CN116041690A - Polyether amine gasoline detergent and synthetic method thereof - Google Patents
Polyether amine gasoline detergent and synthetic method thereof Download PDFInfo
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- CN116041690A CN116041690A CN202310160636.1A CN202310160636A CN116041690A CN 116041690 A CN116041690 A CN 116041690A CN 202310160636 A CN202310160636 A CN 202310160636A CN 116041690 A CN116041690 A CN 116041690A
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
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- 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
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- C10L1/192—Macromolecular compounds
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0244—Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
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- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/10—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation characterized by the catalyst used in the post-polymerisation functionalisation step
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- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Abstract
The invention discloses a polyether amine gasoline detergent and a synthesis method thereof, comprising the following steps: the polyisobutene and phenol are subjected to catalytic reaction in a nitrogen atmosphere to obtain polyisobutene phenol; polyisobutene phenol and epoxypropane or epoxybutane are catalyzed by alkali to obtain polyisobutene phenol polyether; performing continuous reaction on polyisobutene phenol polyether, liquid ammonia and hydrogen in a continuous reactor filled with a nickel catalyst to obtain polyisobutene phenol polyether primary amine; and (3) adding the polyisobutene phenol polyether primary amine and propylene glycol into a reaction kettle, and reacting in the presence of hydrogen and a catalyst to obtain a target product. When the product of the invention is used as a gasoline detergent, the product can efficiently clean carbon deposition of a fuel nozzle, carbon deposition of an air inlet valve and carbon deposition of a combustion chamber without being compounded with other compounding agents, can improve combustion characteristics, reduces pollution emission and has excellent comprehensive performance.
Description
Technical Field
The invention relates to a macromolecular organic amine compound, in particular to a polyisobutene phenol polyether amine gasoline detergent and a synthesis method thereof.
Background
During the running process of the automobile, a great amount of sediments are generated by an engine air inlet system (comprising a carburetor, an oil nozzle and an air inlet valve) and a combustion chamber, so that the normal injection, atomization, mixing and combustion of fuel are seriously affected. Meanwhile, harmful substances such as hydrocarbon, CO, NO and the like in the exhaust emission are rapidly increased, and serious damage is caused to the atmospheric environment.
Engine deposits mainly include Intake Valve Deposits (IVD), fuel injector deposits (PFID), and Combustion Chamber Deposits (CCD).
Liu Zhifeng et al, in the development of research on the structural composition and mechanism of action of a new-generation gasoline detergent, describe that the development of a gasoline detergent is closely related to the upgrading and updating of an engine, and in order to solve the problem of carbon deposition of a carburetor, chevron company 1954 first introduced a first-generation gasoline detergent, which represents a low-molecular (300-400) common amine surfactant. The 80 s electronic fuel injection system has been developed, and simultaneously injector sludge appears, and the company Lubrizol in U.S. firstly develops successfully and puts into production a second generation additive taking succinimide as a main agent, so that the fuel nozzle sediment is solved. The main active ingredient in the patent CN1133873A, CN1167136A, CN1227866A is polyisobutylene succinimide which is a second-generation detergent, and common polyisobutylene and mineral oil carrier liquid, and the type of gasoline detergent has good cleaning and cleaning effects on an oil nozzle and an air inlet valve of a gasoline engine, and can effectively inhibit and clean the formation of carbon deposit on the parts of the gasoline engine. However, this type of gasoline detergent brings the soot cleaned in the fuel intake system to the combustion chamber, and thus, the inclusion of this type of commercially available gasoline detergent causes a significant increase in the deposition of the combustion chamber and the demulsification performance of succinimide is poor.
The third generation gasoline detergent is called a pollution accumulation control additive, is mainly used for solving the problem of pollution accumulation of an air inlet valve, and is represented by polyisobutene amine due to higher air inlet valve temperature (the temperature of the automobile reaches 250-300 ℃ when the automobile runs at a high speed). The main agents such as polyisobutene amine can well solve the problems of deposits of a fuel nozzle and an air inlet valve, but because the main agents have higher thermal stability, incomplete combustion in a combustion chamber easily causes obvious increase of the deposits in the combustion chamber, and the patent CN101723836B, US5346965, US5508356, US5583168 and WO98/12284 propose a chlorination alkylation method for producing polyisobutene amine, belong to a third-generation detergent, easily produce carbon deposition in the combustion chamber, react with chlorine to generate chlorinated polyisobutene, regenerate polyisobutene amine, and have more wastes in production, and residual chlorine corrodes metal when the product is used, thereby bringing serious hidden trouble to an engine.
