CN106318528B - Universal gear lubricating oil composition - Google Patents
Universal gear lubricating oil composition Download PDFInfo
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- CN106318528B CN106318528B CN201510347775.0A CN201510347775A CN106318528B CN 106318528 B CN106318528 B CN 106318528B CN 201510347775 A CN201510347775 A CN 201510347775A CN 106318528 B CN106318528 B CN 106318528B
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Abstract
The present invention relates to a kind of universal gear lubricating oil compositions, including shielding phenolic compounds, extreme pressure anti-wear additives, metal deactivator, Ashless friction modifiers and major amount of lube base oil；The structure of the shielding phenolic compounds is shown in formula (I):
Description
Technical field
The present invention relates to a kind of universal gear lubricating oil compositions.Specifically, the present invention relates to it is a kind of meet GL-5 and
The universal gear lubricating oil composition of the above specification extreme pressure heavy load gear oil product requirement.
Background technique
Lubrication of the automotive gear oil for parts such as mechanical transmission, the gear of drive axle and diverter, bearings, is played
Lubrication, cooling, antirust and buffering effect.With the development of the automobile industry, gear-box volume becomes smaller, load increases, operation item
Part is more severe, causes gear oil temperature to increase, it is desirable that gear oil has higher oxidation stability.Wherein, Modern Car is using double
Curved tooth cylindrical gear, operating condition is more harsh, higher to the requirement of automobile gear oil's service performance, because its axis bias amount is larger,
Speed Gao Shihui keeps the relative sliding velocity between gear wheel face very high, and oil temperature is made to reach 160 DEG C -180 DEG C.Currently, to gear oil
The concern of antioxygenic property is also far from enough.In order to improve the oxidation stability of gear oil, most effective method is that antioxygen is added
Agent.
Unsaturated olefin, aromatic hydrocarbons and a small amount of sulfur-containing compound in lube base oil easily react to form glue with oxygen
Matter, and ultimately form carbon distribution deposit.Carbon deposits make gearbox gear rotation unsmooth, increase the abrasion of gear, shorten tooth
The roller box service life.Therefore, in order to preferably protect gear, gear oil also needs better cleansing performance.
United States Patent (USP) US 5304314 discloses a kind of phenolic compounds for being suitable as sulfur-bearing and arylamine that antioxidant uses.
United States Patent (USP) US 2006/0189824A1 discloses a kind of shielding phenolic compounds containing secondary aromatic amine for being suitable as antioxidant.
But the compound of these prior arts in gear oil in use, the antioxygenic property of oil product, cleansing performance and
Abrasion resistance still remains room for improvement.
In addition, other than the adverse effect of deposit, the corrosion of engine also can serious curtailment engine service life, and
And the corrosion of some key positions largely also influences the performance of operating condition of engine.Pass of the prior art to rustless property
It infuses also far from enough.
Therefore, a kind of general universal gear lubricating oil composition is still required in the prior art, is not only able to meet current
The requirement increasingly harsh to antioxygenic property of more high standard product, and can also show excellent detergent-dispersant performance energy, wear-resistant
Performance and rustless property.
Summary of the invention
The present inventor passes through diligent research on the basis of existing technology, it was found that a kind of novel shielding phenolate conjunction
Object, and it has furthermore been found that general gear lubricating oil composition is prepared as antioxidant by using the shielding phenolic compounds
Object, so that it may solve foregoing problems of the existing technology, and have thus completed the present invention.
Specifically, the present invention relates to the contents of following aspect.
1. a kind of universal gear lubricating oil composition, including shielding phenolic compounds, extreme pressure anti-wear additives, metal deactivator, nothing
Grey friction improver and major amount of lube base oil；
The structure of the shielding phenolic compounds are as follows:
In logical formula (I), each group R is same or different to each other, and is each independently selected from hydrogen, C1-300Linear or branched alkyl group
(preferably C1-10Linear or branched alkyl group or number-average molecular weight Mn are the polyolefin-based of 300-3000), base shown in logical formula (II)
Group shown in group and logical formula (III), on condition that at least one group R is group shown in logical formula (II)；Each group R' is each other
It is identical or different, it is each independently selected from hydrogen and C1-20Linear or branched alkyl group (is preferably each independently selected from hydrogen and C1-4Straight chain
Or branched alkyl),
In aforementioned each logical formula (II), (III) and (IV), it is group each independently that each group L, which is same or different to each other,Wherein group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Linear or branched alkyl group) and C3-20Straight chain or branch
Chain miscellaneous alkyl is preferably selected from hydrogen, C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl；Each group R2It is mutually the same
Or it is different, it is each independently selected from hydrogen, C1-20Shown in group shown in linear or branched alkyl group, logical formula (IV) and logical formula (V)
Group (is preferably each independently selected from hydrogen, C1-10Group shown in linear or branched alkyl group and logical formula (IV))；Each group RbEach other
It is identical or different, it is each independently selected from hydrogen and C1-20Linear or branched alkyl group (is preferably each independently selected from hydrogen and C1-10Straight chain
Or branched alkyl)；Each group RcIt is same or different to each other, is each independently selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Directly
Chain or branched alkyl oxygroup (are preferably each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygen
Base is more preferably in cyclic groupThe contraposition of upper nitrogen-atoms)；Y is 0 to 3 integer (preferably 0 or 1)；Z is 0 to 3
Integer (preferably 0 or 1)；The integer (preferably 1 or 2) that n is 1 to 8；The integer (preferably 0,1 or 2) that n' is 0 to 7, on condition that n'+
N≤8 (preferably n'+n=1 or n'+n=2)；Each group RdIt is same or different to each other, is each independently selected from hydrogen and logical formula (V) institute
The group (preferably hydrogen) shown；Each cyclic groupIt is same or different to each other, is each independently selected from phenyl ring and naphthalene nucleus
(preferably phenyl ring), wherein two adjacent cyclic groupsOptionally pass through additional S atom each other and bridges the two
The N atom of ring and form phenthazine ring, and/or, two adjacent cyclic groupsOptionally pass through additional base each other
Group(wherein group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Linear or branched alkyl group) and C3-20Straight chain or
Branched heteroalkyl groups are preferably selected from hydrogen and C1-10Linear or branched alkyl group) and bridge the N atom of the two rings and form 9,10- bis-
Hydrogen acridine ring,
In logical formula (V), each group R is same or different to each other, and is each independently selected from hydrogen, C1-300Linear or branched alkyl group
(preferably C1-10Linear or branched alkyl group or number-average molecular weight Mn are the polyolefin-based of 300-3000), base shown in logical formula (II)
Group shown in group and logical formula (III) (is preferably each independently selected from hydrogen and C1-300Linear or branched alkyl group)；Each group R' that
This is identical or different, is each independently selected from hydrogen and C1-20Linear or branched alkyl group (is preferably each independently selected from hydrogen and C1-4Directly
Chain or branched alkyl)；Group L is groupWherein group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight chain
Or branched alkyl) and C3-20Linear chain or branched chain miscellaneous alkyl is preferably selected from hydrogen, C1-10Linear or branched alkyl group and C3-10Straight chain or branch
Chain miscellaneous alkyl；A is 0 or 1, and two group R and a group-(S)a- L- occupies three positions of the residue on phenyl ring respectively,
Wherein, the linear chain or branched chain miscellaneous alkyl is selected from the one or more inside linear or branched alkyl group molecular structure
(such as 1 to 4,1 to 3,1 to 2 or 1) group-CH2Being selected from-O- ,-S- and-NR'-, (R' is H or C1-4Straight chain
Or branched alkyl) one of substituting group directly substitute and one inside the group and linear or branched alkyl group molecular structure that obtain
A or multiple (such as 1 to 3,1 to 2 or 1) group-CH <by substituting group-N < is directly substituted and the group of acquisition,
The wherein shielding phenolic compounds at least one group R in its entire molecular structuredIt is hydrogen.
2. according to shielding phenolic compounds described in any preceding aspect, particular compound selected from the following or its arbitrary proportion
Mixture:
3. the manufacturing method of the shielding phenolic compounds, including make shown in phenolic compounds shown in logical formula (X) and general formula (Y)
The first step that reacts in the presence of aldehyde compound (preferably formaldehyde) shown in general formula (Z) of amine compounds, optionally also
Including react the reaction product of the first step with vulcanizing agent (preferably sulphur) and/or with aldehyde compound shown in general formula (Z)
The additional step of (preferably formaldehyde) reaction,
In logical formula (X), each group R0It is same or different to each other, is each independently selected from hydrogen ,-SH and C1-300Linear chain or branched chain
Alkyl (preferably C1-10Linear or branched alkyl group or number-average molecular weight Mn are the polyolefin-based of 300-3000), on condition that at least one
A group R0It is-SH；Each group R' is same or different to each other, and is each independently selected from hydrogen and C1-20Linear or branched alkyl group is (preferably
It is each independently selected from hydrogen and C1-4Linear or branched alkyl group),
In general formula (Y), group R'2Selected from hydrogen, C1-20Linear or branched alkyl group and groupRespectively
Group RbIt is same or different to each other, is each independently selected from hydrogen and C1-20Linear or branched alkyl group (is preferably each independently selected from hydrogen
And C1-10Linear or branched alkyl group)；Each group RcIt is same or different to each other, is each independently selected from hydrogen, C1-20Linear chain or branched chain alkane
Base and C1-20Linear or branched alkyl group oxygroup (is preferably each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Straight chain or
Branched alkyl oxygroup, is more preferably in cyclic groupThe contraposition of upper nitrogen-atoms)；Y be 0 to 3 integer (preferably 0 or
1)；Z is 0 to 3 integer (preferably 0 or 1)；The integer (preferably 1 or 2) that n1 is 1 to 8；Each cyclic groupPhase each other
It is same or different, it is each independently selected from phenyl ring and naphthalene nucleus (preferably phenyl ring),
In general formula (Z), group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Linear or branched alkyl group) and C3-20Straight chain or branch
Chain miscellaneous alkyl is preferably selected from hydrogen, C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl,
Wherein, the linear chain or branched chain miscellaneous alkyl is selected from the one or more inside linear or branched alkyl group molecular structure
(such as 1 to 4,1 to 3,1 to 2 or 1) group-CH2Being selected from-O- ,-S- and-NR'-, (R' is H or C1-4Straight chain
Or branched alkyl) one of substituting group directly substitute and one inside the group and linear or branched alkyl group molecular structure that obtain
A or multiple (such as 1 to 3,1 to 2 or 1) group-CH <by substituting group-N < is directly substituted and the group of acquisition.
4. according to manufacturing method described in any preceding aspect, wherein in the first step, shown in the logical formula (X)
Phenolic compounds and the general formula (Y) shown in amine compounds molar ratio be 1:0.1-10, preferably 1:0.5-5.0, more preferably
The molar ratio of 1:0.8-2.0, aldehyde compound shown in phenolic compounds and the general formula (Z) shown in the logical formula (X) are 1:
0.1-10, preferably 1:0.5-5.0, more preferable 1:0.8-2.0, in the additional step, amine compounds shown in the general formula (Y)
The molar ratio of object and the vulcanizing agent is 1:1-10, preferably 1:1.2-6.0, more preferable 1:1.5-3.0, shown in the general formula (Y)
Amine compounds and the general formula (Z) shown in aldehyde compound molar ratio be 1:0.1-10, preferably 1:0.5-5.0, more preferably
1:0.8-2.0。
5. in the universal gear lubricating oil composition described in any preceding aspect, the shielding phenolic compounds accounts for described logical
With the 0.001%-30% of gear lubricating oil composition total weight, preferably 0.05%-20%, more preferable 0.1%-10%；
The extreme pressure anti-wear additives can be selected from phosphate, olefine sulfide, dialkyl dithiocarbamate and dialkyl group
One of dithiophosphates is a variety of；
The phosphate can be selected from the di-n-butyl phosphite for selecting the production of Shandong Zibo Hui Hua Chemical Co., Ltd.
