CN105218420A - A kind ofly shield phenolic compound, its manufacture method and the application as oxidation inhibitor thereof - Google Patents

A kind ofly shield phenolic compound, its manufacture method and the application as oxidation inhibitor thereof Download PDF

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CN105218420A
CN105218420A CN201410245927.1A CN201410245927A CN105218420A CN 105218420 A CN105218420 A CN 105218420A CN 201410245927 A CN201410245927 A CN 201410245927A CN 105218420 A CN105218420 A CN 105218420A
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straight
branched alkyl
group
general formula
hydrogen
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CN105218420B (en
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苏朔
赵晓光
龙军
段庆华
周涵
武志强
李新华
赵毅
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The present invention relates to a kind of as shown in the formula the shielding phenolic compound shown in (I), its manufacture method and the application as oxidation inhibitor thereof,

Description

A kind ofly shield phenolic compound, its manufacture method and the application as oxidation inhibitor thereof
Technical field
The present invention relates to a kind of novel shielding phenolic compound.Specifically, the present invention relates to a kind of shielding phenolic compound containing sulphur and arylamine, its manufacture method and the application as oxidation inhibitor thereof.
Background technology
The oxidation stability of oil product is one of very important index of oil property.Such as, almost for all lubricating oil products, all oxidation inhibitor must be added, to increase the service life.And along with the fast development of Hyundai Motor, mechanical industry, the power of engine and mechanical means improves constantly, and the working temperature of lubricating oil raises further, and problem of oxidation is more outstanding.Meanwhile, quality of lubrication oil grade improves constantly, and requires that lubricating oil extends the drain period further, and this just proposes requirements at the higher level to the high-temperature oxidation stability of lubricating oil product.
In order to tackle these requirements of prior art, technician is devoted to develop the more excellent novel cpd of antioxidant property, to improve the oxidation stability of oil product always.US Patent No. 5304314 discloses and is a kind ofly suitable as the sulfur-bearing and the phenolic compound of arylamine that oxidation inhibitor uses.U.S. Patent application US2006/0189824A1 discloses a kind of shielding phenolic compound containing secondary aromatic amine being suitable as oxidation inhibitor and using.Canadian Patent CA1219584 discloses and is a kind ofly suitable as the sulfur-bearing and the shielding phenolic compound of three grades of arylamine that oxidation inhibitor uses.But still there is room for improvement in the compound of these prior aries on high-temperature oxidation resistance.
Therefore, current present situation is, still needs a kind of novel compound, and it shows the high-temperature oxidation resistance compared with prior art significantly improved.
Summary of the invention
The present inventor passes through diligent research on the basis of existing technology, find a kind of novel shielding phenolic compound, and found further, by using this shielding phenolic compound as oxidation inhibitor, just can solve the foregoing problems that prior art exists, and this completes the present invention.
Specifically, the present invention relates to the content of following aspect.
1. the shielding phenolic compound shown in general formula (I),
In general formula (I), each radicals R is same to each other or different to each other, and is selected from hydrogen, C independently of one another 1-300straight or branched alkyl (preferred C 1-10what straight or branched alkyl or number-average molecular weight Mn were 300-3000 is polyolefin-based), the group shown in the group shown in general formula (II) and general formula (III), prerequisite is at least one radicals R is the group shown in general formula (II); Each radicals R ' be same to each other or different to each other, be selected from hydrogen and C independently of one another 1-20straight or branched alkyl (is preferably selected from hydrogen and C independently of one another 1-4straight or branched alkyl),
In aforementioned each general formula (II), (III) and (IV), group L is selected from and is optionally selected from C by one or more 1-20alkyl (preferred C 1-20straight or branched alkyl, C 6-20aryl or its combination group) and C 3-20the m+1 valency C that the substituting group that straight or branched mixes alkyl replaces 2-20straight or branched alkyl and be optionally selected from C by one or more 1-20alkyl (preferred C 1-20straight or branched alkyl, C 6-20aryl or its combination group) and C 3-20the m+1 valency C that the substituting group that straight or branched mixes alkyl replaces 3-20straight or branched is mixed alkyl; Group L ' be group wherein radicals R " is selected from hydrogen, C 1-20alkyl (preferred C 1-20straight or branched alkyl) and C 3-20straight or branched is mixed alkyl, is preferably selected from hydrogen, C 1-10straight or branched alkyl and C 3-10straight or branched is mixed alkyl; Each group A is same to each other or different to each other, and is selected from independently of one another with (wherein, each radicals R is same to each other or different to each other, and is selected from hydrogen, C independently of one another 1-300straight or branched alkyl (preferred C 1-10what straight or branched alkyl or number-average molecular weight Mn were 300-3000 is polyolefin-based), the group shown in the group shown in general formula (II) and general formula (III) (is preferably selected from hydrogen and C independently of one another 1-300straight or branched alkyl); Each radicals R ' be same to each other or different to each other, be selected from hydrogen and C independently of one another 1-20straight or branched alkyl (is preferably selected from hydrogen and C independently of one another 1-4straight or branched alkyl); Two radicals R and group-S-occupy residue three positions on phenyl ring respectively), to be at least one group A be prerequisite m is the integer (preferably 1) of 1 to 4; Each radicals R 2be same to each other or different to each other, be selected from hydrogen, C independently of one another 1-20straight or branched alkyl, the group shown in general formula (IV) and the group shown in logical formula V (are preferably selected from hydrogen, C independently of one another 1-10group shown in straight or branched alkyl and general formula (IV)); Each radicals R bbe same to each other or different to each other, be selected from hydrogen and C independently of one another 1-20straight or branched alkyl (is preferably selected from hydrogen and C independently of one another 1-10straight or branched alkyl); Each radicals R cbe same to each other or different to each other, be selected from hydrogen, C independently of one another 1-20straight or branched alkyl and C 1-20straight or branched alkyl oxy (is preferably selected from hydrogen, C independently of one another 1-10straight or branched alkyl and C 1-10straight or branched alkyl oxy, is more preferably in cyclic group the contraposition of upper nitrogen-atoms); Y is the integer (preferably 0 or 1) of 0 to 3; Z is the integer (preferably 0 or 1) of 0 to 3; N is the integer (preferably 1 or 2) of 1 to 8; N' is the integer (preferably 0,1 or 2) of 0 to 7, and prerequisite is n'+n≤8 (preferred n'+n=1 or n'+n=2); Each radicals R dbe same to each other or different to each other, be selected from the group (preferred hydrogen) shown in hydrogen and logical formula V independently of one another; Each cyclic group be same to each other or different to each other, be selected from phenyl ring and naphthalene nucleus (preferred phenyl ring) independently of one another, two wherein adjacent cyclic groups thiodiphenylamine ring is formed each other optionally through the atom N of additional S atom and these two rings of bridge joint, and/or, two adjacent cyclic groups each other optionally through additional group (wherein radicals R " is selected from hydrogen, C 1-20alkyl (preferred C 1-20straight or branched alkyl) and C 3-20straight or branched is mixed alkyl, is preferably selected from hydrogen and C 1-10straight or branched alkyl) and these two rings of bridge joint atom N and form 9,10-acridan ring,
In logical formula V, each group A is same to each other or different to each other, and is selected from independently of one another with wherein each radicals R is same to each other or different to each other, and is selected from hydrogen, C independently of one another 1-300straight or branched alkyl (preferred C 1-10what straight or branched alkyl or number-average molecular weight Mn were 300-3000 is polyolefin-based), the group shown in the group shown in general formula (II) and general formula (III) (is preferably selected from hydrogen and C independently of one another 1-300straight or branched alkyl); Each radicals R ' be same to each other or different to each other, be selected from hydrogen and C independently of one another 1-20straight or branched alkyl (is preferably selected from hydrogen and C independently of one another 1-4straight or branched alkyl); Two radicals R and group-S-occupy residue three positions on phenyl ring respectively; Group L, radicals R 2, radicals R b, radicals R c, radicals R d, cyclic group and y, n, z have the implication identical with general formula (II) respectively with m,
Wherein, described straight or branched alkyl of mixing is selected from one or more (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH of straight or branched alkyl molecule inside configuration 2-(R' is H or C to be selected from-O-,-S-and-NR'- 1-4straight or branched alkyl) one of alternative group directly substitute and obtain group and straight or branched alkyl molecule inside configuration one or more (such as 1 to 3,1 to 2 or 1) replaced group of group-CH<-N< directly substitute and obtain group, wherein this shielding phenolic compound has a radicals R at least in its whole molecular structure dhydrogen.
2., according to the shielding phenolic compound described in any preceding aspect, be selected from following particular compound or the mixture of its arbitrary proportion:
3. one kind shields the manufacture method of phenolic compound, comprise the first step that the amine compound shown in the phenolic compound shown in general formula (X) and general formula (Y) is reacted under the existence of the multi-halogenated compounds shown in general formula (A), optional also comprise the additional step reaction product of described first step and vulcanizing agent (preferred sulphur) being reacted and/or reacts with the aldehyde cpd (preferred formaldehyde) shown in general formula (Z)
In general formula (X), each radicals R 0be same to each other or different to each other, be selected from hydrogen ,-SH and C independently of one another 1-300straight or branched alkyl (preferred C 1-10straight or branched alkyl or number-average molecular weight Mn are the polyolefin-based of 300-3000), prerequisite is at least one radicals R 0-SH; Each radicals R ' be same to each other or different to each other, be selected from hydrogen and C independently of one another 1-20straight or branched alkyl (is preferably selected from hydrogen and C independently of one another 1-4straight or branched alkyl),
In general formula (Y), radicals R ' 2be selected from hydrogen, C 1-20straight or branched alkyl and group each radicals R bbe same to each other or different to each other, be selected from hydrogen and C independently of one another 1-20straight or branched alkyl (is preferably selected from hydrogen and C independently of one another 1-10straight or branched alkyl); Each radicals R cbe same to each other or different to each other, be selected from hydrogen, C independently of one another 1-20straight or branched alkyl and C 1-20straight or branched alkyl oxy (is preferably selected from hydrogen, C independently of one another 1-10straight or branched alkyl and C 1-10straight or branched alkyl oxy, is more preferably in cyclic group the contraposition of upper nitrogen-atoms); Y is the integer (preferably 0 or 1) of 0 to 3; Z is the integer (preferably 0 or 1) of 0 to 3; N1 is the integer (preferably 1 or 2) of 1 to 8; Each cyclic group be same to each other or different to each other, be selected from phenyl ring and naphthalene nucleus (preferred phenyl ring) independently of one another,
In general formula (A), radicals R halobe selected from and be optionally selected from C by one or more 1-20alkyl (preferred C 1-20straight or branched alkyl, C 6-20aryl or its combination group) and C 3-20the m1 valency C that the substituting group that straight or branched mixes alkyl replaces 2-20straight or branched alkyl and be optionally selected from C by one or more 1-20alkyl (preferred C 1-20straight or branched alkyl, C 6-20aryl or its combination group) and C 3-20the m1 valency C that the substituting group that straight or branched mixes alkyl replaces 3-20straight or branched is mixed alkyl, and group Halo is halogen, and m1 is the integer (preferably 2) of 2 to 5,
In general formula (Z), radicals R " is selected from hydrogen, C 1-20alkyl (preferred C 1-20straight or branched alkyl) and C 3-20straight or branched is mixed alkyl, is preferably selected from hydrogen, C 1-10straight or branched alkyl and C 3-10straight or branched is mixed alkyl,
Wherein, described straight or branched alkyl of mixing is selected from one or more (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH of straight or branched alkyl molecule inside configuration 2-(R' is H or C to be selected from-O-,-S-and-NR'- 1-4straight or branched alkyl) one of alternative group directly substitute and obtain group and straight or branched alkyl molecule inside configuration one or more (such as 1 to 3,1 to 2 or 1) replaced group of group-CH<-N< directly substitute and obtain group.
4. according to the manufacture method described in any preceding aspect, wherein in described first step, the mol ratio of the amine compound shown in the phenolic compound shown in described general formula (X) and described general formula (Y) is 1:0.1-10, preferred 1:0.5-5.0, more preferably 1:0.8-2.0, the mol ratio of the multi-halogenated compounds shown in the phenolic compound shown in described general formula (X) and described general formula (A) is 1:0.1-10, preferred 1:0.2-5.0, more preferably 1:0.3-3.0, in described additional step, the mol ratio of the amine compound shown in described general formula (Y) and described vulcanizing agent is 1:1-10, preferred 1:1.2-6.0, more preferably 1:1.5-3.0, the mol ratio of the aldehyde cpd shown in the amine compound shown in described general formula (Y) and described general formula (Z) is 1:0.1-10, preferred 1:0.5-5.0, more preferably 1:0.8-2.0.
5. according to the shielding phenolic compound described in any preceding aspect or according to the purposes of the shielding phenolic compound manufactured by the manufacture method described in any preceding aspect as oxidation inhibitor.
6. a lubricating oil composition, comprise lubricant base and according to the shielding phenolic compound described in any preceding aspect or according to the shielding phenolic compound manufactured by manufacture method described in any preceding aspect as oxidation inhibitor, wherein said oxidation inhibitor accounts for the 0.001-30 % by weight of described lubricating oil composition gross weight, preferred 0.1-10 % by weight.
7., according to the lubricating oil composition described in any preceding aspect, manufacture by described shielding phenolic compound is mixed with described lubricant base.
Technique effect
According to shielding phenolic compound of the present invention, phosphorus element-containing and metallic element, not easily do not produce ash content, is environmentally friendly oxidation inhibitor.
According to shielding phenolic compound of the present invention, with the Compound Phase ratio of prior art, demonstrate the high-temperature oxidation resistance (thermostability) significantly improved, effectively can improve (high temperature) oxidation stability of such as lubricating oil.
According to shielding phenolic compound of the present invention, in a preferred embodiment, while demonstrating excellent high-temperature oxidation resistance, also show excellent rustless property further.This is not available for prior art compound.
According to shielding phenolic compound of the present invention, in a preferred embodiment, while demonstrating excellent high-temperature oxidation resistance, also show excellent cleansing performance (namely settling generates rejection) further.This is not available for prior art compound.
According to shielding phenolic compound of the present invention, in a preferred embodiment, while demonstrating excellent high-temperature oxidation resistance, also show the performance that excellent suppression viscosity increases and suppresses acid number increase further.This is not available for prior art compound.
Embodiment
Below the specific embodiment of the present invention is described in detail, but it is pointed out that protection scope of the present invention not by the restriction of these embodiments, but determined by claims of annex.