Because the C-O-C bond in the polyetheramine is easy to thermally crack, the fourth-generation gasoline detergent takes polyetheramine as a main agent, and can obviously reduce the sediments of a combustion chamber while effectively controlling the sediments of a fuel nozzle and an air inlet valve.
The prior gasoline detergent for vehicles has been developed to the fifth generation, mainly uses polyisobutenyl phenol Mannich adducts as main agents, can change the combustion characteristics of fuel oil on the basis of the performance of the first four generations, reduces the consumption of the fuel oil, and reduces the emission of pollutants such as particulate matters, hydrocarbon compounds and the like. The surface temperature of the intake valve is typically above 300 ℃ when the engine is operating normally, and the polyetheramine has been substantially completely decomposed at 300 ℃, so polyetheramine detergents are more suitable for light duty engines. In recent years, companies such as Texaco, BP and the like take high-activity polyisobutene as a main raw material, and the polyisobutenyl phenol Mannich adduct prepared by Mannich reaction not only can be used as an intermediate of a fuel additive, but also can be directly used as a fuel detergent, and has great advantages in the aspects of removing deposits in an internal combustion engine oil system, an oil nozzle and a spark plug and maintaining the thermal stability and oxidation resistance of fuel. However, the efficiency of removing the carbon deposit in the combustion chamber is weaker, and the carbon deposit can be effectively controlled by compounding the carbon deposit with detergents such as polyether amine, imide, alcohol amine and the like. Patent CN108084301a describes a method for manufacturing a mannich amine detergent, which uses methanesulfonic acid as a catalyst, the methanesulfonic acid has strong corrosion to metallic iron, copper, lead and the like, corrosion to equipment can be caused in production, and the detergent belongs to a fifth generation product, and has weak cleaning effect on carbon deposition in a combustion chamber; patent CN109134714B, CN110357990B, CN112410083a also belongs to the fifth generation of cleaning. The reaction of CN109134714B is essentially the combination of Mannich amine and succinimide, the cleaning effect of the Mannich amine and the succinimide on a combustion chamber is weak, and the cleaning effect of the Mannich amine and the succinimide on the combustion chamber is a certain inhibition effect on carbon deposition in the combustion chamber, and in CN110357990B, excessive phenol raw material is not removed from the system before the Mannich amination reaction, so that polyisobutene phenol and phenol can participate in the Mannich reaction at the same time, byproducts are increased, the yield of target products is reduced, and the product performance is affected.
Patent CN106281509B describes a polyisobutene aniline detergent, which has no C-O-C structure similar to that of polyetheramine, which is easy to thermally crack, and has poor effect of inhibiting and removing carbon deposition in the combustion chamber; patent CN110484314B describes a polyetheramine detergent in which a polyol is first propylene oxide and then reacted with an organic amine; however, the reaction of the polyol and the propylene oxide ring-opening polymerization reaction or the reaction of the polyether and the organic amine is carried out, and the selectivity of each group participating in the reaction is the same due to the multi-functional group, so that a large amount of byproducts are generated, the yield of the target product is low, the separation is difficult, and the product quality is affected.
Disclosure of Invention
Aiming at the defects that the existing gasoline detergent is incomplete in function and needs to be compounded when in use, the invention aims to provide the synthetic method of the polyisobutene phenol polyether amine gasoline detergent, which can efficiently clean carbon deposition of a fuel nozzle, carbon deposition of an air inlet valve and carbon deposition of a combustion chamber, improve combustion characteristics, reduce pollution emission, is excellent in comprehensive performance, does not need to be compounded with other detergents when in use, and is simple in production.
The polyisobutene phenol polyether amine is represented by the following structural formula:
wherein R is propyl or butyl, PIB is polyisobutene, and n is more than or equal to 4 and less than or equal to 7.
