A non-metallic gasoline antiknock agent and its preparation method

Abstract

The present invention provides a non-metallic gasoline antiknock agent and a preparation method thereof, belonging to the technical field of antiknock agents, including the compound shown in Formula I and the compound shown in Formula II, with a mass ratio of 7-10:3-5. The antiknock agent prepared by the present invention has significantly improved effects. Perhaps the furan structures substituted at different positions can provide different combustion paths during the combustion process, having a synergistic effect, thus significantly playing an antiknock role and significantly increasing the octane number of gasoline. Formula I Formula II

Description

Technical Field

[0001] The present invention relates to the technical field of antiknock agents, and particularly to a non-metallic gasoline antiknock agent and a preparation method thereof. Background Art

[0002] The knocking phenomenon that occurs during the use of gasoline engines is mainly related to the composition and properties of gasoline. If gasoline is relatively easy to oxidize, the peroxides formed during the compression process of gasoline engine operation are not easily decomposed, causing the autoignition point of gasoline to decrease. Premature combustion before the spark plug ignites will result in incomplete combustion of gasoline, strong vibration of the engine, and knocking phenomenon. Therefore, the antiknock property of gasoline is an important quality index to measure the quality of gasoline. The higher the octane number, the better the antiknock property of gasoline.

[0003] There are usually two solutions to increase the octane number of gasoline. One is to produce gasoline with a high octane number through petroleum refining means such as catalytic cracking, catalytic reforming, alkylation, etc., and then obtain vehicle gasoline with appropriate antiknock property by blending gasoline with different octane numbers; the other is to add a gasoline antiknock agent to gasoline to improve its antiknock property. The R & D history of gasoline antiknock agents has experienced ash-containing metal additives such as lead-containing, iron-containing, manganese-containing, and alkali metal-containing since the early 20th century. These additives have been prohibited from use due to their own toxicity, easy generation of deposits that clog pipelines, affect the service life of spark plugs, and easily cause the deactivation of three-way catalysts.

[0004] The current problems of gasoline non-metallic antiknock agents mainly include:

[0005] (1) Low efficiency, with a large addition amount in gasoline. For example, the addition amount of methyl tert-butyl ether commonly used in refineries is generally 10%.

[0006] (2) Have an adverse effect on gasoline. The addition of aniline-based gasoline antiknock agents will reduce the combustion rate of gasoline, and at the same time have a greater impact on the induction period of gasoline and the sealing performance of some pipelines in the vehicle.

[0007] Therefore, it is of great significance to develop a non-metallic gasoline antiknock agent with low cost, high efficiency and no adverse effect on gasoline.

[0008] Chinese Patent Publication Text CN 108587705 A discloses a non-metallic gasoline antiknock agent, and the content of each active ingredient and its weight fraction meet the requirements: 15 - 40 parts of an ester-based octane number improver, 10 - 20 parts of an amine-based octane number improver, 15 - 30 parts of an ether-based octane number improver, 10 - 20 parts of an amide-based octane number improver, 15 - 30 parts of an organic phenol-based octane number improver, 3 - 8 parts of an alcohol-based octane number improver, 3 - 8 parts of a cleaning dispersant, and 3 - 8 parts of a cosolvent.

[0009] The Chinese patent authorized version CN 104711049 B discloses a novel non-metallic gasoline antiknock agent, which is composed of an oxygen-containing aromatic amine compound, an ester compound and a phenolic compound, and does not contain metal components; by weight, the oxygen-containing aromatic amine compound is 20-50 parts, the ester compound is 50-80 parts, and the phenolic compound is 0.01-1 part.

[0010] However, the improvement of the octane number after adding the above-prepared non-metallic gasoline antiknock agent to gasoline is not obvious, which limits its application. Summary of the Invention

[0011] The purpose of the present invention is to provide a non-metallic gasoline antiknock agent and its preparation method, which have the characteristics of simple synthesis, good oil solubility, low corrosion, excellent antiknock performance, etc., reduce the occurrence of knocking, have a synergistic effect, thus significantly playing an antiknock role and significantly increasing the octane number of gasoline.

