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
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
• • 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
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
  • C10L1/2366—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amine groups
• • 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
  • C10L1/228—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles
• • 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
  • C10L2200/00—Components of fuel compositions
  • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
  • C10L2200/0259—Nitrogen containing compounds
• • 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
  • 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
• • 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
  • 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 disclosure relates to compositions and methods for emission particulate reductions in gasoline direct injection (GDI) engines using select Mannich detergents.
• Gasoline direct injection (GDI) engines tend to produce higher levels of particulate emission when compared to port fuel injection (PFI) engines.
• PFI port fuel injection
• a method of reducing particulate emission in a gasoline direct injection engine includes: combusting in the engine a gasoline composition including a Mannich detergent as an additive, wherein the Mannich detergent is produced by the reaction of hydrocarbyl-substituted phenol, an amine, and formaldehyde at a molar ratio of 1 : 1-2 : 2-3, and wherein the Mannich detergent is present in the gasoline composition at a concentration of about 40 to about 100 ppm.
• the method of the previous paragraph may be combined with one or more other features, steps, or embodiments in any combination.
• These other features, steps, or embodiments include one or more of the following: the molar ratio of the hydrocarbyl-substituted phenol, amine, and formaldehyde is 1 : 1-2 : 2; and/or wherein the molar ratio of the hydrocarbyl-substituted phenol, amine, and formaldehyde is 1 : 2 : 2; and/or wherein the hydrocarbyl substituent is derived from polyisobutylene and wherein at least 50 mol percent of polyisobutylene macromolecules have a tri-substituted alkene group, or wherein the hydrocarbyl substituent is derived from polyisobutylene and wherein at least 50 mol percent of polyisobutylene macromolecules have a tri-substituted alkene group and a tetra-substituted alken
• the use of any embodiment of this Summary is provided to provide improved particulate emissions reduction in GDI engines.
• the use provides combusting in an engine a gasoline composition including a Mannich detergent as an additive, wherein the Mannich detergent is produced by the reaction of hydrocarbyl-substituted phenol, an amine, and formaldehyde at a molar ratio of 1 : 1-2 : 2-3, and wherein the Mannich detergent is present in the gasoline composition at a concentration of about 40 to about 100 ppm to provide improved particulate emissions.
• the present disclosure relates to fuel additive packages, fuels, and methods of achieving emission particulate reductions in gasoline direct injection (GDI) engines using select Mannich detergents (e.g., reaction products of a hydrocarbyl-substituted hydroxyaromatic compound, an aldehyde, and an amine).
• select Mannich detergents e.g., reaction products of a hydrocarbyl-substituted hydroxyaromatic compound, an aldehyde, and an amine.
• the select Mannich detergents herein for emissions particulate reductions include one or more of the following characteristics: (i) certain molar ratios of the hydroxyaromatic compound, the amine, and the aldehyde; (ii) select oligomer structures; and/or (iii) certain isomeric forms of polyisobutylene substituents on the hydroxyaromatic compound.
• the select Mannich detergent(s) of the fuel additive packages, fuels, and methods herein for improved particulate emissions reduction in GDI engines include (i) a molar ratio of the hydrocarbyl-substituted hydroxyaromatic compound (e.g., a hydrocarbyl-substituted phenol) to amine (e.g., dimethylamino propylamine) to formaldehyde of 1 : 0.9-2.0 : 1.5-3.0 and, more preferably, 1 : 1-2 : 2-3, and even more preferably, 1 : 1-2 : 2, and most preferably, 1 : 2 : 2.
• a molar ratio of the hydrocarbyl-substituted hydroxyaromatic compound e.g., a hydrocarbyl-substituted phenol
• amine e.g., dimethylamino propylamine
• the select Mannich detergent(s) of the fuel additive packages, fuels, and methods herein for improved particulate emissions reductions in GDI engines include (ii) one or more compounds or oligomers having structures defined by the below formulas, which are defined further herein:
• the select Mannich detergent(s) of the fuel additive packages, fuels, and methods herein for particulate emissions reductions includes (iii) certain isomeric forms of a polyisobutylene (PIB) substituent of the hydroxyaromatic group in which, in one approach, at least 50 mol% of the PIB macromolecules have a tri-substituted alkene group (e.g., a so-called conventional PIB).
• PIB polyisobutylene
• the selected Mannich detergent of the compositions, fuels, or methods herein includes a Mannich reactant product having a isomeric forms of the polyisobutylene (PIB) substituent of the hydroxyaromatic comprising both (a) PIB macromolecules having a tri-substituted alkene group and (b) PIB macromolecules having a tetra-substituted alkene group, wherein the proportion of PIB macromolecules having both a tri-substituted and a tetra-substituted alkene group is at least 50 mol%, and wherein the Mannich reactant product and PIB substituent are subjected to conditions under which PIB macromolecules having a tetra-substituted alkene group will react to produce PIB macromolecules having a tri-substituted alkene group.
