Polyacrylate antifoam component for diesel fuel

Abstract

Disclosed is an antifoam component for diesel fuel comprising at least one poly(acrylate) copolymer. Also disclosed are poly(acrylate) polymers prepared by polymerizing (meth)acrylate monomers comprising C1-C 30 alkyl esters of (meth)acrylic acid ("solubility monomers"); (ii) (meth)acrylate monomers comprising C5-C 12 alkyl esters of (meth)acrylic acid ("surface tension monomers"); and (iii) optionally at least one additional monomer comprising solubility monomers, surface tension monomers, monomers comprising C1-C 30 alkyl esters of (meth)acrylic acid ("solubility monomers"); (ii) (meth)acrylate monomers comprising C5-C alkyl esters of (meth)acrylic acid ("surface tension monomers"); and (iii) optionally at least one additional monomer comprising solubility monomers, surface tension monomers, monomers comprising C1-C

Description

[0001] This application is a divisional application of patent application No. 201780070830.3, filed on September 21, 2017, entitled "Polyacrylate defoaming component for diesel fuel". Technical Field

[0002] The disclosed technology relates to compounds that can be used as defoaming components in diesel fuels. In particular, diesel fuel compositions and concentrates containing said defoaming components and their uses are disclosed. Background Technology

[0003] When diesel fuel is pumped into a vehicle's fuel tank ("filling"), it has a tendency to foam and is particularly problematic in point-of-sale applications. A large amount of foam is rapidly generated as diesel fuel is pumped into the tank, significantly reducing the amount of diesel that can be pumped into the tank with each fill.

[0004] Reducing the amount of foam generated during filling would significantly increase the volume of diesel tanks, but there are no viable defoaming options for the North American market. Currently, only nitrogen, oxygen, carbon, and / or hydrogen (“NOCH”)-based chemicals are permitted in North American diesel applications. This excludes known siloxane defoamers as a viable option. Some fluorinated (poly)acrylate defoamers have been shown to function as defoamers in diesel fuels, but they also prevent fluorination in diesel additives. Therefore, there is a need for non-siloxane, fluorine-free defoamers for diesel fuels. Summary of the Invention

[0005] Compositions comprising poly(acrylate) polymers prepared by polymerizing certain (meth)acrylate monomers have surprisingly shown to be effective defoamers in diesel fuel. These (meth)acrylate monomers include C1-C4 monomers containing (meth)acrylic acid. 30 Alkyl ester (meth)acrylate monomers (“multifunctional monomers”). In some embodiments, the multifunctional monomer may include C2-C of (meth)acrylate. 27 Alkyl esters. Weight-average molecular weight (Mn) of poly(acrylate) polymers. w The poly(acrylate) polymer can be from 50,000 to 300,000 Daltons (“Da”) or from 70,000 to 200,000 Da. In other embodiments, the poly(acrylate) polymer can be a homopolymer.

[0006] In other embodiments, the multifunctional monomer may include the C2-C of (meth)acrylic acid. 12 Alkyl esters. Exemplary multifunctional monomers include, but are not limited to, monomers comprising tert-butyl (meth)acrylate and trimethylhexyl (meth)acrylate.

[0007] In some embodiments, a composition comprising at least one poly(acrylate) polymer is prepared by polymerizing the following substances: (i) a (meth)acrylate monomer comprising a C1-C4 alkyl ester of (meth)acrylate (“solubility monomer”); (ii) a C5-C4 alkyl ester of (meth)acrylate. 12 (iii) Alkyl ester (meth)acrylate monomers (“surface tension monomers”); and optionally at least one other monomer, which may comprise a solubility monomer, a surface tension monomer, having a C1-C bond of (meth)acrylate. 30 Alkyl ester monomers (“multifunctional monomers”), or combinations thereof. In other embodiments, the poly(acrylate) polymer may be polymerized using: (i) 5% to 95% by weight of a solubility monomer; (ii) 95% to 5% by weight of a surface tension monomer; (iii) optionally, 2% to 10% by weight of at least one of the other monomers.

[0008] In some embodiments, the poly(acrylate) polymer can be at least one of a copolymer, block polymer, random polymer, terpolymer, or combination thereof. In some embodiments, the poly(acrylate) polymer may have an M value of 50,000 to 300,000 Da or 70,000 to 200,000 Da. w .

[0009] In some embodiments, the composition may comprise a poly(acrylate) polymer having units having the structure of formula (I):

[0010]

[0011] Where R 1 For H or CH3; R 2 For C2-C 10 Straight-chain or branched hydrocarbon groups; R 3 It is a C2-C4 straight-chain or branched hydrocarbon group; R 4 It can be H, OH, or CH3; n1 is an integer from 120 to 3000; n2 is an integer from 0 to 3. In some embodiments, R 2 and / or R 3 It is branched. In other implementations, R 2 It is a linear chain and R 3 It is a branched chain.

[0012] In some embodiments, the multifunctional monomer and / or solubility monomer may comprise C1-C4 alkyl esters of (meth)acrylic acid. In other embodiments, the multifunctional monomer and / or surface tension monomer may comprise C5-C4 alkyl esters of (meth)acrylic acid. 12Alkyl esters. In some embodiments, the multifunctional monomer and / or solubility monomer may include tert-butyl (meth)acrylate, ethyl (meth)acrylate, or combinations thereof. In other embodiments, the multifunctional monomer and / or surface tension monomer may include trimethylhexyl (meth)acrylate. In other embodiments, the solubility monomer may include tert-butyl (meth)acrylate, ethyl (meth)acrylate, or combinations thereof, and the surface tension monomer may include trimethylhexyl (meth)acrylate.

[0013] The aforementioned poly(acrylate) polymer can be added to diesel fuel to reduce the amount of foam generated in the diesel fuel. Based on the total weight of the diesel fuel composition, the poly(acrylate) polymer may be present in the diesel fuel in an amount of 2 ppm to 1000 ppm, or 2 ppm to 100 ppm by weight. Therefore, a method for reducing foam in diesel fuel is also disclosed. The use of at least one poly(acrylate) polymer for reducing foam in diesel fuel is also disclosed.

[0014] A method for reducing the amount of foam generated when filling a vehicle's diesel tank is also disclosed. This method may include adding at least one poly(acrylate) polymer prepared by polymerizing (meth)acrylate monomers to the diesel fuel. The poly(acrylate) polymer may be as described above. Attached Figure Description

[0015] Figure 1 It is a graph showing the surface tension of various poly(acrylates) with different carbon chain lengths. Detailed Implementation

[0016] Various preferred features and implementation schemes will be described below with non-limiting description.

[0017] The disclosed technology provides compositions comprising defoaming components, said defoaming components including poly(acrylate) copolymers. Without limiting this disclosure to the operational theory disclosed herein, it is believed that the defoaming components disrupt foam bubbles by adsorbing onto the bubble surface and reducing its surface tension. Furthermore, the effectiveness of the defoaming component in a given fluid is considered to be a function of two factors relative to a large volume of fluid. The first factor is the solubility of the component in a large volume of fluid. Generally, defoamers with poor solubility (insoluble or almost insoluble) in a fluid have improved performance than readily soluble defoamers. The second factor is the surface tension of the component. Generally, defoaming components with lower surface tension are more effective as defoaming components than those with higher surface tension. Figure 1 It is a graph showing the surface tension of various poly(acrylates) with different carbon chain lengths.

[0018] Traditionally, copolymers of 2-ethylhexyl (meth)acrylate (EHAT or EHMA) and ethyl (meth)acrylate (EAT or EMA) have been used to prepare poly(acrylate) polymers in many organic fluids. These two monomer systems can be tailored to the fluid at hand by adjusting the monomer ratio as follows: a larger percentage of EAT results in lower solubility, while a larger percentage of EHAT results in lower surface tension.

