Crown ether polyether amine, gasoline additive and preparation method thereof

Abstract

The invention discloses crown ether polyether amine, a gasoline additive and a preparation method of the crown ether polyether amine. The crown ether polyether amine is a compound shown as a formula (I) or a formula (II): # imgabs 0 # # imgabs 1 #, wherein R is selected from methyl and / or ethyl; m is equal to 1-5; x is equal to 0-3, y is equal to 2-30, and x + y is equal to 5-30; r1 is selected from methyl and / or ethyl; p is equal to 1-5; x1 is equal to 0-3, y1 is equal to 2-30, and x1 + y1 is equal to 5-30. The gasoline additive disclosed by the invention can be used for efficiently cleaning carbon deposition of a fuel nozzle, carbon deposition of an air inlet valve and carbon deposition of a combustion chamber.

Description

Technical Field

[0001] The invention relates to the technical field of fuel additives, and in particular to a crown ether polyether amine, a gasoline additive and a preparation method thereof. Background Art

[0002] During the operation of the car, a large amount of deposits are generated in the engine intake system (including carburetor, fuel injector, intake valve) and the combustion chamber, affecting the normal injection, atomization, mixing and combustion of the fuel. Carbon deposits on the intake valve can significantly affect the combustion process and directly lead to a sharp increase in NO, CO and HC emissions, causing serious damage to the atmospheric environment. A large number of studies have shown that the use of appropriate detergents is a practical and effective measure to improve gasoline quality and achieve energy conservation and emission reduction.

[0003] Gasoline detergent is a composite gasoline additive with cleaning, dispersing, anti-oxidation and anti-rust properties. When added to automotive gasoline, it can not only inhibit the formation of deposits inside the fuel system, but also quickly disperse and remove the deposits that have been formed, thereby ensuring the normal performance of the vehicle engine and improving the combustion performance of the fuel; it can greatly reduce the HC and CO pollutants in automobile exhaust emissions, thereby purifying automobile exhaust, reducing automobile maintenance costs and saving fuel. At the same time, gasoline detergent itself is a non-metallic ash-free multifunctional composite fuel additive. It will not produce any ash when burned, and will not have any adverse effects such as corrosion and swelling on automobile parts.

[0004] In recent years, hydrocarbon-substituted (poly)amines represented by polyisobutyleneamine (PIBA), amides represented by polyisobutylene succinimide, polyetheramine detergents and Mannich base detergents have been developed one after another. Among them, amide detergents have excellent cleaning ability for deposits at the injection nozzle, but cannot clean deposits at high-temperature components; hydrocarbon-substituted (poly)amines and Mannich base detergents can effectively clean deposits at the injection nozzle and intake valve, but will increase combustion chamber deposits; conventional polyetheramine detergents can effectively remove carbon deposits in the combustion chamber, but their thermal stability is poor, and they are almost completely decomposed when the temperature exceeds 300°C, so they are not effective in cleaning high-temperature components such as intake valves.

[0005] Therefore, there is an urgent need for an additive that can not only efficiently remove carbon deposits in the combustion chamber, but also has a good cleaning effect on high-temperature components such as the intake valve. Summary of the invention

[0006] In order to solve the problems existing in the prior art, the present invention provides a crown ether polyether amine, a gasoline additive and a preparation method thereof. The crown ether polyether amine of the present invention is prepared by using an amino-containing crown ether as an initiator and propylene oxide and optionally butylene oxide under base catalysis; the crown ether-containing polyether reacts with liquid ammonia and hydrogen in the presence of a Raney nickel catalyst to obtain the crown ether polyether amine. The product of the present invention acts as a gasoline detergent, which can not only efficiently clean carbon deposits on fuel nozzles, intake valves and combustion chambers, but also the crown ether group can complex metal ions, improve combustion characteristics, reduce pollution emissions, and has excellent comprehensive performance.

[0007] One of the objects of the present invention is to provide a crown ether polyether amine, wherein the crown ether polyether amine is a compound represented by the following formula (I) or formula (II):

[0008]

[0009] Wherein, R is selected from methyl and / or ethyl; m=1-5; x=0-3, y=2-30, and x+y=5-30; R 1 is selected from methyl and / or ethyl; p=1-5; x1=0-3, y1=2-30, and x1+y1=5-30; when R is selected from methyl and ethyl, it means include and Random arrangement; when R 1 When selected from methyl and ethyl, it means include and Random arrangement.

[0010] In a preferred embodiment of the present invention,

[0011] m=1~4; and / or, x=1~3; and / or, y=5~24, preferably y=5~15; and / or, x+y=8~24; and / or, p=1~4; and / or, x1=1~3; and / or, y1=5~24, preferably y1=5~15; and / or, x1+y1=8~24.

