JP2016518503A - Fuel additive composition - Google Patents

Abstract

The fuel additive composition comprises a polyalkenyl succinimide, a monofunctional or polyfunctional polyisobuteneamine, and a carrier oil selected from the group of mineral oils, polyethers, polyetheramines, esters, and combinations thereof. The polyalkenyl succinimide includes a reaction product of a hydrocarbyl dicarboxylic acid generating reaction intermediate and a nucleophilic reactant. The hydrocarbyl dicarboxylic acid generating reaction intermediate is a reaction product of a polyolefin containing C2-C18 olefin units and having a number average molecular weight (Mn) of about 500-5,000 g / mol and a C4-C10 monounsaturated acid reactant. Including things. The hydrocarbyl dicarboxylic acid generating reaction intermediate contains 0.5 to 10 dicarboxylic acid generating moieties per polyolefin molecule. The nucleophilic reactant is selected from the group of amines, alcohols, amino alcohols, and combinations thereof.

Description

FIELD OF THE DISCLOSURE The present invention relates generally to fuel additive compositions for improving engine fuel economy and reducing deposits in these engines. The fuel additive composition includes polyalkenyl succinimide, polyisobutene amine, and carrier oil.

Description of Related Art Modern vehicles include sophisticated combustion engines that optimize combustion, emissions, performance, durability, and fuel economy. Fuel additive compositions (eg, gasoline performance packages), including additional fuel additives such as fuel economy and surfactant, to further optimize the combustion, exhaust, performance, durability, and fuel economy of such engines Can be added to the fuel.

  These engines typically include one or more pistons disposed within the cylinder. Fuel and air are introduced into the cylinder and ignited to move the piston and drive the engine. The fuel efficiency additive reduces friction between the piston and cylinder, thus reducing fuel consumption and improving engine fuel efficiency.

  The fuel additive composition may comprise a fuel additive, such as a reaction product of a carboxylic acid or derivative thereof and a polyhydric alcohol and / or alkanolamine, and a fatty acid amide and a propoxylated fatty acid amide. The fuel additive composition may also include various fuel additives such as polyalkeneamines and polyalkenyl succinimides. The fuel additive composition may further include various carrier oils known in the art, including mineral oils and synthetic oils.

  However, fuel additive compositions comprising fuel additives such as those described above, such as polyalkenyl succinimides, are generally immiscible with each other. Thus, a fuel additive composition comprising such a fuel additive is often heterogeneous and non-pumpable, or further forms a precipitate, separates into two phases, and / or Can solidify at different temperatures for different times.

  Because such fuel additive compositions are uniform and pumpable over a wide temperature range even at temperatures as low as −20 ° C., the solubilizer is miscible with the additive and the fuel additive composition formed therefrom This is because it is technically and commercially desirable to be used to improve the uniformity of However, these solubilizers are expensive and usually do not contribute to improving engine performance. In some cases, these solubilizers can also cause negative side effects such as poor seal compatibility, oil dilution, and higher levels of combustion chamber deposition. Such deposits cause fuel concentration relative to the air ratio of the engine, increasing emissions of hydrocarbons and carbon monoxide, driving problems such as rough idle and frequent stalls, reduced fuel consumption, and engine life. Bring about a decline.

  Thus, an opportunity to develop an improved fuel additive that is miscible with the additional fuel additive, an improved fuel additive that is stable over a wide range of temperatures and conditions and that improves the fuel economy of an internal combustion engine There remains an opportunity to develop fuel additive compositions formed in

SUMMARY OF THE DISCLOSURE AND ADVANTAGES In some embodiments, the fuel additive composition comprises polyalkenyl succinimide, mono- or polyfunctional polyisobutene amine, and mineral oil, polyether, polyether amine, ester, and combinations thereof Contains a carrier oil selected from the group. The polyalkenyl succinimide itself includes the reaction product of a hydrocarbyl dicarboxylic acid generating reaction intermediate and a nucleophilic reactant. Hydrocarbyl bilge acid production reaction _{intermediates,} C 2 _{-C 18} number-average molecular weight of and about 500～5,000G / mol include olefin unit _{(M n)} a polyolefin and _C 4 _{-C 10} monounsaturated acid reactant having And the reaction product. The hydrocarbyl dicarboxylic acid generating reaction intermediate contains 0.5 to 10 dicarboxylic acid generating moieties per polyolefin molecule. The nucleophilic reactant is selected from the group of amines, alcohols, amino alcohols, and combinations thereof.

  The polyalkenyl succinimide improves the fuel economy of the internal combustion engine when added to the fuel, and is miscible with the polyisobuteneamine and carrier oil contained in the fuel additive composition. Thus, the fuel additive composition has excellent storage stability, remains uniform over a wide range of times and temperatures, and does not require the inclusion of solubilizers. In addition, the fuel additive composition can be added to the fuel in minimal amounts to improve fuel economy and reduce engine deposits and emissions.

DETAILED DESCRIPTION OF THE DISCLOSURE In some aspects, the present disclosure provides a fuel additive composition (“composition”). The composition comprises (A) polyalkenyl succinimide, (B) mono- or polyfunctional polyisobutene amine, and (C) carrier oil. The composition is used in fuels such as diesel fuel, gasoline, kerosene or middle distillate, and heated oil, and can be used as an additive in a lubricant. The composition can be used as a fully formulated fuel additive composition that can be added to the fuel to reduce fuel consumption and thus improve the fuel economy of the internal combustion engine. As a fuel additive, the composition also reduces carburetor, fuel intake systems, and engine deposits, reduces emissions, and improves engine performance.

Polyalkenyl succinimide (A)
In some embodiments, the polyalkenyl succinimide (A) comprises the reaction product of (1) a hydrocarbyl dicarboxylic acid production reaction intermediate and (2) a nucleophilic reactant.

Hydrocarbyl dicarboxylic acid production reaction intermediate (A.1)
In some embodiments, the reaction intermediate (A.1) comprises (A.1.a) a number average molecular weight (M _n ) comprising C _{2 to} C ₁₈ olefin units and from about 500 to 5,000 g / mol. And (A. 1.b) a reaction product of a C _{4 to} C ₁₀ monounsaturated acid reactant. Polyolefin (A.1.a) and C ₄ -C ₁₀ monounsaturated acid reactant (A.1.b) react by different reaction mechanisms under different conditions to react intermediate (A.1) Can be formed.

For example, reaction intermediate (A.1) can be obtained by heating a mixture of polyolefin (A.1.a) and C ₄ -C ₁₀ monounsaturated acid reactant (A.1.b). It can be formed via reaction. In such an “ene” reaction, the polyolefin (A.1.a) is subjected to the addition of a C _{4 to} C ₁₀ monounsaturated acid reactant (A.1.b) at the double bond. As another example, the polyolefin (A.1.a) can be first halogenated, for example, 1-8% by weight, or 3-7% by weight, based on the weight of the polyolefin (A.1.a). Can be chlorinated or brominated with Forming a halogenated polyolefin by passing chlorine or bromine through the polyolefin (A.1.a) at a temperature of 60-160 ° C, alternatively 110-130 ° C, for 0.5-10 hours, alternatively 1-7 hours. . The halogenated polyolefin is then combined with a C _{4 to} C ₁₀ monounsaturated acid reactant (A.1.b) at a temperature of 100 to 250 ° C., or 180 to 235 ° C., for 0.5 to 10 hours, or React for 3-8 hours to form reaction intermediate (A.1).

The hydrocarbyl dicarboxylic acid generating reaction intermediate (A.1) may comprise a polyolefin substituted with a dicarboxylic acid generating moiety. Specifically, the reaction intermediate (A.1) is, for example, 0.5 to 10.0 mol, alternatively 0.5 to 5 mol, alternatively 0.7, per mol of polyolefin (A.1.a). 2.0 moles, or 0.7 to 1.7 moles, or 0.9 to 1.7 moles of _C 4 _{-C 10} monounsaturated acid reactant (A.1.b), i.e., product dicarboxylic acid It is an acid, anhydride, or ester containing a long-chain hydrocarbon (polyolefin (A.1.a)) substituted with a moiety. In one embodiment, the reaction intermediate (A.1) is a polyalkenyl succinic anhydride, such as polyisobutenyl succinic anhydride. These functional ratios of the dicarboxylic acid-generating moiety to the polyolefin, such as 1.2 to 2.0, are the total amount of polyolefin (A.1.a) present in the resulting product formed in the foregoing reaction. Based on.

Polyolefin (A.1.a)
The polyolefin (A. 1.a) of the present disclosure includes C _{2 to} C ₁₈ , C _{2 to} C ₁₀ , C _{2 to} C ₈ , or C _{2 to} C ₆ olefin units. Non-limiting examples of olefin units include ethylene, propylene, butylene, isobutylene, pentene, octene-1, and styrene. In some embodiments, the polyolefin (A.1.a) is a polyalkene. The polyolefin (A.1.a) may be a homopolymer, such as polyisobutylene, or a copolymer of two or more different olefin units. Non-limiting examples of copolymers that can be used to form the polyolefin (A.1.a) include ethylene and propylene, butylene and isobutylene, propylene and isobutylene. Further non-limiting examples of copolymers include small molar amounts, such as 1 to 10 mol% olefin units, and C _{4 to} C ₁₈ nonconjugated diolefin units such as copolymers of isobutylene and butadiene or ethylene. , Propylene, and 1,4-hexadiene.

The polyolefin (A.1.a) may be linear or branched. In some embodiments, the polyolefin (A. 1.a) is a number from 500 to 5,000, alternatively from 750 to 4,000, alternatively from 1,000 to 3,000, alternatively from 1,000 to 2,000 g / mol. It has an average molecular weight ( _Mn ).

  The polyolefin (A.1.a) may be saturated or unsaturated. One non-limiting example of a saturated polyolefin (A.1.a) is an ethylene propylene copolymer made by Ziegler-Natta synthesis using hydrogen as a moderator to control molecular weight. In some embodiments, the polyolefin (A.1.a) is unsaturated. In some embodiments, the polyolefin (A.1.a) contains terminal double bonds.

  For this purpose, in one embodiment, the polyolefin (A.1.a) is the first reactive polyisobutene. The first reactive polyisobutene is a highly reactive polyisobutene having a high content of terminal ethylenic double bonds. The terminal double bond is an alpha olefin double bond, such as a vinylidene double bond. The first reactive polyisobutene has a terminal double bond content greater than 50 mol%, alternatively greater than 70 mol%, alternatively greater than 75 mol%, alternatively greater than 80 mol%, alternatively greater than 85 mol%. Can do. The first reactive polyisobutene may have a uniform polymer backbone that includes greater than 85 wt%, alternatively greater than 90 wt%, alternatively greater than 95 wt% isobutene units.

The first reactive polyisobutene has a number average molecular weight ( _Mn ) of 500 to 5,000 g / mol, alternatively 800 to 4,000 g / mol, alternatively 800 to 3,000 g / mol, alternatively 800 to 2,000 g / mol. Can have. The quotient of the dispersity D (M _w / M _n ), that is, the mass average molecular weight M _w divided by M _n of the first reactive polyisobutene is less than 7, alternatively less than 3, alternatively 1.05-7. In some embodiments, the first reactive polyisobutene has a dispersity D (M _w / M _n ) of less than 3. In some embodiments, the first reactive polyisobutene has a dispersity of less than 2.0 for _Mn of 2,000 or less and a dispersity of less than 1.5 for _Mn of 1,000 or less. In some embodiments, the first reactive polyisobutene is free of organic and inorganic bases, water, alcohols, ethers, acids and peroxides.

  A suitable non-limiting example of the first reactive polyisobutene is polyisobutene commercially available from BASF SE under the trademark GLISSSOPAL®.

C ₄ -C ₁₀ monounsaturated acid reactant (A.1.b)
The C _{4 to} C ₁₀ monounsaturated acid reactant (A.1.b) reacts with the polyolefin (A.1.a) to form a reaction intermediate (A.1.b). The C ₄ -C ₁₀ monounsaturated acid reactant (A.1.b) may be an alpha or beta unsaturated C ₄ -C ₁₀ dicarboxylic acid, anhydride or ester thereof. Non-limiting examples of C ₄ -C ₁₀ monounsaturated acid reactants (A.1.b) include fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, dimethyl fumaric acid, chloro Maleic anhydride, and combinations thereof.

In one embodiment, the C ₄ -C ₁₀ monounsaturated acid reactant (A.1.b) is selected from the group of maleic acid, maleic anhydride, functional derivatives thereof, and combinations thereof. As used in the above sentence, the term functional derivative is the same or equivalent result or product that reacts with the polyolefin (A.1.a), ie the reaction intermediate (A.1). Of maleic acid or maleic anhydride derivatives to form In the case of maleic acid, functional derivatives include, for example, monoalkyl maleate, dialkyl maleate, maleyl dichloride, maleyl bromide, maleic acid monoalkyl ester monochloride, or maleic acid monoalkyl ester monobromide. The alcohol component in the case of maleate is, for example, a lower alkyl group of 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms, for example methyl or ethyl. In some _embodiments, C 4 _{-C 10} monounsaturated acid reactant (A.1.b) is maleic anhydride. In one embodiment, maleic anhydride is reacted with a first reactive polyisobutene to form a reaction intermediate (A.1) comprising polyisobutenyl succinic anhydride.

