CN105272892B - A kind of shielding phenolic compounds, its manufacturing method and its application as antioxidant - Google Patents
A kind of shielding phenolic compounds, its manufacturing method and its application as antioxidant Download PDFInfo
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- CN105272892B CN105272892B CN201410245819.4A CN201410245819A CN105272892B CN 105272892 B CN105272892 B CN 105272892B CN 201410245819 A CN201410245819 A CN 201410245819A CN 105272892 B CN105272892 B CN 105272892B
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Abstract
The present invention relates to one kind to shield phenolic compounds, its manufacturing method and its as the application of antioxidant such as following formula (I) shown in,
Description
Technical field
The present invention relates to a kind of novel shielding phenolic compounds.Specifically, the present invention relates to one kind to contain sulphur and arylamine
Shielding phenolic compounds, its manufacturing method and its application as antioxidant.
Background technique
The oxidation stability of oil product is one of highly important index of oil property.For example, almost for all lubricating oil
For product, antioxidant must be all added, to prolong the service life.Moreover, with Hyundai Motor, the fast development of mechanical industry, hair
The power of motivation and mechanical equipment is continuously improved, and the operating temperature of lubricating oil further increases, and problem of oxidation is more prominent.With this
Meanwhile quality of lubrication oil grade is continuously improved, it is desirable that lubricating oil further extends the drain period, this is just to the high temperature of lubricating oil product
Oxidation stability proposes requirements at the higher level.
In order to cope with the these requirements of the prior art, it is more excellent that technical staff has been devoted to exploitation antioxygenic property
New compound, to improve the oxidation stability of oil product.United States Patent (USP) US5304314, which discloses one kind and is suitable as antioxidant, to be made
The phenolic compounds of sulfur-bearing and arylamine.U.S. Patent application US2006/0189824A1 discloses one kind and is suitable as antioxidant
The shielding phenolic compounds containing secondary aromatic amine used.Canadian Patent CA1219584, which discloses one kind and is suitable as antioxidant, to be made
The shielding phenolic compounds of sulfur-bearing and three-level arylamine.But the compound of these prior arts is on high-temperature oxidation resistance
Still remain room for improvement.
Therefore, current status is that a kind of novel compound is still required, and is shown significant compared with prior art
Improved high-temperature oxidation resistance.
Summary of the invention
The present inventor passes through diligent research on the basis of existing technology, it was found that a kind of novel shielding phenolate conjunction
Object, and it has furthermore been found that by using the shielding phenolic compounds as antioxidant, so that it may it solves of the existing technology aforementioned
Problem, and have thus completed the present invention.
Specifically, the present invention relates to the contents of following aspect.
1. phenolic compounds is shielded shown in a kind of logical formula (I),
In logical formula (I), each group R is same or different to each other, and is each independently selected from hydrogen, C1-300Linear or branched alkyl group
(preferably C1-10Linear or branched alkyl group or number-average molecular weight Mn are the polyolefin-based of 300-3000), base shown in logical formula (II)
Group shown in group and logical formula (III), on condition that at least one group R is group shown in logical formula (II)；Each group R' is each other
It is identical or different, it is each independently selected from hydrogen and C1-20Linear or branched alkyl group (is preferably each independently selected from hydrogen and C1-4Straight chain
Or branched alkyl),
In aforementioned each logical formula (II), (III) and (IV), group L, which is selected from, is optionally selected from C by one or more1-20Alkyl is (excellent
Select C1-20Linear or branched alkyl group, C6-20Aryl or combinations thereof group) and C3-20What the substituent group of linear chain or branched chain miscellaneous alkyl replaced
M+1 valence C2To C19-mLinear or branched alkyl group, optionally by one or more be selected from C1-20Alkyl (preferably C1-20Linear chain or branched chain alkane
Base, C6-20Aryl or combinations thereof group) and C3-20The m+1 valence C that the substituent group of linear chain or branched chain miscellaneous alkyl replaces3To C19-mStraight chain
Or branched heteroalkyl groups and groupWherein each group L'1It is mutually the same
Or it is different, it is each independently selected from C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl, on condition that (1) each group
L'1It is divalent each independently to m+1 valence, so that the group
Generally it is rendered as m+1 valence, and (2) whole group L'1The sum of atomicity be not more than 14, wherein each group L'1Each independently
C is further optionally selected from by one or more1-20Alkyl (preferably C1-20Linear or branched alkyl group, C6-20Aryl or combinations thereof base
Group) and C3-20The substituent group of linear chain or branched chain miscellaneous alkyl replaces；Group L' is groupWherein group R " is selected from
Hydrogen, C1-20Alkyl (preferably C1-20Linear or branched alkyl group) and C3-20Linear chain or branched chain miscellaneous alkyl is preferably selected from hydrogen, C1-10Straight chain
Or branched alkyl and C3-10Linear chain or branched chain miscellaneous alkyl；Each group A is same or different to each other, and is each independently selected from
(wherein, each group R is same or different to each other, and is each independently selected from hydrogen, C1-300Linear or branched alkyl group (preferably C1-10Straight chain
Or branched alkyl or number-average molecular weight Mn are the polyolefin-based of 300-3000), group and logical formula (III) shown in logical formula (II)
Shown in group (be preferably each independently selected from hydrogen and C1-300Linear or branched alkyl group)；Each group R' is same or different to each other,
It is each independently selected from hydrogen and C1-20Linear or branched alkyl group (is preferably each independently selected from hydrogen and C1-4Linear chain or branched chain alkane
Base)；Two group R and a groupThree positions of residue on phenyl ring are occupied respectively), on condition that extremely
A group A is lessM be 1 to 4 integer (preferably
1)；Each group R2It is same or different to each other, is each independently selected from hydrogen, C1-20Base shown in linear or branched alkyl group, logical formula (IV)
Group shown in group and logical formula (V) (is preferably each independently selected from hydrogen, C1-10Shown in linear or branched alkyl group and logical formula (IV)
Group)；Each group RbIt is same or different to each other, is each independently selected from hydrogen and C1-20Linear or branched alkyl group is (preferably respectively independent
Ground is selected from hydrogen and C1-10Linear or branched alkyl group)；Each group RcIt is same or different to each other, is each independently selected from hydrogen, C1-20Straight chain
Or branched alkyl and C1-20Linear or branched alkyl group oxygroup (is preferably each independently selected from hydrogen, C1-10Linear or branched alkyl group and
C1-10Linear or branched alkyl group oxygroup, is more preferably in cyclic groupThe contraposition of upper nitrogen-atoms)；Y be 0 to 3 it is whole
Number (preferably 0 or 1)；Z is 0 to 3 integer (preferably 0 or 1)；The integer (preferably 1 or 2) that n is 1 to 8；The integer that n' is 0 to 7
(preferably 0,1 or 2), on condition that n'+n≤8 (preferably n'+n=1 or n'+n=2)；Each group RdIt is same or different to each other, respectively
Independently selected from group (preferably hydrogen) shown in hydrogen and logical formula (V)；Each cyclic groupIt is same or different to each other, respectively
Independently selected from phenyl ring and naphthalene nucleus (preferably phenyl ring), wherein two adjacent cyclic groupsEach other optionally by additional
S atom and bridge the two rings N atom and form phenthazine ring, and/or, two adjacent cyclic groups
Optionally pass through additional group each other(wherein group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight chain or branch
Alkyl group) and C3-20Linear chain or branched chain miscellaneous alkyl, is preferably selected from hydrogen and C1-10Linear or branched alkyl group) and bridge the two rings N
Atom and form 9,10- acridan ring,
In logical formula (V), each group A is same or different to each other, and is each independently selected from
Wherein each group R is same or different to each other, and is each independently selected from hydrogen, C1-300Linear or branched alkyl group (preferably C1-10Straight chain or
Branched alkyl or number-average molecular weight Mn are the polyolefin-based of 300-3000), group and logical formula (III) institute shown in logical formula (II)
The group shown (is preferably each independently selected from hydrogen and C1-300Linear or branched alkyl group)；Each group R' is same or different to each other, respectively
From independently selected from hydrogen and C1-20Linear or branched alkyl group (is preferably each independently selected from hydrogen and C1-4Linear or branched alkyl group)；
Two group R and a groupThree positions of residue on phenyl ring are occupied respectively；Group L, group R2, base
Group Rb, group Rc, group Rd, cyclic groupAnd y, n, z and m be respectively provided with meaning identical in logical formula (II),
Wherein, the linear chain or branched chain miscellaneous alkyl is selected from the one or more (such as 1 to 4 inside linear or branched alkyl group molecular structure
A, 1 to 3,1 to 2 or 1) group-CH2Being selected from-O- ,-S- and-NR'-, (R' is H or C1-4Linear chain or branched chain alkane
Base) one of substituting group directly substitute and the one or more inside the group and linear or branched alkyl group molecular structure that obtain
(such as 1 to 3,1 to 2 or 1) group-CH <by substituting group-N < is directly substituted and the group of acquisition, wherein the screen
Cover phenolic compounds at least one group R in its entire molecular structuredIt is hydrogen.
2. according to shielding phenolic compounds described in any preceding aspect, particular compound selected from the following or its arbitrary proportion
Mixture:
3. a kind of manufacturing method for shielding phenolic compounds, including make shown in phenolic compounds shown in logical formula (X) and general formula (Y)
Amine compounds polybasic carboxylic acid shown in general formula (A) or derivatives thereof in the presence of the first step that reacts, optionally also
Including react the reaction product of the first step with vulcanizing agent (preferably sulphur) and/or with aldehyde compound shown in general formula (Z)
The additional step of (preferably formaldehyde) reaction,
In logical formula (X), each group R0It is same or different to each other, is each independently selected from hydrogen ,-SH and C1-300Linear chain or branched chain
Alkyl (preferably C1-10Linear or branched alkyl group or number-average molecular weight Mn are the polyolefin-based of 300-3000), on condition that at least one
A group R0It is-SH；Each group R' is same or different to each other, and is each independently selected from hydrogen and C1-20Linear or branched alkyl group is (preferably
It is each independently selected from hydrogen and C1-4Linear or branched alkyl group),
In general formula (Y), group R'2Selected from hydrogen, C1-20Linear or branched alkyl group and groupEach base
Group RbIt is same or different to each other, is each independently selected from hydrogen and C1-20Linear or branched alkyl group (be preferably each independently selected from hydrogen and
C1-10Linear or branched alkyl group)；Each group RcIt is same or different to each other, is each independently selected from hydrogen, C1-20Linear or branched alkyl group
And C1-20Linear or branched alkyl group oxygroup (is preferably each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Straight chain or branch
Alkyl group oxygroup, is more preferably in cyclic groupThe contraposition of upper nitrogen-atoms)；Y is 0 to 3 integer (preferably 0 or 1)；
Z is 0 to 3 integer (preferably 0 or 1)；The integer (preferably 1 or 2) that n1 is 1 to 8；Each cyclic groupIt is mutually the same or
Difference is each independently selected from phenyl ring and naphthalene nucleus (preferably phenyl ring),
In general formula (A), group RLSelected from optionally by one or more selected from C1-20Alkyl (preferably C1-20Linear chain or branched chain alkane
Base, C6-20Aryl or combinations thereof group) and C3-20The m1 valence C that the substituent group of linear chain or branched chain miscellaneous alkyl replaces2To C20-m1Straight chain or
Branched alkyl, optionally by one or more be selected from C1-20Alkyl (preferably C1-20Linear or branched alkyl group, C6-20Aryl or combinations thereof
Group) and C3-20The m1 valence C that the substituent group of linear chain or branched chain miscellaneous alkyl replaces3To C20-m1Linear chain or branched chain miscellaneous alkyl and group(wherein, each group L'1It is same or different to each other, it is respectively independent
Ground is selected from C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl, on condition that (1) each group L'1It is 2 each independently
Valence is to m1 valence, so that the groupGenerally it is rendered as m1
Valence, and (2) whole group L'1The sum of atomicity be not more than 14, wherein each group L'1Each independently optionally further by one
It is a or multiple selected from C1-20Alkyl (preferably C1-20Linear or branched alkyl group, C6-20Aryl or combinations thereof group) and C3-20Straight chain or
The substituent group of branched heteroalkyl groups replaces), the integer (preferably 2) that m1 is 2 to 5,
In general formula (Z), group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Linear or branched alkyl group) and C3-20Straight chain or branch
Chain miscellaneous alkyl is preferably selected from hydrogen, C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl,
Wherein, the linear chain or branched chain miscellaneous alkyl is selected from the one or more inside linear or branched alkyl group molecular structure
(such as 1 to 4,1 to 3,1 to 2 or 1) group-CH2Being selected from-O- ,-S- and-NR'-, (R' is H or C1-4Straight chain
Or branched alkyl) one of substituting group directly substitute and one inside the group and linear or branched alkyl group molecular structure that obtain
A or multiple (such as 1 to 3,1 to 2 or 1) group-CH <by substituting group-N < is directly substituted and the group of acquisition,
And the derivative is selected from the acid anhydrides of the polybasic carboxylic acid and the carboxylic acid halides of the polybasic carboxylic acid.
4. according to manufacturing method described in any preceding aspect, wherein in the first step, shown in the logical formula (X)
Phenolic compounds and the general formula (Y) shown in amine compounds molar ratio be 1:0.1-10, preferably 1:0.5-5.0, more preferably
1:0.8-2.0, phenolic compounds shown in the logical formula (X) rub with polybasic carboxylic acid shown in the general formula (A) or derivatives thereof
You are than being 1:0.1-10, preferably 1:0.2-5.0, more preferable 1:0.3-3.0, in the additional step, shown in the general formula (Y)
Amine compounds and the vulcanizing agent molar ratio be 1:1-10, preferably 1:1.2-6.0, more preferable 1:1.5-3.0, the general formula
(Y) molar ratio of aldehyde compound shown in amine compounds shown in and the general formula (Z) is 1:0.1-10, preferably 1:0.5-5.0,
More preferable 1:0.8-2.0.
5. according to shielding phenolic compounds described in any preceding aspect or according to passing through system described in any preceding aspect
Make purposes of the shielding phenolic compounds of method manufacture as antioxidant.
6. a kind of lubricant oil composite is closed comprising lube base oil and according to shielding phenolate described in any preceding aspect
Object or according to the shielding phenolic compounds by the manufacture of manufacturing method described in any preceding aspect as antioxidant, wherein described in
Antioxidant accounts for the 0.001-30 weight % of the lubricant oil composite total weight, preferably 0.1-10 weight %.
It is by by the shielding phenolic compounds and the profit 7. according to lubricant oil composite described in any preceding aspect
Lubricant base oil mixing and manufacture.
Technical effect
Shielding phenolic compounds according to the present invention, phosphorus element-containing and metallic element, are not likely to produce ash content, are environmental-friendly
The antioxidant of type.
Shielding phenolic compounds according to the present invention shows the high temperature significantly improved compared with the compound of the prior art
Antioxygenic property (thermal stability) can effectively improve (high temperature) oxidation stability of such as lubricating oil.
Shielding phenolic compounds according to the present invention is showing excellent high-temperature oxidation resistant in a preferred embodiment
While performance, excellent rustless property is also exhibited further.This is not available for prior art compound.