• PIB polyisobutylene
• Such PIB groups are referred to as conventional PIB, and Conventional PIB typically has less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol% content of terminal double bonds.
• the isomeric forms of the polyisobutylene (PIB) substituent may have greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol% content of terminal double bonds.
• this alternative PIB substituent is referred to as highly reactive PIB (e.g., "HR-PIB").
• HR-PIB having a number average molecular weight ranging from about 800 to about 5000, as determined by GPC, may be suitable for use in embodiments of the present disclosure.
• HR-PIB is commercially available, or can be synthesized by the polymerization of isobutene in the presence of a non-chlorinated catalyst such as boron trifluoride, as described in US 4,152,499 and/or US 5,739,355 .
• a non-chlorinated catalyst such as boron trifluoride
• HR-PIB may lead to higher conversion rates in the reaction, as well as lower amounts of sediment formation, due to increased reactivity.
• a suitable method is described in U.S. Patent No. 7,897,696 .
• PIB a particular type of PIB has been developed for use in preparing lubricant and gasoline additives, namely PIB having an increased proportion of macromolecules in which the double bond is located at the end of the chain, to make the PIB more reactive.
• This can be achieved by using pure isobutene feedstock and a catalyst based on BF 3 , as reported by Mach et al (Lubrication Science 11-2, Feb 1999 (11) pp 175-185 ). More recently, it has also been achieved using AlCl 3 in a form of complex with ether ( Kostjuk et al, Journal of Polymer Science, Part A: Polymer Chemistry 2013, 51, 471-486 ).
• PIBs containing a high proportion of exo groups are generally referred to as high reactive PIB (e.g., HR-PIB).
• HR-PIB high reactive PIB
• PIBs containing a high proportion of tri, endo, and tetra groups are generally referred to as conventional PIB.
• the select Mannich detergents herein may include a high proportion of conventional PIB-based Mannich reaction products.
• the select Mannich detergents herein may include a high proportion of HR-PIB-based Mannich reaction products.
• Such PIB macromolecules are produced with select conditions, and said conditions comprise contacting the Mannich reactants and the PIB substituent with a source of protons, such as BF 3 /HF.
• the PIB substituent is preferably one in which at least 60 mol% of the PIB macromolecules have a tetra-substituted alkene group, more preferably at least 70 mol%, more preferably still at least 80 mol%, and yet more preferably at least 90 mol%.
• the tetra substituted alkene groups in the PIB macromolecules are located within or attached to a terminal C4 unit in the macromolecule.
• the PIB macromolecules suitable for the detergent compositions, fuels, and particulate emission reduction methods of the present disclosure are of the structure:
• a preferred example of a Mannich detergent of the compositions, fuels, and methods herein is a product obtained or obtainable from a Mannich reaction between an aldehyde, an amine, and a select PIB-substituted hydroxyaromatic compound that has been prepared as described herein and having the noted PIB macromolecules.
• Such a PIB-substituted hydroxyaromatic reagent has been found to be enriched in compounds wherein the PIB substituent is bonded to the aromatic ring in the following manner:
• the present disclosure provides a detergent obtained or obtainable from a Mannich reaction between the aldehyde, the amine, and the selected PIB-hydroxyaromatic compound wherein at least 70 mol% (such as at least 75 mol%, at least 80 mol%, at least 85 mol%, at least 90 mol% or at least 95 mol%) of the molecules has the structure depicted above.
• the tri group will have the following stereochemistry:
• PIB that is enriched in tri-PIB can be reacted with a reagent serving as a source of a group comprising a polar moiety, under conditions appropriate for the PIB to react with said reagent so as to form a compound in which the PIB is bonded to the group comprising a polar moiety.
• the PIB that is enriched in tri-PIB this can be prepared directly.
• polymerisation of isobutylene in hexane with an initiator such as H 2 O, MeOH, tBuCl, TMPCl (2-chloro-2,4,4-trimethyl-pentane) or CumCl (cumyl chloride) in conjunction with EADC (EtAlCl 2 ) in the temperature range of -40 to 25 °C can be used to prepare a PIB product having around 70 % tri-PIB and around 30 % tetra-PIB, with negligible exo- and endo-PIB.
• PIB that is enriched in to some extent in tri-PIB can be prepared from conventional PIB or HR PIB, e.g. by exposing the PIB sample to a Lewis acid or Bronsted-Lowry (protic) acid.
• tri-PIB can be increased by reacting the PIB with said reagent having a group comprising a polar moiety under conditions in which the tetra-PIB will react to produce tri-PIB. This enhances the effective proportion of tri-PIB in situ.
