EP4284902A1 - Verzweigte primäre alkylamine als additive für benzinkraftstoffe - Google Patents

Verzweigte primäre alkylamine als additive für benzinkraftstoffe

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Publication number
EP4284902A1
EP4284902A1 EP22700409.0A EP22700409A EP4284902A1 EP 4284902 A1 EP4284902 A1 EP 4284902A1 EP 22700409 A EP22700409 A EP 22700409A EP 4284902 A1 EP4284902 A1 EP 4284902A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
stands
group
amine
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22700409.0A
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English (en)
French (fr)
Inventor
Jochen Mezger
Marc Walter
Markus Hansch
Szilard Csihony
Mathias LOHMANN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP4284902A1 publication Critical patent/EP4284902A1/de
Pending legal-status Critical Current

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    • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
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    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
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    • C10L1/00—Liquid carbonaceous fuels
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    • 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
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • C—CHEMISTRY; METALLURGY
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
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    • C10L1/224—Amides; Imides carboxylic acid amides, imides
    • C—CHEMISTRY; METALLURGY
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    • C10L1/14—Organic compounds
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    • 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
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    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415—Light distillates, e.g. LPG, naphtha
    • C10L2200/0423—Gasoline
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    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/14—Function and purpose of a components of a fuel or the composition as a whole for improving storage or transport of the fuel
    • C—CHEMISTRY; METALLURGY
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    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines

Definitions

  • the present invention describes the use of certain branched amines as additives for gasoline fuels, especially for reducing injector nozzle fouling in direct injection spark ignition engines.
  • linear amines as additives for different fuels and for different purposes is long known.
  • EP 450704 discloses linear C10- to C2o-amines as additives for reducing fouling of injectors in Diesel engines.
  • WO 2003/76554 discloses the use of hydrocarbyl amines wherein the hydrocarbyl moiety has a number average molecular weight in the range 140 to 255 as an additive for reducing injector nozzle fouling in a direct injection spark ignition engine.
  • Linear alkylamines are preferred, in the examples dodecyl amine (lauryl amine) was used.
  • WO 2004/50806 A2 discloses a composition comprising amines and Mannich adducts as detergent for direct injection spark ignition engines.
  • tridecyl amine is generically disclosed and used in one additive package without disclosing which isomer was used.
  • linear amines tend to solidify at ambient temperatures so that incorporation of linear amines into additive packages requires a minimum temperature or heating of the components before mixing.
  • lauryl amine as disclosed in WO 2003/76554, is solid a room temperature and therefore needs to be molten before formulating an additive package.
  • additive packages comprising lauryl amine as constituent show poor storage stability at low temperatures (see Comparative Examples below).
  • linear amines tend to demix from additive packages so that a higher amount of solvent or a stabiliser or compatibilizer is to be used as an additional component in order to yield stable mixtures. It was an object of the present invention to develop amines as additives for gasoline fuels which exhibit an activity as an additive for reducing injector nozzle fouling comparable to the linear amines known from the prior art or even a higher activity but do not show their disadvantages but are easier to incorporate into an additive package. Furthermore, the storage stability of the amine-containing additive packages should be improved.
  • branched alkyl amines the alkyl group having from 8 to 22, preferably from 10 to 17, more preferably 13 carbon atoms and with a branching of at least 1.0, preferably of from 1.0 to 8.0, more preferably from 1.5 to 7.0 as a fuel additive in gasoline.
  • Another object of the present invention are gasoline additive packages comprising at least one of these branched alkyl amines, at least one deposit control agent, and optionally further gasoline additives.
  • gasoline fuel compositions comprising such additive packages.
  • Such gasoline fuel compositions are preferably suitable for use in a spark ignition engine, for reducing injector nozzle fouling in a direct injection spark ignition engine.
  • further object of the present invention are the use of branched primary alkyl amines, the alkyl group having from 8 to 22, preferably from 10 to 17, more preferably 13 carbon atoms and with a branching of at least 1.0, preferably of from 1 .0 to 8.0, more preferably from 1 .5 to 7.0 for reducing injector nozzle fouling in a direct injection spark ignition engine, the use of additive packages comprising such branched primary alkyl amines for reducing injector nozzle fouling in a direct injection spark ignition engine, and the use of an unleaded gasoline composition comprising a major proportion of a gasoline suitable for use in a spark ignition engine, for reducing injector nozzle fouling in a direct injection spark ignition engine.
  • the branched alkyl amines R-NH2 are primary amines bearing an alkyl group R having from 8 to 22, preferably from 10 to 17, more preferably 13 carbon atoms, the alkyl group having a branching of at least 1 .0, preferably of from 1 .0 to 8.0, more preferably from 1 .5 to 7.0.
  • Branching in the context of the present invention means that the alkyl residue R comprises the required number of branchings.
  • branching index ISO index
  • the branched primary amines can be used as a mixture of amines of different molecular weight or preferably of one single molecular weight.
  • Typical examples of such amines are the branched isomers of octyl amine, nonyl amine, decyl amine, undecyl amine, dodecyl amine, tridecyl amine, tetradecyl amine, pentadecyl amine, hexadecyl amine, and heptadecyl amine, preferably nonyl amine, decyl amine, dodecyl amine, tridecyl amine, tetradecyl amine, hexadecyl amine, heptadecyl amine, eicosyl amine, docosyl amine, and mixtures thereof, more preferably nonyl amine, tridecyl amine, and heptadecyl amine, most preferably tridecyl amine and heptadecyl amine, and especially tridecyl amine.
  • branched octyl amine is 2-amino-2,4,4-trimethyl-pentane.
  • One preferred example for a branched decyl amine is 2-propylheptyl amine.
  • the branched amines according to the present invention are obtainable by oligomerization of propene, isobutene, 1-butene or 2-butene forming a double bondcontaining oligomer, followed by hydroformylation and reductive amination with ammonia.
  • the resulting amine usually is a mixture of isomers.
  • the branched amines of the present invention are obtainable by amination of the corresponding branched alcohols or by reductive amination of the corresponding branched aldehydes.
  • the branching of the amines obtained is the same as that of the underlying alcohols or aldehydes, since the reaction conditions of the amination or reductive amination usually do not affect the branching of the alkyl group.
  • the mixture of isomers my contain one or more of the following isomers:
  • mixtures of such branched amines are mixtures of tertiary alkyl C12- to Cu-amines (CAS No 68955-53-3) or of C - to C22-amines obtainable via Ritter reaction.
  • Amines with tertiary alkyl groups are less preferred since they exhibit a toxicity on inhalation.
  • those amines with the amine group bound to a primary carbon are preferred, i.e. amines bearing a group -CH2-NH2.
  • a tridecylamine isomeric mixture from BASF SE (CAS No: 86089-17-0) obtained by amination from the corresponding tridecanol isomeric mixture with a branching index of 2.2.
  • Such branched alkyl amines exhibit a lower melting point than the corresponding linear alkyl amines and are, therefore, easier to formulate in additive packages.
  • Often such branched alkyl amines are liquid at room temperature, however, usually exhibit a lower melting point than the corresponding linear isomers. With easier formulability is meant that less solvent is needed to achieve a homogenous formulation compared to the corresponding linear alkyl amines.
  • branched primary alkyl amines the alkyl group having from 8 to 22, preferably from 10 to 17, more preferably 13 carbon atoms and with a branching of at least 1.0, preferably of from 1 .0 to 8.0, more preferably from 1 .5 to 7.0 as an additive in a fuel additive package for improving the storage stability and/or formulability of fuel additive packages for gasoline.
  • the degree of branching is preferably described by the ISO index which indicates the average number of branches of the respective alkyl groups.
  • the ISO index indicates the average number of branches of the respective alkyl groups.
  • the n-octyl group contributes 0, methylheptyl groups contribute 1
  • dimethylhexyl groups contribute 2 to the ISO index.