Nucleophilic reactant (A.2)
As described above, the polyalkenyl succinimide (A) includes a reaction product of a hydrocarbyl dicarboxylic acid production reaction intermediate (A.1) and a nucleophilic reaction product (A.2). In some embodiments, the polyalkenyl succinimide (A) is formed via a neutralization reaction between the nucleophilic reactant (A.2) and the hydrocarbyl dicarboxylic acid generating reaction intermediate (A.1). The nucleophilic reactant (A.2) can be selected from the group of amines, alcohols, amino alcohols, and combinations thereof.

  The nucleophilic reactant (A.2) may be a monoamine, oligoamine or polyamine. Since tertiary amines are generally non-reactive with anhydrides, it is desirable to have at least one primary or secondary amine group on the amine.

（式中、Ｒ、Ｒ’及びＲ’’は独立して水素、Ｃ_１〜Ｃ_２５直鎖状又は分枝鎖状のアルキル基、Ｃ_１〜Ｃ_１２アルコキシＣ_２〜Ｃ_６アルキレン基、Ｃ_２〜Ｃ_１２ヒドロキシアミノアルキレン基、及びＣ_１〜Ｃ_１２アルキルアミノＣ_２〜Ｃ_６アルキレン基からなる群から選択され；Ｘは、それぞれ、同一又は２〜６、あるいは２〜４の異なる数であってよく；且つＹは０〜１０、あるいは２〜７、あるいは３〜７の数である）
を有するアミンを含み得る。 The nucleophilic reactant (A.2) is a compound of formula Ia or Ib immediately below:

Wherein R, R ′ and R ″ are independently hydrogen, C ₁ -C ₂₅ linear or branched alkyl group, C ₁ -C ₁₂ alkoxy C ₂ -C ₆ alkylene group, C Selected from the group consisting of _{2 to} C ₁₂ hydroxyaminoalkylene groups and C _{1 to} C ₁₂ alkylamino C _{2 to} C ₆ alkylene groups; X is the same or 2 to 6 or 2 to 4 different numbers, respectively; And Y is a number from 0 to 10, alternatively 2 to 7, alternatively 3 to 7)
An amine having

In some embodiments, the nucleophilic reactant (A.2) is of formula II:
_{H 2 N (CH 2) x} -NH - [(CH 2) y -NH] z - (CH 2) x NH 2 (II)
(Wherein, x and y are each independently an integer of 1 to 5, or 2 to 4, and z is an integer of 0 to 8)
Or a mixture thereof.

  Nucleophilic reactants (A.2) include alkylene polyamines such as methylene polyamine, ethylene polyamine, butylene polyamine, propylene polyamine and pentylene polyamine. In various embodiments, the alkylene polyamine is 2-40, alternatively 2-20, alternatively 2-12, alternatively 2-6, 2-6 total carbon atoms and 1-12, alternatively 2-12, per mole. Or 2 to 9 or 3 to 9 nitrogen atoms. To form the polyalkenyl succinimide (A) of such an embodiment, the nucleophilic reactant (A.2), for example, 0.1 to 3.0 moles, or 0.1 to 2.0 moles per equivalent of amine. Alternatively, 0.2 to 1.0 mole, or 0.2 to 0.6 mole of succinic acid moiety can react to form polyalkenyl succinimide (A).

Examples of the nucleophilic reactant (A.2) include polyoxyalkylene polyamines having a number average molecular weight (M _n ) of 200 to about 4000 g / mol, or 400 to 2000 g / mol, such as polyoxyalkylene amine and polyoxyalkylene. Also included are diamines and polyoxyalkylene triamines. Non-limiting examples of polyoxyalkylene polyamines include polyoxyethylene, polyoxypropylene diamine, and polyoxypropylene triamine having a number average molecular weight ( _Mn ) of 200 to 2000 g / mol.

  Nucleophilic reactants (A.2) also include hydrocarbyl amines or hydrocarbyl amines containing other functional groups such as hydroxy groups, alkoxy groups, amide groups, nitriles, imidazoline groups and the like. For example, in one embodiment, the nucleophilic reactant (A.2) includes a hydrocarbyl amine having 1 to 6, alternatively 1 to 3 hydroxy groups. Such amine groups can react with the acid or anhydride groups of the reaction intermediate (A.1) via their amine function or other function (described immediately above). Specific non-limiting examples of nucleophilic reactant (A.2) include hydroxyamines such as 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, p- (beta- Hydroxyethyl) -aniline, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propane Diol, N- (beta-hydroxy-propyl) -N ′-(beta-amino-ethyl) -piperazine, tris (hydroxy-methyl) amino-methane (also known as trismethylol-aminomethane), 2-amino- 1-butanol, ethanolamine, beta- (beta-hydroxyethoxy) -ethylamine, and the like.

  Nucleophilic reactants (A.2) also include unsaturated alcohols such as unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, propargyl alcohol, 1-cyclohexane-3-ol, and oleyl alcohol. Yet another class of alcohols that can yield the polyalkenyl succinimides (A) of the present disclosure include ether alcohols and amino alcohols such as Ν, Ν, Ν ', N'-tetrahydroxy-trimethylene diamine. From 1 to about 1 oxyalkylene substituted, oxyarylene substituted, aminoalkylene substituted, and aminoarylene substituted alcohol, and alkylene groups having one or more oxyalkylene groups, aminoalkylene groups, or aminoaryleneoxyarylene groups, as exemplified by Mention may be made of ether alcohols having up to about 150 oxyalkylene groups containing 8 carbon atoms.

  Further non-limiting examples of nucleophilic reactants (A.2) include alicyclic diamines such as 1,4-di (aminomethyl) cyclohexane, and heterocyclic nitrogen compounds such as imidazoline, and N-aminoalkylpiperazine is mentioned. Particular non-limiting examples of such amines include 2-pentadecylimidazoline, N- (2-aminoethyl) piperazine, and combinations thereof.

  In one embodiment, the nucleophilic reactant (A.2) includes ethylenediamine, triethylenetetramine, propylenediamine, trimethylenediamine, tripropylenetetramine, tetraethenepentamine, hexaethyleneheptamine, pentaethylenehexamine, and And polyamines selected from the group of combinations. In this embodiment, the nucleophilic reactant (A.2) may be a reaction product of ethylene dichloride and ammonia or a reactive organism of ethyleneimine and a ring-opening agent such as water or ammonia.

  In another embodiment, the nucleophilic reactant (A.2) includes ethylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine. In this embodiment, the ethylene polyamine may be a reaction product of alkylene chloride and ammonia or a reaction product of ethyleneimine and ammonia. These reactions result in a mixture of alkylene polyamines, including cyclic products such as piperazine.

  Various types of combinations and embodiments and examples of nucleophilic reactants (A.2) referenced above may react with reaction intermediate (A.1) to form polyalkenyl succinimide (A). it can.

Polyalkenyl succinimide (A)
The polyalkenyl succinimide (A) of the present disclosure can be a polyalkenyl succinimide (eg, polyisobutenyl succinimide), a diester or acidic ester of succinic acid (eg, partially esterified succinic acid), and even partially Widely defined herein to include esterified polyhydric alcohols or phenols, such as esters having free alcohols or phenolic hydroxyl groups.

  The polyalkenyl succinimide (A) may be or may include polyisobutenyl succinimide including monosuccinimide and bissuccinimide. The ratio of monosuccinimide to bissuccinimide in polyisobutenyl succinimide is, for example, nucleophilic reactant (A.2), such as polyalkenyl succinimide (A), which reacts to form polyisobutenyl succinimide, for example, , May be affected by changing the molar ratio of reaction intermediate (A.1) to amine, eg, polyisobutenyl succinic anhydride. For nucleophilic reactants (A.2), eg, amines, the greater the molar amount of reaction intermediate (A.1), eg, polyisobutenyl succinic anhydride, the greater the amount of monosuccinimide obtained. The reverse is also true. In order to obtain a higher proportion of monosuccinimide, a reaction intermediate (A.2) for 0.7 to 1.3, alternatively 0.9 to 1.1, of a nucleophilic reactant (A.2), for example an amine. 1) For example, a molar ratio of polyisobutenyl succinic anhydride can be used. In order to obtain a higher proportion of bissuccinimide, a reaction intermediate (A.1) to a nucleophilic reactant (A.2), for example an amine, of 3 to 18, or 2.3 to 1.9, for example A molar ratio of polyisobutenyl succinic anhydride can be used. Polyalkenyl succinimides (A), for example polyisobutenyl succinimides having a higher monosuccinimide content, are particularly suitable as additives for fuels (diesel fuel, kerosene, gasoline fuel), while polyalkenyl succinimides (A) For example, polyisobutenyl succinimide having a higher content of bissuccinimide is particularly suitable as an additive for lubricants.

  In order to form the polyalkenyl succinimide (A), an oil solution containing 5 to 95% by weight of the reaction intermediate (A.1) is added to a temperature of 100 to 200 ° C, or 125 to 175 ° C, 0.5 to The nucleophilic reactant (A.2), for example, the above amine, can be obtained by heating for 10 hours or 1 to 6 hours to remove residual water and adding the nucleophilic reactant (A.2). It can be reacted with a reaction intermediate (A.1), for example an alkenyl succinic anhydride. The heating step of the reaction intermediate (A.1) can facilitate the formation of imides or mixtures of imides and amides rather than amides and salts. The reaction ratio of the reaction intermediate (A.1) to the amine equivalent and other nucleophilic reactants (A.2) described herein may vary greatly depending on the reactants and the type of bonds formed. Can change. In some embodiments, the nucleophilic reactant (A.2), for example, 0.1-2.0 mol, alternatively 0.1-2.0 mol, alternatively 0.2-0. A 6 mol dicarboxylic acid partial content (eg grafted maleic anhydride content) is used. For example, about 0.8 moles of pentamine (having two primary amino groups and 5 equivalents of nitrogen per molecule) can be used to form a mixture of amides and imides. A sufficient amount of the product formed by reacting enough maleic anhydride added to 1.6 moles of succinic anhydride group per mole with 1 mole of olefin can be used to form a nitrogenous amine. About 0.4 mole (ie, 1.6 / (0.8 × 5) mole) of succinic anhydride portion per equivalent can be provided.

  In one embodiment, the polyalkenyl succinimide (A) is formed from polyisobutylene substituted with a succinic anhydride group and is a polyethyleneamine, such as tetraethylenepentamine, pentaethylenehexamine, polyoxyethylene and polyoxypropyleneamine, For example, it reacts with polyoxypropylenediamine, trismethylolaminomethane and pentaerythritol, and combinations thereof. As an example, a polyalkenyl succinimide (A) is a polyisobutene substituted with a succinic anhydride group and a hydroxy compound such as pentaerythritol, a polyoxyalkylene polyamine such as polyoxypropylene diamine, and a polyalkylene polyamine such as polyethylene diamine. And can be formed by reacting with tetraethylenepentamine.

  In another embodiment, the polyalkenyl succinimide (A) comprises a reaction product of polyisobutenyl succinic anhydride, a primary amine, and an alcohol. In this embodiment, the polyisobutenyl succinic anhydride, primary amine, and alcohol are reacted at a temperature of 50-200 ° C, alternatively 80-180 ° C, alternatively 80-160 ° C, alternatively 100-160 ° C. Polyisobutenyl succinimide is formed.

The first amine has the following formula:
_{H 2 N (CH 2) x} -NH - [(CH 2) y -NH] z - (CH 2) x NH 2
(Wherein x and y are each independently an integer of 1 to 5, or 2 to 4, and z is an integer of 0 to 8)
Or a mixture thereof.

The alcohol is a monohydric alcohol of the formula R ⁴ OH, wherein R ⁴ is a linear or branched, cyclic or branched cyclic alkyl of 1 to 16 carbon atoms, and Selected from the group consisting of those combinations. In many embodiments, the alcohol is a monohydric alcohol, although polyhydric alcohols are also suitable. The alcohol is of the formula R ⁴ OH, wherein R ⁴ is a linear or branched, cyclic or branched cyclic alkyl of 1 to 16 or 6 to 16 carbon atoms. Monohydric alcohol.

  Specific, non-limiting examples of alcohols include methanol, ethanol, n-propanol, isopropanol, cyclopropyl carbinol, n-butanol, sec-butanol, isobutanol, tert-butanol, 2-hydroxymethylfuran, amyl Alcohol, isoamyl alcohol, vinyl carbinol, cyclohexanol, n-hexanol, 4-methyl-2-pentanol, 2-ethylbutyl alcohol, sec-capryl alcohol, 2-ethylhexanol, n-decanol, lauryl alcohol, isocetyl Alcohols and mixtures thereof are mentioned. In one embodiment, the alcohol is 2-ethylhexanol. Additional specific non-limiting examples of alcohols include phenol, naphthol, (o, p) -alkylphenols such as di-tert-butylphenol, and salicylic acid.

