CN104946351A - Lubricant composition and method for improving anti-wear and friction reduction properties of lubricant - Google Patents
Lubricant composition and method for improving anti-wear and friction reduction properties of lubricant Download PDFInfo
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- CN104946351A CN104946351A CN201410112584.1A CN201410112584A CN104946351A CN 104946351 A CN104946351 A CN 104946351A CN 201410112584 A CN201410112584 A CN 201410112584A CN 104946351 A CN104946351 A CN 104946351A
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- 0 CC(C)(CC(C)(C)N(C)*)*N(C1)C(*)C1c1cc(*)cc(C(*)N(*)CC*)c1O Chemical compound CC(C)(CC(C)(C)N(C)*)*N(C1)C(*)C1c1cc(*)cc(C(*)N(*)CC*)c1O 0.000 description 10
- WEWMOGXHNXAUPA-ACCUITESSA-N CC/C(/Nc1ccccc1)=C\CC(C)C Chemical compound CC/C(/Nc1ccccc1)=C\CC(C)C WEWMOGXHNXAUPA-ACCUITESSA-N 0.000 description 1
- XXYMSQQCBUKFHE-UHFFFAOYSA-N [O-][N+](c(cc1)ccc1Nc1ccccc1)=O Chemical compound [O-][N+](c(cc1)ccc1Nc1ccccc1)=O XXYMSQQCBUKFHE-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a lubricant composition and a method for improving anti-wear and friction reduction properties of a lubricant. The composition contains a Mannich base, an alkyl-naphthalene sulfonate, phenolic ester and/or a thio-phenolic ester antioxidant, alkyl monosulfide phenoxide and lubricant base oil, wherein the Mannich base contains a structural unit (I) and a structural unit (II) shown in the specification, wherein each R1 is same or different and is independently selected from hydrogen, C1-4 straight chain or branched chain alkyl and a single bond respectively; each R' is same or different and is independently selected form hydrogen and C1-6 straight chain or branched chain alkyl respectively; R2 is selected from H, C1-8 alkyl, hydroxyl or nitryl; R3 is selected from C1-6 straight chain or branched chain alkyl; R4 is selected from hydrocarbyl of which the number-average molecular weight Mn is 300-3000; and each y is same or different and is independently selected from an integer from 2 to 5 respectively. The lubricant composition provided by the invention is excellent in clean dispersion property, anti-wear and friction reduction properties and antirust property.
Description
Technical field
The present invention relates to a kind of lubricating oil composition, particularly relate to the lubricating oil composition of detergent-dispersant performance energy, antiwear and friction reduction property, high rust resistance.
Background technology
Unsaturated olefin in lubricant base, aromatic hydrocarbons and a small amount of sulfocompound very easily form colloid with oxygen reaction, and final formation carbon distribution settling, especially key position can the sedimental generation of boost engine in intake valve, piston, oil pan, combustion chamber etc., have 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, produces unnecessary expensive maintenance cost.By adding detergent-dispersant additive as lubricating oil additive in lubricant base, prior art has produced the lubricating oil composition with cleansing performance (settling generation rejection).Use this lubricating oil composition with cleansing performance, effectively can reduce coking and top land carbon deposit, reduce the wearing and tearing of valve system, reduce the corrosive wear of engine parts, extend safe operation cycle and spare part work-ing life of engine.
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.
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.
According to the present invention, the Mannich base that described detergent-dispersant additive comprises the aforesaid any Mannich base of the present invention (or mixture of its arbitrary proportion) or manufactures according to the manufacture method of the aforesaid Mannich base of the present invention.
According to the present invention, in order to manufacture described detergent-dispersant additive, aforesaid thinner can also be added further in described Mannich base.Now, described thinner can be used alone, and also can two or more combinationally use.Certainly, if Mannich base of the present invention has contained a certain amount of described thinner after manufacturing as previously mentioned, so now just can the add-on of the described thinner of corresponding minimizing, even do not need to add described thinner further can directly use as detergent-dispersant additive, this is obvious to those skilled in the art.
