EP0677572B1 - Additif détergent-dispersant pour huiles lubrifiantes pour moteur à combustion interne et son procédé de préparation - Google Patents

Additif détergent-dispersant pour huiles lubrifiantes pour moteur à combustion interne et son procédé de préparation Download PDF

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Publication number
EP0677572B1
EP0677572B1 EP95105672A EP95105672A EP0677572B1 EP 0677572 B1 EP0677572 B1 EP 0677572B1 EP 95105672 A EP95105672 A EP 95105672A EP 95105672 A EP95105672 A EP 95105672A EP 0677572 B1 EP0677572 B1 EP 0677572B1
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Prior art keywords
anhydride
polyisobutylene
molecular weight
dicarboxylic acid
maleic anhydride
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EP95105672A
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German (de)
English (en)
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EP0677572A2 (fr
EP0677572A3 (fr
Inventor
Ferenc Dr. Dénes
János Kis
Jenö Baladincz
János Auer
Gyula Dr. Deák
Laszlo Dr. Bartha
Jenö Dr. Hancsok
Magda Dr. Kovács
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VESZPREMI EGYETEM
Mol Magyar Olaj es Gazipari Rt
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VESZPREMI EGYETEM
Mol Magyar Olaj es Gazipari Rt
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Priority to SI9530234T priority Critical patent/SI0677572T1/xx
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Publication of EP0677572A3 publication Critical patent/EP0677572A3/fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/86—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of 30 or more atoms
    • C10M129/95—Esters
    • 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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/16—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate polycarboxylic
    • 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
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • 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
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/26—Amines
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • 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
    • C10N2040/25—Internal-combustion engines
    • 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
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol-fuelled engines
    • 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
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • 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
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines

