Polyisobutylene succinimide containing crown ether metal complex structure, multifunctional fuel additive and its preparation and application

Abstract

The application discloses a polyisobutylene succinimide containing a crown ether metal complex structure, a multifunctional fuel additive and a preparation method and application thereof. The polyisobutylene succinimide containing the crown ether metal complex structure is prepared from raw materials including polyisobutylene succinic anhydride, a crown ether and a metal salt. The polyisobutylene succinimide surfactant containing the crown ether metal complex structure has higher thermal stability than conventional polyisobutylene succinimide, has excellent dispersibility, and the crown ether group in the molecular structure can be used as a carrier to complex metal ions such as potassium, calcium, magnesium, iron, cerium, platinum and palladium; after being added into fuel oil, the polyisobutylene succinimide can be mixed with the fuel oil to combust, PM formed in the combustion is closely attached to the surface of a metal catalyst, and the temperature of the combustion of the PM is reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of fuel additives, in particular to a polyisobutylene succinimide containing crown ether metal complex structure, a multifunctional fuel additive, and a preparation method and application thereof. BACKGROUND

[0002] The main pollutants of motor vehicle exhaust emissions are carbon monoxide (CO), hydrocarbons (HC), nitrogen oxides (NOx) and particulate matter (PM). According to the data released by the Ministry of Ecology and Environment, automobiles are the main contributors to motor vehicle air pollution emissions, with more than 90% of CO, NOx and PM, and more than 80% of HC. Diesel trucks, which account for 7.9% of the total number of automobiles, emit 60.0% of NOx and 84.6% of PM, and are the top priority for motor vehicle pollution prevention and control.

[0003] With the release and implementation of the national VI emission regulations, the standards for automobile exhaust emissions in China are becoming more and more stringent. In addition to improving oil refining technology, the use of fuel additives has become one of the important technical means to improve fuel quality and improve engine operating conditions.

[0004] Fuel additives are a class of additives used to improve fuel performance, including antiknock agents, antioxidants, metal passivators, anti-icing agents, antistatic additives, anti-wear agents, low-temperature flow improvers, cetane improvers, detergents, combustion improvers, fuel catalytic regeneration additives (FBC), etc. The existing diesel additives on the market have single functions, and there are few multi-effect composite additives, which are mainly used to improve the combustion performance and detergency of diesel, and have no obvious effect on reducing the emission of pollutants from diesel vehicles.

[0005] Diesel fuel detergents primarily use detergent-dispersants, which are highly effective surfactants. Their polar groups have a strong adsorption capacity for existing carbon deposits and sediments, gradually loosening them and washing them off as small particles. Simultaneously, the detergent-dispersant prevents these small particles from forming large particles that aggregate on metal surfaces, thus providing a cleaning effect and protecting the engine's normal operation. Diesel fuel detergents can be divided into two main categories based on whether they contain metal components: ash-containing diesel fuel detergents and ashless diesel fuel detergents. Ash-containing detergents have excellent combustion-promoting and smoke-reducing effects, effectively inhibiting the formation of carbon particles from high-temperature diesel fuel cracking and promoting complete combustion. These mainly include sulfonate-type, high-alkalinity borate sulfonate-type, and salicylate-type detergents. Ashless detergents, particularly small-molecule amines like succinimide, were the first to be used. Later, hydrocarbon-substituted (poly)amines, represented by polyisobutylene amine (PIBA), amides (imides), polyetheramines, and Mannich base detergents were subsequently developed. Imidamine detergents have excellent cleaning ability for deposits on fuel injectors, but they cannot clean deposits on high-temperature components. Hydrocarbon-substituted (poly)amines and Mannich base detergents can effectively clean deposits on fuel injectors and intake valves, but they increase deposits in the combustion chamber. Polyetheramine detergents can efficiently remove carbon deposits in the combustion chamber, but polyetheramines have poor thermal stability and almost completely decompose at temperatures above 300°C, resulting in poor cleaning effects on high-temperature components such as intake valves.

[0006] Fuel borne catalyst (FBC) additives lower the activation energy of soot particles trapped in diesel particulate filters (DPFs) in diesel vehicles, making it easier to break the chemical bonds between soot particles and achieving DPF regeneration at lower temperatures. Currently used FBC catalysts are mainly iron-based and cerium-based organometallic compounds, with organic groups primarily consisting of naphthenic acids, octanoic acid, and oleic acid. These conventional FBC catalysts suffer from drawbacks such as poor dispersibility and limited functionality. Summary of the Invention

[0007] To address the limitations of conventional fuel additives in the prior art, such as limited functionality and poor performance, this invention provides a multifunctional fuel additive containing a crown ether metal complex structure, polyisobutylene succinimide, its preparation method, and its applications. The multifunctional fuel additive of this invention comprises solvent oil, polyisobutylene succinimide containing a crown ether metal complex structure, acetylsyl glycol polyether, and an antioxidant. This multifunctional fuel additive not only exhibits excellent dispersibility, reducing carbon buildup in vehicle engines, but also effectively lowers the equilibrium point temperature, resolving the passive regeneration failure of diesel particulate filters (DPFs) in diesel engines, reducing the number of active regeneration cycles, and extending the regeneration mileage.

[0008] One of the objectives of this invention is to provide a polyisobutylene succinimide with a crown ether metal complex structure, which is prepared from raw materials comprising the following components: polyisobutylene succinic anhydride, crown ether, and metal salt.

