CN104946350B - Lubricant oil composite - Google Patents
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- CN104946350B CN104946350B CN201410112583.7A CN201410112583A CN104946350B CN 104946350 B CN104946350 B CN 104946350B CN 201410112583 A CN201410112583 A CN 201410112583A CN 104946350 B CN104946350 B CN 104946350B
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Abstract
The invention provides a kind of lubricant oil composite, comprising Mannich base, diakylaminomethylene benzotriazole, alkylated diphenylamine and lube base oil, wherein the Mannich base includes following structure unit（I）And construction unit（II）：Wherein, each R1It is identical or different, it is each independently selected from hydrogen, C1‑4Straight or branched alkyl and singly-bound；Each R' is identical or different, is each independently selected from hydrogen and C1‑6Straight or branched alkyl；R2Selected from H, C1‑8Alkyl, hydroxyl or nitro；R3Selected from C1‑6Straight or branched alkyl；R4Selected from the alkyl that number-average molecular weight Mn is 300 3000；Each y is identical or different, is each independently selected from 25 integer.Lubricant oil composite of the invention has excellent detergent-dispersant performance energy and rustless property.
Description
Technical field
The present invention relates to a kind of lubricant oil composite, more particularly to detergent-dispersant performance energy, high rust resistance lubricating oil
Composition.
Background technology
Unsaturated olefin, aromatic hydrocarbons and a small amount of sulfur-containing compound in lube base oil easily form glue with oxygen reaction
Matter, and carbon distribution deposit is ultimately formed, especially can acceleration motor in key positions such as intake valve, piston, oil sump, combustion chambers
The generation of deposit, has a strong impact on the service behaviour of engine, cause engine start difficulty, unstable idle speed, driving it is poor, plus
The problems such as speed is poor, power loss is serious, produces unnecessary expensive maintenance cost.By clear to being added in lube base oil
Used as lube oil additive, prior art is manufactured that with cleansing performance net dispersant（Deposit generates rejection）Profit
Sliding oil composition.Using this lubricant oil composite with cleansing performance, coking and top land carbon deposit can be effectively reduced,
The abrasion of valve system is reduced, the corrosive wear of engine components is reduced, extends safe operation cycle and the spare part service life of engine.
US5725612 reports a kind of Mannich base and its manufacture method.The Mannich base is adjacent by the alkyl that alkyl replaces
Cresols is obtained with aldehyde, amine reaction manufacture, effective in terms of engine deposits generation is suppressed as detersive.
A kind of Mannich base and its manufacture method are reported in US20040168364.The Mannich base is by phenolic compound
Obtained with aldehyde, amine reaction manufacture, the generation of engine deposits can be suppressed as detersive.
The content of the invention
Specifically, the present invention relates to the content of following aspect.
1. a kind of lubricant oil composite, comprising Mannich base, diakylaminomethylene benzotriazole, alkylated diphenylamine and
Lube base oil, wherein the Mannich base includes following structure unit（I）And construction unit（II）：
Wherein, each R1It is identical or different, it is each independently selected from hydrogen, C1-4Straight or branched alkyl and singly-bound, preferably select
From hydrogen, methyl and singly-bound, hydrogen and singly-bound are more preferably selected from；Each R' is identical or different, is each independently selected from hydrogen and C1-6Straight chain
Or branched alkyl, it is preferably selected from hydrogen and methyl, more preferably hydrogen；R2Selected from H, C1-8Alkyl, hydroxyl or nitro, preferably H, C1-4Alkyl
Or hydroxyl, most preferably H；R3Selected from C1-6Straight or branched alkyl, is preferably selected from C1-4Straight or branched alkyl, more preferably methyl；R4
It is 300-3000 selected from number-average molecular weight Mn（It is preferred that 500-2000, more preferably 500-1500）Alkyl；Each y is identical or not
Together, the integer of 2-5, preferably 2 or 3 are each independently selected from.
2. a kind of lubricant oil composite, comprising Mannich base, diakylaminomethylene benzotriazole, alkylated diphenylamine and
Lube base oil, wherein for example following structural formula of the Mannich base（III）It is shown：
Wherein, each A is identical or different, is each independently selected fromAnd hydrogen, preferablyOn condition that at least one A isEach R' is identical or different, each independent
Ground is selected from hydrogen and C1-6Straight or branched alkyl, is preferably selected from hydrogen and methyl, more preferably hydrogen；Each RaIt is identical or different, each solely
On the spot it is selected from hydrogen, C1-4Straight or branched alkyl andBe preferably selected from hydrogen, methyl andBe more preferably selected from hydrogen andPremise
It is at least one RaIt isEach RbIt is identical or different, be each independently selected from hydrogen,And C1-4Straight or branched alkyl, be preferably selected from hydrogen,And methyl, more preferably
Selected from hydrogen andOn condition that at least one RbIt isR2Selected from H, C1-8Alkyl, hydroxyl
Base or nitro, preferably H, C1-4Alkyl or hydroxyl, most preferably H；R3Selected from C1-6Straight or branched alkyl, is preferably selected from C1-4Straight chain
Or branched alkyl, more preferably methyl；R4It is 300-3000 selected from number-average molecular weight Mn（It is preferred that 500-2000, more preferably 500-
1500）Alkyl；Each y is identical or different, is each independently selected from the integer of 2-5, preferably 2 or 3；Each c is identical or different,
The integer of 0-10 is each independently selected from, the integer of 2-5, more preferably 2 or 3 is preferably selected from.
3. a kind of lubricant oil composite, comprising Mannich base, diakylaminomethylene benzotriazole, alkylated diphenylamine and
Lube base oil, wherein the Mannich base is manufactured by following manufacture method, wherein the manufacture method includes
Make structural formula（V）Parahydroxydi-phenylamine compound, structural formula（VI）Phenolic compounds, structural formula（VII）Polyalkylene it is many
Amine and C1-C7Straight or branched saturated aliphatic aldehyde（It is preferred that acetaldehyde or formaldehyde, more preferably formaldehyde, especially formalin, poly
Formaldehyde or paraformaldehyde form）The step of generation Mannich reaction,
Wherein, R2Selected from H, C1-8Alkyl, hydroxyl or nitro, preferably H, C1-4Alkyl or hydroxyl, most preferably H；R3Selected from C1-6
Straight or branched alkyl, is preferably selected from C1-4Straight or branched alkyl, more preferably methyl；R4It is 300- selected from number-average molecular weight Mn
3000（It is preferred that 500-2000, more preferably 500-1500）Alkyl；Each R'bIt is identical or different, be each independently selected from hydrogen and
C1-4Straight or branched alkyl, is preferably selected from hydrogen and methyl, more preferably hydrogen, on condition that at least two R'bIt is hydrogen, more preferably formula
(VII) strand of polyalkylenepolyamines respectively has at least one R' with respect to two endsbIt is hydrogen；Y is selected from the integer of 2-5, excellent
Select 2 or 3；C' is selected from the integer of 1-11, is preferably selected from the integer of 3-6, more preferably 3 or 4.
