CN104560240A - Wear-proof clearing agent composition, diesel oil composition and method for improving wear-proof clearing performance of diesel oil - Google Patents
Wear-proof clearing agent composition, diesel oil composition and method for improving wear-proof clearing performance of diesel oil Download PDFInfo
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Abstract
The invention provides a wear-proof clearing agent composition, a diesel oil composition and a method for improving the wear-proof clearing performance of diesel oil. The wear-proof clearing agent composition comprises a wear-proof agent and Mannich base, wherein the wear-proof agent is one or more of C4-C30 aliphatic acid, aliphatic ester, aliphatic alcohol, aliphatic amine and aliphatic ether; Mannich base comprises structure units (1) and (2) shown in the specification, wherein each R1 is independently selected from hydrogen, C1-C4 straight chain or branched chain alkyl and single bond; each R' is independently selected from hydrogen, C1-C6 straight chain or branched chain alkyl; R2 is selected from C1-C12 straight chain or branched chain alkyl; R3 is selected from C1-C6 straight chain or branched chain alkyl; R4 is selected from hydrocarbyl with a number-average molecular weight Mn of 300-3000; each y is independently selected from integers from 2 to 5. The wear-proof clearing agent composition and the diesel oil composition have excellent wear-proof and cleaning performance, the lubricating performance of the diesel oil can be improved, and the generation of sediments in an engine can be inhibited.
Description
Technical field
The present invention relates to a kind of wear-resistant cleaning agent composition, particularly a kind of wear-resistant cleaning agent composition being applicable to diesel oil.
Background technology
Along with environmental regulation is to the raising of engine emission requirements, the sulphur content in diesel oil is more and more lower.In the sweetening process of producing diesel oil, some components with wear-resistant function remove thereupon, thus cause the lubricity of diesel oil greatly to reduce, make the parts such as diesel motor injection pump and oil thrower occur Fast Wearing, and greatly reduce the work-ing life of engine.Unstable component in diesel oil very easily forms colloid with oxygen reaction, and final forms carbon distribution settling, has a strong impact on the serviceability of engine, the problem such as cause engine starting difficulty, unstable idle speed, driving is poor, accelerating ability is poor, power loss is serious.Usually by adding anti-wear agent and purification agent solves the problems referred to above in diesel oil.
US5725612 reports a kind of Mannich base and manufacture method thereof.The alkyl ortho-cresol that this Mannich base is replaced by alkyl and aldehyde, amine react manufacture and obtain, effective in the generation of suppression engine deposits as purification agent.
A kind of Mannich base and manufacture method thereof is reported in US20040168364.This Mannich base reacts manufacture by phenolic compound and aldehyde, amine and obtains, and can suppress the generation of engine deposits as purification agent.
But still there is room for improvement in the purification agent of this kind of prior art in the generation of suppression settling.
Therefore, prior art still needs a kind of composition of wear-resistant purification agent, and it not only can effectively suppress sedimental generation and can also improve the abrasion resistance of diesel oil.
Prior art is it is known that described Mannich reaction is generally carried out under the protection of inert gas atmosphere.As described rare gas element, such as can enumerate nitrogen and argon gas etc., be not particularly limited.
According to the present invention, after the manufacture method of described Mannich base terminates, after removing moisture and the solvent that may exist by any mode that routine is known from the reaction mixture finally obtained, namely obtain Mannich base.
Therefore, the invention still further relates to the Mannich base manufactured according to the manufacture method of the aforesaid Mannich base of the present invention.
According to the present invention, by the manufacture method of aforesaid Mannich base, as reaction product, single a kind of Mannich base of purity very high (purity such as more than 95%) can be produced, also the mixture be made up of multiple Mannich base can be produced, or the mixture be made up of Mannich base described in one or more and aforementioned thinner (if you are using).These reaction product are all desired by the present invention, and the difference of its existence form does not affect the realization of effect of the present invention.Therefore, without distinction these reaction product are all referred to as Mannich base in this context.Given this, according to the present invention, do not exist and be further purified this reaction product, or from this reaction product, isolate the absolute necessity of Mannich base of a certain ad hoc structure further.Certainly, this purifying or separation are preferred for the further lifting of desired result of the present invention, but unrequired in the present invention.
Summary of the invention
The applicant passes through diligent research on the basis of existing technology, find a kind of novel Mannich base, and by further studying discovery, the Mannich base using this novel is to manufacture the composition of anti-wear agent and purification agent and to comprise the Dresel fuel compositions of said composition, just can solve foregoing problems, and this completes the present invention.
Specifically, the present invention relates to the content of following aspect.
1. a wear-resistant cleaning agent composition, comprises anti-wear agent and Mannich base;
Described anti-wear agent is one or more in lipid acid, fatty acid ester, amine, alcohol and ether;
Described Mannich base, comprises following structural unit (I) and structural unit (II):
Wherein, each R
1identical or different, be selected from hydrogen, C independently of one another
1-4straight or branched alkyl and singly-bound, be preferably selected from hydrogen, methyl and singly-bound, is more preferably selected from hydrogen and singly-bound; Each R' is identical or different, is selected from hydrogen and C independently of one another
1-6straight or branched alkyl, is preferably selected from hydrogen and methyl, more preferably hydrogen; R
2be selected from C
1-12straight or branched alkyl, is more preferably selected from C
5-12straight or branched alkyl; R
3be selected from C
1-6straight or branched alkyl, is preferably selected from C
1-4straight or branched alkyl, more preferably methyl; R
4being selected from number-average molecular weight Mn is the preferred 500-2000 of 300-3000(, more preferably 500-1500) alkyl; Each y is identical or different, is selected from the integer of 2-5 independently of one another, and preferably 2 or 3.
Described Mannich base is for shown in following structural formula (III):
Wherein, each A is identical or different, is selected from independently of one another
and hydrogen, preferably
prerequisite is at least one A
each R' is identical or different, is selected from hydrogen and C independently of one another
1-6straight or branched alkyl, is preferably selected from hydrogen and methyl, more preferably hydrogen; Each R
aidentical or different, be selected from hydrogen, C independently of one another
1-4straight or branched alkyl and
be preferably selected from hydrogen, methyl and
more preferably be selected from hydrogen and
prerequisite is at least one R
abe
each R
bidentical or different, be selected from independently of one another hydrogen,
and C
1-4straight or branched alkyl, be preferably selected from hydrogen,
and methyl, be more preferably selected from hydrogen and
prerequisite is at least one R
bbe
r
2be selected from C
1-12straight or branched alkyl, is more preferably selected from C
5-12straight or branched alkyl; R
3be selected from C
1-6straight or branched alkyl, is preferably selected from C
1-4straight or branched alkyl, more preferably methyl; R
4being selected from number-average molecular weight Mn is the preferred 500-2000 of 300-3000(, more preferably 500-1500) alkyl; Each y is identical or different, is selected from the integer of 2-5 independently of one another, and preferably 2 or 3; Each c is identical or different, is selected from the integer of 0-10 independently of one another, is preferably selected from the integer of 2-5, and more preferably 2 or 3.
2. a wear-resistant cleaning agent composition, comprises anti-wear agent and Mannich base;
Described anti-wear agent is one or more in lipid acid, fatty acid ester, amine, alcohol and ether;
The manufacture method of described Mannich base is: comprise the phenolic compound, the phenolic compound of structural formula (VI), the polyalkylenepolyamines of structural formula (VII) and the C that make structure formula V
1-C
7there is the step of Mannich reaction in straight or branched saturated aliphatic aldehyde (preferred acetaldehyde or formaldehyde, more preferably formaldehyde, especially formalin, paraformaldehyde or paraformaldehyde form),
Wherein, R
2be selected from C
1-12straight or branched alkyl, is more preferably selected from C
5-12straight or branched alkyl; R
3be selected from C
1-6straight or branched alkyl, is preferably selected from C
1-4straight or branched alkyl, more preferably methyl; R
4being selected from number-average molecular weight Mn is the preferred 500-2000 of 300-3000(, more preferably 500-1500) alkyl; Each R'
bidentical or different, be selected from hydrogen and C independently of one another
1-4straight or branched alkyl, is preferably selected from hydrogen and methyl, more preferably hydrogen, and prerequisite is at least two R'
bbe hydrogen, more preferably relative two ends of the molecular chain of the polyalkylenepolyamines of formula (VII) respectively have at least one R'
bhydrogen; Y is selected from the integer of 2-5, and preferably 2 or 3; C' is selected from the integer of 1-11, is preferably selected from the integer of 3-6, and more preferably 3 or 4.
