Porphyrin compound as well as preparation method and application thereof

Abstract

The invention discloses a porphyrin compound as well as a preparation method and application thereof. The porphyrin compound comprises at least one of compounds with a structure as shown in the following formula (I): in the formula (I), R is 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; r5, R6 and R7 are the same or different and are independently selected from H, OH, NH2, Cl, Br, NO2, CnH2n + 1 or OCnH2n + 1, and n is equal to 1-20. The fuel 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 present invention relates to the technical field of fuel additives, and in particular to a porphyrin compound and a preparation method and application thereof. Background Art

[0002] Affected by the refining process, the content of olefins and aromatics in gasoline is relatively high, which easily leads to carbon deposits in the engine's fuel nozzles, intake valves, combustion chambers and other parts. The engine's fuel nozzles are more sensitive to sediments in the fuel and are prone to clogging. Sediments will accumulate on the surface of the intake valves that are used for a long time, which can cause the engine's power to deteriorate, increase fuel consumption, and especially worsen exhaust emissions.

[0003] Effective methods for reducing automobile exhaust pollutant emissions include improving oil refining technology and adding fuel additives. The former requires major technological innovations in refineries and is more difficult to implement, while the latter is much easier to implement. Therefore, fuel additives have become one of the important technical means to improve fuel quality and engine operating conditions. Fuel additives with better effects in the existing technology: for example, additives with polyisobutylene amine, polyisobutylene succinimide and polyether amine as the main agents can not only inhibit the formation of deposits inside the fuel system, but also quickly disperse and remove the deposits that have already formed, thereby ensuring the normal performance of the automobile engine, improving the combustion performance of the fuel, and greatly reducing the HC and CO pollutants in automobile exhaust emissions, thereby purifying automobile exhaust, reducing automobile 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 combustion chamber deposits.

[0004] In summary, there is an urgent need for a fuel additive with good thermal stability 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

[0005] To solve the problems existing in the prior art, the present invention provides a porphyrin compound, a preparation method thereof, and an application thereof. The fuel additive of the present invention can effectively clean carbon deposits on fuel nozzles, intake valves, and combustion chambers.

[0006] One of the objects of the present invention is to provide a porphyrin compound, which is at least one of the compounds having the structure represented by the following formula (I):

[0007]

[0008] In formula (I), 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; R3 、R 4 is selected from methyl or ethyl; y1 = 0 to 40, y2 = 0 to 40, and y1 + y2 = 1 to 40; x1, x2, y1, y2 represent the average degree of polymerization; R 5 、R 6 、R 7 The same or different, independently selected from H, OH, NH2, Cl, Br, NO2, C n H 2n+1 or OC n H 2n+1 , wherein n=1 to 20; preferably,

[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 is selected from methyl; and / or x1=0-24, x2=0-24, and x1+x2=4-24, preferably, x1=0-19, x2=0-19, and x1+x2=6-19; and / or y1=0-20, y2=0-20, and y1+y2=1-20, preferably, y1=0-16, y2=0-16, and y1+y2=8-16; and / or R 5 、R 6 、R 7 The same or different, are independently selected from H, OH, NH2, Cl, Br or NO2. The structure of the porphyrin compound in the present invention is theoretically deduced from the chemical reaction mechanism and the amount of the added raw materials.

[0010] A second object of the present invention is to provide a method for preparing a porphyrin compound, which comprises:

[0011] (i) reacting 1,2-propylene glycol or 1,2-butanediol with propylene oxide or butylene oxide in the presence of a catalyst A to obtain a polyether intermediate;

[0012] (ii) reacting the polyether intermediate obtained in step (i) with butylene oxide or propylene oxide in the presence of catalyst B to obtain a block polyether;

[0013] (iii) dissolving the block polyether and acid binding agent obtained in step (ii) in solvent A, and reacting with p-toluenesulfonyl chloride to obtain polyether p-toluenesulfonate;

[0014] (iv) dissolving the polyether p-toluenesulfonate obtained in step (iii) in solvent B, and reacting the solvent with aminophenylporphyrin to obtain the porphyrin compound.

[0015] The porphyrin compound of the present invention is preferably characterized by being a porphyrin compound prepared by the preparation method of the present invention as described above.

