CN106590819B - Complex lithium grease and preparation method thereof - Google Patents
Complex lithium grease and preparation method thereof Download PDFInfo
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- CN106590819B CN106590819B CN201510664705.8A CN201510664705A CN106590819B CN 106590819 B CN106590819 B CN 106590819B CN 201510664705 A CN201510664705 A CN 201510664705A CN 106590819 B CN106590819 B CN 106590819B
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Abstract
The present invention provides a kind of complex lithium greases and preparation method thereof, and the lubricating grease is on the basis of lubricating grease total weight, including following components: the shielding phenolic compounds of 0.01%-10%, the compound lithium base thickening agent and major amount of lubricating base oil of 5-%35%；The structure of the shielding phenolic compounds is shown in specification.Complex lithium grease of the invention has good colloid stability, splendid mechanical stability, long-life, high temperature antioxidant, rustless property, anti-water drenching energy and extreme pressure property, can be competent in the harsh working condition such as high temperature, high speed, high load capacity, more water.
Description
Technical field
The present invention relates to a kind of lubricating grease, in particular to a kind of complex lithium grease.
Background technique
Complex lithium grease is the high temperature multi-effect lubricating grease to grow up the 1960s, it is than lithium base grease
Dropping point is high, is more suitable for using at high temperature, has good multiple-effect performance, and have to various types of mineral oil and synthetic oil
Very strong thickening ability.But with the development of modern industry, the industrial departments such as bearing, automobile, printing and dyeing, mine, metallurgy, aerospace
The inoxidizability of lubricating grease, high and low temperature resistance and extreme pressure anti-wear, water-resistance, mechanical stability etc. are proposed more and more severe
The requirement at quarter.The service performance of basic rouge tends not to meet actual requirement.
In recent years, complex lithium grease at home and abroad achieves very big development.Such as US 3681242, US
3929651, US 3711407, CN 1052890A, CN 1052891A, CN 1055384A, CN 101705141A report multiple
The composition and preparation method for closing lithium base grease, using 12- hydroxy lithium stearate and binary acid or boric acid, salicylic lithium salts
Two components are combined, and also have compound using three components；CN 101993769A,CN 101481637A,CN 102358863A
The technique of rouge processed is improved respectively, production cost is reduced, the oxidation stability for improving lubricating grease, shortens saponification
Time reduces energy consumption, improves production efficiency and operability.It is preferable that CN 101200670A provides a kind of comprehensive performance
The preparation method of complex lithium grease, by the addition of copper nanoparticle especially to being damaged bearing with repair function.CN
101921650A forms it with soap molecule and acts synergistically, and then improve soap molecule by the way that surfactant is added into formula
Arrangement mode and solidify the ability of base oil to improve the dropping point of lubricating grease.
Lubricating grease claims in storage with the ability resisted the effect of atmosphere when use and keep its property that permanent change does not occur
For oxidation stability, the metal soap as thickening agent is the major reason for causing lubricating grease oxidation deterioration.In order to inhibit to lubricate
The oxidation deterioration of rouge prevents oxidation product from causing the corrosion of metal surface, suitable antioxidant additive is added.Currently, often
Antioxidant is broadly divided into two class of amine and phenols.Phenolic antioxidant generally comprises 2,6-di-tert-butyl p-cresol, and 2,6- bis-
Tert-butyl phenol etc., but it is lower using temperature, generally within 150 DEG C.Amine antioxidants are mainly alkylated diphenylamine, or
Alkylated phenyl-naphthylamines etc..Existing antioxidant still has room for improvement on high temperature antioxygen property.
Summary of the invention
The present invention includes the content of the following aspects:
1. a kind of complex lithium grease, on the basis of lubricating grease total weight, including following components: 0.01%-10%'s
Shield phenolic compounds, the compound lithium base thickening agent and major amount of lubricating base oil of 5-%35%；
The structure of the shielding phenolic compounds is as shown in logical formula (I):
In logical formula (I), each group R is same or different to each other, and is each independently selected from hydrogen, C1-300Linear or branched alkyl group
(preferably C1-10Linear or branched alkyl group or number-average molecular weight Mn are the polyolefin-based of 300-3000), base shown in logical formula (II)
Group shown in group and logical formula (III), on condition that at least one group R is group shown in logical formula (II)；Each group R' is each other
It is identical or different, it is each independently selected from hydrogen and C1-20Linear or branched alkyl group (is preferably each independently selected from hydrogen and C1-4Straight chain
Or branched alkyl),
In aforementioned each logical formula (II), (III) and (IV), it is group each independently that each group L, which is same or different to each other,Wherein group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Linear or branched alkyl group) and C3-20Straight chain or branch
Chain miscellaneous alkyl is preferably selected from hydrogen, C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl；Each group R2It is mutually the same
Or it is different, it is each independently selected from hydrogen, C1-20Shown in group shown in linear or branched alkyl group, logical formula (IV) and logical formula (V)
Group (is preferably each independently selected from hydrogen, C1-10Group shown in linear or branched alkyl group and logical formula (IV))；Each group RbEach other
It is identical or different, it is each independently selected from hydrogen and C1-20Linear or branched alkyl group (is preferably each independently selected from hydrogen and C1-10Straight chain
Or branched alkyl)；Each group RcIt is same or different to each other, is each independently selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Directly
Chain or branched alkyl oxygroup (are preferably each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygen
Base is more preferably in cyclic groupThe contraposition of upper nitrogen-atoms)；Y is 0 to 3 integer (preferably 0 or 1)；Z is 0 to 3
Integer (preferably 0 or 1)；The integer (preferably 1 or 2) that n is 1 to 8；The integer (preferably 0,1 or 2) that n' is 0 to 7, on condition that n'+
N≤8 (preferably n'+n=1 or n'+n=2)；Each group RdIt is same or different to each other, is each independently selected from hydrogen and logical formula (V) institute
The group (preferably hydrogen) shown；Each cyclic groupIt is same or different to each other, is each independently selected from phenyl ring and naphthalene nucleus
(preferably phenyl ring), wherein two adjacent cyclic groupsOptionally pass through additional S atom each other and bridges the two
The N atom of ring and form phenthazine ring, and/or, two adjacent cyclic groupsOptionally pass through additional base each other
Group(wherein group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Linear or branched alkyl group) and C3-20Straight chain or
Branched heteroalkyl groups are preferably selected from hydrogen and C1-10Linear or branched alkyl group) and bridge the N atom of the two rings and form 9,10- bis-
Hydrogen acridine ring,
In logical formula (V), each group R is same or different to each other, and is each independently selected from hydrogen, C1-300Linear or branched alkyl group
(preferably C1-10Linear or branched alkyl group or number-average molecular weight Mn are the polyolefin-based of 300-3000), base shown in logical formula (II)
Group shown in group and logical formula (III) (is preferably each independently selected from hydrogen and C1-300Linear or branched alkyl group)；Each group R' that
This is identical or different, is each independently selected from hydrogen and C1-20Linear or branched alkyl group (is preferably each independently selected from hydrogen and C1-4Directly
Chain or branched alkyl)；Group L is groupWherein group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight chain
Or branched alkyl) and C3-20Linear chain or branched chain miscellaneous alkyl is preferably selected from hydrogen, C1-10Linear or branched alkyl group and C3-10Straight chain or branch
Chain miscellaneous alkyl；A is 0 or 1, and two group R and a group-(S)a- L- occupies three positions of the residue on phenyl ring respectively,
Wherein, the linear chain or branched chain miscellaneous alkyl is selected from the one or more inside linear or branched alkyl group molecular structure
(such as 1 to 4,1 to 3,1 to 2 or 1) group-CH2Being selected from-O- ,-S- and-NR'-, (R' is H or C1-4Straight chain
Or branched alkyl) one of substituting group directly substitute and one inside the group and linear or branched alkyl group molecular structure that obtain
A or multiple (such as 1 to 3,1 to 2 or 1) group-CH <by substituting group-N < is directly substituted and the group of acquisition,
The wherein shielding phenolic compounds at least one group R in its entire molecular structuredIt is hydrogen.
