EP0460309B2 - Modifizierte Lösungsmittelzusammensetzungen - Google Patents

Modifizierte Lösungsmittelzusammensetzungen Download PDF

Info

Publication number
EP0460309B2
EP0460309B2 EP90306128A EP90306128A EP0460309B2 EP 0460309 B2 EP0460309 B2 EP 0460309B2 EP 90306128 A EP90306128 A EP 90306128A EP 90306128 A EP90306128 A EP 90306128A EP 0460309 B2 EP0460309 B2 EP 0460309B2
Authority
EP
European Patent Office
Prior art keywords
dispersant
acylating agent
reaction
boron
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90306128A
Other languages
English (en)
French (fr)
Other versions
EP0460309A1 (de
EP0460309B1 (de
Inventor
Roger Scattergood
Mark Rees
Helen Theresa Ryan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Afton Chemical Ltd
Original Assignee
Afton Chemical Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=8205447&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0460309(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Afton Chemical Ltd filed Critical Afton Chemical Ltd
Priority to DE69021872T priority Critical patent/DE69021872T3/de
Priority to EP90306128A priority patent/EP0460309B2/de
Priority to ZA914157A priority patent/ZA914157B/xx
Priority to AU78134/91A priority patent/AU645809B2/en
Priority to JP3159919A priority patent/JP2966586B2/ja
Priority to CA002043998A priority patent/CA2043998C/en
Publication of EP0460309A1 publication Critical patent/EP0460309A1/de
Publication of EP0460309B1 publication Critical patent/EP0460309B1/de
Publication of EP0460309B2 publication Critical patent/EP0460309B2/de
Application granted granted Critical
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C10M133/56—Amides; Imides
    • 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
    • C10M159/16—Reaction products obtained by Mannich reactions

