CN113736078A - 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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- CN113736078A CN113736078A CN202010462433.4A CN202010462433A CN113736078A CN 113736078 A CN113736078 A CN 113736078A CN 202010462433 A CN202010462433 A CN 202010462433A CN 113736078 A CN113736078 A CN 113736078A
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- 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
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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
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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
Disclosed are a polyetheramine compound, a preparation method and use thereof. The polyether amine compound has a polymer main chain and one or more structures shown in a formula (I) which are connected with the polymer main chain through-O-bonds, wherein the definition of each group is shown in the specification; the polyether amine compound is prepared by the esterification reaction of amino acid and polyether. The polyetheramine compounds of the present invention are suitable for use as detergents, particularly fuel detergents. Compared with the prior art, the polyether amine compound has the advantages of low preparation cost and simple reaction, and has good cleaning and dispersing properties when used as a fuel detergent.
Description
Technical Field
The invention relates to a polyether amine structure and a preparation method thereof. More particularly, the present invention relates to polyetheramines primarily useful as fuel detergents and to a process for their preparation.
Background
Part of the components of liquid fuels form carbon deposits during the operation of internal combustion engines, which results in poor emissions and reduced fuel economy, and fuel detergents function in liquid fuels to inhibit deposit formation. At present, the development of gasoline detergents has become an integral part of the research, development and application of gasoline engines, and on the one hand, with the progress of internal combustion engine technology, advanced internal combustion engine manufacturing technology puts higher requirements on gasoline detergents, for example, the gasoline detergents are put to higher standards by the increasingly widespread application of direct injection gasoline engines in cylinders.
Incomplete combustion of automotive hydrocarbon fuels results in the formation of deposits at various locations such as gasoline engine intake valves and combustion chambers, which carbon deposits adversely affect engine function and exhaust. For example, deposits in the combustion chamber reduce the volume space, and the compression ratio becomes high, which easily causes a knocking phenomenon. The octane requirement for gasoline increases and continued knock can cause stress fatigue or wear of engine components, resulting in shortened vehicle service life and increased maintenance costs. Therefore, the development of gasoline detergents is particularly important in order to clean deposits and prevent deposits from occurring.
The gasoline detergent as one of fuel oil additives has the structure of macromolecular surfactant molecule, which consists of polar group and non-polar group, the polar group can be adsorbed on the surface of deposit molecule and metal, and the non-polar group can raise the oil solubility and prevent the deposit molecule cluster from depositing on the metal parts, so as to play the role of dispersing and cleaning.
For example, additives of monoamine ether compound type and additives of polyether amine compound type are disclosed in USP3440029, EP310875, JP-B-56-48556, JP-A-3-128933, etc.
These etheramine-based compounds substantially exhibit satisfactory cleaning effects. However, in some cases, such as when the engine speed is increased or decreased frequently, the cleaning effect is not good; and the existing method for preparing the polyether amine 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-removing properties, and a method for producing the same.
In one aspect, the present invention provides novel polyetheramine compounds having a polymer backbone and one or more structures of the formula (I) attached to the polymer backbone via an-O-bond
In the formula (I), the compound is shown in the specification,
represents a binding end of an-O-bond;
link represents a linking group and is a single bond or C1-10Alkylene, preferably C1-6Straight or branched alkylene, more preferably C1-4A linear or branched alkylene group;
R1each independently selected from H, -CH3、-CH2OH、-CH2COOH、-(CH2)2COOH、-CH(CH3)2、-CH2CH(CH3)2、-CH(CH3)CH2CH3、-(CH2)4NH2、-CH2CONH2、-(CH2)2CONH2、
-CH(OH)CH3(ii) a And
R2selected from hydrogen.
In one embodiment of the polyether amine compound according to the present invention, it has a structure represented by the following formula (II):
in the formula (II), the compound is shown in the specification,
g and p-O-linkages together represent the backbone of the polyetheramine compound; and
p is an integer of 1 to 10, preferably an integer of 1 to 3, and more preferably 1.
In another embodiment of the polyether amine compound according to the present invention, the 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.
