CN108033979B - A kind of methanol gasoline additive and the preparation method and application thereof - Google Patents
A kind of methanol gasoline additive and the preparation method and application thereof Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 309
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003254 gasoline additive Substances 0.000 title abstract description 17
- 239000003502 gasoline Substances 0.000 claims abstract description 66
- -1 Aromatic amine compound Chemical class 0.000 claims abstract description 52
- 239000000446 fuel Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- ACWYHEGBVSRHNF-UHFFFAOYSA-N BrC1=CC=C(C=C1)O[P] Chemical compound BrC1=CC=C(C=C1)O[P] ACWYHEGBVSRHNF-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 10
- 239000000741 silica gel Substances 0.000 claims description 10
- 229910002027 silica gel Inorganic materials 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007983 Tris buffer Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 229920006395 saturated elastomer Polymers 0.000 abstract description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002735 gasoline substitute Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5325—Aromatic phosphine oxides or thioxides (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/26—Organic compounds containing phosphorus
- C10L1/2608—Organic compounds containing phosphorus containing a phosphorus-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2270/00—Specifically adapted fuels
- C10L2270/02—Specifically adapted fuels for internal combustion engines
- C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to methanol gasoline clean fuel technical fields, and in particular to a kind of methanol gasoline additive, and preparation method and the application for being used to prepare M15-M30 methanol gasoline are further disclosed.Aromatic amine compound of the present invention, it can be used as methanol gasoline additive, after it is mixed with commercial methanol gasoline according to the weight part ratio of 0.5-2:100, it can effectively improve the performance of M15-M30 methanol gasoline, make methanol gasoline keep stablizing under -20~-30 DEG C of cryogenic conditions, do not occur mutually to separate, while the reid method saturated vapor pressure of methanol gasoline is lower than 72kPa, meet national standard, while engine power performance is unaffected.
Description
Technical Field
The invention belongs to the technical field of methanol gasoline clean fuels, and particularly relates to a methanol gasoline additive, and further discloses a preparation method and application thereof in preparation of M15-M30 methanol gasoline.
Background
With the rapid development of the world economy, the automobile keeping amount is rising year by year, the demand of automobile fuel is increasing continuously, and the environmental problems caused by the increase are becoming more serious. With the increasing shortage of world energy reserves, the situation of increasingly exhausted petroleum resources is more severe. At present, the import dependence of petroleum in China exceeds 50%, and energy is in an extremely unsafe state. Energy and environmental problems restrict the rapid development of economy in China. Therefore, the search for new clean alternative energy has become a key topic for promoting the economic development of China.
Alcohols are the most useful fuels for internal combustion engines, except for petroleum and natural gas. The main advantage of using alcohol fuels is that they can achieve much lower emissions than hydrocarbon fuels, which is of great benefit to reduce atmospheric pollution; the method has inheritance compared with the traditional engine technology, and particularly when gasoline-alcohol mixed fuel is used, the structure of the engine can not be changed; in addition, alcohol fuels have a high octane number, and when used as ignition engine fuels, alcohol fuels can be used for engines with a relatively high compression ratio, improve the thermal efficiency of the engines, and are the most promising alternative fuels for internal combustion engines. The methanol is used as a good alternative energy source, has the advantages of wide source, high oxygen content, high octane number, small environmental pollution and the like, and is an ideal vehicle gasoline substitute. However, the current situation of energy sources rich in coal and less in oil in China also provides a wide market space for implementing methanol prepared from coal as an energy product, so that methanol gasoline as an automotive fuel is widely concerned by people in recent years.