[0019] However, for diesel fuel, the molecular weight (M) w EHAT / EAT-based poly(acrylate) polymers with a Da of 40,000-100,000 are not effective defoaming components because they do not provide the combination of the required surface tension and solubility properties. For example, the minimum EAT content required in poly(acrylate) polymers to impart insolubility to diesel fuel is 55% by weight. However, at this level, the surface tension properties of the defoamer are incompatible with diesel fuel. Similarly, at 100% by weight, EHAT-based polymer formulations have sufficiently low surface tension to be active in diesel fuel, but are too soluble and cannot form the necessary defoamer droplets.

[0020] Surprisingly, it was found that the solubility and surface tension of poly(acrylate) polymers can be altered not only by the amount of (meth)acrylate monomers used but also by the type of (meth)acrylate monomers. The choice of certain (meth)acrylate monomers can help drive the solubility or surface tension properties of the resulting poly(acrylate) polymer in the desired direction.

[0021] As used herein, the term "poly(acrylate) polymer" is a polymer derived from a monomer comprising an alkyl ester of (meth)acrylic acid. Poly(acrylate) polymers are commonly referred to as polyacrylates or acrylics. The terms "(meth)acrylic acid," "(meth)acrylate," and related terms include the group consisting of acrylates and methacrylates, where methyl is optional. For example, the term (meth)acrylic acid includes acrylic acid and methacrylic acid. Thus, in some embodiments, (meth)acrylate or acrylate may comprise at least one acrylate, acrylic acid, methacrylate, methacrylic acid, or a combination thereof.

[0022] When reference is made to a particular monomer incorporated into or used in the preparation of the poly(acrylate) polymers disclosed herein, those skilled in the art will recognize that the monomer is incorporated into the poly(acrylate) polymer as at least one unit.

[0023] Surprisingly, it was found that C1-C of (meth)acrylic acid... 30Alkyl ester (meth)acrylate monomers produce poly(acrylate) polymers with solubility and surface tension properties, making them effective defoaming components in diesel fuels. Therefore, these C1-C monomers with (meth)acrylate... 30 Alkyl ester (meth)acrylate monomers are referred to herein as "multifunctional monomers". Therefore, compositions comprising diesel fuel and at least one poly(acrylate) polymer are disclosed, said poly(acrylate) polymer being polymerized by polymerization of C1-C4 groups containing (meth)acrylic acid. 30 It is prepared by using alkyl ester (meth)acrylate monomers (“multifunctional monomers”). Exemplary multifunctional monomers include tert-butyl (meth)acrylate, ethyl (meth)acrylate, and trimethylhexyl (meth)acrylate.

[0024] As used herein, when describing alkyl esters of (meth)acrylic acid, C x -C y It refers to the number of carbon atoms in the alkyl group that is attached to the oxygen in the (meth)acrylate moiety, and does not include the number of carbon atoms in the (meth)acrylate moiety itself.

[0025] In some embodiments, the multifunctional monomer may comprise the C2-C of (meth)acrylic acid. 27 Alkyl ester. In other embodiments, the multifunctional monomer may comprise the C2-C of (meth)acrylic acid. 12 Or C2, C3, C4, C5, C6, C7, C8, C9, C 10 C 11 Or C 12 Alkyl esters. Exemplary multifunctional monomers include, but are not limited to, monomers comprising tert-butyl (meth)acrylate or trimethylhexyl (meth)acrylate, 3,3-dimethylbutyl (meth)acrylate, neopentyl (meth)acrylate, or combinations thereof. In other embodiments, the poly(acrylate) polymer prepared from the multifunctional monomer may be a homopolymer.

[0026] Other (meth)acrylate monomers were found to primarily affect only one factor in the resulting poly(acrylate) polymer. The (meth)acrylate monomers that primarily affect the solubility of the resulting poly(acrylate) polymer are referred to herein as "solubility" monomers. These solubility monomers are (meth)acrylate monomers comprising C1-C4 alkyl esters of (meth)acrylic acid. Exemplary solubility monomers include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate, polyalkylene glycol (“PAG”) (meth)acrylate, and combinations thereof.

[0027] Similarly, the (meth)acrylate monomers that primarily affect the surface tension of the resulting poly(acrylate) polymers are referred to herein as "surface tension" monomers. These surface tension monomers are C5-C monomers containing (meth)acrylic acid. 12 Alkyl ester (meth)acrylate monomers. Exemplary surface tension monomers include, but are not limited to, 2-ethylhexyl (meth)acrylate, 3,5,5-trimethylhexyl (meth)acrylate, and combinations thereof.

[0028] Therefore, compositions comprising at least one poly(acrylate) polymer prepared by polymerizing a solubility monomer and a surface tension monomer are also disclosed. In some embodiments, the poly(acrylate) polymer can be prepared by polymerizing: (i) a (meth)acrylate monomer comprising a C1-C4 alkyl ester of (meth)acrylic acid (“solubility monomer”); (ii) a C5-C4 alkyl ester of (meth)acrylic acid. 12 (iii) Alkyl ester (meth)acrylate monomers (“surface tension monomers”); and optionally at least one other monomer, which may comprise a solubility monomer, a surface tension monomer, having a C1-C of (meth)acrylate. 30 Monomers of alkyl esters (“multifunctional monomers”), or combinations thereof.

[0029] In other embodiments, the poly(acrylate) polymer may be polymerized using: (i) 5% to 95% by weight of a solubility monomer; (ii) 95% to 5% by weight of a surface tension monomer; and (iii) optionally, 2% to 10% by weight of the at least one additional monomer.

[0030] The poly(acrylate) polymer can be at least one of copolymers, block polymers, random polymers, terpolymers, or combinations thereof. In some embodiments, the poly(acrylate) polymer defoaming component used herein typically has a weight-average molecular weight (Mn) of at least 13,000 Da. w In some embodiments, the M of the poly(acrylate) polymer w The range is 50,000 to 300,000 Da, or 70,000 to 200,000 Da.

[0031] As used in this article, weight-average molecular weight (M w Measurements were performed using gel permeation chromatography (“GPC”) based on polystyrene standards (Waters Alliance e2695). The instrument is equipped with a refractive index detector and Waters Empower... TMData acquisition and analysis software. The columns were polystyrene / divinylbenzene (PLgel, (3" Mixed-C" and 100 Å, 5 μm particle size), available from Agilent Technologies). For the mobile phase, individual samples were dissolved in tetrahydrofuran and filtered through a PTFE filter before being injected into the GPC port.

[0032] Waters Alliance e2695 operating conditions:

[0033] Column temperature: 40℃

[0034] Autosampler control: Run time: 45 minutes

[0035] Injection volume: 300 microliters

[0036] Flow rate: 1.0 ml / min

[0037] Differential refractometer (RI) (2414): Sensitivity: 16; Scale factor: 20

[0038] Those skilled in the art will understand that number-average molecular weight (“M”) n () can be measured using techniques similar to those described above.

[0039] The poly(acrylate) polymer defoaming components disclosed herein can be prepared by methods known in the art. Polymerization can be carried out in bulk, emulsion, or solution in the presence of a free radical release agent as a catalyst and in the presence or absence of a known polymerization regulator. In one embodiment, the defoamer can be polymerized in the presence of toluene. In another embodiment, the defoamer can be polymerized in a hydrocarbon oil.

[0040] In some embodiments, the poly(acrylate) polymer may comprise units having the structure of formula (I):

[0041]

[0042] Where R 1 For H or CH3; R 2 For C2-C 10 Straight-chain or branched hydrocarbon groups; R 3 It is a C2-C4 straight-chain or branched hydrocarbon group; R 4 It can be H, OH or CH3; n1 is an integer from 120 to 3000; n2 is an integer from 0 to 3.

[0043] In some implementation schemes, R 2 and / or R 3 It is branched. In other implementations, R 2 It is a linear chain and R 3 It is a branched chain.

[0044] As used herein, the term "hydrocarbon substituent" or "hydrocarbon group" is used in its common sense, as is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and possessing predominantly hydrocarbon characteristics. Examples of hydrocarbon groups include:

[0045] Hydrocarbon substituents, namely aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic- and alicyclic-substituted aromatic substituents, as well as cyclic substituents in which the ring is completed through another part of the molecule (e.g., two substituents together form a ring).