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

[0017] In step (i),

[0018] The catalyst A is at least one of an alkali catalyst and a DMC bimetallic catalyst. Preferably, the alkali catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium ethoxide, and sodium hydride; and / or,

[0019] 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 (6-19):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 (6-19):1; and / or,

[0020] 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,

[0021] The reaction conditions include: a temperature of 110-140° C., preferably 120-135° C.; preferably, the reaction is stopped when the pressure drops to negative pressure.

[0022] In a preferred embodiment of the present invention,

[0023] In step (ii),

[0024] The catalyst B is at least one of an alkali catalyst and a DMC bimetallic catalyst. Preferably, the alkali catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium ethoxide, and sodium hydride; and / or,

[0025] The molar amount of propylene oxide or butylene oxide is 1 to 40 times, preferably 1 to 20 times, more preferably 8 to 16 times the molar amount of the polyether intermediate; and / or,

[0026] 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,

[0027] The reaction conditions include: a temperature of 110-140° C., preferably 120-135° C.; preferably, the reaction is stopped when the pressure drops to negative pressure.

[0028] In a preferred embodiment of the present invention,

[0029] In step (iii),

[0030] The acid binding agent is at least one of pyridine, triethylamine, diisopropylethylamine, sodium acetate, sodium carbonate, and potassium carbonate; and / or,

[0031] 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,

[0032] The solvent A is at least one of dichloromethane, chloroform, carbon tetrachloride, dichloroethane, toluene, xylene, trimethylbenzene, and ethylbenzene; and / or,

[0033] The mass of the solvent A is 1 to 20 times, preferably 1 to 10 times, the mass of the block polyether; and / or,

[0034] The amount of p-toluenesulfonyl chloride is 2 to 12 times, preferably 2 to 10 times, more preferably 2 to 5 times the molar amount of the blocked polyether; and / or,

[0035] The reaction conditions with p-toluenesulfonyl chloride include: a temperature of 0 to 40° C., preferably 5 to 20° C.; and / or a reaction time of 6 to 72 hours, preferably 18 to 48 hours.

[0036] In a preferred embodiment of the present invention,

[0037] In step (iv),

[0038] The structure of the aminophenylporphyrin is shown below:

[0039] Among them, R 5 、R 6 、R 7 The same or different, independently selected from H, OH, NH2, Cl, Br, NO2, C n H 2n+1 or OC n H 2n+1 , wherein n=1 to 20; preferably, R 5 、R 6 、R 7 are the same or different and are independently selected from H, OH, NH2, Cl, Br or NO2; more preferably, the aminophenylporphyrin is one of diaminophenylporphyrin and tetraaminophenylporphyrin.

[0040] In a preferred embodiment of the present invention,

[0041] In step (iv),

[0042] The solvent B is at least one of dichloromethane, chloroform, carbon tetrachloride, dichloroethane, toluene, xylene, trimethylbenzene, ethylbenzene, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; and / or,

[0043] 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,

[0044] The amount of aminophenylporphyrin used is 2 to 6 times, preferably 2.5 to 4 times, the molar amount of polyether p-toluenesulfonate used; and / or,

[0045] The reaction conditions include: a temperature of 40 to 160° C., preferably 80 to 140° C.; and / or a reaction time of 12 to 90 hours, preferably 18 to 60 hours.

[0046] The preparation method of the porphyrin compound of the present invention can adopt the following specific technical scheme:

[0047] (i) placing an initiator 1,2-propylene glycol or 1,2-butanediol and a catalyst A into an autoclave, evacuating the air, then heating the autoclave 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 to not exceed 0.3 MPa, and continuing the reaction at the temperature after the pressure drops to negative pressure, cooling the autoclave to below 80° C., and removing the reaction product to obtain a polyether intermediate;

[0048] (ii) placing the polyether intermediate obtained in step (i) 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 heat-insulating reaction 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;

[0049] (iii) adding the block polyether obtained in step (ii), an acid binding agent, p-toluenesulfonyl chloride, and solvent A to a reaction kettle, and stirring the reaction at 0-40° C. for 6-72 hours; after the reaction is completed, adding deionized water to wash the reaction solution, separating the solution with a separatory funnel, and then evaporating the reaction solution to remove the solvent after washing to obtain polyether p-toluenesulfonate;

[0050] (iv) adding aminophenylporphyrin and solvent B into a reaction kettle, stirring evenly and heating to 40-160° C.; dissolving the polyether p-toluenesulfonate obtained in step (iii) in solvent B, and slowly dripping it into the aminophenylporphyrin solution through a constant pressure dropping funnel, allowing the polyether p-toluenesulfonate and aminophenylporphyrin to react for 12-90 hours. After the reaction is completed, washing with water and extracting with solvent C, washing with water three times, and evaporating the organic phase to remove the solvent to obtain the porphyrin compound.