In another embodiment of the polyether amine compound according to the present invention, the hydroxyl polymer is at least one selected from the group consisting of a polyether having p ' hydroxyl groups and a polyester having p ' hydroxyl groups, preferably a polyether having p ' hydroxyl groups, more preferably an alkylene glycol polymer, particularly preferably a polyether represented by the following formula (III),
in the formula (III), the compound represented by the formula (III),
R0selected from hydrogen atoms and optionally substituted C1-50Preferably selected from hydrogen atoms, C1-20Straight or branched chain alkyl, substituted by one or more C1-20Straight or branched alkyl substituted C6-10Monocyclic or polycyclic aryl and substituted by one or more C1-20Straight or branched alkyl substituted C3-20Monocyclic or polycyclic cycloalkyl group, further preferably selected from hydrogen atom, C5-15Straight or branched chain alkyl and substituted by one or more C5-15Straight or branched chain alkyl substituted phenyl;
n number of RuThe radicals, equal to or different from each other, are each independently selected from C2-24Straight or branched alkylene, preferably each independently selected from C2-12Straight or branched alkylene, more preferably each independently selected from C2-6Straight or branched alkylene, most preferably eachIs independently selected from-CH2-CH2-and-CH2-CH(CH3)-；
n represents the average polymerization degree of the polyether segment, and is an arbitrary number between 1 and 100, preferably an arbitrary number between 1 and 50, and more preferably an arbitrary 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 following formulas, the first and second groups,
R0selected from hydrogen atoms and optionally substituted C1-50Preferably selected from hydrogen atoms, C1-20Straight or branched chain alkyl, substituted by one or more C1-20Straight or branched alkyl substituted C6-10Monocyclic or polycyclic aryl and substituted by one or more C1-20Straight or branched alkyl substituted C3-20Monocyclic or polycyclic cycloalkyl radicals, more preferably selected from hydrogen atoms, C5-15Straight or branched chain alkyl and substituted by one or more C5-15Straight or branched chain alkyl substituted phenyl;
n number of RuThe radicals, equal to or different from each other, are each independently selected from C2-24Straight or branched alkylene, preferably each independently selected from C2-12Straight or branched alkylene, more preferably each independently selected from C2-6Straight or branched alkylene, most preferably each independently selected from-CH2-CH2-and-CH2-CH(CH3)-；
n represents the average polymerization degree of the polyether segment, and is an arbitrary number between 1 and 100, preferably an arbitrary number between 1 and 50, and more preferably an arbitrary number between 5 and 25.
In another embodiment of the polyether amine compound according to the present invention, the polyether amine compound comprises at least one ester carbonyl group in its molecular structure.
In another embodiment of the polyether amine compound according to the present invention, the polyether amine compound may be a single compound comprising the structure of formula (I) or a mixture comprising compounds of formula (I); typically, the polyether amine compound is a mixture comprising a compound having the structure shown in formula (I).
In another aspect, the present invention provides a method for preparing the aforementioned polyether amine compound, comprising reacting a compound having a-COOH group and a-NH group represented by the following formula (IV)2The amino acid of the group is esterified with the polyether of the formula (III)
In the formula (IV), the compound is shown in the specification,
R3selected from H, -CH3、-CH2OH、-CH2COOH、-(CH2)2COOH、-CH(CH3)2、-CH2CH(CH3)2、-CHCH3CH2CH3、-(CH2)4NH2、-CH2CONH2、-(CH2)2CONH2、
-CHOHCH3(ii) a And
R4is an H atom.
In one embodiment of the process 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 amino acid of formula (IV) is reacted with the polyether of formula (III) in a molar ratio of 1:0.1 to 10, preferably 1:0.5 to 5, more preferably 1:0.5 to 2.
In another embodiment of the process according to the invention, the reaction temperature of the amino acid of the formula (IV) with the polyether of the formula (III) is from 80 to 200 ℃ and preferably from 110 to 180 ℃.
In another embodiment of the process according to the invention, the pressure at which the amino acid of formula (IV) is esterified with the polyether of formula (III) is from 0.1 to 10MPa, preferably from 0.1 to 5 MPa.
In another embodiment of the process according to the invention, the reaction time of the esterification reaction 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 method according to the present invention, a water-separating agent may be added in the esterification reaction of the amino acid represented by formula (IV) and the polyether represented by formula (III) to increase the product yield; the water-separating agent includes but is not limited to benzene, toluene, petroleum ether, preferably toluene; the amount of the water separating agent is the conventional amount, and is preferably 5-20% of the mass of the polyether shown in the formula (III).
In a further aspect, the present invention also provides the use of the aforementioned polyether amine compound as a detergent; in particular as a fuel detergent.
In yet another aspect, the present invention provides a fuel detergent comprising the polyether amine compound described above or prepared by the process of the present invention, and optionally a diluent selected from one or more of polyolefins, mineral base oils and polyethers.
In one embodiment of the fuel detergent according to the present invention, the polyether amine compound is 10 to 70 wt%, preferably 30 to 70 wt%, most preferably 50 to 70 wt% of the total mass of the fuel detergent, on a mass basis.
In a further aspect, the present invention provides a fuel composition comprising the aforementioned polyether amine compound or the polyether amine compound prepared according to the method of the present invention or the aforementioned fuel detergent, and a base fuel, wherein the polyether amine 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 polyether amine compound.