[0012] The second object of the present invention is to provide a method for preparing the crown ether polyether amine of one of the objects of the present invention, comprising:

[0013] (1) reacting an amine-containing crown ether with propylene oxide in the presence of an organic solvent and a base catalyst A to obtain a crown ether intermediate;

[0014] (2) reacting the crown ether intermediate obtained in step (1) with butylene oxide and / or propylene oxide in the presence of a base catalyst B to obtain a crown ether polyether;

[0015] (3) introducing liquid ammonia and hydrogen into the crown ether polyether obtained in step (2) in the presence of an amination reaction catalyst to carry out an amination reaction to obtain the crown ether polyether amine.

[0016] In a preferred embodiment of the present invention,

[0017] In step (1),

[0018] The amino-containing crown ether has the following structure:

[0019] Wherein, m=1-5; p=1-5; preferably, the amine-containing crown ether is one of 2-aminomethyl-15-crown-5 ether, 2-aminomethyl-18-crown-6 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 and 4'-aminobenzo-24-crown-8 ether; and / or,

[0020] The base catalyst A is at least one of potassium hydroxide, sodium hydroxide and sodium ethoxide; and / or,

[0021] The organic solvent is at least one of toluene, xylene, trimethylbenzene and ethylbenzene; and / or,

[0022] The molar ratio of propylene oxide to the amine-containing crown ether is (1-4):1, preferably (2-4):1; and / or, the mass ratio of the amine-containing crown ether to the organic solvent is 1:(0.5-5), preferably 1:(0.5-2); and / or, the amount of the base catalyst A is 0.2-2% of the mass of propylene oxide, preferably 1-2%; and / or,

[0023] The reaction temperature is 110-140° C., preferably 120-130° C.; preferably, the reaction is stopped when the pressure drops to negative pressure.

[0024] In a preferred embodiment of the present invention,

[0025] In step (2),

[0026] The base catalyst B is at least one of potassium hydroxide, sodium hydroxide and sodium ethoxide; and / or,

[0027] The total molar amount of propylene oxide and / or butylene oxide is 2 to 30 times, preferably 5 to 24 times, more preferably 5 to 15 times, and further preferably 8 to 12 times the molar amount of the amino-containing crown ether; and / or,

[0028] The amount of the base catalyst B is 0.2 to 2%, preferably 0.2 to 1%, of the total mass of the propylene oxide and butylene oxide introduced in step (2); and / or,

[0029] The reaction temperature is 110-140° C., preferably 120-130° C.; preferably, the reaction is stopped when the pressure drops to negative pressure.

[0030] In a preferred embodiment of the present invention,

[0031] In step (3),

[0032] The amination reaction catalyst is at least one of Raney nickel catalysts; and / or,

[0033] The amount of the amination reaction catalyst is 5-20% of the mass of the crown ether polyether, preferably 5-15%; and / or, the amount of liquid ammonia is 2-20 times, preferably 2-10 times, the molar amount of the crown ether polyether; and / or, the amount of hydrogen is 1-20 times, preferably 1-10 times, the molar amount of the crown ether polyether; and / or,

[0034] The temperature of the amination reaction is 120-220° C., preferably 150-200° C.; and / or, the time of the amination reaction is 2-12 hours, preferably 5-10 hours; and / or, the pressure of the amination reaction is 2-10 MPa, preferably 5-10 MPa.

[0035] The preparation method of the crown ether polyether amine of the present invention can adopt the following specific technical scheme:

[0036] (1) placing an amino-containing crown ether, an organic solvent and a base catalyst A into an autoclave, evacuating the air, and then heating the autoclave to 110-140° C., introducing propylene oxide in a molar ratio of (1-4):1 to the amino-containing crown ether to carry out polymerization reaction, controlling the reaction pressure not to exceed 0.3 MPa, and continuing the heat preservation reaction after the pressure drops to negative pressure, cooling the autoclave to below 80° C., neutralizing the reaction mixture, dehydrating, filtering and distilling off the solvent to obtain a crown ether intermediate;

[0037] (2) placing the crown ether intermediate obtained in step (1) and the base catalyst B into a high-pressure reactor, evacuating the air, then heating to 110-140° C., introducing butylene oxide and / or propylene oxide in a total molar amount of 2-30 times the molar amount of the amino-containing crown ether to carry out polymerization reaction, controlling the reaction pressure not to exceed 0.3 MPa, and continuing the heat-insulating reaction after the pressure drops to negative pressure, cooling to below 80° C., neutralizing, dehydrating, and filtering the reaction mixture to obtain the intermediate product crown ether polyether;

[0038] (3) The crown polyether obtained in step (2) and an amination reaction catalyst are added to a high-pressure reactor, the air is removed by vacuuming, liquid ammonia and hydrogen are introduced, and an amination reaction is carried out at 2 to 10 MPa and 120 to 220° C. for 2 to 12 hours, and then cooled to below 80° C., the reaction mixture is taken out, the insoluble matter is removed by filtration, and the unreacted liquid ammonia is removed from the filtrate to obtain a crown polyether amine.