[0012] The technical solution of the present invention is realized as follows:

[0013] The present invention provides a non-metallic gasoline antiknock agent having the structures shown in Formula I and / or Formula II:

[0014] Formula I;

[0015] Formula II;

[0016] When the non-metallic gasoline antiknock agent is the compound shown in Formula I and the compound shown in Formula II, their mass ratio is 7-10:3-5.

[0017] The present invention further protects a preparation method of the above non-metallic gasoline antiknock agent, comprising the following steps:

[0018] S1. Mix o-cresol and dimethylamine, add formaldehyde, heat under reflux for reaction, add sodium chloride, and continue the reaction to obtain Intermediate 1, the structure of which is as follows: ;

[0019] S2. Mix Intermediate 1 and salicylic acid, add a catalyst, heat under reflux for reaction, and obtain Intermediate 2, the structure of which is as follows: ;

[0020] S3. Mix Intermediate 2 and 3-chloromethylfuran or 2-chloromethylfuran, add a base, heat and stir for reaction to obtain the compound shown in Formula I and the compound shown in Formula II.

[0021] As a further improvement of the present invention, the mass ratio of o-cresol, dimethylamine, formaldehyde and sodium chloride in step S1 is 20-22:20-22:13-15:30-35.

[0022] As a further improvement of the present invention, the time of the heating reflux reaction in step S1 is 1 - 3 h, and the time of the continuous reaction is 15 - 25 min.

[0023] As a further improvement of the present invention, the molar ratio of intermediate 1 to salicylic acid in step S2 is 1:1 - 1.1, and the addition amount of the catalyst is 5 - 10 wt% of the mass of salicylic acid.

[0024] As a further improvement of the present invention, the catalyst in step S2 is concentrated sulfuric acid or p-toluenesulfonic acid.

[0025] As a further improvement of the present invention, the molar ratio of intermediate 2 to 3-chloromethylfuran or 2-chloromethylfuran in step S3 is 1:1 - 1.1.

[0026] As a further improvement of the present invention, the base in step S3 is selected from at least one of triethylamine, diethylamine, NaOH, KOH, and sodium carbonate.

[0027] As a further improvement of the present invention, the temperature of the heating and stirring reaction in step S3 is 50 - 60 °C, and the time is 3 - 5 h.

[0028] The present invention has the following beneficial effects:

[0029] By combining various groups such as phenols, nitrides, substituted furans, esters, and ethers, the present invention gives full play to the advantages of phenolic, furan, ester, ether, and amine compounds, and has the characteristics of simple synthesis, good oil solubility, low corrosion, excellent anti-knock performance, etc. The hydroxyl group in the phenolic compound can provide hydrogen atoms to react with free radicals, thus interrupting the oxidation reaction chain and playing an antioxidant role, which helps to improve the stability of the fuel. It can react with peroxides to decompose peroxides, reduce the influence of peroxides on fuel combustion, and reduce the possibility of knocking. It can also increase the octane number of gasoline. The substituted furan can improve the anti-knock performance of gasoline by preventing the spontaneous combustion of gasoline. When added to gasoline together with an ester anti-knock agent, the octane number of gasoline can be significantly increased. The ester compound contains oxygen atoms, which can provide additional oxygen during the combustion process, promote fuel combustion, improve combustion efficiency, has a high octane number and a low vapor pressure, can improve the combustion performance of the fuel, and reduce engine wear. The ether compound has a high octane number and can effectively improve the anti-knock performance of gasoline. The nitrogen atom in the amine compound can provide a lone pair of electrons to react with free radicals to generate inactive molecules, thus inhibiting the free radical chain reaction, reducing the occurrence of knocking, effectively increasing the octane number of gasoline, and enhancing the anti-knock performance of gasoline.

