A polyetheramine, its preparation method and use

Abstract

The application discloses a polyether amine and a preparation method and application thereof. The polyether amine comprises at least one of compounds containing structures shown in the following formula (1) or formula (2): in the formula (1) and formula (2), R is independently selected from methyl or ethyl; R 1 , R 2 is selected from methyl or ethyl; x1=0-29, x2=0-29, and x1+x2=1-29; R 3 , R 4 is selected from methyl or ethyl; y1=0-40, y2=0-40, and y1+y2=1-40; m=1-5; and n=1-5. The fuel additive containing the polyether amine can efficiently clean fuel nozzle carbon deposition, intake valve carbon deposition and combustion chamber carbon deposition.

Description

Technical Field

[0001] This invention relates to the field of fuel additive technology, specifically to a polyetheramine, its preparation method, and its application. Background Technology

[0002] With the release of the China VI emission standards, emission standards are becoming increasingly stringent, and the requirements for fuel are also becoming more stringent. Besides improving refining technology, the use of fuel additives has become one of the important technical means to improve fuel quality and engine performance. During vehicle operation, a large amount of deposits generated in the engine intake system (including the carburetor, fuel injectors, and intake valves) and combustion chamber affect the normal injection, atomization, mixing, and combustion of fuel. Carbon deposits in the intake valves 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.

[0003] Recent studies have found that additives such as polyisobutylene amine (PIBA), polyisobutylene succinimide, and polyetheramine can both inhibit the formation of deposits inside the fuel system and rapidly disperse and remove existing deposits. This ensures the normal performance of the car engine, improves fuel combustion performance, and significantly reduces HC and CO pollutants in vehicle exhaust emissions, thereby purifying vehicle exhaust, reducing vehicle maintenance costs, and saving fuel. However, these additives have problems such as poor thermal stability, difficulty in cleaning deposits on high-temperature components, and increased deposits in the combustion chamber. Therefore, there is an urgent need for a fuel 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 intake valves. Summary of the Invention

[0004] To address the problems existing in the prior art, this invention provides a polyetheramine, its preparation method, and its applications. The fuel additive containing the polyetheramine of this invention can efficiently clean carbon deposits on fuel injectors, intake valves, and combustion chambers.

[0005] One object of the present invention is to provide a polyetheramine comprising at least one of compounds containing the structure shown in formula (1) or formula (2) below:

[0006]

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

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

[0009] R 1 R 2 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 to 3, and / or n = 1 to 3.

[0013] The structure of the polyetheramine in this invention is theoretically calculated based on the chemical reaction mechanism and the amount of raw materials added.

[0014] A second objective of this invention is to provide a method for preparing polyetheramine according to one of the objectives of this invention, comprising:

[0015] a) React 1,2-propanediol or 1,2-butanediol with propylene oxide or butane oxide in the presence of catalyst A to obtain a polyether intermediate.

[0016] b) The polyether intermediate obtained in step a) is reacted with butane or propylene oxide in the presence of catalyst B to obtain block polyether.

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

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

[0019] The preferred feature of the polyetheramine of the present invention is that it is prepared by the preparation method of the present invention described above.

[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-propanediol 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-propanediol or 1,2-butanediol is (1-29):1, preferably (4-24):1, more preferably (4-12):1; and / or,

[0024] The amount of catalyst A is 0.005–2% of the mass of propylene oxide or butane 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 a 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 butyl oxide is 1 to 40 times that of the polyether intermediate, preferably 1 to 20 times, more preferably 10 to 20 times; and / or,

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

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

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

[0032] In step c),

[0033] The acid-binding agent is at least one selected from 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 the molar amount of p-toluenesulfonyl chloride, preferably 1 to 10 times, more preferably 2 to 4 times; and / or,

[0035] Solvent A is at least one selected from dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, toluene, xylene, trimethylbenzene, and ethylbenzene; and / or,

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

[0037] The amount of p-toluenesulfonyl chloride used is 2 to 12 times the molar amount of the block polyether, preferably 2 to 10 times, more preferably 2 to 6 times; 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 diaminodibenzocrown 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] Solvent B is at least one selected from dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, toluene, xylene, trimethylbenzene, and ethylbenzene; and / or,

