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US20040092412A1 - Emulsifiers, especially based on polyisobutylenamines - Google Patents

Emulsifiers, especially based on polyisobutylenamines Download PDF

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US20040092412A1
US20040092412A1 US10/469,594 US46959403A US2004092412A1 US 20040092412 A1 US20040092412 A1 US 20040092412A1 US 46959403 A US46959403 A US 46959403A US 2004092412 A1 US2004092412 A1 US 2004092412A1
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compound
fuel
alkyl
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Stephan Hueffer
Cordula Mock-Knoblauch
Gregor Schürmann
Arno Lange
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BASF SE
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Definitions

  • the present invention relates to compounds, in particular based on polyisobutyleneamines, which are suitable as emulsifiers for water-in-oil emulsions, processes for the preparation of such compounds and the emulsions themselves.
  • the present invention also relates to the use of such compounds as additives for fuels and lubricants and as corrosion-inhibiting additives in aqueous liquids, and fuels, lubricants, fuel additive concentrates and lubricant additive concentrates and aqueous liquids containing the novel compounds.
  • U.S. Pat. No. 4,225,447 describes water-in-oil emulsions which are used as lubricants and contain a polyisobutenyl-substituted succinic anhydride, an alkali (alkaline earth) metal salt of a polyisobutenyl-substituted succinic acid or a polyisobutenylsubstituted succinamide as an emulsifier.
  • GB-A 2,157,744 discloses drilling fluids which contain both an emulsifier, i.e. graft or block copolymers of polycarboxylic acids and polyethylene glycol, and surfactants.
  • the surfactants used are compounds which are prepared from a polyisobutenyl-substituted succinic anhydride and polyols, polyamines, hydroxycarboxylic acids or amino alcohols.
  • EP-A 0 156 572 describes the use of anionic surface-active substances based on polyisobutenyl-substituted succinic acid derivatives for the preparation of water-in-oil or oil-in-water emulsions.
  • alkoxylated polyisobutylenes as emulsifiers in water-in-fuel emulsions.
  • These alkoxylated polyisobutylenes can be described by the formula R—(CH 2 ) n —(O-A) m —OH.
  • R is a polyisobutylene having a weight average molar mass of from 300 to 2300, preferably from 500 to 2000.
  • A is an alkylene radical of 2 to 8 carbon atoms.
  • m is a number from 1 to 200 which is chosen so that the alkoxylated polyisobutylene contains from 0.2 to 1.5 alkylene oxide units, preferably 0.5 alkylene oxide unit, per C 4 unit; n is either 0 or 1.
  • BASF AG's German Application filed on Jul. 28, 2000 and having the application number 100 36 956.1 describes, inter alia, the use of amides of the formula R1R 2 NR 3 as emulsifiers in water-in-oil emulsions, where R 3 is an acyl radical of a mono- or polycarboxylic acid, R 1 is derived, inter alia, from a poly-1-butylene, poly-2-butylene or isobutylene or a mixture thereof and R 2 may be a polyalkylenepolyamine or a polyalkyleneimine radical.
  • U.S. Pat. No. 5,858,029 describes friction-reducing additives for fuels and lubricants, in particular compounds of the formula R 1 (—O(R 2 )—) a NH(CO)—R 3 —OH, where R 1 is C 1 - to C 60 -alkyl, R 2 is C 1 - to C 4 -alkylene, a is an integer from 1 to 12 and R 3 is C 1 - to C 4 -alkylene or substituted alkylene or cycloalkylene, being used as friction-reducing additives.
  • polyisobutenyl-substituted succinimides may be present as dispersants and polyalkyleneamines, such as polyisobutyleneamines, may be present as surfactants.
  • R 1 is unsubstituted or C 1 -C 1-2 -alkyl-substituted C 1 -C 8 -alkylene or C 2 -C 8 -alkenylene
  • R 2 is linear or branched C 8 -C 350 -alkyl or C 8 -C 350 -alkenyl
  • R 3 and R 4 independently of one another, are each H, methyl or ethyl, and R 3 and R 4 together have not more than 2 carbon atoms,
  • R 5 and R 6 independently of one another, are each H, M + , SO 3 H, SO 3 ⁇ M + , OPO 3 H, OPO 3 ⁇ M + or C(O)R 7 ,
  • M + is NH 4 + , an alkali metal ion or 0.5 alkaline earth metal ion,
  • R 7 is a linear C 2 -C 10 -hydrocarbon radical substituted by at least one hydrophilic group and
