Polyether amine as well as preparation method and application thereof

Abstract

The invention discloses polyether amine as well as a preparation method and application thereof. The polyether amine comprises at least one of compounds with a structure shown in a formula (1) or a formula (2): # imgabs0 # in the formula (1) and the formula (2), R is respectively and independently selected from methyl or ethyl; r1 and R2 are selected from methyl or ethyl; x1 is equal to 0-29, x2 is equal to 0-29, and x1 + x2 is equal to 1-29; r3 and R4 are selected from methyl or ethyl; y1 is equal to 0-40, y2 is equal to 0-40, and y1 + y2 is equal to 1-40; m is equal to 1-5; n is equal to 1-5. According to the fuel additive containing the polyether amine, carbon deposition of a fuel nozzle, carbon deposition of an air inlet valve and carbon deposition of a combustion chamber can be efficiently cleaned.

Description

Technical Field

[0001] The present invention relates to the technical field of fuel additives, in particular to a polyetheramine and a preparation method and application thereof. Background Art

[0002] With the release of the National VI emission regulations, emission standards are becoming increasingly stringent, and fuel requirements are becoming increasingly stringent. In addition to improving refining technology, the use of fuel additives has become a key technical means to enhance fuel quality and improve engine performance. During vehicle operation, large amounts of deposits form in the engine's intake system (including the carburetor, fuel injectors, and intake valves) and combustion chamber, impairing proper fuel injection, atomization, mixing, and combustion. Intake valve carbon deposits can significantly impact the combustion process and directly lead to a sharp increase in NO, CO, and HC emissions, severely damaging the atmospheric environment.

[0003] Recent research has found that additives such as polyisobutyleneamine (PIBA), polyisobutylene succinimide, and polyetheramine can both inhibit the formation of deposits within the fuel system and quickly disperse and remove existing deposits, thereby ensuring proper engine performance, improving fuel combustion performance, and significantly reducing HC and CO pollutants in vehicle exhaust emissions, thereby purifying vehicle exhaust, reducing vehicle maintenance costs, and saving fuel. However, these additives suffer from poor thermal stability, difficulty cleaning deposits from high-temperature components, and increased combustion chamber deposits. Therefore, a fuel additive that not only effectively removes carbon deposits from the combustion chamber but also has a good cleaning effect on high-temperature components such as the intake valve is urgently needed. Summary of the Invention

[0004] To solve the problems existing in the prior art, the present invention provides a polyetheramine and its preparation method and application. The fuel additive containing the polyetheramine of the present invention can effectively clean carbon deposits on fuel nozzles, intake valves and combustion chambers.

[0005] One of the objects of the present invention is to provide a polyetheramine comprising at least one of the compounds having a structure represented by the following formula (1) or formula (2):

[0006]

[0007] In formula (1) and formula (2), R is independently selected from methyl or ethyl; R 1 、R 2 is selected from methyl or ethyl; x1=0 to 29, x2=0 to 29, and x1+x2=1 to 29; R 3 、R 4Selected from methyl or ethyl; y1=0-40, y2=0-40, and y1+y2=1-40; m=1-5; n=1-5; x1, x2, y1, y2 represent the average degree of polymerization.

[0008] In a preferred embodiment of the present invention,

[0009] R 1 、R 2 is selected from methyl and R 3 、R 4 Selected from ethyl, or R 1 、R 2 Selected from ethyl and R 3 、R 4 selected from methyl; and / or,

[0010] x1=0-24, x2=0-24, and x1+x2=4-24; preferably, x1=0-12, x2=0-12, and x1+x2=4-12; and / or,

[0011] y1=0-20, y2=0-20, and y1+y2=1-20; preferably, y1=0-20, y2=0-20, and y1+y2=10-20; and / or,

[0012] m=1~3, and / or, n=1~3.

[0013] The structure of the polyetheramine in the present invention is theoretically deduced from the chemical reaction mechanism and the amount of added raw materials.

