Wt%.
Be present in alkaline-earth metal appropriate vol in the composition and be 10～20Wt% based on composition weight.
The alkaline earth metal hydrocarbyl phenates can cure or not vulcanize, preferably sulfuration.
Suitable sulphur can be present in the composition, and its amount is, based on the weight of composition, and 1～6%, preferably 1.5～3%.
Also can have suitable carbonic acid gas in the composition, its amount is for based on 5～20% of composition weight, and preferably 9～15%.
The preferred TBN value of composition is greater than 350, more preferably greater than 400.
Less than 1000CSt, be preferably less than 750cSt when the viscosity that suitable composition has is 100 ℃, the best is less than the 500cSt(centistoke).
On the other hand, the invention provides a kind of suitable into multifunctional additive for lubricating oils of finished lube of mixing, its acquisition is by reacting with (A), (B), (C), (D), (E) with (F) under the temperature that has improved; (A) be (ⅰ) alkyl phenol or (ⅱ) alkyl phenol and sulphur, choose one or the other of these two; (B) be alkaline earth metal alkali.All can in a plurality of intermediate points addings at reaction intermediate section one or many; (C) be one of following material, have polyvalent alcohol, two or three (second is to fourth) glycol, aklylene glycol alkyl oxide or the polyalkylene glycol alkyl oxide of 2～4 carbon atoms; (D) be lubricating oil; (E) be carbonic acid gas, after each input of component (B), add; (F) based on composition weight from greater than 2% to less than 40% (ⅰ) that fully provide or (ⅱ) the two one of, (ⅰ) being carboxylic acid or its acid anhydride, acyl chlorides or its ester with structure formula I, (ⅱ) is binary or polycarboxylic acid or its acid anhydride, acyl chlorides or its ester that contains 36～100 carbon atoms; The weight ratio of component (A)～(F) transfers to and to a certain degree makes the enriched material of making have the TBN value greater than 300.
Also have on the one hand, the invention provides the technology of the used multifunctional additive for lubricating oils of preparation finished lube, this technology is included under the temperature that has improved reacts (A)～(F) component, and the weight ratio of component (A)～(F) will be suitable for having the preparation greater than the 300TBN enriched material.
One of component in the reaction mixture (A) is (ⅰ) alkyl phenol or (ⅱ) alkyl phenol and sulphur, the two.Product is the alkaline earth metal hydrocarbyl phenates when using component (A) (ⅰ), and product is a sulfurized alkaline earth metal hydrocarbyl phenates when using component (A) (ⅱ).The alkyl phenol that adopts is to derive needed alkyl phenol moieties in the said alkylphenol of associating in front.
What alkaline earth metal alkali (B component) was suitable is alkaline earth metal oxide or oxyhydroxide, preferably oxyhydroxide.Can add calcium hydroxide, for example with the form of white lime.Preferred alkaline-earth metal is calcium, magnesium and barium, preferably calcium.The add-on of alkaline earth metal alkali is relevant with component (A), has greater than 300 with enough generations, is as the criterion more preferably greater than the 350TBN value.This amount depends on that storage is multifactor, comprises the character of sulfenyl phenolate, and it is higher than the general usage quantity of prior art.Component (B) is to the weight ratio of component (A), is typically to be suitable for 0.2～50, preferably between 0.4～10.Alkaline earth metal alkali (B) can integral body be added in the initial reactant, or part is added in the initial reactant, remainingly adds in technology with one or many subsequently.In order to prepare a kind of multifunctional additive for lubricating oils that has when having less than 1000cSt viscosity greater than 350TBN and 100 ℃, special wish at least at twice, preferably repeatedly add component (B), and with component (F) with greater than, be as the criterion with the multifunctional additive for lubricating oils product weight, 10% quantity adds.