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

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

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

[0047] The preparation method of the polyetheramine described in this invention can adopt the following specific technical solutions:

[0048] a) Initiator 1,2-propanediol or 1,2-butanediol and catalyst A are added to a high-pressure reactor, the air is removed by evacuation, and then the temperature is raised to 110-140°C. Propylene oxide or butane oxide with a molar ratio of (1-29):1 to initiator 1,2-propanediol or 1,2-butanediol is introduced to carry out the polymerization reaction. The reaction pressure is controlled not to exceed 0.3 MPa. After the introduction is completed, the reaction is kept at the temperature. After the pressure drops to a negative pressure, the temperature is lowered to below 80°C, and the reaction product is taken out to obtain a polyether intermediate.

[0049] b) The polyether intermediate obtained in step a) and catalyst B are put into a high-pressure reactor, the air is removed by evacuation, and then the temperature is raised to 110-140°C. Butane oxide or propylene oxide with a total molar amount of 1-40 times that of the polyether intermediate is introduced to carry out the polymerization reaction. The reaction pressure is controlled not to exceed 0.3 MPa. After the reaction is completed, the temperature is maintained and the reaction is continued. After the pressure drops to a negative pressure, the temperature is lowered to below 80°C and the reaction product is taken out to obtain block polyether.

[0050] c) Add the block polyether obtained in step b) to the reactor, along with the acid-binding agent, p-toluenesulfonyl chloride and solvent A, and stir the reaction at 0–40°C for 6–72 h. After the reaction is complete, pour the mixture into a beaker, add deionized water to wash the reaction solution, separate the solution using a separatory funnel, and after three water washes, rotary evaporate the reaction solution to obtain polyether p-toluenesulfonate.

[0051] d) Add diaminodibenzo[a]thionyl ether and solvent B to the reaction vessel, stir until homogeneous and heat to 40-160°C; dissolve the polyether p-toluenesulfonate obtained in step c) in solvent B, and slowly add it dropwise through a constant pressure dropping funnel to the above diaminodibenzo[a]thionyl ether solution, allowing the polyether p-toluenesulfonate to react with the diaminodibenzo[a]thionyl ether for 12-90 h. After the reaction is complete, wash with water and evaporate the solvent to obtain the polyetheramine.

[0052] A third objective of this invention is to provide the application of a polyetheramine obtained by one of the objectives of this invention or by the preparation method of another objective of this invention in fuel additives.

[0053] A fourth objective of this invention is to provide a fuel additive comprising solvent oil and a polyetheramine according to one objective of this invention or a polyetheramine prepared by the method for another objective of this invention; preferably,

[0054] The solvent oil is a conventional solvent oil in the art, preferably an alkane solvent oil or an aromatic solvent oil with a boiling range of 60–200°C, or a C6–C4 solvent oil. 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 solvent oil, the polyetheramine is 10 to 100 parts by weight; preferably 20 to 80 parts by weight, more preferably 30 to 60 parts by weight.

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

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

[0058] The structural formula of the acetylenic diol polyether is as follows:

[0059] 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, n1 and n2 may be the same or different, n1+n2 = 0 to 20, and m1, m2, n1, and n2 are not simultaneously 0; (the acetylenic diol polyether is preferably prepared by the method in Chinese Patent 202211702264.2, which is incorporated herein by reference in its entirety) and / or,

[0060] Based on 100 parts by weight of solvent oil, the amount of acetylation diol polyether is 0.5 to 10 parts by weight; preferably 1 to 8 parts by weight, 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 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] The fuel additive formulation of the present invention may also include conventional components in the art, such as other polyethers besides acetylenic glycol polyether, and the dosage is also conventional. Those skilled in the art can adjust it according to the actual situation.

[0066] The fifth objective of this invention is to provide a method for preparing a fuel additive according to the fourth objective of this invention, comprising uniformly mixing components including the polyetheramine, solvent oil, and optionally acetylenic diol polyether to obtain the fuel additive.

[0067] The beneficial effects of this 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 it contains two crown ether structural units in its molecular structure, it has better dispersibility. When used as a component of fuel additive, it can not only efficiently clean carbon deposits in fuel injectors, 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 overall performance. Detailed Implementation

[0069] 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.