[0046] Substituted hydrocarbon substituents, i.e. substituents containing non-hydrocarbon groups, do not alter the primary hydrocarbon properties of the substituent (e.g., halogens (especially chlorine and fluorine), hydroxyl groups, alkoxy groups, mercapto groups, alkyl mercapto groups, nitro groups, nitroso groups, and thiooxy groups) in the context of this invention.

[0047] In the context of this invention, a heterosubstituent, i.e., a substituent having a predominantly hydrocarbon characteristic, contains heteroatoms other than carbon in the ring or chain, or otherwise consists of carbon atoms and includes substituents as pyridyl, furanyl, thiophene, and imidazolyl groups. Heteroatoms include sulfur, oxygen, and nitrogen. Typically, for every ten carbon atoms in the hydrocarbon group, there will be no more than two, or no more than one, non-hydrocarbon substituent; or, the hydrocarbon group may be devoid of non-hydrocarbon substituents. In one embodiment, the hydrocarbon group is devoid of halogen substituents.

[0048] The surface tension of poly(acrylate) polymers varies with the number of carbon atoms in the (meth)acrylate monomer used to prepare the polymer. In some embodiments, the surface tension monomer may comprise C7, C8, C9, C6 atoms of (meth)acrylic acid. 10 C 11 Or C 12 Alkyl esters. In some embodiments, the surface tension monomer may comprise a C9 alkyl ester of (meth)acrylic acid. It has been further found that surface tension monomers with branched alkyl groups tend to produce poly(acrylate) polymers with lower surface tension properties than monomers with the same number of carbon atoms in a linear configuration. Therefore, in some embodiments, R 2 and / or R 3 It can be branched. In other implementations, R 2 It can be a linear chain, R 3 It can be branched. For a given number of carbon atoms, the (meth)acrylate monomer with the lowest surface tension tends to contain a neopentyl group having the structure of formula (II):

[0049]

[0050] Therefore, in some embodiments, (meth)acrylate monomers comprising a terminal neopentyl group are disclosed. Exemplary monomers include, but are not limited to, monomers comprising 2,2-dimethylheptane, 2,2,4-trimethylhexane, 2,2,4,4-tetramethylpentane, 2,2,5-trimethylhexane, and combinations thereof as terminal neopentyl groups. In another embodiment, the surface tension monomer may comprise a C9 alkyl ester of (meth)acrylate having a terminal neopentyl group.

[0051] In some embodiments, the multifunctional monomer and / or solubility monomer may comprise C1-C4 alkyl esters of (meth)acrylic acid. In other embodiments, the multifunctional monomer and / or surface tension monomer may comprise C5-C4 alkyl esters of (meth)acrylic acid. 12 Alkyl esters. In some embodiments, the multifunctional monomer and / or solubility monomer may comprise tert-butyl (meth)acrylate. In other embodiments, the multifunctional monomer and / or surface tension monomer may comprise trimethylhexyl (meth)acrylate. In other embodiments, the solubility monomer may comprise tert-butyl (meth)acrylate, and the surface tension monomer may comprise trimethylhexyl (meth)acrylate.

[0052] In other embodiments, compositions comprising at least two poly(acrylate) polymers are disclosed. The composition may comprise C1-C polymers containing (meth)acrylic acid, polymerized by means of polymerization. 30 A first poly(acrylate) polymer prepared from alkyl ester (meth)acrylate monomers (“multifunctional monomers”) and a second poly(acrylate) polymer prepared by polymerizing: (i) (meth)acrylate monomers comprising C1-C4 alkyl esters of (meth)acrylate (“solubility monomers”); (ii) (meth)acrylate monomers comprising C5-C4 alkyl esters of (meth)acrylate. 12 (iii) Alkyl ester (meth)acrylate monomers (“surface tension monomers”); optionally at least one other monomer comprising a solubility monomer, a surface tension monomer, or a C1-C group comprising (meth)acrylate. 30 Monomers of alkyl esters (“multifunctional monomers”), or combinations thereof.

[0053] The aforementioned poly(acrylate) polymer can be added to diesel fuel to reduce the amount of foam generated in the diesel fuel. Based on the total weight of the diesel fuel composition, the poly(acrylate) polymer can be present in the diesel fuel in an amount from 2 ppm to 1000 ppm by weight, or from 2 ppm to 100 ppm by weight. Therefore, a method for reducing foam in diesel fuel is also disclosed. The use of poly(acrylate) polymer to reduce foam in diesel fuel is also disclosed.

[0054] A method for reducing the amount of foam generated when filling a vehicle's diesel tank is also disclosed. This method may include adding a poly(acrylate) polymer, prepared by polymerizing (meth)acrylate monomers, to the diesel fuel. The poly(acrylate) polymer may be as described above.

[0055] Fuels and fuel compositions

[0056] The fuel compositions described herein may comprise fuels that are liquid at room temperature and can be used to fuel an engine. Fuels are typically liquid under ambient conditions, such as room temperature (20 to 30°C). Fuels may be hydrocarbon fuels, non-hydrocarbon fuels, or mixtures thereof. Hydrocarbon fuels may be diesel fuels as defined in EN 590 or ASTM standard D975. Hydrocarbon fuels may be hydrocarbons prepared by gas-liquid methods, including, for example, hydrocarbons prepared by methods such as the Fischer-Tropsch process.

[0057] Non-hydrocarbon fuels may include transesterified oils and / or fats from plants and animals, such as rapeseed methyl ester and soybean methyl ester. Mixtures of hydrocarbon and non-hydrocarbon fuels may include, for example, diesel fuel and ethanol, and diesel fuel and transesterified vegetable oils, such as rapeseed methyl ester. In one embodiment of the invention, the liquid fuel is an emulsion of water in a hydrocarbon fuel, a non-hydrocarbon fuel, or a mixture thereof.

[0058] In several embodiments, the fuel may have a sulfur content of 5000 ppm or less, 1000 ppm or less, 300 ppm or less, 200 ppm or less, 30 ppm or less, or 10 ppm or less by weight. In another embodiment, the fuel may have a sulfur content of 1 to 100 ppm by weight.

[0059] The fuel is typically present in the fuel composition in an amount greater than 50% by weight, or in other embodiments, greater than 90% by weight, greater than 95% by weight, greater than 99.5% by weight, or greater than 99.8% by weight.

[0060] In some embodiments, the fuel composition may contain at least one combustion improver. Combustion improvers include, for example, octane and cetane number improvers. Suitable cetane number improvers are, for example, aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate, and peroxides such as di-tert-butyl peroxide.

[0061] In yet another embodiment, the fuel composition comprises an antifoaming component of the disclosed technology as described above and at least one demulsifier. Suitable demulsifiers may include, but are not limited to, aryl sulfonates and polyalkoxylated alcohols, such as polyethylene oxide and polypropylene oxide copolymers. The demulsifier may also comprise nitrogen-containing compounds, such as oxazoline and imidazoline compounds and fatty amines, as well as Mannich compounds. Mannich compounds are reaction products of alkylphenols and aldehydes (especially formaldehyde) and amines (especially amine condensates and polyalkylene polyamines). The materials described in the following U.S. patents are illustrative: U.S. Patent Nos. 3,036,003; 3,236,770; 3,414,347; 3,448,047; 3,461,172; 3,539,633; 3,586,629; 3,591,598; 3,634,515; 3,725,480; 3,726,882; and 3,980,569 are incorporated herein by reference. Other suitable demulsifiers are, for example, alkali metal or alkaline earth metal salts of alkyl-substituted phenols and naphthalene sulfonates and alkali metal or alkaline earth metal salts of fatty acids, and neutral compounds such as alcohol alkoxylates, such as alcohol ethoxylates, phenol alkoxylates, such as tert-butylphenol ethoxylate or tert-amylphenol ethoxylate, fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), such as in the form of EO / PO block copolymers, polyethyleneimine, or polysiloxanes. Any commercially available demulsifier can be used, in a suitable amount sufficient to provide a treatment level of 5 to 50 ppm in the fuel. In one embodiment, the fuel composition of the present invention does not contain a demulsifier. Demulsifiers can be used alone or in combination. Some demulsifiers are commercially available, for example from Nalco or Baker Hughes. Typical treatment rates of the fuel by the demulsifier can be 0 to 50 ppm, or 5 to 50 ppm, or 5 to 25 ppm, or 5 to 20 ppm of the total fuel weight.