4. the lubricant oil composite of any preceding aspect, wherein the manufacture method is carried out one of in such a way：
Mode（1）：Comprise the following steps：
First step：Make the structural formula（VI）Phenolic compounds, the structural formula（VII）Polyalkylenepolyamines and institute
State C1-C7Straight or branched saturated aliphatic aldehyde is in 50 DEG C -200 DEG C of reaction temperature（It is preferred that 60 DEG C -150 DEG C, most preferably 80 DEG C -130
℃）Lower generation Mannich reaction, generates intermediate product；
Second step：Make the intermediate product with the structural formula（V）Parahydroxydi-phenylamine compound and the C1-C7
Straight or branched saturated aliphatic aldehyde is in 40 DEG C -200 DEG C of reaction temperature（It is preferred that 60 DEG C -150 DEG C, most preferably 80 DEG C -130 DEG C）Issue
Raw Mannich reaction, generates the Mannich base,
Or
Mode（2）：Comprise the following steps：
First step：Make the structural formula（V）Parahydroxydi-phenylamine compound, the structural formula（VII）Many alkylenes
Quito amine and the C1-C7Straight or branched saturated aliphatic aldehyde is in 40 DEG C -200 DEG C of reaction temperature（It is preferred that 60 DEG C -150 DEG C, it is optimal
Select 80 DEG C -130 DEG C）Lower generation Mannich reaction, generates intermediate product；
Second step：Make the intermediate product with the structural formula（VI）Phenolic compounds and the C1-C7Straight or branched
Saturated aliphatic aldehyde is in 50 DEG C -200 DEG C of reaction temperature（It is preferred that 60 DEG C -150 DEG C, most preferably 80 DEG C -130 DEG C）Lower generation Mannich is anti-
Should, the Mannich base is generated,
Or
Mode（3）：Including making the structural formula（V）Parahydroxydi-phenylamine compound, the structural formula（VI）Phenolate
Compound, the structural formula（VII）Polyalkylenepolyamines and the C1-C7Straight or branched saturated aliphatic aldehyde is in reaction temperature 40
℃-200℃（It is preferred that 60 DEG C -150 DEG C, most preferably 80 DEG C -130 DEG C）It is lower that Mannich reaction occurs and the Mannich base is generated
Step.
5. the lubricant oil composite of any preceding aspect, wherein in the manufacture method, in the mode（1）First
In step, the structural formula（VI）Phenolic compounds, the structural formula（VII）Polyalkylenepolyamines and the C1-C7Straight chain or
Mol ratio between chain is saturated fatty aldehyde is 1:0.3-3:0.3-3.5, preferably 1:0.4-2:0.4-2.5, more preferably 1:0.5-
1.5:0.5-2；In the mode（1）Second step in, the intermediate product and the structural formula（V）Parahydroxydi-phenylamine
Compound and the C1-C7Mol ratio between straight or branched saturated aliphatic aldehyde is 1:0.2-1.5:0.2-2, preferably 1:0.3-
1:0.2-1.5, more preferably 1:0.3-0.8:0.3-1.5；In the mode（2）First step in, the structural formula（V）It is right
Hydroxy diphenylamine compound, the structural formula（VII）Polyalkylenepolyamines and the C1-C7Straight or branched saturated aliphatic aldehyde
Between mol ratio be 1：1.5-2.5：1.5-3, preferably 1：1.7-2.5：1.7-2.8, more preferably 1：1.7-2.2：1.7-2.5；
In the mode（2）Second step in, the intermediate product and the structural formula（VI）Phenolic compounds and the C1-C7Directly
Mol ratio between chain or chain is saturated fatty aldehyde is 1:1.5-3:1.5-3, preferably 1:1.7-2.5:1.7-3, more preferably 1:
1.7-2.3:1.7-2.5；In the mode（3）In, the structural formula（V）Parahydroxydi-phenylamine, the structural formula（VI）'s
Phenolic compounds, the structural formula（VII）Polyalkylenepolyamines and the C1-C7Rubbing between straight or branched saturated aliphatic aldehyde
You are than being 1:1-5:1-3:2-8, preferably 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. the lubricant oil composite of any preceding aspect, wherein in the manufacture method, the Mannich reaction is in choosing
Carried out in the presence of one or more from polyolefin, mineral base oil and polyethers of diluent.
7. the lubricant oil composite of any preceding aspect, wherein in the manufacture method, the structural formula（VI）Phenol
Compound is by the presence of catalyst for alkylation reaction, making structural formula（IV）Phenolic compounds be with number-average molecular weight Mn
300-3000（It is preferred that 500-2000, more preferably 500-1500）Polyolefin occur alkylated reaction and manufacture, the polyene
Hydrocarbon preferably passes through ethene, propylene or C4-C10The homopolymerization of alpha-olefin is obtained by two or more copolymerization in these alkene
The polyolefin for arriving, more preferably polyisobutene,
Wherein R3Selected from C1-6Straight or branched alkyl, is preferably selected from C1-4Straight or branched alkyl, more preferably methyl.
8. the lubricant oil composite of any preceding aspect, wherein in mass, the diakylaminomethylene benzotriazole
Account for the 0.01~5% of the lubricant oil composite gross mass（It is preferred that 0.02%~3%, more preferably 0.05%~1%）, the alkane
Base diphenylamines account for the 0.01~8% of the lubricant oil composite gross mass（It is preferred that 0.02%~5%, more preferably 0.05%~
3%）.
9. the lubricant oil composite of any preceding aspect, wherein the diakylaminomethylene benzotriazole is selected from C1-C12
The diakylaminomethylene benzotriazole of alkyl；The alkylated diphenylamine is selected from C4-C16Alkylated diphenylamine.
10. the lubricant oil composite of any preceding aspect, wherein in mass, the Mannich base accounts for the lubricating oil group
The 0.01%~20% of compound gross mass, preferably 0.02%~15%, more preferably 0.1%~10%.
The lubricant oil composite of 11. any preceding aspects, adds dialkyl dithio amino in the lubricant oil composite
Formic acid esters and/or salt, the dialkyl dithio amino formate and/or salt account for the 0.01 of the lubricant oil composite gross mass
~5%（It is preferred that 0.02%~3%, more preferably 0.05%~2%）.
Specific embodiment
Specific embodiment of the invention is described in detail below, it should be noted however that protection of the invention
Scope is not limited to these specific embodiments, but determined by claims of annex.Do not clearly indicating
In the case of, all percentages, number, ratio being previously mentioned in this specification etc. is all on the basis of weight, unless with weight
The conventional understanding of those skilled in the art is not met when on the basis of amount.
Although can be applicable with similar or identical to method described herein and material in putting into practice or testing the present invention
Method and material be described in herein.
In the context of the present specification, in case of no particular description, number-average molecular weight Mn is by gel infiltration
What chromatography (GPC) was determined.
According to the present invention, a kind of Mannich base is first related to, it includes following structure unit（I）And construction unit
（II）：
In these construction units, each R1It is identical or different, it is each independently selected from hydrogen, C1-4Straight or branched alkyl
And singly-bound；Each R' is identical or different, is each independently selected from hydrogen and C1-6Straight or branched alkyl；R2Selected from H, C1-8Alkyl,
Hydroxyl or nitro, preferably H, C1-4Alkyl or hydroxyl, most preferably H；R3Selected from C1-6Straight or branched alkyl；R4Selected from several equal molecules
Amount Mn is the alkyl of 300-3000；Each y is identical or different, is each independently selected from the integer of 2-5.
According to the present invention, the R1It is preferred that being each independently selected from hydrogen, methyl and singly-bound, more preferably each independently it is selected from
Hydrogen and singly-bound.
An implementation method of the invention, is at the construction unit（I）The contraposition alkyl phenol unit at center and
Speech, preferably two on the left of it R1In one be singly-bound, and another is methyl or hydrogen, and two R on the right side of it1In one
It is singly-bound, and another is methyl or hydrogen.In addition, in the construction unit（II）In, preferably two R1In one be singly-bound, and
Another is methyl or hydrogen.