Component (C) is C 2-C 4Polyvalent alcohol, two or three (second is to fourth) glycol alkyl ether, one of them.Suitable polyvalent alcohol is a kind of dihydroxy alcohol, for example ethylene glycol or propylene glycol, or trihydroxy-alcohol, for example glycerol.Two or three (second is to fourth) glycol is suitably glycol ether or Triethylene glycol.Aklylene glycol alkyl oxide or polyalkylene glycol alkyl oxide be suitable to have following structural formula:
R（OR 1） XOR 2（Ⅱ）
Wherein R is C 1-C 6Alkyl, R 1Be alkylidene group, R 2Be H or C 1-C 6Alkyl, X is the integer of 1-6.The preferred solvent that preferably has the structure formula II comprises ethylene glycol monoemethyl ether or glycol dimethyl ether, the only first or the dme of glycol ether, Triethylene glycol or tetraethylene-glycol.A kind of specially suitable solvent is the only methyl ether (CH of glycol ether 3OCH 2CH 2OCH 2CH 2OH).The mixture that also can adopt glycol and have the glycol ethers of structure formula II.When the glycol ethers of using glycol or structure formula II is made solvent, top-priority be with inorganic halides such as ammonium chloride and a kind of rudimentary-be C 1To C 4Carboxylic acid such as acetate be used in combination.Top-priority component (C) is the only methyl ether of ethylene glycol or glycol ether, and the latter is used in combination with ammonium chloride and acetate.
Component (D) is a lubricating oil, with reference to foregoing multifunctional additive for lubricating oils.
Component (E) is a carbonic acid gas, and it can gaseous state or solid-state, preferably adds with gaseous form.In the gaseous form, be suitable for from reaction mixture, blowing over.The amount that we find to mix in the ordinary course of things carbonic acid gas into increases and increases with the concentration of component (F).In order to prepare the enriched material that has greater than the 350TBN value, carbonic acid gas preferably adds the back along with each (B) component and adds, and repeatedly adds at twice or preferably.
Component (F) is the carboxylic acid of structure formula I, contains two or polycarboxylic acid of 36～100 carbon atoms, or their acid anhydrides, acyl chlorides or its ester, and wherein any is with reference to aforesaid additive concentrate composition.It is aforementioned that what require to provide will be enriched material desired initial budget estimate amount greater than 2% less than 40% amount based on enriched material weight.When calculating this amount, for example, remaining sum should be considered the damage by water consumption from carboxylic acid.
Reaction can be carried out under the condition that thinner exists.Suitable diluent is to have the volatile liquid that satisfies operation operation, that is the volatility that has can make and can promptly remove from reaction mixture when reaction finishes.The example of suitable diluents comprises 2-ethyl hexanol, isooctyl alcohol, iso-heptanol and three decyl alcohol.
React under the condition that is preferably in annexing ingredient-catalyst for reaction existence and carry out.The inorganic halides useful as catalysts, suitable halogenide is hydrogen halide.Ammonium halide or metal halide.The metal part of metal halide is zinc, aluminium or alkaline-earth metal, preferably calcium preferably.Halid halogen part is chlorine preferably.Preferred catalyzer is a hydrogenchloride, calcium chloride, ammonium chloride, aluminum chloride and zinc chloride, preferably calcium chloride.Catalyst consumption preferably is not more than 2.0%Wt/Wt.
The reaction of component (A)～(F) and carboxylation reaction are suitable at 120～200 ℃, be preferably under 130～165 ℃ the high temperature to carry out, yet if desired, the actual temperature of reaction (A)～(F) and the actual temperature of carboxylation can be different.Pressure can be normal atmosphere, is lower than normal atmosphere or is higher than normal atmosphere.
Available ordinary method reclaims enriched material, and for example the fractionation by distillation by component (C) and thinner (if having) reclaims.
At last, pay the utmost attention to this enriched material that filters gained.In general, technology of the present invention will prepare a kind of enriched material with gratifying viscosity, and promptly viscosity and can prepare in the time of 100 ℃ viscosity less than the enriched material of 750cSt or 500cSt less than 1000cSt in the time of 100 ℃.In addition, enriched material generally can have the characteristic of needed viscosity index.This viscosity characteristics has many advantages, because they are convenient to the technology (comprising filtration) of enriched material.Thereby viscosity is greater than 1000cSt when preparing 100 ℃, and its TBN value generally is higher, enriched material also be possible.Filter such enriched material and just brought problem, this problem can by add thinner before filtering and filter after thinner removed solve.Keep the TBN value greater than 300 situation under, the high viscosity enriched material, for example in the time of 100 ℃ viscosity greater than 1000cSt and high TBN value is arranged for example greater than 350 enriched material, can be further by oil addition and diluted, thus in order to filtration.
In the end an aspect the invention provides a kind of finished lube composition, and it comprises the foregoing multifunctional additive for lubricating oils of lubricating oil and q.s so that one 0.5～120 TBN value is provided.