Shielding phenolic compounds according to the present invention is showing excellent high-temperature oxidation resistant in a preferred embodiment
While performance, excellent cleansing performance (i.e. deposit generation rejection) is also exhibited further.This is the prior art
It closes not available for object.
Shielding phenolic compounds according to the present invention is showing excellent high-temperature oxidation resistant in a preferred embodiment
While performance, also exhibits further excellent inhibition viscosity build and inhibit the increased performance of acid value.This is the prior art
Not available for compound.
Specific embodiment
Detailed description of the preferred embodiments below, it should be noted however that protection of the invention
Range is not limited to these specific embodiments, and but is determined by the appended claims.
All publications, patent application, patent and the other bibliography that this specification is mentioned all draw in this for reference.
Unless otherwise defined, all technical and scientific terms used herein all has what those skilled in the art routinely understood to contain
Justice.In case of conflict, it is subject to the definition of this specification.
When this specification with prefix " well known to those skilled in the art ", " prior art " or its export material similar to term
Whens material, substance, method, step, device or component etc., object derived from the prefix is covered this field when the application proposes and is routinely made
Those of with, but also include also being of little use at present, it will but become art-recognized for suitable for those of similar purpose.
In the context of the present specification, other than the content clearly stated, any matters or item that do not mention are equal
It is directly applicable in those of known in the art without carrying out any change.Moreover, any embodiment described herein can be with
It is freely combined with one or more other embodiments described herein, the technical solution or technical idea formed therefrom regards
For the original disclosure of the present invention or a part of original description, and be not considered as not disclosing or be expected herein it is new in
Hold, unless those skilled in the art think that the combination is obvious unreasonable.
In the context of the present invention, statement " halogen " refers to fluorine, chlorine, bromine or iodine.
In the context of the present invention, term " alkyl " has conventionally known in the art meaning, including linear chain or branched chain
Alkyl, linear chain or branched chain alkenyl, linear chain or branched chain alkynyl, naphthenic base, cycloalkenyl, cycloalkynyl radical, aryl or combinations thereof group, wherein
It is preferred that linear or branched alkyl group, linear chain or branched chain alkenyl, aryl or combinations thereof group.It, specifically such as can be with as the alkyl
Enumerate C1-20Alkyl, including C1-20Linear or branched alkyl group, C2-20Linear chain or branched chain alkenyl, C2-20Linear chain or branched chain alkynyl, C3-20
Naphthenic base, C3-20Cycloalkenyl, C3-20Cycloalkynyl radical, C6-20Aryl or combinations thereof group, wherein it is preferred that C1-20Linear or branched alkyl group,
C6-20Aryl or combinations thereof group.As the combination group, for example one or more C can be enumerated1-20Linear or branched alkyl group
(preferably one or more C1-10Linear or branched alkyl group) and one or more C6-20Aryl (preferably one or more phenyl or naphthalene
Base) group that is obtained by Direct Bonding.As the combination group, for example it can further enumerate one or more C1-10Straight chain
Or branched alkyl phenyl, phenyl C1-10Linear or branched alkyl group or one or more C1-10Linear or branched alkyl group phenyl C1-10Straight chain
Or branched alkyl etc., wherein more preferable C1-10Linear or branched alkyl group phenyl (such as tert-butyl-phenyl), phenyl C1-10Straight chain or branch
Alkyl group (such as benzyl) or C1-10Linear or branched alkyl group phenyl C1-10Linear or branched alkyl group (such as t-butylbenzyl).
In the context of the present invention, so-called " linear chain or branched chain miscellaneous alkyl ", refers to linear or branched alkyl group molecule knot
Inside structure (not including the end of main chain or any side chain in the alkyl molecule structure) one or more (such as 1 to 4,1 to
3,1 to 2 or 1) group-CH2Being selected from-O- ,-S- and-NR'-, (R' is H or C1-4One of linear or branched alkyl group)
Substituting group directly substitute and (do not include the alkyl point inside the group that obtains or linear or branched alkyl group molecular structure
The end of main chain or any side chain in minor structure) one or more (such as 1 to 3,1 to 2 or 1) group-CH < quilt
Substituting group-N < directly is substituted and the group that obtains.As the substituting group, preferably-O- or-S-, more preferable-S-.It is aobvious
It is right, for the angle of structural stability, when there are multiple, not Direct Bonding between these substituting groups.Separately
Outside, although the carbon atom number of the linear or branched alkyl group is because of group-CH2Or group-CH < accordingly reduced by substitution, but
In order to state simplicity, the linear chain or branched chain still is referred to the carbon atom number of the substitution foregoing description linear or branched alkyl group
The carbon atom number of miscellaneous alkyl.As the linear chain or branched chain miscellaneous alkyl, for concrete example, C4Straight chained alkyl is such as(group indicated by arrow is not in inside molecular structure in formula, but is in
The end of main chain) directly substituted and will obtain by a substituting group-O- --- CH2-O——CH2-CH3Or --- CH2-CH2-
O——CH3, referred to as C4Linear heteroalkyl group.Alternatively, C4Branched alkyl is such as(arrow in formula
Indicated group is not in inside molecular structure, but be in main chain and side chain end) by a substituting group-N < directly
Substitution will obtainReferred to as C4Branched heteroalkyl groups.According to the present invention, as the straight chain
Or branched heteroalkyl groups, for example C can be enumerated3-20Linear chain or branched chain miscellaneous alkyl, wherein it is preferred that C3-10Linear chain or branched chain miscellaneous alkyl or
C3-6Linear chain or branched chain miscellaneous alkyl.
In the context of the present specification, expression way " number+valence+group " or its refer to similar to term from the group
It removes in corresponding foundation structure (such as chain, ring or combinations thereof etc.) and obtains after the hydrogen atom of quantity representated by the number
Group preferably refers to remove on the carbon atom (preferably saturated carbon atom and/or the non-same carbon atom) contained by the structure
The group obtained after the hydrogen atom of quantity representated by the number.For example, " trivalent linear or branched alkyl group " is referred to from straight
The group for removing 3 hydrogen atoms on chain or branched paraffin (i.e. basic chain corresponding to the linear or branched alkyl group) and obtaining, and
" divalent linear chain or branched chain miscellaneous alkyl " then refer to from the miscellaneous alkane of linear chain or branched chain (the preferably carbon atom contained by the miscellaneous alkane, or
Person is further, from the non-same carbon atom) on remove 2 hydrogen atoms and the group that obtains.
In the case where not clearly indicating, all percentages, number, the ratio etc. being previously mentioned in this specification be all with
On the basis of weight, unless not meeting the conventional understanding of those skilled in the art when using weight as benchmark.
In the context of the present specification, in case of no particular description, number-average molecular weight Mn is by gel infiltration
Chromatography (GPC) measurement.
In the context of the present specification, in case of no particular description, any gel permeation chromatography being related to
(GPC) or the determination condition of GPC spectrogram is equal are as follows: instrument: Waters, US waters2695 type gel osmoticing chromatogram analysis
Instrument；Mobile phase uses tetrahydrofuran, flow velocity 1mL/min, and chromatogram column temperature is 35 DEG C, delivery time 40min, sample quality point
Number is 0.16%-0.20%.
According to the present invention, it is related to shielding phenolic compounds shown in a kind of logical formula (I).
According to the present invention, in logical formula (I), when there are multiple, each group R is same or different to each other, each independently
Selected from hydrogen, C1-300Group shown in group shown in linear or branched alkyl group, logical formula (II) and logical formula (III), on condition that at least
One group R is group shown in logical formula (II).
According to the present invention, in logical formula (I), as the C1-300Linear or branched alkyl group, for example C can be enumerated1-20Directly
Chain or branched alkyl (preferably C1-10Linear or branched alkyl group, more preferable C1-4Linear or branched alkyl group) or it is polyolefin-based.As
Described polyolefin-based, specifically can such as enumerate number-average molecular weight Mn is the polyolefin-based of 300-3000.At this point, as described poly-
The number-average molecular weight Mn of alkylene, preferably 500-2000, more preferable 500-1500.According to the present invention, described polyolefin-based (basic
On) it is saturation (being rendered as chain alkyl structure), but depend on the type or the polyolefin of the polyolefin as starting material
The difference of manufacturing method (for example may also be manufactured containing a small amount of olefinic double bond in polyolefin in the polyolefin-based strand
Remain or introduce in the process), but this has no effect on the realization of effect of the present invention, and the present invention also has no intention to carry out the amount bright
Really, and the present invention still polyolefin-based is classified as " alkyl " for this.
According to embodiment of the present invention, in logical formula (I), there are multiple group R, one of group R is logical
Group shown in formula (II), one in other two group R be it is described polyolefin-based, the other is hydrogen, C1-20Straight chain or branch
Alkyl group (preferably C1-10Linear or branched alkyl group) or logical formula (III) shown in group.
According to embodiment of the present invention, in logical formula (I), when group R is described polyolefin-based, the polyolefin
Base is preferably placed at the contraposition of phenolic hydroxyl group in logical formula (I).
According to the present invention, in logical formula (I), when there are multiple, each group R' is same or different to each other, each independently
Selected from hydrogen and C1-20Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (I), when there are multiple, each group R' it is mutually the same or
Difference is each independently selected from hydrogen and C1-4Linear or branched alkyl group.
According to the present invention, in logical formula (II), m is 1 to 4 integer, preferably 1.
According to the present invention, in logical formula (II), group L is selected from the m+1 valence C optionally replaced2To C19-mLinear or branched alkyl group,
The m+1 valence C optionally replaced3To C19-mLinear chain or branched chain miscellaneous alkyl and group
(referred to as general formula (II-A)), wherein being preferably selected from the m+1 valence C optionally replaced2To C19-mLinear or branched alkyl group and general formula (II-A)
Shown in group, be more preferably selected from the m+1 valence C optionally replaced2To C19-mLinear or branched alkyl group.
According to the present invention, in logical formula (II), in the definition of group L, as the m+1 valence C optionally replaced2Extremely
C19-mLinear or branched alkyl group, the m+1 valence C preferably optionally replaced2To C9-mLinear or branched alkyl group, the m+ more preferably optionally replaced
1 valence C2-6Linear or branched alkyl group.
According to the present invention, in logical formula (II), in the definition of group L, as the m+1 valence C optionally replaced3Extremely
C19-mLinear chain or branched chain miscellaneous alkyl, the m+1 valence C preferably optionally replaced3To C9-mLinear chain or branched chain miscellaneous alkyl more preferably optionally replaces
M+1 valence C3-6Linear chain or branched chain miscellaneous alkyl.
According to the present invention, in logical formula (II), in the definition of group L, so-called optional substitution is referred to optionally by one
A or multiple (such as 1 to 4,1 to 3,1 to 2 or 1) is selected from C1-20Alkyl and C3-20Linear chain or branched chain miscellaneous alkyl
Substituent group replaces.As the substituent group, preferably C1-20Linear or branched alkyl group, C6-20Aryl or combinations thereof group.As described
C1-20Linear or branched alkyl group, preferably C1-10Linear or branched alkyl group, more preferable C1-6Linear or branched alkyl group, for example, methyl or
Ethyl.
According to the present invention, in logical formula (II), in the group shown in general formula (II-A), each group L'1It is mutually the same or
Difference is each independently selected from C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl, is preferably each independently selected from
C1-6Linear or branched alkyl group.
According to the present invention, in logical formula (II), in the group shown in general formula (II-A), necessary condition (1) is: each group
L'1It is divalent each independently to m+1 valence, so that group shown in the general formula (II-A) is generally rendered as m+1 valence.Mirror
In this, in the group shown in general formula (II-A), each group L'1Valence state be variable, and be possibly different from.Therefore,
In the group shown in general formula (II-A), there is no directly provide each group L' by the present invention1Valence state, but this has no effect on ability
Field technique personnel understand and implement the present invention, and each group L'1Valence state can actually be able to by the necessary condition (1)
It is clear.For concrete example, if each group L'1It is ethyl (not yet explicitly valence state), m 2, then shown in the general formula (II-A)
Group may be with one of flowering structure:
According to the present invention, in logical formula (II), in the group shown in general formula (II-A), necessary condition (2) is: whole bases
Group L'1Atomicity (be not counted in each group L'1Upper substituent group that may be present as described below) the sum of be not more than 14, to make
The total atom number for obtaining group shown in the general formula (II-A) (is not counted in each group L'1Upper substitution that may be present as described below
Base) it is not more than 18.
It according to the present invention,, must meeting two above-mentioned in the group shown in general formula (II-A) in logical formula (II)
After wanting condition, each group L'1It can be optionally each independently further by one or more (such as 1 to 4,1 to 3,1
To 2 or 1) it is selected from C1-20Alkyl and C3-20The substituent group of linear chain or branched chain miscellaneous alkyl replaces.It is excellent as the substituent group
Select C1-20Linear or branched alkyl group, C6-20Aryl or combinations thereof group.As the C1-20Linear or branched alkyl group, preferably C1-10
Linear or branched alkyl group, more preferable C1-6Linear or branched alkyl group, such as methyl or ethyl.
According to the present invention, in logical formula (II), each group A is same or different to each other, and is each independently selected from following general formula
(II-1) group shown in group and following general formula shown in (II-2), on condition that at least one group A is following general formula (II-
1) group shown in.
According to the present invention, in general formula (II-1), group R2Selected from hydrogen, C1-20Shown in linear or branched alkyl group, logical formula (IV)
Group and logical formula (V) shown in group.
According to embodiment of the present invention, in general formula (II-1), group R2Selected from hydrogen, C1-10Linear chain or branched chain alkane
Group shown in base and logical formula (IV).
According to the present invention, in general formula (II-1), when there are multiple, each group RbIt is same or different to each other, respectively solely
On the spot it is selected from hydrogen and C1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C1-10Linear or branched alkyl group.
According to embodiment of the present invention, in general formula (II-1), when there are multiple, each group RbIt is mutually the same
Or it is different, it is each independently selected from hydrogen and C1-6Linear or branched alkyl group, preferably hydrogen.
According to the present invention, in general formula (II-1), when there are multiple, each group RcIt is same or different to each other, respectively solely
On the spot it is selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in general formula (II-1), when there are multiple, each group RcIt is mutually the same
Or it is different, it is each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in general formula (II-1), a preferably group RcIn cyclic groupUpper N atom is (that is, with group RdThe N atom of bonding) contraposition.
According to the present invention, in general formula (II-1), y is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in general formula (II-1), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in general formula (II-1), the integer that n is 1 to 8, preferably 1 or 2.
According to the present invention, in general formula (II-1), when there are multiple, each group RdIt is same or different to each other, respectively solely
On the spot it is selected from group, preferably hydrogen shown in hydrogen and logical formula (V).
According to the present invention, in general formula (II-1), when there are multiple, each cyclic group(in general formula (II-
1) inside configuration is rendered as bivalent group) it is same or different to each other, phenyl ring is each independently selected from (preferably at general formula (II-1)
Inside configuration be rendered as 1,4- phenylene) and naphthalene nucleus (be preferably rendered as 1,4- or 2,6- in the inside configuration of general formula (II-1)
Naphthylene), wherein it is preferred that phenyl ring.
