Composition with gasoline cleaning function and its preparation method

Abstract

This invention relates to the field of gasoline detergents, and discloses a composition with gasoline cleaning function and its preparation method. The composition contains an aromatic amide polymer, a Mannich base detergent, a carrier oil, and optional additives, wherein, based on the total weight of the composition, the content of the Mannich base detergent is 10-30% by weight, and the content of the aromatic amide polymer is 5-20% by weight. This invention also discloses a method for preparing the above composition, which includes mixing the aromatic amide polymer, the Mannich base detergent, the carrier oil, and optional additives. This invention combines the Mannich base and the aromatic amide polymer, resulting in a synergistic effect and significant cleaning effect.

Description

Technical Field

[0001] This invention relates to the field of gasoline detergents, and more specifically to compositions having gasoline cleaning function and their preparation methods. Background Technology

[0002] Gasoline fuel contains a large amount of unsaturated hydrocarbons, as well as sulfur and nitrogen compounds. During storage and use, these compounds are easily oxidized into gum by contact with air. This directly leads to the formation of carbon deposits and sediments in the electric injectors, intake valves, and combustion chamber during fuel combustion. Consequently, problems such as poor fuel supply, air-fuel ratio imbalance, incomplete combustion, fuel waste, and reduced engine efficiency are caused. Furthermore, it emits a large amount of harmful gases and increases friction and wear between moving parts.

[0003] To address the numerous problems associated with gasoline combustion, one or more multi-effect compound additives are typically added to existing gasoline fuels. These additives utilize the combined properties of different additives to improve gasoline performance, while simultaneously increasing its detergency and lubricity. Currently, the latest generation of detergents primarily uses Mannich bases, which have high thermal stability and can effectively remove intake valve deposits. However, when used alone, they can increase the formation of deposits in the combustion chamber. Summary of the Invention

[0004] The purpose of this invention is to overcome the problems existing in the prior art and to provide a composition with gasoline cleaning function and its preparation method.

[0005] The inventors of this invention have discovered that combining aromatic amide polymers with Mannich bases can greatly improve detergency. Therefore, in order to achieve the above objective, this invention provides a composition with gasoline detergency function, the composition containing an aromatic amide polymer, a Mannich base detergent, a carrier oil, and optional additives, wherein, based on the total weight of the composition, the content of the Mannich base detergent is 10-30% by weight, and the content of the aromatic amide polymer is 5-20% by weight.

[0006] The present invention also provides a method for preparing the above composition, the method comprising: mixing an aromatic amide polymer, a Mannich base detergent, a carrier oil and optional additives.

[0007] This invention combines Mannich base and aromatic amide polymer, which produce a synergistic effect and a significant cleaning effect. When the gasoline cleaning compound of this invention is added to automotive gasoline at a dosage of 150-450 ppm, it can effectively control the deposits in the engine intake valve and combustion chamber, meeting the requirements of GB19592-2019 for gasoline cleaning performance. Attached Figure Description

[0008] Figure 1The image shows the infrared spectrum of the target product prepared in Example 1.

[0009] Figure 2 This is the infrared spectrum of the target product prepared in Preparation Example 2. Detailed Implementation

[0010] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0011] In this invention, "C1-C6 alkyl" includes straight-chain, branched, and cyclic alkyl groups with a total of 6 carbon atoms, including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclopropyl, methylcyclopropyl, ethylcyclopropyl, cyclopentyl, methylcyclopentyl, cyclohexyl, etc.; "halogen" can refer to F, Cl, Br, I, etc.; C1-C6 alkoxy, -O-(C1-C6 alkyl), C4-C7 cycloalkyl, -NH(C1-C6 alkyl), C6-C8 aryl or C6-C8 heteroaryl, that is, have similar meanings.

[0012] This invention provides a composition with gasoline cleaning function, characterized in that the composition contains an aromatic amide polymer, a Mannich base detergent, a carrier oil, and optional additives, wherein, based on the total weight of the composition, the content of the Mannich base detergent is 10-30% by weight (e.g., 12, 15, 18, 20, 22, 23, 24, 25, 26, 28, 30 or any range or value between the above values, preferably 15-25% by weight), and the content of the aromatic amide polymer is 5-20% by weight (e.g., 6, 8, 9, 10, 11, 12, 15, 18, 20 or any range or value between the above values, preferably 8-15% by weight).

[0013] In a preferred embodiment of the present invention, the weight ratio of the Mannich base detergent to the aromatic amide polymer is 1.5-3, more preferably 1.6-2.7.

[0014] In this invention, the aromatic amide polymer (i.e., the aromatic amide compound) has the structure shown in formula (I).