When the polyether amine is used as a fuel detergent, the polyether amine has excellent cleaning and dispersing properties. The method used by the invention has the following advantages: firstly, one-step reaction can be completed by a 'one-pot method'; the reaction does not involve high pressure and gas, and is a liquid phase reaction; the raw materials are wide and cheap in source, safe and small in toxic and side effects; the catalyst for esterification is mature and can be selected to obtain the optimal catalyst suitable for the reaction, and the reaction can not be doped with impurities such as halogen and the like, and can not influence the corrosion performance of gasoline when being subsequently added into the gasoline; sixthly, the structure of the amino acid is variable, and different structures of the amino acid and polyether can be esterified to obtain different polyether amine products, such as amino acid with a benzene ring or amino acid without a benzene ring.
Drawings
FIG. 1 is an IR spectrum of a polymer prepared in example 1 of the present invention, wherein the peak of C ═ O of the ester carbonyl group is 1740cm-1The characteristic peak of C-O-C is 1108cm-1。
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated in their entirety by reference. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
When the specification derives materials, substances, methods, steps, devices or components, etc. from the words "known to those skilled in the art", "prior art", or equivalents thereof, the words derived encompass those conventionally used in the art at the time of filing this application, but also include those not currently used, but which would become known in the art to be suitable for a similar purpose.
In the context of the present specification, anything or things which are not mentioned, except where explicitly stated, are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or concepts resulting therefrom are considered part of the original disclosure or original disclosure of the invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such a combination to be clearly unreasonable.
Unless otherwise expressly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise not in accordance with the conventional knowledge of those 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" means fluorine, chlorine, bromine or iodine.
In the present specification, the term "single bond" is sometimes used in the definition of a group. By "single bond", it is meant that the group is absent. For example, assume the formula-CH2-A-CH3Wherein the group a is defined as being selected from the group consisting of a single bond and a methylene group. In this respect, if A is a single bond, this means that the group A is absent, in which case the formula is correspondingly simplified to-CH2-CH3。
In the context of the present specification, unless otherwise specified, the term "optionally substituted" means optionally substituted by one or more (e.g., 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) groups selected from hydroxyl, amino, C1-20Straight or branched alkyl, C5-10Monocyclic or polycyclic cycloalkyl and C6-20Aryl group. As said C1-20Straight or branched alkyl, such as C1-10Straight or branched alkyl, C1-6Straight or branched alkyl or C1-4Straight-chain or branched alkyl groups, such as methyl orAnd (4) ethyl. As said C5-10Monocyclic or polycyclic cycloalkyl, such as C5-8Monocyclic or polycyclic cycloalkyl or C5-7Examples of the monocyclic or polycyclic cycloalkyl group include a cyclopentyl group and a cyclohexyl group. As said C6-20Aryl is, for example, C6-10Specific examples of the aryl group include a phenyl group and a naphthyl group.
In the context of the present specification, the molecular weight refers to the number average molecular weight Mn and is determined by Gel Permeation Chromatography (GPC), unless otherwise specified.
In the context of the present specification, any reference to Gel Permeation Chromatography (GPC) or measurement conditions of a GPC profile, unless otherwise specified, is: the instrument is a Waters model 1515 gel permeation chromatograph of Waters corporation in USA; tetrahydrofuran is adopted as a mobile phase, the flow rate is 1mL/min, the temperature of a chromatographic column is 35 ℃, the outflow time is 33min, and the volume fraction of a sample is 0.1%.
In one aspect, the polyether amine 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-bond:
in the formula (I), the compound represented by the formula (I),
represents a bonding end of an-O-bond, and specifically, the structure represented by the formula (I) is bonded to the-O-bond on the polymer main chain to form a covalent bond through an unbound bond at the position represented by the x, and is further connected to the polymer main chain;
link represents a linking group selected from a single bond and C1-10Alkylene group, herein, as said C1-10Alkylene group, for example, C1-10Straight-chain or branched alkylene, preferably C1-6Straight or branched alkylene, further preferably C1-4A linear or branched alkylene group;
R1independently selected from H, -CH3、-CH2OH、-CH2COOH、-(CH2)2COOH、-CH(CH3)2、-CH2CH(CH3)2、-CHCH3CH2CH3、-(CH2)4NH2、-CH2CONH2、-(CH2)2CONH2、
-CHOHCH3；
R2Selected from hydrogen.
It is noted that the-O-linkage is located on the polymer backbone, forming part of the polymer backbone. In view of the above-mentioned manner of attachment, the structures of formula (I) above are generally attached to the polymer backbone in the form of end groups.
