CN108033979A - A kind of methanol gasoline additive and preparation method and application - Google Patents
A kind of methanol gasoline additive and preparation method and application Download PDFInfo
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- CN108033979A CN108033979A CN201711316044.5A CN201711316044A CN108033979A CN 108033979 A CN108033979 A CN 108033979A CN 201711316044 A CN201711316044 A CN 201711316044A CN 108033979 A CN108033979 A CN 108033979A
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- methanol
- methanol gasoline
- amine compound
- aromatic amine
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 330
- 239000003254 gasoline additive Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 14
- -1 Aromatic amine compound Chemical class 0.000 claims abstract description 44
- 239000003502 gasoline Substances 0.000 claims abstract description 38
- 239000000446 fuel Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 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 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 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
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 239000000741 silica gel Substances 0.000 claims description 10
- 229910002027 silica gel Inorganic materials 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 239000011541 reaction mixture Substances 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
- 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
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 abstract description 12
- 238000002156 mixing Methods 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 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
- 238000004458 analytical method Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 230000001846 repelling effect Effects 0.000 description 3
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 150000004982 aromatic amines Chemical class 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
- 238000001514 detection method 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 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
- 239000000463 material Substances 0.000 description 1
- 230000008450 motivation Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003613 toluenes Chemical class 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
Landscapes
- 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 field, and in particular to a kind of methanol gasoline additive, and further disclose its preparation method and be used to prepare the application of M15 M30 methanol gasolines.Aromatic amine compound of the present invention, can use as methanol gasoline additive, by it with commercial methanol gasoline according to 0.5 2：After 100 weight part ratio mixing, it can effectively improve the performance of M15 M30 methanol gasolines, methanol gasoline is set to keep stablizing under 20~30 DEG C of cryogenic conditions, it is not separated, the reid method saturated vapor pressure of methanol gasoline is less than 72kPa at the same time, meet national standard, while engine power performance is unaffected.
Description
Technical field
The invention belongs to methanol gasoline clean fuel technical field, and in particular to a kind of methanol gasoline additive, goes forward side by side one
The open its preparation method of step and the application for being used to prepare M15-M30 methanol gasolines.
Background technology
With developing rapidly for world economy, car ownership just rises year by year, and the demand of vehicle fuel is constantly increasing
Add, the environmental problem thus brought also getting worse.As world energy sources reserves are increasingly short, the shape of petroleum resources increasingly depleted
Will definitely be more severe.The import dependency degree of Chinese oil at present alreadys exceed 50%, and the energy is in one kind and is on the rack total state.
The energy and environmental problem restrict the fast development of China's economy.Therefore, seek new cleaning alternative energy source become promote me
The key subject of state's economic development.
Alcohols is the fuel that internal combustion engine most can be alternative in addition to oil, natural gas.Use the most important advantage of Aalcohols fuel
The discharge more much lower than HC fuel can be reached by also residing in them, be of great benefit to reducing atmosphere pollution；With traditional hair
Motivation technology has inheritance, and during especially with gasoline -ol class fuel combination, engine structure can not have to change；Separately
The octane number of outer Aalcohols fuel is high, when making spark-ignition engine fuel, can be used for compressing higher engine, raising is started
The thermal efficiency of machine, is the most promising substitute fuel of internal combustion engine.Wherein methanol has source as a kind of good alternative energy source
The advantages such as extensively, oxygen content is high, octane number is high, environmental pollution is small, are preferable motor petrol substitutes.It is and China's richness coal, few
The Energy Situation of oil, also provides the wide market space, thus methanol in recent years as energy products to implement ammonia from coal
Gasoline gets more and more people's extensive concerning as vehicle fuel.