2. according to shielding phenolic compounds described in any preceding aspect, particular compound selected from the following or its arbitrary proportion
Mixture:
3. the preparation method of aforementioned shielding phenolic compounds, including make shown in phenolic compounds shown in logical formula (X) and general formula (Y)
The first step that reacts in the presence of aldehyde compound (preferably formaldehyde) shown in general formula (Z) of amine compounds, optionally also
Including react the reaction product of the first step with vulcanizing agent (preferably sulphur) and/or with aldehyde compound shown in general formula (Z)
The additional step of (preferably formaldehyde) reaction,
In logical formula (X), each group R0It is same or different to each other, is each independently selected from hydrogen ,-SH
And C1-300Linear or branched alkyl group (preferably C1-10Linear or branched alkyl group or number-average molecular weight Mn are 300-3000
It is polyolefin-based), on condition that at least one group R0It is-SH；Each group R' is same or different to each other, and is each independently selected from hydrogen
And C1-20Linear or branched alkyl group (is preferably each independently selected from hydrogen and C1-4Linear or branched alkyl group),
In general formula (Y), group R'2Selected from hydrogen, C1-20Linear or branched alkyl group and groupEach base
Group RbIt is same or different to each other, is each independently selected from hydrogen and C1-20Linear or branched alkyl group (be preferably each independently selected from hydrogen and
C1-10Linear or branched alkyl group)；Each group RcIt is same or different to each other, is each independently selected from hydrogen, C1-20Linear or branched alkyl group
And C1-20Linear or branched alkyl group oxygroup (is preferably each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Straight chain or branch
Alkyl group oxygroup, is more preferably in cyclic groupThe contraposition of upper nitrogen-atoms)；Y be 0 to 3 integer (preferably 0 or
1)；Z is 0 to 3 integer (preferably 0 or 1)；The integer (preferably 1 or 2) that n1 is 1 to 8；Each cyclic groupPhase each other
It is same or different, it is each independently selected from phenyl ring and naphthalene nucleus (preferably phenyl ring),
In general formula (Z), group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Linear or branched alkyl group) and C3-20Straight chain or branch
Chain miscellaneous alkyl is preferably selected from hydrogen, C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl,
Wherein, the linear chain or branched chain miscellaneous alkyl is selected from the one or more inside linear or branched alkyl group molecular structure
(such as 1 to 4,1 to 3,1 to 2 or 1) group-CH2Being selected from-O- ,-S- and-NR'-, (R' is H or C1-4Straight chain
Or branched alkyl) one of substituting group directly substitute and one inside the group and linear or branched alkyl group molecular structure that obtain
A or multiple (such as 1 to 3,1 to 2 or 1) group-CH <by substituting group-N < is directly substituted and the group of acquisition.
4. according to the preparation method for shielding phenolic compounds described in any preceding aspect, wherein in the first step,
The molar ratio of amine compounds shown in phenolic compounds shown in the logical formula (X) and the general formula (Y) is 1:0.1-10, preferably 1:
0.5-5.0, more preferable 1:0.8-2.0, aldehyde compound shown in phenolic compounds and the general formula (Z) shown in the logical formula (X)
Molar ratio be 1:0.1-10, preferably 1:0.5-5.0, more preferable 1:0.8-2.0, in the additional step, the general formula (Y)
Shown in the molar ratio of amine compounds and the vulcanizing agent be 1:1-10, preferably 1:1.2-6.0, more preferable 1:1.5-3.0, it is described
The molar ratio of amine compounds shown in general formula (Y) and aldehyde compound shown in the general formula (Z) is 1:0.1-10, preferably 1:0.5-
5.0, more preferable 1:0.8-2.0.
5. complex lithium grease described in any preceding aspect, wherein the shielding phenolic compounds accounts for the compound lithium base
The 0.01%-10% of lubricant composition total weight, preferably 0.05%-5%, more preferable 0.1%-0.5%.
Compound lithium base thickening agent of the present invention can react generation by acid with lithium hydroxide, and the acid is to contain height
The mixed acid of molecule acid and low molecular acid, the polymer acid are C12-C25 fatty acid and/or hydroxy fatty acid, can be the moon
One of cinnamic acid, palmitinic acid, stearic acid and 12- hydroxy stearic acid are a variety of, preferably stearic acid and/or 12- hydroxy stearic acid.
The low molecular acid can be the organic carboxyl acid of C2-C11, can be acetic acid, propionic acid, ethanedioic acid, adipic acid, azelaic acid, the last of the ten Heavenly stems two
Acid and one of terephthalic acid (TPA) are a variety of, preferably the Dicarboxylic Acids of C5-C11, more preferably decanedioic acid, azelaic acid,
One of adipic acid and terephthalic acid (TPA) are a variety of.The molar ratio of the polymer acid and low molecular acid is preferably 1:0.1-1.