The methanol gasoline is a clean fuel for vehicles, which is prepared by adding a certain proportion of denatured methanol into national standard vehicle gasoline according to volume or weight ratio and carrying out strict scientific process. The currently applied methanol gasoline is mainly low-proportion blended methanol gasoline with the methanol content of 10-30 percent. Bench test and driving test show: by using the M15 methanol gasoline, the conventional emission of CO and HC in the tail gas is reduced by about 23 percent and 28 percent respectively compared with the national standard gasoline. The low-proportion methanol gasoline has serious problems in the popularization process, namely high saturated vapor pressure and poor low-temperature startability. Since methanol is a polar oxygen-containing organic compound, when methanol exists in pure form, the molecules are mainly bonded by hydrogen bonds, and the saturated vapor pressure is low (about 14kPa at 20 ℃). However, when methanol is mixed with gasoline according to a certain proportion to prepare methanol gasoline, the intermolecular attraction of the gasoline is weak, and the association among methanol molecules is destroyed, so that the volatilization capacity of the methanol in the solution is much larger than that of pure methanol, thereby forming obvious positive deviation of vapor pressure, namely, the saturated vapor pressure is increased. In addition, methanol forms low boiling azeotropes with some components of gasoline and the saturated vapor pressure is higher than that of the base gasoline. The two factors enable the saturated vapor pressure of the methanol gasoline to be 10-30kpa higher than that of national standard gasoline, which means that when the low-proportion methanol (M15-M25) with higher saturated vapor pressure is used in hot areas at high temperature in summer, air resistance and unsmooth oil supply can be caused, the normal operation of an engine is seriously influenced, and the problem seriously restricts the popularization of the low-proportion methanol gasoline in China, particularly in southern areas; in addition, because two phases of the methanol gasoline are easy to separate at low temperature, the low-proportion methanol gasoline can not be started at minus 25 ℃, the use of the automobile is seriously influenced, and the application and popularization of the methanol gasoline in northern areas are greatly limited.
Disclosure of Invention
Therefore, the invention aims to provide a methanol gasoline additive to solve the problems of high saturated vapor pressure and poor low-temperature start of methanol gasoline in the prior art.
In order to solve the technical problems, the methanol gasoline additive is characterized by comprising arylamine compounds shown in formulas (I) and/or (II):
the mass ratio of the arylamine compound shown in the formula (I) to the arylamine compound shown in the formula (II) is 1: 1.
the invention also discloses a method for preparing the methanol gasoline additive, which comprises the following steps:
(1) adding magnesium and a small amount of iodine into a dry reaction bottle, adding dry THF under the protection of argon, slowly dropwise adding a THF solution containing p-dibromobenzene, reacting at 50 ℃, and then adding phosphorus trichloride for continuous reaction; followed by slow addition of H2O2Stirring, pouring the reaction mixture into water, extracting with dichloromethane, washing with water, drying with anhydrous sodium sulfate, filtering, concentrating, and separating with silica gel column to obtain tris (4-bromophenyl) oxyphosphorus;
(2) taking the tri (4-bromophenyl) oxyphosphorus, diphenylamine, t-BuONa and Pd2(dba)3Adding dry toluene and (t-Bu) into the raw materials under the protection of argon3P n-hexane solution reacts at 100 ℃, then the reaction mixture is poured into water and extracted by dichloromethane, and then the arylamine compound shown in the formula (I) is obtained after drying, filtering, concentrating and silica gel column separation by anhydrous sodium sulfate;
or,
(2') taking the tri (4-bromophenyl) oxyphosphorus, N-phenylnaphthylamine, t-BuONa and Pd2(dba)3Adding dry toluene and (t-Bu) into the raw materials under the protection of argon3And (3) reacting the N-hexane solution at 100 ℃, pouring the reaction mixture into water, extracting with dichloromethane, drying with anhydrous sodium sulfate, filtering, concentrating, and separating with a silica gel column to obtain the arylamine compound shown in the formula (II).
In the step (2), the method also comprises the step of reducing the reaction temperature to 60-70 ℃ for reaction after the reaction is carried out for 2-3 h.
In the step (2'), the reaction is carried out by reducing the reaction temperature to 60-70 ℃ after the reaction is carried out for 2-3 h.
The invention also discloses application of the methanol gasoline additive in preparing methanol fuel.