[0009] In a preferred embodiment of the present invention,

[0010] The polyisobutylene succinic anhydride has a molecular weight of 600-5000, preferably at least one of T2007A and T2007B type polyisobutylene succinic anhydrides; and / or,

[0011] The crown ether is an amino-containing crown ether, preferably at least one of 2-aminomethyl-15-crown-5 ether, 4'-aminobenzo-12-crown-4 ether, 4'-aminobenzo-15-crown-5 ether, 4'-aminobenzo-18-crown-6 ether, 4'-aminobenzo-21-crown-7 ether, diaminodibenzo-14-crown-4 ether, diaminodibenzo-15-crown-5 ether, diaminodibenzo-18-crown-6 ether, and diaminodibenzo-21-crown-7 ether; the crown ether can be commercially available or prepared by conventional methods in the prior art; and / or,

[0012] The metal salt is at least one of the following: chloride, nitrate, acetate, and perchlorate of potassium, calcium, magnesium, iron, cerium, platinum, and palladium.

[0013] In a preferred embodiment of the present invention,

[0014] The preparation method of the polyisobutylene succinimide containing the crown ether metal complex structure includes:

[0015] (1) The crown ether and polyisobutylene succinic anhydride are reacted in solvent A to obtain polyisobutylene succinimide containing a crown ether structure;

[0016] (2) Dissolve the metal salt and the crown ether-containing polyisobutylene succinimide obtained in step (1) in solvent B and solvent C respectively, and then mix them to react and obtain the crown ether-containing metal complex structure polyisobutylene succinimide.

[0017] In a preferred embodiment of the present invention,

[0018] In step (1),

[0019] Solvent A is at least one selected from toluene, xylene, pyridine, N,N-dimethylformamide, and N,N-dimethylacetamide; and / or,

[0020] The molar ratio of the crown ether to polyisobutylene succinic anhydride is 0.5–1.5:1, preferably 1–1.5:1; and / or,

[0021] The mass of solvent A is 1 to 10 times the mass of polyisobutylene succinic anhydride; and / or,

[0022] The reaction temperature is 40–150°C, and the reaction time is 3–18 h. Preferably, the reaction is carried out by stepwise heating, preferably at 40–80°C for 1–6 h, and then the reaction temperature is increased to 80–150°C to continue the reaction for 2–12 h.

[0023] In a preferred embodiment of the present invention,

[0024] In step (2),

[0025] Solvent B is at least one of acetonitrile, ethanol, and water; and / or,

[0026] The solvent C is at least one selected from chloroform, dichloromethane, dichloroethane, and carbon tetrachloride; and / or,

[0027] The amount of solvent B is 1 to 10 times the mass of the crown ether-structured polyisobutylene succinimide; and / or,

[0028] The amount of solvent C used is 0.5 to 5 times the mass of the metal salt; and / or,

[0029] The molar ratio of the metal salt to the crown ether-containing polyisobutylene succinimide is 1–2:1; and / or,

[0030] The reaction temperature is 20–50°C, preferably 25–35°C, and the reaction time is 1–12 h, preferably 6–12 h. Preferably, the reaction is carried out in a constant temperature water bath shaker, and the shaking conditions are preferably 50–500 rpm.

[0031] The preparation method of the polyisobutylene succinimide containing a crown ether metal complex structure according to the present invention can adopt the following specific technical solutions:

[0032] (1) Take crown ether and polyisobutylene succinic anhydride at a molar ratio of 0.5 to 1.5:1 and dissolve them separately in solvent A. Slowly drop the polyisobutylene succinic anhydride solution into a reaction vessel containing crown ether solution. Under nitrogen or argon protection, stir and react at 40 to 80°C for 1 to 6 hours. Then raise the reaction temperature to 80 to 150°C and continue stirring and reacting for 2 to 12 hours. After the reaction is completed, distill under reduced pressure. The residue is polyisobutylene succinimide containing crown ether structure.

[0033] (2) Take metal salt and polyisobutylene succinimide with crown ether structure in a molar ratio of 1 to 2:1, and dissolve them in solvent B and solvent C respectively. Then mix them and shake them in a constant temperature water bath shaker at 20 to 50°C and 50 to 500 rpm for 1 to 12 hours. After evaporating the organic phase to remove the solvent, polyisobutylene succinimide with crown ether metal complex structure is obtained.

[0034] The second objective of this invention is to provide a multifunctional fuel additive for polyisobutylene succinimide containing a crown ether metal complex structure, comprising the following components:

[0035] a) Solvent oil;

[0036] b) One of the objectives of this invention is a polyisobutylene succinimide containing a crown ether metal complex structure;

[0037] c) Acetylene glycol polyether;

[0038] d) Antioxidants.

[0039] In a preferred embodiment of the present invention,

[0040] Each component is based on 100 parts by weight of solvent oil.

[0041] 100 parts by weight of solvent oil;

[0042] 10-50 parts by weight of polyisobutylene succinimide containing a crown ether metal complex structure; preferably 30-50 parts by weight;

[0043] 0.5 to 10 parts by weight of acetylacetonate diol polyether; preferably 2 to 8 parts by weight;

[0044] Antioxidant 0.1 to 2 parts by weight; preferably 0.5 to 2 parts by weight.