[0014] A second object of the present invention is to provide a method for preparing the polyetheramine of one of the objects of the present invention, comprising:

[0015] a) reacting 1,2-propylene glycol or 1,2-butylene glycol with propylene oxide or butylene oxide in the presence of catalyst A to obtain a polyether intermediate;

[0016] b) reacting the polyether intermediate obtained in step a) with butylene oxide or propylene oxide in the presence of catalyst B to obtain a block polyether;

[0017] c) dissolving the block polyether and acid binding agent obtained in step b) in solvent A, and reacting with p-toluenesulfonyl chloride to obtain polyether p-toluenesulfonate;

[0018] d) dissolving the polyether p-toluenesulfonate obtained in step c) in solvent B, and reacting with diaminodibenzocrown ether to obtain the polyetheramine.

[0019] The polyetheramine of the present invention is preferably characterized by being prepared by the above-mentioned preparation method of the present invention.

[0020] In a preferred embodiment of the present invention,

[0021] In step a),

[0022] The catalyst A is at least one of a DMC bimetallic catalyst and an alkaline catalyst. Preferably, the alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium ethoxide, and sodium hydride; and / or,

[0023] The molar ratio of propylene oxide to 1,2-propylene glycol or 1,2-butanediol is (1-29):1, preferably (4-24):1, more preferably (4-12):1; and / or the molar ratio of butylene oxide to 1,2-propylene glycol or 1,2-butanediol is (1-29):1, preferably (4-24):1, more preferably (4-12):1; and / or,

[0024] The amount of the catalyst A is 0.005-2% of the mass of propylene oxide or butylene oxide, preferably 0.01-1%; and / or,

[0025] The reaction temperature is 110-140° C., preferably 120-135° C.; preferably, the reaction is stopped when the pressure drops to negative pressure; and / or,

[0026] In step b),

[0027] The catalyst B is at least one of a DMC bimetallic catalyst and an alkaline catalyst. Preferably, the alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium ethoxide, and sodium hydride; and / or

[0028] The molar amount of propylene oxide or butylene oxide is 1 to 40 times, preferably 1 to 20 times, more preferably 10 to 20 times the molar amount of the polyether intermediate; and / or,

[0029] The amount of the catalyst B is 0.005-2%, preferably 0.01-1%, of the mass of the propylene oxide or butylene oxide introduced in step b); and / or,

[0030] The reaction temperature is 110-140° C., preferably 120-135° C.; preferably, the reaction is stopped when the pressure drops to negative pressure.

[0031] In a preferred embodiment of the present invention,

[0032] In step c),

[0033] The acid binding agent is at least one of pyridine, triethylamine, diisopropylethylamine, sodium acetate, sodium carbonate, and potassium carbonate; and / or,

[0034] The amount of the acid binding agent is 1 to 20 times, preferably 1 to 10 times, more preferably 2 to 4 times the molar amount of p-toluenesulfonyl chloride; and / or,

[0035] The solvent A is at least one of dichloromethane, chloroform, carbon tetrachloride, dichloroethane, toluene, xylene, trimethylbenzene, and ethylbenzene; and / or,

[0036] The amount of the solvent A is 1 to 20 times, preferably 1 to 10 times, more preferably 1 to 5 times the mass of the block polyether; and / or,

[0037] The amount of p-toluenesulfonyl chloride is 2 to 12 times, preferably 2 to 10 times, more preferably 2 to 6 times the molar amount of the blocked polyether; and / or,

[0038] The reaction temperature with p-toluenesulfonyl chloride is 0-40° C., preferably 5-20° C.; and / or the reaction time with p-toluenesulfonyl chloride is 6-72 h, preferably 18-48 h.

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

[0040] In step d),

[0041] The diaminodibenzo crown ether has the following structure:

[0042] wherein m=1-5, preferably m=1-3, n=1-5, preferably n=1-3; preferably, the diaminodibenzo crown ether is one of diaminodibenzo-12-crown-4 ether, diaminodibenzo-14-crown-4 ether, diaminodibenzo-15-crown-5 ether, diaminodibenzo-18-crown-6 ether, diaminodibenzo-21-crown-7 ether and diaminodibenzo-24-crown-8 ether; and / or,

[0043] The solvent B is at least one of dichloromethane, chloroform, carbon tetrachloride, dichloroethane, toluene, xylene, trimethylbenzene, and ethylbenzene; and / or,

[0044] The amount of the solvent B is 1 to 20 times, preferably 1 to 10 times, more preferably 1 to 5 times the mass of the polyether p-toluenesulfonate; and / or,

[0045] The amount of diaminodibenzo crown ether used is 2 to 6 times, preferably 2.5 to 4 times, the molar amount of polyether p-toluenesulfonate used; and / or,

[0046] The reaction temperature is 40 to 160° C., preferably 80 to 140° C.; and / or the reaction time is 12 to 90 hours, preferably 18 to 60 hours.