[0015]

[0016] In formula (I),

[0017] n is an integer between 0 and 6;

[0018] p is 0 or 1;

[0019] R0 can be H, halogen, C1-C6 alkyl, -O-(C1-C6 alkyl) or -COOH;

[0020] R1 is H, C1-C6 alkyl, C1-C6 alkoxy, C4-C7 cycloalkyl, heterocyclic alkyl, aryl, alkylaryl, or heterocyclic aryl;

[0021] R2 can be -O-(C1-C6 alkylene)-, -O-, or -((CH2) k NH) j - substituted or unsubstituted alkylene groups, substituted or unsubstituted sulfinyl groups, substituted or unsubstituted arylene groups, substituted or unsubstituted heteroarylene groups, or Wherein, R5 and R6 are each independently H, halogen, C1-C6 alkyl or C1-C6 alkoxy, and q, r, s, j and k are each independently integers from 0 to 6;

[0022] R3 and R4 are each independently H, halogen, -NH (C1-C6 alkyl), C1-C4 alkyl, C1-C4 alkoxy, substituted or unsubstituted aryloxy, aryl, heteroaryl, wherein the substituted aryl, heteroaryl and aryloxy are substituted by any number of the following substituents: -OH, -COOH, -COOCH3, -NH2, -NH (C1-C6 alkyl), -N (C1-C6 alkyl)2, -NO2, C1-C4 alkyl, C1-C4 alkoxy or halogen;

[0023] Alternatively, R1, R2, R3, and R4 are bonded to each other to form substituted or unsubstituted C3-C8 nitrogen- and / or oxygen- and sulfur-containing heterocycles (which may be saturated or unsaturated heterocycles), wherein the substituents are selected from at least one of H, halogen, C1-C6 alkyl, C1-C6 haloalkyl, -O-(C1-C6 alkyl), aryl, haloaryl, acyl, and -COOH;

[0024] Wherein, C1-C6 haloalkyl preferably includes C3-C6 straight-chain haloalkanes or halocycloalkanes (such as 1-(2-chloroethyl)piperazine); haloaryl preferably includes C6-C10 haloaryl (such as 1-(4-chlorophenyl)piperazine); haloacyl preferably includes chloroacetyl and chloropropionyl.

[0025] J is a polymer long-chain group, selected from polyolefin, polyester or polyether, and the number average molecular weight of the polymer long-chain group is 500-3000.

[0026] According to some embodiments of the present invention, the compound has a structure shown in formula (M) or formula (N):

[0027]

[0028] In equation (M), q, r, and s are each an independent integer from 0 to 4;

[0029] R5 and R6 are each independently H, halogen, C1-C4 alkyl or C1-C4 alkoxy;

[0030] In formula (N), R7 is H, a C1-C4 alkyl group, or a C1-C4 alkoxy group;

[0031] The Q ring is a substituted or unsubstituted five-, six-, or seven-membered heterocycle, and the Q ring is a heterocycle containing at least one (preferably two) nitrogen atoms.

[0032] In formula (M) or formula (N), J represents a polyolefin; wherein the polyolefin is selected from polyethylene, polypropylene, polybutene, polyisobutylene, polypentene, polyhexene, polyoctene, polynonene, and polydecene, and the number average molecular weight of the polyolefin is 500-2500 (for example, it can be any value between 500, 700, 800, 1000, 1200, 1300, 1500, 1800, 2000, 2200, 2300, 2500 or above), more preferably 800-1500.

[0033] According to some embodiments of the present invention, q and r, s are each independently an integer from 1 to 3, R0 is H or C1-C4 alkyl, R1 is H or C1-C4 alkyl, R5 and R6 are each independently H or C1-C4 alkyl, and R3 and R4 are each independently H, halogen or C1-C4 alkyl.

[0034] Alternatively, in formula (N), R0 is H or a C1-C4 alkyl group, Q ring is a nitrogen-containing six-membered heterocycle, and R7 is H or a C1-C4 alkyl group.

[0035] According to some embodiments of the present invention, the compound has a structure represented by formula (M1) or formula (N1):

[0036]

[0037] In formula (M1) or formula (N1), J represents polyisobutylene.

[0038] In this invention, the method for preparing aromatic amide compounds (or aromatic amide polymers) includes the following steps:

[0039] (1) The compound shown in formula (II) is brought into contact with the compound shown in formula (III) to carry out a ring-opening reaction.

[0040]

[0041] (2) The compound shown in formula (IV) is subjected to an imidization reaction with the ring-opening reaction product obtained in step (1).