[0062] The disclosed technology can also be used with demulsifiers comprising hydrocarbon-substituted dicarboxylic acids in free acid or anhydride form, wherein the anhydride can be an intramolecular anhydride, such as succinic anhydride, glutaric anhydride, or phthalic anhydride, or an intermolecular anhydride linking two dicarboxylic acid molecules together. The hydrocarbon substituent may have 12 to 2000 carbon atoms and may include polyisobutylene substituents with a number average molecular weight of 300 to 2800. Exemplary hydrocarbon-substituted dicarboxylic acids include, but are not limited to, hydrocarbon-substituted acids derived from malonic acid, succinic acid, glutaric acid, adipic acid, heptanoic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, phthalic acid, isophthalic acid, terephthalic acid, diethyl ortho-, meta-, or terephthalic acid, maleic acid, fumaric acid, or glutaric acid.

[0063] In another embodiment, the fuel composition further comprises at least one detergent / dispersant. Conventional detergent / dispersant additives are amphiphilic substances having at least one hydrophobic hydrocarbon group with a number average molecular weight of 100 to 10,000 and at least one polar structural moiety selected from (i) a mono- or polyamino group having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties; (ii) a combination of a hydroxyl group and a mono- or polyamino group, at least one nitrogen atom having basic properties; (iii) a carboxyl group or an alkali metal or alkaline earth metal salt thereof; (iv) a sulfonic acid group or an alkali metal or alkaline earth metal salt thereof; (v) a polyoxy-C2-C4 alkylene structural moiety terminated by a hydroxyl group, a mono- or polyamino group having basic properties of at least one nitrogen atom, or a urethane group; (vi) a carboxyl ester group; (vii) a structural moiety derived from succinic anhydride and having hydroxyl and / or amino and / or amide and / or imide groups; and / or (viii) a structural moiety obtained by a Mannich reaction of a substituted phenol with an aldehyde and a monoamine or polyamine.

[0064] The hydrophobic hydrocarbon groups in the above detergent / dispersant additives ensure sufficient solubility in fuels, with a number-average molecular weight (M). n The concentration is 85 to 20,000, or 100 to 10,000, or 300 to 5,000. In one embodiment, the detergent / dispersant additive M... n The range is 300 to 3000, 500 to 2500, 700 to 2500, or 800 to 1500. Typical hydrophobic hydrocarbon groups can be polypropylene, polybutene, and polyisobutylene, with a number average molecular weight M of 300 to 3000, 500 to 2500, 700 to 2500, or 800 to 1500. n The values ​​are 300 to 5000, 300 to 3000, 500 to 2500, or 700 to 2500. In one embodiment, the detergent / dispersant additive M... n The range is 800 to 1500.

[0065] Other performance additives may include high-TBN nitrogen-containing detergents / dispersants, such as succinimides, which are condensation products of hydrocarbon-substituted succinic anhydrides and poly(alkyleneamines). Succinimides are described in more detail in U.S. Patents 4,234,435 and 3,172,892. Another class of ashless dispersants are high molecular weight esters, which are prepared by reacting hydrocarbon acylating agents with polyaliphatic alcohols such as glycerol, pentaerythritol, or sorbitol. These materials are described in more detail in U.S. Patent 3,381,022.

[0066] Nitrogen-containing detergents can be reaction products of carboxylic acid-derived acylating agents and amines. Acylating agents can range from formic acid and its acylated derivatives to acylating agents having high molecular weight aliphatic substituents with up to 5,000, 10,000, or 20,000 carbon atoms. Amino compounds can vary from ammonia itself to amines typically having up to 30 carbon atoms and up to 11 nitrogen atoms with aliphatic substituents. Acylated amino compounds suitable for use in this invention can be amino compounds formed by reacting an acylating agent having at least 8 carbon atoms with a hydrocarbon substituent and a compound containing at least one primary or secondary amine group. The acylating agent can be a monocarboxylic acid or a polycarboxylic acid (or its reactive equivalent), such as substituted succinic acid, phthalic acid, or propionic acid, and the amino compound can be a polyamine or a mixture of polyamines, such as a mixture of ethylene polyamines. Alternatively, the amine can be a hydroxyalkyl-substituted polyamine. The hydrocarbon substituent in such an acylating agent can contain at least 10 carbon atoms. In one embodiment, the hydrocarbon substituent can contain at least 12, for example, 30 or 50 carbon atoms. In yet another embodiment, it may contain up to 200 carbon atoms. The hydrocarbon substituents of the acylinter may have a number average molecular weight (M0) of 170 to 2800. n For example, 250 to 1500. In other embodiments, the M of the substituent... n The number can be from 500 to 1500, or optionally from 500 to 1100. In yet another embodiment, the M of the substituent... n The number can be from 700 to 1300. In another embodiment, the hydrocarbon substituent can have a number average molecular weight of 700 to 1000, or 700 to 850, or, for example, 750.

[0067] Another type of ashless dispersant is Mannich base. These are substances formed by the condensation of higher molecular weight, alkyl-substituted phenols, alkylene polyamines, and aldehydes such as formaldehyde, and are described in more detail in U.S. Patent 3,634,515.

[0068] Useful nitrogen-containing dispersants include the Mannich reaction product between (a) an aldehyde, (b) a polyamine, and (c) an optionally substituted phenol. The phenol can be substituted such that the molecular weight of the Mannich product is less than 7500. Optionally, the molecular weight can be less than 2000, less than 1500, less than 1300, or, for example, less than 1200, less than 1100, less than 1000. In some embodiments, the molecular weight of the Mannich product is less than 900, less than 850, or less than 800, less than 500, or less than 400. The substituted phenol can be substituted with up to four groups on the aromatic ring. For example, it can be a trisubstituted or disubstituted phenol. In some embodiments, the phenol can be a monosubstituted phenol. Substitution can be at the ortho, and / or meta, and / or para positions. To form the Mannich product, the molar ratio of aldehyde to amine is 4:1 to 1:1, or 2:1 to 1:1. The molar ratio of aldehyde to phenol can be at least 0.75:1; preferably 0.75:1 to 4:1, more preferably 1:1 to 4:1, and even more preferably 1:1 to 2:1. For the formation of the preferred Mannich product, the molar ratio of phenol to amine is preferably at least 1.5:1, more preferably at least 1.6:1, even more preferably at least 1.7:1, for example at least 1.8:1, and preferably at least 1.9:1. The molar ratio of phenol to amine can be up to 5:1; for example, it may be up to 4:1 or up to 3.5:1. Suitably, it is up to 3.25:1, up to 3:1, up to 2.5:1, up to 2.3:1, or up to 2.1:1.

[0069] Other dispersants include polymeric dispersant additives, which are typically hydrocarbon-based polymers containing polar functional groups to impart dispersing properties to the polymer. Amines are commonly used to prepare nitrogen-containing dispersants with high TBN. One or more poly(alkyleneamines) can be used, and these can contain one or more poly(alkyleneamines) having 3 to 5 ethylene units and 4 to 6 nitrogen units. These materials include triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA). These materials are generally commercially available as mixtures of various isomers containing a range of ethylene units and nitrogen atoms, as well as various isomer structures (including various cyclic structures). Poly(alkyleneamines) can also contain industrially known relatively high molecular weight amines as ethyleneene groups.