The invention also discloses a methanol fuel, which comprises methanol gasoline and the methanol gasoline additive.
The methanol fuel comprises the following components in parts by weight:
0.5-2 parts of methanol gasoline additive;
methanol gasoline 100.
The methanol gasoline is M15-M30 methanol gasoline.
The invention also discloses a method for preparing the methanol fuel, which comprises the step of adding the methanol gasoline additive into the methanol gasoline and uniformly mixing.
The arylamine compound can be used as a methanol gasoline additive, and the arylamine compound and the methanol gasoline sold in the market are mixed according to the weight ratio of 0.5-2: 100 parts by weight of the methanol gasoline are mixed, so that the performance of the M15-M30 methanol gasoline can be effectively improved, the methanol gasoline can be kept stable at a low temperature of-20 to-30 ℃ without phase separation, meanwhile, the Reid method saturated vapor pressure of the methanol gasoline is lower than 72kPa, the national standard is met, and the dynamic property of an engine is not influenced.
In the method for preparing the arylamine compound, the reaction temperature is adjusted in the reaction process, so that the product yield of the reaction is further improved, and the preparation of a target product is facilitated.
Detailed Description
Example 1
This example prepares an arylamine compound of formula (I) according to the following scheme and procedure:
(1) 100mmol (2.4g) of magnesium and a small amount of iodine are added into a dry reaction flask, 10mL of dry THF is added under the protection of argon, 100mL of THF solution containing 100mmol (23.6g) of p-dibromobenzene is slowly dropped into the reaction flask, the mixture is reacted at 50 ℃ for 4 hours, then 30mmol (4.12g) of phosphorus trichloride is added, and the reaction is continued for 24 hours. Then slowly add 10mLH2O2Stirring for 2 hours, pouring the reaction mixture into water, extracting with dichloromethane, washing with water three times, drying over anhydrous sodium sulfate, filtering, concentrating, separating with silica gel column to obtain 8.3g of tris (4-bromophenyl) oxyphosphorus, calculated yield 56.7%. By characterization, 1HNMR (400MHz, CDCl3) [ ppm]: δ 7.62(dd, J ═ 2.0, 8.4Hz, 6H), 7.50(d, J ═ 8.4Hz, 3H), 7.48(d, J ═ 8.4Hz, 3H), confirming that the product is tris (4-bromophenyl) oxyphosphorus, correct structure;
(2) a dry reaction flask was charged with 8mmol (4.12g) of tris (4-bromophenyl) oxyphosphorus, 36mmol (6.09g) of diphenylamine, 36mmol (3.44g) of t-BuONa and 0.18mmol (162mg) of Pd2(dba)3, 30mL of dry toluene and 0.35mmol (dissolved in 14.4mL of 1% n-hexane solution) (t-Bu)3P were added under argon atmosphere, and the reaction mixture was reacted at 100 ℃ for 12 hours, then poured into water, extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, concentrated, and separated by a silica gel column to obtain 5.02g of the arylamine compound represented by formula (I), the yield was calculated to be 80.4%. By characterization and analysis, 1HNMR (400MHz, DMSO) [ ppm ]: δ 7.44(d, J ═ 8.4Hz, 3H), 7.42(d, J ═ 8.8Hz, 3H), 7.33(t, J ═ 8.0Hz, 12H), 7.13(t, J ═ 7.6Hz, 6H), 7.10(d, J ═ 7.6Hz, 12H), 6.92(d, J ═ 7.2Hz, 6H). 31PNMR [ ppm ]: δ 24.18, confirming that the product is an arylamine compound having the structure shown in formula (I).
Example 2
The procedure and the process for the preparation of arylamine compounds of formula (i) in this example are the same as in example 1 except that in step (2), the reaction temperature is lowered to 80 ℃ after the addition of the starting materials for 2 hours, and the reaction is carried out for 10 hours. The yield of the arylamine compound having the structure shown in the formula (I) was determined and calculated to be 89.6%.
