CN113736078B - Polyether amine, preparation method thereof and application of polyether amine as fuel detergent - Google Patents
Polyether amine, preparation method thereof and application of polyether amine as fuel detergent Download PDFInfo
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- CN113736078B CN113736078B CN202010462433.4A CN202010462433A CN113736078B CN 113736078 B CN113736078 B CN 113736078B CN 202010462433 A CN202010462433 A CN 202010462433A CN 113736078 B CN113736078 B CN 113736078B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
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- 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
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- C10L1/10—Liquid carbonaceous fuels containing additives
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- C10L1/22—Organic compounds containing nitrogen
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- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
- C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)
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Abstract
A polyether amine compound, its preparing process and application are disclosed. The polyether amine compound has a polymer main chain and one or more structures shown in a formula (I) connected with the polymer main chain through an-O-bond, wherein the definition of each group is shown in the specification; the polyetheramine compound is prepared by esterification of an amino acid with a polyether. The polyetheramine compounds of the present invention are suitable for use as detergents, particularly as fuel detergents. In contrast, the polyether amine compound has the advantages of low preparation cost and simple reaction, and has good cleaning and dispersing properties when being used as a fuel oil cleaning agent.
Description
Technical Field
The invention relates to a polyether amine structure and a preparation method thereof. More particularly, the present invention relates to polyetheramines used primarily as fuel detergents and to methods for making the same.
Background
Some components of liquid fuel form deposits during operation of the internal combustion engine, which cause emissions to deteriorate and fuel economy to decline, and fuel detergents function in liquid fuel to inhibit deposit formation. At present, the development of the gasoline detergent has become an integral part of the research and development and application of the gasoline engine, on the one hand, with the progress of the internal combustion engine technology, the advanced internal combustion engine manufacturing technology puts higher demands on the gasoline detergent, for example, the in-cylinder direct injection gasoline engine is widely applied, and the higher standard demands are put on the gasoline detergent.
Incomplete combustion of automotive hydrocarbon fuels causes deposit formation in multiple locations of the gasoline engine intake valves and combustion chambers, etc., which can adversely affect engine function and exhaust gas. For example, deposits in the combustion chamber reduce the volume, and the compression ratio becomes high, which is liable to cause knocking. The octane requirement for gasoline increases and continued knocking can cause stress fatigue or wear to engine components, resulting in reduced vehicle life and increased maintenance costs. Therefore, the development of gasoline detergents is particularly important for cleaning to remove deposits and prevent the occurrence of deposits.
The gasoline detergent is one of fuel oil additives, and is essentially a macromolecular surfactant molecule, and consists of a polar group and a nonpolar group, wherein the polar group can be adsorbed on sediment molecules and metal surfaces, and the nonpolar group improves good oil solubility and prevents sediment molecular clusters from being deposited on metal parts, so that the detergent has the functions of dispersing and cleaning.
For example, U.S. Pat. No. 4, 3440029,310875, JP-B-56-48556, JP-A-3-128933, etc. disclose monoamine ether compound type additives and polyether amine compound type additives.
These etheramine compounds basically exhibit satisfactory cleaning effects. However, in some cases, such as when the engine speed is frequently increased or decreased, the cleaning effect is poor; and the existing method for manufacturing polyetheramine has the defect of higher manufacturing cost.
Disclosure of Invention
The present inventors have conducted intensive and extensive studies in order to solve the problems of the prior art, and as a result, have found a polyetheramine having better engine deposit removal performance and a method for preparing the same.
In one aspect, the present invention provides a novel polyetheramine compound having a polymer backbone and one or more structures represented by the following formula (I) attached to the polymer backbone via-O-linkages
In the formula (I) of the present invention,
* Represents the binding end of an-O-bond;
link represents a linking group and is a single bond or C 1-10 Hydrocarbylene radicals, preferably C 1-6 Linear or branched alkylene, more preferably C 1-4 Linear or branched alkylene;
R 1 each independently selected from H, -CH 3 、-CH 2 OH、-CH 2 COOH、-(CH 2 ) 2 COOH、-CH(CH 3 ) 2 、-CH 2 CH(CH 3 ) 2 、-CH(CH 3 )CH 2 CH 3 、-(CH 2 ) 4 NH 2 、-CH 2 CONH 2 、-(CH 2 ) 2 CONH 2 、
-CH(OH)CH 3 The method comprises the steps of carrying out a first treatment on the surface of the A kind of electronic device with high-pressure air-conditioning system
R 2 Selected from hydrogen.
In one embodiment of the polyetheramine compound according to the present invention, it has a structure represented by the following formula (II):
in the formula (II) of the present invention,
g and p-O-are bonded together to represent the backbone of the polyetheramine compound; a kind of electronic device with high-pressure air-conditioning system
p is an integer of 1 to 10, preferably an integer of 1 to 3, more preferably 1.
In another embodiment of the polyetheramine compound according to the present invention, the main chain is a structure obtained by removing p (p is an integer and 1.ltoreq.p.ltoreq.p ') hydrogen atoms on hydroxyl groups from a hydroxyl polymer having p ' (p ' is an integer of 1 to 10, preferably an integer of 1 to 3, more preferably 1) hydroxyl groups.
In another embodiment of the polyetheramine compound according to the present invention, the hydroxyl polymer is at least one selected from the group consisting of polyethers having p ' hydroxyl groups and polyesters having p ' hydroxyl groups, preferably polyethers having p ' hydroxyl groups, more preferably alkylene glycol polymers, particularly preferably polyethers represented by the following formula (III),
in the formula (III) of the present invention,
R 0 selected from hydrogen atoms and optionally substituted C 1-50 Preferably selected from hydrogen atoms, C 1-20 Linear or branched alkyl, substituted by one or more C' s 1-20 C substituted by straight-chain or branched alkyl groups 6-10 Monocyclic or polycyclic aryl groups and substituted by one or more C' s 1-20 C substituted by straight-chain or branched alkyl groups 3-20 Monocyclic or polycyclic cycloalkyl groups, further preferably selected from hydrogen atoms, C 5-15 Straight-chain or branched alkyl and substituted by one or more C' s 5-15 Phenyl substituted by straight chain or branched alkyl;
n R u The radicals being identical to or different from one another and each independently selected from C 2-24 Linear or branched alkylene groups, preferably each independently selected from C 2-12 Linear or branched alkylene groups, more preferably each independently selected from C 2-6 Linear or branched alkylene groups, most preferably each independently selected from-CH 2 -CH 2 -and-CH 2 -CH(CH 3 )-；
n represents the average degree of polymerization of the polyether segment and is any number between 1 and 100, preferably any number between 1 and 50, more preferably any number between 5 and 25.