  The molar ratio of polyisobutenyl succinic anhydride to alcohol can vary. There is no need to use stoichiometric amounts of alcohol, and a relatively low molar amount of alcohol may be sufficient to form polyisobutenyl succinimide. Examples of the molar ratio of polyisobutenyl succinic anhydride to alcohol are 10-0.5, or 4-0.8.

  In this embodiment, the polyisobutenyl succinic anhydride is first reacted with an alcohol and then with a first amine to form a polyisobutenyl succinimide. More specifically, polyisobutenyl succinic anhydride is first reacted with an alcohol to form a second reaction intermediate comprising a monoester of polyisobutenyl succinic acid, which is then Reacts with amines. In this embodiment, polyisobutenyl succinic anhydride and alcohol are mixed in a reaction vessel. After the polyisobutenyl succinic anhydride and alcohol have reacted, the first amine can be introduced into the reaction vessel. After the reaction, any alcohol that is either unreacted or cleaved alcohol can be removed by conventional methods.

In one embodiment, the second reaction intermediate has (1) a molecular weight M _n of 500 to 5,000 g / mol and a content of terminal double bonds greater than 50 mol%, alternatively greater than 70 mol%. One reactive polyisobutene, (2) maleic anhydride, and (3) the formula R ⁴ OH, wherein R ⁴ is a linear or branched, cyclic or branched chain of 1 to 16 carbon atoms. A reaction product of an alcohol selected from the group consisting of monohydric alcohols (which are branched cyclic alkyls).

  The second reaction intermediate formed during the formation of the polyisobutenyl succinimide can be isolated if desired. The reaction intermediate is not only useful in the formation of polyalkenyl succinimide (A), but can also be used as an additive for fuels or lubricants, alone or in combination with other additives.

  Alternatively, in this embodiment, isolation of the second reaction intermediate is not necessary. In other words, the polyisobutenyl succinic anhydride, the primary amine and the alcohol react simultaneously to form a polyisobutenyl succinimide, i.e., in a single step. After the reaction, any unreacted or cleaved alcohol can be removed by conventional methods.

In another embodiment, the polyalkenyl succinimide (A) has (1) a molecular weight ( _Mn ) of 500 to 5,000 g / mol and a terminal double bond content of greater than 50 mol%, alternatively greater than 75 mol%. A first reactive polyisobutene having, (2) maleic anhydride, and (3) the following formula:
_{H 2 N (CH 2) x} -NH - [(CH 2) y -NH] z - (CH 2) x NH 2
(Wherein, x and y are each independently an integer of 1 to 5, or an integer of 2 to 4, and z is an integer of 0 to 8)
May be the reaction product of the first amine (A.2) having

In another embodiment, the polyalkenyl succinimide (A) has (1) a number average molecular weight ( _Mn ) of 500 to 5,000 g / mol and a terminal double bond of greater than 50 mol%, alternatively greater than 70 mol%. A first reactive polyisobutene having a content, (2) maleic anhydride, and (3) 1 to 10, alternatively 2 to 4 carbon atoms and 1 to 12, or 2 to 2 in each alkylene group. Linear, branched, cyclic or cyclic having 12 or 2 to 9 or 3 to 9 nitrogen atoms, at least one of which is present as a primary amino group The reaction products of branched alkylene polyamines or the corresponding polyisobutenyl succinimides, based on the total weight of the product, are included in their mixtures containing less than 30% by weight.

In another embodiment, the polyalkenyl succinimide (A) comprises a reaction intermediate (A.1) such as polyisobutenyl succinic anhydride and 2-12, alternatively 2-9, per amine molecule, alternatively from _C 2 _{-C 40} or _C 2 _{-C 20} or _C 2 _{-C 12} nucleophilic reactions containing polyalkylene polyamines (A.2) with the reaction product of,, including 3-9 nitrogen atoms . To form a polyalkenyl succinimide (A) of this embodiment, eg, polyisobutenyl succinimide, nucleophilic reactant (A.2), eg, 0.1 to 3.0 per equivalent of amine, or 0.2 to 1.0, or 0.2 to 0.6 moles of succinic acid moieties react to form polyalkenyl succinimide (A).

（式中、ｍは２〜８０、あるいは２〜４０、あるいは２〜２０、あるいは６〜１６の整数である）
を有する。 In some embodiments, the polyalkenyl succinimide (A) has the following structure:

(Where m is an integer from 2 to 80, alternatively 2 to 40, alternatively 2 to 20, alternatively 6 to 16)
Have

  In some embodiments, the polyalkenyl succinimide (A) of the present disclosure includes a minimal amount of the corresponding amide (polyisobutenyl succinimide or polyisobutenyl succinic monoamide). More specifically, the polyalkenyl succinimide (A) is less than 30% by weight, alternatively less than 25% by weight, alternatively less than 20% by weight, alternatively 15%, based on the total weight of the corresponding amide of the polyalkenyl succinimide (A). It may contain less than% by weight of the corresponding amide. Furthermore, the polyalkenyl succinimide (A) is obtained when the polyalkenyl succinimide (A) includes a reaction product of a reaction intermediate (A.1), a nucleophilic reactant (A.2), and an alcohol (A.3). However, it cannot contain the ester fraction and the reaction with the alcohol (A.3) takes place in an intermediate stage. The increased purity of polyalkenyl succinimide (A) (minimum corresponding amide / amide by-product and lack of ester fraction) can be attributed to the process by which polyalkenyl succinimide (A) is formed.

In some embodiments, the polyalkenyl succinimide (A) is greater than 500 g / mol, alternatively greater than 800 g / mol, alternatively greater than 1,000 g / mol, alternatively 500 to 5,000 g / mol, alternatively 750 to 5 Having a number average molecular weight ( _Mn ) of 1,000 g / mol, alternatively 1,000 to 4,000 g / mol, alternatively 1,000 to 3,000 g / mol. Higher molecular weight (eg, M _n > 1,000 g / mol) polyalkenyl succinimide (A) reduces the fuel consumption of an internal combustion engine when added to the combusted fuel. In other words, polyalkenyl succinimide (A) is an effective fuel efficiency additive. In contrast, molecules with low molecular weight (eg, 300-500 g / mole M _n ) when added to the fuel being burned are believed not to reduce fuel consumption of the internal combustion engine. In some embodiments, the hydrophobic part of the molecule consuming known in the art are typically derived usually from synthetic or natural mono- or oligo fatty acids having a chain length of C ₁₂ -C ₂₀ . In contrast, polyalkenyl succinimide (A), as described above, has a C ₄₀ -C ₄₀₀ ; or C ₄₀ -C ₂₀₀ chain length and a number average molecular weight (M _n ) of 500-5,000 g / mol. It can be formed from a first reactive polyisobutene.

  The composition may be added to the fuel in an amount such that it can be present in the fuel in an amount of 10-500 mg / kg of fuel, alternatively 20-200 mg, alternatively 25-75 mg. Furthermore, the polyalkenyl succinimide (A) is 1 to 75 parts by mass, alternatively 1 to 50 parts by mass, alternatively 5 to 40 parts by mass, alternatively 4 to 40 parts by mass, alternatively 6 to 45 parts by mass, per 100 parts by mass of the composition, Alternatively, it may be present in the composition in an amount of 2-20 parts by weight, alternatively 4-15 parts by weight, alternatively 5-12 parts by weight, alternatively 15-45 parts by weight, alternatively 20-35 parts by weight.

Polyisobuteneamine (B)
Referring back, in some embodiments, the composition also includes polyisobuteneamine (B). The polyisobuteneamine (B) as described herein includes monofunctional and polyfunctional polyisobuteneamines. In some embodiments, the polyisobuteneamine (B) comprises the reaction product of (B.1) a second polyolefin and (B.2) a second amine.

Second polyolefin (B.1)
The second polyolefin (B.1) of the present disclosure includes C _{2 to} C ₁₈ , alternatively C _{2 to} C ₁₀ , alternatively C _{2 to} C ₅ olefin units. Non-limiting examples of olefin units include ethylene, propylene, butylene, isobutylene, pentene, octene-1, and styrene. In some embodiments, the second polyolefin (B.1) is a polyalkene. The second polyolefin (B.1) may be a homopolymer, such as polyisobutylene, or a copolymer of two or more different olefin units. Non-limiting examples of copolymers that can be used to form the second polyolefin (B.1) include ethylene and propylene, butylene and isobutylene, propylene and isobutylene. Non-limiting examples of additional copolymers, low molar amount of olefin units, for example, comprise from 1 to 10 mol%, C ₄ -C ₁₈ copolymer is a non-conjugated diolefin units, for example, isobutylene and butadiene copolymers Or a copolymer of ethylene, propylene and 1,4-hexadiene.

The second polyolefin (B.1) may be linear or branched. In some embodiments, the second polyolefin (B.1) is 500 to 5,000 g / mol, alternatively 750 to 4,000 g / mol, alternatively 1,000 to 3,000 g / mol, alternatively 1,000. It has a number average molecular weight ( _Mn ) of ~ 2,000 g / mol.

  In some embodiments, the second polyolefin (B.1) is unsaturated. In some embodiments, the second polyolefin (B.1) contains a terminal double bond.

  To this end, in one embodiment, the second polyolefin (B.1) is a second reactive polyisobutene. The second reactive polyisobutene can be a highly reactive polyisobutene having a high content of terminal ethylenic double bonds. In some embodiments, the second reactive polyisobutene is greater than 50 mole%, alternatively greater than 70 mole%, alternatively greater than 75 mole%, alternatively greater than 80 mole%, or greater than 85 mole%. It has a content of heavy bonds. The second reactive polyisobutene may have a uniform polymer backbone that includes greater than 85 wt%, alternatively greater than 90 wt%, alternatively greater than 95 wt% isobutene units.

In some embodiments, the second reactive polyisobutene is from 500 to 5,000 g / mol, alternatively from 750 to 4,000 g / mol, alternatively from 1,000 to 3,000 g / mol, alternatively from 1,000 to 2, It has a number average molecular weight ( _Mn ) of 000 g / mol. Dispersity _{D (M w / M n)} , i.e., the quotient of the weight average molecular weight _{M w} of the second reactive polyisobutene divided by _{M n} is less than 7, or a 1.05 to 7. In one embodiment, the second reactive polyisobutene has a dispersity D (M _w / M _n ) of less than 3. In some embodiments, the second reactive polyisobutene has a dispersity of less than 2.0 for _{Mn of} 2,000 or less, and a dispersion of less than 1.5 for _{Mn of} 1,000 or less. Have a degree. In some embodiments, the second reactive polyisobutene is free of organic and inorganic bases, water, alcohols, ethers, acids and peroxides.

  A suitable non-limiting example of a second reactive polyisobutene is polyisobutene commercially available from BASF SE under the trademark GLISSSOPAL®.

Second amine (B.2)
As described above, the second polyolefin (B.1) reacts with the second amine (B.2) to form the polyisobuteneamine (B). In some embodiments, the second amine (B.2) has the following formula:
HNR ¹ R ²
Wherein R ¹ and R ² are each independently H, C ₁ -C ₁₈ -alkyl, C ₂ -C ₁₈ -alkenyl, C ₄ -C ₁₈ -cycloalkyl, C ₁ -C ₁₈ -alkylaryl, hydroxy -C 1 _-C 18 _- alkyl, poly (oxyalkyl), polyalkylene polyamine, polyalkylene amine group, or a polyalkylene imine radical, or together with the nitrogen atom to which they are attached, form a heterocyclic ring)
Have

Non-limiting examples of C ₁ -C ₁₈ -alkyl groups include linear or branched groups having 1 to 18 carbon atoms, such as methyl, ethyl, isopropyl or n-propyl, n -Butyl, isobutyl, sec-butyl or tert-butyl, n-pentyl or isopentyl; furthermore n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-tridecyl, n- Examples include tetradecyl, n-pentadecyl and n-hexadecyl and n-octadecyl, as well as mono- or multi-branched analogs thereof; and corresponding groups in which the hydrocarbon chain has one or more ether bridges.

Non-limiting examples of C ₂ -C ₁₈ -alkenyl groups have ₂ to ₁₈ carbon atoms, monovalent or polyunsaturated, or a double bond can be at any position of the hydrocarbon chain Mono- or diunsaturated analogues of the above alkyl groups are mentioned.

Non-limiting examples of C ₄ -C ₁₈ -cycloalkyl groups include cyclobutyl, cyclopentyl and cyclohexyl, and analogs thereof substituted by _{1 to} 3 C ₁ -C ₄ -alkyl groups; C ₁ -C ₄ - alkyl groups, for example, methyl, ethyl, isopropyl or n- propyl, n- butyl, isobutyl, sec- butyl or tert- butyl.