[0051] In a preferred embodiment of the present invention,

[0052] The solvent C is at least one of dichloromethane, chloroform, carbon tetrachloride, dichloroethane, toluene, xylene, trimethylbenzene, and ethylbenzene; and / or,

[0053] The mass of the solvent C is 1 to 20 times, preferably 1 to 10 times, the mass of the polyether p-toluenesulfonate.

[0054] A third object of the present invention is to provide a fuel additive comprising the porphyrin compound of the first object of the present invention or the porphyrin compound obtained by the preparation method of the second object of the present invention.

[0055] In a preferred embodiment of the present invention,

[0056] The fuel additive further comprises solvent oil, acetylene glycol polyether and antioxidant; preferably,

[0057] Each component is calculated based on 100 parts by weight of solvent oil.

[0058] 10 to 100 parts by weight of a porphyrin compound; preferably 20 to 80 parts by weight; more preferably 30 to 60 parts by weight;

[0059] 0.5 to 10 parts by weight of acetylene glycol polyether; preferably 1 to 8 parts by weight; more preferably 1 to 5 parts by weight;

[0060] 0.1 to 2 parts by weight of antioxidant; preferably 0.5 to 2 parts by weight; more preferably,

[0061] 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,

[0062] The structural formula of the acetylene glycol polyether is as follows:

[0063]

[0064] 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,

[0065] 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).

[0066] 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, and those skilled in the art may add them according to actual conditions.

[0067] The fourth object of the present invention is to provide a method for preparing the fuel additive of the third object of the present invention, comprising the step of uniformly mixing components including the porphyrin compound and optional solvent oil, acetylene glycol polyether and antioxidant.

[0068] Compared with the prior art, the present invention has the following beneficial effects:

[0069] The polyether-modified porphyrin compound of the present invention has high thermal stability. Since its molecular structure contains two symmetrical porphyrin structural units, its stability is higher than that of a compound containing only one porphyrin structural unit. The porphyrin group in its molecular structure can serve as a carrier to complex metal ions, effectively removing deposits including metal ions in fuel nozzles, intake valves, and combustion chambers. Moreover, the porphyrin group can complex metal ions, thereby improving combustion characteristics and reducing pollution emissions. DETAILED DESCRIPTION

[0070] 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.

[0071] 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.

[0072] Preparation of decynediol polyoxypropylene (4) ether in Example 1:

[0073] (1) Preparation of nanocatalyst (Mg / Al / Co composite metal oxide catalyst):

[0074] 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.

[0075] (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.

[0076] Preparation of decynediol polyoxyethylene (8) polyoxypropylene (4) ether in Examples 2 and 3:

[0077] (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;

[0078] (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.

[0079] The structure of the acetylene glycol polyether obtained above is theoretically deduced from the reaction mechanism and the added raw materials.

[0080] Example 1

[0081] Preparation of porphyrin compounds:

[0082] (i) 90 g (1 mol) of 1,2-butanediol and 0.5 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 1080 g (15 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 (16) ether intermediate;

[0083] (ii) 1 mol of the above-mentioned polyoxybutylene (16) ether intermediate and 0.25 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 580 g (10 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, 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 (16) polyoxypropylene (10) ether;

[0084] (iii) dissolving 1 mol of polyoxybutylene (16) 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, and the mixture is washed with a separatory funnel. After washing three times with water, the reaction mixture is rotary evaporated to remove the solvent to obtain polyoxybutylene (16) polyoxypropylene (10) ether p-toluenesulfonate;