The lubricating base oil can be one of mineral oil, vegetable oil and synthetic oil or a variety of, preferably 100 DEG C movements
Viscosity is 5-60mm2The lubricating base oil of/s, most preferably 10-30mm2The lubricating base oil of/s.The vegetable oil can be castor-oil plant
One of oil, rapeseed oil, peanut oil and soya-bean oil are a variety of.The synthetic oil can be poly-a-olefin oil (PAO), Esters oil, fluorine
One of oil and silicone oil are a variety of.
Various additives, such as extreme pressure anti-wear additives, antirust agent can also be contained in lubricating grease of the present invention.Wherein, extreme pressure is anti-
Grinding agent accounts for the 0.5-12% of lubricating grease total weight, preferably 0.5-5%, can be two thio Acidic phosphates zinc, two thio dioxanes
Aminocarbamic acid molybdenum, two thio dialkyl amido lead formates, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, two
Molybdenum sulfide, polytetrafluoroethylene (PTFE), thiophosphoric acid molybdenum, chlorinated paraffin, dibutyl dithiocaarbamate antimony, tungsten disulfide, curing
At least one of selenium, fluorographite, calcium carbonate and zinc oxide；Antirust agent accounts for the 0.01-4.5% of lubricating grease total weight, preferably
0.1-2% can be barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid
At least one of.
In the present invention, the content of each component is calculated according to inventory in grease composition.Wherein, compound lithium base is thick
Content=100% of agent × (weight of polymer acid lithium+low molecular acid lithium weight)/lubricating grease total weight.
The present invention provides the preparation methods of the complex lithium grease described in any preceding aspect, comprising: by complex lithium
Base thickening agent and lubricating base oil are uniformly mixed, and are refined in 180-230 DEG C of constant temperature, cooling, and mentioned-above shielding phenolate is added
Object is closed, rouge is ground into.
The preparation method of preferred aforementioned complex lithium grease of the invention, comprising: by partial lubrication base oil, high score
Sub- acid and low molecular acid mixing, heating, are warming up to 85-95 DEG C, and the aqueous solution that lithium hydroxide is added carries out saponification, have reacted
It is warming up to 190-210 DEG C after complete, carries out high temperature refining, remaining lubricating base oil is added and is cooled to 100-120 DEG C, described in addition
Phenolic compounds is shielded, rouge is ground into.
The polymer acid is C12-C20 fatty acid and/or C12-C20 hydroxy fatty acid, and the low molecular acid is C2-
The organic carboxyl acid of C11 can be one of acetic acid, propionic acid, ethanedioic acid, adipic acid, azelaic acid, decanedioic acid and terephthalic acid (TPA)
Or a variety of, preferably one of decanedioic acid, azelaic acid, adipic acid and terephthalic acid (TPA) or a variety of.The polymer acid with it is low
The molar ratio of molecule acid is preferably 1:0.1-1.
The molar ratio of the total amount and lithium hydroxide of the polymer acid and low molecular acid preferably generation saponification etc.
Equivalent proportion, wherein the amount of lithium hydroxide can also excess 1%-10 weight %.
In the aqueous solution of lithium hydroxide the content of water so that saponification can go on smoothly subject to.Usually lithium hydroxide
The 0.1-10 times of weight of dosage, preferably 0.8-8 times of weight.
The dosage of the partial lubrication base oil and remaining lubricating base oil is respectively the total dosage of lubricating base oil
50%-75%, 25%-50%.
The temperature of the saponification is preferably 85-95 DEG C, and the time of saponification is preferably 0.2-1.5 hours, more excellent
It is selected as 0.5-1 hours.
The time of the refining is preferably 5-25 minutes.
Complex lithium grease of the invention has good colloid stability, splendid mechanical stability, long-life, height
Warm antioxidant, rustless property, anti-water drenching energy and extreme pressure property can be competent in the harshnesses such as high temperature, high speed, high load capacity, more water
Working condition.
Specific embodiment
In complex lithium grease of the invention, it is related to shielding phenolic compounds shown in a kind of logical formula (I).
According to the present invention, in logical formula (I), when there are multiple, each group R is same or different to each other, each independently
Selected from hydrogen, C1-300Group shown in group shown in linear or branched alkyl group, logical formula (II) and logical formula (III), on condition that at least
One group R is group shown in logical formula (II).
According to the present invention, in logical formula (I), as the C1-300Linear or branched alkyl group, for example C can be enumerated1-20Directly
Chain or branched alkyl (preferably C1-10Linear or branched alkyl group, more preferable C1-4Linear or branched alkyl group) or it is polyolefin-based.As
Described polyolefin-based, specifically can such as enumerate number-average molecular weight Mn is the polyolefin-based of 300-3000.At this point, as described poly-
The number-average molecular weight Mn of alkylene, preferably 500-2000, more preferable 500-1500.According to the present invention, described polyolefin-based (basic
On) it is saturation (being rendered as chain alkyl structure), but depend on the type or the polyolefin of the polyolefin as starting material
The difference of preparation method (for example may also be manufactured containing a small amount of olefinic double bond in polyolefin in the polyolefin-based strand
Remain or introduce in the process), but this has no effect on the realization of effect of the present invention, and the present invention also has no intention to carry out the amount bright
Really, and the present invention still polyolefin-based is classified as " alkyl " for this.
According to embodiment of the present invention, in logical formula (I), there are multiple group R, one of group R is logical
Group shown in formula (II), one in other two group R be it is described polyolefin-based, the other is hydrogen, C1-20Straight chain or branch
Alkyl group (preferably C1-10Linear or branched alkyl group) or logical formula (III) shown in group.
According to embodiment of the present invention, in logical formula (I), when group R is described polyolefin-based, the polyolefin
Base is preferably placed at the contraposition of phenolic hydroxyl group in logical formula (I).
According to the present invention, in logical formula (I), when there are multiple, each group R' is same or different to each other, each independently
Selected from hydrogen and C1-20Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (I), when there are multiple, each group R' it is mutually the same or
Difference is each independently selected from hydrogen and C1-4Linear or branched alkyl group.
According to the present invention, in logical formula (II), group L is
According to the present invention, in logical formula (II), in the definition of group L, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20
Linear or branched alkyl group) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in logical formula (II), in the definition of group L, group R " be selected from hydrogen,
C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl.
According to the present invention, in logical formula (II), group R2Selected from hydrogen, C1-20Shown in linear or branched alkyl group, logical formula (IV)
Group shown in group and logical formula (V).
According to embodiment of the present invention, in logical formula (II), group R2Selected from hydrogen, C1-10Linear or branched alkyl group
With group shown in logical formula (IV).