Generally speaking, in detergent-dispersant additive of the present invention, in mass, described Mannich base accounts for 10 ~ 70% of described detergent-dispersant additive total mass, and preferably 10 ~ 60%, most preferably 10 ~ 50%.
According to the present invention, in order to manufacture described detergent-dispersant additive, described Mannich base is mixed 1h-6h with described thinner (if you are using) at 20 DEG C-60 DEG C.
Mannich base of the present invention or detergent-dispersant additive are also particularly suitable for manufacturing lubricating oil composition, and this lubricating oil composition shows excellent cleansing performance.Therefore, according to the present invention, relate to a kind of lubricating oil composition further, the Mannich base that it comprises the aforesaid any Mannich base of the present invention (or mixture of its arbitrary proportion), manufacture according to the manufacture method of the aforesaid Mannich base of the present invention or the aforesaid detergent-dispersant additive of the present invention, and lubricant base.
According to the present invention, in order to manufacture described lubricating oil composition, using aforesaid for the present invention Mannich base, by the Mannich base that manufactured by the manufacture method of the aforesaid Mannich base of the present invention or the aforesaid detergent-dispersant additive of the present invention as one of lubricating oil additive, mix according to predetermined proportion or addition with lubricant base and sulfonated alkyl naphathalene, phenolic ester and/or sulfophenates oxidation inhibitor, alkyl monosulfide phenates.
More specifically, in order to manufacture lubricating oil composition of the present invention, above-mentioned each lubricating oil additive can be joined in lubricant base respectively or above-mentioned each lubricating oil additive is mixed and made into enriched material and join in lubricant base again, heating mixes.Mixing temperature is now generally 40 DEG C-90 DEG C, and mixing time is generally 1 hour-6 hours.
According to the present invention, as the addition of described Mannich base or described detergent-dispersant additive, make to account for 0.01% ~ 20% of described lubricating oil composition total mass in the amount (quality criteria) of the described Mannich base of Mannich base or described detergent-dispersant additive, preferably 0.02% ~ 15%, more preferably 0.1% ~ 10%.
Thinner due to the aforementioned use of the present invention is also frequent in fact in the art to be used as lubricant base, therefore in the following description it is directly classified as lubricant base and is not re-used as an independent component and describes separately.
According to the present invention, as described sulfonated alkyl naphathalene, can select in alkyl naphthalene sulfonic acid calcium, alkyl naphthalene sulfonic acid magnesium, alkyl naphthalene sulfonic acid barium and sodium alkyl naphthalene sulfonate one or more, alkyl is wherein C
4-C
24alkyl, preferred C
8-C
16alkyl.The preferred C of described sulfonated alkyl naphathalene
4-C
24the naphthene sulfonic acid calcium of alkyl.
Described sulfonated alkyl naphathalene accounts for 0.01 ~ 10% of described lubricating oil composition total mass, and preferably 0.02% ~ 5%, more preferably 0.05% ~ 3%.
Described phenolic ester and/or sulfophenates oxidation inhibitor are selected from ester with hindered phenol structure and/or monothioester, can 2 be selected, 6-di-tert-butyl-hydroxy phenyl n-octyl propionate, 2, 6-di-tert-butyl-hydroxy phenyl nonyl propionate, 2, 6-di-tert-butyl-hydroxy phenyl n-decyl propionate, 2, 6-di-tert-butyl-hydroxy phenyl third dodecyl gallate, 2, 2'-thiobis [3-(3, 5-di-tert-butyl-hydroxy phenyl) ethyl propionate], thiobis-(3, 5-di-t-butyl-4-hydroxyl benzyl), 2, 2'-thiobis (4-methyl-6-tert-butylphenol) and 4, one or more in 4'-thiobis (6-tert-butyl-m-cresol), the T512 that trade names can select Beijing Xing Pu company to produce, the IRGANOX L-135 that BASF Aktiengesellschaft produces, the T535 that Ruifeng Chemical Co., Ltd., Xinxiang produces, the oxidation inhibitor 1035 that Sichuan Yong Ye Chemical Co., Ltd. produces, the IRGANOX L115 that BASF Aktiengesellschaft produces, the methene 4426-S that Changzhou Ling Chi chemical company produces, the Lowinox TBP-6 that Great Lakes Chemical of the U.S. produces, the Irganox1081 that BASF Aktiengesellschaft produces.Described phenolic ester and/or sulfophenates oxidation inhibitor is 2,6-di-tert-butyl-hydroxy phenyl n-octyl propionates and/or 2,2'-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate] preferably.