Definitions

  • the present invention particularly relates to a grafted polyisobutylene - polysuccinic anhydride based ashless detergent dispersant (DD) additive that increases both viscosity and viscosity index and which can be used advantageously for improving the properties of lubricating oils and to a process for the preparation thereof.
  • DD ashless detergent dispersant
  • the ashless, imide and ester type additives synthesised from alkenyl-succinic acid derivatives have been used for more than thirty years for the improvement of the detergent - dispersant properties of motor oils. Due to their polar and often basic character these additives restrict the formation and surface deposition of the insoluble acidic contaminations formed during the operation of the engine. Thus the life span of the engine and the duration of applicability of oils are significantly increased.
  • the alkenyl-succinic acid derivatives are generally mixed into the lubricating oils together with other metal containing DD additives, with VI improvers, antioxidants, anticorrosion and antiwear components, friction modifiers and foam inhibitors making use of advantageous interactions.
  • the synthesis of such additives is based on the recognition that in the first step of the succinimide synthesis when the polyolefins and the maleic anhydride (MAH) are reacted under specific conditions more than one MAH is coupled to the polyolefin molecule or alternatively the so called olefin - MAH copolymers are formed.
  • the so formed intermediates having more than two carboxylic groups are reacted with amines, polyamines, alcohols, polyalcohols, alkanolamines or their mixtures of various compositions then higher molecular weight polyimide, polyamide, polyester, polyester-amide type end products are obtained (e.g. U.S. Patent No. 4.234,435).
  • a serious disadvantage of this process is that hazardous chlorine is built in the polyolefin molecule during the addition reaction, and referred to the additive, it remains in the end product in a 0.001 - 0.5 weight percent.
  • EP 0 400 866 discloses an oil-soluble composition useful as a multifunctional viscosity improver additive for oleaginous composition
  • EP 0 400 866 discloses an embodiment of said composition which comprises reaction product of (A), (B) and (C) a C 50 to C 400 hydrocarbyl substituted carboxylic acid component containing 1 to 2 carboxylic acid groups or anhydride group.
  • EP 0 002 286 generally discloses an oil-soluble graft copolymer, suitable for use as an additive for lubricating oils and liquid hydrocarbon fuels, comprising substantially linear, substantially saturated, rubbery, olefinic hydrocarbon backbone polymer and graft polymerized thereon, copolymerized units of a monomer system comprising maleic acid and/or maleic anhydride and one or more other monomers copolymerizable with maleic acid or maleic anhydride, said copolymerized units being post-reacted with a polyamino compound containing one primary or secondary amino group or one primary amido group.
  • suitable backbone polymers include ethylene/propylene copolymers, ethylene/propylene/diene modified terpolymers, hydrogenated styrene-butadiene copolymers, styrene-isoprene copolymers and atactic polypropylene.
  • Succinimide derivatives obtained by grafting of ethylene - propylene copolymers have been produced and applied to achieve an additional DD effect beside their main viscosity and viscosity index increasing functions (EP 400866, EP 002286).
  • Successful application of olefin copolymers of a number average molecular weight lower than 15 000 have not been reported probably due to a loss in their flow property improving effect.
  • the invention is based on the recognition that the mentioned drawbacks of the synthesis based on grafting the hydrocarbon polymers limiting the average molecular weight of the applicable raw material can be eliminated by the appropriate control of the grafting reaction.
  • the recommended procedure makes feasible the synthesis of such intermediates from polyolefins of lower average molecular weight and in addition to this the intermediates obtained from polyisobutylenes or especially from their high alpha-olefin containing so called high reactivity homologous are suitable for the preparation of additives of new molecular structure showing higher viscosity and viscosity index improving effect, more advantageous antifriction effect and at the same time exhibit a better compatibility with the sealing materials as compared to the other well known ashless dispersants of molecular weight lower than 15 000.
  • a subject matter of the invention is an additive for use in an oil solution in lubricating oils of internal combustion engines, which contains imides and/or esters and/or ester amides of the reaction product of a polyisobutylene of a number average molecular weight from 800 - 15 000, an unsaturated reactive dicarboxylic acid and/or its anhydride, preferably maleic anhydride, and another low molecular weight unsaturated comonomer,
  • a further subject matter of the invention is a process for preparing a detergent - dispersant additive, wherein a dicarboxylic acid and/or its anhydride, preferably maleic anhydride, and another low molecular weight comonomer with an olefinic double bond or a mixture of such comonomers and/or a copolymer of a low degree of polymerization prepared previously and consisting of unsaturated dicarboxylic acid and/or its anhydride and the comonomer and/or comonomers are grafted to or reacted with a polyisobutylene of an average molecular weight from 800 - 15 000 by an addition reaction using the molar ratio 1.2 - 5.5 : 0.1 - 3.5 : 1 of dicarboxylic acid and/or its anhydride, preferably maleic anhydride : comonomer : polyisobutylene, where the solvent concentration providing homogeneous phase is 10 - 75 weight percent, preferably 35