In another embodiment of the polyetheramine compound according to the present invention, it has a structure represented by the following formula (II-A) or a structure represented by the following formula (II-B), or is a polyetheramine represented by the following formula (II-C) and has a molecular weight of 500 to 3000, preferably 1000 to 2000, more preferably 1000 to 1500,
in the various types of the compositions,
R 0 selected from hydrogen atoms and optionally substituted C 1-50 Preferably selected from hydrogen atoms, C 1-20 Linear or branched alkyl, substituted by one or more C' s 1-20 C substituted by straight-chain or branched alkyl groups 6-10 Monocyclic or polycyclic aryl groups and substituted by one or more C' s 1-20 C substituted by straight-chain or branched alkyl groups 3-20 Monocyclic or polycyclic cycloalkyl groups, more preferably selected from hydrogen atoms, C 5-15 Straight-chain or branched alkyl and substituted by one or more C' s 5-15 Phenyl substituted by straight chain or branched alkyl;
n R u The radicals being identical to or different from one another and each independently selected from C 2-24 Linear or branched alkylene groups, preferably each independently selected from C 2-12 Linear or branched alkylene groups, more preferably each independently selected from C 2-6 Linear or branched alkylene groups, most preferably each independently selected from-CH 2 -CH 2 -and-CH 2 -CH(CH 3 )-；
n represents the average degree of polymerization of the polyether segment and is any number between 1 and 100, preferably any number between 1 and 50, more preferably any number between 5 and 25.
In another embodiment of the polyetheramine compounds according to the present invention, the molecular structure comprises at least one ester carbonyl group.
In another embodiment of the polyetheramine compound according to the present invention, the polyetheramine compound may be a single compound comprising the structure of formula (I), or may be a mixture comprising the structure of formula (I); typically, the polyetheramine compound is a mixture comprising compounds having the structure of formula (I).
In another aspect, the present invention provides a process for producing the aforementioned polyetheramine compound, which comprises reacting a polyether amine compound represented by the following formula (IV) having-COOH groups and-NH groups 2 The amino acid of the group is esterified with polyether shown in the formula (III)
In the formula (IV) of the present invention,
R 3 selected from H, -CH 3 、-CH 2 OH、-CH 2 COOH、-(CH 2 ) 2 COOH、-CH(CH 3 ) 2 、-CH 2 CH(CH 3 ) 2 、-CHCH 3 CH 2 CH 3 、-(CH 2 ) 4 NH 2 、-CH 2 CONH 2 、-(CH 2 ) 2 CONH 2 、
-CHOHCH 3 The method comprises the steps of carrying out a first treatment on the surface of the A kind of electronic device with high-pressure air-conditioning system
R 4 Is an H atom.
In one embodiment of the method according to the invention, the amino acid of formula (IV) is selected from glycine, serine, threonine, glutamic acid, leucine, alanine, isoleucine, aspartic acid, valine, asparagine, glutamine, lysine, phenylalanine, tyrosine and arginine.
In another embodiment of the process according to the invention, the molar ratio of the amino acid of formula (IV) to the polyether of formula (III) is from 1:0.1 to 10, preferably from 1:0.5 to 5, more preferably from 1:0.5 to 2.
In another embodiment of the process according to the invention, the reaction temperature of the amino acid of formula (IV) with the polyether of formula (III) is 80 to 200℃and preferably 110 to 180 ℃.
In another embodiment of the process according to the invention, the pressure of the esterification reaction of the amino acid of formula (IV) with the polyether of formula (III) is from 0.1 to 10MPa, preferably from 0.1 to 5MPa.
In another embodiment of the process according to the invention, the reaction time of the esterification of the amino acid of formula (IV) with the polyether of formula (III) is 2 to 10 hours, preferably 5 to 10 hours.
In another embodiment of the process according to the invention, a water-splitting agent may be added to the esterification reaction of the amino acid of formula (IV) with the polyether of formula (III) to increase the product yield; the water splitting agent includes but is not limited to benzene, toluene, petroleum ether, preferably toluene; the water diversion agent is used in an amount which is 5 to 20 percent of the mass of the polyether shown in the formula (III) in a conventional amount.
In a further aspect, the present invention also provides the use of the foregoing polyetheramine compound as a detergent; in particular as a fuel detergent.
In a further aspect, the present invention provides a fuel detergent comprising the polyetheramine compound described above or a polyetheramine compound prepared by the method of the present invention, and optionally comprising a diluent selected from one or more of a polyolefin, a mineral base oil and a polyether.
In one embodiment of the fuel detergent according to the invention, the polyetheramine compound comprises 10 to 70wt%, preferably 30 to 70wt%, most preferably 50 to 70wt% of the total mass of the fuel detergent.
In a further aspect, the present invention provides a fuel composition comprising the aforementioned polyetheramine compound or polyetheramine compound prepared according to the method of the present invention or the aforementioned fuel detergent, and a base fuel, wherein the polyetheramine compound or the fuel detergent is added in an amount of 30 to 2000mg/kg, preferably 50 to 2000mg/kg, more preferably 50 to 1000mg/kg, based on the total mass of the fuel composition, based on the polyetheramine compound.
When used as a fuel oil cleaning agent, the polyether amine has very excellent cleaning and dispersing performances. The method used by the invention has the following advantages: (1) the one-step reaction can be finished by a one-pot method; (2) the reaction does not involve high pressure or gas, and is liquid phase reaction; (3) the raw materials are wide and cheap in source, safer and less in toxic and side effects; (4) the catalyst for the esterification reaction is mature and can be selected from the mature catalyst, so that the optimal catalyst (5) suitable for the reaction can be obtained, and the impurities such as halogen and the like can not be doped in the reaction, so that the corrosion performance of the gasoline can not be influenced when the gasoline is added subsequently; (6) the structure of the amino acid is changeable, and different polyether amine products, such as amino acid with benzene ring or amino acid without benzene ring, can be obtained by esterifying the amino acid with different structures with polyether.
Drawings
FIG. 1 is an infrared spectrum of a polymer prepared according to example 1 of the present invention, in which the C=O peak of the ester carbonyl group is 1740cm -1 The characteristic peak of C-O-C is 1108cm -1 。
Detailed Description
The following detailed description of embodiments of the invention is provided, but it should be noted that the scope of the invention is not limited by these embodiments, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used in this specification have the meanings commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, definitions, will control.
When the specification derives materials, substances, methods, steps, devices, or components, etc., with the word "known to those skilled in the art", "prior art", or its synonyms, the word derived is intended to encompass those conventionally used in the art at the time of the application, but also includes those which are not yet commonly used at the time of the application, but which would become known in the art to be suitable for similar purposes.