The invention comprises four steps of reactions, including the following steps:
(1) Synthesis of polyisobutene phenol
Dissolving HRPIB (high activity polyisobutene) with alpha-terminal double bond content of more than 80% in organic solvent, and using BF 3 Adding excessive phenol as a catalyst under the condition of nitrogen, stirring and reacting for 6-8 hours at the temperature of 40-60 ℃, then adding water for washing and separating liquid, and removing solvent from an organic phase to obtain polyisobutene phenol.
(2) Synthesis of polyisobutene phenol polyether
And (3) putting the polyisobutene phenol and the base catalyst into a reactor, heating to 110-130 ℃, continuously introducing a certain amount of epoxypropane or epoxybutane to react or a mixture of the epoxypropane and the epoxybutane in a certain proportion, preserving heat for 1-2 hours after the reaction is finished, cooling to below 80 ℃, and carrying out neutralization, dehydration and filtration treatment to obtain the polyisobutene phenol polyether.
(3) Primary amination reaction
The polyisobutene phenol polyether, liquid ammonia and hydrogen are subjected to continuous reaction in a continuous reactor filled with a nickel catalyst (CAT-1), the reaction pressure is 3-10 MPa, the reaction temperature is 120-180 ℃, and the polyisobutene phenol polyether primary amine is obtained by continuous discharging.
Since the starting material HRPIB (high-activity polyisobutylene) is HRPIB having an alpha-terminal double bond content of greater than 80%, about 15% of the double bonds (non-alpha-terminal double bonds) of HRPIB will not react with phenol, and thus the double bonds in the unreacted HRPIB are also saturated by catalytic hydrogenation during the primary amination stage.
Hydrogenation of beta-terminal double bond:
hydrogenation of T-terminal double bond:
(4) Secondary amination reaction
And (3) throwing the polyisobutene phenol polyether primary amine and propylene glycol into a reaction kettle, keeping the pressure of 1-3 MPa and the temperature of 100-130 ℃ in the presence of hydrogen and nickel metal complex (CAT-2), reacting for 4-10 h, filtering after the reaction is finished, and dehydrating in vacuum to obtain the target product.
The solvent in the step (1) is n-hexane, toluene or isopropanol, and the preferred solvent is n-hexane; the mass ratio of the raw materials to the solvent is 1:1 to 3, preferably 1:2, further, the solvent is finally recycled through distillation recovery;
the molar feed ratio of polyisobutene to phenol in step (1) is 1:1.5 to 3, and the reaction time is 6 to 8 hours. Polyisobutene and phenol are used as the raw materials in the first step, the reproduction toxicity of the polyisobutene and phenol is far less than that of micromolecular alkylphenol, and the polyisobutene and phenol meet the use requirements of health and environmental protection;
the chain extender used in step (2) is propylene oxide or butylene oxide. The propylene oxide or butylene oxide is used as the chain growth unit, so that the hydrophilicity of one end of the surfactant can be enhanced, hydrophilic sediment is removed, the dispersibility in oil products is enhanced, the content of oxygen atoms in the fuel oil is increased by the C-O-C structure of the chain growth unit, the fuel oil is combusted more fully, in addition, the C-O-C structure of the chain growth unit is lower in thermal stability, is decomposed more easily under the condition of high temperature of a combustion chamber, has double functions, and greatly reduces the generation of sediment in the combustion chamber; the molar quantity of the introduced epoxypropane or epoxybutane or the mixture of the epoxypropane and epoxybutane is 5-8 times of that of polyisobutene phenol.
The molecular weight of the finished product polyisobutene phenol polyether bis-secondary amine is 2500-3000, PIB is high-activity polyisobutene (HRPIB) with alpha-terminal double bond content more than 80%, the average molecular weight is 900-1100, n is propylene oxide or butylene oxide open-chain polymerization unit, and n value is 4-7. Because the smaller the molecular weight is, the poor thermal stability is, the decomposition is easy, the detergency to the sediment is poor, the molecular weight is too high, the viscosity is increased, the dispersibility is poor, the sediment quality is also improved, the molecular weight of the gasoline detergent synthesized by the method is 2500-3000, the cleaning performance of the gasoline is ensured, and the sediment is avoided;
the nickel catalyst (CAT-1) in the step (3) is Raney nickel.