[0030] The present invention prepares two different compounds shown in Formula I and compounds shown in Formula II through substituted furans at different positions. After the two compounds are combined, the effect of the prepared antiknock agent is significantly improved. Perhaps the furan structures substituted at different positions can provide different combustion paths during the combustion process, thereby regulating the combustion rate and combustion stability of the fuel. The compound shown in Formula I promotes the complete combustion of the fuel, and the compound shown in Formula II can inhibit unstable combustion reactions, thereby reducing the occurrence of knocking, having a synergistic effect, thus significantly playing an antiknock role and significantly increasing the octane number of gasoline. Detailed implementation mode

[0031] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention. Example 1

[0032] This example provides a preparation method of a non-metallic gasoline antiknock agent - the compound shown in Formula I.

[0033] The synthesis route is as follows:

[0034] ;

[0035] It includes the following steps:

[0036] S1. Under nitrogen protection, 20 g of o-methylphenol and 62 g of 33 wt% aqueous dimethylamine solution are mixed, stirred at a constant temperature of 30 °C for 1 h, 37 g of 37 wt% formaldehyde solution is added dropwise, heated to reflux for 1 h, 30 g of sodium chloride is added, and reflux is continued for 15 min. The organic phase is separated, washed, dried, filtered, and the filtrate is distilled under reduced pressure at a pressure of 2.5 kPa to remove water, formaldehyde, and dimethylamine to obtain the product intermediate 1 with a yield of 94.2%; ESI-MS calculated value: C 13 H 23 N 2 O(M+H) + 223.17, measured value: 223.2.

[0037] NMR results: 1 H NMR(300 MHz, CDCl 3 ) δ 6.59 (s, 2H), 5.0 (br, 1H), 3.72 (s, 4H), 2.39 (s, 3H), 2.21 (s, 12H).

[0038] S2. Mix 0.1 mol of intermediate 1 and 0.1 mol of salicylic acid, add them to 200 mL of toluene, add concentrated sulfuric acid, the added amount of the concentrated sulfuric acid is 5 wt% of the mass of salicylic acid, heat under reflux for 8 h, wash the product with NaOH solution until neutral, collect the organic phase, dry it, remove the solvent by distillation under reduced pressure, and separate by column chromatography (ethyl acetate: petroleum ether = 3:1) to obtain intermediate 2 with a yield of 75.3%; ESI-MS calculated value: C 20 H 27 N 2 O 3 (M+H) + 343.19, measured value: 343.2.

[0039] NMR result: 1 H NMR(300 MHz, CDCl 3 ) δ 7.82 (d, J = 5.6 Hz, 1H), 7.39 (m, 1H), 6.87 (m, 1H), 6.75 (s, 2H), 6.80 (d, J = 6.4 Hz, 1H), 5.1 (br, 1H), 3.72 (s, 4H), 2.39 (s, 3H), 2.22 (s, 12H).

[0040] S3. Mix 0.1 mol of intermediate 2 and 0.1 mol of 3-chloromethylfuran, add them to 250 mL of acetonitrile, add 0.3 mol of triethylamine, heat to 50 °C, stir and react for 3 h, wash with water, separate the organic phase, remove the solvent by distillation under reduced pressure, and separate by column chromatography (ethyl acetate: petroleum ether = 1:1) to obtain the compound shown in Formula I with a yield of 91.5%. ESI-MS calculated value: C 25 H 31 N 2 O 4 (M+H) + 423.22, measured value: 423.2.