• tri-PIB can be formed readily from tetra-PIB under suitable conditions, e.g. in the presence of a source of protons.
• Dimitrov et al. Dimitrov et al. (Macromolecules 2011, 44, 1831-1840 ). That reaction pathway has been summarised by Kostjuk et al.
• the present invention also relates to a method of preparing PIB that is highly enriched with tetra-PIB.
• a highly enriched PIB can advantageously be used as a precursor for PIB that is highly enriched in other isomeric forms.
• PIB that is highly enriched in tetra-PIB can be used to prepare a PIB reagent that is highly enriched in tri-PIB, or (if different conditions are used) a PIB reagent that is highly enriched in exo-PIB.
• PIB that is highly enriched with tetra-PIB can be used to form tri-PIB in situ during the preparation of a detergent product.
• the fact that the tetra-PIB can be efficiently reacted to produce other types of PIB in this way means that the high levels of tetra-PIB enrichment possible in accordance with the present invention can effectively be transferred to provide similar levels of tri- and exo-PIB enrichment.
• PIB that is highly enriched with tetra-PIB can be prepared by subjecting a sample of PIB containing a high proportion of exo- and endo-PIB (such as a typical HR PIB) to double bond isomerisation in circumstances in which the back-biting step depicted in Scheme 1 above is inhibited.
• the PIB sample can be subjected to double bond isomerisation in a molecular sieve, wherein the molecular sieve limits the extent to which the macromolecules can adopt the conformation that is needed in order for this intramolecular cyclic reaction to occur.
• the alkene group having the tetra structure in tetra-PIB should be located within or attached to a terminal C4 unit in the macromolecule, and typically has one of the two structures noted below, with the second structure usually being more preferred:
• cation 1 in scheme 2 can be formed from both exo- and endo-PIB. This is illustrated by the following further reaction scheme:
• PIB that is highly enriched in tetra-PIB can advantageously be used, inter alia:
• the PIB that is highly enriched in tetra-PIB can be combined with a reagent having a group comprising a polar moiety under conditions where back-biting (see Scheme 1 above) can arise and indeed is promoted (e.g. protic conditions), thus favouring the production of tri-PIB.
• the more reactive tri-PIB reacts preferentially with said reagent, so as to form detergent compounds having a structure which, as discussed above, imparts altered thermal stability, and has improved detergent activity.
• case (1) similar conditions to those identified in case (3) may be used to encourage back-biting so as to produce tri-PIB.
• This approach might be preferable to the formation of tri-PIB in situ as in approach (3), in instances where the PIB enriched in tri-PIB is intended for use in an application wherein the presence of tetra-PIB may be undesirable for some reason.
• the PIB that is highly enriched in tetra-PIB may be subjected to thermal treatment so as to form exo-PIB via a retro-Alder-ene reaction according to the mechanism depicted below in Scheme 4.
• the hydroxyaromatic compound of the Mannich detergents herein are based on phenol, resorcinol, hydroquinone, and/or phenethylphenol because it is believed two active cites on the aromatic ring (e.g. active ortho positions) are preferred. Most preferably, the hydroxyaromatic compound is based on phenol. Without wishing to be limited by theory, it is also believed that hydroxyaromatic compounds based on cresol, catechol, hydroxydiphenyl, benzylphenol, naphthol, and/or tolylnaphthol are less preferred as they only have one active ortho cite on the aromatic ring having substituents already bonded to at least one ortho position on the aromatic ring.
• representative aldehydes for use in the preparation of Mannich detergents herein include the aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde, stearaldehyde.
• Aromatic aldehydes which may be used include benzaldehyde and salicylaldehyde.
• Illustrative heterocyclic aldehydes for use herein are furfural and thiophene aldehyde, etc.
• formaldehyde-producing reagents such as paraformaldehyde, or aqueous formaldehyde solutions such as formalin. Most preferred is formaldehyde or formalin.
• representative amine reactants for the Mannich detergents herein include, but are not limited to, alkylene polyamines having at least one suitably reactive primary or secondary amino group in the molecule. Other substituents such as hydroxyl, cyano, amido, etc., can be present in the polyamine.
• the alkylene polyamine is a polyethylene polyamine.
• Suitable alkylene polyamine reactants include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and mixtures of such amines having nitrogen contents corresponding to alkylene polyamines of the formula H 2 N- (A-NH-)"H, where A is divalent ethylene or propylene and n is an integer of from 1 to 10, preferably 1 to 4.
• the alkylene polyamines may be obtained by the reaction of ammonia and dihalo alkanes, such as dichloro alkanes.
• the amine may preferably be an aliphatic diamine having one primary or secondary amino group and at least one tertiary amino group in the molecule.