  • Polyisobutylenes of a number average molecular weight between 1300 and 8000 were found to be the most advantageous.
  • Grafting the polar side chain into the PIB main chain results in a combined polymer structure having good thermal and chemical stability as well as viscosity increasing effect characteristic of polyisobutylenes, and at the same time the cold viscosity increasing effect is decreased significantly due to a decrease in the solubility of the polymer.
  • comonomers reactive, polar and apolar monomers of low molecular weight such as ethylene, propylene, butene-1, 1,3-butadiene, isobutylene, C 5-20 alpha olefins, styrene, acrylic acid, methacrylic acid, acrylates and methacrylates prepared from alcohols of C 1-20 , acrylonitrile or their mixtures have been applied.
  • polyisobutylene - polysuccinic acid products prepared from polyisobutylene, unsaturated dicarboxylic acid and/or its anhydride and from comonomer or from comonomer mixture having the general formula I. where:
  • SA succinic anhydride
  • the intermediate consisting of the above long apolar polyisobutylene chain and a shorter, strongly polar, random or alternating copolymer chain is especially suitable for the preparation of the imide and/or ester and/or amide and/or ester-amide derivatives of great dispersing effect, where the derivatives occurring in one polyisobutylene chain could be identical or different.
  • the additive prepared according to this invention could contain components of various average molecular weight in which the average number of molecules linked by the carboxyl groups is between 2 and 100.
  • the additive prepared according to this invention is used advantageously in an oil solution.
  • the concentration of the oil is at least 10 weight percent, preferably between 30 and 80 weight percent.
  • any type of refined oil, lubricating oil or base oil may be used.
  • maleic anhydride and comonomer or comonomers containing olefinic double bond or their copolymers are grafted to the starting polyisobutylenes.
  • the double bonds of the maleic anhydride and the comonomer or the comonomers are activated by a radical initiator and due to the consecutive coupling to the polyisobutylenes and/or due to the coupling of the random or alternating copolymers formed from the maleic anhydride and a comonomer a polymer chain is developed containing several SA groups (general formula I.).
  • the first step of the synthesis of the additive i.e. the reaction of the polyisobutylene and the unsaturated dicarboxylic acid and/or its anhydride, preferably maleic anhydride and comonomer or comonomers is performed in a homogeneous solution at an energetically favourable low temperature, with the suitable choice of the weight ratio corresponding to the molar ratio of the reactants of various reactivity, under circumstances unfavourable for the multiple coupling of the polyisobutylene occasionally in the presence of compounds controlling the structure of side chain containing polar groups.
  • the reaction of the polyisobutylene and the unsaturated dicarboxylic acid and/or its anhydride preferably maleic anhydride and the comonomer or the comonomers was carried out in a solvent containing components also within the boiling range of 110 - 250 °C and in which the reactants and the intermediates were readily dissolved at a concentration of 20 - 75 weight percent, preferably 35 - 60 weight percent with respect to the reaction mixture, in the temperature range 80 - 180 °C, preferably between 120 - 160 °C, within a reaction period of 1 - 16 hours, using 1.2 - 5.5 : 0.1 - 3.5 : 1 maleic anhydride : comonomer : polyisobutylene molar ratio, and applying 5 - 25 weight percent peroxide, with respect to the amount of maleic anhydride, or other type of initiator such as azobisisobutyronitrile or cumene hydroperoxide or if desired, compounds or their mixtures controlling the incorpor
  • organic peroxides such as dibenzoyl peroxide, di-tert-butyl peroxide, azobis-isobutyro dinitrile, azodicarboxylic amide, or their mixture can be used.
  • Compounds used for inhibiting undesirable side reactions such as e.g. decarboxylation, resin formation, or for controlling the MAH : comonomer incorporation ratio could be carboxylic acids with 1 - 20 carbon number, dicarboxylic acids or anhydrides, hydroxycarboxylic acids, ketones, ethers, esters, alcohols, water or the mixtures of these and their derivatives.
  • Isobutyl alcohol, isopropyl alcohol, succinic monobutyl ester can be applied advantageously. If desired, such additives are applied in a concentration of 0.01 - 5 weight percent with respect to the amount of the maleic anhydride.
  • highly reactive species may be formed that may participate in the addition and polymerisation reactions occurring in the reaction mixture.