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

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

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

[0073] 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.

[0074] (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 0.9g of the Mg / Al / Co composite metal oxide catalyst obtained in step (1) above are added to a high-pressure reactor, stirred evenly, and the air in the reactor is replaced with nitrogen three times. The high-pressure reactor is evacuated at 80°C for 30 minutes using a vacuum pump, and then the evacuation is stopped. 0.8mol of propylene oxide is slowly introduced into the reactor through the feed pipe, and the reactor temperature 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 polyoxypropylene (4) ether (TMAD10-PO4). The structural formula of the above decynyl diol 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 decantyne diol polyoxyethylene (8) polyoxypropylene (4) ether in Examples 2 and 3:

[0076] (1) 0.2 mol of tetramethyldecynyl diol (TMAD10) and 0.9 g of the Mg / Al / Co composite metal oxide catalyst obtained 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 then evacuated at 80°C for 30 min using a vacuum pump. The evacuation was then stopped. 1.6 mol of ethylene oxide was slowly introduced into the reactor through the feed pipe, and the reactor temperature was raised to 115°C. The pressure inside the reactor was controlled at around 0.20 MPa, and the reaction was stirred for 4 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 ether (TMAD10-EO8). The structural formula of the above decynyl diol polyoxyethylene 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;

[0077] (2) 0.1 mol TMAD10-EO8 and 0.8 g Mg / Al / Co composite metal oxide catalyst 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). The structural formula of the above decynyl diol polyoxyethylene polyoxypropylene 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.

[0078] The structure of the acetylenic diol polyether obtained above was theoretically calculated based on the reaction mechanism and the added raw materials.

[0079] Example 1

[0080] Preparation of polyetheramine:

[0081] a) 90g (1mol) of 1,2-butanediol and 0.072g of DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were put into a high-pressure reactor, the air was removed by vacuuming, and then the reactor was heated to 135°C. 720g (10mol) of epoxide butane was introduced to carry out the polymerization reaction. The reaction pressure was controlled not to exceed 0.3MPa. 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 polyoxybutene (11) ether intermediate.

[0082] b) 1 mol of the above polyoxybutene (11) ether intermediate and 0.29 g of DMC bimetallic catalyst (Huai'an Bade Polyurethane Technology Co., Ltd.) were added to a high-pressure reactor. The air was removed by evacuation. Then the reactor was heated to 130°C and 580 g (10 mol) of propylene oxide was introduced to carry out the polymerization reaction. The reaction pressure was controlled to not exceed 0.3 MPa. After the reaction was completed, the temperature was kept high. After the pressure dropped to negative pressure, the temperature was lowered to 80°C and the reaction product was taken out to obtain polyoxybutene (11) polyoxypropylene (10) ether.

[0083] c) 1 mol of polyoxybutene (11) polyoxypropylene (10) ether, 618 g (3.2 mol) of p-toluenesulfonyl chloride, and 632 g (8 mol) of pyridine were dissolved in 2000 g of dichloromethane and stirred at 10 °C for 24 h. After the reaction was completed, the mixture was poured into a beaker and deionized water was added to wash the reaction solution. The mixture was separated by a separatory funnel and washed three times with water. The solvent was removed by rotary evaporation to obtain polyoxybutene (11) polyoxypropylene (10) ether p-toluenesulfonate.

[0084] d) Add 2.5 mol of diaminodibenzo-14-crown 4-ether (CAS No.: 440632-91-7) and 664 g of toluene to the reaction vessel, stir evenly and heat to 120℃; dissolve 1 mol of polyoxybutene (11) polyoxypropylene (10) ether p-toluenesulfonate obtained in step c) in 2000 g of toluene, and slowly drop it into the diaminodibenzo-14-crown 4-ether solution through a constant pressure dropping funnel (at a rate of 1 mL / min), react for 24 h, wash with water after the reaction is completed, evaporate the solvent, and obtain polyoxybutene (11) polyoxypropylene (10) ether bis-diaminodibenzo-14-crown 4-ether amine.

