CN106318528A - Universal gear lubricating oil composition - Google Patents
Universal gear lubricating oil composition Download PDFInfo
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Abstract
The invention relates to a universal gear lubricating oil composition. The universal gear lubricating oil composition comprises a hindered phenol compound, an extreme pressure-antiwear additive, a metal passivator, an ashless friction modifier and a major amount of lubricating base oil, wherein the hindered phenol compound has a structure as shown in a formula (I) which is described in the specification. Each group in the formula (I) is as defined in the specification. The universal gear lubricating oil composition in the invention can meet the increasingly stringent requirement of modern products with higher specifications on oxidation resistance and show excellent cleaning and dispersion properties, anti-wear performance and anti-rust performance.
Description
Technical field
The present invention relates to a kind of universal gear lubricating oil composition.Specifically, the present invention relates to one
Meet GL-5 and the general gear lubricating oil composition of above specification extreme pressure heavy load gear oil product requirement
Thing.
Background technology
Automotive gear oil is for parts such as mechanical transmission, drive axle and the gear of steering gear, bearings
Lubrication, play lubrication, cooling, antirust and buffering effect.Along with the development of auto industry, tooth
Roller box volume diminishes, load increases, service condition is more severe, causes gear oil temperature rise, it is desirable to
Gear oil has higher oxidation stability.Wherein, Modern Car uses hypoid gear, working condition
The harshest, automobile gear oil's serviceability is required higher, because its axis bias amount is relatively big, at car
Speed Gao Shihui makes the relative sliding velocity between gear wheel face the highest, makes oil temperature reach 160 DEG C-180 DEG C.
At present, the concern to gear oil antioxygenic property is also nowhere near.Pacify to improve the oxidation of gear oil
Qualitative, maximally effective way is to add antioxidant.
Unsaturated olefin, aromatic hydrocarbons and a small amount of sulfur-containing compound in lube base oil are easily anti-with oxygen
Colloid should be formed, and ultimately form carbon distribution deposit.It is not smooth that carbon deposits makes gearbox gear rotate,
Increase the abrasion of gear, shorten gearbox life.Therefore, in order to preferably protect gear, gear oil
Also need to more preferable cleansing performance.
United States Patent (USP) US 5304314 discloses a kind of sulfur-bearing being suitable as antioxidant use and arylamine
Phenolic compounds.United States Patent (USP) US 2006/0189824A1 discloses a kind of antioxidant that is suitable as
Shielding phenolic compounds containing secondary aromatic amine.
But, when the compound of these prior aries uses in gear oil, the antioxygenic property of oil product,
Still there is room for improvement in cleansing performance and abrasion resistance.
It addition, in addition to the adverse effect of deposit, the corrosion of electromotor also can be started by serious curtailment
The life-span of machine, and the corrosion of some key positions the most also affects the operating mode of electromotor
Energy.The concern of rustless property is also nowhere near by prior art.
Therefore, prior art is still required for a kind of general universal gear lubricating oil composition, and it not only can
The requirement that enough satisfied current more high standard products are the most harsh to antioxygenic property, and can also demonstrate
Excellent detergent-dispersant performance energy, abrasion resistance and rustless property.
Summary of the invention
The present inventor is on the basis of existing technology through diligent research, it was found that a kind of novel screen
Cover phenolic compounds, and it has furthermore been found that by using this shielding phenolic compounds to prepare as antioxidant
Obtain universal gear lubricating oil composition, it is possible to the foregoing problems that solution prior art exists, and by
This completes the present invention.
Specifically, the present invention relates to the content of following aspect.
1. a universal gear lubricating oil composition, including shielding phenolic compounds, extreme pressure anti-wear additives,
Metal deactivator, Ashless friction modifiers and major amount of lube base oil；
The structure of described shielding phenolic compounds is:
In logical formula (I), each group R is same to each other or different to each other, and is each independently selected from hydrogen, C1-300
Straight or branched alkyl (preferably C1-10Straight or branched alkyl or number-average molecular weight Mn are
300-3000's is polyolefin-based), logical group shown in formula (II) and the group shown in logical formula (III),
Premise be at least one group R be logical group shown in formula (II)；Each group R' is mutually the same or not
With, it is each independently selected from hydrogen and C1-20Straight or branched alkyl (is preferably each independently selected from hydrogen
And C1-4Straight or branched alkyl),
In aforementioned each logical formula (II), (III) and (IV), each group L is same to each other or different to each other, respectively
From being group independentlyWherein group R " selected from hydrogen, C1-20Alkyl (preferably C1-20
Straight or branched alkyl) and C3-20The miscellaneous alkyl of straight or branched, is preferably selected from hydrogen, C1-10Straight chain or
Branched alkyl and C3-10The miscellaneous alkyl of straight or branched；Each group R2It is same to each other or different to each other, the most solely
On the spot selected from hydrogen, C1-20Straight or branched alkyl, logical group shown in formula (IV) and logical formula V
Shown group (is preferably each independently selected from hydrogen, C1-10Straight or branched alkyl and logical formula (IV)
Shown group)；Each group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-20Directly
Chain or branched alkyl (are preferably each independently selected from hydrogen and C1-10Straight or branched alkyl)；Each group
RcIt is same to each other or different to each other, is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Directly
Chain or branched alkyl epoxide (are preferably each independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10
Straight or branched alkyl oxy, is more preferably in cyclic groupThe para-position of upper nitrogen-atoms)；y
It it is the integer (preferably 0 or 1) of 0 to 3；Z is the integer (preferably 0 or 1) of 0 to 3；N is 1
Integer (preferably 1 or 2) to 8；N' is the integer (preferably 0,1 or 2) of 0 to 7, and premise is
N'+n≤8 (preferably n'+n=1 or n'+n=2)；Each group RdIt is same to each other or different to each other, independently of one another
Selected from the group (preferably hydrogen) shown in hydrogen and logical formula V；Each cyclic groupMutually the same
Or different, it is each independently selected from phenyl ring and naphthalene nucleus (preferably phenyl ring), two the most adjacent ring groups
GroupFormed optionally through additional S atom and the atom N of bridge joint the two ring each other
Phenothiazine ring, and/or, two adjacent cyclic groupsEach other optionally through additional group(wherein group R " selected from hydrogen, C1-20Alkyl (preferably C1-20Straight or branched alkyl)
And C3-20The miscellaneous alkyl of straight or branched, is preferably selected from hydrogen and C1-10Straight or branched alkyl) and bridge joint
The atom N of the two ring and form 9,10-acridan ring,
In logical formula V, each group R is same to each other or different to each other, and is each independently selected from hydrogen, C1-300
Straight or branched alkyl (preferably C1-10Straight or branched alkyl or number-average molecular weight Mn are 300-3000
Polyolefin-based), logical group shown in formula (II) and the group shown in logical formula (III) (preferably each solely
On the spot selected from hydrogen and C1-300Straight or branched alkyl)；Each group R' is same to each other or different to each other, the most solely
On the spot selected from hydrogen and C1-20Straight or branched alkyl (is preferably each independently selected from hydrogen and C1-4Straight chain
Or branched alkyl)；Group L is groupWherein group R " selected from hydrogen, C1-20Hydrocarbon
Base (preferably C1-20Straight or branched alkyl) and C3-20The miscellaneous alkyl of straight or branched, be preferably selected from hydrogen,
C1-10Straight or branched alkyl and C3-10The miscellaneous alkyl of straight or branched；A is 0 or 1, and two bases
Group R and group-(S)a-L-occupies three positions of residue on phenyl ring respectively,
Wherein, the miscellaneous alkyl of described straight or branched is selected from the one of straight or branched alkyl molecule inside configuration
Individual or multiple (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH2-quilt
Selected from-O-,-S-and-NR'-, (R' is H or C1-4Straight or branched alkyl) one of replacement group
The group that directly substitutes and obtain and straight or branched alkyl molecule inside configuration one or more
(such as 1 to 3,1 to 2 or 1) group-CH < is substituted group-N < directly to replace
Generation and the group that obtains, wherein this shielding phenolic compounds in its whole molecular structure at least
Group RdIt is hydrogen.
2. according to the shielding phenolic compounds described in any preceding aspect, selected from following concrete chemical combination
Thing or the mixture of its arbitrary proportion:
3. shield the manufacture method of phenolic compounds described in, close including making the phenolate shown in logical formula (X)
Amines shown in thing and formula (Y) is at the aldehyde compound (preferably formaldehyde) shown in formula (Z)
In the presence of the first step that reacts, the most also include the product making described first step with
Vulcanizing agent (preferably sulfur) reacts and/or anti-with the aldehyde compound (preferably formaldehyde) shown in formula (Z)
The additional step answered,
In logical formula (X), each group R0It is same to each other or different to each other, is each independently selected from hydrogen ,-SH
And C1-300Straight or branched alkyl (preferably C1-10Straight or branched alkyl or number-average molecular weight Mn
Polyolefin-based for 300-3000), premise is at least one group R0It is-SH；Each group R' is each other
Identical or different, it is each independently selected from hydrogen and C1-20Straight or branched alkyl is (preferably each independent
Ground is selected from hydrogen and C1-4Straight or branched alkyl),
In formula (Y), group R'2Selected from hydrogen, C1-20Straight or branched alkyl and groupEach group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-20
Straight or branched alkyl (is preferably each independently selected from hydrogen and C1-10Straight or branched alkyl)；Each base
Group RcIt is same to each other or different to each other, is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20
Straight or branched alkyl oxy (is preferably each independently selected from hydrogen, C1-10Straight or branched alkyl and
C1-10Straight or branched alkyl oxy, is more preferably in cyclic groupUpper nitrogen-atoms right
Position)；Y is the integer (preferably 0 or 1) of 0 to 3；Z is the integer (preferably 0 or 1) of 0 to 3；
N1 is the integer (preferably 1 or 2) of 1 to 8；Each cyclic groupIt is same to each other or different to each other,
It is each independently selected from phenyl ring and naphthalene nucleus (preferably phenyl ring),
In formula (Z), group R " selected from hydrogen, C1-20Alkyl (preferably C1-20Straight or branched alkane
Base) and C3-20The miscellaneous alkyl of straight or branched, is preferably selected from hydrogen, C1-10Straight or branched alkyl and C3-10
The miscellaneous alkyl of straight or branched,
Wherein, the miscellaneous alkyl of described straight or branched is selected from the one of straight or branched alkyl molecule inside configuration
Individual or multiple (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH2-quilt
Selected from-O-,-S-and-NR'-, (R' is H or C1-4Straight or branched alkyl) one of replacement group
The group that directly substitutes and obtain and straight or branched alkyl molecule inside configuration one or more
(such as 1 to 3,1 to 2 or 1) group-CH < is substituted group-N < directly to replace
Generation and the group that obtains.
4. according to the manufacture method described in any preceding aspect, wherein in described first step, institute
State the mol ratio of the phenolic compounds shown in logical formula (X) and the amines shown in described formula (Y)
For 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0, the phenolate shown in described logical formula (X)
Compound is 1:0.1-10, preferably 1:0.5-5.0 with the mol ratio of the aldehyde compound shown in described formula (Z),
More preferably 1:0.8-2.0, in described additional step, the amines shown in described formula (Y) with
The mol ratio of described vulcanizing agent is 1:1-10, preferably 1:1.2-6.0, more preferably 1:1.5-3.0, described logical
Amines shown in formula (Y) with the mol ratio of the aldehyde compound shown in described formula (Z) is
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, described shielding phenolate
Compound accounts for the 0.001%-30% of described universal gear lubricating oil composition gross weight, preferably
0.05%-20%, more preferably 0.1%-10%；
Described extreme pressure anti-wear additives can be selected from phosphate ester, olefine sulfide, dialkyldithiocarbamacompositions
One or more in salt and dialkyl dithiophosphate；
Described phosphate ester can be selected from the phosphorous acid selecting Shandong Zibo Hui Hua Chemical Co., Ltd. to produce
Di-n-butyl T304, the tricresyl phosphate T306 that Peng Pu chemical plant, Shanghai produces, Germany BASF is public
The Irgalube353 etc. that department produces.Described olefine sulfide can like that selected from Nanjing enlightening minister chemical enterprise has
The sulfide isobutene T321 that limit company, east, Shandong chemical fertilizer factory produce, Lubrizol Corp. of the U.S.