C 1 _-C 18 _- Non-limiting examples of alkyl aryl groups, C ₁ -C 18, as defined above _- mentioned alkyl group, aryl group, fused monocyclic or bicyclic Or derived from non-fused 4-7 membered, especially 6 membered aromatic or heteroaromatic groups such as phenyl, pyridyl, naphthyl and biphenyl.

Non-limiting examples of alkenyl aryl _{group, C 2 ~C 18 - - C} 2 ~C 18 alkenyl group as defined above and the aryl group include groups such as defined above. Non-limiting examples of hydroxy-C ₁ -C ₁₈ -alkyl groups include mono- or polyhydroxylated, or monohydroxylated, particularly those of the above-mentioned C ₁ -C ₁₈ -alkyl groups monohydroxylated at the terminal position. Analogs; for example, 2-hydroxyethyl and 3-hydroxypropyl.

For example, non-limiting examples of poly (oxyalkyl) groups that can be hydroxylated include nitrogen atoms having 2 to 10 C ₁ -C ₄ -alkoxy groups, where individual carbon atoms can contain hydroxyl groups. Examples include groups obtained by alkoxylation. Representative alkoxy groups include methoxy, ethoxy and n-propoxy groups.

Non-limiting examples of polyalkylene polyamine groups include the following formula:
_{Z- (NH-C 1 ~C 6} - alkylene _{-NH) m-C 1 ~C 6} - alkylene (wherein, m is an integer from 0 to 5, Z is H or _C 1 -C ₆ - alkyl is there)
The group of is mentioned. C ₁ -C ₆ -alkyl represents a group such as methyl, ethyl, isopropyl or n-propyl group, n-butyl, isobutyl, sec-butyl or tert-butyl, n-pentyl or isopentyl, furthermore n-hexyl, And C ₁ -C ₆ -alkylene represents the corresponding bridged analog of these groups.

Non-limiting examples of polyalkyleneimine groups include groups containing _{1 to} 10 C ₁ -C ₄ -alkyleneimine groups, particularly ethyleneimine groups. Examples of heterocycles are substituted 5-7 membered heterocycles optionally substituted by ₁ to 3 C ₁ -C ₄ -alkyl groups and optionally having additional ring heteroatoms such as O or N. Is mentioned.

Non-limiting examples of compounds of formula NHR ¹ R ² include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, hexyl. Primary amines such as amines, cyclopentylamine and cyclohexylamine; further formulas CH ₃ —O—C ₂ H ₄ —NH ₂ , C ₂ H ₅ —O—C ₂ H ₄ —NH ₂ , CH ₃ —O—. _{C 3 H 6 -NH 2, C} 2 H 5 -O-C 3 H-NH 2, n-C 4 H 9 -O-C 4 H 8 -NH 2, HO-C 2 H 4 -NH 2, HO -C ₃ primary amines H ₆ -NH _2, and _{HO-C 4 H 8 -NH 2} ; secondary amines, e.g., dimethylamine, diethylamine, methyl ethyl Amine, di -n- propylamine, diisopropylamine, diisobutylamine, di -sec- butylamine, di -tert- butylamine, dipentylamine, dihexylamine, di-cyclopentylamine, dicyclohexylamine and diphenylamine; more formula _(CH 3 -O _{-C 2 H 4) 2 NH,} (C 2 H 5 -O-C 2 H 4) 2 NH, (CH 3 -O-C 3 H 6) 2 NH, (C 2 H 5 -O-C 3 H _{6) 2 NH, (n-} C 4 H 9 -O-C 4 H 8) 2 NH, (HO-C 2 H 4) 2 NH, (HO-C 3 H 6) 2 NH and _{(HO-C 4} Secondary amines of H ₈ ) ₂ NH; heterocyclic amines such as pyrrolidine, piperidine, morpholine and piperazine, as well as substituted derivatives thereof such as N—C ₁ -C ₆ - alkyl piperazine and dimethyl morpholine, polyamines, for _example, C 1 -C ₄ - alkylene diamine, di _-C 1 -C ₄ - alkylene triamine, triethylene _-C 1 -C ₄ - alkylene tetraamine and higher analogs Body: Polyethyleneimine, or oligoethyleneimine consisting of 1 to 10, alternatively 2 to 6 ethyleneimine units. Non-limiting examples of polyamines and polyimines include n-propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, diethylenetriamine, triethylenetetramine and polyethyleneimine, as well as their alkyl products such as 3 -(Dimethylamino) -n-propylamine, N, N-dimethylethylenediamine, Ν, Ν-diethylethylenediamine and Ν, Ν, Ν ', Ν'-tetramethyldiethylenetriamine. Ethylenediamine is yet another non-limiting example.

Polyisobuteneamine (B)
Monofunctional or polyfunctional polyisobuteneamine (B) can be formed via various reactions under various reaction conditions.

  For example, in one embodiment, the monofunctional or polyfunctional polyisobutene amine (B) includes a halogenated hydrocarbon, such as a halogenated polyisobutene, and the reaction product of the second amine described above. More particularly, while the hydrogen halide is being formed, the halogen atoms of the hydrocarbon chain are replaced with polyamine groups. The hydrogen halide can then be removed in any suitable manner, for example as a salt with excess polyamine. The reaction between the halogenated hydrocarbon and the second amine can be carried out at an elevated temperature in the presence of a solvent, for example a solvent having a boiling point of at least 160 ° C.

  As another example, polyisobuteneamine (B) can be formed via alkylation of aliphatic polyamines. For example, a second amine, such as a polyamine, can react with an alkyl or alkenyl halide. The formation of alkylated polyamines involves the formation of hydrogen halides that are removed, for example, as salts of the starting polyamine present in excess.

  As yet another example, a polyalkene having a terminal double bond in which the beta carbon atom has a methyl group, such as a second reactive polyisobutene, can be chlorinated with a stoichiometric amount of chlorine during the release of hydrochloric acid to produce alpha-poly Isobutyl allyl chloride and beta-polyisobutyl methallyl chloride can be produced. During chlorination, side reactions also produce amounts of dichloro compounds. The second amine, eg, polyamine, is then alkylated with the resulting chlorinated compound to form polyisobuteneamine (B). For example, the first reactive polyisobutylene is treated with chlorine in an inert solvent at room temperature, and the resulting polyisobutenyl chloride is converted to monoisobutenyl tetraethylenepentamine or diisobutyl with tetraethylenepentamine. Converted to tenenyltetraethylenepentamine.

In another embodiment, the polyisobuteneamine (B) is a second reactive polyisobutene, the following formula:
HNR ² R ³
Wherein R ² and R ³ are each independently H, C ₁ -C ₁₈ -alkyl, C ₂ -C ₁₈ -alkenyl, C ₄ -C ₁₈ -cycloalkyl, C ₁ -C ₁₈ -alkylaryl, hydroxy _-C 1 _{-C 18} - alkyl, poly (oxyalkyl), polyalkylene polyamine or a polyalkylene amine radical)
A reaction product of a second amine having the formula; or together with the nitrogen atom to which they are attached form a heterocycle.

  For example, monofunctional or polyfunctional polyisobuteneamine (B) can be used for hydroformylation of a second reactive polyisobutene to form an oxo intermediate and subsequent reductive amination of the oxo intermediate in the presence of ammonia. Reaction product formed via

Specifically, the polyisobuteneamine (B) can be prepared by using a rhodium or cobalt catalyst in the presence of CO and H ₂ at a temperature of 80-200 ° C. and a CO / H ₂ pressure of up to 600 bar, using a suitable polyalkene, such as The second reactive polyisobutene can be hydroformylated and then the oxo product can be formed by subjecting it to a Mannich reaction or amination under hydrogenation conditions. The amination reaction can be carried out at 80 to 200 ° C. and at a pressure of 600 bar or lower, alternatively 80 to 300 bar.

  In this formation method, it is advantageous to use a suitable inert solvent to reduce the viscosity of the reaction mixture. Non-limiting examples of such solvents include aliphatic, alicyclic, and aromatic hydrocarbons having a low sulfur content. In one embodiment, an aliphatic solvent is used that does not contain sulfur compounds and contains less than 1% aromatic compounds. Such solvents have the advantage that at high amination temperatures, no heat of hydrogen is released and no hydrogen is consumed. In the amination and hydroformylation reactions, the solvent content may be 0-70% by weight, depending on the viscosity of the polymer and solvent.

In this forming step, 80-90% polybutene conversion can be easily achieved. In one embodiment, a second reactive polybutene containing 80% by weight or more of isobutene and having a number average molecular weight (M _n ) of 300 to 5000 g / mol, alternatively 500 to 2500 g / mol is used. In this embodiment, the second reactive polybutene has an average degree of polymerization P of 10 to 100 and a double bond content E capable of reacting with maleic anhydride of 60 to 90%. A value E of 100% corresponds to a calculated theoretical value in which each molecule of butene or isobutene polymer contains one reactive double bond of this kind. Values are calculated for the reaction of maleic anhydride and polyisobutene at a mass ratio of 5: 1 and the stirred mixture is heated at 200 ° C. for 4 hours.

  Regardless of how the polyisobuteneamine (B) is formed, the polyisobuteneamine (B) of the composition has excellent low temperature properties, eg, low cloud point, low pour point, and is stored at low temperatures. Stable when done. Furthermore, polyisobuteneamine (B) can function as a surfactant in an internal combustion engine when added to the combustion fuel.

  For this purpose, the composition is added to the fuel in an amount such that the polyisobuteneamine (B) can be present in the fuel in an amount of 20 to 2,000 mg, alternatively 50 to 1,000 mg, alternatively 100 to 500 mg per kg of fuel. Can be done. Furthermore, the polyisobuteneamine (B) is 5 to 70 parts by mass, alternatively 10 to 60 parts by mass, alternatively 10 to 40 parts by mass, alternatively 30 to 60 parts by mass, alternatively 5 to 35 parts by mass, or 100 parts by mass of the composition. It can be present in the composition in an amount of 15 to 25 parts by weight.

Carrier oil (C)
Referring back, the composition also includes a carrier oil (C). One or more different carrier oils can be added to the composition, i.e. the carrier oil (C) may comprise a mixture of one or more different types of carrier oils. Carrier oil (C) may include mineral carrier oil, synthetic carrier oil, and combinations thereof. The carrier oil (C) may comprise one or more different carrier oils selected from the group of mineral oils, polyethers, polyetheramines, and esters. The composition may include any carrier oil known in the art, such as those carrier oils not specifically described herein.

As noted above, the composition can include one or more mineral carrier oils. Non-limiting examples of mineral carrier oils include fractions obtained from mineral oil processing, such as kerosene or naphtha, or bright stock or base oil. Non-limiting examples of suitable mineral carrier oils include naphthenic or paraffinic mineral oils having a viscosity of ² to 25 mm ² / s at 100 ° C.

As noted above, the composition can include one or more polyether carrier oils. Non-limiting examples of polyether carrier oils include polyalkylene oxides and propoxylates having a number average molecular weight (M _n ) of 500 g / mol or more. Generally, the polyalkylene oxide carrier oil is one or more alkylene oxides such as ethylene oxide (EO), propylene oxide (PO), and / or butylene oxide (BO) using an initiator in the presence of a catalyst. It is formed by polymerizing. The initiator used to form the polyalkylene oxide can be an alkanol, alkanediol, amine, or alkylphenol. For example, the initiator is 1,6-hexanediol, 1,8-octanediol, 2-ethylhexanol, 2-propylhexanol, isotridecanol, isononylphenol, isodecylphenol and / or isotridecylamine. obtain. The polyalkylene oxide may be linear or branched and may have a random, repeating, or block structure. One non-limiting example of a suitable polyether carrier oil is a polyalkylene oxide formed from 50 moles, or 8-30 moles of propylene oxide or butylene oxide or mixtures thereof per molecule of initiator. Another non-limiting example of a suitable polyether carrier oil is the following formula:
R ⁴ — [O—CH ₂ —CH (CH ₃ )] _n —OH
(Wherein n is an integer of 14 to 17 and R ⁴ is linear or branched C ₈ -C ₁₈ -alkyl or C ₈ -C ₁₈ -alkenyl)
Is a propoxylate having

As noted above, the composition may include one or more polyetheramine carrier oils. Non-limiting examples of polyetheramine carrier oils include polyetheramines and ammonia or primary or secondary based on EO, PO, and / or BO having a number average molecular weight ( _Mn ) of 500 g / mole or more. Grade monoamines or polyamines. Such polyetheramines can be prepared from polyethers by an amination reaction in which the terminal hydroxyl groups are replaced with amino groups with the elimination of water.

As noted above, the composition may include one or more esters of monocarboxylic acid or polycarboxylic acid and alkanol or polyol carrier oil. Non-limiting examples of such ester carrier oils include esters, aliphatic or aromatic monocarboxylic acids or polyesters of monocarboxylic acids or polycarboxylic acids and alkanols or polyols having a minimum viscosity of 2 mm ² / s at 100 ° C. carboxylic acids, and C ₆ -C ₂₄ ester alcohols or ester polyols, isooctanol, isononanol, isodecanol and adipates isotridecanol, phthalate, isophthalate, terephthalate, and trimellitates are mentioned.