[0042]

[0043] In formula (II), formula (III) or formula (IV), J, n, p, R0, R1, R2, R3 or R4 are defined as described in the first aspect above; in formula (III), A is -H, -C1-C3 alkyl, -C1-C3 alkoxy, alkenyl, alkynyl or aryl.

[0044] In this invention, the compound represented by formula (IV) is polyisobutylene with a number-average molecular weight of 800-2500.

[0045] In a preferred embodiment of the present invention, the degree of substitution of the polyolefin succinic anhydride is 0.9-1.3. The saponification value of the polyolefin succinic anhydride is 50-125 mg KOH / g. "Saponification value" refers to the number of milligrams of potassium hydroxide required to saponify 1 gram of sample oil. "Saponification value" is generally an indicator of the content of oily components added to fuel oil or lubricating oil.

[0046] In this invention, the compound represented by formula (II) can be selected from monoamines or polyamines having at least one primary or secondary amino group, and the substituents can be straight-chain or branched, or cyclic, heterocyclic or non-aromatic.

[0047] Wherein, the compound represented by formula (II) can be a straight-chain, branched-chain aliphatic or cyclic aliphatic amine having a primary amino group, such as n-propylamine, n-butylamine, n-pentylamine, isopentylamine isobutylamine, 2-ethylhexylamine, diethylbutylamine, cyclopropylmethylamine, cyclohexylpropylamine, cyclooctylpropylamine, 2-cycloheptylethylamine, and cyclopentylpropylamine.

[0048] Wherein, the compound represented by formula (II) can be a straight-chain or straight-chain aliphatic diamine having two primary amino groups, such as ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butylenediamine and its isomers, pentanediamine and its isomers, hexanediamine and its isomers, heptamethamine and its isomers. For example, N-alkyl-substituted analogs of the above diamine compounds, such as N-monoalkylated alkylenediamines and N,N- or N,N'-dialkylated alkylenediamines, such as N,N-dimethyl-1,3-propanediamine (DMAPA), N,N-diethyl-aminopropylamine.

[0049] Wherein, the compound represented by formula (II) can be a diamine or polyamine having at least one primary amino group and at least one secondary or tertiary amino group, such as dialkyltriamine, trialkyltetraamine, tetraalkylpentamine, pentaalkylhexamine and its N-alkyl-substituted analogues, such as N-monoalkylated alkylene polyamines and N,N-dialkylated alkylene polyamines or N,N'-dialkylated alkylene polyamines.

[0050] The compound represented by formula (II) can be selected from N,N-dimethyldimethylenetriamine, N,N-diethyldimethylenetriamine, N,N-dipropyldimethylenetriamine, N,N-dimethyldiethyl-1,2-triamine, N,N-diethyldiethyl-1,2-triamine, N,N-dipropyldiethyl-1,2-triamine, N,N-dimethyldipropylene-1,3-triamine (i.e., DMAPAPA), N,N-diethyldipropylene-1,3-triamine, N,N-dipropyldipropylene-1,3-triamine, N,N-dipropyldipropylene-1,3-triamine, N,N-dimethyl ... 3-Triamine, N,N-dimethyldibutyl-1,4-triamine, N,N-diethyldibutyl-1,4-triamine, N,N-dipropyldibutyl-1,4-triamine, N,N-dimethyldipentyl-1,5-triamine, N,N-diethyldipentyl-1,5-triamine, N,N-dipropyldipentyl-1,5-triamine, N,N-dimethyldihexyl-1,6-triamine, N,N-diethyldihexyl-1,6-triamine and N,N-dipropyldihexyl-1,6-triamine.

[0051] Wherein, the compound represented by formula (II) may be a non-aromatic heterocyclic monoamine or polyamine having at least one primary amine, comprising a five- or six-membered saturated or monounsaturated heterocycle containing one or two nitrogen atoms and / or one oxygen or sulfur atom or one or two oxygen and / or sulfur atoms as ring members, such as amino-substituted derivatives of furan, pyrrolidine, isoxazolidine, isothiazolidine, pyrazolidine, oxazolidine, thiazolyl, imidazolyl, pyrrolidine, piperidine, piperidinyl, 1,3-dioxane, tetrahydropyran, hexahydropyridazine, hexahydropyrimidine, piperazine and its alkyl-substituted derivatives, preferably N-methylpiperazine.

[0052] In this invention, the compound represented by formula (III) is preferably selected from one of the following compounds:

[0053]

[0054]

[0055] According to some embodiments of the present invention, in step (1), the compound represented by formula (M') or formula (N') is brought into contact with the compound represented by formula (III) to carry out a ring-opening reaction.

[0056]

[0057] In this context, equation (M') or equation (N'), q, r, s, R5, R6 or R7 are the same as defined above.