Anglamol33, the Mobilad C-170 etc. of american exxon-XOM.Described dialkyl disulfides
For carbaminate can be selected from zinc dialkyl dithiocarbamate salt, lead salt and the one of antimonic salt or
Multiple, alkyl therein is the alkyl containing 2 to 12 carbon atoms, preferably contains 2 to 8
The alkyl of individual carbon atom, can be ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, Zhong Ding
Base, n-pentyl, isopentyl, n-hexyl, isohesyl, n-octyl, 2-ethylhexyl, cyclohexyl,
One or more in methylcyclopentyl.Described dialkyl dithiophosphate can be selected from C2-12Alkane
Base ZDDP, is preferably selected from C3-8Alkyl ZDDP, its alkyl can select ethyl, n-pro-pyl, different
Propyl group, normal-butyl, isobutyl group, sec-butyl, n-pentyl, isopentyl, n-hexyl, isohesyl, just
One or more in octyl group, 2-ethylhexyl, cyclohexyl and methylcyclopentyl；
Described extreme pressure anti-wear additives is preferably selected from the combination of olefine sulfide and dialkyl dithiophosphate, should
In combination, mass ratio between the two is 0.1:1-10:1, is preferably in a proportion of 0.2:1-8:1, more excellent
Selecting ratio is 0.3:1-5:1；
Described extreme pressure anti-wear additives accounts for the 0.1%-10% of described universal gear lubricating oil composition gross mass,
Preferably 0.2%-8%, more preferably 0.5%-5%；
Described metal deactivator is in benzotriazole derivant, thiazole and thiadiazoles derivative
One or more, conventional metal deactivator include BTA, benzothiazole, tolyl-triazole,
Octyl group triazole, 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazoles, 2-sulfydryl-5-hydrocarbon replace
-1,3,4-thiadiazoles, 2-dimercapto-5-dithio-1,3,4-thiadiazoles, N, N-dihexyl aminomethylene
Benzotriazole, 2-sulfydryl diazosulfide etc., trade names have T551, T561, T706 etc., permissible
Select T551, T561, T706 etc. that Jinzhou Kangtai Lube Additive Co., Ltd. produces；
The preferred thiadiazoles derivative of described metal deactivator；
Described metal deactivator accounts for the 0.01%-5% of described universal gear lubricating oil composition gross mass,
Preferably 0.02%-3%, more preferably 0.05%-2%；
Described Ashless friction modifiers can be with selected fatty acid amide, polyol esters of fatty acids and fat
One or more in fat race amine, the most aliphatic alkyl is that carbon number is between 6-60
Saturated or that unsaturated alkyl, preferably carbon number are between 10-50 saturated or unsaturated alkyl.
The example of described aliphatic amide includes oleamide, coconut oleoyl amine, oleic acid diethyl amide etc..
Described polyol esters of fatty acids includes fatty glyceride, fatty acid pentaerythritol ester, fatty acid
Glycol ester, fatty acid succinate, fatty acid ethanolamide amine ester, fatty acid diethanolamine ester,
The monoesters of the compounds such as fatty acid triethanolamine ester, dibasic acid esters or polyester, as monoolein,
Oleic acid diglyceride, stearic acid monopentaerythritol ester, lauric acid/dodecanoic acid diethylene glycol dilaurate, oleic acid list are sweet
Grease, oleic acid diethanolamine, triethanolamine oleate etc.；Described aliphatic amine includes that alkyl replaces
The alkyl of monoamine or polyamine, alkoxylate replaces monoamine or polyamine and alkyl ether amine etc.,
Tallow amine and the Adeps Bovis seu Bubali fat ether amines of ethoxylation such as ethoxylation.Described Ashless friction
Modifier can select F10 and F20 etc. of BASF Aktiengesellschaft；
Described Ashless friction modifiers preferred fatty acid amide；
Described Ashless friction modifiers accounts for described universal gear lubricating oil composition gross mass
0.01%-5%, preferably 0.02%-4%, more preferably 0.05%-3%；
Described lube base oil, can select API I, II, III, IV, V class lubricating oil base
One or more in plinth oil, such as can be selected from mineral lubricating oil and synthetic lubricant fluid
Plant or multiple, preferably one or more in II, III and IV class lubricating oil base oil, most preferably
II and/or Group III hydrogenated base oil.
Metal detergent, nothing can also be added in the universal gear lubricating oil composition of the present invention
Ash dispersant, antioxidant, pour-point depressant, viscosity index improver, metal corrosion inhibitor, anti-
One or more other lube oil additives in rust agent and anti-foaming agent.These additives can be single
Solely use, it is also possible in combination of two or more uses, and the routine that its consumption is from this area is used
Amount, is not particularly limited.
6. the manufacture method of the universal gear lubricating oil composition of any preceding aspect, including making
State shielding phenol, extreme pressure anti-wear additives, metal deactivator, Ashless friction modifiers and described lubrication oil base
The step of plinth oil mixing.
Technique effect
Shielding phenolic compounds according to the present invention, phosphorus element-containing and metallic element, be not likely to produce ash,
It is environmentally friendly antioxidant.
Shielding phenolic compounds according to the present invention, compared with the compound of prior art, demonstrates notable
The high-temperature oxidation resistance (heat stability) improved, it is possible to be effectively improved the (high of such as lubricating oil
Temperature) oxidation stability.
Shielding phenolic compounds according to the present invention, in a preferred embodiment, is demonstrating excellence
While high-temperature oxidation resistance, also exhibit further the rustless property of excellence.This is prior art
Not available for compound.
Shielding phenolic compounds according to the present invention, in a preferred embodiment, is demonstrating excellence
While high-temperature oxidation resistance, also exhibit further cleansing performance (the i.e. deposit generation of excellence
Rejection).This is not available for prior art compound.
Shielding phenolic compounds according to the present invention, in a preferred embodiment, is demonstrating excellence
While high-temperature oxidation resistance, also exhibit further suppression viscosity build and the suppression acid number of excellence
The performance increased.This is not available for prior art compound.
According to the universal gear lubricating oil composition of the present invention, in a preferred embodiment, demonstrate
Excellent antioxygenic property, detergent-dispersant performance energy, abrasion resistance and rustless property, fully meets GL-5
And the requirement of above specification extreme pressure heavy load gear lubrication oil product.
Detailed description of the invention
Below the detailed description of the invention of the present invention is described in detail, it should be noted however that this
The protection domain of invention is the most limited to these specific embodiments, but by the claim of annex
Book determines.
All publications, patent application, patent and other list of references that this specification is mentioned all draw
In this for reference.Unless otherwise defined, all technology and scientific terminology used by this specification all have
The implication that those skilled in the art's routine understands.In case of conflict, with the definition of this specification
It is as the criterion.
When this specification is with prefix " as well known to those skilled in the art ", " prior art " or its similar term
When coming derived materials, material, method, step, device or parts etc., the object that this prefix is derived is contained
Lid the application commonly used in the art those when proposing, but also include also being of little use at present, but will become
Any art is known as being applicable to those of similar purpose.
In the context of the present specification, in addition to the content clearly stated, anything do not mentioned
Preferably or item be the most directly suitable for known in the art those and without carrying out any change.And, herein
Any embodiment described all can with one or more other embodiments described herein freely
In conjunction with, the technical scheme formed therefrom or technological thought are accordingly to be regarded as the original disclosure of the present invention or original note
The part carried, and it is not considered as the new content the most not disclosing or expecting, unless ability
Field technique personnel think that this combination is the most irrational.
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 implication,
Including straight or branched alkyl, straight or branched thiazolinyl, straight or branched alkynyl, cycloalkyl, cyclenes
Base, cycloalkynyl radical, aryl or a combination thereof group, wherein preferred straight or branched alkyl, straight or branched
Thiazolinyl, aryl or a combination thereof group.As described alkyl, C the most such as can be enumerated1-20Alkyl,
Including C1-20Straight or branched alkyl, C2-20Straight or branched thiazolinyl, C2-20Straight or branched alkynyl,
C3-20Cycloalkyl, C3-20Cycloalkenyl group, C3-20Cycloalkynyl radical, C6-20Aryl or a combination thereof group, Qi Zhongyou
Select C1-20Straight or branched alkyl, C6-20Aryl or a combination thereof group.As described combination group,
Such as can enumerate one or more C1-20Straight or branched alkyl (the most one or more C1-10
Straight or branched alkyl) and one or more C6-20Aryl (the most one or more phenyl or naphthalene
Base) group that obtained by Direct Bonding.As described combination group, one such as can be entered
Step enumerates one or many C1-10Straight or branched alkyl phenyl, phenyl C1-10Straight or branched alkyl or
Person one or many C1-10Straight or branched alkyl phenyl C1-10Straight or branched alkyl etc., the most excellent
Select C1-10Straight or branched alkyl phenyl (such as tert-butyl-phenyl), phenyl C1-10Straight or branched
Alkyl (such as benzyl) or C1-10Straight or branched alkyl phenyl C1-10Straight or branched alkyl
(such as t-butylbenzyl).
In the context of the present invention, so-called " the miscellaneous alkyl of straight or branched ", refer to straight or branched
Alkyl molecule inside configuration (not including main chain or the end of any side chain in this alkyl molecule structure)
One or more (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH2-
(R' is H or C to be selected from-O-,-S-and-NR'-1-4Straight or branched alkyl) one of replacement base
Group or straight or branched alkyl molecule inside configuration that group directly substitutes and obtains (do not include
Main chain or the end of any side chain in this alkyl molecule structure) one or more (such as 1 to 3
Individual, 1 to 2 or 1) group-CH <substituted group-N < directly to substitute and the base that obtains
Group.As described replacement group, preferably-O-or-S-, more preferably-S-.It is apparent that from structure
For the angle of stability, when existing multiple, these substitute between groups not Direct Bonding.
Although it addition, the carbon number of this straight or branched alkyl is because of group-CH2-or group-CH < quilt
Substitute and reduce accordingly, but in order to state simplicity, still with this instead front described straight or branched alkane
The carbon number of base refers to the carbon number of the miscellaneous alkyl of described straight or branched.As described straight chain or
The miscellaneous alkyl of chain, for concrete example, C4Straight chained alkyl is such as
(in formula, the group indicated by arrow is not in inside molecular structure, and is in the end of main chain) quilt
One substitutes group-O-and directly substitutes acquisition-CH2-O-CH2-CH3Or
-CH2-CH2-O-CH3, referred to as C4Linear heteroalkyl group.Or, C4Branched alkyl
Such as(in formula, the group indicated by arrow is not in inside molecular structure,
And it is in the end of main chain and side chain) < directly substituting will acquisition to be substituted group-N by oneReferred to as C4Branched heteroalkyl groups.According to the present invention, as described directly
Chain or branched heteroalkyl groups, such as can enumerate C3-20The miscellaneous alkyl of straight or branched, wherein preferably C3-10
The miscellaneous alkyl of straight or branched or C3-6The miscellaneous alkyl of straight or branched.
In the context of the present specification, expression way " numeral+valency+group " or its similar term refer to
Be from the base structure (such as chain, ring or a combination thereof etc.) corresponding to this group removing this numeral
The group obtained after the hydrogen atom of representative quantity, preferably refers to from the carbon atom contained by this structure
(preferably saturated carbon atom and/or non-same carbon atom) upper quantity removed representated by this numeral
The group obtained after hydrogen atom.For example, " trivalent straight or branched alkyl " refers to from straight chain
Or branched paraffin (i.e. basic chain corresponding to this straight or branched alkyl) upper remove 3 hydrogen atoms and
The group obtained, " the miscellaneous alkyl of divalent straight or branched " then refers to from the miscellaneous alkane of straight or branched
(preferably from the carbon atom contained by this miscellaneous alkane, or further, from non-same carbon atom)
The group removing 2 hydrogen atoms and obtain.
In the case of not clearly indicating, all percents of being previously mentioned in this specification, number,
Ratios etc. are all on the basis of weight, unless do not met those skilled in the art time on the basis of weight
Conventional understanding.
In the context of the present specification, in case of no particular description, number-average molecular weight Mn
Measured by gel permeation chromatography (GPC).