  • y and z independently of one another, are each an integer from 0 to 50 and
  • R 5 is H if y is 0, and R 6 is H if z is 0.
  • novel compounds (I) can be used as emulsifiers in water-in-oil emulsions.
  • the fact that frequently lower concentrations than with the use of conventional emulsifiers are required for producing stable emulsions is an advantage. If the novel compounds are used in oil-in-water emulsions, stable vesicles can be produced under the action of ultrasound.
  • novel compounds can also be used in a variety of ways, for example as additives in fuels and lubricants, as corrosion-inhibiting additives in aqueous liquids and as dispersants for pigments, such as TiO 2 .
  • the present invention also relates to processes for the preparation of the compounds (I). These processes are shown schematically in FIG. 1.
  • dicarboxylic acids and amines can be reacted with one another both in organic solvents and in the absence of a solvent.
  • Suitable organic solvents are, for example, Solvesso® 150 from Shell and isododecane.
  • the reaction is carried out under reduced pressure, for example at from 5 to 50 mbar, and the resulting water is distilled off continuously during the reaction. Purification of the resulting bisamides (II)—before further reaction—is generally unnecessary.
  • the bisamide (II) thus obtainable is then reacted with alkylene oxides (III) by a process known to a person skilled in the art to give alcohols of the formula I in which R 5 and R 6 are each H (FIG. 1, Reaction step a2).
  • This reaction is carried out in general in the presence of a conventional basic catalyst, such as KOH, NaOH, NaOMe, KtBuO, Ca(OH) 2 or CaO, or a support catalyst, such as a zeolite.
  • Hydrophilic groups can be introduced into the novel compounds (I) thus obtainable, in which R 5 and R 6 are each H.
  • alkali (alkaline earth) metal salts such as alkali (alkaline earth) metal hydroxides
  • compounds (I) in which R 5 and R 6 are each H can be prepared by first reacting amines R 2 —NH 2 with alkylene oxides (III) to give alcohols of the formula IV. Dicarboxylic acids HO 2 C—R 1 —CO 2 H are then reacted with the alcohols (IV), in general under the same reaction conditions which are applied to the reaction of the dicarboxylic acids HO 2 C—R 1 —CO 2 H with the amines R 2 —NH 2 .
  • Dicarboxylic acids HO 2 C—R 1 —CO 2 H in which R 1 is C 1 -C 8 -alkylene or C 2 -C 8 -alkenylene and is unsubstituted or substituted by C 1 -C 12 -alkyl are used.
  • alkenylene also includes polyunsaturated bivalent hydrocarbon radicals R 1 .
  • Suitable dicarboxylic acids are, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, which may carry C 1 -C 12 -alkyl groups in any desired position.
  • the use of unsubstituted dicarboxylic acids is preferred.
  • succinic acid, glutaric acid, adipic acid, pimelic acid or suberic acid is preferably used, particularly preferably succinic acid, glutaric acid or adipic acid.
  • amines R 2 —NH 2 in which R 2 is linear or branched C 8 -C 350 -alkyl or C 8 -C 350 -alkenyl are suitable for the preparation of compounds (1) in which R 5 and R 6 are each H.
  • alkenyl also includes polyunsaturated hydrocarbon radicals R 2 .
  • Amines R 2 —NH 2 in which R 2 is C 22 -C 350 -polyisobutenyl are preferably used.
  • Polyisobutyleneamines R 2 —NH 2 where R 2 is C 22 -C 350 -polyisobutenyl are prepared from the corresponding polyisobutylenes by standard processes, as described, for example, in DE-A 196 20 262, EP-A 0 244 616 and WO-A 97/03946.
  • the amount of amino groups can be determined by titration with HCl and then converted into mg KOH per g of substance. The amount of amino groups per unit weight of substance is then the amine number.
  • polyisobutylenes which have a number average molecular weight from 300 to 5000, preferably from 500 to 2300, particularly preferably from 500 to 1000, are used for the preparation of the polyisobutyleneamines.
  • polyisobutylenes having a number average molecular weight within said ranges those which have a high content of vinylidene groups are preferably used. In the context of the present invention, this is understood as meaning an amount of ⁇ 70, preferably ⁇ 80, particularly preferably ⁇ 85, mol % of vinylidene groups.