[0039] The third object of the present invention is to provide a gasoline additive comprising the following components:

[0040] 1) Solvent oil;

[0041] 2) The crown ether polyetheramine of one of the purposes of the present invention or the crown ether polyetheramine obtained by the preparation method of the second purpose of the present invention;

[0042] 3) acetylenic glycol polyethers;

[0043] 4) Antioxidants;

[0044] Preferably,

[0045] Each component is calculated based on 100 parts by weight of solvent oil.

[0046] Crown ether polyether amine 10 to 100 parts by weight; preferably 20 to 80 parts by weight;

[0047] 0.5 to 10 parts by weight of acetylene glycol polyether; preferably 2 to 8 parts by weight;

[0048] Antioxidant 0.1 to 2 parts by weight; preferably 0.5 to 2 parts by weight.

[0049] In a preferred embodiment of the present invention,

[0050] The structural formula of the acetylene glycol polyether is as follows:

[0051]

[0052] Among them, R2 and R3 are methyl groups, R1 and R4 are the same or different and are independently selected from alkyl groups containing 3 to 8 carbon atoms; m1 and m2 are the same or different, m1+m2=0 to 16, n1 and n2 are the same or different, n1+n2=0 to 20, and m1, m2, n1, and n2 are not 0 at the same time.

[0053] (The acetylene glycol polyether is preferably prepared by the method in Chinese Patent No. 202211702264.2, which is incorporated herein in its entirety)

[0054] In a preferred embodiment of the present invention,

[0055] The solvent oil is a conventional solvent oil in the prior art, preferably an alkane solvent oil with a boiling range of 60 to 200° C., an aromatic solvent oil with a boiling range of 60 to 200° C., a C6 to C 12 At least one of alkyl alcohols, more preferably at least one of 60# solvent oil, 80# solvent oil, and 100# solvent oil; and / or,

[0056] The antioxidant is a conventional antioxidant in the prior art, and is preferably at least one of phenylenediamine, alkylphenylenediamine, p-tert-butylphenol, and 2,6-di-tert-butyl-p-cresol.

[0057] Conventional components in the art, such as polyether, etc., may also be added to the formula of the gasoline additive of the present invention. The amount used is also conventional and can be adjusted by technicians according to actual conditions.

[0058] The fourth object of the present invention is to provide a method for preparing the gasoline additive of the third object of the present invention, comprising uniformly mixing components including solvent oil, crown ether polyether amine, acetylene glycol polyether and antioxidant according to the stated amounts to obtain the gasoline additive.

[0059] Compared with the prior art, the present invention has the following beneficial effects:

[0060] Crown ether is a macrocyclic polyether containing multiple ethylene oxide structural units in the molecule. The crown ether containing active amino groups is first reacted with propylene oxide and optional butylene oxide to prepare polyoxypropylene polyoxybutylene ether containing crown ether, and then reacted with liquid ammonia and hydrogen to obtain crown ether polyether amine. The thermal stability of this polyether amine containing crown ether structural units is higher than that of conventional polyether amines, and has excellent dispersibility. The crown ether group in the molecular structure can be used as a carrier to complex metal ions. On the one hand, it can effectively remove the sediments including metal ions in the pipeline and combustion chamber. On the other hand, when the crown ether polyether amine is complexed with metal ions such as iron, cerium, palladium, etc., the particulate matter (PM) formed by mixed combustion with fuel will be closely attached to the surface of the metal catalyst of the particle trap, reducing the temperature of PM combustion. In addition, the acetylene glycol polyether contained in the gasoline additive of the present invention has low foaming and defoaming properties, is not easy to foam during use, can be firmly adsorbed on the metal surface, and inhibits the corrosion of the metal wall. DETAILED DESCRIPTION

[0061] The present invention is described in detail below in conjunction with specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the contents of the present invention still fall within the scope of protection of the present invention.

[0062] The raw materials used in the examples of the present invention are all conventional commercially available raw materials.

[0063] The structure of the crown ether polyetheramine obtained in the embodiment of the present invention is theoretically deduced through the chemical reaction mechanism and the added raw materials.