  • the lower the ISO index the greater the linearity of the molecules in the respective group.
  • the degree of branching is defined as the number of methyl groups in a molecule of the amine minus 1.
  • the average degree of branching is the statistical average of the degree of branching of the molecules of a sample.
  • the average degree of branching can be preferably determined by 1 H-NMR spectroscopy as follows: a sample of the amine is firstly subject to derivatization by means of trichloroacetyl isocyanate (TAI) (literature: A. K. Bose, P. R. Srinivasan, Tetrahedron 1975, 3025; A. Postma et al., Polymer 2006, 1899).
  • TAI trichloroacetyl isocyanate
  • the signals ⁇ 1 ppm are assigned to the methyl groups.
  • the average degree of branching (ISO index) can be calculated as follows from the spectrum obtained in this way:
  • ISO index ((A(CH 3 )/3) I (A(CH 2 -NH 2 )/2)) - 1 where A(CH 3 ) is the signal area corresponding to the methyl protons and A(CH 2 -NH 2 ) is the signal area of the methylene protons in the CH 2 -NH 2 group.
  • Primary amines bearing methine protons adjacent to the amino group H 2 NCHR may be analysed analogously. In the case of amines bearing a quaternary carbon atom adjacent to the amino group another distinct and assignable proton signal may be used for determining the ISO index.
  • the ISO index determined according to the above- mentioned method may be used.
  • 1 H 1D spectra were recorded using the zg pulse program with 64k data points, the relaxation delay D1 was chosen as 5 seconds, and 64 transients were recorded.
  • the relaxation delay D1 was chosen as 5 seconds, and 64 transients were recorded.
  • 32k data points were used, an exponential window function with a line broadening of 0.3 Hz was applied. Automatic baseline correction was used, phase correction was performed manually by the user.
  • Phase sensitive HSQC spectra were recorded using the hsqcedetgpsisp2.3 pulse sequence, with 4k data points in the direct and 256 data points in the indirect dimension using 8 transients per increment. Experiments were optimized for a 1 JC-H coupling constant of 144 Hz.
  • the relaxa- tion delay D1 was set to 1.0 s.
  • 1024 x 1024 data points were Fourier transformed, and a quadratic sine function with a sine bell shift of 2 was applied.
  • Samples were prepared by dissolution of the pure analyte in deuterated chloroform with traces of TMS as internal reference. The samples were transferred into 5 mm NMR tubes. Deuterated solvents were purchased from Euriso-Top GmbH and used as received.
  • the gasoline additive packages respectively gasoline compositions according to the present invention comprise at least one deposit control agent, selected from the group consisting of
  • polyalkenemono- or polyalkenepolyamines having a number average molecular weight in the range 300 to 5000, preferably selected from the group consisting of
  • polyalkenemono- or polyalkenepolyamines having a number average molecular weight in the range 300 to 5000.
  • the deposit control agent is a polyalkenemono- or polyalkenepolyamines, especially a polyisobutene amine having a number average molecular weight in the range 300 to 5000.
  • the at least one quaternary nitrogen component refer, in the context of the present invention, to nitrogen compounds quaternized in the presence of an acid or in an acid-free manner, preferably obtainable by addition of a compound comprising at least one oxygen- or nitrogen- containing group reactive with an anhydride and additionally at least one quaternizable amino group onto a polycarboxylic anhydride compound and subsequent quaternization.
  • the quaternary nitrogen component is an ammonium compound, however in the context of the present document morpholinium, piperidinium, piperazinium, pyrrolidinium, imid- azolinium or pyridinium cations are also encompassed by the phrase "quaternary nitrogen component".
  • the quaternary ammonium compounds are preferably of the formula
  • A' stands for an anion, preferably a carboxylate R 5 COO' or a carbonate R 5 O-COO', and
  • R 1 , R 2 , R 3 , R 4 , and R 5 independently of another are an organic residue with from 1 to 100 carbon atoms, substituted or unsubstituted, preferably unsubstituted, linear or branched alkyl, alkenyl or hydroxyalkyl residue with 1 to 100, more preferably 1 to 75, even more preferably 1 to 30, most preferably 1 to 25 and especially 1 to 20 carbon atoms,
  • R 5 additionally may be substituted or unsubstituted cycloalkyl or aryl residues bearing 5 to 20, preferably 5 to 12 carbon atoms.
  • the anion may be multiply charged negatively, e.g. if anions of dibasic acids are used, in this case the stoichiometric ratio of the ammonium ions to the anions corresponds to the ratio of positive and negative charges.
  • the carbon atoms may be interrupted by one or more oxygen and/or sulphur atoms and/or one or more substituted or unsubstituted imino groups, and may be substituted by Ce-Ci2-aryl, C5-Ci2-cycloalkyl or a five- or six-membered, oxygen-, nitrogen- and/or sulphur-containing heterocycle or two of them together form an unsaturated, saturated or aro- matic ring which may be interrupted by one or more oxygen and/or sulphur atoms and/or one or more substituted or unsubstituted imino groups, where the radicals mentioned may each be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and/or heterocycles.
  • Two of the residues R 1 to R 4 may together form an unsaturated, saturated or aromatic ring, preferably a five-, six- or seven-membered ring (including the nitrogen atom of the ammonium ion).
  • ammonium cation may be a morpholinium, piperidinium, piperazinium, pyrroli- dinium, imidazolinium or pyridinium cation.
  • Ci-C2o-alkyl which may be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and/or heterocycles is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, eicosyl, 1 ,1 -dimethylpropyl, 1 ,1 -dimethylbutyl, 1 , 1 ,3,3- tetramethylbutyl, benzyl, 1 -phenylethyl, 2-phenylethyl, a,a
  • C2-C2o-alkyl interrupted by one or more oxygen and/or sulphur atoms and/or one or more substituted or unsubstituted imino groups is, for example, 5-hydroxy-3-oxa-pentyl, 8-hydroxy-3,6- dioxaoctyl, 11-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 11 -hydroxy-4,8- dioxaundecyl, 15-hydroxy-4,8,12-trioxapentadecyl, 9-hydroxy-5-oxanonyl, 14-hydroxy-5,10- oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxaoctyl, 11-methoxy-3,6,9- trioxaundecyl, 7-methoxy-4-oxaheptyl, 11-methoxy-4,8-d
  • two radicals form a ring, they can together be 1 ,3-propylene, 1 ,4-butylene, 1 ,5-pentylene, 2- oxa-1 ,3-propylene, 1-oxa-1 ,3-propylene, 2-oxa-1 ,3-propylene, 1-oxa-1 ,3-propenylene, 1-aza-
  • the number of oxygen and/or sulphur atoms and/or imino groups is not subject to any restrictions. In general, there will be no more than 5 in the radical, preferably no more than 4 and very particularly preferably no more than 3.
  • Substituted and unsubstituted imino groups can be, for example, imino, methylimino, isopropylimino, n-butylimino or tert-butylimino.
  • functional groups can be carboxy, carboxamide, hydroxy, di(Ci-C4-alkyl)amino, C1-C4- alkyloxycarbonyl, cyano or Ci-C4-alkyloxy,
  • Ce-Ci2-aryl which may be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and/or heterocycles is, for example, phenyl, tolyl, xylyl, a-naphthyl, p- naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tertbutylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, e
  • 2.4- or 2,6-dinitrophenyl 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl, C5-Ci2-cycloalkyl which may be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and/or heterocycles is, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocycl
  • Ci to C4-alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
  • the residues R 1 to R 5 are preferably C2-Cis-alkyl or Ce-Ci2-aryl, more preferably C4-Ci6-alkyl or Ce-Ci2-aryl, and even more preferably C4-Ci6-alkyl or Ce-aryl.
  • the residues R 1 to R 5 may be saturated or unsaturated, preferably saturated.
  • Preferred residues R 1 to R 5 do not bear any heteroatoms other than carbon or hydrogen.