[0045] In a preferred embodiment of the present invention,

[0046] The structural formula of the acetylenic diol polyether is as follows:

[0047]

[0048] Wherein, R2 and R3 are methyl groups; R1 and R4 may be the same or different, and are independently selected from alkyl groups containing 3 to 8 carbon atoms; m1 and m2 may be the same or different, m1+m2 = 0 to 16, preferably m1+m2 = 2 to 10; n1 and n2 may be the same or different, n1+n2 = 0 to 20, preferably n1+n2 = 2 to 10; and m1, m2, n1, and n2 are not simultaneously 0; and / or,

[0049] The solvent oil is an alkane solvent oil with a boiling range of 60–200℃, an aromatic solvent oil with a boiling range of 60–200℃, or a C6–C4 solvent oil. 12 At least one of alkyl alcohols; and / or,

[0050] The antioxidant is at least one of phenylenediamine, alkylphenylenediamine, p-tert-butylphenol, and 2,6-di-tert-butyl-p-cresol.

[0051] The formulation of the multifunctional fuel additive of the present invention may also include conventional components in the art, such as propylene glycol polyether, glycerol polyether, nonylphenol polyether, etc., and the dosage is also conventional, which can be adjusted by technicians according to actual conditions.

[0052] The third objective of this invention is to provide a method for preparing a multifunctional fuel additive containing a crown ether metal complex structure of polyisobutylene succinimide, which is also an objective of this invention. The method includes mixing components including solvent oil, polyisobutylene succinimide containing a crown ether metal complex structure, acetylsyl glycol polyether, and antioxidant in the stated amounts until uniformly mixed to obtain the multifunctional fuel additive containing a crown ether metal complex structure of polyisobutylene succinimide.

[0053] The fourth objective of this invention is to provide an application of a multifunctional fuel additive containing a crown ether metal complex structure of polyisobutylene succinimide, which is also the second objective of this invention, or a multifunctional fuel additive containing a crown ether metal complex structure of polyisobutylene succinimide prepared by the method of the third objective of this invention, in diesel vehicle fuel. The multifunctional fuel additive is used in a blend with the fuel at a ratio of 1 / 10000 to 1 / 10.

[0054] Crown ethers are macrocyclic polyethers containing multiple oxyethylene group structural units in their molecules. Polyisobutylene succinimide, a surfactant containing crown ether functional groups, is formed by the amidation reaction of crown ethers containing active amino groups and polyisobutylene succinic anhydride. It has a crown ether ring as the polar head, succinimide as the linking group, and polyisobutylene as the lipophilic group. This crown ether-containing polyisobutylene succinimide surfactant exhibits higher thermal stability than conventional polyisobutylene succinimide and excellent dispersibility. The crown ether group in the molecular structure can act as a carrier to complex metal ions such as potassium, calcium, magnesium, iron, cerium, platinum, and palladium. When added to fuel oil and mixed with it for combustion, the resulting particulate matter (PM) adheres tightly to the surface of the metal catalyst, reducing the combustion temperature of the PM.

[0055] The beneficial effects of this invention are as follows:

[0056] The multifunctional polyisobutylene succinimide fuel additive with a crown ether metal complex structure described in this invention is used by mixing the additive with fuel at a ratio of 1 / 10000 to 1 / 10. It exhibits good solubility and not only has excellent dispersibility, reducing the amount of carbon deposits in vehicle engines, but also effectively lowers the equilibrium point temperature, resolving the failure of passive regeneration of diesel particulate filters (DPFs) in diesel engines, reducing the number of active regeneration cycles, and extending the regeneration mileage. In addition, the acetylenic glycol polyether has low foaming and defoaming properties, making it less prone to foaming during use. The acetylenic glycol surfactant can be firmly adsorbed onto metal surfaces, inhibiting corrosion of metal walls such as exhaust pipes at high temperatures. Detailed Implementation

[0057] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0058] All raw materials used in the examples are conventional commercially available raw materials.

[0059] Preparation of decantyne diol polyoxyethylene (4) ether in Example 1:

[0060] (1) Preparation of nanocatalysts (Mg / Al / Co composite metal oxide catalysts):

[0061] Prepare a mixed solution I of NaOH and Na₂CO₃ with a molar ratio of 2:1 (100 mL, where the molar concentration of Na₂CO₃ is 0.5 mol / L). Prepare a mixed solution II of Mg(NO₃)₂ and Al(NO₃)₃ with a molar ratio of 3:1 (100 mL, where the molar concentration of Al(NO₃)₃ is 0.5 mol / L). Prepare an equal volume of CoNO₃ solution to the concentration of mixed solution II. The concentration of Al(NO3)3 was 1 / 5; the CoNO3 solution was kept at 60℃ and mixed solution I and mixed solution II were added dropwise simultaneously with vigorous stirring, and the pH value was controlled at 8.5-9.5 during the dropwise addition; after the dropwise addition was completed, the reaction solution was stirred at a constant temperature for 30 min, and then placed in an oven at 100℃ for crystallization for 12 hours; the crystallized slurry was filtered and washed until the filtrate was neutral, and the filter cake was placed in an oven to dry; the dried solid was ball-milled to obtain the Mg / Al / Co composite metal oxide catalyst.

[0062] (2) 0.2 mol of tetramethyldecynediol (abbreviated as TMAD10, the structural formula of tetramethyldecynediol is: Among them, R2 and R3 are -CH3, and R1 and R4 are both -CH2CH(CH3)2) and 0.9g of the Mg / Al / Co composite metal oxide catalyst obtained in step (1) above are added into a high-pressure reactor, stirred evenly, and the air in the reactor is replaced with nitrogen three times. The high-pressure reactor is evacuated for 30 minutes at 80°C using a vacuum pump, and the evacuation is stopped. 0.8mol of ethylene oxide is slowly introduced into the reactor through the feed pipe, and the temperature of the reactor is raised to 115°C. The pressure in the reactor is controlled at about 0.20MPa, and the reaction is stirred for 4 hours. After the pressure in the reactor drops to negative pressure, the reaction is stopped, the reaction mixture is taken out, and the nano-catalyst is removed by microporous membrane filtration to obtain decynyl diol polyoxyethylene (4) ether (TMAD10-EO4);

[0063] The structural formula of the above-mentioned decantyne diol polyoxyethylene (4) ether (TMAD10-EO4) is as follows: Among them, R2 and R3 are -CH3, R1 and R4 are both -CH2CH(CH3)2, m1+m2=4, n1+n2=0.