In the context of the present specification, in case of no particular description, any gel related to
The condition determination of permeation chromatography (GPC) or GPC spectrogram is: instrument: Waters, US
Waters2695 type gel osmoticing chromatogram analysis instrument；Flowing uses oxolane mutually, and flow velocity is
1mL/min, chromatogram column temperature is 35 DEG C, delivery time 40min, and sample quality mark is
0.16%-0.20%.
According to the present invention, relate to the shielding phenolic compounds shown in a kind of logical formula (I).
According to the present invention, in logical formula (I), when existing multiple, each group R mutually the same or
Difference, is each independently selected from hydrogen, C1-300Straight or branched alkyl, logical group shown in formula (II)
With the group shown in logical formula (III), premise be at least one group R be logical base shown in formula (II)
Group.
According to the present invention, in logical formula (I), as described C1-300Straight or branched alkyl, such as
C can be enumerated1-20Straight or branched alkyl (preferably C1-10Straight or branched alkyl, more preferably C1-4
Straight or branched alkyl) or polyolefin-based.As described polyolefin-based, the most such as can enumerate
Number-average molecular weight Mn is the polyolefin-based of 300-3000.Now, as described polyolefin-based number
Average molecular weight Mn, preferably 500-2000, more preferably 500-1500.According to the present invention, described polyene
Alkyl (substantially) is saturated (being rendered as chain alkyl structure), but depends on as initial former
Material polyolefinic kind or the difference of this polyolefin production process, this polyolefin-based strand in also
A small amount of olefinic double bond (such as remain in polyolefin manufacturing process or introduce) may be contained, 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 this amount clearly, and this
Invention still polyolefin-based classifies as " alkyl " by this.
According to an embodiment of the invention, in logical formula (I), there is multiple group R, its
In group R be logical group shown in formula (II), one in two other group R is described
Polyolefin-based, another is hydrogen, C1-20Straight or branched alkyl (preferably C1-10Straight or branched alkane
Base) or logical formula (III) shown in group.
According to an embodiment of the invention, in logical formula (I), when group R is described polyene
During alkyl, this is polyolefin-based is preferably placed at the para-position of phenolic hydroxyl group in logical formula (I).
According to the present invention, in logical formula (I), when existing multiple, each group R' mutually the same or
Difference, is each independently selected from hydrogen and C1-20Straight or branched alkyl.
According to an embodiment of the invention, in logical formula (I), when existing multiple, each base
Group R' is same to each other or different to each other, and is each independently selected from hydrogen and C1-4Straight or branched alkyl.
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 " selected from hydrogen,
C1-20Alkyl (preferably C1-20Straight or branched alkyl) and C3-20The miscellaneous alkyl of straight or branched.
According to an embodiment of the invention, in logical formula (II), in the definition of group L,
Group R " selected from hydrogen, C1-10Straight or branched alkyl and C3-10The miscellaneous alkyl of straight or branched.
According to the present invention, in logical formula (II), group R2Selected from hydrogen, C1-20Straight or branched alkyl,
Logical group shown in formula (IV) and the group shown in logical formula V.
According to an embodiment of the invention, in logical formula (II), group R2Selected from hydrogen, C1-10
Group shown in straight or branched alkyl and logical formula (IV).
According to the present invention, in logical formula (II), when existing multiple, each group RbMutually the same or
Difference, is each independently selected from hydrogen and C1-20Straight or branched alkyl, is preferably each independently selected from
Hydrogen and C1-10Straight or branched alkyl.
According to an embodiment of the invention, in logical formula (II), when existing multiple, each base
Group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-6Straight or branched alkyl, preferably
Hydrogen.
According to the present invention, in logical formula (II), when existing multiple, each group RcMutually the same or
Difference, is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight or branched alkyl
Epoxide.
According to an embodiment of the invention, in logical formula (II), when existing multiple, each base
Group RcIt is same to each other or different to each other, is each independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10
Straight or branched alkyl oxy.
According to an embodiment of the invention, in logical formula (II), preferably one group RcIt is in
Cyclic groupUpper atom N is (that is, with group RdBonding atom N) para-position.
According to the present invention, in logical formula (II), y is the integer of 0 to 3, preferably 0 or 1.
According to the present invention, in logical formula (II), z is the integer of 0 to 3, preferably 0 or 1.
According to the present invention, in logical formula (II), n is the integer of 1 to 8, preferably 1 or 2.
According to the present invention, in logical formula (II), when existing multiple, each group RdMutually the same or
Difference, is each independently selected from the group shown in hydrogen and logical formula V, preferably hydrogen.
According to the present invention, in logical formula (II), when existing multiple, each cyclic group(
The inside configuration of logical formula (II) is rendered as divalent group) it is same to each other or different to each other, select independently of one another
From phenyl ring (the preferably inside configuration in logical formula (II) is rendered as 1,4-phenylene) with naphthalene nucleus is (preferably
Inside configuration in logical formula (II) is rendered as Isosorbide-5-Nitrae-or 2,6-naphthylene), wherein preferred phenyl ring.
According to an embodiment of the invention, in logical formula (II), two adjacent cyclic groupsEach other can be by additional S atom (not showing in structural formula) and bridge joint the two
The atom N of ring is (that is, with group RdThe atom N of bonding) and form phenothiazine ring, i.e.
According to this embodiment of the present invention, in logical formula (II), there is plural ring
GroupTime, if at least two of which (adjacent) cyclic groupForm institute
State phenothiazine ring, it is not necessary that require these cyclic groupsIn each of which and phase
Another adjacent cyclic groupForm this phenothiazine ring.
According to an embodiment of the invention, in logical formula (II), two adjacent cyclic groupsEach other can be by additional group(not showing in structural formula) and bridge
Connect the atom N of the two ring (that is, with group RdThe atom N of bonding) and form 9,10-dihydro
Acridine ring, i.e.
According to the present invention, at groupIn, group R " selected from hydrogen, C1-20Alkyl is (excellent
Select C1-20Straight or branched alkyl) and C3-20The miscellaneous alkyl of straight or branched.
According to an embodiment of the invention, at groupIn, group R " selected from hydrogen
And C1-10Straight or branched alkyl.
According to this embodiment of the present invention, in logical formula (II), there is plural ring
GroupTime, if at least two of which (adjacent) cyclic groupForm institute
State 9,10-acridan ring, it is not necessary that require these cyclic groupsIn each
All with another adjacent cyclic groupForm this 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 " selected from hydrogen,
C1-20Alkyl (preferably C1-20Straight or branched alkyl) and C3-20The miscellaneous alkyl of straight or branched.
According to an embodiment of the invention, in logical formula (III), in the definition of group L,
Group R " selected from hydrogen, C1-10Straight or branched alkyl and C3-10The miscellaneous alkyl of straight or branched.
According to the present invention, in logical formula (III), group R2Selected from hydrogen, C1-20Straight or branched alkane
Base, logical group shown in formula (IV) and the group shown in logical formula V.
According to an embodiment of the invention, in logical formula (III), group R2Selected from hydrogen, C1-10
Group shown in straight or branched alkyl and logical formula (IV).
According to the present invention, in logical formula (III), when existing multiple, each group RbMutually the same
Or different, it is each independently selected from hydrogen and C1-20Straight or branched alkyl, selects the most independently of one another
From hydrogen and C1-10Straight or branched alkyl.
According to an embodiment of the invention, in logical formula (III), when existing multiple, each base
Group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-6Straight or branched alkyl, preferably
Hydrogen.
According to the present invention, in logical formula (III), when existing multiple, each group RcMutually the same
Or different, it is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight or branched alkane
Base epoxide.
According to an embodiment of the invention, in logical formula (III), when existing multiple, each base
Group RcIt is same to each other or different to each other, is each independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10
Straight or branched alkyl oxy.
According to an embodiment of the invention, in logical formula (III), preferably one group RcPlace
In cyclic groupUpper atom N is (that is, with group RdBonding atom N) para-position.
According to the present invention, in logical formula (III), y is the integer of 0 to 3, preferably 0 or 1.
According to the present invention, in logical formula (III), z is the integer of 0 to 3, preferably 0 or 1.
According to the present invention, in logical formula (III), n is the integer of 1 to 8, preferably 1 or 2.
According to the present invention, in logical formula (III), when existing multiple, each group RdMutually the same
Or different, it is each independently selected from the group shown in hydrogen and logical formula V, preferably hydrogen.
According to the present invention, in logical formula (III), when existing multiple, each cyclic group(
The inside configuration of logical formula (III) is rendered as divalent group) it is same to each other or different to each other, select independently of one another
From phenyl ring (the preferably inside configuration in logical formula (III) is rendered as 1,4-phenylene) with naphthalene nucleus is (preferably
Inside configuration in logical formula (III) is rendered as Isosorbide-5-Nitrae-or 2,6-naphthylene), wherein preferred phenyl ring.
According to an embodiment of the invention, in logical formula (III), two adjacent cyclic groupsEach other can be by additional S atom (not showing in structural formula) and bridge joint the two
The atom N of ring is (that is, with group RdThe atom N of bonding) and form phenothiazine ring, i.e.
According to this embodiment of the present invention, in logical formula (III), there is plural ring
GroupTime, if at least two of which (adjacent) cyclic groupForm institute
State phenothiazine ring, it is not necessary that require these cyclic groupsIn each of which and phase
Another adjacent cyclic groupForm this phenothiazine ring.
According to an embodiment of the invention, in logical formula (III), two adjacent cyclic groupsEach other can be by additional group(not showing in structural formula) and bridge
Connect the atom N of the two ring (that is, with group RdThe atom N of bonding) and form 9,10-dihydro
Acridine ring, i.e.
According to the present invention, at groupIn, group R " selected from hydrogen, C1-20Alkyl is (excellent
Select C1-20Straight or branched alkyl) and C3-20The miscellaneous alkyl of straight or branched.
According to an embodiment of the invention, at groupIn, group R " selected from hydrogen
And C1-10Straight or branched alkyl.
According to this embodiment of the present invention, in logical formula (III), there is plural ring
GroupTime, if at least two of which (adjacent) cyclic groupForm institute
State 9,10-acridan ring, it is not necessary that require these cyclic groupsIn each
All with another adjacent cyclic groupForm this acridan ring.
According to the present invention, in logical formula (IV), when existing multiple, each group RbMutually the same
Or different, it is each independently selected from hydrogen and C1-20Straight or branched alkyl, selects the most independently of one another
From hydrogen and C1-10Straight or branched alkyl.
According to an embodiment of the invention, in logical formula (IV), when existing multiple, each base
Group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-6Straight or branched alkyl, preferably
Hydrogen.
According to the present invention, in logical formula (IV), when existing multiple, each group RcMutually the same
Or different, it is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight or branched alkane
Base epoxide.
According to an embodiment of the invention, in logical formula (IV), when existing multiple, each base
Group RcIt is same to each other or different to each other, is each independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10
Straight or branched alkyl oxy.
According to an embodiment of the invention, in logical formula (IV), preferably one group RcPlace
In cyclic groupUpper atom N is (that is, with group RdBonding atom N) para-position.
According to the present invention, in logical formula (IV), y is the integer of 0 to 3, preferably 0 or 1.
According to the present invention, in logical formula (IV), z is the integer of 0 to 3, preferably 0 or 1.
According to the present invention, in logical formula (IV), n' is the integer of 0 to 7, preferably 0,1 or 2,
Premise is n'+n≤8.According to an embodiment of the invention, n'+n=1 or n'+n=2.Here, n
Identical with the definition in aforementioned formula (II).
According to the present invention, in logical formula (IV), when existing multiple, each group RdMutually the same
Or different, it is each independently selected from the group shown in hydrogen and logical formula V, preferably hydrogen.
According to the present invention, in logical formula (IV), when existing multiple, each cyclic group(
The inside configuration of logical formula (IV) is rendered as divalent group) it is same to each other or different to each other, select independently of one another
From phenyl ring (the preferably inside configuration in logical formula (IV) is rendered as 1,4-phenylene) with naphthalene nucleus is (preferably
Inside configuration in logical formula (II) is rendered as Isosorbide-5-Nitrae-or 2,6-naphthylene), wherein preferred phenyl ring.