Example 3
The procedure and the process for the preparation of the arylamine compound of the formula (I) in this example are the same as those of example 1 except that in the step (2), the reaction temperature is lowered to 70 ℃ after the raw materials are added for reaction for 3 hours, and the reaction is further carried out for 9 hours. The yield of the arylamine compound having the structure shown in the formula (I) was detected and calculated to be 90.1%.
Comparative example 1
This comparative example shows the same route and preparation method of the arylamine compound represented by the formula (I) as in example 1, except that in the step (2), the reaction was carried out for 12 hours while controlling the reaction temperature to 80 ℃. The yield of the arylamine compound having the structure represented by the formula (I) was found to be 77.9%.
Example 4
This example prepares an arylamine compound of formula (II) according to the following scheme and procedure:
(1) 100mmol (2.4g) of magnesium and a small amount of iodine are added into a dry reaction flask, 10mL of dry THF is added under the protection of argon, 100mL of THF solution containing 100mmol (23.6g) of p-dibromobenzene is slowly dropped into the reaction flask, the mixture is reacted at 50 ℃ for 4 hours, then 30mmol (4.12g) of phosphorus trichloride is added, and the reaction is continued for 24 hours. Then slowly add 10mLH2O2Stirring for 2 hours, pouring the reaction mixture into water, extracting with dichloromethane, washing three times with water, drying over anhydrous sodium sulfate, filtering, concentrating, separating with silica gel column to obtain 8.3g of tris (4-bromophenyl) oxyphosphorus, calculated yield 56.7%. By characterization, 1HNMR (400MHz, CDCl3) [ ppm]: δ 7.62(dd, J ═ 2.0, 8.4Hz, 6H), 7.50(d, J ═ 8.4Hz, 3H), 7.48(d, J ═ 8.4Hz, 3H), confirming that the product is tris (4-bromophenyl) oxyphosphorus, correct structure;
(2') A dry reaction flask was charged with 8mmol (4.12g) of tris (4-bromophenyl) oxyphosphorus prepared above, 36mmol (7.89g) of N-phenylnaphthylamine, 36mmol (3.44g) of t-BuONa and 0.18mmol (162mg) of Pd2(dba)3, and under the protection of argon, 30mL of dry toluene and 0.35mmol (dissolved in 14.4mL of 1% N-hexane solution) (t-Bu)3P were added, and the reaction mixture was reacted at 100 ℃ for 12 hours, and then poured into water, extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, concentrated, and separated on a silica gel column to obtain 5.84g of an arylamine compound represented by formula (II) with a calculated yield of 78.6%. By characterization and analysis, 1HNMR (400MHz, DMSO) [ ppm ]: δ 7.97(d, J ═ 8.0Hz, 3H), 7.90(d, J ═ 8.0Hz, 3H), 7.78(d, J ═ 8.4Hz, 3H), 7.53(t, J ═ 8.0Hz, 3H), 7.47(t, J ═ 8.0Hz, 3H), 7.35-7.39(m, 6H), 7.29(d, J ═ 8.8Hz, 3H), 7.26(t, J ═ 8.8Hz, 6H), 7.23(d, J ═ 7.6Hz, 3H), 7.09(d, J ═ 8.4Hz, 6H), 7.02(t, J ═ 7.2Hz, 3H), 6.73(d, J ═ 8.0Hz, 6H). 31PNMR [ ppm ]: delta 24.09, confirming that the product is the arylamine compound with the structure shown in the formula (II).
Example 5
This example is similar to example 4 in the way and method for preparing the arylamine compound represented by the formula (II), except that in the step (2'), after the reaction is carried out for 2 hours by adding the raw materials, the reaction temperature is reduced to 80 ℃ and then the reaction is carried out for 10 hours. The yield of the arylamine compound having the structure represented by the formula (II) was found to be 88.3%.