  • reaction products have been identified by their 13 C and 1 H NMR spectra using deuterated chloroform as solvent. It has been pointed out that under the experimental circumstances applied in this invention the monomers added to the reaction mixture are mostly coupled to the ⁇ -double bond of the polyisobutylenes. This has been proved by the disappearance of the 13 C peaks at 114.5 and 143.6 ppm characteristic of the terminal double bonds of the polyisobutylenes, as well as the peaks of the 1 H spectra at 4.3 ppm and of the 13 C peaks at 136.6 ppm typical of the maleic anhydride and of the peaks characteristic of the double bonds of the comonomers. Experiments with maleic anhydride enriched in 13 C isotope proved the existence of bonds characteristic of the built in comonomer groups forming the grafted copolymer chains.
  • the solvent can be recovered by stripping out the components of a boiling point below 250 °C and the remaining heavier part, if desired, can be diluted in 20 - 60 weight percent by refined oil, preferably by a refined oil having viscosity of 2 - 15 mm 2 /s, at 100 °C.
  • the solution of the intermediate can be filtered without or with the addition of a filtration aid or filtration improving material in a 0.5 - 5 weight percent concentration.
  • the intermediate prepared according to this invention is reacted in the second so called acylation step with polyamines, polyalcohols, alcanol amines containing at least two reactive groups and/or their mixtures and/or their derivatives by using hydrocarbon and/or refined oil as solvent at 120 - 235 °C, in inert e.g.
  • a polysuccinimide and/or polyamide and/or polyester and/or polyester-amide based mixture of the additive is obtained (such as the polysuccinimide, general formula II.) where one or more components can be formed with significantly different molecular weights depending on the reagents and molar ratios used.
  • the important feature of the additive prepared according to this invention is due to the new structure of the intermediate.
  • this intermediate the presumably reactive SA and other groups are closely located at the end of the long polyisobutylene chain. Consequently, the growing of the macromolecule by multiple or chain like coupling is not hindered sterically, as in the case of other intermediates where the SA groups are randomly located either at the end or in between the polyisobutylene chains.
  • a multifunctional polyamine component e.g. ethylene- diamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, cyclic polyamine e.g. piperazine, diethyleneamino piperazine or the mixtures of these; as polyalcohol e.g. ethylene glycol, diethylene glycol, triethylene glycol, glycerol, trimethylol propane or pentaerythritol; as amino-alcohol e.g. ethanolamine, diethanolamine, triethanolamine, or the mixtures and derivatives of these can be used.
  • polyalcohol e.g. ethylene glycol, diethylene glycol, triethylene glycol, glycerol, trimethylol propane or pentaerythritol
  • amino-alcohol e.g. ethanolamine, diethanolamine, triethanolamine, or the mixtures and derivatives of these can be used.
  • the average molecular weight of the lower average molecular weight polymer is less than six times the number average molar weight of the polyisobutylene used as raw material.
  • the experimental circumstances of the acylation have to be chosen in such a way as to promote the formation of multiple couplings in the amide, imide and ester formation condensation reactions, i.e. that result in compounds characterised by polyamide, polyimide and polyester structure or by their combination. This can be achieved by keeping the molar ratio of the succinic anhydride group of the intermediate and the component to be acylated in the 0.7 - 5.5 : 1 range, preferably in the 1.7 - 4.5 : 1 range.
  • acidic or basic compounds such as petroleum sulfonic acid, p-toluenesulfonic acid, sulfuric acid, potassium hydroxide, triethanolamine, ethanolamine or ion exchange resin, preferably in hydrogen ion form can be used in the acylation reaction.
  • the petroleum sulfonic acid can be used especially advantageously which so far has been suggested as a catalyst only in the preparation of low molecular weight ( M n ⁇ 3500) alkenyl succinic esters (Hungarian Patent No. 205.778).
  • a structure modifying step can be applied as a finishing one.
  • a modifying compound is added in a 0.1 - 8 weight percent concentration referred to the reaction mixture, which is then stirred for 0.5 - 10 hours, at 80 - 230 °C temperature, in inert atmosphere.
  • the usual modifying chemicals can be applied, such as sulfur, active sulfur containing compounds, phosphorus pentasulfide, boric acid or its derivative, zinc containing compounds like zinc dialkyldithiophosphate, copper compounds including organic copper salts or complexes, molybdenum dioxide, organic acids e.g. fatty acids, glycolic acids, malic acid, fumaric acid, amides, alkenyl succinimide, their mixture or their derivatives.
  • the volatile components can be stripped off from the reaction mixture in vacuum, at 160 - 210 °C, the reaction product is then diluted by refined oil, and if desired, it can be filtered without or with the use of filtration aids.
  • the various components of different average molecular weight of the end product exhibit characteristic differences, the additives containing the lower molecular weight components in a higher concentration have a higher acid neutralising capacity and deposition removing effect, whereas the products containing the higher molecular weight components in a higher concentration have a significant dispersion stabilising, viscosity and viscosity index increasing as well as an anti-wear effect.
  • the degree of polydispersity characterising the molecular weight distribution is the ratio of the weight average and number average molecular weights.