According to the present invention, in logical formula (II), when there are multiple, each group RbIt is same or different to each other, it is respectively independent
Ground is selected from hydrogen and C1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C1-10Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (II), when there are multiple, each group RbIt is mutually the same or
Difference is each independently selected from hydrogen and C1-6Linear or branched alkyl group, preferably hydrogen.
According to the present invention, in logical formula (II), when there are multiple, each group RcIt is same or different to each other, it is respectively independent
Ground is selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (II), when there are multiple, each group RcIt is mutually the same or
Difference is each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (II), a preferably group RcIn cyclic groupUpper N atom is (that is, with group RdThe N atom of bonding) contraposition.
According to the present invention, in logical formula (II), y is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (II), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (II), the integer that n is 1 to 8, preferably 1 or 2.
According to the present invention, in logical formula (II), when there are multiple, each group RdIt is same or different to each other, it is respectively independent
Ground is selected from group, preferably hydrogen shown in hydrogen and logical formula (V).
According to the present invention, in logical formula (II), when there are multiple, each cyclic group(in logical formula (II)
Inside configuration is rendered as bivalent group) it is same or different to each other, phenyl ring is each independently selected from (preferably in the structure of logical formula (II)
Inside is rendered as Isosorbide-5-Nitrae-phenylene) and naphthalene nucleus (being preferably rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene in the inside configuration of logical formula (II)),
Wherein preferred phenyl ring.
According to embodiment of the present invention, in logical formula (II), two adjacent cyclic groupsEach other
By additional S atom (not showing in structural formula) and the N atom of the two rings can be bridged (that is, with group RdThe N of bonding is former
Son) and form phenthazine ring, i.e.,
Embodiment according to the present invention, in logical formula (II), there are more than two cyclic groups
When, as long as wherein at least two (adjacent) cyclic groupForm the phenthazine ring, it is not necessary that it is required that
These cyclic groupsEach of with another adjacent cyclic groupForm the phenthazine
Ring.
According to embodiment of the present invention, in logical formula (II), two adjacent cyclic groupsEach other
Additional group can be passed through(not showing in structural formula) and the N atom of the two rings is bridged (that is, and group
RdThe N atom of bonding) and form 9,10- acridan ring, i.e.,
According to the present invention, in groupIn, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight chain or
Branched alkyl) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in groupIn, group R " is selected from hydrogen and C1-10Straight chain
Or branched alkyl.
Embodiment according to the present invention, in logical formula (II), there are more than two cyclic groups
When, as long as wherein at least two (adjacent) cyclic group9, the 10- acridan ring is formed, is not had
These cyclic groups of exclusive requirementEach of with another adjacent cyclic groupBeing formed should
Acridan ring.
According to the present invention, in logical formula (III), group L is
According to the present invention, in logical formula (III), in the definition of group L, group R " is selected from hydrogen, C1-20Alkyl is (preferably
C1-20Linear or branched alkyl group) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in logical formula (III), in the definition of group L, group R " be selected from hydrogen,
C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl.
According to the present invention, in logical formula (III), group R2Selected from hydrogen, C1-20Shown in linear or branched alkyl group, logical formula (IV)
Group and logical formula (V) shown in group.
According to embodiment of the present invention, in logical formula (III), group R2Selected from hydrogen, C1-10Linear or branched alkyl group
With group shown in logical formula (IV).
According to the present invention, in logical formula (III), when there are multiple, each group RbIt is same or different to each other, it is respectively independent
Ground is selected from hydrogen and C1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C1-10Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (III), when there are multiple, each group RbIt is mutually the same
Or it is different, it is each independently selected from hydrogen and C1-6Linear or branched alkyl group, preferably hydrogen.
According to the present invention, in logical formula (III), when there are multiple, each group RcIt is same or different to each other, it is respectively independent
Ground is selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (III), when there are multiple, each group RcIt is mutually the same
Or it is different, it is each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (III), a preferably group RcIn cyclic groupUpper N atom is (that is, with group RdThe N atom of bonding) contraposition.
According to the present invention, in logical formula (III), y is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (III), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (III), the integer that n is 1 to 8, preferably 1 or 2.
According to the present invention, in logical formula (III), when there are multiple, each group RdIt is same or different to each other, it is respectively independent
Ground is selected from group, preferably hydrogen shown in hydrogen and logical formula (V).
According to the present invention, in logical formula (III), when there are multiple, each cyclic group(in logical formula (III)
Inside configuration be rendered as bivalent group) be same or different to each other, be each independently selected from phenyl ring (preferably in logical formula (III)
Inside configuration is rendered as 1,4- phenylene) and naphthalene nucleus (be preferably rendered as the Asia 1,4- or 2,6- naphthalene in the inside configuration of logical formula (III)
Base), wherein it is preferred that phenyl ring.
According to embodiment of the present invention, in logical formula (III), two adjacent cyclic groupsThat
This can by additional S atom (not shown in structural formula) and bridge the two rings N atom (that is, with group RdThe N of bonding
Atom) and form phenthazine ring, i.e.,
Embodiment according to the present invention, in logical formula (III), there are more than two cyclic groupsWhen, as long as wherein at least two (adjacent) cyclic groupThe phenthazine ring is formed,
It is not necessary to require these cyclic groupsEach of with another adjacent cyclic group
Form the phenthazine ring.
According to embodiment of the present invention, in logical formula (III), two adjacent cyclic groupsThat
This can pass through additional group(not shown in structural formula) and bridge the two rings N atom (that is, with
Group RdThe N atom of bonding) and form 9,10- acridan ring, i.e.,
According to the present invention, in groupIn, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight chain or
Branched alkyl) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in groupIn, group R " is selected from hydrogen and C1-10Straight chain
Or branched alkyl.
Embodiment according to the present invention, in logical formula (III), there are more than two cyclic groupsWhen, as long as wherein at least two (adjacent) cyclic groupForm the acridan
Ring, it is not necessary that it is required that these cyclic groupsEach of with another adjacent cyclic groupForm the acridan ring.
According to the present invention, in logical formula (IV), when there are multiple, each group RbIt is same or different to each other, it is respectively independent
Ground is selected from hydrogen and C1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C1-10Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (IV), when there are multiple, each group RbIt is mutually the same or
Difference is each independently selected from hydrogen and C1-6Linear or branched alkyl group, preferably hydrogen.
According to the present invention, in logical formula (IV), when there are multiple, each group RcIt is same or different to each other, it is respectively independent
Ground is selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (IV), when there are multiple, each group RcIt is mutually the same or
Difference is each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in logical formula (IV), a preferably group RcIn cyclic groupUpper N atom is (that is, with group RdThe N atom of bonding) contraposition.