Methanol gasoline refers in national standard motor petrol, in volume or weight than adding a certain proportion of denatured methyl alcohol, warp
A kind of clean fuel for vehicle that stringent scientific technology is formulated.The methanol gasoline applied at present is mainly methanol content in 10-
30% low ratio mixes burning methanol gasoline.Bench test and road performance test show：Use M15 methanol gasolines, tail gas Routine purges
CO and HC reduces by 23% and 28% or so than national standard gasoline respectively.Low ratio methanol gasoline is also tight there are some in extension process
The problem of weight -- saturated vapor pressure is high and low-temperature startup is poor.Since methanol is then the oxygen-containing organic compound of polarity, work as methanol
Intermolecular to be mainly combined with hydrogen bond in the presence of pure material, its saturated vapour pressure is relatively low (about 14kPa at 20 DEG C).But when
Methanol by a certain percentage with gasoline mixed preparing methanol gasoline when, since gravitation is weak between petrol molecule, destroy between methanol molecules
Association, thus the developability of methanol will be bigger than pure methanol more in solution, so as to form obvious vapour pressure overgauge, i.e.,
Saturated vapor pressure raises.In addition, methanol can form low-boiling azeotrope with some components in gasoline, saturated vapor pressure can compare base
Plinth gasoline is high.Both factors cause the saturated vapor pressure ratio high 10-30kpa of national standard gasoline of methanol gasoline, it means that
The area of summer high temperature sweltering heat uses the methanol (M15-M25) of the low ratio of this higher saturated vapor pressure, it is possible to produces gas
Resistance, fuel feeding be not smooth, seriously affects engine work, this problem seriously restricts low ratio methanol gasoline national special
It is the popularization of southern area；Further, since under low-temperature condition, the two-phase of methanol gasoline is easy to separate so that low ratio first
Alcohol gasoline can not start substantially at -25 DEG C, seriously affect automobile use so that application of the methanol gasoline in northern area
It is extremely limited.
The content of the invention
For this reason, the technical problems to be solved by the invention are to provide a kind of methanol gasoline additive, to solve existing skill
In art under the saturated vapor pressure height and cold-starting of methanol gasoline the problem of difference.
In order to solve the above technical problems, a kind of methanol gasoline additive of the present invention, it is characterised in that including formula
(I) and/or the aromatic amine compound shown in (II)：
The mass ratio of the aromatic amine compound shown in aromatic amine compound and formula (II) shown in the formula (I) is 1：1.
The invention also discloses a kind of method for preparing the methanol gasoline additive, include the following steps：
(1) magnesium and a small amount of iodine are added in dry reaction bulb, argon gas protection is lower to add dry THF, and is slowly added dropwise
THF solution containing paradibromobenzene, is reacted under the conditions of 50 DEG C, and then adding phosphorus trichloride, the reaction was continued；Then slowly add
Enter H2O2Stir and be simultaneously poured into water reaction mixture, extract and washed with dichloromethane, then with anhydrous sodium sulfate it is dry, filter,
Three (4- bromophenyls) oxygen phosphorus are obtained after concentration, silica gel post separation, it is spare；
(2) above-mentioned three (4- bromophenyls) oxygen phosphorus and diphenylamines, t-BuONa and Pd are taken2(dba)3For raw material, protected in argon gas
Under, add dry toluene and containing (t-Bu)3P hexane solutions, are reacted under the conditions of 100 DEG C, are then fallen reaction mixture
Enter in water, and extracted with dichloromethane, then to obtain formula (I) institute after anhydrous sodium sulfate drying, filtering, concentration, silica gel post separation
The aromatic amine compound shown；
Alternatively,
(2 ') take above-mentioned three (4- bromophenyls) oxygen phosphorus and N- nonoxes, t-BuONa and Pd2(dba)3For raw material, in argon
Under gas shielded, dry toluene is added and containing (t-Bu)3P hexane solutions, are reacted under the conditions of 100 DEG C, then will reaction it is mixed
Compound is poured into water, and is extracted with dichloromethane, then to obtain formula after anhydrous sodium sulfate drying, filtering, concentration, silica gel post separation
(II) aromatic amine compound shown in.
In the step (2), after being additionally included in reaction progress 2-3h, reduce what reaction temperature was reacted to 60-70 DEG C
Step.
In the step (2 '), after being additionally included in reaction progress 2-3h, reduce what reaction temperature was reacted to 60-70 DEG C
Step.
The invention also discloses the purposes that the methanol gasoline additive is used to prepare methanol fuel.
The invention also discloses a kind of methanol fuel, including methanol gasoline and the methanol gasoline additive.
The methanol fuel, includes the component of following parts by weight：
Methanol gasoline additive 0.5-2；
Methanol gasoline 100.
The methanol gasoline is M15-M30 methanol gasolines.
Add the invention also discloses a kind of method for preparing the methanol fuel, including by the methanol gasoline additive
The step of being mixed is added in the methanol gasoline.
Aromatic amine compound of the present invention, can use as methanol gasoline additive, by itself and commercial methanol gasoline
According to 0.5-2：After 100 weight part ratio mixing, the performance of M15-M30 methanol gasolines is can effectively improve, makes methanol gasoline -20
Keep stablizing under~-30 DEG C of cryogenic conditions, be not separated, while the reid method saturated vapor pressure of methanol gasoline is less than
72kPa, meets national standard, while engine power performance is unaffected.
The present invention is prepared in the method for the aromatic amine compound, by way of adjusting reaction temperature during the reaction,
The product yield of reaction is further increased, is more advantageous to the preparation of target product.