According to the present invention, the R' is each identical or different, preferably identical, and is preferably each independently selected from hydrogen and first
Base, more preferably hydrogen.
According to the present invention, the R2Selected from H, C1-8Alkyl, hydroxyl or nitro, preferably H, C1-4Alkyl or hydroxyl, most preferably
H。
According to the present invention, the R3It is preferably selected from C1-4Straight or branched alkyl, more preferably methyl or ethyl.
It is the alkyl of 300-3000 as the number-average molecular weight Mn according to the present invention, such as can enumerates and divide equally from number
Son amount Mn is the polyolefin of 300-3000（The especially end of the molecular polyolefin chain）Remove the hydrocarbon obtained after a hydrogen atom
Base（Referred to as polyene hydrocarbon residue）.Wherein, as the polyolefin or the number-average molecular weight Mn of the polyene hydrocarbon residue, preferably 500-
2000, more preferably 500-1500.As the polyolefin, such as can enumerate by ethene, propylene or C4-C10Alpha-olefin（Than
Such as n-butene, isobutene, n-pentene, n-hexylene, positive octene or positive decene）Homopolymerization or by two kinds in these alkene
Or polyolefin obtained from various copolymerization, wherein more preferably polyisobutene（PIB）.
According to the present invention, the y is identical or different, preferably identical.The y preferably 2 or 3, more preferably 2.
According to the present invention, so-called " Mannich base includes construction unit（I）And construction unit（II）", it is meant that：Institute
State and be capable of detecting when the construction unit in Mannich base（I）With the construction unit（II）Coexist.Therefore, according to the present invention,
The Mannich base can be a kind of single compound, be capable of detecting when in the structure of the compound or tell both
Exist while construction unit, i.e., be present in the structure of the compound simultaneously.In addition, the Mannich base can also be various
The mixture of compound, as long as be capable of detecting when from the mixture or existed i.e. while telling both construction units
Can.Now, both construction units can be present in the structure of same compound simultaneously, it is also possible to be respectively present in and do not assimilate
In the structure of compound, wherein it is preferred that the former.Preferably, the mixture includes at least one compound, wherein both structures
Unit is present in the structure of the compound simultaneously.The detection or resolution means herein being related to be it is commonly used in the art,
1H-NMR or gel permeation chromatography (GPC) can such as be enumerated.
According to the present invention, exist concurrently with when in a structure for compound, both construction units can be by altogether
With mutual common unitOrAnd Direct Bonding, it is also possible to by linking group（The y is as defined above, and preferably with construction unit（I）And construction unit（II）
In y it is identical；The R1It is as defined above；The x is the integer of 0-8, the preferably integer of 0-3, more preferably 1）In respective list
At key or R1（Only when R1 is singly-bound）Place's indirect linkage.
According to the present invention, in the Mannich base, the construction unit（I）With the construction unit（II）Mol ratio
Generally 1:1 to 1:15, preferably 1:1 to 1:8, more preferably 1:2 to 1:6, or 1:2 to 1:4.
An implementation method of the invention, substantially by the construction unit in the Mannich base（I）, the knot
Structure unit（II）Constituted with the optional linking group.Here so-called " substantially " is referred to except construction unit（I）、
Construction unit（II）Even if with the other structures unit or group outside linking group in the presence of also only accounting for the Mannich base totality
Below 5mol%, more preferably preferably below 2mol%, below 0.5mol%, or conduct（Inevitably）Impurity is present.
An implementation method of the invention, for example following structural formula of the Mannich base（III）It is shown.
In the structural formula, each A is identical or different, is each independently selected fromAnd hydrogen, it is preceding
Carry is that at least one A isEach R' is identical or different, is each independently selected from hydrogen and C1-6Directly
Chain or branched alkyl；Each RaIt is identical or different, it is each independently selected from hydrogen, C1-4Straight or branched alkyl andOn condition that at least one RaIt isEach
RbIt is identical or different, be each independently selected from hydrogen,And C1-4Straight or branched alkyl, on condition that at least
One RbIt isR2Selected from H, C1-8Alkyl, hydroxyl or nitro, preferably H, C1-4Alkyl or hydroxyl, it is optimal
Select H；R3Selected from C1-6Straight or branched alkyl；R4It is the alkyl of 300-3000 selected from number-average molecular weight Mn；Each y is identical or not
Together, it is each independently selected from the integer of 2-5；Each c is identical or different, is each independently selected from the integer of 0-10.
According to the present invention, the A is preferably identical, is more preferably
According to the present invention, the R' is each identical or different（It is preferred that identical）, and be preferably each independently selected from hydrogen and
Methyl, more preferably hydrogen.
According to the present invention, the RaIt is preferred that be each independently selected from hydrogen, methyl and
Be more preferably selected from hydrogen andIn each structureIn, preferably
One of RaIt isAnd another RaIt is hydrogen or methyl, or two RaIt is
According to the present invention, the RbIt is preferred that be each independently selected from hydrogen,And methyl, more preferably
Be each independently selected from hydrogen and
According to the present invention, in the structural formula（III）In, preferably whole RbIn 1-15 beOr whole RbIn 1-8 beOr whole RbIn 2-6
It isOr whole RbIn 2-4 beOr whole RbIn 4
It isAnd remaining RbIt is hydrogen or methyl.
According to the present invention, the R2Selected from H, C1-8Alkyl, hydroxyl or nitro, preferably H, C1-4Alkyl or hydroxyl, most preferably
H。
According to the present invention, the R3It is preferably selected from C1-4Straight or branched alkyl, more preferably methyl or ethyl.
It is the alkyl of 300-3000 as the number-average molecular weight Mn according to the present invention, such as can enumerates and divide equally from number
Son amount Mn is the polyolefin of 300-3000（The especially end of the molecular polyolefin chain）Remove the hydrocarbon obtained after a hydrogen atom
Base（Referred to as polyene hydrocarbon residue）.Wherein, as the polyolefin or the number-average molecular weight Mn of the polyene hydrocarbon residue, preferably 500-
2000, more preferably 500-1500.As the polyolefin, such as can enumerate by ethene, propylene or C4-C10Alpha-olefin（Than
Such as n-butene, isobutene, n-pentene, n-hexylene, positive octene or positive decene）Homopolymerization or by two kinds in these alkene
Or polyolefin obtained from various copolymerization, wherein more preferably polyisobutene（PIB）.
According to the present invention, the y is identical or different, preferably identical.The y preferably 2 or 3, more preferably 2.
According to the present invention, the c is identical or different, is preferably each independently selected from the integer of 2-5, more preferably 2 or 3.
According to the present invention, foregoing Mannich base can be with single one kind（It is pure）The form of compound exists, manufactures or make
With, it is also possible to the mixture of wherein two or more（In any proportion）Form exist, manufacture or use, this has no effect on
The realization of effect of the present invention.
According to the present invention, foregoing Mannich base can such as be manufactured by following manufacture method.
According to the present invention, the manufacture method includes making structural formula（V）Parahydroxydi-phenylamine compound, structural formula（VI）
Phenolic compounds, structural formula（VII）Polyalkylenepolyamines and C1-C7There is Mannich reaction in straight or branched saturated aliphatic aldehyde
The step of.
Wherein, R2Selected from H, C1-8Alkyl, hydroxyl or nitro, preferably H, C1-4Alkyl or hydroxyl, most preferably H；R3Selected from C1-6
Straight or branched alkyl；R4It is the alkyl of 300-3000 selected from number-average molecular weight Mn；Each R'bIt is identical or different, independently of one another
Selected from hydrogen and C1-4Straight or branched alkyl, on condition that at least two R'bIt is hydrogen；Y is selected from the integer of 2-5；C' is selected from the whole of 1-11
Number.