• suitable polyamines include N, N, N", N"- tetraalkyldialkylenetriamines (two terminal tertiary amino groups and one central secondary amino group), N, N, N', N"-tetraalkyltrialkylenetetramines (one terminal tertiary amino group, two internal tertiary amino groups and one terminal primary amino group), N, N, N', N", N′′′-pentaalkyltrialkylenetetramines (one terminal tertiary amino group, two internal tertiary amino groups and one terminal secondary amino group), N, N-dihydroxyalkyl- alpha, omega-alkylenediamines (one terminal tertiary amino group and one terminal primary amino group), N, N, N'-trihydroxyalkyl- alpha, omega-alkylenediamine
• these alkyl groups are methyl and/or ethyl groups.
• Preferred polyamine reactants are N, N-dialkyl-alpha, omegaalkylenediamine, such as those having from 3 to about 6 carbon atoms in the alkylene group and from 1 to about 12 carbon atoms in each of the alkyl groups, which most preferably are the same but which can be different. Most preferred is N, N-dimethyl-1, 3-propanediamine and N-methyl piperazine.
• polyamines having one reactive primary or secondary amino group that can participate in the Mannich condensation reaction, and at least one sterically hindered amino group that cannot participate directly in the Mannich condensation reaction to any appreciable extent include N- (tert-butyl)-1, 3propanediamine, N-neopentyl-1, 3-propanediamine, N-(tert-butyl)-1-methyl-1, 2ethanediamine, N- (tert-butyl)-1-methyl-1, 3-propanediamine, and 3,5-di (tertbutyl) aminoethylpiperazine.
• alkylation of the hydroxyaromatic compound may be performed in the presence of an alkylating catalyst at a temperature in the range of about 0°C to about 200°C, preferably about 0 to about 100°C.
• Acidic catalysts may be used to promote Friedel Crafts alkylation. Possible catalysts for use in this regard include sulphuric acid, BF3, aluminum phenoxide, methanesulphonic acid, cationic exchange resin, acidic clays and modified zeolites.
• the preferred configuration of the alkyl-substituted hydroxyaromatic compound is that of a para-substituted mono-alkylphenol.
• the condensation reaction among the alkylphenol, the specified amine(s), and the aldehyde may be conducted at a temperature in the range of about 40°C to about 200°C.
• the reaction can be conducted in bulk (no diluent or solvent) or in a solvent or diluent. Water is evolved and can be removed by azeotropic distillation during the course of the reaction.
• the Mannich reaction products are formed by reacting a molar ratio of the hydrocarbyl-substituted hydroxyaromatic compound (preferably, the PIB-substituted phenol) to the amine (preferably, dimethylaminopropylamine) to formaldehyde of 1 to 0.9-2.0 to 1.5-3.0 and, more preferably, 1 to 1-2 to 2-3, and even more preferably, 1 to 1-2 to 2, and most preferably, 1 to 2 to 2.
• a molar ratio of 1:1:1 does not provide sufficient emission particulate reduction in the context of GDI engines.
• the present disclosure also provides a Mannich detergent product comprising a compound which includes the noted PIB substituent of a Mannich reaction product having a structure of Formula I below: wherein
• Mannich reaction products herein are compounds having the structures of Formula (Ia), (Ib), and/or (Ic) below with a preferred example for the -NR 4 R 5 group of these structure being -NH(CH 2 ) 3 N(CH 3 ) 2 and Q as defined above: Mannich detergents and methods of preparing such detergents suitable for the present disclosure are also described in US 2018/0223017 , which is incorporated herein by reference.
• additional examples of exemplary compounds of the Mannich reaction products herein include one or more of the following oligomer structures (with the following compounds or oligomers having Q as defined above and the -NR 4 R 5 group being either -N(CH 3 ) 2 or -NH(CH 2 ) 3 N(CH 3 ) 2 and R' being C1 to C4 and preferably C3):
• a generic oligomer structure of the Mannich reaction products herein has the exemplary structure of Formula II below with X being an integer selected from 2 to 10 or an integer to form an oligomer molecular weight of about 300 to about 2000 g/mol: wherein Q is defined above and R 1 of Formula II above is a C1 to C10 group (preferably, a C1 to C4 group, and more preferably a C3 group), and R 2 and R 3 of Formula II above are, independently, C1 to C4 alkyl groups, and preferably C1 groups.
• the present disclosure also provides the use of any embodiment of the Mannich detergent products as defined herein in a fuel (or alternatively a lubricant) to achieve particulate emission reductions.
• a fuel or alternatively a lubricant
• any embodiment of the Mannich detergent products herein is used as a detergent in gasoline fuel combusted in a direct injection gasoline (DIG) engine to achieve the particulate emission reductions.
• DIG direct injection gasoline
• particulate emission reductions are measured as set forth in EP 3 775 112 B1 (e.g., Example 3 and paragraphs 298 to 303 thereof), which is incorporated herein by reference in its entirety.