According to embodiment of the present invention, in general formula (II-1), two adjacent cyclic groups
By additional S atom (not showing in structural formula) and the N atom of the two rings can be bridged (that is, with group R each otherdBonding
N atom) and form phenthazine ring, i.e.,
Embodiment according to the present invention, in general formula (II-1), there are more than two cyclic groupsWhen, as long as wherein at least two (adjacent) cyclic groupThe phenthazine ring is formed, is not had
It is necessary to require these cyclic groupsEach of with another adjacent cyclic groupIt is formed
The phenthazine ring.
According to embodiment of the present invention, in general formula (II-1), two adjacent cyclic groups
Additional group can be passed through each other(not shown in structural formula) and bridge the two rings N atom (that is, with
Group RdThe N atom of bonding) and form 9,10- acridan ring, i.e.,
According to the present invention, in groupIn, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight chain or
Branched alkyl) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in groupIn, group R " is selected from hydrogen and C1-10Straight chain
Or branched alkyl.
Embodiment according to the present invention, in general formula (II-1), there are more than two cyclic groupsWhen, as long as wherein at least two (adjacent) cyclic groupForm the acridan ring
, it is not necessary that it is required that these cyclic groupsEach of with another adjacent cyclic groupForm the acridan ring.
According to the present invention, in general formula (II-2), when there are multiple, each group R is same or different to each other, respectively independent
Ground is selected from hydrogen, C1-300Group shown in group shown in linear or branched alkyl group, logical formula (II) and logical formula (III).
According to the present invention, in general formula (II-2), two group R and a groupIt occupies respectively
Three positions of residue on phenyl ring.
According to embodiment of the present invention, in general formula (II-2), when there are multiple, each group R is mutually the same
Or it is different, it is each independently selected from hydrogen and C1-300Linear or branched alkyl group.
According to the present invention, in general formula (II-2), as the C1-300Linear or branched alkyl group, for example C can be enumerated1-20
Linear or branched alkyl group (preferably C1-10Linear or branched alkyl group, more preferable C1-4Linear or branched alkyl group) or it is polyolefin-based.Make
To be described polyolefin-based, specifically can such as enumerate number-average molecular weight Mn is the polyolefin-based of 300-3000.At this point, as described
Polyolefin-based number-average molecular weight Mn, preferably 500-2000, more preferable 500-1500.According to the present invention, the polyolefin-based (base
In sheet) it is saturation (being rendered as chain alkyl structure), but depend on the type or the polyene of the polyolefin as starting material
The difference of hydrocarbon manufacturing method, may also be containing a small amount of olefinic double bond (such as in polyolefin system in the polyolefin-based strand
Remain or introduce during making), but this has no effect on the realization of effect of the present invention, and the present invention also has no intention to carry out the amount bright
Really, and the present invention still polyolefin-based is classified as " alkyl " for this.
According to embodiment of the present invention, in general formula (II-2), there are multiple group R, one of group R is
It is described polyolefin-based, the other is hydrogen or C1-20Linear or branched alkyl group (preferably C1-10Linear or branched alkyl group, more preferable C1-4
Linear or branched alkyl group).
According to embodiment of the present invention, in general formula (II-2), when group R is described polyolefin-based, this is poly-
Alkylene is preferably placed at the contraposition of phenolic hydroxyl group in general formula (II-2).
According to the present invention, in general formula (II-2), when there are multiple, each group R' is same or different to each other, respectively solely
On the spot it is selected from hydrogen and C1-20Linear or branched alkyl group.
According to embodiment of the present invention, in general formula (II-2), when there are multiple, each group R' is mutually the same
Or it is different, it is each independently selected from hydrogen and C1-4Linear or branched alkyl group.
According to the present invention, in logical formula (III), group L' is group
According to the present invention, in logical formula (III), in the definition of group L', group R " is selected from hydrogen, C1-20Alkyl is (preferably
C1-20Linear or branched alkyl group) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in logical formula (III), in the definition of group L', group R " be selected from hydrogen,
C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl, is preferably selected from hydrogen and C1-10Linear or branched alkyl group.
According to the present invention, in logical formula (III), group R2Selected from hydrogen, C1-20Shown in linear or branched alkyl group, logical formula (IV)
Group and logical formula (V) shown in group.
According to embodiment of the present invention, in logical formula (III), group R2Selected from hydrogen, C1-10Linear or branched alkyl group
With group shown in logical formula (IV).
According to the present invention, in logical formula (III), when there are multiple, each group RbIt is same or different to each other, it is respectively independent
Ground is selected from hydrogen and C1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C1-10Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (III), when there are multiple, each group RbIt is mutually the same
Or it is different, it is each independently selected from hydrogen and C1-6Linear or branched alkyl group, preferably hydrogen.
According to the present invention, in logical formula (III), when there are multiple, each group RcIt is same or different to each other, it is respectively independent
Ground is selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (III), when there are multiple, each group RcIt is mutually the same
Or it is different, it is each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (III), a preferably group RcIn cyclic groupUpper N atom is (that is, with group RdThe N atom of bonding) contraposition.
According to the present invention, in logical formula (III), y is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (III), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (III), the integer that n is 1 to 8, preferably 1 or 2.
According to the present invention, in logical formula (III), when there are multiple, each group RdIt is same or different to each other, it is respectively independent
Ground is selected from group, preferably hydrogen shown in hydrogen and logical formula (V).
According to the present invention, in logical formula (III), when there are multiple, each cyclic group(in logical formula (III)
Inside configuration be rendered as bivalent group) be same or different to each other, be each independently selected from phenyl ring (preferably in logical formula (III)
Inside configuration is rendered as 1,4- phenylene) and naphthalene nucleus (be preferably rendered as the Asia 1,4- or 2,6- naphthalene in the inside configuration of logical formula (III)
Base), wherein it is preferred that phenyl ring.
According to embodiment of the present invention, in logical formula (III), two adjacent cyclic groupsThat
This can by additional S atom (not shown in structural formula) and bridge the two rings N atom (that is, with group RdThe N of bonding
Atom) and form phenthazine ring, i.e.,
Embodiment according to the present invention, in logical formula (III), there are more than two cyclic groupsWhen, as long as wherein at least two (adjacent) cyclic groupThe phenthazine ring is formed,
It is not necessary to require these cyclic groupsEach of with another adjacent cyclic group
Form the phenthazine ring.
According to embodiment of the present invention, in logical formula (III), two adjacent cyclic groupsThat
This can pass through additional group(not shown in structural formula) and bridge the two rings N atom (that is, with
Group RdThe N atom of bonding) and form 9,10- acridan ring, i.e.,
According to the present invention, in groupIn, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight chain or
Branched alkyl) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in groupIn, group R " is selected from hydrogen and C1-10Straight chain
Or branched alkyl.
Embodiment according to the present invention, in logical formula (III), there are more than two cyclic groups
When, as long as wherein at least two (adjacent) cyclic group9, the 10- acridan ring is formed, is not had
These cyclic groups of exclusive requirementEach of with another adjacent cyclic groupBeing formed should
Acridan ring.
According to the present invention, in logical formula (IV), when there are multiple, each group RbIt is same or different to each other, it is respectively independent
Ground is selected from hydrogen and C1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C1-10Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (IV), when there are multiple, each group RbIt is mutually the same or
Difference is each independently selected from hydrogen and C1-6Linear or branched alkyl group, preferably hydrogen.
According to the present invention, in logical formula (IV), when there are multiple, each group RcIt is same or different to each other, it is respectively independent
Ground is selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (IV), when there are multiple, each group RcIt is mutually the same or
Difference is each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (IV), a preferably group RcIn cyclic groupUpper N atom is (that is, with group RdThe N atom of bonding) contraposition.
According to the present invention, in logical formula (IV), y is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (IV), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (IV), the integer that n' is 0 to 7, preferably 0,1 or 2, on condition that n'+n≤8.According to
An embodiment of the invention, n'+n=1 or n'+n=2.Here, n is identical as the definition in aforementioned formula (II-1).
According to the present invention, in logical formula (IV), when there are multiple, each group RdIt is same or different to each other, it is respectively independent
Ground is selected from group, preferably hydrogen shown in hydrogen and logical formula (V).
According to the present invention, in logical formula (IV), when there are multiple, each cyclic group(in logical formula (IV)
Inside configuration is rendered as bivalent group) it is same or different to each other, phenyl ring is each independently selected from (preferably in the structure of logical formula (IV)
Inside is rendered as Isosorbide-5-Nitrae-phenylene) and naphthalene nucleus (being preferably rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene in the inside configuration of logical formula (IV)),
Wherein preferred phenyl ring.
According to embodiment of the present invention, in logical formula (IV), two adjacent cyclic groupsThat
This can by additional S atom (not shown in structural formula) and bridge the two rings N atom (that is, with group RdThe N of bonding
Atom) and form phenthazine ring, i.e.,
Embodiment according to the present invention, in logical formula (IV), there are more than two cyclic groups
When, as long as wherein at least two (adjacent) cyclic groupForm the phenthazine ring, it is not necessary that it is required that
These cyclic groupsEach of with another adjacent cyclic groupForm the phenthazine
Ring.
According to embodiment of the present invention, in logical formula (IV), two adjacent cyclic groupsThat
This can pass through additional group(not shown in structural formula) and bridge the two rings N atom (that is, with
Group RdThe N atom of bonding) and form 9,10- acridan ring, i.e.,
According to the present invention, in groupIn, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight chain or
Branched alkyl) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in groupIn, group R " is selected from hydrogen and C1-10Straight chain
Or branched alkyl.
Embodiment according to the present invention, in logical formula (IV), there are more than two cyclic groups
When, as long as wherein at least two (adjacent) cyclic group9, the 10- acridan ring is formed, is not had
These cyclic groups of exclusive requirementEach of with another adjacent cyclic groupIt is formed
The acridan ring.
According to the present invention, in logical formula (V), m is 1 to 4 integer, preferably 1.
According to the present invention, in logical formula (V), group L is selected from the m+1 valence C optionally replaced2To C19-mLinear or branched alkyl group is appointed
Choose the m+1 valence C in generation3To C19-mLinear chain or branched chain miscellaneous alkyl and group
(referred to as general formula (V-A)), wherein being preferably selected from the m+1 valence C optionally replaced2To C19-mLinear or branched alkyl group and general formula (V-A) institute
The group shown is more preferably selected from the m+1 valence C optionally replaced2To C19-mLinear or branched alkyl group.
According to the present invention, in logical formula (V), in the definition of group L, as the m+1 valence C optionally replaced2To C19-m
Linear or branched alkyl group, the m+1 valence C preferably optionally replaced2To C9-mLinear or branched alkyl group, the m+1 valence more preferably optionally replaced
C2-6Linear or branched alkyl group.
According to the present invention, in logical formula (V), in the definition of group L, as the m+1 valence C optionally replaced3To C19-m
Linear chain or branched chain miscellaneous alkyl, the m+1 valence C preferably optionally replaced3To C9-mLinear chain or branched chain miscellaneous alkyl, the m more preferably optionally replaced
+ 1 valence C3-6Linear chain or branched chain miscellaneous alkyl.
According to the present invention, in logical formula (V), in the definition of group L, so-called optional substitution is referred to optionally by one
Or multiple (such as 1 to 4,1 to 3,1 to 2 or 1) are selected from C1-20Alkyl and C3-20Linear chain or branched chain miscellaneous alkyl takes
Replace for base.As the substituent group, preferably C1-20Linear or branched alkyl group, C6-20Aryl or combinations thereof group.As described
C1-20Linear or branched alkyl group, preferably C1-10Linear or branched alkyl group, more preferable C1-6Linear or branched alkyl group, for example, methyl or
Ethyl.
According to the present invention, in logical formula (V), in the group shown in general formula (V-A), each group L'1It is mutually the same or not
Together, it is each independently selected from C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl, is preferably each independently selected from
C1-6Linear or branched alkyl group.
According to the present invention, in logical formula (V), in the group shown in general formula (V-A), necessary condition (1) is: each group
L'1It is divalent each independently to m+1 valence, so that group shown in the general formula (V-A) is generally rendered as m+1 valence.In view of
This, in the group shown in general formula (V-A), each group L'1Valence state be variable, and be possibly different from.Therefore, logical
In group shown in formula (V-A), there is no directly provide each group L' by the present invention1Valence state, but this has no effect on this field skill
Art personnel understand and implement the present invention, and each group L'1Valence state can actually be able to by the necessary condition (1) it is bright
Really.For concrete example, if each group L'1It is ethyl (not yet explicitly valence state), m 2, then base shown in the general formula (V-A)
Group may be with one of flowering structure:
According to the present invention, in logical formula (V), in the group shown in general formula (V-A), necessary condition (2) is: whole groups
L'1Atomicity (be not counted in each group L'1Upper substituent group that may be present as described below) the sum of be not more than 14 so that
The total atom number of group shown in the general formula (V-A) (is not counted in each group L'1Upper substituent group that may be present as described below)
No more than 18.
According to the present invention, in logical formula (V), in the group shown in general formula (V-A), two necessity above-mentioned is being met
After condition, each group L'1It can be optionally each independently further by one or more (such as 1 to 4,1 to 3,1 to 2
It is a or 1) be selected from C1-20Alkyl and C3-20The substituent group of linear chain or branched chain miscellaneous alkyl replaces.As the substituent group, preferably
C1-20Linear or branched alkyl group, C6-20Aryl or combinations thereof group.As the C1-20Linear or branched alkyl group, preferably C1-10Directly
Chain or branched alkyl, more preferable C1-6Linear or branched alkyl group, such as methyl or ethyl.
According to the present invention, in logical formula (V), each group A is same or different to each other, and is each independently selected from following general formula
(V-1) group shown in group and following general formula shown in (V-2).
According to the present invention, in general formula (V-1), group R2Selected from hydrogen, C1-20Shown in linear or branched alkyl group, logical formula (IV)
Group and logical formula (V) shown in group.
According to embodiment of the present invention, in general formula (V-1), group R2Selected from hydrogen, C1-10Linear or branched alkyl group
With group shown in logical formula (IV).
According to the present invention, in general formula (V-1), when there are multiple, each group RbIt is same or different to each other, it is respectively independent
Ground is selected from hydrogen and C1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C1-10Linear or branched alkyl group.
According to embodiment of the present invention, in general formula (V-1), when there are multiple, each group RbIt is mutually the same
Or it is different, it is each independently selected from hydrogen and C1-6Linear or branched alkyl group, preferably hydrogen.
According to the present invention, in general formula (V-1), when there are multiple, each group RcIt is same or different to each other, it is respectively independent
Ground is selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in general formula (V-1), when there are multiple, each group RcIt is mutually the same
Or it is different, it is each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in general formula (V-1), a preferably group RcIn cyclic groupUpper N atom is (that is, with group RdThe N atom of bonding) contraposition.
According to the present invention, in general formula (V-1), y is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in general formula (V-1), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in general formula (V-1), the integer that n is 1 to 8, preferably 1 or 2.
According to the present invention, in general formula (V-1), when there are multiple, each group RdIt is same or different to each other, it is respectively independent
Ground is selected from group, preferably hydrogen shown in hydrogen and logical formula (V).