According to the present invention, the R3It is preferably selected from C1-4Straight or branched alkyl, more preferably methyl or ethyl.
It is the alkyl of 300-3000 as the number-average molecular weight Mn according to the present invention, such as can enumerates and divide equally from number
Son amount Mn is the polyolefin of 300-3000（The especially end of the molecular polyolefin chain）Remove the hydrocarbon obtained after a hydrogen atom
Base（Also referred to as polyene hydrocarbon residue）.Wherein, as the polyolefin or the number-average molecular weight Mn of the polyene hydrocarbon residue, preferably
500-2000, more preferably 500-1500.
In the context of the present specification, depending on starting polyolefin species or the difference of manufacture method, the polyolefin
Residue is probably saturation（It is rendered as chain alkyl）, it is also possible to contain a certain amount of olefinic double bond in polymer chain（Such as
Remained in polyolefin manufacturing process）, but this has no effect on the realization of effect of the present invention, and the present invention also has no intention to enter the amount
Row is clear and definite.
As the polyolefin, such as can enumerate by ethene, propylene or C4-C10Alpha-olefin（Such as n-butene, isobutyl
Alkene, n-pentene, n-hexylene, positive octene or positive decene）Homopolymerization or by the copolymerization of two or more in these alkene
Obtained from polyolefin, wherein more preferably polyisobutene（PIB）.
According to the present invention, the structural formula（VI）Phenolic compounds can by the presence of catalyst for alkylation reaction,
Make structural formula（IV）Phenolic compounds and the polyolefin（Number-average molecular weight Mn be 300-3000, preferably 500-2000, more preferably
500-1500）Generation alkylated reaction and manufacture.Certainly, the structural formula（VI）Phenolic compounds can also directly using commercially available
Product.
Wherein R3The same formula of definition（VI）, more preferably methyl.
According to the present invention, the polyolefin preferably passes through ethene, propylene or C4-C10The homopolymerization of alpha-olefin or by these
Polyolefin obtained from two or more copolymerization in alkene.As the C4-C10Alpha-olefin, such as can enumerate n-butene,
Isobutene, n-pentene, n-hexylene, positive octene and positive decene.
According to the present invention, at least 20wt% in these polyolefin（Preferably at least 50wt%, more preferably at least 70wt%）Polymerization
Thing chain contains olefinic double bond in its end.The olefinic double bond is usually in the form of the ethenylidene or vinyl of high reaction activity
Exist.
According to the present invention, as the polyolefin, more preferably polybutene.Unless otherwise indicated, term as used herein
" polybutene " broadly includes the polymer as obtained from 1- butylene or isobutylene homopolymerisation, and by 1- butylene, 2- butylene and different
Prepared by passing through copolymerization two or three in butylene polymer.The commercially available prod of such polymer is likely to containing negligible
Other olefinic components of amount, but this has no effect on implementation of the invention.
According to the present invention, as the polyolefin, further preferred polyisobutene（PIB）Or the poly- isobutyl of high reaction activity
Alkene（HR-PIB）.In this kind of polyisobutene, at least 20wt%（Preferably at least 50wt%, more preferably at least 70wt%）Total end
Olefinic double bond is provided by methyl ethenylidene.
As the catalyst for alkylation reaction, such as can enumerate Lewis acid catalysts, such as selected from alchlor,
Boron trifluoride, butter of tin, titanium tetrabromide, boron trifluoride phenol, boron trifluoride alcohol complex and boron trifluoride ether network
One or more in compound, wherein it is preferred that boron trifluoride etherate and/or boron trifluoride methanol complex compound.These
Catalyst for alkylation reaction can directly use commercially available product.
According to the present invention, in the alkylated reaction, the polyolefin, the structural formula（IV）Phenolic compounds, institute
The mol ratio stated between catalyst for alkylation reaction can be such as 1：1-3：0.1-0.5, preferably 1：1.5-3：0.1-0.4, most
It is preferred that 1：1.5-3：0.2-0.4, but this is not limited to sometimes.
According to the present invention, the reaction time of the alkylated reaction is such as 0.5h-10h, most preferably preferably 1h-8h, 3h-
5h, but this is not limited to sometimes.
According to the present invention, the reaction temperature of the alkylated reaction is such as 0 DEG C -200 DEG C, preferably 10 DEG C -150 DEG C, most
It is preferred that 20 DEG C -100 DEG C, but this is not limited to sometimes.
According to the present invention, the alkylated reaction can be carried out in the presence of the solvent.As the solvent, such as can be with
Enumerate C6-10Alkane（Such as hexane, heptane, octane, nonane or decane etc.）.Wherein, hexane and heptane are preferably used, more preferably
Use hexane.
According to the present invention, after the alkylated reaction terminates, by conventional methods from the reactant mixture for finally obtaining
After middle removing catalyst for alkylation reaction, unreacted reactant and the solvent that may be used, that is, obtain described structural formula
（VI）Phenolic compounds.
According to the present invention, the R'bIt is identical or different, preferably it is each independently selected from hydrogen and methyl.It is further preferred that formula
(VII) strand of polyalkylenepolyamines respectively has at least one R' with respect to two endsbHydrogen, i.e., following formula (VII-1).
Wherein R'b, y and c' the same formula of definition (VII).
According to the present invention, as the polyalkylenepolyamines, such as can enumerate selected from Diethylenetriamine, three second tetramines, four
One kind or many in the amine of second five, five second hexamines, the amine of six second seven, the amine of seven second eight, the amine of eight second nine, the amine of nine second ten and ten second undecylamines
Kind, wherein it is preferred that Diethylenetriamine.
According to the present invention, the polyalkylenepolyamines such as can be by ammonia and alkylene dihalide such as dichloro alkanes reaction system
Make, it is also possible to 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, more preferably 3 or 4.
According to the present invention, the C1-C7The preferred acetaldehyde of straight or branched saturated aliphatic aldehyde or formaldehyde, more preferably formaldehyde.As
The 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 the Mannich base can such as be carried out one of in such a way.
Mode（1）：Comprise the following steps：
First step：Make the structural formula（VI）Phenolic compounds, the structural formula（VII）Polyalkylenepolyamines and institute
State C1-C7Straight or branched saturated aliphatic aldehyde is in 50 DEG C -200 DEG C of reaction temperature（It is preferred that 60 DEG C -150 DEG C, most preferably 80 DEG C -130
℃）Lower generation Mannich reaction, generates intermediate product；With
Second step：Make the intermediate product with the structural formula（V）Parahydroxydi-phenylamine compound and the C1-C7
Straight or branched saturated aliphatic aldehyde is in 40 DEG C -200 DEG C of reaction temperature（It is preferred that 60 DEG C -150 DEG C, most preferably 80 DEG C -130 DEG C）Issue
Raw Mannich reaction, generates the Mannich base.
Mode（2）：Comprise the following steps：
First step：Make the structural formula（V）Parahydroxydi-phenylamine compound, the structural formula（VII）Many alkylenes
Quito amine and the C1-C7Straight or branched saturated aliphatic aldehyde is in 40 DEG C -200 DEG C of reaction temperature（It is preferred that 60 DEG C -150 DEG C, it is optimal
Select 80 DEG C -130 DEG C）Lower generation Mannich reaction, generates intermediate product；With
Second step：Make the intermediate product with the structural formula（VI）Phenolic compounds and the C1-C7Straight or branched
Saturated aliphatic aldehyde is in 50 DEG C -200 DEG C of reaction temperature（It is preferred that 60 DEG C -150 DEG C, most preferably 80 DEG C -130 DEG C）Lower generation Mannich is anti-
Should, generate the Mannich base.