  • polyisobutylenes which have a number average molecular weight within the abovementioned ranges, a high content of vinylidene groups and a uniform polymer skeleton structure are particularly preferably used.
  • polyisobutylenes having a uniform polymer skeleton structure are those polyisobutylenes which are composed of at least 85, preferably at least 90, particularly preferably at least 95, % by weight of isobutylene units.
  • Polyisobutylenes having a number average molecular weight within said ranges, a high content of vinylidene groups and a uniform skeleton structure may furthermore have a polydispersity of ⁇ 2.5, preferably ⁇ 2.0.
  • Polydispersity is understood as meaning the quotient M w /M n of weight average molecular weight M w and number average molecular weight M n .
  • the polydispersity is a measure of the molecular weight distribution of a polymer.
  • Polyisobutylenes which have a number average molecular weight within said ranges, are composed substantially of isobutylene units and have a high content of vinylidene groups are obtainable, for example, under the trade name Glissopal® from BASF AG, such as Glissopal® 1000 having an M n of 1000, Glissopal® V 33 having an M n of 550 and Glissopal® 2300 having an M n of 2300.
  • polyisobutyleneamines examples are the compounds obtainable under the trade name Kerocom® PIBA from BASF AG.
  • alkylene oxides (III) are ethylene oxide, propylene oxide, 1-butylene oxide and 2-butylene oxide. Ethylene oxide and propylene oxide are preferably used.
  • R 7 is a linear C 2 -C 10 -hydrocarbon radical substituted by at least one hydrophilic group
  • C 2 -C 10 -hydrocarbon radical includes C 2 -C 10 -aLkyl, C 2 -C 10 -alkenyl and C 7 -C 10 -alkylaryl.
  • hydrophilic groups also includes positively or negatively charged groups, and the term alkenyl includes both monounsaturated and polyunsaturated hydrocarbon radicals.
  • hydrophilic groups are —NH 2 , —NH 3 + , —NR 3 + where R is C 1 -C 6 -alkyl, —CO 2 H, —CO 2 ⁇ , OPO 3 H and OPO 3 ⁇ .
  • R 7 —CO 2 H corresponds, for example, to amino acids having at least one additional carboxyl group in the molecule.
  • novel compounds (I) can be used as emulsifiers in the preparation of water-in-oil emulsions.
  • the present invention also relates to its use. It may be necessary to purify these compounds and their intermediates, for example when these compounds are used as emulsifiers for water-in-oil emulsions in the cosmetics or pharmaceutical sector.
  • novel water-in-oil emulsions contain in general from 95 to 60% by weight of oil, from 3 to 35% by weight of water and from 0.2 to 10% by weight of a novel compound of the formula I.
  • Examples of vegetable, animal or synthetic oils or fats are triglycerides and glycol esters (esters of glycolic acid) of lauric acid, myristic acid, stearic acid, palmitic acid, oleic acid, linoleic acid and linolenic acid.
  • Compounds of the formula I are also used in water-in-oil emulsions in which the oil phase is formed by a fuel or a light or heavy heating oil.
  • Compounds of the formula I in which R 5 and R 6 are not H are preferably used, and compounds of the formula I in which R 5 and R 6 are each SO 3 H, SO 3 ⁇ M + or C(O)R 7 are particularly preferably used.
  • All conventional fuels may be used, for example diesel fuels, gasoline fuel and kerosene. Diesel fuel is preferably used.
  • Novel water-in-fuel emulsions may also contain one or more C 1 -C 4 -alcohols and/or monoethylene glycol, in particular monoethylene glycol.
  • the amount of C 1 -C 4 -alcohol and/or monoethylene glycol used is from 5 to 50% by weight, based on the amount of water.
  • the temperature range in which the emulsion is stable can be broadened.
  • novel water-in-fuel emulsions have high stability and good efficiency during combustion. It is also possible to obtain good exhaust gas values, the emission of soot and NO x being significantly reduced, in particular in diesel engines. Substantially complete and residue-free combustion without deposits on the components of the combustion apparatus, for example injection nozzles, pistons, annular grooves, valves and cylinder head, can be achieved.
  • the water-in-fuel emulsions according to the present invention may have further components.