[0085] Preparation of fuel additives:

[0086] Mix 100 parts by weight of 60# solvent oil, 50 parts by weight of polyoxybutene (11) polyoxypropylene (10) ether bis-diaminodibenzo-14-crown-4 etheramine, 2 parts by weight of decynyl diol polyoxypropylene (4) ether, and 0.5 parts by weight of p-phenylenediamine at 50°C to obtain fuel additive a.

[0087] Example 2

[0088] Preparation of polyetheramine:

[0089] a) 90g (1mol) of 1,2-butanediol and 0.36g of DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were put into a high-pressure reactor, the air was removed by vacuuming, and then the reactor was heated to 125°C. 360g (5mol) of epoxide butane was introduced to carry out the polymerization reaction. The reaction pressure was controlled not to exceed 0.3MPa. 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 polyoxybutene (6) ether intermediate.

[0090] b) 1 mol of the above polyoxybutene (6) ether intermediate and 0.23 g of DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were added to a high-pressure reactor. The air was removed by evacuation. Then the reactor was heated to 130°C and 1160 g (20 mol) of propylene oxide was introduced to carry out the polymerization reaction. The reaction pressure was controlled to not exceed 0.3 MPa. After the reaction was completed, the temperature was kept high. After the pressure dropped to negative pressure, the temperature was lowered to 80°C and the reaction product was taken out to obtain polyoxybutene (6) polyoxypropylene (20) ether.

[0091] c) 1 mol of polyoxybutene (6) polyoxypropylene (20) ether, 927 g (4.9 mol) of p-toluenesulfonyl chloride, and 948 g (12 mol) of pyridine were dissolved in 4000 g of dichloroethane and stirred at 20 °C for 24 h. After the reaction was completed, the mixture was poured into a beaker and deionized water was added to wash the reaction solution. The mixture was separated by a separatory funnel and washed three times with water. The solvent was removed by rotary evaporation to obtain polyoxybutene (6) polyoxypropylene (20) ether p-toluenesulfonate.

[0092] d) Add 4 mol of diaminodibenzo-18-crown 6 ether (CAS No.: 31406-52-7) and 1568 g of xylene to the reactor, stir evenly and heat to 100℃; dissolve 1 mol of polyoxybutene (6) polyoxypropylene (20) ether p-toluenesulfonate obtained in step c) in 2000 g of xylene, and slowly drop it into the diaminodibenzo-18-crown 6 ether solution through a constant pressure dropping funnel (at a rate of 1 mL / min), react for 48 h, wash with water after the reaction is completed, evaporate the solvent, and obtain polyoxybutene (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 polyoxybutene (6), polyoxypropylene (20) ether bis-diaminodibenzo-18-crown-6 etheramine, 4 parts by weight of decynyl glycol polyoxyethylene (8), polyoxypropylene (4) ether, and 0.5 parts by weight of p-tert-butylphenol are mixed evenly at 50°C to obtain fuel additive b.

[0095] Example 3

[0096] Preparation of polyetheramine:

[0097] a) 76g (1mol) of 1,2-propanediol and 0.12g of DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were put into a high-pressure reactor, the air was removed by vacuuming, and then the reactor was heated to 130°C. 522g (9mol) of propylene oxide was introduced to carry out the polymerization reaction. The reaction pressure was controlled not to exceed 0.3MPa. After the reaction was completed, the temperature was kept high. 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) ether intermediate.

[0098] b) 1 mol of the above polyoxypropylene (10) ether intermediate and 0.43 g of DMC bimetallic catalyst (Huai'an Bade Polyurethane Technology Co., Ltd.) were added to a high-pressure reactor. The air was removed by evacuation. Then the reactor was heated to 135°C and 1080 g (15 mol) of epoxide butane was introduced for polymerization. The reaction pressure was controlled to not exceed 0.3 MPa. After the introduction was completed, the reaction was kept at a constant temperature. After the pressure dropped to a negative pressure, the temperature was lowered to 80°C and the reaction product was taken out to obtain polyoxypropylene (10) polyoxybutene (15) ether.