In addition to the amination reaction in step (3), about 15% of non-alpha-terminal double bonds of the HRPIB in the HRPIB raw material are not reacted with phenol, and in the primary amination stage in step (3), the double bonds in the non-reacted HRPIB are saturated by catalytic hydrogenation, so that the finished product has no unsaturated bonds, the chemical stability of the product is better, the gel forming trend in the fuel is slower, and the final finished product amine detergent performance and use effect are better.
The nickel metal complex structure in the step (4) is as follows:
reflux the nickel halide and PNHP ligand in n-butanol solution under nitrogen protection for 3-5 hr, purifying and separating, and mixing with XCH 2 SiMe 3 And (3) carrying out a reaction at the temperature of 80-100 ℃ to obtain the target catalyst.
The reaction of an alcohol with an amine to form a new amine and release of water is a thermodynamically favored process, however, the first step in the reaction of an alcohol with an amine involves activation of hydrocarbon bonds on the ortho carbon of the hydroxyl group of the alcohol, which bonds are generally high in energy, and thus it is difficult for the reaction between an alcohol and an amine to occur under general conditions. The metal catalyst can reduce the bond energy of hydrocarbon bond activation, so that the hydrogen-borrowing reaction can be carried out under milder conditions. The alcohol is dehydrogenated to carbonyl compound under the action of metal catalyst, the carbonyl compound can react with amine to produce imine, and the metal catalyst can reuse hydrogen removed from alcohol to reduce imine intermediate to obtain secondary amine structure.
The ratio of the polyisobutene phenol polyether primary amine to the propylene glycol is 2:1, the reaction pressure is 1-3 MPa, the temperature is 100-130 ℃, and the reaction time is 4-10 hours.
Compared with the prior art, the invention has the following beneficial effects:
when the compound is used as a gasoline detergent, the compound can efficiently clean carbon deposition of a fuel nozzle, carbon deposition of an air inlet valve and carbon deposition of a combustion chamber without being compounded with other compounding agents, can improve combustion characteristics, reduces pollution emission and has excellent comprehensive performance.
Detailed Description
1. Synthetic examples of polyisobutene phenol polyether amine gasoline detergents:
example 1:
high-activity polyisobutene (molecular weight 900, alpha-terminal double bond content > 80%) and phenol (molar ratio 1:2.5) were dissolved in n-hexane solvent (mass ratio of starting material to solvent 1:2) in BF 3 And (3) carrying out catalytic reaction for 6 hours, wherein the reaction temperature is 60 ℃, then adding water to wash the separated liquid to remove the solvent, obtaining the polyisobutene phenol, and finally, recycling the solvent through distillation.
Under the action of a base catalyst, polyisobutene phenol and epoxypropane (the mol ratio is 1:8) are subjected to polymerization reaction at the temperature of 120 ℃ and under the pressure of 0.35MPa, and then the polyisobutene phenol polyether is obtained through refining treatment.
And then the polyisobutene phenol polyether is sent into a continuous reactor, the reaction is carried out under the conditions of hydrogen, ammonia and nickel catalyst and the pressure is kept at 3MPa, the temperature is 120 ℃, and the polyisobutene phenol polyether primary amine is obtained after continuous discharging.
Finally, the polyisobutene phenol polyether primary amine and propylene glycol are put into a reaction kettle according to the mol ratio of 2:1, and react under the action of a catalyst CAT-2 of a hydrogen-nickel complex, the reaction pressure is 2MPa, the temperature is 120 ℃, after the reaction is carried out for 6 hours, the target product is obtained after dehydration and filtration treatment, and the secondary amine content of the product is 98.04%.
Wherein the preparation process of the catalyst CAT-2 comprises the following steps: from NiCl 2 Reflux with PNHP ligand in n-butanol solution under nitrogen protection for 3 hr, purifying, separating, and mixing with ClCH 2 SiMe 3 The target catalyst is obtained by reaction at 100 ℃, wherein NiCl 2 PNHP ligand, clCH 2 SiMe 3 The molar ratio of (2) is 1:1:1.
