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WO1997018281A1 - Derives de composes carbonyle s'utilisant comme additifs multifonctionnels pour carburants et lubrifiants - Google Patents

Derives de composes carbonyle s'utilisant comme additifs multifonctionnels pour carburants et lubrifiants Download PDF

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Publication number
WO1997018281A1
WO1997018281A1 PCT/US1996/018267 US9618267W WO9718281A1 WO 1997018281 A1 WO1997018281 A1 WO 1997018281A1 US 9618267 W US9618267 W US 9618267W WO 9718281 A1 WO9718281 A1 WO 9718281A1
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Prior art keywords
polyamine
composition
polymer
dispersant
functionalized
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PCT/US1996/018267
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English (en)
Inventor
Stanley James Brois
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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Publication of WO1997018281A1 publication Critical patent/WO1997018281A1/fr
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    • C—CHEMISTRY; METALLURGY
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    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
    • C10L1/303—Organic compounds compounds not mentioned before (complexes) derived from metals boron compounds
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    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
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    • C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/32—Wires, ropes or cables lubricants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/34—Lubricating-sealants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/36—Release agents or mold release agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/38—Conveyors or chain belts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/40—Generators or electric motors in oil or gas winning field
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/42—Flashing oils or marking oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/44—Super vacuum or supercritical use
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/50—Medical uses
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • This invention relates to carbonyl containing compound derivatives as additives useful in oleaginous compositions such as fuels, lubricants, power transmission fluids, and the like.
  • Oleaginous substances have found wide industrial use Unfortunately, many oleaginous compositions contain additives which contain chlorine which is environmentally undesirable Also, many of today's high performance applications for oleaginous compositions require multifunctional additives.
  • vicinal polycarbonyl (VP) monomers Organic compounds containing two or more carbonyl groups in a row are generally referred to as vicinal polycarbonyl (VP) monomers
  • VP monomers with unsaturated hydrocarbons, including unsaturated hydrocarbon polymers, will produce carbonyl containing adducts as disclosed in US-A-5057564 and USSN 935604 These adducts are referred to herein as ene adducts
  • various hydrocarbons, and especially saturated hydrocarbons, and saturated hydrocarbon polymers have been found to react with VP monomers in the presence of a free radical initiator These compounds are disclosed, for example, in US-A- 5288811 and 5274051, and are referred to herein as radical adducts
  • USSN 242,750 discloses a product formed by reacting (a) an adduct of a hydrocarbon and a vicinal polycarbonyl compound, the adduct having a value of n greater than 1, wherein n is the average number of vicinal polycarbonyl compounds incorporated per adduct chain, with (b) a reagent selected from the group consisting of nucleophiles, electrophiles, metal salts and metal complexes
  • the present invention provides improved oleaginous compositions such as fuels, lube oils, and the like, by incorporating into these compositions additives prepared from the reaction product of a functionalized polymer and a polyamine metaborate (herein referred to as PMB) These products have multifunctional properties.
  • USSN-242,750 relates to an adduct of a hydrocarbon and a vicinal polycarbonyl compound, the adduct having a value of n greater than 1, wherein n is the average number of vicinal polycarbonyl compounds inco ⁇ orated per adduct chain.
  • the hydrocarbon is typically a saturated or unsaturated hydrocarbon or hydrocarbon polymer with an Mn value ranging from about 200 to about 10 million
  • the hydrocarbon optionally contains polar substituents.
  • the VP compound (alternatively referred to herein as "VP monomer”) is cyclic or acyclic.
  • the adduct is an ene adduct or a radical adduct.
  • the adduct can be further reacted with a reagent to obtain a product, wherein the reagent is selected from the group consisting of nucleophiles, electrophiles, metal salts and metal complexes.
  • the reagent can be selected from (i) nucleophiles selected from the group consisting of amines, hydrazines, hydrazine derivatives, alcohols. water, polyamines.
  • polyols, amino alcohols, amino thiols- (ii) electrophiles selected from the group consisting of carboxy anhydrides, carboxy esters, borate esters, phosphate and phosphate esters; (iii) metal salts containing metal ions selected from the group consisting of alkali metals, alkaline earth metals, and transition metals and (iv) metal complexes containing metal ions selected from the group consisting of alkali metals, alkaline earth metals, and transition metals.
  • the product obtained from the above-described adduct can be post-treated with an electrophilic reagent such as a borating, acylating or thio acid reagent or a metal ion, to obtain a post-product.
  • the present invention relates to functionalized polymers, wherein a post product is prepared by derivatizing said functionalized polymer with a polyamine metaborate. It has been surprisingly found that this process, hereinafter referred to as Bor-Amination, provides the following advantages.
  • Conventional derivatization (e.g. amination) and post treatment (e.g. boration) requires two steps.
  • the present invention requires only one step.
  • the final product of the present invention contains less sediment than the product from separate amination and boration steps. This is believed to be due to a more complete reaction between the polyamine and boric acid than between the conventional functionalized polymer-polyamine adduct which is post treated with boric acid in a separate step.
  • the present invention further relates to oleaginous compositions comprising a major amount of an oleaginous substance selected from fuels and oils and a minor amount ofthe post-product.
  • the present invention relates to lubricating oil compositions comprising a lubricating oil and a dispersant .
  • said dispersant comprises the reaction product of a functionalized polymer and a polyamine metaborate.
  • the dispersant is prepared from a polymer functionalized using a reaction selected from the group consisting of halogen assisted, thermal ene, free radical grafting using a catalyst, phenol alkylation and carbonylation via Koch.
  • the dispersant can be derived from polymer functionalized by groups ofthe formula -CO-Y-R 3 , wherein Y is O or S, and either R 3 is H, hydrocarbyl, aryl, substituted aryl and at least 50 mole % of the functionalized groups are attached to a tertiary carbon atom of the copolymer.
  • the functionalized polymer is derived from polymers selected from the group consisting of poly-n-butene, polyisobutylene, and ethylene alpha olefin copolymers.
  • the alpha olefin comprises butene.
  • the polymer number average molecular weight is about 500 to about 20,000.