According to the present invention, in logical formula (IV), y is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (IV), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in logical formula (IV), the integer that n' is 0 to 7, preferably 0,1 or 2, on condition that n'+n≤8.According to
An embodiment of the invention, n'+n=1 or n'+n=2.Here, n is identical as the definition in aforementioned formula (II).
According to the present invention, in logical formula (IV), when there are multiple, each group RdIt is same or different to each other, it is respectively independent
Ground is selected from group, preferably hydrogen shown in hydrogen and logical formula (V).
According to the present invention, in logical formula (IV), when there are multiple, each cyclic group(in logical formula (IV)
Inside configuration is rendered as bivalent group) it is same or different to each other, phenyl ring is each independently selected from (preferably in the structure of logical formula (IV)
Inside is rendered as Isosorbide-5-Nitrae-phenylene) and naphthalene nucleus (being preferably rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene in the inside configuration of logical formula (II)),
Wherein preferred phenyl ring.
According to embodiment of the present invention, in logical formula (IV), two adjacent cyclic groupsEach other
By additional S atom (not showing in structural formula) and the N atom of the two rings can be bridged (that is, with group RdThe N of bonding is former
Son) and form phenthazine ring, i.e.,
Embodiment according to the present invention, in logical formula (IV), there are more than two cyclic groups
When, as long as wherein at least two (adjacent) cyclic groupForm the phenthazine ring, it is not necessary that it is required that
These cyclic groupsEach of with another adjacent cyclic groupForm the phenthazine
Ring.
According to embodiment of the present invention, in logical formula (IV), two adjacent cyclic groupsEach other
Additional group can be passed through(not showing in structural formula) and the N atom of the two rings is bridged (that is, and base
Group RdThe N atom of bonding) and form 9,10- acridan ring, i.e.,
According to the present invention, in groupIn, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Straight chain or
Branched alkyl) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in groupIn, group R " is selected from hydrogen and C1-10Straight chain
Or branched alkyl.
Embodiment according to the present invention, in logical formula (IV), there are more than two cyclic groups
When, as long as wherein at least two (adjacent) cyclic group9, the 10- acridan ring is formed, must not
It is required that these cyclic groupsEach of with another adjacent cyclic groupForm the 9,10-
Acridan ring.
According to the present invention, in logical formula (V), when there are multiple, each group R is same or different to each other, each independently
Selected from hydrogen, C1-300Group shown in group shown in linear or branched alkyl group, logical formula (II) and logical formula (III).
According to embodiment of the present invention, in logical formula (V), when there are multiple, each group R is mutually the same or not
Together, hydrogen and C are each independently selected from1-300Linear or branched alkyl group.
According to the present invention, in logical formula (V), as the C1-300Linear or branched alkyl group, for example C can be enumerated1-20Directly
Chain or branched alkyl (preferably C1-10Linear or branched alkyl group, more preferable C1-4Linear or branched alkyl group) or it is polyolefin-based.As
Described polyolefin-based, specifically can such as enumerate number-average molecular weight Mn is the polyolefin-based of 300-3000.At this point, as described poly-
The number-average molecular weight Mn of alkylene, preferably 500-2000, more preferable 500-1500.According to the present invention, described polyolefin-based (basic
On) it is saturation (being rendered as chain alkyl structure), but depend on the type or the polyolefin of the polyolefin as starting material
The difference of preparation method (for example may also be manufactured containing a small amount of olefinic double bond in polyolefin in the polyolefin-based strand
Remain or introduce in the process), but this has no effect on the realization of effect of the present invention, and the present invention also has no intention to carry out the amount bright
Really, and the present invention still polyolefin-based is classified as " alkyl " for this.
According to embodiment of the present invention, in logical formula (V), there are multiple group R, one of group R is institute
State it is polyolefin-based, the other is hydrogen or C1-20Linear or branched alkyl group (preferably C1-10Linear or branched alkyl group, more preferable C1-4Directly
Chain or branched alkyl).
According to embodiment of the present invention, in logical formula (V), when group R is described polyolefin-based, the polyolefin
Base is preferably placed at the contraposition of phenolic hydroxyl group in logical formula (V).
According to the present invention, in logical formula (V), when there are multiple, each group R' is same or different to each other, each independently
Selected from hydrogen and C1-20Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (V), when there are multiple, each group R' it is mutually the same or
Difference is each independently selected from hydrogen and C1-4Linear or branched alkyl group.
According to the present invention, in logical formula (V), group L is group
According to the present invention, in logical formula (V), in the definition of group L, group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20
Linear or branched alkyl group) and C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in logical formula (V), in the definition of group L, group R " be selected from hydrogen,
C1-10Linear or branched alkyl group and C3-10Linear chain or branched chain miscellaneous alkyl.
According to a preferred embodiment of the present invention, in logical formula (V), in the definition of group L, group R " is selected from hydrogen
And C1-10Linear or branched alkyl group.
According to the present invention, in logical formula (V), two group R and a group-(S)a- L- occupies benzene in logical formula (V) respectively
Three positions of residue on ring.
According to the present invention, in logical formula (V), a is 0 or 1, preferably 1.
According to the present invention, the shielding phenolic compounds is defined as previously described (such as such as logical formula (I) or further such as general formula
(V) shown in), it is necessary to it include structureAs phenol unit.According to a preferred embodiment of the present invention, the shielding
Phenolic compounds includes at most 5, at most 3, at most 2 or at most 1 phenol units in its entire molecular structure.
According to the present invention, the shielding phenolic compounds is defined as previously described (such as such as logical formula (II) or further as logical
Formula (III) or (IV) are shown), it is necessary to it include structureAs amine unit.According to the present invention one it is excellent
The embodiment of choosing, the shielding phenolic compounds in its entire molecular structure comprising at most 15, at most 10, at most 8,
At most 6, at most 4, at most 3 or at most 2 amine units.
According to the present invention, the shielding phenolic compounds preferably at least has (preferably 2,3 in its entire molecular structure
It is a or 4 or more) group RdIt is hydrogen.Specifically, the shielding phenolic compounds preferably contains in its entire molecular structure
Have selected from least one of following hydrogen amine unit (1), hydrogen amine unit (2) and hydrogen amine unit (3).In these hydrogen amine units,
Cyclic groupIt is identical as the definition in logical formula (II) with group R ".
