EP1495058A1 - Polyisobutene-amines - Google Patents

Polyisobutene-amines

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Publication number
EP1495058A1
EP1495058A1 EP03724959A EP03724959A EP1495058A1 EP 1495058 A1 EP1495058 A1 EP 1495058A1 EP 03724959 A EP03724959 A EP 03724959A EP 03724959 A EP03724959 A EP 03724959A EP 1495058 A1 EP1495058 A1 EP 1495058A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
polyisobutene
reaction
subsequent
polyisobutenamines
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP03724959A
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German (de)
English (en)
Inventor
Hans Peter Rath
Arno Lange
Dietmar Posselt
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BASF SE
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BASF SE
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Publication of EP1495058A1 publication Critical patent/EP1495058A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/08—Butenes
    • C08F10/10—Isobutene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/08—Butenes
    • C08F110/10—Isobutene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16

Definitions

  • the present invention relates to new polyisobutene amines whose polyisobutene residues have a polydispersity of less than or equal to 1.4, a process for their preparation and the use of the polyisobutene amines as fuel additives.
  • Polyisobutenamines are understood to mean oligomeric compounds of the general formula R a -X, in which R a is a polyisobutenyl radical with a number average molecular weight M N in the range from 500 to 1500 and X is a polar, organic radical which has one or more amino groups.
  • R a is a polyisobutenyl radical with a number average molecular weight M N in the range from 500 to 1500
  • X is a polar, organic radical which has one or more amino groups.
  • Polyisobutenamines are of outstanding importance as fuel additives for gasoline and diesel engines, especially for keeping valves and carburetor or injection systems clean, and as lubricant additives (see also M. Rossenbeck in Catalysts, Surfactants, Mineral Oil Additives, ed. J. Falbe, U. Hasserodt, S 223, G. Thieme Verlag, Stuttgart 1978).
  • the polyisobutenamines are generally prepared by functionalizing reactive polyisobutenes, i.e. Polyisobutenes that have a terminal reactive functionality. Olefinic end groups are particularly suitable for functionalization. Polyisobutenes with a high content of olefinically unsaturated end groups are therefore advantageous for the preparation of the polyisobutenamines (see formulas (A) and (B)).
  • the polyisobutenamines produced by functionalizing the aforementioned polyisobutenes have unsatisfactory viscosity behavior, particularly at low temperatures, and can therefore lead to undesirable side effects in engines, for example.
  • This deficiency is generally remedied by the addition of large amounts of what are known as carrier oils, which have no or only inadequate detergent action and are only intended to improve the viscosity properties of the conventional polyisobutenamines.
  • the proportion of carrier oil in the additized fuels generally clearly exceeds the proportion of polyisobutenamine.
  • the present invention is based on the object of providing polyisobutenamines which at the same time have a high detergent action and improved viscosity behavior.
  • the polyisobutenamines should manage with a significantly reduced proportion of additional auxiliaries, in particular carrier oils, without adversely affecting the properties of the additive compositions.
  • Polyisobutene derivatives with a narrow molecular weight distribution of the polyisobutene residues can in principle be produced by so-called "living" cationic polymerization of isobutene, see e.g. Kennedy and Ivan “Carbocationic Macromolecular Engineering", Hanser Publishers 1992 and US 5,169,914.
  • Living cationic polymerization means the polymerization of olefins in the presence of an initiator system which contains a compound suitable for the formation of carbocations, e.g. a benzyl halide or a tert. Alkyl halide or a corresponding benzyl or alkyl ether or ester as an initiator and a Lewis acid as a coinitiator.
  • the polyisobutene derivatives obtained in this way generally have a halogen atom as the end group and are therefore not suitable for the preparation of polyisobutenamines.
  • polyisobutenes with a high olefinic end group content of more than 80 mol% and a polydispersity below 1.4 can be prepared by "living" cationic polymerization if isobutene is polymerized in the presence of an initiator system which acts as an initiator at least one compound of the general formula III,
  • polyisobutenes obtainable in this way can be converted into polyisobutenamines in a manner known per se because of the high proportion of reactive olefinic end groups.
  • the present invention thus relates to polyisobutenamines of the general formula I:
  • R stands for a polyisobutenyl radical with a number average molecular weight M N in the range from 500 to 1500, which has a polydispersity M W / M N below 1.4 and X stands for an organic radical having amino groups.