[0064] Preparation of decantyne diol polyoxyethylene (8) ether in Example 3:

[0065] By changing the amount of ethylene oxide fed in the above steps to 1.6 mol, a decantyne glycol polyoxyethylene (8) ether (TMAD10-EO8) with an EO(C2H4O) number of 8 was obtained.

[0066] The structural formula of the above-mentioned decantyne glycol polyoxyethylene (8) ether (TMAD10-EO8) is as follows: Among them, R2 and R3 are -CH3, R1 and R4 are both -CH2CH(CH3)2, m1+m2=8, n1+n2=0.

[0067] Preparation of decantyne diol polyoxyethylene (8) polyoxypropylene (4) ether in Example 2:

[0068] 0.1 mol TMAD10-EO8 and 0.8 g of the Mg / Al / Co composite metal oxide catalyst obtained in step (1) above were added to a high-pressure reactor and stirred evenly. The air inside the reactor was replaced with nitrogen three times. The reactor was evacuated at 80°C for 30 min using a vacuum pump. The evacuation was then stopped. 0.4 mol propylene oxide was introduced into the reactor through the feed pipe, and the reactor temperature was raised to 125°C. The pressure inside the reactor was controlled at about 0.3 MPa. The reactor was stirred for 12 h. The reaction was stopped after the pressure inside the reactor dropped to negative pressure. The reaction mixture was removed and the nano-catalyst was removed by microporous membrane filtration to obtain decynyl diol polyoxyethylene (8) polyoxypropylene (4) ether (TMAD10-EO8-PO4).

[0069] The structural formula of the above-mentioned decynyl diol polyoxyethylene (8) polyoxypropylene (4) ether (TMAD10-EO8-PO4) is as follows: Among them, R2 and R3 are -CH3, R1 and R4 are both -CH2CH(CH3)2, m1+m2=8, n1+n2=4.

[0070] Example 1

[0071] Preparation of polyisobutylene succinimide containing a 2-aminomethyl-15-crown-5 ether-Fe complex structure: (1) Take 2-aminomethyl-15-crown-5 ether and polyisobutylene succinic anhydride T2007A at a molar ratio of 1.1:1 and dissolve them separately in pyridine. Slowly drop the polyisobutylene succinic anhydride pyridine solution (mass concentration of 20%) into a reaction vessel containing a crown ether pyridine solution (mass concentration of 50%). Under nitrogen protection, stir at 60°C (speed of 400 rpm) for 3 h. Then raise the reaction temperature to 120°C and continue stirring (speed of 400 rpm) for 6 h. After the reaction is completed, distill under reduced pressure and the residue is... (2) Take ferric acetate and polyisobutylene succinimide with crown ether structure in a molar ratio of 1:1, and dissolve them in water and chloroform respectively (the mass ratio of water to ferric acetate is 1:1, and the mass ratio of chloroform to polyisobutylene succinimide with crown ether structure is 1:1). Then mix the two and shake them in a constant temperature water bath shaker (model: SHA-B) at 30°C and 300 rpm for 8 hours. After separating the aqueous phase, remove the solvent from the organic phase to obtain polyisobutylene succinimide with 2-aminomethyl-15-crown-5 ether-Fe complex structure.

[0072] Preparation of a multifunctional fuel additive containing a 2-aminomethyl-15-crown-5-ether-Fe complex structure, polyisobutylene succinimide:

[0073] Multifunctional fuel additive #1 was prepared by mixing 30 parts by weight of polyisobutylene succinimide containing a 2-aminomethyl-15-crown-5 ether-Fe complex structure, 100 parts by weight of No. 6 solvent oil, 2.5 parts by weight of decynyl diol polyoxyethylene (4) ether, and 0.6 parts by weight of p-phenylenediamine at 50°C.

[0074] Solubility of Multifunctional Fuel Additive 1#: When multifunctional fuel additive-1# is mixed with diesel at a volume ratio of 1:10, it disperses well and shows no stratification or sedimentation after 12 months of storage.

[0075] The low-temperature dispersion performance of the multifunctional fuel additive was tested using the sludge spot dispersion test method. The sludge spot dispersion value (SDT) was used to evaluate the low-temperature dispersion performance of the dispersant; the higher the SDT value, the better the sludge dispersion performance of the dispersant at low temperatures. The sludge dispersibility test was conducted according to the SH / T0623-95 procedure. Without the multifunctional fuel additive, the STD value was 20. After adding 10% of multifunctional fuel additive #1, the STD value increased to 51, indicating that multifunctional fuel additive #1 has good sludge dispersion performance.

[0076] The nozzle coking test was conducted according to the methods and technical requirements specified in SH / T0764 "Test Method for Coking of Diesel Engine Nozzles (XUD-9 Method)". Without the addition of multi-functional fuel additive, the average air flow loss of cylinders 1-4 at a needle valve lift of 0.1 mm was 85.5%. After adding No. 1 multi-functional fuel additive at a fuel additive to diesel volume ratio of 1:1000, the average air flow loss of cylinders 1-4 at a needle valve lift of 0.1 mm was 22.2%. This multi-functional fuel additive has an excellent effect on removing engine carbon deposits.