[0047] The preparation method of the polyetheramine of the present invention can adopt the following specific technical scheme:

[0048] a) placing an initiator 1,2-propylene glycol or 1,2-butanediol and a catalyst A into an autoclave, evacuating the air, then heating to 110-140° C., introducing propylene oxide or butylene oxide at a molar ratio of (1-29):1 to the initiator 1,2-propylene glycol or 1,2-butanediol to carry out polymerization reaction, controlling the reaction pressure not to exceed 0.3 MPa, and continuing to keep the temperature for reaction after the pressure drops to negative pressure, cooling to below 80° C., and taking out the reaction product to obtain a polyether intermediate;

[0049] b) placing the polyether intermediate obtained in step a) and catalyst B into an autoclave, evacuating the air, then heating the autoclave to 110-140° C., introducing butylene oxide or propylene oxide in a total molar amount of 1-40 times the molar amount of the polyether intermediate, and carrying out polymerization reaction, controlling the reaction pressure not to exceed 0.3 MPa, and continuing the reaction at the heat preservation after the pressure drops to negative pressure, cooling the autoclave to below 80° C., and taking out the reaction product to obtain a block polyether;

[0050] c) adding the block polyether obtained in step b), an acid binding agent, p-toluenesulfonyl chloride, and solvent A to a reactor, and stirring the mixture at 0-40° C. for 6-72 hours; after the reaction is complete, the mixture is poured into a beaker, deionized water is added, and the mixture is washed with a separatory funnel. After washing three times with water, the reaction mixture is rotary evaporated to obtain polyether p-toluenesulfonate;

[0051] d) adding diaminodibenzo-crown ether and solvent B into a reaction kettle, stirring evenly and heating to 40-160° C.; dissolving the polyether p-toluenesulfonate obtained in step c) in solvent B and slowly dripping it into the diaminodibenzo-crown ether solution through a constant pressure dropping funnel, allowing the polyether p-toluenesulfonate and diaminodibenzo-crown ether to react for 12-90 hours. After the reaction is complete, washing with water and evaporating the solvent to obtain the polyetheramine.

[0052] The third object of the present invention is to provide a use of the polyetheramine of the first object of the present invention or the polyetheramine obtained by the preparation method of the second object of the present invention in fuel additives.

[0053] A fourth object of the present invention is to provide a fuel additive comprising solvent oil and the polyetheramine of one of the objects of the present invention or the polyetheramine obtained by the preparation method of the second object of the present invention; preferably,

[0054] 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 12At least one of alkyl alcohols, more preferably at least one of 60# solvent oil, 80# solvent oil, and 100# solvent oil; and / or,

[0055] Based on 100 parts by weight of the solvent oil, the polyetheramine is 10 to 100 parts by weight, preferably 20 to 80 parts by weight, and more preferably 30 to 60 parts by weight.

[0056] In a preferred embodiment of the present invention,

[0057] The fuel additive further comprises acetylene glycol polyether; preferably,

[0058] The structural formula of the acetylene glycol polyether is as follows:

[0059] Wherein, 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 all 0; (the acetylene glycol polyether is preferably prepared by the method described in Chinese Patent No. 202211702264.2, which is incorporated herein in its entirety) and / or,

[0060] Based on 100 parts by weight of the solvent oil, the amount of the acetylene glycol polyether is 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, and more preferably 1 to 5 parts by weight.

[0061] In a preferred embodiment of the present invention,

[0062] The fuel additive also includes an antioxidant; preferably,

[0063] The antioxidant is a conventional antioxidant in the prior art, preferably at least one of phenylenediamine, alkylphenylenediamine, p-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-ethylphenol, and 4,4-butylene-bis(3-methyl-6-tert-butylphenol); and / or

[0064] Based on 100 parts by weight of solvent oil, the antioxidant is 0.1 to 2 parts by weight, preferably 0.5 to 2 parts by weight.