  • the polymers can be functionalized with a carboxylic acid moiety including maleic anhydride.
  • the polyamine metaborate is prepared by a process comprising, heating a mixture of polyamine and boric acid comprising about three moles of boric acid per each amino group of the polyamine for a time and a temperature sufficient to form a clear liquid.
  • the preferred polyamine is heavy polyamine.
  • the present invention even further relates to a process for preparing a low sediment dispersant prepared by reacting a functionalized polymer with a polyamine metaborate, wherein the polyamine metaborate is prepared by reacting polyamine and boric acid at a temperature of from about 80°C to about 130°C for from about a half hour to about 120 hours.
  • the polyamine and boric acid can also be mixed at ambient temperature (e.g. 20 to 30°C) and if necessary heated to higher temperatures (e.g. 80 to 130°C) to complete the reaction.
  • Carbonyl containing compounds include consisting of (a) ene and radical adducts having one or more VP monomers per adduct, (b) products derived from said ene and radical adducts, and (c) post-products derived from said products, which are useful in oleaginous compositions, especially as multifunctional additives, dispersants, and dispersant viscosity modifiers.
  • the adducts are prepared via the ene and radical addition of VP monomers to unsaturated and saturated hydrocarbons and polymers respectively, with Mn values ranging from about 200 to about 10 million.
  • the hydrocarbon and polymer reactants may contain one or more polar substituents, provided that the polar substituents are compatible with the ene and radical chemistry involved in the functionalization with VP monomers.
  • the adducts can be further reacted with a variety of nucleophiles, electrophiles, and metal ions to form products which in turn can be reacted with borating reagents, thio acids, and metal ions to form post-products
  • Oleaginous compositions containing the adduces, produces, and post- products are encompassed within this invention.
  • Oleaginous substances include fuels, oils, and other lubricants such as greases.
  • Unsaturated Substrates In general, the olefinic hydrocarbons and polymers with which VP monomers can be reacted are well known in the art. These oil soluble olefinic compounds comprise substantially saturated hydrocarbon backbones, yet they have a minor amount of ethylenic unsaturation which is available for adduct formation by means of the thermal ene addition process. Olefins which form useful ene adducts with VP monomers will typically be long chain, straight, and/or branched alkenes consisting of about 10 or more carbon atoms suitable so as to provide oil solubility.
  • Useful alkenes include C12 to C30 olefins, such as dodecene-1, 2-propylnonene-l, 2-hexyloctene-l, pentadecene-1, octadecene-1, octadecene-9, docosene-1, and pentatriacontene-17 and diolefins such as hexadecadiene- 1, 1 5, eicosadiene- 1, 19, 2, 19-dimethyl-eicosadiene- 1, 19, and octahydrosqualene.
  • olefins such as dodecene-1, 2-propylnonene-l, 2-hexyloctene-l, pentadecene-1, octadecene-1, octadecene-9, docosene-1, and pentatriacontene-17 and diolefins such as he
  • Oligomers of C3, to Cj2 olefins preferably of C3 to Cg olefins, both alpha-olefins and internal olefins are also useful. These preferably include from 2 to 8 repeating units, as typified by pentaisobutylene and octapropylene, and trimers of alpha-olefins such as 1-decene.
  • Other useful unsaturated substrates can incorporate one or more polar groups
  • the optimal number and type of polar groups attached to the alkene depends upon the oil solubility of the adducts with VP monomers, as well as their effectiveness as additives.
  • Useful olefins containing one or more polar groups include unsaturated alcohols such as 7-dodecen-l-ol, oleyl alcohol and cholesterol; ethers; carboxylic acids, esters and amides such as undecenylic acid, 2-dodecenyl succinic acid.
  • Oil soluble olefinic polymers which form useful ene adducts will generally have a number average molecular weight Mn) of about 500 to about 20K when the ene adducts are used for dispersant and detergent applications, and from about 10K to about one million, and most generally from about 20K to about 200K for dispersant- viscosity improver applications.
  • Preferred V.I. improver polymers will generally have a narrow range of molecular weight, as determined by the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) Polymers having a Mw/Mn of less than about 10, for example from about 1 to about 4 are most desirable
  • the olefinic polymers useful in this invention may be essentially amorphous in character, including those with up to about 25 percent by weight of crystalline segments as determined by x-ray or differential scanning calorimetry. Additionally, the polymers may be of any of the tapered or block copolymers known in the prior art or the copolymers of alpha-olefins comprised of chains of intra-molecularly heterogenous and inter-molecularly homogenous monomer units, such as those prepared by the process of US-A-4540753.
  • Suitable hydrocarbon polymers include homopolymers and copolymers of one or more monomers of C2 to C30, e.g., C2 to Cg olefins, including both alphaolefins and internal olefins, which may be straight or branched, aliphatic, aromatic, alkylaromatic, and cycloaliphatic.
  • these will be polymers of ethylene with C3 to C30 olefins, preferably copolymers of ethylene and propylene, and more preferably, copolymers of ethylene and butene
  • polymers of other olefins include polymers of ethylene or polymers of propylene which contain nonconjugated diolefins, such as 1,4-hexadiene.
  • copolymers of isobutylene and butadiene and the like.
  • suitable hydrocarbon polymers containing, olefinic unsaturation well known in the art include hydrogenated or partially hydrogenated homopolymers, and random, tapered or block polymers (copolymers including te ⁇ olymers and tetrapolymers) of conjugated dienes and or monovinyl aromatic compounds with, optionally, alpha-olefins or lower alkenes e.g., C3 to Cig alpha-olefins or lower alkenes.
  • the conjugated dienes include isoprene, butadiene, 2,3-dimethylbutadiene, piperylene and/or mixtures thereof
  • the monovinyl aromatic compounds are preferably monovinyl monoaromatic compounds, such as styrene or alkylated styrenes substituted at the alpha-carbon atoms of the styrene, such as alphamethylstyrene, or at ring carbons, such as methylstyrene, ethylstyrene, propylstyrene, isopropyl-styrene, butyl- styrene, isobutylstyrene, and tert-butylstyrene.