[0099] c) 1 mol of polyoxypropylene (10) polyoxybutene (15) ether, 773 g (4.1 mol) of p-toluenesulfonyl chloride, and 790 g (10 mol) of pyridine were dissolved in 4000 g of dichloroethane and stirred at 5 °C for 48 h. After the reaction was completed, the mixture was poured into a beaker and deionized water was added to wash the reaction solution. The mixture was separated by a separatory funnel and washed three times with water. The solvent was removed by rotary evaporation to obtain polyoxypropylene (10) polyoxybutene (15) ether p-toluenesulfonate.

[0100] d) Add 4 mol of diaminodibenzo-15-crown 5-ether (CAS No.: 313496-30-9) and 1392 g of ethylbenzene to the reaction vessel, stir evenly and heat to 110℃; dissolve 1914 g (1 mol) of polyoxypropylene (10) polyoxybutene (15) ether p-toluenesulfonate obtained in step c) in 2000 g of ethylbenzene, and slowly drop it into the diaminodibenzo-15-crown 5-ether solution through a constant pressure dropping funnel (at a rate of 1 mL / min), react for 48 h, wash with water after the reaction is completed, evaporate the solvent, and obtain polyoxypropylene (10) polyoxybutene (15) ether bis-diaminodibenzo-15-crown 5-ether amine.

[0101] Preparation of fuel additives:

[0102] Mix 100 parts by weight of 100# solvent oil, 40 parts by weight of polyoxypropylene (10), polyoxybutene (15) ether bis-diaminodibenzo-15-crown-5 etheramine, 1 part by weight of decynyl glycol polyoxyethylene (8), polyoxypropylene (4) ether, and 0.5 parts by weight of p-tert-butylphenol at 50°C to obtain fuel additive c.

[0103] Comparative Example 1

[0104] Preparation of polyoxybutene-polyoxypropylene etheramine:

[0105] a) 90g (1mol) of 1,2-butanediol and 0.36g of DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were put into a high-pressure reactor, the air was removed by vacuuming, and then the reactor was heated to 125°C. 360g (5mol) of epoxide butane was introduced to carry out the polymerization reaction. The reaction pressure was controlled not to exceed 0.3MPa. 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 polyoxybutene (6) ether intermediate.

[0106] b) 1 mol of the above polyoxybutene (6) ether intermediate and 0.23 g of DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were added to a high-pressure reactor. The air was removed by evacuation. Then the reactor was heated to 130°C and 1160 g (20 mol) of propylene oxide was introduced to carry out the polymerization reaction. The reaction pressure was controlled to not exceed 0.3 MPa. After the reaction was completed, the temperature was kept high. After the pressure dropped to negative pressure, the temperature was lowered to 80°C and the reaction product was taken out to obtain polyoxybutene (6) polyoxypropylene (20) ether.

[0107] c) 500g of polyoxybutene (6)polyoxypropylene (20) ether and 50g of Raney nickel catalyst (CAS No. 7440-02-0) were added to a reaction vessel. The air inside the vessel was removed by vacuuming. 90g of liquid ammonia and 6mol of hydrogen were introduced. The amination reaction was carried out at 9MPa and 190℃ for 8h. Then the mixture was cooled to 80℃. The mixture obtained from the reaction was taken out, filtered to remove insoluble matter, and the unreacted liquid ammonia was evaporated from the filtrate to obtain polyoxybutene (6)polyoxypropylene (20) ether amine.

[0108] Preparation of fuel additives:

[0109] 100 parts by weight of 80# solvent oil, 50 parts by weight of polyoxybutylene (6), polyoxypropylene (20), etheramine, 4 parts by weight of decynyl glycol polyoxyethylene (8), polyoxypropylene (4), ether (same as in Example 2), and 0.5 parts by weight of p-tert-butylphenol are mixed evenly 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 polyoxybutene (6) polyoxypropylene (20) ether prepared in Comparative Example 2, 4 parts by weight of decynyl glycol polyoxyethylene (8) polyoxypropylene (4) ether amine (same as Example 2), and 0.5 parts by weight of p-tert-butylphenol are mixed evenly at 50°C to obtain fuel additive e.