  • the invention further relates to a process for the preparation of the polyisobutenamines I, which comprises the following steps:
  • a Lewis acid selected from covalent metal chlorides and semimetal chlorides
  • m represents 0, 1, 2, 3 or 4 and FG halogen, OH, alkyloxy, acyloxy, CH 2 C (CH 3 ) CH 2 OH or a group
  • CH 2 - C / ° ⁇ CH 2 means CH 3
  • step ii) introduction of a radical having amino groups on the olefinic double bond of the polyisobutene obtained in step i) in a manner known per se.
  • Polyisobutenyl radicals are understood to mean those organic hydrocarbon radicals which are composed predominantly, preferably 80 mol% and in particular 90 mol%, of repeating units of the formula [-CH 2 -C (CH 3 ) 2 ] -, including those Residues should be recorded in which the carbon atom, which is adjacent to the C atom bearing the group X, can also have an OH group due to the production process.
  • the group X can be bound both to the ⁇ -C atom and to the ⁇ or ⁇ -C atom of the polyisobutenyl radical (see formulas A and B).
  • Such polyisobutenes with a polydispersity M N of up to 1.3 and in particular up to 1.2 are preferred.
  • the number average molecular weight M N is preferably in the range from 600 to 1400, in particular 650 to 1300, for example approximately 670 or 1300.
  • Suitable groups X are basically all organic radicals which contain at least one, e.g. Have 1 to 40 basic, primary, secondary or tertiary amino groups.
  • the molecular weight of these X radicals should preferably not exceed the molecular weight of the polyisobutenyl radical and is preferably in the range from 16 to 1000.
  • suitable functional groups X obey the general formula II
  • R 'de notes hydrogen, alkyl, hydroxyalkyl, aminoalkyl, cycloalkyl, aryl, aralkyl or a group -Y-NR! R 2 ,
  • Alk is C 2 -C 4 alkylene
  • p and q independently of one another are an integer from 0 to 25 and R "is hydrogen, alkyl or aryl
  • Alk ' is alkylene which is represented by 1, 2 or 3 non-adjacent oxygen atoms may be interrupted or represent cycloalkylene
  • R 1 and R 2 together with the nitrogen atom to which they are attached form an optionally substituted, saturated heterocycle which optionally contains a further heteroatom, selected from oxygen and nitrogen.
  • Alkyl stands for a linear or branched alkyl radical with 1 to 12 and preferably 1 to 6 carbon atoms e.g. for methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 2-pentyl, iso-pentyl, neopentyl, n-hexyl, 2- Methyl-l-pentyl, n-heptyl, 2-ethylhex-l-yl, 2-methylhex-l-yl, n-octyl, n-decyl, 2-methyldec-l-yl, n-dodecyl, etc.
  • Cycloalkyl stands for a cycloaliphatic radical with preferably 5 to 10 carbon atoms, which can be substituted by 1, 2, 3 or 4 -CC 4 alkyl groups, for example for cyclopentyl, cyclohexyl or cycloheptyl, 1-methylcyclopentyl, 1-methylcyclohexyl, 4,4-dimethylcyclohexyl.
  • Aryl is e.g. for phenyl or naphthyl, which may be substituted like cycloalkyl.
  • Aralkyl stands for alkyl, preferably C 4 -C 4 alkyl, in particular methyl or ethyl, which is substituted by aryl, in particular phenyl, that is to say, for example, for benzyl or phenylethyl.
  • Hydroxyalkyl stands for alkyl with preferably 1 to 6 and in particular 2 to 4 carbon atoms, which has a hydroxy group as a substituent: e.g. for 2-hydroxyethyl, 2- or 3-hydroxybutyl, 2-, 3- or 4-hydroxybutyl.
  • Aminoalkyl stands for alkyl with preferably 1 to 6 and in particular 2 to 4 carbon atoms, which has an NH 2 -, NH (C ⁇ -C 4 -alkyl) - or N (-C-C 4 -alkyl) 2 group as a substituent : for example for 2-aminoethyl, 2- or 3-aminopropyl, 2-methylaminoethyl, 2- or 3-methylaminopropyl, 2-dimethylaminoethyl, 2- or 3-dimethylaminopropyl.
  • Alkyloxy stands for alkyl bound via an oxygen atom. Accordingly, aryloxy, cycloalkyloxy and arylalkyloxy are aryl, cycloalkyl or arylalkyl bonded via an oxygen atom.
  • Acyloxy represents an oxygen-bonded alkylcarbonyl radical which preferably has 1 to 6 carbon atoms in the alkyl part, for example acetyloxy, propionyloxy, butyroxy etc.
  • Alkylene stands for a divalent linear or branched
  • C 2 -C 4 alkylene is, for example, 1,2-ethylene, 1,2- or 1,3-propylene.