The manufacture method of the Mannich base of any preceding aspect, carry out one of in such a way:
Mode (1): comprise the following steps:
First step: make the polyalkylenepolyamines of the phenolic compound of described structural formula (VI), described structural formula (VII) and described C
1-C
7there is Mannich reaction in straight or branched saturated aliphatic aldehyde, generate intermediate product under temperature of reaction 50 DEG C-200 DEG C (preferably 60 DEG C-150 DEG C, most preferably 80 DEG C-130 DEG C); With
Second step: make the phenolic compound of described intermediate product and described structure formula V and described C
1-C
7there is Mannich reaction in straight or branched saturated aliphatic aldehyde, generate described Mannich base under temperature of reaction 40 DEG C-200 DEG C (preferably 60 DEG C-150 DEG C, most preferably 80 DEG C-130 DEG C),
Or
Mode (2): comprise the following steps:
First step: make the polyalkylenepolyamines of the phenolic compound of described structure formula V, described structural formula (VII) and described C
1-C
7there is Mannich reaction in straight or branched saturated aliphatic aldehyde, generate intermediate product under temperature of reaction 40 DEG C-200 DEG C (preferably 60 DEG C-150 DEG C, most preferably 80 DEG C-130 DEG C); With
Second step: make the phenolic compound of described intermediate product and described structural formula (VI) and described C
1-C
7there is Mannich reaction in straight or branched saturated aliphatic aldehyde, generate described Mannich base under temperature of reaction 50 DEG C-200 DEG C (preferably 60 DEG C-150 DEG C, most preferably 80 DEG C-130 DEG C),
Or
Mode (3): comprise the polyalkylenepolyamines and described C that make the phenolic compound of described structure formula V, the phenolic compound of described structural formula (VI), described structural formula (VII)
1-C
7mannich reaction is there is and generates the step of described Mannich base in straight or branched saturated aliphatic aldehyde under temperature of reaction 40 DEG C-200 DEG C (preferably 60 DEG C-150 DEG C, most preferably 80 DEG C-130 DEG C).
The manufacture method of the Mannich base of any preceding aspect, wherein in the first step of described mode (1), the phenolic compound of described structural formula (VI), the polyalkylenepolyamines of described structural formula (VII) and described C
1-C
7mol ratio between straight or branched saturated aliphatic aldehyde is 1:0.3-3:0.3-3.5, preferred 1:0.4-2:0.4-2.5, more preferably 1:0.5-1.5:0.5-2; In the second step of described mode (1), the phenolic compound of described intermediate product and described structure formula V and described C
1-C
7mol ratio between straight or branched saturated aliphatic aldehyde is 1:0.2-1.5:0.2-2, preferred 1:0.3-1:0.2-1.5, more preferably 1:0.3-0.8:0.3-1.5; In the first step of described mode (2), the polyalkylenepolyamines of the phenolic compound of described structure formula V, described structural formula (VII) and described C
1-C
7mol ratio between straight or branched saturated aliphatic aldehyde is 1:1.5-2.5:1.5-3, preferred 1:1.7-2.5:1.7-2.8, more preferably 1:1.7-2.2:1.7-2.5; In the second step of described mode (2), the phenolic compound of described intermediate product and described structural formula (VI) and described C
1-C
7mol ratio between straight or branched saturated aliphatic aldehyde is 1:1.5-3:1.5-3, preferred 1:1.7-2.5:1.7-3, more preferably 1:1.7-2.3:1.7-2.5; In described mode (3), the polyalkylenepolyamines of the phenolic compound of described structure formula V, the phenolic compound of described structural formula (VI), described structural formula (VII) and described C
1-C
7mol ratio between straight or branched saturated aliphatic aldehyde is 1:1-5:1-3:2-8, preferred 1:1.5-4.5:1.5-2.5:3-7, more preferably 1:1.8-4.3:1.8-2.3:3.5-6.5.
The manufacture method of the Mannich base of any preceding aspect, wherein said Mannich reaction is carried out under the existence being selected from one or more the thinner in polyolefine, mineral base oil and polyethers.
The manufacture method of the Mannich base of any preceding aspect, the phenolic compound of wherein said structural formula (VI) is by under catalyst for alkylation reaction existence, the phenolic compound of structural formula (IV) and number-average molecular weight Mn is made to be the preferred 500-2000 of 300-3000(, more preferably 500-1500) polyolefine generation alkylated reaction manufacture, described polyolefine is preferably by ethene, propylene or C
4-C
10the homopolymerization of alpha-olefin or the polyolefine obtained by two or more copolymerization in these alkene, more preferably polyisobutene,
Wherein R
3definition with aspect 3.
Described anti-wear agent in wear-resistant cleaning agent composition of the present invention is one or more in the lipid acid of C4 ~ C30, fatty acid ester, fatty alcohol, aliphatic amide and aliphatic ether, such as can select in caproic acid, capric acid, dodecylic acid, hexadecanoic acid, stearic acid, capric acid butyl ester, dodecanoate, tetradecanoic acid monooctyl ester, hexadecanoic acid propyl ester, butyl stearate, octanol, undecyl alcohol, tetradecyl alcohol, V-1326, octylame, 1,5-pentamethylene diamine, n-Laurylamine, dodecane dimethylamine, b-butyl ether, butyl ether, amyl ether, first heptyl ether and second octyl ether one or more.
One or more in the lipid acid of the preferred C12 ~ C24 of described anti-wear agent, fatty acid ester and fatty alcohol.
In wear-resistant cleaning agent composition of the present invention, the mass ratio between described anti-wear agent and described Mannich base is 10:1 ~ 1:10, preferred 8:1 ~ 1:8, most preferably 5:1 ~ 1:5.
3. a Dresel fuel compositions, comprise Base Diesel and the wear-resistant cleaning agent composition according to any preceding aspect, wherein said wear-resistant cleaning agent composition accounts for 30 ~ 2000mg/kg of Dresel fuel compositions total mass, preferably 50 ~ 2000mg/kg, more preferably 50 ~ 1000mg/kg.Described Base Diesel can select ordinary diesel oil and/or biofuel.
4. improving a method for the wear-resistant cleansing performance of diesel oil, is joined in diesel oil by the wear-resistant cleaning agent composition of any preceding aspect.
Technique effect
Wear-resistant cleaning agent composition of the present invention and Dresel fuel compositions have excellent wear-resistant, cleansing performance, can improve the lubricity of diesel oil, suppress sedimental generation in engine.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum spectrogram of embodiment 1 polyisobutenyl ortho-cresol.
Fig. 2 is the phenyl ring district nucleus magnetic hydrogen spectrum spectrogram of embodiment 1 polyisobutenyl ortho-cresol.
Fig. 3 is the nucleus magnetic hydrogen spectrum spectrogram contrast of embodiment 2 Mannich base and embodiment 1 polyisobutenyl ortho-cresol.
Fig. 4 is embodiment 2 Mannich base and embodiment 1 polyisobutenyl ortho-cresol phenyl ring district nucleus magnetic hydrogen spectrum spectrogram comparison diagram.
Fig. 5 is the GPC spectrogram of embodiment 1 polyisobutenyl ortho-cresol.
Fig. 6 is the GPC spectrogram of embodiment 2 Mannich base.
Fig. 7 is the GPC spectrogram of embodiment 5 Mannich base.
Embodiment
Below the specific embodiment of the present invention is described in detail.
When clearly not indicating, all percentage ratios, number, ratio etc. mentioned in this specification sheets are all benchmark with weight, unless do not met the routine understanding of those skilled in the art when being benchmark with weight.
In the context of the present specification, in case of no particular description, number-average molecular weight Mn is measured by gel permeation chromatography (GPC).
In the context of the present specification, in case of no particular description, the condition determination of any gel permeation chromatography (GPC) of relating to or GPC spectrogram is: instrument: Waters, US waters2695 type gel osmoticing chromatogram analysis instrument; Moving phase adopts tetrahydrofuran (THF), and flow velocity is 1mL/min, and chromatogram column temperature is 35 DEG C, elution time 40min, and sample quality mark is 0.16%-0.20%.