According to an embodiment of the invention, in logical formula (IV), two adjacent cyclic groupsEach other can be by additional S atom (not showing in structural formula) and bridge joint the two
The atom N of ring is (that is, with group RdThe atom N of bonding) and form phenothiazine ring, i.e.
According to this embodiment of the present invention, in logical formula (IV), there is plural ring
GroupTime, if at least two of which (adjacent) cyclic groupForm institute
State phenothiazine ring, it is not necessary that require these cyclic groupsIn each of which and phase
Another adjacent cyclic groupForm this phenothiazine ring.
According to an embodiment of the invention, in logical formula (IV), two adjacent cyclic groupsEach other can be by additional group(not showing in structural formula) and bridge
Connect the atom N of the two ring (that is, with group RdThe atom N of bonding) and form 9,10-dihydro
Acridine ring, i.e.
According to the present invention, at groupIn, group R " selected from hydrogen, C1-20Alkyl is (excellent
Select C1-20Straight or branched alkyl) and C3-20The miscellaneous alkyl of straight or branched.
According to an embodiment of the invention, at groupIn, group R " selected from hydrogen
And C1-10Straight or branched alkyl.
According to this embodiment of the present invention, in logical formula (IV), there is plural ring
GroupTime, if at least two of which (adjacent) cyclic groupForm institute
State 9,10-acridan ring, it is not necessary that require these cyclic groupsIn each
All with another adjacent cyclic groupForm this acridan ring.
According to the present invention, in logical formula V, when existing multiple, each group R mutually the same or
Difference, is each independently selected from hydrogen, C1-300Straight or branched alkyl, logical group shown in formula (II)
With the group shown in logical formula (III).
According to an embodiment of the invention, in logical formula V, when existing multiple, each base
Group R is same to each other or different to each other, and is each independently selected from hydrogen and C1-300Straight or branched alkyl.
According to the present invention, in logical formula V, as described C1-300Straight or branched alkyl, than
As C can be enumerated1-20Straight or branched alkyl (preferably C1-10Straight or branched alkyl, more preferably C1-4
Straight or branched alkyl) or polyolefin-based.As described polyolefin-based, the most such as can enumerate
Number-average molecular weight Mn is the polyolefin-based of 300-3000.Now, as described polyolefin-based number
Average molecular weight Mn, preferably 500-2000, more preferably 500-1500.According to the present invention, described polyene
Alkyl (substantially) is saturated (being rendered as chain alkyl structure), but depends on as initial former
Material polyolefinic kind or the difference of this polyolefin production process, this polyolefin-based strand in also
A small amount of olefinic double bond (such as remain in polyolefin manufacturing process or introduce) may be contained, 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 this amount clearly, and this
Invention still polyolefin-based classifies as " alkyl " by this.
According to an embodiment of the invention, in logical formula V, there is multiple group R, its
In a group R be described polyolefin-based, another is hydrogen or C1-20Straight or branched alkyl is (excellent
Select C1-10Straight or branched alkyl, more preferably C1-4Straight or branched alkyl).
According to an embodiment of the invention, in logical formula V, when group R is described polyene
During alkyl, this is polyolefin-based is preferably placed at the para-position of phenolic hydroxyl group in logical formula V.
According to the present invention, in logical formula V, when existing multiple, each group R' mutually the same or
Difference, is each independently selected from hydrogen and C1-20Straight or branched alkyl.
According to an embodiment of the invention, in logical formula V, when existing multiple, each base
Group R' is same to each other or different to each other, and is each independently selected from hydrogen and C1-4Straight or branched alkyl.
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 " selected from hydrogen,
C1-20Alkyl (preferably C1-20Straight or branched alkyl) and C3-20The miscellaneous alkyl of straight or branched.
According to an embodiment of the invention, in logical formula V, in the definition of group L,
Group R " selected from hydrogen, C1-10Straight or branched alkyl and C3-10The miscellaneous alkyl of straight or branched.
According to one preferred embodiment of the invention, in logical formula V, in the definition of group L
In, group R " selected from hydrogen and C1-10Straight or branched alkyl.
According to the present invention, in logical formula V, two group R and group-(S)a-L-accounts for respectively
According to three positions of the residue on phenyl ring in logical formula V.
According to the present invention, in logical formula V, a is 0 or 1, preferably 1.
According to the present invention, described shielding phenolic compounds define as previously mentioned (such as such as logical formula (I) or
Person is further as shown in logical formula V), it is necessary to comprise structureAs phenol unit.According to this
Invent one preferred embodiment, described shielding phenolic compounds comprise in its whole molecular structure to
Many 5, at most 3, at most 2 or at most 1 described phenol unit.
According to the present invention, described shielding phenolic compounds define as previously mentioned (such as such as logical formula (II) or
Person is further as shown in logical formula (III) or (IV)), it is necessary to comprise structure
As amine unit.According to one preferred embodiment of the invention, described shielding phenolic compounds is whole at it
Individual molecular structure comprises at most 15, at most 10, at most 8, at most 6, at most 4
Individual, at most 3 or at most 2 described amine units.
According to the present invention, described shielding phenolic compounds preferably at least has one in its whole molecular structure
(preferably 2,3 or 4 or more) group RdIt is hydrogen.Specifically, described shielding phenol
Compound preferably contains selected from following hydrogen amine unit (1), hydrogen amine unit (2) in its whole molecular structure
With at least one in hydrogen amine unit (3).In these hydrogen amine units, cyclic groupWith
Group R " identical with the definition in logical formula (II).
According to a preferred embodiment of the present invention, described shielding phenolic compounds is tied at its whole molecule
Containing at least one described hydrogen amine unit (1) in structure.
Specifically, to shield phenolic compoundsAs a example by, this compound is whole at it
Individual molecular structure comprises 2 described phenol units and 2 described amine units, and comprises 1 described hydrogen
Amine unit (1).
According to the present invention, as described shielding phenolic compounds, following compound such as can be enumerated
Or the mixture of its arbitrary proportion, but the present invention is not limited to this.
According to the present invention, the shielding phenolic compounds shown in aforementioned formula (I) can be with single one (pure)
Presented in compound, manufacture or use, it is also possible to (pressing with the mixture of wherein two or more
Arbitrary proportion) presented in, manufacture or use, this has no effect on the realization of effect of the present invention.
According to the present invention, the shielding phenolic compounds shown in aforementioned formula (I) can be by following system
The method of making manufactures, but is sometimes not limited to this.
According to this manufacture method of the present invention, including making the phenolic compounds shown in logical formula (X) and leading to
Amines shown in formula (Y) reacts in the presence of the aldehyde compound shown in formula (Z)
First step.
According to the present invention, in logical formula (X), when existing multiple, each group R0It is same to each other or different to each other,
It is each independently selected from hydrogen ,-SH and C1-300Straight or branched alkyl, premise is at least one group
R0It is-SH.
According to the present invention, in logical formula (X), as described C1-300Straight or branched alkyl, than
As C can be enumerated1-20Straight or branched alkyl (preferably C1-10Straight or branched alkyl, more preferably C1-4
Straight or branched alkyl) or polyolefin-based.As described polyolefin-based, the most such as can enumerate
Number-average molecular weight Mn is the polyolefin-based of 300-3000.Now, as described polyolefin-based number
Average molecular weight Mn, preferably 500-2000, more preferably 500-1500.According to the present invention, described polyene
Alkyl (substantially) is saturated (being rendered as chain alkyl structure), but depends on as initial former
Material polyolefinic kind or the difference of this polyolefin production process, this polyolefin-based strand in also
A small amount of olefinic double bond (such as remain in polyolefin manufacturing process or introduce) may be contained, 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 this amount clearly, and this
Invention still polyolefin-based classifies as " alkyl " by this.
According to an embodiment of the invention, in logical formula (X), there is multiple group R0, its
In a group R0It is-SH, two other group R0In one be described polyolefin-based, another
Individual is hydrogen or C1-20Straight or branched alkyl (preferably C1-10Straight or branched alkyl).
According to an embodiment of the invention, in logical formula (X), at group R0It it is described polyene
During alkyl, this is polyolefin-based is preferably placed at the para-position of phenolic hydroxyl group in logical formula (X).
According to the present invention, in logical formula (X), when existing multiple, each group R' mutually the same or
Difference, is each independently selected from hydrogen and C1-20Straight or branched alkyl.
According to an embodiment of the invention, in logical formula (X), when existing multiple, each base
Group R' is same to each other or different to each other, and is each independently selected from hydrogen and C1-4Straight or branched alkyl.
According to the present invention, as the phenolic compounds shown in described logical formula (X), can directly use city
The product sold, it is also possible to manufactured by conventionally known in the art method, the most particularly limit
System.It addition, as the phenolic compounds shown in described logical formula (X), can only use one, it is possible to
Use with in combination of two or more.
According to the present invention, as the manufacture method of the phenolic compounds shown in described logical formula (X), such as
Can enumerate in the presence of catalyst for alkylation reaction, make the phenolic compounds shown in formula (X') with poly-
Alkene (number-average molecular weight Mn is 300-3000, preferably 500-2000, more preferably 500-1500) is sent out
The method of raw alkylated reaction.
According to the present invention, in formula (X'), group R' has identical with aforementioned formula (X)
Implication.
According to the present invention, formula (X') exist three group R'0, one of them group R'0It is-SH,
Another group R'0It is H, the 3rd group R'0It is hydrogen ,-SH or C1-20Straight or branched alkane
Base (preferably C1-10Straight or branched alkyl).
According to an embodiment of the invention, in formula (X'), at least one group R'0It is
H, and this group R'0It is in the para-position of phenolic hydroxyl group in formula (X').
According to the present invention, described polyolefin is preferably by ethylene, propylene or C4-C10The homopolymerization of alpha-olefin
Or the polyolefin obtained by the two or more copolymerization in these alkene.As described C4-C10
Alpha-olefin, such as can enumerate n-butene, isobutene., n-pentene, n-hexylene, positive octene and the positive last of the ten Heavenly stems
Alkene.
According to the present invention, and at least 20wt% in these polyolefin (preferably at least 50wt%, the most extremely
Few 70wt%) polymer chain contain olefinic double bond at its end.This olefinic double bond is usually anti-with height
Presented in answering ethenylidene or the vinyl of activity.
According to the present invention, as described polyolefin, more preferably polybutene.Except as otherwise noted, herein
The term " polybutene " used broadly includes the polymerization obtained by 1-butylene or isobutylene homopolymerisation
Thing, and by gather prepared by copolymerization of two or three in 1-butylene, 2-butylene and isobutene.
Compound.The commercially available prod of this base polymer is likely to other olefinic component containing negligible quantity, but this
Have no effect on the enforcement of the present invention.
According to the present invention, as described polyolefin, further preferred polyisobutylene (PIB), it is also referred to as
High-activity polyisobutylene.In this kind of polyisobutylene, at least 20wt% (preferably at least 50wt%,
More preferably at least 70wt%) total terminal ethylenic double bond provided by methyl ethenylidene.
As described catalyst for alkylation reaction, such as can enumerate Lewis acid catalyst, such as select
From aluminum chloride, boron trifluoride, butter of tin, titanium tetrabromide, boron trifluoride phenol, borontrifluoride
One or more in boron alcohol complex and boron trifluoride ether complex, wherein preferred boron trifluoride second
Ether complexes and/or boron trifluoride methanol complex.These catalyst for alkylation reaction can directly make
With commercially available product.
According to the present invention, in described alkylated reaction, described polyolefin, described formula (X') institute
Mol ratio between the phenolic compounds shown, described catalyst for alkylation reaction can be such as 1:1-3:
0.1-0.5, preferably 1:1.5-3:0.1-0.4, most preferably 1:1.5-3:0.2-0.4, but the most not
It is limited to this.
According to the present invention, the response time of described alkylated reaction is such as 0.5h-10h, preferably 1h-8h,
Most preferably 3h-5h, but sometimes it is not limited to this.
According to the present invention, the reaction temperature of described alkylated reaction is such as 0 DEG C-200 DEG C, preferably 10 DEG C
-150 DEG C, most preferably 20 DEG C-100 DEG C, but sometimes it is not limited to this.