T304, the tricresyl phosphate T306 of the Shanghai chemical plant Peng Pu production, the Irgalube353 etc. of BASF Corp. of Germany's production.Institute
State the sulfide isobutene that olefine sulfide can be produced selected from Nanjing Aidichen Chemical Enterprise Co., Ltd., Shandong east chemical fertilizer factory
T321, the Anglamol33 of Lubrizol Corp., the U.S., american exxon-Mobil Corporation Mobilad C-170 etc..The dioxane
Base dithiocar-bamate can be selected from the one or more of zinc dialkyl dithiocarbamate salt, lead salt and antimonic salt,
In alkyl be the alkyl containing 2 to 12 carbon atoms, the preferably alkyl containing 2 to 8 carbon atoms, can be ethyl,
N-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohesyl, n-octyl, 2- ethyl
One of hexyl, cyclohexyl, methylcyclopentyl are a variety of.The dialkyl dithiophosphate can be selected from C2-12Alkyl
ZDDP is preferably selected from C3-8Alkyl ZDDP, alkyl can select ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, Zhong Ding
One of base, n-pentyl, isopentyl, n-hexyl, isohesyl, n-octyl, 2- ethylhexyl, cyclohexyl and methylcyclopentyl or
It is a variety of；
The extreme pressure anti-wear additives are preferably selected from the combination of olefine sulfide and dialkyl dithiophosphate, both in the combination
Between mass ratio be 0.1:1-10:1, be preferably in a proportion of 0.2:1-8:1, more preferable ratio is 0.3:1-5:1；
The extreme pressure anti-wear additives account for the 0.1%-10% of the universal gear lubricating oil composition gross mass, preferably 0.2%-
8%, more preferable 0.5%-5%；
The metal deactivator is selected from one of benzotriazole derivative, thiazole and thiadiazoles derivative or more
Kind, common metal deactivator includes benzotriazole, benzothiazole, tolyl-triazole, octyl triazole, 2- sulfydryl benzo thiophene
Azoles, 2,5- dimercapto -1,3,4- thiadiazoles, 2- sulfydryl -5- hydrocarbon substitution -1,3,4- thiadiazoles, 2- dimercapto -5- two thio -1,
3,4- thiadiazoles, N, N- dihexyl aminomethylene benzotriazole, 2- sulfydryl diazosulfide etc., trade names have T551, T561,
T706 etc., T551, T561, T706 etc. that Jinzhou Kangtai Lube Additive Co., Ltd. can be selected to produce；
The preferred thiadiazoles derivative of metal deactivator；
The metal deactivator accounts for the 0.01%-5% of the universal gear lubricating oil composition gross mass, preferably
0.02%-3%, more preferable 0.05%-2%；
The Ashless friction modifiers can be with one of selected fatty acid amide, polyol esters of fatty acids and aliphatic amine
Or it is a variety of, wherein aliphatic alkyl is saturation or unsaturated alkyl of the carbon atom number between 6-60, preferably carbon atom number exists
Saturation or unsaturated alkyl between 10-50.The example of the aliphatic amide includes oleamide, coconut oleoyl amine, oleic acid two
Glycollic amide etc..The polyol esters of fatty acids includes fatty glyceride, fatty acid pentaerythritol ester, fatty acid ethylene glycol
The compounds such as ester, fatty acid succinate, fatty acid ethanolamide amine ester, fatty acid diethanolamine ester, fatty acid triethanolamine ester
Monoesters, dibasic acid esters or polyester, as monoolein, oleic acid diglyceride, stearic acid monopentaerythritol ester, lauric acid/dodecanoic acid ethylene glycol are double
Ester, monoolein, oleic acid diethanol amine, triethanolamine oleate etc.；The aliphatic amine include alkyl replace monoamine or
Polyamine, alkoxylated alkyl replace monoamine or polyamine and alkyl ether amine etc., as ethoxylation tallow amine and
The butter fat ether amines of ethoxylation.The Ashless friction modifiers can select F10 and F20 of BASF Aktiengesellschaft etc.；
The Ashless friction modifiers preferably fatty acid amides；
The Ashless friction modifiers account for the 0.01%-5% of the universal gear lubricating oil composition gross mass, preferably
0.02%-4%, more preferable 0.05%-3%；
The lube base oil can select one of API I, II, III, IV, V class lubricating oil base oil or more
Kind, for example one of mineral lubricating oil and synthetic lubricant fluid or a variety of, preferably II, III and IV class lubricating oil base can be selected from
One of plinth oil is a variety of, most preferably II and/or Group III hydrogenated base oil.
Metal detergent, ashless dispersant, antioxygen can also be added in universal gear lubricating oil composition of the invention
One of agent, pour-point depressant, viscosity index improver, metal corrosion inhibitor, antirust agent and anti-foaming agent or various other lubrications
Oil additive.These additives can be used alone, and can also be used with combination of two or more, and its dosage is from this field
Conventional amount used is not particularly limited.
6. the manufacturing method of the universal gear lubricating oil composition of any preceding aspect, including make the shielding phenol, extreme pressure
The step of antiwear additive, metal deactivator, Ashless friction modifiers and the lube base oil mix.
Technical effect
Shielding phenolic compounds according to the present invention, phosphorus element-containing and metallic element, are not likely to produce ash content, are environmental-friendly
The antioxidant of type.
Shielding phenolic compounds according to the present invention shows the high temperature significantly improved compared with the compound of the prior art
Antioxygenic property (thermal stability) can effectively improve (high temperature) oxidation stability of such as lubricating oil.
Shielding phenolic compounds according to the present invention is showing excellent high-temperature oxidation resistant in a preferred embodiment
While performance, excellent rustless property is also exhibited further.This is not available for prior art compound.
Shielding phenolic compounds according to the present invention is showing excellent high-temperature oxidation resistant in a preferred embodiment
While performance, excellent cleansing performance (i.e. deposit generation rejection) is also exhibited further.This is the prior art
It closes not available for object.
Shielding phenolic compounds according to the present invention is showing excellent high-temperature oxidation resistant in a preferred embodiment
While performance, also exhibits further excellent inhibition viscosity build and inhibit the increased performance of acid value.This is the prior art
Not available for compound.
Universal gear lubricating oil composition according to the present invention shows excellent antioxygen in a preferred embodiment
Change performance, detergent-dispersant performance energy, abrasion resistance and rustless property, sufficiently meets GL-5 and above specification extreme pressure heavy load gear profit
The requirement of lubricating oil product.
Specific embodiment
Detailed description of the preferred embodiments below, it should be noted however that protection of the invention
Range is not limited to these specific embodiments, and but is determined by the appended claims.
All publications, patent application, patent and the other bibliography that this specification is mentioned all draw in this for reference.
Unless otherwise defined, all technical and scientific terms used herein all has what those skilled in the art routinely understood to contain
Justice.In case of conflict, it is subject to the definition of this specification.
When this specification with prefix " well known to those skilled in the art ", " prior art " or its export material similar to term
Whens material, substance, method, step, device or component etc., object derived from the prefix is covered this field when the application proposes and is routinely made
Those of with, but also include also being of little use at present, it will but become art-recognized for suitable for those of similar purpose.
In the context of the present specification, other than the content clearly stated, any matters or item that do not mention are equal
It is directly applicable in those of known in the art without carrying out any change.Moreover, any embodiment described herein can be with
It is freely combined with one or more other embodiments described herein, the technical solution or technical idea formed therefrom regards
For the original disclosure of the present invention or a part of original description, and be not considered as not disclosing or be expected herein it is new in
Hold, unless those skilled in the art think that the combination is obvious unreasonable.
In the context of the present invention, statement " halogen " refers to fluorine, chlorine, bromine or iodine.
In the context of the present invention, term " alkyl " has conventionally known in the art meaning, including linear chain or branched chain
Alkyl, linear chain or branched chain alkenyl, linear chain or branched chain alkynyl, naphthenic base, cycloalkenyl, cycloalkynyl radical, aryl or combinations thereof group, wherein
It is preferred that linear or branched alkyl group, linear chain or branched chain alkenyl, aryl or combinations thereof group.It, specifically such as can be with as the alkyl
Enumerate C1-20Alkyl, including C1-20Linear or branched alkyl group, C2-20Linear chain or branched chain alkenyl, C2-20Linear chain or branched chain alkynyl, C3-20
Naphthenic base, C3-20Cycloalkenyl, C3-20Cycloalkynyl radical, C6-20Aryl or combinations thereof group, wherein it is preferred that C1-20Linear or branched alkyl group,
C6-20Aryl or combinations thereof group.As the combination group, for example one or more C can be enumerated1-20Linear or branched alkyl group
(preferably one or more C1-10Linear or branched alkyl group) and one or more C6-20Aryl (preferably one or more phenyl or naphthalene
Base) group that is obtained by Direct Bonding.As the combination group, for example it can further enumerate one or more C1-10Straight chain
Or branched alkyl phenyl, phenyl C1-10Linear or branched alkyl group or one or more C1-10Linear or branched alkyl group phenyl C1-10Straight chain
Or branched alkyl etc., wherein more preferable C1-10Linear or branched alkyl group phenyl (such as tert-butyl-phenyl), phenyl C1-10Straight chain or branch
Alkyl group (such as benzyl) or C1-10Linear or branched alkyl group phenyl C1-10Linear or branched alkyl group (such as t-butylbenzyl).
In the context of the present invention, so-called " linear chain or branched chain miscellaneous alkyl ", refers to linear or branched alkyl group molecule knot
Inside structure (not including the end of main chain or any side chain in the alkyl molecule structure) one or more (such as 1 to 4,1 to
3,1 to 2 or 1) group-CH2Being selected from-O- ,-S- and-NR'-, (R' is H or C1-4One of linear or branched alkyl group)
Substituting group directly substitute and (do not include the alkyl point inside the group that obtains or linear or branched alkyl group molecular structure
The end of main chain or any side chain in minor structure) one or more (such as 1 to 3,1 to 2 or 1) group-CH < quilt
Substituting group-N < directly is substituted and the group that obtains.As the substituting group, preferably-O- or-S-, more preferable-S-.Obviously
, for the angle of structural stability, when there are multiple, not Direct Bonding between these substituting groups.Though in addition,
The carbon atom number of the right linear or branched alkyl group is because of group-CH2Or group-CH < accordingly reduced by substitution, but for table
Simplicity is stated, still refers to the linear chain or branched chain miscellaneous alkyl with the carbon atom number of the substitution foregoing description linear or branched alkyl group
Carbon atom number.As the linear chain or branched chain miscellaneous alkyl, for concrete example, C4Straight chained alkyl is such as(group indicated by arrow is not in inside molecular structure in formula, but is located
In the end of main chain) it is directly substituted by a substituting group-O- by acquisition-CH2-O-CH2-CH3Or-CH2-CH2-O-CH3, referred to as
For C4Linear heteroalkyl group.Alternatively, C4Branched alkyl is such as(group indicated by arrow in formula
It is not in inside molecular structure, but is in the end of main chain and side chain) it will be obtained by a substituting group-N < directly substitutionReferred to as C4Branched heteroalkyl groups.According to the present invention, as the miscellaneous alkane of the linear chain or branched chain
Base, for example C can be enumerated3-20Linear chain or branched chain miscellaneous alkyl, wherein it is preferred that C3-10Linear chain or branched chain miscellaneous alkyl or C3-6Straight chain or
Branched heteroalkyl groups.
In the context of the present specification, expression way " number+valence+group " or its refer to similar to term from the group
It removes in corresponding foundation structure (such as chain, ring or combinations thereof etc.) and obtains after the hydrogen atom of quantity representated by the number
Group preferably refers to remove on the carbon atom (preferably saturated carbon atom and/or the non-same carbon atom) contained by the structure
The group obtained after the hydrogen atom of quantity representated by the number.For example, " trivalent linear or branched alkyl group " is referred to from straight
The group for removing 3 hydrogen atoms on chain or branched paraffin (i.e. basic chain corresponding to the linear or branched alkyl group) and obtaining, and
" divalent linear chain or branched chain miscellaneous alkyl " then refer to from the miscellaneous alkane of linear chain or branched chain (the preferably carbon atom contained by the miscellaneous alkane, or
Person is further, from the non-same carbon atom) on remove 2 hydrogen atoms and the group that obtains.
In the case where not clearly indicating, all percentages, number, the ratio etc. being previously mentioned in this specification be all with
On the basis of weight, unless not meeting the conventional understanding of those skilled in the art when using weight as benchmark.
In the context of the present specification, in case of no particular description, number-average molecular weight Mn is by gel infiltration
Chromatography (GPC) measurement.
In the context of the present specification, in case of no particular description, any gel permeation chromatography being related to
(GPC) or the determination condition of GPC spectrogram is equal are as follows: instrument: Waters, US waters2695 type gel osmoticing chromatogram analysis
Instrument；Mobile phase uses tetrahydrofuran, flow velocity 1mL/min, and chromatogram column temperature is 35 DEG C, delivery time 40min, sample quality point
Number is 0.16%-0.20%.
According to the present invention, it is related to shielding phenolic compounds shown in a kind of logical formula (I).
According to the present invention, in logical formula (I), when there are multiple, each group R is same or different to each other, each independently
Selected from hydrogen, C1-300Group shown in group shown in linear or branched alkyl group, logical formula (II) and logical formula (III), on condition that at least
One group R is group shown in logical formula (II).