Mode（3）：Including making the structural formula（V）Parahydroxydi-phenylamine compound, the structural formula（VI）Phenolate
Compound, the structural formula（VII）Polyalkylenepolyamines and the C1-C7Straight or branched saturated aliphatic aldehyde is in reaction temperature 40
℃-200℃（It is preferred that 60 DEG C -150 DEG C, most preferably 80 DEG C -130 DEG C）It is lower that Mannich reaction occurs and the Mannich base is generated
Step.
According to the present invention, from for the angle of Mannich base for obtaining higher degree, preferred embodiment（1）.
According to the present invention, in the mode（1）First step in, the structural formula（VI）Phenolic compounds, the knot
Structure formula（VII）Polyalkylenepolyamines and the C1-C7Mol ratio between straight or branched saturated aliphatic aldehyde is 1:0.3-3:
0.3-3.5, preferably 1:0.4-2:0.4-2.5, more preferably 1:0.5-1.5:0.5-2.The present invention does not have to the reaction time of the step
There is special limitation, such as can enumerate 1h-10h, most preferably preferably 2h-8h, 3h-6h.
According to the present invention, in the mode（1）Second step in, the intermediate product and the structural formula（V）It is right
Hydroxy diphenylamine compound and the C1-C7Mol ratio between straight or branched saturated aliphatic aldehyde is 1:0.2-1.5:0.2-2,
It is preferred that 1:0.3-1:0.2-1.5, more preferably 1:0.3-0.8:0.3-1.5.The present invention is to the reaction time of the step without special
Limitation, such as can enumerate 1h-10h, most preferably preferably 2h-8h, 3h-6h.
According to the present invention, in the mode（2）First step in, the structural formula（V）Parahydroxydi-phenylamine chemical combination
Thing, the structural formula（VII）Polyalkylenepolyamines and the C1-C7Mol ratio between straight or branched saturated aliphatic aldehyde is
1：1.5-2.5：1.5-3, preferably 1：1.7-2.5：1.7-2.8, more preferably 1：1.7-2.2：1.7-2.5.The present invention is to the step
Reaction time have no particular limits, such as can enumerate 1h-10h, most preferably preferably 2h-8h, 3h-6h.
According to the present invention, in the mode（2）Second step in, the intermediate product and the structural formula（VI）Phenol
Compound and the C1-C7Mol ratio between straight or branched saturated aliphatic aldehyde is 1:1.5-3:1.5-3, preferably 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 to the reaction time of the step, such as
1h-10h, most preferably preferably 2h-8h, 3h-6h can be enumerated.
According to the present invention, in the mode（3）In, the structural formula（V）Parahydroxydi-phenylamine compound, the structure
Formula（VI）Phenolic compounds, the structural formula（VII）Polyalkylenepolyamines and the C1-C7Straight or branched saturated aliphatic aldehyde
Between mol ratio be 1:1-5:1-3:2-8, preferably 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 is to which（3）Reaction time have no particular limits, such as can enumerate 1h-10h, preferably
2h-8h, most preferably 3h-6h.
According to the present invention, foregoing Mannich reaction can be carried out in the presence of diluent and/or solvent.As described
Diluent, such as can enumerate selected from one or more in polyolefin, mineral base oil and polyethers.As the solvent, than
C6-20 aromatic hydrocarbon can such as be enumerated（Such as toluene and dimethylbenzene）Deng.Wherein, toluene or dimethylbenzene are preferably used.
According to the present invention, the diluent and/or solvent can be in any stages of the Mannich reaction according to ability
The conventional amount used in domain is added.Such as, can be in mode（1）The beginning of first step or during carrying out and/or mode（1）The
The beginning of two steps or during carrying out, mode（2）The beginning of first step or during carrying out and/or mode（2）The
The beginning of two steps or during carrying out or mode（3）Beginning or add during carrying out, special limit
It is fixed.
According to the present invention, as the mineral base oil, such as API I, II, Group III mineral lubricant oil base can be selected
One or more in plinth oil, 40 DEG C of viscosity are preferably selected from for 20-120 centistokes（cSt）, ore deposit of the viscosity index (VI) at least more than 50
One or more in thing lube base oil, 40 DEG C of viscosity are more preferably selected from for 28-110 centistokes（cSt）, viscosity index (VI) at least
One or more in mineral lubricant oil base oil more than 80.
According to the present invention, as the polyolefin, such as can enumerate by ethene, propylene or C4-C10Alpha-olefin it is equal
Gather or by one or more in polyolefin obtained from two or more copolymerization in these alkene, preferably 100 DEG C are glued
It is 2-25 centistokes to spend（cSt）（It is preferred that 100 DEG C of viscosity are 6-10 centistokes（cSt））Poly alpha olefin（PAO）In one or more.
Wherein, as the C4-C10Alpha-olefin, such as can enumerate n-butene, isobutene, n-pentene, n-hexylene, positive octene and the positive last of the ten Heavenly stems
Alkene.In addition, the number-average molecular weight Mn of the polyolefin is generally 500-3000, most preferably preferably 500-2500,500-1500.
According to the present invention, as the polyethers, such as the polymer generated by alcohol and epoxide reaction can be enumerated.
As the alcohol, such as can enumerate ethylene glycol and/or 1,3-PD.As the epoxides, such as can enumerate ring
Oxidative ethane and/or expoxy propane.In addition, the number-average molecular weight Mn of the polyethers is generally 500-3000, preferably 700-3000, most
It is preferred that 1000-2500.
Known in the art, the Mannich reaction is typically carried out under the protection of inert gas atmosphere.As institute
Inert gas is stated, such as can enumerate nitrogen and argon gas etc., be not particularly limited.
According to the present invention, after the manufacture method of the Mannich base terminates, by conventionally known any mode from most
After removing moisture and solvent that may be present in the reactant mixture for obtaining eventually, that is, obtain Mannich base.
Therefore, the Mannich base the invention further relates to be manufactured according to the manufacture method of the foregoing Mannich base of the present invention.
According to the present invention, by the manufacture method of foregoing Mannich base, as product, it is possible to produce purity is non-
Chang Gao（Purity such as more than 95%）Single a kind of Mannich base, it is also possible to produce the mixing being made up of various Mannich bases
Thing, or Mannich base and foregoing diluent as described in one or more（If you are using）The mixture of composition.These are anti-
It is all that desired by the present invention, the difference of its existence form has no effect on the realization of effect of the present invention to answer product.Therefore, this explanation
These product are collectively termed as Mannich base without distinction in book context.In consideration of it, according to the present invention, and do not exist
The product is further purified, or the exhausted of the Mannich base of a certain ad hoc structure is further separated out from the product
To necessity.Certainly, the purifying or to separate be preferred, but Yu Benfa for the further lifting of Expected Results of the present invention
It is bright not necessarily.
According to the present invention, the detergent-dispersant additive includes the foregoing any Mannich base of the present invention（Or its arbitrary proportion
Mixture）Or the Mannich base manufactured according to the manufacture method of the foregoing Mannich base of the present invention.
According to the present invention, in order to manufacture the detergent-dispersant additive, can also in the Mannich base further add before
The diluent stated.Now, the diluent be can be used alone, it is also possible to which combination of two or more is used.Certainly, if this hair
Bright Mannich base has contained a certain amount of diluent after manufacturing as previously described, then now just can accordingly subtract
The addition of few diluent, in this embodiment it is not even necessary to make directly as detergent-dispersant additive by further adding the diluent
With this is to those skilled in the art obvious.