According to one embodiment of the present invention, the polyether amine compound has a structure represented by the following formula (II):
in the formula (II), the compound represented by the formula (II),
g and p-O-bonds together represent the backbone of the polymer, so that both G and-O-bonds are part of the polyetheramine backbone;
p is an integer of 1 to 10, preferably an integer of 1 to 3, and 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 present invention, for example, the polyether amine compound may have the following exemplary structure:
in the formulae (II-A) and (II-B)
R0Selected from hydrogen atoms and optionally substituted C1-50Preferably selected from hydrogen atoms, C1-20Straight or branched chain alkyl, substituted by one or more C1-20Straight or branched alkyl substituted C6-10Monocyclic or polycyclic aryl and substituted by one or more C1-20Straight or branched alkyl substituted C3-20Monocyclic or polycyclic cycloalkyl group, further preferably selected from hydrogen atom, C5-15Straight or branched chain alkyl and substituted by one or more C5-15Straight or branched chain alkyl substituted phenyl;
n number of RuThe radicals, equal to or different from each other, are each independently selected from C2-24Straight or branched alkylene, preferably each independently selected from C2-12Straight or branched alkylene, more preferably each independently selected from C2-6Straight or branched alkylene, more preferably each independently selected from-CH2-CH2-and-CH2-CH(CH3)-；
n represents the average polymerization degree of the polyether chain segment and is selected from any value between 1 and 100, more preferably from any value between 1 and 50, and more preferably from any value between 5 and 25; the other groups and values are defined as described for 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, among others.
Specifically, there may be mentioned polyesters having a corresponding number of free hydroxyl groups and polyethers having a corresponding number of free hydroxyl groups, with polyethers having a corresponding number of free hydroxyl groups being preferred.
Examples of the polyether having a corresponding number of free hydroxyl groups include a polyether having a hydroxyl group at one or both ends of a polymer chain, and a polyether having a larger number of 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, an alkylene glycol polymer represented by the following formula (III):
in the formula (III), the compound represented by the formula (III),
R0selected from hydrogen atoms and optionally substituted C1-50As said C1-50The hydrocarbon group of (2) includes, for example, C1-20Straight or branched chain alkyl, substituted by one or more C1-20Straight or branched alkyl substituted C6-10Monocyclic or polycyclic aryl and substituted by one or more C1-20Straight or branched alkyl substituted C3-20Monocyclic or polycyclic cycloalkyl, especially C5-15Straight or branched chain alkyl, phenyl and cyclohexyl;
wherein, as R0As specific examples of (3), there may be mentioned dodecylphenyl group or nonylphenyl group;
n number of RuThe radicals, equal to or different from each other, are each independently selected from C2-24Straight or branched alkylene, preferably each independently selected from C2-12Straight or branched alkylene, more preferably each independently selected from C2-6Straight or branched alkylene, more preferably each independently selected from-CH2-CH2-and-CH2-CH(CH3) -, more preferably-CH2-CH(CH3)-；
n is the average polymerization degree of the polyether chain segment and is any value between 1 and 100, preferably any value between 1 and 50, and more preferably any value between 5 and 25. Generally speaking, the polymerization degree of the polyether chain segment is between 5 and 25, the nonpolar carbon-oxygen chain is longer, the oil solubility is good, carbon deposition can be better wrapped, and the carbon deposition is dispersed in oil, so that the polyether chain segment has more excellent cleaning and dispersing performances. However, if the polymerization degree is too high, the nonpolar chain of the polyetheramine molecule is too long, and the polyetheramine molecule is not completely adsorbed on the particle surface, and thus the polyetheramine molecule forms a ring or is bonded to the adjacent particle surface, so that the "bridging" flocculation between the particles is caused, and the cleaning effect is not good.
Further, in the formula (III), when R isuWhen two or more are present, different units-O-RuThey may be bonded in random, block or alternating manner in any desired ratio, provided that the overall (average) number of these 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 molecular weight of the polyetheramine is 500 to 2000, preferably 1000 to 1500.
According to another preferred embodiment of the present invention, the molecular weight of the polyether amine compound of the formula (II-A) or (II-B) may be 500 to 2000, preferably 1000 to 1500.
In another aspect, the method of making the polyetheramine compound according to the present invention comprises: containing a-COOH group and-NH represented by the following formula (IV)2The amino acids of the radicals are esterified with polyethers of the formula (III) above:
in the formula (IV), the compound is shown in the specification,
R3selected from H, -CH3、-CH2OH、-CH2COOH、-(CH2)2COOH、-CH(CH3)2、-CH2CH(CH3)2、-CHCH3CH2CH3、-(CH2)4NH2、-CH2CONH2、-(CH2)2CONH2、
-CH(OH)CH3；
R4Is an H atom.
In one embodiment of the process according to the invention, the compound of formula (IV) contains a-COOH group and-NH2The 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. One or more of alanine and phenylalanine are preferred.