According to the present invention, in logical formula (I), as the C1-300Linear or branched alkyl group, for example C can be enumerated1-20Directly
Chain or branched alkyl (preferably C1-10Linear or branched alkyl group, more preferable C1-4Linear or branched alkyl group) or it is polyolefin-based.As
Described polyolefin-based, specifically can such as enumerate number-average molecular weight Mn is the polyolefin-based of 300-3000.At this point, as described poly-
The number-average molecular weight Mn of alkylene, preferably 500-2000, more preferable 500-1500.According to the present invention, described polyolefin-based (basic
On) it is saturation (being rendered as chain alkyl structure), but depend on the type or the polyolefin of the polyolefin as starting material
The difference of manufacturing method (for example may also be manufactured containing a small amount of olefinic double bond in polyolefin in the polyolefin-based strand
Remain or introduce in the process), but this has no effect on the realization of effect of the present invention, and the present invention also has no intention to carry out the amount bright
Really, and the present invention still polyolefin-based is classified as " alkyl " for this.
According to embodiment of the present invention, in logical formula (I), there are multiple group R, one of group R is logical
Group shown in formula (II), one in other two group R be it is described polyolefin-based, the other is hydrogen, C1-20Straight chain or branch
Alkyl group (preferably C1-10Linear or branched alkyl group) or logical formula (III) shown in group.
According to embodiment of the present invention, in logical formula (I), when group R is described polyolefin-based, the polyolefin
Base is preferably placed at the contraposition of phenolic hydroxyl group in logical formula (I).
According to the present invention, in logical formula (I), when there are multiple, each group R' is same or different to each other, each independently
Selected from hydrogen and C1-20Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (I), when there are multiple, each group R' it is mutually the same or
Difference is each independently selected from hydrogen and C1-4Linear or branched alkyl group.
According to the present invention, in logical formula (II), group L is
According to the present invention, in logical formula (II), in the definition of group L, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20
Linear or branched alkyl group) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in logical formula (II), in the definition of group L, group R " be selected from hydrogen,
C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl.
According to the present invention, in logical formula (II), group R2Selected from hydrogen, C1-20Shown in linear or branched alkyl group, logical formula (IV)
Group shown in group and logical formula (V).
According to embodiment of the present invention, in logical formula (II), group R2Selected from hydrogen, C1-10Linear or branched alkyl group
With group shown in logical formula (IV).
According to the present invention, in logical formula (II), when there are multiple, each group RbIt is same or different to each other, it is respectively independent
Ground is selected from hydrogen and C1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C1-10Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (II), when there are multiple, each group RbIt is mutually the same or
Difference is each independently selected from hydrogen and C1-6Linear or branched alkyl group, preferably hydrogen.
According to the present invention, in logical formula (II), when there are multiple, each group RcIt is same or different to each other, it is respectively independent
Ground is selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (II), when there are multiple, each group RcIt is mutually the same or
Difference is each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (II), a preferably group RcIn cyclic groupUpper N atom is (that is, with group RdThe N atom of bonding) contraposition.
According to the present invention, in logical formula (II), y is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (II), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (II), the integer that n is 1 to 8, preferably 1 or 2.
According to the present invention, in logical formula (II), when there are multiple, each group RdIt is same or different to each other, it is respectively independent
Ground is selected from group, preferably hydrogen shown in hydrogen and logical formula (V).
According to the present invention, in logical formula (II), when there are multiple, each cyclic group(in logical formula (II)
Inside configuration is rendered as bivalent group) it is same or different to each other, phenyl ring is each independently selected from (preferably in the structure of logical formula (II)
Inside is rendered as Isosorbide-5-Nitrae-phenylene) and naphthalene nucleus (being preferably rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene in the inside configuration of logical formula (II)),
Wherein preferred phenyl ring.
According to embodiment of the present invention, in logical formula (II), two adjacent cyclic groupsEach other
By additional S atom (not showing in structural formula) and the N atom of the two rings can be bridged (that is, with group RdThe N of bonding is former
Son) and form phenthazine ring, i.e.,
Embodiment according to the present invention, in logical formula (II), there are more than two cyclic groups
When, as long as wherein at least two (adjacent) cyclic groupForm the phenthazine ring, it is not necessary that it is required that
These cyclic groupsEach of with another adjacent cyclic groupForm the phenthazine
Ring.
According to embodiment of the present invention, in logical formula (II), two adjacent cyclic groupsEach other
Additional group can be passed through(not showing in structural formula) and the N atom of the two rings is bridged (that is, and base
Group RdThe N atom of bonding) and form 9,10- acridan ring, i.e.,
According to the present invention, in groupIn, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight chain or
Branched alkyl) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in groupIn, group R " is selected from hydrogen and C1-10Straight chain
Or branched alkyl.
Embodiment according to the present invention, in logical formula (II), there are more than two cyclic groups
When, as long as wherein at least two (adjacent) cyclic group9, the 10- acridan ring is formed, is not had
These cyclic groups of exclusive requirementEach of with another adjacent cyclic groupIt is formed
The acridan ring.
According to the present invention, in logical formula (III), group L is
According to the present invention, in logical formula (III), in the definition of group L, group R " is selected from hydrogen, C1-20Alkyl is (preferably
C1-20Linear or branched alkyl group) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in logical formula (III), in the definition of group L, group R " be selected from hydrogen,
C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl.
According to the present invention, in logical formula (III), group R2Selected from hydrogen, C1-20Shown in linear or branched alkyl group, logical formula (IV)
Group and logical formula (V) shown in group.
According to embodiment of the present invention, in logical formula (III), group R2Selected from hydrogen, C1-10Linear or branched alkyl group
With group shown in logical formula (IV).
According to the present invention, in logical formula (III), when there are multiple, each group RbIt is same or different to each other, it is respectively independent
Ground is selected from hydrogen and C1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C1-10Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (III), when there are multiple, each group RbIt is mutually the same
Or it is different, it is each independently selected from hydrogen and C1-6Linear or branched alkyl group, preferably hydrogen.
According to the present invention, in logical formula (III), when there are multiple, each group RcIt is same or different to each other, it is respectively independent
Ground is selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (III), when there are multiple, each group RcIt is mutually the same
Or it is different, it is each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (III), a preferably group RcIn cyclic groupUpper N atom is (that is, with group RdThe N atom of bonding) contraposition.
According to the present invention, in logical formula (III), y is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (III), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (III), the integer that n is 1 to 8, preferably 1 or 2.
According to the present invention, in logical formula (III), when there are multiple, each group RdIt is same or different to each other, it is respectively independent
Ground is selected from group, preferably hydrogen shown in hydrogen and logical formula (V).
According to the present invention, in logical formula (III), when there are multiple, each cyclic group(in logical formula (III)
Inside configuration be rendered as bivalent group) be same or different to each other, be each independently selected from phenyl ring (preferably in logical formula (III)
Inside configuration is rendered as 1,4- phenylene) and naphthalene nucleus (be preferably rendered as the Asia 1,4- or 2,6- naphthalene in the inside configuration of logical formula (III)
Base), wherein it is preferred that phenyl ring.
According to embodiment of the present invention, in logical formula (III), two adjacent cyclic groupsThat
This can by additional S atom (not shown in structural formula) and bridge the two rings N atom (that is, with group RdThe N of bonding
Atom) and form phenthazine ring, i.e.,
Embodiment according to the present invention, in logical formula (III), there are more than two cyclic groupsWhen, as long as wherein at least two (adjacent) cyclic groupThe phenthazine ring is formed, is not had
It is necessary to require these cyclic groupsEach of with another adjacent cyclic groupShape
At the phenthazine ring.
According to embodiment of the present invention, in logical formula (III), two adjacent cyclic groupsThat
This can pass through additional group(not shown in structural formula) and bridge the two rings N atom (that is, with
Group RdThe N atom of bonding) and form 9,10- acridan ring, i.e.,
According to the present invention, in groupIn, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight chain or
Branched alkyl) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in groupIn, group R " is selected from hydrogen and C1-10Straight chain
Or branched alkyl.
Embodiment according to the present invention, in logical formula (III), there are more than two cyclic groupsWhen, as long as wherein at least two (adjacent) cyclic groupForm the acridan ring
, it is not necessary that it is required that these cyclic groupsEach of with another adjacent cyclic groupForm the acridan ring.
According to the present invention, in logical formula (IV), when there are multiple, each group RbIt is same or different to each other, it is respectively independent
Ground is selected from hydrogen and C1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C1-10Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (IV), when there are multiple, each group RbIt is mutually the same or
Difference is each independently selected from hydrogen and C1-6Linear or branched alkyl group, preferably hydrogen.
According to the present invention, in logical formula (IV), when there are multiple, each group RcIt is same or different to each other, it is respectively independent
Ground is selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (IV), when there are multiple, each group RcIt is mutually the same or
Difference is each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (IV), a preferably group RcIn cyclic groupUpper N atom is (that is, with group RdThe N atom of bonding) contraposition.
According to the present invention, in logical formula (IV), y is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (IV), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (IV), the integer that n' is 0 to 7, preferably 0,1 or 2, on condition that n'+n≤8.According to
An embodiment of the invention, n'+n=1 or n'+n=2.Here, n is identical as the definition in aforementioned formula (II).
According to the present invention, in logical formula (IV), when there are multiple, each group RdIt is same or different to each other, it is respectively independent
Ground is selected from group, preferably hydrogen shown in hydrogen and logical formula (V).
According to the present invention, in logical formula (IV), when there are multiple, each cyclic group(in logical formula (IV)
Inside configuration is rendered as bivalent group) it is same or different to each other, phenyl ring is each independently selected from (preferably in the structure of logical formula (IV)
Inside is rendered as Isosorbide-5-Nitrae-phenylene) and naphthalene nucleus (being preferably rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene in the inside configuration of logical formula (II)),
Wherein preferred phenyl ring.
According to embodiment of the present invention, in logical formula (IV), two adjacent cyclic groupsEach other
By additional S atom (not showing in structural formula) and the N atom of the two rings can be bridged (that is, with group RdThe N of bonding is former
Son) and form phenthazine ring, i.e.,
Embodiment according to the present invention, in logical formula (IV), there are more than two cyclic groups
When, as long as wherein at least two (adjacent) cyclic groupForm the phenthazine ring, it is not necessary that it is required that
These cyclic groupsEach of with another adjacent cyclic groupForm the phenthazine
Ring.
According to embodiment of the present invention, in logical formula (IV), two adjacent cyclic groupsEach other
Additional group can be passed through(not showing in structural formula) and the N atom of the two rings is bridged (that is, and base
Group RdThe N atom of bonding) and form 9,10- acridan ring, i.e.,
According to the present invention, in groupIn, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight chain or
Branched alkyl) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in groupIn, group R " is selected from hydrogen and C1-10Straight chain
Or branched alkyl.
Embodiment according to the present invention, in logical formula (IV), there are more than two cyclic groups
When, as long as wherein at least two (adjacent) cyclic group9, the 10- acridan ring is formed, is not had
These cyclic groups of exclusive requirementEach of with another adjacent cyclic groupBeing formed should
Acridan ring.
According to the present invention, in logical formula (V), when there are multiple, each group R is same or different to each other, each independently
Selected from hydrogen, C1-300Group shown in group shown in linear or branched alkyl group, logical formula (II) and logical formula (III).
According to embodiment of the present invention, in logical formula (V), when there are multiple, each group R is mutually the same or not
Together, hydrogen and C are each independently selected from1-300Linear or branched alkyl group.
According to the present invention, in logical formula (V), as the C1-300Linear or branched alkyl group, for example C can be enumerated1-20Directly
Chain or branched alkyl (preferably C1-10Linear or branched alkyl group, more preferable C1-4Linear or branched alkyl group) or it is polyolefin-based.As
Described polyolefin-based, specifically can such as enumerate number-average molecular weight Mn is the polyolefin-based of 300-3000.At this point, as described poly-
The number-average molecular weight Mn of alkylene, preferably 500-2000, more preferable 500-1500.According to the present invention, described polyolefin-based (basic
On) it is saturation (being rendered as chain alkyl structure), but depend on the type or the polyolefin of the polyolefin as starting material
The difference of manufacturing method (for example may also be manufactured containing a small amount of olefinic double bond in polyolefin in the polyolefin-based strand
Remain or introduce in the process), but this has no effect on the realization of effect of the present invention, and the present invention also has no intention to carry out the amount bright
Really, and the present invention still polyolefin-based is classified as " alkyl " for this.