Described phenolic ester and/or sulfophenates oxidation inhibitor account for 0.01 ~ 5% of described lubricating oil composition total mass, and preferably 0.02% ~ 3%, more preferably 0.05% ~ 2%.
Described alkyl monosulfide phenates be selected from calcium sulfenyl phenolate, sulfenyl phenolate magnesium and sulfenyl phenolate barium one or more, alkyl is wherein C
2-C
18alkyl, preferred C
4-C
16alkyl, preferred calcium sulfenyl phenolate, most preferably SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER.
Described alkyl monosulfide phenates accounts for 0.01 ~ 10% of described lubricating oil composition total mass, and preferably 0.1% ~ 5%, more preferably 0.5% ~ 3%.
According to the present invention, as described lubricant base, can select in API I, II, III, IV, V class lubricating oil base oil one or more, such as can enumerate be selected from mineral lubricating oils and ucon oil one or more.
According to the present invention, described lubricant base viscosity index is generally greater than 80, saturated hydrocarbon content massfraction is greater than 90% and sulphur content massfraction is less than 0.03%.
In lubricating oil composition of the present invention, also preferably add dialkyl dithio amino formate and/or salt, alkyl is wherein C
1-12alkyl, preferred C
1-8alkyl can be one or more in ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl and 2-ethylhexyl.Described dialkyl dithiocarbamate can select in zinc dialkyl dithiocarbamate, molybdenum dialkyldithiocarbamacompositions, copper dialkyldithiocarbamate, antimony dialkyl-dithiocarbamate and Bismuth dibutyldithiocarbamate one or more, preferred zinc dialkyl dithiocarbamate.
Described dialkyl dithio amino formate and/or salt account for 0.01 ~ 5% of described lubricating oil composition total mass, and preferably 0.02% ~ 3%, more preferably 0.05% ~ 2%.
One or more other lubricating oil additives in pour point depressant, viscosity index improver, metal corrosion inhibitor, rust-preventive agent and kilfoam can also be added in lubricating oil composition of the present invention, its consumption, from the conventional amount used of this area, is not particularly limited.
Lubricating oil composition of the present invention has excellent detergent-dispersant performance energy, antiwear and friction reduction property and rustless property.
Summary of the invention
Specifically, the present invention relates to the content of following aspect.