In some embodiments, the composition has the following formula:
R ⁴ — [O—CH ₂ —CH (CH ₃ )] _n —OH
(In the formula, n is an integer of 8 to 35, or 14 to 17, and R ⁴ is a linear or branched C ₈ -C ₁₈ -alkyl or C ₈ -C ₁₈ -alkenyl)
A propoxylate carrier oil having

In one embodiment, R ⁴ is a linear or branched alkyl of 10 to 16 carbon atoms, or a mixture thereof. In another embodiment, R ⁴ is an alkyl of 12 to 14 carbon atoms or a mixture of such alkyl groups. In yet another embodiment, R ⁴ has 13 carbon atoms.

  In one embodiment, n is an integer from 12-18. In another embodiment, n is an integer from 14-17. In yet another embodiment, n is an integer from 14-16. In yet another embodiment, n is 15. Of course, since many production methods produce a mixture of compounds with varying molecular weight distributions, the above numerical data for n is an average value.

In one embodiment, the propoxylate carrier oil has the above formula where n is 14-16, alternatively 15, and R ⁴ is a branched C ₁₃ -alcohol, especially C ₁₃ -monoalcohol. Branched _{C 13 alcohols,} C 2 -C ₆ - olefins can be obtained, especially oligomerization of _{C 3} olefins or _{C 4} olefins, and by subsequent hydroformylation.

  The propoxylate carrier oil of this embodiment is used at 120-160 ° C, or 130-160 ° C, to obtain the desired adduct, alkali, for example, sodium hydroxide solution, potassium hydroxide solution, sodium methylate, potassium Produced by reacting propylene oxide with an alcohol as an initiator molecule in the presence of methylate or another alkali metal alkoxide. After the alkoxylation is complete, the propoxy carrier oil removes the catalyst, for example by treatment with magnesium silicate. In one embodiment, the propoxylate carrier oil is propoxylated isotridecanol.

（式中、Ｒ^５及びＲ^６は互いに独立してそれぞれ分枝鎖状又は直鎖状のＣ_６〜Ｃ_３０アルキル基であり、２つの基Ｒ^７のうちの１つはメチルであり且つ他は水素であり且つｑは１〜１００である）
を有するジアルキルフェノール−開始プロポキシレートのキャリアオイルを含む。この実施態様は、モノアルキルフェノール開始プロポキシレートキャリアオイルも含み、このプロポキシレートキャリアオイルは上記の式によって表されるが、但し、Ｒ^６は省略される。 In another embodiment, the composition has the following formula:

Wherein R ⁵ and R ⁶ are each independently a branched or straight chain C ₆ -C ₃₀ alkyl group, one of the two groups R ⁷ is methyl and the other Is hydrogen and q is 1-100)
A dialkylphenol-initiated propoxylate carrier oil having This embodiment also includes a monoalkylphenol-initiated propoxylate carrier oil, which is represented by the formula above, with the exception that R ⁶ is omitted.

  In general, any mixture of the above carrier oils can be included in the carrier oil (C) of the composition. To this end, in another embodiment, the carrier oil (C) comprises a mixture of polyether carrier oil and ester carrier oil.

Suitable polyether carrier oils include polyalkylene oxides having a number average molecular weight ( _Mn ) of 500 g / mol or more. The polyalkylene oxides of this embodiment can be formed from initiators such as aliphatic and aromatic mono-, di- or polyalcohols or further amines or amides and alkylphenols. The polyalkylene oxide of this embodiment can be formed from alkylene oxides such as ethylene oxide EO, PO, and BO, although higher oxides can also be used to form these polyalkylene oxides.

Suitable ester carrier oils include esters of aliphatic or aromatic monocarboxylic acids or polycarboxylic acids with long chain alcohols, polyol esters (eg, neopentyl glycol, pentaerythritol, or tris of corresponding monocarboxylic acids). Based on methylolpropane) and oligomers or polymer esters, such as those based on dicarboxylic acids, polyols and monoalcohols, and long chain aliphatic alcohols and aromatic dicarboxylic acids, tricarboxylic acids and tetras composed solely of carbon, hydrogen and oxygen Examples include esters with carboxylic acids, the total number of carbon atoms in the ester is 22 or more, and the molecular weight is 370 to 1500 g / mol, or 414 to 1200 g / mol. Suitable esters may have a minimum viscosity of 2 mm ² / s at 100 ° C. In one embodiment, the ester is isooctanol, isononanol, isodecanol and isotridecanol adipate, phthalate, isophthalate, terephthalate and trimellitate, and combinations thereof.

  The carrier oil (C) may also function to carry components of the composition ((A), (B), etc.) and reduce deposits in the region of the engine intake valve. For this reason, the composition is added to the fuel in an amount such that the carrier oil (C) is usually added to the fuel in an amount of 10 to 2,000 mg, or 20 to 1,000 mg, or 50 to 500 mg per kg of fuel. Can be added. Furthermore, the carrier oil (C) is 2 to 94 parts by mass, alternatively 2 to 80 parts by mass, alternatively 5 to 60 parts by mass, alternatively 10 to 30 parts by mass, or 12 to 18 parts by mass, per 100 parts by mass of the composition. Alternatively, it may be present in the composition in an amount of 5-15 parts by weight, alternatively 2-20 parts by weight.

Additives Compositions include surfactants, lubricant additives, corrosion inhibitors, antioxidants, demulsifiers, metal deactivators, dehazers, markers, solvents, cetane improvers, defoamers One or more additions different from the above components (A) and (B) and (C), selected from the group of solubilizers, deodorizers, dehazers, and other additives Agents can be included. The composition may include solubilizers, but does not require them. Solubilizers are materials known in the art that improve the miscibility of the components contained in the fuel additive composition and thus improve the homogeneity of the fuel additive composition.

Surfactant One or more surfactants different from the above components (A) and (B) can be added to the composition. Preferable examples include surfactants other than polyisobuteneamine (B) having a surfactant action and / or a valve seat wear suppressing action. Suitable, non-limiting examples of one or more surfactants include neutral metal sulfonates, phenates and salicylates, and combinations thereof, described below.

One suitable surfactant is a number average molecular weight of 85 to 20,000 and (a) a monoamino or polyamino group having up to 6 nitrogen atoms with at least one nitrogen atom having basic properties; (b) A nitro group that can be combined with a hydroxyl group; (C) a hydroxyl group in combination with a mono- or polyamino group in which at least one nitrogen atom has basic properties; (d) a carboxyl group or their alkali metals or their alkaline earth metals (E) a sulfonic acid group or an alkali metal or alkaline earth metal salt thereof; (f) terminated with a hydroxyl group, a monoamino group or a polyamino group, or a carbamate group, wherein at least one nitrogen atom has basic properties. are polyoxy _-C 2 -C ₄ - alkylene group; (g) carboxylic ester groups; and / or (H) is a compound having at least one hydrophobic hydrocarbon group having at least one polar moiety selected from the moieties obtained by Mannich reaction of aldehydes and monoamines or polyamines with substituted phenols.

Hydrophobic hydrocarbon groups in the aforementioned surfactants that improve the solubility of the composition in the fuel have a number average molecular weight (M _{n) of} 85 to 20,000, alternatively 113 to 5,000, alternatively 300 to 5,000. ). Examples of hydrophobic hydrocarbon groups, particularly hydrophobic hydrocarbon groups associated with the polar moieties (a), (c), (h) and (i) are 300 to 5,000 g / mol, or 500 to 2 respectively. , 500 g / mole, or polypropenyl, polybutenyl and polyisobutenyl groups having a number average molecular weight ( _Mn ) of 700 to 2,300 g / mole.

Surfactant (a) containing a monoamino group or polyamino group can be either polypropene or a conventional polybutene or polyisobutene having a number average molecular weight ( _Mn ) of 300 to 5,000, i.e. mainly having internal double bonds. It may be a polyalkene monoamine based or a polyalkene polyamine. Polybutenes or polyisobutenes with internal double bonds mainly (usually in the β and γ positions) are used as starting materials in the preparation of surfactants, and possible synthetic routes include chlorination and subsequent amination or carbonyl or By oxidation of double bonds using air or ozone to obtain carboxyl compounds and subsequent amination under reducing (hydrogenation) conditions. The amine used for the amination can be, for example, ammonia, a monoamine or a polyamine, for example dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine.

  The surfactant (a) containing a monoamino group may be a hydrogenation product of a reaction product of polyisobutene having a mean polymerization degree P of 5 to 100 and nitrogen oxide or a mixture of nitrogen oxide and oxygen. . The surfactant (a) containing a monoamino group may be a compound obtained from polyisobutene epoxide by reaction with amine and subsequent dehydration and reduction of amino alcohol.

  Surfactant (b) containing a nitro group, which may be a combination with a hydroxyl group, is a reaction of polyisobutene with a mean degree of polymerization P of 5-100 or 10-100 with nitrogen oxides or a mixture of nitrogen oxides and oxygen It can be a product. These reaction products are generally a mixture of hydroxynitropolyisobutene (eg, alpha-nitro-beta-hydroxypolyisobutene) mixed with pure nitropolyisobutene (eg, alpha, beta-dinitropolyisobutene).

A surfactant having a hydroxyl group in combination with monoamino or polyamino (c) is a polyisobutene epoxide obtained from a polyisobutene having a terminal double bond and a number average molecular weight ( _Mn ) of 300 to 5,000, and ammonia or a monoamine. Alternatively, it may be a reaction product with a polyamine.

Carboxyl groups or their alkali metal or alkaline earth metal salt surfactants comprising (d) is a copolymer of _C 2 _{-C 40} olefins and maleic anhydride having a total molar mass of 500 to 20,000, Part or all of the carboxyl group was converted to an alkali metal or alkaline earth metal salt and the remainder of the carboxyl group reacted with an alcohol or amine. Such surfactants can be used in combination with polyisobuteneamine (B) to prevent valve seat wear.

  The surfactant (e) comprising a sulfonic acid group or an alkali metal or alkaline earth metal salt thereof can be an alkali metal or alkaline earth metal salt of an alkyl sulfosuccinate. Such surfactants can also be used in combination with polyisobuteneamine (B) to prevent wetting of the valve seat.

Surfactant (f) comprising a polyoxy-C ₂ -C ₄ -alkylene moiety is a C ₂ -C ₆₀ alkanol, C ₆ -C ₃₀ -alkanediol, mono- or di-C ₂ -C ₃₀ -alkylamine, C ₁ -C ₃₀ - alkyl cyclohexanol or _C 1 _{-C 30} - alkyl phenols by reaction with hydroxyl groups or ethylene oxide from 1 to 30 moles per amino group and / or propylene oxide and / or butylene oxide, and polyether amines In this case, it may be a polyether or polyetheramine obtained by subsequent reductive amination with ammonia, monoamine or polyamine. In the case of polyethers, such products can also have carrier oil properties. Examples of these surfactants include tridecanol butoxylate, isotridecanol butoxylate, isononylphenol butoxylate and polyisobutenol butoxylate and propoxylate, as well as reaction products corresponding to ammonia.

The surfactant (g) containing a carboxylic ester group is an ester of a monocarboxylic acid, dicarboxylic acid or tricarboxylic acid and a long-chain alkanol or polyol, particularly those having a minimum viscosity of 2 mm ² / s at 100 ° C. obtain. The monocarboxylic acid, dicarboxylic acid or tricarboxylic acid used may be an aliphatic or aromatic acid, and particularly suitable ester alcohols or ester polyols are, for example, long-chain chains having 6 to 24 carbon atoms. Typical. Examples of esters include adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol. Such products can also have carrier oil properties.

  Surfactants (h) containing moieties obtained by Mannich reaction of substituted phenols with aldehydes and monoamines or polyamines include polyisobutene-substituted phenols and formaldehyde and monoamines or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylene. It may be a reaction product with pentamine or dimethylaminopropylamine.

Lubricity additive One or more lubricity additives can also be added to the composition. Non-limiting examples of lubricity additives include certain carboxylic acids or fatty acids, alkenyl succinic esters, bis (hydroxyalkyl) fatty amines, hydroxyacetamide or castor oil. The above carboxylic acids or fatty acids may be present as monomer and / or dimer species.

Corrosion inhibitors One or more corrosion inhibitors may also be included in the composition. Non-limiting examples of corrosion inhibitors include ammonium salts of organic carboxylic acids that tend to form films. Heteroaromatic compounds can also be included as corrosion inhibitors for non-ferrous metals. Amines for lowering the pH can also be included with the corrosion inhibitor.

Antioxidants One or more antioxidants or stabilizers may also be included in the composition. Non-limiting examples of antioxidants or stabilizers include amines such as paraphenylenediamine, dicyclohexylamine, morpholine or their amine derivatives, phenolic antioxidants such as 2,4-di-tert-butylphenol. Or 3,5-di-tert-butyl-4-hydroxyphenyl-propionic acid and its derivatives.