[0058] According to some embodiments of the present invention, in step (1), 2-[(2-ethoxy)-N,N-dimethyl]ethylamine or N-methylpiperazine is contacted with the compound shown in formula (III) to carry out a ring-opening reaction.

[0059] According to some embodiments of the present invention, the conditions for the ring-opening reaction may include: a temperature of 20-110°C (20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C or any value between the above values), and a time of 0.25-3h (0.25h, 0.5h, 0.15h, 2h, 2.5h, 3h or any value between the above values).

[0060] According to some embodiments of the present invention, the ring-opening reaction is carried out under an inert atmosphere, preferably provided by nitrogen.

[0061] According to some embodiments of the present invention, in step (1), the molar ratio of the compound represented by formula (II) to the compound represented by formula (III) can be 1:(0.8-2.5).

[0062] The present invention does not impose any particular restrictions on the feeding method in step (1), as long as it meets the requirements of the present invention. In order to obtain better results, when the compound shown in formula (II) contains two or more primary amine groups, preferably, the molar ratio of the compound shown in formula (II) to the compound shown in formula (III) is 1:(0.9-1.1), and the feeding method of the ring-opening reaction is as follows: relative to 0.05 mol of the compound shown in formula (II), the compound shown in formula (III) is added to the compound shown in formula (II) at a rate of 0.001-0.005 mol / min (any value between 0.001 mol / min, 0.002 mol / min, 0.003 mol / min, 0.004 mol / min, 0.005 mol / min or above) at 20-40°C (the imidization reaction has already started during the dropwise addition), and the imidization reaction is continued at 60-100°C for 1-3 h.

[0063] In this invention, the ring-opening reaction is carried out in the presence of a first solvent. There is no particular limitation on the amount of the first solvent used, as long as it meets the requirements of this invention. Preferably, the amount of the first solvent is 1-10 g relative to 1 g of the compound represented by formula (II).

[0064] In this invention, the first solvent is selected from at least one of ethyl acetate, petroleum ether, and C6-C8 alkanes.

[0065] The present invention does not impose any special restrictions on the post-processing steps of step (1). It can be carried out in accordance with the conventional post-processing methods in the field, or no special post-processing can be carried out. The system after the reaction in step (1) can be directly cooled to below 50°C and used directly for the next reaction.

[0066] According to some embodiments of the present invention, in step (2), the conditions for the imide reaction may include: a temperature of 50-200℃ (50℃, 60℃, 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, 190℃, 200℃ or any value between the above), and a time of 1-6h.

[0067] According to some embodiments of the present invention, the amount of compound shown in formula (IV) can be 0.8-2 mol (any value between 0.8 mol, 0.9 mol, 1.0 mol, 1.1 mol, 1.3 mol, 1.5 mol, 1.7 mol, 1.9 mol, 2.0 mol or above) relative to 1 mol of compound shown in formula (II).

[0068] This invention does not impose any particular restrictions on the feeding method of the materials in step (2). However, in order to control the yield of more monoimide products in step (2) (some products in step (1) contain multiple primary amines), the feeding method of the materials in step (2) is preferably as follows: relative to 0.05 mol of the compound shown in formula (II), at 40-60°C and under an inert atmosphere, the compound shown in formula (IV) is fed at a rate of 0.0005-0.008 mol / min (e.g., 0.0005 mol / min, 0.001 mol / min). The concentration of the reaction product in step (1) is 0.0015-0.005 mol / min, 0.002 mol / min, 0.003 mol / min, 0.004 mol / min, 0.005 mol / min, 0.006 mol / min, 0.007 mol / min, 0.008 mol / min or any value between these values. After the addition is complete, the temperature is raised to 90-180℃ and the reaction continues for 1-5 hours.

[0069] In this invention, in step (2), the imidization reaction is carried out in the presence of a second solvent. The amount of the second solvent is not particularly limited, as long as it meets the requirements of this invention. Preferably, the amount of the second solvent is 1-10 g relative to 1 g of the compound represented by formula (II).

[0070] In this invention, the second solvent is selected from at least one of ethyl acetate, petroleum ether, and C6-C8 alkanes.

[0071] In this invention, the first solvent and the second solvent may be the same or different.

[0072] In this invention, in step (2), the imidization reaction is carried out under an inert atmosphere, which is preferably provided by nitrogen.

[0073] The present invention does not impose any particular restrictions on the post-processing steps of step (2). It can be carried out in accordance with the conventional post-processing methods of imidization in the art, or the reaction system can be washed with a saturated sodium chloride solution (there is no particular restriction on the amount of saturated sodium chloride used, as long as it is sufficient to wash away the remaining ring-opening products in the system of step (2)). After removing the solvent, the compound (product) of the present invention can be obtained. The product after removing the solvent can be directly used as a fuel detergent.