In the context of this specification, any matters or matters not mentioned are directly applicable to those known in the art without modification except as explicitly stated. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are all deemed to be part of the original disclosure or original description of the present invention, and should not be deemed to be a new matter which has not been disclosed or contemplated herein, unless such combination is clearly unreasonable by those skilled in the art.
Unless explicitly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise clear to the routine knowledge of a person skilled in the art.
Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.
In the context of the present specification, the expression "halogen" refers to fluorine, chlorine, bromine or iodine.
In this specification, the term "single bond" is sometimes used in the definition of a group. By "single bond" is meant that the group is absent. For example, assume the structural formula-CH 2 -A-CH 3 Wherein the group A is defined as selected from single bonds and methylene groups. In view of this, if A is a single bond, this means that the group A is absent, in which case the formula is correspondingly reduced to-CH 2 -CH 3 。
In the context of the present specification, where not specifically stated, the term "optionally substituted" means optionally substituted with one or more (e.g. 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) groups selected from hydroxy, amino, C 1-20 Straight-chain or branched alkyl, C 5-10 Monocyclic or polycyclic cycloalkyl and C 6-20 The substituents of the aryl groups are substituted. As said C 1-20 Examples of the linear or branched alkyl group include C 1-10 Straight-chain or branched alkyl, C 1-6 Straight-chain or branched alkyl or C 1-4 Examples of the linear or branched alkyl group include methyl and ethyl. As said C 5-10 Examples of monocyclic or polycyclic cycloalkyl groups include C 5-8 Monocyclic or polycyclic cycloalkyl or C 5-7 Examples of the monocyclic or polycyclic cycloalkyl group include cyclopentyl and cyclohexyl. As said C 6-20 Examples of the aryl group include C 6-10 Examples of the aryl group include phenyl and naphthyl.
In the context of the present specification, the molecular weight is the number average molecular weight Mn, and is determined by Gel Permeation Chromatography (GPC), unless otherwise specified.
In the context of the present specification, unless otherwise specified, any reference to Gel Permeation Chromatography (GPC) or measurement conditions of GPC spectra are: the instrument is a Waters1515 gel permeation chromatograph of the Waters company of the united states; the mobile phase adopts tetrahydrofuran, the flow rate is 1mL/min, the chromatographic column temperature is 35 ℃, the outflow time is 33min, and the sample volume fraction is 0.1%.
In one aspect, the polyetheramine compounds according to the present invention have a polymer backbone and one or more structures represented by the following formula (I) attached to the polymer backbone via an-O-linkage:
In the case of the formula (I),
* Representing the bond end of the-O-bond, specifically, the structure shown in the formula (I) is bonded with the-O-bond on the polymer main chain through the non-bond at the position shown in the formula to form a covalent bond, and is further connected with the polymer main chain;
link represents a linking group selected from single bonds and C 1-10 Alkylene, as the C 1-10 Examples of hydrocarbylene groups include C 1-10 Linear or branched alkylene, preferably C 1-6 Straight-chain or branched alkylene, further preferably C 1-4 Linear or branched alkylene;
R 1 independently selected from H, -CH 3 、-CH 2 OH、-CH 2 COOH、-(CH 2 ) 2 COOH、-CH(CH 3 ) 2 、-CH 2 CH(CH 3 ) 2 、-CHCH 3 CH 2 CH 3 、-(CH 2 ) 4 NH 2 、-CH 2 CONH 2 、-(CH 2 ) 2 CONH 2 、
-CHOHCH 3 ；
R 2 Selected from hydrogen.
It is noted that the-O-linkage is located on the polymer backbone and forms a part of the polymer backbone. In view of the above manner of attachment, the structure represented by formula (I) above is typically attached to the polymer backbone in the form of end groups.
According to one embodiment of the present invention, the polyetheramine compound has a structure represented by the following formula (II):
in the case of the formula (II),
g and p-O-linkages together represent the backbone of the polymer, so that both G and-O-linkages are part of the polyetheramine backbone;
p is an integer of 1 to 10, preferably an integer of 1 to 3, more preferably 1.
According to one embodiment of the present invention, the polymer main chain is a structure obtained by removing hydrogen atoms on p (p is an integer and 1.ltoreq.p.ltoreq.p ') hydroxyl groups from a hydroxyl polymer having p ' (p ' is an integer of 1 to 10, preferably an integer of 1 to 3, more preferably 1) hydroxyl groups.
Accordingly, G has a structure obtained by removing p hydroxyl groups from a hydroxyl polymer having p' hydroxyl groups.
According to one embodiment of the invention, for example, the polyetheramine compound may have the following exemplary structure:
in the formulae (II-A) and (II-B)
R 0 Selected from hydrogen atoms and optionally substituted C 1-50 Preferably selected from hydrogen atoms, C 1-20 Linear or branched alkyl, substituted by one or more C' s 1-20 C substituted by straight-chain or branched alkyl groups 6-10 Monocyclic or polycyclic aryl groups and substituted by one or more C' s 1-20 C substituted by straight-chain or branched alkyl groups 3-20 Monocyclic or polycyclic cycloalkyl groups, further preferably selected from hydrogen atoms, C 5-15 Straight-chain or branched alkyl and substituted by one or more C' s 5-15 Phenyl substituted by straight chain or branched alkyl;
n R u The radicals being identical to or different from one another and each independently selected from C 2-24 Linear or branched alkylene groups, preferably each independently selected from C 2-12 Linear or branched alkylene groups, more preferably each independently selected from C 2-6 Linear or branched alkylene groups, more preferably each independently selected from-CH 2 -CH 2 -and-CH 2 -CH(CH 3 )-；
n represents an average degree of polymerization of the polyether segment and is selected from any number between 1 and 100, more preferably from any number between 1 and 50, still more preferably from any number between 5 and 25; the other groups and values are defined as in formula (I).
According to one embodiment of the present invention, as the parent polymer of the polyetheramine compound, the hydroxyl polymer may be those commonly used in the art in designing fuel detergents, including but not limited to polyesters, polyethers, and enol polymers, and the like.
Specifically, polyesters having a corresponding number of free hydroxyl groups and polyethers having a corresponding number of free hydroxyl groups, preferably polyethers having a corresponding number of free hydroxyl groups, may be mentioned.
Examples of the polyether having a corresponding number of free hydroxyl groups include polyethers having hydroxyl groups at one or both ends of a polymer chain, and polyethers having more hydroxyl groups obtained by using a comonomer such as a polyol.