Definitions

  • This invention relates to novel modified ashless dispersants, to processes for their production, and to their use in liquid hydrocarbonaceous media.
  • ashless is used in the normal art-recognized sense of denoting that the composition is devoid of metals such as alkali or alkaline earth metals, zinc or other metals that tend to produce metal-containing residues.
  • boron is not deemed a metal as the compositions of this invention do contain boron.
  • a continuing problem in the art of lubrication is to provide lubricant compositions which satisfy the demands imposed upon them by the original equipment manufacturers.
  • One such requirement is that the lubricant not contribute to premature deterioration of seals, clutch face plates or other parts made from fluoroelastomers.
  • basic nitrogen-containing dispersants such as succinimide dispersants commonly used in oils tend to exhibit a strong adverse effect upon fluoroelastomers, by causing them to lose their flexibility and tensile strength, to become embrittled, and in severe cases, to disintegrate.
  • European Patent Application 0 136 185 discloses a process for boronation of hydrocarbyl-substituted succinimide dispersants.
  • the products of this process are said to be compatible with fluoroelastomers. Boronation increases the viscosity of the dispersant adversely effecting handlability.
  • US 4,686,054 discloses a process for making a diimide dispersant with a fixed mole ratio of 2.3 to 3.0 moles of anhydride per mole of polyamine by reacting in sequence a polyalkenyl succinic anhydride, an alkylene polyamine and a dicarboxylic acid anhydride.
  • an oil soluble dispersant composition formed by reacting a basic nitrogen-containing ashless dispersant (i) with at least one dibasic acylating agent containing up to 6, and preferably 4, carbon atoms, and (ii) with at least one boron compound, said reactions (i) and (ii) being conducted concurrently or sequentially in any order such that the initial ashless dispersant is chemically modified via acylation in (i) and by boronation in (ii).
  • This dispersant composition has good compatibility with fluoroelastomers. It also has good handlability arising from lower viscosity compared to corresponding products produced by boronation alone.
  • any boron compound or compounds can be used provided it is or they are capable of reacting with the basic nitrogen-containing ashless dispersant to introduce boron moieties into the dispersant, it is preferred to conduct the boronation in (ii) using at least one boron acid or ester or anhydride thereof, or any combination thereof.
  • the preferred acylating agents used in the reaction identified as (i) above are maleic anhydride, maleic acid, fumaric acid, malic acid or any combination of any two, any three or all four of these compounds.
  • Ashless dispersants utilised in the foregoing processing include hydrocarbyl succinimides, hydrocarbyl succinamides, mixed ester/amides of hydrocarbyl-substituted succinic acids, Mannich condensation products of hydrocarbyl-substituted phenols, formaldehyde and polyamines, and amine dispersants formed by reacting high molecular weight aliphatic or alicyclic halides with amines, such as polyalkylene polyamines. Mixtures of such dispersants can also be used.
  • Such basic nitrogen-containing ashless dispersants are well known lubricating oil additives, and methods for their preparation are extensively described in the patent literature.
  • hydrocarbyl-substituted succinimides and succinamides and methods for their preparation are described, for example, in U.S. Pat. Nos. 3,018,247; 3,018,250; 3,018,291; 3,172,892; 3,185,704; 3,219,666; 3,272,746; 3,361,673; and 4,234,435.
  • Mixed ester-amides of hydrocarbyl-substituted succinic acid using alkanols, amines, and/or aminoalkanols are described, for example, in U.S. Pat. Nos.
  • Mannich dispersants which are condensation products of hydrocarbyl-substituted phenols, formaldehyde and polyamines are described, for example, in U.S. Pat. Nos. 3,368,972; 3,413,347; 3,539,633; 3,697,574; 3,725,277; 3,725,480; 3,726,882; 3,798,247; and 3,803,039.
  • Amine dispersants and methods for their production from high molecular weight aliphatic or alicyclic halides and amines are described, for example, in U.S. Pat. Nos. 3,275,554; 3,438,757; 3,454,555; and 3,565,804.
  • the preferred ashless dispersants are hydrocarbyl succinimides in which the hydrocarbyl substituent is a hydrogenated or unhydrogenated polyolefin group and preferably a polyisobutene group having a number average molecular weight (as measured by gel permeation chromatography) of from 250 to 10,000, and more preferably from 500 to 5,000, and most preferably from 750 to 2,500.
  • the ashless dispersant is most preferably an alkenyl succinimide such as is available commercially from Ethyl Petroleum Additives, Inc. and Ethyl Petroleum Additives, Ltd. as HITEC® 644 and HITEC® 646 additives.
  • Another embodiment of this invention is the provision of a dispersant prepared as above having the ability when formulated in a finished engine lubricating oil of satisfying the requirements of the ASTM sequence VE engine tests for API "SG" performance (see ASTM 315 H, part III Seq. VE), and the requirements of the Volkswagen P.VW 3334 Elastomer Compatibility Test and/or the requirements of the CCMC Oil-Elastomer Compatibility Test (CEC L-39-T-87) and/or the fluoroelastomer seal test in accordance with the TO-3 Caterpillar Specification.
  • Another embodiment of this invention involves the provision of lubricating oil additive concentrates containing an effective amount of an improved dispersant composition of this invention.
  • Still another embodiment of this invention is an oil of lubricating viscosity containing an effective amount of an improved dispersant composition of this invention.
  • Still further embodiments of this invention are processes for producing the improved dispersant compositions of this invention.
  • One such embodiment comprises reacting a basic nitrogen-containing ashless dispersant with at least one dibasic acylating agent containing up to 6, and preferably 4, carbon atoms, and with at least one boron compound, said reactions being conducted concurrently or sequentially in any order such that the initial ashless dispersant is chemically modified via acylation and by boronation.
  • Another such embodiment of this invention comprises reacting a boronated basic nitrogen-containing ashless dispersant with at least one dibasic acylating agent containing up to 6, and preferably 4, carbon atoms, such that the resultant boronated ashless dispersant is chemically modified via acylation.
  • Another such embodiment of this invention comprises reacting an ashless dispersant which has been acylated with at least one dibasic acylating agent containing up to 6, and preferably 4, carbon atoms, with at least one boron compound, such that the resultant acylated ashless dispersant is chemically modified via boronation.
  • the process of this invention can be applied to any basic nitrogen-containing ashless dispersant susceptible to acylation and boronation.
  • the process can be applied to any of the basic nitrogen-containing dispersants referred to hereinabove.
  • the preferred basic nitrogen-containing dispersants utilized in the practise of this invention are the hydrocarbyl succinimides.
  • succinimide is meant to encompass the completed reaction product from reaction between a hydrocarbyl substituted succinic acylating agent and a polyamine and is intended to encompass compounds wherein the product may have amide, amidine, and/or salt linkages in addition to the imide linkage of the type that results from the reaction of a primary amino group and an anhydride moiety.
  • succinimides most preferred are those formed by use as one of the reactants of at least one aliphatic hydrocarbyl substituted succinic acylating agent in which the hydrocarbyl substituent contains an average of at least 40 carbon atoms.
  • a preferred category of such acylating agents is comprised of at least one hydrocarbyl substituted succinic acylating agent in which the substituent is principally alkyl, alkenyl, or polyethylenically unsaturated alkenyl, or any combination thereof and wherein such substituent has an average of from 50 to 5000 carbon atoms.
  • acylating agent is (a) at least one polyisobutenyl substituted succinic acid or (b) at least one polyisobutenyl substituted succinic anhydride or (c) a combination of at least one polyisobutenyl substituted succinic acid and at least one polyisobutenyl substituted succinic anhydride in which the polyisobutenyl substituent in (a), (b) or (c) is derived from polyisobutene having a number average molecular weight in the range of 700 to 5,000.
  • the substituted succinic acylating agents are those which can be characterised by the presence within their structure of two groups or moieties.
  • the first group or moiety is a substituent group derived from a polyalkene.
  • the polyalkene from which the substituted groups are derived is characterized by an M n (number average molecular weight) value of from about 500 to about 10,000, and preferably in the range of from about 700 to about 5,000.
  • the second group or moiety is the succinic group, a group characterised by the structure wherein X and X' are the same or different provided at least one of X and X' is such that the substituted succinic acylating agent can function as a carboxylic acylating agent.
  • at least one of X and X' must be such that the substituted acylating agent can esterify alcohols, form amides or amine salts with ammonia or amines, form metal salts with reactive metals or basically reacting metal compounds, and otherwise functions as a conventional carboxylic acid acylating agent.
  • Transesterification and transamidation reactions are considered, for purposes of this invention, as conventional acylation reactions.
  • X and/or X' is usually -OH, -O-hydrocarbyl; -O - M + where M + represents one equivalent of a metal, ammonium or amine cation, -NH 2 , -Cl, -Br, and together, X and X' can be -O- so as to form the anhydride.
  • M + represents one equivalent of a metal, ammonium or amine cation, -NH 2 , -Cl, -Br, and together, X and X' can be -O- so as to form the anhydride.
  • the specific identity of any X or X' group which is not one of the above is not critical so long as its presence does not prevent the remaining group from entering into acylation reactions.
  • X and X' are each such that both carboxyl functions of the succinic group can enter into acylation reactions.