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 1:0.1 to 10, preferably 1:0.5 to 5, more preferably 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 reactant raw materials is reduced to the maximum extent, and the cost is reduced.
In one embodiment of the process according to the invention, the esterification reaction temperature of the amino acid of the formula (IV) with the polyether of the 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 the conversion rate can be improved, side reactions can be reduced, and the color and the quality of the product can be controlled.
In one embodiment of the process according to the invention, the pressure of the esterification reaction is from 0.1 to 10MPa, preferably from 0.1 to 5 MPa.
In one embodiment of the process according to the invention, the esterification reaction time is 2 to 10 hours, preferably 5 to 10 hours.
In an alternative embodiment of the process according to the invention, it is also included to add an esterification catalyst, such as hydrogen chloride, concentrated sulfuric acid, p-toluenesulfonic acid, solid acids, thionyl chloride and the like catalysts, to the esterification reaction.
In an alternative embodiment of the method according to the present invention, it may further comprise adding a water-separating agent to the esterification reactant, wherein the water-separating agent includes, but is not limited to, benzene, toluene, petroleum ether, preferably toluene.
In a further alternative embodiment of the process according to the invention, the water-separating agent may be used in an amount which is conventional per se, but is preferably 5% to 20% by mass of the polyether of the formula (III).
The water-separating agent can be removed after the reaction is finished by methods known to those skilled in the art.
The water-separating agent may be removed after the reaction is completed by a method known to those skilled in the art. In addition, after the preparation of the polyetheramine has been completed, the polyetheramine can be obtained by removing the optionally added catalyst and water-separating 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 bases), such as fuel detergents, especially gasoline detergents. The detergent exhibits excellent deposit formation inhibiting properties. Here, the detergent includes any of the polyether amine compounds described previously in the present invention or the polyether amine compound produced according to the production method described previously in 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 invention, as said mineral base oil, one or more of mineral lubricant base oils of APII, II, III groups may be used, preferably one or more selected from mineral lubricant base oils having a viscosity of 20 to 120 centistokes (cSt) at 40 ℃ and a viscosity index of at least 50 or more, more preferably one or more selected from mineral lubricant base oils having a viscosity of 28 to 110 centistokes (cSt) at 40 ℃ and a viscosity index of at least 80 or more.
According to the invention, the polyolefin may be, for example, ethylene, propylene or C4-C10Homopolymers of alpha-olefins or one or more of the polyolefins obtained by copolymerization of two or more of these olefins, preferably one or more Polyalphaolefins (PAO) having a viscosity of 2 to 5 centistokes (cSt) at 100 ℃, preferably a viscosity of 6 to 10 centistokes (cSt) at 100 ℃. Wherein is as C4-C10Examples of the α -olefin include n-butene, isobutene, n-pentene, n-hexene, n-octene, and n-decene. In addition, the number average molecular weight Mn of the polyolefin is generally 500-3000, preferably 500-2500, and most preferably 500-1500.
According to the present invention, examples of the polyether include polymers obtained by reacting an alcohol with an epoxide. 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 number average molecular weight Mn of the polyether is generally 500-3000, preferably 700-3000, and most preferably 1000-2500.
Generally, in the detergents of the invention, the polyetheramine compound comprises 10 to 70 wt%, preferably 30 to 70 wt%, most preferably 50 to 70 wt%, of the total mass of the detergent, on a mass basis.
According to the invention, for the manufacture of the detergent, the polyether amine compound and the diluent (if used) are mixed for 1 to 6 hours at 20 to 60 ℃.
The polyether amine compound or detergent of the present invention is also particularly suitable for producing a fuel composition exhibiting excellent deposit formation-suppressing properties. Thus, according to the present invention, there is further provided a fuel composition comprising any of the polyether amine compounds of the present invention as described above, the polyether amine compound produced by the above-described production process of the present invention or the detergent of the present invention as described above, and a base fuel.
According to the present invention, the polyether amine compound or the detergent is generally 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 polyether amine compound.
According to the present invention, the base fuel includes, for example, base fuels used in spark ignition or compression ignition internal combustion engines, such as motor gasoline, aviation gasoline, and diesel fuel, which contain lead or do not contain lead.
In addition to the polyether amine compound and the detergent, other additional additives may be included in the fuel composition according to the present invention. Examples of the additional additives 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 amount conventionally used in the art.
The invention is further illustrated by the following examples which describe preferred embodiments but are not to be construed as limiting the invention, any person skilled in the art may apply the above-mentioned disclosure to equally varied equivalent embodiments.
The reagents used in the following examples are all commercially available reagents. The evaluation of detergency performance in the examples and comparative examples was evaluated in accordance with the following methods.
A gasoline engine intake valve deposit simulation test method (GB/T37322-2019) is adopted.