According to the present invention, first relate to a kind of Mannich base, it comprises following structural unit (I) and structural unit (II):
In these structural units, each R
1identical or different, be selected from hydrogen, C independently of one another
1-4straight or branched alkyl and singly-bound; Each R' is identical or different, is selected from hydrogen and C independently of one another
1-6straight or branched alkyl; R
2be selected from C
1-12straight or branched alkyl; R
3be selected from C
1-6straight or branched alkyl; R
4be selected from the alkyl that number-average molecular weight Mn is 300-3000; Each y is identical or different, is selected from the integer of 2-5 independently of one another.
According to the present invention, described R
1preferably be selected from hydrogen, methyl and singly-bound independently of one another, be more preferably selected from hydrogen and singly-bound independently of one another.
According to an embodiment of the invention, with regard to the contraposition alkylphenol unit being in described structural unit (I) center, two R preferably on the left of it
1in one be singly-bound, and another is methyl or hydrogen, and two R on the right side of it
1in one be singly-bound, and another is methyl or hydrogen.In addition, in described structural unit (II), preferably two R
1in one be singly-bound, and another is methyl or hydrogen.
According to the present invention, described R' is identical or different separately, preferably identical, and is preferably selected from hydrogen and methyl independently of one another, more preferably hydrogen.
According to the present invention, described R
2be preferably selected from C
5-12straight or branched alkyl, more preferably C
8-12the octyl group of straight or branched alkyl, such as octyl group, decyl, nonyl, undecyl or dodecyl, especially straight chain, decyl, nonyl, undecyl or dodecyl.
According to the present invention, described R
3be preferably selected from C
1-4straight or branched alkyl, more preferably methyl or ethyl.
According to the present invention, be the alkyl of 300-3000 as described number-average molecular weight Mn, the alkyl (being called polyolefine residue) obtained after the polyolefine (especially the end of this molecular polyolefin chain) that such as can to enumerate from number-average molecular weight Mn be 300-3000 removes a hydrogen atom.Wherein, as the number-average molecular weight Mn of described polyolefine or described polyolefine residue, preferred 500-2000, more preferably 500-1500.As described polyolefine, such as can enumerate by ethene, propylene or C
4-C
10the homopolymerization of alpha-olefin (such as n-butene, iso-butylene, positive amylene, n-hexylene, positive octene or positive decene) or the polyolefine obtained by the copolymerization of two or more in these alkene, wherein more preferably polyisobutene (PIB).
According to the present invention, described y is identical or different, preferably identical.Described y preferably 2 or 3, more preferably 2.
According to the present invention, so-called " Mannich base comprises structural unit (I) and structural unit (II) ", its implication is: can detect that in described Mannich base described structural unit (I) and described structural unit (II) coexist.For this reason, according to the present invention, described Mannich base can be single a kind of compound, exists, be namely present in the structure of this compound simultaneously in the structure of this compound while can detecting or tell these two kinds of structural units.In addition, described Mannich base also can be the mixture of multiple compounds, as long as exist can detect or tell these two kinds of structural units from this mixture while.Now, these two kinds of structural units can be present in the structure of same compound simultaneously, also can be present in the structure of different compound respectively, wherein preferably the former.Preferably, this mixture comprises at least one compound, and wherein these two kinds of structural units are present in the structure of this compound simultaneously.This detection herein related to or resolution means are that this area routine uses, and such as can enumerate 1H-NMR or gel permeation chromatography (GPC).
According to the present invention, when being present at the same time in the structure of a compound, these two kinds of structural units can by sharing common unit each other
and Direct Bonding, also can pass through linking group
(definition of described y is the same, and preferably identical with the y in structural unit (II) with structural unit (I); Described R
1definition the same; Described x is the integer of the integer of 0-8, preferred 0-3, more preferably 1) and at respective singly-bound place or R
1(only work as R
1when being singly-bound) place's indirect linkage.
According to the present invention, in described Mannich base, the mol ratio of described structural unit (I) and described structural unit (II) is generally 1:1 to 1:15, preferred 1:1 to 1:8, more preferably 1:2 to 1:6, or 1:2 to 1:4.
According to an embodiment of the invention, be substantially made up of described structural unit (I), described structural unit (II) and optional described linking group in described Mannich base.Here so-called " substantially " refers to, except structural unit (I), structural unit (II) even and if other structural units except linking group or group exist, also overall below the 5mol% of described Mannich base is only accounted for, preferred below 2mol%, more preferably below 0.5mol%, or exist as (inevitably) impurity.
According to an embodiment of the invention, described Mannich base is as shown in following structural formula (III).
In this structural formula, each A is identical or different, is selected from independently of one another
and hydrogen, to be at least one A be prerequisite
each R' is identical or different, is selected from hydrogen and C independently of one another
1-6straight or branched alkyl; Each R
aidentical or different, be selected from hydrogen, C independently of one another
1-4straight or branched alkyl and
prerequisite is at least one R
abe
each R
bidentical or different, be selected from independently of one another hydrogen,
and C
1-4straight or branched alkyl, prerequisite is at least one R
bbe
r
2be selected from C
1-12straight or branched alkyl; R
3be selected from C
1-6straight or branched alkyl; R
4be selected from the alkyl that number-average molecular weight Mn is 300-3000; Each y is identical or different, is selected from the integer of 2-5 independently of one another; Each c is identical or different, is selected from the integer of 0-10 independently of one another.
According to the present invention, described A is preferably identical, is more preferably
According to the present invention, described R' is identical or different (preferably identical) separately, and be preferably selected from hydrogen and methyl independently of one another, more preferably hydrogen.
According to the present invention, described R
apreferably be selected from independently of one another hydrogen, methyl and
more preferably be selected from hydrogen and
in each described structure
preferably one of them R
abe
and another R
ahydrogen or methyl, or two R
abe
According to the present invention, described R
bpreferably be selected from independently of one another hydrogen,
and methyl, be more preferably selected from independently of one another hydrogen and
According to the present invention, in described structural formula (III), preferably whole R
bin 1-15 be
or all R
bin 1-8 be
or all R
bin 2-6 be
or all R
bin 2-4 be
or all R
bin 4 be
and remaining R
bhydrogen or methyl.
According to the present invention, described R
2be preferably selected from C
5-12straight or branched alkyl, more preferably C
8-12the octyl group of straight or branched alkyl, such as octyl group, decyl, nonyl, undecyl or dodecyl, especially straight chain, decyl, nonyl, undecyl or dodecyl.
According to the present invention, described R
3be preferably selected from C
1-4straight or branched alkyl, more preferably methyl or ethyl.
According to the present invention, be the alkyl of 300-3000 as described number-average molecular weight Mn, the alkyl (being called polyolefine residue) obtained after the polyolefine (especially the end of this molecular polyolefin chain) that such as can to enumerate from number-average molecular weight Mn be 300-3000 removes a hydrogen atom.Wherein, as the number-average molecular weight Mn of described polyolefine or described polyolefine residue, preferred 500-2000, more preferably 500-1500.As described polyolefine, such as can enumerate by ethene, propylene or C
4-C
10the homopolymerization of alpha-olefin (such as n-butene, iso-butylene, positive amylene, n-hexylene, positive octene or positive decene) or the polyolefine obtained by the copolymerization of two or more in these alkene, wherein more preferably polyisobutene (PIB).
According to the present invention, described y is identical or different, preferably identical.Described y preferably 2 or 3, more preferably 2.
According to the present invention, described c is identical or different, is preferably selected from the integer of 2-5 independently of one another, and more preferably 2 or 3.
According to the present invention, aforesaid Mannich base can exist with the form of single one (pure) compound, manufactures or use, can exist with the form of wherein two or more mixture (in any proportion), manufacture or use, this does not affect the realization of effect of the present invention yet.
According to the present invention, aforesaid Mannich base such as can be manufactured by following manufacture method.
According to the present invention, described manufacture method comprises the phenolic compound, the phenolic compound of structural formula (VI), the polyalkylenepolyamines of structural formula (VII) and the C that make structure formula V
1-C
7the step of straight or branched saturated aliphatic aldehyde generation Mannich reaction.
Wherein, R
2be selected from C
1-12straight or branched alkyl; R
3be selected from C
1-6straight or branched alkyl; R
4be selected from the alkyl that number-average molecular weight Mn is 300-3000; Each R'
bidentical or different, be selected from hydrogen and C independently of one another
1-4straight or branched alkyl, prerequisite is at least two R'
bhydrogen; Y is selected from the integer of 2-5; C' is selected from the integer of 1-11.