  • One of the unsatisfied valences in the grouping of Formula I forms a carbon-to-carbon bond with a carbon atom in the substituent group. While other such unsatisfied valence may be satisfied by a similar bond with the same or different substituent group, all but the said one such valence is usually satisfied by a hydrogen atom.
  • substituted succinic acylating agents wherein the succinic groups are the same or different is within ordinary skill of the art and can be accomplished through conventional procedures such as treating the substituted succinic acylating agents themselves (for example, hydrolysing the anhydride to the free acid or converting the free acid to an acid chloride with thionyl chloride) and/or selecting the appropriate maleic or fumaric reactants.
  • the polyalkenes from which the substituent groups are derived are homopolymers and interpolymers of polymerisable olefin monomers of 2 to about 16 carbon atoms; usually 2 to about 6 carbon atoms.
  • the interpolymers are those in which two or more olefin monomers are interpolymerised according to well-known conventional procedures to form polyalkenes having units within their structure derived from each of said two or more olefin monomers.
  • the polymers used include binary copolymers, terpolymers, tetrapolymers, and the like.
  • the polyalkenes from which the substituent groups are derived are often referred to as polyolefin(s).
  • mono-olefinic monomers such as ethylene, propylene, 1-butene, isobutene, and 1-octene or polyolefinic monomers (usually diolefinic monomers) such as 1,3-butadiene and isoprene.
  • polymerisable internal olefin monomers characterised by the presence within their structure of the group can also be used to form the polyalkenes.
  • internal olefin monomers When internal olefin monomers are employed, they normally will be employed with terminal olefins to produce polyalkenes which are interpolymers.
  • a particular polymerisable olefin monomer can be classified as both a terminal olefin and an internal olefin, it is usually categorised as a terminal olefin.
  • An example of such a monomer is 1,3-pentadiene (i.e., piperylene).
  • polyalkenes from which the substituent groups of the succinic acylating agents are derived generally are hydrocarbon polyalkenes, they can contain non-hydrocarbon groups such as lower alkoxy, lower alkyl mercapto, hydroxy, mercapto, oxo, nitro, halo, cyano, carboalkoxy (i.e., where "alkyl” is usually lower alkyl, namely an alkyl group containing up to about 7 carbon atoms), alkanoyloxy (or carbalkoxy, i.e., where "alkyl” is usually lower alkyl), and the like, provided the non-hydrocarbon substituents do not substantially interfere with formation of the substituted succinic acid acylating agents.
  • non-hydrocarbon groups such as lower alkoxy, lower alkyl mercapto, hydroxy, mercapto, oxo, nitro, halo, cyano, carboalkoxy (i.e., where "alky
  • non-hydrocarbon groups normally will not contribute more than about 10% by weight of the total weight of the polyalkenes. Since the polyalkene can contain such non-hydrocarbon substituents, it is apparent that the olefin monomers from which the polyalkenes are made can also contain such substituents. Normally, however, as a matter of practicality and expense, the olefin monomers and the polyalkenes used are free from non-hydrocarbon groups, except chloro groups which usually facilitate the formation of the substituted succinic acylating agents.
  • the polyalkenes may include aromatic groups (especially phenyl groups and lower alkyl- and-/or lower alkoxy-substituted phenyl groups such as p-tert-butylphenyl) and cycloaliphatic groups such as would be obtained from polymerisable cyclic olefins or cycloaliphatic substituted-polymerisable acyclic olefins, the polyalkenes usually will be free from such groups. Nevertheless, polyalkenes derived from interpolymers of both 1,3-dienes and styrenes such as 1,3-butadiene and styrene or 4-tert-butyl-styrene are exceptions to this generalisation. Similarly, the olefin monomers from which the polyalkenes are prepared can contain both aromatic and cycloaliphatic groups.
  • aliphatic hydrocarbon polyalkenes free from aromatic and cycloaliphatic groups are preferred for use in preparing the substituted succinic acylating agents.
  • Particularly preferred are polyalkenes which are derived from homopolymers and interpolymers of terminal hydrocarbon olefins of 2 to about 8 carbon atoms, most especially from 2 to 4 carbon atoms. While interpolymers of terminal olefins are usually preferred, interpolymers optionally containing up to about 40% of polymer units derived from internal olefins of up to about 8 carbon atoms are also preferred.
  • the most preferred polyalkenes are polypropylenes and polyisobutenes.
  • terminal and internal olefin monomers which can be used to prepare the polyalkenes according to conventional, well-known polymerisation techniques include ethylene; propylene; 1-butene; 2-butene; isobutene; 1-pentene; 1-hexene; 1-heptene, 1-octene; 1-nonene; 1-decene; 4-methyl-1-pentene; propylenetetramer; diisobutylene; isobutylene trimer; 1,2-butadiene; 1,3-butadiene; 1,2-pentadiene; 1,3-pentadiene; 1,4-pentadiene; isoprene; 1,5-hexadiene; 2-chloro-1,3-butadiene; 2-methyl-1-heptene; 4-cyclohexyl-1-butene; 3-pentene; 4-octene; 3,3-dimethyl-1-pentene; styrene; 2,4-dichlorostyren
  • polyalkenes include polypropylenes, polybutenes, ethylene-propylene copolymers, styrene-isobutene copolymers, isobutene-1,3-butadiene copolymers, propene-isoprene copolymers, isobutene-chloroprene copolymers, isobutene-4-methylstyrene copolymers, copolymers of 1-hexene with 1,3-hexadiene, copolymers of 1-octene with 1-hexene, copolymers of 1-heptene with 1-pentene, copolymers of 3-methyl-1-butene with 1-octene, copolymers of 3,3-dimethyl-1-pentene with 1-hexene, and terpolymers of isobutene, styrene and piperylene.
  • interpolymers include copolymer of 95% (by weight) of isobutene with 5% (by weight) of styrene; terpolymer of 98% of isobutene with 1% of piperylene and 1% of chloroprene; terpolymer of 95% of isobutene with 2% of 1-butene and 3% of 1-hexene; terpolymer of 60% of isobutene with 20% of 1-pentene and 20% of 1-octene; copolymer of 80% of 1-hexene and 20% of 1-heptene; terpolymer of 90% of isobutene with 2% of cyclohexene and 8% of propylene; and copolymer of 80% of ethylene and 20% of propylene.
  • Preferred sources of polyalkenes are the polyisobutenes obtained by polymerisation of C 4 refinery streams which contain both n-butene and isobutene in various proportions using a Lewis acid catalyst such as aluminum trichloride or boron tri-fluoride. These polybutenes usually contain predominantly (for example, greater than about 80% of the total repeating units) of repeating units of the configuration
  • conventional techniques known to those skilled in the art include suitably controlling polymerisation temperatures, regulating the amount and type of polymerisation initiator and/or catalyst, employing chain terminating groups in the polymerisation procedure, and the like.
  • Other conventional techniques such as stripping (including vacuum stripping) a very light end and/or oxidatively or mechanically degrading high molecular weight polyalkene to produce lower molecular weight polyalkenes can also be used.
  • maleic or fumaric acidic reactants of the general formula wherein X and X' are as defined hereinbefore.
  • the maleic and fumaric reactants will be one or more compounds corresponding to the formula wherein R and R' are as previously defined herein.
  • the maleic or fumaric reactants will be maleic acid, fumaric acid, maleic anhydride, or a mixture of two or more of these.
  • the maleic reactants are usually preferred over the fumaric reactants because the former are more readily available and are, in general, more readily reacted with the polyalkenes (or derivatives thereof) to prepare the substituted succinic acylating agents.
  • the most preferred reactants are maleic acid, maleic anhydride, and mixtures of these.
  • succinic reactant any of a variety of known procedures can be used to produce the substituted succinic acylating agents.
  • maleic reactant the term is generic to the reactants corresponding to Formulas IV and V above including mixtures of such reactants.
  • One procedure for preparing the substituted succinic acylating agents is illustrated, in part, by the two-step procedure described in U.S. Pat. No. 3,219,666. It involves first chlorinating the polyalkene until there is an average of at least about one chloro group for each molecule of polyalkene. Chlorination involves merely contacting the polyalkene with chlorine gas until the desired amount of chlorine is incorporated into the chlorinated polyalkene. Chlorination is generally carried out at a temperature of about 75°C to about 125°C. If desired, a diluent can be used in the chlorination procedure. Suitable diluents for this purpose include poly- and perchlorinated and/or fluorinated alkanes and benzenes.
  • the second step in the two-step chlorination procedure is to react the chlorinated polyalkene with the maleic reactant at a temperature usually within the range of about 100°C to about 200°C.
  • the mole ratio of chlorinated polyalkene to maleic reactant is usually about 1:1.
  • a mole of chlorinated polyalkene may be regarded as the the weight of chlorinated polyalkene corresponding to the M n value of the unchlorinated polyalkene.
  • a stoichiometric excess of maleic reactant can be used, for example, a mole ratio of 1:2.
  • the ratio of chlorinated polyalkene to maleic reactant may be referred to in terms of equivalents, an equivalent weight of chlorinated polyalkene being the weight corresponding to the M n value divided by the average number of chloro groups per molecule of chlorinated polyalkene.
  • the equivalent weight of a maleic reactant is its molecular weight.
  • the ratio of chlorinated polyalkene to maleic reactant will normally be such as to provided about one equivalent of maleic reactant for each mole of chlorinated polyalkene up to about one equivalent of maleic reactant for each equivalent of chlorinated polyalkene with the understanding that it is normally desirable to provide an excess of maleic reactant; for example, an excess of about 5% to about 25% by weight. Unreacted excess maleic reactant may be stripped from the reaction product, usually under vacuum, or reacted during a further stage of the process as explained below.