  • C 2 -C 2 o-alkylene represents the groups mentioned for C 2 -C 3 alkylene and, for example, butane-1,2-diyl, butane-2,3-diyl, butane-1, 3-diyl or butane -l, 4-diyl, pentane-l, 2-diyl, pentane-2,3-diyl, pentane-l, 3-diyl, pentane-l, 4-diyl, pentane-2,4-diyl or pentane-l , 5-diyl, hexane-1,6-diyl, 2,2,4-trimethylpentane-l, 4-diyl
  • Carbon atoms can be replaced by oxygen atoms which are neither adjacent to one another nor to the connecting sites.
  • alkylene groups generally have 5 to 20 carbon atoms. Examples include: 3-0xapentane-l, 5-diyl, 3-oxahexane-1,6-diyl, 4-0xaheptane-l, 7-diyl,
  • C 5 -C 2 o-Cycloalkylene stands for a divalent cycloaliphatic radical with preferably 5 to 20 C atoms. Examples include cyclopentane-1,2- and cyclopentane-1,3-diyl,
  • R 1 and R 2 have one of the meanings given below: hydrogen, Ci-Ce-alkyl, phenyl, 2-hydroxyethyl, 2-aminoethyl, 3-aminopropyl, 2 di- (C ⁇ -C 4 alkyl) aminoethyl, 3-di- (C ⁇ -C4 alkyl) aminopropyl, or radicals of the formula [CH 2 -CH 2 -0] p.-CH 2 -CH 2 0H and [CH 2 -CH 2 -NH] g ' -CH 2 -CH 2 NH 2 , wherein p' and q 'are independently a number from 1 to 20; as well as those compounds of the formula I in which NRR 2 is a piperidine, piperazine, N- (C ⁇ -C 4 -alkyl) piperazine or a
  • R 1 and R 2 are hydrogen.
  • A is preferably methylene.
  • R ' is preferably hydrogen, Ci-C ß- alkyl, 2-hydroxyethyl, 2-aminoethyl, 3-.amino propyl, 2-di- (-C 4 alkyl) aminoethyl, 3-di- (C ⁇ -C4 alkyl) aminopropyl or a radical of formula [CH 2 -CH 2 -0] p.-CH 2 -CH 2 OH or [CH 2 -CH 2 -NH] q. CH 2 -CH 2 NH 2 , where p 'and q' are independently a number from 1 to 10.
  • alk then preferably represents 1,2-ethylene, 1,2-propylene or 1,3-propylene.
  • R "then preferably represents hydrogen and Alk 'preferably represents alkylene having 2 to 10 carbon atoms, which can be interrupted by 1, 2 or 3 non-adjacent oxygen atoms.
  • the polymerization of the isobutene is triggered by the initiator system comprising a Lewis acid and at least one compound of the general formula III. It is believed that the Lewis acid forms a carbocation or at least one ionogenic complex with compound III, which interacts with the olefinically unsaturated double bond of the isobutene and thereby generates a positive (partial) charge on the tertiary carbon atom of the isobutene. This in turn interacts with another isobutene molecule while continuing the polymerization reaction.
  • Lewis acids examples include the (semi-) metal chlorides BCI 3 , TiCl 4 , VCI 5 , SnCl 4 , FeCl 3 .
  • Preferred (semi-) metal chlorides are BCI 3 and TiCl.
  • FG preferably represents halogen and especially chlorine.
  • compound III in an amount of at least 10 -2 mol per mol of isobutene, preferably in the range from 0.02 to 0.3 and in particular in the range from 0.05 to Use 0.2 mol per mol of isobutene. It must be taken into account here that the molecular weight achieved of the polyisobutene produced by the process according to the invention depends on the amount of compound III in such a way that with increasing amount of compound III, based on isobutene, the molecular weight of the polyisobutene decreases.
  • the Lewis acid is naturally used in the process according to the invention in an amount sufficient to produce the polyisobutenes to form the initiator complex. This is usually ensured even at low concentrations of the Lewis acid in the reaction medium, usually at least 0.01 mol / 1. As a rule, the Lewis acid in the reaction medium will therefore not exceed a concentration of 3 mol / 1, preferably 2 mol / 1 and particularly preferably 1 mol / 1. In particular, the concentration is in the range from 0.1 to 2 mol / 1 and particularly preferably in the range from 0.2 to 1 mol / 1.
  • the initiator system preferably comprises at least one further aprotic polar compound IV which is suitable for complex formation with the Lewis acid or the carbocation or ionogenic complex formed under reaction conditions from Lewis acid and compound I.
  • Lewis bases electron donors
  • the initiator system preferably comprises at least one further aprotic polar compound IV which is suitable for complex formation with the Lewis acid or the carbocation or ionogenic complex formed under reaction conditions from Lewis acid and compound I.