Top-priority finished lube composition is that the multifunctional additive for lubricating oils with capacity makes that its TBN value is 0.5～100.
The amount that is present in the multifunctional additive for lubricating oils in the finished lube depends on its practical situation of final use.Therefore, for the amount of the multifunctional additive for lubricating oils that exists in the marine lubricant, more suitable is that the TBN value that is enough to provide is 9～100, and is used for the lubricating oil of motor car engine, and the TBN value that this amount will be enough to provide is 4～20.
Finished lube also can be mixed the into traditional lubrication oil additive of one or more other types of significant quantity, viscosity index improver for example, and anti-friction decreases agent, antioxidant, dispersion agent, rust-preventive agent, this class material such as pour point reducer; Direct form or mix in the finished lube by the form of concentrate composition intermediary.
Except can be used as the additive of mixing lubricating oil composition into uses, this multifunctional additive for lubricating oils of the present invention also can be used as fuel dope.
The present invention will be described further by reference the following example.
All use term " TBN " among all embodiment.TBN is a total basicnumber, measures with the method for ASTMD 2896.With milligram KOH/ gram is unit.
Method with ASTMD 445 is measured viscosity.
Among all embodiment, except that offering some clarification on, the C of employing 12-alkylphenol is the commercialization product that the phenol alkylation obtained by with the propylene tetramer.
Embodiment 1
Materials:
C 13-alkylphenol: 75 grams
Lubricating oil (100SN): 131 grams
Lime: 82 grams
Sulphur: 23 grams
Stearic acid: 70 grams
Calcium chloride: 4 grams
2-Ethylhexyl Alcohol: 112 grams
Method:
(a) material is heated to 145～165 ℃/700mmHg and adds ethylene glycol 36 grams simultaneously,
(b) mixture is incubated one hour when 165 ℃/700mmHg,
(c) when 165 ℃/1 crust, add carbonic acid gas 40 grams,
(d) miscellany is cooled to 125 ℃/700mmHg,
(e) when 125 ℃/700mmHg, add lime 35 grams,
(f) miscellany is heated to 165 ℃/700mmHg and be incubated a hour,
(g) when 165 ℃/1 crust, add carbonic acid gas 20 grams,
(h) when 200 ℃/10mmHg with product and separated from solvent, and,
(i) product is filtered, it is fast that filtration velocity is wanted.
Product weight:
Thick product: 436 grams
Distillment: 169 grams
Product composition after the filtration:
Calcium: 14.1%W/W
Sulphur: 2.9%W/W
CO 2：12.4%W/W
TBN：396
V 100：308CSt
BPHV150：1
Stearic acid: 16.1%W/W
This example explanation: according to the present invention, adopt " twice add lime " technology can prepare multifunctional additive for lubricating oils with high TBN value and appropriate viscosity.
Embodiment 2
Materials: except the total amount of used lime was increased to 117 grams (according with the feeding quantity summation twice) from 82 grams, other were all identical with embodiment 1.
Method: except carbonic acid gas add-on in the step (c) from 40 grams increase to 60 grams and omit step (d), (e), (f) and (g), all the other are identical with embodiment 1.Filtration velocity is slow.
Product weight:
Thick product: 514 grams
Product composition after the filtration:
Calcium: 14.1%W/W
Sulphur: 3.0%W/W
CO 2：12.3%W/W
TBN：390
V 100：7600cSt
Stearic acid: 13.6%W/W
This example explanation: the concentrated phenates of additive that adopts " once adding lime " technology to prepare to have high TBN value, but the product viscosity that obtains under this routine condition is as can not be in commercial applications without lubricating oil dilution.
Embodiment 3
Materials: with embodiment 1.
Method: except in step (g) with carbonic acid gas from 20 grams increase to 40 grams and the following step is added in step (g) afterwards, step (h) and (i) before, other are all with embodiment 1:
(j) mixture is cooled to 120 ℃,
(k) in the time of 120 ℃, add lime 35 grams,
(l) miscellany is heated to 165 ℃/700mmHg, and
(m) carbonic acid gas 50 grams are added in the miscellany.
Product weight:
Thick product: 484 grams
Distillment: 169 grams
Filter the back product composition:
Calcium: 15.8%W/W
Sulphur: 2.6%W/W
CO 2：15.0%W/W
TBN：439
V 100：506cSt
Stearic acid: 14.5%W/W
This example explanation: can prepare multifunctional additive for lubricating oils with high TBN value by " three times add lime " of the present invention technology.