[0113] Comparative Example 3

[0114] Preparation of fuel additives:

[0115] 100 parts by weight of 80# solvent oil, 50 parts by weight of polyetheramine D2000, 4 parts by weight of decynyl glycol polyoxyethylene (8) polyoxypropylene (4) ether (same as in Example 2), and 0.5 parts by weight of p-tert-butylphenol are mixed evenly at 50°C to obtain fuel additive f.

[0116] Test case

[0117] Commercially available gasoline detergents with the same concentration (recommended ratio: 800 mg / L (calculated as polyetheramine)) and fuel additives from Examples 1-3 and Comparative Examples 1-3 were added to 92# base gasoline. The carbon deposit removal data were compared according to the method of GB / T19230.6. The data comparison is shown in Table 1 below.

[0118] Table 1. Performance comparison of fuel additives in the examples and comparative examples.

[0119]

[0120] As can be seen from Examples 2 and Comparative Examples 1-2 and Table 1, compared with the addition of crown-free polyetheramines (Comparative Example 1) prepared under the same conditions of the present invention using conventional initiators (such as propylene glycol or butylene glycol) to fuel additives, or crown-free polyetheramines + amino crown ethers prepared under the same conditions of the present invention (Comparative Example 2), fuel additives containing the specific polyetheramines of the present invention have significantly better cleaning effects on the fuel intake system and combustion chamber of automobile engines.

[0121] As can be seen from Example 2, Comparative Example 3 and Table 1, compared with the polyetheramine of the present invention, the fuel additive containing the polyetheramine of the present invention has a significantly more obvious cleaning effect on the fuel intake system and combustion chamber of automobile engines.

Claims

1. A polyetheramine comprising at least one of a compound having a structure represented by formula (1) or formula (2): Equation (1) Equation (2) In formulas (1) and (2), R is independently selected from methyl or ethyl; R 1 R 2 Selected from methyl or ethyl; x1 = 0~29, x2 = 0~29, and x1 + x2 = 1~29; 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, characterized in that: R 1 R 2 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 as described in claim 1 or 2, comprising: a) React 1,2-propanediol or 1,2-butanediol with propylene oxide or butane oxide in the presence of catalyst A to obtain a polyether intermediate. b) The polyether intermediate obtained in step a) is reacted with butane or propylene oxide in the presence of catalyst B to obtain block polyether. c) Dissolve the block polyether and acid-binding agent obtained in step b) in solvent A, and react with p-toluenesulfonyl chloride to obtain polyether p-toluenesulfonate; d) Dissolve the polyether p-toluenesulfonate obtained in step c) in solvent B and react it with diaminodibenzocrown ether to obtain the polyetheramine.

4. The preparation method according to claim 3, characterized in that: In step a), The catalyst A is at least one of a DMC bimetallic catalyst and an alkaline catalyst; and / or... The molar ratio of propylene oxide to 1,2-propanediol or 1,2-butanediol is (1~29):1; and / or, the molar ratio of butylene oxide to 1,2-propanediol or 1,2-butanediol is (1~29):1; and / or, The amount of catalyst A is 0.005~2% of the mass of propylene oxide or butane oxide; and / or, The reaction temperature is 110~140℃; and / or, In step b), The catalyst B is at least one of a DMC bimetallic catalyst and an alkaline catalyst; and / or The molar amount of propylene oxide or butyl oxide is 1 to 40 times the molar amount of the polyether intermediate; and / or, The amount of catalyst B is 0.005-2% of the mass of propylene oxide or butane oxide introduced in step b); and / or, The reaction temperature is 110~140℃.

5. The preparation method according to claim 4, characterized in that: In step a), The alkaline catalyst is at least one selected from sodium hydroxide, potassium hydroxide, sodium ethoxide, and sodium hydride; and / or, The molar ratio of propylene oxide to 1,2-propanediol or 1,2-butanediol is (4~24):1; and / or, the molar ratio of butylene oxide to 1,2-propanediol or 1,2-butanediol is (4~24):1; and / or, The amount of catalyst A is 0.01~1% of the mass of propylene oxide or butane oxide; and / or, The reaction temperature is 120~135℃; and / or, In step b), The alkaline catalyst is at least one selected from sodium hydroxide, potassium hydroxide, sodium ethoxide, and sodium hydride; and / or, The molar amount of propylene oxide or butyl oxide is 1 to 20 times the molar amount of the polyether intermediate; and / or, The amount of catalyst B is 0.01-1% of the mass of propylene oxide or butane oxide introduced in step b); and / or, The reaction temperature is 120~135℃.