  • R 1 to R 4 are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, 2-propylheptyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, eicosyl, 1 ,1 -dimethylpropyl, 1 ,1 -di methyl butyl, 1 , 1 ,3,3- tetramethylbutyl, benzyl, 1 -phenylethyl, 2-phenylethyl, a,a-dimethylbenzyl, benzhydryl, p- tolylmethyl or 1-(p-butylphenyl)ethyl,
  • At least one of the residues R 1 to R 4 is selected from the group consisting of 2-hydroxyethyl, hydroxyprop-1-yl, hydroxyprop-2-yl, 2-hydroxy butyl or 2-hydroxy-2- phenylethyl.
  • R 5 is a polyolefin-homo- or copolymer, preferably a polypropylene, polybutene or polyisobutene residue, with a number-average molecular weight (M n ) of 85 to 20000, for example 113 to 10 000, or 200 to 10000 or 350 to 5000, for example 350 to 3000, 500 to 2500, 700 to 2500, or 800 to 1500.
  • M n number-average molecular weight
  • anions A' are the anions of acetic acid, propionic acid, butyric acid, 2- ethylhexanoic acid, trimethylhexanoic acid, 2-propylheptanoic acid, isononanoic acid, versatic acids, decanoic acid, undecanoic acid, dodecanoic acid, saturated or unsaturated fatty acids with 12 to 24 carbon atoms, or mixtures thereof, salicylic acid, oxalic acid mono-Ci-C4-alkyl ester, phthalic acid mono-Ci-C4-alkyl ester, Ci2-Cioo-alkyl- and -alkenyl succinic acid, especially dodecenyl succinic acid, hexadecenyl succinic acid, eicosenyl succinic acid, and polyisobutenyl succinic acid. Further examples are methyl carbonate, ethyl carbonate, n-butyl carbonate
  • the nitrogen compounds quaternized in the presence of an acid or in an acid-free manner are obtainable by addition of a compound which comprises at least one oxygen- or nitrogen-containing group reactive with an anhydride and additionally at least one quaternizable amino group onto a polycarboxylic anhydride compound and subsequent quater- nization, especially with an epoxide, e.g. styrene or propylene oxide, in the absence of free acid, as described in WO 2012/004300, or with a carboxylic ester, e.g. dimethyl oxalate or methyl salicylate.
  • a compound which comprises at least one oxygen- or nitrogen-containing group reactive with an anhydride and additionally at least one quaternizable amino group onto a polycarboxylic anhydride compound and subsequent quater- nization especially with an epoxide, e.g. styrene or propylene oxide, in the absence of free acid, as described in WO 2012/004300,
  • Suitable compounds having at least one oxygen- or nitrogen-containing group reactive with anhydride and additionally at least one quaternizable amino group are especially polyamines having at least one primary or secondary amino group and at least one tertiary amino group, especially N,N-dimethyl-1 ,3-propane diamine, N,N-dimethyl-1 ,2-ethane diamine or N,N, N'-trimethyl-1 ,2-ethane diamine.
  • Useful polycarboxylic anhydrides are especially dicarboxylic acids such as succinic acid, having a relatively long-chain hydrocarbyl substituent, preferably having a number-average molecular weight M n for the hydrocarbyl substituent of 200 to 10.000, in particular of 350 to 5000.
  • Such a quaternized nitrogen compound is, for example, the reaction product, obtained at 40°C, of polyisobutenylsuccinic anhydride, in which the polyisobutenyl radical typically has an M n of 1000, with 3-(dimethylamino)propylamine, which constitutes a polyisobutenylsuccinic monoamide and which is subsequently quaternized with dimethyl oxalate or methyl salicylate or with styrene oxide or propylene oxide in the absence of free acid.
  • the quaternized ammonium compound is of formula wherein in this formula
  • PIB stands for a polyisobutenyl residue having a number average molecular weight M n of from 550 to 2300, preferably from 650 to 1500 and more preferably from 750 to 1300 g/mol,
  • R stands for an Ci- to C4-alkyl or hydroxy-Ci- to C4-alkyl, preferably methyl or 2-hydroxypropyl, and
  • A' stands for an anion, preferably carboxylate R 5 COO' or a carbonate R 5 O-COO' as defined above, more preferably acetate, salicylate or methyloxalate.
  • the quaternized ammonium compound is of formula wherein in this formula
  • PIB stands for a polyisobutenyl residue having a number average molecular weight M n of from 550 to 2300, preferably from 650 to 1500 and more preferably from 750 to 1300 g/mol
  • R stands for a hydroxy-Ci- to C4-al kyl , preferably 2-hydroxypropyl.
  • the quaternized compound is of formula wherein in this formula
  • PIB stands for a polyisobutenyl residue having a number average molecular weight M n of from 550 to 2300, preferably from 650 to 1500 and more preferably from 750 to 1300 g/mol
  • R stands for an Ci- to C4-alkyl or hydroxy-Ci- to C4-alkyl, preferably methyl
  • A' stands for an anion, preferably carboxylate R 5 COO' or a carbonate R 5 O-COO' as defined above, more preferably salicylate or methyloxalate.
  • the quaternized ammonium compound is of formula wherein in this formula
  • R a stands for Ci-C2o-alkyl, preferably Cg- to Ci?-alkyl, more preferably for undecyl, tridecyl, pentadecyl or heptadecyl,
  • R b stands for a hydroxy-Ci- to C4-al kyl , preferably 2-hydroxypropyl or 2-hydroxy butyl
  • A' stands for an anion, preferably carboxylate R 5 COO', as defined above, more preferably R 5 COO' being a carboxylate of a fatty acid, especially k being acetate, 2-ethylhexanoate, oleate, polyisobutenyl succinate or monoesters of polyisobutenyl succinate.
  • the quaternized ammonium compound is of formula wherein in this formula
  • R stands for an Ci- to C4-al kyl , preferably methyl
  • k stands for an anion, preferably carboxylate R 5 COO' or a carbonate R 5 O-COO' as defined above, more preferably salicylate or methyloxalate.
  • the quaternized ammonium compound is of formula wherein in this formula
  • R a and R b independently of another stand for Ci-C2o-alkyl or hydroxy-Ci- to C4-alkyl, preferably R a stands for Ci-C2o-alkyl, preferably ethyl, n-butyl, n-octyl, n-dodecyl, tetradecyl or hexadecyl, and R b stands for hydroxy-Ci- to C4-alkyl, preferably 2-hydroxypropyl,
  • A' stands for an anion, preferably carboxylate R 5 COO' or a carbonate R 5 O-COO' as defined above, more preferably Ci2-Cioo-alkyl- and -alkenyl succinic acid, especially dodecenyl succinic acid, hexadecenyl succinic acid, eicosenyl succinic acid, and polyisobutenyl succinic acid.
  • Mannich adducts are obtainable as described in US 8449630 B2, column 7, line 35 to column 9, line 52.
  • the Mannich adducts are obtainable by reaction of
  • At least one hydrocarbyl-substituted phenol preferably a phenol of formula V of US 8449630 B2, more preferably para hydrocarbyl-substituted phenol or para hydrocarbyl-substituted orthocresol, with
  • aldehyde preferably acetaldehyde or formaldehyde, more preferably formaldehyde
  • amine preferably selected from the group consisting of octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eicosylamine, cyclooctylamine, cyclodecylamine di-n-butylamine, diisobutylamine, di-tert-butylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, di(2-ethylhexylamine), dinonylamine, didecylamine, N- 1 b methylcyclohexylamine
  • the hydrocarbyl residue of the at least one hydrocarbyl-substituted phenol preferably has a number average molecular weight Mn of from 85 to 5000, preferably of from 113 to 2500, more preferably of from 550 to 1500, and especially from 750 to 1100.
  • the hydrocarbyl residue is a polyisobutene radical of the beforementioned molecular weight, more preferably derived from a "reactive" polyisobutene radical as defined in US 8449630 B2.