[0064] Preparation of decynediol polyoxypropylene (4) ether in Example 1:

[0065] (1) Preparation of nanocatalyst (Mg / Al / Co composite metal oxide catalyst):

[0066] Prepare a mixed solution I of NaOH and Na2CO3 with a molar concentration of 2:1 (the volume of mixed solution I is 100 mL, wherein 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 concentration of 3:1 (the volume of mixed solution II is 100 mL, wherein the molar concentration of Al(NO3)3 is 0.5 mol / L), prepare a CoNO3 solution of equal volume to that of mixed solution II, and its concentration is 1 / 5 of the molar concentration of Al(NO3)3 in the reaction mixture; keep the CoNO3 solution at a constant temperature of 60°C, and add mixed solution I and mixed solution II thereto simultaneously under vigorous stirring, and control the pH value to be 8.5-9.5 during the addition process; after the addition is completed, stir the reaction solution at a constant temperature for 30 minutes, and then put it into a 100°C oven for crystallization for 12 hours; the crystallized slurry is filtered and washed until the filtrate becomes neutral, and the filter cake is placed in an oven for drying; the dried solid is ball-milled in a ball mill to obtain a Mg / Al / Co composite metal oxide catalyst.

[0067] (2) 0.2 mol of tetramethyldecynediol (abbreviated as TMAD10, the structural formula of tetramethyldecynediol is: wherein R2 and R3 are -CH3, and R1 and R4 are both -CH2CH(CH3)2) and 0.9 g of the Mg / Al / Co composite metal oxide catalyst obtained in the above step (1) are put into a high-pressure reactor, stirred evenly, the air in the reactor is replaced with nitrogen three times, and the high-pressure reactor is evacuated for 30 min at 80° C. using a vacuum pump, and the evacuation is stopped; 0.8 mol of propylene oxide is slowly introduced into the reactor through a feed pipe, and the temperature of the reactor is increased to 115° C., the pressure in the reactor is controlled at about 0.20 MPa, and the reaction is stirred for 4 h; the reaction is stopped after the pressure in the reactor drops to negative pressure, the reaction mixture is taken out, and the nanocatalyst is removed by microporous membrane filtration to obtain decynediol polyoxypropylene (4) ether (TMAD10-PO4); the structural formula of the above decynediol polyoxypropylene (4) ether (TMAD10-PO4) is: Among them, R2 and R3 are -CH3, R1 and R4 are both -CH2CH(CH3)2, m1+m2=0, n1+n2=4.

[0068] Preparation of decynediol polyoxyethylene (8) polyoxypropylene (4) ether in Example 2:

[0069] (1) 0.2 mol of tetramethyldecynediol (TMAD10) and 0.9 g of the Mg / Al / Co composite metal oxide catalyst obtained above were put into a high-pressure reactor, stirred evenly, the air in the reactor was replaced with nitrogen for 3 times, and the high-pressure reactor was evacuated with a vacuum pump at 80° C. for 30 min, and the evacuation was stopped; 1.6 mol of ethylene oxide was slowly introduced into the reactor through a feed pipe, and the temperature of the reactor was raised to 115° C., the pressure in the reactor was controlled at about 0.20 MPa, and the reaction was stirred for 4 h; the reaction was stopped after the pressure in the reactor dropped to negative pressure, the reaction mixture was taken out, and the nanocatalyst was removed by microporous membrane filtration to obtain decynediol polyoxyethylene ether (TMAD10-EO8); the structural formula of the decynediol polyoxyethylene ether (TMAD10-EO8) is: Wherein, R2 and R3 are -CH3, R1 and R4 are both -CH2CH(CH3)2, m1+m2=8, n1+n2=0;

[0070] (2) 0.1 mol TMAD10-EO8 and 0.8 g Mg / Al / Co composite metal oxide catalyst were put into a high-pressure reactor, stirred evenly, the air in the reactor was replaced with nitrogen for 3 times, and the high-pressure reactor was evacuated with a vacuum pump at 80° C. for 30 min, and the evacuation was stopped; 0.4 mol propylene oxide was introduced into the reactor through a feed pipe, and the temperature of the reactor was increased to 125° C., the pressure in the reactor was controlled at about 0.3 MPa, and the reaction was stirred for 12 h; the reaction was stopped after the pressure in the reactor dropped to negative pressure, the reaction mixture was taken out, and the nanocatalyst was removed by microporous membrane filtration to obtain decynediol polyoxyethylene (8) polyoxypropylene (4) ether (TMAD10-EO8-PO4); the structural formula of the above-mentioned acetylene glycol polyoxyethylene polyoxypropylene ether (TMAD10-EO8-PO4) is: Among them, R2 and R3 are -CH3, R1 and R4 are both -CH2CH(CH3)2, m1+m2=8, n1+n2=4.