All publications, patent application, patent and other reference that this specification sheets is mentioned all draw in this for reference.Unless otherwise defined, all technology that this specification sheets is used and scientific terminology all have the implication that those skilled in the art's routine is understood.In case of conflict, be as the criterion with the definition of this specification sheets.
When this specification sheets comes derived materials, material, method, step, device or parts etc. with prefix " as well known to those skilled in the art ", " prior art " or its similar term, the object that this prefix is derived contain that the routine of this area when the application proposes uses those, but also comprising and being also of little use at present, but will becoming art-recognized for being applicable to those of similar object.
In the context of the present specification, except the content clearly stated, do not mention anything should or item all be directly suitable for known in the art those and without the need to carrying out any change.And, any embodiment described herein all freely can combine with one or more other embodiments described herein, the technical scheme formed therefrom or technological thought are all considered as a part for the original open or original description of the present invention, and should not be considered to be the fresh content not disclosing or expected herein, unless those skilled in the art think that this combination is obviously irrational.
In the context of the present invention, state " halogen " and refer to fluorine, chlorine, bromine or iodine.
In the context of the present invention, term " alkyl " has the conventional known implication in this area, comprise straight or branched alkyl, straight or branched thiazolinyl, straight or branched alkynyl, cycloalkyl, cycloalkenyl group, cycloalkynyl radical, aryl or its combination group, wherein preferred straight or branched alkyl, straight or branched thiazolinyl, aryl or its combination group.As described alkyl, specifically such as C can be enumerated 1-20alkyl, comprises C 1-20straight or branched alkyl, C 2-20straight or branched thiazolinyl, C 2-20straight or branched alkynyl, C 3-20cycloalkyl, C 3-20cycloalkenyl group, C 3-20cycloalkynyl radical, C 6-20aryl or its combination group, wherein preferred C 1-20straight or branched alkyl, C 6-20aryl or its combination group.As described combination group, such as one or more C can be enumerated 1-20straight or branched alkyl (preferred one or more C 1-10straight or branched alkyl) and one or more C 6-20the group that aryl (preferred one or more phenyl or naphthyl) is obtained by Direct Bonding.As described combination group, such as one or many C can be enumerated further 1-10straight or branched alkyl phenyl, phenyl C 1-10straight or branched alkyl or one or many C 1-10straight or branched alkyl phenyl C 1-10straight or branched alkyl etc., wherein more preferably C 1-10straight or branched alkyl phenyl (such as tert-butyl-phenyl), phenyl C 1-10straight or branched alkyl (such as benzyl) or C 1-10straight or branched alkyl phenyl C 1-10straight or branched alkyl (such as t-butylbenzyl).
In the context of the present invention, so-called " straight or branched mix alkyl ", refers to one or more (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH of straight or branched alkyl molecule inside configuration (not comprising the end of main chain or any side chain in this alkyl molecule structure) 2-(R' is H or C to be selected from-O-,-S-and-NR'- 1-4straight or branched alkyl) one of alternative group directly substitute and obtain group or straight or branched alkyl molecule inside configuration (not comprising the end of main chain or any side chain in this alkyl molecule structure) one or more (such as 1 to 3,1 to 2 or 1) replaced group of group-CH<-N< directly substitute and obtain group.As described alternative group, preferably-O-or-S-, more preferably-S-.It is apparent that from the angle of structural stability, when existing multiple, not Direct Bonding between these alternative groups.In addition, although the carbonatoms of this straight or branched alkyl is because group-CH 2-or the replaced and corresponding minimizing of group-CH<, but easy in order to state, before still substituting with this, the carbonatoms of described straight or branched alkyl refers to described straight or branched and to mix the carbonatoms of alkyl.To mix alkyl as described straight or branched, concrete example, C 4straight chained alkyl such as (group in formula indicated by arrow is not in molecular structure inside, but is in the end of main chain) is directly substituted acquisition-CH by an alternative group-O- 2-O-CH 2-CH 3or-CH 2-CH 2-O-CH 3, be referred to as C 4linear heteroalkyl group.Or, C 4branched-chain alkyl such as (group in formula indicated by arrow is not in molecular structure inside, but is in the end of main chain and side chain) is directly substituted will obtain by an alternative group-N< be referred to as C 4branched heteroalkyl groups.According to the present invention, to mix alkyl as described straight or branched, such as can enumerate C 3-20straight or branched is mixed alkyl, wherein preferred C 3-10straight or branched is mixed alkyl or C 3-6straight or branched is mixed alkyl.
In the context of the present specification, phraseology " numeral+valency+group " or its similar term refer to the group obtained after the hydrogen atom of the quantity representated by foundation structure (such as chain, ring or its combination etc.) this numeral of removing corresponding to this group, preferably refer to the group obtained after the hydrogen atom of the quantity representated by this numeral of carbon atom (preferred saturated carbon atom and/or non-same carbon atom) removing contained by this structure.For example, the group that " 3 valency straight or branched alkyl " refers to removing 3 hydrogen atoms from straight or branched alkane (the basic chain namely corresponding to this straight or branched alkyl) and obtain, " divalent straight or branched mix alkyl " then refers to and mixes alkane (preferably from the carbon atom contained by this assorted alkane from straight or branched, or further, from non-same carbon atom) removing 2 hydrogen atoms and the group obtained.
When clearly not indicating, all percentage ratios, number, ratio etc. mentioned in this specification sheets are all benchmark with weight, unless do not met the routine understanding of those skilled in the art when being benchmark with weight.
In the context of the present specification, in case of no particular description, number-average molecular weight Mn is measured by gel permeation chromatography (GPC).
In the context of the present specification, in case of no particular description, the condition determination of any gel permeation chromatography (GPC) of relating to or GPC spectrogram is: instrument: Waters, US waters2695 type gel osmoticing chromatogram analysis instrument; Moving phase adopts tetrahydrofuran (THF), and flow velocity is 1mL/min, and chromatogram column temperature is 35 DEG C, elution time 40min, and sample quality mark is 0.16%-0.20%.
According to the present invention, relate to the shielding phenolic compound shown in a kind of general formula (I).
According to the present invention, in general formula (I), when existing multiple, each radicals R is same to each other or different to each other, and is selected from hydrogen, C independently of one another 1-300straight or branched alkyl, the group shown in the group shown in general formula (II) and general formula (III), prerequisite is at least one radicals R is the group shown in general formula (II).
According to the present invention, in general formula (I), as described C 1-300straight or branched alkyl, such as can enumerate C 1-20straight or branched alkyl (preferred C 1-10straight or branched alkyl, more preferably C 1-4straight or branched alkyl) or polyolefin-based.As described polyolefin-based, specifically such as can enumerate number-average molecular weight Mn is the polyolefin-based of 300-3000.Now, as described polyolefin-based number-average molecular weight Mn, preferred 500-2000, more preferably 500-1500.According to the present invention, described polyolefin-based (substantially) is saturated (being rendered as chain alkyl structure), but depend on the difference of polyolefinic kind as starting raw material or this polyolefin production process, also may containing a small amount of olefinic double bond (such as residual or introducing in polyolefin manufacturing process) in this polyolefin-based molecular chain, but this does not affect the realization of effect of the present invention, the present invention also has no intention to carry out clearly this amount, and the present invention still polyolefin-basedly to classify as this " alkyl ".
According to an embodiment of the invention, in general formula (I), there is multiple radicals R, one of them radicals R is the group shown in general formula (II), and one in two other radicals R is described polyolefin-based, and another is hydrogen, C 1-20straight or branched alkyl (preferred C 1-10straight or branched alkyl) or the group shown in general formula (III).
According to an embodiment of the invention, in general formula (I), when radicals R be described polyolefin-based time, this is polyolefin-based is preferably placed at the contraposition of phenolic hydroxyl group in general formula (I).
According to the present invention, in general formula (I), when existing multiple, each radicals R ' be same to each other or different to each other, be selected from hydrogen and C independently of one another 1-20straight or branched alkyl.
According to an embodiment of the invention, in general formula (I), when existing multiple, each radicals R ' be same to each other or different to each other, be selected from hydrogen and C independently of one another 1-4straight or branched alkyl.
According to the present invention, in general formula (II), group L is selected from the optional m+1 valency C replaced 2-20straight or branched alkyl and the optional m+1 valency C replaced 3-20straight or branched is mixed alkyl, is preferably selected from the optional m+1 valency C replaced 2-10straight or branched alkyl and the optional m+1 valency C replaced 3-10straight or branched is mixed alkyl, is more preferably selected from the optional m+1 valency C replaced 2-6straight or branched alkyl and the optional m+1 valency C replaced 3-6straight or branched is mixed alkyl, is more preferably selected from the optional m+1 valency C replaced 2-6straight or branched alkyl.According to the present invention, in general formula (II), in the definition of group L, what is called optionally replaces, and refers to and is optionally selected from C by one or more (such as 1 to 4,1 to 3,1 to 2 or 1) 1-20alkyl and C 3-20straight or branched mix alkyl substituting group replace.As described substituting group, preferred C 1-20straight or branched alkyl, C 6-20aryl or its combination group.As described C 1-20straight or branched alkyl, preferred C 1-10straight or branched alkyl, more preferably C 1-6straight or branched alkyl, such as methyl or ethyl.
According to the present invention, in general formula (II), m is the integer of 1 to 4, preferably 1.
According to the present invention, in general formula (II), each group A is same to each other or different to each other, be selected from the group shown in the group shown in following general formula (II-1) and following general formula (II-2) independently of one another, prerequisite is at least one group A is the group shown in following general formula (II-1).
According to the present invention, in general formula (II-1), radicals R 2be selected from hydrogen, C 1-20straight or branched alkyl, the group shown in general formula (IV) and the group shown in logical formula V.
According to an embodiment of the invention, in general formula (II-1), radicals R 2be selected from hydrogen, C 1-10group shown in straight or branched alkyl and general formula (IV).
According to the present invention, in general formula (II-1), when existing multiple, each radicals R bbe same to each other or different to each other, be selected from hydrogen and C independently of one another 1-20straight or branched alkyl, is preferably selected from hydrogen and C independently of one another 1-10straight or branched alkyl.
According to an embodiment of the invention, in general formula (II-1), when existing multiple, each radicals R bbe same to each other or different to each other, be selected from hydrogen and C independently of one another 1-6straight or branched alkyl, preferred hydrogen.
According to the present invention, in general formula (II-1), when existing multiple, each radicals R cbe same to each other or different to each other, be selected from hydrogen, C independently of one another 1-20straight or branched alkyl and C 1-20straight or branched alkyl oxy.
According to an embodiment of the invention, in general formula (II-1), when existing multiple, each radicals R cbe same to each other or different to each other, be selected from hydrogen, C independently of one another 1-10straight or branched alkyl and C 1-10straight or branched alkyl oxy.
According to an embodiment of the invention, in general formula (II-1), a preferably radicals R cbe in cyclic group upper atom N is (that is, with radicals R dthe atom N of bonding) contraposition.
According to the present invention, in general formula (II-1), y is the integer of 0 to 3, preferably 0 or 1.
According to the present invention, in general formula (II-1), z is the integer of 0 to 3, preferably 0 or 1.
According to the present invention, in general formula (II-1), n is the integer of 1 to 8, preferably 1 or 2.
According to the present invention, in general formula (II-1), when existing multiple, each radicals R dbe same to each other or different to each other, be selected from the group shown in hydrogen and logical formula V independently of one another, preferred hydrogen.
According to the present invention, in general formula (II-1), when existing multiple, each cyclic group (being rendered as divalent group in the inside configuration of general formula (II-1)) is same to each other or different to each other, be selected from phenyl ring independently of one another and (be preferably rendered as 1 in the inside configuration of general formula (II-1), 4-phenylene) and naphthalene nucleus (be preferably rendered as 1 in the inside configuration of general formula (II-1), 4-or 2,6-naphthylidene), wherein preferred phenyl ring.
According to an embodiment of the invention, in general formula (II-1), two adjacent cyclic groups the atom N of additional S atom (not showing in structural formula) and these two rings of bridge joint can be passed through each other (that is, with radicals R dthe atom N of bonding) and form thiodiphenylamine ring, namely
According to this embodiment of the present invention, in general formula (II-1), there is plural cyclic group time, as long as wherein at least two (adjacent) cyclic groups form described thiodiphenylamine ring, there is no need to require these cyclic groups in each all with another adjacent cyclic group form this thiodiphenylamine ring.
According to an embodiment of the invention, in general formula (II-1), two adjacent cyclic groups each other can by additional group the atom N of (not showing in structural formula) and these two rings of bridge joint is (that is, with radicals R dthe atom N of bonding) and form 9,10-acridan ring, namely
According to the present invention, at group in, radicals R " is selected from hydrogen, C 1-20alkyl (preferred C 1-20straight or branched alkyl) and C 3-20straight or branched is mixed alkyl.
According to an embodiment of the invention, at group in, radicals R " is selected from hydrogen and C 1-10straight or branched alkyl.
According to this embodiment of the present invention, in general formula (II-1), there is plural cyclic group time, as long as wherein at least two (adjacent) cyclic groups form described 9,10-acridan rings, there is no need to require these cyclic groups in each all with another adjacent cyclic group form this 9,10-acridan ring.
According to the present invention, in general formula (II-2), when existing multiple, each radicals R is same to each other or different to each other, and is selected from hydrogen, C independently of one another 1-300straight or branched alkyl, the group shown in the group shown in general formula (II) and general formula (III).
According to the present invention, in general formula (II-2), two radicals R and group-S-occupy residue three positions on phenyl ring respectively.
According to an embodiment of the invention, in general formula (II-2), when existing multiple, each radicals R is same to each other or different to each other, and is selected from hydrogen and C independently of one another 1-300straight or branched alkyl.
According to the present invention, in general formula (II-2), as described C 1-300straight or branched alkyl, such as can enumerate C 1-20straight or branched alkyl (preferred C 1-10straight or branched alkyl, more preferably C 1-4straight or branched alkyl) or polyolefin-based.As described polyolefin-based, specifically such as can enumerate number-average molecular weight Mn is the polyolefin-based of 300-3000.Now, as described polyolefin-based number-average molecular weight Mn, preferred 500-2000, more preferably 500-1500.According to the present invention, described polyolefin-based (substantially) is saturated (being rendered as chain alkyl structure), but depend on the difference of polyolefinic kind as starting raw material or this polyolefin production process, also may containing a small amount of olefinic double bond (such as residual or introducing in polyolefin manufacturing process) in this polyolefin-based molecular chain, but this does not affect the realization of effect of the present invention, the present invention also has no intention to carry out clearly this amount, and the present invention still polyolefin-basedly to classify as this " alkyl ".