[0041] NMR result: 1 H NMR(300 MHz, CDCl 3 ) δ 8.10 (d, J = 6.5 Hz, 1H), 7.32 (m, 1H), 7.25 (d, J = 5.1 Hz, 1H), 7.15 (s, 1H), 6.85 - 6.92 (m, 2H), 6.68 (s, 2H), 6.22 (d, J = 5.0 Hz, 1H), 5.2 (s, 2H), 3.58 (s, 4H), 2.32 (s, 3H), 2.21 (s, 12H). Example 2

[0042] This embodiment provides a preparation method of a non-metallic gasoline antiknock agent - the compound shown in Formula I, comprising the following steps:

[0043] S1. Under nitrogen protection, 22 g of o-methylphenol and 64 g of 33 wt% aqueous dimethylamine solution are mixed, stirred at a constant temperature of 30 °C for 1 h, 39 g of 37 wt% formaldehyde solution is added dropwise, heated to reflux for 3 h, 35 g of sodium chloride is added, and reflux is continued for 25 min. The organic phase is separated, washed, dried, filtered, and the filtrate is distilled under reduced pressure at a pressure of 2.5 kPa to remove water, formaldehyde and dimethylamine, obtaining the product intermediate 1 with a yield of 95.5%;

[0044] S2. 0.1 mol of intermediate 1 and 0.11 mol of salicylic acid are mixed and added to 200 mL of toluene, and p-toluenesulfonic acid is added, and the addition amount of p-toluenesulfonic acid is 10 wt% of the mass of salicylic acid. It is heated to reflux for 8 h, and the product is washed with NaOH solution until neutral. The organic phase is collected, dried, the solvent is removed by distillation under reduced pressure, and column chromatography separation (ethyl acetate: petroleum ether = 3:1) is carried out to obtain intermediate 2 with a yield of 76.9%;

[0045] S3. 0.1 mol of intermediate 2 and 0.11 mol of 3-chloromethylfuran are mixed and added to 250 mL of acetonitrile, 0.3 mol of diethylamine is added, heated to 60 °C, stirred and reacted for 5 h, washed with water, the organic phase is separated, the solvent is removed by distillation under reduced pressure, and column chromatography separation (ethyl acetate: petroleum ether = 1:1) is carried out to obtain the compound shown in Formula I with a yield of 92.1%. Example 3

[0046] This embodiment provides a preparation method of a non-metallic gasoline antiknock agent - the compound shown in Formula II.

[0047] The synthesis route is as follows:

[0048] ;

[0049] Comprising the following steps:

[0050] S1. Under nitrogen protection, 21 g of o-methylphenol and 63 g of 33 wt% aqueous dimethylamine solution are mixed, stirred at a constant temperature of 30 °C for 1 h, 38 g of 37 wt% formaldehyde solution is added dropwise, heated to reflux for 2 h, 32 g of sodium chloride is added, and reflux is continued for 20 min. The organic phase is separated, washed, dried, filtered, and the filtrate is distilled under reduced pressure at a pressure of 2.5 kPa to remove water, formaldehyde and dimethylamine, obtaining the product intermediate 1 with a yield of 95.8%;

[0051] S2. Mix 0.1 mol of intermediate 1 and 0.105 mol of salicylic acid, add them to 200 mL of toluene, add concentrated sulfuric acid, and the addition amount of the concentrated sulfuric acid is 7 wt% of the mass of salicylic acid. Heat under reflux for 8 h, wash the product with NaOH solution until neutral, collect the organic phase, dry it, remove the solvent by distillation under reduced pressure, and separate it by column chromatography (ethyl acetate: petroleum ether = 3:1) to obtain intermediate 2 with a yield of 76.5%;

[0052] S3. Mix 0.1 mol of intermediate 2 and 0.105 mol of 2-chloromethylfuran, add them to 250 mL of acetonitrile, add 0.3 mol of triethylamine, heat to 55 °C, stir and react for 4 h, wash with water, separate the organic phase, remove the solvent by distillation under reduced pressure, and separate it by column chromatography (ethyl acetate: petroleum ether = 1:1) to obtain the compound shown in Formula II with a yield of 92.0%. ESI-MS calculated value: C 25 H 31 N 2 O 4 (M + H) + 423.22, measured value: 423.2.