In general, in detergent-dispersant additive of the invention, in mass, the Mannich base accounts for the detergent-dispersant additive
The 10~70% of gross mass, preferably 10~60%, most preferably 10~50%.
According to the present invention, in order to manufacture the detergent-dispersant additive, by the Mannich base and the diluent（If used
If）In 20 DEG C of -60 DEG C of mixing 1h-6h.
Mannich base of the invention or detergent-dispersant additive are also particularly well-suited for manufacturing lubricant oil composite, the lubricating oil composition
Thing shows excellent cleansing performance.Therefore, according to the present invention, further to a kind of lubricant oil composite, it includes this hair
Bright foregoing any Mannich base（Or the mixture of its arbitrary proportion）, according to the manufacture method of the foregoing Mannich base of the present invention
The Mannich base or the foregoing detergent-dispersant additive of the present invention of manufacture, and lube base oil.
According to the present invention, in order to manufacture the lubricant oil composite, by the foregoing Mannich base of the present invention, by by this hair
The Mannich base or the foregoing detergent-dispersant additive of the present invention of the manufacture method manufacture of bright foregoing Mannich base are used as lubricating oil
One of additive, with lube base oil and diakylaminomethylene benzotriazole, alkylated diphenylamine according to predetermined ratio
Or addition is well mixed.
More specifically, in order to manufacture lubricant oil composite of the invention, above-mentioned each lube oil additive can be distinguished
It is added in lube base oil or above-mentioned each lube oil additive is mixed and made into concentrate and is then added to lube base oil
In, heating is well mixed.Mixing temperature now is generally 40 DEG C -90 DEG C, and incorporation time is generally -6 hours 1 hour.
According to the present invention, as the Mannich base or the addition of the detergent-dispersant additive so that in terms of Mannich base
The Mannich base or the detergent-dispersant additive amount（Quality criteria）Account for the 0.01% of the lubricant oil composite gross mass
~20%, preferably 0.02%~15%, more preferably 0.1%~10%.
Because the foregoing diluent for using of the present invention frequently as lube base oil actually in the art also through using,
Therefore it is directly classified as lube base oil in the following description separately to be described without being re-used as a single component.
According to the present invention, the diakylaminomethylene benzotriazole is selected from C1-C12The diakylaminomethylene of alkyl
Benzotriazole, preferably C1-C8The diakylaminomethylene benzotriazole of alkyl, can select N, N- di-n-butyl aminomethylene benzene
Triazole, di-n-hexyl aminomethylene benzotriazole, N, N- bis-（2- ethylhexyls）- aminomethylene benzotriazole, trade names bag
Include the CUVAN303 of R.T.Vanderbilt companies, the T551 of Jinzhou Kangtai Lube Additive Co., Ltd..
The diakylaminomethylene benzotriazole accounts for the 0.01~5% of the lubricant oil composite gross mass, preferably
0.02%~3%, more preferably 0.05%~1%.
According to the present invention, as the alkylated diphenylamine, C can be selected4-C16Alkylated diphenylamine, preferably C4-C8Alkane
Base diphenylamines, can select IRGANOXL-01, IRGANOX L-57 of Ciba of BASF Aktiengesellschaft production, and Beijing is emerging
The T534 of general company's production, the LZ5150A of Lu Borun Lan Lian additives Co., Ltd production, the production of Vanderbilt companies of the U.S.
VANLUBE NA, VANLUBE961, dioctyl diphenylamine VANLUBE81, TUV chemical company production it is right, to ' two
Di-iso-octyldiphenylamine RC7001.
The alkylated diphenylamine accounts for the 0.01~8% of the lubricant oil composite gross mass, and preferably 0.02%~5%, more
It is preferred that 0.05%~3%.
According to the present invention, as the lube base oil, can be from API I, II, III, IV, V class lubricating oil basis
One or more in oil, such as one or more in can enumerating selected from mineral lubricating oil and synthetic lubricant fluid.
According to the present invention, it is big that the viscosity index (VI) of the lube base oil is generally higher than 80, saturated hydrocarbon content mass fraction
In 90% and sulfur content mass fraction be less than 0.03%.
Dialkyl dithio amino formate and/or salt are further preferably added in lubricant oil composite of the invention, wherein
Alkyl be C1-12Alkyl, preferably C1-8Alkyl, can be ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, just
One or more in amyl group, isopentyl, n-hexyl, isohesyl, n-octyl and 2- ethylhexyls.The dialkyl dithio ammonia
Base formates can select zinc dialkyl dithiocarbamate, molybdenum dialkyldithiocarbamacompositions, dialkyl dithio ammonia
One or more in base copper formate, antimony dialkyl-dithiocarbamate and Bismuth dibutyldithiocarbamate, preferably two
Alkyl zinc dithiocarbamate, trade names can select VAN LUBE AZ.The dialkyl dithio amino formate
Trade names can select T323.
The dialkyl dithio amino formate and/or salt account for the 0.01~5% of the lubricant oil composite gross mass,
It is preferred that 0.02%~3%, more preferably 0.05%~2%.
Pour-point depressant, viscosity index improver, metal erosion can also be added to suppress in lubricant oil composite of the invention
One or more other lube oil additive in agent, antirust agent and anti-foaming agent, its consumption from the conventional amount used of this area, not
There is special restriction.
Lubricant oil composite of the invention has excellent detergent-dispersant performance energy and rustless property.
Embodiment
The present invention is illustrated using embodiment in further detail below, but the present invention is not limited to these embodiments.
Following table gives the detail of the chemicals used in embodiment and comparative example.
| Reagent name | Specification | Index | Source |
| Orthoresol | CP | ≥98.0% | Chemical Reagent Co., Ltd., Sinopharm Group |
| Polyisobutene | HR-PIB | Mn=1000 | Fine chemicals Co., Ltd of Jilin Chemical group |
| Diethylenetriamine | CP | ≥98.0% | Beijing Chemical Plant |
| Three second tetramines | CP | ≥95.0% | Chemical Reagent Co., Ltd., Sinopharm Group |
| Tetren | CP | ≥90.0% | Chemical Reagent Co., Ltd., Sinopharm Group |
| Parahydroxydi-phenylamine | Tokyo chemical conversion industry Co., Ltd. | ||
| 4- hydroxyl -2'- nitrodiphenylamines | Tokyo chemical conversion industry Co., Ltd. | ||
| 4,4'- diaminourea biphenols | Tokyo chemical conversion industry Co., Ltd. |
The synthesizing polyisobutylene orthoresol of embodiment 1
In the 500ml four-hole boiling flasks equipped with agitator, thermometer, condenser pipe and dropping funel, 34.93g is added
(0.323mol) orthoresol, the BFEE catalyst of 6.88g (0.048mol), 100ml n-hexanes solvent and 161.61g
The polyisobutene of (0.162mol)（Mn=1000）2h is reacted at 80 DEG C.After reaction terminates, use quality fraction is 5% hydroxide
Potassium solution cleaning reactant mixture once, and is washed to neutrality to remove catalyst with hot water, and then vacuum distillation removes solvent
And unreacted orthoresol.The hydroxyl valency of synthetic product polyisobutene orthoresol is 53.49mg/g.Hydroxy value measuring refers to GB/
Acetic anhydride method in T7383-2007.