  • the present invention also includes star polymers as disclosed in patents such as US-A-371 1406, 4108945, 41 16917, 5049294 and 5070131.
  • copolymer as used herein is thus meant to include te ⁇ olymers, and tetrapolymers of ethylene, C3 to C2 alphaolefins, non- conjugated diolefins, and mixtures of such diolef ⁇ ns, and of isobutylene with C4 to C j g non-conjugated diolefins, and mixtures of such diolefins.
  • the amount of non- conjugated diolefin will generally range from about 0.5 to 20 wt percent, and preferably from about 1 to about 10 wt percent, based on the total amount of ethylene and alpha-olefin present.
  • non-conjugated dienes that may be used in forming adducts targeted for use as dispersant viscosity modifiers (VM's), include acyclic dienes such as 1,4-hexadiene; alicyclic dienes such as 1 ,4-cyclo-hexadiene, 4- vinylcyclohexene and 4-aIlylcyclohexene, and alicyclic fused and bridged ring dienes such as tetrahydroindene, dicyclo-pentadiene, bicyclo[2.2.
  • acyclic dienes such as 1,4-hexadiene
  • alicyclic dienes such as 1 ,4-cyclo-hexadiene, 4- vinylcyclohexene and 4-aIlylcyclohexene
  • alicyclic fused and bridged ring dienes such as tetrahydroindene, dicyclo-pentadiene, bicyclo[2.2.
  • the ene adducts can be prepared by various processes in which the unsaturated hydrocarbon or polymer and the VP monomers are intimately intermixed and reacted at a temperature at which thermal ene addition occurs without appreciable decomposition. Generally, reaction temperatures within the range of from about 20°C to about 200°C are useful. The reaction temperature will vary depending upon the particular unsaturated hydrocarbon or polymer and VP monomer that are employed. Effective mixing of the olefinic polymer and the VP monomer can be achieved by combining these reactants together with a solvent or neat.
  • the ene adducts can be prepared in solution, in which case the unsaturated hydrocarbon or polymer substrate is dissolved in a solvent such as toluene, xylene, synthetic oil, mineral oil or other suitable solvents, and mixtures thereof and the VP monomer is added as is, or as a solution, to the dissolved hydrocarbon
  • a solvent such as toluene, xylene, synthetic oil, mineral oil or other suitable solvents, and mixtures thereof and the VP monomer is added as is, or as a solution, to the dissolved hydrocarbon
  • the mixture can then be reacted at temperatures of about 50°C to about 200°C for several hours (reaction is monitored by IR analysis) in the substantial absence of air, preferably under a blanket of inert gas, such as nitrogen until ene adduction is complete
  • a trace of an antioxidant such as BHT (butylated hydroxy toluene) can be used.
  • the ene adducts are separated from the reaction mixture by stripping off the solvent, and further diluted with appropriate lubricating oil packages for desired intermediate or end use purposes.
  • Ene and radical adducts formed in mineral or synthetic oils can be used directly in product forming reactions, or a specific ene use.
  • the proportions of the reactants vary according to the particular olefinic hydrocarbon employed, but normally will range between about 0.01 and 3, and preferably between about 0.1 and 2 moles of the VP monomer per mole of ethylenic unsaturation in the polymer.
  • the degree of ethylenic unsaturation of the polymer is measured by several methods which are known to those of ordinary skill in this art, including nuclear magnetic resonance (NMR), calibrated infrared spectroscopy, refractive index comparisons (particularly for ethylene-propylene-norbornene te ⁇ olymers), and calibrated iodine titration measurements.
  • a high VP monomer/olefin ratio usually affords high n values owing to multiple ene reactions on each reactive olefinic site.
  • n values of about 20-40 or greater can be obtained.
  • the mixture of hydrocarbon and VP monomer When the mixture of hydrocarbon and VP monomer has sufficiently iow melt viscosity for effective mixing, they may be reacted without a solvent in a stirred mixer or in a masticator.
  • a neat polyolefin such as ethylene butene- 1 copolymer (Mn of approximately 2K, and about 55 wt% ethylene) and an equimolar amount of VP monomer, such as IT or AX, are combined in a nitrogen-purged reactor and stirred at about 160°C for about 6 hours, or until infrared analysis indicates complete reaction.
  • Mn ethylene butene- 1 copolymer
  • IT or AX equimolar amount of VP monomer
  • Ene adduct formation is usually quick and quantitative, and multiple ene adductions can be achieved by using an excess ofthe VP monomer.
  • Useful free radical initiators, I, essential to the formation of the radical adducts of this invention include dialkyl peroxides such as di-teitiary-butyl peroxide,2,5- dimethyl-2,5-di-tertiary-butyl-peroxy-hexane, di-cumyl peroxide; alkyl peroxides such as tertiary-butyl hydroperoxide.
  • tertiary-octyl hydroperoxide cumene hydroperoxide, aroyl peroxides such as benzoyl peroxide; peroxyl esters such as tertiary-butyl peroxypivalate, tertiary-butyl perbenzoate, and azo compounds such as azo-bis- isobutyronitrile.
  • Any free radical initiator with a suitable half life at the reaction temperatures between about 80°C and 200°C can be used, as well as ionizing radiation
  • the radical-initiated reaction of VP monomers can be applied to a wide spectrum of hydrocarbons (R Z H) selected from the group consisting of (a) normal alkanes such as decane, hexadecane, octadecane, tricosane, and paraffins having about 10 to about 40 carbons; branched alkanes such as trimethyldecane, tetramethylpentadecane (pristane), squalane, white oils, Nujols, mineral oils, hydrogenated oligomers and co-oligomers of ethylene, propylene, butylene and higher molecular weight olefin oligomers having 10 to about 40 carbons, (b) substituted hydrocarbons consisting of normal and branched alkanes with about 10 to about 40 carbons may feature one or more functional groups
  • Homopolymers of ethylene such as high and low density polyethylene, atactic or crystalline polypropylene, polybutene, polyisobutylene homopolymers and copolymers of higher alpha-olefins, copolymers of ethylene with propylene EPR, which may also contain unconjugated dieries (EPDM), copolymers of ethylene with buteries or higher alpha-olefins, copolymers of propylene with buteries, and higher alpha-olefins.