[0085] (iv) 1610 g (2.5 mol) of 5,15-(aminophenyl)-10,20-phenylporphyrin (CAS No.: 116206-75-8) and 3864 g of N,N-dimethylformamide were added to a reaction kettle, stirred evenly, and heated to 120° C.; 1 mol of polyoxybutylene (16) polyoxypropylene (10) ether p-toluenesulfonate obtained in step (iii) was dissolved in 2000 g of N,N-dimethylformamide, and The mixture was slowly dripped (at a rate of 1 mL / min) into the 5,15-(aminophenyl)-10,20-phenylporphyrin solution through a constant pressure dropping funnel and reacted for 24 hours. After the reaction was completed, the mixture was washed with water and 3000 g of dichloromethane was added for extraction. The organic phase was repeatedly washed with water for 3 times and the solvent was evaporated to obtain polyoxybutylene (16) polyoxypropylene (10) ether bis-5,15-(aminophenyl)-10,20-phenylporphyrin ether amine (i.e., porphyrin compound).

[0086] Preparation of fuel additives:

[0087] 100 parts by weight of 60# solvent oil, 50 parts by weight of polyoxybutylene (16) polyoxypropylene (10) ether bis-5,15-(aminophenyl)-10,20-phenylporphyrin ether amine, 2 parts by weight of decynediol polyoxypropylene (4) ether, and 0.5 parts by weight of p-phenylenediamine were mixed uniformly at 50° C. to obtain fuel additive I#.

[0088] Example 2

[0089] Preparation of porphyrin compounds:

[0090] (i) 90 g (1 mol) of 1,2-butanediol and 0.6 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 1368 g (19 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 (20) ether intermediate;

[0091] (ii) 1 mol of the above-mentioned polyoxybutylene (20) ether intermediate and 0.4 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 870 g (15 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 polyoxybutylene (20) polyoxypropylene (15) ether;

[0092] (iii) dissolving 1 mol of polyoxybutylene (20) polyoxypropylene (15) ether, 927 g of p-toluenesulfonyl chloride, and 948 g of pyridine in 4000 g of dichloroethane, and stirring the mixture at 20° C. for 24 h; after the reaction is completed, 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 remove the solvent to obtain polyoxybutylene (20) polyoxypropylene (15) ether p-toluenesulfonate;

[0093] (iv) 2022 g (3 mol) of 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (CAS No.: 22112-84-1) and 4044 g of N,N-dimethylacetamide were added to a reaction kettle, stirred evenly, and heated to 100° C.; 1 mol of polyoxybutylene (20) polyoxypropylene (15) ether p-toluenesulfonate obtained in step (iii) was dissolved in 3000 g of N,N-dimethylacetamide, and the mixture was stirred for 2 h. The reaction mixture was slowly dripped (at a rate of 1 mL / min) into the 5,10,15,20-tetrakis(4-aminophenyl)porphyrin solution through a constant pressure dropping funnel and reacted for 48 hours. After the reaction was completed, the mixture was washed with water and 3000 g of dichloromethane was added for extraction. The organic phase was repeatedly washed with water for 3 times and the solvent was evaporated to obtain polyoxybutylene (20) polyoxypropylene (15) ether bis-5,10,15,20-tetrakis(4-aminophenyl)porphyrin ether amine (i.e., porphyrin compound).

[0094] Preparation of fuel additives:

[0095] 100 parts by weight of 80# solvent oil, 50 parts by weight of polyoxybutylene (20) polyoxypropylene (15) ether bis-5,10,15,20-tetrakis(4-aminophenyl)porphyrin 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 II#.

[0096] Example 3

[0097] Preparation of porphyrin compounds:

[0098] (i) 76 g (1 mol) of 1,2-propylene glycol and 0.3 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 348 g (6 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., and the reaction product was taken out to obtain a narrow distribution polyoxypropylene (7) ether intermediate;

[0099] (ii) 1 mol of the above-mentioned polyoxypropylene (7) 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., and 1080 g (15 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 narrow distribution polyoxypropylene (7) polyoxybutylene (15) ether;

[0100] (iii) dissolving 1 mol of polyoxypropylene (7) polyoxybutylene (15) ether, 773 g of p-toluenesulfonyl chloride, and 790 g of pyridine in 3000 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, and the mixture is washed with a separatory funnel. After washing three times with water, the reaction mixture is rotary evaporated to remove the solvent to obtain polyoxypropylene (7) polyoxybutylene (15) ether p-toluenesulfonate;