Embodiment 4
Materials: except with the consumption of lubricating oil from 131 grams increase drop to 43 grams to 158 grams and stearic consumption from 70 grams, all the other are all with embodiment 1.
Method: in step (d) cooling temperature of miscellany is become 125 ℃ from 135 ℃, all the other are all with embodiment 1.
Product weight:
Thick product: 442 grams
Distillment: 155 grams
Filter the back product composition:
Calcium: 14.1%W/W
Sulphur: 2.9%W/W
CO 2：11.9%W/W
TBN：393
V 100：3440cSt
Stearic acid: 9.8%W/W
Compare the explanation of this example with embodiment 1: although still can prepare the product with high TBN value under the sour water that is lower than 10%W/W is flat, product viscosity also is high.
Embodiment 5
Materials:
C 12-alkylphenol: 35.3 grams
Lubricating oil (100SN): 131 grams
Sulphur: 14.7 grams
Calcium chloride: 4.0 grams
Stearic acid: 109.1 grams
2-Ethylhexyl Alcohol: 224 grams
Method: (a) miscellany is heated to 120 ℃,
(b) 120 ℃/2 " add lime 82 grams during the Hg vacuum,
(c) 145～165 ℃/2 " add ethylene glycol 36 grams during Hg,
(d) with miscellany 165 ℃/2 " Hg kept one hour,
(e) add carbonic acid gas 40 grams,
(f) miscellany is cooled to 130 ℃ and in 130 ℃/2 " Hg adds lime 35 gram,
(g) with miscellany 165 ℃/2 " kept during Hg one hour,
(h) in the time of 165 ℃, add carbonic acid gas 20 grams,
(i) 200 ℃/30 " during Hg solvent is separated from product, and
(j) product is filtered.
Product weight:
Thick product: 397 grams
Distillment: 245 grams
Filter the back product composition:
Calcium: 13.6%W/W
Sulphur: 1.2%W/W
CO 2：13.9%W/W
TBN：376
V 100：142cSt
V 40：1881cSt
VI：180
Carboxylic acid: 27.5%W/W
This example explanation: add the stearic acid of 27.5%W/W,, can obtain to have the high TBN value product of appropriate viscosity based on end product weight.
Embodiment 6
Materials: except with C 12The consumption of-alkylphenol from 35.3 the gram drop to 15.6 the gram and with stearic acid dosage from 109.1 the gram increase to 128.7 the gram beyond, all the other are all with embodiment 5.
Method: with embodiment 5.
Product weight:
Thick product: 416 grams
Distillment: 242 grams
Filter the back product composition:
Calcium: 14.5%W/W
Sulphur: 1.0%W/W
CO 2：13.6%W/W
TBN(milligram KOH/ gram): 395
V 100：255cSt
V 40：3100cSt
VI：221
Stearic acid: 30.9%W/W
This example explanation: the product that the stearic acid of adding 30.9%W/W can obtain having high TBN value.
Embodiment 7～13
Materials: it is as shown in the table.
Method:
(a) miscellany that alkylphenol, lubricating oil, calcium chloride, stearic acid and 2-Ethylhexyl Alcohol are constituted is heated to 120 ℃/700mmHg,
(b) when 120 ℃/700mmHg, add lime
(c) when 145 ℃～165 ℃/700mmHg, add ethylene glycol and miscellany kept one hour at 165 ℃/700mmHg,
(d) when 165 ℃/1 crust, add carbonic acid gas,
(e) reclaim solvent at 200 ℃/10mmHg, and
(f) product is filtered.
Product weight: it is as shown in the table.
Filter the back product composition: it is as shown in the table.
This example explanation: adopt " once adding lime " technology to account for all can to prepare in 2.6～29.7% the entire area of enriched material gross weight to have the multifunctional additive for lubricating oils that is higher than the 300TBN value for stearic acid content.