According to an embodiment of the invention, in general formula (II-2), there is multiple radicals R, one of them radicals R is described polyolefin-based, and another is hydrogen or C 1-20straight or branched alkyl (preferred C 1-10straight or branched alkyl, more preferably C 1-4straight or branched alkyl).
According to an embodiment of the invention, in general formula (II-2), when radicals R be described polyolefin-based time, this is polyolefin-based 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 existing multiple, each radicals R ' be same to each other or different to each other, be selected from hydrogen and C independently of one another 1-20straight or branched alkyl.
According to an embodiment of the invention, in general formula (II-2), when existing multiple, each radicals R ' be same to each other or different to each other, be selected from hydrogen and C independently of one another 1-4straight or branched alkyl.
According to the present invention, in general formula (III), group L ' be group
According to the present invention, in general formula (III), group L ' definition in, radicals R " is selected from hydrogen, C 1-20alkyl (preferred C 1-20straight or branched alkyl) and C 3-20straight or branched is mixed alkyl.
According to an embodiment of the invention, in general formula (III), group L ' definition in, radicals R " is selected from hydrogen, C 1-10straight or branched alkyl and C 3-10straight or branched is mixed alkyl, is preferably selected from hydrogen and C 1-10straight or branched alkyl.
According to the present invention, in general formula (III), radicals R 2be selected from hydrogen, C 1-20straight or branched alkyl, the group shown in general formula (IV) and the group shown in logical formula V.
According to an embodiment of the invention, in general formula (III), radicals R 2be selected from hydrogen, C 1-10group shown in straight or branched alkyl and general formula (IV).
According to the present invention, in general formula (III), when existing multiple, each radicals R bbe same to each other or different to each other, be selected from hydrogen and C independently of one another 1-20straight or branched alkyl, is preferably selected from hydrogen and C independently of one another 1-10straight or branched alkyl.
According to an embodiment of the invention, in general formula (III), when existing multiple, each radicals R bbe same to each other or different to each other, be selected from hydrogen and C independently of one another 1-6straight or branched alkyl, preferred hydrogen.
According to the present invention, in general formula (III), when existing multiple, each radicals R cbe same to each other or different to each other, be selected from hydrogen, C independently of one another 1-20straight or branched alkyl and C 1-20straight or branched alkyl oxy.
According to an embodiment of the invention, in general formula (III), when existing multiple, each radicals R cbe same to each other or different to each other, be selected from hydrogen, C independently of one another 1-10straight or branched alkyl and C 1-10straight or branched alkyl oxy.
According to an embodiment of the invention, in general formula (III), a preferably radicals R cbe in cyclic group upper atom N is (that is, with radicals R dthe atom N of bonding) contraposition.
According to the present invention, in general formula (III), y is the integer of 0 to 3, preferably 0 or 1.
According to the present invention, in general formula (III), z is the integer of 0 to 3, preferably 0 or 1.
According to the present invention, in general formula (III), n is the integer of 1 to 8, preferably 1 or 2.
According to the present invention, in general formula (III), when existing multiple, each radicals R dbe same to each other or different to each other, be selected from the group shown in hydrogen and logical formula V independently of one another, preferred hydrogen.
According to the present invention, in general formula (III), when existing multiple, each cyclic group (being rendered as divalent group in the inside configuration of general formula (III)) is same to each other or different to each other, be selected from phenyl ring independently of one another and (be preferably rendered as 1 in the inside configuration of general formula (III), 4-phenylene) and naphthalene nucleus (be preferably rendered as 1 in the inside configuration of general formula (III), 4-or 2,6-naphthylidene), wherein preferred phenyl ring.
According to an embodiment of the invention, in general formula (III), two adjacent cyclic groups the atom N of additional S atom (not showing in structural formula) and these two rings of bridge joint can be passed through each other (that is, with radicals R dthe atom N of bonding) and form thiodiphenylamine ring, namely
According to this embodiment of the present invention, in general formula (III), there is plural cyclic group time, as long as wherein at least two (adjacent) cyclic groups form described thiodiphenylamine ring, there is no need to require these cyclic groups in each all with another adjacent cyclic group form this thiodiphenylamine ring.
According to an embodiment of the invention, in general formula (III), two adjacent cyclic groups each other can by additional group the atom N of (not showing in structural formula) and these two rings of bridge joint is (that is, with radicals R dthe atom N of bonding) and form 9,10-acridan ring, namely
According to the present invention, at group in, radicals R " is selected from hydrogen, C 1-20alkyl (preferred C 1-20straight or branched alkyl) and C 3-20straight or branched is mixed alkyl.
According to an embodiment of the invention, at group in, radicals R " is selected from hydrogen and C 1-10straight or branched alkyl.
According to this embodiment of the present invention, in general formula (III), there is plural cyclic group time, as long as wherein at least two (adjacent) cyclic groups form described 9,10-acridan rings, there is no need to require these cyclic groups in each all with another adjacent cyclic group form this 9,10-acridan ring.
According to the present invention, in general formula (IV), when existing multiple, each radicals R bbe same to each other or different to each other, be selected from hydrogen and C independently of one another 1-20straight or branched alkyl, is preferably selected from hydrogen and C independently of one another 1-10straight or branched alkyl.
According to an embodiment of the invention, in general formula (IV), when existing multiple, each radicals R bbe same to each other or different to each other, be selected from hydrogen and C independently of one another 1-6straight or branched alkyl, preferred hydrogen.
According to the present invention, in general formula (IV), when existing multiple, each radicals R cbe same to each other or different to each other, be selected from hydrogen, C independently of one another 1-20straight or branched alkyl and C 1-20straight or branched alkyl oxy.
According to an embodiment of the invention, in general formula (IV), when existing multiple, each radicals R cbe same to each other or different to each other, be selected from hydrogen, C independently of one another 1-10straight or branched alkyl and C 1-10straight or branched alkyl oxy.
According to an embodiment of the invention, in general formula (IV), a preferably radicals R cbe in cyclic group upper atom N is (that is, with radicals R dthe atom N of bonding) contraposition.
According to the present invention, in general formula (IV), y is the integer of 0 to 3, preferably 0 or 1.
According to the present invention, in general formula (IV), z is the integer of 0 to 3, preferably 0 or 1.
According to the present invention, in general formula (IV), n' is the integer of 0 to 7, preferably 0,1 or 2, and prerequisite is n'+n≤8.According to an embodiment of the invention, n'+n=1 or n'+n=2.At this, n is identical with the definition in aforementioned formula (II-1).
According to the present invention, in general formula (IV), when existing multiple, each radicals R dbe same to each other or different to each other, be selected from the group shown in hydrogen and logical formula V independently of one another, preferred hydrogen.
According to the present invention, in general formula (IV), when existing multiple, each cyclic group (being rendered as divalent group in the inside configuration of general formula (IV)) is same to each other or different to each other, be selected from phenyl ring independently of one another and (be preferably rendered as 1 in the inside configuration of general formula (IV), 4-phenylene) and naphthalene nucleus (be preferably rendered as 1 in the inside configuration of general formula (IV), 4-or 2,6-naphthylidene), wherein preferred phenyl ring.
According to an embodiment of the invention, in general formula (IV), two adjacent cyclic groups the atom N of additional S atom (not showing in structural formula) and these two rings of bridge joint can be passed through each other (that is, with radicals R dthe atom N of bonding) and form thiodiphenylamine ring, namely
According to this embodiment of the present invention, in general formula (IV), there is plural cyclic group time, as long as wherein at least two (adjacent) cyclic groups form described thiodiphenylamine ring, there is no need to require these cyclic groups in each all with another adjacent cyclic group form this thiodiphenylamine ring.
According to an embodiment of the invention, in general formula (IV), two adjacent cyclic groups each other can by additional group the atom N of (not showing in structural formula) and these two rings of bridge joint is (that is, with radicals R dthe atom N of bonding) and form 9,10-acridan ring, namely
According to the present invention, at group in, radicals R " is selected from hydrogen, C 1-20alkyl (preferred C 1-20straight or branched alkyl) and C 3-20straight or branched is mixed alkyl.
According to an embodiment of the invention, at group in, radicals R " is selected from hydrogen and C 1-10straight or branched alkyl.
According to this embodiment of the present invention, in general formula (IV), there is plural cyclic group time, as long as wherein at least two (adjacent) cyclic groups form described 9,10-acridan rings, there is no need to require these cyclic groups in each all with another adjacent cyclic group form this 9,10-acridan ring.
According to the present invention, in logical formula V, group L is selected from the optional m+1 valency C replaced 2-20straight or branched alkyl and the optional m+1 valency C replaced 3-20straight or branched is mixed alkyl, is preferably selected from the optional m+1 valency C replaced 2-10straight or branched alkyl and the optional m+1 valency C replaced 3-10straight or branched is mixed alkyl, is more preferably selected from the optional m+1 valency C replaced 2-6straight or branched alkyl and the optional m+1 valency C replaced 3-6straight or branched is mixed alkyl, is more preferably selected from the optional m+1 valency C replaced 2-6straight or branched alkyl.According to the present invention, in logical formula V, in the definition of group L, what is called optionally replaces, and refers to and is optionally selected from C by one or more (such as 1 to 4,1 to 3,1 to 2 or 1) 1-20alkyl and C 3-20straight or branched mix alkyl substituting group replace.As described substituting group, preferred C 1-20straight or branched alkyl, C 6-20aryl or its combination group.As described C 1-20straight or branched alkyl, preferred C 1-10straight or branched alkyl, more preferably C 1-6straight or branched alkyl, such as methyl or ethyl.
According to the present invention, in logical formula V, m is the integer of 1 to 4, preferably 1.
According to the present invention, in logical formula V, each group A is same to each other or different to each other, and is selected from the group shown in the group shown in following general formula (V-1) and following general formula (V-2) independently of one another.
According to the present invention, in general formula (V-1), radicals R 2be selected from hydrogen, C 1-20straight or branched alkyl, the group shown in general formula (IV) and the group shown in logical formula V.
According to an embodiment of the invention, in general formula (V-1), radicals R 2be selected from hydrogen, C 1-10group shown in straight or branched alkyl and general formula (IV).
According to the present invention, in general formula (V-1), when existing multiple, each radicals R bbe same to each other or different to each other, be selected from hydrogen and C independently of one another 1-20straight or branched alkyl, is preferably selected from hydrogen and C independently of one another 1-10straight or branched alkyl.
According to an embodiment of the invention, in general formula (V-1), when existing multiple, each radicals R bbe same to each other or different to each other, be selected from hydrogen and C independently of one another 1-6straight or branched alkyl, preferred hydrogen.
According to the present invention, in general formula (V-1), when existing multiple, each radicals R cbe same to each other or different to each other, be selected from hydrogen, C independently of one another 1-20straight or branched alkyl and C 1-20straight or branched alkyl oxy.
According to an embodiment of the invention, in general formula (V-1), when existing multiple, each radicals R cbe same to each other or different to each other, be selected from hydrogen, C independently of one another 1-10straight or branched alkyl and C 1-10straight or branched alkyl oxy.
According to an embodiment of the invention, in general formula (V-1), a preferably radicals R cbe in cyclic group upper atom N is (that is, with radicals R dthe atom N of bonding) contraposition.
According to the present invention, in general formula (V-1), y is the integer of 0 to 3, preferably 0 or 1.
According to the present invention, in general formula (V-1), z is the integer of 0 to 3, preferably 0 or 1.
According to the present invention, in general formula (V-1), n is the integer of 1 to 8, preferably 1 or 2.
According to the present invention, in general formula (V-1), when existing multiple, each radicals R dbe same to each other or different to each other, be selected from the group shown in hydrogen and logical formula V independently of one another, preferred hydrogen.
According to the present invention, in general formula (V-1), when existing multiple, each cyclic group (being rendered as divalent group in the inside configuration of general formula (V-1)) is same to each other or different to each other, be selected from phenyl ring independently of one another and (be preferably rendered as 1 in the inside configuration of general formula (V-1), 4-phenylene) and naphthalene nucleus (be preferably rendered as 1 in the inside configuration of general formula (V-1), 4-or 2,6-naphthylidene), wherein preferred phenyl ring.
According to an embodiment of the invention, in general formula (V-1), two adjacent cyclic groups the atom N of additional S atom (not showing in structural formula) and these two rings of bridge joint can be passed through each other (that is, with radicals R dthe atom N of bonding) and form thiodiphenylamine ring, namely
According to this embodiment of the present invention, in general formula (V-1), there is plural cyclic group time, as long as wherein at least two (adjacent) cyclic groups form described thiodiphenylamine ring, there is no need to require these cyclic groups in each all with another adjacent cyclic group form this thiodiphenylamine ring.
According to an embodiment of the invention, in general formula (V-1), two adjacent cyclic groups each other can by additional group the atom N of (not showing in structural formula) and these two rings of bridge joint is (that is, with radicals R dthe atom N of bonding) and form 9,10-acridan ring, namely
According to the present invention, at group in, radicals R " is selected from hydrogen, C 1-20alkyl (preferred C 1-20straight or branched alkyl) and C 3-20straight or branched is mixed alkyl.
According to an embodiment of the invention, at group in, radicals R " is selected from hydrogen and C 1-10straight or branched alkyl.
According to this embodiment of the present invention, in general formula (V-1), there is plural cyclic group time, as long as wherein at least two (adjacent) cyclic groups form described 9,10-acridan rings, there is no need to require these cyclic groups in each all with another adjacent cyclic group form this 9,10-acridan ring.
According to the present invention, in general formula (V-2), when existing multiple, each radicals R is same to each other or different to each other, and is selected from hydrogen, C independently of one another 1-300straight or branched alkyl, the group shown in the group shown in general formula (II) and general formula (III).
According to the present invention, in general formula (V-2), two radicals R and group-S-occupy residue three positions on phenyl ring respectively.
According to an embodiment of the invention, in general formula (V-2), when existing multiple, each radicals R is same to each other or different to each other, and is selected from hydrogen and C independently of one another 1-300straight or branched alkyl.
According to the present invention, in general formula (V-2), as described C 1-300straight or branched alkyl, such as can enumerate C 1-20straight or branched alkyl (preferred C 1-10straight or branched alkyl, more preferably C 1-4straight or branched alkyl) or polyolefin-based.As described polyolefin-based, specifically such as can enumerate number-average molecular weight Mn is the polyolefin-based of 300-3000.Now, as described polyolefin-based number-average molecular weight Mn, preferred 500-2000, more preferably 500-1500.According to the present invention, described polyolefin-based (substantially) is saturated (being rendered as chain alkyl structure), but depend on the difference of polyolefinic kind as starting raw material or this polyolefin production process, also may containing a small amount of olefinic double bond (such as residual or introducing in polyolefin manufacturing process) in this polyolefin-based molecular chain, but this does not affect the realization of effect of the present invention, the present invention also has no intention to carry out clearly this amount, and the present invention still polyolefin-basedly to classify as this " alkyl ".