  • the Mannich adduct is of formula wherein
  • R 10 is a hydrocarbyl residue with a number average molecular weight Mn of from 85 to 5000, preferably of from 113 to 2500, more preferably of from 550 to 1500, and most preferably of from 750 to 1100, and especially is a polyisobutene radical of the before-mentioned molecular weight, more preferably derived from a "reactive" polyisobutene radical,
  • R 11 is hydrogen, methyl, ethyl, iso-propyl, n-butyl, tert-butyl, but-2-yl, or amyl, preferably hydrogen or methyl, and more preferably methyl,
  • R 12 and R 13 independently of another are Ci- to Ce-alkyl, preferably Ci- to C4-alkyl, more preferably are methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, even more preferably are methyl, ethyl or n-butyl, or R 12 and R 13 together the nitrogen atom form a five- or six-membered ring, preferably a pyrrolidine, piperidine or morpholine ring, and
  • R 14 is bivalent alkylene residue having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 2 or 3 carbon atoms, most preferably selected from the group consisting of methylene, 1 ,2-ethylene, 1 ,2-propylene, 1 ,3-propylene, 1 ,4-butylene, and 1 ,6-hexylene, and especially being 1 ,2-ethylene or 1 ,3-propylene.
  • Such additives based on high- reactivity polyisobutene which can be prepared from the polyisobutene which may comprise up to 20% by weight of n-butene units by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are known especially from EP-A 244 616.
  • additives comprising monoamino groups are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described more particularly in DE-A 19620262.
  • polyalkylene radicals examples include polyisobutenyl radicals derived from what are called “high-reactivity" polyisobutenes which feature a high content of terminal double bonds. Terminal double bonds are alpha-olefinic double bonds of the type
  • Polymer which are also referred to collectively as vinylidene double bonds are also referred to collectively as vinylidene double bonds.
  • Suitable high-reactivity polyisobutenes are, for example, polyisobutenes which have a proportion of vinylidene double bonds of greater than 70 mol%, especially greater than 80 mol% or greater than 85 mol%. Preference is given especially to polyisobutenes which have homogeneous polymer skeletons. Homogeneous polymer skeletons are possessed especially by those polyisobutenes formed from isobutene units to an extent of at least 85% by weight, preferably to an extent of at least 90% by weight and more preferably to an extent of at least 95% by weight.
  • Such high-reactivity polyisobutenes preferably have a number-average molecular weight within the abovementioned range.
  • the high-reactivity polyisobutenes may have a polydispersity in the range from 1.05 to 7, especially of about 1.1 to 2.5, for example of less than 1.9 or less than 1.5. Polydispersity is understood to mean the quotient of weight-average molecular weight Mw divided by the number-average molecular weight Mn.
  • Glissopal® 2300 2300
  • Other number-average molecular weights can be established in a manner known in principle by mixing polyisobutenes of different numberaverage molecular weights or by extractive enrichment of polyisobutenes of particular molecular weight ranges.
  • polyisobutenes Due to their high proportion of vinylidene double bonds these polyisobutenes are especially reactive to undergo hydroformylation and subsequent amination, preferably with ammonia, to yield the corresponding polyisobutene amines, which represent a preferred embodiment of the present invention.
  • Suitable corrosion inhibitors are, for example, succinic esters or hemiesters, in particular with polyols, fatty acid derivatives, for example oleic esters, oligomerized fatty acids, such as dimeric fatty acid, substituted ethanolamines, and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany) or HiTEC 536 (Afton Corporation).
  • fatty acids or fatty acid derivatives preferably oleic acid or its esters
  • - oligomerized fatty acids preferably dimeric fatty acid, more preferably dimeric oleic acid (CAS: 61788-89-4), - alkyl or alkenyl substituted succinic acids, esters or hemiesters, and
  • - oligomerized fatty acids preferably dimeric fatty acid, more preferably dimeric oleic acid (CAS: 61788-89-4),
  • the succinic acids, esters or hemiesters are preferably substituted with Cs- to Cwo-alkyl or -alkenyl radicals.
  • succinic acids or hemiesters follow formula wherein
  • R 20 is a Cs- to Cwo-alkyl or Cs- to Cwo-alkenyl group, preferably Cs- to Cwo-alkenyl, more preferably C12- to Cgo-alkenyl, and even more preferably C - to Cso-alkenyl group
  • R 21 is hydrogen or Ci- to C2o-alkyl or C2- to C4-hydroxyalkyl, preferably hydrogen.
  • the underlying succinic acid anhydrides are obtainable by thermal ene reaction of Cs- to Cwo-alkenes, preferably oligomers or polymers of propene, 1 -butene or isobutene, with maleic anhydride.
  • the above-mentioned corrosion inhibitors are obtainable from such anhydrides by hydrolysis or reaction with the appropriate alcohol. Olefin-i ic acid
  • the olefin-carboxylic acid copolymer (A) is a copolymer obtainable by
  • (Ac) optionally at least one further aliphatic or cycloaliphatic olefin which has at least 4 carbon atoms and is different than (Ab) and
  • (Ad) optionally one or more further copolymerizable monomers other than monomers (Aa), (Ab) and (Ac), selected from the group consisting of
  • N-vinyl compounds selected from the group consisting of vinyl compounds of heterocycles containing at least one nitrogen atom, N-vinylamides or N-vinyllactams,
  • a second optional reaction step (II) partly or fully hydrolyzing and/or saponifying anhydride or carboxylic ester functionalities present in the copolymer obtained from (I), the second reaction step being run at least when the copolymer obtained from reaction step (I) does not comprise any free carboxylic functionalities.
  • the monomer (Aa) is at least one, preferably one to three, more preferably one or two and most preferably exactly one ethylenically unsaturated, preferably a,p-ethylenically unsaturated, mono- or dicarboxylic acid(s) or derivatives thereof, preferably a dicarboxylic acid or derivatives thereof.
  • - mono- or dialkyl esters preferably mono- or di-Ci-C4-alkyl esters, more preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters, and
  • mixed esters preferably mixed esters having different C1-C4 alkyl components, more preferably mixed methyl ethyl esters.
  • the derivatives are anhydrides in monomeric form or di-Ci-C4-alkyl esters, more preferably anhydrides in monomeric form.
  • Ci-C4-alkyl is understood to mean methyl, ethyl, /so-propyl, n- propyl, n-butyl, /so-butyl, sec-butyl and tert-butyl, preferably methyl and ethyl, more preferably methyl.
  • Examples of a,p-ethylenically unsaturated mono- or dicarboxylic acids are those mono- or dicarboxylic acids or derivatives thereof in which the carboxyl group or, in the case of dicarboxylic acids, at least one carboxyl group, preferably both carboxyl groups, is/are conjugated to the ethylenically unsaturated double bond.
  • Examples of ethylenically unsaturated mono- or dicarboxylic acids that are not a,p-ethylenically unsaturated are cis-5-norbornene-endo-2,3-dicarboxylic anhydride, exo-3, 6-e poxy- 1 ,2, 3,6- tetrahydrophthalic anhydride and cis-4-cyclohexene-1 ,2-dicarboxylic anhydride.
  • Examples of a,p-ethylenically unsaturated monocarboxylic acids are acrylic acid, methacrylic acid, crotonic acid and ethylacrylic acid, preferably acrylic acid and methacrylic acid, referred to in this document as (meth)acrylic acid for short, and more preferably acrylic acid.
  • Particularly preferred derivatives of a,p-ethylenically unsaturated monocarboxylic acids are methyl acrylate, ethyl acrylate, n-butyl acrylate and methyl methacrylate.