[0074] In this invention, the Mannich base detergent can be a Mannich base commonly used in the art, but is preferably a Mannich base having the structure shown in formula (V):

[0075]

[0076] In equation (V), R 11 and R 12 Each group is independently selected from C1-C5 alkylene groups; PIB is a polyisobutylene group. More preferably, R 11 It is methylene. More preferably, R 12 The component is ethylene. More preferably, the number-average molecular weight of PIB is 800-1300. The Mannich base with this structure can exert a better synergistic effect with aromatic amide polymers compared with Mannich bases with other structures, thereby further improving the detergency performance.

[0077] The carrier oil used in this invention is a common carrier oil in the art. Based on the total weight of the composition, the content of the carrier oil can be 10-50% by weight, preferably 40-45% by weight.

[0078] Preferably, the carrier oil is at least one selected from polyether synthetic oil, polyalphaolefin synthetic oil (PAO), and mineral oil. The kinematic viscosity of the carrier oil at 100°C can be 10-100 mm⁻¹. 2 / s (The test method for kinematic viscosity is based on GB / T265-1988).

[0079] More preferably, the structure of the polyether synthetic oil is as shown in formula (VI):

[0080]

[0081] In equation (VI), R 13 It represents a hydrogen atom, a methyl group, or an ethyl group, and k is an integer from 3 to 20.

[0082] In this invention, the additive can be at least one of the additives commonly used in gasoline detergents, such as demulsifiers, rust inhibitors, and diluents. The demulsifier is mainly used to improve the demulsification performance of the composition, preventing it from being emulsified into a W / O (water / oil) emulsion, and can be selected from at least one of polyether polymers (such as DL32), polyoxyethylene propylene glycol ethers (such as SP169), and tetrapolyoxypropylene derivatives of amines (such as T1001). The rust inhibitor is mainly used to improve the rust prevention function of the composition, preventing it from corroding equipment during use, and can be selected from at least one of heptadecanylimidazoline alkenyl succinate (such as T703), dodecenyl succinic acid (such as T746), and alkenyl succinate (such as T747). The diluent is mainly used to improve the viscosity of the composition for ease of use, and can be selected from at least one of aromatic solvent oils (such as S-1000, S-1500), kerosene, and dearomatized solvent oils (such as D60, D70).

[0083] Preferably, the content of the demulsifier is 0.5-1% by weight, more preferably 0.6-0.9% by weight, based on the total weight of the composition.

[0084] Preferably, the rust inhibitor content is 0.5-1% by weight, more preferably 0.5-0.9% by weight, based on the total weight of the composition.

[0085] Preferably, the diluent content is 10-30% by weight, more preferably 22.5-28.5% by weight, based on the total weight of the composition.

[0086] According to the most preferred embodiment of the present invention, the composition comprises 24-25% by weight of Mannich base detergent, 9-11% by weight of aromatic amide polymer A1, 40-42% by weight of carrier oil (polyether synthetic oil and mineral oil 600SN in a volume ratio of 1-2), 0.5-0.6% by weight of demulsifier T1001, 0.5-0.6% by weight of rust inhibitor T746, and 23.5-24% by weight of diluent S1000.

[0087] The present invention also provides a method for preparing the composition as described above, characterized in that the method comprises: mixing an aromatic amide polymer, a Mannich base detergent, a carrier oil, and optional additives.

[0088] According to the present invention, it is sufficient to mix the individual components; there are no particular requirements for the mixing conditions. However, preferably, the mixing conditions include a temperature of 45-60°C and a time of 0.5-1.5 hours. Under these conditions, a yellow, clear, and transparent composition (gasoline detergent complex) can be obtained.

[0089] The present invention will be described in detail below through embodiments.

[0090] Unless otherwise specified, all reagents used in this invention are of analytical grade and are commercially available.

[0091] Unless otherwise specified, the number-average molecular weight Mn was determined by gel permeation chromatography (GPC). The determination conditions for any GPC or GPC chromatograms mentioned are as follows: instrument: Waters 1515 gel permeation chromatograph (Waters, Inc.); mobile phase: tetrahydrofuran; flow rate: 1 mL / min; column temperature: 35 °C; elution time: 33 min; sample volume fraction: 0.1-0.15%.

[0092] The saponification value was analyzed and determined according to SY2604-77.