According to an embodiment of the invention, in general formula (V-2), there is multiple radicals R, one of them radicals R is described polyolefin-based, and another is hydrogen or C 1-20straight or branched alkyl (preferred C 1-10straight or branched alkyl, more preferably C 1-4straight or branched alkyl).
According to an embodiment of the invention, in general formula (V-2), when radicals R be described polyolefin-based time, this is polyolefin-based 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 existing multiple, each radicals R ' be same to each other or different to each other, be selected from hydrogen and C independently of one another 1-20straight or branched alkyl.
According to an embodiment of the invention, in general formula (V-2), when existing multiple, each radicals R ' be same to each other or different to each other, be selected from hydrogen and C independently of one another 1-4straight or branched alkyl.
According to the present invention, described shielding phenolic compound defines as previously mentioned (such as general formula (I) or further as shown in general formula (II-2) or general formula (V-2)), must comprise structure as phenol unit.According to the present invention one preferred embodiment, described shielding phenolic compound comprises 5 at the most, 3 at the most, at the most 2 or 1 described phenol unit at the most in its whole molecular structure.
According to the present invention, described shielding phenolic compound defines as previously mentioned (such as general formula (II-1) or further as Suo Shi general formula (III), general formula (IV) or general formula (V-1)), must comprise structure as amine unit.According to the present invention one preferred embodiment, described shielding phenolic compound comprises 15 at the most, 10 at the most, at the most 8, at the most 6, at the most 4, at the most 3 or 2 described amine units at the most in its whole molecular structure.
According to the present invention, described shielding phenolic compound preferably has (preferably 2,3 or 4 or more a) radicals R at least in its whole molecular structure dhydrogen.Specifically, described shielding phenolic compound preferably in its whole molecular structure containing be selected from following hydrogen amine unit (1), hydrogen amine unit (2) and hydrogen amine unit (3) at least one.In these hydrogen amine units, cyclic group " identical with the definition in general formula (II-1) with radicals R.
According to a preferred embodiment of the present invention, described shielding phenolic compound contains hydrogen amine unit (1) described at least one in its whole molecular structure.
Specifically, to shield phenolic compound for example, this compound comprises 2 described phenol units and 2 described amine units in its whole molecular structure, and comprises 1 described hydrogen amine unit (1).
According to the present invention, as described shielding phenolic compound, such as can enumerate following compound or the mixture of its arbitrary proportion, but the present invention is not limited to this.
According to the present invention, shielding phenolic compound shown in aforementioned formula (I) can exist with the form of single one (pure) compound, manufactures or use, can exist with the form of wherein two or more mixture (in any proportion), manufacture or use, this does not affect the realization of effect of the present invention yet.
According to the present invention, the shielding phenolic compound shown in aforementioned formula (I) can be manufactured by following manufacture method, but is sometimes not limited to this.
According to this manufacture method of the present invention, comprise the first step that the amine compound shown in the phenolic compound shown in general formula (X) and general formula (Y) is reacted under the existence of the multi-halogenated compounds shown in general formula (A).
According to the present invention, in general formula (X), when existing multiple, each radicals R 0be same to each other or different to each other, be selected from hydrogen ,-SH and C independently of one another 1-300straight or branched alkyl, prerequisite is at least one radicals R 0-SH.
According to the present invention, in general formula (X), as described C 1-300straight or branched alkyl, such as can enumerate C 1-20straight or branched alkyl (preferred C 1-10straight or branched alkyl, more preferably C 1-4straight or branched alkyl) or polyolefin-based.As described polyolefin-based, specifically such as can enumerate number-average molecular weight Mn is the polyolefin-based of 300-3000.Now, as described polyolefin-based number-average molecular weight Mn, preferred 500-2000, more preferably 500-1500.According to the present invention, described polyolefin-based (substantially) is saturated (being rendered as chain alkyl structure), but depend on the difference of polyolefinic kind as starting raw material or this polyolefin production process, also may containing a small amount of olefinic double bond (such as residual or introducing in polyolefin manufacturing process) in this polyolefin-based molecular chain, but this does not affect the realization of effect of the present invention, the present invention also has no intention to carry out clearly this amount, and the present invention still polyolefin-basedly to classify as this " alkyl ".
According to an embodiment of the invention, in general formula (X), there is multiple radicals R 0, one of them radicals R 0-SH, two other radicals R 0in one be described polyolefin-based, another is hydrogen or C 1-20straight or branched alkyl (preferred C 1-10straight or branched alkyl).
According to an embodiment of the invention, in general formula (X), in radicals R 0be described polyolefin-based time, this is polyolefin-based is preferably placed at the contraposition of phenolic hydroxyl group in general formula (X).
According to the present invention, in general formula (X), when existing multiple, each radicals R ' be same to each other or different to each other, be selected from hydrogen and C independently of one another 1-20straight or branched alkyl.
According to an embodiment of the invention, in general formula (X), when existing multiple, each radicals R ' be same to each other or different to each other, be selected from hydrogen and C independently of one another 1-4straight or branched alkyl.
According to the present invention, as the phenolic compound shown in described general formula (X), can directly use commercially available product, also can be manufactured by the conventional known method in this area, not special restriction.In addition, as the phenolic compound shown in described general formula (X), only can use one, also can two or more combinationally use.
According to the present invention, as the manufacture method of the phenolic compound shown in described general formula (X), such as can enumerate under catalyst for alkylation reaction exists, (number-average molecular weight Mn is 300-3000 to make the phenolic compound shown in general formula (X') and polyolefine, preferred 500-2000, more preferably 500-1500) there is the method for alkylated reaction.
According to the present invention, in general formula (X'), radicals R ' there is the implication identical with aforementioned formula (X).
According to the present invention, the middle existence of general formula (X') three radicals R ' 0, one of them radicals R ' 0-SH, another radicals R ' 0h, the 3rd radicals R ' 0hydrogen ,-SH or C 1-20straight or branched alkyl (preferred C 1-10straight or branched alkyl).
According to an embodiment of the invention, in general formula (X'), at least one radicals R ' 0h, and this radicals R ' 0be in the contraposition of phenolic hydroxyl group in general formula (X').
According to the present invention, described polyolefine is preferably by ethene, propylene or C 4-C 10the homopolymerization of alpha-olefin or the polyolefine obtained by two or more copolymerization in these alkene.As described C 4-C 10alpha-olefin, such as can enumerate n-butene, iso-butylene, positive amylene, n-hexylene, positive octene and positive decene.
According to the present invention, in these polyolefine, at least the polymer chain of 20wt% (preferably at least 50wt%, more preferably at least 70wt%) contains olefinic double bond at its end.This olefinic double bond is generally exist with the form of the vinylidene of high reaction activity or vinyl.
According to the present invention, as described polyolefine, more preferably polybutene.Except as otherwise noted, term as used herein " polybutene " broadly comprises the polymkeric substance obtained by 1-butylene or isobutylene homopolymerisation, and by two or three in 1-butylene, 2-butylene and iso-butylene by copolymerization and obtained polymkeric substance.Other olefinic component of negligible quantity also may be contained in the commercially available prod of this base polymer, but this does not affect enforcement of the present invention.
According to the present invention, as described polyolefine, preferred polyisobutene (PIB) further, also referred to as high-activity polyisobutylene.In this kind of polyisobutene, at least total terminal ethylenic double bond of 20wt% (preferably at least 50wt%, more preferably at least 70wt%) is provided by methyl vinylidene.
As described catalyst for alkylation reaction, such as can enumerate Lewis acid catalyst, such as be selected from aluminum chloride, boron trifluoride, tin tetrachloride, titanium tetrabromide, boron trifluoride phenol, boron trifluoride alcohol complex and boron trifluoride ether complex one or more, wherein preferably boron trifluoride ethyl ether complex and/or boron trifluoride methanol complex compound.These catalyst for alkylation reaction can directly use commercially available product.
According to the present invention, in described alkylated reaction, mol ratio between described polyolefine, the phenolic compound shown in described general formula (X'), described catalyst for alkylation reaction can be such as 1:1-3:0.1-0.5, preferred 1:1.5-3:0.1-0.4, most preferably 1:1.5-3:0.2-0.4, but be sometimes not limited to this.
According to the present invention, the reaction times of described alkylated reaction is such as 0.5h-10h, preferred 1h-8h, most preferably 3h-5h, but is sometimes not limited to this.
According to the present invention, the temperature of reaction of described alkylated reaction is such as 0 DEG C-200 DEG C, preferably 10 DEG C-150 DEG C, most preferably 20 DEG C-100 DEG C, but is sometimes not limited to this.
According to the present invention, described alkylated reaction can carry out in the presence of the solvent.As described solvent, such as C can be enumerated 6-10alkane (such as hexane, heptane, octane, nonane or decane etc.).Wherein, preferably use hexane and heptane, more preferably use hexane.
According to the present invention, after described alkylated reaction terminates, remove catalyst for alkylation reaction, unreacted reactant and the solvent that may use by conventional methods from the reaction mixture finally obtained after, namely obtain the phenolic compound shown in described general formula (X).
According to the present invention, in general formula (Y), radicals R ' 2be selected from hydrogen, C 1-20straight or branched alkyl and group
According to the present invention, in general formula (Y), when existing multiple, each radicals R bbe same to each other or different to each other, be selected from hydrogen and C independently of one another 1-20straight or branched alkyl, is preferably selected from hydrogen and C independently of one another 1-10straight or branched alkyl.
According to an embodiment of the invention, in general formula (Y), when existing multiple, each radicals R bbe same to each other or different to each other, be selected from hydrogen and C independently of one another 1-6straight or branched alkyl, preferred hydrogen.
According to the present invention, in general formula (Y), when existing multiple, each radicals R cbe same to each other or different to each other, be selected from hydrogen, C independently of one another 1-20straight or branched alkyl and C 1-20straight or branched alkyl oxy.
According to an embodiment of the invention, in general formula (Y), when existing multiple, each radicals R cbe same to each other or different to each other, be selected from hydrogen, C independently of one another 1-10straight or branched alkyl and C 1-10straight or branched alkyl oxy.
According to an embodiment of the invention, in general formula (Y), a preferably radicals R cbe in cyclic group upper atom N is (that is, with radicals R dthe atom N of bonding) contraposition.
According to the present invention, in general formula (Y), y is the integer of 0 to 3, preferably 0 or 1.
According to the present invention, in general formula (Y), z is the integer of 0 to 3, preferably 0 or 1.
According to the present invention, in general formula (Y), n1 is the integer of 1 to 8, preferably 1 or 2.
According to the present invention, in general formula (Y), when existing multiple, each cyclic group (being rendered as divalent group in the inside configuration of general formula (Y)) is same to each other or different to each other, be selected from phenyl ring independently of one another and (be preferably rendered as 1 in the inside configuration of general formula (Y), 4-phenylene) and naphthalene nucleus (be preferably rendered as 1 in the inside configuration of general formula (Y), 4-or 2,6-naphthylidene), wherein preferred phenyl ring.
According to the present invention, as the amine compound shown in described general formula (Y), can directly use commercially available product, not special restriction.In addition, as the amine compound shown in described general formula (Y), only can use one, also can two or more combinationally use.
According to the present invention, in general formula (A), radicals R halobe selected from the optional m1 valency C replaced 2-20straight or branched alkyl and the optional m1 valency C replaced 3-20straight or branched is mixed alkyl, is preferably selected from the optional m1 valency C replaced 2-10straight or branched alkyl and the optional m1 valency C replaced 3-10straight or branched is mixed alkyl, is more preferably selected from the optional m1 valency C replaced 2-6straight or branched alkyl and the optional m1 valency C replaced 3-6straight or branched is mixed alkyl, is more preferably selected from the optional m1 valency C replaced 2-6straight or branched alkyl.
According to the present invention, in general formula (A), in radicals R halodefinition in, what is called optionally replaces, and refers to and is optionally selected from C by one or more (such as 1 to 4,1 to 3,1 to 2 or 1) 1-20alkyl and C 3-20straight or branched mix alkyl substituting group replace.As described substituting group, preferred C 1-20straight or branched alkyl, C 6-20aryl or its combination group.As described C 1-20straight or branched alkyl, preferred C 1-10straight or branched alkyl, more preferably C 1-6straight or branched alkyl, such as methyl or ethyl.
According to the present invention, in general formula (A), group Halo is halogen, comprises fluorine, chlorine, bromine and iodine, wherein preferred chlorine.
According to the present invention, in general formula (A), m1 is the integer of 2 to 5, preferably 2.
According to the present invention, as the multi-halogenated compounds shown in described general formula (A), only can use one, also can two or more combinationally use.
According to the present invention, in the manufacture method of described shielding phenolic compound, in described first step, the mol ratio of the amine compound shown in the phenolic compound shown in described general formula (X) and described general formula (Y) is generally 1:0.1-10, preferred 1:0.5-5.0, more preferably 1:0.8-2.0.
According to the present invention, in the manufacture method of described shielding phenolic compound, in described first step, the mol ratio of the multi-halogenated compounds shown in the phenolic compound shown in described general formula (X) and described general formula (A) is generally 1:0.1-10, preferred 1:0.2-5.0, more preferably 1:0.3-3.0.
According to the present invention, in the manufacture method of described shielding phenolic compound, described first step can carry out in the presence of the solvent.As described solvent, such as C can be enumerated 2-10aliphatic nitrile (such as acetonitrile etc.), C 6-20aromatic hydrocarbon (such as benzene,toluene,xylene and isopropyl benzene), C 6-10alkane (such as normal hexane, hexanaphthene and sherwood oil), C 1-6fatty alcohol (such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol and ethylene glycol), C 2-20halohydrocarbon (such as methylene dichloride, tetracol phenixin, chlorobenzene and 1,2-dichlorobenzene), C 3-10ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C 3-10acid amides (such as dimethyl formamide, N,N-DIMETHYLACETAMIDE and N-Methyl pyrrolidone) etc.As described solvent, preferred C 6-20aromatic hydrocarbon (such as benzene,toluene,xylene and isopropyl benzene), C 3-10ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C 3-10acid amides (such as dimethyl formamide, N,N-DIMETHYLACETAMIDE and N-Methyl pyrrolidone) etc.These solvents only can use one, also can two or more combinationally use.