Embodiment
Embodiment 1
Aromatic amine compound of the present embodiment shown according to following route and step formula (I)：
(1) 100mmol (2.4g) magnesium and a small amount of iodine are added in dry reaction bulb, argon gas protection is lower to add 10mL dryings
THF, be slowly added dropwise the THF solution that 100mL contains 100mmol (23.6g) paradibromobenzene, when reaction 4 is small under the conditions of 50 DEG C, so
Afterwards add 30mmol (4.12g) phosphorus trichloride, the reaction was continued 24 it is small when.It is then slowly added into 10mLH2O2Stir 2 it is small when, will be anti-
Mixture is answered to be poured into water, dichloromethane extraction, three times, anhydrous sodium sulfate drying, filtering, concentrate, after silica gel post separation for washing
8.3g tri- (4- bromophenyls) oxygen phosphorus is obtained, is computed yield as 56.7%.Through phenetic analysis, 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), it was demonstrated that
The product is three (4- bromophenyls) oxygen phosphorus, and structure is correct；
(2) 8mmol (4.12g) three (4- bromophenyls) oxygen phosphorus, 36mmol (6.09g) hexichol are added in dry reaction bulb
Amine, 36mmol (3.44g) t-BuONa and 0.18mmol (162mg) Pd2 (dba) 3, under argon gas protection, add 30mL drying first
Benzene and 0.35mmol (being dissolved in 14.4mL1% hexane solutions) (t-Bu) 3P, then will be anti-when reaction 12 is small under the conditions of 100 DEG C
Answer mixture to be poured into water, extracted with dichloromethane, then to be obtained after anhydrous sodium sulfate drying, filtering, concentration, silica gel post separation
Aromatic amine compound shown in 5.02g formulas (I), calculates its yield as 80.4%.Through phenetic 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, it was demonstrated that
The product is the aromatic amine compound with structure shown in formula (I).
Embodiment 2
The route and preparation method of aromatic amine compound shown in the present embodiment formula (I) only exist with embodiment 1, its difference
In in the step (2), adding after raw material carries out reaction 2h, reaction temperature be cooled to 80 DEG C, then carry out reaction 10h.Through
Detection and calculating, the yield with the aromatic amine compound of structure shown in formula (I) are 89.6%.
Embodiment 3
The route and preparation method of aromatic amine compound shown in the present embodiment formula (I) only exist with embodiment 1, its difference
In in the step (2), adding after raw material carries out reaction 3h, reaction temperature be cooled to 70 DEG C, then carry out reaction 9h.Through
Detection and calculating, the yield with the aromatic amine compound of structure shown in formula (I) are 90.1%.
Comparative example 1
The route and preparation method of aromatic amine compound shown in this comparative example formula (I) only exist with embodiment 1, its difference
In in the step (2), 80 DEG C of controlling reaction temperature carries out reaction 12h.After testing and calculate, there is structure shown in formula (I)
The yield of aromatic amine compound is 77.9%.
Embodiment 4
Aromatic amine compound of the present embodiment shown according to following route and step formula (II)：
(1) 100mmol (2.4g) magnesium and a small amount of iodine are added in dry reaction bulb, argon gas protection is lower to add 10mL dryings
THF, be slowly added dropwise the THF solution that 100mL contains 100mmol (23.6g) paradibromobenzene, when reaction 4 is small under the conditions of 50 DEG C, so
Afterwards add 30mmol (4.12g) phosphorus trichloride, the reaction was continued 24 it is small when.It is then slowly added into 10mLH2O2Stir 2 it is small when, will be anti-
Mixture is answered to be poured into water, dichloromethane extraction, three times, anhydrous sodium sulfate drying, filtering, concentrate, after silica gel post separation for washing
8.3g tri- (4- bromophenyls) oxygen phosphorus is obtained, it is 56.7% to calculate yield.Through phenetic analysis, 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), it was demonstrated that
The product is three (4- bromophenyls) oxygen phosphorus, and structure is correct；
(2 ') add 8mmol obtained above (4.12g) three (4- bromophenyls) oxygen phosphorus, 36mmol in dry reaction bulb
(7.89g) N- nonoxes, 36mmol (3.44g) t-BuONa and 0.18mmol (162mg) Pd2 (dba) 3, are protected in argon gas
Under, add 30mL dry toluenes and 0.35mmol (being dissolved in 14.4mL1% hexane solutions) (t-Bu) 3P, it is anti-under the conditions of 100 DEG C
Answer 12 it is small when, then reaction mixture is poured into water, dichloromethane extraction, anhydrous sodium sulfate is dry, filtering, concentration, silica gel
The aromatic amine compound shown in 5.84g formulas (II) is obtained after post separation, it is 78.6% to calculate yield.Through phenetic 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]：δ 24.09, it was demonstrated that the product is to have shown in formula (II)
The aromatic amine compound of structure.