[0070] In one embodiment, the fuel composition may additionally comprise a quaternary ammonium salt. The quaternary ammonium salt may comprise (a) a compound comprising (i) at least one tertiary amino group as described above, and (ii) a hydrocarbon substituent having a number average molecular weight of 100 to 5000, or 250 to 4000, or 100 to 4000, or 100 to 2500, or 3000; and (b) a quaternizing agent suitable for converting the tertiary amino group of (a) and (i) into quaternary nitrogen, as described above. The following patents were granted: U.S. Patent No. 7,951,211, issued May 31, 2011; U.S. Patent No. 8,083814, issued December 27, 2011; and U.S. Publication No. 2013 / 0118062, published May 16, 2013; 2012 / 0010112, published January 12, 2012; 2013 / 0133243, published May 30, 2013; 2008 / 0113890, published May 15, 2008; 2011 / 0219674, published September 15, 2011; US2012 / 0149617, published May 14, 2012; US2013 / 0225463, published August 29, 2013; and US... US2011 / 0258917, US2011 / 0315107 published on December 29, 2011, US2013 / 0074794 published on March 28, 2013, US2012 / 0255512 published on October 11, 2012, US2013 / 0333649 published on December 19, 2013, US2013 / 0118062 published on May 16, 2013, International Publication WO2011 / 141731 published on November 17, 2011, US2011 / 095819 published on August 11, 2011, and February 7, 2013 Other quaternary ammonium salts are described more comprehensively in WO2013 / 017886 published on Japan, WO2013 / 070503 published on May 16, 2013, WO2011 / 110860 published on September 15, 2011, WO2013 / 017889 published on February 7, 2013, and WO2013 / 017884 published on February 7, 2013.

[0071] Quaternary ammonium salts can be prepared by acylating agents with hydrocarbon-substituted groups, for example, those with a number-average molecular weight greater than 1200 M. n Polyisobutylsuccinic acid or anhydride with hydrocarbon substituents, having a number average molecular weight of 300-750, or having a number average molecular weight of 1000M n Polyisobutyl succinic acid or anhydride with hydrocarbon substituents.

[0072] In one embodiment, the additional salt may be an imide prepared by reacting a nitrogen-containing compound with a hydrocarbon-substituted acylating agent, wherein the hydrocarbon-substituted acylating agent has a number-average molecular weight of 1300 to 3000. In one embodiment, the quaternary ammonium compound prepared by reacting a nitrogen-containing compound with a hydrocarbon-substituted acylating agent is an amide or ester, wherein the hydrocarbon-substituted acylating agent has a number-average molecular weight greater than 1200 M. n Hydrocarbon substituents or hydrocarbon substituents having a number average molecular weight of 300 to 750.

[0073] In one embodiment, the additional quaternary ammonium salt nitrogen-containing compound is an imidazole or nitrogen-containing compound of the following formula:

[0074]

[0075] R can be a C1-C6 alkylene group; R1 and R2 can each be a C1-C6 alkylene group independently; R3, R4, R5 and R6 can each be hydrogen or a C1-C6 hydrocarbon group.

[0076] In other embodiments, the quaternizing agent used to prepare the additional quaternary ammonium salt may be a dialkyl sulfate, an alkyl halide, a hydrocarbon-substituted carbonate, a hydrocarbon epoxide, a carboxylate, an alkyl ester, or a mixture thereof. In some cases, the quaternizing agent may be a hydrocarbon epoxide. In some cases, the quaternizing agent may be a hydrocarbon epoxide bonded to an acid. In some cases, the quaternizing agent may be a salicylate, oxalate, or terephthalate. In one embodiment, the hydrocarbon epoxide is an alcohol-functionalized epoxide or a C4-C epoxide. 14 Epoxides.

[0077] In some implementations, the quaternizing agent is multifunctional, resulting in the additional quaternary ammonium salt being a coupled quaternary ammonium salt.

[0078] The typical treatment rate of the additional detergent / dispersant for the fuel of the present invention is 0 to 500 ppm, or 0 to 250 ppm, or 0 to 100 ppm, or 5 to 250 ppm, or 5 to 100 ppm, or 10 to 100 ppm.

[0079] In yet another embodiment, the fuel composition further comprises a cold flow improver. The cold flow improver is typically selected from (1) C2- to C 40 (1) A copolymer of an olefin with at least one other olefinically unsaturated monomer; (2) a comb polymer; (3) a polyoxyethylene; (4) a polar nitrogen compound; and (5) a poly(meth)acrylate made of a straight-chain alcohol having 10-22 carbon atoms. A mixture of different representatives from one of specific categories (1) to (5) or a mixture of representatives from different categories (1) to (5) may be used.

[0080] Suitable C2-C for copolymers of category (1) 40 The olefin monomer is, for example, those having 2 to 20, especially 2 to 10, carbon atoms, and 1 to 3, preferably 1 or 2, carbon-carbon double bonds, particularly having one carbon-carbon double bond. In the latter case, the carbon-carbon double bonds may be arranged at the end (α-olefin) or internally. However, α-olefins are preferred, more preferably α-olefins having 2 to 6 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, and especially ethylene. At least one other olefinically unsaturated monomer of class (1) is preferably selected from carboxylic acid alkenyl esters; for example, C-type carboxylic acids having 2 to 21 carbon atoms. 2- To C 14- Alkenyl esters, such as vinyl and propylene esters, whose hydrocarbon groups can be straight-chain or branched, preferably vinyl esters, and suitable examples of carboxylic acid alkenyl esters are as follows: vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propylene esters, (meth)acrylates; for example, (meth)acrylic acid with C1-C 20 Esters of alkanols, especially C1-C 10 Alkyl alcohols, particularly methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, and decanol, and their structural isomers and other alkenes; preferably, with a molecular weight higher than the above C2-C 40 - An olefinic monomer, wherein the olefinic monomer used is ethylene or propylene, or other suitable olefins, especially C. 10 -C 40 -α-olefin.

[0081] Suitable (1) type copolymers are also those comprising two or more different alkenyl carboxylic esters in copolymer form, differing in alkenyl functionality and / or carboxylic acid groups. Also suitable are copolymers comprising, together with the carboxylic alkenyl ester, at least one olefin and / or at least one (meth)acrylate in copolymer form.

[0082] C2-C 40 -α-olefins, C1-C of alkene-bonded unsaturated monocarboxylic acids having 3-15 carbon atoms. 20 -alkyl esters and C-16 saturated monocarboxylic acids having 2 to 21 carbon atoms 2- To C 14- Terpolymers of alkenyl esters are also suitable as (K1) class copolymers. Such terpolymers are described in WO 2005 / 054314. This typical terpolymer is formed from ethylene, 2-ethylhexyl acrylate, and vinyl acetate.

[0083] The at least one or more olefinically unsaturated monomers are copolymerized in copolymers of class (1) in an amount preferably from 1 to 50% by weight, particularly from 10 to 45% by weight, particularly from 20 to 40% by weight, based on the total copolymer. Therefore, the majority weight proportion of monomer units in copolymers of class (1) typically comes from C2-C. 40 Alkyl olefins. Number average molecular weight M of class (1) copolymers n It can be 1,000 to 20,000, or 1,000 to 10,000 or 1,000 to 8,000.

[0084] Typical comb polymers of component (2) can be obtained, for example, by copolymerizing maleic anhydride or fumaric acid with another olefinically unsaturated monomer, such as with an α-olefin or an unsaturated ester like vinyl acetate, and subsequently with an alcohol esterifying the anhydride or acid functional group having at least 10 carbon atoms. Other suitable comb polymers are copolymers of α-olefins and esterified comonomers, such as esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid. Suitable comb polymers can also be polyfumarates or polymaleates. Homopolymers and copolymers of vinyl ethers are also suitable comb polymers. Comb polymers suitable as components of class (2) are, for example, those described in WO 2004 / 035715 and “Comb-Like Polymers. Structure and Properties”, NAPlaté and VP Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pp. 117-253 (1974). Mixtures of comb polymers are also suitable.

[0085] Suitable polyoxyolefins as components of class (3) are, for example, polyoxyolefin esters, polyoxyolefin ethers, mixed polyoxyolefin esters / ethers, and mixtures thereof. These polyoxyolefin compounds preferably contain at least one linear alkyl group, preferably at least two linear alkyl groups, each having 10-30 carbon atoms, and a polyoxyolefin group with a number-average molecular weight of up to 5000. Such polyoxyolefin compounds are described, for example, in EP-A061 895 and in U.S. Patent No. 4,491,455. Specific polyoxyolefin compounds are based on polyethylene glycol and polypropylene glycol with a number-average molecular weight of 100 to 5000. Also suitable are polyoxyolefin monoesters and diesters of fatty acids (e.g., stearic acid or behenic acid) having 10 to 30 carbon atoms.