According to the present invention, described R
2be preferably selected from C
5-12straight or branched alkyl, more preferably C
8-12the octyl group of straight or branched alkyl, such as octyl group, decyl, nonyl, undecyl or dodecyl, especially straight chain, decyl, nonyl, undecyl or dodecyl.
According to the present invention, described R
3be preferably selected from C
1-4straight or branched alkyl, more preferably methyl or ethyl.
According to the present invention, be the alkyl of 300-3000 as described number-average molecular weight Mn, the alkyl (also referred to as polyolefine residue) obtained after the polyolefine (especially the end of this molecular polyolefin chain) that such as can to enumerate from number-average molecular weight Mn be 300-3000 removes a hydrogen atom.Wherein, as the number-average molecular weight Mn of described polyolefine or described polyolefine residue, preferred 500-2000, more preferably 500-1500.
In the context of the present specification, depend on the difference of starting polyolefin kind or manufacture method, described polyolefine residue may be saturated (being rendered as chain alkyl), also a certain amount of olefinic double bond (such as remaining in polyolefin manufacturing process) may be contained in polymer chain, but this does not affect the realization of effect of the present invention, the present invention also has no intention to carry out clearly this amount.
As described polyolefine, such as can enumerate by ethene, propylene or C
4-C
10the homopolymerization of alpha-olefin (such as n-butene, iso-butylene, positive amylene, n-hexylene, positive octene or positive decene) or the polyolefine obtained by the copolymerization of two or more in these alkene, wherein more preferably polyisobutene (PIB).
According to the present invention, the phenolic compound of described structural formula (VI) can by under catalyst for alkylation reaction existence, (number-average molecular weight Mn is 300-3000 to make the phenolic compound of structural formula (IV) and described polyolefine, preferred 500-2000, more preferably 500-1500) there is alkylated reaction and manufacture.Certainly, the phenolic compound of described structural formula (VI) also directly can use commercially available prod.
Wherein R
3definition cotype (VI), more preferably methyl.
According to the present invention, described polyolefine is preferably by ethene, propylene or C
4-C
10the homopolymerization of alpha-olefin or the polyolefine obtained by two or more copolymerization in these alkene.As described C
4-C
10alpha-olefin, such as can enumerate n-butene, iso-butylene, positive amylene, n-hexylene, positive octene and positive decene.
According to the present invention, at least 20wt%(preferably at least 50wt% in these polyolefine, more preferably at least 70wt%) polymer chain contain olefinic double bond at its end.This olefinic double bond is generally exist with the form of the vinylidene of high reaction activity or vinyl.
According to the present invention, as described polyolefine, more preferably polybutene.Except as otherwise noted, term as used herein " polybutene " broadly comprises the polymkeric substance obtained by 1-butylene or isobutylene homopolymerisation, and by two or three in 1-butylene, 2-butylene and iso-butylene by copolymerization and obtained polymkeric substance.Other olefinic component of negligible quantity also may be contained in the commercially available prod of this base polymer, but this does not affect enforcement of the present invention.
According to the present invention, as described polyolefine, preferred polyisobutene (PIB) or high-activity polyisobutylene (HR-PIB) further.In this kind of polyisobutene, at least 20wt%(preferably at least 50wt%, more preferably at least 70wt%) total terminal ethylenic double bond provided by methyl vinylidene.
As described catalyst for alkylation reaction, such as can enumerate Lewis acid catalyst, such as be selected from aluminum chloride, boron trifluoride, tin tetrachloride, titanium tetrabromide, boron trifluoride phenol, boron trifluoride alcohol complex and boron trifluoride ether complex one or more, wherein preferably boron trifluoride ethyl ether complex and/or boron trifluoride methanol complex compound.These catalyst for alkylation reaction can directly use commercially available product.
According to the present invention, in described alkylated reaction, mol ratio between described polyolefine, the phenolic compound of described structural formula (IV), described catalyst for alkylation reaction can be such as 1:1-3:0.1-0.5, preferred 1:1.5-3:0.1-0.4, most preferably 1:1.5-3:0.2-0.4, but be sometimes not limited to this.
According to the present invention, the reaction times of described alkylated reaction is such as 0.5h-10h, preferred 1h-8h, most preferably 3h-5h, but is sometimes not limited to this.
According to the present invention, the temperature of reaction of described alkylated reaction is such as 0 DEG C-200 DEG C, preferably 10 DEG C-150 DEG C, most preferably 20 DEG C-100 DEG C, but is sometimes not limited to this.
According to the present invention, described alkylated reaction can carry out in the presence of the solvent.As described solvent, such as C can be enumerated
6-10alkane (such as hexane, heptane, octane, nonane or decane etc.).Wherein, preferably use hexane and heptane, more preferably use hexane.
According to the present invention, after described alkylated reaction terminates, remove catalyst for alkylation reaction, unreacted reactant and the solvent that may use by conventional methods from the reaction mixture finally obtained after, namely obtain described structural formula (VI) phenolic compound.
According to the present invention, described R'
bidentical or different, be preferably selected from hydrogen and methyl independently of one another.It is further preferred that relative two ends of the molecular chain of the polyalkylenepolyamines of formula (VII) respectively have at least one R'
bhydrogen, namely following formula (VII-1).
Wherein R'
b, y and c' definition cotype (VII).
According to the present invention, as described polyalkylenepolyamines, such as can enumerate be selected from Diethylenetriamine, three second tetramines, tetraethylene-pentamine, five second hexamines, six second seven amine, seven second eight amine, eight second nine amine, nine second ten amine and ten second undecylamines one or more, wherein preferred Diethylenetriamine.
According to the present invention, described polyalkylenepolyamines such as can be reacted by ammonia and alkylene dihalide such as dichloro alkanes and manufacture, and also can directly use commercially available product.
According to the present invention, y preferably 2 or 3.
According to the present invention, c' is preferably selected from the integer of 3-6, and more preferably 3 or 4.
According to the present invention, described C
1-C
7the preferred acetaldehyde of straight or branched saturated aliphatic aldehyde or formaldehyde, more preferably formaldehyde.As described formaldehyde, such as can use its aqueous solution, paraformaldehyde or paraformaldehyde form, be not particularly limited.
According to the present invention, the manufacture method of described Mannich base such as can be carried out one of in such a way.
Mode (1): comprise the following steps:
First step: make the polyalkylenepolyamines of the phenolic compound of described structural formula (VI), described structural formula (VII) and described C
1-C
7there is Mannich reaction in straight or branched saturated aliphatic aldehyde, generate intermediate product under temperature of reaction 50 DEG C-200 DEG C (preferably 60 DEG C-150 DEG C, most preferably 80 DEG C-130 DEG C); With
Second step: make the phenolic compound of described intermediate product and described structure formula V and described C
1-C
7there is Mannich reaction in straight or branched saturated aliphatic aldehyde, generate described Mannich base under temperature of reaction 40 DEG C-200 DEG C (preferably 60 DEG C-150 DEG C, most preferably 80 DEG C-130 DEG C).
Mode (2): comprise the following steps:
First step: make the polyalkylenepolyamines of the phenolic compound of described structure formula V, described structural formula (VII) and described C
1-C
7there is Mannich reaction in straight or branched saturated aliphatic aldehyde, generate intermediate product under temperature of reaction 40 DEG C-200 DEG C (preferably 60 DEG C-150 DEG C, most preferably 80 DEG C-130 DEG C); With
Second step: make the phenolic compound of described intermediate product and described structural formula (VI) and described C
1-C
7there is Mannich reaction in straight or branched saturated aliphatic aldehyde, generate described Mannich base under temperature of reaction 50 DEG C-200 DEG C (preferably 60 DEG C-150 DEG C, most preferably 80 DEG C-130 DEG C).
Mode (3): comprise the polyalkylenepolyamines and described C that make the phenolic compound of described structure formula V, the phenolic compound of described structural formula (VI), described structural formula (VII)
1-C
7mannich reaction is there is and generates the step of described Mannich base in straight or branched saturated aliphatic aldehyde under temperature of reaction 40 DEG C-200 DEG C (preferably 60 DEG C-150 DEG C, most preferably 80 DEG C-130 DEG C).