  • dicarboxylic acids examples include maleic acid, fumaric acid, itaconic acid (2- methylenebutanedioic acid), citraconic acid (2-methylmaleic acid), glutaconic acid (pent-2-ene- 1 ,5-dicarboxylic acid), 2,3-dimethylmaleic acid, 2-methylfumaric acid, 2,3-dimethylfumaric acid, methylenemalonic acid and tetrahydrophthalic acid, preferably maleic acid and fumaric acid and more preferably maleic acid and derivatives thereof.
  • monomer (Aa) is maleic anhydride.
  • Monomer (Ab) is at least one, preferably one to four, more preferably one to three, even more preferably one or two and most preferably exactly one a-olefin(s) having from at least 12 up to and including 30 carbon atoms.
  • the a-olefins (Ab) preferably have at least 14, more preferably at least 16 and most preferably at least 18 carbon atoms.
  • the a-olefins (Ab) have up to and including 28, more preferably up to and including 26 and most preferably up to and including 24 carbon atoms.
  • the a-olefins may be one or more linear or branched, preferably linear, 1 -alkene.
  • Examples of these are 1-dodecene, 1-tridecene, 1 -tetradecene, 1 -pentadecene, 1-hexadecene, 1 -heptadecene, 1- octadecene, 1-nonodecene, 1-eicosene, 1-docosene, 1 -tetracosene, 1- hexacosene, preference being given to 1 -octadecene, 1-eicosene, 1-docosene and 1- tetracosene, and mixtures thereof.
  • a-olefin are those olefins which are oligomers or polymers of C2 to C12 olefins, preferably of C3 to C10 olefins, more preferably of C4 to Ce olefins.
  • olefins which are oligomers or polymers of C2 to C12 olefins, preferably of C3 to C10 olefins, more preferably of C4 to Ce olefins.
  • Examples thereof are ethene, propene, 1 -butene, 2-butene, isobutene, pentene isomers and hexene isomers, preference being given to ethene, propene, 1 -butene, 2-butene and isobutene.
  • a-olefins include oligomers and polymers of propene, 1 -butene, 2- butene, isobutene, and mixtures thereof, particularly oligomers and polymers of propene or isobutene or of mixtures of 1 -butene and 2-butene.
  • oligomers preference is given to the trimers, tetramers, pentamers and hexamers, and mixtures thereof.
  • olefin (Ab) In addition to the olefin (Ab), it is optionally possible to incorporate at least one, preferably one to four, more preferably one to three, even more preferably one or two and especially exactly one further aliphatic or cycloaliphatic olefin(s) (Ac) which has/have at least 4 carbon atoms and is/are different than (Ab) by polymerization into the inventive copolymer.
  • the olefins (Ac) may be olefins having a terminal (a-)double bond or those having a nonterminal double bond, preferably having an a-double bond.
  • the olefin (Ac) preferably comprises olefins having 4 to fewer than 12 or more than 30 carbon atoms. If the olefin (Ac) is an olefin having 12 to 30 carbon atoms, this olefin (Ac) does not have an a-double bond.
  • aliphatic olefins examples include 1 -butene, 2-butene, isobutene, pentene isomers, hexene isomers, heptene isomers, octene isomers, nonene isomers, decene isomers, undecene isomers and mixtures thereof.
  • cycloaliphatic olefins are cyclopentene, cyclohexene, cyclooctene, cyclodecene, cyclododecene, a- or p-pinene and mixtures thereof, limonene and norbornene.
  • olefins (Ac) are polymers having more than 30 carbon atoms of propene, 1- butene, 2-butene or isobutene or of olefin mixtures comprising the latter, preferably of isobutene or of olefin mixtures comprising the latter, more preferably having a mean molecular weight M w in the range from 500 to 5000 g/mol, preferably 650 to 3000 and more preferably 800 to 1500 g/mol.
  • the oligomers or polymers comprising isobutene in copolymerized form have a high content of terminal ethylenic double bonds (a-double bonds), for example at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol% and most preferably at least 80 mol%.
  • a-double bonds terminal ethylenic double bonds
  • suitable isobutene sources are either pure isobutene or isobutene-containing C4 hydrocarbon streams, for example C4 raffinates, especially "raffinate 1", C4 cuts from isobutane dehydrogenation, C4 cuts from steamcrackers and from FCC crackers (fluid catalyzed cracking), provided that they have substantially been freed of 1 ,3-butadiene present therein.
  • C4 hydrocarbon stream from an FCC refinery unit is also known as a "b/b" stream.
  • Suitable isobutene-containing C4 hydrocarbon streams are, for example, the product stream of a propyleneisobutane cooxidation or the product stream from a metathesis unit, which are generally used after customary purification and/or concentration.
  • Suitable C4 hydrocarbon streams comprise generally less than 500 ppm, preferably less than 200 ppm, of butadiene.
  • the presence of 1- butene and of cis- and trans-2-butene is substantially uncritical.
  • the isobutene concentration in said C4 hydrocarbon streams is in the range from 40% to 60% by weight.
  • raffinate 1 generally consists essentially of 30% to 50% by weight of isobutene, 10% to 50% by weight of 1 -butene, 10% to 40% by weight of cis- and trans-2-butene and 2% to 35% by weight of butanes; in the polymerization process the unbranched butenes in the raffinate 1 are generally virtually inert, and only the isobutene is polymerized.
  • the monomer source used for polymerization is a technical C4 hydrocarbon stream having an isobutene content of 1% to 100% by weight, especially of 1% to 99% by weight, in particular of 1% to 90% by weight, more preferably of 30% to 60% by weight, especially a raffinate 1 stream, a b/b stream from an FCC refinery unit, a product stream from a propylene-isobutane cooxidation or a product stream from a metathesis unit.
  • raffinate 1 stream is used as isobutene source
  • the use of water as the sole initiator or as further initiator has been found to be useful, particularly when polymerization is effected at temperatures of -20°C to +30°C, especially of 0°C to +20°C.
  • temperatures of - 20°C to +30°C, especially of 0°C to +20°C it is possible to dispense with the use of an initiator when using a raffinate 1 stream as isobutene source.
  • Said isobutene-containing monomer mixture may comprise small amounts of contaminants such as water, carboxylic acids or mineral acids without causing any critical yield or selectivity losses. It is appropriate to the purpose to avoid accumulation of these impurities by removing such harmful substances from the isobutene-containing monomer mixture, for example, by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.
  • the monomer mixture comprises preferably at least 5% by weight, more preferably at least 10% by weight and especially at least 20% by weight of isobutene, and preferably at most 95% by weight, more preferably at most 90% by weight and especially at most 80% by weight of comonomers.
  • the mixture of the olefins (Ab) and optionally (Ac), averaged to their molar amounts have at least 12 carbon atoms, preferably at least 14, more preferably at least 16 and most preferably at least 17 carbon atoms.
  • the upper limit is less relevant and is generally not more than 60 carbon atoms, preferably not more than 55, more preferably not more than 50, even more preferably not more than 45 and especially not more than 40 carbon atoms.
  • the optional monomer (Ad) is at least one monomer, preferably one to three, more preferably one or two and most preferably exactly one monomer(s) selected from the group consisting of (Ada) vinyl esters, (Adb) vinyl ethers,
  • N-vinyl compounds selected from the group consisting of vinyl compounds of heterocycles containing at least one nitrogen atom, N-vinylamides or N-vinyllactams, (Adf) ethylenically unsaturated aromatics and
  • vinyl esters are vinyl esters of C2- to Ci2-carboxylic acids, preferably vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pentanoate, vinyl hexanoate, vinyl octanoate, vinyl 2-ethylhexanoate, vinyl decanoate, and vinyl esters of Versatic Acids 5 to 10, preferably vinyl esters of 2,2-dimethylpropionic acid (pivalic acid, Versatic Acid 5), 2,2-dimethylbutyric acid (neohexanoic acid, Versatic Acid 6), 2,2-dimethylpentanoic acid (neoheptanoic acid, Versatic Acid 7), 2,2-dimethylhexanoic acid (neooctanoic acid, Versatic Acid 8), 2,2-dimethylheptanoic acid (neononanoic acid, Versatic Acid 9) or 2,2-dimethyloctanoic acid (neodecanoic acid, Versatic Acid 9) or 2,2-d
  • vinyl ethers are vinyl ethers of Ci- to Ci2-alkanols, preferably vinyl ethers of methanol, ethanol, /so-propanol, n-propanol, n-butanol, /so-butanol, sec-butanol, tert-butanol, n- hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol) or 2-ethylhexanol.