[0086] The polar nitrogen compounds suitable as components of class (4) can be ionic or nonionic and can have at least one or at least two substituents, having the general formula >NR. 7 In the tertiary nitrogen atom form, where R 7 It is C8-C 40Hydrocarbon group. The nitrogen substituent can also be quaternized, i.e., in a cationic form. Examples of such nitrogen compounds are ammonium salts and / or amides, which can be obtained by reacting at least one amine substituted with at least one hydrocarbon group with a carboxylic acid having 1-4 carboxyl groups or a suitable derivative thereof. The amine may contain at least one straight-chain C8-C group. 40 Alkyl groups. Primary amines suitable for preparing the polar nitrogen compounds are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine, and higher linear homologues. Secondary amines suitable for this purpose are, for example, di-octadecylamine and methylphenylamine. Mixtures of amines, especially those available on an industrial scale, are also suitable for this purpose, such as aliphatic amines or hydrogenated tallow amines, as described, for example, in the section “Amines, aliphatic” of Ullmann’s Encyclopedia of Industrial Chemistry, 6th edition. Acids suitable for this reaction are, for example, cyclohexane-1,2-dicarboxylic acids, cyclohexene-1,2-dicarboxylic acids, cyclopentane-1,2-dicarboxylic acids substituted with long-chain hydrocarbon groups, naphthalene-1,2-dicarboxylic acids, phthalic acids, isophthalic acids, terephthalic acids, and succinic acids.

[0087] Suitable poly(meth)acrylates as class (5) cold flow modifiers are homopolymers or copolymers of acrylates and methacrylates. Preferably, copolymers of at least two different (meth)acrylates differ in their esterification alcohols. The copolymer optionally contains another different olefinically unsaturated monomer in a copolymeric form. The weight-average molecular weight of the polymer is preferably from 50,000 to 500,000. The polymer can be methacrylic acid and saturated C... 14 and C 15 Copolymers of alcoholic methacrylates, wherein the acid groups have been neutralized with hydrogenated tallow amine. Suitable poly(meth)acrylates are described, for example, in WO 00 / 44857.

[0088] Cold flow improvers or mixtures of different cold flow improvers are added to middle distillate fuels or diesel fuels, preferably in amounts of 0-5000 ppm by weight, or 10-5000 ppm by weight, or 20-2000 ppm by weight, or 50 to 1000 ppm by weight, or 100 to 700 ppm by weight, for example 200 to 500 ppm by weight.

[0089] In addition to the poly(acrylate) polymer defoaming components disclosed herein, other defoamers and / or foam inhibitors may be used. These additional foam inhibitors include copolymers of polysiloxanes, ethyl acrylate and 2-ethylhexyl acrylate, and optionally vinyl acetate; demulsifiers include fluorinated polysiloxanes, trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers. The disclosed techniques can also be combined with siloxane-containing defoamers C5-C.17 Alcohols are used together. In other embodiments, additional defoamers may include organosiloxanes, such as polydimethylsiloxane, polyethylsiloxane, polydiethylsiloxane, polyacrylate and polymethacrylate, trimethyl-trifluoropropylmethylsiloxane, etc.

[0090] The compositions disclosed herein may also contain lubrication improvers or friction modifiers, typically based on fatty acids or fatty acid esters. Typical examples are tall oil fatty acids, such as those described in, for example, WO 98 / 004656, and glyceryl monooleate. Natural or synthetic oils, such as the reaction products of triglycerides and alkanolamines, as described in U.S. Patent 6,743,266B2, are also suitable as such lubrication improvers. Further examples include commercial tall oil fatty acids containing polycyclic hydrocarbons and / or rosin acids.

[0091] The compositions disclosed herein may also contain additives to reduce the amount of metals dissolved in the fuel (reducing "metal pickup"). These additives may be hydrocarbons substituted with at least two carboxyl functional groups in the form of an acid or at least one carboxyl functional group in the form of an anhydride. Suitable metal pickup additives include diacid polymers derived from fatty acids and / or polyolefins, including polyolefins. Exemplary polyolefins include C 10 -C 20 Polyolefins, C 12 -C 18 Polyolefins and / or C 16 -C 18 Polyolefins. Polyolefins are characterized by M... n The number average molecular weight is at least about 300. In some embodiments, the metal-collecting additive comprises more hydrocarbon-substituted succinic anhydride groups. In some embodiments, the hydrocarbon-substituted acylated agent comprises one or more hydrolyzed hydrocarbon-substituted succinic anhydride groups (i.e., hydrocarbon-substituted succinic acid). In some embodiments, the hydrocarbon substituents are derived from homopolymers and / or copolymers containing 2 to 10 carbon atoms. In some embodiments, the aforementioned hydrocarbon substituents are derived from polyisobutylene. In one embodiment, the metal-collecting additive comprises hydrolyzed polyisobutylene succinic anhydride (PIBSA) or polyisobutylene succinic acid.

[0092] Additive package

[0093] The poly(acrylate) polymer defoaming components disclosed herein can be provided in additive package compositions containing one or more of the above-described additives. The additive package compositions can contain one or more additives in concentrated solutions suitable for addition to diesel fuel. Exemplary additive package compositions are included in Table 1. The amounts shown are weight percentages based on the total weight of the additive package.

[0094] Table 1

[0095]

[0096] Industrial applications

[0097] In one embodiment, the invention can be used for liquid fuels in internal combustion engines. The internal combustion engine can be a diesel engine. Exemplary internal combustion engines include, but are not limited to, compression ignition engines; four-stroke cycles; liquid fuels supplied via direct injection, indirect injection, common rail, and single-fuel injector systems; light-duty (e.g., passenger car) and heavy-duty (e.g., commercial truck) engines; and engines using hydrocarbon and non-hydrocarbon fuels and mixtures thereof as fuel. The engine can be part of an integrated emissions system incorporated into the aforementioned components; an EGR system; an aftertreatment system including a three-way catalyst, an oxidation catalyst, a NOx absorbent and catalyst, catalytic and non-catalytic particulate filters, optionally using a fuel catalyst; variable valve timing; and injection time and rate shaping.

[0098] In one embodiment, the technology can be used with a diesel engine having a direct fuel injection system, where fuel is injected directly into the engine's combustion chamber. The ignition pressure can be greater than 1000 bar, and in one embodiment, the ignition pressure can be greater than 1350 bar. Therefore, in another embodiment, the direct fuel injection system can be a high-pressure direct fuel injection system with an ignition pressure greater than 1350 bar. Exemplary types of high-pressure direct fuel injection systems include, but are not limited to, unit direct injection (or "pump and nozzle") systems and common rail systems. In a unit direct injection system, a high-pressure fuel pump, a fuel metering system, and fuel injectors are combined into a single unit. A common rail system has a series of injectors connected to the same accumulator or rail. The rail is in turn connected to a high-pressure fuel pump. In yet another embodiment, the unit direct injection or common rail system may also include an optional turbocharged or booster direct injection system.

[0099] A method for reducing the amount of foam generated when filling a vehicle's diesel tank is also disclosed. This method may include adding a poly(acrylate) polymer made from (meth)acrylate monomers to the diesel fuel. The poly(acrylate) polymer may be as described above.

[0100] It is known that some of the materials described above can interact in the final formulation, such that the final formulation may differ from the initially added components. For example, metal ions (e.g., detergents) can migrate to other acidic or anionic sites of other molecules. The resulting products, including those formed when the compositions of the present invention are used in their intended purpose, may not be readily described. However, all such modifications and reaction products are included within the scope of the present invention; the present invention includes compositions prepared by mixing the aforementioned components.

[0101] The following examples illustrate the disclosed technology. These examples are not exhaustive and are not intended to limit the scope of the disclosed technology.