[0101] (iv) 1890 g (3 mol) of 4-(10,15,20-triphenylporphyrin-5-yl)aniline (CAS No.: 67605-64-5) and 4000 g of N,N-dimethylformamide were added to a reaction kettle, stirred evenly and heated to 110° C.; 1 mol of polyoxypropylene (7) polyoxybutylene (15) ether p-toluenesulfonate obtained in step (iii) was dissolved in 2000 g of N,N-dimethylformamide and heated to 4000 g by a constant temperature. The solution was slowly dripped (at a rate of 1 mL / min) into the 4-(10,15,20-triphenylporphyrin-5-yl)aniline solution using a dropping funnel and reacted for 48 h. After the reaction was completed, the solution was washed with water and 3000 g of dichloromethane was added for extraction. The organic phase was repeatedly washed with water for 3 times and the solvent was evaporated to obtain polyoxypropylene (7) polyoxybutylene (15) ether bis-4-(10,15,20-triphenylporphyrin-5-yl)aniline ether amine (i.e., porphyrin compound).

[0102] Preparation of fuel additives:

[0103] 100 parts by weight of 100# solvent oil, 40 parts by weight of polyoxypropylene (7) polyoxybutylene (15) ether bis-4-(10,15,20-triphenylporphyrin-5-yl) aniline ether amine, 1 part by weight of decynediol polyoxyethylene (8) polyoxypropylene (4) ether, and 0.5 part by weight of p-tert-butylphenol are mixed uniformly at 50°C to obtain fuel additive III#.

[0104] Comparative Example 1

[0105] Preparation of polyoxybutylene polyoxypropylene ether amine:

[0106] (i) 90 g (1 mol) of 1,2-butanediol and 0.5 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 1080 g (15 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 (16) ether intermediate;

[0107] (ii) 1 mol of the above-mentioned polyoxybutylene (16) ether intermediate and 0.25 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 580 g (10 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, 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 (16) polyoxypropylene (10) ether;

[0108] (iii) 500 g of polyoxybutylene (16) polyoxypropylene (10) 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 (16) polyoxypropylene (10) ether amine.

[0109] Preparation of fuel additives:

[0110] Fuel additive IV# was obtained by mixing 100 parts by weight of 60# solvent oil, 50 parts by weight of polyoxybutylene (16) polyoxypropylene (10) ether amine, 2 parts by weight of decynediol polyoxypropylene (4) ether, and 0.5 parts by weight of p-phenylenediamine at 50°C.

[0111] Comparative Example 2

[0112] Preparation of fuel additives:

[0113] Fuel additive V# was obtained by mixing 100 parts by weight of 60# solvent oil, 21 parts by weight of 5,15-(aminophenyl)-10,20-phenylporphyrin (CAS No.: 116206-75-8), 29 parts by weight of polyoxybutylene (16) polyoxypropylene (10) ether amine prepared in Comparative Example 1, 2 parts by weight of decynediol polyoxypropylene (4) ether (same as in Example 1), and 0.5 parts by weight of p-phenylenediamine at 50°C.

[0114] Comparative Example 3

[0115] Preparation of fuel additives:

[0116] Fuel additive VI# was obtained by mixing 100 parts by weight of 60# solvent oil, 50 parts by weight of polyetheramine D400, 2 parts by weight of decynediol polyoxypropylene (4) ether (same as in Example 1), and 0.5 parts by weight of p-phenylenediamine at 50°C.

[0117] Test Case

[0118] 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.

[0119] Table 1 Performance comparison of fuel additives in Examples and Comparative Examples

[0120]

[0121] As can be seen from Example 2, Comparative Examples 1-2, and Table 1, compared with adding a 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 further adding an amino-containing porphyrin (Comparative Example 2), the fuel additive containing the polyether bisporphyrinamine of the present invention has a significantly better cleaning effect on the fuel intake system and combustion chamber of the automobile engine.

[0122] It can be seen from Example 2, Comparative Example 3 and Table 1 that, compared with the polyether bisporphyrinamine of the present invention and the polyether bisporphyrinamine conventionally used in the prior art, the fuel additive containing the polyether bisporphyrinamine of the present invention has a more significant cleaning effect on the fuel intake system and combustion chamber of the automobile engine.