[0053] NMR result: 1 H NMR (300 MHz, CDCl 3 ) δ8.13 (d, J = 6.5 Hz, 1H), 7.40 (m, 1H), 7.32 (d, J = 5.2 Hz, 1H), 7.15 (s, 1H), 6.90 - 6.98 (m, 2H), 6.68 (s, 2H), 6.19 (d, J = 4.8 Hz, 1H), 5.22 (s, 2H), 3.57 (s, 4H), 2.34 (s, 3H), 2.25 (s, 12H). Example 4

[0054] This example provides a preparation method of a non-metallic gasoline antiknock agent - the compound shown in Formula II, including the following steps:

[0055] S1. Under nitrogen protection, mix 21 g of o-methylphenol and 63 g of 33 wt% aqueous dimethylamine solution, stir at a constant temperature of 30 °C for 1 h, dropwise add 38 g of 37 wt% formaldehyde solution, heat under reflux for 2 h, add 32 g of sodium chloride, continue refluxing for 20 min, separate the organic phase, wash, dry, filter, and distill the filtrate under reduced pressure at a pressure of 2.5 kPa to remove water, formaldehyde, and dimethylamine to obtain the product intermediate 1 with a yield of 95.7%;

[0056] S2. Mix 0.1 mol of intermediate 1 and 0.105 mol of salicylic acid, add them to 200 mL of toluene, add p-toluenesulfonic acid, and the addition amount of the p-toluenesulfonic acid is 8 wt% of the mass of salicylic acid. Heat under reflux for 8 h, wash the product with NaOH solution until neutral, collect the organic phase, dry it, remove the solvent by distillation under reduced pressure, and separate it by column chromatography (ethyl acetate: petroleum ether = 3:1) to obtain intermediate 2 with a yield of 75.9%;

[0057] S3. Mix 0.1 mol of intermediate 2 and 0.105 mol of 2-chloromethylfuran, add them to 250 mL of acetonitrile, add 0.3 mol of NaOH, heat to 55 °C, stir and react for 4 h, wash with water, separate the organic phase, remove the solvent by distillation under reduced pressure, and separate it by column chromatography (ethyl acetate: petroleum ether = 1:1) to obtain the compound shown in Formula II with a yield of 92.2%. Example 5

[0058] A non-metallic gasoline antiknock agent comprises the compound shown in Formula I and the compound shown in Formula II, and the mass ratio is 7:3. Example 6

[0059] A non-metallic gasoline antiknock agent comprises the compound shown in Formula I and the compound shown in Formula II, and the mass ratio is 10:5. Example 7

[0060] A non-metallic gasoline antiknock agent comprises the compound shown in Formula I and the compound shown in Formula II, and the mass ratio is 8:4.

[0061] Comparative Example 1

[0062] A non-metallic gasoline antiknock agent comprises the compound shown in Formula I and the compound shown in Formula II, and the mass ratio is 10:1.

[0063] Comparative Example 2

[0064] A non-metallic gasoline antiknock agent comprises the compound shown in Formula I and the compound shown in Formula II, and the mass ratio is 1:10.

[0065] Test Example 1

[0066] Using 75# aviation gasoline and 70# vehicle gasoline as base oils, at a temperature of 27 °C, add the non-metallic gasoline antiknock agents prepared in Examples 1, 3, 5 - 7 and Comparative Examples 1 - 2 to the base oils at an addition amount of 5 wt%, observe the dissolution situation, and the results are shown in Table 1.

[0067] Table 1 ;

[0068] As can be seen from the above table, the non-metallic gasoline antiknock agent prepared by the present invention has good solubility in both 75# aviation gasoline and 70# vehicle gasoline.

[0069] Test Example 2

[0070] Using 75# aviation gasoline as the base oil, according to the method of GB / T 5096-85, a copper sheet with a purity > 99.5% was suspended and immersed in the base oil containing 5wt% of the non-metallic gasoline antiknock agents prepared in Examples 1, 3, 5-7 and Comparative Examples 1-2, as well as commercially available methylcyclopentadienyl manganese tricarbonyl for 2 h. The results are shown in Table 2.