[0102] Example

[0103] Preparation of Composition 1 of the present invention (TBAT:TMHAT, 95:05 by weight) - in the toluene process:

[0104] Composition 1 of the present invention was prepared by thoroughly mixing a monomer mixture in a glass vial with tert-butyl acrylate (TBAT) (190.0 g), 3,5,5-trimethylhexyl acrylate (TMHAT) (10.0 g), and tert-butyl peroxy-2-ethylhexanoate (TBPE) (0.22 g). Then, 66.67 g of the monomer mixture was transferred together with 100.0 g of toluene to a 1 L round-bottom flask equipped with a mechanical stirrer, a Claisen connector with a water-cooled condenser and a nitrogen inlet (set to 0.2 standard cubic feet per hour (scfh)), a thermocouple, and a stopper (“reaction vessel”). The mixture was heated to 90 °C. The remaining 133.3 g of the monomer mixture was added over 180 minutes using a peristaltic pump, maintaining the temperature at 90 °C during the addition. After all the monomer mixture was transferred to the reaction vessel, the reaction temperature was maintained at 90 °C for 180 minutes. The temperature was then adjusted to 100°C, and TBPE (0.06 g) was added to the reaction vessel and maintained for 60 minutes. Similarly, three more TBPE (0.06 g) aliquots were added, and the reaction was carried out for 60 minutes after each addition. Once complete monomer consumption was observed, 100.0 g of toluene was added and the mixture was stirred for 30 minutes. The contents of the reaction vessel were cooled to obtain M. w A colorless liquid with a concentration of 146,746 Da was produced. A portion of the colorless liquid (50 g) was transferred to a 25 mL single-necked round-bottom flask, and toluene was removed by rotary evaporation. The purified bottom product contained a poly(acrylate) polymer.

[0105] Preparation of Composition 2 of the present invention (TBAT:TMHAT, 90:10 by weight) - in the toluene process:

[0106] Composition 2 of the present invention was prepared by thoroughly mixing a monomer mixture in a glass vial with tert-butyl acrylate (TBAT) (180.0 g), 3,5,5-trimethylhexyl acrylate (TMHAT) (20.0 g), and tert-butyl peroxy-2-ethylhexanoate (TBPE) (0.22 g). Then, 66.67 g of the monomer mixture was transferred together with 100.0 g of toluene to a 1 L round-bottom flask equipped with a mechanical stirrer, a Claisen connector with a water-cooled condenser and a nitrogen inlet (set to 0.2 standard cubic feet per hour (scfh)), a thermocouple, and a stopper (“reaction vessel”). The mixture was heated to 90 °C. The remaining 133.3 g of the monomer mixture was added over 180 minutes using a peristaltic pump, maintaining the temperature at 90 °C during the addition. After all the monomer mixture was transferred to the reaction vessel, the reaction temperature was maintained at 90 °C for 180 minutes. The temperature was then adjusted to 100°C, and TBPE (0.06 g) was added to the reaction vessel and maintained for 60 minutes. Similarly, three more TBPE (0.06 g) aliquots were added, and the reaction was carried out for 60 minutes after each addition. Once complete monomer consumption was observed, 100.0 g of toluene was added and the mixture was stirred for 30 minutes. The contents of the reaction vessel were cooled to obtain M. w It is a colorless liquid with a concentration of 155,702 Da. A portion of the colorless liquid (50 g) was transferred to a 25 mL single-necked round-bottom flask, and toluene was removed by rotary evaporation. The purified bottom product contained a poly(acrylate) polymer.

[0107] Preparation of Composition 3 of the present invention (TBAT:TMHAT:EAT, 75:20:05 by weight) - in toluene process: (preliminary example)

[0108] Composition 3 of the present invention was prepared by thoroughly mixing tert-butyl acrylate (TBAT) (150.0 g), 3,5,5-trimethylhexyl acrylate (TMHAT) (40.0 g), ethyl acrylate (EAT) (10.0 g), and tert-butyl peroxy-2-ethylhexanoate (TBPE) (0.22 g) in a glass vial. Then, 66.67 g of the monomer mixture was transferred together with 100.0 g of toluene into a 1 L round-bottom flask equipped with a mechanical stirrer, a Claisen connector with a water-cooled condenser and a nitrogen inlet (set to 0.2 standard cubic feet per hour (scfh)), a thermocouple, and a stopper (“reaction vessel”). The mixture was heated to 90 °C. The remaining 133.3 g of the monomer mixture was added over 180 minutes using a peristaltic pump, maintaining the temperature at 90 °C during the addition. After all the monomer mixture was transferred to the reaction vessel, the reaction temperature was maintained at 90 °C for 180 minutes. The temperature was then adjusted to 100°C, and TBPE (0.06 g) was added to the reaction vessel and maintained for 60 minutes. Similarly, three more TBPE (0.06 g) aliquots were added, and the reaction was carried out for 60 minutes after each addition. Once complete monomer consumption was observed, 100.0 g of toluene was added and the mixture was stirred for 30 minutes. The contents of the reaction vessel were cooled, and M was calculated. w The concentration was 95,000 Da. A portion of the colorless liquid (50 g) was transferred to a 25 mL single-necked round-bottom flask, and toluene was removed by rotary evaporation. The purified bottom product contained a poly(acrylate) polymer.

[0109] Preparation of Composition 4 of the present invention (TBAT:TMHAT:PEGA, 78:20:02 by weight) - in toluene process: (preliminary example)

[0110] Composition 4 of the present invention was prepared by thoroughly mixing tert-butyl acrylate (TBAT) (156.0 g), 3,5,5-trimethylhexyl acrylate (TMHAT) (40.0 g), poly(ethylene glycol) acrylate (PEGAT) (4.0 g), and tert-butyl peroxy-2-ethylhexanoate (TBPE) (0.22 g) in a glass vial. Then, 66.67 g of the monomer mixture was transferred together with 100.0 g of toluene into a 1 L round-bottom flask equipped with a mechanical stirrer, a Claisen connector with a water-cooled condenser and a nitrogen inlet (set to 0.2 standard cubic feet per hour (scfh)), a thermocouple, and a stopper (“reaction vessel”). The mixture was heated to 90 °C. The remaining 133.3 g of the monomer mixture was added over 180 minutes using a peristaltic pump, maintaining the temperature at 90 °C during the addition. After all the monomer mixture was transferred to the reaction vessel, the reaction temperature was maintained at 90 °C for 180 minutes. The temperature was then adjusted to 100°C, and TBPE (0.06 g) was added to the reaction vessel and maintained for 60 minutes. Similarly, three more TBPE (0.06 g) aliquots were added, and the reaction was carried out for 60 minutes after each addition. Once complete monomer consumption was observed, 100.0 g of toluene was added and the mixture was stirred for 30 minutes. The contents of the reaction vessel were cooled, and M was calculated. w The concentration was 150,000 Da. A portion of the colorless liquid (50 g) was transferred to a 25 mL single-necked round-bottom flask, and toluene was removed by rotary evaporation. The purified bottom product contained a poly(acrylate) polymer.

[0111] Preparation of Composition 5 of the present invention (TBAT:TMHAT, 95:05 by weight) - in oil process: (preliminary example)

[0112] Composition 5 of the present invention was prepared by thoroughly mixing tert-butyl acrylate (TBAT) (190.0 g), 3,5,5-trimethylhexyl acrylate (TMHAT) (10.0 g), and tert-butyl peroxy-2-ethylhexanoate (TBPE) (0.22 g) in a glass vial. Then, 66.67 g of the monomer mixture and 100.0 g of mineral oil (SFNF) with a kinematic viscosity of ~3.7 cSt at 100 °C were transferred to a 1 L round-bottom flask equipped with a mechanical stirrer, a Claisen connector with a water-cooled condenser and a nitrogen inlet (set to 0.2 standard cubic feet per hour (scfh)), a thermocouple, and a stopper (“reaction vessel”). The mixture was heated to 90 °C. The remaining 133.3 g of the monomer mixture was added over 180 minutes using a peristaltic pump, maintaining the temperature at 90 °C during the addition. After all the monomer mixture was transferred to the reaction vessel, the reaction temperature was maintained at 90 °C for 180 minutes. The temperature was then adjusted to 100°C, and the first finishing dose of TBPE (0.06 g) was added, followed by stirring of the reaction mixture for another 60 minutes. The second finishing dose of TBPE (0.06 g) was added, and the reaction mixture was stirred at 100°C for another 60 minutes. The third and fourth doses of TBPE (0.06 g each) were added, followed by stirring at 100°C for 60 minutes after each dose. Gas chromatography was used to monitor the monomer conversion of tert-butyl acrylate to a target level of less than 1%, and the monomer conversion of 3,5,5-trimethylhexyl acrylate to a target level of less than 0.1%. After the desired monomer conversion was achieved, an additional 100.0 g of SFNF was added to the reaction vessel, and the reaction mixture was stirred at 100°C for 30 minutes. The contents of the reaction vessel were cooled. The resulting contents contained a poly(acrylate) polymer in SFNF with a calculated Mo of 150,000 Da. w (Approximately 50% active ingredients).