  • Lewis bases electron donors
  • heteroatom which is selected, for example, from oxygen, nitrogen, phosphorus and sulfur atoms.
  • donor compounds IV are pyridines such as pyridine and substituted pyridines, in particular sterically hindered pyridines, furthermore N, N-dialkylamides of aliphatic or aromatic carboxylic acids such as N, N-dimethylacetamide, N-alkyllactams such as N-methylpyrrolidone, dialkyl ethers such as diethyl ether and diisopropyl ether, cyclic ethers, such as
  • Tetrahydrofuran trialkylamines such as triethylamine, C 1 -C 4 -alkyl esters of aliphatic Ci-C ⁇ -carboxylic acids such as ethyl acetate, dialkyl thioethers or alkylaryl thioethers such as methylphenylsulfide, dialkylsulfoxides such as dimethylsulfoxide, alkylnitriles such as acetonitrile and propionphosphine, tri-ethylphosphine, tri-ethylphosphinyl tri-phylphosphine, tri-tri-phylphosphine, tri-ethyl-tri-phylphosphine, butylphosphine and triphenylphosphine and non-polymerizable, aprotic organosilicon compounds which have at least one organic radical bonded via oxygen. This residue usually has 1 to 20 carbon atoms. Examples of such radicals are alkyloxy
  • pyridine and sterically hindered pyridine derivatives and, in particular, organosilicon compounds are preferred.
  • At least one organosilicon compound is used as the donor.
  • Sterically hindered pyridines are those which have bulky alkyl groups at least in the 2- and 6-position of the pyridine ring, e.g. 2, 6-diisopropylpyridine and 2,6-di-tert-butylpyridine.
  • the donor IV and in particular the organosilicon compound is preferably used in an amount such that the molar ratio of donor molecules IV to the metal atoms or the semimetal atoms in the Lewis acid is in the range from 1: 1000 to 1: 1, preferably in the range from 1: 1000 to 1: 2, and particularly preferably in the range from 1: 1000 to 1: 5.
  • the organosilicon compounds suitable as donor IV can contain one or more, e.g. 2 or 3, silicon atoms with at least one organic radical bonded via oxygen. Those organosilicon compounds are preferred which have one, two or three, and in particular 2 or 3, organic radicals bonded via oxygen per silicon atom.
  • Preferred organosilicon compounds are those which have the general formula IVa:
  • n 1, 2 or 3
  • R a can be the same or different and independently of one another are C 1 -C 2 -alkyl, C 5 -C 7 -cycloalkyl, aryl or aryl-C 1 -C 4 -alkyl, the three last-mentioned radicals also being one or more C ⁇ -C ⁇ o May have alkyl groups as substituents, and
  • variable n is preferably 1 or 2.
  • the variable R a preferably denotes a C 1 -C 6 -alkyl group, and in particular a branched alkyl group or an alkyl group bonded via a secondary C atom, such as isopropyl, isobutyl, 2-butyl, or a 5-, 6- or 7-membered cycloalkyl group.
  • the variable R 2 preferably represents a C 1 -C 4 -alkyl group.
  • Examples of such preferred compounds are dimethoxy diisopropyl silane, dimethoxy isobutyl isopropyl silane, dimethoxy diisobutyl silane, dimethoxy dicyclopentyl silane, diethoxy isobutyl-2-butyl silane, diethoxy isobutyl isopropyl silane, triethoxy silane benzyl silane triethoxy silane.
  • isobutene itself and isobutene-containing C 4 -hydrocarbon streams are suitable as isobutene feedstocks for the process according to the invention, for example C 4 raffinates from steam crackers, C 4 cuts from isobutane dehydrogenation, C 4 cuts from steam crackers, C 4 -Cuts from FCC crackers (FCC: Fluid Catalyzed Cracking), provided that they are largely free of 1,3-butadiene contained in them.
  • C 4 hydrocarbon streams suitable according to the invention generally contain less than 500 ppm, preferably less than 200 ppm, of butadiene. When using C 4 cuts as feed material, the hydrocarbons other than isobutene assume the role of an inert solvent.
  • Suitable solvents are all low molecular weight, organic compounds which differ from compounds III and IV and from isobutene, which have no protons which can be abstracted and which are liquid under the polymerization conditions, if appropriate as a mixture with one another.
  • Preferred solvents are hydrocarbons, e.g.