According to the present invention, in general formula (V-1), when there are multiple, each cyclic group(at general formula (V-1)
Inside configuration be rendered as bivalent group) be same or different to each other, be each independently selected from phenyl ring (preferably in general formula (V-1)
Inside configuration is rendered as 1,4- phenylene) and naphthalene nucleus (be preferably rendered as the Asia 1,4- or 2,6- naphthalene in the inside configuration of general formula (V-1)
Base), wherein it is preferred that phenyl ring.
According to embodiment of the present invention, in general formula (V-1), two adjacent cyclic groupsThat
This can by additional S atom (not shown in structural formula) and bridge the two rings N atom (that is, with group RdThe N of bonding
Atom) and form phenthazine ring, i.e.,
Embodiment according to the present invention, in general formula (V-1), there are more than two cyclic groupsWhen, as long as wherein at least two (adjacent) cyclic groupThe phenthazine ring is formed,
It is not necessary to require these cyclic groupsEach of with another adjacent cyclic groupShape
At the phenthazine ring.
According to embodiment of the present invention, in general formula (V-1), two adjacent cyclic groupsThat
This can pass through additional group(not shown in structural formula) and bridge the two rings N atom (that is, with
Group RdThe N atom of bonding) and form 9,10- acridan ring, i.e.,
According to the present invention, in groupIn, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight chain or
Branched alkyl) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in groupIn, group R " is selected from hydrogen and C1-10Straight chain
Or branched alkyl.
Embodiment according to the present invention, in general formula (V-1), there are more than two cyclic groupsWhen, as long as wherein at least two (adjacent) cyclic groupForm the acridan
Ring, it is not necessary that it is required that these cyclic groupsEach of with another adjacent cyclic groupForm the acridan ring.
According to the present invention, in general formula (V-2), when there are multiple, each group R is same or different to each other, respectively independent
Ground is selected from hydrogen, C1-300Group shown in group shown in linear or branched alkyl group, logical formula (II) and logical formula (III).
According to the present invention, in general formula (V-2), two group R and a groupIt occupies respectively
Three positions of residue on phenyl ring.
According to embodiment of the present invention, in general formula (V-2), when there are multiple, each group R it is mutually the same or
Difference is each independently selected from hydrogen and C1-300Linear or branched alkyl group.
According to the present invention, in general formula (V-2), as the C1-300Linear or branched alkyl group, for example C can be enumerated1-20
Linear or branched alkyl group (preferably C1-10Linear or branched alkyl group, more preferable C1-4Linear or branched alkyl group) or it is polyolefin-based.Make
To be described polyolefin-based, specifically can such as enumerate number-average molecular weight Mn is the polyolefin-based of 300-3000.At this point, as described
Polyolefin-based number-average molecular weight Mn, preferably 500-2000, more preferable 500-1500.According to the present invention, the polyolefin-based (base
In sheet) it is saturation (being rendered as chain alkyl structure), but depend on the type or the polyene of the polyolefin as starting material
The difference of hydrocarbon manufacturing method, may also be containing a small amount of olefinic double bond (such as in polyolefin system in the polyolefin-based strand
Remain or introduce during making), but this has no effect on the realization of effect of the present invention, and the present invention also has no intention to carry out the amount bright
Really, and the present invention still polyolefin-based is classified as " alkyl " for this.
According to embodiment of the present invention, in general formula (V-2), there are multiple group R, one of group R is
It is described polyolefin-based, the other is hydrogen or C1-20Linear or branched alkyl group (preferably C1-10Linear or branched alkyl group, more preferable C1-4
Linear or branched alkyl group).
According to embodiment of the present invention, in general formula (V-2), when group R is described polyolefin-based, the polyene
Alkyl is preferably placed at the contraposition of phenolic hydroxyl group in general formula (V-2).
According to the present invention, in general formula (V-2), when there are multiple, each group R' is same or different to each other, respectively independent
Ground is selected from hydrogen and C1-20Linear or branched alkyl group.
According to embodiment of the present invention, in general formula (V-2), when there are multiple, each group R' is mutually the same
Or it is different, it is each independently selected from hydrogen and C1-4Linear or branched alkyl group.
According to the present invention, the shielding phenolic compounds is defined as previously described (such as such as logical formula (I) or further such as general formula
(II-2) or shown in general formula (V-2)), it is necessary to it include structureAs phenol unit.According to the present invention one it is preferred
Embodiment, the shielding phenolic compounds is in its entire molecular structure comprising at most 5, at most 3, at most 2 or extremely
More 1 phenol unit.
According to the present invention, the shielding phenolic compounds is defined as previously described (such as such as general formula (II-1) or further such as
Shown in logical formula (III), logical formula (IV) or general formula (V-1)), it is necessary to it include structureAs amine list
Member.According to a preferred embodiment of the present invention, the shielding phenolic compounds includes at most 15 in its entire molecular structure
A, at most 10, at most 8, at most 6, at most 4, at most 3 or at most 2 amine units.
According to the present invention, the shielding phenolic compounds preferably at least has (preferably 2,3 in its entire molecular structure
It is a or 4 or more) group RdIt is hydrogen.Specifically, the shielding phenolic compounds preferably contains in its entire molecular structure
Have selected from least one of following hydrogen amine unit (1), hydrogen amine unit (2) and hydrogen amine unit (3).In these hydrogen amine units,
Cyclic groupIt is identical as the definition in general formula (II-1) with group R ".
A preferred embodiment according to the present invention, the shielding phenolic compounds is in its entire molecular structure containing extremely
A few hydrogen amine unit (1).
Specifically, to shield phenolic compoundsFor, the compound is in its entire molecule
Include 2 phenol units and 3 amine units in structure, and includes 1 hydrogen amine unit (1).
According to the present invention, as the shielding phenolic compounds, for example following compound or its arbitrary proportion can be enumerated
Mixture, but the present invention is not limited thereto.
According to the present invention, shielding phenolic compounds shown in aforementioned formula (I) can be with a kind of single shape of (pure) compound
Formula exist, make or use, can also with the form of the mixture (in any proportion) of two or more of them exist, manufacture or
It uses, this has no effect on the realization of effect of the present invention.
According to the present invention, shielding phenolic compounds shown in aforementioned formula (I) can pass through manufacturing method system below
It makes, but is not limited thereto.
The manufacturing method according to the present invention, including make amination shown in phenolic compounds shown in logical formula (X) and general formula (Y)
The first step to react in the presence of closing object polybasic carboxylic acid shown in general formula (A) or derivatives thereof.
According to the present invention, lead in formula (X), when there are multiple, each group R0It is same or different to each other, selects each independently
From hydrogen ,-SH and C1-300Linear or branched alkyl group, on condition that at least one group R0It is-SH.
According to the present invention, in logical formula (X), as the C1-300Linear or branched alkyl group, for example C can be enumerated1-20Directly
Chain or branched alkyl (preferably C1-10Linear or branched alkyl group, more preferable C1-4Linear or branched alkyl group) or it is polyolefin-based.As
Described polyolefin-based, specifically can such as enumerate number-average molecular weight Mn is the polyolefin-based of 300-3000.At this point, as described poly-
The number-average molecular weight Mn of alkylene, preferably 500-2000, more preferable 500-1500.According to the present invention, described polyolefin-based (basic
On) it is saturation (being rendered as chain alkyl structure), but depend on the type or the polyolefin of the polyolefin as starting material
The difference of manufacturing method (for example may also be manufactured containing a small amount of olefinic double bond in polyolefin in the polyolefin-based strand
Remain or introduce in the process), but this has no effect on the realization of effect of the present invention, and the present invention also has no intention to carry out the amount bright
Really, and the present invention still polyolefin-based is classified as " alkyl " for this.
According to embodiment of the present invention, in logical formula (X), there are multiple group R0, one of group R0Be-
SH, other two group R0In one be it is described polyolefin-based, the other is hydrogen or C1-20Linear or branched alkyl group is (preferably
C1-10Linear or branched alkyl group).
According to embodiment of the present invention, in logical formula (X), in group R0When being described polyolefin-based, the polyene
Alkyl is preferably placed at the contraposition of phenolic hydroxyl group in logical formula (X).
According to the present invention, in logical formula (X), when there are multiple, each group R' is same or different to each other, each independently
Selected from hydrogen and C1-20Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (X), when there are multiple, each group R' it is mutually the same or
Difference is each independently selected from hydrogen and C1-4Linear or branched alkyl group.
According to the present invention, as phenolic compounds shown in the logical formula (X), commercially available product can be directly used, it can also
To be manufactured by conventionally known in the art method, it is not particularly limited.In addition, as shown in the logical formula (X)
Phenolic compounds, can be used only one kind, can also be used with combination of two or more.
According to the present invention, the manufacturing method as phenolic compounds shown in the logical formula (X), for example can enumerate in alkyl
In the presence of changing catalysts, make phenolic compounds shown in general formula (X') and polyolefin (number-average molecular weight Mn 300-3000, it is excellent
Select 500-2000, more preferable 500-1500) occur alkylated reaction method.
According to the present invention, in general formula (X'), group R' has and identical meaning in aforementioned formula (X).
According to the present invention, there are three group R' in general formula (X')0, one of group R'0It is-SH, another group
R'0It is H, third group R'0It is hydrogen ,-SH or C1-20Linear or branched alkyl group (preferably C1-10Linear or branched alkyl group).
According to embodiment of the present invention, in general formula (X'), at least one group R'0It is H, and group R'0
The contraposition of phenolic hydroxyl group in general formula (X').
According to the present invention, the polyolefin preferably passes through ethylene, propylene or C4-C10The homopolymerization of alpha-olefin passes through these
Polyolefin obtained from two or more copolymerization in alkene.As the C4-C10Alpha-olefin, for example, can enumerate n-butene,
Isobutene, n-pentene, n-hexylene, positive octene and positive decene.
According to the present invention, at least 20wt% (preferably at least 50wt%, more preferably at least 70wt%) in these polyolefin
Polymer chain contains olefinic double bond at its end.The olefinic double bond is usually with the ethenylidene of high reaction activity or vinyl
Existing for form.
According to the present invention, as the polyolefin, more preferable polybutene.Unless otherwise indicated, term as used herein
" polybutene " broadly includes the polymer as obtained from 1- butylene or isobutylene homopolymerisation, and by 1- butylene, 2- butylene and different
Pass through polymer prepared by copolymerization two or three in butylene.It the commercial product of this quasi polymer may also be containing negligible
Other olefinic components of amount, but this has no effect on implementation of the invention.
According to the present invention, as the polyolefin, further preferred polyisobutene (PIB), also referred to as high reaction activity are poly-
Isobutene.In this kind of polyisobutene, total end alkene of at least 20wt% (preferably at least 50wt%, more preferably at least 70wt%)
Belonging to double bond is provided by methyl ethenylidene.
As the catalyst for alkylation reaction, for example Lewis acid catalyst can be enumerated, for example, selected from alchlor,
Boron trifluoride, tin tetrachloride, titanium tetrabromide, boron trifluoride phenol, boron trifluoride alcohol complex and boron trifluoride ether network
One of object or a variety of is closed, wherein it is preferred that boron trifluoride etherate and/or boron trifluoride methanol complex compound.These
Catalyst for alkylation reaction can directly use commercially available product.
According to the present invention, in the alkylated reaction, phenolic compounds shown in the polyolefin, the general formula (X'),
Molar ratio between the catalyst for alkylation reaction such as can be 1:1-3:0.1-0.5, preferably 1:1.5-3:0.1-0.4,
Most preferably 1:1.5-3:0.2-0.4, but is not limited thereto.
According to the present invention, the reaction time of the alkylated reaction is such as 0.5h-10h, preferably 1h-8h, most preferably 3h-
5h, but is not limited thereto.
According to the present invention, the reaction temperature of the alkylated reaction is such as 0 DEG C -200 DEG C, preferably 10 DEG C -150 DEG C, most
It is preferred that 20 DEG C -100 DEG C, but is not limited thereto.
According to the present invention, the alkylated reaction can be in the presence of a solvent.As the solvent, such as can be with
Enumerate C6-10Alkane (such as hexane, heptane, octane, nonane or decane etc.).Wherein, it is preferable to use hexane and heptane, more preferably
Use hexane.
According to the present invention, after the alkylated reaction, by conventional methods from the reaction mixture finally obtained
It is middle remove catalyst for alkylation reaction, unreacted reactant and the solvent that may use after, that is, obtain the logical formula (X) institute
The phenolic compounds shown.
According to the present invention, in general formula (Y), group R'2Selected from hydrogen, C1-20Linear or branched alkyl group and group
According to the present invention, in general formula (Y), when there are multiple, each group RbIt is same or different to each other, each independently
Selected from hydrogen and C1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C1-10Linear or branched alkyl group.
According to embodiment of the present invention, in general formula (Y), when there are multiple, each group RbIt is mutually the same or
Difference is each independently selected from hydrogen and C1-6Linear or branched alkyl group, preferably hydrogen.
According to the present invention, in general formula (Y), when there are multiple, each group RcIt is same or different to each other, each independently
Selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in general formula (Y), when there are multiple, each group RcIt is mutually the same or
Difference is each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in general formula (Y), a preferably group RcIn cyclic groupUpper N atom is (that is, with group RdThe N atom of bonding) contraposition.
According to the present invention, in general formula (Y), y is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in general formula (Y), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in general formula (Y), the integer that n1 is 1 to 8, preferably 1 or 2.
According to the present invention, in general formula (Y), when there are multiple, each cyclic group(in the knot of general formula (Y)
Bivalent group is rendered as inside structure) it is same or different to each other, phenyl ring is each independently selected from (preferably in the structure of general formula (Y)
Portion is rendered as Isosorbide-5-Nitrae-phenylene) and naphthalene nucleus (being preferably rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene in the inside configuration of general formula (Y)), wherein
It is preferred that phenyl ring.
According to the present invention, as amine compounds shown in the general formula (Y), commercially available product can be directly used, not
There is special limitation.In addition, one kind can be used only as amine compounds shown in the general formula (Y), it can also be two kinds or more
Kind is applied in combination.
According to the present invention, in general formula (A), the integer that m1 is 2 to 5, preferably 2.
According to the present invention, in general formula (A), group RLSelected from the m1 valence C optionally replaced2To C20-m1Linear or branched alkyl group,
The m1 valence C optionally replaced3To C20-m1Linear chain or branched chain miscellaneous alkyl and group
(referred to as general formula (A-A)), wherein being preferably selected from the m1 valence C optionally replaced2To C20-m1Linear or branched alkyl group and general formula (A-A) institute
The group shown is more preferably selected from the m1 valence C optionally replaced2To C20-m1Linear or branched alkyl group.
According to the present invention, in general formula (A), in group RLDefinition in, as the m1 valence C optionally replaced2Extremely
C20-m1Linear or branched alkyl group, the m1 valence C preferably optionally replaced2To C10-m1Linear or branched alkyl group more preferably optionally replaces
M1 valence C2-6Linear or branched alkyl group.
According to the present invention, in general formula (A), in group RLDefinition in, as the m1 valence C optionally replaced3Extremely
C20-m1Linear chain or branched chain miscellaneous alkyl, the m1 valence C preferably optionally replaced3To C10-m1Linear chain or branched chain miscellaneous alkyl, more preferably optionally takes
The m1 valence C in generation3-6Linear chain or branched chain miscellaneous alkyl.