  • the resulting polyalkenyl-substituted succinic acylating agent is, optionally, again chlorinated if the desired number of succinic groups are not present in the product. If there is present, at the time of this subsequent chlorination, any excess maleic reactant from the second step, the excess will react as additional chlorine is introduced during the subsequent chlorination. Otherwise, additional maleic reactant is introduced during and/or subsequent to the additional chlorination step. This technique can be repeated until the total number of succinic groups per equivalent weight of substituent groups reaches the desired level.
  • Another procedure for preparing substituted succinic acid acylating agents utilizes a process described in U.S. Pat. No. 3,912,764 and U.K. Pat. No. 1,440,219.
  • the polyalkene and the maleic reactant are first reacted by heating them together in a direct alkylation procedure.
  • chlorine is introduced into the reaction mixture to promote reaction of the remaining unreacted maleic reactants.
  • 0.3 to 2 or more moles of maleic anhydride are used in the reaction for each mole of olefin polymer; i.e., polyalkene.
  • the direct alkylation step is conducted at temperatures of 180°C to 250°C. During the chlorine-introducing stage, a temperature of 160°C to 225°C is employed.
  • the polyalkene is sufficiently fluid at 140°C and above, there is no need to utilize an additional substantially inert, normally liquid solvent/diluent in the one-step process.
  • a solvent/diluent it is preferably one that resists chlorination such as the poly- and per-chlorinated and/or -fluorinated alkanes, cycloalkanes, and benzenes.
  • Chlorine may be introduced continuously or intermittently during the one-step process.
  • the rate of introduction of the chlorine is not critical although, for maximum utilisation of the chlorine, the rate should be about the same as the rate of consumption of chlorine in the course of the reaction.
  • the introduction rate of chlorine exceeds the rate of consumption, chlorine is evolved from the reaction mixture. It is often advantageous to use a closed system, including superatmospheric pressure, in order to prevent loss of chlorine so as to maximize chlorine utilisation.
  • the minimum temperature at which the reaction in the one-step process takes place at a reasonable rate is about 140°C.
  • the minimum temperature at which the process is normally carried out is in the neighborhood of 140°C.
  • the preferred temperature range is usually between about 160°C and about 220°C. Higher temperatures such as 250°C or even higher may be used but usually with little advantage. In fact, excessively high temperatures may be disadvantageous because of the possibility that thermal degradation of either or both of the reactants may occur at excessively high temperatures.
  • the molar ratio of maleic reactant to chlorine is such that there is at least about one mole of chlorine for each mole of maleic reactant to be incorporated into the product. Moreover, for practical reasons, a slight excess, usually in the neighborhood of about 5% to about 30% by weight of chlorine, is utilised in order to offset any loss of chlorine from the reaction mixture. Larger amounts of excess chlorine may be used.
  • the other principal reactant utilized in forming the succinimides which preferably are used in the process of this invention is one or a mixture of polyamines which preferably has at least one primary amino group in the molecule and which additionally contains an average of at least two other amino nitrogen atoms in the molecule.
  • the polyamines should contain at least two primary amino groups in the molecule.
  • One preferred type of polyamines is comprised of alkylene polyamines such as those represented by the formula H 2 N(CH 2 ) n (NH(CH 2 ) n ) m NH 2 wherein n is 2 to about 10 (preferably 2 to 4, more preferably 2 to 3, and most preferably 2) and m is 0 to 10, (preferably 1 to about 6).
  • Illustrative are ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, spermine, pentaethylene hexamine, propylene diamine (1,3-propanediamine), butylene diamine (1,4-butanediamine), hexamethylene diamine (1,6-hexanediamine), decamethylene diamine (1,10-decanediamine), and the like.
  • Preferred for use is tetraethylene pentamine or a mixture of ethylene polyamines which approximates tetraethylene pentamine.
  • Commercially available mixtures of polyethylene polyamines e.g., E-100 and S-1107 available from Dow Chemical Company
  • often contain minor amounts of cyclic species such as aminoalkyl-substituted piperazines and the like.
  • polyamines are comprised of hydrocarbyl polyamines containing from 10 to 50 weight percent acyclic alkylene polyamines and 50 to 90 weight percent cyclic alkylene polyamines.
  • a mixture consisting essentially of polyethylene polyamines, especially a mixture having an overall average composition approximating that of polyethylene pentamine or a mixture having an overall average composition approximating that of polyethylene tetramine.
  • Another useful mixture has an overall average composition approximating that of polyethylene hexamine.
  • polyalkylene and polyethylene when utilized in conjunction with such terms as “polyamine”, “tetramine”, “pentamine”, “hexamine”, etc., denote that some of the adjacent nitrogen atoms in the product mixture are joined by a single alkylene group whereas other adjacent nitrogen atoms in the product mixture are joined by two alkylene groups thereby forming a cyclic configuration, i.e., a substituted piperazinyl structure.
  • the " - " (whether horizontal or vertical) represents an alkylene group each of which contains up to 6 carbon atoms, preferably from 2 to 4 carbon atoms, and most preferably is the ethylene (dimethylene) group, i.e., the -CH 2 CH 2 - group.
  • aliphatic polyamines containing one or more ether oxygen atoms and/or one or more hydroxyl groups in the molecule. Mixtures of various polyamines of the type referred to above are also suitable.
  • any polyamine having at least one primary amino group and an average of at least three amino nitrogen atoms in the molecule can be used in forming the succinimide utilised in the practise of this invention.
  • Product mixtures known in the trade as "triethylene tetramine”, “tetraethylene pentamine”, and “pentaethylene hexamine” are most preferred.
  • mole ratios of the hydrocarbyl substituted succinic acylating agent to polyamine reactant ranges from about 1 : 1 to about 4 : 1, and preferably from about 1.5 : 1 to about 3 : 1.
  • dibasic acylating agents can be reacted with the basic nitrogen-containing ashless dispersant (e.g., succinimide, Mannich reaction product, succinic acid esteramide, etc.) in the reaction of (i) above.
  • the principal requirement is that such acylating agent contain at most 6 carbon atoms in the molecule.
  • the most preferred acylating agents for use in reaction (i) contain 4 carbon atoms in the molecule.
  • use can be made of dibasic acids and anhydrides, ester and acyl halides thereof which contain a total of up to 6 carbon atoms in the molecule (excluding carbon atoms of an esterifying alcohol).
  • adipic acid succinic acid, lower alkyl-substituted succinic acid, succinic anhydride, lower alkyl-substituted succinic anhydride, glutaric acid, and like dibasic acids, anhydrides, acyl halides, and esters which contain (excluding carbon atoms of esterifying alcohols) up to 6 carbon atoms in the molecule.
  • Preferred are maleic acid, maleic anhydride, fumaric acid and malic acid. Most preferred is maleic anhydride.
  • the other reactant(s) with which the basic nitrogen-containing dispersant is reacted either before, during or subsequent to reaction with the above dibasic acylating agent is a boron compound or mixture of boron compounds capable of introducing boron-containing species into the ashless dispersant undergoing such reaction.
  • Any boron compound, organic or inorganic, capable of undergoing such reaction can thus be used. Accordingly, use can be made of such inorganic boron compounds as the boron acids, and the boron oxides, including their hydrates.
  • Typical organic boron compounds include esters of boron acids, such as the orthoborate esters, metaborate esters, biborate esters, pyroboric acid esters, and the like.
  • boron acids such as boric acid, boronic acid, tetraboric acid, metaboric acid, pyroboric acid
  • esters of such acids such as mono-, di- and tri-organic esters with alcohols having 1 to 20 carbon atoms, e.g., methanol, ethanol, propanol, isopropanol, the butanols, the pentanols, the hexanols, the octanols, the decanols, ethylene glycol, propylene glycol and the like
  • boron oxides such as boron oxide and boron oxide hydrate.
  • the preferred boron reactant is boric acid, sometimes referred to as orthoboric acid.
  • boric acid sometimes referred to as orthoboric acid.
  • alkyl boranes alkyl boroxines, diborane and diborane-amine addition complexes, and many other reactive boron compounds.
  • any temperature at which the desired reaction(s) occur at a satisfactory reaction rate can be used.
  • the acylation reaction between the basic nitrogen-containing dispersant (boronated or unboronated) and the dibasic acylating agent is conducted at temperatures in the range of 80 to 200°C, more preferably 140 to 180°C.
  • the boronation reaction is likewise normally performed at temperatures within either of the foregoing ranges. However, departures from these ranges can be made whenever deemed necessary or desirable.
  • These reactions may be conducted in the presence or absence of an ancillary diluent or liquid reaction medium, such as a mineral lubricating oil solvent.
  • Suitable solvent oils include lubricating oils having a viscosity (ASTM D 445) of 2 to 40, preferably 3 to 12 centistokes (cSt) at 100°C, with the primarily paraffinic mineral oils such as Solvent 100 Neutral being particularly preferred.
  • Other types of lubricating oil base stocks can be used, such as synthetic lubricants including polyesters, poly- ⁇ -olefins, and the like. Blends of mineral oil and synthetic lubricating oils are also suitable for various applications in accordance with this invention.
  • the dibasic acylating agent is employed in amounts ranging from about 0.01 to about 0.5 moles per average equivalent of nitrogen in the initial ashless dispersant(s), with the proviso that the resultant product contains at least 0.05 equivalent of basic nitrogen.
  • the amount of dibasic acylating agent employed ranges from about 0.02 to about 0.3 moles per average equivalent of nitrogen in the initial ashless dispersant with the proviso that the resultant product contains at 0.1 equivalent of basic nitrogen.