  • further emulsifiers such as sodium laurylsulfate, quaternary ammonium salts, such as ammonium nitrate, alkylglycosides, lecithins, polyethylene glycol ethers and esters, sorbitan oleates, stearates and ricinoleates, C 13 -oxo alcohol ethoxylates and alkylphenol ethoxylates, and the block copolymers of ethylene oxide and propylene oxide, such as the Pluronic® grades from BASF AG.
  • emulsifiers such as sodium laurylsulfate, quaternary ammonium salts, such as ammonium nitrate, alkylglycosides, lecithins, polyethylene glycol ethers and esters, sorbitan oleates, stearates and ricinoleates, C 13
  • a combination of one or more of the abovementioned further emulsifiers together with the novel emulsifiers is preferably used for the novel water-in-fuel emulsions.
  • these further emulsifiers are employed in amounts of from 0.5 to 5, preferably from 1 to 2.5, % by weight, based on the total composition.
  • the amount of this further emulsifier is chosen so that the total amount of emulsifier, i.e. novel emulsifier plus further emulsifier, does not exceed the amount of from 0.2 to 10% by weight stated for the novel emulsifier alone.
  • the chosen novel emulsifier is mixed with the oil, the water and the further, optionally usable components and is emulsified in a manner known per se.
  • the emulsification can be effected in a rotor mixer, by means of a mixing nozzle or by means of an ultrasound probe. Particularly good results were obtained when a mixing nozzle of the type disclosed in BASF AG's German Application, application number 198 56 604 of Dec. 8, 1998, was used.
  • Water-in-oil emulsions for the cosmetics sector can be prepared in the same way as water-in-fuel emulsions.
  • novel compounds (I) In addition to their surfactant and emulsifying properties, the novel compounds (I) also have a lubricity-improving and corrosion-inhibiting effect. Moreover, they improve the antiwear behavior of liquids.
  • the novel compounds (I) are therefore used as additives for lubricants, fuels and aqueous liquids, such as radiator liquids or drilling and cutting fluids. This use likewise forms the subject of the present invention.
  • novel compounds (I) can be added directly—together with other components—to the fuels and lubricants.
  • the novel compounds (I) can first be mixed with other components to give fuel or lubricant additive concentrates.
  • These novel fuel or lubricant additive concentrates can be added in undiluted form or after dilution with one or more solvents or carrier oils to the fuels or lubricants. The addition in dilute form is preferred.
  • novel fuels generally contain—in addition to conventional components—at least one novel compound of the formula I in an amount of from 10 to 5 000, preferably from 20 to 2000, ppm, based on the total amount.
  • Novel lubricants contain in general from 90 to 99.9, preferably from 95 to 99.5, % by weight of a liquid, semisolid or solid lubricant and from 0.1 to 10, preferably from 0.5 to 5, % by weight of a novel compound (I), based on the total amount.
  • Novel fuel additive concentrates and lubricant additive concentrates contain—in addition to conventional components—at least one novel compound of the formula I in amounts of from 0.1 to 80, in particular from 0.5 to 60, % by weight, based on the total weight of the concentrate.
  • novel fuels and fuel additive concentrates may also contain fuel additives as described, for example, in European Patent Applications EP-A 0 277 345, 0 356 725, 0 476 485, 0 484 736, 0 539 821, 0 543 225, 0 548 617, 0 561 214, 0 567 810 and 0 568 873, German Patent Applications DE-A 39 42 860, 43 09 074, 43 09 271, 43 13 088, 44 12 489, 0 44 25 834, 195 25 938, 196 06 845, 196 06 846, 196 15 404, 196 06 844, 196 16 569, 196 18 270 and 196 14 349, and WO-A 96/03479.
  • Further conventional components are, for example, further corrosion-inhibiting additives, antioxidants, stabilizers, antistatic agents, organometallic compounds, antiwear additives, markers and cetane number improvers, flow improvers, biocides, such as glutaraldehyde or glyoxal.
  • the biocides are usually used in an amount of from 0.01 to 3% by weight, based on the total weight of the concentrate.
  • Examples of further corrosion-inhibiting additives are those based on ammonium salts of organic carboxylic acids, which salts tend to form films, or on heterocyclic aromatics for corrosion protection of nonferrous metals.