Table
Embodiment 789 10 11 12 13
The stearic acid of product
Content (%W/W) 2.6 7.7 12.9 18.2 18.0 23.0 29.7
Materials amount (gram)
Lubricating oil 131 131 131 131 131 131 131
C 12-alkylphenol 135 115 95 75 75 55 36
Lime 82 82 82 82 82 82 85
Sulphur 23 23 23 23 23 23 15
Stearic acid 10 30 50 70 70 90 113
U-Ramin MC 4444444
(b) add lime 70 grams,
(c) mixture is heated to 165 ℃/700mmHg and adds ethylene glycol 32 gram from 145 ℃,
(d) miscellany was kept 5 minutes when the 165 ℃/700mmHg,
(e) when 165 ℃/1 crust, add carbonic acid gas 44 grams,
(f) miscellany is cooled to 120 ℃ and add lime 60 gram,
(g) miscellany was kept 5 minutes when the 165 ℃/700mmHg,
(h) when 165 ℃/1 crust, add carbonic acid gas 44 grams,
(i) when 200 ℃/10mmHg, pass through the Separation and Recovery solvent, and
(j) product is filtered.
Product weight:
Thick product: 408 grams
Distillment: 245 grams
Filter the back product composition:
Calcium: 16.0%W/W
Sulphur: 2.6%W/W
CO 2：14.6%W/W
TBN：450
V 100：488cSt
Stearic acid: 14.5%W/W
This example explanation: can prepare the multifunctional additive for lubricating oils that has up to 450TBN value and satisfactory viscosity with technology of the present invention.
Embodiment 15
Materials:
C 12-alkylphenol: 64 grams
Lubricating oil (100SN): 111 grams
Sulphur: 20 grams
Stearic acid: 59 grams
Acetate: 2 grams
Ammonium chloride: 3 grams
The only methyl ether of glycol ether: 40 grams
Method:
(a) material is heated to 120 ℃/100mmHg,
(b) add lime 70 grams,
(c) miscellany is heated to 165 ℃/700mmHg from 145 ℃, adds only methyl ether 90 grams of glycol ether simultaneously,
(d) miscellany was kept one hour when the 165 ℃/700mmHg,
(e) add carbonic acid gas 34 grams,
(f) miscellany is cooled to 120 ℃ and add lime 30 gram,
(g) miscellany was kept one hour when the 165 ℃/700mmHg,
(h) add carbonic acid gas 17 grams,
(i) when 200 ℃/10mmHg, pass through the Separation and Recovery solvent, and
(j) product is filtered.
Product weight:
Thick product: 361 grams
Distillment: 146 grams
2-ethylhexanol 112 112 112 112 112 112 112
Ethylene glycol 36 36 36 36 36 36 36
CO 228 28 28 28 40 40 40
Product weight (gram) 389 391 386 385 389 391 382
Distillment (gram) 158 159
Filter the back product
Composition
Calcium (%) 11.2 11.0 11.1 11.2 11.0 11.1 11.1
Sulphur (%) 3.7 3.6 3.4 3.0 3.0 2.7 1.6
CO 2（%） 6.5 6.9 7.1 6.5 8.2 10.8 10.2
TBN 314 310 311 310 308 312 302
V 100（cSt） 286 190 163 160 109 128 84
Embodiment 14
Materials:
C 12-alkylphenol: 64 grams
Lubricating oil (100SN): 111 grams
Sulphur: 20 grams
Stearic acid: 59 grams
Calcium chloride: 4 grams
2-Ethylhexyl Alcohol: 190 grams
Method:
(a) material is heated to 120 ℃/700mmHg,
Filter the back product composition:
Calcium: 14.1%W/W
Sulphur: 2.7%W/W
CO 2：12.4%W/W
TBN：394
V 100：164cSt
Stearic acid: 16.3%W/W
The explanation of this example: in the technology of the present invention, the only methyl ether of glycol ether can be used as component (c) and ammonium chloride is used as catalyzer.
Embodiment 16
Materials:
C 12-alkylphenol: 64 grams
Lubricating oil (100SN): 73 grams
C 13-straight chain alpha alkene: 38 grams
Sulphur: 23 grams
Stearic acid: 59 grams
Calcium chloride: 3 grams
2-Ethylhexyl Alcohol: 190 grams
Method: except spent glycol in step (c) (31 gram) replaces the only methyl ether of a diethyl acetal (90 gram) and step (d) and (g) time of keeping when the 165 ℃/700mmHg of middle miscellany became 10 minutes by one hour, other are all with embodiment 15.
Product weight:
Thick product: 373 grams
Distillment: 239 grams
Filter the back product composition:
Calcium: 14.4%W/W
Sulphur: 2.3%W/W
CO 2：13.3%W/W
TBN：405
V 100：460CSt
Stearic acid: 15.8%W/W
The explanation of this example: long carbochain alhpa olefin can be combined in reaction.