1. a lubricating oil composition, comprises Mannich base, sulfonated alkyl naphathalene, phenolic ester and/or sulfophenates oxidation inhibitor, alkyl monosulfide phenates and lubricant base, and wherein said 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 H, C
1-8alkyl, hydroxyl or nitro, preferred H, C
1-4alkyl or hydroxyl, most preferably H; 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. a lubricating oil composition, comprises Mannich base, sulfonated alkyl naphathalene, phenolic ester and/or sulfophenates oxidation inhibitor, alkyl monosulfide phenates and lubricant base, and wherein said Mannich base is as 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 H, C
1-8alkyl, hydroxyl or nitro, preferred H, C
1-4alkyl or hydroxyl, most preferably H; 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 lubricating oil composition, comprise Mannich base, sulfonated alkyl naphathalene, phenolic ester and/or sulfophenates oxidation inhibitor, alkyl monosulfide phenates and lubricant base, wherein said Mannich base is manufactured by following manufacture method, and wherein said manufacture method comprises the p-hydroxydiphenylamine 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 H, C
1-8alkyl, hydroxyl or nitro, preferred H, C
1-4alkyl or hydroxyl, most preferably H; 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. the lubricating oil composition of any preceding aspect, wherein said manufacture method is 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);
Second step: make the p-hydroxydiphenylamine 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 p-hydroxydiphenylamine 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);
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 p-hydroxydiphenylamine compound making described structure formula V, the phenolic compound of described structural formula (VI), the polyalkylenepolyamines of described structural formula (VII) and described C
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. the lubricating oil composition of any preceding aspect, wherein in described manufacture method, 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 p-hydroxydiphenylamine 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 p-hydroxydiphenylamine 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 p-hydroxydiphenylamine 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. the lubricating oil composition of any preceding aspect, wherein in described manufacture method, described Mannich reaction is carried out under the existence being selected from one or more the thinner in polyolefine, mineral base oil and polyethers.
7. the lubricating oil composition of any preceding aspect, wherein in described manufacture method, the phenolic compound of described 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
3be selected from C
1-6straight or branched alkyl, is preferably selected from C
1-4straight or branched alkyl, more preferably methyl.
8. the lubricating oil composition of any preceding aspect, wherein in mass, 0.01 ~ 10%(that described sulfonated alkyl naphathalene accounts for described lubricating oil composition total mass preferably 0.02% ~ 5%, more preferably 0.05% ~ 3%), 0.01 ~ 5%(that described phenolic ester and/or sulfophenates oxidation inhibitor account for described lubricating oil composition total mass preferably 0.02% ~ 3%, more preferably 0.05% ~ 2%), 0.01 ~ 10%(that described alkyl monosulfide phenates accounts for described lubricating oil composition total mass preferably 0.1% ~ 5%, more preferably 0.5% ~ 3%).
9. the lubricating oil composition of any preceding aspect, wherein said sulfonated alkyl naphathalene be selected from alkyl naphthalene sulfonic acid calcium, alkyl naphthalene sulfonic acid magnesium, alkyl naphthalene sulfonic acid barium and sodium alkyl naphthalene sulfonate one or more, alkyl is wherein C
4-C
24alkyl; Described phenolic ester and/or sulfophenates oxidation inhibitor are selected from ester with hindered phenol structure and/or monothioester; Described alkyl monosulfide phenates be selected from calcium sulfenyl phenolate, sulfenyl phenolate magnesium and sulfenyl phenolate barium one or more, alkyl is wherein C
2-C
18alkyl.
10. the lubricating oil composition of any preceding aspect, wherein in mass, described Mannich base accounts for 0.01% ~ 20% of described lubricating oil composition total mass, and preferably 0.02% ~ 15%, more preferably 0.1% ~ 10%.
The lubricating oil composition of 11. any preceding aspect, dialkyl dithio amino formate and/or salt is added in described lubricating oil composition, 0.01 ~ 5%(that described dialkyl dithio amino formate and/or salt account for described lubricating oil composition total mass preferably 0.02% ~ 3%, more preferably 0.05% ~ 2%).
12. 1 kinds of methods improving lubrication oil antiwear antifriction performance, is characterized in that, by above-mentioned Mannich base, sulfonated alkyl naphathalene, phenolic ester and/or sulfophenates oxidation inhibitor, alkyl monosulfide phenates and lubricant base mixing.
Embodiment
Below the specific embodiment of the present invention is described in detail, but it is pointed out that protection scope of the present invention not by the restriction of these embodiments, but determined by claims of annex.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.
Although can with being similar to or being equal to method as herein described and material in practice or test the present invention, the method be suitable for 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 measured by gel permeation chromatography (GPC).