  • Preferred (meth)acrylic esters (Adc) are (meth)acrylic esters of C5- to Ci2-alkanols, preferably of n-pentanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol), 2- ethylhexanol or 2-propylheptanol. Particular preference is given to pentyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate.
  • Examples of monomers (Add) are allyl alcohols and allyl ethers of C2- to Ci2-alkanols, preferably allyl ethers of methanol, ethanol, /so-propanol, n-propanol, n-butanol, /so-butanol, secbutanol, tert-butanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol) or 2-ethylhexanol.
  • Examples of vinyl compounds (Ade) of heterocycles comprising at least one nitrogen atom are N-vinylpyridine, N-vinylimidazole and N-vinylmorpholine.
  • Preferred compounds (Ade) are N-vinylamides or N-vinyllactams.
  • N-vinylamides or N-vinyllactams are N-vinylformamide, N-vinylacetamide, N- vinylpyrrolidone and N-vinylcaprolactam.
  • Adf ethylenically unsaturated aromatics
  • Adg a,p-ethylenically unsaturated nitriles
  • Examples of (meth)acrylamides are acrylamide and methacrylamide.
  • allylamines are allylamine, dialkylallylamine and trialkylallylammonium halides.
  • Preferred monomers (Ad) are (Ada), (Adb), (Adc), (Ade) and/or (Adf), more preferably (Ada), (Adb) and/or (Adc), even more preferably (Ada) and/or (Adc) and especially (Adc).
  • the incorporation ratio of the monomers (Aa) and (Ab) and optionally (Ac) and optionally (Ad) in the polymer obtained from reaction step (I) is generally as follows:
  • the molar ratio of (Aa)/((Ab) and (Ac)) (in total) is generally from 10:1 to 1 :10, preferably 8:1 to 1 :8, more preferably 5:1 to 1:5, even more preferably 3:1 to 1:3, particularly 2:1 to 1 :2 and especially 1.5:1 to 1:1.5.
  • the molar incorporation ratio of maleic anhydride to monomers ((Ab) and (Ac)) (in total) is about 1 :1.
  • the molar ratio of obligatory monomer (Ab) to monomer (Ac), if present, is generally of 1 :0.05 to 10, preferably of 1:0.1 to 6, more preferably of 1 :0.2 to 4, even more preferably of 1 :0.3 to 2.5 and especially 1 :0.5 to 1.5.
  • no optional monomer (Ac) is present in addition to monomer (Ab).
  • the proportion of one or more of the monomers (Ad), if present, based on the amount of the monomers (Aa), (Ab) and optionally (Ac) (in total) is generally 5 to 200 mol%, preferably 10 to 150 mol%, more preferably 15 to 100 mol%, even more preferably 20 to 50 mol% and especially 0 to 25 mol%.
  • no optional monomer (Ad) is present.
  • the anhydride or carboxylic ester functionalities present in the copolymer obtained from (I) are partly or fully hydrolyzed and/or saponified.
  • Reaction step (II) is obligatory in case the copolymer obtained from reaction step (I) does not comprise free carboxylic acid groups.
  • Hydrolization of anhydride groups is preferred over saponification of ester groups.
  • 10% to 100% of the anhydride or carboxylic ester functionalities present are hydrolyzed and/or saponified, preferably at least 20%, more preferably at least 30%, even more preferably at least 50% and particularly at least 75% and especially at least 85%.
  • the amount of water that corresponds to the desired hydrolysis level is added and the copolymer obtained from (I) is heated in the presence of the added water.
  • a temperature of preferably 20 to 150°C is sufficient for the purpose, preferably 60 to 100°C.
  • the reaction can be conducted under pressure in order to prevent the escape of water.
  • the anhydride functionalities in the copolymer are converted selectively, whereas any carboxylic ester functionalities present in the copolymer react at least only to a minor degree, if at all.
  • the copolymer is reacted with an amount of a strong base corresponding to the desired saponification level in the presence of water.
  • Strong bases used may preferably be hydroxides, oxides, carbonates or hydrogencarbonates of alkali metals or alkaline earth metals.
  • the copolymer obtained from (I) is then heated in the presence of the added water and the strong base.
  • a temperature of preferably 20 to 130°C is sufficient for the purpose, preferably 50 to 110°C. If required, the reaction can be conducted under pressure. It is also possible to hydrolyze the carboxylic ester functionalities with water in the presence of an acid. Acids used are preferably mineral acids, carboxylic acids, sulfonic acids or phosphorus acids having a pKa of not more than 5, more preferably not more than 4.
  • acetic acid formic acid, oxalic acid, salicylic acid, substituted succinic acids, aromatically substituted or unsubstituted benzenesulfonic acids, sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid; the use of acidic ion exchange resins is also conceivable.
  • anhydrides especially maleic anhydride being monomers (Aa)
  • such anhydride moieties are partly or fully, especially fully hydrolysed while potentially existing ester groups in the copolymer remain intact. In this case no saponification in step (II) takes place.
  • the copolymer obtained from (I) is then heated in the presence of the added water and the acid.
  • a temperature of preferably 40 to 200°C is sufficient for the purpose, preferably 80 to 150°C. If required, the reaction can be conducted under pressure.
  • step (II) may be preferable to remove these acid anions from the copolymer with the aid of an ion exchanger and preferably exchange them for hydroxide ions or carboxylate ions, more preferably hydroxide ions. This is the case especially when the acid anions present in the copolymer are halides or contain sulfur or nitrogen.
  • the copolymer obtained from reaction step (II) generally has a weight-average molecular weight Mw of 0.5 to 20 kDa, preferably 0.6 to 15, more preferably 0.7 to 7, even more preferably 1 to 7 and especially 1.5 to 4 kDa (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).
  • the number-average molecular weight Mn is usually from 0.5 to 10 kDa, preferably 0.6 to 5, more preferably 0.7 to 4, even more preferably 0.8 to 3 and especially 1 to 2 kDa (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).
  • the polydispersity is generally from 1 to 10, preferably from 1.1 to 8, more preferably from 1.2 to 7, even more preferably from 1 .3 to 5 and especially from 1 .5 to 3.
  • the content of acid groups in the copolymer is preferably from 1 to 8 mmol/g of copolymer, more preferably from 2 to 7.5, even more preferably from 3 to 7 mmol/g of copolymer.
  • the copolymers comprise a high proportion of adjacent carboxylic acid groups, which is determined by a measurement of adjacency. For this purpose, a sample of the copolymer is heat-treated between two Teflon films at a temperature of 290°C for a period of 30 minutes and an FTIR spectrum is recorded at a bubble-free site. The IR spectrum of Teflon is subtracted from the spectra obtained, the layer thickness is determined and the content of cyclic anhydride is determined.
  • the adjacency is at least 10%, preferably at least 15%, more preferably at least 20%, even more preferably at least 25% and especially at least 30%.
  • the olefin-carboxylic acid copolymer (A) is applied in the form of the free acid, i.e. COOH groups are present, or in the form of the anhydride which may be an intramolecular anhydride or an intermolecular anhydride linking two dicarboxylic acid molecules together, preferably in the form of a free acid.
  • the carboxylic functions may be present in salt form, e.g. as alkali or alkaline metal salts salts or as ammonium or substituted ammonium salts, depending on the pH value of the liquid phase.