[0065] Conventional components in the art, such as other polyethers besides acetylene glycol polyether, may also be added to the formulation of the fuel additive of the present invention. The amounts used are also conventional amounts and can be adjusted by those skilled in the art according to actual conditions.

[0066] The fifth object of the present invention is to provide a method for preparing the fuel additive of the fourth object of the present invention, comprising uniformly mixing components including the polyetheramine, solvent oil and optional acetylene glycol polyether to obtain the fuel additive.

[0067] The beneficial effects of the present invention are as follows:

[0068] The polyetheramine containing crown ether structural units of the present invention has higher thermal stability than conventional polyetheramines, and because its molecular structure contains two crown ether structural units, it has more excellent dispersibility. When used as a component of a fuel additive, it can not only efficiently clean carbon deposits on fuel nozzles, intake valves, and combustion chambers, but also the crown ether groups can complex metal ions, improve combustion characteristics, and reduce pollution emissions, resulting in excellent comprehensive performance. DETAILED DESCRIPTION

[0069] The present invention will be described in detail below with reference to specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made by those skilled in the art to the present invention based on the contents of the present invention still fall within the scope of protection of the present invention.

[0070] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0071] Preparation of decynediol polyoxypropylene (4) ether in Example 1:

[0072] (1) Preparation of nanocatalyst (Mg / Al / Co composite metal oxide catalyst):

[0073] 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 an equal volume of CoNO3 solution to that of mixed solution II, and its concentration is The molar concentration of Al(NO3)3 in the reaction mixture is 1 / 5; the CoNO3 solution is kept at a constant temperature of 60°C, and the mixed solution I and the mixed solution II are added dropwise thereto simultaneously under vigorous stirring, and the pH value is controlled to be 8.5-9.5 during the addition process; after the addition is completed, the reaction solution is stirred at a constant temperature for 30 minutes, and then placed in 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.

[0074] (2) 0.2 mol of tetramethyldecynediol (abbreviated as TMAD10, the structural formula of tetramethyldecynediol is: wherein R2 and R3 are -CH3, R1 and R4 are both -CH2CH(CH3)2) and 0.9g of the Mg / Al / Co composite metal oxide catalyst obtained in the above step (1) are put into a high-pressure reactor and stirred evenly. 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 propylene oxide is slowly introduced into the reactor through a 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; 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.

[0075] Preparation of decynediol polyoxyethylene (8) polyoxypropylene (4) ether in Examples 2 and 3:

[0076] (1) 0.2 mol of tetramethyldecynediol (abbreviated as TMAD10) and 0.9 g of the Mg / Al / Co composite metal oxide catalyst obtained above were put into a high-pressure reactor and stirred evenly. The air in the reactor was replaced with nitrogen three times. The high-pressure reactor was evacuated at 80° C. for 30 min using a vacuum pump 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 above 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;

[0077] (2) 0.1 mol TMAD10-EO8 and 0.8 g Mg / Al / Co composite metal oxide catalyst were put into a high-pressure reactor and stirred evenly. The air in the reactor was replaced with nitrogen three times. The high-pressure reactor was evacuated at 80° C. for 30 min using a vacuum pump 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 raised 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.

[0078] The structure of the acetylene glycol polyether obtained above is theoretically deduced from the reaction mechanism and the added raw materials.

[0079] Example 1

[0080] Preparation of polyetheramine:

[0081] a) 90 g (1 mol) of 1,2-butanediol and 0.072 g of a DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were placed in a high-pressure reactor, and the air was removed by vacuum. The reactor was then heated to 135° 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 reaction was continued at the temperature. After the pressure dropped to negative pressure, the temperature was lowered to 80° C., and the reaction product was taken out to obtain a polyoxybutylene (11) ether intermediate;

[0082] b) 1 mol of the above-mentioned polyoxybutylene (11) ether intermediate and 0.29 g of a DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were placed in an autoclave, and the air was removed by vacuum. The autoclave was then heated to 130° 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 reaction was completed, the reaction was continued at the temperature, and after the pressure dropped to negative pressure, the temperature was lowered to 80° C., and the reaction product was taken out to obtain polyoxybutylene (11) polyoxypropylene (10) ether;