According to the present invention, in the manufacture method of described shielding phenolic compound, in described first step, can not catalyzer be added, also can add catalyzer.As described catalyzer, such as basic catalyst can be enumerated.As described basic catalyst, alkali-metal oxyhydroxide such as sodium hydroxide and potassium hydroxide etc. such as can be enumerated, or alkali-metal salt of weak acid such as sodium-acetate, Potassium ethanoate, sodium carbonate, salt of wormwood, sodium bicarbonate and saleratus etc.These catalyzer only can use one, also can two or more combinationally use.As the consumption of described catalyzer, directly with reference to the conventional amount used of prior art, can be not particularly limited.
According to the present invention, in the manufacture method of described shielding phenolic compound, to reaction times of described first step, there is no particular limitation, but be generally 0.1h-48h, preferred 0.2-12h, most preferably 0.5-6h.
According to the present invention, in the manufacture method of described shielding phenolic compound, to the temperature of reaction of described first step, there is no particular limitation, but be generally 0-200 DEG C, preferred 20-180 DEG C, most preferably 60-120 DEG C.
According to the present invention, in the manufacture method of described shielding phenolic compound, after described first step terminates, after removing the volatile matter such as the solvent that may exist by the separation method (such as evaporation etc.) that routine is known from the reaction mixture (reaction mixture hereinafter referred to as first step) that this first step obtains, the reaction product of first step can be obtained.
According to an embodiment of the invention, the manufacture method of described shielding phenolic compound optionally also comprises the additional step (hereinafter referred to as additional step A) that the reaction product that makes described first step and vulcanizing agent react (forming thiodiphenylamine ring).
According to an embodiment of the invention, the manufacture method of described shielding phenolic compound optionally also comprises the additional step (hereinafter referred to as additional step B) that the reaction product that makes described first step and the aldehyde cpd shown in general formula (Z) react (forming 9,10-acridan ring).
According to the present invention, in general formula (Z), radicals R " is selected from hydrogen, C 1-20alkyl (preferred C 1-20straight or branched alkyl) and C 3-20straight or branched is mixed alkyl.
According to an embodiment of the invention, in general formula (Z), radicals R " is selected from hydrogen, C 1-10straight or branched alkyl and C 3-10straight or branched is mixed alkyl.
According to the present invention one preferred embodiment, in general formula (Z), radicals R " is selected from hydrogen and C 1-10straight or branched alkyl.
According to the present invention, as the aldehyde cpd shown in described general formula (Z), such as C can be enumerated 1-6fatty aldehyde and phenyl aldehyde.
According to an embodiment of the invention, as described C 1-6fatty aldehyde, such as can enumerate C 1-6straight or branched saturated aliphatic aldehyde, specifically such as acetaldehyde or formaldehyde, more preferably formaldehyde.As described formaldehyde, such as can use its aqueous solution, paraformaldehyde or paraformaldehyde form, be not particularly limited.
According to the present invention, in the manufacture method of described shielding phenolic compound, can only carry out described additional step A, also can only carry out described additional step B, also not only can carry out described additional step A but also carry out described additional step B.When not only carrying out described additional step A but also carry out described additional step B, to the precedence of described additional step A and described additional step B, there is no particular limitation, can first carry out described additional step A, described additional step B is carried out again after this additional step A terminates, or first carry out described additional step B, after this additional step B terminates, carry out described additional step A again.In addition, product (that is, from the reaction product of last additional step) separating step can be had between each additional step, also can there is no product separation step, be not particularly limited.
According to an embodiment of the invention, in the manufacture method of described shielding phenolic compound, described additional step A carries out after described first step terminates.Now, the reaction product of described first step is separated as previously mentioned from the reaction mixture of described first step.Or the reaction product of described first step also can without this separation, and directly be used for carrying out described additional step A with the form of the reaction mixture of described first step.Or described additional step A also can carry out after described additional step B terminates.When described additional step A carries out after described additional step B terminates, the reaction product of described additional step B is as described herein to be separated from the reaction mixture of described additional step B.Or the reaction product of described additional step B also can without this separation, and directly be used for carrying out described additional step A with the form of the reaction mixture of described additional step B.
According to an embodiment of the invention, in the manufacture method of described shielding phenolic compound, in described additional step A, as described vulcanizing agent, such as sulphur and sulfur dichloride etc. can be enumerated, wherein preferred sulphur.As described sulphur, such as sulphur or sublimed sulphur can be enumerated.
According to the present invention, in the manufacture method of described shielding phenolic compound, in described additional step A, the mol ratio of the amine compound shown in described general formula (Y) and described vulcanizing agent is generally 1:1-10, preferred 1:1.2-6.0, more preferably 1:1.5-3.0.
According to the present invention, in the manufacture method of described shielding phenolic compound, described additional step A can carry out in the presence of the solvent.As described solvent, such as C can be enumerated 2-10aliphatic nitrile (such as acetonitrile etc.), C 6-20aromatic hydrocarbon (such as benzene,toluene,xylene and isopropyl benzene), C 6-10alkane (such as normal hexane, hexanaphthene and sherwood oil), C 1-6fatty alcohol (such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol and ethylene glycol), C 2-20halohydrocarbon (such as methylene dichloride, tetracol phenixin, chlorobenzene and 1,2-dichlorobenzene), C 3-10ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C 3-10acid amides (such as dimethyl formamide, N,N-DIMETHYLACETAMIDE and N-Methyl pyrrolidone) etc.These solvents only can use one, also can two or more combinationally use.
According to the present invention, in the manufacture method of described shielding phenolic compound, described additional step A generally carries out in the presence of a catalyst.As described catalyzer, the prior art conventional catalyzer adopted for this purpose such as can be enumerated, specifically such as iodine.As the consumption of described catalyzer, directly with reference to the conventional amount used of prior art, can be not particularly limited.
According to the present invention, in the manufacture method of described shielding phenolic compound, to reaction times of described additional step A, there is no particular limitation, but be generally 0.1h-24h, preferred 0.2h-12h, most preferably 0.5h-4h.
According to the present invention, in the manufacture method of described shielding phenolic compound, to the temperature of reaction of described additional step A, there is no particular limitation, but be generally 60 DEG C-300 DEG C, preferably 120 DEG C-240 DEG C, most preferably 150 DEG C-200 DEG C.
According to the present invention, in the manufacture method of described shielding phenolic compound, after described additional step A terminates, after removing the volatile matter such as the solvent that may exist by the separation method (such as evaporation etc.) that routine is known from the reaction mixture that this additional step A obtains, the reaction product of additional step A can be obtained, or also without this separation, follow-up reactions steps (than additional step B as the aforementioned) can be directly used in.
According to an embodiment of the invention, in the manufacture method of described shielding phenolic compound, described additional step B carries out after described first step terminates.When described additional step B carries out after described first step terminates, the reaction product of described first step is separated as previously mentioned from the reaction mixture of described first step.Or the reaction product of described first step also can without this separation, and directly be used for carrying out described additional step B with the form of the reaction mixture of described first step.Or described additional step B also can carry out after described additional step A terminates.When described additional step B carries out after described additional step A terminates, the reaction product of described additional step A is as described herein to be separated from the reaction mixture of described additional step A.Or the reaction product of described additional step A also can without this separation, and directly be used for carrying out described additional step B with the form of the reaction mixture of described additional step A.
According to the present invention, in the manufacture method of described shielding phenolic compound, in described additional step B, the mol ratio of the aldehyde cpd shown in the amine compound shown in described general formula (Y) and described general formula (Z) is generally 1:0.1-10, preferred 1:0.5-5.0, more preferably 1:0.8-2.0.
According to the present invention, in the manufacture method of described shielding phenolic compound, described additional step B can carry out in the presence of the solvent.As described solvent, such as C can be enumerated 2-10aliphatic nitrile (such as acetonitrile etc.), C 6-20aromatic hydrocarbon (such as benzene,toluene,xylene and isopropyl benzene), C 6-10alkane (such as normal hexane, hexanaphthene and sherwood oil), C 1-6fatty alcohol (such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol and ethylene glycol), C 2-20halohydrocarbon (such as methylene dichloride, tetracol phenixin, chlorobenzene and 1,2-dichlorobenzene), C 3-10ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C 3-10acid amides (such as dimethyl formamide, N,N-DIMETHYLACETAMIDE and N-Methyl pyrrolidone) etc.These solvents only can use one, also can two or more combinationally use.
According to the present invention, in the manufacture method of described shielding phenolic compound, in described additional step B, can not catalyzer be added, also can add catalyzer.As described catalyzer, such as inorganic acid catalyst and organic acid catalyst can be enumerated.As described inorganic acid catalyst, such as hydrochloric acid, sulfuric acid and phosphoric acid etc. can be enumerated.As described organic acid catalyst, such as methylsulphonic acid, ethylsulfonic acid, thionamic acid and tosic acid etc. can be enumerated.As the consumption of described catalyzer, directly with reference to the conventional amount used of prior art, can be not particularly limited.
According to the present invention, in the manufacture method of described shielding phenolic compound, in the initial stage or the process of carrying out of described additional step B, the amine compound shown in described general formula (Y) can also be added as required further, the group shown in aforementioned formula (III) is formed thus while formation 9,10-acridan ring.Now, the mol ratio of the aldehyde cpd shown in the amine compound shown in described general formula (Y) and described general formula (Z) is generally 1:0.1-10, preferred 1:0.5-5.0, more preferably 1:0.8-2.0.
According to the present invention, in the manufacture method of described shielding phenolic compound, to reaction times of described additional step B, there is no particular limitation, but be generally 0.1h-24h, preferred 0.2h-12h, most preferably 0.5h-6h.
According to the present invention, in the manufacture method of described shielding phenolic compound, to the temperature of reaction of described additional step B, there is no particular limitation, but be generally 0 DEG C-250 DEG C, preferably 20 DEG C-180 DEG C, most preferably 60 DEG C-120 DEG C.
According to the present invention, in the manufacture method of described shielding phenolic compound, after described additional step B terminates, after removing the volatile matter such as the solvent that may exist by the separation method (such as evaporation etc.) that routine is known from the reaction mixture that this additional step B obtains, the reaction product of additional step B can be obtained, or also without this separation, follow-up reactions steps (than additional step A as the aforementioned) can be directly used in.
Prior art is it is known that aforementioned all reactions steps (comprising described first step, described additional step A and described additional step B) are generally carried out under the protection of inert gas atmosphere.As described rare gas element, such as can enumerate nitrogen and argon gas etc., be not particularly limited.
According to the present invention, in the manufacture method of described shielding phenolic compound, as the reaction product of the reaction product of described first step, the reaction product of described additional step A or described additional step B, can be single one shielding phenolic compound (such as the shielding phenolic compound shown in aforementioned formula (I)), also can be the mixture comprising multiple shielding phenolic compound.These reaction product are all desired by the present invention, and the difference of its existence form does not affect the realization of effect of the present invention.Therefore, without distinction these reaction product are all referred to as shielding phenolic compound of the present invention in this context.Given this, according to the present invention, do not exist and be further purified these reaction product, or from these reaction product, isolate the absolute necessity of shielding phenolic compound of a certain ad hoc structure further.Certainly, this purifying or separation are preferred sometimes for the further lifting of desired result of the present invention, but unrequired in the present invention.Even so, as described purifying or separation method, such as can enumerate, by the method such as column chromatography method or preparative chromatography, purifying or separation etc. be carried out to described reaction product.
According to an embodiment of the invention, also relate to the shielding phenolic compound manufactured according to the manufacture method of the aforesaid shielding phenolic compound of the present invention.
Shielding phenolic compound of the present invention, owing to showing excellent high-temperature oxidation resistance, is therefore particularly suitable as oxidation inhibitor and uses, especially as the lubricating oil composition of oxidation inhibitor for the manufacture of (high temperature) oxidation stability of expectation excellence.Given this, according to an embodiment of the invention, relate to a kind of lubricating oil composition, it comprises lubricant base and the aforesaid any shielding phenolic compound (or mixture of its arbitrary proportion) of the present invention.
According to the present invention, as described lubricant base, any lubricant base that this area routines such as mineral base oil, animal oil, vegetables oil or synthetic base oil use such as can be enumerated.As described mineral base oil, such as can enumerate the mineral base oil that viscosity index is greater than 80, or saturated hydrocarbon content massfraction is greater than 90% and the sulphur content massfraction mineral base oil that is less than 0.03%.As described synthetic base oil, such as polyolefine, synthetic ester, silicone oil and polyethers etc. can be enumerated.These lubricant bases only can use one, also can two or more combinationally use.
According to an embodiment of the invention, in described lubricating oil composition, described oxidation inhibitor accounts for the 0.001-30 % by weight of described lubricating oil composition gross weight, preferred 0.1-10 % by weight.
According to the present invention, described lubricating oil composition also optionally comprises other lubricating oil additives being selected from metal detergent, ashless dispersant, anti-friction composition, anti-wear agent, extreme pressure agent, viscosity index improver, metal corrosion inhibitor, rust-preventive agent, pour point depressant and kilfoam further.These other lubricating oil additives only can use one, also can two or more combinationally use, and its respective consumption with reference to the conventional amount used of prior art, can be not particularly limited.
According to the present invention, in order to manufacture described lubricating oil composition, aforesaid for the present invention shielding phenolic compound (or mixture of its arbitrary proportion) is mixed according to predetermined proportion or consumption with described lubricant base (and other lubricating oil additives used as required), can also heat if desired, be not particularly limited.
According to the preferred embodiment of the present invention, described lubricating oil composition is owing to comprising shielding phenolic compound of the present invention as oxidation inhibitor, while showing excellent high-temperature oxidation resistance, also show further and be selected from rustless property, cleansing performance (settling generation rejection), suppress viscosity to increase performance and suppress at least one in acid number increase performance.These excellent properties be the oxidation inhibitor of prior art can not provide simultaneously.In addition, shielding phenolic compound of the present invention not phosphorus element-containing and metallic element, not easily produces ash content during burning, and effectively can reduce the particulate emissions (the important origin cause of formation of haze) of engine, be environmentally friendly oxidation inhibitor.
Embodiment
Below adopt embodiment in further detail the present invention to be described, but the present invention is not limited to these embodiments.
Performance in embodiment and comparative example is evaluated as follows.
(1) high-temperature oxidation resistance evaluation
Lubricating oil composition embodiment or comparative example manufactured is as test sample, adopt Pressurized Differential scanning amount thermal test (PDSC) to evaluate the antioxidant property of this test sample, represent with the oxidation induction period of test sample (unit is min).The temperature of PDSC test is 210 DEG C, and pressure is 0.5MPa, and oxygen gas flow rate is 100mL/min.