According to embodiment of the present invention, in logical formula (V), there are multiple group R, one of group R is institute
State it is polyolefin-based, the other is hydrogen or C1-20Linear or branched alkyl group (preferably C1-10Linear or branched alkyl group, more preferable C1-4Directly
Chain or branched alkyl).
According to embodiment of the present invention, in logical formula (V), when group R is described polyolefin-based, the polyolefin
Base is preferably placed at the contraposition of phenolic hydroxyl group in logical formula (V).
According to the present invention, in logical formula (V), when there are multiple, each group R' is same or different to each other, each independently
Selected from hydrogen and C1-20Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (V), when there are multiple, each group R' it is mutually the same or
Difference is each independently selected from hydrogen and C1-4Linear or branched alkyl group.
According to the present invention, in logical formula (V), group L is group
According to the present invention, in logical formula (V), in the definition of group L, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20
Linear or branched alkyl group) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in logical formula (V), in the definition of group L, group R " be selected from hydrogen,
C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl.
According to a preferred embodiment of the present invention, in logical formula (V), in the definition of group L, group R " is selected from hydrogen
And C1-10Linear or branched alkyl group.
According to the present invention, in logical formula (V), two group R and a group-(S)a- L- occupies benzene in logical formula (V) respectively
Three positions of residue on ring.
According to the present invention, in logical formula (V), a is 0 or 1, preferably 1.
According to the present invention, the shielding phenolic compounds is defined as previously described (such as such as logical formula (I) or further such as general formula
(V) shown in), it is necessary to it include structureAs phenol unit.According to a preferred embodiment of the present invention, the screen
Phenolic compounds is covered in its entire molecular structure comprising at most 5, at most 3, at most 2 or at most 1 phenol units.
According to the present invention, the shielding phenolic compounds is defined as previously described (such as such as logical formula (II) or further as logical
Formula (III) or (IV) are shown), it is necessary to it include structureAs amine unit.One according to the present invention
Preferred embodiment, the shielding phenolic compounds include at most 15, at most 10, at most 8 in its entire molecular structure
A, at most 6, at most 4, at most 3 or at most 2 amine units.
According to the present invention, the shielding phenolic compounds preferably at least has (preferably 2,3 in its entire molecular structure
It is a or 4 or more) group RdIt is hydrogen.Specifically, the shielding phenolic compounds preferably contains in its entire molecular structure
Have selected from least one of following hydrogen amine unit (1), hydrogen amine unit (2) and hydrogen amine unit (3).In these hydrogen amine units,
Cyclic groupIt is identical as the definition in logical formula (II) with group R ".
A preferred embodiment according to the present invention, the shielding phenolic compounds is in its entire molecular structure containing extremely
A few hydrogen amine unit (1).
Specifically, to shield phenolic compoundsFor, the compound is in its entire molecule knot
Include 2 phenol units and 2 amine units in structure, and includes 1 hydrogen amine unit (1).
According to the present invention, as the shielding phenolic compounds, for example following compound or its arbitrary proportion can be enumerated
Mixture, but the present invention is not limited thereto.
According to the present invention, shielding phenolic compounds shown in aforementioned formula (I) can be with a kind of single shape of (pure) compound
Formula exist, make or use, can also with the form of the mixture (in any proportion) of two or more of them exist, manufacture or
It uses, this has no effect on the realization of effect of the present invention.
According to the present invention, shielding phenolic compounds shown in aforementioned formula (I) can pass through manufacturing method system below
It makes, but is not limited thereto.
The manufacturing method according to the present invention, including make amination shown in phenolic compounds shown in logical formula (X) and general formula (Y)
The first step to react in the presence of closing object aldehyde compound shown in general formula (Z).
According to the present invention, lead in formula (X), when there are multiple, each group R0It is same or different to each other, selects each independently
From hydrogen ,-SH and C1-300Linear or branched alkyl group, on condition that at least one group R0It is-SH.
According to the present invention, in logical formula (X), as the C1-300Linear or branched alkyl group, for example C can be enumerated1-20Directly
Chain or branched alkyl (preferably C1-10Linear or branched alkyl group, more preferable C1-4Linear or branched alkyl group) or it is polyolefin-based.As
Described polyolefin-based, specifically can such as enumerate number-average molecular weight Mn is the polyolefin-based of 300-3000.At this point, as described poly-
The number-average molecular weight Mn of alkylene, preferably 500-2000, more preferable 500-1500.According to the present invention, described polyolefin-based (basic
On) it is saturation (being rendered as chain alkyl structure), but depend on the type or the polyolefin of the polyolefin as starting material
The difference of manufacturing method (for example may also be manufactured containing a small amount of olefinic double bond in polyolefin in the polyolefin-based strand
Remain or introduce in the process), but this has no effect on the realization of effect of the present invention, and the present invention also has no intention to carry out the amount bright
Really, and the present invention still polyolefin-based is classified as " alkyl " for this.
According to embodiment of the present invention, in logical formula (X), there are multiple group R0, one of group R0Be-
SH, other two group R0In one be it is described polyolefin-based, the other is hydrogen or C1-20Linear or branched alkyl group is (preferably
C1-10Linear or branched alkyl group).
According to embodiment of the present invention, in logical formula (X), in group R0When being described polyolefin-based, the polyene
Alkyl is preferably placed at the contraposition of phenolic hydroxyl group in logical formula (X).
According to the present invention, in logical formula (X), when there are multiple, each group R' is same or different to each other, each independently
Selected from hydrogen and C1-20Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (X), when there are multiple, each group R' it is mutually the same or
Difference is each independently selected from hydrogen and C1-4Linear or branched alkyl group.
According to the present invention, as phenolic compounds shown in the logical formula (X), commercially available product can be directly used, it can also
To be manufactured by conventionally known in the art method, it is not particularly limited.In addition, as shown in the logical formula (X)
Phenolic compounds, can be used only one kind, can also be used with combination of two or more.
According to the present invention, the manufacturing method as phenolic compounds shown in the logical formula (X), for example can enumerate in alkyl
In the presence of changing catalysts, make phenolic compounds shown in general formula (X') and polyolefin (number-average molecular weight Mn 300-3000, it is excellent
Select 500-2000, more preferable 500-1500) occur alkylated reaction method.
According to the present invention, in general formula (X'), group R' has and identical meaning in aforementioned formula (X).
According to the present invention, there are three group R' in general formula (X')0, one of group R'0It is-SH, another group
R'0It is H, third group R'0It is hydrogen ,-SH or C1-20Linear or branched alkyl group (preferably C1-10Linear or branched alkyl group).
According to embodiment of the present invention, in general formula (X'), at least one group R'0It is H, and group R'0
The contraposition of phenolic hydroxyl group in general formula (X').
According to the present invention, the polyolefin preferably passes through ethylene, propylene or C4-C10The homopolymerization of alpha-olefin passes through these
Polyolefin obtained from two or more copolymerization in alkene.As the C4-C10Alpha-olefin, for example, can enumerate n-butene,
Isobutene, n-pentene, n-hexylene, positive octene and positive decene.
According to the present invention, at least 20wt% (preferably at least 50wt%, more preferably at least 70wt%) in these polyolefin
Polymer chain contains olefinic double bond at its end.The olefinic double bond is usually with the ethenylidene of high reaction activity or vinyl
Existing for form.
According to the present invention, as the polyolefin, more preferable 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
Pass through polymer prepared by copolymerization two or three in butylene.It the commercial product of this quasi polymer may also be 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), also referred to as high reaction activity are poly-
Isobutene.In this kind of polyisobutene, total end alkene of at least 20wt% (preferably at least 50wt%, more preferably at least 70wt%)
Belonging to double bond is provided by methyl ethenylidene.
As the catalyst for alkylation reaction, for example Lewis acid catalyst can be enumerated, for example, selected from alchlor,
Boron trifluoride, tin tetrachloride, titanium tetrabromide, boron trifluoride phenol, boron trifluoride alcohol complex and boron trifluoride ether network
One of object or a variety of is closed, 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, phenolic compounds shown in the polyolefin, the general formula (X'),
Molar ratio between the catalyst for alkylation reaction such as can be 1:1-3:0.1-0.5, preferably 1:1.5-3:0.1-0.4,
Most preferably 1:1.5-3:0.2-0.4, but is not limited thereto.
According to the present invention, the reaction time of the alkylated reaction is such as 0.5h-10h, preferably 1h-8h, most preferably 3h-
5h, but is not limited thereto.
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 is not limited thereto.
According to the present invention, the alkylated reaction can be in the presence of a solvent.As the solvent, such as can be with
Enumerate C6-10Alkane (such as hexane, heptane, octane, nonane or decane etc.).Wherein, it is preferable to use hexane and heptane, more preferably
Use hexane.
According to the present invention, after the alkylated reaction, by conventional methods from the reaction mixture finally obtained
It is middle remove catalyst for alkylation reaction, unreacted reactant and the solvent that may use after, that is, obtain the logical formula (X) institute
The phenolic compounds shown.
According to the present invention, in general formula (Y), group R'2Selected from hydrogen, C1-20Linear or branched alkyl group and group
According to the present invention, in general formula (Y), when there are multiple, each group RbIt is same or different to each other, each independently
Selected from hydrogen and C1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C1-10Linear or branched alkyl group.
According to embodiment of the present invention, in general formula (Y), when there are multiple, each group RbIt is mutually the same or
Difference is each independently selected from hydrogen and C1-6Linear or branched alkyl group, preferably hydrogen.
According to the present invention, in general formula (Y), when there are multiple, each group RcIt is same or different to each other, each independently
Selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in general formula (Y), when there are multiple, each group RcIt is mutually the same or
Difference is each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in general formula (Y), a preferably group RcIn cyclic groupUpper N atom is (that is, with group RdThe N atom of bonding) contraposition.
According to the present invention, in general formula (Y), y is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in general formula (Y), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in general formula (Y), the integer that n1 is 1 to 8, preferably 1 or 2.
According to the present invention, in general formula (Y), when there are multiple, each cyclic group(in the knot of general formula (Y)
Bivalent group is rendered as inside structure) it is same or different to each other, phenyl ring is each independently selected from (preferably in the structure of general formula (Y)
Portion is rendered as Isosorbide-5-Nitrae-phenylene) and naphthalene nucleus (being preferably rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene in the inside configuration of general formula (Y)), wherein
It is preferred that phenyl ring.
According to the present invention, as amine compounds shown in the general formula (Y), commercially available product can be directly used, not
There is special limitation.In addition, one kind can be used only as amine compounds shown in the general formula (Y), it can also be two kinds or more
Kind is applied in combination.
According to the present invention, in general formula (Z), group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Linear or branched alkyl group) and
C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in general formula (Z), group R " is selected from hydrogen, C1-10Linear or branched alkyl group
And C3-10Linear chain or branched chain miscellaneous alkyl.
According to a preferred embodiment of the present invention, in general formula (Z), group R " is selected from hydrogen and C1-10Linear chain or branched chain
Alkyl.
According to the present invention, as aldehyde compound shown in the general formula (Z), for example C can be enumerated1-6Aliphatic aldehyde and benzene
Formaldehyde.
According to embodiment of the present invention, as the C1-6Aliphatic aldehyde, for example C can be enumerated1-6Straight chain or branch
Chain saturated aliphatic aldehyde, specifically such as acetaldehyde or formaldehyde, more preferable formaldehyde.As the formaldehyde, for example, can be used its aqueous solution,
Paraformaldehyde or paraformaldehyde form, are not particularly limited.
According to the present invention, as aldehyde compound shown in the general formula (Z), one kind can be used only, can also two kinds or
Multiple combinations use.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the first step, the general formula
(X) molar ratio of phenolic compounds shown in and amine compounds shown in the general formula (Y) is generally 1:0.1-10, preferably 1:0.5-
5.0, more preferable 1:0.8-2.0.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the first step, the general formula
(X) molar ratio of phenolic compounds shown in and aldehyde compound shown in the general formula (Z) is generally 1:0.1-10, preferably 1:0.5-
5.0, more preferable 1:0.8-2.0.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, the first step can depositing in solvent
In lower progress.As the solvent, for example C can be enumerated2-10Aliphatic nitrile (such as acetonitrile etc.), C6-20Aromatic hydrocarbon (such as benzene,
Toluene, dimethylbenzene and isopropylbenzene), C6-10Alkane (such as n-hexane, hexamethylene and petroleum ether), C1-6Aliphatic alcohol (such as first
Alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C2-20Halogenated hydrocarbons (such as methylene chloride, carbon tetrachloride, chlorobenzene and
1,2- dichloro-benzenes), C3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C3-10Amide (such as dimethylformamide,
Dimethyl acetamide and N-Methyl pyrrolidone) etc..One kind can be used only in these solvents, can also be made with combination of two or more
With.