According to the present invention, described alkylated reaction can be carried out in the presence of the solvent.As described molten
Agent, such as can enumerate C6-10Alkane (such as hexane, heptane, octane, nonane or decane etc.).
Wherein, hexane and heptane are preferably used, more preferably use hexane.
According to the present invention, after described alkylated reaction terminates, by conventional methods from finally obtaining
Reactant mixture removes catalyst for alkylation reaction, unreacted reactant and the solvent that may use
Afterwards, the phenolic compounds shown in described logical formula (X) is i.e. obtained.
According to the present invention, in formula (Y), group R'2Selected from hydrogen, C1-20Straight or branched alkane
Base and group
According to the present invention, in formula (Y), when existing multiple, each group RbMutually the same or
Difference, is each independently selected from hydrogen and C1-20Straight or branched alkyl, is preferably each independently selected from
Hydrogen and C1-10Straight or branched alkyl.
According to an embodiment of the invention, in formula (Y), when existing multiple, each base
Group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-6Straight or branched alkyl, preferably
Hydrogen.
According to the present invention, in formula (Y), when existing multiple, each group RcMutually the same or
Difference, is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight or branched alkyl
Epoxide.
According to an embodiment of the invention, in formula (Y), when existing multiple, each base
Group RcIt is same to each other or different to each other, is each independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10
Straight or branched alkyl oxy.
According to an embodiment of the invention, in formula (Y), preferably one group RcIt is in
Cyclic groupUpper atom N is (that is, with group RdBonding atom N) para-position.
According to the present invention, in formula (Y), y is the integer of 0 to 3, preferably 0 or 1.
According to the present invention, in formula (Y), z is the integer of 0 to 3, preferably 0 or 1.
According to the present invention, in formula (Y), n1 is the integer of 1 to 8, preferably 1 or 2.
According to the present invention, in formula (Y), when existing multiple, each cyclic group(
The inside configuration of formula (Y) is rendered as divalent group) it is same to each other or different to each other, select independently of one another
From phenyl ring (the preferably inside configuration at formula (Y) is rendered as 1,4-phenylene) with naphthalene nucleus is (preferably
Inside configuration at formula (Y) is rendered as Isosorbide-5-Nitrae-or 2,6-naphthylene), wherein preferred phenyl ring.
According to the present invention, as the amines shown in described formula (Y), can directly use city
The product sold, is not particularly limited.It addition, as the amine compounds shown in described formula (Y)
Thing, can only use one, it is also possible in combination of two or more uses.
According to the present invention, in formula (Z), group R " selected from hydrogen, C1-20Alkyl (preferably C1-20
Straight or branched alkyl) and C3-20The miscellaneous alkyl of straight or branched.
According to an embodiment of the invention, in formula (Z), group R " selected from hydrogen, C1-10
Straight or branched alkyl and C3-10The miscellaneous alkyl of straight or branched.
According to one preferred embodiment of the invention, in formula (Z), group R " selected from hydrogen and
C1-10Straight or branched alkyl.
According to the present invention, as the aldehyde compound shown in described formula (Z), C such as can be enumerated1-6
Aliphatic aldehyde and benzaldehyde.
According to an embodiment of the invention, as described C1-6Aliphatic aldehyde, such as can enumerate
C1-6Straight or branched saturated aliphatic aldehyde, the most such as acetaldehyde or formaldehyde, more preferably formaldehyde.As institute
State formaldehyde, such as can be to use its aqueous solution, paraformaldehyde or paraformaldehyde form, the most especially
Restriction.
According to the present invention, as the aldehyde compound shown in described formula (Z), can only use one,
Can also in combination of two or more use.
According to the present invention, in the manufacture method of described shielding phenolic compounds, in described first step,
Phenolic compounds shown in described logical formula (X) and the amines shown in described formula (Y) mole
Ratio generally 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0.
According to the present invention, in the manufacture method of described shielding phenolic compounds, in described first step,
Phenolic compounds shown in described logical formula (X) and the aldehyde compound shown in described formula (Z) mole
Ratio generally 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0.
According to the present invention, in the manufacture method of described shielding phenolic compounds, described first step is permissible
Carry out in the presence of the solvent.As described solvent, C such as can be enumerated2-10Aliphatic nitrile (ratio
Such as acetonitrile etc.), C6-20Aromatic hydrocarbon (such as benzene,toluene,xylene and isopropylbenzene), C6-10Alkane (ratio
Such as normal hexane, hexamethylene and petroleum ether), C1-6Aliphatic alcohol (such as methanol, ethanol, normal propyl alcohol,
Isopropanol, n-butyl alcohol and ethylene glycol), C2-20Halogenated hydrocarbons (such as dichloromethane, carbon tetrachloride, chlorine
Benzene 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 acetylamide and N-Methyl pyrrolidone) etc..These
Solvent can only use one, it is also possible in combination of two or more uses.
According to the present invention, in the manufacture method of described shielding phenolic compounds, in described first step,
Catalyst can be added without, it is also possible to add catalyst.As described catalyst, such as can enumerate
Inorganic acid catalyst and organic acid catalyst.As described inorganic acid catalyst, salt such as can be enumerated
Acid, sulphuric acid and phosphoric acid etc..As described organic acid catalyst, pyrovinic acid, second such as can be enumerated
Base sulfonic acid, sulfamic acid and p-methyl benzenesulfonic acid etc..
As the consumption of described catalyst, can be directly with reference to the conventional amount used of prior art, not
Particularly limit.
According to the present invention, in the manufacture method of described shielding phenolic compounds, to described first step
Response time, there is no particular limitation, but generally 0.1h-24h, preferably 0.2h-12h, most preferably
0.5h-6h。
According to the present invention, in the manufacture method of described shielding phenolic compounds, to described first step
There is no particular limitation for reaction temperature, but generally 0 DEG C-250 DEG C, preferably 20 DEG C-180 DEG C, optimum
Select 60 DEG C-120 DEG C.
According to the present invention, in the manufacture method of described shielding phenolic compounds, tie at described first step
After bundle, by conventionally known separation method (such as evaporation etc.) from this first step obtain anti-
The middle solvent that may be present etc. that removes of mixture (the hereinafter referred to as reactant mixture of first step) is answered to wave
After volatile material, the product of first step can be obtained.
According to an embodiment of the invention, the manufacture method of described shielding phenolic compounds is the most also wrapped
Include the additional step making the product of described first step and vulcanizing agent react (forming phenothiazine ring)
(hereinafter referred to as additional step A).
According to an embodiment of the invention, the manufacture method of described shielding phenolic compounds is the most also wrapped
Include the product making described first step and react (shape with the aldehyde compound shown in aforementioned formula (Z)
Become acridan ring) additional step (hereinafter referred to as additional step B).
According to the present invention, in the manufacture method of described shielding phenolic compounds, can only carry out described attached
Add step A, it is also possible to only carry out described additional step B, it is also possible to both carried out described additional step A
Carry out again described additional step B.Not only carrying out described additional step A but also carry out described additional step B
Time, to the precedence of described additional step A and described additional step B, there is no particular limitation,
Can first carry out described additional step A, carry out described additional after this additional step A terminates again
Step B, or first carry out described additional step B, after this additional step B terminates, carry out institute again
State additional step A.It addition, can have product between each additional step (that is, from previous extra step
Rapid product) separating step, it is also possible to there is no product separating step, be not particularly limited.
According to an embodiment of the invention, in the manufacture method of described shielding phenolic compounds, institute
State additional step A to terminate to carry out afterwards at described first step.Now, described first step is anti-
Product is answered to separate from the reactant mixture of described first step the most as previously mentioned.Or, institute
The product stating first step can also be without this separation, and directly anti-with described first step
Answer the form of mixture for carrying out described additional step A.Or, described additional step A also may be used
To terminate to carry out afterwards at described additional step B.When described additional step A is at described additional step
When B terminates to carry out afterwards, the product of described additional step B is the most as described herein from described attached
Add in the reactant mixture of step B and separate.Or, the product of described additional step B
Without this separation, and directly can also be used for the form of the reactant mixture of described additional step B
Carry out described additional step A.
According to an embodiment of the invention, in the manufacture method of described shielding phenolic compounds,
In described additional step A, as described vulcanizing agent, sulfur and sulfur dichloride etc. such as can be enumerated,
Wherein preferred sulfur.As described sulfur, sulfur or Sublimed Sulfur such as can be enumerated.
According to the present invention, in the manufacture method of described shielding phenolic compounds, at described additional step A
In, the amines shown in described formula (Y) is generally 1:1-10 with the mol ratio of described vulcanizing agent,
Preferably 1:1.2-6.0, more preferably 1:1.5-3.0.
According to the present invention, in the manufacture method of described shielding phenolic compounds, described additional step A
Can carry out in the presence of the solvent.As described solvent, C such as can be enumerated2-10Aliphatic nitrile
(such as acetonitrile etc.), C6-20Aromatic hydrocarbon (such as benzene,toluene,xylene and isopropylbenzene), C6-10
Alkane (such as normal hexane, hexamethylene and petroleum ether), C1-6Aliphatic alcohol (such as methanol, ethanol,
Normal propyl alcohol, isopropanol, n-butyl alcohol and ethylene glycol), C2-20Halogenated hydrocarbons (such as dichloromethane, tetrachloro
Change carbon, 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 acetylamide and N-Methyl pyrrolidone)
Deng.These solvents can only use one, it is also possible in combination of two or more uses.
According to the present invention, in the manufacture method of described shielding phenolic compounds, described additional step A
Typically carry out in the presence of a catalyst.As described catalyst, such as can enumerate prior art is
This purpose and the conventional catalyst used, the most such as iodine.As the consumption of described catalyst, permissible
Directly with reference to the conventional amount used of prior art, it is not particularly limited.
According to the present invention, in the manufacture method of described shielding phenolic compounds, to described additional step A
There is no particular limitation response time, but generally 0.1h-24h, preferably 0.2h-12h, most preferably
0.5h-4h。
According to the present invention, in the manufacture method of described shielding phenolic compounds, to described additional step A
Reaction temperature there is no particular limitation, 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 manufacture method of described shielding phenolic compounds, at described additional step A
After end, obtained from this additional step A by conventionally known separation method (such as evaporation etc.)
After the reactant mixture obtained removes the volatile material such as solvent that may be present, can obtain additional
The product of step A, or follow-up reaction step can also be directly used in without this separation
Suddenly (than additional step B as the aforementioned).
According to an embodiment of the invention, in the manufacture method of described shielding phenolic compounds, institute
State additional step B to terminate to carry out afterwards (as single step), also at described first step
Can carry out with described first step simultaneously, be not particularly limited.As described additional step B
When described first step terminates to carry out afterwards, the product of described first step is the most as previously mentioned
Separate from the reactant mixture of described first step.Or, the reaction of described first step is produced
Thing without this separation, and directly can also be used for the form of the reactant mixture of described first step
Carry out described additional step B.Or, described additional step B can also be at described additional step A
Carry out after end.When described additional step B terminates to carry out afterwards at described additional step A,
The product reaction from described additional step A the most as described herein of described additional step A mixes
Compound is separated.Or, the product of described additional step A can also be without this point
From, and directly be used for carrying out described extra step with the form of the reactant mixture of described additional step A
Rapid B.It addition, when described additional step B is carried out with described first step simultaneously, directly to described
(such as in the beginning of described first step or at described first step in the reaction system of first step
During carrying out) add the aldehyde compound shown in described formula (Z) i.e. according to hereinafter provided consumption
Can.
According to the present invention, in the manufacture method of described shielding phenolic compounds, at described additional step B
In, as the aldehyde compound shown in described formula (Z), C such as can be enumerated1-6Aliphatic aldehyde and
Benzaldehyde.As described C1-6Aliphatic aldehyde, such as can enumerate C1-6Straight or branched saturated fat
Aldehyde, the most such as acetaldehyde or formaldehyde, more preferably formaldehyde.As described formaldehyde, such as can be used it
Aqueous solution, paraformaldehyde or paraformaldehyde form, be not particularly limited.
According to the present invention, in the manufacture method of described shielding phenolic compounds, at described additional step B
In, the amines shown in described formula (Y) and the aldehyde compound shown in described formula (Z)
Mol ratio is generally 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0.