According to the present invention, in general formula (A), in group RLDefinition in, so-called optional substitution refers to optionally by one
Or multiple (such as 1 to 4,1 to 3,1 to 2 or 1) are selected from C1-20Alkyl and C3-20Linear chain or branched chain miscellaneous alkyl takes
Replace for base.As the substituent group, preferably C1-20Linear or branched alkyl group, C6-20Aryl or combinations thereof group.As described
C1-20Linear or branched alkyl group, preferably C1-10Linear or branched alkyl group, more preferable C1-6Linear or branched alkyl group, for example, methyl or
Ethyl.
According to the present invention, in general formula (A), in the group shown in general formula (A-A), each group L'1It is mutually the same or not
Together, it is each independently selected from C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl, is preferably each independently selected from
C1-6Linear or branched alkyl group.
According to the present invention, in general formula (A), in the group shown in general formula (A-A), necessary condition (1) is: each group
L'1It is divalent each independently to m1 valence, so that group shown in the general formula (A-A) is generally rendered as m1 valence.In view of
This, in the group shown in general formula (A-A), each group L'1Valence state be variable, and be possibly different from.Therefore, logical
In group shown in formula (A-A), there is no directly provide each group L' by the present invention1Valence state, but this has no effect on this field skill
Art personnel understand and implement the present invention, and each group L'1Valence state can actually be able to by the necessary condition (1) it is bright
Really.For concrete example, if each group L'1It is ethyl (not yet explicitly valence state), m1 3, then base shown in the general formula (A-A)
Group may be with one of flowering structure:
According to the present invention, in general formula (A), in the group shown in general formula (A-A), necessary condition (2) is: whole groups
L'1Atomicity (be not counted in each group L'1Upper substituent group that may be present as described below) the sum of be not more than 14 so that
The total atom number of group shown in the general formula (A-A) (is not counted in each group L'1Upper substituent group that may be present as described below)
No more than 18.
According to the present invention, in general formula (A), in the group shown in general formula (A-A), two necessity above-mentioned is being met
After condition, each group L'1It can be optionally each independently further by one or more (such as 1 to 4,1 to 3,1 to 2
It is a or 1) be selected from C1-20Alkyl and C3-20The substituent group of linear chain or branched chain miscellaneous alkyl replaces.As the substituent group, preferably
C1-20Linear or branched alkyl group, C6-20Aryl or combinations thereof group.As the C1-20Linear or branched alkyl group, preferably C1-10Directly
Chain or branched alkyl, more preferable C1-6Linear or branched alkyl group, such as methyl or ethyl.
According to the present invention, the derivative as polybasic carboxylic acid shown in the general formula (A), for example the polynary carboxylic can be enumerated
The acid anhydrides and carboxylic acid halides of acid.As the carboxylic acid halides, for example acyl fluorides, acyl chlorides and acylbromide can be enumerated, wherein it is preferred that acyl chlorides.
According to the present invention, one kind can be used only in polybasic carboxylic acid shown in the general formula (A) or derivatives thereof, can also be with
Combination of two or more uses.In addition, can directly be used as polybasic carboxylic acid shown in the general formula (A) or derivatives thereof
Commercially available product, is not particularly limited.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the first step, the general formula
(X) molar ratio of phenolic compounds shown in and amine compounds shown in the general formula (Y) is generally 1:0.1-10, preferably 1:0.5-
5.0, more preferable 1:0.8-2.0.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the first step, the general formula
(X) molar ratio of phenolic compounds shown in and polybasic carboxylic acid shown in the general formula (A) or derivatives thereof is generally 1:0.1-10,
It is preferred that 1:0.2-5.0, more preferable 1:0.3-3.0.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, the first step can depositing in solvent
In lower progress.As the solvent, for example C can be enumerated2-10Aliphatic nitrile (such as acetonitrile etc.) and C6-20Aromatic hydrocarbon (such as benzene,
Toluene, dimethylbenzene and isopropylbenzene) etc..One kind can be used only in these solvents, can also be used with combination of two or more.
According to the present invention, it in the manufacturing method of the shielding phenolic compounds, in the first step, can be added without
Catalyst can also be added in catalyst.Specifically, being urged when using polybasic carboxylic acid shown in the general formula (A) as described
Agent, for example basic catalyst can be enumerated.As the basic catalyst, for example the hydroxide ratio of alkali metal can be enumerated
The salt of weak acid of such as sodium hydroxide and potassium hydroxide or alkali metal such as sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, carbonic acid
Hydrogen sodium and saleratus etc..One kind can be used only in these catalyst, can also be used with combination of two or more.It is urged as described
The dosage of agent can be not particularly limited directly referring to the conventional amount used of the prior art.In addition, using described logical
When the acid anhydrides of polybasic carboxylic acid shown in formula (A), as the catalyst, for example transition metal salt can be enumerated, specifically such as may be used
To enumerate cobaltous dichloride and ruthenium trichloride etc..One kind can be used only in these catalyst, can also be used with combination of two or more.
As the dosage of the catalyst, can be not particularly limited directly referring to the conventional amount used of the prior art.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction time of the first step
There are special restriction, but generally 0.2h-12h, preferably 0.2-12h, most preferably 0.5-6h.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction temperature of the first step
There are special restriction, but generally 0-200 DEG C, preferably 10-150 DEG C, most preferably 20-120 DEG C.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, after the first step terminates, pass through
Reaction mixture that conventionally known separation method (such as evaporation etc.) is obtained from the first step (hereinafter referred to as first step
Reaction mixture) in remove the volatile materials such as solvent that may be present after, can be obtained the reaction product of first step.
According to embodiment of the present invention, the manufacturing method of the shielding phenolic compounds optionally further includes making described the
The additional step (hereinafter referred to as additional step A) that the reaction product of one step reacts with vulcanizing agent and (forms phenthazine ring).
According to embodiment of the present invention, the manufacturing method of the shielding phenolic compounds optionally further include make it is described
The additional step that the reaction product of first step reacts with aldehyde compound shown in general formula (Z) and (forms acridan ring)
(hereinafter referred to as additional step B).
According to the present invention, in general formula (Z), group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Linear or branched alkyl group) and
C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in general formula (Z), group R " is selected from hydrogen, C1-10Linear or branched alkyl group
And C3-10Linear chain or branched chain miscellaneous alkyl.
According to a preferred embodiment of the present invention, in general formula (Z), group R " is selected from hydrogen and C1-10Linear chain or branched chain
Alkyl.
According to the present invention, as aldehyde compound shown in the general formula (Z), for example C can be enumerated1-6Aliphatic aldehyde and benzene
Formaldehyde.
According to embodiment of the present invention, as the C1-6Aliphatic aldehyde, for example C can be enumerated1-6Straight chain or branch
Chain saturated aliphatic aldehyde, specifically such as acetaldehyde or formaldehyde, more preferable formaldehyde.As the formaldehyde, for example, can be used its aqueous solution,
Paraformaldehyde or paraformaldehyde form, are not particularly limited.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step A can be only carried out,
The additional step B can be only carried out, can also not only carry out the additional step A but also carries out the additional step B.Both it is carrying out
The additional step A carries out the additional step B again when, do not have to the precedence of the additional step A and the additional step B
There is special restriction, can first carry out the additional step A, carries out the additional step again after additional step A terminates
B, or the additional step B is first carried out, the additional step A is carried out again after additional step B terminates.In addition, each attached
Product (that is, reaction product from previous additional step) separating step can be had by adding between step, can also be without product point
From step, it is not particularly limited.
According to embodiment of the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step A
It is carried out after the first step terminates.At this point, the reaction product of the first step is as previously described from described first
It is separated in the reaction mixture of step.Alternatively, the reaction product of the first step can also be straight without the separation
It connects in the form of the reaction mixture of the first step for carrying out the additional step A.Alternatively, the additional step A
It can be carried out after the additional step B terminates.When the additional step A after the additional step B terminates when carrying out,
The reaction product of the additional step B is separated from the reaction mixture of the additional step B as described herein.
Alternatively, the reaction product of the additional step B can also be directly mixed with the reaction of the additional step B without the separation
The form of object is closed for carrying out the additional step A.
According to embodiment of the present invention, in the manufacturing method of the shielding phenolic compounds, in the extra step
In rapid A, as the vulcanizing agent, for example sulphur and sulfur dichloride can be enumerated etc., wherein it is preferred that sulphur.As the sulphur, such as can
To enumerate sulphur or sublimed sulfur.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the additional step A, the general formula
(Y) molar ratio of amine compounds shown in and the vulcanizing agent is generally 1:1-10, preferably 1:1.2-6.0, more preferable 1:1.5-
3.0。
According to the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step A can depositing in solvent
In lower progress.As the solvent, for example C can be enumerated2-10Aliphatic nitrile (such as acetonitrile etc.), C6-20Aromatic hydrocarbon (such as benzene,
Toluene, dimethylbenzene and isopropylbenzene), C6-10Alkane (such as n-hexane, hexamethylene and petroleum ether), C1-6Aliphatic alcohol (such as first
Alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C2-20Halogenated hydrocarbons (such as methylene chloride, carbon tetrachloride, chlorobenzene and
1,2- dichloro-benzenes), C3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C3-10Amide (such as dimethylformamide,
Dimethyl acetamide and N-Methyl pyrrolidone) etc..One kind can be used only in these solvents, can also be made with combination of two or more
With.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step A is generally in catalyst
In the presence of carry out.As the catalyst, for example the catalyst that the prior art uses for this purpose and routinely can be enumerated, specifically
Such as iodine.As the dosage of the catalyst, can be not particularly limited directly referring to the conventional amount used of the prior art.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction time of the additional step A
There are special restriction, but generally 0.1h-24h, preferably 0.2h-12h, most preferably 0.5h-4h.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction temperature of the additional step A
There are special restriction, but generally 60 DEG C -300 DEG C, preferably 120 DEG C -240 DEG C, most preferably 150 DEG C -200 DEG C.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, after the additional step A terminates, lead to
Cross conventionally known separation method (such as evaporation etc.) removed from the reaction mixture that additional step A is obtained it is that may be present
After the volatile materials such as solvent, the reaction product of additional step A can be obtained, or can also be without the separation, directly
For subsequent reaction step (than additional step B as the aforementioned).
According to embodiment of the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step B
It is carried out after the first step terminates.When the additional step B after the first step terminates when carrying out, described
The reaction product of one step is separated from the reaction mixture of the first step as previously described.Alternatively, described
The reaction product of one step can also be directly used in the form of the reaction mixture of the first step without the separation
Carry out the additional step B.Alternatively, the additional step B can also be carried out after the additional step A terminates.When described
For additional step B when carrying out after the additional step A terminates, the reaction product of the additional step A is as described herein
It is separated from the reaction mixture of the additional step A.Alternatively, the reaction product of the additional step A can also be without
The separation is crossed, and for carrying out the additional step B directly in the form of the reaction mixture of the additional step A.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, in the additional step B, the general formula
(Y) molar ratio of amine compounds shown in and aldehyde compound shown in the general formula (Z) is generally 1:0.1-10, preferably 1:0.5-
5.0, more preferable 1:0.8-2.0.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, the additional step B can depositing in solvent
In lower progress.As the solvent, for example C can be enumerated2-10Aliphatic nitrile (such as acetonitrile etc.), C6-20Aromatic hydrocarbon (such as benzene,
Toluene, dimethylbenzene and isopropylbenzene), C6-10Alkane (such as n-hexane, hexamethylene and petroleum ether), C1-6Aliphatic alcohol (such as first
Alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C2-20Halogenated hydrocarbons (such as methylene chloride, carbon tetrachloride, chlorobenzene and
1,2- dichloro-benzenes), C3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C3-10Amide (such as dimethylformamide,
Dimethyl acetamide and N-Methyl pyrrolidone) etc..One kind can be used only in these solvents, can also be made with combination of two or more
With.
According to the present invention, it in the manufacturing method of the shielding phenolic compounds, in the additional step B, can be not added
Enter catalyst, catalyst can also be added.As the catalyst, for example inorganic acid catalyst and organic acid catalysis can be enumerated
Agent.As the inorganic acid catalyst, for example hydrochloric acid, sulfuric acid and phosphoric acid can be enumerated etc..As the organic acid catalyst, than
Methane sulfonic acid, ethylsulfonic acid, sulfamic acid and p-methyl benzenesulfonic acid can such as be enumerated.It, can be with as the dosage of the catalyst
Directly referring to the conventional amount used of the prior art, it is not particularly limited.
According to the present invention, it is described shielding phenolic compounds manufacturing method in, the additional step B incipient stage or
During person carries out, amine compounds shown in the general formula (Y) can also further be added as needed, thus forming 9,
Group shown in aforementioned formula (III) is formed while 10- acridan ring.At this point, amine compounds shown in the general formula (Y)
1:0.1-10, preferably 1:0.5-5.0, more preferable 1:0.8- are generally with the molar ratio of aldehyde compound shown in the general formula (Z)
2.0。
According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction time of the additional step B
There are special restriction, but generally 0.1h-24h, preferably 0.2h-12h, most preferably 0.5h-6h.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, do not have to the reaction temperature of the additional step B
There are special restriction, but generally 0 DEG C -250 DEG C, preferably 20 DEG C -180 DEG C, most preferably 60 DEG C -120 DEG C.
According to the present invention, in the manufacturing method of the shielding phenolic compounds, after the additional step B terminates, lead to
Cross conventionally known separation method (such as evaporation etc.) removed from the reaction mixture that additional step B is obtained it is that may be present
After the volatile materials such as solvent, the reaction product of additional step B can be obtained, or can also be without the separation, directly
For subsequent reaction step (than additional step A as the aforementioned).
It is known in the art, aforementioned all reaction step (including the first step, the additional step A and
The additional step B) generally carried out under the protection of inert gas atmosphere.As the inert gas, for example nitrogen can be enumerated
Gas and argon gas etc., are not particularly limited.
According to the present invention, it is described shielding phenolic compounds manufacturing method in, as the first step reaction product,
The reaction product of the reaction product of the additional step A or the additional step B can be a kind of single shielding phenolic compounds
(for example shielding phenolic compounds shown in aforementioned formula (I)) is also possible to the mixture comprising a variety of shielding phenolic compounds.These
Reaction product is all desired by the present invention, and the difference of existence form has no effect on the realization of effect of the present invention.Therefore, this theory
These reaction products are collectively termed as to shielding phenolic compounds of the invention without distinction in bright book context.In consideration of it, according to
The present invention, and be not present and these reaction products are further purified, or be further separated out a certain spy from these reaction products
Determine the absolute necessity of the shielding phenolic compounds of structure.Certainly, the purifying or separation are for the further of desired effect of the present invention
It is sometimes preferred for promotion, but for the present invention not necessarily.Even so, as the purifying or separation method,
For example it can enumerate and the reaction product is purified or separated by the methods of column chromatography method or preparation chromatography.
According to embodiment of the present invention, the manufacturing method according to present invention shielding phenolic compounds above-mentioned is further related to
The shielding phenolic compounds of manufacture.
Shielding phenolic compounds of the invention is due to showing excellent high-temperature oxidation resistance, particularly suitable as anti-
Oxygen agent uses, and is used to manufacture the lubricant oil composite for expecting excellent (high temperature) oxidation stability especially as antioxidant.Mirror
In this, according to embodiment of the present invention, it is related to a kind of lubricant oil composite, it includes lube base oils and the present invention
Any shielding phenolic compounds (or mixture of its arbitrary proportion) above-mentioned.