(2) settling generates rejection evaluation
The lubricating oil composition of embodiment or comparative example manufacture is carried out as test sample the base chamber coking simulation test simulating piston deposit.The method is that 300ml test sample is added coking plate analog meter, be heated to 150 DEG C, employing continuous mode is the aluminium sheet spilled oil of 310 DEG C to temperature, weighs Jiao's amount that aluminium sheet generates after 6 hours, represent with sediment yield (unit is mg), the settling on simulation piston.Coking amount is higher, and the piston detergency representing this test sample is poorer.
(3) rustless property evaluation
According to BRT ball rust test method; the lubricating oil composition manufactured using embodiment or comparative example is as test sample; in the bench testing process of whole 18 hours; the Metal Ball continuous contact acidic liquid protected by described test sample and air; after off-test; measure Metal Ball plane of reflection intensity, obtain gray scale test value, be used for evaluating corrosion degree.The injection speed of acetic acid/Hydrogen bromide/hydrochloric acid/deionized water solution is 0.19 ml/hour, and air draught is 40 ml/min, and oil temperature is 48 DEG C.Corrosion degree is higher, shows that the rustless property of test sample is poorer.
(4) viscosity is suppressed to increase assessment of performance
The lubricating oil composition of embodiment or comparative example manufacture is carried out IIIE simulation test (VIT) as test sample.The test conditions of the method is 180 DEG C, 72h, and oxygen flow is 5L/h, calculates the viscosity rate of increase (%) of sample before and after test.
(5) acid number is suppressed to increase assessment of performance
The lubricating oil composition of embodiment or comparative example manufacture is carried out IIIE simulation test (VIT) as test sample.The test conditions of the method is 180 DEG C, 72h, and oxygen flow is 5L/h, calculates the acid number increasing amount (mgKOHg of sample before and after test -1).
Embodiment 1
In the 500ml four-hole boiling flask that agitator, thermometer, prolong and dropping funnel are housed, add the polyisobutene (Mn=1000 of 58.79g (0.323mol) the 2-tertiary butyl-6-mercapto-phenol, the boron trifluoride diethyl etherate (catalyst for alkylation reaction) of 6.88g (0.048mol), 100ml normal hexane solvent and 161.61g (0.162mol), fine chemicals company limited of Jilin Chemical group manufactures), at 80 DEG C of reaction 2h.After reaction terminates, functional quality mark be the potassium hydroxide solution cleaning reaction mixture of 5% once, and be washed to neutral remove catalyzer with hot water, then underpressure distillation removes desolventizing and unreacted phenol, obtain polyisobutene mercapto-phenol, hydroxyl value is 53.49mgKOH/g.Hydroxy value measuring is with reference to the acetic anhydride method in GB/T7383-2007.
Example reaction formula is as follows:
Nucleus magnetic hydrogen spectrum spectrum analysis from polyisobutene mercapto-phenol product: chemical shift 1.40 place is the characteristic peak of tertiary butyl hydrogen on polyisobutene mercapto-phenol phenyl ring; Chemical shift 3.58 place is unimodal is the characteristic peak of sulfydryl hydrogen on polyisobutene mercapto-phenol phenyl ring; Chemical shift 4.84 place is unimodal is the characteristic peak of hydroxyl hydrogen on polyisobutene mercapto-phenol phenyl ring; Unimodal and the unimodal characteristic peak being respectively two hydrogen on polyisobutene mercapto-phenol phenyl ring in 7.20 places in chemical shift 7.12 place.Be 1 by the Definitions On Integration of hydroxyl hydrogen on phenyl ring, obtain the integration of hydrogen on phenyl ring, sulfydryl hydrogen and hydroxyl hydrogen than being 0.95:0.97:1.05:0.94, close to theoretical 1:1:1:1:1, from nuclear magnetic spectrogram analysis, synthesize the polyisobutene mercapto-phenol alkylate of the para-orientation of expection.
Embodiment 2
Under nitrogen protection atmosphere; in the 250ml four-hole boiling flask that agitator, thermometer, prolong and dropping funnel are housed; add 30.58 grams of (156mmol) 2-sulfydryl-4-methyl-6-methylphenols; 15.79 grams of (112mmol) 1; the chloro-2-methylbutane of 4-bis-, 32.38 grams of (176mmol) 4-aminodiphenylamines, 3.45 grams of (25mmol) salt of wormwood and 100mL toluene; rapid stirring, at 90 DEG C of reaction 1h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, and obtains final shielding phenol product by column chromatography for separation.
Characterization of The Products data are as follows:
1HNMR(300MHz，CDCl 3)：δ1.00(3H)，1.31(1H)，1.40(9H)，1.78(1H)，1.98(1H)，2.37(3H)，2.99(2H)，3.33(2H)，4.83(1H)，6.95-7.26(12H)，7.55(1H)；
13CNMR(75MHz，CDCl 3)：δ20.4，21.2，30.1，33.7，34.5，43.8，114.3，118.9，119.4，121.8，125.8，129.5，132.3，133.5，146.1，149.0，150.8；
C 28h 36n 2oS calculated value C74.96, H8.09, N6.24, O3.57, S7.15; Measured value: C74.88, H8.13, N6.21, O3.54, S7.09.
Embodiment 3
Under nitrogen protection atmosphere; in the 250ml four-hole boiling flask that agitator, thermometer, prolong and dropping funnel are housed; add 31.65 grams of (133mmol) 2; 6-di-t-butyl-4-mercapto-phenol; 11.66 grams of (62mmol) ethylene dibromides, 28.15 grams of (153mmol) 4-aminodiphenylamines, 0.79 gram of (7.5mmol) sodium carbonate and 100mL benzene; rapid stirring, at 25 DEG C of reaction 24h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, and obtains final shielding phenol product by column chromatography for separation.
Characterization of The Products data are as follows:
1HNMR(300MHz，CDCl 3)：δ1.36(18H)，3.15(2H)，3.63(2H)，5.17(1H)，5.32(1H)，6.97-7.26(11H)，7.55(1H)；
13CNMR(75MHz，CDCl 3)：δ29.6，32.7，34.6，47.5，114.3，118.9，119.4，121.8，126.2，127.5，129.5，132.3，136.5，146.1，149.0，153.5；
C 28h 36n 2oS calculated value C74.96, H8.09, N6.24, O3.57, S7.15; Measured value C75.06, H8.13, N6.11, O3.61, S7.09.
Embodiment 4
Under nitrogen protection atmosphere; in the 250ml four-hole boiling flask that agitator, thermometer, prolong and dropping funnel are housed; add 8.57 grams (36mmol) 2,6-di-t-butyl-4-mercapto-phenol, 2.15 grams of (15mmol) dichloroethyl ether; 10.14 grams of (39mmol) N; N'-phenylbenzene-Isosorbide-5-Nitrae-phenylenediamine, 0.55 gram of (5.1mmol) sodium carbonate and 100mL toluene; rapid stirring, at 90 DEG C of reaction 4h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, and obtains final shielding phenol product by column chromatography for separation.
Characterization of The Products data are as follows:
1HNMR(300MHz，CDCl 3)：δ1.36(18H)，2.98(2H)，3.34(2H)，3.63(2H)，3.76(2H)，5.32(1H)，6.80-7.27(16H)，7.55(1H)；
13CNMR(75MHz，CDCl 3)：δ29.6，32.1，34.6，46.9，69.4，69.6，114.0，116.6，117.1，119.3，121.8，126.2，129.2，136.5，142.8，146.1，148.7，153.5；
C 36h 44n 2o 2s calculated value C76.02, H7.80, N4.92, O5.63, S5.64; Measured value C76.09, H7.85, N4.83, O5.65, S5.60.
Embodiment 5
Under nitrogen protection atmosphere; in the 250ml four-hole boiling flask that agitator, thermometer, prolong and dropping funnel are housed; add 20.23 grams (85mmol) 2,6-di-t-butyl-4-mercapto-phenol, 12.99 grams of (115mmol) 1; 3-propylene dichloride; 18.49 grams of (69mmol) N-(1,3-dimethylbutyl)-N'-diphenyl-para-phenylene diamines, 0.76 gram of (7.2mmol) sodium carbonate and 150mL benzene; rapid stirring, at 85 DEG C of reaction 3h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, and obtains final shielding phenol product by column chromatography for separation.
Characterization of The Products data are as follows:
1HNMR(300MHz，CDCl 3)：δ0.80(6H)，1.11-1.21(5H)，1.36(18H)，1.67(1H)，2.16-3.47(6H)，5.32(1H)，6.80-7.17(7H)，7.55(1H)；
13CNMR(75MHz，CDCl 3)：δ22.4，24.6，34.6，45.2，52.7，58.6，115.4，116.6，119.4，121.8，126.2，129.5，136.6，144.1，153.5；
C 35h 50n 2oS calculated value: C76.87, H9.22, N5.12, O2.93, S5.86; Measured value: C76.95, H9.28, N5.08, O2.87, S5.80.
Embodiment 6
Under nitrogen protection atmosphere; in the 250ml four-hole boiling flask that agitator, thermometer, prolong and dropping funnel are housed; add 3.57 grams of (15mmol) 2; 6-di-t-butyl-4-mercapto-phenol; 20.81 grams of (103mmol) 1; 3-dibromopropane; 21.76 grams of (103mmol) N-phenyl-N '-[4-(phenyl amino) phenyl]-1; 4-phenylenediamine; 0.29 gram of (2.1mmol) sodium carbonate and 150mL benzene; rapid stirring, at 110 DEG C of reaction 4h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, and obtains final shielding phenol product by column chromatography for separation.
Characterization of The Products data are as follows:
1HNMR(300MHz，CDCl 3)：δ1.36(18H)，1.94(2H)，2.95(2H)，3.43(2H)，5.32(1H)，6.80-7.17(16H)，7.20(1H)，7.26(4H)，7.55(1H)；
13CNMR(75MHz，CDCl 3)：δ28.5，29.6，29.9，34.6，47.2，114.0，116.6，117.7，118.4，121.8，126.2，129.2，132.3，136.5，142.8，146.1，148.7，153.5；
C 41h 47n 3oS calculated value C78.18, H7.52, N6.67, O2.54, S5.09; Measured value C78.29, H7.57, N6.55, O2.51, S5.10.
Embodiment 7
Under nitrogen protection atmosphere; in the 250ml four-hole boiling flask that agitator, thermometer, prolong and dropping funnel are housed; add 34.51 grams of (145mmol) 2; 6-di-t-butyl-4-mercapto-phenol; 5.95 grams of (35mmol) 2-chloroethyl-3-chloropropyl methylamines, 4.49 grams of (21mmol) 4-amino-4'-methoxy diphenylamines, 0.28 gram of (2.6mmol) sodium carbonate and 150mL benzene; rapid stirring, at 90 DEG C of reaction 2h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, and obtains final shielding phenol product by column chromatography for separation.
Characterization of The Products data are as follows:
1HNMR(300MHz，CDCl 3)：δ1.36(18H)，2.27(3H)，2.65(2H)，2.99(2H)，3.09(2H)，3.46(2H)，3.76(3H)，4.10(1H)，5.32(1H)，6.97-7.17(10H)，7.20(1H)；
13CNMR(75MHz，CDCl 3)：δ29.6，34.5，35.1，40.6，45.2，53.4，54.3，55.5，114.3，118.9，120.1，126.2，132.3，136.5，149.0，153.4，154.5；
C 32h 45n 3o 2s calculated value C71.73, H8.47, N7.84, O5.97, S5.98; Measured value C71.69, H8.43, N7.91, O5.92, S5.95.
Embodiment 8
Under nitrogen protection atmosphere; in the 250ml four-hole boiling flask that agitator, thermometer, prolong and dropping funnel are housed, add 21.66 grams (91mmol) 2,6-di-t-butyl-4-mercapto-phenol; 1.07 grams of (9.51mmol) 1; 3-propylene dichloride, 6.51 grams of (25mmol) N, N'-phenylbenzene-1; 4-phenylenediamine; 0.65 gram of (6.5mmol) saleratus and 150mL benzene, stir rapidly, at 70 DEG C of reaction 6h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, and obtains final shielding phenol product by column chromatography for separation.
Characterization of The Products data are as follows:
1HNMR(300MHz，CDCl 3)：δ1.36(18H)，2.26(2H)，3.05(2H)，3.48(2H)，5.32(1H)，6.80-7.17(12H)，7.27(2H)，7.55(1H)；
13CNMR(75MHz，CDCl 3)：δ28.5，29.6，33.4，34.6，44.2，81.5，114.0，117.1，119.4，121.8，126.2，129.5，136.6，142.8，146.1，148.7，153.4；
C 35h 42n 2oS calculated value C78.02, H7.86, N5.20, O2.97, S5.95; Measured value: C78.09, H7.91, N5.15, O2.93, S5.87.
Embodiment 9
Under nitrogen protection atmosphere; in the 250ml four-hole boiling flask that agitator, thermometer, prolong and dropping funnel are housed, add 8.33 grams (35mmol) 2,6-di-t-butyl-4-mercapto-phenol; 10.30 grams of (51mmol) 1; 3-dibromopropane, 9.61 grams of (31mmol) N, N'-phenylbenzene-2; 6-naphthylene diamine; 0.24 gram of (1.71mmol) salt of wormwood and 150mL toluene, stir rapidly, at 110 DEG C of reaction 4h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, and obtains final shielding phenol product by column chromatography for separation.
Characterization of The Products data are as follows:
1HNMR(300MHz，CDCl 3)：δ1.36(18H)，1.99(2H)，3.06(2H)，3.52(2H)，5.32(1H)，5.80(1H)，6.99-7.27(15H)，7.40(1H)，7.84(2H)；
13CNMR(75MHz，CDCl 3)：δ28.5，29.6，29.9，34.6，43.0，106.9，111.1，114.0，116.5，119.9，121.4，126.2，128.9，129.1，129.4，136.5，140.7，142.8，147.5，148.7，153.5；
C 39h 44n 2oS calculated value C79.55, H7.53, N4.76, O2.72, S5.45; Measured value C79.49, H7.51, N4.79, O2.70, S5.41.
Embodiment 10
Under nitrogen protection atmosphere; in the 250ml four-hole boiling flask that agitator, thermometer, prolong and dropping funnel are housed; add 6.19 grams of (26mmol) 2; 6-di-t-butyl-4-mercapto-phenol; 13.16 grams of (92mmol) dichloroethyl ether, 3.84 grams of (17mmol) N-sec.-propyl-N'-diphenyl-para-phenylene diamines, 0.43 gram of (3.1mmol) salt of wormwood and 150mL ethanol; rapid stirring, at 80 DEG C of reaction 2h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, and obtains final shielding phenol product by column chromatography for separation.