  • a succinimide as the initial ashless dispersant, it is preferred to utilise an amount of the dibasic acylating agent such that the total mole ratio of (a) dibasic acylating agent plus (b) the aliphatic hydrocarbyl substituted succinic acylating agent used in forming the initial succinimide falls in the range of from 1.5 to 3.5 moles of (a) and (b) per mole of polyamine, more preferably 1.6 to 2.8 moles of (a) and (b) per mole of polyamine, and most preferably 1.6 to 2.2 moles of (a) and (b) per mole of polyamine.
  • departures from such proportions may be utilised if found efficacious in any given situation.
  • the amounts used should be sufficient to introduce up to about 5%, and preferably from about 0.05 to about 2.5% of boron (expressed as weight % of elemental boron) into the overall final co-reacted dispersant.
  • the dispersants of this invention are formed by subjecting a basic nitrogen-containing ashless dispersant to two reactions, namely, acylation with at least one dibasic acylating agent and boronation with at least one boronation reagent. Ordinarily these reactions will be conducted either concurrently or in sequence. It is, of course, not necessary that both reactions be conducted in the same plant or at periods of time proximate to each other.
  • boronated basic nitrogen-containing ashless dispersants which are available as articles of commerce need only be subjected to acylation with a dibasic acylating agent of the type described hereinabove in order to produce a novel boronated-acylated ashless dispersant of this invention.
  • acylated basic nitrogen-containing ashless dispersant from a given supplier (i.e., a basic nitrogen-containing ashless dispersant which has been subjected to acylation with a dibasic acylating agent of the type described hereinabove) and subject the same to boronation in order to produce a novel acylated-boronated ashless dispersant of this invention.
  • a suitable acylated basic nitrogen-containing ashless dispersant from a given supplier
  • a basic nitrogen-containing ashless dispersant which has been subjected to acylation with a dibasic acylating agent of the type described hereinabove
  • the novel products of this invention can be produced in accordance with this invention by two or more distinct and separate parties, if desired.
  • Treating agents used for this purpose include, for example, carbon disulphide, hydrogen sulphide, sulphur, sulphur chloride, alkenyl cyanides, mono-, tri-, tetra-, etc.
  • carboxylic acid acylating agents aldehyde, ketones, urea, thiourea, guanidine, dicyanodiamide, hydrocarbyl phosphates, hydrocarbyl phosphites, hydrocarbyl thiophosphates, hydrocarbyl thiophosphites, phosphorus sulphides, phosphorus oxides, phosphoric acid, phosphorous acid, hydrocarbyl thiocyanates, hydrocarbyl isocyanates, hydrocarbyl isothiocyanates, epoxides, episulphides, formaldehyde or formaldehyde producing compounds plus phenols, sulphur plus phenols, and many others.
  • novel compositions of this invention can be used as ashless dispersants in a wide variety of oleaginous fluids and as detergents or deposit reducers in hydrocarbonaceous fuels such as gasoline, diesel fuel, kerosene, burner fuel, gas oil, jet fuel, turbine fuel, and the like. They can be used in lubricating oil and functional fluid compositions, such as automotive crankcase lubricating oils, automatic transmission fluids, gear oils, hydraulic oils, cutting oils, etc.
  • the lubricant may be a mineral oil, a synthetic oil, a natural oil such as a vegetable oil, or a mixture thereof, e.g. a mixture of a mineral oil and a synthetic oil.
  • Suitable mineral oils include those of appropriate viscosity refined from crude oil of any source including Gulf Coast, Midcontinent, Pennsylvania, California, Alaska, Middle East, North Sea and the like. Standard refinery operations may be used in processing the mineral oil.
  • Synthetic oils include both hydrocarbon synthetic oils and synthetic esters.
  • Useful synthetic hydrocarbon oils include liquid ⁇ -olefin polymers of appropriate viscosity.
  • Hydrocarbon oils include liquid ⁇ -olefin polymers of appropriate viscosity.
  • hydrogenated or unhydrogenated liquid oligomers of C 6 -C 16 ⁇ -olefins such as hydrogenated or unhydrogenated ⁇ -decene trimer.
  • Alkyl benzenes of appropriate viscosity, e.g. didodecylbenzene, can also be used.
  • Useful synthetic esters include the esters of monocarboxylic and polycarboxylic acids with monohydroxy alcohols and polyols. Typical examples are didodecyl adipate, trimethylolpropane tripelargonate, pentaerythritol tetracaproate, di-(2-ethylhexyl) adipate, and dilauryl sebacate.
  • Complex esters made from mixtures of mono- and di-carboxylic acids and mono- and/or polyhydric alkanols can also be used.
  • Typical natural oils that may be used include castor oil, olive oil, peanut oil, rapeseed oil, corn oil, sesame oil, cottonseed oil, soybean oil, sunflower oil, safflower oil, hemp oil, linseed oil, tung oil, oiticica oil, jojoba oil, and the like. Such oils may be partially or fully hydrogenated, if desired.
  • Viscosity index improvers may be included in the mineral, synthetic and natural oils (or any blends thereof) in order to achieve the viscosity properties deemed necessary or desirable.
  • the finished lubricating oil compositions and additive concentrates of this invention containing the present ashless dispersant systems will usually also contain other well-known additives in order to partake of their special properties.
  • additives which can be employed in the lubricants and functional fluids and additive concentrates of this invention are those of the types described hereinafter.
  • the lubricants and functional fluids of this invention are of particular utility in applications wherein the oil of lubricating viscosity comes in contact with fluoroelastomers.
  • the compatibility of the lubricant or functional fluid of this invention so utilised is significantly enhanced as compared to the corresponding lubricant or functional fluid containing the corresponding untreated basic nitrogen-containing ashless dispersant.
  • polyisobutenylsuccinic anhydride PIBSA
  • TEPA tetraethylene pentamine
  • MA maleic anhydride
  • boric acid is added to the second stage reaction mixture at a temperature of 150-155°C in an amount corresponding to 4.0 moles per mole of TEPA initially employed.
  • the mixture is heated at 150°C for one hour and then water formed in the third stage reaction is removed by applying a vacuum of 40 mm for one hour.
  • the resulting succinimide is both acylated and boronated and had a nitrogen content of 1.74%, and a boron content of 1.20%.
  • Example 2 The procedure of Example 1 is repeated except that the amount of boric acid is reduced to 3.0 moles per mole of TEPA initially used. The final product, diluted to 1.70% nitrogen content with 100 solvent neutral mineral oil contains 0.82% boron.
  • Example 1 Repetition of Example 1 wherein the amount of boric acid is still further reduced to 2.0 moles per mole of TEPA initially used yields a concentrate (diluted as in Example 1) having a boron content of 0.62%.
  • Example 1 is repeated but using 3.0 moles of boric acid per mole of TEPA initially used.
  • the product concentrate (diluted as in Example 1) contains 0.88% boron.
  • Example 1 The procedure of Example 1 is repeated except that the reaction with boric acid is conducted before the reaction with maleic anhydride and the amount of boric acid used corresponds to 3.0 moles per mole of TEPA used in the first stage reaction.
  • the final product (diluted as in Example 1) contains 0.9% boron.
  • polyisobutenylsuccinic anhydride PIBSA
  • TEPA tetraethylene pentamine
  • MA maleic anhydride
  • boric acid (BA) is added to the second stage reaction product in an amount equivalent to 3.0 moles per mole of TEPA used in the first stage and the resultant mixture is heated at 150-155°C for 2 1/2 hours.
  • the additive concentrate has a nitrogen content of 1.8% and a boron content of 0.90%.
  • Example 7 The procedure of Example 7 is repeated except that in the first stage the PIBSA and TEPA are reacted in a molar ratio of 1.7:1. In the second stage the MA is used in amount equivalent to a mole ratio of 0.4:1 relative to the TEPA used in the first stage. In the third stage, the boric acid (3.0 moles per mole of TEPA used in the first stage reaction) is added in an oil slurry. The product on dilution has a nitrogen content of 1.95% and a boron content of 0.64%.
  • PIBSA polyisobutenylsuccinic anhydride
  • maleic anhydride is added to the first stage reaction product in an amount equivalent to 0.35 mole per mole of TEPA used in the first stage and the resultant mixture is heated at 165-170°C for 1 1/2 hours after which mineral oil is added.
  • boric acid is added to the second stage reaction product in an amount equivalent to 0.4 mole per mole of TEPA used in the first stage and the resultant mixture is heated at 150-155°C for 3 hours.
  • the product has a nitrogen content of 1.85% and a boron content of 0.15%.
  • crankcase lubricating oils for use in internal combustion engines containing various substituted succinimide dispersants were formulated.
  • Each such oil contained, in addition to the succinimide dispersant, conventional amounts of overbased sulphonates, zinc dialkyl dithiophosphate, antioxidant, viscosity index improver, rust inhibitor, and antifoam agent to provide an SAE 15W/40 crankcase lubricant oil.
  • the respective lubricants containing the succinimide dispersants of Examples 1-6 and 9 each contained an amount of such dispersant to provide a nitrogen content of 0.10%. In the case of the lubricants containing the succinimide dispersants of Examples 7 and 8, the nitrogen contents provided by the dispersants were 0.13%.
  • Another feature of this invention is that the combined acylating and boronation reactions, whether run serially in either order or concurrently, can yield products having lower viscosities and consequent improved handleability as compared to corresponding products formed using either acylation or boronation only.
  • a succinimide formed as in the first stage of Example 1 and boronated with boric acid to a level of 1.6% boron (1.8% nitrogen) has a viscosity of approximately 2900 cSt at 100°C.
  • a product formed by reacting PIBSA with TEPA and thereafter reacting the succinimide with maleic anhydride (MA) (mole ratios of PIBSA : TEPA : MA 2.05 : 1 : 1.
  • crankcase lubricant contained a formulation of the type utilised in the Sequence VE Test except that the dispersant was a compound of this invention formed as in Example 7.