More specifically, as the polyether having a corresponding number of free hydroxyl groups, there may be mentioned, in particular, alkylene glycol polymers represented by the following formula (III):
in the formula (III) of the present invention,
R 0 selected from hydrogen atoms and optionally substituted C 1-50 As the hydrocarbon group of (C) 1-50 Examples of the hydrocarbon group of (C) include C 1-20 Linear or branched alkyl, substituted by one or more C' s 1-20 C substituted by straight-chain or branched alkyl groups 6-10 Monocyclic or polycyclic aryl groups and substituted by one or more C' s 1-20 C substituted by straight-chain or branched alkyl groups 3-20 Monocyclic or polycyclic cycloalkyl, especially C 5-15 Straight or branched alkyl, phenyl and cyclohexyl;
wherein R is as R 0 Specific examples of (a) include dodecylphenyl and nonylphenyl;
n R u The radicals being identical to or different from one another and each independently selected from C 2-24 Linear or branched alkylene groups, preferably each independently selected from C 2-12 Linear or branched alkylene groups, more preferably each independently selected from C 2-6 Linear or branched alkylene groups, more preferably each independently selected from-CH 2 -CH 2 -and-CH 2 -CH(CH 3 ) -, more preferably-CH 2 -CH(CH 3 )-；
n is the average degree of polymerization of the polyether segments and is any number between 1 and 100, preferably any number between 1 and 50, more preferably any number between 5 and 25. Generally, the degree of polymerization of the polyether chain segment is between 5 and 25, the nonpolar carbon-oxygen chain is long, the oil solubility is good, carbon deposit can be better wrapped, and the carbon deposit is dispersed in the oil, so that the polyether chain segment has more excellent cleaning dispersion performance. However, if the polymerization degree is too high, the polyether amine molecules have too long nonpolar chains, and the polyether amine molecules cannot be completely adsorbed on the surfaces of particles to form rings or combine with the surfaces of adjacent particles, so that 'bridging' flocculation among particles is caused, and the cleaning effect is poor.
Further, in formula (III), when R u When two or more, the different units-O-R u Bonding between them can be carried out in random, block or alternating fashion in any desired ratio, provided that the total (average) number of units is n.
According to a preferred embodiment of the present invention, the polyetheramine compound is preferably a polyetheramine represented by the following formula (II-C), and the polyetheramine has a molecular weight of 500 to 2000, preferably 1000 to 1500.
According to another preferred embodiment of the present invention, the polyether amine compounds of the formula (II-A) and (II-B) may also have a molecular weight of 500 to 2000, preferably 1000 to 1500.
In another aspect, the method of preparing the polyetheramine compound according to the present invention comprises: containing-COOH groups and-NH groups represented by the following formula (IV) 2 The amino acid of the group is esterified with a polyether of formula (III):
in the formula (IV) of the present invention,
R 3 selected from H, -CH 3 、-CH 2 OH、-CH 2 COOH、-(CH 2 ) 2 COOH、-CH(CH 3 ) 2 、-CH 2 CH(CH 3 ) 2 、-CHCH 3 CH 2 CH 3 、-(CH 2 ) 4 NH 2 、-CH 2 CONH 2 、-(CH 2 ) 2 CONH 2 、
-CH(OH)CH 3 ；
R 4 Is an H atom.
In one embodiment of the process according to the invention, the compound of formula (IV) contains-COOH groups and-NH groups 2 The amino acid of the group is selected from one or more of glycine, serine, threonine, glutamic acid, leucine, alanine, isoleucine, aspartic acid, valine, asparagine, glutamine, lysine, phenylalanine, tyrosine and arginine. Preferably one or more of alanine and phenylalanine.
In one embodiment of the process according to the invention, the molar ratio between the amino acid of formula (IV) and the polyether of formula (III) in the esterification reaction is from 1:0.1 to 10, preferably from 1:0.5 to 5, more preferably from 1:0.5 to 2. The molar ratio of the reactants is in the range, so that the product yield is improved, the input of the reactant raw materials is reduced to the greatest extent, and the cost is further reduced.
In one embodiment of the process according to the invention, the esterification reaction temperature of the amino acid of formula (IV) with the polyether of formula (III) is from 80 to 200℃and preferably from 110 to 180 ℃. The reaction temperature range is selected, so that the reaction speed and conversion rate can be improved, side reactions can be reduced, and the color and quality of the product can be controlled.
In one embodiment of the process according to the invention, the esterification reaction is carried out at a pressure of from 0.1 to 10MPa, preferably from 0.1 to 5MPa.
In one embodiment of the process according to the invention, the time of the esterification reaction is from 2 to 10 hours, preferably from 5 to 10 hours.
In an alternative embodiment of the process according to the invention, it is also possible to add an esterification catalyst, such as hydrogen chloride, concentrated sulfuric acid, p-toluene sulfonic acid, solid acid, thionyl chloride, etc., to the esterification reactant.
In an alternative embodiment of the process according to the present invention, it may further comprise adding a water-splitting agent to the esterification reactant, wherein the water-splitting agent includes, but is not limited to, benzene, toluene, petroleum ether, preferably toluene.
In another alternative embodiment of the process according to the invention, the water-splitting agent may be used in an amount conventional for this but preferably is 5% to 20% by mass of the polyether of formula (III).
The water-splitting agent can be removed after the end of the reaction in a manner known to the person skilled in the art.
It should be noted that the water-splitting agent may be removed after the reaction is completed by a method known to those skilled in the art. Alternatively, after the preparation of the polyetheramine, the polyetheramine can be obtained by removing the optionally added catalyst and water-splitting agent from the finally obtained reaction mixture in a conventional manner.
The polyetheramine compounds of the present invention are particularly suitable for the manufacture of detergents (detergent base agents), such as fuel detergents, in particular gasoline detergents. The detergent exhibits excellent deposit formation inhibiting properties. Here, the detergent includes any of the polyether amine compounds described in the foregoing of the present invention or a polyether amine compound produced according to the foregoing production method of the present invention.
According to the present invention, a diluent may be further added to the polyether amine compound in order to manufacture the detergent. Examples of the diluent include mineral base oils, polyolefins, and polyethers. These diluents may be used alone or in combination of two or more.
According to the present invention, as the mineral base oil, for example, one or more of APII, II, III mineral lubricating base oils may be used, preferably one or more selected from mineral lubricating base oils having a viscosity of 20 to 120 centi-si (cSt) at 40 ℃ and a viscosity index of at least 50 or more, and more preferably one or more selected from mineral lubricating base oils having a viscosity of 28 to 110 centi-si (cSt) at 40 ℃ and a viscosity index of at least 80 or more.
According to the invention, examples of the polyolefin include those obtained by reacting ethylene, propylene or C 4 -C 10 Homopolymers of alpha-olefins or one or more of polyolefins obtained by copolymerization of two or more of these olefins, preferably one or more of Polyalphaolefins (PAO) having a viscosity of from 2 to 5 centiSt (cSt) at 100℃, preferably a viscosity of from 6 to 10 centiSt at 100℃. Wherein as C 4 -C 10 Examples of the α -olefin include n-butene, isobutylene, n-pentene, n-hexene, n-octene and n-decene. In addition, the polyolefin generally has a number average molecular weight Mn of from 500 to 3000, preferably from 500 to 2500, most preferably from 500 to 1500.