[0071] Preparation of decynediol polyoxypropylene (8) ether in Example 3:

[0072] 0.2 mol of tetramethyldecynediol (TMAD10 for short) and 0.9 g of the Mg / Al / Co composite metal oxide catalyst obtained above were put into a high-pressure reactor, stirred evenly, the air in the reactor was replaced with nitrogen for 3 times, and the high-pressure reactor was evacuated with a vacuum pump at 80° C. for 30 min, and the evacuation was stopped; 1.6 mol of propylene oxide was slowly introduced into the reactor through a feed pipe, and the temperature of the reactor was raised to 115° C., the pressure in the reactor was controlled at about 0.20 MPa, and the reaction was stirred for 4 h; the reaction was stopped after the pressure in the reactor dropped to negative pressure, the reaction mixture was taken out, and the nanocatalyst was removed by microporous membrane filtration to obtain decynediol polyoxypropylene (8) ether (TMAD10-PO8); the structural formula of the decynediol polyoxypropylene (8) ether (TMAD10-PO8) is: Among them, R2 and R3 are -CH3, R1 and R4 are both -CH2CH(CH3)2, m1+m2=0, n1+n2=8.

[0073] The structure of the acetylene glycol polyether obtained above is theoretically deduced from the reaction mechanism and the added raw materials.

[0074] Example 1

[0075] Preparation of crown ether polyether amine:

[0076] (1) 249 g (1 mol) of 2-aminomethyl-15-crown-5 ether, 250 mL of xylene and 1.82 g of potassium hydroxide were placed in a high-pressure reactor, and the air was removed by vacuum. The reactor was then heated to 125° C., and 116 g (2 mol) of propylene oxide was introduced to carry out polymerization reaction. The reaction pressure was controlled not to exceed 0.3 MPa. After the reaction was completed, the temperature was kept high and the reaction was continued. After the pressure dropped to negative pressure, the temperature was lowered to 80° C. The reaction mixture was neutralized with phosphonic acid to a pH of 7, dehydrated, filtered to remove insoluble matter, and the solvent was evaporated to obtain a structure of Crown ether intermediates;

[0077] (2) 365 g (1 mol) of the crown ether intermediate and 5.0 g of potassium hydroxide were placed in an autoclave, and the air was removed by vacuum. Then the autoclave was heated to 130° C., and 720 g (10 mol) of butylene oxide was introduced to carry out polymerization reaction. The reaction pressure was controlled not to exceed 0.3 MPa. After the reaction was completed, the temperature was kept high and the reaction was continued. After the pressure dropped to negative pressure, the temperature was lowered to 80° C. The mixture obtained by the reaction was neutralized with phosphonic acid to a pH of 7, dehydrated, and filtered to remove insoluble matter to obtain a structure of The intermediate product 2-aminomethyl-15-crown-5 ether polyoxypropylene polyoxybutylene ether;

[0078] (3) 542 g of 2-aminomethyl-15-crown-5 ether polyoxypropylene polyoxybutylene ether and 50 g of Raney nickel catalyst (CAS No. 7440-02-0) were placed in a reaction kettle, and the air in the kettle was removed by vacuum. 85 g of liquid ammonia and 5 mol of hydrogen were introduced, and an amination reaction was carried out at 8 MPa and 180° C. for 8 h, and then cooled to 80° C. The reaction mixture was taken out, and the insoluble matter was filtered out. The unreacted liquid ammonia was evaporated from the filtrate to obtain 2-aminomethyl-15-crown-5 ether polyoxypropylene polyoxybutylene ether amine, which was named crown ether polyether amine-1#, and its structural formula is Where p = 2, x1 = 1, y1 = 10, R 1 It is ethyl.

[0079] Preparation of gasoline additives:

[0080] 100 parts by weight of 60# solvent oil, 50 parts by weight of crown ether polyetheramine-1#, 2 parts by weight of decynediol polyoxypropylene (4) ether, and 0.5 parts by weight of p-phenylenediamine were uniformly mixed at 50° C. to obtain gasoline additive 1#.

[0081] Example 2

[0082] Preparation of crown ether polyether amine:

[0083] (1) 283 g (1 mol) of 4'-aminobenzo-15-crown-5 ether, 250 mL of xylene and 2.0 g of potassium hydroxide were placed in a high-pressure reactor, and the air was removed by vacuum. The reactor was then heated to 125° C., and 116 g of propylene oxide was introduced to carry out polymerization reaction. The reaction pressure was controlled not to exceed 0.3 MPa. After the reaction was completed, the reaction was continued at a temperature of 80° C. after the pressure dropped to negative pressure. The reaction mixture was neutralized with phosphonic acid to a pH of 7, dehydrated, filtered to remove insoluble matter, and the solvent was evaporated to obtain a structure of Crown ether intermediates;