• the present disclosure also provides the use of Mannich detergents as described herein having a substituent PIB group enriched in tri-PIB (e.g. PIB in which at least 50, 60, 70, 80, 90 or 95 mol% of the PIB macromolecules have a tri-substituted alkene group) to achieve particulate emission reductions in GDI engines (as measured pursuant to EP 3 775 112 B1 ).
• a substituent PIB group enriched in tri-PIB e.g. PIB in which at least 50, 60, 70, 80, 90 or 95 mol% of the PIB macromolecules have a tri-substituted alkene group
• the present disclosure also provides the use of Mannich detergents as described herein and formed by reacting a molar ratio of the hydrocarbyl-substituted hydroxyaromatic compound (preferably, the PIB-substituted phenol) to the amine (preferably, dimethylaminopropylamine) to formaldehyde of 1 to 0.9-2.0 to 1.5-3.0 and, more preferably, 1 to 1-2 to 2-3, and even more preferably, 1 to 1-2 to 2, and most preferably, 1 to 2 to 2 in order to achieve particulate emission reductions in GDI engines (as measured pursuant to EP 3 775 112 B1 ).
• Mannich detergents as described herein and formed by reacting a molar ratio of the hydrocarbyl-substituted hydroxyaromatic compound (preferably, the PIB-substituted phenol) to the amine (preferably, dimethylaminopropylamine) to formaldehyde of 1 to 0.9-2.0 to 1.5-3.0 and
• the present disclosure also provides the use of Mannich detergents as shown by any formula or oligomer of this disclosure in order to achieve particulate emission reductions in GDI engines (as measured pursuant to EP 3 775 112 B1 ).
• the present disclosure also provides a method of reducing particulate emissions of a GDI engine, which method includes adding to the engine (e.g., via a gasoline fuel or via a lubricant) any embodiment of the PIB-substituted Mannich detergent(s) as defined herein.
• the method includes reducing particulate emissions in the GDI engine, and more particularly, where the method includes fuelling the GDI engine with gasoline including any embodiment of the PIB-substituted Mannich detergent(s) as defined herein and combusting the gasoline including the PIB-substituted Mannich detergent as defined herein to achieve particulate emission reductions as measured via EP 3 775 112 B1 (e.g., Example 3 and paragraphs 298 to 303 thereof).
• the method includes fuelling the GDI engine with gasoline including any embodiment of the PIB-substituted Mannich detergent(s) as defined herein and combusting the gasoline including the PIB-substituted Mannich detergent as defined herein to achieve particulate emission reductions as measured via EP 3 775 112 B1 (e.g., Example 3 and paragraphs 298 to 303 thereof).
• the present disclosure also provides an additive composition comprising any embodiment of the Mannich detergent product as defined herein and a carrier fluid.
• the additive composition is preferably for use in adding the product to a fuel or lubricant composition.
• the present disclosure also provides a fuel and/or a lubricant comprising any embodiment of the disclosure.
• the disclosure provides gasoline including any embodiment of the Mannich detergent product of the disclosure.
• the size of the PIB group of the detergent products of the present disclosure is not particularly limited. However, preferably it has a number average molecular weight of at least 400, such as at least 500, at least 600, at least 700, at least 800, or at least 900. It preferably has a number average molecular weight of no more than 5000, such as no more than 4000, or 3000, or 2000, or 1500, or 1200. Number average molecular is determined as described below.
• the detergent products of the present disclosure are added to gasoline fuel, they may be added in an amount of from about 1 to about 5000 ppm by weight, especially from about 5 to about 3000 ppm by weight, in particular from about 10 to about 1000 ppm by weight.
• the detergent products are added to a gasoline fuel in amount of about 5 to about 500 ppm, about 10 to about 400 ppm, about 20 to about 300 ppm, about 30 to about 200 ppm, or about 40 to about 100 ppm.
• emission particulate reductions (as measured using the procedures of EP 3 775 112 as described herein) using the Mannich detergents as described herein may obtain emission particulate reductions of at least about 90 percent, at least about 92 percent, at least about 94 percent, at least about 96 percent, or at least about 98 percent as compared to a base fuel without the Mannich detergents herein.
• compositions and methods of combusting a gasoline fuel in GDI engines using the Mannich detergents as described herein may also result in no more than about 100,000 particles per cubic centimeter when tested according to the procedures of EP 3 775 112 , no more than about 80,000 particles per cubic centimeter, no more than about 60,000 particles per cubic centimeter, no more than about 50,000 particles per cubic centimeter, no more than 40,000 particles per cubic centimeter, or no more than 30,000 particles per cubic centimeter.