According to the present invention, examples of the polyether include polymers produced by reacting alcohols with epoxides. Examples of the alcohol include ethylene glycol and/or 1, 3-propanediol. Examples of the epoxide include ethylene oxide and/or propylene oxide. In addition, the polyether generally has a number average molecular weight Mn of from 500 to 3000, preferably from 700 to 3000, most preferably from 1000 to 2500.
Generally, in the detergents of the present invention, the polyetheramine compound comprises, by mass, from 10 to 70wt%, preferably from 30 to 70wt%, most preferably from 50 to 70wt% of the total mass of the detergent.
According to the invention, for the manufacture of the detergent, the polyetheramine compound is mixed with the diluent (if used) at 20-60 ℃ for 1-6 hours.
The polyetheramine compounds or detergents of the present invention are also particularly suitable for the manufacture of fuel compositions which exhibit excellent deposit formation inhibition properties. Thus, according to the present invention, it further relates to a fuel composition comprising any of the polyetheramine compounds described in the foregoing in accordance with the present invention, polyetheramine compounds manufactured according to the foregoing manufacturing method in accordance with the present invention or the foregoing detergent in accordance with the present invention, and a base fuel.
According to the present invention, the polyether amine compound or the detergent is added in an amount of generally 30 to 2000mg/kg, preferably 50 to 2000mg/kg, more preferably 50 to 1000mg/kg, based on the total mass of the fuel composition, based on the polyether amine compound.
According to the present invention, examples of the base fuel include base fuels used in spark ignition or compression ignition internal combustion engines, such as motor gasoline, aviation gasoline, diesel oil, and the like, which contain or contain no lead.
In addition to the polyetheramine compound and the detergent, other additional additives may be included in the fuel composition according to the present invention. Examples of the additional additive include a scale remover, an antioxidant, a diluent, a metal deactivator, a corrosion inhibitor, an antistatic agent, a demulsifier, an antiknock agent, a lubricant additive, and a combustion improver. These additional additives may be used alone or in combination of two or more, and the amount thereof is not particularly limited, from the amounts conventionally used in the art.
The invention is further illustrated by the following examples which describe preferred embodiments and are not to be construed as limiting the invention, as any equivalent examples of equivalents may be modified by those skilled in the art using the teachings set forth above.
The reagents used in the examples below were all commercially available reagents. Evaluation of the detergency performance concerning examples and comparative examples was evaluated as follows.
A gasoline engine intake valve deposit simulation test method (GB/T37322-2019) was used.
Specifically, the deposit simulation test method for the gasoline engine air inlet valve measures the deposit of the simulated air inlet valve, the test gasoline in the oil tank flows through a measuring system to enter a nozzle, the test gasoline is mixed with air and sprayed onto 1 weighed aluminum plate which is heated to 175 ℃ in a flat spraying mode, and the deposit mass obtained by spraying 300mL of the test gasoline is collected. Deposit mass fraction obtained by dividing the deposit mass obtained by 300mL of base gasoline and the deposit mass difference obtained by 300mL of test gasoline by 300mL of base gasoline was taken as an intake system deposit reduction rate (%).
The deposit reduction rate is an important index for evaluating the detergency of a detergent, and the greater the value, the more detergency. The deposit formation amount (m) of the simulated air inlet valve is measured according to the GB/T37322-2019-simulated air inlet valve deposit test method of the gasoline engine IVD Mg), the deposit decrease rate (%) was calculated according to the following formula.
Wherein m is IVD,0 And m IVD The sediment generation amounts of the air inlet valve are simulated by the blank gasoline and the detergent-added gasoline respectively, and mg is calculated.
Example 1
The polymer of example 1 was prepared from nonylphenol polyether and alanine. At room temperature, 4.45g (0.050 mol) alanine, 89.7g (0.065 mol) nonylphenol polyoxypropylene ether and SO accounting for 0.1% -5% of the total mass of the reactants are added into a three-neck flask 4 2- /ZrO 2 And (3) adding 30mL of toluene serving as a water knockout agent into the solid superacid esterification catalyst, heating to 150 ℃ for 40min under the protection of nitrogen, stirring, and keeping the reaction for 7h to finish the reaction. Filtration was performed using a filter funnel to obtain a mixture. Toluene was removed under reduced pressure to give a viscous pale yellow liquid, i.eThe polyetheramine compound of example 1 was obtained.
Example 2
The compound of example 2 was prepared from nonylphenol polyether and phenylalanine. At room temperature, 4.45g (0.050 mol) alanine, 103.5g (0.075 mol) nonylphenol polyoxypropylene ether and p-toluenesulfonic acid esterification catalyst accounting for 0.1% -5% of the total mass of the reactants are added into a three-neck flask, 30mL toluene as a water knockout agent is added, the temperature is raised to 160 ℃ for 40min under the protection of nitrogen, and stirring is carried out, the reaction is kept for 8h, and the reaction is completed. Filtration was performed using a filter funnel to obtain a mixture. The water-splitting agent toluene was removed under reduced pressure to obtain a viscous pale yellow liquid, namely, the polyether amine compound of example 2.
Example 3
The compound of example 3 was prepared from stearyl polyoxyethylene polyoxypropylene ether and alanine. 0.050mol of alanine, 70.1g (0.055 mol) of stearyl polyoxyethylene polyoxypropylene ether are added into a four-necked flask, 25mL of toluene as a water knockout agent is added, and SO exists 4 2- /ZrO 2 Under the condition of the solid super acid catalyst, the nitrogen is protected to heat up to 150 ℃, and the mixture is stirred and kept for reaction for 8 hours, and the reaction is completed. Filtration was performed using a filter funnel to obtain a mixture. The water-splitting agent toluene was removed under reduced pressure to obtain a viscous liquid, which was the polyether amine compound of example 3.
Example 4
Example 4 was prepared from stearyl polyoxyethylene polyoxypropylene ether and phenylalanine. 0.050mol of phenylalanine and 70.1g (0.055 mol) of stearyl polyoxyethylene polyoxypropylene ether are added into a four-neck flask, 30mL of water knockout toluene is added, the temperature is raised to 150 ℃ under the protection of nitrogen in the presence of a p-toluenesulfonic acid catalyst, and the mixture is stirred and kept for reaction for 8 hours, so that the reaction is completed. Filtration was performed using a filter funnel to obtain a mixture. The water-splitting agent toluene was removed under reduced pressure to obtain a viscous liquid, which was the polyether amine compound of example 4.