[0113] The effectiveness of the poly(acrylate) polymer disclosed herein in reducing foam in diesel fuel was tested by observing the amount of foam produced and the time taken for the foam to collapse.

[0114] For testing, 100 ml of added diesel fuel was transferred to the graduated cylinder using a pressurized syringe nozzle positioned 245 mm above it. The volume of foam generated was monitored as the diesel fuel was transferred, and the maximum volume of foam (“maximum foam”) was recorded in milliliters immediately after the transfer. The foam volume immediately after the transfer was also recorded in milliliters (“settle foam”). The surface of the added diesel fuel was then visually monitored. A stopwatch was used to measure the time it took for the foam to visually disappear from the surface of the added diesel fuel, and the time was recorded in seconds (“collapse time”).

[0115] The test was repeated 5 times, and the average maximum foam, settling foam, and collapse time were calculated. The average foam test results for various poly(acrylate) polymers in diesel fuel at different treatment rates are shown in Table 2 below.

[0116] Table 2

[0117]

[0118] The results show that poly(acrylate) polymers are effective defoamers compared with known silicone-containing defoamers and have at least the same or even improved performance.

[0119] Other suitable test methods for measuring the effectiveness of the poly(acrylate) polymers disclosed herein in reducing foam in diesel fuel include those developed by the Association. The document “Determination of the foaming tendency of diesel fuels” published and distributed by de Normalisation (NF M 07-075) (AFNOR-www.afnor.org).

[0120] Each of the above-mentioned documents is incorporated herein by reference, including any prior applications, whether or not specifically listed above, claiming priority. Reference to any document is not an admission that the document is qualified as prior art or constitutes general knowledge of any person skilled in the art within any jurisdiction. Unless expressly indicated in the examples or otherwise, all numerical values ​​for amounts of materials, reaction conditions, molecular weights, number of carbon atoms, etc., specified in this specification should be understood to be modified by “about”. It should be understood that the upper and lower limits, ranges, and proportioning limitations described herein can be combined independently. Similarly, the ranges and amounts of each element of the invention can be used in conjunction with the ranges or amounts of any other element. As used herein, the term “comprising” is also intended to include alternative embodiments as “consistently made of” and “composed of”. “Constitutes substantially made of” allows for the inclusion of substances that do not materially affect the essential and novel characteristics of the composition under consideration.

Claims

1. A composition comprising diesel fuel and at least one poly(acrylate) polymer having a weight-average molecular weight (Mn) of 50,000 to 300,000 Da. w () and by polymerization of C1-C containing (meth)acrylic acid with terminal neopentyl groups. 30 It is prepared by using alkyl ester (meth)acrylate polyfunctional monomers, wherein the polyfunctional monomers include tert-butyl acrylate and trimethylhexyl acrylate and wherein the weight ratio of tert-butyl acrylate to trimethylhexyl acrylate is 90:10 to 95:

5.

2. The composition according to claim 1, wherein the M of the at least one poly(acrylate) polymer w It ranges from 70,000 to 200,000 Da.

3. The composition according to claim 1, wherein the at least one poly(acrylate) polymer is present in diesel fuel in an amount of 2 ppm to 1000 ppm by weight, based on the total weight of the composition.

4. The composition according to claim 2, wherein the at least one poly(acrylate) polymer is present in diesel fuel in an amount of 2 ppm to 1000 ppm by weight, based on the total weight of the composition.

5. The composition according to claim 4, wherein the at least one poly(acrylate) polymer is present in diesel fuel at an amount of 2 ppm to 100 ppm by weight, based on the total weight of the composition.

6. The composition according to any one of claims 1-5, wherein the foaming in the composition is reduced compared to diesel fuels that do not contain at least one poly(acrylate) polymer.

7. A composition comprising a weight-average molecular weight ("M") having a weight-average molecular weight ("M") of 50,000 to 300,000 Da. w ") and at least one poly(acrylate) polymer prepared by polymerizing the following substances: (i) Monomers containing C1-C4 alkyl esters of (meth)acrylic acid; (ii) C5-C containing (meth)acrylic acid 12 Alkyl ester (meth)acrylate surface tension monomers; and (iii) Optionally, at least one additional monomer comprising a solubility monomer, a surface tension monomer, or a C1-C group comprising (meth)acrylic acid. 30 Multifunctional monomers of alkyl esters, or combinations thereof, and In this monomer, at least one of the (meth)acrylate surface tension monomers or optionally other monomers has a terminal neopentyl group. The (meth)acrylate solubility monomers mentioned above include tert-butyl acrylate. The surface tension monomers of the (meth)acrylate include trimethylhexyl acrylate, and The weight ratio of tert-butyl acrylate to trimethylhexyl acrylate is 90:10 to 95:

5.

8. The composition according to claim 7, wherein the at least one poly(acrylate) polymer is a copolymer.

9. The composition according to claim 7, wherein the at least one poly(acrylate) polymer is at least one of a block polymer, a random polymer, a terpolymer, or a combination thereof.

10. The composition according to any one of claims 7-9, wherein the M of the at least one poly(acrylate) polymer w It ranges from 70,000 to 200,000 Da.

11. The composition according to any one of claims 7-9, further comprising diesel fuel, wherein the at least one poly(acrylate) polymer is present in the diesel fuel in an amount of 2 ppm to 1000 ppm by weight, based on the total weight of the composition comprising the diesel fuel.

12. The composition of claim 11, wherein the at least one poly(acrylate) polymer is present in the diesel fuel in an amount of 2 ppm to 100 ppm by weight, based on the total weight of the composition containing diesel fuel.

13. A composition comprising a weight-average molecular weight ("M") having a mass fraction of 50,000 to 300,000 Da. w ”) and by polymerizing C1-C containing (meth)acrylic acid 30 A first poly(acrylate) polymer prepared from alkyl ester (meth)acrylate polyfunctional monomers and a second poly(acrylate) polymer prepared by polymerizing the following substances: (i) Monomers containing C1-C4 alkyl esters of (meth)acrylic acid; (ii) C5-C containing (meth)acrylic acid 12 Alkyl ester (meth)acrylate surface tension monomers; and (iii) Optionally, at least one additional monomer comprising a solubility monomer, a surface tension monomer, or a C1-C group comprising (meth)acrylic acid. 30 Multifunctional monomers of alkyl esters, or combinations thereof, and In this monomer, at least one of the (meth)acrylate surface tension monomers or optionally other monomers has a terminal neopentyl group. The (meth)acrylate solubility monomers mentioned above include tert-butyl acrylate. The surface tension monomers of the (meth)acrylate include trimethylhexyl acrylate, and The weight ratio of tert-butyl acrylate to trimethylhexyl acrylate is 90:10 to 95:

5.

14. A method for reducing foam in diesel fuel, the method comprising adding at least one poly(acrylate) polymer according to any one of claims 1-12 to the diesel fuel.

15. A method for reducing the amount of foam generated when filling a vehicle diesel tank, the method comprising adding at least one poly(acrylate) polymer according to any one of claims 1-12 to diesel fuel.

16. Use of at least one poly(acrylate) polymer according to any one of claims 1-12 for reducing foam in diesel fuel.

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