  • acyclic alkanes with 2 to 8 and preferably 3 to 7 carbon atoms such as ethane, iso- and n-propane, n-butane and its isomers, n-pentane and its isomers, n-hexane and its isomers and n-heptane and its isomers, cyclic alkanes with 5 to 8 carbon atoms such as cyclopentane, cyclohexane, cycloheptane, acyclic alkenes with preferably 2 to 8 carbon atoms such as ethene, iso- and n-propene, n-butene, n-pentene, n-hexene and n-heptene, cyclic olefins such as cyclopentene, cyclohexene and cycloheptene, aromatic hydrocarbons such as toluene, xylene, ethylbenz
  • solvents themselves are suitable, but also mixtures of these solvents. Mixtures are particularly preferred when the solvent has a melting point above the desired polymerization temperature.
  • Solvents and solvent mixtures which comprise at least one hydrocarbon are particularly preferred.
  • solvent mixtures which contain at least one Include hydrocarbon and at least one haloalkane are particularly preferred.
  • solvent mixtures which contain at least one Include hydrocarbon and at least one haloalkane are particularly preferred.
  • solvent mixtures which comprise at least one aromatic hydrocarbon, in particular toluene, and at least one chloroalkane, in particular methyl chloride or methylene chloride are particularly preferred.
  • the volume ratio of hydrocarbon to halogenated hydrocarbon is preferably in the range from 1:10 to 10: 1, in particular in the range from 4: 1 to 1: 4.
  • the chloroalkanes in these mixtures do not include any compounds in which chlorine atoms are located on secondary or tertiary carbon atoms.
  • ternary solvent mixtures which comprise at least one aromatic hydrocarbon, in particular toluene, at least one cyclic or acyclic alkane having 4 to 7 C atoms, in particular hexane, and at least one chloroalkane, in particular methyl chloride or methylene chloride.
  • the volume ratio of the three aforementioned components is then selected so that the ratio of alkane to aromatic is in the range from 1:10 to 10: 1 and the volume ratio of alkane + aromatic to haloalkane is in the range from 10: 1 to 1: 1. If the polymerization is carried out with evaporative cooling, the solvents or the solvent mixtures still contain up to 50% by volume, for example 5 to 50% by volume, preferably 10 to 30% by volume, of an easily evaporable solvent component , for example ethylene.
  • the polymerization is carried out under largely aprotic, in particular under anhydrous, reaction conditions.
  • Aprotic or anhydrous reaction conditions are understood to mean that the water content (or the content of protic impurities) in the reaction mixture is less than 50 ppm, and in particular less than 5 ppm.
  • the input materials will therefore be dried physically and / or by chemical measures before they are used.
  • the aliphatic or cycloaliphatic hydrocarbons preferably used as solvents can be mixed with an organometallic compound, for example an organolithium, organomagnesium or organoaluminum compound, in an amount sufficient to remove traces of water from the solvent after customary pre-cleaning and predrying.
  • the solvent treated in this way is then condensed directly into the reaction vessel.
  • the solvents and the isobutene are pre-cleaned or predried in a customary manner, preferably by treatment with solid drying agents such as molecular sieves or pre-dried oxides such as calcium oxide or barium oxide.
  • solid drying agents such as molecular sieves or pre-dried oxides such as calcium oxide or barium oxide.
  • pre-dried oxides such as calcium oxide or barium oxide.
  • the process according to the invention will be carried out at temperatures below room temperature (25 ° C) and preferably below 0 ° C, e.g. in the range from 0 to -140 ° C, preferably in the range from -30 to -120 ° C, and particularly preferably in the range from -40 to -110 ° C.
  • room temperature 25 ° C
  • 0 ° C room temperature
  • a reaction temperature preferably in the range from 0 to -140 ° C
  • preferably in the range from -30 to -120 ° C preferably in the range from -40 to -110 ° C.
  • the reaction pressure is of minor importance and depends in a known manner on the equipment used and other reaction conditions.
  • the isobutene or the isobutene-containing feed is polymerized spontaneously when the initiator system used according to the invention is mixed with the isobutene or the isobutene-containing feed in the inert organic solvent at the desired reaction temperature.
  • This can be done by initially charging isobutene in the inert solvent, cooling to the reaction temperature and then adding the initiator system.
  • One can also proceed in such a way that the initiator system is placed in the solvent and then the isobutene or the isobutene-containing feed is added, either all at once or according to consumption.
  • part or all of the isobutene or the isobutene-containing starting material can be introduced into the solvent and then the initiator system can be added.
  • the remaining amounts of isobutene or isobutene-containing feed material are then fed in during the reaction, for example in accordance with their consumption.
  • the procedure is generally such that the components of the initiator system are added separately.
  • the procedure will generally be to add compound III and, if appropriate, compound IV and then the Lewis acid.