According to the present invention, it in the manufacturing method of the shielding phenolic compounds, in the first step, can be added without
Catalyst can also be added in catalyst.As the catalyst, for example inorganic acid catalyst and organic acid catalysis can be enumerated
Agent.As the inorganic acid catalyst, for example hydrochloric acid, sulfuric acid and phosphoric acid can be enumerated etc..As the organic acid catalyst, than
Methane sulfonic acid, ethylsulfonic acid, sulfamic acid and p-methyl benzenesulfonic acid can such as be enumerated.
As the dosage of the catalyst, can be not particularly limited directly referring to the conventional amount used of the prior art.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction time of the first step
There are special restriction, but generally 0.1h-24h, preferably 0.2h-12h, most preferably 0.5h-6h.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction temperature of the first step
There are special restriction, but generally 0 DEG C -250 DEG C, preferably 20 DEG C -180 DEG C, most preferably 60 DEG C -120 DEG C.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, after the first step terminates, pass through
Reaction mixture that conventionally known separation method (such as evaporation etc.) is obtained from the first step (hereinafter referred to as first step
Reaction mixture) in remove the volatile materials such as solvent that may be present after, can be obtained the reaction product of first step.
According to embodiment of the present invention, the manufacturing method of the shielding phenolic compounds optionally further includes making described the
The additional step (hereinafter referred to as additional step A) that the reaction product of one step reacts with vulcanizing agent and (forms phenthazine ring).
According to embodiment of the present invention, the manufacturing method of the shielding phenolic compounds optionally further includes making described the
The extra step that the reaction product of one step reacts with aldehyde compound shown in aforementioned formula (Z) and (forms acridan ring)
Suddenly (hereinafter referred to as additional step B).
According to the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step A can be only carried out,
The additional step B can be only carried out, can also not only carry out the additional step A but also carries out the additional step B.Both it is carrying out
The additional step A carries out the additional step B again when, do not have to the precedence of the additional step A and the additional step B
There is special restriction, can first carry out the additional step A, carries out the additional step again after additional step A terminates
B, or the additional step B is first carried out, the additional step A is carried out again after additional step B terminates.In addition, each attached
Product (that is, reaction product from previous additional step) separating step can be had by adding between step, can also be without product point
From step, it is not particularly limited.
According to embodiment of the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step A
It is carried out after the first step terminates.At this point, the reaction product of the first step is as previously described from described first
It is separated in the reaction mixture of step.Alternatively, the reaction product of the first step can also be straight without the separation
It connects in the form of the reaction mixture of the first step for carrying out the additional step A.Alternatively, the additional step A
It can be carried out after the additional step B terminates.When the additional step A after the additional step B terminates when carrying out,
The reaction product of the additional step B is separated from the reaction mixture of the additional step B as described herein.Or
The reaction product of person, the additional step B can also directly be mixed without the separation with the reaction of the additional step B
The form of object is for carrying out the additional step A.
According to embodiment of the present invention, in the manufacturing method of the shielding phenolic compounds, in the extra step
In rapid A, as the vulcanizing agent, for example sulphur and sulfur dichloride can be enumerated etc., wherein it is preferred that sulphur.As the sulphur, such as can
To enumerate sulphur or sublimed sulfur.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the additional step A, the general formula
(Y) molar ratio of amine compounds shown in and the vulcanizing agent is generally 1:1-10, preferably 1:1.2-6.0, more preferable 1:1.5-
3.0。
According to the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step A can depositing in solvent
In lower progress.As the solvent, for example C can be enumerated2-10Aliphatic nitrile (such as acetonitrile etc.), C6-20Aromatic hydrocarbon (such as benzene,
Toluene, dimethylbenzene and isopropylbenzene), C6-10Alkane (such as n-hexane, hexamethylene and petroleum ether), C1-6Aliphatic alcohol (such as first
Alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C2-20Halogenated hydrocarbons (such as methylene chloride, carbon tetrachloride, chlorobenzene and
1,2- dichloro-benzenes), C3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C3-10Amide (such as dimethylformamide,
Dimethyl acetamide and N-Methyl pyrrolidone) etc..One kind can be used only in these solvents, can also be made with combination of two or more
With.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step A is generally in catalyst
In the presence of carry out.As the catalyst, for example the catalyst that the prior art uses for this purpose and routinely can be enumerated, specifically
Such as iodine.As the dosage of the catalyst, can be not particularly limited directly referring to the conventional amount used of the prior art.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction time of the additional step A
There are special restriction, but generally 0.1h-24h, preferably 0.2h-12h, most preferably 0.5h-4h.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction temperature of the additional step A
There are special restriction, but generally 60 DEG C -300 DEG C, preferably 120 DEG C -240 DEG C, most preferably 150 DEG C -200 DEG C.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, after the additional step A terminates, lead to
Cross conventionally known separation method (such as evaporation etc.) removed from the reaction mixture that additional step A is obtained it is that may be present
After the volatile materials such as solvent, the reaction product of additional step A can be obtained, or can also be without the separation, directly
For subsequent reaction step (than additional step B as the aforementioned).
According to embodiment of the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step B
(as independent step) can be carried out after the first step terminates, can also be carried out simultaneously with the first step,
It is not particularly limited.When the additional step B after the first step terminates when carrying out, the first step it is anti-
Product is answered to separate from the reaction mixture of the first step as previously described.Alternatively, the first step is anti-
Answer product described attached for carrying out directly in the form of the reaction mixture of the first step without the separation
Add step B.Alternatively, the additional step B can also be carried out after the additional step A terminates.When the additional step B exists
When the additional step A is carried out after terminating, the reaction product of the additional step A is as described herein from the extra step
It is separated in the reaction mixture of rapid A.Alternatively, the reaction product of the additional step A can also be straight without the separation
It connects in the form of the reaction mixture of the additional step A for carrying out the additional step B.In addition, working as the additional step B
When being carried out simultaneously with the first step, directly into the reaction system of the first step (such as in the first step
Start or during the first step carries out) hydroformylation shown in the general formula (Z) is added according to hereinafter provided dosage
Close object.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the additional step B, as described
Aldehyde compound shown in general formula (Z), for example C can be enumerated1-6Aliphatic aldehyde and benzaldehyde.As the C1-6Aliphatic aldehyde, than
C can such as be enumerated1-6Linear chain or branched chain saturated aliphatic aldehyde, specifically such as acetaldehyde or formaldehyde, more preferable formaldehyde.As the formaldehyde,
For example its aqueous solution, paraformaldehyde or paraformaldehyde form can be used, it is not particularly limited.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the additional step B, the general formula
(Y) molar ratio of amine compounds shown in and aldehyde compound shown in the general formula (Z) is generally 1:0.1-10, preferably 1:0.5-
5.0, more preferable 1:0.8-2.0.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step B is (as individual step
When rapid progress) it can be in the presence of a solvent.As the solvent, for example C can be enumerated2-10Aliphatic nitrile (such as second
Nitrile etc.), C6-20Aromatic hydrocarbon (such as benzene,toluene,xylene and isopropylbenzene), C6-10Alkane (such as n-hexane, hexamethylene and petroleum
Ether), C1-6Aliphatic alcohol (such as methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C2-20Halogenated hydrocarbons (such as two
Chloromethanes, carbon tetrachloride, chlorobenzene and 1,2- dichloro-benzenes), C3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C3-10
Amide (such as dimethylformamide, dimethyl acetamide and N-Methyl pyrrolidone) etc..One kind can be used only in these solvents,
It can also be used with combination of two or more.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the additional step B (as individual
When step carries out) in, it can be added without catalyst, catalyst can also be added.As the catalyst, for example nothing can be enumerated
Machine acid catalyst and organic acid catalyst.As the inorganic acid catalyst, for example hydrochloric acid, sulfuric acid and phosphoric acid can be enumerated etc..
As the organic acid catalyst, for example methane sulfonic acid, ethylsulfonic acid, sulfamic acid and p-methyl benzenesulfonic acid can be enumerated etc..Make
For the dosage of the catalyst, can be not particularly limited directly referring to the conventional amount used of the prior art.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, to the additional step B (as individual
When step carries out) there is no particular limitation reaction time, but generally 0.1h-24h, preferably 0.2h-12h, most preferably 0.5h-
6h。
According to the present invention, in the manufacturing method of the shielding phenolic compounds, to the additional step B (as individual
When step carries out) reaction temperature there is no particular limitation, but generally 0 DEG C -250 DEG C, preferably 20 DEG C -180 DEG C, most preferably 60
℃-120℃。
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the additional step B (as individual
When step carries out) terminate after, the reaction that is obtained by conventionally known separation method (such as evaporation etc.) from additional step B
After removing the volatile materials such as solvent that may be present in mixture, the reaction product of additional step B, Huo Zheye can be obtained
Subsequent reaction step can be directly used in without the separation (than additional step A as the aforementioned).
It is known in the art, aforementioned all reaction step (including the first step, the additional step A and
The additional step B) generally carried out under the protection of inert gas atmosphere.As the inert gas, for example nitrogen can be enumerated
Gas and argon gas etc., are not particularly limited.
According to the present invention, it is described shielding phenolic compounds manufacturing method in, as the first step reaction product,
The reaction product of the reaction product of the additional step A or the additional step B can be a kind of single shielding phenolic compounds
(for example shielding phenolic compounds shown in aforementioned formula (I)) is also possible to the mixture comprising a variety of shielding phenolic compounds.These
Reaction product is all desired by the present invention, and the difference of existence form has no effect on the realization of effect of the present invention.Therefore, this theory
These reaction products are collectively termed as to shielding phenolic compounds of the invention without distinction in bright book context.In consideration of it, according to
The present invention, and be not present and these reaction products are further purified, or be further separated out a certain spy from these reaction products
Determine the absolute necessity of the shielding phenolic compounds of structure.Certainly, the purifying or separation are for the further of desired effect of the present invention
It is sometimes preferred for promotion, but for the present invention not necessarily.Even so, as the purifying or separation method,
For example it can enumerate and the reaction product is purified or separated by the methods of column chromatography method or preparation chromatography.
According to embodiment of the present invention, the manufacturing method according to present invention shielding phenolic compounds above-mentioned is further related to
The shielding phenolic compounds of manufacture.
Shielding phenolic compounds of the invention is due to showing excellent high-temperature oxidation resistance, particularly suitable as anti-
Oxygen agent uses, and is used to manufacture the lubricant oil composite for expecting excellent (high temperature) oxidation stability especially as antioxidant.Mirror
In this, according to embodiment of the present invention, it is related to a kind of universal gear lubricating oil composition, it includes the present invention is above-mentioned
Any shielding phenolic compounds (or mixture of its arbitrary proportion), extreme pressure anti-wear additives, metal deactivator, Ashless friction modifiers and
Major amount of lube base oil.
Embodiment
The present invention is illustrated using embodiment in further detail below, however, the present invention is not limited to these examples.
Performance in embodiment and comparative example is evaluated as follows.
(1) high-temperature oxidation resistance is evaluated
The lubricant oil composite that embodiment or comparative example are manufactured is as test specimen, using Pressurized Differential scanning amount heat examination
The antioxygenic property that (PDSC) evaluates the test specimen is tested, is indicated with the oxidation induction period (unit is min) of test specimen.PDSC
The temperature of test is 210 DEG C, pressure 0.5MPa, oxygen gas flow rate 100mL/min.
(2) deposit generates rejection evaluation
The hair of simulation piston deposit is carried out using the lubricant oil composite that embodiment or comparative example manufacture as test specimen
Motivation crankcase coking simulation test.This method is that coking plate analog meter is added in 300ml test specimen, is heated to 150 DEG C, adopts
The aluminium sheet spilled oil for being 310 DEG C to temperature with continuation mode weighs the burnt amount generated on aluminium sheet after 6 hours, (single with sediment yield
Position is mg) it indicates, simulate the deposit on piston.Coking amount is higher, and the piston detergency for representing this test specimen is poorer.
(3) rustless property is evaluated
According to BRT ball rust test method, using the lubricant oil composite that embodiment or comparative example manufacture as test specimen,
During entire bench test in 18 hours, the metal ball continuous contact acidic liquid and sky protected by the test specimen
Gas measures metal spherical reflector intensity, gray scale test value is obtained, for evaluating corrosion degree after the end of the test.Acetic acid/hydrogen
Bromic acid/hydrochloric acid/deionized water solution injection rate is 0.19 ml/hour, and air draught is 40 ml/mins, and oil temperature is
48℃.Corrosion degree is higher, shows that the rustless property of test specimen is poorer.