[0084] (2) 399 g (1 mol) of the crown ether intermediate and 5.0 g of potassium hydroxide were placed in a high-pressure reactor, and the air was removed by vacuum. Then, the reactor was heated to 125° C., and 580 g (10 mol) of propylene oxide was introduced to carry out polymerization reaction. The reaction pressure was controlled not to exceed 0.3 MPa. After the propylene oxide was introduced, the reaction was continued at a temperature of 80° C. after the pressure dropped to negative pressure. The mixture obtained by the reaction was neutralized with phosphonic acid to a pH of 7, dehydrated, and filtered to remove insoluble matter, to obtain a structure of The intermediate product 4'-aminobenzo-15-crown-5 ether polyoxypropylene ether;

[0085] (3) 490 g of 4'-aminobenzo-15-crown-5 ether polyoxypropylene and 60 g of Raney nickel catalyst (CAS No. 7440-02-0) were placed in a reaction kettle, and the air in the kettle was removed by vacuum. 90 g of liquid ammonia and 5 mol of hydrogen were introduced, and an amination reaction was carried out at 6 MPa and 160° C. for 6 h. The reaction mixture was then cooled to 80° C., and the insoluble matter was removed by filtration. The unreacted liquid ammonia was removed from the filtrate to obtain 4'-aminobenzo-15-crown-5 ether polyoxypropylene ether amine, which was named crown ether polyether amine-2#, and its structural formula is Wherein, m=2, x=1, y=10, and R is a methyl group.

[0086] Preparation of gasoline additives:

[0087] 100 parts by weight of 80# solvent oil, 35 parts by weight of crown ether polyetheramine-2#, 2 parts by weight of decynediol polyoxyethylene (8) polyoxypropylene (4) ether, and 0.5 parts by weight of p-tert-butylphenol were mixed uniformly at 50° C. to obtain gasoline additive 2#.

[0088] Example 3

[0089] Preparation of crown ether polyether amine:

[0090] (1) 327 g (1 mol) of 4'-aminobenzo-18-crown-6 ether, 250 mL of xylene and 2.0 g of sodium ethoxide are placed in a high-pressure reactor, and the air is removed by vacuum. Then, the reactor is heated to 125° C., 116 g of propylene oxide is introduced into the reactor for polymerization, and the reaction pressure is controlled not to exceed 0.3 MPa. After the reaction is completed, the reaction is continued at a temperature of 80° C. after the pressure drops to negative pressure. The mixture obtained by the reaction is neutralized with phosphonic acid to a pH of 7, dehydrated, filtered to remove insoluble matter, and the solvent is evaporated to obtain a crown ether intermediate;

[0091] (2) 443 g (1 mol) of the crown ether intermediate and 5.0 g of potassium hydroxide were placed in a high-pressure reactor, and the air was removed by vacuum. Then, the reactor was heated to 130° C., and 360 g (5 mol) of butylene oxide and 232 g (4 mol) of propylene oxide were introduced to carry out polymerization reaction. The reaction pressure was controlled not to exceed 0.3 MPa. After the reaction was completed, the temperature was kept high and the reaction was continued. After the pressure dropped to negative pressure, the temperature was lowered to 80° C., and the reaction mixture was neutralized with phosphonic acid to a pH of 7, dehydrated, and filtered to remove insoluble matter to obtain the intermediate product 4'-aminobenzo-18-crown-6 ether polyoxypropylene polyoxybutylene ether;

[0092] (3) 500 g of 4'-aminobenzo-18-crown-6 ether polyoxypropylene polyoxybutylene ether and 50 g of Raney nickel catalyst (CAS No. 7440-02-0) were placed in a reaction kettle, and the air in the kettle was removed by vacuum. 90 g of liquid ammonia and 6 mol of hydrogen were introduced, and an amination reaction was carried out at 9 MPa and 190° C. for 8 h, and then cooled to 80° C. The reaction mixture was taken out, and the insoluble matter was filtered out. The unreacted liquid ammonia was evaporated from the filtrate to obtain 4'-aminobenzo-18-crown-6 ether polyoxypropylene polyoxybutylene ether amine, which was named crown ether polyether amine-3#, and its structural formula is Among them, m=3, x=1, y=9, and R is methyl and ethyl.

[0093] Preparation of gasoline additives:

[0094] 100 parts by weight of 100# solvent oil, 50 parts by weight of crown ether polyetheramine-3#, 2 parts by weight of decynediol polyoxypropylene (8) ether, and 0.5 parts by weight of 2,6-di-tert-butyl-p-cresol are uniformly mixed at 50° C. to obtain gasoline additive 3#.