Specifically, the intake valve deposit simulation test method of the gasoline engine measures the deposit simulating the intake valve, makes the test gasoline in the oil tank flow through the measuring system and enter the nozzle, mixes with air and sprays the test gasoline in a flat spray mode onto 1 aluminum plate which is weighed and heated to 175 ℃, and collects the deposit quality obtained after the injection of 300mL of test gasoline is finished. The intake system deposit decline rate (%) was determined as the difference between the deposit quality obtained for 300mL of base gasoline and the deposit quality obtained for 300mL of test gasoline divided by the deposit mass fraction obtained for 300mL of base gasoline.
The deposit reduction rate is an important index for evaluating detergency of a detergent, and the larger the value, the stronger the detergency. Measuring the deposit formation amount (m) of the simulated intake valve according to GB/T37322-2019-gasoline engine intake valve deposit simulation test methodIVDMg), the deposit decrease rate (%) was calculated according to the following formula.
Wherein m isIVD,0And mIVDThe simulated intake valve deposit formation amount and mg of blank gasoline and gasoline added with detergent are respectively.
Example 1
The polymer of example 1 was prepared from nonylphenol polyether and alanine. Adding 4.45g (0.050mol) of alanine and 89.7g (0.065mol) of nonylphenol polyoxypropylene ether into a three-neck flask at room temperature, wherein SO accounts for 0.1-5% of the total mass of reactants4 2-/ZrO2Adding 30mL of water-separating agent toluene into the solid super acidic 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, to obtain the polyether amine compound of example 1.
Example 2
The compound of example 2 was prepared from nonylphenol polyether and phenylalanine. Adding 4.45g (0.050mol) of alanine, 103.5g (0.075mol) of nonylphenol polyoxypropylene ether, a p-toluenesulfonic acid esterification catalyst accounting for 0.1-5% of the total mass of reactants, adding 30mL of water-dividing agent toluene, 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-separating agent toluene was removed under reduced pressure to obtain a viscous pale yellow liquid, to obtain 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 and 70.1g (0.055mol) of stearyl alcohol polyoxyethylene polyoxypropylene ether were put into a four-neck flask, 25mL of toluene as a water-separating agent was added, and the mixture was allowed to stand in the presence of SO4 2-/ZrO2And under the condition of a solid super acidic catalyst, heating to 150 ℃ under the protection of nitrogen, stirring, and keeping the reaction for 8 hours to finish the reaction. Filtration was performed using a filter funnel to obtain a mixture. The water-separating agent toluene was removed under reduced pressure to obtain a viscous liquid, to obtain the polyether amine compound of example 3.
Example 4
Example 4 was prepared from stearyl polyoxyethylene polyoxypropylene ether and phenylalanine. Adding 0.050mol of phenylalanine and 70.1g (0.055mol) of octadecanol polyoxyethylene polyoxypropylene ether into a four-neck flask, adding 30mL of water-separating agent toluene, heating to 150 ℃ under the protection of nitrogen in the presence of a p-toluenesulfonic acid catalyst, stirring, and keeping the reaction for 8 hours to finish the reaction. Filtration was performed using a filter funnel to obtain a mixture. The water-separating agent toluene was removed under reduced pressure to obtain a viscous liquid, to obtain the polyether amine compound of example 4.
Example 5
Example 5 was prepared from nonylphenol polyoxypropylene ether and glutamic acid. Adding 7.35g (0.050mol) of glutamic acid, 89.7g (0.065mol) of nonylphenol polyoxypropylene ether and SO accounting for 0.1-5 percent of the total mass of reactants into a three-neck flask at room temperature4 2-/ZrO2Adding 30mL of water-separating agent toluene 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, to obtain the polyether amine compound of example 5.
Example 6
The polymer of example 6 was prepared from nonylphenol polyether and glycine. 3.75g (0.050mol) of glycine and 67.4g (0.06mol) of nonylphenol polyoxypropylene ether are added into a three-neck flask at room temperature, and SO accounting for 0.1-5 percent of the total mass of reactants4 2-/ZrO2Adding 30mL of water-separating agent toluene 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-separating agent toluene was removed under reduced pressure to obtain a viscous pale yellow liquid, to obtain the polyether amine compound of example 6.
Example 7
The polymer of example 7 was prepared from propylene glycol polyoxyethylene allyl ether (Mn ═ 1200) and alanine. 8.26g (0.050mol) alanine, 8, was added to a three-necked flask at room temperature4g (0.07mol) propylene glycol polyether, SO accounting for 0.1-5 percent of the total mass of reactants4 2-/ZrO2Adding 30mL of water-separating agent toluene 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-separating agent toluene was removed under reduced pressure to obtain a viscous pale yellow liquid, to obtain 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. Adding 8.26g (0.050mol) of alanine and 65g (0.065mol) of n-octanol polyether into a three-neck flask at room temperature, wherein SO accounts for 0.1-5% of the total mass of reactants4 2-/ZrO2Adding 30mL of water-separating agent toluene 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-separating agent toluene was removed under reduced pressure to obtain a viscous pale yellow liquid, to obtain the polyether amine compound of example 8.