A preferred embodiment according to the present invention, the shielding phenolic compounds is in its entire molecular structure containing extremely
A few hydrogen amine unit (1).
Specifically, to shield phenolic compoundsFor, the compound is in its entire molecule knot
Include 2 phenol units and 2 amine units in structure, and includes 1 hydrogen amine unit (1).
According to the present invention, as the shielding phenolic compounds, for example following compound or its arbitrary proportion can be enumerated
Mixture, but the present invention is not limited thereto.
According to the present invention, shielding phenolic compounds shown in aforementioned formula (I) can be with a kind of single shape of (pure) compound
Formula exist, make or use, can also with the form of the mixture (in any proportion) of two or more of them exist, manufacture or
It uses, this has no effect on the realization of effect of the present invention.
According to the present invention, shielding phenolic compounds shown in aforementioned formula (I) can pass through preparation method system below
It makes, but is not limited thereto.
The preparation method according to the present invention, including make amination shown in phenolic compounds shown in logical formula (X) and general formula (Y)
The first step to react in the presence of closing object aldehyde compound shown in general formula (Z).
According to the present invention, lead in formula (X), when there are multiple, each group R0It is same or different to each other, selects each independently
From hydrogen ,-SH and C1-300Linear or branched alkyl group, on condition that at least one group R0It is-SH.
According to the present invention, in logical formula (X), as the C1-300Linear or branched alkyl group, for example C can be enumerated1-20Directly
Chain or branched alkyl (preferably C1-10Linear or branched alkyl group, more preferable C1-4Linear or branched alkyl group) or it is polyolefin-based.As
Described polyolefin-based, specifically can such as enumerate number-average molecular weight Mn is the polyolefin-based of 300-3000.At this point, as described poly-
The number-average molecular weight Mn of alkylene, preferably 500-2000, more preferable 500-1500.According to the present invention, described polyolefin-based (basic
On) it is saturation (being rendered as chain alkyl structure), but depend on the type or the polyolefin of the polyolefin as starting material
The difference of preparation method (for example may also be manufactured containing a small amount of olefinic double bond in polyolefin in the polyolefin-based strand
Remain or introduce in the process), but this has no effect on the realization of effect of the present invention, and the present invention also has no intention to carry out the amount bright
Really, and the present invention still polyolefin-based is classified as " alkyl " for this.
According to embodiment of the present invention, in logical formula (X), there are multiple group R0, one of group R0Be-
SH, other two group R0In one be it is described polyolefin-based, the other is hydrogen or C1-20Linear or branched alkyl group is (preferably
C1-10Linear or branched alkyl group).
According to embodiment of the present invention, in logical formula (X), in group R0When being described polyolefin-based, the polyene
Alkyl is preferably placed at the contraposition of phenolic hydroxyl group in logical formula (X).
According to the present invention, in logical formula (X), when there are multiple, each group R' is same or different to each other, each independently
Selected from hydrogen and C1-20Linear or branched alkyl group.
According to embodiment of the present invention, in logical formula (X), when there are multiple, each group R' it is mutually the same or
Difference is each independently selected from hydrogen and C1-4Linear or branched alkyl group.
According to the present invention, as phenolic compounds shown in the logical formula (X), commercially available product can be directly used, it can also
To be manufactured by conventionally known in the art method, it is not particularly limited.In addition, as shown in the logical formula (X)
Phenolic compounds, can be used only one kind, can also be used with combination of two or more.
According to the present invention, the preparation method as phenolic compounds shown in the logical formula (X), for example can enumerate in alkyl
In the presence of changing catalysts, make phenolic compounds shown in general formula (X') and polyolefin (number-average molecular weight Mn 300-3000, it is excellent
Select 500-2000, more preferable 500-1500) occur alkylated reaction method.
According to the present invention, in general formula (X'), group R' has and identical meaning in aforementioned formula (X).
According to the present invention, there are three group R' in general formula (X')0, one of group R'0It is-SH, another group
R'0It is H, third group R'0It is hydrogen ,-SH or C1-20Linear or branched alkyl group (preferably C1-10Linear or branched alkyl group).
According to embodiment of the present invention, in general formula (X'), at least one group R'0It is H, and group R'0
The contraposition of phenolic hydroxyl group in general formula (X').
According to the present invention, the polyolefin preferably passes through ethylene, propylene or C4-C10The homopolymerization of alpha-olefin passes through these
Polyolefin obtained from two or more copolymerization in alkene.As the C4-C10Alpha-olefin, for example, can enumerate n-butene,
Isobutene, n-pentene, n-hexylene, positive octene and positive decene.
According to the present invention, at least 20wt% (preferably at least 50wt%, more preferably at least 70wt%) in these polyolefin
Polymer chain contains olefinic double bond at its end.The olefinic double bond is usually with the ethenylidene of high reaction activity or vinyl
Existing for form.
According to the present invention, as the polyolefin, more preferable polybutene.Unless otherwise indicated, term as used herein
" polybutene " broadly includes the polymer as obtained from 1- butylene or isobutylene homopolymerisation, and by 1- butylene, 2- butylene and different
Pass through polymer prepared by copolymerization two or three in butylene.It the commercial product of this quasi polymer may also be containing negligible
Other olefinic components of amount, but this has no effect on implementation of the invention.
According to the present invention, as the polyolefin, further preferred polyisobutene (PIB), also referred to as high reaction activity are poly-
Isobutene.In this kind of polyisobutene, total end alkene of at least 20wt% (preferably at least 50wt%, more preferably at least 70wt%)
Belonging to double bond is provided by methyl ethenylidene.
As the catalyst for alkylation reaction, for example Lewis acid catalyst can be enumerated, for example, selected from alchlor,
Boron trifluoride, tin tetrachloride, titanium tetrabromide, boron trifluoride phenol, boron trifluoride alcohol complex and boron trifluoride ether network
One of object or a variety of is closed, wherein it is preferred that boron trifluoride etherate and/or boron trifluoride methanol complex compound.These
Catalyst for alkylation reaction can directly use commercially available product.
According to the present invention, in the alkylated reaction, phenolic compounds shown in the polyolefin, the general formula (X'),
Molar ratio between the catalyst for alkylation reaction such as can be 1:1-3:0.1-0.5, preferably 1:1.5-3:0.1-0.4,
Most preferably 1:1.5-3:0.2-0.4, but is not limited thereto.
According to the present invention, the reaction time of the alkylated reaction is such as 0.5h-10h, preferably 1h-8h, most preferably 3h-
5h, but is not limited thereto.