[0095] Comparative Example 1

[0096] Preparation of nonylphenol polyoxypropylene polyoxybutylene ether amine:

[0097] (1) 220 g (1 mol) of nonylphenol and 2.0 g of potassium hydroxide are placed in a high-pressure reactor, and the air is removed by vacuuming. The reactor is then heated to 135° C., 348 g (6 mol) of propylene oxide is first introduced to carry out polymerization reaction, and then 360 g (5 mol) of butylene oxide is introduced to carry out polymerization reaction. The reaction pressure is controlled not to exceed 0.3 MPa. After the reaction is completed, the reaction is continued at a temperature of 80° C. after the pressure drops to negative pressure. The mixture obtained by the reaction is neutralized with phosphonic acid to a pH of 7, dehydrated, and filtered to remove insoluble matter to obtain nonylphenol polyoxypropylene polyoxybutylene ether;

[0098] (2) 500 g of nonylphenol polyoxypropylene polyoxybutylene ether and 50 g of Raney nickel catalyst (CAS No. 7440-02-0) were placed in a reaction kettle, and the air in the kettle was removed by vacuum. 90 g of liquid ammonia and 6 mol of hydrogen were introduced, and an amination reaction was carried out at 9 MPa and 190° C. for 8 h, and then cooled to 80° C. The reaction mixture was taken out, and the insoluble matter was removed by filtration. The unreacted liquid ammonia was removed from the filtrate to obtain nonylphenol polyoxypropylene polyoxybutylene ether amine.

[0099] Preparation of gasoline additives:

[0100] 100 parts by weight of 100# solvent oil, 50 parts by weight of nonylphenol polyoxypropylene polyoxybutylene ether amine, 2 parts by weight of decynediol polyoxypropylene (8) ether (same as in Example 3), and 0.5 parts by weight of 2,6-di-tert-butyl-p-cresol were mixed uniformly at 50° C. to obtain gasoline additive 4#.

[0101] Comparative Example 2

[0102] Preparation of gasoline additives:

[0103] 100 parts by weight of 100# solvent oil, 16 parts by weight of 4'-aminobenzo-18-crown-6 ether, 50 parts by weight of nonylphenol polyoxypropylene polyoxybutylene ether amine prepared in Comparative Example 1, 2 parts by weight of decynediol polyoxypropylene (8) ether (same as Example 3), and 0.5 parts by weight of 2,6-di-tert-butyl-p-cresol were mixed uniformly at 50° C. to obtain gasoline additive 5#.

[0104] Comparative Example 3

[0105] Preparation of gasoline additives:

[0106] 100 parts by weight of 60# solvent oil, 50 parts by weight of polyetheramine D230, 2 parts by weight of decynediol polyoxypropylene (4) ether (same as in Example 1), and 0.5 parts by weight of p-phenylenediamine were mixed uniformly at 50° C. to obtain gasoline additive 6#.

[0107] Test Example 1

[0108] The same concentration (recommended ratio: 800 mg / L (in terms of polyetheramine)) of commercial gasoline detergent and the gasoline additives in Examples 1 to 3 and Comparative Examples 1 to 3 were added to 92# base gasoline, and the carbon removal data were compared according to the method of GB / T19230.6. The data comparison is shown in Table 1 below.

[0109] Table 1 Performance comparison of gasoline additives in the embodiments and comparative examples

[0110]

[0111] It can be seen from Example 3, Comparative Examples 1-2 and Table 1 that, compared with adding a polyetheramine prepared under the same conditions of the present invention using a conventional initiator in the art (such as nonylphenol) to the gasoline additive (Comparative Example 1) or further adding an amino-containing crown ether (Comparative Example 2), the gasoline additive containing the crown ether polyetheramine of the present invention obviously has a better cleaning effect on the fuel intake system and combustion chamber of the automobile engine.

[0112] It can be seen from Example 1, Comparative Example 3 and Table 1 that compared with the crown ether polyetheramine of the present invention and the conventional polyetheramine used in the prior art, the gasoline additive containing the crown ether polyetheramine of the present invention has a more obvious cleaning effect on the fuel intake system and combustion chamber of the automobile engine.

[0113] As can be seen from Examples 1-3 and Table 1, the crown ether polyetheramine gasoline additive of the present invention, when added to commercially available automotive gasoline, has an obvious cleaning effect on the fuel intake system and combustion chamber of the automobile engine. Thus, the engine operating condition can be kept in a good state for a long time, the fuel consumption will not increase too fast, and the exhaust harmful emission will be reduced, thereby reducing the engine maintenance cost and extending the engine service life.

Claims

1. A crown ether polyether amine, wherein the crown ether polyether amine is a compound represented by the following formula (I) or formula (II): in, R is selected from methyl and / or ethyl; m=1-5; x=0-3, y=2-30, and x+y=5-30; R 1 Selected from methyl and / or ethyl; p=1-5; x1=0-3, y1=2-30, and x1+y1=5-30.