(4) high-frequency reciprocating friction test abrasion resistance is evaluated
The lubricant oil composite that embodiment or comparative example manufacture is subjected to high-frequency reciprocating friction test as test specimen.It should
The experimental condition of method is load 1000g, frequency 20Hz, 100 DEG C of temperature, test period 60min, records wear scar diameter.Mill
Spot diameter is smaller, shows that the abrasion resistance of test specimen is better.
Embodiment 1
In the 500ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 58.79g is added
Boron trifluoride ether (the alkylated reaction catalysis of (0.323mol) 2- tert-butyl -6- mercapto-phenol, 6.88g (0.048mol)
Agent), polyisobutene (Mn=1000, the Jilin Chemical group fine chemicals of 100ml n-hexane solvent and 161.61g (0.162mol)
Co., Ltd's manufacture), in 80 DEG C of reaction 2h.After reaction, reaction is cleaned using the potassium hydroxide solution that mass fraction is 5%
Mixture is primary, and is washed to neutrality with hot water to remove catalyst, and then vacuum distillation removes solvent and unreacted phenol, obtains
Obtain polyisobutene mercapto-phenol, hydroxyl value 53.49mgKOH/g.Hydroxy value measuring is with reference to the acetic anhydride method in GB/T7383-2007.
Example reaction equation is as follows:
From the nucleus magnetic hydrogen spectrum spectrum analysis of polyisobutene mercapto-phenol product: being polyisobutene at chemical shift 1.40
The characteristic peak of tert-butyl hydrogen on mercapto-phenol phenyl ring；It is unimodal for sulfydryl on polyisobutene mercapto-phenol phenyl ring at chemical shift 3.58
The characteristic peak of hydrogen；The unimodal characteristic peak for hydroxyl hydrogen on polyisobutene mercapto-phenol phenyl ring at chemical shift 4.84；Chemical shift
At 7.12 it is unimodal and 7.20 at it is unimodal be respectively polyisobutene mercapto-phenol phenyl ring on two hydrogen characteristic peak.By hydroxyl on phenyl ring
The Definitions On Integration of hydrogen is 1, and the integral for obtaining hydrogen on phenyl ring, sulfydryl hydrogen and hydroxyl hydrogen compares for 0.95:0.97:1.05:0.94, is approached
Theoretical 1:1:1:1:1 is analyzed from nuclear magnetic spectrogram, has been synthesized the polyisobutene mercapto-phenol alkylation that expected contraposition replaces and has been produced
Object.
Embodiment 2
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
30.58 grams of (156mmol) 2- sulfydryl -4- methyl -6- methylphenols of addition, 9.29 grams of (112mmol) formaldehyde, 32.38 grams
(176mmol) 4-aminodiphenylamine and 100mL toluene stir rapidly, in 100 DEG C of reaction 2h.To which after reaction, decompression is steamed
A small amount of water of solvent and generation is removed in distillation, and obtains the shielding phenol product of structure shown in title by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.40 (9H), 2.37 (3H), 4.02 (1H), 4.83 (2H), 6.95-7.00
(12H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 21.2,30.1,34.1,49.9,114.3,118.9,119.4,121.8,
122.2,125.8,126.5,129.5,131.8,132.3,133.5,143.3,150.8；
C24H28N2OS calculated value C 73.43, H 7.19, N 7.14, O 4.08, S 8.17；Measured value: C 73.31, H
7.23, N 7.21, O 3.99, S 8.28.
Embodiment 3
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
31.65 grams of (133mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 1.86 grams of (62mmol) formaldehyde, 28.15 grams
(153mmol) 4-aminodiphenylamine, 0.75 gram of (7.5mmol) hydrochloric acid and 150mL isopropanol stir rapidly, react at 25 DEG C
24h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and is obtained shown in title by column chromatography for separation
The shielding phenol product of structure.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36-1.54 (18H), 3.75 (1H), 4.80 (2H), 5.32 (1H), 6.80
(2H), 6.97 (5H), 7.17 (2H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,51.2,119.4,121.8,126.5,129.5,131.4,
136.6,144.5,153.4；
C27H34N2OS calculated value C 74.61, H 7.88, N 6.45, O 3.68, S 7.38；Measured value: C 74.52, H
7.84, N 6.51, O 3.73, S 7.40.
Embodiment 4
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
8.57 grams of (36mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 1.24 grams of (15mmol) formaldehyde, 10.14 grams (39mmol)
N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL toluene stir rapidly, in 90 DEG C of reaction 4h.To after reaction, be evaporated under reduced pressure
A small amount of water of solvent and generation is removed, and the shielding phenol product of structure shown in title is obtained by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 5.23 (2H), 6.80-7.02 (10H), 7.17 (2H), 7.26
(4H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,55.2,117.1,121.8,126.2,129.5,136.6,
143.6,153.4；
C33H38N2OS calculated value C 77.60, H 7.50, N 5.48, O 3.13, S 6.28；Measured value: C 77.71, H
7.52, N 5.53, O 3.10, S 6.23.
Embodiment 5
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
20.23 grams of (85mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 9.54 grams of (115mmol) formaldehyde, 18.49 grams
(69mmol) N- (1,3- dimethylbutyl)-N'- diphenyl-para-phenylene diamine and 150mL benzene stir rapidly, in 85 DEG C of reaction 3h.To
After reaction, vacuum distillation removes a small amount of water of solvent and generation, and obtains structure shown in title by column chromatography for separation
Shield phenol product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 0.80 (6H), 1.11-1.21 (4H), 1.36 (18H), 1.67 (2H), 3.47
(1H), 4.80 (2H), 5.32 (1H), 6.80 (2H), 6.97 (5H), 7.17 (2H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 17.9,22.4,29.6,34.6,45.2,52.7,58.6,119.4,121.8,
126.2,129.5,131.2,136.6,144.1,146.1,153.4；
C33H46N2OS calculated value: C 76.40, H 8.94, N 5.40, O 3.08, S 6.18；Measured value: C 76.48, H
8.96, N 5.35, O 3.09, S 6.12.
Embodiment 6
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
3.57 grams of (15mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 5.14 grams of (62mmol) formaldehyde, 21.76 grams (103mmol)
N- phenyl-N '-[4- (phenyl amino) phenyl]-Isosorbide-5-Nitrae-phenylenediamine and 150mL toluene stir rapidly, in 110 DEG C of reaction 2h.To
After reaction, vacuum distillation removes a small amount of water of solvent and generation, and obtains structure shown in title by column chromatography for separation
Shield phenol product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 5.20 (2H), 5.32 (1H), 6.80-7.02 (14H), 7.17
(2H), 7.20 (1H), 7.26 (4H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,55.5,117.1,120.4,126.2,129.5,132.3,
136.6,142.8,146.1,153.4；
C36H43N3OS calculated value C 77.83, H 7.20, N 6.98, O 2.66, S 5.33；Measured value: C 77.69, H
7.19, N 7.08, O 2.65, S 5.38.
Embodiment 7
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
34.51 grams of (145mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 2.91 grams of (35mmol) formaldehyde, 4.49 grams (21mmol)
4- amino -4'- methoxy diphenylamine, 0.26 gram of (2.61mmol) hydrochloric acid and 150mL benzene stir rapidly, in 90 DEG C of reaction 2h.To
After reaction, vacuum distillation removes a small amount of water of solvent and generation, and obtains structure shown in title by column chromatography for separation
Shield phenol product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 3.72-3.76 (4H), 4.80 (2H), 5.32 (1H), 6.97-
7.06 (8H), 7.17 (2H), 7.20 (1H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,51.1,55.5,114.6,118.9,121.8,124.7,
126.5,132.3,136.6,144.5,153.4,154.5；
C28H36N2O2S calculated value C 72.38, H 7.81, N 6.03, O 6.89, S 6.90；Measured value: C 72.37, H
7.69, N 6.12, O 6.80, S 6.83.
Embodiment 8
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
Addition gram 21.66 (91mmol) 2,6- di-t-butyl -4- mercapto-phenols, 1.35 grams of (9.51mmol) aldehyde C-9s, 6.51 grams
(25mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL benzene stir rapidly, in 70 DEG C of reaction 6h.To after reaction, subtract
A small amount of water of solvent and generation is distilled off in pressure, and obtains the shielding phenol product of structure shown in title by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 0.88 (3H), 1.08-1.85 (24H), 5.23 (1H), 5.32 (1H), 6.80
(1H), 6.97 (8H), 7.17 (2H), 7.26 (4H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 14.1,22.6,29.6,31.7,34.6,41.6,60.8,116.6,119.4,
121.8,126.5,129.5,131.4,136.6,142.8,144.5,146.1,153.4；
C38H48N2OS calculated value C 78.57, H 8.33, N 4.82, O 2.75, S 5.52；Measured value: C 78.62, H
8.25, N 4.75, O 2.81, S 5.42.
Embodiment 9
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
8.33 grams of (35mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 4.23 grams of (51mmol) formaldehyde, 9.61 grams of (31mmol) N,
N'- diphenyl -2,6- naphthylenediamine and 150mL toluene stir rapidly, in 110 DEG C of reaction 4h.To after reaction, be evaporated under reduced pressure
A small amount of water of solvent and generation is removed, and the shielding phenol product of structure shown in title is obtained by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 5.25 (2H), 5.32 (1H), 5.80 (1H), 6.99-7.06
(7H), 7.17 (3H), 7.26 (4H), 7.40 (2H), 7.84 (2H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,54.8,106.9,118.6,123.3,126.2,129.2,
136.6,142.8,148.3,153.5；
C37H41N2OS calculated value C 79.24, H 7.19, N 5.00, O 2.85, S 5.72；Measured value: C 79.20, H
7.23, N 5.14, O 2.72, S 5.65.
Embodiment 10
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
6.19 grams of (26mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 9.57 grams of (92mmol) 3- methylthiopropionaldehyde aldehyde, 3.13 grams
(17mmol) 4-aminodiphenylamine and 150mL toluene stir rapidly, in 80 DEG C of reaction 2h.To after reaction, be evaporated under reduced pressure
A small amount of water of solvent and generation is removed, and the shielding phenol product of structure shown in title is obtained by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36-1.54 (18H), 2.12-2.80 (7H), 3.47 (1H), 4.97 (1H),
5.32 (1H), 6.97 (7H), 7.17 (2H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 15.2,29.6,31.9,34.6,41.7,60.2,114.3,119.4,121.8,
126.2,129.5,132.4,136.6,144.5,146.1,153.5；
C30H40N2OS2Calculated value C 70.82, H 7.92, N 5.51, O 3.14, S 12.60；Measured value: C 70.75, H
7.83, N 5.46, O 3.20, S 12.71.
Embodiment 11
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
4.99 grams of (21mmol) 2,6- di-t-butyl -4- mercapto-phenols, 4.4 grams of (53mmol) formaldehyde, 5.70 grams of (31mmol) N- are added
Diphenyl-para-phenylene diamine and 150mL ethyl alcohol stir rapidly, after 60 DEG C of reaction 2.5h, are down to room temperature, 7.05 grams (85mmol) is added
Formaldehyde is warming up to 85 DEG C of reaction 2.5h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and passes through column
Chromatography obtains the shielding phenol product of structure shown in title.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 3.74 (1H), 4.12 (2H), 4.59 (1H), 4.83 (2H),
5.32 (1H), 6.97-7.11 (5H), 7.17 (2H), 7.24 (2H)；
13C NMR (75MHz, CDCl3): δ 29.6,33.1,34.6,50.6,119.4,123.3,126.2,126.7,
127.9,136.6,140.5,142.9,153.4；
C26H34N2OS calculated value C 75.29, H 7.67, N 6.27, O 3.58, S 7.18；Measured value: C 75.20, H
7.59, N 6.29, O 3.65, S 7.22.
Embodiment 12
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
19.52 grams of (82mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 10.04 grams of (121mmol) formaldehyde, 19.93 grams
(94mmol) 4- amino -4'- ethyl diphenylamines and 150mL dimethylbenzene stir rapidly, after 90 DEG C of reaction 3h, are down to room temperature, add
Enter 10.11 grams of (316mmol) sulphur and 0.04 gram of (0.35mmol) iodine, is warming up to 150 DEG C of reaction 8h.To after reaction, depressurize
A small amount of water of solvent and generation is distilled off, and the shielding phenol product of structure shown in title is obtained by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.23 (1H), 1.36 (18H), 2.61 (2H), 3.77 (1H), 4.84 (2H),
5.32 (1H), 5.70 (1H), 6.98 (5H), 7.17 (2H), 7.49 (1H)；
13C NMR (75MHz, CDCl3): δ 15.60,29.6,34.6,50.7,118.9,121.8,126.2,129.7,
136.6,141.2,146.1,153.4；
C29H36N2OS2Calculated value C 70.69, H 7.36, N 5.69, O 3.25, S 13.02；Measured value: C 70.77, H
7.41, N 5.67, O 3.17, S 12.93.