[0083] c) dissolving 1 mol of polyoxybutylene (11) polyoxypropylene (10) ether, 618 g (3.2 mol) of p-toluenesulfonyl chloride, and 632 g (8 mol) of pyridine in 2000 g of dichloromethane, and stirring the mixture at 10° C. for 24 hours; after the reaction is completed, the mixture is poured into a beaker, deionized water is added to wash the reaction solution, and the solution is separated using a separatory funnel. After washing with water three times, the reaction solution is rotary evaporated to remove the solvent to obtain polyoxybutylene (11) polyoxypropylene (10) ether p-toluenesulfonate;

[0084] d) 2.5 mol of diaminodibenzo-14-crown-4 ether (CAS No.: 440632-91-7) and 664 g of toluene are added to a reactor, stirred evenly, and heated to 120° C.; 1 mol of the polyoxybutylene (11) polyoxypropylene (10) ether p-toluenesulfonate obtained in step c) is dissolved in 2000 g of toluene, and slowly added dropwise (at a rate of 1 mL / min) to the diaminodibenzo-14-crown-4 ether solution through a constant pressure dropping funnel, and the reaction is carried out for 24 hours. After the reaction is completed, the mixture is washed with water and the solvent is evaporated to obtain polyoxybutylene (11) polyoxypropylene (10) ether bis-diaminodibenzo-14-crown-4 ether amine.

[0085] Preparation of fuel additives:

[0086] 100 parts by weight of 60# solvent oil, 50 parts by weight of polyoxybutylene (11) polyoxypropylene (10) ether bis-diaminodibenzo-14-crown-4 ether amine, 2 parts by weight of decynediol polyoxypropylene (4) ether, and 0.5 parts by weight of p-phenylenediamine are mixed uniformly at 50°C to obtain fuel additive a.

[0087] Example 2

[0088] Preparation of polyetheramine:

[0089] a) 90 g (1 mol) of 1,2-butanediol and 0.36 g of a DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were placed in a high-pressure reactor, and the air was removed by vacuum. The reactor was then heated to 125° C., and 360 g (5 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., and the reaction product was taken out to obtain a polyoxybutylene (6) ether intermediate;

[0090] b) 1 mol of the above-mentioned polyoxybutylene (6) ether intermediate and 0.23 g of a DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were placed in a high-pressure reactor, and the air was removed by vacuum. The reactor was then heated to 130° C., and 1160 g (20 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 reaction was continued at the temperature, and after the pressure dropped to negative pressure, the temperature was lowered to 80° C., and the reaction product was taken out to obtain polyoxybutylene (6) polyoxypropylene (20) ether;

[0091] c) dissolving 1 mol of polyoxybutylene (6) polyoxypropylene (20) ether, 927 g (4.9 mol) of p-toluenesulfonyl chloride, and 948 g (12 mol) of pyridine in 4000 g of dichloroethane, and stirring the mixture at 20° C. for 24 hours; after the reaction is completed, the mixture is poured into a beaker, deionized water is added to wash the reaction solution, and the solution is separated using a separatory funnel. After washing three times with water, the reaction solution is rotary evaporated to remove the solvent to obtain polyoxybutylene (6) polyoxypropylene (20) ether p-toluenesulfonate;

[0092] d) 4 mol of diaminodibenzo-18-crown-6 ether (CAS No.: 31406-52-7) and 1568 g of xylene are added to a reactor, stirred evenly, and heated to 100° C.; 1 mol of the polyoxybutylene (6) polyoxypropylene (20) ether p-toluenesulfonate obtained in step c) is dissolved in 2000 g of xylene, and slowly added dropwise (at a rate of 1 mL / min) to the diaminodibenzo-18-crown-6 ether solution through a constant pressure dropping funnel. The reaction is carried out for 48 hours. After the reaction is completed, the mixture is washed with water and the solvent is evaporated to obtain polyoxybutylene (6) polyoxypropylene (20) ether bis-diaminodibenzo-18-crown-6 ether amine.

[0093] Preparation of fuel additives:

[0094] 100 parts by weight of 80# solvent oil, 50 parts by weight of polyoxybutylene (6) polyoxypropylene (20) ether bis-diaminodibenzo-18-crown-6 ether amine, 4 parts by weight of decynediol polyoxyethylene (8) polyoxypropylene (4) ether, and 0.5 parts by weight of p-tert-butylphenol are mixed uniformly at 50°C to obtain fuel additive b.