Example 5
Example 5 was prepared from nonylphenol polyoxypropylene ether and glutamic acid. 7.35g (0.050 mol) of glutamic acid was added to the three-necked flask at room temperature, 89.7g (0.065 mol) of nonylphenol polyoxypropylene ether accounting for 0.1 to 5 percent of SO of the total mass of the reactants 4 2- /ZrO 2 And (3) adding 30mL of toluene serving as a water knockout agent into the solid super acidic catalyst, heating to 150 ℃ for 40min under the protection of nitrogen, stirring, and keeping the reaction for 7h to finish the reaction. Filtration was performed using a filter funnel to obtain a mixture. Toluene was removed under reduced pressure to give a viscous pale yellow liquid, namely, a polyether amine compound of example 5.
Example 6
The polymer of example 6 was prepared from nonylphenol polyether and glycine. At room temperature, 3.75g (0.050 mol) glycine, 67.4g (0.06 mol) nonylphenol polyoxypropylene ether and SO accounting for 0.1-5% of the total mass of the reactants are added into a three-neck flask 4 2- /ZrO 2 And (3) adding 30mL of toluene serving as a water knockout agent into the solid super acidic catalyst, heating to 160 ℃ for 40min under the protection of nitrogen, stirring, and keeping the reaction for 8h to finish the reaction. Filtration was performed using a filter funnel to obtain a mixture. The water-splitting agent toluene was removed under reduced pressure to obtain a viscous pale yellow liquid, namely, the polyether amine compound of example 6.
Example 7
The polymer of example 7 was prepared from propylene glycol polyoxyethylene propylene ether (mn=1200) and alanine. At room temperature, 8.26g (0.050 mol) alanine, 84g (0.07 mol) propylene glycol polyether and SO accounting for 0.1-5% of the total mass of the reactants are added into a three-neck flask 4 2- /ZrO 2 And (3) adding 30mL of toluene serving as a water knockout agent into the solid super acidic catalyst, heating to 160 ℃ for 40min under the protection of nitrogen, stirring, and keeping the reaction for 8h to finish the reaction. Filtration was performed using a filter funnel to obtain a mixture. The water-splitting agent toluene was removed under reduced pressure to obtain a viscous pale yellow liquid, namely, the polyether amine compound of example 7.
Example 8
The polymer of example 8 was prepared from n-octanol polyoxypropylene ether (mn=1000) and alanine. At room temperature, 8.26g (0.050 mol) alanine and 65g (0.065 mol) n-octanol polyether accounting for 0.1 to 5 percent of the total mass of the reactants are added into a three-neck flask 4 2- /ZrO 2 And (3) adding 30mL of toluene serving as a water knockout agent into the solid super acidic catalyst, heating to 160 ℃ for 40min under the protection of nitrogen, stirring, and keeping the reaction for 8h to finish the reaction. Filtration was performed using a filter funnel to obtain a mixture. The water-splitting agent toluene was removed under reduced pressure to obtain a viscous pale yellow liquid, namely, the polyether amine compound of example 8.
Comparative example
Preparation of the polyetheramines available
1) And (3) preparation of polyether. A mixture of 220g of nonylphenol and 2.0g of potassium hydroxide was added to the reaction vessel, the air in the reactor was replaced with nitrogen, the temperature was raised to about 140℃and about 696g of propylene oxide was continuously pumped into the reaction vessel for reaction until the pressure was no longer changed, and the reaction was continued at 140℃until the pressure was no longer changed. After the reaction was completed, the reaction mass was cooled to room temperature, neutralized with acetic acid, and the catalyst was removed by washing with water. Evaporating water and volatile matters under reduced pressure to obtain the polyether product with molecular weight of 898.
2) Putting polyether prepared in the step 1), 45g of modified Raney nickel catalyst and two kilograms of ammonia gas into a 1L autoclave, filling hydrogen gas to an initial pressure of 10-14Mpa, heating, preserving heat for a plurality of hours at the reaction temperature of 200-240 ℃, cooling to room temperature after the reaction is finished, evacuating gas in the autoclave, opening the autoclave, discharging, filtering to remove the catalyst, and then removing water and excessive liquid ammonia from the liquid by reduced pressure distillation to obtain the product polyetheramine. The structural formula is as follows:
detergency simulation evaluation experiment
The detergent properties of the compounds of the examples and comparative examples were evaluated on an L-2 gasoline engine intake valve deposit simulation tester. The polymers of examples and comparative examples were dissolved in base gasoline to prepare gasoline compositions having a polymer content of 300ppm, respectively. These gasoline compositions were each continuously reciprocated at a flow rate of 1.54mL/min to a deposit collecting plate having a deposit collecting plate temperature of 175 ℃. The sediment collection panels were treated and weighed after the end of the experiment and the sediment reduction rate was calculated. The results are shown in Table 1. .
TABLE 1
| Sediment/mg | Deposit decline rate/% | |
| Blank sample | 10.7 | ---- |
| Example 1 | 0.5 | 95.33 |
| Example 2 | 0.6 | 94.39 |
| Example 3 | 0.8 | 92.52 |
| Example 4 | 1.1 | 89.72 |
| Example 5 | 1.4 | 86.92 |
| Example 6 | 2.1 | 80.37 |
| Example 7 | 0.9 | 91.58 |
| Example 8 | 1.0 | 90.65 |
| Comparative example | 1.3 | 87.85 |
As can be seen from Table 1, the polyether amine compound of the present invention has more excellent detergency than the polyether amine synthesized by the conventional method (comparative example), can effectively reduce the formation of gasoline deposits, and has a mild reaction process, readily available raw materials and can be completed in one step. In addition, in contrast to the requirements of GB/T37322-2019, if the measured deposit is less than 2.8mg, the detergent can be preliminarily judged to be capable of being subjected to the next bench test, otherwise, the detergent cannot pass the bench test. As can be seen from Table 1, the detergents of the present invention were evaluated to less than 2.8mg of sediment, and were satisfactory for further evaluation.
The embodiments described herein are for illustrative purposes only and are not intended to limit the scope of the present invention, as various other alternatives, modifications, and improvements may be made by those skilled in the art within the scope of the present invention, and therefore the present invention is not limited to the above embodiments, but only by the appended claims.