According to the present invention, from the angle of Mannich base obtaining higher degree, optimal way (1).
According to the present invention, in the first step of described mode (1), the phenolic compound of described structural formula (VI), the polyalkylenepolyamines of described structural formula (VII) and described C
1-C
7mol ratio between straight or branched saturated aliphatic aldehyde is 1:0.3-3:0.3-3.5, preferred 1:0.4-2:0.4-2.5, more preferably 1:0.5-1.5:0.5-2.The present invention has no particular limits in the reaction times to this step, such as can enumerate 1h-10h, preferred 2h-8h, most preferably 3h-6h.
According to the present invention, in the second step of described mode (1), the phenolic compound of described intermediate product and described structure formula V and described C
1-C
7mol ratio between straight or branched saturated aliphatic aldehyde is 1:0.2-1.5:0.2-2, preferred 1:0.3-1:0.2-1.5, more preferably 1:0.3-0.8:0.3-1.5.The present invention has no particular limits in the reaction times to this step, such as can enumerate 1h-10h, preferred 2h-8h, most preferably 3h-6h.
According to the present invention, in the first step of described mode (2), the polyalkylenepolyamines of the phenolic compound of described structure formula V, described structural formula (VII) and described C
1-C
7mol ratio between straight or branched saturated aliphatic aldehyde is 1:1.5-2.5:1.5-3, preferred 1:1.7-2.5:1.7-2.8, more preferably 1:1.7-2.2:1.7-2.5.The present invention has no particular limits in the reaction times to this step, such as can enumerate 1h-10h, preferred 2h-8h, most preferably 3h-6h.
According to the present invention, in the second step of described mode (2), the phenolic compound of described intermediate product and described structural formula (VI) and described C
1-C
7mol ratio between straight or branched saturated aliphatic aldehyde is 1:1.5-3:1.5-3, preferred 1:1.7-2.5:1.7-3, more preferably 1:1.7-2.3:1.7-2.5.The present invention has no particular limits in the reaction times to this step, such as can enumerate 1h-10h, preferred 2h-8h, most preferably 3h-6h.
According to the present invention, in described mode (3), the polyalkylenepolyamines of the phenolic compound of described structure formula V, the phenolic compound of described structural formula (VI), described structural formula (VII) and described C
1-C
7mol ratio between straight or branched saturated aliphatic aldehyde is 1:1-5:1-3:2-8, preferred 1:1.5-4.5:1.5-2.5:3-7, more preferably 1:1.8-4.3:1.8-2.3:3.5-6.5.The present invention has no particular limits in the reaction times to which (3), such as can enumerate 1h-10h, preferred 2h-8h, most preferably 3h-6h.
According to the present invention, aforesaid Mannich reaction can be carried out under the existence of thinner and/or solvent.As described thinner, such as can enumerate be selected from polyolefine, mineral base oil and polyethers one or more.As described solvent, such as C can be enumerated
6-20aromatic hydrocarbon (such as toluene and dimethylbenzene) etc.Wherein, preferably toluene or dimethylbenzene is used.
According to the present invention, described thinner and/or solvent can add according to the conventional amount used of this area in any stage of described Mannich reaction.Such as, can add in the beginning of mode (1) first step or the process of carrying out and/or in the beginning of mode (1) second step or the process of carrying out, in the beginning of mode (2) first step or the process of carrying out and/or in the beginning of mode (2) second step or the process of carrying out or in the beginning of mode (3) or the process of carrying out, be not particularly limited.
According to the present invention, as described mineral base oil, such as can select in API I, II, III class mineral lubricant oil base oil one or more, being preferably selected from 40 DEG C of viscosity is one or more in 20-120 centistoke (cSt), the viscosity index mineral lubricant oil base oil at least more than 50, and being more preferably selected from 40 DEG C of viscosity is one or more in 28-110 centistoke (cSt), the viscosity index mineral lubricant oil base oil at least more than 80.
According to the present invention, as described polyolefine, such as can enumerate by ethene, propylene or C
4-C
10one or more in the homopolymerization of alpha-olefin or the polyolefine that obtained by two or more copolymerization in these alkene, preferably 100 DEG C of viscosity is one or more in the poly-alpha olefins (PAO) of 2-25 centistoke (cSt) (preferably 100 DEG C of viscosity are 6-10 centistoke (cSt)).Wherein, as described C
4-C
10alpha-olefin, such as can enumerate n-butene, iso-butylene, positive amylene, n-hexylene, positive octene and positive decene.In addition, described polyolefinic number-average molecular weight Mn is generally 500-3000, preferred 500-2500, most preferably 500-1500.
According to the present invention, as described polyethers, the polymkeric substance generated by alcohol and epoxide reaction such as can be enumerated.As described alcohol, such as ethylene glycol and/or 1,3-PD can be enumerated.As described epoxide, such as oxyethane and/or propylene oxide can be enumerated.In addition, the number-average molecular weight Mn of described polyethers is generally 500-3000, preferred 700-3000, most preferably 1000-2500.
Embodiment
Below adopt embodiment in further detail the present invention to be described, but the present invention is not limited to these embodiments.
Following table 1 gives the detail of the pharmaceutical chemicals used in embodiment and comparative example.
Table 1
| Reagent name | Specification | Index | Source |
| Ortho-cresol | CP | ≥98.0% | Chemical Reagent Co., Ltd., Sinopharm Group |
| Polyisobutene | HR-PIB | Mn=1000 | Fine chemicals company limited of Jilin Chemical group |
| Diethylenetriamine | CP | ≥98.0% | Beijing Chemical Plant |
| Three second tetramines | CP | ≥95.0% | Chemical Reagent Co., Ltd., Sinopharm Group |
| Tetraethylene-pentamine | CP | ≥90.0% | Chemical Reagent Co., Ltd., Sinopharm Group |
| Formaldehyde | AR | CH 2O：37.0～40.0% | Chemical Reagent Co., Ltd., Sinopharm Group |
| Paraformaldehyde | AR | ≥94.0% | Chemical Reagent Co., Ltd., Sinopharm Group |
| Boron trifluoride diethyl etherate | CP | BF 3：47.0～47.7% | Chemical Reagent Co., Ltd., Sinopharm Group |
Continued 1
| Reagent name | Specification | Index | Source |
| Butanols | CP | ≥98.0 | Chemical Reagent Co., Ltd., Sinopharm Group |
| Toluene | ≥99.7 | Beijing Chemical Plant | |
| Dimethylbenzene | AR | ≥99.0% | Beijing Chemical Plant |
| 4-tert.-amyl phenol | 99% | AlfaAesar (Tianjin) Chemical Co., Ltd. | |
| 4-nonyl phenol | Tokyo changes into Industrial Co., Ltd | ||
| 4-4-dodecylphenol | Tokyo changes into Industrial Co., Ltd |
Anti-wear agent used in the present invention comprises:
Anti-wear agent 1, stearic acid, is labeled as KM-1, Chemical Reagent Co., Ltd., Sinopharm Group;
Anti-wear agent 2, tetradecanoic acid monooctyl ester, is labeled as KM-2, Chemical Industry Science Co., Ltd of Hengchang of Shishi City;
Anti-wear agent 3, V-1326, is labeled as KM-3, Chemical Reagent Co., Ltd., Sinopharm Group;
Anti-wear agent 4, tetradecyl alcohol, is labeled as KM-4, Chemical Reagent Co., Ltd., Sinopharm Group;
Anti-wear agent 5, butyl stearate, is labeled as KM-5, Chemical Reagent Co., Ltd., Sinopharm Group;
The ordinary diesel oil used: the capital mark 0# diesel oil that Sinopec Yanshan Mountain branch office produces;
The biofuel used: the biofuel that the Oleum Gossypii semen biofuel of being produced by Sinopec Shijiazhuang refinery branch office and plam oil biofuel mix with volume ratio 60:40.
Embodiment 1
In the 500ml four-hole boiling flask that agitator, thermometer, prolong and dropping funnel are housed, add the polyisobutene of 34.93g (0.323mol) ortho-cresol, the boron trifluoride diethyl etherate (catalyst for alkylation reaction) of 6.88g (0.048mol), 100ml normal hexane solvent and 161.61g (0.162mol), at 80 DEG C of reaction 2h.After reaction terminates, functional quality mark be the potassium hydroxide solution cleaning reaction mixture of 5% once, and be washed to neutral remove catalyzer with hot water, then underpressure distillation removes desolventizing and unreacted ortho-cresol, obtain polyisobutene ortho-cresol, hydroxyl value is 53.49mgKOH/g.Hydroxy value measuring is with reference to the acetic anhydride method in GB/T7383-2007.