  • stabilizers are those based on amines, such as p-phenylenediamine, dicyclohexylamine or derivatives thereof or on phenols, such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid.
  • organometallic compounds are ferrocene or methylcyclopentadienyl-manganesetricarbonyl.
  • cetane number improvers are organic C 2 -C 10 -nitrates, such as 2-ethylhexyl nitrate, and inorganic cetane number improvers for the aqueous phase, such as ammonium nitrate. 2-Ethylhexyl nitrate and ammonium nitrate are preferably used.
  • the cetane number improvers are usually used in an amount of from 0.05 to 5% by weight, based on the total weight of the concentrate.
  • the suitable solvents for the novel fuel and lubricant additive concentrates are aliphatic and aromatic hydrocarbons, such as solvent naphtha, isododecane, mihagol, the fuels and lubricants themselves and carrier oils.
  • Carrier oils which likewise serve for diluting the fuel additive concentrates and lubricant additive concentrates, are, for example, mineral carrier oils (base oils), in particular those of the viscosity class Solvent Neutral (SN) 100 to 500, and synthetic carrier oils based on polyolefins, (poly)esters, (alkylphenol-initiated) polyethers or (aliphatic) (alkylphenolinitiated) polyetheramines, and carrier oils based on alkoxylated long-chain alcohols or phenols.
  • base oils mineral carrier oils
  • base oils in particular those of the viscosity class Solvent Neutral (SN) 100 to 500
  • carrier oils based on alkoxylated long-chain alcohols or phenols.
  • particularly suitable synthetic carrier oils are those based on polyolefins, preferably those based on polyisobutylene and on poly- ⁇ -olefins, having a number average molecular weight of from 400 to 1800.
  • Polyethylene oxides, polypropylene oxides, polybutene oxides and mixtures thereof are also suitable carrier oils.
  • Further suitable carrier oils and carrier oil mixtures are described, for example, in DE-A 38 38 918, DE-A 38 26 608, DE-A 41 42 241, DE-A 43 09 074, U.S. Pat. No. 4,877,416 and EP-A 0 452 328.
  • Novel aqueous liquids contain the novel compounds (I), if required in combination with further conventional corrosion-inhibiting additives, in general in an amount of from about 11 to 10% by weight, based on the total amount.
  • composition of the compounds prepared is shown in table 1.
  • the polyisobutyleneamine used was Kerocom® PIBA from BASF AG.
  • the acid number is a measure of the amount of acid groups, is determined by titration with KOH and is stated in mg KOH per g of substance.
  • the acid numbers were 22 in the case of C1, 26 in the case of C2 and 41 in the case of C3.
  • the products were neutralized batchwise at 25° C. with 25% strength by weight aqueous NaOH solution.
  • emulsifier mixture in diesel fuel was prepared, which emulsifier mixture was composed of 6 parts of a novel compound (C1, C2, C3, D1, D2 or D3) and 2 parts of a C 13 -oxo alcohol ethoxylate (Lutensol® TO 7 from BASF AG), and 2 parts of an alkylphenol ethoxylate (Emulan® OP 25). 500 g of this mixture were stirred with 100 ml of water for 15 minutes at a speed of 24, 000 rpm using an Ultra-Turrax® (Jahnke and Kunkel laboratory apparatus T25).
  • a 20 ⁇ 40 mm iron sheet is blasted with 40 ⁇ m glass beads and then—analogously to ASTM D-665—immersed in the emulsions prepared under Example 1 and stored for 24 hours at 40 ⁇ 1° C. After 24 hours, the iron sheet is investigated for rust formation.
  • the meanings are as follows: ++ no rust formation; +0 slight rust deposit; ⁇ 0 rust formation on more than 25% of the area of the test sheet; — rust formation on more than 50% of the test sheet.
  • novel compounds B3, C1, D1 and D2 were each dissolved individually in an additivefree diesel fuel (Miro, Düsseldorf).
  • the concentration of additive in the diesel fuel was 75 ppm.
  • the assessment of the antiwear behavior was carried out by the HFRR test (high frequency roller rig test), which was carried out according to ISO 12156-1. The length of the resulting furrows was measured and was used as a measure for the wear. The shorter the furrows, the better was the wear protection of the additive introduced.