  • At least 50 % of all carboxylic acid groups are available in the form of the free acid as COOH-groups, more preferably at least 66 %, very preferably at least 75 %, even more preferably at least 85 %, and especially at least 95%.
  • a single olefin-carboxylic acid copolymer (A) or a mixture of different olefin-carboxylic acid copolymers (A) may be used.
  • Carrier oils additionally used may be of mineral or synthetic nature. Suitable mineral carrier oils are fractions obtained in crude oil processing, such as brightstock or base oils having viscosities, for example, from the SN 500 - 2000 class; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. Likewise useful is a fraction which is obtained in the refining of mineral oil and is known as “hydrocrack oil” (vacuum distillate cut having a boiling range of from about 360 to 500°C, obtainable from natural mineral oil which has been catalytically hydrogenated under high pressure and isomerized and also deparaffinized). Likewise suitable are mixtures of the abovementioned mineral carrier oils.
  • suitable synthetic carrier oils are polyolefins (polyalphaolefins or polyinternalole- fins), (poly)esters, (poly)alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-started polyethers, alkylphenol-started polyetheramines and carboxylic esters of long-chain alkanols.
  • suitable polyethers or polyetheramines are preferably compounds comprising pol- yoxy-C2- to C4-alkylene moieties obtainable by reacting C2- to Ceo-alkanols, Ce- to C30- alkanediols, mono- or di-C2- to Cso-alkylamines, Ci- to Cso-alkylcyclohexanols or Ci- to C30- alkylphenols with 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group, and, in the case of the polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines.
  • the polyetheramines used may be poly-C2- to Ce-alkylene oxide amines or functional derivatives thereof. Typical examples thereof are tridecanol butoxylates or isotridecanol butox- ylates, isononylphenol butoxylates and also polyisobutenol butoxylates and propoxylates, and also the corresponding reaction products with ammonia.
  • carboxylic esters of long-chain alkanols are more particularly esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as described more particularly in DE-A 38 38 918.
  • the mono-, di- or tricarboxylic acids used may be aliphatic or aromatic acids; particularly suitable ester alcohols or ester polyols are long-chain representatives having, for example, 6 to 24 carbon atoms.
  • esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, for example di(n- or isotridecyl) phthalate.
  • suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, preferably about 5 to 30, more preferably 10 to 30 and especially 15 to 30 C3- to Ce-alkylene oxide units, for example propylene oxide, n-butylene oxide and isobutylene oxide units, or mixtures thereof, per alcohol molecule.
  • suitable starter alcohols are long-chain alkanols or phenols substituted by long-chain alkyl in which the long-chain alkyl radical is especially a straight-chain or branched Ce- to C -alkyl radical.
  • Particular examples include tridecanol, heptadecanol and nonylphenol.
  • Particularly preferred alcohol-started polyethers are the reaction products (polyetherification products) of monohydric aliphatic Ce- to Cis-alcohols with C3- to Ce-alkylene oxides.
  • monohydric aliphatic Ce-Cis-alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octa- decanol and the constitutional and positional isomers thereof.
  • the alcohols can be used either in the form of the pure isomers or in the form of technical grade mixtures.
  • a particularly preferred alcohol is tridecanol.
  • C3- to Ce-alkylene oxides are propylene oxide, such as 1 ,2-propylene oxide, butylene oxide, such as 1 ,2-butylene oxide, 2,3-butylene oxide, isobutyl- ene oxide or tetra hydrofuran, pentylene oxide and hexylene oxide. Particular preference among these is given to C3- to C4-alkylene oxides, i.e.
  • propylene oxide such as 1 ,2-propylene oxide and butylene oxide such as 1 ,2-butylene oxide, 2,3-butylene oxide and isobutylene oxide.
  • butylene oxide is used.
  • Further suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A 10 102 913.
  • Particular carrier oils are synthetic carrier oils, particular preference being given to the abovedescribed alcohol-started polyethers.
  • Typical other additives in the additive packages or fuels according to the invention may be friction modifier, dehazers, antioxidants, metal deactivators, and solvents for the packages.
  • Suitable friction modifiers are based typically on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, as described, for example, in WO 98/004656, and glyceryl monooleate.
  • the reaction products, described in US 6743266 B2, of natural or synthetic oils, for example triglycerides, and alkanolamines are also suitable as such friction modifier.
  • lubricity improvers are described in WO 15/059063 and WO 10/005720. Furthermore, hydroxyl group-substituted tertiary amines as disclosed in WO 2014/23853 are preferred as friction modifiers.
  • Suitable dehazer are, for example, the alkali metal or alkaline earth metal salts of alkylsubstituted phenol- and naphthalenesulfonates and the alkali metal or alkaline earth metal salts of fatty acids, and also neutral compounds such as alcohol alkoxylates, e.g. alcohol ethoxylates, phenol alkoxylates, e.g. tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate, fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), for example including in the form of EO/PO block copolymers, polyethyleneimines or else polysiloxanes.
  • EO ethylene oxide
  • PO propylene oxide
  • dehazers are EO/PO-based alkoxylates of alkylphenol-formaldehyde condensates (Novolac, resol or calixarene type), EO/PO-based alkoxylates of diols (e.g. propandiol, ethylene glycole), triols (e.g. glycerol or trimethylolpropane), ethylene diamine, or polyethyleneimine.
  • Further suitable dehazers are alkybenzene sulfonic acids, dialkylsulfosuccinates or alkali metal or ammonium salts thereof. Suitable dehazers are described in WO 96/22343. Further suitable dehazers based on diglycidyl ethers are described in US 3383326 and US 3511882.
  • dehazers are, for example, alkoxylated phenol-formaldehyde condensates, for example the products available under the trade names NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite).
  • NALCO 7D07 Naalco
  • TOLAD 2683 Petrolite
  • Suitable antioxidants are, for example, substituted phenols, such as 2,6-di-tert-butylphenol, 2,6- di-tert-butyl-4-methyl phenol, 2,4-di-tert-butyl-6-methylphenol, preferably hindered phenols with an ester group bearing radical in paraposition, such as 3-[3,5-bis-(dimethylethyl)-4-hydroxy- phenyl] propanoic acid Ce- to C2o-alkyl esters, e.g. 2-ethylhexyl- or stearylester, and also phenylenediamines such as N,N'-di-sec-butyl-p-phenylenediamine.
  • substituted phenols such as 2,6-di-tert-butylphenol, 2,6- di-tert-butyl-4-methyl phenol, 2,4-di-tert-butyl-6-methylphenol
  • Suitable metal deactivators are, for example, salicylic acid derivatives such as N,N'- disalicylidene-1 ,2-propanediamine.
  • Suitable solvents are, for example, nonpolar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, white spirit and products sold under the trade names SHELLSOL (Royal Dutch/Shell Group) and EXXSOL (ExxonMobil), and also polar organic solvents, for example, alcohols such as 2-ethylhexanol, 2-propylheptanol, decanol, isotridecanol and isoheptadecanol.
  • solvents are usually added to the fuel together with the aforementioned additives and coadditives, which they are intended to dissolve or dilute for better handling.
  • Another object of the present invention is a fuel additive package for gasoline fuels, comprising
  • At least one branched primary alkyl amine the alkyl group having from 8 to 22, preferably from 10 to 17, more preferably 13 carbon atoms and with a branching of at least 1.0, preferably of from 1.0 to 8.0, more preferably from 1.5 to 7.0,
  • polyalkenemono- or polyalkenepolyamines having a number average molecular weight in the range 300 to 5000
  • the at least one further gasoline fuel additive is selected from the group consisting of corrosion inhbitors, carrier oils, and solvents.
  • gasoline fuels mean liquid hydrocarbon distillate fuels boiling in the gasoline range. It is in principle suitable for use in all types of gasoline, including "light” and “severe” gasoline species.
  • the gasoline fuels may also contain amounts of other fuels such as, for example, ethanol.