  • EPDM unconjugated dieries
  • the resulting polymers are preferably hydrogenated to saturate substantially all of the ethylenic unsaturation
  • Useful polymers include hydrogenated poly-alpha- olefins. styrene butadiene and/or isoprene block, and tapered copolymers, hydrogenated styrene isoprene block, and hydrogenated star branched polyisoprene polymers.
  • the radical-induced reactions of VP monomers with hydrocarbon and/or polymer substrates can occur in the neat state, in a melt, or in solution, bulk modifications can be effected in polymer processing equipment such as a rubber mill, an extruder, and a Brabender or Banbury mixer.
  • Radical grafting of high molecular weight polymers may also be conducted without a solvent, as in a melt, and is a preferred route to multifunctional viscosity improvers (MFVI)
  • MFVI multifunctional viscosity improvers
  • Polymer processing equipment such as a rubber mill, an extruder, a Banbury mixer, Brabender mixer, and the like are used. Reaction temperatures ranging from about 90°C to about 220°C, and reaction times ranging from about 1 minute to about 1 hour are employed Reaction times will vary with the nature and amount of polymer, the VP monomer, the reactant ratio and melt reaction conditions, and accordingly, IR analysis for example, is used to ascertain complete reaction
  • the polymer when grafting in solution, the polymer is dissolved in a suitable solvent, such as chlorobenzene, dichlorobenzene, or mineral oil, and heated to temperatures ranging from about 90°C to about 180°C depending upon the radical initiator used
  • a suitable solvent such as chlorobenzene, dichlorobenzene, or mineral oil
  • the VP monomer is added and heated for a suitable period to free any radical-reactive carbonyl groups which may be tied up as a hydrate, alcoholate, or polar solvate
  • the radical initiator is added in one dose, or dropwise over a suitable time span, usually from about 5 to 60 minutes
  • Another option is to add a mixture of compatible monomer and peroxide in a suitable solvent to the hydrocarbon or polymer solution at an addition rate and suitable reaction temperature consistent with the half life of the radical initiator
  • the reaction mixture is heated, with stirring, until visual color changes infrared analysis, and/or NMR analysis indicate that the radical addition of the VP monomer to the hydro
  • the products of this invention are prepared by reacting a wide assortment of ene and radical adducts with selected nucleophiles, electrophiles and metal ions according to the following protocol:
  • vicinal polyketones such as indantrione (IT), naphthalene 1,2,3,4- tetrone, rhodizonic acid, triquinoyl, croconic acid, leuconic acid, dimethyl triketone, and diphenyl triketone;
  • vicinal polycarbonyl containing amides such as alloxan (AX), 1,3- dimethylalloxan, quinoline-2,3,4 -trione, and
  • nucleophiles such as amines, hydrazines, alcohols, water, polyamines, polyols, amino alcohols, amino thiols, and dithiols;
  • electrophiles such as acylating agents like carboxy anhydrides and esters, borate esters, phosphate and phosphate esters; and [c] metal salts and metal complexes; produce a wide assortment of products consisting of antioxidants, antioxidant dispersants, dispersant viscosity modifiers, detergents, and multifunctional additives for fuels and lubes.
  • the structure and yield of products derived from the chemistry, outlined above are a sensitive function of reactant structure and reaction parameters.
  • the strictures depicted for the characterized products illustrate in part, the multiple reaction pathways involved in product formation.
  • related products some of which can be chain extended in nature and not easily defined, will often be present.
  • the products derived from lc, 2c, and 3c via reaction with the nucleophiles, electrophiles, and metal salts and metal complexes can be complex mixtures which are highly useful as fuel and lube additives.
  • the reactions are conducted by contacting, e.g., mixing, the adduct with the nucleophile, electrophile, or metal reagent as the case may be, neat or in a suitable solvent at a temperature, and time sufficient to form the product.
  • the precise conditions for carrying out the reactions are not critical. Electrophilic reactions will usually involve the hydroxyl group attached to the ene or radical adduct.
  • Useful electrophiles for reacting with adducts to from products include carboxylic acids, anhydrides, and esters, phosphates, phosphates, boric acid, and borate esters
  • Useful metals that react with adducts include alkali metals such as lithium, sodium, potassium, alkaline earth metals such as calcium, magnesium, barium; and transition metals such as copper, nickel, and cobalt.
  • Useful carriers (counter ions) for the alkali and alkaline earth metals include acetate, carbonate, bicarbonate, and counter ions; carriers for the transition metals include acetate ion, and oxygen-containing ligands such as acetylacetone (2,4-pentanedione)
  • Useful nucleophiles include mono-reactive nucleophiles, such as monoamine, hydrazine, and monohydric alcohol reagents, and poly-reactive nucleophiles such as polyamine, amino alcohol, and polyol reagents.
  • Useful amines feature a NH2 or NH group capable of reacting with the adducts of the present invention.
  • the NH2 or NH functional group can be attached to linear and/or branched alkanes having from about I to 100 carbons.
  • the NH2, NH, or aminoalkyl groups can also be attached to homocyclic rings such as a cycloalkane having from 3) to about 18 members, aromatic rings, or fused aromatic by benzene and naphthalene, respectively- heterocyclic rings, or fused heterocyclic rings having 5 or 6 members consisting of carbon, nitrogen, oxygen and sulfur.
  • All of the above described amines can contain substituents including ethers, polyethers, thioethers and polythioethers, carboxyl, carboxamide and nitrile groups, sulfur-oxygen substituents; and phosphorus-oxygen substituents.
  • substituents including ethers, polyethers, thioethers and polythioethers, carboxyl, carboxamide and nitrile groups, sulfur-oxygen substituents; and phosphorus-oxygen substituents.