[0077] Bench tests were conducted using a Weichai WP13 heavy-duty diesel engine. The bench test setup included the diesel engine, dynamometer, aftertreatment system (including DOC, DPF, and SCR), and data acquisition system. The engine operating point was adjusted to regulate exhaust temperature, and the DPF deposit equilibrium point temperature was measured, starting at 300°C and increasing by 20°C each time, ending at 440°C. The continuous passive regeneration equilibrium point temperature was determined by measuring the pressure difference across the DPF. For the same aftertreatment system (DPF including catalyst coating), the equilibrium point temperature was 400°C before the addition of fuel additives. Adding #1 multi-functional fuel additive to the diesel at a volume ratio of 1:100 reduced the equilibrium point temperature by 92°C.

[0078] A small truck equipped with a 2.0L CTI diesel engine was used for a real-vehicle test. The truck's DPF volume was 3.3L, with a rated maximum carbon load of 20g, and the regeneration interval was approximately 500km. During the test, a No. 1 multi-functional fuel additive was added to the diesel fuel at a concentration of 10mg / kg (based on iron content). Before the test, it was estimated that the DPF would trigger regeneration after approximately 400km of driving. After adding the No. 1 multi-functional fuel additive, the actual regeneration interval was triggered after approximately 4600km of driving, significantly extending the DPF regeneration interval.

[0079] Example 2

[0080] Preparation of polyisobutylene succinimide containing a 4'-aminobenzo-15-crown-5-Ce complex structure: (1) Take 4'-aminobenzo-15-crown-5 and polyisobutylene succinic anhydride T2007B at a molar ratio of 1.4:1 and dissolve them in toluene respectively. Slowly drop the polyisobutylene succinic anhydride toluene solution (mass concentration of 20%) into a reaction vessel containing a crown ether toluene solution (mass concentration of 50%). Under argon protection, stir at 60°C (speed of 400 rpm) for 6 h. Then raise the reaction temperature to 120°C and continue stirring (speed of 400 rpm) for 10 h. After the reaction is finished, reduce the pressure. Distillation, the residue is polyisobutylene succinimide containing the 4'-aminobenzo-15-crown-5-Ce complex structure; (2) Take cerium acetate and polyisobutylene succinimide containing the crown ether structure at a molar ratio of 1.8:1, and dissolve them in solvents ethanol and dichloromethane (the mass ratio of ethanol to cerium acetate is 1:1, and the mass ratio of dichloromethane to polyisobutylene succinimide containing the crown ether structure is 1:1), then mix the two and shake them in a constant temperature water bath shaker at 30°C and 400 rpm for 10 hours. After removing the solvent, polyisobutylene succinimide containing the 4'-aminobenzo-15-crown-5-Ce complex structure is obtained;

[0081] Preparation of a multifunctional fuel additive containing a polyisobutylene succinimide complex structure with a 4'-aminobenzo-15-crown-5-Ce complex:

[0082] Multifunctional fuel additive #2 was prepared by mixing 40 parts by weight of polyisobutylene succinimide containing a 4'-aminobenzo-15-crown-5-Ce complex structure, 100 parts by weight of No. 6 solvent oil, 4 parts by weight of decantyne glycol polyoxyethylene (8) polyoxypropylene (4) ether, and 0.8 parts by weight of p-tert-butylphenol at 50°C.

[0083] Solubility of Multifunctional Fuel Additive 2: When multifunctional fuel additive 2 is mixed with diesel at a volume ratio of 1:10, it disperses well and shows no stratification or sedimentation after 12 months of storage.

[0084] The low-temperature dispersion performance of the multifunctional fuel additive was tested using the sludge spot dispersion test method. The sludge spot dispersion value (SDT) was used to evaluate the low-temperature dispersion performance of the dispersant; the higher the SDT value, the better the sludge dispersion performance of the dispersant at low temperatures. The sludge dispersibility test was conducted according to the SH / T0623-95 procedure. Without the multifunctional fuel additive, the STD value was 20. After adding 10% of multifunctional fuel additive #2, the STD value increased to 46, indicating that multifunctional fuel additive #2 has good sludge dispersion performance.

[0085] The nozzle coking test was conducted according to the methods and technical requirements specified in SH / T0764 "Test Method for Coking of Diesel Engine Nozzles (XUD-9 Method)". Without the addition of multi-functional fuel additive, the average air flow loss of cylinders 1-4 when the needle valve lift was 0.1 mm was 85.5%. After adding No. 2 multi-functional fuel additive at a fuel additive to diesel volume ratio of 1:1000, the average air flow loss of cylinders 1-4 when the needle valve lift was 0.1 mm was 23.4%. This multi-functional fuel additive has an excellent effect on removing carbon deposits from the engine.

[0086] Bench tests were conducted using a Weichai WP13 heavy-duty diesel engine. The bench test setup included the diesel engine, a dynamometer, an aftertreatment system comprising a DOC (Diesel Oxide Catalyst), a diesel particulate filter (DPF), and an SCR (Self-Resistant Catalyst), and a data acquisition system. The engine operating point was adjusted to regulate exhaust temperature, and the DPF deposit equilibrium point temperature was measured, starting at 300°C and increasing by 20°C each time, ending at 440°C. The continuous passive regeneration equilibrium point temperature was determined by measuring the pressure difference across the DPF. For the same aftertreatment system (DPF including catalyst coating), the equilibrium point temperature was 400°C before the addition of fuel additives. Adding a No. 2 multi-functional fuel additive to the diesel fuel at a volume ratio of 1:100 reduced the equilibrium point temperature by 90°C.