Example 2:
high-activity polyisobutene (molecular weight 900, alpha-terminal double bond content > 80%) and phenol (molar ratio 1:3) are dissolved in normal hexane solvent (mass ratio of raw material to solvent is 1:3), and reacted for 7h under the catalysis of BF3 at the reaction temperature of 55 ℃, then water is added for washing, separating and desolventizing to obtain polyisobutene phenol, and finally the solvent is recycled through distillation.
Under the action of a base catalyst, polyisobutene phenol and epoxypropane (the mol ratio is 1:8) are subjected to polymerization reaction at the temperature of 125 ℃ and under the pressure of 0.35MPa, and then the polyisobutene phenol polyether is obtained through refining treatment.
And then the polyisobutene phenol polyether is sent into a continuous reactor, the reaction is carried out under the conditions of hydrogen, ammonia and nickel catalyst and the pressure is kept at 3MPa, the temperature is 180 ℃, and the polyisobutene phenol polyether primary amine is obtained after continuous discharging.
Finally, the polyisobutene phenol polyether primary amine and propylene glycol are put into a reaction kettle according to the mol ratio of 2:1, and react under the action of a catalyst CAT-2 of a hydrogen-nickel complex, the reaction pressure is 2MPa, the temperature is 120 ℃, after 4 hours of reaction, the target product is obtained after dehydration and filtration treatment, and the secondary amine content of the product is 98.15 percent.
Wherein the preparation process of the catalyst CAT-2 comprises the following steps: from NiBr 2 Reflux with PNHP ligand in n-butanol solution under nitrogen protection for 5 hr, purifying, separating, and mixing with ClCH 2 SiMe 3 The target catalyst is obtained by reaction at 80 ℃, wherein NiBr 2 PNHP ligand, clCH 2 SiMe 3 The molar ratio of (2) is 1:1:1.
Example 3:
high-activity polyisobutene (molecular weight 900, alpha-terminal double bond content > 80%) and phenol (molar ratio 1:2.7) are dissolved in toluene solvent (mass ratio of raw material to solvent is 1:1), and reacted for 8 hours under the catalysis of BF3 at the reaction temperature of 60 ℃, then water is added for washing, separating and desolventizing to obtain polyisobutene phenol, and finally the solvent is recycled through distillation.
Under the action of a base catalyst, the polyisobutene phenol and the epoxybutane (the mol ratio is 1:5) are subjected to polymerization reaction at the temperature of 120 ℃ and the pressure of 0.35MPa, and then the polyisobutene phenol polyether is obtained through refining treatment.
And then the polyisobutene phenol polyether is sent into a continuous reactor, the reaction is carried out under the conditions of hydrogen, ammonia and nickel catalyst and the pressure is kept at 3MPa, the temperature is 180 ℃, and the polyisobutene phenol polyether primary amine is obtained after continuous discharging.
Finally, the polyisobutene phenol polyether primary amine and propylene glycol are put into a reaction kettle according to the mol ratio of 2:1, and react under the action of a catalyst CAT-2 of a hydrogen-nickel complex, the reaction pressure is 2MPa, the temperature is 120 ℃, after 7 hours of reaction, the target product is obtained after dehydration and filtration treatment, and the secondary amine content of the product is 98.41 percent.
Wherein the preparation process of the catalyst CAT-2 comprises the following steps: from NiF 2 Reflux with PNHP ligand in n-butanol solution under nitrogen protection for 3 hr, purifying, separating, and mixing with ClCH 2 SiMe 3 The target catalyst is obtained by reaction at 80 ℃, wherein NiBr 2 PNHP ligand, clCH 2 SiMe 3 The molar ratio of (2) is 1:1:1.
Example 4:
high-activity polyisobutene (molecular weight 1000, alpha-terminal double bond content > 80%) and phenol (molar ratio 1:2.5) are dissolved in normal hexane solvent (mass ratio of raw material to solvent is 1:3), and reacted for 8 hours under the catalysis of BF3 at the reaction temperature of 40 ℃, then water is added for washing, separating and desolventizing to obtain polyisobutene phenol, and finally the solvent is recycled through distillation recovery.
Under the action of a base catalyst, the polyisobutene phenol and the epoxybutane (the mol ratio is 1:5.5) are subjected to polymerization reaction at the temperature of 120 ℃ and the pressure of 0.35MPa, and then the polyisobutene phenol polyether is obtained through refining treatment.