  • the time at which the initiator is added then counts as the time at which both components of the initiator system are contained in the reaction vessel.
  • the polymerization can also be designed as a continuous process.
  • the input materials i.e. the monomers to be polymerized
  • the solvent and the initiator system of the polymerization reaction continuously increase and continuously remove reaction product, so that more or less stationary polymerization conditions are established in the reactor.
  • the components of the initiator system can be added either separately or together, preferably diluted in the solvent.
  • the isobutene to be polymerized or the isobutene-containing feedstocks can be supplied as such, diluted with a solvent or as an isobutene-containing hydrocarbon stream.
  • the components of the initiator system diluted in the solvent can be added via multi-component nozzles in order to achieve thorough mixing of the components.
  • the heat of reaction in the discontinuous as well as in the continuous reaction is carried out in a customary manner, for example by internally installed heat exchangers, by external heat exchangers and / or by wall cooling and / or by using evaporative cooling.
  • the use of ethene and / or mixtures of ethene with other hydrocarbons and / or halogenated hydrocarbons as solvents has proven particularly useful here, since ethene is not only inexpensive but also has a boiling point in the desired polymerization temperature range.
  • Suitable reactors for carrying out the process according to the invention are in principle all reactors which are customarily used in a cationic polymerization of isobutene, for example a cationic polymerization of isobutene with boron trifluoride-oxygen complexes.
  • the reaction is carried out batchwise, the usual ones are used Stirred kettles, which are preferably equipped with evaporative cooling, external (external) heat exchangers, suitable mixers, inlets, heat exchanger elements and inerting devices.
  • the continuous reaction can be carried out in the conventional reaction vessels, reaction cascades, tube reactors, tube bundle reactors, in particular circular tube and tube bundle reactors, which are preferably equipped in the manner described above for reaction vessels.
  • the latter is deactivated after the polymerization in the manner customary for cationic polymerization reactions, preferably by adding a protic compound, in particular
  • alcohols such as methanol, ethanol, n-propanol
  • the substances used for deactivation are preferably introduced into a diluent, for example one of the so-called solvents.
  • the agent used for the deactivation or its mixture is preferably cooled to polymerization temperature with an inert solvent before the deactivation in order to avoid undesirable side reactions.
  • the solvents are usually in suitable units, for example in rotary, falling film or thin film evaporators or by flash evaporation (expansion of the reaction solution behind a heat exchanger in pipes or
  • the bottom temperature is preferably 50 ° C to 250 ° C and in particular 150 ° C to 230 ° C.
  • elevated temperatures e.g. above
  • the 45 polyisobutenes produced in step a) of the process according to the invention have a high content of olefinically unsaturated end groups of the general formula (A) and / or (B).
  • the end group content is usually at least 80 mol%, in total particularly at least 90 mol%, and particularly preferably at least 95 mol%, based on the polymer chains.
  • the polyisobutenes obtained according to the invention advantageously also have a favorable value for the position of the maximum of the molecular weight distribution (M p ).
  • the peak maximum M p of the molecular weight distribution of the polyisobutenes according to the invention is preferably less than 10% above the value of the number average molecular weight. In many cases the peak maximum M p is even less than 8% or even less than 6% above the number average molecular weight.
  • Functionality X is introduced in step b) of the method according to the invention in a manner known per se.
  • Overviews of suitable processes for amino functionalization can be found in EP-A 382 405, the documents listed below and in WO 98/20053 and the literature cited therein.
  • the literature describes numerous processes for the preparation of OH or aldehyde-functionalized polyisobutenes (see, for example, EP-A 468 966).
  • the polyisobutene derivatives thus produced can be aminofunctionalized in a manner known per se by reductive amination.
  • the amines used in these methods and in method (7) generally have the structure on which Group II is based.
  • suitable amines include ammonia, ethylene-1,2-diamine, propylene-1,2-diamine, propylene-1,3-diamine, butylene diamines, the monoalkyl, dialkyl and Trialkyl derivatives of these amines, such as, for example, N, N-dimethylpropylene-1,3-diamine.
  • polyalkylene polyamines whose alkylene radicals have no more than 6 carbon atoms
  • polyethylene polyamines such as diethylene triamine, triethylene tetramine and tetraethylene pentamine and polypropylene polyamines.
  • mono- or dialkylamines in which the alkyl radicals are interrupted by one or more non-adjacent oxygen atoms and which may also have hydroxyl groups or further amino groups such as 4,7-dioxadecane-1, 10-diamine, ethanolamine , 3-aminopropanol, 2- (2-aminoethoxy) ethanol, N- (2-aminoethyl) ethanolamine.