According to the present invention, as the lube base oil, for example mineral base oil, animal oil, vegetable oil can be enumerated
Or any lube base oil that synthetic base oil etc. is commonly used in the art.As the mineral base oil, for example can lift
Mineral base oil of the viscosity index (VI) greater than 80 or saturated hydrocarbon content mass fraction are greater than 90% and sulfur content mass fraction out
Mineral base oil less than 0.03%.As the synthetic base oil, for example polyolefin, synthetic ester, silicone oil can be enumerated and gathered
Ether etc..One kind can be used only in these lube base oils, can also be used with combination of two or more.
According to embodiment of the present invention, in the lubricant oil composite, the antioxidant accounts for the lubricating oil
The 0.001-30 weight % of composition total weight, preferably 0.1-10 weight %.
According to the present invention, the lubricant oil composite also optionally further include selected from metal detergent, ashless dispersant,
Anti-friction composition, antiwear additive, extreme pressure agent, viscosity index improver, metal corrosion inhibitor, antirust agent, pour-point depressant and anti-foaming agent its
His lube oil additive.One kind can be used only in these other lube oil additives, can also be used with combination of two or more, and
And its respective dosage is referred to the conventional amount used of the prior art, is not particularly limited.
According to the present invention, in order to manufacture the lubricant oil composite, by present invention shielding phenolic compounds above-mentioned (or its
The mixture of meaning ratio) with the lube base oil (and other lube oil additives used as needed) according to predetermined
Ratio or dosage are uniformly mixed, it may also be necessary to be heated, be not particularly limited.
According to the preferred embodiment of the present invention, the lubricant oil composite is due to including shielding phenolic compounds of the invention
As antioxidant, while showing excellent high-temperature oxidation resistance, also exhibit further selected from rustless property, peace and quiet
Performance (deposit generation rejection) inhibits viscosity build performance and acid value is inhibited to increase at least one of performance.These
Excellent properties are that the antioxidant of the prior art cannot provide simultaneously.In addition, the not phosphorous member of shielding phenolic compounds of the invention
Element and metallic element, when burning, are not likely to produce ash content, can be effectively reduced engine particulate emissions (haze it is important at
Cause), it is environmentally friendly antioxidant.
Embodiment
The present invention is illustrated using embodiment in further detail below, however, the present invention is not limited to these examples.
Performance in embodiment and comparative example is evaluated as follows.
(1) high-temperature oxidation resistance is evaluated
The lubricant oil composite that embodiment or comparative example are manufactured is as test specimen, using Pressurized Differential scanning amount heat examination
The antioxygenic property that (PDSC) evaluates the test specimen is tested, is indicated with the oxidation induction period (unit is min) of test specimen.PDSC
The temperature of test is 210 DEG C, pressure 0.5MPa, oxygen gas flow rate 100mL/min.
(2) deposit generates rejection evaluation
The hair of simulation piston deposit is carried out using the lubricant oil composite that embodiment or comparative example manufacture as test specimen
Motivation crankcase coking simulation test.This method is that coking plate analog meter is added in 300ml test specimen, is heated to 150 DEG C, adopts
The aluminium sheet spilled oil for being 310 DEG C to temperature with continuation mode weighs the burnt amount generated on aluminium sheet after 6 hours, (single with sediment yield
Position is mg) it indicates, simulate the deposit on piston.Coking amount is higher, and the piston detergency for representing this test specimen is poorer.
(3) rustless property is evaluated
According to BRT ball rust test method, using the lubricant oil composite that embodiment or comparative example manufacture as test specimen,
During entire bench test in 18 hours, the metal ball continuous contact acidic liquid and sky protected by the test specimen
Gas measures metal spherical reflector intensity, gray scale test value is obtained, for evaluating corrosion degree after the end of the test.Acetic acid/hydrogen
Bromic acid/hydrochloric acid/deionized water solution injection rate is 0.19 ml/hour, and air draught is 40 ml/mins, and oil temperature is
48℃.Corrosion degree is higher, shows that the rustless property of test specimen is poorer.
(4) inhibit viscosity build assessment of performance
The lubricant oil composite that embodiment or comparative example manufacture is subjected to IIIE simulation test (VIT) as test specimen.
The experimental condition of this method is 180 DEG C, 72h, oxygen flow 5L/h, calculates the viscosity build rate (%) of test front and back sample.
(5) acid value is inhibited to increase assessment of performance
The lubricant oil composite that embodiment or comparative example manufacture is subjected to IIIE simulation test (VIT) as test specimen.
The experimental condition of this method is 180 DEG C, 72h, oxygen flow 5L/h, calculates the acid value incrementss of test front and back sample
(mgKOH·g-1)。
Embodiment 1
In the 500ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel, 58.79g is added
Boron trifluoride ether (the alkylated reaction catalysis of (0.323mol) 2- tert-butyl -6- mercapto-phenol, 6.88g (0.048mol)
Agent), polyisobutene (Mn=1000, the Jilin Chemical group fine chemicals of 100ml n-hexane solvent and 161.61g (0.162mol)
Co., Ltd's manufacture), in 80 DEG C of reaction 2h.After reaction, reaction is cleaned using the potassium hydroxide solution that mass fraction is 5%
Mixture is primary, and is washed to neutrality with hot water to remove catalyst, and then vacuum distillation removes solvent and unreacted phenol, obtains
Obtain polyisobutene mercapto-phenol, hydroxyl value 53.49mgKOH/g.Hydroxy value measuring is with reference to the acetic anhydride method in GB/T7383-2007.
Example reaction equation is as follows:
From the nucleus magnetic hydrogen spectrum spectrum analysis of polyisobutene mercapto-phenol product: being polyisobutene at chemical shift 1.40
The characteristic peak of tert-butyl hydrogen on mercapto-phenol phenyl ring；It is unimodal for sulfydryl on polyisobutene mercapto-phenol phenyl ring at chemical shift 3.58
The characteristic peak of hydrogen；The unimodal characteristic peak for hydroxyl hydrogen on polyisobutene mercapto-phenol phenyl ring at chemical shift 4.84；Chemical shift
At 7.12 it is unimodal and 7.20 at it is unimodal be respectively polyisobutene mercapto-phenol phenyl ring on two hydrogen characteristic peak.By hydroxyl on phenyl ring
The Definitions On Integration of hydrogen is 1, and the integral for obtaining hydrogen on phenyl ring, sulfydryl hydrogen and hydroxyl hydrogen compares for 0.95:0.97:1.05:0.94, is approached
Theoretical 1:1:1:1:1 is analyzed from nuclear magnetic spectrogram, has been synthesized the polyisobutene mercapto-phenol alkylation that expected contraposition replaces and has been produced
Object.
Embodiment 2
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
30.58 grams of (156mmol) 2- sulfydryl -4- methyl -6- methylphenols of addition, 11.21 grams of (112mmol) succinic anhydrides, 32.38 grams
(176mmol) 4-aminodiphenylamine, 3.45 grams of (25mmol) potassium carbonate and 100mL acetone stir rapidly, react at room temperature 2h.
To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and obtains final shielding phenol by column chromatography for separation
Product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.40 (9H), 2.37 (3H), 2.86 (2H), 3.01 (2H), 4.84 (1H),
6.95-7.26 (11H), 7.45 (1H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 21.2,30.1,34.5,36.4,39.3,114.3,119.4,121.8,
125.8,129.5,132.3,133.5,137.5,146.1,153.5,174.0,196.9；
C27H30N2O3S calculated value C70.10, H6.54, N6.06, O10.38, S6.93；Measured value: C70.03, H6.54,
N6.01, O10.47, S6.85.
Embodiment 3
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
31.65 grams of (133mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 7.94 grams of (62mmol) adipic anhydrides, 28.15 grams
(153mmol) 4-aminodiphenylamine, 0.79 gram of (7.5mmol) sodium carbonate and 100mL isopropanol stir rapidly, room temperature reaction
24h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and obtains final screen by column chromatography for separation
Cover phenol product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 1.57 (2H), 1.72 (2H), 2.23 (2H), 2.66 (2H),
5.32 (2H), 6.97-7.26 (9H), 7.45 (1H), 7.48 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 24.9,25.4,29.6,34.6,37.8,43.5,114.3,119.3,121.8,
123.8,126.2,132.3,136.5,137.5,146.1,153.4,171.6,196.9；
C32H40N2O3S calculated value C72.14, H7.57, N5.26, O9.01, S6.02；Measured value: C72.24, H7.59,
N5.18, O9.05, S5.95.
Embodiment 4
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
8.57 grams of (36mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 2.56 grams (15mmol) 2,2 '-oxidation diethyl acyl chlorides,
10.14 grams of (39mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamines and 100mL toluene stir rapidly, 90 DEG C of reaction 4h.Wait react knot
Shu Hou, vacuum distillation remove a small amount of water of solvent and generation, and obtain final shielding phenol product by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 4.11 (2H), 4.33 (2H), 5.32 (1H), 6.97-7.48
(16H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,69.2,71.9,116.6,119.3,121.8,126.2,
127.3,127.7,129.1,129.5,136.5,141.9,142.8,146.1,153.5,165.1,189.9；
C36H40N2O4S calculated value C72.45, H6.76, N4.69, O10.72, S5.37；Measured value: C72.40, H6.71,
N4.72, O10.78, S5.35.
Embodiment 5
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
20.23 grams of (85mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 16.22 grams of (115mmol) malonyl chlorides, 18.49 grams
(69mmol) N- (1,3- dimethylbutyl)-N'- diphenyl-para-phenylene diamine, 0.76 gram of (7.2mmol) sodium carbonate and 150mL acetonitrile,
Stirring rapidly reacts at room temperature 3h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and is chromatographed by column
Isolated final shielding phenol product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 0.80 (6H), 1.11 (3H), 1.36 (15H), 1.54-1.72 (6H), 3.67-
3.91 (3H), 5.32 (1H), 6.80-7.17 (11H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 17.92,22.4,24.6,29.6,31.9,34.6,44.6,52.7,53.1,
115.4,116.6,119.4,121.8,126.2,129.5,131.4,136.6,142.8,146.1,153.5,161.7,
187.6；
C35H46N2O3S calculated value: C73.13, H8.07, N4.87, O8.35, S5.58；Measured value: C73.08, H8.01,
N4.84, O8.42, S5.63.
Embodiment 6
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
3.57 grams of (15mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 8.74 grams of (62mmol) malonyl chlorides, 21.76 grams
(103mmol) N- phenyl-N '-[4- (phenyl amino) phenyl]-Isosorbide-5-Nitrae-phenylenediamine and 100mL toluene stir rapidly, and 110 DEG C anti-
Answer 4h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and obtains final screen by column chromatography for separation
Cover phenol product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 3.79 (2H), 5.32 (1H), 6.97-7.17 (14H), 7.20
(1H), 7.22-7.35 (6H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,52.8,114.3,116.3,117.7,119.3,121.8,
126.2,126.7,127.3,129.3,132.4,136.5,141.9,142.8,143.3,146.1,153.5,162.1,
186.2；
C41H43N3O3S calculated value C74.85, H6.59, N6.39, O7.30, S4.87；Measured value: C74.81, H6.51,
N6.45, O7.24, S4.85.
Embodiment 7
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
34.51 grams of (145mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 5.11 grams of (35mmol) N- methyliminodiacetic acids,
4.49 grams of (21mmol) 4- amino -4'- methoxy diphenylamines, 0.28 gram of (2.6mmol) sodium carbonate and 100mL toluene, are stirred rapidly
It mixes, 90 DEG C of reaction 4h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and is obtained by column chromatography for separation
To final shielding phenol product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 2.27 (3H), 3.73 (2H), 3.76 (3H), 4.06 (2H),
5.23 (1H), 6.97-7.17 (8H), 7.20 (1H), 7.48 (2H), 8.24 (1H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,45.2,55.0,55.5,114.3,119.3,120.6,
121.5,126.2,132.3,136.5,137.5,153.4,154.5,163.1,192.6；
C32H41N3O4S calculated value C68.18, H7.33, N7.45, O11.35, S5.69；Measured value: C68.11, H7.29,
N7.52, O11.38, S5.57.
Embodiment 8
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
21.66 grams of (91mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 0.99 gram of (9.51mmol) malonic acid, 6.51 grams
(25mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine, 0.65 gram of (6.5mmol) saleratus and 150mL toluene stir rapidly,
150 DEG C of reaction 6h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and is obtained by column chromatography for separation
Final shielding phenol product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 3.85 (2H), 5.32 (1H), 6.80-7.17 (10H), 7.27
(4H), 7.35 (2H), 7.55 (1H)；13C NMR (75MHz, CDCl3): δ 29.6,34.6,52.6,116.6,119.4,121.8,
122.6,126.2,127.7,129.5,136.6,142.8,146.1,153.4,161.8,186.3；C35H38N2O3S calculated value
C74.17, H6.76, N4.94, O8.47, S5.66；Measured value: C74.25, H6.81, N4.83, O8.41, S5.59.
Embodiment 9
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask that blender, thermometer, condenser pipe and dropping funel are housed
In, 8.33 grams of (35mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 7.19 grams of (51mmol) malonyl chlorides, 9.61 grams
(31mmol) N, N'- diphenyl -2,6- naphthylenediamine, 0.68 gram of (4.9mmol) saleratus and 150mL toluene stir rapidly,
110 DEG C of reaction 4h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and is obtained by column chromatography for separation
Final shielding phenol product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 3.84 (2H), 5.32 (1H), 5.80 (1H), 7.00-7.84
(18H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,52.8,106.9,111.0,116.5,119.9,120.7,
121.8,126.2,127.7,128.9,129.1,136.5,140.8,142.8,153.5,160.5,186.2；
C39H40N2O3S calculated value C75.94, H6.54, N4.54, O7.78, S5.20；Calculated value: C75.85, H6.51,
N4.63, O7.72, S5.23.
Embodiment 10
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
6.19 grams of (26mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 16.38 grams of (92mmol) thio-2 acids, 3.84 grams
(17mmol) N- isopropyl-N'- diphenyl-para-phenylene diamine and 150mL toluene stir rapidly, in 80 DEG C of reaction 2h.To the end of reacting
Afterwards, vacuum distillation removes a small amount of water of solvent and generation, and obtains final shielding phenol product by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.19 (6H), 1.36 (18H), 3.74 (1H), 3.94 (2H), 3.96 (2H),
5.32 (1H), 6.80-7.26 (11H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 20.6,29.6,34.6,34.7,41.9,48.2,116.6,119.3,121.8,
126.2,129.5,136.5,139.6,142.8,146.1,153.5,166.2,189.8；
C33H42N2O3S2Calculated value C68.48, H7.31, N4.84, O8.29, S11.08；Calculated value C68.41, H7.28,
N4.91, O8.30, S11.11.