And then the polyisobutene phenol polyether is sent into a continuous reactor, the reaction is carried out under the conditions of hydrogen, ammonia and nickel catalyst and the pressure is kept at 4MPa, the temperature is 160 ℃, and the polyisobutene phenol polyether primary amine is obtained after continuous discharging.
Finally, the polyisobutene phenol polyether primary amine and propylene glycol are put into a reaction kettle according to the mol ratio of 2:1, and react under the action of a catalyst CAT-2 of a hydrogen-nickel complex, the reaction pressure is 2MPa, the temperature is 120 ℃, after the reaction is carried out for 6 hours, the target product is obtained after dehydration and filtration treatment, and the secondary amine content of the product is 97.87%.
Wherein the preparation process of the catalyst CAT-2 comprises the following steps: from NiI 2 Reflux with PNHP ligand in n-butanol solution under nitrogen protection for 4 hr, purifying, separating, and mixing with ClCH 2 SiMe 3 The target catalyst is obtained by reaction at 100 ℃, wherein NiI 2 PNHP ligand, clCH 2 SiMe 3 The molar ratio of (2) is 1:1:1.
Example 5:
high-activity polyisobutene (molecular weight 1100, alpha-terminal double bond content > 80%) and phenol (molar ratio 1:1.5) are dissolved in normal hexane solvent (mass ratio of raw material to solvent is 1:2), and reacted for 8 hours under the catalysis of BF3 at the reaction temperature of 40 ℃, then water is added for washing, separating and desolventizing to obtain polyisobutene phenol, and finally the solvent is recycled through distillation recovery.
Under the action of a base catalyst, polyisobutene phenol and epoxypropane (the mol ratio is 1:5) are subjected to polymerization reaction at the temperature of 120 ℃ and under the pressure of 0.35MPa, and then the polyisobutene phenol polyether is obtained through refining treatment.
And then the polyisobutene phenol polyether is sent into a continuous reactor, the reaction is carried out under the conditions of hydrogen, ammonia and nickel catalyst and the pressure is kept at 7MPa, the temperature is 160 ℃, and the polyisobutene phenol polyether primary amine is obtained after continuous discharging.
Finally, the polyisobutene phenol polyether primary amine and propylene glycol are put into a reaction kettle according to the mol ratio of 2:1, and react under the action of a catalyst CAT-2 of a hydrogen-nickel complex, the reaction pressure is 1MPa, the temperature is 130 ℃, after 10 hours of reaction, the target product is obtained after dehydration and filtration treatment, and the secondary amine content of the product is 98.93 percent.
Wherein the preparation process of the catalyst CAT-2 comprises the following steps: from NiCl 2 Reflux with PNHP ligand in n-butanol solution under nitrogen protection for 4 hr, purifying, separating, and mixing with ClCH 2 SiMe 3 The target catalyst is obtained by reaction at 90 ℃, wherein NiCl 2 PNHP ligand, clCH 2 SiMe 3 The molar ratio of (2) is 1:1:1.
Example 6:
high-activity polyisobutene (molecular weight 1050, alpha-terminal double bond content > 80%) and phenol (molar ratio 1:2.5) are dissolved in toluene solvent (mass ratio of raw material to solvent is 1:3), and reacted for 6 hours under the catalysis of BF3 at the reaction temperature of 60 ℃, then water is added for washing, separating and desolventizing to obtain polyisobutene phenol, and finally the solvent is recycled through distillation.
Under the action of a base catalyst, polyisobutene phenol and epoxypropane (the mol ratio is 1:6.5) are subjected to polymerization reaction at the temperature of 120 ℃ and under the pressure of 0.35MPa, and then the polyisobutene phenol polyether is obtained through refining treatment.
And then the polyisobutene phenol polyether is sent into a continuous reactor, the reaction is carried out under the conditions of hydrogen, ammonia and nickel catalyst and the pressure is kept at 10MPa, the temperature is 150 ℃, and the polyisobutene phenol polyether primary amine is obtained after continuous discharging.
Finally, the polyisobutene phenol polyether primary amine and propylene glycol are put into a reaction kettle according to the mol ratio of 2:1, and react under the action of a catalyst CAT-2 of a hydrogen-nickel complex, wherein the reaction pressure is 3MPa, the temperature is 100 ℃, after 8 hours of reaction, the target product is obtained after dehydration and filtration treatment, and the secondary amine content of the product is 98.22 percent.