• a base fuel devoid of the Mannich detergents (or other detergent additives) commonly has more than 3,000,000 particles per cubic centimeter when evaluated according to the methods of EP 3 775 112 .
• the select Mannich detergents have a structure of formula (II) shown above and also features (i) a molar ratio of the hydrocarbyl-substituted hydroxyaromatic compound (e.g., a hydrocarbyl-substituted phenol) to amine (e.g., dimethylaminopropylamine) to formaldehyde of 1 to 0.9-2.0 to 1.5-3.0 and, more preferably, 1 to 1-2 to 2-3, and even more preferably, 1 to 1-2 to 2, and most preferably, 1 to 2 to 2.
• amine e.g., dimethylaminopropylamine
• formaldehyde 1 to 0.9-2.0 to 1.5-3.0 and, more preferably, 1 to 1-2 to 2-3, and even more preferably, 1 to 1-2 to 2, and most preferably, 1 to 2 to 2.
• Q in formula (II) is conventional PIB or HR-PIB.
• the select Mannich detergents have a structure of formula (II) shown above, wherein Q is a conventional PIB.
• These Mannich detergents may further feature (i) a molar ratio of the hydrocarbyl-substituted hydroxyaromatic compound (e.g., a hydrocarbyl-substituted phenol) to amine (e.g., dimethylaminopropylamine) to formaldehyde of 1 to 0.9-2.0 to 1.5-3.0 and, more preferably, 1 to 1-2 to 2-3, and even more preferably, 1 to 1-2 to 2, and most preferably, 1 to 2 to 2.
• a hydrocarbyl-substituted hydroxyaromatic compound e.g., a hydrocarbyl-substituted phenol
• amine e.g., dimethylaminopropylamine
• the select Mannich detergents have a structure of formula (II) shown above, wherein Q is a HR-PIB.
• These Mannich detergents may further feature (i) a molar ratio of the hydrocarbyl-substituted hydroxyaromatic compound (e.g., a hydrocarbyl-substituted phenol) to amine (e.g., dimethylaminopropylamine) to formaldehyde of 1 to 0.9-2.0 to 1.5-3.0 and, more preferably, 1 to 1-2 to 2-3, and even more preferably, 1 to 1-2 to 2, and most preferably, 1 to 2 to 2.
• a hydrocarbyl-substituted hydroxyaromatic compound e.g., a hydrocarbyl-substituted phenol
• amine e.g., dimethylaminopropylamine
• the select Mannich detergents are Mannich which contains a substituent of conventional PIB.
• These Mannich detergents may further feature (i) a molar ratio of the hydrocarbyl-substituted hydroxyaromatic compound (e.g., a hydrocarbyl-substituted phenol) to amine (e.g., dimethylaminopropylamine) to formaldehyde of 1 to 0.9-2.0 to 1.5-3.0 and, more preferably, 1 to 1-2 to 2-3, and even more preferably, 1 to 1-2 to 2, and most preferably, 1 to 2 to 2.
• a molar ratio of the hydrocarbyl-substituted hydroxyaromatic compound e.g., a hydrocarbyl-substituted phenol
• amine e.g., dimethylaminopropylamine
• the select Mannich detergents are Mannich which contains a substituent of HR-PIB.
• These Mannich detergents may further feature (i) a molar ratio of the hydrocarbyl-substituted hydroxyaromatic compound (e.g., a hydrocarbyl-substituted phenol) to amine (e.g., dimethylaminopropylamine) to formaldehyde of 1 to 0.9-2.0 to 1.5-3.0 and, more preferably, 1 to 1-2 to 2-3, and even more preferably, 1 to 1-2 to 2, and most preferably, 1 to 2 to 2.
• a molar ratio of the hydrocarbyl-substituted hydroxyaromatic compound e.g., a hydrocarbyl-substituted phenol
• amine e.g., dimethylaminopropylamine
• compositions, gasoline fuel, or methods of the present disclosure may be included in the compositions, gasoline fuel, or methods of the present disclosure and, if used, would be added in amounts customary for this purpose.
• One or more optional compounds may be present in the fuel additives, fuels, or methods of the disclosed embodiments herein as needed for a particular application and/or fuel type.
• the fuel additive or fuels may contain conventional quantities of cetane improvers, octane improvers, corrosion inhibitors, cold flow improvers (CFPP additive), pour point depressants, solvents, demulsifiers, lubricity additives, friction modifiers, amine stabilizers, combustion improvers, detergents, dispersants, antioxidants, heat stabilizers, conductivity improvers, metal deactivators, marker dyes, organic nitrate ignition accelerators, cyclomatic manganese tricarbonyl compounds, carrier fluids, and the like.