  • the presence of these substituents in amine containing alkanes, homocycles, and heterocycles imparts new and useful properties to the additive products. Reaction of the above amines with adducts lc, 2c and 3c, depending on reaction conditions, produces a wide assortment of useful amide imide and imine derivatives. The reduction ofthe imines with boranes affords useful amine products
  • Hydrazines useful in the present invention include hydrazine groups attached to alkanes, homocyclics, and heterocyclics as described above. Reaction of the above hvdrazines with adducts lc, 2c and 3c of the present invention affords useful hydrazide and hydrazone products Reduction of certain hydrazones with borohydride. for example, gives useful substituted hydrazine derivatives Monohydric alcohols useful in the present invention include hydroxy alkanes, hydroxy and hydroxyalkyl containing homocycles, and heterocycles as well as their substituted derivatives by analogy with the amines described above.
  • polyamines, amino alcohols, and polyhydric alcohols are reacted with the ene and radical adducts to give a wide variety of useful products.
  • An important feature of polyreactive nucleophiles is their ability to couple two or more adducts together thereby chain extending the product, and oftimes enhancing the viscometric properties of the product Moreover, the presence of multiple functionality in the radical and ene adducts leads to even more pronounced Mn increases, and enhanced V.I. performance owing to the ability of polyamines to induce chain extension via reaction with multiple functional groups attached to the adducts
  • Useful polyamines and substituted polyamines feature two or more amino groups selected from NH2 and/or NH radicals which are capable of reacting with the adducts of the present invention.
  • the amine groups can be attached to alkanes, homocycles, and heterocycles, in addition, the polyamine derivatives may also contain one or more substituents.
  • Useful polyamines feature two or more amino radicals such as NH2 and/or NH, and are attached to alkanes or branched alkanes containing from about 2 to about ten thousand carbons.
  • Other useful polyamines are those where the amino or aminoalkyl groups are attached to a homocycle, a heterocycle, or. wherein the NH groups ofthe polyamine are members ofa heterocyclic ring having from about 6 to about 30 members
  • the cyclic polyamines may contain other heteroatoms such as oxygen and sulfur. Examples of polyamines bearing alkane and substituted alkane groups include.
  • EDA ethylenediamine
  • PDA l,3-propane-diamine
  • DETA diethylenetriamine
  • TETA tri- ethylenetetramine
  • TEPA tetraethylenepentamine
  • PEHA pentaethyienehexamine
  • Another aspect of the present invention involves the post-treatment of the products Id, 2d, and 3d to further enhance their properties as fuel and lube additives.
  • the post-treatment, or "capping" of polyamine and polyol derivatives of Id, 2d, and 3d, with electrophilic reagents can endow these products with enhanced seal compatibility properties; enhanced product stability; antioxidant properties and improved chelating, complexing, and aggregation properties.
  • These attributes translate into improved dispersancy viscometrics and fluoroelastomer seal compatibility properties for the additives ofthe present invention.
  • Useful "capping" reagents for the post-treatment of products Id, 2d, and 3d include: boron-oxygen compounds, alkane carboxylic acids, anhydrides, and esters; 5- ,6-, and 7-membered lactones; alpha, beta-unsaturated acids and esters; diketones, and 1.3-keto esters, oxiranes, and thiranes, aldehydes, and ketones, isocyanates, and isothiocyanates, sulfur and sulfur-oxygen reagents; and phosphorus-oxygen and phosphorus-sulfur reagents.
  • Post-products containing boron can be formed via the addition of boric acid, ester or metaborate ester to the aminated adducts ofthe present invention.
  • a preferred method of the present invention involves the direct treatment of adducts with a soluble form of boron which is prepared by combining a mixture of a polyamine and boric acid, and heating the mixture at about 130°C until a clear liquid polyamine metaborate (PMB) salt is obtained as shown below wherein T is selected from the group consisting of ethylene, propylene, trimethylene, and (CH2CH2NH) X CH2CH2, and x is a numerical value ranging from about 1 to about 10.
  • Addition of the PMB to an adduct of the present invention at about 120°C to about 180°C appears to "bor-aminate" the adduct, and produces a borated polyamine dispersant in one step.
  • Polyalkenyl (e.g. polybutene) succinimides are a widely used class of dispersant for lubricant and fuels applications. They are prepared by the reaction of, for example, polyisobutylene with maleic anhydride to form polyisobutenyl-succinic anhydride, and then subsequently undergo a condensation reaction with ethylene amines
  • the dispersants of the present invention include this class of functionalized polymers but which undergo a condensation reaction with PMB.
  • the preferred dispersants of the present invention are based on the ethylene alpha-olefin polymers as disclosed in USSN 992, 192 and inco ⁇ orated herein by reference.
  • the preferred ethylene alpha-olefin copoiymer is ethylene butene
  • the preferred ethylene content is about 30 weight percent to about 50 weight percent Even more preferred is about 35 weight percent to about 45 weight percent. Most preferred is about 39 weight percent ethylene.
  • the ethylene content on a molar basis is preferably about 40 percent to about 67 percent. More preferred is about 45 to about 60 mole % ethylene.
  • R ⁇ in the above formula is alkyl of from 1 to 8 carbon atoms and more preferably is alkyl of from 1 to 2 carbon atoms
  • useful comonomers with ethylene in this invention include propylene, 1-butene, hexene-1, octene-1, etc., and mixtures thereof (e g mixtures of propylene and 1 -butene, and the like)
  • Preferred polymers are copolymers of ethylene and propylene and ethylene and butene- 1 Most preferred are copolymers of ethylene and butene- 1
  • Preferred ranges of number average molecular weights (Mn) for the copolymer are from 500 to 20,000, preferably from 1,000 to 8,000, even more preferably from 2,000 to 6,000 Most preferred are about 2,500
  • a convenient method for such determination is by size exclusion chromatography (also known as gel permeation chromatography (GPC) which additionally provides molecular weight distribution information
  • Such polymers generally possess an int ⁇ nsic viscosity (as measured in tetralin at 135°C) of between 0 025 and 0 6 dl/g, preferably between 0 05 and 0 5 dl/g, most preferably between 0 075 and 0 4 dl g
  • These polymers preferably exhibit a degree of crystallinity such that, when functionalized, they are essentially amo ⁇ hous
  • the preferred ethylene alpha-olefin polymers are further characterized in that up to about 95% and more of the polymer chains possess terminal vinylidene-type unsaturation
  • the preferred ethylene alpha-olefin polymer comprises polymer chains, at least about 30% of which possess terminal vinylidene unsaturation. Preferably at least about 50%, more preferably at least about 60%, and most preferably at least about 75% (e.g. 75 to 98%), of such polymer chains exhibit terminal vinylidene unsaturation
  • the percentage of polymer chains exhibiting terminal vinylidene unsaturation may be determined by FTLR spectroscopic analysis, titration, HNMR, or C13NMR.