[0087] A small truck equipped with a 2.0L CTI diesel engine was used for a real-vehicle test. The truck's DPF volume was 3.3L, with a rated maximum carbon load of 20g, and the vehicle's regeneration interval mileage was approximately 500km. During the test, a No. 2 multi-functional fuel additive was added to the diesel fuel at a concentration of 10mg / kg (based on cerium content). Before the test, it was estimated that the DPF would trigger regeneration after approximately 400km of driving. After adding the No. 2 multi-functional fuel additive, the actual regeneration interval mileage was approximately 4400km, significantly extending the DPF regeneration interval mileage.

[0088] Example 3

[0089] Preparation of polyisobutylene succinimide containing a diaminodibenzo-18-crown-6-Ce complex structure: (1) Diaminodibenzo-18-crown-6 and polyisobutylene succinic anhydride T2007B were taken at a molar ratio of 1.2:1 and dissolved in xylene respectively. The polyisobutylene succinic anhydride xylene solution (mass concentration of 20%) was slowly added dropwise to a reaction vessel containing a crown ether xylene solution (mass concentration of 50%). Under argon protection, the reaction was stirred at 60°C (speed of 400 rpm) for 6 h. Then the reaction temperature was increased to 130°C and the stirring was continued (speed of 400 rpm) for 10 h. After the reaction was completed, (2) Cerium acetate and polyisobutylene succinimide with crown ether structure were taken at a molar ratio of 1.2:1 and dissolved in solvents ethanol and dichloromethane (the mass ratio of ethanol to cerium acetate was 1:1, and the mass ratio of dichloromethane to polyisobutylene succinimide with crown ether structure was 1:1). The two were then mixed and shaken in a constant temperature water bath shaker at 30°C and 400 rpm for 10 hours. After removing the solvent, polyisobutylene succinimide with diaminodibenzo-18-crown-6-Ce complex structure was obtained.

[0090] Preparation of a multifunctional fuel additive containing a diaminodibenzo-18-crown-6-Ce complex structure of polyisobutylene succinimide:

[0091] Multifunctional fuel additive #3 was prepared by mixing 50 parts by weight of polyisobutylene succinimide containing a diaminodibenzo-18-crown-6-Ce complex structure, 100 parts by weight of isooctanol, 5 parts by weight of decantyne glycol polyoxyethylene (8) ether, and 1 part by weight of 2,6-di-tert-butyl-p-cresol at 50°C.

[0092] Solubility of Multifunctional Fuel Additive 3#: When multifunctional fuel additive 3# is mixed with diesel at a volume ratio of 1:10, it disperses well and shows no stratification or sedimentation after 12 months of storage.

[0093] The low-temperature dispersion performance of the multifunctional fuel additive was tested using the sludge spot dispersion test method. The sludge spot dispersion value (SDT) was used to evaluate the low-temperature dispersion performance of the dispersant; the higher the SDT value, the better the sludge dispersion performance of the dispersant at low temperatures. The sludge dispersibility test was conducted according to the SH / T0623-95 procedure. Without the multifunctional fuel additive, the STD value was 20. After adding 10% of the multifunctional fuel additive #3, the STD value increased to 55, indicating that the #3 multifunctional fuel additive has good sludge dispersion performance.

[0094] The nozzle coking test was conducted according to the methods and technical requirements specified in SH / T0764 "Test Method for Coking of Diesel Engine Nozzles (XUD-9 Method)". Without the addition of multi-functional fuel additive, the average air flow loss of cylinders 1-4 when the needle valve lift was 0.1 mm was 85.5%. After adding No. 3 multi-functional fuel additive at a fuel additive to diesel volume ratio of 1:1000, the average air flow loss of cylinders 1-4 when the needle valve lift was 0.1 mm was 20.6%. This multi-functional fuel additive has an excellent effect on removing carbon deposits from the engine.

[0095] Bench tests were conducted using a Weichai WP13 heavy-duty diesel engine. The bench test setup included the diesel engine, dynamometer, aftertreatment system including DOC, DPF (DPF) and SCR, and data acquisition system. The exhaust temperature was adjusted by regulating the engine's operating point, and the DPF deposit equilibrium point temperature was measured, starting at 300℃ and increasing by 20℃ each time, ending at 440℃. The continuous passive regeneration equilibrium point temperature was determined by measuring the pressure difference across the DPF. For the same aftertreatment system (DPF including catalyst coating), the equilibrium point temperature was 400℃ before the addition of fuel additives. Adding No. 3 multi-functional fuel additive to the diesel at a volume ratio of 1:100 reduced the equilibrium point temperature by 95℃.

[0096] A small truck equipped with a 2.0L CTI diesel engine was used for a real-vehicle test. The truck's DPF volume was 3.3L, with a rated maximum carbon load of 20g, and the vehicle's regeneration interval mileage was approximately 500km. During the test, a No. 3 multi-functional fuel additive was added to the diesel fuel at a concentration of 10mg / kg (based on cerium content). Before the test, it was estimated that the DPF would trigger regeneration after approximately 400km of driving. After adding the No. 3 multi-functional fuel additive, the actual regeneration interval mileage was approximately 4800km, significantly extending the DPF regeneration interval mileage.