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US10/469,594 2001-03-01 2002-02-28 Emulsifiers, especially based on polyisobutylenamines Abandoned US20040092412A1 (en)

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DE10109845.6 2001-03-01
DE10109845A DE10109845A1 (de) 2001-03-01 2001-03-01 Emulgatoren, insbesondere auf Basis von Polyisobutylenaminen
PCT/EP2002/002197 WO2002070633A2 (de) 2001-03-01 2002-02-28 Emulgatoren, insbesondere auf basis von polyisobutylenaminen

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Cited By (6)

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US20050217613A1 (en) * 2002-03-28 2005-10-06 Tiziano Ambrosini Method for reducing emission of pollutants from an internal combusion engine, and fuel emulsion comprising water and a liquid hydrocarbon
WO2006106112A3 (de) * 2005-04-05 2007-05-10 Basf Ag Verwendung von polyisobuten enthaltenden copolymerisaten in wasch-, dusch- und badepräparaten
US20070213238A1 (en) * 2006-03-13 2007-09-13 Sigworth William D Lubricant composition for cellulosic-thermoplastic composite
US20110144270A1 (en) * 2004-02-13 2011-06-16 Total Petrochemicals Research Feluy Additivising polymer powders
US20130059927A1 (en) * 2010-05-12 2013-03-07 Basf Se Emulsions of Polyisobutenes, Substance and Process
US20140357537A1 (en) * 2013-05-30 2014-12-04 Halliburton Energy Services, Inc. Branched Emulsifier for High-Temperature Acidizing

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JP2011511859A (ja) * 2008-02-01 2011-04-14 ビーエーエスエフ ソシエタス・ヨーロピア 特殊なポリイソブテンアミンおよび燃料中の洗剤としての該化合物の使用
CN112391190B (zh) * 2020-11-17 2022-02-25 西南石油大学 Co2/n2开关型双循环萃取工艺及其应用

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US3946074A (en) * 1970-10-05 1976-03-23 Akzona Incorporated Plant growth regulatory agents and process
US4225447A (en) * 1979-01-08 1980-09-30 Mobil Oil Corporation Emulsifiable lubricant compositions
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US20050217613A1 (en) * 2002-03-28 2005-10-06 Tiziano Ambrosini Method for reducing emission of pollutants from an internal combusion engine, and fuel emulsion comprising water and a liquid hydrocarbon
US8511259B2 (en) * 2002-03-28 2013-08-20 Cam Technologie S.P.A. Method for reducing emission of pollutants from an internal combusion engine, and fuel emulsion comprising water and a liquid hydrocarbon
US20110144270A1 (en) * 2004-02-13 2011-06-16 Total Petrochemicals Research Feluy Additivising polymer powders
WO2006106112A3 (de) * 2005-04-05 2007-05-10 Basf Ag Verwendung von polyisobuten enthaltenden copolymerisaten in wasch-, dusch- und badepräparaten
US20070213238A1 (en) * 2006-03-13 2007-09-13 Sigworth William D Lubricant composition for cellulosic-thermoplastic composite
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US20140357537A1 (en) * 2013-05-30 2014-12-04 Halliburton Energy Services, Inc. Branched Emulsifier for High-Temperature Acidizing

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WO2002070633A2 (de) 2002-09-12
CN1630703A (zh) 2005-06-22
WO2002070633A3 (de) 2003-11-27
DE10109845A1 (de) 2002-09-05
MXPA03007384A (es) 2003-12-04
AU2002247747A1 (en) 2002-09-19
CA2439308A1 (en) 2002-09-12

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