  • a crankcase lubricant formulated for diesel engine service and containing 5.8% by weight of a dispersant of this invention formed as in Example 4 gave in the same test procedure a piston merit value of 74.
  • a Petter W-1 Test was conducted using the CEC L-02-A-78 Test Procedure. A bearing weight loss of 5.7 mg was obtained using a crankcase lubricating oil formulation in which the dispersant was produced as in Example 7.
  • crankcase lubricant formulations can be formed utilising the dispersant compositions of this invention.
  • Additive concentrates of this invention generally contain 10 to 95 weight percent of one or more ashless dispersants of this invention, 0 to 90 weight percent liquid diluent and 0 to 90 weight percent of other additives commonly employed in lubricants and functional fluids.
  • the dispersants utilised according to the invention can be incorporated in a wide variety of lubricants. They can be used in lubricating oil compositions, such as automotive crankcase lubricating oils, automatic transmission fluids, or gear oils in effective amounts to provide active ingredient concentrations in finished formulations generally within the range of 0.5 to 10 weight percent, for example, 1 to 9 weight percent, preferably 2 to 8 weight percent, of the total composition.
  • the dispersants are admixed with the lubricating oils as dispersant solution concentrates which usually contain up to about 50 weight percent of the active ingredient additive compound dissolved in mineral oil, preferably a mineral oil having an ASTM D-445 viscosity of 2 to 40, preferably 3 to 12 centistokes at 100°C.
  • the lubricating oil not only can be hydrocarbon oils of lubricating viscosity derived from petroleum but also can be natural oils of suitable viscosities such as rapeseed oil, etc., and synthetic lubricating oils such as hydrogenated polyolefin oils; poly- ⁇ -olefins (e.g., hydrogenated or unhydrogenated ⁇ -olefin oligomers such as hydrogenated poly-1-decene); alkyl esters of dicarboxylic acids; complex esters of dicarboxylic acid, polyglycol and alcohol; alkyl esters of carbonic or phosphoric acids; polysilicones; fluorohydrocarbon oils; and mixtures or lubricating oils and synthetic oils in any proportion.
  • hydrocarbon oils of lubricating viscosity derived from petroleum but also can be natural oils of suitable viscosities such as rapeseed oil, etc., and synthetic lubricating oils such as hydrogenated polyolefin oils; poly- ⁇ -ole
  • lubricating oil for this disclosure includes all the foregoing.
  • the useful dispersant may be conveniently dispersed as a concentrate of 10 to 80 weight percent of mineral oil, e.g., Solvent 100 Neutral oil with or without other additives being present and such concentrates are a further embodiment of this invention.
  • additives which may be included in the lubricants, functional fluids and additive concentrates of this invention include such substances as zinc dialkyl (C 3 -C 10 ), dicycloalkyl (C 5 -C 20 ), and/or diaryl (C 6 -C 20 ) dithiophosphate wear inhibitors, generally present in amounts of about 0.5 to 5 weight percent.
  • Useful detergents include the oil-soluble normal basic or overbased metal, e.g., calcium, magnesium, barium, etc., salts of petroleum naphthenic acids, petroleum sulfonic acids, alkyl benzene sulfonic acids, oil-soluble fatty acids, alkyl salicylic acids, sulphurised or unsulphurised alkyl phenates, and hydrolysed or unhydrolysed phosphosulphurised polyolefins.
  • Gasoline engine crankcase lubricants typically contain, for example, from 0.5 to 5 weight percent of one or more detergent additives.
  • Diesel engine crankcase oils may contain substantially higher levels of detergent additives.
  • Preferred detergents are the calcium and magnesium normal or overbased phenates, sulphurised phenates or sulfonates.
  • Pour point depressants which may be present in amounts of from 0.01 to 1 weight percent in the lubricant or functional fluid include wax alkylated aromatic hydrocarbons, olefin polymers and copolymers, and acrylate and methacrylate polymers and copolymers.
  • Viscosity index improvers the concentrations of which may vary in the lubricants from 0.2 to 15 weight percent, (preferably from about 0.5 to about 5 weight percent) depending on the viscosity grade required, include hydrocarbon polymers grafted with, for example, nitrogen-containing monomers, olefin polymers such as polybutene, ethylene-propylene copolymers, hydrogenated polymers and copolymers and terpolymers of styrene with isoprene and/or butadiene, polymers of alkyl acrylates or alkyl methacrylates, copolymers of alkyl methacrylates with N-vinyl pyrrolidone or dimethylaminoalkyl methacrylate, post-grafted polymers of ethylene-propylene with an active monomer such as maleic anhydride which may be further reacted with an alcohol or an alkylene polyamine, styrene/maleic anhydride polymers post-treated with alcohols and amines
  • Antiwear activity can be provided by about 0.01 to 2 weight percent in the oil of the aforementioned metal dihydrocarbyl dithiophosphates and the corresponding precursor esters, phosphosulphurised pinenes, sulphurised olefins and hydrocarbons, sulphurised fatty esters and alkyl polysulphides.
  • Preferred are the zinc dihydrocarbyl dithiophosphates which are salts of dihydrocarbyl esters of dithiophosphoric acids.
  • additives include effective amounts of friction modifiers or fuel economy additives such as the alkyl phosphonates as disclosed in U.S. 4,356,097, aliphatic hydrocarbyl substituted succinimides as disclosed in EPO 0020037, dimer acid esters, as disclosed in U.S. 4,105,571, oleamide, etc., which are present in the oil in amounts of 0.1 to 5 weight percent.
  • fuel economy additives such as the alkyl phosphonates as disclosed in U.S. 4,356,097, aliphatic hydrocarbyl substituted succinimides as disclosed in EPO 0020037, dimer acid esters, as disclosed in U.S. 4,105,571, oleamide, etc.
  • Glycerol oleates are another example of fuel economy additives and these are usually present in very small amounts, such as 0.05 to 0.2 weight percent based on the weight of the formulated oil.
  • Antioxidants are also usually employed in the additive concentrates and lubricants and functional fluids of this invention.
  • Preferred are hindered phenolic antioxidants, methylene bridged alkylphenols, secondary aromatic amines, sulphurised phenols, alkyl phenothiazines, substituted triazines and ureas, and copper compounds such as copper naphthenate and copper oleate, among others.
  • the oil of lubricating viscosity will contain 0.001 to 2.5 weight percent of antioxidant.
  • component (i) in the foregoing composition is an oil-soluble mixture of said mononuclear monohydric phenols. It is likewise preferred that component (ii) of the foregoing composition be an oil-soluble mixture of said methylene-bridged tertiary alkyl-substituted phenols.
  • an antioxidant composition which comprises a combination of (i) an oil soluble mixture of sterically-hindered tertiary alkylated monohydric phenols, (ii) an oil-soluble mixture of sterically-hindered tertiary alkylated methylene-bridged polyphenols, and (iii) at least one oil-soluble aromatic secondary amine, the proportions of (i), (ii) and (iii) being such that the weight percentage of nitrogen in component (iii) relative to the total weight of components (i), (ii) and (iii) is in the range of 0.05% to 1.5%, preferably in the range of 0.1% to 0.8%, and most preferably in the range of 0.3% to 0.7%, and the weight ratio of monohydric phenols:methylene-bridged polyphenols in the composition is in the range of 15:1 to 1:2, preferably in the range of 10:1 to 1:1, and most preferably in the range of 5:1 to 1:1.
  • Preferred secondary aromatic amines are alkyl diphenylamines containing 1 or 2 alkyl substituents each having up to about 16 carbon atoms, phenyl- ⁇ -naphthylamine, phenyl- ⁇ -naphthylamine, alkyl- or aralkyl-substituted phenyl- ⁇ -naphthylamine containing 1 or 2 alkyl or aralkyl groups each having up to about 16 carbon atoms, alkyl- or aralkyl-substituted phenyl- ⁇ -naphthylamine containing 1 or 2 alkyl or aralkyl groups each having up to about 16 carbon atoms, and similar compounds.
  • Naugalube 438L a material which is understood to be predominantly a 4,4'-dinonyldiphenylamine (i.e., bis(4-nonylphenyl)amine) wherein the nonyl groups are branched.
  • compositions of this invention can be included in the compositions of this invention, provided of course that they are compatible with the ashless dispersant of this invention and the other component or components being employed.
  • This invention also includes among its embodiments improved methods of lubricating mechanical parts in the presence of at least one fluoroelastomer surface.
  • the lubrication is effected by means of a lubricating oil or functional fluid containing an ashless dispersant of this invention.
  • the practise of such methods results in a lower -- oftentimes a substantially lower -- amount of degradation of the fluoroelastomer contacted by the lubricating oil or functional fluid containing such ashless dispersant as compared to the amount of degradation that would occur under the same conditions using the same oil or fluid composition containing the same total quantity of the corresponding initial untreated ashless dispersant.
  • this invention provides the use of a lubricating oil or functional fluid containing the dispersant composition of the invention for lubricating a mechanical mechanism containing moving parts to be lubricated, and having a fluoroelastomer in contact with at least a portion of such lubricating oil or functional fluid during operation of such mechanism.
  • a lubricating oil or functional fluid containing the dispersant composition of the invention for lubricating a mechanical mechanism containing moving parts to be lubricated, and having a fluoroelastomer in contact with at least a portion of such lubricating oil or functional fluid during operation of such mechanism.
  • crankcases of internal combustion engines are the crankcases of internal combustion engines; vehicular transmissions; hydraulic systems; hypoid axles; mechanical steering drives in passenger cars, in trucks, and in cross-country vehicles; planetary hub reduction axles and transfer gear boxes in utility vehicles such as trucks; pinion hub reduction gear boxes; synchromesh and synchroniser type gear boxes; power take-off gears; and limited slip rear axles.
  • the ashless dispersant can also be utilised in metal working, machining, and cutting oils such as are applied to work pieces during cutting and shaping operations.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Lubricants (AREA)