[0097] Comparative Example 1

[0098] Preparation of the 2-aminomethyl-15-crown-5 ether-Fe complex: First, 2-aminomethyl-15-crown-5 ether was dissolved in chloroform to prepare a 0.5 mol / L crown ether solution; second, ferric acetate was dissolved in water to prepare a 0.5 mol / L iron salt solution; third, the crown ether solution from the first step and the iron salt solution from the second step were mixed at a volume ratio of 1:1 and placed in a constant temperature water bath shaker and shaken at 30℃ and 200 rpm for 8 hours; the filter residue after filtering the mixture from the third step was dried to obtain the 2-aminomethyl-15-crown-5 ether-Fe complex.

[0099] Preparation of a multifunctional fuel additive containing 2-aminomethyl-15-crown-5-ether-Fe complex and polyisobutylene succinimide (2-aminomethyl-15-crown-5-ether-Fe complex and polyisobutylene succinimide added at approximately a molar ratio of 1:1):

[0100] Take 7 parts by weight of 2-aminomethyl-15-crown-5 ether-Fe complex, 23 parts by weight of commercially available polyisobutylene succinimide (brand name T154A), 100 parts by weight of 6# solvent oil, 2.5 parts by weight of decynyl diol polyoxyethylene (4) ether, and 0.6 parts by weight of p-phenylenediamine, mix them evenly at 50°C to prepare multifunctional fuel additive-4#.

[0101] Solubility of Multifunctional Fuel Additive 4#: When multifunctional fuel additive 4# is mixed with diesel at a volume ratio of 1:10, it disperses well and shows no stratification or sedimentation after 12 months of storage.

[0102] The low-temperature dispersion performance of the multifunctional fuel additive was tested using the sludge spot dispersion test method. The sludge spot dispersion value (SDT) was used to evaluate the low-temperature dispersion performance of the dispersant; the higher the SDT value, the better the sludge dispersion performance of the dispersant at low temperatures. The sludge dispersibility test was conducted according to the SH / T0623-95 procedure. Without the multifunctional fuel additive, the STD value was 20. After adding 10% of the multifunctional fuel additive #4, the STD value increased to 38, indicating that the #4 multifunctional fuel additive has good sludge dispersion performance.

[0103] The nozzle coking test was conducted according to the methods and technical requirements specified in SH / T0764 "Test Method for Coking of Diesel Engine Nozzles (XUD-9 Method)". Without the addition of multi-functional fuel additive, the average air flow loss of cylinders 1-4 when the needle valve lift was 0.1 mm was 85.5%. After adding No. 4 multi-functional fuel additive at a fuel additive to diesel volume ratio of 1:1000, the average air flow loss of cylinders 1-4 when the needle valve lift was 0.1 mm was 36.4%. This multi-functional fuel additive has a good effect on removing carbon deposits from the engine.

[0104] Bench tests were conducted using a Weichai WP13 heavy-duty diesel engine. The bench test setup included the diesel engine, dynamometer, aftertreatment system (including DOC, DPF, and SCR), and data acquisition system. The engine operating point was adjusted to regulate exhaust temperature, and the DPF deposit equilibrium point temperature was measured, starting at 300°C and increasing by 20°C each time, ending at 440°C. The continuous passive regeneration equilibrium point temperature was determined by measuring the pressure difference across the DPF. For the same aftertreatment system (DPF including catalyst coating), the equilibrium point temperature was 400°C before the addition of fuel additives. Adding #4 multi-functional fuel additive to the diesel at a volume ratio of 1:100 reduced the equilibrium point temperature by 82°C.

[0105] A small truck equipped with a 2.0L CTI diesel engine was used for a real-vehicle test. The truck's DPF volume was 3.3L, with a rated maximum carbon load of 20g, and the vehicle's regeneration interval was approximately 500km. During the test, a No. 4 multi-functional fuel additive was added to the diesel fuel at a concentration of 10mg / kg (based on iron content). Before the test, it was estimated that the DPF would trigger regeneration after approximately 400km of driving. After adding the No. 4 multi-functional fuel additive, the actual regeneration interval was triggered after approximately 3900km of driving, extending the DPF regeneration interval.

[0106] As can be seen from Examples 1-3 and Comparative Example 1, the polyisobutylene succinimide containing a crown ether metal complex structure in Examples 1-3 of the present invention has better dispersibility than the polyisobutylene succinimide in Comparative Example 1, which adds the crown ether metal complex and polyisobutylene succinimide together to the fuel additive. This results in a more effective reduction of carbon deposits in vehicle engines, and can also more effectively lower the equilibrium point temperature, solve the problem of passive regeneration failure of diesel particulate filter (DPF), reduce the number of active regenerations, and extend the regeneration mileage.

Claims

1. A polyisobutylene succinimide containing a crown ether metal complex structure, prepared from a raw material comprising the following components: polyisobutylene succinic anhydride, a crown ether, and a metal salt; wherein the crown ether is an amino-containing crown ether; and the metal salt is at least one selected from the chloride, nitrate, acetate, and perchlorate of potassium, calcium, magnesium, iron, cerium, platinum, and palladium. The preparation method of the polyisobutylene succinimide containing the crown ether metal complex structure includes: (1) The crown ether and polyisobutylene succinic anhydride are reacted in solvent A to obtain polyisobutylene succinimide containing the crown ether structure; (2) Dissolve the metal salt and the polyisobutylene succinimide with crown ether structure obtained in step (1) in solvent B and solvent C respectively, and then mix them to react and obtain the polyisobutylene succinimide with crown ether metal complex structure.