Example 3
This example is similar to example 4 in the way and method for preparing the arylamine compound represented by the formula (II), except that in the step (2'), after the reaction is carried out for 3 hours by adding the raw materials, the reaction temperature is reduced to 70 ℃ and then the reaction is carried out for 9 hours. The yield of the arylamine compound having the structure represented by the formula (II) was found to be 89.0%.
Comparative example 2
This comparative example was the same as example 4 in the route and preparation method for the arylamine compound represented by the formula (II), except that in the step (2'), the reaction was carried out for 12 hours while controlling the reaction temperature to 80 ℃. The yield of the arylamine compound having the structure represented by the formula (II) was found to be 76.2% by detection and calculation.
Application example 1
0.5kg of arylamine compound with the structure shown in the formula (I) is added into 100kg of commercial M15 methanol gasoline and mixed evenly to prepare M15 denatured methanol fuel.
Application example 2
Taking 2kg of arylamine compound with the structure shown in the formula (II), adding the arylamine compound into 100kg of commercial M15 methanol gasoline, and uniformly mixing to obtain M15 modified methanol fuel.
Application example 3
0.25kg of arylamine compound with the structure shown in the formula (I) and 0.25kg of arylamine compound with the structure shown in the formula (II) are respectively added into 100kg of commercial M15 methanol gasoline and mixed evenly to prepare M15 modified methanol fuel.
The modified methanol fuel of M15 prepared above was measured for its national standard value and gasoline, and the main technical indicators such as saturated vapor pressure, distillation characteristics, low temperature phase separation resistance, water resistance, octane number, etc. were measured using the commercial M15 methanol gasoline used in application examples 1-3 as a control, and are reported in Table 1 below.
TABLE 1 comparison of M15 methanol gasoline of the present invention with standard value and main technical index of the existing M15 methanol gasoline
Therefore, the methanol gasoline additive disclosed by the invention can effectively improve the performance of M15 methanol gasoline, especially the high-temperature air resistance performance and the low-temperature stability.
Application example 4
Taking 2kg of arylamine compound with the structure shown in the formula (I), adding the arylamine compound into 100kg of commercial M20 methanol gasoline, and uniformly mixing to obtain M20 denatured methanol fuel.
Application example 5
0.5kg of arylamine compound with the structure shown in the formula (II) is added into 100kg of commercial M20 methanol gasoline and mixed evenly to prepare M20 denatured methanol fuel.
Application example 6
1kg of arylamine compound with the structure shown in the formula (I) and 1kg of arylamine compound with the structure shown in the formula (II) are respectively added into 100kg of commercial M20 methanol gasoline and mixed evenly to prepare M20 denatured methanol fuel.
The modified methanol fuel of M20 prepared as described above was measured for its national standard value as well as for its main technical indicators such as saturated vapor pressure, distillation characteristics, low temperature phase separation resistance, water resistance, octane number, etc., by using the commercial M20 methanol gasoline used in application examples 4-6 as a reference, and is reported in Table 2 below.
TABLE 2 comparison of the M20 methanol gasoline of the present invention with standard value and the main technical index of the existing M20 methanol gasoline
Therefore, the methanol gasoline additive disclosed by the invention can effectively improve the performance of M20 methanol gasoline, especially the high-temperature air resistance performance and the low-temperature stability.
Application example 7
1.2kg of arylamine compound with the structure shown in the formula (I) is added into 100kg of commercial M25 methanol gasoline and mixed evenly to prepare M25 denatured methanol fuel.
Application example 8
1.2kg of arylamine compound with the structure shown in the formula (II) is added into 100kg of commercial M25 methanol gasoline and mixed evenly to prepare the denatured methanol fuel.
Application example 9
0.6kg of arylamine compound with the structure shown in the formula (I) and 0.6kg of arylamine compound with the structure shown in the formula (II) are respectively added into 100kg of commercial M25 methanol gasoline and mixed evenly to prepare M25 modified methanol fuel.
The modified methanol fuel M25 prepared above was measured for its national standard value as well as for its main technical indicators such as saturated vapor pressure, distillation characteristics, low temperature phase separation resistance, water resistance, octane number, etc., by using commercially available M25 methanol gasoline used in application examples 7-9 as a reference, and reported in Table 3 below.