Claims (23)

  1. Öllösliche Dispergiermittelzusammensetzung, die durch Umsetzen eines basischen Stickstoff enthaltenden aschefreien Dispergiermittels (i) mit mindestens einem dibasischen Acylierungsmittel mit bis zu 6 Kohlenstoffatomen pro Molekül und (ii) mit mindestens einer Borverbindung hergestellt wird, wobei die Reaktionen (i) und (ii) gleichzeitig oder nacheinander in beliebiger Reihenfolge so durchgeführt werden, daß das aschefreie Dispergiermittel in (i) durch Acylierung und in (ii) durch Borierung chemisch modifiziert wird.
  2. Zusammensetzung nach Anspruch 1, in der die mit (i) bezeichnete Reaktion vor der mit (ii) bezeichneten Reaktion durchgeführt wird.
  3. Zusammensetzung nach Anspruch 1, in der die mit (ii) bezeichnete Reaktion vor der mit (i) bezeichneten Reaktion durchgeführt wird.
  4. Zusammensetzung nach Anspruch 1, in der die mit (i) und (ii) bezeichneten Reaktionen gleichzeitig durchgeführt werden.
  5. Zusammensetzung nach einem der Ansprüche 1 bis 4, in der die mit (ii) bezeichnete Reaktion unter Verwendung von (a) mindestens einer Borsäure oder eines Anhydrids oder Esters davon oder (b) einer beliebigen Kombination davon durchgeführt wird.
  6. Zusammensetzung nach einem der Ansprüche 1 bis 5, in der das in der mit (i) bezeichneten Reaktion verwendete Acylierungsmittel Maleinsäureanhydrid, Maleinsäure, Fumarsäure, Äpfelsäure oder eine Kombination aus beliebigen zwei oder drei oder allen vier der vorstehenden Substanzen ist.
  7. Zusammensetzung nach einem der Ansprüche 1 bis 6, in der das basische Stickstoff enthaltende Ausgangsdispergiermittel ein Succinimiddispergiermittel mit durchschnittlich mindestens 3 Stickstoffatomen pro Molekül ist.
  8. Zusammensetzung nach einem der Ansprüche 1 bis 6, in der das basische Stickstoff enthaltende Ausgangsdispergiermittel ein Succinimiddispergiermittel ist, das aus einem Alkyl- oder Alkenyl-Bernsteinsäureacylierungsmittel mit durchschnittlich mindestens 40 Kohlenstoffatomen in der Alkyl- oder Alkenylgruppe und einer Alkylen-Polyaminmischung mit durchschnittlich mindestens 3 Stickstoffatomen pro Molekül hergestellt ist.
  9. Zusammensetzung nach einem der Ansprüche 1 bis 6, in der das basische Stickstoff enthaltende Ausgangsdispergiermittel ein Succinimiddispergiermittel ist, das aus einem von Polyisobuten mit einem zahlenmittleren Molekulargewicht im Bereich von 50 bis 10.000 abgeleiteten PolyisobutenylBernsteinsäureacylierungsmittel und einer Ethylenpolyaminmischung einschließlich cyclischer und acyclischer Strukturen hergestellt ist, wobei die Mischung eine durchschnittliche Gesamtzusammensetzung ähnlich der einer Mischung im Bereich von Triethylentetramin bis Pentaethylenhexamin aufweist.
  10. Zusammensetzung nach einem der Ansprüche 1 bis 9, in der das bzw. die dibasischen Acylierungsmittel in Mengen von etwa 0,01 bis etwa 0,5 Mol pro durchschnittlichem Stickstoffäquivaient im bzw. in den aschefreien Ausgangsdispergiermitteln verwendet werden, vorausgesetzt, daß das dabei entstehende Produkt mindestens 0,05 Äquivalent basischen Stickstoff enthält, wobei die Borverbindung(en) in ausreichenden Mengen eingesetzt werden, um bis zu etwa 5 % Bor, ausgedrückt in Gew.-% elementaren Bors, in das fertige, zusammen umgesetzte Gesamtdispergiermittel einzubringen.
  11. Zusammensetzung nach einem der Ansprüche 7 bis 9, in der das bzw. die dibasischen Acylierungsmittei in solchen Mengen eingesetzt werden, daß das Gesamtmolverhältnis von (a) dibasischem Acylierungsmittel plus (b) dem mit aliphatischem Hydrocarbyl substituierten, zur Herstellung des Ausgangssuccinimids verwendeten Bernsteinsäureacylierungsmittels in den Bereich von 1,5 bis 3,5 Mol (a) und (b) pro Mol Polyamin fällt, wobei die Borverbindung(en) in ausreichenden Mengen eingesetzt werden, um bis zu etwa 0,5 bis 2,5 % Bor, ausgedrückt in Gew.-% elementaren Bors, in das fertige, zusammen umgesetzte Gesamtdispergiermittel einzubringen.
  12. Schmieröl- oder funktionelle Fluidzusammensetzung, die ein öl von Schmierviskosität und eine in einem der Ansprüche 1 bis 11 definierte Dispergiermittelzusammensetzung enthält.
  13. Additivkonzentrat mit einer in einem der Ansprüche 1 bis 11 definierten Dispergiermittelzusammensetzung.
  14. Verfahren, bei dem ein basisches Stickstoff enthaltendes aschefreies Dispergiermittel mit mindestens einem dibasischen Acylierungsmittel mit bis zu 6 Kohlenstoffatomen im Molekül und mindestens einer Borverbindung zur Umsetzung gebracht wird, wobei diese Reaktionen entweder gleichzeitig oder in beliebiger Reihenfolge nacheinander so durchgeführt werden, daß das aschefreie Dispergiermittel durch Acylierung und Borierung chemisch modifiziert wird.
  15. Verfahren nach Anspruch 14, bei dem die Reaktion mit dem dibasischen Acylierungsmittel vor der Reaktion mit der Borverbindung durchgeführt wird.
  16. Verfahren nach Anspruch 14, bei dem die Reaktion mit dem dibasischen Acylierungsmittel nach der Reaktion mit der Borverbindung durchgeführt wird.
  17. Verfahren nach Anspruch 14, bei dem die Reaktion mit dem dibasischen Acylierungsmittel und die Reaktion mit der Borverbindung gleichzeitig durchgeführt werden.
  18. Verfahren nach einem der Ansprüche 14 bis 17, in dem das dem Verfahren unterzogene basische Stickstoff enthaltende Ausgangsdispergiermittel ein Succinimiddispergiermittel mit durchschnittlich mindestens 3 Stickstofffatomen pro Molekül ist.
  19. Verfahren nach einem der Ansprüche 14 bis 17, in dem das dem Verfahren unterzogene basische Stickstoff enthaltende Dispergiermittel aus einem Alkyl- oder Alkenyl-Bernsteinsäureacylierungsmittel mit durchschnittlich mindestens 40 Kohlenstofffatomen in der Alkyl- oder Alkenylgruppe und einer Alkylen-Polyaminmischung mit durchschnittlich mindestens 3 Stickstofffatomen pro Molekül hergestellt ist.
  20. Verfahren nach einem der Ansprüche 14 bis 17, in dem das basische Stickstoff enthaltende Ausgangsdispergiermittel ein Succinimiddispergiermittel ist, das aus einem von Polyisobuten mit einem zahlenmittleren Molekulargewicht im Bereich von 50 bis 10.000 abgeleiteten Polyisobutenyl-Bernsteinsäureacylierungsmittel und einer Ethylenpolyaminmischung einschließlich cyclischer und acyclischer Strukturen hergestellt ist, wobei die Mischung eine durchschnittliche Gesamtzusammensetzung ähnlich der einer Mischung im Bereich von Triethylentetramin bis Pentaethylenhexamin aufweist.
  21. Verfahren nach einem der Ansprüche 14 bis 20, bei dem das Dicarbonsäureacylierungsmittel Maleinsäure Maleinsäureanhydrid Fumarsäure, Äpfelsäure oder eine beliebige Kombination davon ist und die Borverbindung mindestens eine Borsäure oder ein Anhydrid oder Ester bzw. eine beliebige Kombination davon ist.
  22. Verfahren zum Schmieren mechanischer Teile in Gegenwart mindestens einer Fluorelastomeroberfläche, bei dem die Schmierung mittels eines eine Dispergiermittelzusammensetzung nach einem der Ansprüche 1 bis 11 enthaltenden Schmieröls oder funktionellen Fluids erfolgt.
  23. Verwendung eines eine Dispergiermittelzusammensetzung nach einem der Ansprüche 1 bis 11 enthaltenden Schmieröls oder funktionellen Fluids zum Schmieren eines mechanischen Mechanismus, der zu schmierende bewegliche Teile enthält und ein Fluorelastomer aufweist, das während des Betriebs eines solchen Mechanismus in Kontakt mit mindestens einem Teil dieses Schmieröls oder funktionellen Fluids ist.
EP90306128A 1990-06-06 1990-06-06 Modifizierte Lösungsmittelzusammensetzungen Expired - Lifetime EP0460309B2 (de)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DE69021872T DE69021872T3 (de) 1990-06-06 1990-06-06 Modifizierte Lösungsmittelzusammensetzungen.
EP90306128A EP0460309B2 (de) 1990-06-06 1990-06-06 Modifizierte Lösungsmittelzusammensetzungen
ZA914157A ZA914157B (en) 1990-06-06 1991-05-30 Modified dispersant compositions
AU78134/91A AU645809B2 (en) 1990-06-06 1991-06-03 Modified dispersant compositions
JP3159919A JP2966586B2 (ja) 1990-06-06 1991-06-05 改良分散剤配合物
CA002043998A CA2043998C (en) 1990-06-06 1991-06-06 Dispersant compositions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP90306128A EP0460309B2 (de) 1990-06-06 1990-06-06 Modifizierte Lösungsmittelzusammensetzungen