Comparative example
Preparation of the existing polyetheramines
1) And (3) preparing polyether. A mixture of 220g of nonylphenol and 2.0g of potassium hydroxide was charged to a 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 to react until the pressure did not change and the reaction was continued at 140 ℃ until the pressure did not change. After completion of the reaction, the reaction was cooled to room temperature, neutralized with acetic acid, and washed with water to remove the catalyst. And (3) evaporating under reduced pressure to remove water and volatile matters to obtain the polyether product with the molecular weight of 898.
2) Putting the polyether prepared in the step 1), 45g of modified Raney nickel catalyst and two kilograms of ammonia gas into a 1L autoclave, filling hydrogen to initial pressure of 10-14Mpa, starting heating, keeping the temperature for a plurality of hours at the reaction temperature of 200 plus one material at 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 carrying out reduced pressure distillation on the liquid to remove water and excessive liquid ammonia to obtain the product polyetheramine. The structural formula is as follows:
evaluation experiment for detergency simulation
The cleaning performance of the example and comparative compounds was 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. Each of these gasoline compositions was continuously fed back and forth to the deposit collection plate at a rate of 1.54mL/min, with a deposit collection plate temperature of 175 ℃. After the experiment was completed, the sediment collection plates were treated and weighed and the sediment reduction rate was calculated. The results are shown in Table 1. .
TABLE 1
| Deposit/mg | Reduction of the sediment/%) | |
| 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 cleaning performance of the polyether amine compound of the present invention is more excellent than that of polyether amine synthesized by a conventional method (comparative example), the generation of gasoline deposits can be effectively reduced, the reaction process is mild, the raw materials are easily available, and the reaction 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, it is preliminarily judged that the detergent can be subjected to the next bench test, otherwise it fails. As can be seen from Table 1, when the detergents of the invention are evaluated, the deposits are less than 2.8mg, which meets the requirements and can be further evaluated.
The described embodiments of the present invention are for illustrative purposes only and are not intended to limit the scope of the present invention, and those skilled in the art may make various other substitutions, alterations, and modifications within the scope of the present invention, and thus, the present invention is not limited to the above-described embodiments, but only by the claims.
Claims (18)
1. A polyetheramine compound having a polymer main chain and one or more structures represented by the following formula (I) bonded to the polymer main chain through-O-bonds
In the formula (I), the compound is shown in the specification,
represents a binding end of an-O-bond;
link represents a linking group and is a single bond or C1-10Alkylene, preferably C1-6Straight or branched alkylene, more preferably C1-4A linear or branched alkylene group;
R1each independently selected from H, -CH3、-CH2OH、-CH2COOH、-(CH2)2COOH、-CH(CH3)2、-CH2CH(CH3)2、-CHCH3CH2CH3、-(CH2)4NH2、-CH2CONH2、-(CH2)2CONH2、
-CH(OH)CH3(ii) a And
R2selected from hydrogen.
2. The polyetheramine compound according to claim 1, which has the structure represented by the following formula (II)
In the formula (II), the compound is shown in the specification,
g and p-O-linkages together represent the backbone of the polyetheramine compound; and
p is an integer of 1 to 10, preferably an integer of 1 to 3, and more preferably 1.
3. The polyetheramine compound according to claim 2, wherein the main chain is a structure obtained by removing p (p is an integer, and 1. ltoreq. p.ltoreq.p ') hydroxyl hydrogen atoms 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.
4. The polyether amine compound according to claim 3, wherein the hydroxyl polymer is at least one selected from the group consisting of a polyether having p ' hydroxyl groups and a polyester having p ' hydroxyl groups, preferably a polyether having p ' hydroxyl groups, more preferably an alkylene glycol polymer, particularly preferably a polyether represented by the following formula (III),
in the formula (III), the compound represented by the formula (III),
R0selected from hydrogen atoms and optionally substituted C1-50A hydrocarbon group, preferably selected from a hydrogen atom, C1-20Straight or branched chain alkyl, substituted by one or more C1-20Straight or branched alkyl substituted C6-10Monocyclic or polycyclic aryl and substituted by one or more C1-20Straight or branched alkyl substituted C3-20Monocyclic or polycyclic cycloalkyl group, further preferably selected from hydrogen atom, C5-15Straight or branched chain alkyl and substituted by one or more C5-15Substituted by straight-chain or branched alkyl groupsPhenyl of (a);
n number of RuThe radicals, equal to or different from each other, are each independently selected from C2-24Straight or branched alkylene, preferably each independently selected from C2-12Straight or branched alkylene, more preferably each independently selected from C2-6Straight or branched alkylene, more preferably each independently selected from-CH2-CH2-and-CH2-CH(CH3)-；
n represents the average polymerization degree of the polyether segment, and is an arbitrary number between 1 and 100, preferably an arbitrary number between 1 and 50, and more preferably an arbitrary number between 5 and 25.