  Non-limiting examples of antioxidants include alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6 -Di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl- 4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert -Butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6 (1'-methyl) Undeca-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadeca-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) ) Phenol, and combinations thereof.

Other non-limiting examples of suitable antioxidants include alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2 , 4-Dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol, and combinations thereof; hydroquinone and alkylated hydroquinone, such as 2,6-di-tert-butyl-4- Methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2, 5-di-tert-butyl-4-hydroxyanisole, 3, -Di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis- (3,5-di-tert-butyl-4-hydroxyphenyl) adipate, and Combinations thereof; hydroxylated thiodiphenyl ethers such as 2,2′-thiobis (6-tert-butyl-4-methylphenol), 2,2′-thiobis (4-octylphenol), 4,4′-thiobis (6 -Tert-butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis- (3,6-di-sec-amylphenol), 4,4′-bis- (2,6-dimethyl-4-hydroxyphenyl) disulfide, and combinations thereof; Bisphenols such as 2,2′-methylenebis (6-tert-butyl-4-methylphenol), 2,2′-methylenebis (6-tert-butyl-4-ethylphenol), 2,2′-methylenebis [ 4-methyl-6- (α-methylcyclohexyl) phenol], 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis (6-nonyl-4-methylphenol), 2 , 2′-methylenebis (4,6-di-tert-butylphenol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 2,2′-ethylidenebis (6-tert-butyl-) 4-isobutylphenol), 2,2′-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2′-methylene [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-methylenebis (6-tert-butyl-2) -Methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl)- 4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methyl-) Phenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis [3,3-bis (3′-tert-butyl-4′-hydroxyphenyl) butyrate], Bis (3-tert-butyl-4-hydroxy-5-methyl-phenyl) dicyclopentadiene, bis [2- (3′-tert-butyl-2′-hydroxy-5′-methylbenzyl) -6-tert- Butyl-4-methylphenyl] terephthalate, 1,1-bis- (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra- (5-tert-butyl) -4-hydroxy-2-methylphenyl) pentane, and combinations thereof (which may be used as antioxidants); O-, N- and S-benzyl compounds, such as 3,5,3 ′, 5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tris- (3,5-di -Tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol terephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) ) Sulfide, isooctyl-3,5 di-tert-butyl-4-hydroxybenzyl mercaptoacetate, and combinations thereof; hydroxybenzylated malonate such as dioctadecyl-2,2-bis- (3,5-di-) tert-butyl-2-hydroxybenzyl) -malonate, di-octadeci -2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) -malonate, di-dodecyl mercaptoethyl-2,2-bis- (3,5-di-tert-butyl-4-hydroxybenzyl) Malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, and combinations thereof; Triazine compounds such as 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4, 6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyl mercapto-4,6-bis (3,5 -Di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3 Triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6 Dimethylbenzyl 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di- tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate And combinations thereof; aromatic hydroxybenzyl compounds such as 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1 , 4-Bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl -4-hydroxybenzyl) phenol, and combinations thereof; benzylphosphonates such as dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4- Hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctyl Decyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, and combinations thereof; acylaminophenol; For example, 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate; [3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionic acid and mono- or polyhydric alcohols such as methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, Neopentyl glycol, thiodiethylene glycol , Diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, Ν, Ν'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri Esters with methylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane, and combinations thereof; β- (5-tert-butyl-4-hydroxy -3-methylphenyl) propionic acid and mono- or polyhydric alcohols such as methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol , Neopentyl glycol, thiodi Ethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, Ν, Ν'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, Esters with trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane, and combinations thereof; 13- (3,5-dicyclohexyl-4- Hydroxyphenyl) propionic acid and mono- or polyhydric alcohols such as methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl Glico Thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, Ν, Ν'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexane Esters with diols, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane, and combinations thereof; 3,5-di-tert-butyl -4-hydroxyphenylacetic acid and monohydric or polyhydric alcohols such as methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neo Pentyl glycol Thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, Ν, Ν'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, Esters with trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane, and combinations thereof; compounds containing nitrogen, such as β- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionic acid amides such as N, N′-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N′-bis (3,5-di-tert Butyl-4-hydroxyphenylpropionyl) trimethylenediamine, N, N′-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine; amic acid compounds such as N, N′-diisopropyl- p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, Ν, Ν′-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N′-bis (1- Ethyl-3-methylpentyl) -p-phenylenediamine, N, N′-bis (1-methylheptyl) -p-phenylenediamine, N, N′-dicyclohexyl-p-phenylenediamine, N, N′-diphenyl- p-phenylenediamine, N, N′-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N′-phenyl- -Phenylenediamine, N- (1,3-dimethyl-butyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N '-Phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, such as p, p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4 -Butyrylaminophenol, 4-nonanoylaminofe , 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4′-diamino Diphenylmethane, 4,4′-diaminodiphenylmethane, Ν, Ν, Ν ′, Ν′-tetramethyl-4,4′-diaminodiphenylmethane, 1,2-bis [(2-methyl-phenyl) amino] ethane, 1, 2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ′, 3′-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, monoalkylation and Dialkylated tert-butyl / tert-octyldiphenylamine mixtures, monoalkylated and dialkylated Sopropyl / isohexyl diphenylamine mixture, monoalkylated and dialkylated tert-butyldiphenylamine mixture, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, N-allylphenothiazine, Ν, Ν, Ν ′, Ν′-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine, bis ( 2,2,6,6-tetramethylpiperid-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one and 2,2,6,6-tetramethylpiperidin-4-ol And combinations thereof; aliphatic or aromatic phosphites, esters of thiodipropionic acid or thiodiacetic acid, or dithiocarbamine Acid or dithiophosphoric acid salts, 2,2,12,12-tetramethyl-5,9-dihydroxy-3,7,1 trithiatridecane and 2,2,15,15-tetramethyl-5,12-dihydroxy- 3,7,10,14-tetrathiahexadecane, and combinations thereof; and sulfurized fatty esters, sulfurized fats and sulfurized olefins, and combinations thereof.

Demulsifiers One or more demulsifiers may also be included in the composition. A single demulsifier can be included in the composition, but more than one demulsifier can be included in the composition. Each demulsifier may include one or more solvents that facilitate the dispersion of the demulsifier in the composition. Thus, the one or more demulsifiers and one or more solvents contained therein are collectively referred to as (D) a demulsifier package. When added to the composition, the demulsifier package (D) prevents the fuel with the additive along with the composition from forming an emulsion with water. Specifically, when the fuel with water and additive is mixed, the anti-emulsifier package (D) increases the rate at which the water and fuel with additive is separated into layers, and the water in the fuel layer Reduce the amount, reduce the amount of non-aqueous components in the water, and prevent the formation of an emulsion layer. The properties imparted to the fuel with additives by the demulsifier package (D) are collectively referred to as the demulsifying properties of the demulsifier package (D).

  ASTM test method D1094-07 and ExxonMobil analysis method AM-S529-08 can be used to test the demulsifying properties of the demulsifier package (D). In such tests, the composition comprising the demulsifier package (D) is mixed with the fuel to form a fuel with additives. The fuel with the additive is then mixed with water and tested according to the method as described above to determine the degree of emulsification of the fuel with the additive and water.

  As described in the background, fuel additive compositions and other additives including polyalkenyl succinimides can phase separate over time, particularly at low temperatures (eg, temperatures below 23 ° C.). Exxon Mobil analysis method FWI-013 can be used to test the storage stability (ie, homogeneity and resistance to phase separation) of the composition. The compositions disclosed herein are homogeneous and resistant to phase separation when stored “neat”, that is, in a fuel with no additives. Demulsifiers can provide anti-emulsifying properties to fuels with additives, but demulsifiers can also cause phase separation of the composition over time or when exposed to low temperatures. The demulsifier package (D) used with the composition disclosed herein imparts strong demulsifying properties to the composition and does not cause phase separation of the composition during storage.

  The demulsifier package (D) may include a demulsifier selected from salts of fatty acids, alkylaminocarboxylic acids, organic sulfur compounds (eg, sulfonic acids, alkylaryl sulfonates), polyethers, and combinations thereof. The demulsifier package (D) includes any combination of demulsifiers selected from the chemical genus described in the previous sentence, and may include two or more chemical species from each chemical genus .

Polyetherols contain the reaction product of a base molecule (also known as an initiator) and an alkylene oxide in a chemical reaction known as alkoxylation. The base molecule is selected to confer specific physical properties to the polyetherol, for example, base molecules comprising N or cyclic hydrocarbons can be used to form the polyetherol. The alkylene oxide can be selected from the group of EO, PO, BO, and combinations thereof. Alkoxylation allows control of the hydrophilic-lipophilic balance value (“HLB value”), M _n , and various other properties of the resulting polyetherol. Alkoxylation can be carried out to form polyetherols having “block” structures (block polyethers) and / or “random” structures. In some embodiments, the polyetherol can have a heteric structure. For example, polyetherols may have a heteric (or random) EO, PO structure as a whole. As another example, polyetherols are heteric but may have uniform blocks, such as blocks containing EO and blocks containing PO. As yet another example, polyetherols can have heteric blocks and uniform blocks, such as blocks containing all EO and blocks containing random EO, PO. Thus, the base molecule and the type and amount of alkylene oxide used to alkoxylate the base molecule can be varied to achieve specific properties, such as calculated HLB values and M _n. This can improve the demulsibility of certain demulsifiers in the fuel composition with additives.

  Demulsifier packages (D) include alkoxylated butyl, amyl, and nonylphenol resins, alkoxylated alkylphenol formaldehyde resins, alkoxylated epoxy resins, alkoxylated polyethyleneimines, oxyalkylated alkylphenols, amine alkoxylates, EO polyethers (eg, Nonylphenol ethoxylate), PO polyetherols, EP / PO block polyetherols, and combinations thereof. The polyetherol can be a block copolymer, a random copolymer, or a hybrid thereof. In one embodiment, the demulsifier package (D) comprises a combination of the above exemplary polyetherols.

  As described above, the demulsifier package (D) may also include one or more organic sulfur compounds. Specific non-limiting examples of suitable organosulfur compounds include sulfonic acids, alkylaryl sulfonates, and combinations thereof. Specific, non-limiting examples of suitable sulfonic acids include dodecyl benzene sulfonic acid and other alkyl benzene sulfonic acids. In one embodiment, the demulsifier package (D) comprises sulfonic acid.

  In some embodiments, the demulsifier package (D) contains less than 2,000 ppm, alternatively less than 1,500 ppm, alternatively 100-1,000 ppm sulfur. Thus, in various embodiments, the demulsifier package (D) is commonly used to detect sulfur content in fuels with additives when used in the compositions described herein. Deliver less sulfur to the fuel than can be detected by the devices and test methods used.

  In one embodiment, the demulsifier package (D) is substantially free of sulfur. As used herein with reference to a substantially sulfur-free demulsifier package (D), “substantially free” means that the demulsifier package (D) contains 100 parts by weight of the demulsifier package (D). As a reference, less than about 25 parts, alternatively less than about 10 parts, alternatively less than about 5 parts, alternatively less than about 1 part, alternatively less than about 0.5 part, alternatively less than about 0.2 part, or about It means that the sulfur-containing composition is contained in an amount of less than 0.15 parts by mass or 0 parts by mass. Alternatively, in one embodiment, the demulsifier package (D) is less than 50 mg, alternatively less than 25 mg, alternatively less than 1.5 mg, alternatively less than 1 mg, alternatively less than 0.5 mg, per kg of fuel, at the treatment rates described herein. Less than, alternatively less than 0.2 mg, alternatively less than 0.1 mg, alternatively less than 0.05 mg, alternatively less than 0.01 mg.

  The composition has a demulsifier (or demulsifier package (D)) of 0.5 to 500 mg, alternatively 0.5 to 200 mg, alternatively 0.5 to 100 mg, alternatively 0.5 to 50 mg, alternatively 1 It can be added to the fuel in an amount such that it can be present in the fuel in an amount of 25 mg. Furthermore, the demulsifier package (D) is less than 5 parts by weight, alternatively less than 4 parts by weight, alternatively less than 3 parts by weight, alternatively less than 2.5 parts by weight, alternatively less than 2 parts by weight, or less than 1 part by weight per 100 parts by weight of the composition. Less than 5 parts by weight, alternatively less than 1 part by weight, alternatively less than 0.8 part by weight, alternatively 0.1 to 5 parts by weight, alternatively 0.2 to 2.5 parts by weight, alternatively 0.2 to 2 parts by weight, or It can be present in the composition in an amount of 0.2-1 parts by weight, alternatively 0.2-2 parts by weight, alternatively 0.2-0.8 parts by weight.