Example reaction formula is as follows:
Fig. 1 is the nucleus magnetic hydrogen spectrum spectrogram of embodiment 1 polyisobutenyl ortho-cresol, and Fig. 2 is the phenyl ring district nucleus magnetic hydrogen spectrum spectrogram of embodiment 1 polyisobutenyl ortho-cresol.Composition graphs 1 and Fig. 2 known: chemical shift 2.261 is the characteristic peak of methyl hydrogen on polyisobutenyl ortho-cresol phenyl ring; Chemical shift 4.516 place is the characteristic peak of hydroxyl hydrogen on polyisobutenyl ortho-cresol phenyl ring; Chemical shift 6.69 place is H1 by the doublet adjoining CH and to split point; The chemical shift 7.06 place doublet that to be H2 to be split point by the CH adjoined; Chemical shift 7.10 place, because on the CH of H3 two ends, H is replaced by methyl and polyisobutenyl respectively, so H3 is 1 unimodal.Be 3 by the Definitions On Integration of methyl hydrogen, obtain the integration of hydrogen on phenyl ring, hydroxyl hydrogen and methyl hydrogen than being 0.97:0.98:0.97:0.97:3.00, close to theoretical 1:1:1:1:3, from nuclear magnetic spectrogram analysis, synthesize the polyisobutenyl ortho-cresol alkylate of the para-orientation of expection.
Embodiment 2
Polyisobutene ortho-cresol 47.16g (0.045mol) obtained in embodiment 1 is added to 500ml to be under nitrogen protection equipped with in the four-hole boiling flask of agitator, thermometer and skimmer; then the quadrol of 2.70g (0.045mol), 3.83g (0.047mol) formaldehyde is added; and the toluene adding 47ml is as reaction solvent; after 80 DEG C of reaction 1.5h; be cooled to room temperature; add the 4-nonyl phenol of 4.97g (0.0225mol), 3.83g (0.047mol) formaldehyde, at 70 DEG C of reaction 1h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, obtains final Mannich base.
Example reaction formula is as follows:
Fig. 3 is the nucleus magnetic hydrogen spectrum spectrogram contrast of embodiment 2 Mannich base and embodiment 1 polyisobutenyl ortho-cresol, and Fig. 4 is embodiment 2 Mannich base and embodiment 1 polyisobutenyl ortho-cresol phenyl ring district nucleus magnetic hydrogen spectrum spectrogram comparison diagram.Can find out from Fig. 3 and Fig. 4: chemical shift 3.7 is that formaldehyde carbonyl transforms the displacement peak of Hydrogen Proton on the methylene radical that generates; Chemical shift 2.45 place is the chemical shift peak of proton on 2 methylene radical on quadrol; Comparative example 2 and embodiment 1 find because hydroxyl ortho-hydrogens remaining on polyisobutenyl ortho-cresol phenyl ring take part in Mannich reaction in addition, the chemical shift peak of the Hydrogen Proton of Gu Benhuanqu is reduced to 2 by 3, has synthesized the Mannich base product of expection from nuclear magnetic spectrogram analysis.
Fig. 5 is the GPC spectrogram of embodiment 1 polyisobutenyl ortho-cresol, and Fig. 6 is the GPC spectrogram of embodiment 2 Mannich base.As can be seen from Fig. 5 and Fig. 6, because the raw material participating in Mannich reaction doubles, the molecular weight of Mannich base product increases to some extent, thus proves the Mannich base product obtaining expection.
Embodiment 3
Polyisobutene ortho-cresol 44.92g (0.043mol) obtained in embodiment 1 is added to 500ml to be under nitrogen protection equipped with in the four-hole boiling flask of agitator, thermometer and skimmer; then the Diethylenetriamine of 4.64g (0.043mol), 3.65g (0.045mol) formaldehyde is added; and the dimethylbenzene adding 47ml is as reaction solvent; after 90 DEG C of reaction 1.5h; be cooled to room temperature; add 5.64g (0.0215mol) 4-4-dodecylphenol, 3.65g (0.045mol) formaldehyde, at 70 DEG C of reaction 1h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, obtains final Mannich base.
Embodiment 4
Polyisobutene ortho-cresol 53.37g (0.051mol) obtained in embodiment 1 is added to 500ml to be under nitrogen protection equipped with in the four-hole boiling flask of agitator, thermometer and skimmer; then the three second tetramines of 7.46g (0.051mol), 4.38g (0.054mol) formaldehyde is added; and the dimethylbenzene adding 54ml is as reaction solvent; after 100 DEG C of reaction 1.5h; be cooled to room temperature; add 2.76g (0.0255mol) p-cresol, 4.38g (0.054mol) formaldehyde, at 80 DEG C of reaction 1h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, obtains final Mannich base.
Embodiment 5
Polyisobutene ortho-cresol 58.80g (0.056mol) obtained in embodiment 1 is added to 500ml to be under nitrogen protection equipped with in the four-hole boiling flask of agitator, thermometer and skimmer; then the Diethylenetriamine of 2.89g (0.028mol), 4.78g (0.059mol) formaldehyde is added; and the toluene adding 53ml is as reaction solvent; after 100 DEG C of reaction 1.5h; be cooled to room temperature; add 1.51g (0.014mol) p-cresol, 2.39g (0.029mol) formaldehyde, at 80 DEG C of reaction 1h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, obtains final Mannich base.
Fig. 7 is the GPC spectrogram of embodiment 5 Mannich base.As can be seen from Fig. 5, Fig. 6 and Fig. 7, because the raw material participating in Mannich reaction doubles, the molecular weight of Mannich base product increases to some extent, thus proves the Mannich base product obtaining expection.
The example reaction formula of embodiment 5 is as follows:
Embodiment 6
Polyisobutene ortho-cresol 40.01g (0.038mol) obtained in embodiment 1 is added to 500ml to be under nitrogen protection equipped with in the four-hole boiling flask of agitator, thermometer and skimmer; then the tetraethylene-pentamine of 3.61g (0.019mol), 3.25g (0.040mol) formaldehyde is added; and the dimethylbenzene adding 38ml is as reaction solvent; after 80 DEG C of reaction 1.5h; be cooled to room temperature; add the 4-nonyl phenol of 2.10g (0.0095mol), 1.63g (0.020mol) formaldehyde, at 70 DEG C of reaction 1h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, obtains final Mannich base.
Embodiment 7
Polyisobutene ortho-cresol 51.33g (0.049mol) obtained in embodiment 1 is added to 500ml to be under nitrogen protection equipped with in the four-hole boiling flask of agitator, thermometer and skimmer; then the three second tetramines of 3.58g (0.024mol), 1.53g (0.051mol) paraformaldehyde is added; and the toluene adding 48ml is as reaction solvent; after 90 DEG C of reaction 1.5h; be cooled to room temperature; add 3.15g (0.012mol) 4-4-dodecylphenol, 0.78g (0.026mol) paraformaldehyde, at 70 DEG C of reaction 1h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, obtains final Mannich base.
Embodiment 8
Quadrol 2.86g (0.048mol) and 4-dodecyl phenol 6.24g (0.024mol) is added to 500ml under nitrogen protection agitator is housed, in the four-hole boiling flask of thermometer and skimmer, then the dimethylbenzene of 49ml is added as reaction solvent, add formaldehyde solution 3.86g (0.048mol) at 50 DEG C and react 0.5 hour, then be warming up to 110 DEG C and continue reaction 2.5 hours, be cooled to 50 DEG C, add polyisobutene ortho-cresol 45.11g (0.043mol) obtained in embodiment 1, after polyisobutene ortho-cresol dissolves completely, add the formaldehyde solution of 3.40g (0.043mol), be warming up to 120 DEG C and continue reaction 2h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, obtains final Mannich base.