According to the present invention, in the manufacture method of described shielding phenolic compounds, described additional step B (makees
When carrying out for single step) can carry out in the presence of the solvent.As described solvent, such as may be used
To enumerate C2-10Aliphatic nitrile (such as acetonitrile etc.), C6-20Aromatic hydrocarbon (such as benzene, toluene, diformazan
Benzene and isopropylbenzene), C6-10Alkane (such as normal hexane, hexamethylene and petroleum ether), C1-6Aliphatic alcohol
(such as methanol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol and ethylene glycol), C2-20Halogenated hydrocarbons (ratio
Such as dichloromethane, 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 acetylamide and
N-Methyl pyrrolidone) etc..These solvents can only use one, it is also possible in combination of two or more
Use.
According to the present invention, in the manufacture method of described shielding phenolic compounds, at described additional step B
In (when carrying out as single step), catalyst can be added without, it is also possible to add catalyst.
As described catalyst, inorganic acid catalyst and organic acid catalyst such as can be enumerated.As described
Inorganic acid catalyst, such as can enumerate hydrochloric acid, sulphuric acid and phosphoric acid etc..As described organic acid catalysis
Agent, such as can enumerate pyrovinic acid, ethylsulfonic acid, sulfamic acid and p-methyl benzenesulfonic acid etc..As
The consumption of described catalyst, can be directly with reference to the conventional amount used of prior art, the most particularly limit
Fixed.
According to the present invention, in the manufacture method of described shielding phenolic compounds, to described additional step B
The response time of (when carrying out as single step), there is no particular limitation, but generally
0.1h-24h, preferably 0.2h-12h, most preferably 0.5h-6h.
According to the present invention, in the manufacture method of described shielding phenolic compounds, to described additional step B
There is no particular limitation for the reaction temperature of (when carrying out as single step), 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 manufacture method of described shielding phenolic compounds, at described additional step B
After (when carrying out as single step) terminates, (such as steamed by conventionally known separation method
Send out) from the reactant mixture that this additional step B obtains, remove the volatility such as solvent that may be present
After material, the product of additional step B can be obtained, or can also without this separation,
It is directly used in follow-up reactions steps (than additional step A as the aforementioned).
Known in the art, aforementioned all of reactions steps (includes described first step, described
Additional step A and described additional step B) typically carry out under the protection of inert gas atmosphere.As
Described noble gas, such as can enumerate nitrogen and argon etc., be not particularly limited.
According to the present invention, in the manufacture method of described shielding phenolic compounds, as described first step
Product, the product of described additional step A or the product of described additional step B,
Can be single a kind of shielding phenolic compounds (the such as shielding phenolic compounds shown in aforementioned formula (I)),
It can also be the mixture comprising multiple shielding phenolic compounds.These product are all that present invention institute is pre-
Phase, the difference of its existence form has no effect on the realization of effect of the present invention.Therefore, in this specification
The most without distinction these product are collectively termed as the shielding phenolic compounds of the present invention.In view of
This, according to the present invention, do not exist and be further purified these product, or produce from these reactions
Thing is further separated out the absolute necessity of the shielding phenolic compounds of a certain ad hoc structure.Certainly, should
Purification or separation are preferred for the lifting further of Expected Results of the present invention sometimes, but in this
For invention not necessarily.Even so, as described purification or separation method, such as can enumerate
By the method such as column chromatography method or preparative hplc described product is purified or separation etc..
According to an embodiment of the invention, further relate to according to the present invention aforesaid shielding phenolic compounds
Manufacture method manufacture shielding phenolic compounds.
The shielding phenolic compounds of the present invention is owing to showing the high-temperature oxidation resistance of excellence, the most especially
It is suitable as antioxidant to use, expects excellent (high temperature) oxygen especially as antioxidant for manufacturing
Change the lubricant oil composite of stability.In consideration of it, according to an embodiment of the invention, relate to one
Kind of universal gear lubricating oil composition, its comprise the aforesaid any shielding phenolic compounds of the present invention (or its
The mixture of arbitrary proportion), extreme pressure anti-wear additives, metal deactivator, Ashless friction modifiers and main
The lube base oil of amount.
Embodiment
Hereinafter use embodiment that the present invention is described in further detail, but the present invention is not limited to these in fact
Execute example.
Performance in embodiment and comparative example is evaluated as follows.
(1) high-temperature oxidation resistance evaluation
Lubricant oil composite embodiment or comparative example manufactured, as test specimen, uses Pressurized Differential
The antioxygenic property of this test specimen is evaluated in scanning amount heat test (PDSC), lures with the oxidation of test specimen
Lead the phase (unit is min) to represent.The temperature of PDSC test is 210 DEG C, and pressure is 0.5MPa,
Oxygen gas flow rate is 100mL/min.
(2) deposit generates rejection evaluation
The lubricant oil composite of embodiment or comparative example manufacture is simulated piston as test specimen
The engine crankcase coking simulation test of deposit.The method is to be added into by 300ml test specimen
Burnt plate analog meter, is heated to 150 DEG C, use continuation mode to the aluminium sheet spilled oil that temperature is 310 DEG C,
Weigh the burnt amount generated on aluminium sheet after 6 hours, represent, mould with sediment yield (unit is mg)
Intend the deposit on piston.Coking amount is the highest, and the piston detergency representing this test specimen is the poorest.
(3) rustless property evaluation
According to BRT ball rust test method, the lubricant oil composite manufactured with embodiment or comparative example
As test specimen, during the bench test of whole 18 hours, protected by described test specimen
Metal ball continuous contact acidic liquid and air, after off-test, measure metal ball reflecting surface strong
Degree, obtains gray scale test value, is used for evaluating corrosion degree.Acetic acid/hydrobromic acid/hydrochloric acid/deionization is water-soluble
The injection rate of liquid is 0.19 ml/hour, and air draught is 40 ml/min, and oil temperature is 48 DEG C.
Corrosion degree is the highest, shows that the rustless property of test specimen is the poorest.
(4) high-frequency reciprocating friction test abrasion resistance evaluation
The lubricant oil composite of embodiment or comparative example manufacture is carried out high-frequency reciprocating as test specimen
Friction test.The experimental condition of the method is load 1000g, frequency 20Hz, temperature 100 DEG C, examination
The time of testing is 60min, records wear scar diameter.Wear scar diameter is the least, shows the wear resistence of test specimen
Can be the best.
Embodiment 1
Equipped with in the 500ml four-hole boiling flask of agitator, thermometer, condensing tube and Dropping funnel, add
Enter 58.79g (0.323mol) the 2-tert-butyl group-6-mercapto-phenol, the boron trifluoride second of 6.88g (0.048mol)
Ether (catalyst for alkylation reaction), 100ml normal hexane solvent and 161.61g's (0.162mol) is poly-different
Butylene (Mn=1000, fine chemicals company limited of Jilin Chemical group manufactures), reacts 2h at 80 DEG C.
After reaction terminates, the potassium hydroxide solution using mass fraction to be 5% cleans reactant mixture once,
And it is washed to neutral to remove catalyst with hot water, then reduce pressure and solvent and unreacted is distilled off
Phenol, it is thus achieved that polyisobutylene mercapto-phenol, hydroxyl value is 53.49mgKOH/g.Hydroxy value measuring reference
Acetic anhydride method in GB/T7383-2007.
Example reaction equation is as follows:
Nucleus magnetic hydrogen spectrum spectrum analysis from polyisobutylene mercapto-phenol product: chemical shift 1.40
Place is the characteristic peak of tert-butyl group hydrogen on polyisobutylene mercapto-phenol phenyl ring；At chemical shift 3.58 unimodal
For the characteristic peak of sulfydryl hydrogen on polyisobutylene mercapto-phenol phenyl ring；Unimodal at chemical shift 4.84 is poly-
The characteristic peak of hydroxyl hydrogen on isobutene. mercapto-phenol phenyl ring；At chemical shift 7.12 unimodal and 7.20 at
The characteristic peak of two hydrogen on unimodal respectively polyisobutylene mercapto-phenol phenyl ring.By hydroxyl hydrogen on phenyl ring
Definitions On Integration is 1, and the integration ratio obtaining hydrogen on phenyl ring, sulfydryl hydrogen and hydroxyl hydrogen is
0.95:0.97:1.05:0.94, close to theoretical 1:1:1:1:1, from nuclear magnetic spectrogram analysis, has synthesized expection
The polyisobutylene mercapto-phenol alkylate of para-orientation.
Embodiment 2
Under nitrogen protection atmosphere, at the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, add 30.58 grams of (156mmol) 2-sulfydryl-4-methyl-6-methylphenols, 9.29
Gram (112mmol) formaldehyde, 32.38 grams of (176mmol) 4-aminodiphenylamines and 100mL first
Benzene, stirs rapidly, reacts 2h at 100 DEG C.After question response terminates, decompression is distilled off solvent and life
The a small amount of water become, 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 1.40 (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 value of calculation C 73.43, H 7.19, N 7.14, O 4.08, S 8.17；Measure
Value: C 73.31, H 7.23, N 7.21, O 3.99, S 8.28.
Embodiment 3
Under nitrogen protection atmosphere, at the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, add 31.65 grams of (133mmol) 2,6-di-t-butyl-4-mercapto-phenol, 1.86
Gram (62mmol) formaldehyde, 28.15 grams of (153mmol) 4-aminodiphenylamines, 0.75 gram (7.5mmol)
Hydrochloric acid and 150mL isopropanol, stir rapidly, reacts 24h at 25 DEG C.After question response terminates, subtract
Pressure is distilled off a small amount of water of solvent and generation, and obtains structure shown in title by column chromatography for separation
Shielding phenol product.
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 value of calculation C 74.61, H 7.88, N 6.45, O 3.68, S 7.38；Measure
Value: C 74.52, H 7.84, N 6.51, O 3.73, S 7.40.
Embodiment 4
Under nitrogen protection atmosphere, at the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, add 8.57 grams of (36mmol) 2,6-di-t-butyl-4-mercapto-phenol, 1.24
Gram (15mmol) formaldehyde, 10.14 grams of (39mmol) N, N'-diphenyl-Isosorbide-5-Nitrae-phenylenediamines and 150mL
Toluene, stirs rapidly, reacts 4h at 90 DEG C.After question response terminates, decompression be distilled off solvent and
The a small amount of water generated, 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 value of calculation C 77.60, H 7.50, N 5.48, O 3.13, S 6.28；Measure
Value: C 77.71, H 7.52, N 5.53, O 3.10, S 6.23.
Embodiment 5
Under nitrogen protection atmosphere, at the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, add 20.23 grams of (85mmol) 2,6-di-t-butyl-4-mercapto-phenol, 9.54
Gram (115mmol) formaldehyde, 18.49 grams of (69mmol) N-(1,3-dimethylbutyl)-N'-phenyl pair
Phenylenediamine and 150mL benzene, stir rapidly, reacts 3h at 85 DEG C.After question response terminates, decompression is steamed
Evaporate removing solvent and a small amount of water of generation, and obtained the shielding of structure shown in title by column chromatography for separation
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 value of calculation: C 76.40, H 8.94, N 5.40, O 3.08, S 6.18；Measure
Value: C 76.48, H 8.96, N 5.35, O 3.09, S 6.12.
Embodiment 6
Under nitrogen protection atmosphere, at the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, add 3.57 grams of (15mmol) 2,6-di-t-butyl-4-mercapto-phenol, 5.14
Gram (62mmol) formaldehyde, 21.76 grams of (103mmol) N-phenyl-N '-[4-(phenyl amino) benzene
Base]-Isosorbide-5-Nitrae-phenylenediamine and 150mL toluene, stir rapidly, react 2h at 110 DEG C.Question response terminates
After, decompression is distilled off 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 (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 value of calculation C 77.83, H 7.20, N 6.98, O 2.66, S 5.33；Measure
Value: C 77.69, H 7.19, N 7.08, O 2.65, S 5.38.
Embodiment 7
Under nitrogen protection atmosphere, at the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, add 34.51 grams of (145mmol) 2,6-di-t-butyl-4-mercapto-phenol, 2.91
Gram (35mmol) formaldehyde, 4.49 grams of (21mmol) 4-amino-4'-methoxy diphenylamines, 0.26 gram
(2.61mmol) hydrochloric acid and 150mL benzene, stir rapidly, reacts 2h at 90 DEG C.Question response is tied
Shu Hou, decompression is distilled off a small amount of water of solvent and generation, and obtains title institute by column chromatography for separation
Show the shielding phenol product of structure.