Embodiment 11
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
4.99 grams of (21mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 6.78 grams of (53mmol) adipic anhydrides, 5.70 grams
(31mmol) 4-aminodiphenylamine and 150mL ethyl alcohol stir rapidly, in 60 DEG C of reaction 2h, are down to room temperature, are added 7.05 grams
(85mmol) formaldehyde is warming up to 85 DEG C of reaction 2.5h.To after reaction, be evaporated under reduced pressure a small amount of water for removing solvent and generation,
And final shielding phenol product is obtained by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 1.57-2.66 (8H), 4.15 (2H), 5.32 (1H), 6.80-
7.24 (9H), 8.73 (1H)；
13C NMR (75MHz, CDCl3): δ 24.9,25.3,29.6,32.6,34.6,37.8,43.6,113.0,116.3,
118.9,119.2,123.3,123.9,124.6,126.2,127.9,136.5,139.5,140.5,153.4,174.0,
196.9；
C33H40N2O3S calculated value C72.76, H7.40, N5.14, O8.81, S5.89；Measured value C72.69, H7.35,
N5.23, O8.78, S5.83.
Embodiment 12
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
19.52 grams of (82mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 17.06 grams of (121mmol) succinyl chlorides, 19.93 grams
(94mmol) 4- amino -4'- ethyl diphenylamines, 2.22 grams of (16.1mmol) potassium carbonate and 150mL toluene stir rapidly, room temperature
After reacting 1h, 10.11 grams of (316mmol) sulphur and 0.04 gram of (0.35mmol) iodine are added in toluene layer, is warming up to 150 DEG C of reactions
8h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and obtains final shielding by column chromatography for separation
Phenol product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.23 (3H), 1.36 (18H), 2.61 (2H), 2.94 (2H), 3.09 (2H),
5.32 (1H), 5.70 (1H), 6.98-7.17 (7H), 7.93 (1H)；13C NMR (75MHz, CDCl3): δ 15.60,29.0,
29.6,34.6,36.1,115.9,116.1,118.9,124.9,126.2,127.9,129.7,136.6,141.2,146.2,
153.4,174.0；C32H38N2O3S calculated value C68.29, H6.81, N4.98, O8.53, S11.40；Measured value: C68.11,
H6.75, N4.86, O8.59, S11.61.
Embodiment 13
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
10.95 grams of (46mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 8.11 grams of (48mmol) glutaryl chlorine, 13.78 grams
(53mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL trimethylbenzene stir rapidly, after 85 DEG C of reaction 1h, are added 3.82
Gram (46mmol) formaldehyde continues after 85 DEG C of reaction 1h, is down to room temperature, 10.11 grams of (316mmol) sulphur of addition and 0.27 gram
(2.11mmol) iodine is warming up to 180 DEG C of reaction 1h.To after reaction, be evaporated under reduced pressure a small amount of water for removing solvent and generation, and
The shielding phenol product of structure shown in title is obtained by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 2.11-2.81 (6H), 4.21 (2H), 5.32 (1H), 6.44
(1H), 6.50-7.37 (12H)；
13C NMR (75MHz, CDCl3): δ 21.2,29.6,32.2,34.6,35.4,43.0,114.4,116.0,119.1,
120.6,121.6,124.3,126.6,127.0,130.2,133.8,136.5,141.1,153.5,166.3,196.9；
C38H40N2O3S2Calculated value C71.66, H6.33, N4.40, O7.54, S10.07；Measured value C71.59, H6.28,
N4.49, O7.51, S10.10.
Embodiment 14
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
21.66 grams of (91mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 12.55 grams of (89mmol) malonyl chlorides, 6.62 grams
(36mmol) 4-aminodiphenylamine, 0.62 gram of (4.51mmol) potassium carbonate and 150mL isopropanol stir rapidly, anti-at 80 DEG C
Answer 3h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and obtains final screen by column chromatography for separation
Cover phenol product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (36H), 3.98 (4H), 5.32 (1H), 6.80-7.26 (13H), 7.55
(1H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,52.1,104.6,116.6,117.7,119.3,121.8,
124.6,126.2,129.45,136.5,142.8,146.1,153.5,156.9,186.8；
C46H56N2O6S2Calculated value C69.31, H7.08, N3.51, O12.04, S8.05；Calculated value C69.25, H7.01,
N3.57, O12.01, S7.99.
Embodiment 15
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
8.57 grams of (36mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 26.68 grams of (92mmol) 1,2- glycol ester glutaric acids,
13.06 grams of (71mmol) 4-aminodiphenylamines and 150mL toluene stir rapidly, in 90 DEG C of reaction 4h.To after reaction,
Vacuum distillation removes a small amount of water of solvent and generation, and obtains final shielding phenol product by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (12H), 1.54 (6H), 2.04 (4H), 2.29-2.67 (8H), 4.23
(4H), 5.32 (1H), 6.97-7.26 (9H), 7.45 (1H), 7.48 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 20.9,21.3,29.6,31.98,33.9,34.6,34.9,43.0,62.0,
114.3,115.9,119.3,121.8,126.2,129.5,132.3,136.5,137.5,146.1,153.5,171.6,
173.5,196.9；
C38H48N2O7S calculated value C67.43, H7.15, N4.14, O16.55, S4.74；Calculated value C67.53, H7.19,
N4.08, O16.47, S4.76.
Embodiment 16
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
18.56 grams of (78mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 11.21 grams of (92mmol) succinic acid, 11.23 grams
(32mmol) N- phenyl-N '-[4- (phenyl amino) phenyl]-Isosorbide-5-Nitrae-phenylenediamine and 150mL toluene stir rapidly, anti-at 100 DEG C
Answer 3h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and obtains final screen by column chromatography for separation
Cover phenol product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36-1.54 (36H), 2.89-3.19 (8H), 5.32 (2H), 6.80-7.35
(22H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.4,35.5,37.8,93.8,116.6,122.5,126.2,
127.6,129.2,141.9,142.8,143.3,15.7,173.2,196.9；
C60H69N3O6S2Calculated value C72.62, H7.01, N4.23, O9.67, S6.46；Measured value C72.65, H7.07,
N4.26, O9.61, S6.42.
Embodiment 17
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
47.16 grams of (45mmol) polyisobutene mercapto-phenols (manufacture of embodiment 1) of addition, 5.11 grams of (51mmol) succinic anhydrides, 9.75
Gram (53mmol) 4-aminodiphenylamine, 0.86 gram of (8.15mmol) sodium carbonate and 150mL benzene stir rapidly, react at 80 DEG C
2.5h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and obtains final screen by column chromatography for separation
Cover phenol product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 0.88,0.99,1.02,1.40,1.41,1.46,1.52,1.64,1.68,
1.92,2.21-2.29,2.57,2.74,4.86,6.97,7.00,7.02,7.26,7.35,7.55；13C NMR (75MHz,
CDCl3): δ 23.9,24.9,25.4,28.2,30.1,34.5,34.5,35.4,38.4,43.6,51.1,116.0,117.7,
119.4,121.8,126.7,129.5,133.6,142.8,146.1,154.5,173.3.
Embodiment 18
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
29.34 grams of (28mmol) polyisobutene mercapto-phenols (manufacture of embodiment 1) of addition, 2.91 grams of (35mmol) Adipoyl Chlorides, 6.24
Gram (24mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine, 0.34 gram of (3.2mmol) sodium carbonate and 150mL benzene stir rapidly, 60
DEG C reaction 2h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and is obtained finally by column chromatography for separation
Shielding phenol product.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 0.82,0.99,1.02,1.40,1.46,1.52,1.60,1.68,1.92,
2.21-2.29,2.59,2.74,4.86,6.80,6.97,7.02,7.17,7.26,7.55；13C NMR (75MHz, CDCl3): δ
23.9,25.0,25.4,28.2,30.1,34.5,35.3,38.4,43.6,48.6,51.1,116.6,119.4,121.8,
125.2,126.8,127.3,129.5,133.6,142.8,143.3,146.1,154.5,173.3.
Comparative example 1
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
20.23 grams of (85mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 7.22 grams of (87mmol) formaldehyde, 14.37 grams (85mmol)
Diphenylamines and 150mL methanol stir rapidly, in 60 DEG C of reaction 2h.To which after reaction, vacuum distillation removes solvent and generation
A small amount of water, and final shielding phenol product is obtained by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 5.21 (2H), 5.32 (1H), 6.99 (6H), 7.17 (2H),
7.27(4H)；13C NMR (75MHz, CDCl3): δ 29.6,34.6,55.2,120.4,123.3,125.9,126.2,129.2,
136.6,150.0,153.5；C27H33NOS calculated value C77.28, H7.93, N3.34, O3.81, S7.64；Measured value: C77.22,
H7.89, N3.31, O3.83, S7.67.
Comparative example 2
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
10.71 grams of (52mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 1.89 grams of (63mmol) formaldehyde, 17.42 grams (65mmol)
N- (1,3- dimethylbutyl)-N'- diphenyl-para-phenylene diamine and 150mL methanol stir rapidly, in 70 DEG C of reaction 4h.Wait react knot
Shu Hou, vacuum distillation remove a small amount of water of solvent and generation, and obtain final shielding phenol product by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 0.80 (6H), 1.11 (3H), 1.29 (1H), 1.36 (18H), 3.45 (1H),
4.53 (2H), 5.32 (2H), 6.97-7.07 (9H), 7.26 (2H), 7.55 (1H)；13C NMR (75MHz, CDCl3): δ 17.9,
22.40,24.6,30.4,34.3,45.7,54.5,56.7,116.6,120.4,121.8,125.9,128.9,129.5,
135.6,146.1,153.5,154.8；C33H46N2O calculated value C81.43, H9.53, N5.76, O3.29；Measured value: C81.38,
H9.51, N5.79, O3.31.
Comparative example 3
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
9.24 grams of (33mmol) 2,6- di-t-butyl -4- (3- mercaptopropyi) phenol of addition, 3.07 grams of (37mmol) formaldehyde, 11.71 grams
(45mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL benzene stir rapidly, in 80 DEG C of reaction 4h.To after reaction, subtract
A small amount of water of solvent and generation is distilled off in pressure, and obtains final shielding phenol product by column chromatography for separation.
Characterization of The Products data are as follows:
1H NMR (300MHz, CDCl3): δ 1.40 (18H), 1.99 (1H), 2.61-2.80 (6H), 4.63 (2H), 5.32
(1H), 6.97-7.02 (12H), 7.26 (4H), 7.55 (1H)；13C NMR (75MHz, CDCl3): δ 28.7,31.1,34.3,
35.7,54.1,117.1,119.4,123.3,124.8,129.2,131.8,136.0,142.8,144.9,146.1,151.9；
C36H44N2OS calculated value C78.22, H8.02, N5.07, O2.89, S5.80；Measured value: C78.27, H7.96, N4.98, O2.92,
S5.83。
Embodiment 19-35 and comparative example 4-8
Respectively by the shielding phenolic compounds of embodiment 2-18 and comparative example 1-3 according to the composition and ratio and lubricating oil of table 1
Base oil obtains the lubricant oil composite of embodiment 19-35 and the lubricant oil composite of comparative example 4-6 in 40 DEG C of mixing 2h.
In addition, antioxidant is mixed 2h at 40 DEG C with lube base oil by the composition and ratio of table 2, the lubrication of comparative example 7-10 is obtained
Fluid composition.Wherein, the gross mass based on a lubricant oil composite, the additive amount of antioxidant are 0.5 weight %, the lubrication
Oil base oil selects Shanghai Gaoqiao petrochemical industry II class hydrogenated base oil.In addition, using the base oil that antioxidant is not added as blank
Sample.
Table 1
| Lubricant oil composite | Antioxidant | Lube base oil | Antioxidant additive amount |
| Embodiment 19 | Embodiment 2 | II | 0.50% |
| Embodiment 20 | Embodiment 3 | II | 0.50% |
| Embodiment 21 | Embodiment 4 | II | 0.50% |
| Embodiment 22 | Embodiment 5 | II | 0.50% |
| Embodiment 23 | Embodiment 6 | II | 0.50% |
| Embodiment 24 | Embodiment 7 | II | 0.50% |
| Embodiment 25 | Embodiment 8 | II | 0.50% |
| Embodiment 26 | Embodiment 9 | II | 0.50% |
| Embodiment 27 | Embodiment 10 | II | 0.50% |
| Embodiment 28 | Embodiment 11 | II | 0.50% |
| Embodiment 29 | Embodiment 12 | II | 0.50% |
| Embodiment 30 | Embodiment 13 | II | 0.50% |
| Embodiment 31 | Embodiment 14 | II | 0.50% |
| Embodiment 32 | Embodiment 15 | II | 0.50% |
| Embodiment 33 | Embodiment 16 | II | 0.50% |
| Embodiment 34 | Embodiment 17 | II | 0.50% |
| Embodiment 35 | Embodiment 18 | II | 0.50% |
| Comparative example 4 | Comparative example 1 | II | 0.50% |
| Comparative example 5 | Comparative example 2 | II | 0.50% |
| Comparative example 6 | Comparative example 3 | II | 0.50% |
| Blank sample | - | II | - |
Table 2
Using the lubricant oil composite of embodiment 19-35, the lubricant oil composite of comparative example 4-10 and the blank sample as
Test specimen has carried out high-temperature oxidation resistance evaluation, and PDSC test temperature is 210 DEG C, and measurement result is as shown in table 3.
Table 3
Using the lubricant oil composite of embodiment 19-35, the lubricant oil composite of comparative example 4-10 and the blank sample as
Test specimen has carried out deposit and has generated rejection evaluation, and QZX experiment measurement result is as shown in table 4.
Table 4
| Lubricant oil composite | Sediment yield (mg) |
| Embodiment 22 | 13.6 |
| Embodiment 25 | 12.1 |
| Embodiment 29 | 11.2 |
| Embodiment 31 | 15.7 |
| Embodiment 34 | 6.3 |
| Embodiment 35 | 4.8 |
| Comparative example 4 | 19.5 |
| Comparative example 5 | 23.4 |
| Comparative example 6 | 20.8 |
| Comparative example 7 | 21.6 |
| Comparative example 8 | 25.6 |
| Comparative example 9 | 19.2 |
| Comparative example 10 | 18.5 |
| Blank sample | 32.8 |
Using the lubricant oil composite of embodiment 19-35, the lubricant oil composite of comparative example 4-10 and the blank sample as
Test specimen, has carried out rustless property evaluation, and BRT ball rust test measurement result is as shown in table 5.
Table 5
| Lubricant oil composite | Corrosion degree |
| Embodiment 22 | Slightly |
| Embodiment 25 | Slightly |
| Embodiment 29 | Slightly |
| Embodiment 31 | Moderate |
| Embodiment 34 | Slightly |
| Embodiment 35 | Slightly |
| Comparative example 4 | Moderate |
| Comparative example 5 | Moderate |
| Comparative example 6 | Moderate |
| Comparative example 7 | Moderate |
| Comparative example 8 | Moderate |
| Comparative example 9 | Moderate |
| Comparative example 10 | Moderate |
| Blank sample | Seriously |
Using the lubricant oil composite of embodiment 19-35, the lubricant oil composite of comparative example 4-10 and the blank sample as
Test specimen, has carried out inhibition viscosity build and acid value increases assessment of performance, and measurement result is as shown in table 6.