• cetane improvers octane improvers
• corrosion inhibitors corrosion inhibitors
• cold flow improvers CFPP additive
• pour point depressants solvents
• demulsifiers demulsifiers
• lubricity additives friction modifiers
• amine stabilizers combustion improvers
• detergents dispersants
• antioxidants antioxidants
• heat stabilizers conductivity improvers
• metal deactivators marker dyes
• compositions described herein may contain about 10 weight percent or less, or in other aspects, about 5 weight percent or less, based on the total weight of the additive concentrate, of one or more of the above optional additives.
• the fuels may contain suitable amounts of conventional fuel blending components such as methanol, ethanol, dialkyl ethers, 2-ethylhexanol, and the like.
• detergents include but are not limited to succinimides, other Mannich base detergents, PIB amine detergents, quaternary ammonium detergents, bis-aminotriazole detergents as generally described in U.S. patent application Ser. No. 13/450,638 , and a reaction product of a hydrocarbyl substituted dicarboxylic acid, or anhydride and an aminoguanidine, wherein the reaction product has less than one equivalent of amino triazole group per molecule as generally described in U.S. patent application Ser. Nos. 13/240,233 and 13/454,697 .
• organic nitrate ignition accelerators that include aliphatic or cycloaliphatic nitrates in which the aliphatic or cycloaliphatic group is saturated, and that contain up to about 12 carbons may be used.
• organic nitrate ignition accelerators examples include methyl nitrate, ethyl nitrate, propyl nitrate, isopropyl nitrate, allyl nitrate, butyl nitrate, isobutyl nitrate, sec-butyl nitrate, tert-butyl nitrate, amyl nitrate, isoamyl nitrate, 2-amyl nitrate, 3-amyl nitrate, hexyl nitrate, heptyl nitrate, 2-heptyl nitrate, octyl nitrate, isooctyl nitrate, 2-ethylhexyl nitrate, nonyl nitrate, decyl nitrate, undecyl nitrate, dodecyl nitrate, cyclopentyl nitrate, cyclohexyl
• metal deactivators useful in the compositions of the present application are disclosed in U.S. Pat. No. 4,482,357 , the disclosure of which is herein incorporated by reference in its entirety.
• metal deactivators include, for example, salicylidene-o-aminophenol, disalicylidene ethylenediamine, disalicylidene propylenediamine, and N,N'-disalicylidene-1,2-diaminopropane.
• Suitable optional cyclomatic manganese tricarbonyl compounds which may be employed in the compositions of the present application include, for example, cyclopentadienyl manganese tricarbonyl, methylcyclopentadienyl manganese tricarbonyl, indenyl manganese tricarbonyl, and ethylcyclopentadienyl manganese tricarbonyl.
• cyclopentadienyl manganese tricarbonyl methylcyclopentadienyl manganese tricarbonyl
• indenyl manganese tricarbonyl and ethylcyclopentadienyl manganese tricarbonyl.
• ethylcyclopentadienyl manganese tricarbonyl ethylcyclopentadienyl manganese tricarbonyl.
• suitable cyclomatic manganese tricarbonyl compounds are disclosed in U.S. Pat. No. 5,575,823 and U.S. Pat. No.
• the additives of the present application and optional additives used in formulating the fuels of this disclosure may be blended into the base fuel individually or in various sub-combinations.
• the additive components of the present application may be blended into the fuel concurrently using an additive concentrate, as this takes advantage of the mutual compatibility and convenience afforded by the combination of ingredients when in the form of an additive concentrate. Also, use of a concentrate may reduce blending time and lessen the possibility of blending errors.
• hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having a predominantly hydrocarbon character.
• Each hydrocarbyl group is independently selected from hydrocarbon substituents, and substituted hydrocarbon substituents containing one or more of halo groups, hydroxyl groups, alkoxy groups, mercapto groups, nitro groups, nitroso groups, amino groups, pyridyl groups, furyl groups, imidazolyl groups, oxygen and nitrogen, and wherein no more than two non-hydrocarbon substituents are present for every ten carbon atoms in the hydrocarbyl group.
• percent by weight or "wt%”, unless expressly stated otherwise, means the percentage the recited component represents to the weight of the entire composition. All percent numbers herein, unless specified otherwise, is weight percent.
• alkyl refers to straight, branched, cyclic, and/or substituted saturated chain moieties from about 1 to about 200 carbon atoms.
• alkenyl refers to straight, branched, cyclic, and/or substituted unsaturated chain moieties from about 3 to about 30 carbon atoms.
• aryl refers to single and multi-ring aromatic compounds that may include alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and/or heteroatoms including, but not limited to, nitrogen, and oxygen.
• molecular weight is determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (with a Mp of about 162 to about 14,000 as the calibration reference).
• Mp molecular weight
• the molecular weight (Mn) for any embodiment herein may be determined with a gel permeation chromatography (GPC) instrument obtained from Waters or the like instrument and the data processed with Waters Empower Software or the like software.