Embodiment 13
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
10.95 grams of (46mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 3.98 grams of (48mmol) formaldehyde, 13.78 grams (53mmol)
N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL trimethylbenzene stir rapidly, after 85 DEG C of reaction 1h, are added 3.82 grams
(46mmol) formaldehyde continues after 85 DEG C of reaction 1h, is down to room temperature, and 10.11 grams of (316mmol) sulphur and 0.27 gram is added
(2.11mmol) iodine is warming up to 180 DEG C of reaction 1h.To after reaction, be evaporated under reduced pressure a small amount of water for removing solvent and generation, and
The shielding phenol product of structure shown in title is obtained by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 4.26 (2H), 5.18 (2H), 5.32 (1H), 6.40 (1H),
6.97 (8H), 7.17 (2H), 7.37 (2H)；
13C NMR (75MHz, CDCl3): δ 29.6,33.6,34.6,54.3,106.5,114.4,119.4,121.8,
126.2,129.5,136.6,141.9,144.5,153.4；
C34H36N2OS2Calculated value C 73.87, H 6.56, N 5.07, O 2.89, S 11.60；Measured value: C 73.91, H
6.49, N 5.02, O 2.94, S 11.49.
Embodiment 14
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
21.66 grams of (91mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 7.39 grams of (89mmol) formaldehyde, 6.62 grams (36mmol)
4-aminodiphenylamine, 0.45 gram of (4.51mmol) sodium hydroxide and 150mL isopropanol stir rapidly, in 80 DEG C of reaction 3h.To
After reaction, vacuum distillation removes a small amount of water of solvent and generation, and obtains structure shown in title by column chromatography for separation
Shield phenol product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36-1.54 (36H), 4.82 (4H), 5.32 (2H), 6.97 (7H), 7.17
(4H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,56.5,106.5,119.4,121.8,126.5,129.5,
131.4,136.6,144.5,146.1,153.4；
C42H56N2O2S2Calculated value C 73.64, H 8.24, N 4.09, O 4.67, S 9.36；Measured value: C 73.59, H
8.21, N 4.15, O 4.62, S 9.34.
Embodiment 15
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
6.55 grams of (36mmol) 2- tert-butyl -4- mercapto-phenols, 7.64 grams of (92mmol) formaldehyde, 13.06 grams of (71mmol) N- benzene are added
Base p-phenylenediamine and 150mL toluene stir rapidly, in 90 DEG C of reaction 4h.To which after reaction, vacuum distillation removes solvent and life
At a small amount of water, and the shielding phenol product of structure shown in title is obtained by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (9H), 3.81 (1H), 4.38 (2H), 4.69 (2H), 5.29 (1H),
6.95-7.00 (15H), 7.17 (1H), 7.26 (4H), 7.55 (1H), 8.62 (1H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,43.5,50.8,114.3,119.4,121.8,125.4,
129.5,132.3,136.6,145.2,146.1,149.0,153.4；
C36H38N4OS calculated value C 75.23, H 6.66, N 9.75, O 2.78, S 5.58；Measured value: C 75.27, H
6.69, N 9.68, O 2.79, S 5.51.
Embodiment 16
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
11.66 grams of (49mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 10.92 grams of (53mmol) 2,6- DI-tert-butylphenol compounds,
7.89 grams of (95mmol) formaldehyde, 11.23 grams of (32mmol) N- phenyl-N '-[4- (phenyl amino) phenyl]-Isosorbide-5-Nitrae-phenylenediamine and
150mL toluene stirs rapidly, in 100 DEG C of reaction 3h.To after reaction, be evaporated under reduced pressure a small amount of water for removing solvent and generation,
And the shielding phenol product of structure shown in title is obtained by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36-1.54 (36H), 4.91 (2H), 5.22 (2H), 5.32 (2H), 6.97-
7.07 (16H), 7.17 (2H), 7.20 (1H), 7.27 (4H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.4,55.6,56.9,93.6,119.4,123.3,126.5,
129.2,131.4,136.6,142.8,146.1,153.4；
C54H65N3O2S calculated value C 79.08, H 7.99, N 5.12, O 3.90, S 3.91；Measured value: C 79.15, H
8.03, N 5.01, O 3.87, S 3.85.
Embodiment 17
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
47.16 grams of (45mmol) polyisobutene mercapto-phenols (manufacture of embodiment 1) of addition, 4.23 grams of (51mmol) formaldehyde, 9.75 grams
(53mmol) 4-aminodiphenylamine and 150mL benzene stir rapidly, in 80 DEG C of reaction 2.5h.To after reaction, be evaporated under reduced pressure
A small amount of water of solvent and generation is removed, and the shielding phenol product of structure shown in title is obtained by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 0.88,0.98,1.02,1.24,1.40,2.42,4.86,6.97,7.02,
7.14,7.26,7.55；
13C NMR (75MHz, CDCl3): δ 28.2,30.1,32.3,34.5,38.1,49.8,59.1,114.3,119.4,
121.8,122.0,127.3,129.5,132.3,143.3,146.1,151.3.
Embodiment 18
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
29.34 grams of (28mmol) polyisobutene mercapto-phenols (manufacture of embodiment 1) of addition, 2.91 grams of (35mmol) formaldehyde, 6.24 grams
(24mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL toluene stir rapidly, in 90 DEG C of reaction 2h.To after reaction,
Vacuum distillation removes a small amount of water of solvent and generation, and obtains the shielding phenol product of structure shown in title by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 0.88,0.98,1.02,1.24,1.40,2.42,4.00,4.86,5.56,
6.97,7.02,7.14,7.26,7.55；
13C NMR (75MHz, CDCl3): δ 28.2,30.1,32.3,33.1,34.5,38.1,49.8,59.1,114.3,
119.4,121.8,125.2,122.0,127.3,129.5,132.3,143.3,146.1,151.3.
Comparative example 1
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
20.23 grams of (85mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 7.22 grams of (87mmol) formaldehyde, 14.37 grams (85mmol)
Diphenylamines and 150mL methanol stir rapidly, in 60 DEG C of reaction 2h.To which after reaction, vacuum distillation removes solvent and generation
A small amount of water, and the shielding phenol product of structure shown in title is obtained by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 5.21 (2H), 5.32 (1H), 6.99 (6H), 7.17 (2H),
7.27(4H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,55.2,120.4,123.3,125.9,126.2,129.2,
136.6,150.0,153.5；
C27H33NOS calculated value C 77.28, H 7.93, N 3.34, O 3.81, S 7.64；Measured value: C 77.22, H
7.89, N 3.31, O 3.83, S 7.67.
Comparative example 2
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
10.71 grams of (52mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 1.89 grams of (63mmol) formaldehyde, 17.42 grams (65mmol)
N- (1,3- dimethylbutyl)-N'- diphenyl-para-phenylene diamine and 150mL methanol stir rapidly, in 70 DEG C of reaction 4h.Wait react knot
Shu Hou, vacuum distillation remove a small amount of water of solvent and generation, and obtain the shielding phenol of structure shown in title by column chromatography for separation
Product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 0.80 (6H), 1.11 (3H), 1.29 (1H), 1.36 (18H), 3.45 (1H),
4.53 (2H), 5.32 (2H), 6.97-7.07 (9H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 17.9,22.40,24.6,30.4,34.3,45.7,54.5,56.7,116.6,
120.4,121.8,125.9,128.9,129.5,135.6,146.1,153.5,154.8；
C33H46N2O calculated value C 81.43, H 9.53, N 5.76, O 3.29；Measured value: C 81.38, H 9.51, N
5.79, O 3.31.
Comparative example 3
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
9.24 grams of (33mmol) 2,6- di-t-butyl -4- (3- mercaptopropyi) phenol of addition, 3.07 grams of (37mmol) formaldehyde, 11.71 grams
(45mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL benzene stir rapidly, in 80 DEG C of reaction 4h.To after reaction, subtract
A small amount of water of solvent and generation is distilled off in pressure, and obtains the shielding phenol product of structure shown in title by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.40 (18H), 1.99 (1H), 2.61-2.80 (6H), 4.63 (2H), 5.32
(1H), 6.97-7.02 (12H), 7.26 (4H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 28.7,31.1,34.3,35.7,54.1,117.1,119.4,123.3,
124.8,129.2,131.8,136.0,142.8,144.9,146.1,151.9；
C36H44N2OS calculated value C 78.22, H 8.02, N 5.07, O 2.89, S 5.80；Measured value: C 78.27, H
7.96, N 4.98, O 2.92, S 5.83.
Comparative example 4~7
The composition of the comparative example 4~7 of antioxidant is shown in Table 1.
Table 1
The embodiment 19~28 and comparative example 8~14 of universal gear lubricating oil composition
The embodiment 19~28 of universal gear lubricating oil composition and the formula composition of comparative example 8~14 are shown in Table 2,3.It will
In table each component be added to scale reconcile container in, 45 DEG C heating stirring 2 hours, respectively prepare obtain GL-5 rank
Universal gear lubricating oil composition.
Some lube oil additives used in specific are as follows:
Extreme pressure anti-wear additives: sulfide isobutene, normal-butyl n-octyl zinc dithiophosphate；
Metal deactivator: the thio -1,3,4- thiadiazoles of 2- dimercapto -5- two；
Ashless friction modifiers: oleamide；
Lube base oil: II class lubricating oil base oil 100N, II class lubricating oil base oil 150N.
Table 2
Table 3
Calorimetric test (PDSC) evaluation test embodiment 19~28 is scanned using Pressurized Differential and comparative example 8~14 carries out
The high-temperature oxidation resistance of oil product is indicated with the oxidation induction period (unit is min) of test specimen.PDSC test temperature be
220 DEG C, pressure 0.5MPa, oxygen gas flow rate 100mL/min.Oxidation induction period is longer, shows the high temperature antioxygen of test specimen
It is better to change performance.
Using engine crankcase coking simulation test testing example 19~28 and the detergency of comparative example 8~14
Energy.This method be by 300ml test specimen be added coking plate analog meter, be heated to 150 DEG C, use continuation mode to temperature for
310 DEG C of aluminium sheet spilled oil is weighed the burnt amount generated on aluminium sheet after 6 hours, is indicated with sediment yield (unit is mg), simulation is lived
Deposit beyond the Great Wall.Coking amount is higher, and the detergency for representing this test specimen is poorer.
The high temperature for carrying out oil product to embodiment 19~28 and comparative example 8~14 using high-frequency reciprocating frictional testing machine is wear-resistant
Damage test, experimental condition are as follows: load 1000g, frequency 20Hz, temperature is 100 DEG C, test period 60min.Wear scar diameter is got over
It is small, show that the anti-wear and wear-resistant performance of test specimen is better.
BRT ball rust test is carried out to embodiment 19~28 and comparative example 8~14, is manufactured with embodiment or comparative example
Lubricant oil composite is as test specimen, during entire bench test in 18 hours, the gold protected by the test specimen
Belong to ball continuous contact acidic liquid and air, after the end of the test, measure metal spherical reflector intensity, obtain gray scale test value,
For determining corroded area, thus the resistant to rust ability of qualification test sample.Acetic acid/hydrobromic acid/hydrochloric acid/deionized water solution
Injection rate is 0.19 ml/hour, and air draught is 40 ml/mins, and oil temperature is 48 DEG C.Appraisal result is higher, shows to try
The rustless property for testing sample is better.
PDSC test, coking simulation test, high-frequency reciprocating friction test and BRT ball rust test test result such as table 4
It is shown.
Table 4
From table 4, it can be seen that universal gear lubricating oil composition of the present invention has excellent high-temperature oxidation resistance, peace and quiet
Dispersion performance, preferable abrasion-resistance and lower coefficient of friction and excellent anti-corrosion ability.