Wherein the preparation process of the catalyst CAT-2 comprises the following steps: from NiBr 2 Reflux with PNHP ligand in n-butanol solution under nitrogen protection for 3 hr, purifying, separating, and mixing with ClCH 2 SiMe 3 The target catalyst is obtained by reaction at 90 ℃, wherein NiBr 2 PNHP ligand, clCH 2 SiMe 3 The molar ratio of (2) is 1:1:1.
2. Analysis of results:
the Mannich amine gasoline detergent, the polyether amine detergent with the same content concentration and the gasoline detergent synthesized by the method are respectively added into gasoline, and carbon deposit removal and environmental protection data comparison are carried out according to the methods of GB/T19230-2003 and GB18352.3-2005, wherein the data comparison is as follows.
As can be seen from comparison of table data, the product of the invention is used as a gasoline detergent, and can efficiently clean carbon deposition of a fuel nozzle, carbon deposition of an air inlet valve and carbon deposition of a combustion chamber without being compounded with other compounding agents, improve combustion characteristics, reduce pollution emission and have excellent comprehensive performance.
Claims (10)
1. A polyisobutene phenol polyetheramine compound represented by formula 1:
Wherein R is propyl or butyl, PIB is polyisobutene, and n is more than or equal to 4 and less than or equal to 7.
2. The method for synthesizing a compound of claim 1, comprising the steps of:
(1) Synthesis of polyisobutene phenol
Selecting alpha-terminalPolyisobutene having a double bond content of more than 80% is dissolved in an organic solvent in the form of BF 3 Adding excessive phenol as a catalyst under the condition of nitrogen, stirring and reacting for 6-8 hours at the temperature of 40-60 ℃, then adding water for washing and separating liquid, and removing solvent from an organic phase to obtain polyisobutene phenol;
(2) Synthesis of polyisobutene phenol polyether
Putting polyisobutylene phenol and a base catalyst into a reactor, heating to 110-130 ℃, continuously introducing quantitative propylene oxide or butylene oxide for reaction or a mixture of the two, preserving heat for 1-2 hours after the introduction, cooling to below 80 ℃ for neutralization, dehydration and filtration treatment to obtain polyisobutylene phenol polyether;
(3) Primary amination reaction
Performing continuous reaction on polyisobutene phenol polyether, liquid ammonia and hydrogen in a continuous reactor filled with a nickel catalyst, wherein the reaction pressure is 3-10 MPa, the reaction temperature is 120-180 ℃, and continuously discharging to obtain polyisobutene phenol polyether primary amine;
(4) Secondary amination reaction
And (3) throwing the polyisobutene phenol polyether primary amine and propylene glycol into a reaction kettle, keeping the pressure of 1-3 MPa and the temperature of 100-130 ℃ in the presence of hydrogen and nickel metal complex, reacting for 4-10 h, filtering after the reaction is finished, and dehydrating in vacuum to obtain the target product.
3. The synthetic method according to claim 2, wherein in the step (1), the organic solvent is n-hexane, toluene or isopropanol, the mass ratio of the raw material to the organic solvent is 1:1-3, and the raw material is polyisobutylene and phenol.
4. The method according to claim 3, wherein in the step (1), the organic solvent is n-hexane, and the mass ratio of the raw material to the organic solvent is 1:2.
5. The synthetic method of claim 2 wherein in step (1) the polyisobutylene has an average molecular weight of 900 to 1100.
6. The synthetic method according to claim 2, wherein in the step (1), the molar feed ratio of the polyisobutylene and the phenol in the step (1) is 1:1.5-3.
7. The synthetic method according to claim 2, wherein in the step (2), the molar amount of propylene oxide or butylene oxide or a mixture of both is 5 to 8 times that of the polyisobutene phenol.
8. The method of claim 2, wherein in step (4), the nickel metal complex structure is as follows:
9. the synthetic method of claim 2 wherein in step (4), the molar ratio of the polyisobutene phenol polyether primary amine to propylene glycol is 2:1.
10. Use of the compound of claim 1 as a gasoline detergent.
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