Embodiment 5
With embodiment 4, it is distinguished only the route and preparation method of aromatic amine compound shown in the present embodiment formula (II)
It is, in the step (2 '), after adding raw material and carrying out reaction 2h, reaction temperature is cooled to 80 DEG C, then reacted
10h.After testing and calculate, the yield with the aromatic amine compound of structure shown in formula (II) is 88.3%.
Embodiment 3
With embodiment 4, it is distinguished only the route and preparation method of aromatic amine compound shown in the present embodiment formula (II)
It is, in the step (2 '), after adding raw material and carrying out reaction 3h, reaction temperature is cooled to 70 DEG C, then carry out reaction 9h.
After testing and calculate, the yield with the aromatic amine compound of structure shown in formula (II) is 89.0%.
Comparative example 2
With embodiment 4, it is distinguished only the route and preparation method of aromatic amine compound shown in this comparative example formula (II)
It is, in the step (2 '), 80 DEG C of controlling reaction temperature carries out reaction 12h.After testing and calculate, there is knot shown in formula (II)
The yield of the aromatic amine compound of structure is 76.2%.
Application examples 1
The aromatic amine compound 0.5kg of structure shown in formula (I) is taken, adds into the commercially available M15 methanol gasolines of 100kg and mixes, is made
Obtain M15 denatured methyl alcohol fuel.
Application examples 2
The aromatic amine compound 2kg of structure shown in modus ponens (II), adds into the commercially available M15 methanol gasolines of 100kg and mixes, and is made
M15 denatured methyl alcohol fuel.
Application examples 3
The aromatic amine compound 0.25kg of structure shown in formula (I), the aromatic amine compound 0.25kg of structure shown in formula (II) are taken, point
Do not add into the commercially available M15 methanol gasolines of 100kg and mix, M15 denatured methyl alcohol fuel is made.
Measure the M15 denatured methyl alcohols fuel and gasoline national normal value of above-mentioned preparation, and the city to be used in application examples 1-3
M15 methanol gasolines are sold as control, measure it in saturated vapor pressure, distillation characteristic, low-temperature resistance phase separation performance, water repelling property, pungent
The key technical indexes such as alkane value, are recorded in table 1 below.
The M15 methanol gasolines of the present invention of table 1 are contrasted with standard value and the key technical indexes of existing M15 methanol gasolines
As it can be seen that methanol gasoline additive of the present invention can be effectively improved the performance of M15 methanol gasolines, especially high temperature
Vapour lock performance and low-temperature stability.
Application examples 4
The aromatic amine compound 2kg of structure shown in formula (I) is taken, adds into the commercially available M20 methanol gasolines of 100kg and mixes, is made
M20 denatured methyl alcohol fuel.
Application examples 5
The aromatic amine compound 0.5kg of structure shown in modus ponens (II), adds into the commercially available M20 methanol gasolines of 100kg and mixes, system
Obtain M20 denatured methyl alcohol fuel.
Application examples 6
The aromatic amine compound 1kg of structure shown in formula (I), the aromatic amine compound 1kg of structure shown in formula (II) are taken, is separately added into
Mixed into the commercially available M20 methanol gasolines of 100kg, M20 denatured methyl alcohol fuel is made.
Measure the M20 denatured methyl alcohols fuel and gasoline national normal value of above-mentioned preparation, and the city to be used in application examples 4-6
M20 methanol gasolines are sold as control, measure it in saturated vapor pressure, distillation characteristic, low-temperature resistance phase separation performance, water repelling property, pungent
The key technical indexes such as alkane value, are recorded in table 2 below.
The M20 methanol gasolines of the present invention of table 2 are contrasted with standard value and the key technical indexes of existing M20 methanol gasolines
As it can be seen that methanol gasoline additive of the present invention can be effectively improved the performance of M20 methanol gasolines, especially high temperature
Vapour lock performance and low-temperature stability.
Application examples 7
The aromatic amine compound 1.2kg of structure shown in formula (I) is taken, adds into the commercially available M25 methanol gasolines of 100kg and mixes, is made
Obtain M25 denatured methyl alcohol fuel.
Application examples 8
The aromatic amine compound 1.2kg of structure shown in modus ponens (II), adds into the commercially available M25 methanol gasolines of 100kg and mixes, system
Obtain denatured methyl alcohol fuel.