According to the present invention, the reaction temperature of the alkylated reaction is such as 0 DEG C -200 DEG C, preferably 10 DEG C -150 DEG C, most
It is preferred that 20 DEG C -100 DEG C, but is not limited thereto.
According to the present invention, the alkylated reaction can be in the presence of a solvent.As the solvent, such as can be with
Enumerate C6-10Alkane (such as hexane, heptane, octane, nonane or decane etc.).Wherein, it is preferable to use hexane and heptane, more preferably
Use hexane.
According to the present invention, after the alkylated reaction, by conventional methods from the reaction mixture finally obtained
It is middle remove catalyst for alkylation reaction, unreacted reactant and the solvent that may use after, that is, obtain the logical formula (X) institute
The phenolic compounds shown.
According to the present invention, in general formula (Y), group R'2Selected from hydrogen, C1-20Linear or branched alkyl group and group
According to the present invention, in general formula (Y), when there are multiple, each group RbIt is same or different to each other, each independently
Selected from hydrogen and C1-20Linear or branched alkyl group is preferably each independently selected from hydrogen and C1-10Linear or branched alkyl group.
According to embodiment of the present invention, in general formula (Y), when there are multiple, each group RbIt is mutually the same or
Difference is each independently selected from hydrogen and C1-6Linear or branched alkyl group, preferably hydrogen.
According to the present invention, in general formula (Y), when there are multiple, each group RcIt is same or different to each other, each independently
Selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in general formula (Y), when there are multiple, each group RcIt is mutually the same or
Difference is each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygroup.
According to embodiment of the present invention, in general formula (Y), a preferably group RcIn cyclic groupUpper N atom is (that is, with group RdThe N atom of bonding) contraposition.
According to the present invention, in general formula (Y), y is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in general formula (Y), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in general formula (Y), the integer that n1 is 1 to 8, preferably 1 or 2.
According to the present invention, in general formula (Y), when there are multiple, each cyclic group(in the knot of general formula (Y)
Bivalent group is rendered as inside structure) it is same or different to each other, phenyl ring is each independently selected from (preferably in the structure of general formula (Y)
Portion is rendered as Isosorbide-5-Nitrae-phenylene) and naphthalene nucleus (being preferably rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene in the inside configuration of general formula (Y)), wherein
It is preferred that phenyl ring.
According to the present invention, as amine compounds shown in the general formula (Y), commercially available product can be directly used, not
There is special limitation.In addition, one kind can be used only as amine compounds shown in the general formula (Y), it can also be two kinds or more
Kind is applied in combination.
According to the present invention, in general formula (Z), group R " is selected from hydrogen, C1-20Alkyl (preferably C1-20Linear or branched alkyl group) and
C3-20Linear chain or branched chain miscellaneous alkyl.
According to embodiment of the present invention, in general formula (Z), group R " is selected from hydrogen, C1-10Linear or branched alkyl group
And C3-10Linear chain or branched chain miscellaneous alkyl.
According to a preferred embodiment of the present invention, in general formula (Z), group R " is selected from hydrogen and C1-10Linear chain or branched chain
Alkyl.
According to the present invention, as aldehyde compound shown in the general formula (Z), for example C can be enumerated1-6Aliphatic aldehyde and benzene
Formaldehyde.
According to embodiment of the present invention, as the C1-6Aliphatic aldehyde, for example C can be enumerated1-6Straight chain or branch
Chain saturated aliphatic aldehyde, specifically such as acetaldehyde or formaldehyde, more preferable formaldehyde.As the formaldehyde, for example, can be used its aqueous solution,
Paraformaldehyde or paraformaldehyde form, are not particularly limited.
According to the present invention, as aldehyde compound shown in the general formula (Z), one kind can be used only, can also two kinds or
Multiple combinations use.
According to the present invention, in the preparation method of the shielding phenolic compounds, in the first step, the general formula
(X) molar ratio of phenolic compounds shown in and amine compounds shown in the general formula (Y) is generally 1:0.1-10, preferably 1:0.5-
5.0, more preferable 1:0.8-2.0.
According to the present invention, in the preparation method of the shielding phenolic compounds, in the first step, the general formula
(X) molar ratio of phenolic compounds shown in and aldehyde compound shown in the general formula (Z) is generally 1:0.1-10, preferably 1:0.5-
5.0, more preferable 1:0.8-2.0.
According to the present invention, in the preparation method of the shielding phenolic compounds, the first step can depositing in solvent
In lower progress.As the solvent, for example C can be enumerated2-10Aliphatic nitrile (such as acetonitrile etc.), C6-20Aromatic hydrocarbon (such as benzene,
Toluene, dimethylbenzene and isopropylbenzene), C6-10Alkane (such as n-hexane, hexamethylene and petroleum ether), C1-6Aliphatic alcohol (such as first
Alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C2-20Halogenated hydrocarbons (such as methylene chloride, carbon tetrachloride, chlorobenzene and
1,2- dichloro-benzenes), C3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C3-10Amide (such as dimethylformamide,
Dimethyl acetamide and N-Methyl pyrrolidone) etc..One kind can be used only in these solvents, can also be made with combination of two or more
With.
According to the present invention, it in the preparation method of the shielding phenolic compounds, in the first step, can be added without
Catalyst can also be added in catalyst.As the catalyst, for example inorganic acid catalyst and organic acid catalysis can be enumerated
Agent.As the inorganic acid catalyst, for example hydrochloric acid, sulfuric acid and phosphoric acid can be enumerated etc..As the organic acid catalyst, than
Methane sulfonic acid, ethylsulfonic acid, sulfamic acid and p-methyl benzenesulfonic acid can such as be enumerated.
As the dosage of the catalyst, can be not particularly limited directly referring to the conventional amount used of the prior art.
According to the present invention, in the preparation method of the shielding phenolic compounds, do not have to the reaction time of the first step
There are special restriction, but generally 0.1h-24h, preferably 0.2h-12h, most preferably 0.5h-6h.
According to the present invention, in the preparation method of the shielding phenolic compounds, do not have to the reaction temperature of the first step
There are special restriction, but generally 0 DEG C -250 DEG C, preferably 20 DEG C -180 DEG C, most preferably 60 DEG C -120 DEG C.
According to the present invention, in the preparation method of the shielding phenolic compounds, after the first step terminates, pass through
Reaction mixture that conventionally known separation method (such as evaporation etc.) is obtained from the first step (hereinafter referred to as first step
Reaction mixture) in remove the volatile materials such as solvent that may be present after, can be obtained the reaction product of first step.