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 H, C
1-8alkyl, hydroxyl or nitro, preferred H, C
1-4alkyl or hydroxyl, most preferably H; 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 selected from H, C
1-8alkyl, hydroxyl or nitro, preferred H, C
1-4alkyl or hydroxyl, most preferably H.
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
or
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 when R1 is 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 H, C
1-8alkyl, hydroxyl or nitro, preferred H, C
1-4alkyl or hydroxyl, most preferably H; 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
in, 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 selected from H, C
1-8alkyl, hydroxyl or nitro, preferred H, C
1-4alkyl or hydroxyl, most preferably H.
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 p-hydroxydiphenylamine 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 H, C
1-8alkyl, hydroxyl or nitro, preferred H, C
1-4alkyl or hydroxyl, most preferably H; 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
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 p-hydroxydiphenylamine 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 p-hydroxydiphenylamine 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 p-hydroxydiphenylamine compound making described structure formula V, the phenolic compound of described structural formula (VI), the polyalkylenepolyamines of described structural formula (VII) and described C
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 p-hydroxydiphenylamine 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 p-hydroxydiphenylamine 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 p-hydroxydiphenylamine 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, C6-20 aromatic hydrocarbon (such as toluene and dimethylbenzene) etc. such as can be enumerated.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 gives the detail of the pharmaceutical chemicals used in embodiment and comparative example.
| 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 |
| P-hydroxydiphenylamine | Tokyo changes into Industrial Co., Ltd | ||
| 4-hydroxyl-2'-nitrodiphenylamine | Tokyo changes into Industrial Co., Ltd | ||
| 4,4'-diamino biphenol | Tokyo changes into Industrial Co., Ltd |
Embodiment 1 synthesizing polyisobutylene ortho-cresol
In the 500ml four-hole boiling flask that agitator, thermometer, prolong and dropping funnel are housed, add the polyisobutene (Mn=1000) of 34.93g (0.323mol) ortho-cresol, the boron trifluoride diethyl etherate catalyzer 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.The hydroxyl valency of synthetic product polyisobutene ortho-cresol is 53.49mg/g.Hydroxy value measuring is with reference to the acetic anhydride method in GB/T7383-2007.
Example reaction formula is as follows:
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 four mouthfuls of beakers 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 p-hydroxydiphenylamine of 4.17g (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 purification agent.Example reaction formula is as follows:
Embodiment 3
Polyisobutene ortho-cresol 53.37g (0.051mol) obtained in embodiment 1 is added to 500ml to be under nitrogen protection equipped with in four mouthfuls of beakers of agitator, thermometer and skimmer; then the triethylene tetramine 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 5.87g (0.0255mol) 4-hydroxyl-2'-nitrodiphenylamine, 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 purification agent.Example reaction formula reference example 2.
Embodiment 4
Polyisobutene ortho-cresol 58.80g (0.056mol) obtained in embodiment 1 is added to 500ml to be under nitrogen protection equipped with in four mouthfuls of beakers 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 2.59g (0.014mol) p-hydroxydiphenylamine, 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 purification agent.Example reaction formula is as follows:
Embodiment 5
Polyisobutene ortho-cresol 40.01g (0.038mol) obtained in embodiment 1 is added to 500ml to be under nitrogen protection equipped with in four mouthfuls of beakers 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 4 of 1.91g (0.0095mol); 4'-diamino biphenol, 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 purification agent.Example reaction formula reference example 4.
Adopt following Mannich base purification agent purification agent as a comparison:
Contrast Mannich base purification agent, prepares by the embodiment 2 in CN103374085A, is labeled as DQJ-1;
Contrast Mannich base purification agent, prepares by the embodiment 4 in CN103374085A, is labeled as DQJ-2;
Contrast Mannich base purification agent, prepares by the embodiment 5 in CN103374085A, is labeled as DQJ-3;
Contrast Mannich base purification agent, prepares by the embodiment 6 in CN103374085A, is labeled as DQJ-4;
The embodiment 6 ~ 9 of lubricating oil composition and comparative example 1 ~ 7
The embodiment 6 ~ 9 of lubricating oil composition and the formula composition of comparative example 1 ~ 7 are in table 1,2.Component each in table joined to scale and be in harmonious proportion in container, 50 DEG C of heated and stirred 2 hours, preparation obtained embodiment and the comparative example of lubricating oil composition respectively.