  • N-amino-C 2 -C 6 -alkylpiperazines are N-amino-C 2 -C 6 -alkylpiperazines.
  • Ammonia is preferably used.
  • the polyisobutenamines obtained in methods (1) to (7) can also be alkoxylated by mixing them in a known manner, if appropriate with addition of alkoxides as catalysts, with C 1 -C 4 -alkylene oxides such as ethylene oxide, propylene oxide or 1, 2-butylene oxide.
  • the alkylene oxides are preferably used in a molar ratio of 1: 1 to 1: 2, based on the nitrogen atoms in II. Methods for this are known from the prior art.
  • alkylene oxide is first added to the NH bond with ring opening.
  • alkylene oxide is then added to the OH group released in the presence of suitable catalysts, for example using OH _ catalysis analogously to the method described in EP-A 398 100 or using DMC catalysts (double metal cyanide catalysts) analogously to that in Method described in WO 00/14045.
  • suitable catalysts for example using OH _ catalysis analogously to the method described in EP-A 398 100 or using DMC catalysts (double metal cyanide catalysts) analogously to that in Method described in WO 00/14045.
  • the polyisobutenamines according to the invention are distinguished from the prior art polyisobutenamines with the same number average molecular weight both by an improved detergent action and by improved viscosity properties, in particular at low temperature. This effect is particularly important when used as a fuel additive. Because of these advantageous properties of the polyisobutenamines according to the invention, they can be used with significantly smaller amounts of auxiliaries, such as carrier oils, and thus, with good to very good effectiveness, enable a significantly reduced total proportion of additives in the compositions.
  • auxiliaries such as carrier oils
  • the present invention thus also relates to the use of the polyisobutenamines I according to the invention as fuel additives.
  • Fuels suitable for additives are basically all gasoline suitable for gasoline engines, which in addition to hydrocarbons as the main constituent can also contain other low molecular weight components, for example alcohols such as methanol, ethanol or tert-butanol, and ethers, for example methyl tert-butyl ether.
  • the fuels usually contain other additives such as corrosion inhibitors, stabilizers, antioxidants, demulsifiers, antistatic agents or ferrocenes.
  • the polyisobutenamines according to the invention are preferably added to the fuel in an amount of 10 to 5000 ppm and in particular in an amount of 50 to 1000 ppm.
  • the polyisobutenamines I according to the invention are generally used together with so-called carrier oils.
  • Carrier oils are e.g. from K. Owen, Gasoline and Diesel Fuel Additives, John Wiley &
  • Carrier oils based on polyalkylene glycols e.g. their ethers and / or esters as described in US Pat. No. 5,004,478 or DE-A 3838918.
  • alkylene oxides such as ethylene oxide, propylene oxide or
  • 1,2-butylene oxide degree of alkoxylation preferably in the range from 10 to 50
  • 1,2-butylene oxide degree of alkoxylation preferably in the range from 10 to 50
  • propoxylates of dialkylphenols as described in DE-A 4142241
  • mineral carrier oils hydrocarbon oils, base oils
  • olefin polymers with molecular weights M N 400 to 1800, especially based on poly-n-butene or polyisobutene (hydrogenated or non-hydrogenated) are suitable.
  • the proportion of carrier oil, based on the total weight of the fuel, is generally in the range from 10 to 1000 ppm, preferably 20 to 500
  • the weight ratio of polyisobutenamine I to carrier oil is preferably in the range of at least 1: 1 and is preferably in the range of 1: 1 to 20: 1 and in particular
  • polyisobutenamines according to the invention can also be used as fuel additives without a carrier oil.
  • the present invention further relates to additive concentrates.
  • the additive concentrates can also contain conventional detergent additives.
  • Contain 40 additives e.g. from J. Falbe et al., Tenside und Mineralöladditive, G. Thieme Verlag, Stuttgart 1978, p. 223ff or K. Owen (loc. cit) p. 23ff.
  • their proportion will generally not exceed the proportion of polyisobutenes according to the invention and is preferably below 25
  • the molecular weight (M N , M w ) was determined in the manner described above by means of GPC, mass spectrometry and / or by means of ⁇ -NMR spectroscopy.
  • the double bond content was determined by means of 1 H-NMR spectroscopy (integration of the vinyl protons against methyl and methylene protons) or via the chlorine content.
  • the residual chlorine content was determined by elemental analysis.
  • Production Example 1 Production of a polyisobutene with an M N of 670
  • reaction vessel A 2 1 four-necked flask was used as the reaction vessel, the one with dry ice cooler, dropping funnel, thermometer, septum, magnetic stirrer and another dropping funnel, which dried a bed of molecular sieve (3 ⁇ , 250 g; 16 h at 150 ° C./2 mbar ) and has a dry ice cooler.