Claims (66)
1. Use of a polyetheramine compound having a polymer backbone and one or more structures of formula (I) attached to the polymer backbone by an-O-bond as a cleaning agent
In the formula (I) of the present invention,
* Represents the binding end of an-O-bond;
link represents a linking group and is C 1-10 Hydrocarbylene radicals;
R 1 each independently selected from H, -CH 3 、-CH 2 OH、-CH 2 COOH、-(CH 2 ) 2 COOH、-CH(CH 3 ) 2 、-CH 2 CH(CH 3 ) 2 、-CHCH 3 CH 2 CH 3 、-(CH 2 ) 4 NH 2 、-CH 2 CONH 2 、-(CH 2 ) 2 CONH 2 、
-CH(OH)CH 3 The method comprises the steps of carrying out a first treatment on the surface of the A kind of electronic device with high-pressure air-conditioning system
R 2 Selected from hydrogen;
the preparation method of the polyether amine compound comprises the following steps of preparing the polyether amine compound shown in the formula (IV) and containing-COOH groups and-NH 2 The amino acid of the group is subjected to esterification reaction with polyether shown in a formula (III):
in the formula (IV) of the present invention,
R 3 selected from H, -CH 3 、-CH 2 OH、-CH 2 COOH、-(CH 2 ) 2 COOH、-CH(CH 3 ) 2 、-CH 2 CH(CH 3 ) 2 、-CHCH 3 CH 2 CH 3 、-(CH 2 ) 4 NH 2 、-CH 2 CONH 2 、-(CH 2 ) 2 CONH 2 、
-CH(OH)CH 3 ；
R 4 Selected from H atoms;
the polyether represented by the formula (III) is shown below,
in the formula (III) of the present invention,
R 0 selected from hydrogen atoms and optionally substituted C 1-50 A hydrocarbon group;
n R u The radicals being identical to or different from one another and each independently selected from C 2-24 Linear or branched alkylene;
n represents the average degree of polymerization of the polyether segment and is any number between 1 and 100.
2. The use according to claim 1, R 0 Selected from hydrogen atoms, C 1-20 Linear or branched alkyl, substituted by one or more C' s 1-20 C substituted by straight-chain or branched alkyl groups 6-10 Monocyclic or polycyclic aryl groups and substituted by one or more C' s 1-20 C substituted by straight-chain or branched alkyl groups 3-20 A monocyclic or polycyclic cycloalkyl group;
n R u The radicals being identical to or different from one another and each independently selected from C 2-12 Linear or branched alkylene;
n represents an average degree of polymerization of the polyether segment and is any number between 1 and 50.
3. Use according to claim 2, R 0 Selected from hydrogen atoms, C 5-15 Straight-chain or branched alkyl and substituted by one or more C' s 5-15 Phenyl substituted by straight chain or branched alkyl;
n R u The radicals being identical to or different from one another and each being independently selected from-CH 2 -CH 2 -and-CH 2 -CH(CH 3 )-；
n represents an average degree of polymerization of the polyether segment and is any number between 5 and 25.
4. The use according to claim 1, link is C 1-6 Linear or branched alkylene groups.
5. The method according to claim 4, wherein Link represents C 1-4 Linear or branched alkylene groups.
6. The use according to claim 1, having the structure of formula (II)
In the formula (II) of the present invention,
g represents the main chain of the polyetheramine compound; a kind of electronic device with high-pressure air-conditioning system
p is an integer of 1 to 10.
7. The method according to claim 6, wherein p is an integer from 1 to 3.
8. The use according to claim 7, p is 1.
9. The use according to claim 6, wherein the main chain is a structure obtained by removing p hydroxyl hydrogen atoms from a hydroxyl polymer having p' hydroxyl groups;
p' is an integer of 1 to 10;
p is an integer and 1.ltoreq.p.ltoreq.p'.
10. The use according to claim 9, p' is an integer from 1 to 3.
11. The use according to claim 10, p' being 1.
12. The use according to claim 9, wherein the hydroxyl polymer is at least one selected from the group consisting of polyethers with p 'hydroxyl groups and polyesters with p' hydroxyl groups.
13. The use according to claim 9, wherein the hydroxyl polymer is a polyether with p' hydroxyl groups.
14. The use according to claim 9, wherein the hydroxyl polymer is selected from alkylene glycol polymers.
15. The process according to claim 9, wherein the hydroxyl polymer is a polyether represented by the following formula (III),
16. the use according to claim 1, wherein the polyetheramine compound has a structure represented by the following formula (II-A) or a structure represented by the following formula (II-B) or is polyetheramine represented by the following formula (II-C) and has a molecular weight of 500 to 3000,
17. the use according to claim 16, said molecular weight being 1000-2000.
18. The use according to claim 16, said molecular weight being 1000-1500.
19. Use according to claim 1, wherein the polyetheramine compound comprises at least one ester carbonyl group.
20. The use according to claim 1, wherein the molar ratio of the amino acid of formula (IV) to the polyether of formula (III) is 1:0.1 to 10.
21. The use according to claim 20, wherein the molar ratio of the amino acid of formula (IV) to the polyether of formula (III) is 1:0.5 to 5.
22. The use according to claim 20, wherein the molar ratio of the amino acid of formula (IV) to the polyether of formula (III) is 1:0.5 to 2.
23. The use according to claim 1, wherein the reaction temperature of the amino acid of formula (IV) with the polyether of formula (III) is 80 to 200 ℃.
24. The use according to claim 23, wherein the reaction temperature of the amino acid of formula (IV) with the polyether of formula (III) is 110 to 180 ℃.
25. The use according to claim 1, wherein the esterification reaction is carried out at a pressure of 0.1 to 10MPa.
26. The use according to claim 25, wherein the esterification reaction is carried out at a pressure of 0.1 to 5MPa.
27. The use according to claim 1, wherein the time of the esterification reaction is 2 to 10 hours.
28. The use according to claim 27, wherein the time of the esterification reaction is from 5 to 10 hours.
29. The process according to claim 1, wherein the polyether amine compound is prepared by adding a water-splitting agent to the esterification reaction, wherein the water-splitting agent is selected from one or more of benzene, toluene and petroleum ether.
30. The use according to claim 29, wherein the water-dividing agent is used in an amount of 5 to 20% by mass of the polyether of formula (III).