Example reaction equation is as follows：
Embodiment 2
Obtained polyisobutene orthoresol 47.16g (0.045mol) in embodiment 1 is added to 500ml under nitrogen protection
In four mouthfuls of beakers equipped with agitator, thermometer and knockout, ethylenediamine, the 3.83g of 2.70g (0.045mol) are subsequently adding
(0.047mol) formaldehyde, and add the toluene of 47ml as reaction dissolvent, after reacting 1.5h at 80 DEG C, room temperature is cooled to, add
The parahydroxydi-phenylamine of 4.17g (0.0225mol), 3.83g (0.047mol) formaldehyde, 1h is reacted at 70 DEG C.After question response terminates,
Vacuum distillation removes a small amount of water of solvent and generation, obtains final Mannich Base Detergent.Example reaction equation is as follows：
Embodiment 3
Obtained polyisobutene orthoresol 53.37g (0.051mol) in embodiment 1 is added to 500ml under nitrogen protection
In four mouthfuls of beakers equipped with agitator, thermometer and knockout, be subsequently adding 7.46g (0.051mol) triethylene tetramine,
4.38g (0.054mol) formaldehyde, and add the dimethylbenzene of 54ml as reaction dissolvent, after reacting 1.5h at 100 DEG C, it is cooled to room
Temperature, adds 5.87g (0.0255mol) 4- hydroxyl -2'- nitrodiphenylamines, 4.38g (0.054mol) formaldehyde, and 1h is reacted at 80 DEG C.
After question response terminates, vacuum distillation removes a small amount of water of solvent and generation, obtains final Mannich Base Detergent.Example is reacted
Formula reference implementation example 2.
Embodiment 4
Obtained polyisobutene orthoresol 58.80g (0.056mol) in embodiment 1 is added to 500ml under nitrogen protection
In four mouthfuls of beakers equipped with agitator, thermometer and knockout, be subsequently adding 2.89g (0.028mol) diethylenetriamine,
4.78g (0.059mol) formaldehyde, and add the toluene of 53ml as reaction dissolvent, after reacting 1.5h at 100 DEG C, it is cooled to room
Temperature, adds 2.59g (0.014mol) parahydroxydi-phenylamine, 2.39g (0.029mol) formaldehyde, and 1h is reacted at 80 DEG C.Question response knot
Shu Hou, vacuum distillation removes a small amount of water of solvent and generation, obtains final Mannich Base Detergent.Example reaction equation is as follows：
Embodiment 5
Obtained polyisobutene orthoresol 40.01g (0.038mol) in embodiment 1 is added to 500ml under nitrogen protection
In four mouthfuls of beakers equipped with agitator, thermometer and knockout, be subsequently adding 3.61g (0.019mol) TEPA,
3.25g (0.040mol) formaldehyde, and add the dimethylbenzene of 38ml as reaction dissolvent, after reacting 1.5h at 80 DEG C, it is cooled to room
Temperature, adds 4,4'- diaminourea biphenol, 1.63g (0.020mol) formaldehyde of 1.91g (0.0095mol), and 1h is reacted at 70 DEG C.
After question response terminates, vacuum distillation removes a small amount of water of solvent and generation, obtains final Mannich Base Detergent.Example is reacted
Formula reference implementation example 4.
Using following Mannich Base Detergent detersive as a comparison：
Contrast Mannich Base Detergent, is prepared, labeled as DQJ-1 by the embodiment 2 in CN103374085A；
Contrast Mannich Base Detergent, is prepared, labeled as DQJ-2 by the embodiment 4 in CN103374085A；
Contrast Mannich Base Detergent, is prepared, labeled as DQJ-3 by the embodiment 5 in CN103374085A；
Contrast Mannich Base Detergent, is prepared, labeled as DQJ-4 by the embodiment 6 in CN103374085A；
The embodiment 6~9 and comparative example 1~6 of lubricant oil composite
The embodiment 6~9 of lubricant oil composite and the formula composition of comparative example 1~6 are shown in Table 1,2.By each component in table
It is added to scale in mediation container, in 50 DEG C of heating stirrings 2 hours, the implementation for obtaining lubricant oil composite is prepared respectively
Example and comparative example.
Some lube oil additives for specifically being used are as follows：
N, N- bis-（2- ethylhexyls）- aminomethylene benzotriazole, R.T.Vanderbilt companies of the U.S., the trade mark
CUVAN303；
N, N- di-n-butyl aminomethylene benzotriazole, Jinzhou Kangtai Lube Additive Co., Ltd., trade mark T551；
The tert-butyl group/di-iso-octyldiphenylamine, Beijing Xing Pu fine chemical technologies development company, trade mark T534；
Dioctyl diphenylamine, Vanderbilt companies of the U.S., trade mark VAN LUBE81；
Zinc diamyldithiocarbamate, R.T.Vanderbilt companies of the U.S., trade mark VAN LUBE AZ；
Dialkyl dithio amino formate, Ruifeng Chemical Co., Ltd., Xinxiang, trade mark T323；
Lube base oil, III-4 base oils（Viscosity index (VI) is 121）；
Lube base oil, III-6 base oils（Viscosity index (VI) is 122）.
These lubricant oil composites are simulated the engine crankcase coking mould of piston deposit as test specimen
Intend experiment.The method is that 300ml test specimens are added into coking plate analog meter, 150 DEG C is heated to, using continuous mode to temperature
Spilled oil on the aluminium sheet for 310 DEG C is spent, the burnt amount generated on aluminium sheet, the deposit on simulation piston are weighed after 6 hours.Coking amount
Higher, the piston detergency for representing this test specimen is poorer.The deposit result of each lubricant oil composite QZX experiment is same to see
Table 1,2.
BRT ball rust tests are that instead of the engine rig test of the D of program II, are mainly used to engine evaluated lubricating oil
Anticorrosive and corrosion ability.During the bench test of whole 18 hours, the metal ball continuous contact for testing oil guard is acid
Liquid and air, after off-test, measure metal spherical reflector intensity, obtain gray scale test value, for determining corroded area,
So as to the resistant to rust ability of qualification test sample.The injection rate of acetic acid/hydrobromic acid/hydrochloric acid/deionized water solution is 0.19 milli
L/h, air draught is 40 ml/mins, and oil temperature is 48 DEG C.Appraisal result is higher, shows the rustless property of test specimen
Better.Above-mentioned ball rust test is carried out using the lubricant oil composite of the embodiment of the present invention and comparative example as test specimen, is tested
The results are shown in Table 1,2.
Table 1
Table 2
Claims (9)
1. a kind of lubricant oil composite, comprising Mannich base, diakylaminomethylene benzotriazole, alkylated diphenylamine and lubrication
Oil base oil, wherein the Mannich base includes following structure unit (I) and construction unit (II)：
Wherein, each R1It is identical or different, it is each independently selected from hydrogen, C1-4Straight or branched alkyl and singly-bound；Each R' is identical
Or it is different, it is each independently selected from hydrogen and C1-6Straight or branched alkyl；R2Selected from H, C1-8Alkyl, hydroxyl or nitro；R3It is selected from
C1-6Straight or branched alkyl；R4It is the alkyl of 300-3000 selected from number-average molecular weight Mn；Each y is identical or different, each independent
Integer of the ground selected from 2-5.