  • the polymers can be prepared by polymerizing monomer mixtures comprising ethylene with other monomers such as alpha-olefins, preferably from 3 to 4 carbon atoms in the presence of a metallocene catalyst system comprising at least one metallocene (e.g. a cyclopentadienyl-transition metal compound) and an activator, e.g alumoxane compound
  • a metallocene catalyst system comprising at least one metallocene (e.g. a cyclopentadienyl-transition metal compound) and an activator, e.g alumoxane compound
  • the comonomer content can be controlled through selection of the metallocene catalyst component and by controlling partial pressure of the monomers.
  • the dispersants of the present invention can be prepared by derivatization, using PMB, of polymers functionalized by the Koch reaction, wherein the polymer backbone has Mn>500, and functionalization is by groups ofthe formula
  • R 3 is H, hydrocarbyl and at least 50 mole % of the functional groups are attached to a tertiary carbon atom of the polymer backbone or R 3 is aryl, substituted aryl or substituted hydrocarbyl
  • the functionalized polymer may be depicted by the formula
  • POLY is a hydrocarbon polymer backbone having a number average molecular weight of at least 500, n is a number greater than 0 and represents the functionality or average number of functional group per polymer chain
  • R 1 , R 2 and R 3 may be the same or different and are each H, hydrocarbyl with the proviso that either Rl and R 2 are selected such that at least 50 mole % of the CR*R 2 groups wherein both R* and R 2 are not H, or R 3 is aryl, substituted aryl or substituted hydrocarbyl.
  • the Koch reaction permits controlled functionalization of unsaturated polymers.
  • a carbon of the carbon-carbon double bond is substituted with hydrogen, it will result in an "iso" functional group, i.e. one of R ⁇ or R 2 is H; or when a carbon ofthe double bond is fully substituted with hydrocarbyl groups it will result in a "neo" functional group, i.e. both Rl or R 2 are non-hydrogen groups.
  • Polymers produced by processes which result in terminally unsaturated polymer chain can be functionalized to a relatively high yield in accordance with the Koch reaction. It has been found that the neo acid functionalized polymer can be derivatized to a relatively high yield.
  • the Koch process also makes use of relatively inexpensive materials, i.e. carbon monoxide at relatively low temperatures and pressures. Also the leaving group -YR 3 can be removed and recycled upon derivatizing the Koch functionalized polymer with amine.
  • the process for preparing the functionalized polymer of the present invention comprises the steps of catalytically reacting in admixture:
  • nucleophilic trapping agent selected from the group consisting of water, hydroxy-containing compounds and thiol-containing compounds, the reaction being conducted a) in the absence of reliance on transition metal as a catalyst; or b) with at least one acid catalyst having a Hammett acidity of less than 7; or c) wherein functional groups are formed at least 40 mole % of the ethylenic double bonds; or d) wherein the nucleophilic trapping agent has a pKa of less than 12.
  • the polymers having at least one ethylenic double bond are reacted via a Koch mechanism to form carbonyl or thio carbonyl group-containing compounds, which may subsequently be derivatized.
  • the polymers react with carbon monoxide in the presence of an acid catalyst or a catalyst preferably complexed with the nucleophilic trapping agent.
  • a preferred catalyst is BF3 and preferred catalyst complexes include BF3 ⁇ 2O and BF3 complexed with 2,4-dichlorophenol.
  • the starting polymer reacts with carbon monoxide at points of unsaturation to form either iso- or neo- acyl groups with the nucleophilic trapping agent, e.g. with water, alcohol (preferably a substituted phenol) or thiol to form respectively a carboxylic acid, carboxylic ester group, or thio ester.
  • At least one polymer having at least one carbon-carbon double bond is contacted with an acid catalyst or catalyst complex having a Hammet Scale acidity value of less than -7, preferably from -8.0 to -1 1.5 and most preferably from -10 to -1 1 5
  • an acid catalyst or catalyst complex having a Hammet Scale acidity value of less than -7, preferably from -8.0 to -1 1.5 and most preferably from -10 to -1 1 5
  • a carbenium ion may form at the site of one of carbon-carbon double bonds
  • the carbenium ion may then react with carbon monoxide to form an acylium cation
  • the acylium cation may react with at least one nucleophilic trapping agent as defined herein.
  • At least 40 mole %, preferably at least 50 mole %, more preferably at least 80 mole %, and most preferably 90 mole % of the polymer double bonds will react to form acyl groups wherein the non-carboxyl portion of the acyl group is determined by the identity ofthe nucleophilic trapping agent, i.e. water forms acid, alcohol forms acid ester and thiol forms thio ester.
  • the polymer functionalized by the recited process of the present invention can be isolated using fluoride salts
  • the fluoride salt can be selected from the group consisting of ammonium fluoride and sodium fluoride
  • nucleophilic trapping agents are selected from the group consisting of water, monohydric alcohols, polyhydric alcohols hydroxyl-containing aromatic compounds and hetero substituted phenolic compounds
  • the catalyst and nucleophilic trapping agent can be added separately or combined to form a catalytic complex
  • reaction mixture is further reacted with water or another nucleophilic trapping agent such as an alcohol or phenolic or thiol compound
  • nucleophilic trapping agent such as an alcohol or phenolic or thiol compound
  • the use of water releases the catalyst to form an acid.
  • hydroxy trapping agents releases the catalyst to form an ester
  • a thiol releases the catalyst to form a thio ester.