[0095] Example 3

[0096] Preparation of polyetheramine:

[0097] a) 76 g (1 mol) of 1,2-propylene glycol and 0.12 g of a DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were placed in a high-pressure reactor, and the air was removed by vacuum. The reactor was then heated to 130° C., and 522 g (9 mol) of propylene oxide was introduced to carry out a polymerization reaction. The reaction pressure was controlled not to exceed 0.3 MPa. After the reaction was completed, the reaction was continued at the temperature. After the pressure dropped to negative pressure, the temperature was lowered to 80° C., and the reaction product was taken out to obtain a polyoxypropylene (10) ether intermediate;

[0098] b) 1 mol of the above-mentioned polyoxypropylene (10) ether intermediate and 0.43 g of a DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were placed in a high-pressure reactor, and the air was removed by vacuum. The reactor was then heated to 135° C., 1080 g (15 mol) of butylene oxide was introduced to carry out polymerization reaction, and the reaction pressure was controlled not to exceed 0.3 MPa. After the reaction was completed, the reaction was continued at the temperature, and after the pressure dropped to negative pressure, the temperature was lowered to 80° C., and the reaction product was taken out to obtain polyoxypropylene (10) polyoxybutylene (15) ether;

[0099] c) dissolving 1 mol of polyoxypropylene (10) polyoxybutylene (15) ether, 773 g (4.1 mol) of p-toluenesulfonyl chloride, and 790 g (10 mol) of pyridine in 4000 g of dichloroethane, and stirring the mixture at 5° C. for 48 hours; after the reaction is completed, the mixture is poured into a beaker, deionized water is added to wash the reaction solution, and the solution is separated using a separatory funnel. After washing three times with water, the reaction solution is rotary evaporated to remove the solvent to obtain polyoxypropylene (10) polyoxybutylene (15) ether p-toluenesulfonate;

[0100] d) 4 mol of diaminodibenzo-15-crown-5 ether (CAS No.: 313496-30-9) and 1392 g of ethylbenzene are added to a reactor, stirred evenly, and heated to 110° C.; 1914 g (1 mol) of polyoxypropylene (10) polyoxybutylene (15) ether p-toluenesulfonate obtained in step c) is dissolved in 2000 g of ethylbenzene and slowly added dropwise (at a rate of 1 mL / min) to the diaminodibenzo-15-crown-5 ether solution through a constant pressure dropping funnel. The mixture is reacted for 48 hours. After the reaction is completed, the mixture is washed with water and the solvent is evaporated to obtain polyoxypropylene (10) polyoxybutylene (15) ether bis-diaminodibenzo-15-crown-5 ether amine.

[0101] Preparation of fuel additives:

[0102] Fuel additive C was obtained by uniformly mixing 100 parts by weight of 100# solvent oil, 40 parts by weight of polyoxypropylene (10) polyoxybutylene (15) ether bis-diaminodibenzo-15-crown-5 ether amine, 1 part by weight of decynediol polyoxyethylene (8) polyoxypropylene (4) ether, and 0.5 parts by weight of p-tert-butylphenol at 50°C.

[0103] Comparative Example 1

[0104] Preparation of polyoxybutylene polyoxypropylene ether amine:

[0105] a) 90 g (1 mol) of 1,2-butanediol and 0.36 g of a DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were placed in a high-pressure reactor, and the air was removed by vacuum. The reactor was then heated to 125° C., and 360 g (5 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., and the reaction product was taken out to obtain a polyoxybutylene (6) ether intermediate;

[0106] b) 1 mol of the above-mentioned polyoxybutylene (6) ether intermediate and 0.23 g of a DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were placed in a high-pressure reactor, and the air was removed by vacuum. The reactor was then heated to 130° C., and 1160 g (20 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 reaction was continued at the temperature, and after the pressure dropped to negative pressure, the temperature was lowered to 80° C., and the reaction product was taken out to obtain polyoxybutylene (6) polyoxypropylene (20) ether;

[0107] c) 500 g of polyoxybutylene (6) polyoxypropylene (20) 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. 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 polyoxybutylene (6) polyoxypropylene (20) ether amine.