Concrete some lubricating oil additives used are as follows:
Dinonylnaphthalene sulfonic acid calcium, U.S. Jin Shi industrial special chemical company, trade mark NA-SUL729;
Dinonylnaphthalene sulfonic acid magnesium, U.S. Jin Shi industrial special chemical company, trade mark NA-SUL MG;
2,6-di-tert-butyl-hydroxy phenyl n-octyl propionate, Beijing Xing Pu fine chemical technology development company, trade mark T512;
2,2'-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate, Ruifeng Chemical Co., Ltd., Xinxiang, trade mark T535;
Calcium sulfenyl phenolate, total basicnumber >=240mgKOH/g, Ruifeng Chemical Co., Ltd., Xinxiang, trade mark T122;
Zinc diamyldithiocarbamate, R.T.Vanderbilt company of the U.S., trade mark VAN LUBE AZ;
Dialkyl dithio amino formate, Ruifeng Chemical Co., Ltd., Xinxiang, trade mark T323;
Lubricant base, II base oil 100N(viscosity index is 115);
Lubricant base, II base oil 150N(viscosity index is 109).
These lubricating oil compositions are carried out as test sample the base chamber coking simulation test simulating piston deposit.The method is that 300ml test sample is added coking plate analog meter, is heated to 150 DEG C, adopts continuous print mode to be spilled oil on the aluminium sheet of 310 DEG C to temperature, weighs Jiao's amount that aluminium sheet generates after 6 hours, the settling on simulation piston.Coking amount is higher, and the piston detergency representing this test sample is poorer.The settling result of each lubricating oil composition QZX experiment is same in table 1,2.
The high temperature adopting the high-frequency reciprocating frictional testing machines composition to embodiment 6 ~ 9 and comparative example 1 ~ 7 to carry out oil product resistance to wears test, and test conditions is: load 1000g, and frequency is 20Hz, and temperature is 100 DEG C, and test period is 60min.The wear-resistant result of high temperature is as shown in table 1,2.
BRT ball rust test is the engine rig test of replacement program II D, is mainly used to the anticorrosive of engine evaluated lubricating oil and corrosion ability.In the bench testing process of whole 18 hours, the Metal Ball continuous contact acidic liquid of test oil guard and air, after off-test; measure Metal Ball plane of reflection intensity; obtain gray scale test value, be used for determining corroded area, thus the resistant to tarnishing ability of qualification test sample.The injection speed of acetic acid/Hydrogen bromide/hydrochloric acid/deionized water solution is 0.19 ml/hour, and air draught is 40 ml/min, and oil temperature is 48 DEG C.Appraisal result is higher, shows that the rustless property of test sample is better.The lubricating oil composition of the embodiment of the present invention and comparative example is carried out above-mentioned ball rust test as test sample, and test-results is in table 1,2.