Characterization of The Products data are as follows:
1HNMR(300MHz，CDCl 3)：δ1.19(6H)，1.36(18H)，3.04(2H)，3.25(2H)，3.35(2H)，3.43(1H)，3.49(2H)，5.32(1H)，6.80-7.26(11H)，7.55(1H)；
13CNMR(75MHz，CDCl 3)：δ19.9，29.6，31.9，34.6，44.5，54.3，69.24，116.6，117.2，119.3，121.8，126.2，129.5，136.5，142.8，146.1，153.4，154.8；
C 33h 46n 2o 2s calculated value C74.11, H8.67, N5.24, O5.98, S6.00; Measured value C74.05, H8.61, N5.29, O5.93, S6.07.
Embodiment 11
Under nitrogen protection atmosphere; in the 250ml four-hole boiling flask that agitator, thermometer, prolong and dropping funnel are housed; add 4.99 grams of (21mmol) 2; 6-di-t-butyl-4-mercapto-phenol; 7.56 grams of (31mmol) 1; 6-dibromo-hexane; 5.70 grams of (31mmol) 4-aminodiphenylamines; 0.12 gram of (0.85mmol) salt of wormwood and 150mL ethanol; rapid stirring, after 60 DEG C of reaction 2.5h, is down to room temperature; add 7.05 grams of (85mmol) formaldehyde, be warming up to 85 DEG C of reaction 2.5h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, and is obtained the shielding phenol product of structure shown in title by column chromatography for separation.
Characterization of The Products data are as follows:
1HNMR(300MHz，CDCl 3)：δ1.32(2H)，1.36(18H)，1.41(2H)，1.64-1.81(4H)，2.93-3.28(4H)，4.14(2H)，4.43(1H)，4.59(1H)，5.32(1H)，6.82-7.21(9H)；
13CNMR(75MHz，CDCl 3)：δ26.8，28.3，28.6，29.6，31.8，33.1，34.3，44.56，113.0，118.9，119.6，122.4，123.3，125.1，126.4，127.9，132.2，140.5，148.5，153.4；
C 33h 44n 2oS calculated value C76.70, H8.58, N5.42, O3.10, S6.20; Measured value C76.69, H8.51, N5.49, O3.12, S6.18.
Embodiment 12
Under nitrogen protection atmosphere, agitator is being housed, thermometer, in the 250ml four-hole boiling flask of prolong and dropping funnel, add 19.52 grams of (82mmol) 2, 6-di-t-butyl-4-mercapto-phenol, 39.20 grams of (121mmol) 1, the iodo-2-methylbutane of 4-bis-, 19.93 grams of (94mmol) 4-amino-4'-ethyl pentanoic, 2.22 grams of (16.1mmol) salt of wormwood and 100mL toluene, rapid stirring, after 90 DEG C of reaction 3h, be down to room temperature, 10.11 grams of (316mmol) sulphur and 0.04 gram of (0.35mmol) iodine is added in toluene layer, be warming up to 150 DEG C of reaction 8h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, and obtains final shielding phenol product by column chromatography for separation.
Characterization of The Products data are as follows:
1HNMR(300MHz，CDCl 3)：δ1.00(3H)，1.23(3H)，1.36(18H)，1.87(2H)，2.06(1H)，2.65(2H)，2.82(2H)，3.29(2H)，4.25(1H)，5.32(1H)，5.70(1H)，6.72(1H)，6.98-7.08(4H)，7.17(2H)，7.49(1H)；
13cNMR (75MHz, CDCl 3): δ 15.60,20.3,29.0,29.6,34.6,44.2,113.7,116.1,118.9,126.2,127.9,129.7,136.6,141.2,146.1,153.4; C 33h 44n 2oS 2calculated value C72.22, H8.08, N5.10, O2.92, S11.68; Measured value: C72.29, H8.14, N5.08, O2.86, S11.57.
Embodiment 13
Under nitrogen protection atmosphere; in the 250ml four-hole boiling flask that agitator, thermometer, prolong and dropping funnel are housed; add 10.95 grams (46mmol) 2,6-di-t-butyl-4-mercapto-phenol, 8.42 grams of (48mmol) 1; 1; 1-trichloromethyl ethane, 18.95 grams of (103mmol) 4-aminodiphenylamines, 0.71 gram of (5.12mmol) salt of wormwood and 150mL benzene; rapid stirring, at 85 DEG C of reaction 1h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, and is obtained the shielding phenol product of structure shown in title by column chromatography for separation.
Characterization of The Products data are as follows:
1HNMR(300MHz，CDCl 3)：δ1.01(3H)，1.36(18H)，2.89(2H)，3.03(4H)，4.25(2H)，5.32(1H)，69.7-7.26(20H)，7.55(2H)；
13CNMR(75MHz，CDCl 3)：δ21.4，29.6，34.6，38.0，43.2，54.0，114.3，118.7，119.3，121.8，126.2，129.5，132.3，136.5，146.1，149.0，153.4；
C 43h 52n 4oS calculated value C76.74, H7.79, N8.33, O2.38, S4.76; Measured value C76.69, H7.73, N8.45, O2.32, S4.71.
Embodiment 14
Under nitrogen protection atmosphere; in the 250ml four-hole boiling flask that agitator, thermometer, prolong and dropping funnel are housed; add 21.66 grams of (91mmol) 2; 6-di-t-butyl-4-mercapto-phenol, 17.98 grams (89mmol) 1,2-dibromopropane; 6.62 grams of (36mmol) 4-aminodiphenylamines; 0.62 gram of (5.12mmol) salt of wormwood and 150mL Virahol, stir rapidly, at 80 DEG C of reaction 3h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, and is obtained the shielding phenol product of structure shown in title by column chromatography for separation.
Characterization of The Products data are as follows:
1HNMR(300MHz，CDCl 3)：δ1.36(36H)，1.95(4H)，3.04(4H)，3.12(4H)，5.32(2H)，6.80-7.26(13H)，7.55(1H)；
13CNMR(75MHz，CDCl 3)：δ28.5，29.6，34.6，48.4，101.3，116.6，117.1，119.3，121.8，126.2，129.5，136.5，142.8，146.1，149.1，153.4；
C 46h 64n 2o 2s 2calculated value C74.55, H8.70, N3.78, O4.32, S8.65; Measured value C74.59, H8.73, N3.67, O4.35, S8.64.
Embodiment 15
Under nitrogen protection atmosphere; in the 250ml four-hole boiling flask that agitator, thermometer, prolong and dropping funnel are housed; add 7.70 grams of (36mmol) 2-tertiary butyls-4; 6-dimercapto phenol, 10.40 grams (92mmol) 1,2-propylene dichloride; 13.06 grams of (71mmol) 4-aminodiphenylamines; 0.43 gram of (3.15mmol) salt of wormwood and 150mL toluene, stir rapidly, at 90 DEG C of reaction 4h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, and is obtained the shielding phenol product of structure shown in title by column chromatography for separation.
Characterization of The Products data are as follows:
1HNMR(300MHz，CDCl 3)：δ1.36(9H)，1.88(4H)，2.85(4H)，3.17(4H)，3.55(2H)，6.97-7.26(19H)，7.28(1H)，7.55(2H)，8.30(1H)；
13CNMR(75MHz，CDCl 3)：δ28.8，29.2，30.0，31.4，34.5，44.8，45.4，113.5，114.3，118.9，121.8，122.7，125.3，126.2，129.5，132.3，146.4，149.0，154.9；
C 40h 46n 4oS 2calculated value C72.47, H6.99, N8.45, O2.41, S9.67; Measured value C72.52, H7.03, N8.37, O2.43, S9.64.
Embodiment 16
Under nitrogen protection atmosphere; in the 250ml four-hole boiling flask that agitator, thermometer, prolong and dropping funnel are housed; add 18.56 grams of (78mmol) 2-tertiary butyl-4-mercapto-phenols; 10.74 grams of (95mmol) 1; 2-propylene dichloride; 11.23 grams of (32mmol) N-phenyl-N '-[4-(phenyl amino) phenyl]-1; 4-phenylenediamine; 0.79 gram of (5.71mmol) salt of wormwood and 150mL toluene; rapid stirring, at 100 DEG C of reaction 3h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, and is obtained the shielding phenol product of structure shown in title by column chromatography for separation.
Characterization of The Products data are as follows:
1HNMR(300MHz，CDCl 3)：δ1.36(36H)，2.02(4H)，3.03(4H)，3.50(4H)，5.32(2H)，6.80-7.17(18H)，7.20(1H)，7.27(4H)；
13CNMR(75MHz，CDCl 3)：δ28.5，29.6，30.1，31.8，34.6，49.9，92.4，114.0，116.6，117.1，122.0，126.2，129.2，136.5，142.8，148.7，153.4；
C 58h 73n 3o 2s 2calculated value C76.69, H8.10, N4.63, O3.52, S7.06; Measured value C76.61, H8.05, N4.71, O3.49, S7.03.
Embodiment 17
Under nitrogen protection atmosphere; in the 250ml four-hole boiling flask that agitator, thermometer, prolong and dropping funnel are housed; add 47.16 grams of (45mmol) polyisobutene mercapto-phenols (embodiment 1 manufactures), 6.48 grams of (51mmol) Isosorbide-5-Nitrae-dichlorobutane; 13.78 grams of (53mmol) N; N'-phenylbenzene-Isosorbide-5-Nitrae-phenylenediamine, 0.86 gram of (8.15mmol) sodium carbonate and 150mL benzene; rapid stirring, at 80 DEG C of reaction 2.5h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, and obtains final shielding phenol product by column chromatography for separation.
Characterization of The Products data are as follows:
1HNMR(300MHz，CDCl 3)：δ0.88，0.98，1.33，1.40，1.59，1.64，1.73，1.82，1.93，3.25，3.38，3.71，4.86，6.97，7.02，7.19，7.26，7.55；
13CNMR(75MHz，CDCl 3)：δ27.1，28.9，30.1，31.6，32.3，34.5，37.9，43.9，57.1，114.0，117.7，119.4，121.8，129.5，131.6，144.5，146.1，148.7，155.0。
Embodiment 18
Under nitrogen protection atmosphere; in the 250ml four-hole boiling flask that agitator, thermometer, prolong and dropping funnel are housed; add 29.34 grams of (28mmol) polyisobutene mercapto-phenols (embodiment 1 manufactures); 2.91 grams of (35mmol) formaldehyde, 6.24 grams of (24mmol) N, N'-phenylbenzene-1; 4-phenylenediamine; 0.34 gram of (3.2mmol) sodium carbonate and 150mL toluene, stir rapidly, at 90 DEG C of reaction 2h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, and obtains final shielding phenol product by column chromatography for separation.
Characterization of The Products data are as follows:
1HNMR(300MHz，CDCl 3)：δ0.86，0.98，1.02，1.40，1.60，1.83，2.59，3.25，3.72，4.86，6.80，6.97，7.02，7.17，7.26，7.55；
13CNMR(75MHz，CDCl 3)：δ28.2，30.1，32.3，33.1，34.5，38.1，49.8，59.1，114.3，119.4，121.8，125.2，122.0，127.3，129.5，132.3，143.3，146.1，151.3。
Comparative example 1
Under nitrogen protection atmosphere; in the 250ml four-hole boiling flask that agitator, thermometer, prolong and dropping funnel are housed; add 20.23 grams of (85mmol) 2; 6-di-t-butyl-4-mercapto-phenol; 7.22 grams of (87mmol) formaldehyde; 14.37 grams of (85mmol) pentanoic and 150mL methyl alcohol, stir rapidly, at 60 DEG C of reaction 2h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, and obtains final shielding phenol product by column chromatography for separation.
Characterization of The Products data are as follows:
1HNMR(300MHz，CDCl 3)：δ1.36(18H)，5.21(2H)，5.32(1H)，6.99(6H)，7.17(2H)，7.27(4H)；
13CNMR(75MHz，CDCl 3)：δ29.6，34.6，55.2，120.4，123.3，125.9，126.2，129.2，136.6，150.0，153.5；
C 27h 33nOS 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 that agitator, thermometer, prolong and dropping funnel are housed; add 10.71 grams of (52mmol) 2; 6-di-t-butyl-4-mercapto-phenol; 1.89 grams of (63mmol) formaldehyde, 17.42 grams of (65mmol) N-(1,3-dimethylbutyl)-N'-diphenyl-para-phenylene diamines and 150mL methyl alcohol; rapid stirring, at 70 DEG C of reaction 4h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, and obtains final shielding phenol product by column chromatography for separation.
Characterization of The Products data are as follows:
1HNMR(300MHz，CDCl 3)：δ0.80(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)；
13CNMR(75MHz，CDCl 3)：δ17.9，22.40，24.6，30.4，34.3，45.7，54.5，56.7，116.6，120.4，121.8，125.9，128.9，129.5，135.6，146.1，153.5，154.8；
C 33h 46n 2o 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 that agitator, thermometer, prolong and dropping funnel are housed; add 9.24 grams of (33mmol) 2; 6-di-t-butyl-4-(3-mercaptopropyi) phenol, 3.07 grams of (37mmol) formaldehyde, 11.71 grams of (45mmol) N; N'-phenylbenzene-1; 4-phenylenediamine and 150mL benzene, stir rapidly, at 80 DEG C of reaction 4h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, and obtains final shielding phenol product by column chromatography for separation.
Characterization of The Products data are as follows:
1HNMR(300MHz，CDCl 3)：δ1.40(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)；
13CNMR(75MHz，CDCl 3)：δ28.7，31.1，34.3，35.7，54.1，117.1，119.4，123.3，124.8，129.2，131.8，136.0，142.8，144.9，146.1，151.9；
C 36h 44n 2oS 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 the shielding phenolic compound of embodiment 2-18 and comparative example 1-3 is mixed 2h with lubricant base at 40 DEG C according to the composition of table 1 and proportioning, obtain the lubricating oil composition of embodiment 19-35 and the lubricating oil composition of comparative example 4-6.In addition, by the composition of table 2 and proportioning, oxidation inhibitor is mixed 2h with lubricant base at 40 DEG C, obtain the lubricating oil composition of comparative example 7-10.Wherein, based on the total mass of individual lubricating oil composition, the addition of oxidation inhibitor is 0.5 % by weight, and described lubricant base selects Shanghai Gaoqiao petrochemical industry II class hydrogenated base oil.In addition, not add the described base oil of oxidation inhibitor as blank sample.