[0108] Preparation of fuel additives:

[0109] Fuel additive d was obtained by uniformly mixing 100 parts by weight of 80# solvent oil, 50 parts by weight of polyoxybutylene (6) polyoxypropylene (20) ether amine, 4 parts by weight of decynediol polyoxyethylene (8) polyoxypropylene (4) ether (same as in Example 2), and 0.5 parts by weight of p-tert-butylphenol at 50°C to obtain fuel additive d.

[0110] Comparative Example 2

[0111] Preparation of fuel additives:

[0112] 100 parts by weight of 80# solvent oil, 16 parts by weight of diaminodibenzo-18-crown-6 ether, 34 parts by weight of polyoxybutylene (6) polyoxypropylene (20) ether prepared in Comparative Example 2, 4 parts by weight of decynediol polyoxyethylene (8) polyoxypropylene (4) ether amine (same as in Example 2), and 0.5 parts by weight of p-tert-butylphenol were mixed uniformly at 50°C to obtain fuel additive e.

[0113] Comparative Example 3

[0114] Preparation of fuel additives:

[0115] Fuel additive f was obtained by mixing 100 parts by weight of 80# solvent oil, 50 parts by weight of polyetheramine D2000, 4 parts by weight of decynediol polyoxyethylene (8) polyoxypropylene (4) ether (same as in Example 2), and 0.5 parts by weight of p-tert-butylphenol at 50°C.

[0116] Test Case

[0117] The same concentration (recommended ratio: 800 mg / L (calculated as polyetheramine)) of a commercially available gasoline detergent and the fuel additives of Examples 1 to 3 and Comparative Examples 1 to 3 were added to 92# base gasoline, and carbon deposit removal data were compared according to the method of GB / T 19230.6. The data comparison is shown in Table 1 below.

[0118] Table 1 Performance comparison of fuel additives in Examples and Comparative Examples

[0119]

[0120] As can be seen from Example 2, Comparative Examples 1-2 and Table 1, compared with the addition of a crown ether-free polyetheramine prepared under the same conditions of the present invention using a conventional initiator in the art (such as propylene glycol or butanediol) to the fuel additive (Comparative Example 1) or a crown ether-free polyetheramine + an amino-containing crown ether prepared under the same conditions of the present invention (Comparative Example 2), the fuel additive containing the specific polyetheramine of the present invention has a significantly better cleaning effect on the fuel intake system and combustion chamber of the automobile engine.

[0121] It can be seen from Example 2, Comparative Example 3 and Table 1 that, compared with the polyetheramine conventionally used in the prior art and the polyetheramine of the present invention, the fuel additive containing the polyetheramine of the present invention has a more significant cleaning effect on the fuel intake system and combustion chamber of the automobile engine.

Claims

1. A polyetheramine comprising at least one of the compounds having a structure represented by the following formula (1) or formula (2): In formula (1) and formula (2), R is independently selected from methyl or ethyl; R 1 、R 2 is selected from methyl or ethyl; x1=0 to 29, x2=0 to 29, and x1+x2=1 to 29; R 3 、R 4 Selected from methyl or ethyl; y1=0-40, y2=0-40, and y1+y2=1-40; m=1-5; n=1-5.

2. The polyetheramine according to claim 1, wherein: R 1 、R 2 is selected from methyl and R 3 、R 4 Selected from ethyl, or R 1 、R 2 Selected from ethyl and R 3 、R 4 selected from methyl; and / or, x1=0-24, x2=0-24, and x1+x2=4-24; and / or, y1=0-20, y2=0-20, and y1+y2=1-20; and / or, m=1~3, and / or, n=1~3.

3. A method for preparing the polyetheramine according to claim 1 or 2, comprising: a) reacting 1,2-propylene glycol or 1,2-butylene glycol with propylene oxide or butylene oxide in the presence of catalyst A to obtain a polyether intermediate; b) reacting the polyether intermediate obtained in step a) with butylene oxide or propylene oxide in the presence of catalyst B to obtain a block polyether; c) dissolving the block polyether and acid binding agent obtained in step b) in solvent A, and reacting with p-toluenesulfonyl chloride to obtain polyether p-toluenesulfonate; d) dissolving the polyether p-toluenesulfonate obtained in step c) in solvent B, and reacting with diaminodibenzocrown ether to obtain the polyetheramine.