Metal Deactivator One or more metal deactivators may also be included in the composition. Non-limiting examples of one or more metal deactivators include benzotriazole and its derivatives, such as 4- or 5-alkylbenzotriazole (eg, triazole) and its derivatives, 4, 5, 6, 7 -Tetrahydrobenzotriazole and 5,5'-methylenebisbenzotriazole; benzotriazole or Mannich bases of triazole, such as 1- [bis (2-ethylhexyl) aminomethyl) triazole and 1- [bis (2-ethylhexyl) aminomethyl ) Benzotriazole; and alkoxyalkyl benzotriazoles such as 1- (nonyloxymethyl) benzotriazole, 1- (1-butoxyethyl) benzotriazole and 1- (1-cyclohexyloxybutyl) triazole and combinations thereof. I can get lost.

  Additional non-limiting examples of one or more metal deactivators include 1,2,4-triazole and its derivatives, such as 3-alkyl (or aryl) -1,2,4-triazole, and Mannich bases of 1,2,4-triazole, such as 1- [bis (2-ethylhexyl) aminomethyl-1,2,4-triazole; alkoxyalkyl-1,2,4-triazole, such as 1- (1 -Butoxyethyl) -1,2,4-triazole; and acylated 3-amino-1,2,4-triazole, imidazole derivatives such as 4,4′-methylenebis (2-undecyl-5-methylimidazole) and Bis [(N-methyl) imidazol-2-yl] carbinol octyl ether, and combinations thereof.

  Further non-limiting examples of one or more metal deactivators include sulfur-containing heterocyclic compounds such as 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole and their Derivatives; and 3,5-bis [di (2-ethylhexyl) aminomethyl] -1,3,4-thiadiazolin-2-one, and combinations thereof. Yet another non-limiting example of one or more metal deactivators includes amino compounds such as salicylidenepropylenediamine, salicylaminoguanidine and salts thereof, and combinations thereof.

Dehazer
One or more smoke suppressants may also be included in the composition. Non-limiting examples of smoke suppressants include alkoxylated phenol-formaldehyde condensates.

Markers One or more markers may also be included in the composition. Markers can be used for coloring and / or traceability of the composition. The marker may also allow quantitative analysis of fuel with additives at refineries, roadsides, or in the laboratory. That is, the marker may allow determination of the amount of composition contained in the fuel with the additive.

Solvent One or more solvents may also be included in the composition. The solvent used in the composition can be an inert, stable, lipophilic (ie, soluble in fuel) organic solvent that boils in the range of about 65 ° C to 205 ° C. For example, aliphatic or aromatic hydrocarbon solvents such as benzene, toluene, xylene or high boiling aromatic hydrocarbons or aromatic thinners are used. Aliphatic alcohols of about 3 to 8 carbon atoms, such as isopropanol, isobutyl carbinol, n-butanol, 2-ethylhexanol, and the like, can also be used in compositions in combination with hydrocarbon solvents. Is suitable.

Composition The composition is not particularly limited in the present disclosure as long as it comprises polyalkenyl succinimide (A), polyisobuteneamine (B), and carrier oil (C).

  In various embodiments, the composition consists essentially of or consists of polyalkenyl succinimide (A), polyisobuteneamine (B), and carrier oil (C). In an embodiment consisting essentially of polyalkenyl succinimide (A), polyisobuteneamine (B), and carrier oil (C), the composition is typically a material or material compound that affects the basic properties of the composition, such as Not including, but not limited to, additional solubilizers.

  In various embodiments, the composition consists essentially of or consists of polyalkenyl succinimide (A), polyisobuteneamine (B), carrier oil (C), demulsifier package (D), and solvent. In an embodiment consisting essentially of polyalkenyl succinimide (A), polyisobuteneamine (B), carrier oil (C), demulsifier package (D), and solvent, the composition affects the basicity of the composition. Does not contain other materials or material compounds.

  In various other embodiments, the composition is substantially free of sulfur. As used herein with respect to a composition that is substantially free of sulfur, “substantially free” means that the composition is less than about 5 parts by weight, or about 4 parts, based on 100 parts by weight of the composition. In an amount of less than part by weight, alternatively less than about 3 parts by weight, alternatively less than about 2 parts by weight, alternatively less than about 1 part by weight, alternatively less than about 0.5 parts by weight, alternatively less than about 0.25 parts by weight, or alternatively 0 parts by weight Means including sulfur-containing compounds.

  The sulfur limit in fuel in many parts of the world is less than 30 ppm, less than 20 ppm, or even less than 10 ppm (mg / kg fuel) sulfur. In general, the sulfur limit in fuels is directed to less than 10 ppm sulfur worldwide. In some embodiments, the composition delivers an amount of sulfur to the fuel that is less than that which can be detected by equipment and test methods commonly used to detect sulfur content in the fuel. In various embodiments, the composition provides the fuel with as much sulfur as the amount of fuel that has not been added additives is “rounded up” to the nearest ppm limit. In some embodiments, the composition is less than 50 mg / kg, alternatively less than 25 mg, alternatively less than 1.5 mg, alternatively less than 1 mg, alternatively less than 0.5 mg, alternatively less than 0 mg / kg of fuel at the treatment rates described herein. Less than 2 mg, alternatively less than 0.1 mg, alternatively less than 0.05 mg, alternatively less than 0.01 mg of sulfur.

  In some embodiments, the composition is based on 100 parts by weight of the composition, 1 to 75 parts by weight of polyalkenyl succinimide (A), 15 to 25 parts by weight of polyisobuteneamine (B), 5 to 70 parts by weight. Part of carrier oil (C), 2 to 94 parts by weight of solvent, and less than 5 parts by weight of demulsifier package (D).

  In another embodiment, the composition is based on 100 parts by weight of the composition, 20 to 35 parts by weight of polyalkenyl succinimide (A), 15 to 25 parts by weight of polyisobuteneamine (B), 5 to 15 parts by weight. Carrier oil (C), 28-55 parts by weight solvent, less than 5 parts by weight demulsifier package (D), and less than 0.5 parts by weight marker.

  In another embodiment, the composition is based on 100 parts by weight of the composition, 4-15 parts by weight of polyalkenyl succinimide (A), 30-60 parts by weight of polyisobutenamine (B), 12-18 parts by weight. Carrier oil (C), 16-20 parts by weight solvent, 0.35-0.5 parts by weight corrosion inhibitor, 0.5-3.5 parts by weight smoke suppressant, and 0.5-1. Contains 5 parts by weight of marker. In one embodiment, the composition comprises a polyalkenyl succinimide (A) in an amount of about 6 parts by weight, a polyisobuteneamine (B) in an amount of about 34.67 parts by weight, and a carrier oil (C ), Each based on the total weight of the composition.

  The present disclosure also provides a process for mixing components, such as a process for mixing polyalkenyl succinimide (A), polyisobuteneamine (B), carrier oil (C), and demulsifier package (D), and solvents and other additives. A method of forming a composition. In various embodiments, the mixing step is not performed with a specific order of addition. For example, all components can be mixed in a single, simultaneous process to form a composition. In other embodiments, the mixing step is performed in a certain order of addition. For example, in one embodiment, the fatty alcohol solvent, the demulsifier package (D), and the marker are mixed together. Next, an aromatic solvent is added to the mixture and mixed, polyisobuteneamine (B) is added to the mixture and mixed, and carrier oil (C) is added to the mixture and mixed. Finally, polyisobutenyl succinimide (A) is added to the mixture and mixed to form the composition.

  The composition can be used as an additive in fuels such as diesel fuel, gasoline fuel, heating oil, and kerosene or middle distillate. When the compositions are used as additives in diesel fuel, they can be in any effective amount, or in an amount of 10 to 10,000 mg, alternatively 10 to 5,000 mg, alternatively 50 to 1,000 mg per kg of diesel fuel. Can be used in When the compositions are used as additives in gasoline fuel, they can be used in any effective amount, or in an amount of 10 to 10,000 mg, alternatively 10 to 5,000 mg, alternatively 50 to 2,000 mg per kg of gasoline fuel. Can be used. When the compositions are used as additives in heating oils, they can be used optionally in effective amounts, or in amounts of 10 to 1,000 mg, or 50 to 500 mg per kg of heating oil.

  The present disclosure also includes a method for improving the fuel consumption of an internal combustion engine. The method includes adding a composition to the fuel. The composition may be added to the fuel in the amounts described in the previous paragraph. For example, in one embodiment of the method, 10 to 10,000 mg of composition is added per kg of fuel.

  The present disclosure also includes a fuel comprising the composition. The composition may be included in the fuel in the amounts described above. For example, 1 kg of fuel may contain 10 to 10,000 mg of composition.

  The following examples are intended to illustrate the present disclosure and should not be considered as limiting the scope of the present disclosure.

Examples Polyisobutenyl succinimides are formed according to the present disclosure. Specifically, the polyisobutenyl succinimide has (1) a C _{40 to} C ₂₀₀ chain length and a number average molecular weight (M _n ) greater than 1,000 g / mol and a terminal double bond content greater than 75 mol%. A reaction product of polyisobutene having a ratio, (2) maleic anhydride, and (3) tetraethylenepentamine, wherein each mole of polyisobutene is functionalized with 1-2 moles of maleic anhydride .

Polyisobutenyl succinimide is added to the fuel, and the fuel with the additive is added to the US Federal Test Procedure-Highway Fuel Efficiency Test (US Environmental Protection Agency Test Protocol, C.F.R. Tested to determine fuel economy according to Part 600, subpart B). Standard US regular unleaded gasoline was used in the test. For each vehicle, fuel consumption was first determined using fuel with no additive, and then with fuel with additive formed at a dose of 190 mg / kg. The fuel efficiency test results are listed in Table 1 below.

  Referring now to Table 1, the use of polyisobutenyl succinimide in the fuel with the additive resulted in an average fuel saving of 2.3% for the five cars tested. Furthermore, the fuel economy benefits of polyisobutenyl succinimide are additional as they show little activity in either type of high frequency reciprocating rig (HFRR) test, as described below in Example 1. It is even more astonishing because it is miscible with other fuel additives.

  Example 1 is a fuel additive composition comprising polyisobutenyl succinimide and is in accordance with the present disclosure. Comparative Examples 1 and 2 are fuel additive compositions containing fuel economy additives known in the art. Specifically, the fuel additive composition of Comparative Example 1 includes a fatty acid amide and the fuel additive composition of Comparative Example 2 includes a propoxylated fatty acid amide. The fuel additive compositions of Example 1 and Comparative Examples 1 and 2 are listed in Table 2 below. The amounts listed in Table 2 are parts by weight based on 100 parts by weight of the fuel additive composition.

In addition, the fuel additive compositions of Example 1 and Comparative Examples 1 and 2 were stored at −20 ° C. for 6 weeks and then tested for evidence of phase separation. The results of the phase separation test are also listed in Table 2 below.

  Referring now to Table 2, the fuel additive composition of Example 1 comprising polyisobutenyl succinimide, polyisobuteneamine, and propoxylate carrier oil is clear even after 6 weeks storage at −20 ° C. and It remains single phase. However, the fuel additive compositions of Comparative Examples 1 and 2 form a separate phase after 6 weeks storage at -20 ° C.

Example 2 is a fuel additive composition according to the present disclosure comprising polyisobutenyl succinimide, polyisobuteneamine, polyether carrier oil, and an anti-emulsifier package. The fuel additive composition of Example 2 is set forth in Table 3 below. To form the fuel additive composition of Example 2, the fatty alcohol solvent, the demulsifier component, and the marker are mixed together. Thereafter, an aromatic solvent was added to the mixture and mixed, polyisobuteneamine was added to the mixture and mixed, and a polyether carrier oil was added to the mixture and mixed. Finally, polyisobutenyl succinimide was added to the mixture and mixed to form the fuel additive composition of Example 2.

  The fuel loaded with the fuel additive composition of Example 2 was tested according to ASTM D 1094-07. The ASTM D 1094-07 test method determines the miscibility of components in gasoline with additives and water and the effect of these components on volume change and the fuel-water interface. In this test method, fuel samples were shaken in a graduated cylinder with phosphate buffer at room temperature. The cleanliness of the glass cylinder, as well as the volume change of the water layer and the appearance of the interface between the layers, were received as a water reaction of the fuel. The fuel with additive added using the fuel additive composition of Example 2 was tested and (1) (a complete lack of all emulsions and / or treated fuel layer in either water layer Settling) and has minimal lacing at the interface between the fuel and the water layer. Thus, the fuel additive composition of Example 2, comprising polyisobutenyl succinimide, polyisobuteneamine, polyether carrier oil, and anti-emulsifier package, was resistant to emulsification upon exposure to water. It was.

  Referring now to Table 4, the miscibility of fuel with additive and water using the fuel additive composition of Example 2 was also tested over repeated timing cycles in a multi-contact test. In this test, each individual cycle is referred to as contact. Specifically, 200 ml of fuel added with the fuel additive composition of Example 2 is mixed with 20 ml of water in a glass container, and set at the highest setting on a mechanical reciprocating shaker. Shake for 5 minutes. Thereafter, the sample was held for 24 hours without stirring, and observation was performed regarding the fuel layer, the water layer, and the interface between them. The fuel was then decanted from the glass container, 200 ml of fresh fuel with additives added using the fuel additive composition of Example 2 was added to the glass container, the cycle was repeated 10 times, and the results are shown in Table 4 Describe. The number of contacts is the number of times that the fuel and water with additives are in contact, so there are 10 contacts per test, with each contact being 24 hours apart.