Embodiment 17
Materials: polyisobutene (38 gram) replaced C that has 500 Mn except employing 18In addition, all the other are all with embodiment 16 for-α alkene (38 gram).
Method: with embodiment 16.
Product weight:
Crude product: 363 grams
Distillment: 246 grams
Cross the filtered product composition:
Calcium: 14.3%W/W
Sulphur: 2.8%W/W
CO 2：13.8%W/W
TBN：406
V 100：697cSt
V 40：26，600cSt
VI：175
Stearic acid: 16.3%W/W
This example explanation polyisobutene can be by reaction bonded.
Embodiment 18
Materials:
C 12-alkylphenol: 55.2 grams
Lubricating oil (100SN): 131 grams
Sulphur: 23 grams
Calcium chloride: 4 grams
Tallow fatty acid: 89.8 grams
2-Ethylhexyl Alcohol: 112 grams
Method: except that omit step (f), (g) and (h), i.e. employing " the disposable lime that adds " technology, all the other are all with embodiment 5.
Product weight:
Thick product: 396 grams
Distillment: 151 grams
Filter the back product composition:
Calcium: 10.8%W/W
Sulphur: 3.1%W/W
CO 2：11.3%W/W
TBN：305
V 100：388cSt
V 40：20，000cSt
VI：101
Carboxylic acid: 22.7%W/W
This routine explanation can adopt tallow fatty acid to obtain the concentrated additive of high TBN value.
The contrast experiment
Materials:
C 12-alkylphenol: 75 grams
Lubricating oil (100SN): 131 grams
Sulphur: 23 grams
Calcium chloride: 4 grams
Acetate: 15 grams
2-Ethylhexyl Alcohol: 112 grams
Method: step (a)～(d) is with embodiment 5.After this miscellany becomes the heavy-gravity non-uniform material.It is invalid to stir, along with the cooling miscellany becomes gel.The stopping of reaction.
This description of test can not be acetate as the used carboxylic acid of technology of the present invention.
Embodiment 19
Materials:
C 12-alkylphenol: 135 grams
Lubricating oil (100SN): 131 grams
Lime: 82 grams
Sulphur: 23 grams
Stearic acid: 10 grams
Calcium chloride: 4 grams
Method:
(a) material is heated to 145 ℃/700mmHg and add isooctyl alcohol 112 gram,
(b) miscellany is heated to 165 ℃/700mmHg and adds ethylene glycol 36 gram from 145 ℃,
(c) miscellany was kept one hour in 165 ℃/700mmHg,
(d) add carbonic acid gas 28 grams at 165 ℃/1 crust,
(e) when 210 ℃/1 crust, pass through the Separation and Recovery solvent, and
(f) product is filtered.
Product weight:
Thick product: 380 grams
Distillment: 144 grams
Filter the back product composition:
Calcium: 10.8%W/W
Sulphur: 3.6%W/W
CO 2：6.0%W/W
TBN：301
V 100：216cSt
Stearic acid: 2.6%W/W

Claims (30)

1, a kind ofly be suitable for mixing the into multifunctional additive for lubricating oils of finished lube composition, this multifunctional additive for lubricating oils comprises:
(a) lubricating oil,
(b) the alkyl phenates of calcium, magnesium and the barium of a kind of sulfuration that dissolves in lubricating oil or unvulcanised, this phenates are to mix into more than 2% by reaction, and one of following material of (based on the enriched material gross weight) below 40% is improved:
(i) at least a carboxylic acid with structure formula I,
Figure 87108239_IMG2
Wherein R is C 10-C 24Alkyl or alkenyl and R 1Be H or C 1-C 4Alkyl or-CH 2-COOH, or acid anhydride or ester that should acid,
The binary or polyprotonic acid or its acid anhydride or the ester that (ii) contain 36～100 carbon atoms,
The TBN value of this enriched material is greater than 300, and the viscosity under 100 ℃ is less than 1000cSt.
2, according to the multifunctional additive for lubricating oils of claim 1, wherein the amount of lubricating oil accounts for 10～90% of composition weight.
3, according to the multifunctional additive for lubricating oils of claim 1 or 2, alkyl phenates wherein is a calcium alkyl phenates.
4, according to the multifunctional additive for lubricating oils of above-mentioned each claim, alkyl phenates wherein is a sulfurized alkyl phenates.