  • the xylene and other unreacted lighter components can be removed by distillation carried out at 140 °C, at 15 kPa pressure, for 1.5 hours.
  • 1200 g refined lubricating oil (viscosity 3.5 mm 2 /s at 100 °C, viscosity index 95, pour point -22 °C) is added to the intermediate. After homogenization at 135 - 150°C and clarification the mixture is filtered in the presence of 3.5 weight percent filtration aid.
  • the acid number of the yellow - brown, viscous, oily intermediate is 43.0 mg KOH/g, its maleic anhydride content is 1.5 mg/g and it contains 1.7 succinic anhydride group on the average referred to a PIB molecule.
  • M n 2250
  • SAE-30 base oil viscosity 9.5 mm 2 /s at 100 °C
  • MOL Rt. solvent of high aromatic content having the trade name AROMATOL
  • reaction mixture is then stirred for further 6 hours and the AROMATOL and the other lighter components are boiled off at 155 °C, and 12 kPa pressure.
  • To the intermediate 250 g SN-150/A (MOL Rt.) refined oil is added at 120 °C.
  • the so obtained intermediate is first clarified with 2 weight percent filtration aid and in the presence of 1 weight percent of a filtration improving material it is filtered at 110 °C.
  • the acid number of the diluted and filtered intermediate is 39.7 mg KOH/g, its maleic anhydride content is 2.8 mg/g and it contains 1.6 succinic anhydride group on average referred to a PIB molecule.
  • the increase in the average molecular weight is less than 60 percent and the fraction of the compounds containing more than one succinic anhydride group per molecule is more than 55 percent.
  • the unreacted maleic anhydride was removed at 195 °C and 10 kPa pressure, the product was then mixed with 1150 g refined lubricating oil mentioned in Example "A" and the obtained mixture was filtered in the presence of 3 weight percent filtration aid.
  • the acid number of the filtered and diluted intermediate is 23.9 mg KOH/g, its maleic anhydride content is 1.3 mg/g and it contains 3.3 succinic anhydride group, on average, referred to a PIB molecule.
  • the increase in the average molecular weight and the widening of the molar weight distribution is less than 20 percent and the fraction of the compounds containing more than one SA group per molecule is 42 weight percent.
  • Example "A" 1200 g (0.5 mole) polypropylene and a 9 : 1 weight ratio mixture of an SN 150/A base oil (commercial product of the MOL Rt.) and kerosine were added. The mixture was heated to 80 ⁇ 4 °C and under stirring 98.6 g (1 mole) maleic anhydride and 4.2 g di-benzoyl peroxide were added, the mixture was stirred for 2 hours and the temperature was raised to 160 °C and the following components were added to it: 33 g isobutylene; as initiator 11.4 g di-tert-butyl peroxide; in 2 - 2 equal fractions per hour 43.3 g maleic anhydride, 6.5 g succinic monobutyl ester; 33 g styrene and within 6 hours in 5 equal fractions 88.7 g maleic anhydride.
  • initiator 11.4 g di-tert-butyl peroxide in 2 - 2 equal fractions per hour 43.3 g
  • the unreacted, lighter components were removed at 200 °C and at 10 kPa pressure during one and half hour.
  • the product was then diluted with 1060 g of the base oil mentioned in Example "B" and the obtained mixture was filtered in the presence of 4 weight percent filtration aid, the acid number of the filtered and diluted intermediate was 60.1mg KOH/g, its maleic anhydride content was 2.1 mg/g, its average SA : PP succination ratio was 2.4, the fraction of the components containing more than one SA group per molecule was 64 percent, the increase in the average molecular weight was less than 60 percent, and the measured widening of the molar weight distribution was 68 percent.
  • the acid number of the filtered and diluted intermediate was 9.3 mg KOH/g, its maleic anhydride content was 1.7 percentage, its average dicarboxylic acid - polyisobutylene coupling ratio was 2.3, the fraction of the compounds containing more than one group originating from the dicarboxylic acid was 47 percent, the increase in the average molecular weight and in the widening of the molar weight distribution were less than 10 percent.
  • the saponification number of the filtered and diluted intermediate was 78.8 mg KOH/g, its maleic anhydride content was 1.9 mg KOH/g, its average SA : PIB succination ratio was 3.1, the increase of the average molecular weight was less than 30 percent, the widening of the molar weight distribution was 40 percent, the fraction of the components containing more than one succinic anhydride group per molecule was 65 percent.
  • Example " A” The lighter components of the mixture were removed as in Example “ A " and the obtained intermediate was diluted by 1300 g of the oil mentioned in Example “ B “ , its acid number after clarification and filtration was 31.6 mg KOH/g, its free maleic anhydride content was 3.2 mg/g, the increase of its average molecular weight was less than 15 percent, the widening of the molar weight distribution was 45 percent, the average SA : PIB molar ratio was 1.3 the fraction of the components containing more than one succinic anhydride group per molecule was 35 percent.