• the GPC instrument may be equipped with a Waters Separations Module and Waters Refractive Index detector (or the like optional equipment).
• the GPC operating conditions may include a guard column, 4 Agilent PLgel columns (length of 300x7.5 mm, particle size of 5 ⁇ , and pore size ranging from 100-10000 ⁇ ) with the column temperature at about 40°C. Un-stabilized HPLC grade tetrahydrofuran (THF) may be used as solvent, at a flow rate of 0.38 mL/min.
• THF Un-stabilized HPLC grade tetrahydrofuran
• the GPC instrument may be calibrated with commercially available polystyrene (PS) standards having a narrow molecular weight distribution ranging from 500 - 380,000 g/mol. The calibration curve can be extrapolated for samples having a mass less than 500 g/mol.
• PS polystyrene
• Samples and PS standards can be in dissolved in THF and prepared at concentration of 0.1-0.5 weight percent and used without filtration.
• GPC measurements are also described in US 5,266,223 , which is incorporated herein by reference.
• the GPC method additionally provides molecular weight distribution information; see, for example, W. W. Yau, J. J. Kirkland and D. D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979 , also incorporated herein by reference.
• a major amount refers to greater than 50 weight percent (greater than 60 weight percent, greater than 70 weight percent, greater than 80 weight percent or greater than 90 weight percent), and a minor amount refers to less than 50 weight percent (less than 40 weight percent, less than 30 weight percent, less than 20 weight percent, or less than 10 weight percent).
• PIB-Phenol using Conventional PIB is as follows: 430.00g (0.464 mol) conventional PIB was added to an addition funnel. The PIB was about 900 molecular weight and contained ⁇ 10% alpha-vinylidene double bonds. 78.66g (0.835 mol) phenol was dissolved in 50g heptane at 40°C under nitrogen in a 4-neck 2000 mL round bottomed flask. 13.18g BF 3 OEt 2 (0.092mol) was added to the phenol / heptane mixture. The PIB was added to the reaction flask over the course of 70 minutes.
• the reaction was stirred at 40-42°C for an additional 2 hours at which point it was quenched with ammonia gas.
• the reaction was diluted with heptane and filtered. Solvent was removed by rotary distillation and excess phenol was removed by vacuum distillation at 130°C and 0.5 mmHg; 409 g (86% yield excluding transfer loss).
• the nominal molecular weight was 1284 as determined by Quantitative Carbon-NMR Integration, which corresponds to 1.32% OH.
• HR PIB-Mannich detergents were prepared in a similar manner as described in Example 1 above (using HR PIB instead).
• the Mannich reaction products prepared Examples 1 and 2 were combusted in a base fuel and particulate emissions were evaluated according to the procedures of Example 3 from EP 3 775 112 B1 . More particularly, the vehicle test was carried out on a chassis dynamometer test cell, with a 2014 BMW mini Cooper S having a B48 direct injection spark ignition engine, with a turbocharger and an engine displacement of 1998 cubic centimeters. The vehicle was operated at a constant engine speed of 3500 rpm for 24 hours. The chassis dynamometer was controlled with the US Government EPA-specified test vehicle coefficients to properly simulate driving the test vehicle on the open road. The particulate emissions were directly measured by a Cambustion DMS500 Mark II instrument, connected directly to the mini Cooper tailpipe.
• the Cambustion DMS500 Mark II counted the particulate emissions regularly over the 24 hour test period, to ensure the emissions were known throughout the test.
• the instrument returned a particulate number (PN) in units of N per cubic centimeter.
• PN particulate number
• the PN for the 24 th hour was calculated by averaging the emissions measured at the end of each 20-minute interval of the final hour. Particulate emissions were also evaluated of the base fuel (without additives). Results are provided in Table 2 below.
• Table 2 Emission Testing Fuel Detergent Detergent, ppm 24 hour Particle Number Result (#/cm 3 ) % Improvement to Base Fuel Gasoline Fuel N/A N/A 3,256,007 - Gasoline Fuel Inventive Mannich (Example 1) 90 28,615 99.1% Gasoline Fuel* Inventive Mannich (Example 1) 90 43,286 98.6% *using new injectors in GDI engine.
• each range disclosed herein is to be interpreted as a disclosure of each specific value within the disclosed range that has the same number of significant digits.
• a range from 1 to 4 is to be interpreted as an express disclosure of the values 1, 2, 3 and 4 as well as any range of such values.
• each lower limit of each range disclosed herein is to be interpreted as disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compounds, substituent or parameter.
• this disclosure to be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or with each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is, it is also further understood that any range between the endpoint values within the broad range is also discussed herein.
• a range from 1 to 4 also means a range from 1 to 3, 1 to 2, 2 to 4, 2 to 3, and so forth.

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