5, according to the multifunctional additive for lubricating oils of above-mentioned each claim, the alkyl phenol moieties in wherein oil-soluble alkyl phenates is derived by at least a alkylphenol, and the alkyl of alkylphenol contains 9～28 carbon atoms.
6, according to the multifunctional additive for lubricating oils of claim 5, wherein the alkyl phenol moieties is to make phenol alkylation gained C by the propylene tetramer 12-alkylphenol deutero-.
7, according to the multifunctional additive for lubricating oils of claim 6, wherein R is C in the carboxylic acid of structure formula I 10-C 24Straight chained alkyl and R 1Be H.
8, according to any one multifunctional additive for lubricating oils in the claim 1～6, wherein mix the mixture of the carboxylic acid that into has the structure formula I, this mixture is a series of business level acid, comprise saturated and unsaturation sour.
9, according to each multifunctional additive for lubricating oils in the claim 1～6, wherein mix into stearic acid.
10, according to each multifunctional additive for lubricating oils in the claim 1～6, wherein mix the binary or polycarboxylic acid or its acid anhydride that into have 36～100 carbon atoms.
11, according to the multifunctional additive for lubricating oils of claim 10, wherein be mixed with polyisobutylene succinic acid or polyisobutylene succinic anhydride.
12, according to the multifunctional additive for lubricating oils of above-mentioned each claim, wherein mix (ⅰ) of component (b) into or amount (ⅱ) and be enriched material weight greater than 10%～35%(weight).
13, according to the multifunctional additive for lubricating oils of claim 12, wherein mix into (ⅰ) or 12～20%(weight that amount (ⅱ) is enriched material weight of component (b)).
14, according to the multifunctional additive for lubricating oils of above-mentioned each claim, wherein the TBN value of enriched material is greater than 350.
15, according to the multifunctional additive for lubricating oils of claim 13, wherein the TBN value of enriched material is greater than 400.
16, according to the multifunctional additive for lubricating oils of above-mentioned each claim, wherein 100 ℃ of following viscosity less than 500cSt.
17, a kind ofly be suitable for mixing the into multifunctional additive for lubricating oils of finished lube, this enriched material can be at high temperature exists in catalyzer and down following material is reacted and obtain:
(A) (ⅰ) alkyl phenol or (ⅱ) alkyl phenol and sulphur,
(B) calcium, magnesium or barium alkali not only can once join in the initial reaction agent entirely but also can partly be added in the initial reaction agent in reaction, and the remainder one or many is added in follow-up phase.
(C) C 2-C 4Polyvalent alcohol, two or three (C 2-C 4) glycol, aklylene glycol alkyl oxide or polyalkylene glycol alkyl oxide,
(D) lubricating oil,
(E) carbonic acid gas, with the each adding back of (B) component add and
(F) present in an amount at least sufficient to reach enriched material weight more than 2%, below 40%
(ⅰ) have carboxylic acid or its acid anhydride or the ester of structure formula I, or
(ⅱ) contain binary or polycarboxylic acid or its acid anhydride or the ester of 36～100 carbon atoms
Component (A) will make the TBN value of enriched material greater than 300 to the weight ratio of (F).
18, according to the preparation method of each multifunctional additive for lubricating oils in the claim 1～16, this method comprises at high temperature reacts following material:
(A) (ⅰ) alkyl phenol or (ⅱ) alkyl phenol and sulphur,
(B) calcium, magnesium or barium alkali not only can once join in the initial reaction agent entirely but also can partly be added in the initial reaction agent in reaction, and the remainder one or many is added in follow-up phase,
(C) C 2-C 4Polyvalent alcohol, two or three (C 2-C 4) glycol, aklylene glycol alkyl oxide or polyalkylene glycol alkyl oxide,
(D) lubricating oil
(E) carbonic acid gas, with the each adding back of (B) component add and
(F) present in an amount at least sufficient to reach enriched material weight more than 2%, below 40%
(ⅰ) have carboxylic acid or its acid anhydride or the ester of structure side's (I), or
(ⅱ) contain binary or polycarboxylic acid or its acid anhydride or the ester of 36～100 carbon atoms
Component (A) will make the TNB value of enriched material greater than 300 to the weight ratio of (F).
19, according to the method for claim 18, wherein component (B) is a lime.
20, according to the method for claim 18 or 19, wherein component (B) is 0.4～10 to the weight ratio of component (A).