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 value of calculation C 72.38, H 7.81, N 6.03, O 6.89, S 6.90；Measure
Value: C 72.37, H 7.69, N 6.12, O 6.80, S 6.83.
Embodiment 8
Under nitrogen protection atmosphere, at the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, addition gram 21.66 (91mmol) 2,6-di-t-butyl-4-mercapto-phenol, 1.35
Gram (9.51mmol) aldehyde C-9,6.51 grams of (25mmol) N, N'-diphenyl-Isosorbide-5-Nitrae-phenylenediamines and 150mL
Benzene, stirs rapidly, reacts 6h at 70 DEG C.After question response terminates, decompression is distilled off solvent and life
The a small amount of water become, 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 (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 value of calculation C 78.57, H 8.33, N 4.82, O 2.75, S 5.52；Measure
Value: C 78.62, H 8.25, N 4.75, O 2.81, S 5.42.
Embodiment 9
Under nitrogen protection atmosphere, at the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, add 8.33 grams of (35mmol) 2,6-di-t-butyl-4-mercapto-phenol, 4.23
Gram (51mmol) formaldehyde, 9.61 grams of (31mmol) N, N'-diphenyl-2,6-naphthylenediamine and 150mL
Toluene, stirs rapidly, reacts 4h at 110 DEG C.After question response terminates, decompression be distilled off solvent and
The a small amount of water generated, 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 value of calculation C 79.24, H 7.19, N 5.00, O 2.85, S 5.72；Measure
Value: C 79.20, H 7.23, N 5.14, O 2.72, S 5.65.
Embodiment 10
Under nitrogen protection atmosphere, at the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, add 6.19 grams of (26mmol) 2,6-di-t-butyl-4-mercapto-phenol, 9.57
Gram (92mmol) 3-methylthiopropionaldehyde aldehyde, 3.13 grams of (17mmol) 4-aminodiphenylamines and 150mL
Toluene, stirs rapidly, reacts 2h at 80 DEG C.After question response terminates, decompression be distilled off solvent and
The a small amount of water generated, 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；
C30H40N2OS2Value of calculation C 70.82, H 7.92, N 5.51, O 3.14, S 12.60；Survey
Definite value: C 70.75, H 7.83, N 5.46, O 3.20, S 12.71.
Embodiment 11
Under nitrogen protection atmosphere, at the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, add 4.99 grams of (21mmol) 2,6-di-t-butyl-4-mercapto-phenol, 4.4 grams
(53mmol) formaldehyde, 5.70 grams of (31mmol) 4-aminodiphenylamines and 150mL ethanol,
Stirring rapidly, after 60 DEG C of reaction 2.5h, is down to room temperature, adds 7.05 grams of (85mmol) formaldehyde,
It is warming up to 85 DEG C of reaction 2.5h.After question response terminates, decompression is distilled off a small amount of of solvent and generation
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), 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 value of calculation C 75.29, H 7.67, N 6.27, O 3.58, S 7.18；Measure
Value: C 75.20, H 7.59, N 6.29, O 3.65, S 7.22.
Embodiment 12
Under nitrogen protection atmosphere, at the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, add 19.52 grams of (82mmol) 2,6-di-t-butyl-4-mercapto-phenol, 10.04
Gram (121mmol) formaldehyde, 19.93 grams of (94mmol) 4-amino-4'-ethyl diphenylamines and 150mL
Dimethylbenzene, stirs rapidly, after 90 DEG C of reaction 3h, is down to room temperature, adds 10.11 grams (316mmol)
Sulfur and 0.04 gram of (0.35mmol) iodine, be warming up to 150 DEG C of reaction 8h.After question response terminates, subtract
Pressure is distilled off a small amount of water of solvent and generation, and obtains structure shown in title by column chromatography for separation
Shielding phenol product.
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；
C29H36N2OS2Value of calculation C 70.69, H 7.36, N 5.69, O 3.25, S 13.02；Survey
Definite value: C 70.77, H 7.41, N 5.67, O 3.17, S 12.93.
Embodiment 13
Under nitrogen protection atmosphere, at the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, add 10.95 grams of (46mmol) 2,6-di-t-butyl-4-mercapto-phenol, 3.98
Gram (48mmol) formaldehyde, 13.78 grams of (53mmol) N, N'-diphenyl-Isosorbide-5-Nitrae-phenylenediamines and 150mL
Trimethylbenzene, stirs rapidly, after 85 DEG C of reaction 1h, adds 3.82 grams of (46mmol) formaldehyde,
Continue, after 85 DEG C of reaction 1h, to be down to room temperature, add 10.11 grams of (316mmol) sulfur and 0.27
Gram (2.11mmol) iodine, is warming up to 180 DEG C of reaction 1h.After question response terminates, decompression is distilled off
Solvent and a small amount of water of generation, and the shielding phenol product of structure shown in title is obtained by column chromatography for separation
Thing.
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；
C34H36N2OS2Value of calculation C 73.87, H 6.56, N 5.07, O 2.89, S 11.60；Survey
Definite value: C 73.91, H 6.49, N 5.02, O 2.94, S 11.49.
Embodiment 14
Under nitrogen protection atmosphere, at the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, add 21.66 grams of (91mmol) 2,6-di-t-butyl-4-mercapto-phenol, 7.39
Gram (89mmol) formaldehyde, 6.62 grams of (36mmol) 4-aminodiphenylamines, 0.45 gram (4.51mmol)
Sodium hydroxide and 150mL isopropanol, stir rapidly, reacts 3h at 80 DEG C.After question response terminates,
Decompression is distilled off a small amount of water of solvent and generation, and obtains structure shown in title by column chromatography for separation
Shielding 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；
C42H56N2O2S2Value of calculation C 73.64, H 8.24, N 4.09, O 4.67, S 9.36；Measure
Value: C 73.59, H 8.21, N 4.15, O 4.62, S 9.34.
Embodiment 15
Under nitrogen protection atmosphere, at the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, add 6.55 grams of (36mmol) 2-tert-butyl group-4-mercapto-phenols, 7.64 grams (92mmol)
Formaldehyde, 13.06 grams of (71mmol) 4-aminodiphenylamines and 150mL toluene, stir rapidly,
4h is reacted at 90 DEG C.After question response terminates, decompression is distilled off a small amount of water of 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 (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 value of calculation C 75.23, H 6.66, N 9.75, O 2.78, S 5.58；Measure
Value: C 75.27, H 6.69, N 9.68, O 2.79, S 5.51.
Embodiment 16
Under nitrogen protection atmosphere, at the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, add 11.66 grams of (49mmol) 2,6-di-t-butyl-4-mercapto-phenol, 10.92
Gram (53mmol) 2,6-DI-tert-butylphenol compounds, 7.89 grams of (95mmol) formaldehyde, 11.23 grams (32mmol)
N-phenyl-N '-[4-(phenyl amino) phenyl]-Isosorbide-5-Nitrae-phenylenediamine and 150mL toluene, stir rapidly,
3h is reacted at 100 DEG C.After question response terminates, decompression is distilled off a small amount of water of 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 value of calculation C 79.08, H 7.99, N 5.12, O 3.90, S 3.91；Measure
Value: C 79.15, H 8.03, N 5.01, O 3.87, S 3.85.
Embodiment 17
Under nitrogen protection atmosphere, at the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, add 47.16 grams of (45mmol) polyisobutylene mercapto-phenols (embodiment 1 manufactures),
4.23 gram (51mmol) formaldehyde, 9.75 grams of (53mmol) 4-aminodiphenylamines and 150mL
Benzene, stirs rapidly, reacts 2.5h at 80 DEG C.After question response terminates, decompression be distilled off solvent and
The a small amount of water generated, 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, at the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, add 29.34 grams of (28mmol) polyisobutylene mercapto-phenols (embodiment 1 manufactures),
2.91 grams of (35mmol) formaldehyde, 6.24 grams of (24mmol) N, N'-diphenyl-Isosorbide-5-Nitrae-phenylenediamines and 150mL
Toluene, stirs rapidly, reacts 2h at 90 DEG C.After question response terminates, decompression be distilled off solvent and
The a small amount of water generated, 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,
4.00,4.86,5.56,6.97,7.02,7.14,7.26,7.55；
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, at the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, add 20.23 grams of (85mmol) 2,6-di-t-butyl-4-mercapto-phenol, 7.22
Gram (87mmol) formaldehyde, 14.37 grams of (85mmol) diphenylamines and 150mL methanol, stir rapidly
Mix, react 2h at 60 DEG C.After question response terminates, decompression is distilled off a small amount of water of 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), 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 value of calculation C 77.28, H 7.93, N 3.34, O 3.81, S 7.64；Measure
Value: C 77.22, H 7.89, N 3.31, O 3.83, S 7.67.
Comparative example 2
Under nitrogen protection atmosphere, at the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, add 10.71 grams of (52mmol) 2,6-di-t-butyl-4-mercapto-phenol, 1.89
Gram (63mmol) formaldehyde, 17.42 grams of (65mmol) N-(1,3-dimethylbutyl)-N'-phenyl are to benzene
Diamidogen and 150mL methanol, stir rapidly, reacts 4h at 70 DEG C.After question response terminates, decompression is steamed
Evaporate removing solvent and a small amount of water of generation, and obtained the shielding of structure shown in title by column chromatography for separation
Phenol 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 value of calculation 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, at the 250ml equipped with agitator, thermometer, condensing tube and Dropping funnel
In four-hole boiling flask, add 9.24 grams of (33mmol) 2,6-di-t-butyl-4-(3-mercaptopropyi) phenol,
3.07 grams of (37mmol) formaldehyde, 11.71 grams of (45mmol) N, N'-diphenyl-Isosorbide-5-Nitrae-phenylenediamines and
150mL benzene, stirs rapidly, reacts 4h at 80 DEG C.After question response terminates, decompression is distilled off molten
Agent and a small amount of water of 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 1.40 (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 value of calculation C 78.22, H 8.02, N 5.07, O 2.89, S 5.80；Measure
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 of universal gear lubricating oil composition～28 and comparative example 8～14
The embodiment 19 of universal gear lubricating oil composition～28 and the formula composition of comparative example 8～14
It is shown in Table 2,3.Component each in table is joined to scale in mediation container, stir 45 DEG C of heating
Mixing 2 hours, preparation obtains GL-5 rank universal gear lubricating oil composition respectively.
Some lube oil additives specifically used are as follows:
Extreme pressure anti-wear additives: sulfide isobutene, normal-butyl n-octyl zinc dithiophosphate；
Metal deactivator: 2-dimercapto-5-dithio-1,3,4-thiadiazoles；
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
Use Pressurized Differential scanning amount heat test (PDSC) evaluation test embodiment 19～28 and ratio
Relatively example 8～14 carries out the high-temperature oxidation resistance of oil product, with the oxidation induction period (unit of test specimen
It is min) represent.The temperature of PDSC test is 220 DEG C, and pressure is 0.5MPa, and oxygen gas flow rate is
100mL/min.Oxidation induction period is the longest, shows that the high-temperature oxidation resistance of test specimen is the best.
Use engine crankcase coking simulation test testing example 19～28 and comparative example 8～14
Cleansing performance.The method is that 300ml test specimen is added coking plate analog meter, is heated to
150 DEG C, use continuation mode to the aluminium sheet spilled oil that temperature is 310 DEG C, weigh aluminium sheet after 6 hours
The burnt amount of upper generation, represents with sediment yield (unit is mg), the deposit on simulation piston.
Coking amount is the highest, and the detergency representing this test specimen is the poorest.
Use high-frequency reciprocating frictional testing machine to embodiment 19～28 and comparative example 8～14 carry out oil product
The wear-resistant test of high temperature, experimental condition is: load 1000g, frequency is 20Hz, and temperature is 100 DEG C,
Test period is 60min.Wear scar diameter is the least, shows that the anti-wear and wear-resistant performance of test specimen is the best.