  • Example " B” The lighter unreacted components of the mixture were removed as in Example “ B “ and the obtained intermediate was diluted by 1300 g of the base oil mentioned in Example “ B “. Its acid number after clarification and filtration again according to Example “ B “ was 87.6 mg /g, its free maleic anhydride content was 3.0 mg/g, the average SA : PIB succination ratio was 1.5; the increase of its average molecular weight was 60 percent, the widening of the molar weight distribution was less than 68 percent, the fraction of the components containing more than one succinic anhydride group per molecule was 47 percent.
  • the saponification number of the filtered and diluted intermediate was 70.3 mg KOH/g, its maleic anhydride content was 2.5 mg/g, its average number of the succinic anhydride groups linked to one PIB molecule was 1.6.
  • the fraction of the components containing more than 3 succinic anhydride groups per molecule was 34 percent, the increase of the average molecular weight was 550 percent, the widening of the molar weight distribution was 85 percent referred to the polyisobutylene used as raw material.
  • Example " E” Into the stirred tank reactor described in Example “ 1 " 844.5 g of the intermediate according to Example “ E " was weighed. Under stirring in inert atmosphere, 1.24 g diethylenetriamine was added at room temperature then at 70 °C 2.27 g tetraethylenepentamine was added and the reaction was carried out for 2 hours at 130 °C. Then a further 0.6 g diethylenetriamine and 1.1 g of tetraethylenepentamine were added in drops to the reaction mixture. The reaction was carried out under atmospheric pressure for 4 hours at 190 °C, and was filtered at 120 °C in the presence of 1 weight percent filtration aid. The nitrogen content of the obtained product was 0.2 weight percent, the ratio of the higher and lower molecular weight components was 0.1.
  • Example " F” Into the stirred tank reactor described in Example “ 1 " 711.9 g of the intermediate according to Example “ F " was weighed and in the presence of 0.2 weight percent petroleum-sulfonic acid catalyst, 6.0 g ethylenediamine was added to this mixture at room temperature and at atmospheric pressure, then the temperature was raised to 190 °C, and the pressure to 15x10 2 kPa and the acylation reaction was carried out for 6 hours. To the reaction mixture 11.3 g tetraethylene- pentamine was added and at 215 °C, and 10 3 kPa pressure the reactants were mixed for 2 hours. After filtration at 120 °C in the presence of 1 weight percent filtration aid the nitrogen content of the obtained product was 0.9 weight percent, the ratio of the higher and lower molecular weight components was 1.25.
  • Example "H” Into the stirred tank reactor described in Example " 1 " 711.3 g of the intermediate prepared according to Example “H” was weighed then in nitrogen atmosphere 10.3 g diethylenetriamine was added at room temperature and at 120°C, 37.8 g tetraethylenepentamine was added and the acylation reaction carried out for 2 hours at 250 °C was followed by the addition of 13.6 g pentaerythritol and 2.4 g of petroleum sulfonic acid as catalyst. After a 3 hours final reaction period at 15 kPa pressure the product was filtered in the presence of 3 weight percent filtration aid. The difficult-to-filtrate product was only partially soluble in base oil due to its 2.2 percent nitrogen content.
  • Example " 1" 768.5 g of the acylation reagent used in Example “ I " was weighed, in inert atmosphere, at atmospheric pressure. Under continuous stirring at 80 °C, first 21.2 g diethylene glycol was added in 0.5 hours using a 80 °C/hour heating rate, then 18.9 g tetraethylenepentamine was added in drops to the reaction mixture and the acylation reaction was carried out at 180 °C, under atmospheric pressure for 6 hours. The nitrogen content of the filtered end product was 0.82 weight percent, the ratio of the higher and lower molecular weight components was 0.4.
  • oil content of all the end products was adjusted to 50 percent before further use.
  • oil content of the end product prepared in the various examples was lower than 50 percent then it was adjusted to this value by dilution with the oil component used in the synthesis.
  • refined lubricating oils characterised in Examples " A " and " B " were used.
  • the efficiency of the detergent - dispersant effect of the additives mentioned in the above examples was evaluated according to the method described by L.Bartha et al.: Method of determination of optimum composition of detergent - dispersant engine oil additives, Hung. J. Ind. Chem.,1979 7, 359-366.
  • the potential detergent - dispersant effect (PDDE) values are given in terms of percentage as the 225th part of the sum of the dispersion stabilising effect of the additive (detergent index, DI, %) and its washing effect (M, mm).
  • the deposition reducing effect was evaluated by identical methods given in the above quoted publication on the basis of results obtained by the so called panel coking method.
  • the dispersant effect of the additive has also been evaluated by the so called spot dispersancy test method.
  • the oil mixture containing the additive or additives to be investigated is mixed in a high speed mixer with 2 percent carbon black of a specific quality and the suspension obtained is treated in six different ways (keeping them at various temperatures, in the presence or absence of water) and from the six suspensions samples are dropped on filter paper and the ratio of the diameters of the carbon black and the oil spots is evaluated after 48 hours.
  • the theoretical maximum of the sum of the six results is 600 percent, the higher the dispersant effect the higher this value.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Detergent Compositions (AREA)