[0093]

[0094] Preparation Example 1

[0095] 8.16 g (0.05 mol) of the compound shown in formula (III) (where R0 is H and A is H) and 15 g of aromatic S150 solvent (Shanghai Huishuo Technology Co., Ltd.) were added to a three-necked flask. 4.81 g (0.048 mol) of N-methylpiperazine (NMPRZ) was slowly added dropwise at 0.01 mol / min to the system containing the compound shown in formula (III) under stirring at 30 °C. After the addition was complete, the temperature was raised to 95 °C under a nitrogen atmosphere, and the ring-opening reaction was maintained for 2 h. Then the temperature was lowered to 50 °C, and 50 g ( 0.05 mol) of polyisobutylene maleic anhydride (PIBSA) (prepared according to the method described in CN1315317A, with a number-average molecular weight Mn = 2300, a saponification value of 60 mg KOH / g, and a degree of substitution X = 1.3) was dissolved in 20 g of aromatic hydrocarbon S150 solvent. Under nitrogen protection and stirring, the solution was added to the product of the above ring-opening reaction at a rate of 0.006 mol / min. The temperature was controlled at 55 °C. After the addition was complete, the temperature was raised to 160 °C and maintained for 3 h. The product was washed with a saturated sodium chloride solution to remove the solvent, yielding the target product A1 as shown in formula (N1). The infrared spectrum of the compound shown in formula (N1) is shown below. Figure 1 .

[0096] Figure 1 In the ring-opening reaction product NMPRZ-DH, all the characteristic absorption peaks of the primary amine disappeared, and the carbonyl absorption peak of PIBSA at 1788 cm⁻¹ also disappeared, indicating that the reactants reacted completely. -1 and 1777cm -1The absorption peak at 1636 cm⁻¹ indicates the formation of an imide carbonyl group, suggesting that the primary amine on the benzene ring has formed an imide with PIBSA (polyisobutylene succinic anhydride). -1 The peak at this location represents the stretching vibration absorption peak of C=O in tertiary amides.

[0097] Preparation Example 2

[0098] 7.71 g (0.052 mol) of 2-[(2-ethoxy)-N,N-dimethyl]ethylamine (EDOBA) and 15 g of aromatic S150 solvent (S150 aromatic solvent oil, purchased from Shanghai Huishuo Technology Co., Ltd.) were added to a three-necked flask. 8.16 g (0.05 mol) of the compound shown in formula (III) (where R0 is H and A is H) was dispersed in 15 g of aromatic S150 solvent. Under stirring at 25 °C, the solution of the compound shown in formula (III) was slowly added dropwise to the system containing EDOBA at a rate of 0.0015 mol / min. After the addition was complete, the temperature was raised to 55 °C under a nitrogen atmosphere. The ring-opening reaction was carried out and maintained for 0.5 h. Then, the temperature was lowered to 50 °C, and 50 g (0.05 mol) of polyisobutylene maleic anhydride (prepared according to the method described in CN1315317A, polyisobutylene number-average molecular weight Mn = 2300, saponification value 60 mg KOH / g, degree of substitution X = 1.3) was dissolved in 20 g of aromatic hydrocarbon S150 solvent. Under nitrogen protection and stirring, this solution was added to the product of the above ring-opening reaction at a rate of 0.001 mol / min. The temperature was controlled at 55 °C. After the addition was complete, the temperature was raised to 160 °C and maintained for 3 h. The product was washed with a saturated sodium chloride solution to remove the solvent, yielding the target product A2 as shown in formula (M1). The infrared spectrum of the compound shown in formula (M1) is shown below. Figure 2 .

[0099] like Figure 2 As shown, 3377cm -1 The peak at 1631 cm⁻¹ represents the stretching vibration absorption peak of the primary amine in EDOBA. -1 The absorption peak at 1708 cm⁻¹ represents the stretching vibration of C=O in amides. -1 and 1772cm -1 The peak at this point represents the stretching vibration absorption peak of C=O in imide.

[0100] Preparation Example 3

[0101] 8.16 g (0.05 mol) of the compound shown in formula (III) (where R0 is H and A is H) and 15 g of aromatic S150 solvent (S150 aromatic solvent oil, purchased from Shanghai Huishuo Technology Co., Ltd.) were added to a three-necked flask. At 25 °C with stirring, 8.00 g (0.054 mol) of 2-[(2-ethoxy)-N,N-dimethyl]ethylamine (EDOBA) was slowly added dropwise at a rate of 0.0027 mol / min to the system containing the compound shown in formula (III). After the addition was complete, the temperature was raised to 55 °C under a nitrogen atmosphere to carry out the ring-opening reaction and maintain the reaction. 0.5 h; then cool down to 50 °C, and dissolve 50 g (0.05 mol) of polyisobutylene maleic anhydride (prepared according to the method described in CN1315317A, polyisobutylene number-average molecular weight Mn = 2300, saponification value 60 mg KOH / g, degree of substitution X = 1.3) in 20 g of aromatic S150 solvent. Under nitrogen protection and stirring, add the product of the above ring-opening reaction at a rate of 0.001 mol / min. Control the temperature at 55 °C. After the addition is complete, raise the temperature to 160 °C and maintain it for 3 h. Wash with saturated sodium chloride solution to remove the solvent and obtain compound A3 as shown in formula (M1).