  • the reaction vessel was evacuated twice and rinsed with dry
  • Example 1 (Amino functionalization of the polyisobutene from Preparation Example 1):
  • Example 1 The hydroboration / oxidative cleavage and subsequent reductive amination was carried out as in Example 1.
  • the degree of functionalization was 98% by weight, the amine number 20.4.
  • the fuel additive from comparative example 2 not according to the invention is a commercially available isobutenamine (Kerocom PIBA) from BASF based on a polyisobutene with a number average molecular weight of 1000 and a polydispersity of 1.65, which is obtained by hydroformylation and subsequent reductive amination with ammonia according to Example 1 EP-A 244 616 was obtained.
  • Kerocom PIBA isobutenamine
  • M w weight average molecular weight
  • MM N polydispersity

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  • Chemical & Material Sciences (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des polyisobutène-amines de formule R-X, dans laquelle R représente un groupe polyisobutényle possédant un poids moléculaire moyen en nombre MN compris entre 500 et 1500, avec une polydispersité MW/MN inférieure à 1,4, et X représente un groupe organique comprenant des groupes amino. L'invention concerne en outre un procédé de production de ces composés et leur utilisation comme additifs dispersants dans des compositions de carburant. L'invention concerne également des concentrés d'additifs contenant au moins une polyisobutène-amine dans une proportion comprise entre 0,1 et 80 % en poids.
EP03724959A 2002-04-05 2003-04-04 Polyisobutene-amines Withdrawn EP1495058A1 (fr)

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DE10215108 2002-04-05
DE10215108A DE10215108A1 (de) 2002-04-05 2002-04-05 Polyisobutenamine
PCT/EP2003/003548 WO2003085011A1 (fr) 2002-04-05 2003-04-04 Polyisobutene-amines

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CN (1) CN100453565C (fr)
AR (1) AR039238A1 (fr)
AU (1) AU2003227566B2 (fr)
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US8362153B2 (en) * 2006-12-15 2013-01-29 Chevron Oronite Company Llc Polyisobutenyl sulfonates having low polydispersity
US20090053959A1 (en) * 2007-08-21 2009-02-26 Sudhin Datta Soft and Elastic Nonwoven Polypropylene Compositions
AU2009209587B2 (en) 2008-02-01 2013-08-22 Basf Se Special polyisobutene amines, and use thereof as detergents in fuels
US8552122B2 (en) * 2009-03-31 2013-10-08 The University Of Southern Mississippi Amine-terminated telechelic polymers and precursors thereto and methods for their preparation
US8920524B2 (en) 2009-12-18 2014-12-30 Chevron Oronite Company Llc Polyisobutenyl alcohols and fuel compositions
WO2011075536A2 (fr) * 2009-12-18 2011-06-23 Chevron Oronite Company Llc Polyoléfines fonctionnalisées par carbonyl-ène
US8673275B2 (en) 2010-03-02 2014-03-18 Basf Se Block copolymers and their use
CA2789068A1 (fr) 2010-03-02 2011-09-06 Basf Se Copolymeres sequences et leur utilisation
US20110218295A1 (en) * 2010-03-02 2011-09-08 Basf Se Anionic associative rheology modifiers
WO2012175158A1 (fr) 2011-06-22 2012-12-27 Byk-Chemie Gmbh Copolymères en peignes tensioactifs
AU2012342721A1 (en) * 2011-11-23 2014-07-03 Basf Se Amine mixture
CN106281509B (zh) * 2016-08-30 2018-10-12 深圳市广昌达石油添加剂有限公司 一种用作汽油清净剂的新型聚异丁烯胺及其合成方法
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MY139760A (en) 2009-10-30
CA2479940C (fr) 2011-02-01
CN1646575A (zh) 2005-07-27
WO2003085011A1 (fr) 2003-10-16
BR0308690A (pt) 2005-01-25
NZ535387A (en) 2007-01-26
PL209010B1 (pl) 2011-07-29
AR039238A1 (es) 2005-02-16
IL163980A0 (en) 2005-12-18
PL373240A1 (en) 2005-08-22
HRP20041032A2 (en) 2004-12-31
JP4197298B2 (ja) 2008-12-17
KR20040106314A (ko) 2004-12-17
US7291681B2 (en) 2007-11-06
AU2003227566A1 (en) 2003-10-20
NO20044253L (no) 2004-10-07
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CN100453565C (zh) 2009-01-21
MXPA04008985A (es) 2004-12-07

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