To embodiment 19～28 and comparative example 8～14 carry out BRT ball rust test, with embodiment or
The lubricant oil composite that comparative example manufactures was as test specimen, the bench test of whole 18 hours
Cheng Zhong, the metal ball continuous contact acidic liquid protected by described test specimen and air, at test knot
Shu Hou, measures metal ball reflecting surface intensity, obtains gray scale test value, is used for determining corroded area, from
And the resistant to rust ability of qualification test sample.The injection speed of acetic acid/hydrobromic acid/hydrochloric acid/deionized water solution
Degree is 0.19 ml/hour, and air draught is 40 ml/min, and oil temperature is 48 DEG C.Appraisal result
The highest, show that the rustless property of test specimen is the best.
PDSC test, coking simulation test, high-frequency reciprocating friction test and BRT ball rust test
Test result is as shown in table 4.
Table 4
From table 4, it can be seen that the high temperature that universal gear lubricating oil composition of the present invention has excellence resists
Oxidation susceptibility, detergent-dispersant performance energy, preferable abrasion-resistance and relatively low coefficient of friction and excellence
Anti-corrosion ability.
Claims (10)
1. a universal gear lubricating oil composition, including shielding phenolic compounds, extreme pressure anti-wear additives,
Metal deactivator, Ashless friction modifiers and major amount of lube base oil, described shielding phenolate is closed
The structure of thing is:
In logical formula (I), each group R is same to each other or different to each other, and is each independently selected from hydrogen, C1-300
Straight or branched alkyl (preferably C1-10Straight or branched alkyl or number-average molecular weight Mn are
300-3000's is polyolefin-based), logical group shown in formula (II) and the group shown in logical formula (III),
Premise be at least one group R be logical group shown in formula (II)；Each group R' is mutually the same or not
With, it is each independently selected from hydrogen and C1-20Straight or branched alkyl (is preferably each independently selected from hydrogen
And C1-4Straight or branched alkyl),
In aforementioned each logical formula (II), (III) and (IV), each group L is same to each other or different to each other, respectively
From being group independentlyWherein group R " selected from hydrogen, C1-20Alkyl (preferably C1-20
Straight or branched alkyl) and C3-20The miscellaneous alkyl of straight or branched, is preferably selected from hydrogen, C1-10Straight chain or
Branched alkyl and C3-10The miscellaneous alkyl of straight or branched；Each group R2It is same to each other or different to each other, the most solely
On the spot selected from hydrogen, C1-20Straight or branched alkyl, logical group shown in formula (IV) and logical formula V
Shown group (is preferably each independently selected from hydrogen, C1-10Straight or branched alkyl and logical formula (IV)
Shown group)；Each group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-20Directly
Chain or branched alkyl (are preferably each independently selected from hydrogen and C1-10Straight or branched alkyl)；Each group
RcIt is same to each other or different to each other, is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Directly
Chain or branched alkyl epoxide (are preferably each independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10
Straight or branched alkyl oxy, is more preferably in cyclic groupThe para-position of upper nitrogen-atoms)；y
It it is the integer (preferably 0 or 1) of 0 to 3；Z is the integer (preferably 0 or 1) of 0 to 3；N is 1
Integer (preferably 1 or 2) to 8；N' is the integer (preferably 0,1 or 2) of 0 to 7, and premise is
N'+n≤8 (preferably n'+n=1 or n'+n=2)；Each group RdIt is same to each other or different to each other, independently of one another
Selected from the group (preferably hydrogen) shown in hydrogen and logical formula V；Each cyclic groupMutually the same
Or different, it is each independently selected from phenyl ring and naphthalene nucleus (preferably phenyl ring), two the most adjacent ring groups
GroupFormed optionally through additional S atom and the atom N of bridge joint the two ring each other
Phenothiazine ring, and/or, two adjacent cyclic groupsEach other optionally through additional group(wherein group R " selected from hydrogen, C1-20Alkyl (preferably C1-20Straight or branched alkyl)
And C3-20The miscellaneous alkyl of straight or branched, is preferably selected from hydrogen and C1-10Straight or branched alkyl) and bridge joint
The atom N of the two ring and form 9,10-acridan ring,
In logical formula V, each group R is same to each other or different to each other, and is each independently selected from hydrogen, C1-300
Straight or branched alkyl (preferably C1-10Straight or branched alkyl or number-average molecular weight Mn are 300-3000
Polyolefin-based), logical group shown in formula (II) and the group shown in logical formula (III) (preferably each solely
On the spot selected from hydrogen and C1-300Straight or branched alkyl)；Each group R' is same to each other or different to each other, the most solely
On the spot selected from hydrogen and C1-20Straight or branched alkyl (is preferably each independently selected from hydrogen and C1-4Straight chain
Or branched alkyl)；Group L is groupWherein group R " selected from hydrogen, C1-20Hydrocarbon
Base (preferably C1-20Straight or branched alkyl) and C3-20The miscellaneous alkyl of straight or branched, be preferably selected from hydrogen,
C1-10Straight or branched alkyl and C3-10The miscellaneous alkyl of straight or branched；A is 0 or 1, and two bases
Group R and group-(S)a-L-occupies three positions of residue on phenyl ring respectively,
Wherein, the miscellaneous alkyl of described straight or branched is selected from the one of straight or branched alkyl molecule inside configuration
Individual or multiple (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH2-quilt
Selected from-O-,-S-and-NR'-, (R' is H or C1-4Straight or branched alkyl) one of replacement group
The group that directly substitutes and obtain and straight or branched alkyl molecule inside configuration one or more
(such as 1 to 3,1 to 2 or 1) group-CH < is substituted group-N < directly to replace
Generation and the group that obtains, wherein this shielding phenolic compounds in its whole molecular structure at least
Group RdIt is hydrogen.
2. according to the universal gear lubricating oil composition described in claim 1, it is characterised in that institute
State shielding phenolic compounds selected from following particular compound or the mixture of its arbitrary proportion:
3. according to the universal gear lubricating oil composition described in claim 1, it is characterised in that institute
The manufacture method stating shielding phenolic compounds includes making logical phenolic compounds shown in formula (X) and formula (Y)
Shown amines occurs in the presence of the aldehyde compound (preferably formaldehyde) shown in formula (Z)
The first step of reaction, the most also includes that the product making described first step is with vulcanizing agent (preferably
Sulfur) reaction and/or the additional step that reacts with the aldehyde compound (preferably formaldehyde) shown in formula (Z),
In logical formula (X), each group R0It is same to each other or different to each other, is each independently selected from hydrogen ,-SH
And C1-300Straight or branched alkyl (preferably C1-10Straight or branched alkyl or number-average molecular weight Mn
Polyolefin-based for 300-3000), premise is at least one group R0It is-SH；Each group R' is each other
Identical or different, it is each independently selected from hydrogen and C1-20Straight or branched alkyl is (preferably each independent
Ground is selected from hydrogen and C1-4Straight or branched alkyl),
In formula (Y), group R'2Selected from hydrogen, C1-20Straight or branched alkyl and groupEach group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-20
Straight or branched alkyl (is preferably each independently selected from hydrogen and C1-10Straight or branched alkyl)；Each base
Group RcIt is same to each other or different to each other, is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20
Straight or branched alkyl oxy (is preferably each independently selected from hydrogen, C1-10Straight or branched alkyl and
C1-10Straight or branched alkyl oxy, is more preferably in cyclic groupUpper nitrogen-atoms right
Position)；Y is the integer (preferably 0 or 1) of 0 to 3；Z is the integer (preferably 0 or 1) of 0 to 3；
N1 is the integer (preferably 1 or 2) of 1 to 8；Each cyclic groupIt is same to each other or different to each other,
It is each independently selected from phenyl ring and naphthalene nucleus (preferably phenyl ring),
In formula (Z), group R " selected from hydrogen, C1-20Alkyl (preferably C1-20Straight or branched alkane
Base) and C3-20The miscellaneous alkyl of straight or branched, is preferably selected from hydrogen, C1-10Straight or branched alkyl and C3-10
The miscellaneous alkyl of straight or branched,
Wherein, the miscellaneous alkyl of described straight or branched is selected from the one of straight or branched alkyl molecule inside configuration
Individual or multiple (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH2-quilt
Selected from-O-,-S-and-NR'-, (R' is H or C1-4Straight or branched alkyl) one of replacement group
The group that directly substitutes and obtain and straight or branched alkyl molecule inside configuration one or more
(such as 1 to 3,1 to 2 or 1) group-CH < is substituted group-N < directly to replace
Generation and the group that obtains.
4. according to the universal gear lubricating oil composition described in claim 3, it is characterised in that
In described first step, shown in the phenolic compounds shown in described logical formula (X) and described formula (Y)
The mol ratio of amines be 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0, described
Logical phenolic compounds shown in formula (X) with the mol ratio of the aldehyde compound shown in described formula (Z) is
1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0, in described additional step, described formula
(Y) amines shown in is 1:1-10, preferably 1:1.2-6.0 with the mol ratio of described vulcanizing agent,
Shown in more preferably 1:1.5-3.0, the amines shown in described formula (Y) and described formula (Z)
The mol ratio of aldehyde compound be 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0.
5., according to the universal gear lubricating oil composition one of claim 1-4 Suo Shu, its feature exists
In, described extreme pressure anti-wear additives selected from phosphate ester, olefine sulfide, dialkyl dithiocarbamate and
One or more in dialkyl dithiophosphate；Described metal deactivator derives selected from benzotriazole
One or more in thing, thiazole and thiadiazoles derivative；Described Ashless friction modifiers
One or more in fatty acid amide, polyol esters of fatty acids and aliphatic amine；Described
Lube base oil one in API I, II, III, IV, V class lubricating oil base oil or
Multiple.
6. according to the universal gear lubricating oil composition described in claim 5, it is characterised in that institute
State extreme pressure anti-wear additives and be selected from olefine sulfide and the combination of dialkyl dithiophosphate, both in this combination
Between mass ratio be 0.1:1-10:1；Described metal deactivator is selected from thiadiazoles derivative；Described
Ashless friction modifiers is selected from fatty acid amide.
7. according to the universal gear lubricating oil composition described in claim 5, it is characterised in that institute
State shielding phenolic compounds and account for the 0.001%-30% of described universal gear lubricating oil composition gross mass；
Described extreme pressure anti-wear additives accounts for the 0.1%-10% of described universal gear lubricating oil composition gross mass；Described
Metal deactivator accounts for the 0.01%-5% of described universal gear lubricating oil composition gross mass；Described ashless
Friction improver accounts for the 0.01%-5% of described universal gear lubricating oil composition gross mass.
8. according to the universal gear lubricating oil composition described in claim 5, it is characterised in that institute
State shielding phenolic compounds and account for the 0.05%-20% of described universal gear lubricating oil composition gross mass；
Described extreme pressure anti-wear additives accounts for the 0.2%-8% of described universal gear lubricating oil composition gross mass；Described gold
Belong to passivator and account for the 0.02%-3% of described universal gear lubricating oil composition gross mass；Described ashless rub
Wipe modifier and account for the 0.02%-4% of described universal gear lubricating oil composition gross mass.
9. according to the universal gear lubricating oil composition described in claim 5, it is characterised in that
In described universal gear lubricating oil composition add metal detergent, ashless dispersant, antioxidant,
In pour-point depressant, viscosity index improver, metal corrosion inhibitor, antirust agent and anti-foaming agent one
Plant or multiple.
10. the manufacture method of the universal gear lubricating oil composition that one of claim 1-4 is described,
Including making described shielding phenol, extreme pressure anti-wear additives, metal deactivator, Ashless friction modifiers and institute
State the step of lube base oil mixing.
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| CN106590851A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Compressor lubricating oil composition and preparation method thereof |
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| CN106590830A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Fully synthetic extreme pressure industrial gear lubricating oil composition and manufacture method thereof |
| CN109679709A (en) * | 2017-10-18 | 2019-04-26 | 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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| CN106590851A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Compressor lubricating oil composition and preparation method thereof |
| CN106590829A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | High-speed diesel fuel engine lubricating oil composition in railway and preparation method thereof |
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| 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 |
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| 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 |
| 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 |
| CN109679709A (en) * | 2017-10-18 | 2019-04-26 | 中国石油化工股份有限公司 | Universal gear lubricating oil composition and preparation method thereof |
| 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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