Claims (6)

  1. Additif pour utilisation dans une solution huileuse dans des huiles lubrifiantes pour moteurs à combustion interne, qui contient des imides et/ou des esters et/ou des esters amides du produit de la réaction d'un poly-isobutylène d'un poids moléculaire moyen numérique de 800 à 15.000, d'un acide dicarboxylique réactif insaturé et/ou de son anhydride, de préférence l'anhydride maléique, et d'un autre comonomère insaturé de faible poids moléculaire,
    dans lequel ledit produit de la réaction contient en moyenne 1,6 à 6,0 acides dicarboxyliques et/ou son anhydride, de préférence des groupes anhydride succinique, par chaíne de poly-isobutylène,
    dans ledit produit de la réaction la concentration des molécules contenant plus d'un acide dicarboxylique et/ou son anhydride, de préférence le groupe anhydride succinique, est supérieur à 25%,
    l'élargissement de la distribution des poids moléculaires dudit produit de la réaction est inférieur à 70 pour cent, par rapport au poly-isobutylène de départ,
    et dans ledit produit de la réaction le poly-isobutylène est greffé sur ou mis à réagir avec un acide dicarboxylique et/ou son anhydride, de préférence l'anhydride succinique, contenant le copolymère formé à partir d'un comonomère insaturé de faible poids moléculaire, d'un poids moléculaire inférieur à 500, ou à partir d'un mélange de tels comonomères, et à partir d'un acide dicarboxylique réactif insaturé et/ou de son anhydride, de préférence l'anhydride maléique, en utilisant un rapport molaire de 1,2-5,5 :0,1-3,5 :1 = acide dicarboxylique et/ou son anhydride, de préférence l'anhydride maléique:comonomère:poly-isobutylène, et
    lesdits imides et/ou esters et/ou esters amides dudit produit de la réaction sont obtenus en faisant réagir les groupes acide dicarboxylique et/ou son anhydride, de préférence l'anhydride succinique du copolymère lié au poly-isobutylène dans un rapport de 0,7-5,5 avec des composés au moins bifonctionnels contenant un ou plusieurs groupes amines et/ou hydroxyles.
  2. Additif selon la revendication 1, dans lequel ledit produit de la réaction contient en moyenne 1,8 à 4,0 groupes anhydride succinique par chaíne de poly-isobutylène.
  3. Additif selon la revendication 1, dans lequel le nombre moyen de molécules liées par la réaction des groupes carboxyliques est compris entre 2 et 100 dans les constituants de divers poids moléculaires moyens.
  4. Procédé de préparation d'un additif détergent-dispersant, dans lequel un acide dicarboxylique et/ou son anhydride, de préférence l'anhydride maléique, et un autre comonomère de faible poids moléculaire comportant une double liaison oléfinique ou leurs copolymères sont greffés à un poly-isobutylène d'un poids moléculaire moyen de 800 à 15.000 par une réaction d'addition en utilisant un rapport molaire de 1,2-5,5 :0,1-3,5 :1 de l'acide dicarboxylique et/ou de son anhydride, de préférence l'anhydride maléique:comonomère:poly-isobutylène, dans lequel la concentration du solvant donnant la phase homogène est de 10 à 75 pour cent en poids, de préférence de 35 à 60 pour cent en poids par rapport au mélange réactionnel, en présence de 5 à 25 pour cent en poids d'un initiateur de la polymérisation radicalaire et de 0,01 à 5 pour cent en poids, par rapport à l'acide dicarboxylique et/ou son anhydride, de préférence l'anhydride maléique, d'un constituant de contrôle du rapport d'incorporation du monomère, sous une pression de 1 - 15 x 102 kPa et de préférence dans une atmosphère d'azote et/ou d'hydrocarbure, à 80-180°C, en 1 à 16 heures, pendant que la concentration de l'acide dicarboxylique et/ou de son anhydride, de préférence l'anhydride maléique, et du comonomère est maintenue en-dessous de 5 pour cent en poids, l'intermédiaire obtenu est débarrassé de sa teneur en solvant et est dilué avec une huile de base raffinée, si on le désire, et, si nécessaire, il est clarifié et filtré en présence d'un adjuvant de filtration, l'intermédiaire est mis en réaction avec des composés au moins bifonctionnels contenant un ou plusieurs groupes amines et/ou hydroxyles, pendant que le rapport des composés portant les groupes acide dicarboxylique et/ou son anhydride, de préférence l'anhydride succinique, et les groupes amines et/ou hydroxyles est de 0,7 à 5,5, dans lequel la réaction est effectuée sous une pression de 0,05 à 6 x 102 kPa, à une température de 120 à 235°C, en 2 à 15 heures et facultativement en présence d'un catalyseur à 0,1 à 2 pour cent en poids, par rapport au mélange réactionnel, et le produit, si on le désire, est modifié d'une façon habituelle, dilué et filtré.
  5. Procédé selon la revendication 4, dans lequel la réaction entre le poly-isobutylène, l'anhydride maléique et le comonomère est effectuée dans un solvant ou dans un mélange de solvants ayant des constituants hydrocarbonés dont le point d'ébullition est inférieur à 250°C, à une concentration d'au moins 3 pour cent en poids.
  6. Procédé selon la revendication 4, dans lequel la modification est réalisée avec des composés contenant du bore, du soufre, du cuivre et/ou du molybdène et/ou un anhydride succinique ou un ester amide de polyalkényle.
EP95105672A 1994-04-15 1995-04-13 Additif détergent-dispersant pour huiles lubrifiantes pour moteur à combustion interne et son procédé de préparation Expired - Lifetime EP0677572B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
SI9530234T SI0677572T1 (en) 1994-04-15 1995-04-13 Detergent-dispersant additive for lubricating oils of internal combustion engines and its preparation process