Claims (19)
1. a kind of universal gear lubricating oil composition, including shielding phenolic compounds, extreme pressure anti-wear additives, metal deactivator, ashless rub
Wipe modifier and major amount of lube base oil, the structure of the shielding phenolic compounds are as follows:
In logical formula (I), each group R is same or different to each other, and is each independently selected from hydrogen, C1-300Linear or branched alkyl group, general formula
(II) group shown in group shown in and logical formula (III), on condition that at least one group R is group shown in logical formula (II)；
Each group R' is same or different to each other, and is each independently selected from hydrogen and C1-20Linear or branched alkyl group,
In aforementioned each logical formula (II), (III) and (IV), it is group each independently that each group L, which is same or different to each other,Wherein group R " is selected from hydrogen, C1-20Alkyl and C3-20Linear chain or branched chain miscellaneous alkyl；Each group R2It is mutually the same
Or it is different, it is each independently selected from hydrogen, C1-20Shown in group shown in linear or branched alkyl group, logical formula (IV) and logical formula (V)
Group；Each group RbIt is same or different to each other, is each independently selected from hydrogen and C1-20Linear or branched alkyl group；Each group RcEach other
It is identical or different, it is each independently selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup；Y is 0 to 3
Integer；Z is 0 to 3 integer；The integer that n is 1 to 8；The integer that n' is 0 to 7, on condition that n'+n≤8；Each group RdEach other
It is identical or different, it is each independently selected from group shown in hydrogen and logical formula (V)；Each cyclic groupIt is mutually the same or not
Together, it is each independently selected from phenyl ring and naphthalene nucleus, wherein two adjacent cyclic groupsOptionally pass through additional S each other
Atom forms phenthazine ring with the N atom for bridging the two rings, and/or, two adjacent cyclic groupsEach other
Optionally pass through additional groupWith bridge the two rings N atom and form 9,10- acridan ring, wherein
Group R " is selected from hydrogen, C1-20Alkyl and C3-20Linear chain or branched chain miscellaneous alkyl,
In logical formula (V), each group R is same or different to each other, and is each independently selected from hydrogen, C1-300Linear or branched alkyl group, general formula
(II) group shown in group shown in and logical formula (III)；Each group R' is same or different to each other, be each independently selected from hydrogen and
C1-20Linear or branched alkyl group；Group L is groupWherein group R " is selected from hydrogen, C1-20Alkyl and C3-20Straight chain
Or branched heteroalkyl groups；A is 0 or 1, and two group R and a group-(S)a- L- occupies the residue on phenyl ring three respectively
Position,
Wherein, the linear chain or branched chain miscellaneous alkyl is selected from one or more groups-inside linear or branched alkyl group molecular structure
CH2The group and linear or branched alkyl group that the substituting group for being selected from one of-O- ,-S- and-NR'- is directly substituted and obtained divide
One or more group-CH inside minor structure <by substituting group-N < are directly substituted and the group of acquisition, wherein in-NR'-
R' is H or C1-4Linear or branched alkyl group, the shielding phenolic compounds at least one group R in its entire molecular structuredIt is
Hydrogen.
2. universal gear lubricating oil composition described in accordance with the claim 1, which is characterized in that each group R is selected each independently
From hydrogen, C1-10Linear or branched alkyl group or number-average molecular weight Mn are base shown in polyolefin-based, the logical formula (II) of 300-3000
Group shown in group and logical formula (III)；Each group R' is each independently selected from hydrogen and C1-4Linear or branched alkyl group；
Group R " is selected from hydrogen, C1-20Linear or branched alkyl group and C3-20Linear chain or branched chain miscellaneous alkyl；Each group R2It selects each independently
From hydrogen, C1-10Group shown in linear or branched alkyl group and logical formula (IV)；Each group RbIt is each independently selected from hydrogen and C1-10Straight chain
Or branched alkyl；Each group RcIt is each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygen
Base；Y is 0 or 1；Z is 0 or 1；N is 1 or 2；N' is 0 or 1, on condition that n'+n=1 or n'+n=2；Each group RdFor hydrogen；Each ring
GroupSelected from phenyl ring.
3. universal gear lubricating oil composition according to claim 2, which is characterized in that group R " is selected from hydrogen, C1-10Straight chain
Or branched alkyl and C3-10Linear chain or branched chain miscellaneous alkyl.
4. universal gear lubricating oil composition according to claim 2, which is characterized in that each group RcIn cyclic groupThe contraposition of upper nitrogen-atoms.
5. universal gear lubricating oil composition according to claim 2, which is characterized in that each group R is selected each independently
From hydrogen, C1-10Linear or branched alkyl group or number-average molecular weight Mn are the polyolefin-based of 300-3000.
6. universal gear lubricating oil composition described in accordance with the claim 1, which is characterized in that the shielding phenolic compounds is selected from
The mixture of particular compound below or its arbitrary proportion:
7. universal gear lubricating oil composition described in accordance with the claim 1, which is characterized in that the system of the shielding phenolic compounds
Making method includes closing amine compounds hydroformylation shown in general formula (Z) shown in phenolic compounds shown in logical formula (X) and general formula (Y)
The first step to react in the presence of object optionally further includes reacting the reaction product of the first step with vulcanizing agent
And/or the additional step reacted with aldehyde compound shown in general formula (Z),
In logical formula (X), each group R0It is same or different to each other, is each independently selected from hydrogen ,-SH and C1-300Linear chain or branched chain alkane
Base, on condition that at least one group R0It is-SH；Each group R' is same or different to each other, and is each independently selected from hydrogen and C1-20Straight chain
Or branched alkyl,
In general formula (Y), group R'2Selected from hydrogen, C1-20Linear or branched alkyl group and groupEach group Rb
It is same or different to each other, is each independently selected from hydrogen and C1-20Linear or branched alkyl group；Each group RcIt is same or different to each other, respectively
From independently selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup；Y is 0 to 3 integer；Z be 0 to
3 integer；The integer that n1 is 1 to 8；Each cyclic groupBe same or different to each other, be each independently selected from phenyl ring and
Naphthalene nucleus,
In general formula (Z), group R " is selected from hydrogen, C1-20Alkyl and C3-20Linear chain or branched chain miscellaneous alkyl,
Wherein, the linear chain or branched chain miscellaneous alkyl is selected from one or more groups-inside linear or branched alkyl group molecular structure
CH2The group and linear or branched alkyl group that the substituting group for being selected from one of-O- ,-S- and-NR'- is directly substituted and obtained divide
One or more group-CH inside minor structure <by substituting group-N < are directly substituted and the group of acquisition, wherein in-NR'-
R' is H or C1-4Linear or branched alkyl group.
8. universal gear lubricating oil composition according to claim 7, which is characterized in that hydroformylation shown in general formula (Z) is closed
Object is formaldehyde；The vulcanizing agent is sulphur；
Each group R0It is each independently selected from hydrogen ,-SH and C1-10Linear or branched alkyl group or number-average molecular weight Mn are 300-3000
It is polyolefin-based；Each group R' is each independently selected from hydrogen and C1-4Linear or branched alkyl group；
Each group RbIt is each independently selected from hydrogen and C1-10Linear or branched alkyl group；Each group RcIt is each independently selected from hydrogen, C1-10
Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygroup；Y is 0 or 1；Z is 0 or 1；N1 is 1 or 2；Each cyclic groupSelected from phenyl ring；Group R " is selected from hydrogen, C1-20Linear or branched alkyl group and C3-20Linear chain or branched chain miscellaneous alkyl.
9. universal gear lubricating oil composition according to claim 8, which is characterized in that each group RcIn cyclic groupThe contraposition of upper nitrogen-atoms.
10. universal gear lubricating oil composition according to claim 8, which is characterized in that group R " is selected from hydrogen, C1-10Directly
Chain or branched alkyl and C3-10Linear chain or branched chain miscellaneous alkyl.
11. universal gear lubricating oil composition according to claim 7, which is characterized in that in the first step, institute
The molar ratio for stating amine compounds shown in phenolic compounds shown in logical formula (X) and the general formula (Y) is 1:0.1-10, the general formula
(X) molar ratio of phenolic compounds shown in and aldehyde compound shown in the general formula (Z) is 1:0.1-10, in the additional step
In, the molar ratio of amine compounds shown in the general formula (Y) and the vulcanizing agent is 1:1-10, amine shown in the general formula (Y)
The molar ratio of compound and aldehyde compound shown in the general formula (Z) is 1:0.1-10.
12. universal gear lubricating oil composition according to claim 7, which is characterized in that in the first step, institute
The molar ratio for stating amine compounds shown in phenolic compounds shown in logical formula (X) and the general formula (Y) is 1:0.5-5.0, described logical
The molar ratio of phenolic compounds shown in formula (X) and aldehyde compound shown in the general formula (Z) is 1:0.5-5.0, described additional
In step, the molar ratio of amine compounds shown in the general formula (Y) and the vulcanizing agent is 1:1.2-6.0, general formula (Y) institute
The molar ratio of aldehyde compound shown in the amine compounds and the general formula (Z) shown is 1:0.5-5.0.
13. universal gear lubricating oil composition according to claim 7, which is characterized in that in the first step, institute
The molar ratio for stating amine compounds shown in phenolic compounds shown in logical formula (X) and the general formula (Y) is 1:0.8-2.0, described logical
The molar ratio of phenolic compounds shown in formula (X) and aldehyde compound shown in the general formula (Z) is 1:0.8-2.0, described additional
In step, the molar ratio of amine compounds shown in the general formula (Y) and the vulcanizing agent is 1:1.5-3.0, general formula (Y) institute
The molar ratio of aldehyde compound shown in the amine compounds and the general formula (Z) shown is 1:0.8-2.0.
14. according to universal gear lubricating oil composition described in one of claim 1-13, which is characterized in that the extreme-pressure anti-wear
Agent is selected from one of phosphate, olefine sulfide, dialkyl dithiocarbamate and dialkyl dithiophosphate or more
Kind；The metal deactivator is selected from one of benzotriazole derivative, thiazole and thiadiazoles derivative or a variety of；It is described
Ashless friction modifiers are selected from one of fatty acid amide, polyol esters of fatty acids and aliphatic amine or a variety of；The lubrication
Oil base oil is selected from one of APII, II, III, IV, V class lubricating oil base oil or a variety of.
15. universal gear lubricating oil composition according to claim 14, which is characterized in that the extreme pressure anti-wear additives are selected from
The combination of olefine sulfide and dialkyl dithiophosphate, the mass ratio in the combination between the two are 0.1:1-10:1；It is described
Metal deactivator is selected from thiadiazoles derivative；The Ashless friction modifiers are selected from fatty acid amide.
16. universal gear lubricating oil composition according to claim 14, which is characterized in that the shielding phenolic compounds accounts for
The 0.001%-30% of the universal gear lubricating oil composition gross mass；The extreme pressure anti-wear additives account for the general gear lubrication
The 0.1%-10% of fluid composition gross mass；The metal deactivator accounts for the universal gear lubricating oil composition gross mass
0.01%-5%；The Ashless friction modifiers account for the 0.01%-5% of the universal gear lubricating oil composition gross mass.
17. universal gear lubricating oil composition according to claim 14, which is characterized in that the shielding phenolic compounds accounts for
The 0.05%-20% of the universal gear lubricating oil composition gross mass；The extreme pressure anti-wear additives account for the general gear lubrication
The 0.2%-8% of fluid composition gross mass；The metal deactivator accounts for the universal gear lubricating oil composition gross mass
0.02%-3%；The Ashless friction modifiers account for the 0.02%-4% of the universal gear lubricating oil composition gross mass.
18. universal gear lubricating oil composition according to claim 14, which is characterized in that in the general gear lubrication
Metal detergent, ashless dispersant, antioxidant, pour-point depressant, viscosity index improver, metal erosion inhibition are added in fluid composition
One of agent, antirust agent and anti-foaming agent are a variety of.
19. the manufacturing method of universal gear lubricating oil composition described in one of claim 1-13, including make the shielding phenol,
The step of extreme pressure anti-wear additives, metal deactivator, Ashless friction modifiers and the lube base oil mix.
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| CN106590830B (en) * | 2015-10-19 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of fully synthetic extreme pressure lubricating oil for industrial gears composition and its manufacturing method |
| CN106590852B (en) * | 2015-10-19 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of industrial lubrication fluid composition and its manufacturing method |
| CN106590851B (en) * | 2015-10-19 | 2019-11-15 | 中国石油化工股份有限公司 | Compressor lubrication fluid composition and its manufacturing method |
| CN106590828B (en) * | 2015-10-19 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of heavy duty automobile gear lubricating oil composition and its manufacturing method |
| CN106590829B (en) * | 2015-10-19 | 2019-11-15 | 中国石油化工股份有限公司 | Railway high speed diesel engine lubricating oil composite and its manufacturing method |
| CN106590832B (en) * | 2015-10-19 | 2019-11-15 | 中国石油化工股份有限公司 | Gas engine lubricant oil composite and its manufacturing method |
| CN109679709B (en) * | 2017-10-18 | 2022-06-24 | 中国石油化工股份有限公司 | Universal gear lubricating oil composition and preparation method thereof |
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