5. The polyetheramine compound according to claim 1 or 2, which has a structure represented by the following formula (II-A), a structure represented by the following formula (II-B), or 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 following formulas, the first and second groups,
R0selected from hydrogen atoms and optionally substituted C1-50Preferably selected from hydrogen atoms, C1-20Straight or branched chain alkyl, substituted by one or more C1-20Straight or branched alkyl substituted C6-10Monocyclic or polycyclic aryl and substituted by one or more C1-20Straight or branched alkyl substituted C3-20Monocyclic or polycyclic cycloalkyl radicals, more preferably selected from hydrogen atoms, C5-15Straight or branched chain alkyl and substituted by one or more C5-15Straight or branched chain alkyl substituted phenyl;
n number of RuThe radicals, equal to or different from each other, are each independently selected from C2-24Straight or branched alkylene, preferably each independently selected from C2-12Straight or branched alkylene, more preferably each independently selected from C2-6Straight or branched alkylene, most preferably each independently selected from-CH2-CH2-and-CH2-CH(CH3)-；
n represents the average polymerization degree of the polyether segment, and is an arbitrary number between 1 and 100, preferably an arbitrary number between 1 and 50, and more preferably an arbitrary number between 5 and 25.
6. The polyetheramine compound of claim 1 or 2, which contains at least one ester carbonyl group.
7. A process for producing a polyetheramine compound according to any one of claims 1 to 6, which comprises reacting a compound represented by the following formula (IV) containing a-COOH group and-NH2The amino acids of the radicals are esterified with polyethers of the formula (III) above:
in the formula (IV), the compound is shown in the specification,
R3selected from H, -CH3、-CH2OH、-CH2COOH、-(CH2)2COOH、-CH(CH3)2、-CH2CH(CH3)2、-CHCH3CH2CH3、-(CH2)4NH2、-CH2CONH2、-(CH2)2CONH2、
-CH(OH)CH3；
R4Selected from H atoms.
8. The method according to claim 7, wherein the amino acid represented by formula (IV) is selected from one or more of glycine, serine, threonine, glutamic acid, leucine, alanine, isoleucine, aspartic acid, valine, asparagine, glutamine, lysine, phenylalanine, leucine and arginine.
9. The process according to claim 7, wherein the molar ratio of the amino acid of formula (IV) to the polyether of formula (III) is 1:0.1 to 10, preferably 1:0.5 to 5, more preferably 1:0.5 to 2.
10. The process according to claim 7, wherein the reaction temperature of the amino acid of formula (IV) with the polyether of formula (III) is from 80 to 200 ℃, preferably from 110 to 180 ℃.
11. A process according to claim 7, wherein the pressure of the esterification reaction is from 0.1 to 10MPa, preferably from 0.1 to 5 MPa.
12. A process according to claim 7, wherein the esterification reaction time is 2 to 10 hours, preferably 5 to 10 hours.
13. The method according to any one of the preceding claims 7 to 12, further comprising adding a water-separating agent to the esterification reaction, wherein the water-separating agent is selected from one or more of benzene, toluene and petroleum ether.
14. The method according to claim 14, wherein the amount of the water-separating agent is 5-20% of the mass of the polyether represented by the formula (III).
15. Use of the polyether amine compound according to any one of claims 1 to 6 and the polyether amine compound produced by the method according to any one of claims 7 to 14 as a detergent.
16. A fuel detergent comprising the polyetheramine compound of any one of claims 1 to 6 or the polyetheramine compound produced by the process of any one of claims 7 to 14, and optionally a diluent selected from one or more of polyolefins, mineral base oils and polyethers.
17. The fuel detergent of claim 16, wherein the polyetheramine compound is 10 to 70 wt%, preferably 30 to 70 wt%, most preferably 50 to 70 wt%, of the total mass of the fuel detergent, on a mass basis.
18. A fuel oil composition comprising the polyether amine compound of any one of claims 1 to 6 or the polyether amine compound prepared by the method of any one of claims 7 to 14 or the fuel oil detergent of any one of claims 16 to 17, and a base fuel, wherein the polyether amine compound or the fuel oil 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 oil composition, based on the polyether amine compound.
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