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
HU9401100 1994-04-15
HU9401100A HU214008B (hu) 1994-04-15 1994-04-15 Detergens-diszpergens adalékok belső égésű motorok kenőolajaihoz és előállítási eljárásuk

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EP0677572A2 EP0677572A2 (fr) 1995-10-18
EP0677572A3 EP0677572A3 (fr) 1996-12-18
EP0677572B1 true EP0677572B1 (fr) 1999-01-07

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AT (1) ATE175439T1 (fr)
CZ (1) CZ292648B6 (fr)
DE (1) DE69507068T2 (fr)
DK (1) DK0677572T3 (fr)
ES (1) ES2128606T3 (fr)
GR (1) GR3029741T3 (fr)
HU (1) HU214008B (fr)
PL (1) PL180877B1 (fr)
RO (1) RO119551B1 (fr)
RU (1) RU2139921C1 (fr)
SI (1) SI0677572T1 (fr)
SK (1) SK281687B6 (fr)
UA (1) UA45337C2 (fr)
WO (1) WO1995028460A1 (fr)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
US11193053B2 (en) 2017-04-13 2021-12-07 Bl Technologies, Inc. Wax inhibitors for oil compositions and methods of using wax inhibitors to reduce wax deposition from oil

Families Citing this family (8)

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Publication number Priority date Publication date Assignee Title
EP0733697B1 (fr) * 1995-03-24 2000-05-10 Ethyl Petroleum Additives Limited Dispersants post-traités
DE69624522T2 (de) * 1995-03-24 2003-06-26 Ethyl Petroleum Additives Ltd., Bracknell Schmieröldispergiermittel
HU213255B (en) * 1995-09-25 1997-05-28 Mol Magyar Olaj Es Gazipari Rt Multiple- stage engineoil and lubricant composition and additive-pocket
CA2189918C (fr) * 1995-11-13 2005-01-25 Richard Mark Scott Additifs de dispersion
FI112796B (fi) * 2000-04-14 2004-01-15 Valtion Teknillinen Menetelmä oligo-/polymeripihkahappoaimididendrimeerien valmistamiseksi ja niiden käyttö
US6906011B2 (en) * 2001-11-09 2005-06-14 Chevron Oronite Company Llc Polymeric dispersants prepared from copolymers of low molecular weight polyisobutene and unsaturated acidic reagent
CN101284897B (zh) * 2008-06-05 2010-06-02 上海交通大学 马来酸酐接枝聚异丁烯共聚物的溶剂热制备方法
CN114717037A (zh) * 2021-01-06 2022-07-08 中国石油天然气股份有限公司 一种耐高温无灰分散剂的制备方法

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US161452A (en) * 1875-03-30 Improvement in rotary reversing and cut-off valves
US440659A (en) * 1890-11-18 Darning-last
US4036772A (en) * 1975-03-03 1977-07-19 The Lubrizol Corporation Esters made from the reaction product of low molecular weight ethylenically unsaturated acylating agents and oxidized ethylene-propylene interpolymers
EP0031236A2 (fr) * 1979-12-20 1981-07-01 The British Petroleum Company p.l.c. Additifs pour lubrifiant, leur procédé de préparation et lubrifiants les contenant
GB2102813A (en) * 1981-06-29 1983-02-09 Exxon Research Engineering Co Haze-free polymer additives for fuels and lubricants
EP0355895A2 (fr) * 1988-08-05 1990-02-28 Shell Internationale Researchmaatschappij B.V. Procédé de préparation de dérivés de l'anhydride succinique

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GB8329082D0 (en) * 1983-11-01 1983-12-07 Bp Chem Int Ltd Low molecular weight polymers of 1-olefins
IN172215B (fr) * 1987-03-25 1993-05-08 Lubrizol Corp
CA2015061A1 (fr) * 1989-05-30 1990-11-30 Antonio Gutierrez Additifs multifonctionnels modifiant l'indice de viscosite, derives de polyamines contenant un groupe amine primaire et au moins un groupe amine secondaire

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US161452A (en) * 1875-03-30 Improvement in rotary reversing and cut-off valves
US440659A (en) * 1890-11-18 Darning-last
US4036772A (en) * 1975-03-03 1977-07-19 The Lubrizol Corporation Esters made from the reaction product of low molecular weight ethylenically unsaturated acylating agents and oxidized ethylene-propylene interpolymers
EP0031236A2 (fr) * 1979-12-20 1981-07-01 The British Petroleum Company p.l.c. Additifs pour lubrifiant, leur procédé de préparation et lubrifiants les contenant
GB2102813A (en) * 1981-06-29 1983-02-09 Exxon Research Engineering Co Haze-free polymer additives for fuels and lubricants
EP0355895A2 (fr) * 1988-08-05 1990-02-28 Shell Internationale Researchmaatschappij B.V. Procédé de préparation de dérivés de l'anhydride succinique

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Publication number Priority date Publication date Assignee Title
US11193053B2 (en) 2017-04-13 2021-12-07 Bl Technologies, Inc. Wax inhibitors for oil compositions and methods of using wax inhibitors to reduce wax deposition from oil
US11261369B2 (en) 2017-04-13 2022-03-01 Bl Technologies, Inc. Maleic anhydride copolymer with broadly dispersed ester side chain as wax inhibitor and wax crystallization enhancer

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SK281687B6 (sk) 2001-06-11
EP0677572A2 (fr) 1995-10-18
SK131596A3 (en) 1997-07-09
CZ299796A3 (en) 1997-04-16
GR3029741T3 (en) 1999-06-30
HU214008B (hu) 1998-04-28
PL180877B1 (pl) 2001-04-30
HU9401100D0 (en) 1994-07-28
RO119551B1 (ro) 2004-12-30
DE69507068D1 (de) 1999-02-18
CZ292648B6 (cs) 2003-11-12
ATE175439T1 (de) 1999-01-15
EP0677572A3 (fr) 1996-12-18
DK0677572T3 (da) 1999-09-13
WO1995028460A1 (fr) 1995-10-26
RU2139921C1 (ru) 1999-10-20
SI0677572T1 (en) 1999-06-30
PL316793A1 (en) 1997-02-17
ES2128606T3 (es) 1999-05-16
UA45337C2 (uk) 2002-04-15
DE69507068T2 (de) 1999-07-01

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