The emulsion was observed for the mixture of fuel additive composition of Example 2 and water as follows:
0) Both water layer and fuel layer are clean without racing skins or bubbles;
1) A slight skin at the interface between water and fuel layer that does not break when the bottle is tilted;
2) A slight skin at the oil-water interface that is heavier than 1) and usually with dirt and bubbles on the skin (no evidence of emulsion);
3) Minimum amount of emulsion at the bottom and center of the bottle. This is a circular shape with a diameter of about 1/4 to 1 inch;
4) Emulsion at the bottom of the bottle with approximately the same amount of emulsion at the interface between water and fuel layer (3));
5) The emulsion at the bottom of the bottle moves upward and the thickness of the emulsion at the interface is slightly thicker than 4).
6) The amount of emulsion increases with the emulsion film that forms on the side of the bottle surrounding the water layer;
7) The emulsion at the bottom of the water layer is almost solid and the water layer is hardly visible;
8) Emulsions with bubbles and aqueous layer are no longer visible;
9) Emulsions where the emulsion slightly above 75% is a solid;
10) The emulsion is almost completely solid, with only a few bubbles visible; and 11) The emulsion is completely solid.

Furthermore, observations regarding the water layer and the fuel layer were made using “C” for transparency and “H” for turbidity.

  Referring now to Table 4, the fuel additive composition of Example 2 comprising polyisobutenyl succinimide, polyisobuteneamine, polyether carrier oil, and demulsifier package is exposed to multi-contact exposure to water. In some cases, it was resistant to emulsification.

Referring now to Table 5, the storage stability of the fuel additive composition of Example 2 was also tested at 23 ° C and -15 ° C. To test storage stability, 100 ml of the fuel additive composition of Example 2 was added to a centrifuge vessel having a conical bottom end. Centrifugal containers are generally transparent and are marked in quantity on the sides. The conical portion of the centrifuge vessel is approximately the size of a sharp pencil tip. Samples were held for 4 weeks and observations were made weekly for layer separation and the amount of precipitate formed. After the test, a digital photograph of the centrifuge tip of the centrifuge container was taken.

  Referring now to Table 5, the fuel additive composition of Example 2 comprising polyisobutenyl succinimide, polyisobutene amine, polyether carrier oil, and demulsifier package was prepared at 23 ° C. and −15 ° C. for 4 weeks. It remained transparent and single phase after storage. Furthermore, there was little (less than 0.05 ml per 100 ml composition) or no precipitate formation at the bottom of the clear centrifuge vessel.

  The appended claims are not limited to the expressions and specific compounds, compositions, or methods set forth in the detailed description, which may vary between the specific embodiments falling within the scope of the appended claims. It should be understood. For any Markush group that relies on this specification to describe particular features or aspects of the various embodiments, each different, special and / or unexpected result is independent of all other Markush members. May be obtained from each member of the Markush group. Each member of the Markush group may be relied upon individually or in combination to provide adequate support for specific embodiments within the scope of the appended claims.

  Furthermore, any ranges and sub-ranges dependent on describing various embodiments of the present disclosure are included within the scope of the appended claims, independently and comprehensively, and such values are considered herein. It should be understood that all ranges, including integer values and / or fractional values, are described and assumed, even if not explicitly stated therein. Those skilled in the art will appreciate that the listed ranges and subranges fully describe and enable the various embodiments of the present disclosure, and that such ranges and subranges are relevant one half, one third, four minutes. It will be readily understood that it can be described in more detail in 1/5, etc. By way of example only, the “0.1-0.9” range is the lower third, ie 0.1-0.3, the middle third, ie 0.4-0.6. Can be described in more detail in the upper third, i.e. 0.7-0.9, which are included individually and comprehensively within the scope of the appended claims, individually and And / or is comprehensively dependent and provides appropriate support for certain embodiments within the scope of the appended claims. In addition, for terms that define or modify ranges such as “at least”, “greater”, “less than”, “below”, etc., it is understood that such terms include subranges and / or upper or lower limits Should. As another example, a range of “at least 10” essentially includes at least 10-35 subranges, at least 10-25 subranges, 25-35 subranges, etc., each subrange being individually And / or comprehensively, and provides appropriate support for specific embodiments within the scope of the appended claims. Finally, individual numerical values within the disclosed ranges may depend on particular embodiments within the scope of the appended claims and provide adequate support for such embodiments. For example, the range “from 1 to 9” includes various individual integers, such as 3, and individual numerical values (or fractions) including a decimal point, such as 4.1, which are specified within the scope of the appended claims. Depending on the embodiment and provides appropriate support for the embodiment.

  Further, the mass percentages or other numerical values or ranges of the above values may vary and may be further defined as any value or range of values, both in whole and in part, within these ranges and values above. And / or from the above values and / or ranges of values ± 5%, ± 10%, ± 15%, ± 20%, ± 25%, ± 30%, etc., as long as the variation remains within the scope of this disclosure It is possible that only changes are allowed. As an example, any of the numerical values or ranges described herein may be further defined as “about” and may themselves vary according to this paragraph. As used in the previous sentence, the word about means quite close.

  It should be understood that the present disclosure has been described by way of example, and that the terms used are intended to be descriptive in nature rather than limiting. Many modifications and variations of the present disclosure are possible in light of the above teachings, and the disclosure may be implemented in other ways than those specifically described.

Claims (29)

A fuel additive composition comprising:
(A) polyalkenyl succinimide,
(1) Hydrocarbyl dicarboxylic acid production reaction intermediate,
(A) a polyolefin comprising C _{2 to} C ₁₈ olefin units and having a number average molecular weight (M _n ) of about 500 to 5,000 g / mol, and (b) a C _{4 to} C ₁₀ monounsaturated acid reactant. Including reaction products,
The hydrocarbyl dicarboxylic acid generating reaction intermediate comprising 0.5 to 10 dicarboxylic acid generating moieties per molecule of the polyolefin; and (2) a demand selected from the group of amines, alcohols, amino alcohols, and combinations thereof. The polyalkenyl succinimide comprising a reaction product of a nuclear reactant;
The fuel additive composition comprising: (B) a monofunctional or polyfunctional polyisobuteneamine; and (C) a carrier oil selected from the group of mineral oils, polyethers, polyetheramines, esters, and combinations thereof. .   The fuel additive composition of claim 1, further comprising (D) a demulsifier package.   The fuel additive composition of claim 2, wherein the demulsifier package (D) comprises a demulsifier selected from fatty acid salts, alkylaminocarboxylic acids, organic sulfur compounds, polyetherols and combinations thereof.   The polyetherol is an alkoxylated alkylphenol resin, alkoxylated alkylphenol formaldehyde resin, alkoxylated epoxy resin, alkoxylated polyethyleneimine, amine alkoxylate, ethoxylated polyetherol, propoxylated polyetherol, ethoxylated-propoxylated 4. The fuel additive composition according to claim 3, selected from polyetherols and combinations thereof.   The fuel additive composition according to claim 4, wherein the polyetherol is a block copolymer.   The fuel additive composition according to claim 4, wherein the polyetherol is a random copolymer.   The fuel additive composition according to any one of claims 2 to 6, wherein the demulsifier package (D) is substantially free of sulfur.   The fuel additive composition according to any one of claims 3 to 6, wherein the organic sulfur compound contains a sulfonic acid.   The fuel additive composition according to any one of claims 1 to 8, wherein the polyolefin (a) is a first reactive polyisobutene having a content of terminal double bonds exceeding 50 mol%. The C _{4 to} C ₁₀ monounsaturated acid reactant (b) is selected from the group of maleic acid, maleic anhydride, functional derivatives thereof, and combinations thereof. A fuel additive composition according to claim 1.   The fuel additive composition according to any one of claims 1 to 10, wherein the hydrocarbyl dicarboxylic acid production reaction intermediate (1) is a polyalkenyl succinic anhydride.   The fuel additive composition according to any one of claims 1 to 11, wherein the hydrocarbyl dicarboxylic acid production reaction intermediate (1) is polyisobutenyl succinic anhydride.   The fuel additive composition according to any one of claims 1 to 12, wherein the nucleophilic reactant (2) comprises tetraethylenepentamine. The nucleophilic reactant (2), one molecule is _C 2 _{-C 40} polyalkylene polyamine containing 2 to 9 nitrogen atoms per nucleophilic reactant per equivalent of 0.1 to 3.0 moles of a dicarboxylic The fuel additive composition according to any one of claims 1 to 13, wherein an acid moiety reacts to form the polyalkenyl succinimide (A). The reaction intermediate (1), wherein the polyalkenyl succinimide (A) is further defined as a polyisobutylene having a number average molecular weight ( _Mn ) of about 500 to 5,000 molecular weight substituted with a succinic anhydride moiety; 1 is a reaction product of a C ₂ -C ₄₀ further defined by the nucleophilic reactant polyalkylene polyamine containing 3 to 9 nitrogen atoms per molecule (2), one of the claims 1 to 14 2. The fuel additive composition according to item 1. The polyalkenyl succinimide (A) is
(1) a polyisobutenyl succinic anhydride; and (2) a reaction product of a first amine,
In doing so, the polyisobutenyl succinic anhydride first reacts with the alcohol and then with the first amine to form the polyisobutenyl succinimide, either unreacted or cleaved alcohol. 16. The fuel additive composition according to any one of claims 1 to 15, wherein the alcohol that is is optionally removed. The alcohol is a monohydric alcohol of the formula R ¹ OH, wherein R ¹ is a linear or branched, cyclic or branched cyclic alkyl of ¹ to 16 carbon atoms The fuel additive composition of claim 16, selected from the group consisting of: and combinations thereof. Said first amine has the following formula:
_{H 2 N (CH 2) x} -NH - [(CH 2) y -NH] z - (CH 2) x NH 2
18. A fuel additive composition according to claim 16 or 17, wherein x and y are each independently an integer from 1 to 5 and z is an integer from 0 to 8, or a mixture thereof. . The polyalkenyl succinimide (A) has the following general structure:
(A) the following general structure;

(Where m is an integer from 2 to 80)
19. A fuel additive composition according to any one of claims 1 to 18 having a polyisobutenyl succinimide having   The monofunctional or polyfunctional polyisobuteneamine (B) has a content of terminal double bonds in excess of 50 mol% to form an oxo intermediate, and subsequent hydroformylation of the second reactive polyisobutene 20. The fuel additive composition according to any one of claims 1 to 19, comprising a reaction product formed via reductive amination of an oxo intermediate. A second reactive polyisobutene in which the monofunctional or polyfunctional polyisobuteneamine (B) has a content of terminal double bonds of more than 50 mol%;
HNR ² R ³
Wherein R ² and R ³ are each independently H, C ₁ -C ₁₈ -alkyl, C ₂ -C ₁₈ -alkenyl, C ₄ -C ₁₈ -cycloalkyl, C ₁ -C ₁₈ -alkylaryl, hydroxy -C 1 _-C 18 _- alkyl, poly (oxyalkyl), or a polyalkylene polyamine or a polyalkylene amine radical; or, together with the nitrogen atom to which they are attached, form a heterocyclic ring)
21. The fuel additive composition according to any one of claims 1 to 20, comprising a reaction product with a second amine having:   The fuel additive composition according to claim 20 or 21, wherein the second reactive polyisobutene has a dispersity of less than 6. 23. The fuel additive composition according to any one of claims 20 to 22, wherein the second reactive polyisobutene has a number average molecular weight ( _Mn ) of 500 to 5,000 g / mol. The carrier oil (C) has the following formula:
R ⁴ — [O—CH ₂ —CH (CH ₃ )] _n —OH
(In the formula, n is an integer of 8 to 35 and R ⁴ is a long chain or branched chain C ₈ -C ₁₈ -alkyl or C ₈ -C ₁₈ -alkenyl)
24. The fuel additive composition according to any one of claims 1 to 23, comprising a propoxylate carrier oil having   25. The fuel additive composition according to any one of claims 1 to 24, wherein the carrier oil (C) comprises propoxylated isotridecanol.   1 to 75 parts by mass of the polyalkenyl succinimide (A), 5 to 70 parts by mass of the polyisobuteneamine (B), and 2 to 94 parts by mass of the carrier oil with respect to 100 parts by mass of the fuel additive composition. The fuel additive composition according to any one of claims 2 to 25, comprising (C) and less than 5 parts by mass of the demulsifier package (D).   27. A fuel to which an additive containing 10 to 10,000 mg of fuel additive composition according to any one of claims 1 to 26 is added per kg of fuel.   28. The additive-added fuel of claim 27, wherein less than 1.5 mg of sulfur per kg of additive-added fuel is provided to the additive-added fuel by the fuel additive composition.   A method for reducing the fuel consumption of an internal combustion engine, comprising the step of adding the fuel additive composition according to any one of claims 1 to 28 to a fuel.