Application examples 9
The aromatic amine compound 0.6kg of structure shown in formula (I), the aromatic amine compound 0.6kg of structure shown in formula (II) are taken, respectively
Addition is mixed into the commercially available M25 methanol gasolines of 100kg, and M25 denatured methyl alcohol fuel is made.
Measure the M25 denatured methyl alcohols fuel and gasoline national normal value of above-mentioned preparation, and the city to be used in application examples 7-9
M25 methanol gasolines are sold as control, measure it in saturated vapor pressure, distillation characteristic, low-temperature resistance phase separation performance, water repelling property, pungent
The key technical indexes such as alkane value, are recorded in table 3 below.
The M25 methanol gasolines of the present invention of table 3 are contrasted with standard value and the key technical indexes of existing M25 methanol gasolines
As it can be seen that methanol gasoline additive of the present invention can be effectively improved the performance of M25 methanol gasolines, especially high temperature
Vapour lock performance and low-temperature stability.
After testing, methanol gasoline additive of the present invention equally has preferable performance improvement for M30 methanol gasolines
Effect.
Obviously, the above embodiments are merely examples for clarifying the description, and the restriction not to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (10)
1. a kind of methanol gasoline additive, it is characterised in that including the aromatic amine compound shown in formula (I) and/or (II)：
2. methanol gasoline additive according to claim 1, it is characterised in that the aromatic amine compound shown in the formula (I)
Mass ratio with the aromatic amine compound shown in formula (II) is 1：1.
A kind of 3. method for preparing the methanol gasoline additive of claim 1 or 2, it is characterised in that include the following steps：
(1) magnesium and a small amount of iodine are added in dry reaction bulb, argon gas protection is lower to add dry THF, and be slowly added dropwise containing
The THF solution of paradibromobenzene, is reacted under the conditions of 50 DEG C, and then adding phosphorus trichloride, the reaction was continued；It is then slowly added to H2O2
Stir and be simultaneously poured into water reaction mixture, extract and washed with dichloromethane, then with anhydrous sodium sulfate is dry, filtering, concentrate,
Three (4- bromophenyls) oxygen phosphorus are obtained after silica gel post separation, it is spare；
(2) above-mentioned three (4- bromophenyls) oxygen phosphorus and diphenylamines, t-BuONa and Pd are taken2(dba)3For raw material, under argon gas protection,
Add dry toluene and containing (t-Bu)3P hexane solutions, are reacted under the conditions of 100 DEG C, reaction mixture then are poured into water
In, and extracted with dichloromethane, then to be obtained after anhydrous sodium sulfate drying, filtering, concentration, silica gel post separation shown in formula (I)
Aromatic amine compound；
Alternatively,
(2 ') take above-mentioned three (4- bromophenyls) oxygen phosphorus and N- nonoxes, t-BuONa and Pd2(dba)3For raw material, protected in argon gas
Under shield, dry toluene is added and containing (t-Bu)3P hexane solutions, are reacted under the conditions of 100 DEG C, then by reaction mixture
It is poured into water, and is extracted with dichloromethane, then to obtain formula (II) after anhydrous sodium sulfate drying, filtering, concentration, silica gel post separation
Shown aromatic amine compound.
4. the method according to claim 3 for preparing the methanol gasoline additive, it is characterised in that the step (2)
In, be additionally included in reaction carry out 2-3h after, reduce reaction temperature to 60-70 DEG C reacted the step of.
5. the method for preparing the methanol gasoline additive according to claim 3 or 4, it is characterised in that the step
In (2 '), be additionally included in reaction carry out 2-3h after, reduce reaction temperature to 60-70 DEG C reacted the step of.
6. the methanol gasoline additive of claim 1 or 2 is used to prepare the purposes of methanol fuel.
A kind of 7. methanol fuel, it is characterised in that including methanol gasoline, and the methanol gasoline addition described in claim 1 or 2
Agent.
8. methanol fuel according to claim 7, it is characterised in that include the component of following parts by weight：
Methanol gasoline additive 0.5-2；
Methanol gasoline 100.
9. the methanol fuel according to claim 7 or 8, it is characterised in that the methanol gasoline is M15-M30 methanol vapors
Oil.
A kind of 10. method for preparing claim 7-9 any one of them methanol fuels, it is characterised in that including by the first
Ethanol gasoline additive is added into the step of being mixed in the methanol gasoline.
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| CN114957299A (en) * | 2022-02-24 | 2022-08-30 | 川北医学院 | Fluorescent probe for detecting apoptotic cells and preparation method thereof |
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