[0071] Table 2 ;

[0072] Note: The copper strip corrosion test method for petroleum products is classified according to the corrosion standard color plate. 1a and 1b indicate: in Grade 1 of light discoloration, a is light orange, almost the same as the newly polished copper strip; b is dark orange.

[0073] As can be seen from the above table, the non-metallic gasoline antiknock agent prepared by the present invention has no obvious corrosiveness.

[0074] Test Example 3

[0075] The experiment on the influence of gasoline antiknock performance was determined according to the gasoline octane number determination method of GB / T 5032-1995.

[0076] Test objects: The non-metallic gasoline antiknock agents prepared in Examples 1, 3, 5-7 and Comparative Examples 1-2, as well as commercially available methylcyclopentadienyl manganese tricarbonyl.

[0077] Addition amount: 1wt%.

[0078] The octane number of 1# base gasoline (straight-run gasoline): 67; the octane number of 2# base gasoline (a mixed oil of straight-run gasoline and commercially available 93# gasoline in a volume ratio of 2:3): 85; the octane number of 3# base gasoline (commercially available 90# gasoline): 90.4.

[0079] Experimental conditions: Room temperature 15°C, humidity 29%. Pressure 10215 kPa, calculation correction value 5, lubricating oil pressure 193105 kPa, lubricating oil temperature 135°C, intake air temperature 40 - 50°C, mixture temperature 150°C, coolant temperature 100°C, amplification value 180, broadening value 174, engine speed 600 r / min. The influence of antiknock performance was determined on an octane number tester.

[0080] The results are shown in Table 3.

[0081] Table 3 ;

[0082] As can be seen from the above table, the non-metallic gasoline antiknock agent prepared in Examples 5-7 of the present invention can significantly improve the octane number of gasoline.

[0083] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A non-metallic gasoline antiknock agent, characterized in that: Having the structure shown in Formula I and / or Formula II: Formula I; Formula II; When the non-metallic gasoline antiknock agent is the compound represented by Formula I and the compound represented by Formula II, the mass ratio thereof is 7-10:3-5.

2. A method for preparing the non-metallic gasoline antiknock agent as claimed in claim 1, characterized in that: The following steps are involved: S1. Mix o-methylphenol and dimethylamine, add formaldehyde, heat to reflux reaction, add sodium chloride, and continue the reaction to obtain intermediate 1, the structure of which is as follows: ; S2. Intermediate 1 and salicylic acid are mixed, a catalyst is added, and the mixture is heated under reflux to react to obtain intermediate 2, the structure of which is as follows: ; The catalyst is concentrated sulfuric acid or p-toluenesulfonic acid; S3. The intermediate 2 and 3-chloromethylfuran or 2-chloromethylfuran are mixed, a base is added, and the mixture is heated and stirred to react to obtain a compound of formula I or a compound of formula II.

3. The preparation method according to claim 2, characterized in that: The mass ratio of o-cresol, dimethylamine, formaldehyde and sodium chloride in step S1 is 20-22:20-22:13-15:30-35.

4. The preparation method according to claim 2, characterized in that: The heating reflux reaction time in step S1 is 1-3 hours, and the continued reaction time is 15-25 minutes.

5. The preparation method according to claim 2, characterized in that: In step S2, the molar ratio of the intermediate 1 to salicylic acid is 1:1-1.1, and the amount of the catalyst added is 5-10wt% of the mass of salicylic acid.

6. The preparation method according to claim 2, characterized in that: The molar ratio of the intermediate 2, 3-chloromethylfuran or 2-chloromethylfuran in step S3 is 1:1-1.

1.

7. The preparation method according to claim 2, characterized in that: The base in step S3 is selected from at least one of triethylamine, diethylamine, NaOH, KOH and sodium carbonate.

8. The preparation method according to claim 2, characterized in that: The temperature of the heating and stirring reaction in step S3 is 50-60° C. and the time is 3-5 h.

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