31. A fuel detergent comprising a polyetheramine compound having a polymer backbone and one or more structures of formula (I) attached to the polymer backbone by an-O-bond, and optionally comprising one or more diluents selected from the group consisting of polyolefin, mineral base oil and polyether
In the formula (I) of the present invention,
* Represents the binding end of an-O-bond;
link represents a linking group and is C 1-10 Hydrocarbylene radicals;
R 1 each independently selected from H, -CH 3 、-CH 2 OH、-CH 2 COOH、-(CH 2 ) 2 COOH、-CH(CH 3 ) 2 、-CH 2 CH(CH 3 ) 2 、-CHCH 3 CH 2 CH 3 、-(CH 2 ) 4 NH 2 、-CH 2 CONH 2 、-(CH 2 ) 2 CONH 2 、
-CH(OH)CH 3 The method comprises the steps of carrying out a first treatment on the surface of the A kind of electronic device with high-pressure air-conditioning system
R 2 Selected from hydrogen;
the preparation method of the polyether amine compound comprises the following steps of preparing the polyether amine compound shown in the formula (IV) and containing-COOH groups and-NH 2 The amino acid of the group is subjected to esterification reaction with polyether shown in a formula (III):
in the formula (IV) of the present invention,
R 3 selected from H, -CH 3 、-CH 2 OH、-CH 2 COOH、-(CH 2 ) 2 COOH、-CH(CH 3 ) 2 、-CH 2 CH(CH 3 ) 2 、-CHCH 3 CH 2 CH 3 、-(CH 2 ) 4 NH 2 、-CH 2 CONH 2 、-(CH 2 ) 2 CONH 2 、
-CH(OH)CH 3 ；
R 4 Selected from H atoms;
the polyether represented by the formula (III) is shown below,
in the formula (III) of the present invention,
R 0 selected from hydrogen atoms and optionally substituted C 1-50 A hydrocarbon group;
n R u The radicals being identical to or different from one another and each independently selected from C 2-24 Linear or branched alkylene;
n represents the average degree of polymerization of the polyether segment and is any number between 1 and 100.
32. The fuel detergent of claim 31, R 0 Selected from hydrogen atoms, C 1-20 Linear or branched alkyl, substituted by one or more C' s 1-20 C substituted by straight-chain or branched alkyl groups 6-10 Monocyclic or polycyclic aryl groups and substituted by one or more C' s 1-20 C substituted by straight-chain or branched alkyl groups 3-20 A monocyclic or polycyclic cycloalkyl group;
n R u The radicals being identical to or different from one another and each independently selected from C 2-12 Linear or branched alkylene;
n represents an average degree of polymerization of the polyether segment and is any number between 1 and 50.
33. The fuel detergent of claim 32, R 0 Selected from the group consisting ofHydrogen atom, C 5-15 Straight-chain or branched alkyl and substituted by one or more C' s 5-15 Phenyl substituted by straight chain or branched alkyl;
n R u The radicals being identical to or different from one another and each being independently selected from-CH 2 -CH 2 -and-CH 2 -CH(CH 3 )-；
n represents an average degree of polymerization of the polyether segment and is any number between 5 and 25.
34. The fuel detergent of claim 31 wherein Link is C 1-6 Linear or branched alkylene groups.
35. The fuel detergent of claim 34 wherein Link represents C 1-4 Linear or branched alkylene groups.
36. The fuel detergent of claim 31 having a structure represented by the following formula (II)
In the formula (II) of the present invention,
g represents the main chain of the polyetheramine compound; a kind of electronic device with high-pressure air-conditioning system
p is an integer of 1 to 10.
37. The fuel detergent of claim 36, wherein p is an integer from 1 to 3.
38. The fuel detergent of claim 37, wherein p is 1.
39. The fuel detergent of claim 31 wherein said backbone is a structure obtained by removing p hydroxyl hydrogen atoms from a hydroxyl polymer having p' hydroxyl groups;
p' is an integer of 1 to 10;
p is an integer and 1.ltoreq.p.ltoreq.p'.
40. The fuel detergent according to claim 39, wherein p' is an integer of 1 to 3.
41. The fuel detergent according to claim 40, p' is 1.
42. The fuel detergent of claim 39 wherein the hydroxyl polymer is at least one selected from the group consisting of polyethers having p 'hydroxyl groups and polyesters having p' hydroxyl groups.
43. The fuel detergent of claim 39 wherein the hydroxyl polymer is a polyether with p' hydroxyl groups.
44. The fuel detergent of claim 39 wherein the hydroxyl polymer is selected from alkylene glycol polymers.
45. The fuel detergent according to claim 39 wherein the hydroxyl polymer is a polyether represented by the following formula (III),
46. the fuel detergent according to claim 31, wherein the polyetheramine compound has a structure represented by the following formula (II-A) or a structure represented by the following formula (II-B) or is a polyetheramine represented by the following formula (II-C) and has a molecular weight of 500 to 3000,
47. the fuel detergent according to claim 46, wherein the molecular weight is 1000 to 2000.
48. The fuel detergent according to claim 46, wherein the molecular weight is 1000 to 1500.
49. The fuel detergent of claim 31, wherein the polyetheramine compound comprises at least one ester carbonyl group.
50. The fuel detergent of claim 31, wherein the molar ratio of the amino acid of formula (IV) to the polyether of formula (III) is 1:0.1 to 10.
51. The fuel detergent according to claim 50, wherein the molar ratio of the amino acid represented by formula (IV) to the polyether represented by formula (III) is 1:0.5 to 5.
52. The fuel detergent according to claim 50, wherein the molar ratio of the amino acid represented by formula (IV) to the polyether represented by formula (III) is 1:0.5-2.
53. The fuel detergent of claim 31, wherein the reaction temperature of the amino acid of formula (IV) and the polyether of formula (III) is 80 to 200 ℃.
54. The fuel detergent according to claim 53, wherein the reaction temperature of the amino acid represented by formula (IV) and the polyether represented by formula (III) is 110 to 180 ℃.
55. The fuel detergent of claim 31 wherein the esterification reaction is at a pressure of 0.1 to 10MPa.
56. The fuel detergent of claim 31 wherein the esterification reaction is at a pressure of 0.1 to 5MPa.
57. The fuel detergent of claim 31 wherein the time of the esterification reaction is from 2 to 10 hours.
58. The fuel detergent of claim 57, wherein the time of the esterification reaction is from 5 to 10 hours.
59. The fuel detergent of claim 31, wherein the polyetheramine compound is prepared by adding a water-splitting agent to the esterification reaction, wherein the water-splitting agent is selected from one or more of benzene, toluene, and petroleum ether.
60. The fuel detergent according to claim 59, wherein the water-splitting agent is used in an amount of 5 to 20% by mass of the polyether represented by formula (III).
61. The fuel detergent of claim 31, wherein the polyetheramine compound comprises 10 to 70 weight percent of the total mass of the fuel detergent.
62. The fuel detergent of claim 61, wherein the polyetheramine compound comprises 30 to 70 weight percent of the total mass of the fuel detergent.
63. The fuel detergent of claim 61, wherein the polyetheramine compound comprises 50 to 70 weight percent of the total mass of the fuel detergent.
64. A fuel composition comprising the fuel detergent according to any one of claims 31 to 63, and a base fuel, wherein the polyether amine compound or the fuel detergent is added in an amount of 30 to 2000mg/kg based on the total mass of the fuel composition, based on the polyether amine compound.
65. The fuel composition of claim 64, wherein said polyetheramine compound or said fuel detergent is added in an amount of 50 to 2000mg/kg.
66. The fuel composition of claim 64, wherein said polyetheramine compound or said fuel detergent is added in an amount of 50 to 1000mg/kg.
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