2. a kind of lubricant oil composite, comprising Mannich base, diakylaminomethylene benzotriazole, alkylated diphenylamine and lubrication
Oil base oil, wherein the Mannich base is as shown in following structure formula (III)：
Wherein, each A is identical or different, is each independently selected fromAnd hydrogen, on condition that at least one A isEach R' is identical or different, is each independently selected from hydrogen and C1-6Straight or branched alkyl；Each Ra
It is identical or different, it is each independently selected from hydrogen, C1-4Straight or branched alkyl and
On condition that at least one RaIt isEach RbIt is identical or different, it is each independently selected from
Hydrogen,And C1-4Straight or branched alkyl, on condition that at least one RbIt isR2
Selected from H, C1-8Alkyl, hydroxyl or nitro；R3Selected from C1-6Straight or branched alkyl；R4It is 300-3000 selected from number-average molecular weight Mn
Alkyl；Each y is identical or different, is each independently selected from the integer of 2-5；Each c is identical or different, is each independently selected from
The integer of 0-10.
3. a kind of lubricant oil composite, comprising Mannich base, diakylaminomethylene benzotriazole, alkylated diphenylamine and lubrication
Oil base oil, wherein the Mannich base is manufactured by following manufacture method, wherein the manufacture method includes making knot
The parahydroxydi-phenylamine compound of structure formula (V), the phenolic compounds of structure formula (VI), the polyalkylenepolyamines of structure formula (VII) and
C1-C7The step of there is Mannich reaction in straight or branched saturated aliphatic aldehyde,
Wherein, R2Selected from H, C1-8Alkyl, hydroxyl or nitro；R3Selected from C1-6Straight or branched alkyl；R4Selected from number-average molecular weight Mn
It is the alkyl of 300-3000；Each R'bIt is identical or different, it is each independently selected from hydrogen and C1-4Straight or branched alkyl, on condition that
At least two R'bIt is hydrogen；Y is selected from the integer of 2-5；C' is selected from the integer of 1-11；
Wherein described manufacture method is carried out one of in such a way：
Mode (1)：Comprise the following steps：
First step：Make phenolic compounds, the polyalkylenepolyamines and the C of the structure formula (VII) of the structure formula (VI)1-
C7There is Mannich reaction in straight or branched saturated aliphatic aldehyde, generate intermediate product at 50 DEG C -200 DEG C of reaction temperature；With
Second step：Make the parahydroxydi-phenylamine compound and the C of the intermediate product and the structure formula (V)1-C7Straight chain
Or chain is saturated fatty aldehyde occurs Mannich reaction at 40 DEG C -200 DEG C of reaction temperature, the Mannich base is generated,
Or
Mode (2)：Comprise the following steps：
First step：Make the polyalkylene of the parahydroxydi-phenylamine compound of the structure formula (V), the structure formula (VII) many
Amine and the C1-C7There is Mannich reaction in straight or branched saturated aliphatic aldehyde, at 40 DEG C -200 DEG C of reaction temperature in the middle of generation
Product；With
Second step：Make the phenolic compounds and the C of the intermediate product and the structure formula (VI)1-C7Straight or branched saturation
There is Mannich reaction in fatty aldehyde, generate the Mannich base at 50 DEG C -200 DEG C of reaction temperature,
Or
Mode (3)：Including make the parahydroxydi-phenylamine compound of the structure formula (V), the phenolic compounds of the structure formula (VI),
The polyalkylenepolyamines and the C of the structure formula (VII)1-C7Straight or branched saturated aliphatic aldehyde is in 40 DEG C -200 of reaction temperature
The step of there is Mannich reaction at DEG C and generate the Mannich base；
Wherein in the manufacture method, in the first step of the mode (1), the phenolic compounds of the structure formula (VI),
The polyalkylenepolyamines of the structure formula (VII) and the C1-C7Mol ratio between straight or branched saturated aliphatic aldehyde is 1:
0.3-3:0.3-3.5；In the second step of the mode (1), the intermediate product is with the structure formula (V) to hydroxyl two
Aniline compound and the C1-C7Mol ratio between straight or branched saturated aliphatic aldehyde is 1:0.2-1.5:0.2-2；Described
In the first step of mode (2), the parahydroxydi-phenylamine compound of the structure formula (V), many alkylenes of the structure formula (VII)
Quito amine and the C1-C7Mol ratio between straight or branched saturated aliphatic aldehyde is 1：1.5-2.5：1.5-3；In the mode
(2) in second step, the phenolic compounds and the C of the intermediate product and the structure formula (VI)1-C7Straight or branched is satisfied
Mol ratio and fatty aldehyde between is 1:1.5-3:1.5-3；In the mode (3), the structure formula (V) to hydroxyl hexichol
Amines, the phenolic compounds of the structure formula (VI), the polyalkylenepolyamines and the C of the structure formula (VII)1-C7Straight chain
Or the mol ratio between chain is saturated fatty aldehyde is 1:1-5:1-3:2-8.
4. it is described graceful according to the lubricant oil composite described in claim 3, it is characterised in that wherein in the manufacture method
Ni Xi is carried out in the presence of reacting one or more in selected from polyolefin, mineral base oil and polyethers of diluent.
5. according to the lubricant oil composite described in claim 3, it is characterised in that wherein in the manufacture method, the knot
The phenolic compounds of structure formula (VI) is by the presence of catalyst for alkylation reaction, making the phenolic compounds of structure formula (IV) equal with number
There is alkylated reaction and manufacture in molecular weight Mn for the polyolefin of 300-3000,
Wherein R3Selected from C1-6Straight or branched alkyl.
6. according to the lubricant oil composite that one of claim 1-5 is described, it is characterised in that wherein in mass, the dioxane
Base aminomethylene benzotriazole accounts for the 0.01~5% of the lubricant oil composite gross mass, and the alkylated diphenylamine accounts for described
The 0.01~8% of lubricant oil composite gross mass.
7. according to the lubricant oil composite described in claim 6, it is characterised in that wherein described diakylaminomethylene benzene three
Azoles is selected from C1-C12The diakylaminomethylene benzotriazole of alkyl；The alkylated diphenylamine is selected from C4-C16Alkylation hexichol
Amine.
8. according to the lubricant oil composite that one of claim 1-5 is described, it is characterised in that wherein in mass, the Manny
Uncommon alkali accounts for the 0.01%~20% of the lubricant oil composite gross mass.
9. according to the lubricant oil composite that one of claim 1-5 is described, it is characterised in that added in the lubricant oil composite
Dialkyl dithio amino formate and/or salt, the dialkyl dithio amino formate and/or salt account for the lubricating oil group
The 0.01~5% of compound gross mass.
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| US5030249A (en) * | 1990-10-01 | 1991-07-09 | Texaco Inc. | Gasoline detergent additive |
| US5725612A (en) * | 1996-06-07 | 1998-03-10 | Ethyl Corporation | Additives for minimizing intake valve deposits, and their use |
| CN101768484A (en) * | 2008-12-26 | 2010-07-07 | 中国石油化工股份有限公司 | Diesel composition |
| CN103374085A (en) * | 2012-04-26 | 2013-10-30 | 中国石油化工股份有限公司 | Mannich base and manufacturing method and application thereof |
-
2014
- 2014-03-25 CN CN201410112583.7A patent/CN104946350B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5030249A (en) * | 1990-10-01 | 1991-07-09 | Texaco Inc. | Gasoline detergent additive |
| US5725612A (en) * | 1996-06-07 | 1998-03-10 | Ethyl Corporation | Additives for minimizing intake valve deposits, and their use |
| CN101768484A (en) * | 2008-12-26 | 2010-07-07 | 中国石油化工股份有限公司 | Diesel composition |
| CN103374085A (en) * | 2012-04-26 | 2013-10-30 | 中国石油化工股份有限公司 | Mannich base and manufacturing method and application thereof |
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