2. The crown ether polyetheramine according to claim 1, characterized in that: m=1~4; and / or, x=1~3; and / or, y=5~24; and / or, x+y=8~24; and / or, p=1~4; and / or, x1=1~3; and / or, y1=5~24; and / or, x1+y1=8~24.

3. A method for preparing a crown ether polyetheramine as claimed in any one of claims 1 to 2, comprising: (1) reacting an amine-containing crown ether with propylene oxide in the presence of an organic solvent and a base catalyst A to obtain a crown ether intermediate; (2) reacting the crown ether intermediate obtained in step (1) with butylene oxide and / or propylene oxide in the presence of a base catalyst B to obtain a crown ether polyether; (3) introducing liquid ammonia and hydrogen into the crown ether polyether obtained in step (2) in the presence of an amination reaction catalyst to carry out an amination reaction to obtain the crown ether polyether amine.

4. The preparation method according to claim 3, characterized in that: In step (1), The amino-containing crown ether has the following structure: Wherein, m=1-5; p=1-5; preferably, the amine-containing crown ether is one of 2-aminomethyl-15-crown-5 ether, 2-aminomethyl-18-crown-6 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 and 4'-aminobenzo-24-crown-8 ether; and / or, The base catalyst A is at least one of potassium hydroxide, sodium hydroxide and sodium ethoxide; and / or, The organic solvent is at least one of toluene, xylene, trimethylbenzene and ethylbenzene; and / or, The molar ratio of propylene oxide to the amine-containing crown ether is (1-4):1, preferably (2-4):1; and / or, the mass ratio of the amine-containing crown ether to the organic solvent is 1:(0.5-5), preferably 1:(0.5-2); and / or, the amount of the base catalyst A is 0.2-2% of the mass of propylene oxide, preferably 1-2%; and / or, The reaction temperature is 110-140°C, preferably 120-130°C.

5. The preparation method according to claim 3, characterized in that: In step (2), The base catalyst B is at least one of potassium hydroxide, sodium hydroxide and sodium ethoxide; and / or, The total molar amount of propylene oxide and / or butylene oxide is 2 to 30 times, preferably 5 to 24 times, the molar amount of the amino-containing crown ether; and / or, The amount of the base catalyst B is 0.2 to 2%, preferably 0.2 to 1%, of the total mass of the propylene oxide and butylene oxide introduced in step (2); and / or, The reaction temperature is 110-140°C, preferably 120-130°C.

6. The preparation method according to claim 3, characterized in that: In step (3), The amination reaction catalyst is at least one of Raney nickel catalysts; and / or, The amount of the amination reaction catalyst is 5-20% of the mass of the crown ether polyether, preferably 5-15%; and / or, the amount of liquid ammonia is 2-20 times, preferably 2-10 times, the molar amount of the crown ether polyether; and / or, the amount of hydrogen is 1-20 times, preferably 1-10 times, the molar amount of the crown ether polyether; and / or, The temperature of the amination reaction is 120-220° C., preferably 150-200° C.; and / or, the time of the amination reaction is 2-12 hours, preferably 5-10 hours; and / or, the pressure of the amination reaction is 2-10 MPa, preferably 5-10 MPa.

7. A gasoline additive comprising the following components: 1) Solvent oil; 2) The crown ether polyetheramine according to any one of claims 1 to 2 or the crown ether polyetheramine obtained by the preparation method according to any one of claims 3 to 6; 3) acetylenic glycol polyethers; 4) Antioxidants; Preferably, Each component is calculated based on 100 parts by weight of solvent oil. Crown ether polyether amine 10 to 100 parts by weight; preferably 20 to 80 parts by weight; 0.5 to 10 parts by weight of acetylene glycol polyether; preferably 2 to 8 parts by weight; Antioxidant 0.1 to 2 parts by weight; preferably 0.5 to 2 parts by weight.

8. The gasoline additive according to claim 7, characterized in that: The structural formula of the acetylene glycol polyether is as follows: Among them, R2 and R3 are methyl groups, R1 and R4 are the same or different and are independently selected from alkyl groups containing 3 to 8 carbon atoms; m1 and m2 are the same or different, m1+m2=0 to 16, n1 and n2 are the same or different, n1+n2=0 to 20, and m1, m2, n1, and n2 are not 0 at the same time.

9. The gasoline additive according to claim 7, characterized in that: The solvent oil is an alkane solvent oil with a boiling range of 60 to 200° C., an aromatic solvent oil with a boiling range of 60 to 200° C., a C6 to C 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.

10. A method for preparing the gasoline additive according to any one of claims 7 to 9, comprising uniformly mixing components including solvent oil, crown ether polyether amine, acetylene glycol polyether and antioxidant according to the amounts mentioned above to obtain the gasoline additive.

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