  • Koch product also referred to herein as functionalized polymer
  • De ⁇ vatization reactions involving ester functionalized polymer will typically have to displace the alcohol derived moiety therefrom Consequently, the alcohol derived portion of the Koch functionalized polymer is sometimes referred to herein as a leaving group
  • the ease with which a leaving group is displaced during derivatization will depend on its acidity, i e. the higher the acidity the more easily it will be displaced.
  • the acidity, in turn, of the alcohol is expressed in terms of its pKa The pKa value is determined from the corresponding acidic species in water at room temperature
  • Preferred nucleophilic trapping agents include water and hydroxy group containing compounds.
  • Useful hydroxy trapping agents include aliphatic compounds such as monohydric and polyhydric alcohols or aromatic compounds such as phenols and naphthols
  • the aromatic hydroxy compounds from which the esters of this invention may be derived are illustrated by the following specific examples phenol, naphthol, cresol, resorcinol, catechoi, 2-chlorophenol Particularly preferred is 2,4- dichlorophenol
  • the polymer added to the reactant system can be in a liquid phase
  • the polymer can be dissolved in an inert solvent
  • the polymer, catalyst, nucleophilic trapping agent and CO are fed to the reactor in a single step
  • the reactor contents are then held for a desired amount of time under the pressure of the carbon monoxide
  • the reaction time can range up to 5 hours and typically 0 5 to 4 and more typically from 1 to 2 hours
  • the reactor contents can then be discharged and the product which is a Koch functionalized polymer comprising either a carboxylic acid or carboxylic ester or thiol ester functional groups separated Upon discharge, any unreacted CO can be vented off Nitrogen can be used to flush the reactor and the vessel to receive the polymer
  • the functionalized polymer containing reaction mixture may be a single phase, a combination of a partitionable polymer and acid phase or an emulsion with either the polymer phase or acid phase being the continuous phase
  • the functionalized polymer is recovered by suitable means
  • the functionalized polymer whether prepared by halogenation, "ene” reaction, free radical grafting, phenol alkylation, or the Koch reaction is then derivatized with the PMB to make the dispersant of the present invention
  • Polyalkylene amines e g polyethylene amines
  • the preferred amines are "heavy polyamines"
  • the heavy polyamine as the term is used herein refers to polyamines containing more than six nitrogens per molecule, but preferably polyamine oligomers containing 7 or more nitrogens per molecule and with 2 or more primary amines per molecule
  • the heavy polyamine comprises more than 28 wt % (e g >32 wt %) total nitrogen and an equivalent weight of p ⁇ mary amme groups of 120-160 grams per equivalent
  • Commercial dispersants are based on the reaction of carboxylic acid moieties with a polyamine such as tetraethylenepentamine (TEPA) with five nitrogens per molecule
  • TEPA tetraethylenepentamine
  • PAM commercial polyamines known generically as PAM, contain a mixture of ethylene amines where TEPA and pentaethylene hexamine (PEHA) are the major part of the polyamine, usually less than about 80% Typical PAM is commercially available from suppliers such as the Dow Chemical Company under the trade name E-100 or from the Union Carbide
  • the heavy polyamine preferably comprises essentially no oxygen.
  • Typical analysis of HA-2 gives primary nitrogen values of about 7.8 milliequivalents (meq) (e.g. 7.7 - 7.8) of primary amine per gram of polyamine. This calculates to be about an equivalent weight (EW) of 128 grams per equivalent (g/eq).
  • EW equivalent weight
  • the total nitrogen content is about 32.0 - 33.0 wt. %.
  • Commercial PAM analyzes for 8.7 - 8.9 meq of primary amine per gram of PAM and has a nitrogen content of about 33 to about 34 wt. %.
  • Post-products containing boron can be formed via the addition of boric acid, ester or metaborate ester to aminated adducts of functionalized polymers including aminated polyalkenyl-succinic anhydrides, carboxylic acids, and esters.
  • a new, and preferred method for producing said post-products containing boron involves contacting adducts such as polyalkenyl succinic anhydrides, carboxylic acids, and esters with a soluble form of boron which is prepared by combining a mixture of a polyamine and boric acid, and heating the mixture at about 1 10°C to about 130°C until a clear liquid polyamine metaborate (PMB) salt is obtained as shown below wherein T is selected from the group consisting of ethylene, propylene, trimethylene, and (CH2CH2NH) X CH2CH2; and x is a numerical value ranging from about 1 to about 10.
  • adducts such as polyalkenyl succinic anhydrides, carboxylic acids, and esters
  • PMB polyamine metaborate
  • Electrophiles such as ethyl acetate, acetic anhydride, ethyl ortho-acetate, ethyl acetoacetate, and 2,4-pentandione react with polyamine-modified additives, thereby passivating their basic properties, and as a consequence, enhancing their seal compatibility properties.
  • thioacids such as sulfanes (di-, tri- and tetrasulfane), thiosulfuric acid, and thiophosphoric acid to polyamine-treated adducts produces salt derivatives with enhanced seal compatibility properties as well as antioxidant properties.
  • the adducts, products, and post-products have been found to be especially useful as fuel and lube additives.
  • the adducts, products and post-products of this invention are useful additives for fuels in the gasoline boiling range, for preventing or reducing deposits in the combustion chamber, and adjacent surfaces such as valves, ports, and spark plugs, and thereby reducing octane requirements.
  • the additives i.e., the adducts, products and post-products
  • a base oil in which the additives are dissolved or dispersed.
  • Such base oils may be natural or synthetic and include those conventionally employed as crankcase lubricating oils for spark-ignited and compression-Ignited internal combustion engines, such as automobile and truck engines, marine and railroad diesel engines, and the like.
  • compositions contain from about 0.01 to about 10 wt %, e.g., and preferably from about 0.1 to about 6 wt.%, based on the weight of said composition.
  • the additives of the present invention can be inco ⁇ orated into the lubricating oil in any convenient way.
  • they can be added directly to the oil by dispersing, or dissolving the same in the oil at the desired level of concentration, typically with the aid of a suitable solvent such as toluene, cyclohexane, or tetrahydrofuran.