21, according to each method in the claim 18～20, wherein component (C) is an ethylene glycol.
22, according to each method in the claim 18～20, wherein component (C) is the only methyl ether of glycol ether.
23, according to each method in the claim 18～22, wherein carbonic acid gas (component (E)) with twice or repeatedly add each interpolation of component (B) after add.
24, according to each method of claim 18～23, wherein there is thinner.
25, according to each method in the claim 18～24, wherein catalyzer is an inorganic halides.
26, according to the method for claim 25, the halogenation of wherein said inorganic halides catalyzer partly is a chlorine.
27, according to each method among the claim 18-26, wherein catalyzer is a calcium chloride.
28, finished lube composition is comprising lubricating oil and present in an amount at least sufficient to make TBN to reach 0.5～120 the described multifunctional additive for lubricating oils of claim 1-16.
29, according to the finished lube composition of claim 28, wherein lubricating oil is that marine lubricant and having presents in an amount at least sufficient to make TBN to reach 9～100 multifunctional additive for lubricating oils to exist.
30, according to the finished lube composition of claim 28, wherein lubricating oil is that motor car engine is with lubricating oil and have and present in an amount at least sufficient to make TBN to reach 4～20 multifunctional additive for lubricating oils to exist.
CN87108239A 1986-11-29 1987-11-29 Alkaline earth metal hydrocarbyl phenates, their sulphurised derivates, their production and use thereof Expired CN1015642B (en)

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EP0273588B2 (en) 2001-03-28
ES2051752T3 (en) 1994-07-01
NO176147C (en) 1995-02-08
SG101192G (en) 1992-12-04
KR890700159A (en) 1989-03-10
CA1305697C (en) 1992-07-28
FI883502A0 (en) 1988-07-25
DE3781126D1 (en) 1992-09-17
AU608792B2 (en) 1991-04-18
DK419888A (en) 1988-07-27
ZA878939B (en) 1989-07-26
CN87108239A (en) 1988-06-15
NO176147B (en) 1994-10-31
JPH01501399A (en) 1989-05-18
KR890700158A (en) 1989-03-10
JPH01501400A (en) 1989-05-18
DK419788A (en) 1988-07-27
DE3781126T2 (en) 1993-03-04
BR8707551A (en) 1989-03-14
AU8237287A (en) 1988-06-16
ATE79396T1 (en) 1992-08-15
WO1988003945A1 (en) 1988-06-02
FI883503A0 (en) 1988-07-25
FI93653B (en) 1995-01-31
GB8628609D0 (en) 1987-01-07
EP0271262B1 (en) 1992-08-12
JPH0631384B2 (en) 1994-04-27
FI93654C (en) 1995-05-10
FI93654B (en) 1995-01-31
NO883349D0 (en) 1988-07-28
KR960010992B1 (en) 1996-08-14
CN87108344A (en) 1988-06-22
IN169547B (en) 1991-11-09
DK419888D0 (en) 1988-07-27
CA1305696C (en) 1992-07-28
WO1988003944A1 (en) 1988-06-02
AU8238087A (en) 1988-06-16
NO883349L (en) 1988-09-22
JPH0631383B2 (en) 1994-04-27
NO883348D0 (en) 1988-07-28
EP0271262A1 (en) 1988-06-15
FI883503A (en) 1988-07-25
DE3781118D1 (en) 1992-09-17
MX169106B (en) 1993-06-22
DE3781118T2 (en) 1992-12-17
DK419788D0 (en) 1988-07-27
BR8707550A (en) 1989-03-14
ES2051751T3 (en) 1994-07-01
EP0273588B1 (en) 1992-08-12
FI93653C (en) 1995-05-10
AU609075B2 (en) 1991-04-26
GR3006112T3 (en) 1993-06-21
NO302763B1 (en) 1998-04-20
GR3006075T3 (en) 1993-06-21
FI883502A (en) 1988-07-25
KR960010991B1 (en) 1996-08-14
IN172581B (en) 1993-10-16
EP0273588A1 (en) 1988-07-06
ZA878938B (en) 1989-07-26
EP0271262B2 (en) 2002-05-29
CN1012074B (en) 1991-03-20
MX169105B (en) 1993-06-22
DE3781126T3 (en) 2001-08-02
ATE79395T1 (en) 1992-08-15
DK175287B1 (en) 2004-08-09

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