Table 6
| Lubricant oil composite | Viscosity build rate (%) | Acid value incrementss (mgKOHg-1) |
| Embodiment 19 | 25.6 | 2.631 |
| Embodiment 20 | 22.1 | 2.035 |
| Embodiment 21 | 20.4 | 1.967 |
| Embodiment 22 | 23.6 | 1.639 |
| Embodiment 23 | 18.4 | 2.004 |
| Embodiment 24 | 19.1 | 1.569 |
| Embodiment 25 | 24.7 | 1.812 |
| Embodiment 26 | 20.6 | 1.645 |
| Embodiment 27 | 19.3 | 1.996 |
| Embodiment 28 | 20.9 | 2.733 |
| Embodiment 29 | 25.2 | 2.317 |
| Embodiment 30 | 23.3 | 1.962 |
| Embodiment 31 | 20.8 | 2.775 |
| Embodiment 32 | 19.9 | 2.284 |
| Embodiment 33 | 24.1 | 1.965 |
| Embodiment 34 | 22.5 | 1.882 |
| Embodiment 35 | 20.7 | 2.337 |
| Comparative example 4 | 33.5 | 4.621 |
| Comparative example 5 | 27.5 | 3.482 |
| Comparative example 6 | 25.8 | 5.168 |
| Comparative example 7 | 27.6 | 2.953 |
| Comparative example 8 | 30.5 | 3.846 |
| Comparative example 9 | 28.1 | 5.429 |
| Comparative example 10 | 24.7 | 6.517 |
| Blank sample | 67.2 | 24.525 |
Although a specific embodiment of the invention is described in detail above in conjunction with the embodiments, need to refer to
Out, the scope of protection of the present invention is not limited by these specific embodiments, but by claims of annex Lai
It determines.Those skilled in the art can in the range of not departing from technical idea and purport of the invention to these embodiments into
Row change appropriate, and the embodiment after these changes is obviously also included within protection scope of the present invention.
Claims (14)
1. phenolic compounds is shielded shown in a kind of logical formula (I),
In logical formula (I), each group R is same or different to each other, and is each independently selected from hydrogen, C1-300Linear or branched alkyl group, general formula
(II) group shown in group shown in and logical formula (III), on condition that at least one group R is group shown in logical formula (II)；
Each group R' is same or different to each other, and is each independently selected from hydrogen and C1-20Linear or branched alkyl group,
In aforementioned each logical formula (II), (III) and (IV), group L, which is selected from, is optionally selected from C by one or more1-20Alkyl and C3-20Directly
The m+1 valence C that chain or the substituent group of branched heteroalkyl groups replace2To C19-mLinear or branched alkyl group is optionally selected from by one or more
C1-20Alkyl and C3-20The m+1 valence C that the substituent group of linear chain or branched chain miscellaneous alkyl replaces3To C19-mLinear chain or branched chain miscellaneous alkyl and base
GroupWherein each group L'1It is same or different to each other, respectively solely
On the spot it is selected from C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl, on condition that (1) each group L'1Each independently
It is divalent to m+1 valence, so that the groupGenerally it is in
It is now m+1 valence, and (2) whole group L'1The sum of atomicity be not more than 14, wherein each group L'1Each independently optionally into one
Step is selected from C by one or more1-20Alkyl and C3-20The substituent group of linear chain or branched chain miscellaneous alkyl replaces；Group L' is groupWherein group R " is selected from hydrogen, C1-20Alkyl and C3-20Linear chain or branched chain miscellaneous alkyl；Each group A it is mutually the same or
Difference is each independently selected from On condition that at least one group A is
M is 1 to 4 integer；Each group R2It is same or different to each other, is each independently selected from hydrogen, C1-20Linear or branched alkyl group, general formula
(IV) group shown in group shown in and logical formula (V)；Each group RbBe same or different to each other, be each independently selected from hydrogen and
C1-20Linear or branched alkyl group；Each group RcIt is same or different to each other, is each independently selected from hydrogen, C1-20Linear or branched alkyl group
And C1-20Linear or branched alkyl group oxygroup；Y is 0 to 3 integer；Z is 0 to 3 integer；The integer that n is 1 to 8；N' is 0 to 7
Integer, on condition that n'+n≤8；Each group RdIt is same or different to each other, is each independently selected from base shown in hydrogen and logical formula (V)
Group；Each cyclic groupIt is same or different to each other, is each independently selected from phenyl ring and naphthalene nucleus, wherein two adjacent rings
GroupIt optionally by additional S atom and bridges the N atoms of the two rings each other and forms phenthazine ring, and/
Or, two adjacent cyclic groupsOptionally pass through additional group each otherWith bridge the two rings
N atom and form 9,10- acridan ring,
In logical formula (V), each group A is same or different to each other, and is each independently selected from Wherein each group R is same or different to each other, and is each independently selected from hydrogen, C1-300Directly
Group shown in group shown in chain or branched alkyl, logical formula (II) and logical formula (III)；Each group R' is same or different to each other,
It is each independently selected from hydrogen and C1-20Linear or branched alkyl group；Two group R and a groupIt accounts for respectively
According to three positions of residue on phenyl ring；Group L, group R2, group Rb, group Rc, group Rd, cyclic groupAnd y,
N, z and m be respectively provided with meaning identical in logical formula (II),
Wherein, the linear chain or branched chain miscellaneous alkyl is selected from one or more groups-inside linear or branched alkyl group molecular structure
CH2The group and linear or branched alkyl group that the substituting group for being selected from one of-O- ,-S- and-NR'- is directly substituted and obtained divide
One or more group-CH inside minor structure <by substituting group-N < are directly substituted and the group of acquisition, wherein the shielding phenol
Compound at least one group R in its entire molecular structuredIt is hydrogen.
2. according to the shielding phenolic compounds of claim 1, which is characterized in that
Each group R is each independently selected from hydrogen, C1-10The polyene that linear or branched alkyl group or number-average molecular weight Mn are 300-3000
Group shown in group shown in alkyl, logical formula (II) and logical formula (III)；Each group R' is each independently selected from hydrogen and C1-4Directly
Chain or branched alkyl；Group L, which is selected from, is optionally selected from C by one or more1-20Linear or branched alkyl group, C6-20Aryl or combinations thereof
Group and C3-20The m+1 valence C that the substituent group of linear chain or branched chain miscellaneous alkyl replaces2To C19-mLinear or branched alkyl group, optionally by one or
It is multiple to be selected from C1-20Linear or branched alkyl group, C6-20Aryl or combinations thereof group and C3-20The substituent group of linear chain or branched chain miscellaneous alkyl takes
The m+1 valence C in generation3To C19-mLinear chain or branched chain miscellaneous alkyl and group
Each group L'1C is further optionally selected from by one or more each independently1-20Linear or branched alkyl group, C6-20Aryl or its group
Close group and C3-20The substituent group of linear chain or branched chain miscellaneous alkyl replaces；Group R " is selected from hydrogen, C1-20Linear or branched alkyl group and C3-20
Linear chain or branched chain miscellaneous alkyl；Two group R and a groupThree positions of residue on phenyl ring are occupied respectively
It sets；M is 1；Each group R2It is each independently selected from hydrogen, C1-10Group shown in linear or branched alkyl group and logical formula (IV)；Each group
RbIt is each independently selected from hydrogen and C1-10Linear or branched alkyl group；Each group RcIt is each independently selected from hydrogen, C1-10Linear chain or branched chain
Alkyl and C1-10Linear or branched alkyl group oxygroup；Y is 0 or 1；Z is 0 or 1；N is 1 or 2；N' is 0,1 or 2, n'+n=1 or n'+n
=2；Each group RdFor hydrogen；Each cyclic groupFor phenyl ring.
3. according to the shielding phenolic compounds of claim 1, which is characterized in that group R " is selected from hydrogen, C1-10Linear or branched alkyl group and
C3-10Linear chain or branched chain miscellaneous alkyl.
4. according to the shielding phenolic compounds of claim 1, which is characterized in that each group RcIn cyclic groupUpper nitrogen
The contraposition of atom.
5. shielding the manufacturing method of phenolic compounds described in one of Claims 1 to 4, including make phenolic compounds shown in logical formula (X)
With react in the presence of the polybasic carboxylic acid shown in general formula (A) of amine compounds shown in general formula (Y) or derivatives thereof
One step, optionally further include make the reaction product of the first step reacted with vulcanizing agent and/or with hydroformylation shown in general formula (Z)
The additional step of object reaction is closed,
In logical formula (X), each group R0It is same or different to each other, is each independently selected from hydrogen ,-SH and C1-300Linear chain or branched chain alkane
Base, on condition that at least one group R0It is-SH；Each group R' is same or different to each other, and is each independently selected from hydrogen and C1-20Straight chain
Or branched alkyl,
In general formula (Y), group R'2Selected from hydrogen, C1-20Linear or branched alkyl group and groupEach group RbThat
This is identical or different, is each independently selected from hydrogen and C1-20Linear or branched alkyl group；Each group RcIt is same or different to each other, respectively
Independently selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup；Y is 0 to 3 integer；Z is 0 to 3
Integer；The integer that n1 is 1 to 8；Each cyclic groupIt is same or different to each other, is each independently selected from phenyl ring and naphthalene
Ring,
In general formula (A), group RLSelected from optionally by one or more selected from C1-20Alkyl and C3-20Linear chain or branched chain miscellaneous alkyl takes
The m1 valence C replaced for base2To C20-m1Linear or branched alkyl group, optionally by one or more be selected from C1-20Alkyl and C3-20Straight chain or
The m1 valence C that the substituent group of branched heteroalkyl groups replaces3To C20-m1Linear chain or branched chain miscellaneous alkyl and groupEach group L'1It is same or different to each other, is each independently selected from
C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl, on condition that (1) each group L'1It is divalent each independently to m1
Valence, so that the groupIt is generally rendered as m1 valence, and
(2) whole group L'1The sum of atomicity be not more than 14, wherein each group L'1Each independently optionally further by one or more
It is a to be selected from C1-20Alkyl and C3-20The substituent group of linear chain or branched chain miscellaneous alkyl replaces, the integer that m1 is 2 to 5,
In general formula (Z), group R " is selected from hydrogen, C1-20Alkyl and C3-20Linear chain or branched chain miscellaneous alkyl,
Wherein, the linear chain or branched chain miscellaneous alkyl is selected from one or more groups-inside linear or branched alkyl group molecular structure
CH2The group and linear or branched alkyl group that the substituting group for being selected from one of-O- ,-S- and-NR'- is directly substituted and obtained divide
One or more group-CH inside minor structure <by substituting group-N < are directly substituted and the group of acquisition, and the derivative
Object is selected from the acid anhydrides of the polybasic carboxylic acid and the carboxylic acid halides of the polybasic carboxylic acid；
In the first step, phenolic compounds shown in the logical formula (X) rubs with amine compounds shown in the general formula (Y)
You are than being 1:0.1-10, phenolic compounds shown in the logical formula (X) and polybasic carboxylic acid shown in the general formula (A) or derivatives thereof
Molar ratio be 1:0.1-10, in the additional step, amine compounds shown in the general formula (Y) rub with the vulcanizing agent
, than being 1:1-10, the molar ratio of amine compounds shown in the general formula (Y) and aldehyde compound shown in the general formula (Z) is 1 for you:
0.1-10。
6. manufacturing method according to claim 5, which is characterized in that the vulcanizing agent is sulphur；Hydroformylation shown in general formula (Z)
Conjunction object is formaldehyde, is led in formula (X), each group R0It is each independently selected from hydrogen ,-SH and C1-10Linear or branched alkyl group or number are equal
Molecular weight Mn is the polyolefin-based of 300-3000；Each group R' is each independently selected from hydrogen and C1-4Linear or branched alkyl group, each base
Group RbIt is each independently selected from hydrogen and C1-10Linear or branched alkyl group；Each group RcIt is each independently selected from hydrogen, C1-10Straight chain or branch
Alkyl group and C1-10Linear or branched alkyl group oxygroup；Y is 0 or 1；Z is 0 or 1；N1 is 1 or 2；Each cyclic group
For phenyl ring；In general formula (A), group RLSelected from optionally by one or more selected from C1-20Linear or branched alkyl group, C6-20Aryl or
A combination thereof group and C3-20The m1 valence C that the substituent group of linear chain or branched chain miscellaneous alkyl replaces2To C20-m1Linear or branched alkyl group is appointed
Choosing is selected from C by one or more1-20Linear or branched alkyl group, C6-20Aryl or combinations thereof group and C3-20Linear chain or branched chain is miscellaneous
The m1 valence C that the substituent group of alkyl replaces3To C20-m1Linear chain or branched chain miscellaneous alkyl and groupEach group L'1Each independently optionally further by one or more
It is a to be selected from C1-20Linear or branched alkyl group, C6-20Aryl or combinations thereof group and C3-20The substituent group of linear chain or branched chain miscellaneous alkyl takes
Generation, m1 2, group R " are selected from hydrogen, C1-20Linear or branched alkyl group and C3-20Linear chain or branched chain miscellaneous alkyl.
7. manufacturing method according to claim 5, which is characterized in that each group RcIn cyclic groupUpper nitrogen is former
The contraposition of son.
8. manufacturing method according to claim 5, which is characterized in that group R " is selected from hydrogen, C1-10Linear or branched alkyl group and
C3-10Linear chain or branched chain miscellaneous alkyl.
9. manufacturing method according to claim 5, wherein in the first step, phenolate shown in the logical formula (X)
The molar ratio for closing amine compounds shown in object and the general formula (Y) is 1:0.5-5.0, phenolic compounds shown in the logical formula (X)
Molar ratio with polybasic carboxylic acid shown in the general formula (A) or derivatives thereof is 1:0.2-5.0, in the additional step, institute
The molar ratio for stating amine compounds shown in general formula (Y) and the vulcanizing agent is 1:1.2-6.0, amination shown in the general formula (Y)
The molar ratio for closing aldehyde compound shown in object and the general formula (Z) is 1:0.5-5.0.
10. manufacturing method according to claim 5, wherein in the first step, phenolate shown in the logical formula (X)
The molar ratio for closing amine compounds shown in object and the general formula (Y) is 1:0.8-2.0, phenolic compounds shown in the logical formula (X)
Molar ratio with polybasic carboxylic acid shown in the general formula (A) or derivatives thereof is 1:0.3-3.0, in the additional step, institute
The molar ratio for stating amine compounds shown in general formula (Y) and the vulcanizing agent is 1:1.5-3.0, amination shown in the general formula (Y)
The molar ratio for closing aldehyde compound shown in object and the general formula (Z) is 1:0.8-2.0.
11. according to shielding phenolic compounds described in one of Claims 1 to 4 or according to by described in claim 5~10
Purposes of the shielding phenolic compounds of manufacturing method manufacture as antioxidant.
12. a kind of lubricant oil composite, comprising lube base oil and according to shielding phenolate described in one of Claims 1 to 4
Close object or according to the shielding phenolic compounds by the manufacturing method manufacture described in one of claim 5~10 as antioxidant,
Wherein the antioxidant accounts for the 0.001-30 weight % of the lubricant oil composite total weight.
13. lubricant oil composite according to claim 12, which is characterized in that the antioxidant accounts for the lubricating oil composition
The 0.1-10 weight % of object total weight.
It is by by the shielding phenolic compounds and the profit 14. according to lubricant oil composite described in claim 12 or 13
Lubricant base oil mixing and manufacture.
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