Embodiment 9
Three second tetramine 5.70g (0.039mol) and p-cresol 1.95g (0.018mol) are added to 500ml to be under nitrogen protection equipped with in the four-hole boiling flask of agitator, thermometer and skimmer; then the dimethylbenzene of 49ml is added as reaction solvent; 1.41g (0.047mol) paraformaldehyde is added at 80 DEG C; be warming up to 120 DEG C of reactions 2.5 hours gradually; then obtained polyisobutene ortho-cresol 40.91g (0.039mol) is added in embodiment 1 and after dissolving completely; add the paraformaldehyde of 1.20g (0.040mol), continue reaction 2h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, obtains final Mannich base.
Embodiment 10
Polyisobutene ortho-cresol 39.86g (0.038mol), quadrol 2.46g (0.041mol) obtained in embodiment 1,4-tert.-amyl phenol 3.06g (0.019mol) are added to 500ml under nitrogen protection and are equipped with in the four-hole boiling flask of agitator, thermometer and skimmer; and the dimethylbenzene adding 44ml is as reaction solvent; temperature risen to 80 DEG C and stir; the paraformaldehyde of 3.18g (0.106mol) is added after question response system stirs; and be warming up to 130 DEG C gradually, react 4h at this temperature.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, obtains final Mannich base.
Embodiment 11
By polyisobutene ortho-cresol 45.11g (0.043mol) obtained in embodiment 1, tetraethylene-pentamine 4.16g (0.022mol), 4-nonyl phenol 2.42g (0.011mol) is added to 500ml under nitrogen protection and agitator is housed, in the four-hole boiling flask of thermometer and skimmer, and the toluene adding 50ml is as reaction solvent, reaction system is stirred, be warming up to 45 ~ 50 DEG C, drip the formaldehyde solution of 5.92g (0.073mol) gradually and control in 0.5h, reaction is continued 0.5 hour after formaldehyde solution dropwises, then be warming up to 110 DEG C gradually and continue reaction 4h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, obtains final Mannich base.
Comparative example 1
The polyisobutene ortho-cresol 51.27g(0.049mol obtained by embodiment 1) be added to 500ml under nitrogen protection and be equipped with in the four-hole boiling flask of agitator, thermometer and skimmer; then add 9.28g(0.049mol) tetraethylene-pentamine, 4.77g(0.059mol) formaldehyde; and the dimethylbenzene adding 37ml is as reaction solvent, at 80 DEG C of reaction 1.5h.After reaction terminates, underpressure distillation removes a small amount of water of desolventizing and generation, obtains final Mannich base.
Comparative example 2
The polyisobutene ortho-cresol 48.27g(0.046mol obtained by embodiment 1) be added to 500ml under nitrogen protection and be equipped with in the four-hole boiling flask of agitator, thermometer and skimmer; then add 3.36g(0.023mol) three second tetramines, 4.46(0.055mol) g formaldehyde; and the toluene adding 45ml is as reaction solvent; be warming up to mixing temperature to stir; drip 4.46(0.055mol) g formaldehyde in reactor, 80 DEG C reaction 1.5h.After reaction terminates, underpressure distillation removes a small amount of water of desolventizing and generation, obtains final Mannich base.
Dresel fuel compositions embodiment 12 ~ 19 and comparative example 3 ~ 8
Anti-wear agent and Mannich base are joined by a certain percentage in different types of Base Diesel respectively, be uniformly mixed the embodiment 12 ~ 19 and comparative example 3 ~ 8 that obtain Dresel fuel compositions, the formula composition of each embodiment and comparative example is in table 2.
Adopt the abrasion resistance of the fixed each Dresel fuel compositions of CEC-F-06-A-96 method evaluation.Instrument is high-frequency reciprocating tester (the High-Frequenency ReciprocatingRig that PCS company of Britain produces, HFRR), the grinding defect diameter (Wear Scar Diameter, WSD) during mensuration 60 DEG C, by correcting the impact of temperature and humidity, must report the result WS1.4.
Tinsel sedimentation is adopted to evaluate the cleansing performance of each Dresel fuel compositions.Instrument is the peace and quiet type determinator of L-3 type derv fuel oil (production of Lanzhou Wei Ke petrochemical industry instrument company), concrete operation method is: the weight weighing the sediment trap of a cleaning, be heated to 250 DEG C, with the flow velocity of 2mL/min, Dresel fuel compositions is continued to flow on sediment trap afterwards, after 50min, sediment trap is toasted under the high temperature of 180 DEG C, oxidation generates one deck paint film, then this sediment trap is flooded 2min in normal heptane, then the weight being attached with sedimental sediment trap is weighed, and it is mg that the difference between clean sediment trap is heavily sediment yield D(unit).
Wear-resistant cleaning agent composition of the present invention has lower sediment yield, lower grinding defect diameter, and illustrate that wear-resistant cleaning agent composition of the present invention and Dresel fuel compositions have better cleansing performance and abrasion resistance, test result is as shown in table 3.
Table 2
Table 3
Claims (10)
1. a wear-resistant cleaning agent composition, comprises anti-wear agent and Mannich base;
Described anti-wear agent is one or more in the lipid acid of C4 ~ C30, fatty acid ester, fatty alcohol, aliphatic amide and aliphatic ether;
Described Mannich base, comprises following structural unit (I) and structural unit (II):
Wherein, each R
1identical or different, be selected from hydrogen, C independently of one another
1-4straight or branched alkyl and singly-bound, be preferably selected from hydrogen, methyl and singly-bound, is more preferably selected from hydrogen and singly-bound; Each R' is identical or different, is selected from hydrogen and C independently of one another
1-6straight or branched alkyl, is preferably selected from hydrogen and methyl, more preferably hydrogen; R
2be selected from C
1-12straight or branched alkyl, is more preferably selected from C
5-12straight or branched alkyl; R
3be selected from C
1-6straight or branched alkyl, is preferably selected from C
1-4straight or branched alkyl, more preferably methyl; R
4being selected from number-average molecular weight Mn is the preferred 500-2000 of 300-3000(, more preferably 500-1500) alkyl; Each y is identical or different, is selected from the integer of 2-5 independently of one another, and preferably 2 or 3.
2. according to wear-resistant cleaning agent composition according to claim 1, it is characterized in that, described Mannich base, as following structural formula (III) represents:
Wherein, each A is identical or different, is selected from independently of one another
and hydrogen, preferably
prerequisite is at least one A
each R' is identical or different, is selected from hydrogen and C independently of one another
1-6straight or branched alkyl, is preferably selected from hydrogen and methyl, more preferably hydrogen; Each R
aidentical or different, be selected from hydrogen, C independently of one another
1-4straight or branched alkyl and
be preferably selected from hydrogen, methyl and
more preferably be selected from hydrogen and
prerequisite is at least one R
abe
each R
bidentical or different, be selected from independently of one another hydrogen,
and C
1-4straight or branched alkyl, be preferably selected from hydrogen,
and methyl, be more preferably selected from hydrogen and
prerequisite is at least one R
bbe
r
2be selected from C
1-12straight or branched alkyl, is more preferably selected from C
5-12straight or branched alkyl; R
3be selected from C
1-6straight or branched alkyl, is preferably selected from C
1-4straight or branched alkyl, more preferably methyl; R
4being selected from number-average molecular weight Mn is the preferred 500-2000 of 300-3000(, more preferably 500-1500) alkyl; Each y is identical or different, is selected from the integer of 2-5 independently of one another, and preferably 2 or 3; Each c is identical or different, is selected from the integer of 0-10 independently of one another, is preferably selected from the integer of 2-5, and more preferably 2 or 3.
3. a wear-resistant cleaning agent composition, comprises anti-wear agent and Mannich base;
Described anti-wear agent is one or more in the lipid acid of C4 ~ C30, fatty acid ester, fatty alcohol, aliphatic amide and aliphatic ether;
The manufacture method of described Mannich base comprises: make the phenolic compound of the phenolic compound of structure formula V, structural formula (VI), the polyalkylenepolyamines of structural formula (VII) and C
1-C
7there is the step of Mannich reaction in straight or branched saturated aliphatic aldehyde (preferred acetaldehyde or formaldehyde, more preferably formaldehyde, especially formalin, paraformaldehyde or paraformaldehyde form),
Wherein, R
2be selected from C
1-12straight or branched alkyl, is more preferably selected from C
5-12straight or branched alkyl; R
3be selected from C
1-6straight or branched alkyl, is preferably selected from C
1-4straight or branched alkyl, more preferably methyl; R
4being selected from number-average molecular weight Mn is the preferred 500-2000 of 300-3000(, more preferably 500-1500) alkyl; Each R'
bidentical or different, be selected from hydrogen and C independently of one another
1-4straight or branched alkyl, is preferably selected from hydrogen and methyl, more preferably hydrogen, and prerequisite is at least two R'
bbe hydrogen, more preferably relative two ends of the molecular chain of the polyalkylenepolyamines of formula (VII) respectively have at least one R'
bhydrogen; Y is selected from the integer of 2-5, and preferably 2 or 3; C' is selected from the integer of 1-11, is preferably selected from the integer of 3-6, and more preferably 3 or 4.