6. The preparation method according to claim 3, characterized in that: In step c), The acid-binding agent is at least one selected from pyridine, triethylamine, diisopropylethylamine, sodium acetate, sodium carbonate, and potassium carbonate; and / or, The amount of the acid-binding agent is 1 to 20 times the molar amount of p-toluenesulfonyl chloride; and / or, Solvent A is at least one selected from dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, toluene, xylene, trimethylbenzene, and ethylbenzene; and / or, The amount of solvent A is 1 to 20 times the mass of the block polyether; and / or, The amount of p-toluenesulfonyl chloride used is 2 to 12 times the molar amount of the block polyether; and / or, The reaction temperature with p-toluenesulfonyl chloride is 0~40℃; and / or the reaction time with p-toluenesulfonyl chloride is 6~72 h.

7. The preparation method according to claim 6, characterized in that: In step c), The amount of the acid-binding agent is 1 to 10 times the molar amount of p-toluenesulfonyl chloride; and / or, The amount of solvent A is 1 to 10 times the mass of the block polyether; and / or, The amount of p-toluenesulfonyl chloride used is 2 to 10 times the molar amount of the block polyether; and / or, The reaction temperature with p-toluenesulfonyl chloride is 5~20℃; and / or the reaction time with p-toluenesulfonyl chloride is 18~48 h.

8. The preparation method according to claim 3, characterized in that: In step d), The diaminodibenzocrown ether has the following structure: or Where m = 1~5, n = 1~5; and / or, Solvent B is at least one selected from dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, toluene, xylene, trimethylbenzene, and ethylbenzene; and / or, The amount of solvent B is 1 to 20 times the mass of polyether p-toluenesulfonate; and / or, The amount of the diaminodibenzocrown ether is 2 to 6 times the molar amount of the polyether p-toluenesulfonate; and / or, The reaction temperature is 40~160℃; and / or the reaction time is 12~90 h.

9. The preparation method according to claim 8, characterized in that: In step d), The diaminodibenzocrown ether has the following structure: or Where m = 1~3, n = 1~3; and / or, The amount of solvent B is 1 to 10 times the mass of polyether p-toluenesulfonate; and / or, The amount of the diaminodibenzocrown ether is 2.5 to 4 times the molar amount of the polyether p-toluenesulfonate; and / or, The reaction temperature is 80~140℃; and / or the reaction time is 18~60 h.

10. The preparation method according to claim 9, characterized in that: In step d), 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.

11. The use of a polyetheramine as described in any one of claims 1-2 or a polyetheramine prepared by any one of claims 3-10 in a fuel additive.

12. A fuel additive comprising solvent oil and the polyetheramine according to any one of claims 1-2 or the polyetheramine obtained by any one of claims 3-10.

13. The fuel additive as described in claim 12, characterized in that: 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 amount of polyetheramine is 10 to 100 parts by weight per 100 parts by weight of solvent oil.

14. The fuel additive as described in claim 13, characterized in that: Based on 100 parts by weight of solvent oil, the amount of polyetheramine is 20 to 80 parts by weight.

15. The fuel additive as described in claim 12, characterized in that: The fuel additive also includes acetylenic diol polyether.

16. The fuel additive as described in claim 15, 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, m1+m2=0~16, n1 and n2 may be the same or different, n1+n2=0~20, and m1, m2, n1, and n2 are not simultaneously 0; and / or, Based on 100 parts by weight of solvent oil, the amount of acetylation diol polyether is 0.5 to 10 parts by weight.

17. The fuel additive as described in claim 16, characterized in that: Based on 100 parts by weight of solvent oil, the amount of acetylation diol polyether is 1 to 8 parts by weight.

18. A method for preparing a fuel additive as described in any one of claims 12-17, comprising uniformly mixing components including the polyetheramine, solvent oil, and optionally acetylenic diol polyether to obtain the fuel additive.

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