  • gasoline fuels which may be used according to the present invention exhibit, in addition, one or more of the following features:
  • the aromatics content of the gasoline fuel is preferably not more than 50 volume % and more preferably not more than 35 volume %. Preferred ranges for the aromatics content are from 1 to 45 volume % and particularly from 5 to 35 volume %.
  • the sulfur content of the gasoline fuel is preferably not more than 100 ppm by weight and more preferably not more than 10 ppm by weight. Preferred ranges for the sulfur content are from 0.5 to 150 ppm by weight and particularly from 1 to 10 ppm by weight.
  • the gasoline fuel has an olefin content of not more than 21 volume %, preferably not more than 18 volume %, and more preferably not more than 10 volume %. Preferred ranges for the olefin content are from 0.1 to 21 volume % and particularly from 2 to 18 volume %.
  • the gasoline fuel has a benzene content of not more than 1.0 volume % and preferably not more than 0.9 volume %. Preferred ranges for the benzene content are from 0 to 1.0 volume % and preferably from 0.05 to 0.9 volume %.
  • the gasoline fuel has an oxygen content of not more than 45 weight %, preferably from 0 to 45 weight %, and most preferably from 0.1 to 3.7 weight % (first type) or most preferably from 3.7 to 45 weight % (second type).
  • the gasoline fuel of the second type mentioned above is a mixture of lower alcohols such as methanol or especially ethanol, which derive preferably from natural source like plants, with mineral oil based gasoline, i.e. usual gasoline produced from crude oil.
  • An example for such gasoline is "E 85", a mixture of 85 volume % of ethanol with 15 volume % of mineral oil based gasoline.
  • a fuel containing 100 % of a lower alcohol, especially ethanol, is suitable.
  • the amount of alcohols and ethers contained in the gasoline may vary over wide ranges. Typical maximum contents are e.g. methanol 15% by volume, ethanol 85% by volume, isopropanol 20% by volume, tert-butanol 15% by volume, isobutanol 20% by volume and ethers containing 5 or more carbon atoms in the molecule 30% by volume.
  • the summer vapor pressure of the gasoline fuel is usually not more than 70 kPa and preferably not more than 60 kPa (at 37°C).
  • the research octane number ("RON") of the gasoline fuel is usually from 90 to 100.
  • a usual range for the corresponding motor octane number (“MON”) is from 80 to 90.
  • Another object of the present invention is a gasoline fuel, comprising
  • At least one branched primary alkyl amine the alkyl group having from 8 to 22, preferably from 10 to 17, more preferably 13 carbon atoms and with a branching of at least 1.0, preferably of from 1.0 to 8.0, more preferably from 1.5 to 7.0,
  • polyalkenemono- or polyalkenepolyamines having a number average molecular weight in the range 300 to 5000
  • the at least one further gasoline fuel additive is selected from the group consisting of corrosion inhbitors, carrier oils, and solvents.
  • the gasoline fuels according to the present invention comprise said at least one branched alkyl amine in an amount of from 10 to 3000 ppm, preferably from 15 to 1000 ppm, more preferably from 20 to 500 ppm, most preferably from 25 to 250 ppm.
  • the deposit control agent or mixture of a plurality of such additives is present in the gasoline fuels in the case of polyalkenemono- or polyalkenepolyamines or Mannich adducts typically in an amount of from 10 to 1000 ppm by weight, preferably of from 25 to 500 ppm by weight, more preferably of from 50 to 250 ppm by weight (based on the gasoline composition).
  • quaternary ammonium compounds as deposit control agents they are typically present in the gasoline fuels in an amount of from 10 to 100 ppm by weight, preferably of from 20 to 50 ppm by weight (based on the gasoline composition).
  • the one or more corrosion inhibitors, if any, are present in the gasoline fuels normally in an amount of from 0.1 to 10 ppm by weight, preferably of from 0.2 to 8 ppm by weight, more preferably of from 0.3 to 7 ppm by weight, most preferably of from 0.5 to 5 ppm by weight, for example of from 1 to 3 ppm by weight.
  • the one or more carrier oils, if any, are present in the gasoline fuels normally in an amount of form 10 to 3.000 ppm by weight, preferably of from 20 to 1000 ppm by weight, more preferably of from 50 to 700 ppm by weight, most preferably of from 70 to 500 ppm by weight.
  • One or more dehazers as additive component, if any, are present in the gasoline fuels generally in an amount of from 0.5 to 100 ppm by weight, preferably of from 1 to 50 ppm by weight, more preferably of from 1.5 to 40 ppm by weight, most preferably of from 2 to 30 ppm by weight, for example of from 3 to 20 ppm by weight.
  • the other additive components described above each, if any, are present in the gasoline fuels generally in an amount of from 0.5 to 200 ppm by weight, preferably of from 1 to 100 ppm by weight, more preferably of from 1.5 to 40 ppm by weight, most preferably of from 2 to 30 ppm by weight.
  • Subject matter of the present invention is also a fuel additive concentrate suitable for use in gasoline fuels comprising
  • Example 1 Determination of injector cleanliness with a direct injection spark ignition engine.
  • the test method is a preliminary version of the upcoming CEC test for injector fouling in DISI engines (TDG-F-113) and was published by D. Weissenberger, J. Pilbeam, "Characterisation of Gasoline Fuels in a DISI Engine", lecture held at Technische Akademie Esslingen, June 27, 2017.
  • the test engine is a VW EA111 1.4L TSI engine with 125 kW.
  • the test procedure is a steady state test at an engine speed of 2000 rpm and a constant torque of 56 Nm.
  • test procedure is performed with the following injectors: Magneti Marelli 03C 906 036 E.
  • Reference oil RL-271 from Garrmann Carless was used as engine oil.
  • dirty-up is achieved by running the engine over 48 hours as described for the keep-clean procedure (see above) with base fuel.
  • the relative change of activation time is determined as described above for the keep-clean test.
  • the subsequent clean-up run is done with additized base fuel over 10 h.
  • 3 data points are determined within 15 minutes, which mean value gives the activation time at end of clean-up test.
  • the test result for the clean-up is the relative change of activation time of the injectors relative to the aver-age activation time determined at the end of the dirty-up phase
  • test was run with an EN 228 compliant low sulfur Garrmann DISI TSI fuel according to CEC RF-83 mod complying with EN 228.
  • the dirty-up phase used fuel without additive and was run for 48 hours, the clean-up phase using additized fuel for 10 hours.
  • Run 1 the fuel contained 300 mg/kg PI BA* and 30 mg/kg linear dodecylamin
  • the fuel contained 300 mg/kg PI BA* and 30 mg/kg branched tridecylamin obtained by amination from the corresponding tridecanol isomeric mixture with a branching index of 2.2 determined following the above-mentioned procedure.
  • Nozzle coking is measured as change of activation time of the injector (tij), which is measured periodically within the test procedure. Due to nozzle coking, the hole diameters of the injector holes are reduced, and the activation time adjusted by the Engine Control Unit (ECU) accordingly.
  • the activation time in milliseconds is a direct readout from the ECU via ECU control soft- ware. A prolongation of activation time is an indicator for nozzle coking.
  • the test duration was
  • the additive package comprising the branched alkyl amine according to the invention shows at least the same activity in reducing injector nozzle fouling as the linear dodecyl amine according to the prior art, if not even an improved activity.
  • Example 2 Determination of storage stability of a fully formulated gasoline additive package
  • the carrier fluid used is a propoxylated tridecanol derived from trimerbutene (after hydroformylation and hydrogenation). Clear formulations were obtained in both cases.
  • Comparative Formulation 2 using the same weight composition of the components as Formulation 1 according to the invention exhibits a much worse storage stability than Formulation 1.

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EP22700409.0A 2021-01-27 2022-01-17 Verzweigte primäre alkylamine als additive für benzinkraftstoffe Pending EP4284902A1 (de)

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US20240101919A1 (en) 2024-03-28

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