2. The polyisobutylene succinimide with a crown ether metal complex structure as described in claim 1, characterized in that: The molecular weight of the polyisobutylene succinic anhydride is 600-5000; and / or, The crown ether is at least one of 2-aminomethyl-15-crown-5 ether, 4'-aminobenzo-12-crown-4 ether, 4'-aminobenzo-15-crown-5 ether, 4'-aminobenzo-18-crown-6 ether, 4'-aminobenzo-21-crown-7 ether, diaminodibenzo-14-crown-4 ether, diaminodibenzo-15-crown-5 ether, diaminodibenzo-18-crown-6 ether, and diaminodibenzo-21-crown-7 ether.

3. The polyisobutylene succinimide with a crown ether metal complex structure as described in claim 1, characterized in that: In step (1), Solvent A is at least one selected from toluene, xylene, pyridine, N,N-dimethylformamide, and N,N-dimethylacetamide; and / or, The molar ratio of the crown ether to polyisobutylene succinic anhydride is 0.5~1.5:1; and / or, The mass of solvent A is 1 to 10 times the mass of polyisobutylene succinic anhydride; and / or, The reaction temperature is 40~150℃, and the reaction time is 3~18h.

4. The polyisobutylene succinimide with a crown ether metal complex structure as described in claim 3, characterized in that: In step (1), The molar ratio of the crown ether to polyisobutylene succinic anhydride is 1~1.5:1; and / or, The reaction is carried out using a stepwise heating method.

5. The polyisobutylene succinimide with a crown ether metal complex structure as described in claim 4, characterized in that: In step (1), The reaction is carried out at 40~80℃ for 1~6 hours, and then the reaction temperature is increased to 80~150℃ to continue the reaction for 2~12 hours.

6. The polyisobutylene succinimide with a crown ether metal complex structure as described in claim 1, characterized in that: In step (2), Solvent B is at least one of acetonitrile, ethanol, and water; and / or, The solvent C is at least one selected from chloroform, dichloromethane, dichloroethane, and carbon tetrachloride; and / or, The amount of solvent B is 1 to 10 times the mass of the crown ether-structured polyisobutylene succinimide; and / or, The mass of solvent C is 0.5 to 5 times the mass of the metal salt; and / or, The molar ratio of the metal salt to the crown ether-containing polyisobutylene succinimide is 1~2:1; and / or, The reaction temperature is 20~50℃, and the reaction time is 1~12h.

7. The polyisobutylene succinimide with a crown ether metal complex structure as described in claim 6, characterized in that: In step (2), The reaction was carried out in a constant temperature water bath shaker at a shaking temperature of 50-500 rpm.

8. A multifunctional fuel additive containing a crown ether metal complex structure, comprising the following components: a) Solvent oil; b) Polyisobutylene succinimide with a crown ether metal complex structure as described in any one of claims 1-7; c) Acetylene glycol polyether; d) Antioxidants.

9. The multifunctional fuel additive containing a crown ether metal complex structure of polyisobutylene succinimide as described in claim 8, characterized in that: Each component is based on 100 parts by weight of solvent oil. 100 parts by weight of solvent oil; 10-50 parts by weight of polyisobutylene succinimide containing a crown ether metal complex structure; 0.5-10 parts by weight of acetylenic diol polyether; Antioxidant 0.1~2 parts by weight.

10. The multifunctional fuel additive containing a crown ether metal complex structure of polyisobutylene succinimide as described in claim 9, characterized in that: Each component is based on 100 parts by weight of solvent oil. 100 parts by weight of solvent oil; 30-50 parts by weight of polyisobutylene succinimide containing a crown ether metal complex structure; 2-8 parts by weight of acetylenic diol polyether; Antioxidant 0.5 to 2 parts by weight.

11. The multifunctional fuel additive containing a crown ether metal complex structure of polyisobutylene succinimide as described in claim 8, characterized in that: The structural formula of the acetylenic diol polyether is as follows: Wherein, R2 and R3 are methyl groups; R1 and R4 may be the same or different, and are independently selected from alkyl groups containing 3 to 8 carbon atoms; m1 and m2 may be the same or different, with m1 + m2 = 0 to 16; n1 and n2 may be the same or different, with n1 + n2 = 0 to 20; and m1, m2, n1, and n2 are not simultaneously 0; and / or, The solvent oil is an alkane solvent oil with a boiling range of 60~200℃, an aromatic solvent oil with a boiling range of 60~200℃, or a C6~C4 solvent oil. 12 At least one of alkyl alcohols; and / or, The antioxidant is at least one of phenylenediamine, alkylphenylenediamine, p-tert-butylphenol, and 2,6-di-tert-butyl-p-cresol.

12. A method for preparing a multifunctional fuel additive containing a crown ether metal complex structure of polyisobutylene succinimide as described in any one of claims 8-11, comprising mixing components including solvent oil, polyisobutylene succinimide containing a crown ether metal complex structure, acetylsyl glycol polyether, and antioxidant uniformly to obtain the multifunctional fuel additive containing a crown ether metal complex structure of polyisobutylene succinimide.

13. The application of a multifunctional polyisobutylene succinimide fuel additive with a crown ether metal complex structure as described in any one of claims 8-11, or a multifunctional polyisobutylene succinimide fuel additive with a crown ether metal complex structure prepared by the method of claim 12, in diesel vehicle fuel, wherein the multifunctional fuel additive is used in a blend with the fuel at a ratio of 1 / 10000 to 1 / 10.

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