Table 1
Lubricating oil composition Oxidation inhibitor Lubricant base Oxidation inhibitor addition
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 lubricating oil composition of the lubricating oil composition of embodiment 19-35, comparative example 4-10 and described blank sample as test sample, carried out high-temperature oxidation resistance evaluation, PDSC test temperature is 210 DEG C, and measurement result is as shown in table 3.
Table 3
Using the lubricating oil composition of the lubricating oil composition of embodiment 19-35, comparative example 4-10 and described blank sample as test sample, carried out settling and generated rejection evaluation, QZX experiment measurement result is as shown in table 4.
Table 4
Lubricating oil composition Sediment yield (mg)
Embodiment 22 16.9
Embodiment 25 15.1
Embodiment 29 10.8
Embodiment 31 13.5
Embodiment 34 6.8
Embodiment 35 7.1
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 lubricating oil composition of the lubricating oil composition of embodiment 19-35, comparative example 4-10 and described blank sample as test sample, carried out rustless property evaluation, BRT ball rust test measurement result is as shown in table 5.
Table 5
Lubricating oil composition 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 lubricating oil composition of the lubricating oil composition of embodiment 19-35, comparative example 4-10 and described blank sample as test sample, carried out suppression viscosity and increased and acid number increase assessment of performance, measurement result is as shown in table 6.
Table 6
Lubricating oil composition Viscosity rate of increase (%) Acid number increasing amount (mgKOHg -1)
Embodiment 19 25.7 2.523
Embodiment 20 21.3 1.967
Embodiment 21 20.9 2.031
Embodiment 22 23.4 1.834
Embodiment 23 21.6 2.007
Embodiment 24 19.9 1.679
Embodiment 25 21.5 1.372
Embodiment 26 18.7 2.021
Embodiment 27 19.3 2.318
Embodiment 28 21.7 1.936
Embodiment 29 20.6 2.217
Embodiment 30 22.3 1.894
Embodiment 31 19.3 2.334
Embodiment 32 21.5 2.119
Embodiment 33 24.3 1.793
Embodiment 34 23.8 2.106
Embodiment 35 21.5 1.984
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 be described in detail the specific embodiment of the present invention above in conjunction with the embodiments, it is pointed out that protection scope of the present invention not by the restriction of these embodiments, but determined by claims of annex.Those skilled in the art can carry out suitable change to these embodiments in the scope not departing from technological thought of the present invention and purport, and the embodiment after these changes is obviously also included within protection scope of the present invention.

Claims (7)

1. the shielding phenolic compound shown in general formula (I),
In general formula (I), each radicals R is same to each other or different to each other, and is selected from hydrogen, C independently of one another 1-300straight or branched alkyl (preferred C 1-10what straight or branched alkyl or number-average molecular weight Mn were 300-3000 is polyolefin-based), the group shown in the group shown in general formula (II) and general formula (III), prerequisite is at least one radicals R is the group shown in general formula (II); Each radicals R ' be same to each other or different to each other, be selected from hydrogen and C independently of one another 1-20straight or branched alkyl (is preferably selected from hydrogen and C independently of one another 1-4straight or branched alkyl),
In aforementioned each general formula (II), (III) and (IV), group L is selected from and is optionally selected from C by one or more 1-20alkyl (preferred C 1-20straight or branched alkyl, C 6-20aryl or its combination group) and C 3-20the m+1 valency C that the substituting group that straight or branched mixes alkyl replaces 2-20straight or branched alkyl and be optionally selected from C by one or more 1-20alkyl (preferred C 1-20straight or branched alkyl, C 6-20aryl or its combination group) and C 3-20the m+1 valency C that the substituting group that straight or branched mixes alkyl replaces 3-20straight or branched is mixed alkyl; Group L ' be group wherein radicals R " is selected from hydrogen, C 1-20alkyl (preferred C 1-20straight or branched alkyl) and C 3-20straight or branched is mixed alkyl, is preferably selected from hydrogen, C 1-10straight or branched alkyl and C 3-10straight or branched is mixed alkyl; Each group A is same to each other or different to each other, and is selected from independently of one another with (wherein, each radicals R is same to each other or different to each other, and is selected from hydrogen, C independently of one another 1-300straight or branched alkyl (preferred C 1-10what straight or branched alkyl or number-average molecular weight Mn were 300-3000 is polyolefin-based), the group shown in the group shown in general formula (II) and general formula (III) (is preferably selected from hydrogen and C independently of one another 1-300straight or branched alkyl); Each radicals R ' be same to each other or different to each other, be selected from hydrogen and C independently of one another 1-20straight or branched alkyl (is preferably selected from hydrogen and C independently of one another 1-4straight or branched alkyl); Two radicals R and group-S-occupy residue three positions on phenyl ring respectively), to be at least one group A be prerequisite m is the integer (preferably 1) of 1 to 4; Each radicals R 2be same to each other or different to each other, be selected from hydrogen, C independently of one another 1-20straight or branched alkyl, the group shown in general formula (IV) and the group shown in logical formula V (are preferably selected from hydrogen, C independently of one another 1-10group shown in straight or branched alkyl and general formula (IV)); Each radicals R bbe same to each other or different to each other, be selected from hydrogen and C independently of one another 1-20straight or branched alkyl (is preferably selected from hydrogen and C independently of one another 1-10straight or branched alkyl); Each radicals R cbe same to each other or different to each other, be selected from hydrogen, C independently of one another 1-20straight or branched alkyl and C 1-20straight or branched alkyl oxy (is preferably selected from hydrogen, C independently of one another 1-10straight or branched alkyl and C 1-10straight or branched alkyl oxy, is more preferably in cyclic group the contraposition of upper nitrogen-atoms); Y is the integer (preferably 0 or 1) of 0 to 3; Z is the integer (preferably 0 or 1) of 0 to 3; N is the integer (preferably 1 or 2) of 1 to 8; N' is the integer (preferably 0,1 or 2) of 0 to 7, and prerequisite is n'+n≤8 (preferred n'+n=1 or n'+n=2); Each radicals R dbe same to each other or different to each other, be selected from the group (preferred hydrogen) shown in hydrogen and logical formula V independently of one another; Each cyclic group be same to each other or different to each other, be selected from phenyl ring and naphthalene nucleus (preferred phenyl ring) independently of one another, two wherein adjacent cyclic groups thiodiphenylamine ring is formed each other optionally through the atom N of additional S atom and these two rings of bridge joint, and/or, two adjacent cyclic groups each other optionally through additional group (wherein radicals R " is selected from hydrogen, C 1-20alkyl (preferred C 1-20straight or branched alkyl) and C 3-20straight or branched is mixed alkyl, is preferably selected from hydrogen and C 1-10straight or branched alkyl) and these two rings of bridge joint atom N and form 9,10-acridan ring,
In logical formula V, each group A is same to each other or different to each other, and is selected from independently of one another with wherein each radicals R is same to each other or different to each other, and is selected from hydrogen, C independently of one another 1-300straight or branched alkyl (preferred C 1-10what straight or branched alkyl or number-average molecular weight Mn were 300-3000 is polyolefin-based), the group shown in the group shown in general formula (II) and general formula (III) (is preferably selected from hydrogen and C independently of one another 1-300straight or branched alkyl); Each radicals R ' be same to each other or different to each other, be selected from hydrogen and C independently of one another 1-20straight or branched alkyl (is preferably selected from hydrogen and C independently of one another 1-4straight or branched alkyl); Two radicals R and group-S-occupy residue three positions on phenyl ring respectively; Group L, radicals R 2, radicals R b, radicals R c, radicals R d, cyclic group and y, n, z have the implication identical with general formula (II) respectively with m,
Wherein, described straight or branched alkyl of mixing is selected from one or more (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH of straight or branched alkyl molecule inside configuration 2-(R' is H or C to be selected from-O-,-S-and-NR'- 1-4straight or branched alkyl) one of alternative group directly substitute and obtain group and straight or branched alkyl molecule inside configuration one or more (such as 1 to 3,1 to 2 or 1) replaced group of group-CH<-N< directly substitute and obtain group, wherein this shielding phenolic compound has a radicals R at least in its whole molecular structure dhydrogen.
2., according to shielding phenolic compound according to claim 1, be selected from following particular compound or the mixture of its arbitrary proportion:
3. one kind shields the manufacture method of phenolic compound, comprise the first step that the amine compound shown in the phenolic compound shown in general formula (X) and general formula (Y) is reacted under the existence of the multi-halogenated compounds shown in general formula (A), optional also comprise the additional step reaction product of described first step and vulcanizing agent (preferred sulphur) being reacted and/or reacts with the aldehyde cpd (preferred formaldehyde) shown in general formula (Z)
In general formula (X), each radicals R 0be same to each other or different to each other, be selected from hydrogen ,-SH and C independently of one another 1-300straight or branched alkyl (preferred C 1-10straight or branched alkyl or number-average molecular weight Mn are the polyolefin-based of 300-3000), prerequisite is at least one radicals R 0-SH; Each radicals R ' be same to each other or different to each other, be selected from hydrogen and C independently of one another 1-20straight or branched alkyl (is preferably selected from hydrogen and C independently of one another 1-4straight or branched alkyl),
In general formula (Y), radicals R ' 2be selected from hydrogen, C 1-20straight or branched alkyl and group each radicals R bbe same to each other or different to each other, be selected from hydrogen and C independently of one another 1-20straight or branched alkyl (is preferably selected from hydrogen and C independently of one another 1-10straight or branched alkyl); Each radicals R cbe same to each other or different to each other, be selected from hydrogen, C independently of one another 1-20straight or branched alkyl and C 1-20straight or branched alkyl oxy (is preferably selected from hydrogen, C independently of one another 1-10straight or branched alkyl and C 1-10straight or branched alkyl oxy, is more preferably in cyclic group the contraposition of upper nitrogen-atoms); Y is the integer (preferably 0 or 1) of 0 to 3; Z is the integer (preferably 0 or 1) of 0 to 3; N1 is the integer (preferably 1 or 2) of 1 to 8; Each cyclic group be same to each other or different to each other, be selected from phenyl ring and naphthalene nucleus (preferred phenyl ring) independently of one another,
In general formula (A), radicals R halobe selected from and be optionally selected from C by one or more 1-20alkyl (preferred C 1-20straight or branched alkyl, C 6-20aryl or its combination group) and C 3-20the m1 valency C that the substituting group that straight or branched mixes alkyl replaces 2-20straight or branched alkyl and be optionally selected from C by one or more 1-20alkyl (preferred C 1-20straight or branched alkyl, C 6-20aryl or its combination group) and C 3-20the m1 valency C that the substituting group that straight or branched mixes alkyl replaces 3-20straight or branched is mixed alkyl, and group Halo is halogen, and m1 is the integer (preferably 2) of 2 to 5,
In general formula (Z), radicals R " is selected from hydrogen, C 1-20alkyl (preferred C 1-20straight or branched alkyl) and C 3-20straight or branched is mixed alkyl, is preferably selected from hydrogen, C 1-10straight or branched alkyl and C 3-10straight or branched is mixed alkyl,
Wherein, described straight or branched alkyl of mixing is selected from one or more (such as 1 to 4,1 to 3,1 to 2 or 1) group-CH of straight or branched alkyl molecule inside configuration 2-(R' is H or C to be selected from-O-,-S-and-NR'- 1-4straight or branched alkyl) one of alternative group directly substitute and obtain group and straight or branched alkyl molecule inside configuration one or more (such as 1 to 3,1 to 2 or 1) replaced group of group-CH<-N< directly substitute and obtain group.
4. according to manufacture method according to claim 3, wherein in described first step, the mol ratio of the amine compound shown in the phenolic compound shown in described general formula (X) and described general formula (Y) is 1:0.1-10, preferred 1:0.5-5.0, more preferably 1:0.8-2.0, the mol ratio of the multi-halogenated compounds shown in the phenolic compound shown in described general formula (X) and described general formula (A) is 1:0.1-10, preferred 1:0.2-5.0, more preferably 1:0.3-3.0, in described additional step, the mol ratio of the amine compound shown in described general formula (Y) and described vulcanizing agent is 1:1-10, preferred 1:1.2-6.0, more preferably 1:1.5-3.0, the mol ratio of the aldehyde cpd shown in the amine compound shown in described general formula (Y) and described general formula (Z) is 1:0.1-10, preferred 1:0.5-5.0, more preferably 1:0.8-2.0.
5. according to the shielding phenolic compound described in claim 1 or 2 or according to the purposes of the shielding phenolic compound manufactured by the manufacture method described in claim 3 or 4 as oxidation inhibitor.
6. a lubricating oil composition, comprise lubricant base and according to the shielding phenolic compound described in claim 1 or 2 or according to the shielding phenolic compound manufactured by manufacture method described in claim 3 or 4 as oxidation inhibitor, wherein said oxidation inhibitor accounts for the 0.001-30 % by weight of described lubricating oil composition gross weight, preferred 0.1-10 % by weight.
7., according to lubricating oil composition according to claim 6, manufacture by described shielding phenolic compound is mixed with described lubricant base.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111056924A (en) * 2018-10-16 2020-04-24 中国石油化工股份有限公司 Phenolic compound and preparation method and application thereof

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CA1219584A (en) * 1983-02-10 1987-03-24 John D. Spivack N-substitute (4-hydroxyphenylthiomethyl) amine or ureide stabilizers
US4772405A (en) * 1985-08-26 1988-09-20 Ciba-Geigy Corporation Lubricant compositions which contain sulfur-containing phenol derivatives, and novel sulfur-containing phenol derivatives
US5304314A (en) * 1991-12-27 1994-04-19 Mobil Oil Corporation Sulfur-containing ester derivatives of arylamines and hindered phenols as multifunctional antiwear and antioxidant additives for lubricants

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CA1219584A (en) * 1983-02-10 1987-03-24 John D. Spivack N-substitute (4-hydroxyphenylthiomethyl) amine or ureide stabilizers
US4551259A (en) * 1983-12-14 1985-11-05 Mobil Oil Corporation Phenolic antioxidants and lubricants containing same
US4772405A (en) * 1985-08-26 1988-09-20 Ciba-Geigy Corporation Lubricant compositions which contain sulfur-containing phenol derivatives, and novel sulfur-containing phenol derivatives
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Publication number Priority date Publication date Assignee Title
CN111056924A (en) * 2018-10-16 2020-04-24 中国石油化工股份有限公司 Phenolic compound and preparation method and application thereof
CN111056924B (en) * 2018-10-16 2022-11-15 中国石油化工股份有限公司 Phenolic compound and preparation method and application thereof

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