[0102] Preparation Example 4

[0103] The preparation was carried out in the same manner as in Example 2, except that the solution of the compound shown in formula (III) was slowly added dropwise to the system containing EDOBA at a rate of 0.008 mol / min to obtain compound A4.

[0104] Preparation Example 5

[0105]

[0106] The above compound (M0) was prepared by reacting polyisobutylene succinic anhydride with triethylenetetramine (TETA).

[0107] At room temperature, 7.02 g (0.048 mol) of triethylenetetramine (TETA) and 15 g of aromatic S150 solvent were added to a three-necked flask. Under a nitrogen atmosphere, 40 g (0.04 mol) of polyisobutylene succinic anhydride (prepared according to the method described in CN1315317A, polyisobutylene number-average molecular weight Mn = 2300, saponification value 60 mg KOH / g, degree of substitution X = 1.3) was dissolved in 20 g of aromatic S150 solvent. The solution was slowly added to the triethylenetetramine under stirring and nitrogen protection, with the temperature controlled at 55 °C. After the addition was complete, the temperature was raised to 140 °C and maintained for 3 h. The solvent was then removed to obtain the above compound M0.

[0108] Examples 1-4

[0109] According to the types and weight percentages shown in Table 1, the product of the preparation example (aromatic amide polymer) was mixed with a Mannich base (structure as shown in formula (V), R) 11 For methylene, R 12 Ethylene (PIB with a number average molecular weight of 1000), carrier oil, demulsifier, rust inhibitor, and diluent are added to a flask and stirred at 50-60℃ for 1-2 hours to obtain a dark yellow, clear, and transparent gasoline detergent compound.

[0110] The structure of polyether synthetic oil is shown in formula (VI) (where R... 13 Methyl group (k=15), kinematic viscosity at 100°C is 45 mm. 2 / s, purchased from Maoming Petrochemical;

[0111] Mineral oil 600SN (kinematic viscosity of 100 mm at 100°C) 2 / s) and PAO10 (kinematic viscosity of 10 mm at 100℃) 2 / s) purchased from Maoming Petrochemical;

[0112] T1001 and SP169 were purchased from Jiangsu Boer Petroleum Additives Co., Ltd. and Hubei Qifei Pharmaceutical Chemical Co., Ltd., respectively.

[0113] T746, T747, and T703 all come from Wuxi Southern Petroleum Additives Co., Ltd.

[0114] S1000, S-1500, kerosene, and D70 were all purchased from Maoming Petrochemical.

[0115] Table 1

[0116]

[0117] Example 5

[0118] The gasoline detergent compound was prepared according to the method of Example 1, except that the content of aromatic amide polymer was 5% by weight and the content of Mannich base was 30% by weight.

[0119] Example 6

[0120] The gasoline detergent compound was prepared according to the method of Example 1, except that the content of aromatic amide polymer was 20% by weight and the content of Mannich base was 15% by weight.

[0121] Comparative Example 1

[0122] The gasoline detergent compound was prepared according to the method of Example 1, except that the aromatic amide polymer was replaced with an equal amount of Mannich base.

[0123] Comparative Examples 2-5

[0124] The gasoline cleaning compound was prepared according to the method of Example 1, except that the Mannich base was replaced with an equal amount of A1-A4 prepared in Preparation Examples 1-4.

[0125] Comparative Example 6

[0126] The gasoline detergent compound was prepared in accordance with the method of Example 1, except that the aromatic amide polymer was replaced with the MO obtained in Preparation Example 5.

[0127] Test case

[0128] Cleanliness simulation experiment

[0129] Referring to GB / T37322-2019, the above-mentioned gasoline detergent compound was added to 300ml of automotive Beijing VI gasoline at the specified dosage (300ppm, approximately 0.0673g). Its detergent performance was evaluated using an L-2 gasoline engine intake valve deposit simulation tester. Combustion chamber deposits were simulated using an SDT-Q600 TGA-DSC thermogravimetric analyzer. The residual rate of the sample after treatment at 400℃ for 0.8h (=weight difference of deposits before and after treatment at 400℃ / weight of deposits before treatment at 400℃×100%) represented the increase in combustion chamber deposits. The performance evaluation results of the compound gasoline detergent are shown in Table 2.