Table 1
Table 2
Claims (12)
1. a lubricating oil composition, comprises Mannich base, sulfonated alkyl naphathalene, phenolic ester and/or sulfophenates oxidation inhibitor, alkyl monosulfide phenates and lubricant base, and wherein said 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 H, C
1-8alkyl, hydroxyl or nitro, preferred H, C
1-4alkyl or hydroxyl, most preferably H; 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. a lubricating oil composition, comprises Mannich base, sulfonated alkyl naphathalene, phenolic ester and/or sulfophenates oxidation inhibitor, alkyl monosulfide phenates and lubricant base, and wherein said Mannich base is as 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 H, C
1-8alkyl, hydroxyl or nitro, preferred H, C
1-4alkyl or hydroxyl, most preferably H; 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 lubricating oil composition, comprise Mannich base, sulfonated alkyl naphathalene, phenolic ester and/or sulfophenates oxidation inhibitor, alkyl monosulfide phenates and lubricant base, wherein said Mannich base is manufactured by following manufacture method, and wherein said manufacture method comprises the p-hydroxydiphenylamine 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 H, C
1-8alkyl, hydroxyl or nitro, preferred H, C
1-4alkyl or hydroxyl, most preferably H; 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 lubricating oil composition according to claim 3, it is characterized in that, wherein said manufacture method is 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 p-hydroxydiphenylamine 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 p-hydroxydiphenylamine 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 p-hydroxydiphenylamine compound making described structure formula V, the phenolic compound of described structural formula (VI), the polyalkylenepolyamines of described structural formula (VII) and described C
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 lubricating oil composition according to claim 4, it is characterized in that, wherein in described manufacture method, 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 p-hydroxydiphenylamine 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 p-hydroxydiphenylamine 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 p-hydroxydiphenylamine 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 lubricating oil composition according to claim 3, it is characterized in that, wherein in described manufacture method, described Mannich reaction is carried out under the existence being selected from one or more the thinner in polyolefine, mineral base oil and polyethers.
7. according to lubricating oil composition according to claim 3, it is characterized in that, wherein in described manufacture method, the phenolic compound of described 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.
8. according to the lubricating oil composition one of claim 1-7 Suo Shu, it is characterized in that, wherein in mass, 0.01 ~ 10%(that described sulfonated alkyl naphathalene accounts for described lubricating oil composition total mass preferably 0.02% ~ 5%, more preferably 0.05% ~ 3%), 0.01 ~ 5%(that described phenolic ester and/or sulfophenates oxidation inhibitor account for described lubricating oil composition total mass preferably 0.02% ~ 3%, more preferably 0.05% ~ 2%), 0.01 ~ 10%(that described alkyl monosulfide phenates accounts for described lubricating oil composition total mass preferably 0.1% ~ 5%, more preferably 0.5% ~ 3%).
9., according to lubricating oil composition according to claim 8, it is characterized in that, wherein said sulfonated alkyl naphathalene be selected from alkyl naphthalene sulfonic acid calcium, alkyl naphthalene sulfonic acid magnesium, alkyl naphthalene sulfonic acid barium and sodium alkyl naphthalene sulfonate one or more, alkyl is wherein C
4-C
24alkyl; Described phenolic ester and/or sulfophenates oxidation inhibitor are selected from ester with hindered phenol structure and/or monothioester; Described alkyl monosulfide phenates be selected from calcium sulfenyl phenolate, sulfenyl phenolate magnesium and sulfenyl phenolate barium one or more, alkyl is wherein C
2-C
18alkyl.
10., according to the lubricating oil composition one of claim 1-7 Suo Shu, it is characterized in that, wherein in mass, 0.01% ~ 20%(that described Mannich base accounts for described lubricating oil composition total mass preferably 0.02% ~ 15%, more preferably 0.1% ~ 10%).
11. according to the lubricating oil composition one of claim 1-7 Suo Shu, it is characterized in that, dialkyl dithio amino formate and/or salt is added in described lubricating oil composition, 0.01 ~ 5%(that described dialkyl dithio amino formate and/or salt account for described lubricating oil composition total mass preferably 0.02% ~ 3%, more preferably 0.05% ~ 2%).
12. 1 kinds of methods improving lubrication oil antiwear antifriction performance, is characterized in that, by Mannich base, sulfonated alkyl naphathalene, phenolic ester and/or sulfophenates oxidation inhibitor described one of in claim 1-7, alkyl monosulfide phenates and lubricant base mixing.
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| CN115537247A (en) * | 2022-10-08 | 2022-12-30 | 晏翔 | Wear-resistant additive, wear-resistant lubricating oil and preparation method |
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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 |
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