[0123] As can be seen from Examples 1-3 and Table 1, the polyether bisporphyrinamine fuel additive of the present invention, when added to commercially available automotive gasoline, significantly cleans both the fuel intake system and the combustion chamber of a vehicle engine. This maintains excellent engine operating conditions over time, prevents excessive increases in fuel consumption, and reduces harmful exhaust emissions, thereby reducing engine maintenance costs and extending engine life.

Claims

1. A porphyrin compound, comprising at least one of the compounds having the structure represented by the following formula (I): In formula (I), 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 is selected from methyl or ethyl; y1=0-40, y2=0-40, and y1+y2=1-40; R 5 、R 6 、R 7 The same or different, independently selected from H, OH, NH2, Cl, Br, NO2, C n H 2n+1 or OC n H 2n+1 ,in, n=1-20; preferably, 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 is 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, R 5 、R 6 、R 7 are the same or different and are independently selected from H, OH, NH2, Cl, Br or NO2.

2. A method for preparing a porphyrin compound as claimed in claim 1, comprising: (i) reacting 1,2-propylene glycol or 1,2-butanediol with propylene oxide or butylene oxide in the presence of a catalyst A to obtain a polyether intermediate; (ii) reacting the polyether intermediate obtained in step (i) with butylene oxide or propylene oxide in the presence of catalyst B to obtain a block polyether; (iii) dissolving the block polyether and acid binding agent obtained in step (ii) in solvent A, and reacting with p-toluenesulfonyl chloride to obtain polyether p-toluenesulfonate; (iv) dissolving the polyether p-toluenesulfonate obtained in step (iii) in solvent B, and reacting the solvent with aminophenylporphyrin to obtain the porphyrin compound.

3. The preparation method according to claim 2, wherein: In step (i), The catalyst A is at least one of an alkali catalyst and a DMC bimetallic catalyst. Preferably, the alkali 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 conditions include: a temperature of 110-140°C, preferably 120-135°C.

4. The preparation method according to claim 2, wherein: In step (ii), The catalyst B is at least one of an alkali catalyst and a DMC bimetallic catalyst. Preferably, the alkali 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% of the mass of the propylene oxide or butylene oxide introduced in step b), preferably 0.01-1%; and / or, The reaction conditions include: a temperature of 110-140°C, preferably 120-135°C.

5. The preparation method according to claim 2, wherein: In step (iii), 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 mass of the 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 conditions with p-toluenesulfonyl chloride include: a temperature of 0 to 40° C., preferably 5 to 20° C.; and / or a reaction time of 6 to 72 hours, preferably 18 to 48 hours.

6. The preparation method according to claim 2, wherein: In step (iv), The structure of the aminophenylporphyrin is shown below: Among them, R 5 、R 6 、R 7 The same or different, independently selected from H, OH, NH2, Cl, Br, NO2, C n H 2n+1 or OC n H 2n+1 , wherein n=1 to 20; preferably, R 5 、R 6 、R 7 are the same or different and are independently selected from H, OH, NH2, Cl, Br or NO2; more preferably, the aminophenylporphyrin is one of diaminophenylporphyrin and tetraaminophenylporphyrin.

7. The preparation method according to claim 2, wherein: In step (iv), The solvent B is at least one of dichloromethane, chloroform, carbon tetrachloride, dichloroethane, toluene, xylene, trimethylbenzene, ethylbenzene, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; 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 aminophenylporphyrin used is 2 to 6 times, preferably 2.5 to 4 times, the molar amount of polyether p-toluenesulfonate used; and / or, The reaction conditions include: a temperature of 40 to 160° C., preferably 80 to 140° C.; and / or a reaction time of 12 to 90 hours, preferably 18 to 60 hours.

8. A fuel additive comprising the porphyrin compound according to claim 1 or the porphyrin compound obtained by the preparation method according to any one of claims 2 to 7.

9. The fuel additive according to claim 8, characterized in that: The fuel additive further comprises solvent oil, acetylene glycol polyether and antioxidant; preferably, Each component is calculated based on 100 parts by weight of solvent oil. 10 to 100 parts by weight of a porphyrin compound; preferably 20 to 80 parts by weight; 0.5 to 10 parts by weight of acetylene glycol polyether; preferably 1 to 8 parts by weight; 0.1 to 2 parts by weight of antioxidant; preferably 0.5 to 2 parts by weight; more 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 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, The antioxidant is 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).

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

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