  • a suitable solvent such as toluene, cyclohexane, or tetrahydrofuran.
  • these additives may be blended with a suitable oil soluble solvent or base oil to form a concentrate, which may then be blended with a lubricating oil base stock to obtain the final formulation.
  • Concentrates will typically contain from about 2 to about 80 wt.%, and preferably from about 5 to about 40 wt.% based on the weight ofthe additive.
  • Suitable polyamines include: EDA, PDA, DETA, TETA, TEPA, Polyamine-H, and o- phenylene diamine.
  • the additive of the present When employed in a lubricating oil composition, the additive of the present enhanced dispersancy and/or V.I. improvement.
  • Conventional additives as well as additives of the present invention can be used to meet the particular requirements of a lubricating oil composition.
  • the lubricating oil base stock for the additives of the present invention typically is adapted to perform a selected, function by the incorporation of additives therein to form lubricating oil compositions (i.e., formulations).
  • Representative additives typically present In such formulations include viscosity modifiers, corrosion inhibitors, oxidation inhibitors, friction modifiers, other dispersants. anti- foaming assents, anti-wear agents, pour point depressants, detergents, rust inhibitors and the like.
  • compositions containing the above additives are typically blended into the base oil in amounts which are effective to provide their normal attendant function. Representative effective amounts of such additives are illustrated as follows:
  • weight percents expressed herein are based on active ingredient (a.i.) content of the additive, and/or upon the total weight of any additive-package, or formulation which will be the sum ofthe a.i. weight of each additive plus the weight of total oil or diluent.
  • number average molecular weight is determined by Gel Permeation Chromatography (GPC).
  • GPC Gel Permeation Chromatography
  • the sediment level of the products is determined by variations of test method ASTM D-97 that are know to those skilled in the art. D-97 is inco ⁇ orated by reference herein in its entirety for all pu ⁇ oses.
  • Example 2 About a tenth mole (23.4 grams) of Polyamine-H (a commercial polyamine composed primarily of ethylene amines heavier than TEPA with the PEHA cut left in the product, and analyzing for 33 % nitrogen) was stirred at 120°C in a 250 ml beaker, while 12.4 grams of boric acid were added in gram portions over a 5 minute period. The mixture was stirred at 120°C for about an hour, or until a clear solution was obtained. The clear, amber-colored PAM metaborate (PMB) reagent analyzed for 6.05%) boron and 23.29% nitrogen
  • PMB PAM metaborate
  • TEPA tetraethylene pentamine
  • Example 4 About a tenth mole ( 18.9 grams ) of tetraethylene pentamine ( TEPA ) was stirred at room temperature in a 500 ml beaker, while 6.2 grams ( 0 1 mole ) of boric acid were added in one portion The mixture was then stirred at 120°C for about a half hour, or until a clear yellow solution of TEPA-metaborate was obtained
  • PLBSA polyisobutenyl succinic anhydride
  • Mn* 1000 and a saponification value of 108 were stirred at about 150°C in an open beaker.
  • Bor-amination of the PLBSA was effected by adding about 5 1 grams of the clear yellow solution of TEPA-metaborate prepared in Example 3 directly to the PLBSA reagent stirred at 150°C.
  • Some frothing was caused by the rapid evolution of water produced during amidation, but ceased after stirring for several minutes After heating at 150°C for about 4 hours, the reaction mixture was rotoevaporated for about 2 hours at about 120°C. Infrared analysis of the residue indicated that the amidation of PLBSA by TEPA-metaborate was complete. The sediment level ofthe product was negligible.
  • PIBSA polyisobutenyl succinic anhydride

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Abstract

La présente invention concerne des dispersants pour huiles lubrifiantes comprenant le produit de réaction d'un polymère fonctionnalisé et d'un métaborate de polyamine. Ce polymère fonctionnalisé est préparé à l'aide de réactions choisies dans le groupe composé des réactions avec adjuvants halogénés, ène thermique, greffe radicalaire au moyen d'un catalyseur, alkylation du phénol et carbonylation par Koch. Le métaborate de polyamine est le produit de réaction d'une polyamine et d'un acide borique.
PCT/US1996/018267 1995-11-15 1996-11-13 Derives de composes carbonyle s'utilisant comme additifs multifonctionnels pour carburants et lubrifiants Ceased WO1997018281A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1053485A (fr) * 1963-09-03 1964-08-26
US3284410A (en) * 1965-06-22 1966-11-08 Lubrizol Corp Substituted succinic acid-boron-alkylene amine-cyanamido derived additive and lubricating oil containing same
US3344069A (en) * 1965-07-01 1967-09-26 Lubrizol Corp Lubricant additive and lubricant containing same
DE1645266A1 (de) * 1964-04-16 1970-09-17 Mobil Oil Corp Verfahren zur Herstellung eines borierten Reaktionsproduktes
WO1994013709A2 (fr) * 1992-12-17 1994-06-23 Exxon Chemical Patents Inc Polymeres fonctionnalises par la reaction de koch et leurs derives
WO1995031488A1 (fr) * 1994-05-13 1995-11-23 Exxon Research And Engineering Company Composes carbonyles et leurs derives utilises comme additifs multifonctionnels de carburants et de lubrifiants

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1053485A (fr) * 1963-09-03 1964-08-26
DE1645266A1 (de) * 1964-04-16 1970-09-17 Mobil Oil Corp Verfahren zur Herstellung eines borierten Reaktionsproduktes
US3284410A (en) * 1965-06-22 1966-11-08 Lubrizol Corp Substituted succinic acid-boron-alkylene amine-cyanamido derived additive and lubricating oil containing same
US3344069A (en) * 1965-07-01 1967-09-26 Lubrizol Corp Lubricant additive and lubricant containing same
WO1994013709A2 (fr) * 1992-12-17 1994-06-23 Exxon Chemical Patents Inc Polymeres fonctionnalises par la reaction de koch et leurs derives
WO1995031488A1 (fr) * 1994-05-13 1995-11-23 Exxon Research And Engineering Company Composes carbonyles et leurs derives utilises comme additifs multifonctionnels de carburants et de lubrifiants

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