4. The preparation method according to claim 1, wherein: In step a), The catalyst A is at least one of a DMC bimetallic catalyst and an alkaline catalyst. Preferably, the alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium ethoxide, and sodium hydride; and / or, The molar ratio of propylene oxide to 1,2-propylene glycol or 1,2-butanediol is (1-29):1, preferably (4-24):1; and / or the molar ratio of butylene oxide to 1,2-propylene glycol or 1,2-butanediol is (1-29):1, preferably (4-24):1; and / or, The amount of the catalyst A is 0.005-2% of the mass of propylene oxide or butylene oxide, preferably 0.01-1%; and / or, The reaction temperature is 110-140°C, preferably 120-135°C; and / or, In step b), The catalyst B is at least one of a DMC bimetallic catalyst and an alkaline catalyst. Preferably, the alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium ethoxide, and sodium hydride; and / or The molar amount of propylene oxide or butylene oxide is 1 to 40 times, preferably 1 to 20 times, the molar amount of the polyether intermediate; and / or, The amount of the catalyst B is 0.005-2%, preferably 0.01-1%, of the mass of the propylene oxide or butylene oxide introduced in step b); and / or, The reaction temperature is 110-140°C, preferably 120-135°C.

5. The preparation method according to claim 1, wherein: In step c), The acid binding agent is at least one of pyridine, triethylamine, diisopropylethylamine, sodium acetate, sodium carbonate, and potassium carbonate; and / or, The amount of the acid binding agent is 1 to 20 times, preferably 1 to 10 times, the molar amount of p-toluenesulfonyl chloride; and / or, The solvent A is at least one of dichloromethane, chloroform, carbon tetrachloride, dichloroethane, toluene, xylene, trimethylbenzene, and ethylbenzene; and / or, The amount of solvent A is 1 to 20 times, preferably 1 to 10 times, the mass of the block polyether; and / or, The amount of p-toluenesulfonyl chloride is 2 to 12 times, preferably 2 to 10 times, the molar amount of the blocked polyether; and / or, The reaction temperature with p-toluenesulfonyl chloride is 0-40° C., preferably 5-20° C.; and / or the reaction time with p-toluenesulfonyl chloride is 6-72 h, preferably 18-48 h.

6. The preparation method according to claim 1, wherein: In step d), The diaminodibenzo crown ether has the following structure: wherein m=1-5, preferably m=1-3, n=1-5, preferably n=1-3; preferably, the diaminodibenzo crown ether is one of diaminodibenzo-12-crown-4 ether, diaminodibenzo-14-crown-4 ether, diaminodibenzo-15-crown-5 ether, diaminodibenzo-18-crown-6 ether, diaminodibenzo-21-crown-7 ether and diaminodibenzo-24-crown-8 ether; and / or, The solvent B is at least one of dichloromethane, chloroform, carbon tetrachloride, dichloroethane, toluene, xylene, trimethylbenzene, and ethylbenzene; and / or, The amount of the solvent B is 1 to 20 times, preferably 1 to 10 times, the mass of the polyether p-toluenesulfonate; and / or, The amount of diaminodibenzo crown ether used is 2 to 6 times, preferably 2.5 to 4 times, the molar amount of polyether p-toluenesulfonate used; and / or, The reaction temperature is 40 to 160° C., preferably 80 to 140° C.; and / or the reaction time is 12 to 90 hours, preferably 18 to 60 hours.

7. Use of the polyetheramine according to any one of claims 1 to 2 or the polyetheramine obtained by the preparation method according to any one of claims 3 to 6 in a fuel additive.

8. A fuel additive comprising solvent oil and the polyetheramine according to any one of claims 1 to 2 or the polyetheramine obtained by the preparation method according to any one of claims 3 to 6; preferably, 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 Based on 100 parts by weight of the solvent oil, the polyetheramine is 10 to 100 parts by weight, preferably 20 to 80 parts by weight.

9. The fuel additive according to claim 8, characterized in that: The fuel additive further comprises acetylene glycol polyether; preferably, The structural formula of the acetylene glycol polyether is as follows: wherein 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 all 0; and / or, Based on 100 parts by weight of solvent oil, the amount of acetylene glycol polyether is 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight.

10. A method for preparing the fuel additive according to any one of claims 8 to 9, comprising uniformly mixing components comprising the polyetheramine, solvent oil, and optionally acetylene glycol polyether to obtain the fuel additive.

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