Publications (3)

Publication Number Publication Date
EP0460309A1 EP0460309A1 (de) 1991-12-11
EP0460309B1 EP0460309B1 (de) 1995-08-23
EP0460309B2 true EP0460309B2 (de) 2000-07-05

Family

ID=8205447

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90306128A Expired - Lifetime EP0460309B2 (de) 1990-06-06 1990-06-06 Modifizierte Lösungsmittelzusammensetzungen

Country Status (6)

Country Link
EP (1) EP0460309B2 (de)
JP (1) JP2966586B2 (de)
AU (1) AU645809B2 (de)
CA (1) CA2043998C (de)
DE (1) DE69021872T3 (de)
ZA (1) ZA914157B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8933001B2 (en) 2010-03-31 2015-01-13 Chevron Oronite Company Llc Method for improving fluorocarbon elastomer seal compatibility

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5454962A (en) * 1993-06-25 1995-10-03 Ethyl Petroleum Additives, Inc. Fluoroelastomer-friendly crankcase and drivetrain lubricants and their use
JP3920363B2 (ja) * 1994-01-14 2007-05-30 エチル・ペトロリアム・アデイテイブズ・リミテツド 潤滑油のための分散剤
GB9506102D0 (en) * 1995-03-24 1995-05-10 Ethyl Petroleum Additives Ltd Dispersants for lubricating oil
EP0733697B1 (de) * 1995-03-24 2000-05-10 Ethyl Petroleum Additives Limited Nachbehandelte Dispergiermittel
GB2301104B (en) 1995-05-23 1998-11-11 Ethyl Petroleum Additives Ltd Process for the preparation of polyalkene-substituted succinic acylating agents
GB2307685B (en) * 1995-12-01 1999-07-07 Ethyl Petroleum Additives Ltd Seal compatible diesel dispersants
GB2312212B (en) * 1996-04-19 1999-09-29 Ethyl Petroleum Additives Ltd Dispersants
CN1081229C (zh) * 1998-12-25 2002-03-20 中国石油化工集团公司 含硼后交联丁二酰亚胺无灰分散剂及其制备
EP1078977B1 (de) 1999-07-30 2010-01-27 Afton Chemical Limited Schmiermittelzusammensetzungen
DE60036885T2 (de) * 1999-12-27 2008-02-14 Idemitsu Kosan Co. Ltd. Succinimidverbindungen und deren verwendung
EP1409620B1 (de) * 2001-07-05 2014-01-15 The Lubrizol Corporation Mit niedrigem chlorinhalt versehene, polyolefin-substituierte und mit amin reagierende ungesättigte alpha-beta-carboxyverbindungen
US20080256848A1 (en) 2007-04-19 2008-10-23 Brennan Timothy J Middle distillate fuels with a sustained conductivity benefit
US20080256849A1 (en) 2007-04-19 2008-10-23 Kulinowski Alexander M Conductivity of middle distillate fuels with a combination of detergent and cold flow improver
US8993496B2 (en) 2010-03-31 2015-03-31 Chevron Oronite Company Llc Method for improving fluorocarbon elastomer seal compatibility
US8901050B2 (en) 2010-03-31 2014-12-02 Chevron Oronite Company Llc Method for improving copper corrosion performance
US9150811B2 (en) 2010-03-31 2015-10-06 Cherron Oronite Company LLC Method for improving copper corrosion performance
US8716202B2 (en) 2010-12-14 2014-05-06 Chevron Oronite Company Llc Method for improving fluorocarbon elastomer seal compatibility
BR112015008109A2 (pt) * 2012-10-12 2018-04-24 Basf Se composição lubrificante, e, pacote de aditivo para uma composição lubrificante.
JP2016501284A (ja) 2012-11-16 2016-01-18 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ フルオロポリマーシール適合性向上のためのエポキシ化合物含有潤滑油組成物
CN111690081A (zh) * 2020-06-23 2020-09-22 新乡市瑞丰新材料股份有限公司 一种硼化高分子量无灰分散剂的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3367943A (en) † 1963-11-01 1968-02-06 Exxon Research Engineering Co Process for preparing oil soluble additives which comprises reacting a c2 to c5 alkylene oxide with (a) reaction product of an alkenylsuccinic anhydride and an aliphaticpolyamine (b) reaction product of alkenylsuccinic anhydride, a c1 to c30 aliphatic hydrocarbon carboxylic acid and an aliphatic polyamine
JPS51130408A (en) † 1975-05-10 1976-11-12 Karonaito Kagaku Kk Oil-soluble lubricant additives
EP0132383A2 (de) † 1983-07-25 1985-01-30 Amoco Corporation Borierung von Polyamin-Dispergiermitteln mit Polyborat-Estern
EP0136185A2 (de) † 1983-09-29 1985-04-03 Edwin Cooper, Inc. Verfahren zur Borierung von Dispergiermitteln, borierte Dispergiermittel und diese enthaltende flüssige Zusammensetzungen
EP0451380A1 (de) † 1990-04-10 1991-10-16 Ethyl Petroleum Additives Limited Bernsteinsäureimid-Zusammensetzungen

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1443981A (fr) * 1964-04-16 1966-07-01 Socony Mobil Oil Co Nouveaux produits de réaction acides carboxyliques-polyamines dérivés succiniques contenant du bore et compositions lubrifiantes qui contiennent ces produits
US3287271A (en) * 1965-01-21 1966-11-22 Chevron Res Combined detergent-corrosion inhibitors
US3442808A (en) * 1966-11-01 1969-05-06 Standard Oil Co Lubricating oil additives
US3723460A (en) * 1969-10-10 1973-03-27 Standard Oil Co Polymeric succinimides and their derivatives as fuel and motor oil additives
DE2845903C3 (de) * 1978-10-21 1982-07-29 Heinz 6550 Bad Kreuznach Jung Biegsame Schnecke für ein Schneckengetriebe
US4234435A (en) * 1979-02-23 1980-11-18 The Lubrizol Corporation Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation
US4338205A (en) * 1980-08-25 1982-07-06 Exxon Research & Engineering Co. Lubricating oil with improved diesel dispersancy
US4686054A (en) * 1981-08-17 1987-08-11 Exxon Research & Engineering Co. Succinimide lubricating oil dispersant
JPH0696610B2 (ja) * 1984-02-09 1994-11-30 ザ ル−ブリゾル コ−ポレイシヨン 置換カルボン酸およびその誘導体の製造方法
US4908145A (en) * 1987-09-30 1990-03-13 Amoco Corporation Engine seal compatible dispersants for lubricating oils

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3367943A (en) † 1963-11-01 1968-02-06 Exxon Research Engineering Co Process for preparing oil soluble additives which comprises reacting a c2 to c5 alkylene oxide with (a) reaction product of an alkenylsuccinic anhydride and an aliphaticpolyamine (b) reaction product of alkenylsuccinic anhydride, a c1 to c30 aliphatic hydrocarbon carboxylic acid and an aliphatic polyamine
JPS51130408A (en) † 1975-05-10 1976-11-12 Karonaito Kagaku Kk Oil-soluble lubricant additives
EP0132383A2 (de) † 1983-07-25 1985-01-30 Amoco Corporation Borierung von Polyamin-Dispergiermitteln mit Polyborat-Estern
EP0136185A2 (de) † 1983-09-29 1985-04-03 Edwin Cooper, Inc. Verfahren zur Borierung von Dispergiermitteln, borierte Dispergiermittel und diese enthaltende flüssige Zusammensetzungen
EP0451380A1 (de) † 1990-04-10 1991-10-16 Ethyl Petroleum Additives Limited Bernsteinsäureimid-Zusammensetzungen

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8933001B2 (en) 2010-03-31 2015-01-13 Chevron Oronite Company Llc Method for improving fluorocarbon elastomer seal compatibility

Also Published As

Publication number Publication date
CA2043998C (en) 2003-08-12
DE69021872D1 (de) 1995-09-28
AU645809B2 (en) 1994-01-27
DE69021872T3 (de) 2003-02-13
CA2043998A1 (en) 1991-12-07
DE69021872T2 (de) 1996-01-18
EP0460309A1 (de) 1991-12-11
EP0460309B1 (de) 1995-08-23
JPH04227995A (ja) 1992-08-18
AU7813491A (en) 1991-12-12
JP2966586B2 (ja) 1999-10-25
ZA914157B (en) 1993-02-24

Similar Documents

Publication Publication Date Title
EP0451380B1 (de) Bernsteinsäureimid-Zusammensetzungen
EP0460309B2 (de) Modifizierte Lösungsmittelzusammensetzungen
US5225093A (en) Gear oil additive compositions and gear oils containing the same
JP2807901B2 (ja) パワートランスミッティング組成物において有用な添加剤の相乗的組合せ
US5176840A (en) Gear oil additive composition and gear oil containing the same
EP0277729B1 (de) Veschleissschutz-Schmiermittelzusammensetzungen mit geringem Phosphorgehalt
AU667582B2 (en) Diesel lubricants and methods
CA1284145C (en) Diesel lubricants and methods
EP0271937A2 (de) Schmiermittelzusammensetzung
US5505868A (en) Modified dispersant compositions
JP2537667B2 (ja) 向上した錆止めを得るための新規な油質組成物用添加剤
CA2034983C (en) Dispersant compositions
CA1303598C (en) Nitrogen containing dispersants treated with mineral acids
EP0456925B1 (de) Antioxidationszusammensetzungen
JPH03210395A (ja) ギヤ油及びその添加剤
GB2231873A (en) Lubricating compositions
EP0408735B1 (de) Hydroxyalkanphosphonsäuren, deren derivate und diese enthaltende schmiermittel
EP0537386B1 (de) Modifizierte Dispergierzusammensetzungen
JPH02175795A (ja) 新規なエチレン―α―オレフィン共重合体置換されたアミノフェノ・マンニッヒ塩基潤滑剤分散剤添加物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE ES FR GB IT NL SE

17P Request for examination filed

Effective date: 19911115

17Q First examination report despatched

Effective date: 19920504

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE ES FR GB IT NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 19950823

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19950823

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19950823

REF Corresponds to:

Ref document number: 69021872

Country of ref document: DE

Date of ref document: 19950928

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19951123

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: EXXON CHEMICAL PATENTS INC.

Effective date: 19960517

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20000517

Year of fee payment: 11

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20000531

Year of fee payment: 11

27A Patent maintained in amended form

Effective date: 20000705

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): BE DE ES FR GB IT NL SE

ET3 Fr: translation filed ** decision concerning opposition
REG Reference to a national code

Ref country code: DE

Ref legal event code: 8570

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010630

BERE Be: lapsed

Owner name: ETHYL PETROLEUM ADDITIVES LTD

Effective date: 20010630

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020228

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20060626

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20060731

Year of fee payment: 17

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20070606

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070606