4. according to wear-resistant cleaning agent composition according to claim 3, it is characterized in that, the manufacture method of described Mannich base, carry out one of in such a way:
Mode (1): comprise the following steps:
First step: make the polyalkylenepolyamines of the phenolic compound of described structural formula (VI), described structural formula (VII) and described C
1-C
7there is Mannich reaction in straight or branched saturated aliphatic aldehyde, generate intermediate product under temperature of reaction 50 DEG C-200 DEG C (preferably 60 DEG C-150 DEG C, most preferably 80 DEG C-130 DEG C); With
Second step: make the phenolic compound of described intermediate product and described structure formula V and described C
1-C
7there is Mannich reaction in straight or branched saturated aliphatic aldehyde, generate described Mannich base under temperature of reaction 40 DEG C-200 DEG C (preferably 60 DEG C-150 DEG C, most preferably 80 DEG C-130 DEG C),
Or
Mode (2): comprise the following steps:
First step: make the polyalkylenepolyamines of the phenolic compound of described structure formula V, described structural formula (VII) and described C
1-C
7there is Mannich reaction in straight or branched saturated aliphatic aldehyde, generate intermediate product under temperature of reaction 40 DEG C-200 DEG C (preferably 60 DEG C-150 DEG C, most preferably 80 DEG C-130 DEG C); With
Second step: make the phenolic compound of described intermediate product and described structural formula (VI) and described C
1-C
7there is Mannich reaction in straight or branched saturated aliphatic aldehyde, generate described Mannich base under temperature of reaction 50 DEG C-200 DEG C (preferably 60 DEG C-150 DEG C, most preferably 80 DEG C-130 DEG C),
Or
Mode (3): comprise the polyalkylenepolyamines and described C that make the phenolic compound of described structure formula V, the phenolic compound of described structural formula (VI), described structural formula (VII)
1-C
7mannich reaction is there is and generates the step of described Mannich base in straight or branched saturated aliphatic aldehyde under temperature of reaction 40 DEG C-200 DEG C (preferably 60 DEG C-150 DEG C, most preferably 80 DEG C-130 DEG C).
5., according to wear-resistant cleaning agent composition according to claim 4, it is characterized in that, in the first step of described mode (1), the phenolic compound of described structural formula (VI), the polyalkylenepolyamines of described structural formula (VII) and described C
1-C
7mol ratio between straight or branched saturated aliphatic aldehyde is 1:0.3-3:0.3-3.5, preferred 1:0.4-2:0.4-2.5, more preferably 1:0.5-1.5:0.5-2; In the second step of described mode (1), the phenolic compound of described intermediate product and described structure formula V and described C
1-C
7mol ratio between straight or branched saturated aliphatic aldehyde is 1:0.2-1.5:0.2-2, preferred 1:0.3-1:0.2-1.5, more preferably 1:0.3-0.8:0.3-1.5; In the first step of described mode (2), the polyalkylenepolyamines of the phenolic compound of described structure formula V, described structural formula (VII) and described C
1-C
7mol ratio between straight or branched saturated aliphatic aldehyde is 1:1.5-2.5:1.5-3, preferred 1:1.7-2.5:1.7-2.8, more preferably 1:1.7-2.2:1.7-2.5; In the second step of described mode (2), the phenolic compound of described intermediate product and described structural formula (VI) and described C
1-C
7mol ratio between straight or branched saturated aliphatic aldehyde is 1:1.5-3:1.5-3, preferred 1:1.7-2.5:1.7-3, more preferably 1:1.7-2.3:1.7-2.5; In described mode (3), the polyalkylenepolyamines of the phenolic compound of described structure formula V, the phenolic compound of described structural formula (VI), described structural formula (VII) and described C
1-C
7mol ratio between straight or branched saturated aliphatic aldehyde is 1:1-5:1-3:2-8, preferred 1:1.5-4.5:1.5-2.5:3-7, more preferably 1:1.8-4.3:1.8-2.3:3.5-6.5.
6. according to the wear-resistant cleaning agent composition one of claim 1-5 Suo Shu, it is characterized in that, described anti-wear agent is one or more in the lipid acid of C12 ~ C24, fatty acid ester and fatty alcohol.
7. according to the wear-resistant cleaning agent composition one of claim 1-5 Suo Shu, it is characterized in that, described anti-wear agent is one or more in caproic acid, capric acid, dodecylic acid, hexadecanoic acid, stearic acid, capric acid butyl ester, dodecanoate, tetradecanoic acid monooctyl ester, hexadecanoic acid propyl ester, butyl stearate, octanol, undecyl alcohol, tetradecyl alcohol, V-1326, octylame, 1,5-pentamethylene diamine, n-Laurylamine, dodecane dimethylamine, b-butyl ether, butyl ether, amyl ether, first heptyl ether and second octyl ether.
8. according to the wear-resistant cleaning agent composition one of claim 1-5 Suo Shu, it is characterized in that, the mass ratio between described anti-wear agent and described Mannich base is 10:1 ~ 1:10.
9. a Dresel fuel compositions, comprise the wear-resistant cleaning agent composition that one of Base Diesel and claim 1-5 are described, wherein said wear-resistant cleaning agent composition accounts for 30 ~ 2000mg/kg of Dresel fuel compositions total mass.
10. improving a method for the wear-resistant cleansing performance of diesel oil, is joined in diesel oil by the wear-resistant cleaning agent composition one of claim 1-5 Suo Shu.
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| CN105779085A (en) * | 2016-02-26 | 2016-07-20 | 北京雅士科莱恩石油化工有限公司 | Diesel oil clearing agent containing friction modifier and saving fuel oil and preparing method thereof |
| CN109957441A (en) * | 2019-02-18 | 2019-07-02 | 江苏拉雅科技有限公司 | A kind of lubricating oil composition for diesel engine and preparation method thereof |
| CN111423433A (en) * | 2019-01-10 | 2020-07-17 | 中国石油天然气股份有限公司 | Extracting agent, preparation method and application thereof |
| CN112745971A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Diesel lubricity improver, preparation method thereof and diesel composition |
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| CN103374443A (en) * | 2012-04-26 | 2013-10-30 | 中国石油化工股份有限公司 | Gasoline engine oil composition and preparation method thereof |
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| US20040168364A1 (en) * | 2001-05-04 | 2004-09-02 | Macduff Malcolm G.J. | Ortho-alkylphenol derived mannich detergent composition and concentrate, fuel and method thereof |
| US20080141583A1 (en) * | 2006-12-15 | 2008-06-19 | Afton Chemical Corporation | Mannich detergents for hydrocarbon fuels |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105779085A (en) * | 2016-02-26 | 2016-07-20 | 北京雅士科莱恩石油化工有限公司 | Diesel oil clearing agent containing friction modifier and saving fuel oil and preparing method thereof |
| CN105779085B (en) * | 2016-02-26 | 2018-10-23 | 北京雅士科莱恩石油化工有限公司 | A kind of diesel oil detergent and preparation method thereof for saving fuel oil containing friction improver |
| CN111423433A (en) * | 2019-01-10 | 2020-07-17 | 中国石油天然气股份有限公司 | Extracting agent, preparation method and application thereof |
| CN111423433B (en) * | 2019-01-10 | 2022-02-01 | 中国石油天然气股份有限公司 | Extracting agent, preparation method and application thereof |
| CN109957441A (en) * | 2019-02-18 | 2019-07-02 | 江苏拉雅科技有限公司 | A kind of lubricating oil composition for diesel engine and preparation method thereof |
| CN112745971A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Diesel lubricity improver, preparation method thereof and diesel composition |
| CN112745971B (en) * | 2019-10-29 | 2022-07-15 | 中国石油化工股份有限公司 | Diesel lubricity improver, preparation method thereof and diesel composition |
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