TABLE 3 comparison of the M25 methanol gasoline of the present invention with standard value and the main technical index of the existing M25 methanol gasoline
Therefore, the methanol gasoline additive disclosed by the invention can effectively improve the performance of M25 methanol gasoline, especially the high-temperature air resistance performance and the low-temperature stability.
The methanol gasoline additive has a good performance improvement effect on M30 methanol gasoline.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. Use of an arylamine compound for the preparation of methanol fuels, characterized in that said arylamine compound is selected from the structures represented by the following formulae (i) and/or (ii):
2. the use according to claim 1, wherein the mass ratio of the arylamine compound represented by the formula (i) to the arylamine compound represented by the formula (ii) is 1: 1.
3. use according to claim 1 or 2, characterized in that the arylamine compound is prepared according to the following steps:
(1) adding magnesium and a small amount of iodine into a dry reaction bottle, adding dry THF under the protection of argon, slowly dropwise adding a THF solution containing p-dibromobenzene, reacting at 50 ℃, and then adding phosphorus trichloride for continuous reaction; followed by slow addition of H2O2Stirring, pouring the reaction mixture into water, extracting with dichloromethane, washing with water, drying with anhydrous sodium sulfate, filtering, concentrating, and separating with silica gel column to obtain tris (4-bromophenyl) oxyphosphorus;
(2) taking the tri (4-bromophenyl) oxyphosphorus, diphenylamine, t-BuONa and Pd2(dba)3Adding dry toluene and (t-Bu) into the raw materials under the protection of argon3P n-hexane solution reacts at 100 ℃, then the reaction mixture is poured into water and extracted by dichloromethane, and then the arylamine compound shown in the formula (I) is obtained after drying, filtering, concentrating and silica gel column separation by anhydrous sodium sulfate;
or,
(2') taking the tri (4-bromophenyl) oxyphosphorus, N-phenylnaphthylamine, t-BuONa and Pd2(dba)3Adding dry toluene and (t-Bu) into the raw materials under the protection of argon3And (3) reacting the N-hexane solution at 100 ℃, pouring the reaction mixture into water, extracting with dichloromethane, drying with anhydrous sodium sulfate, filtering, concentrating, and separating with a silica gel column to obtain the arylamine compound shown in the formula (II).
4. The use according to claim 3, wherein the step (2) further comprises the step of reducing the reaction temperature to 60-70 ℃ for carrying out the reaction after the reaction is carried out for 2-3 hours.
5. The use according to claim 4, wherein the step (2') further comprises the step of reducing the reaction temperature to 60-70 ℃ for carrying out the reaction after the reaction is carried out for 2-3 hours.
6. A methanol fuel, which is characterized by comprising methanol gasoline and arylamine compounds with the structures shown as the following formulas (I) and/or (II):
7. the methanol fuel of claim 6, comprising the following components in parts by weight:
0.5-2 parts of the arylamine compound;
methanol gasoline 100.
8. The methanol fuel of claim 6 or 7, characterized in that the methanol gasoline is M15-M30 methanol gasoline.
9. A method for producing the methanol fuel according to any one of claims 6 to 8, characterized by comprising a step of adding the aromatic amine compound to the methanol gasoline to mix them uniformly.
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| CN101747372A (en) * | 2010-01-21 | 2010-06-23 | 中国科学院长春应用化学研究所 | Arylamine compound, organic electroluminescent device containing arylamine compound and preparation method thereof |
| CN102031164A (en) * | 2010-12-31 | 2011-04-27 | 北京华阳禾生能源技术发展有限公司 | Carbinol gasoline additive and preparation method and application thereof |
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| CN102031164A (en) * | 2010-12-31 | 2011-04-27 | 北京华阳禾生能源技术发展有限公司 | Carbinol gasoline additive and preparation method and application thereof |
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