[0130] Table 2

[0131]

[0132]

[0133] As shown in Table 2, the aromatic amide polymer B in the examples has a very good synergistic effect with the Mannich base, and the sediment reduction rate is concentrated between 80-90%, with the best cleaning performance reaching over 90%.

[0134] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various specific technical features in any suitable manner. To avoid unnecessary repetition, the present invention will not describe the various possible combinations separately. However, these simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A composition having gasoline cleaning function, characterized in that, The composition contains an aromatic amide polymer, a Mannich base detergent, a carrier oil, and optional additives, wherein, based on the total weight of the composition, the content of the Mannich base detergent is 15-25% by weight, and the content of the aromatic amide polymer is 8-15% by weight. The aromatic amide polymer has the structure shown in formula (I): （I）， In formula (I), n is an integer between 0 and 6; p is 0 or 1; R0 can be H, halogen, C1-C6 alkyl, -O-(C1-C6 alkyl) or -COOH; R1 is H, C1-C6 alkyl, C1-C6 alkoxy, or C4-C7 cycloalkyl; R2 can be -O-(C1-C6 alkylene)-, -O-, or -((CH2) k NH) j - substituted or unsubstituted alkylene groups, substituted or unsubstituted sulfinyl groups, substituted or unsubstituted heteroaryl groups, or In this context, R5 and R6 are each independently H, halogen, C1-C6 alkyl or C1-C6 alkoxy, and q, r, s, j and k are each independently integers from 0 to 6. R3 and R4 are each independently H, halogen, -NH (C1-C6 alkyl), C1-C4 alkyl, C1-C4 alkoxy, substituted or unsubstituted aryl, wherein the substituted aryl is substituted by any number of the following substituents: -OH, -COOH, -COOCH3, -NH2, -NH (C1-C6 alkyl), -N (C1-C6 alkyl)2, -NO2, C1-C4 alkyl, C1-C4 alkoxy or halogen; In formula (I), J is a polymer long-chain group, selected from polyolefin, polyester or polyether, and the number average molecular weight of the polymer long-chain group is 500-3000. Alternatively, the aromatic amide polymer has the structure shown in formula (N1). (N1), In formula (N1), J represents polyisobutylene; The structure of the Mannich base detergent is shown in formula (V): （V） In equation (V), R 11 and R 12 Each is independently selected from C1-C5 alkylene groups; PIB is a polyisobutylene group.

2. The composition according to claim 1, wherein, R1 is an alkylaryl or heterocyclic aryl group.

3. The composition according to claim 1, wherein, R2 is a substituted or unsubstituted aryl group.

4. The composition according to claim 1, wherein, R3 and R4 are each independently a substituted or unsubstituted heteroaryl group, wherein the substituted heteroaryl group is substituted by any number of the following substituents: -OH, -COOH, -COOCH3, -NH2, -NH(C1-C6 alkyl), -N(C1-C6 alkyl)2, -NO2, C1-C4 alkyl, C1-C4 alkoxy or halogen.

5. The composition according to claim 1, wherein, R3 and R4 are each independently a substituted or unsubstituted aryloxy group, wherein the substituted aryloxy group is substituted by any number of the following substituents: -OH, -COOH, -COOCH3, -NH2, -NH (C1-C6 alkyl), -N (C1-C6 alkyl)2, -NO2, C1-C4 alkyl, C1-C4 alkoxy, or halogen.

6. The composition according to any one of claims 1-5, wherein, The aromatic amide polymer has the structure shown in formula (M1): （M1）； In formula (M1), J represents polyisobutylene.

7. The composition according to any one of claims 1-5, wherein, The carrier oil content is 10-50% by weight, based on the total weight of the composition.

8. The composition according to claim 7, wherein, The carrier oil content is 40-45% by weight, based on the total weight of the composition.

9. The composition according to any one of claims 1-5, wherein, The carrier oil is at least one of polyether synthetic oil, polyalphaolefin synthetic oil, and mineral oil.

10. The composition according to any one of claims 1-5, wherein, The additive is selected from at least one of demulsifiers, rust inhibitors, and diluents.

11. The composition according to claim 10, wherein, Based on the total weight of the composition, the content of the demulsifier is 0.5-1% by weight, the content of the rust inhibitor is 0.5-1% by weight, and the content of the diluent is 10-30% by weight.

12. A method for preparing the composition according to any one of claims 1-11, characterized in that, The method includes mixing an aromatic amide polymer, a Mannich base detergent, a carrier oil, and optional additives.

13. The method according to claim 12, wherein, The mixing conditions include a temperature of 45-60℃ and a time of 0.5-1.5h.

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