According to embodiment of the present invention, the preparation method of the shielding phenolic compounds optionally further includes making described the
The additional step (hereinafter referred to as additional step A) that the reaction product of one step reacts with vulcanizing agent and (forms phenthazine ring).
According to embodiment of the present invention, the preparation method of the shielding phenolic compounds optionally further includes making described the
The extra step that the reaction product of one step reacts with aldehyde compound shown in aforementioned formula (Z) and (forms acridan ring)
Suddenly (hereinafter referred to as additional step B).
According to the present invention, in the preparation method of the shielding phenolic compounds, the additional step A can be only carried out,
The additional step B can be only carried out, can also not only carry out the additional step A but also carries out the additional step B.Both it is carrying out
The additional step A carries out the additional step B again when, do not have to the precedence of the additional step A and the additional step B
There is special restriction, can first carry out the additional step A, carries out the additional step again after additional step A terminates
B, or the additional step B is first carried out, the additional step A is carried out again after additional step B terminates.In addition, each attached
Product (that is, reaction product from previous additional step) separating step can be had by adding between step, can also be without product point
From step, it is not particularly limited.
According to embodiment of the present invention, in the preparation method of the shielding phenolic compounds, the additional step A
It is carried out after the first step terminates.At this point, the reaction product of the first step is as previously described from described first
It is separated in the reaction mixture of step.Alternatively, the reaction product of the first step can also be straight without the separation
It connects in the form of the reaction mixture of the first step for carrying out the additional step A.Alternatively, the additional step A
It can be carried out after the additional step B terminates.When the additional step A after the additional step B terminates when carrying out,
The reaction product of the additional step B is separated from the reaction mixture of the additional step B as described herein.Or
The reaction product of person, the additional step B can also directly be mixed without the separation with the reaction of the additional step B
The form of object is for carrying out the additional step A.
According to embodiment of the present invention, in the preparation method of the shielding phenolic compounds, in the extra step
In rapid A, as the vulcanizing agent, for example sulphur and sulfur dichloride can be enumerated etc., wherein it is preferred that sulphur.As the sulphur, such as can
To enumerate sulphur or sublimed sulfur.
According to the present invention, in the preparation method of the shielding phenolic compounds, in the additional step A, the general formula
(Y) molar ratio of amine compounds shown in and the vulcanizing agent is generally 1:1-10, preferably 1:1.2-6.0, more preferable 1:1.5-
3.0。
According to the present invention, in the preparation method of the shielding phenolic compounds, the additional step A can depositing in solvent
In lower progress.As the solvent, for example C can be enumerated2-10Aliphatic nitrile (such as acetonitrile etc.), C6-20Aromatic hydrocarbon (such as benzene,
Toluene, dimethylbenzene and isopropylbenzene), C6-10Alkane (such as n-hexane, hexamethylene and petroleum ether), C1-6Aliphatic alcohol (such as first
Alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C2-20Halogenated hydrocarbons (such as methylene chloride, carbon tetrachloride, chlorobenzene and
1,2- dichloro-benzenes), C3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C3-10Amide (such as dimethylformamide,
Dimethyl acetamide and N-Methyl pyrrolidone) etc..One kind can be used only in these solvents, can also be made with combination of two or more
With.
According to the present invention, in the preparation method of the shielding phenolic compounds, the additional step A is generally in catalyst
In the presence of carry out.As the catalyst, for example the catalyst that the prior art uses for this purpose and routinely can be enumerated, specifically
Such as iodine.As the dosage of the catalyst, can be not particularly limited directly referring to the conventional amount used of the prior art.
According to the present invention, in the preparation method of the shielding phenolic compounds, do not have to the reaction time of the additional step A
There are special restriction, but generally 0.1h-24h, preferably 0.2h-12h, most preferably 0.5h-4h.
According to the present invention, in the preparation method of the shielding phenolic compounds, do not have to the reaction temperature of the additional step A
There are special restriction, but generally 60 DEG C -300 DEG C, preferably 120 DEG C -240 DEG C, most preferably 150 DEG C -200 DEG C.
According to the present invention, in the preparation method of the shielding phenolic compounds, after the additional step A terminates, lead to
Cross conventionally known separation method (such as evaporation etc.) removed from the reaction mixture that additional step A is obtained it is that may be present
After the volatile materials such as solvent, the reaction product of additional step A can be obtained, or can also be without the separation, directly
For subsequent reaction step (than additional step B as the aforementioned).
According to embodiment of the present invention, in the preparation method of the shielding phenolic compounds, the additional step B
(as independent step) can be carried out after the first step terminates, can also be carried out simultaneously with the first step,
It is not particularly limited.When the additional step B after the first step terminates when carrying out, the first step it is anti-
Product is answered to separate from the reaction mixture of the first step as previously described.Alternatively, the first step is anti-
Answer product described attached for carrying out directly in the form of the reaction mixture of the first step without the separation
Add step B.Alternatively, the additional step B can also be carried out after the additional step A terminates.When the additional step B exists
When the additional step A is carried out after terminating, the reaction product of the additional step A is as described herein from the extra step
It is separated in the reaction mixture of rapid A.Alternatively, the reaction product of the additional step A can also be straight without the separation
It connects in the form of the reaction mixture of the additional step A for carrying out the additional step B.In addition, working as the additional step B
When being carried out simultaneously with the first step, directly into the reaction system of the first step (such as in the first step
Start or during the first step carries out) hydroformylation shown in the general formula (Z) is added according to hereinafter provided dosage
Close object.
According to the present invention, in the preparation method of the shielding phenolic compounds, in the additional step B, as described
Aldehyde compound shown in general formula (Z), for example C can be enumerated1-6Aliphatic aldehyde and benzaldehyde.As the C1-6Aliphatic aldehyde, than
C can such as be enumerated1-6Linear chain or branched chain saturated aliphatic aldehyde, specifically such as acetaldehyde or formaldehyde, more preferable formaldehyde.As the formaldehyde,
For example its aqueous solution, paraformaldehyde or paraformaldehyde form can be used, it is not particularly limited.
According to the present invention, in the preparation method of the shielding phenolic compounds, in the additional step B, the general formula
(Y) molar ratio of amine compounds shown in and aldehyde compound shown in the general formula (Z) is generally 1:0.1-10, preferably 1:0.5-
5.0, more preferable 1:0.8-2.0.
According to the present invention, in the preparation method of the shielding phenolic compounds, the additional step B is (as individual step
When rapid progress) it can be in the presence of a solvent.As the solvent, for example C can be enumerated2-10Aliphatic nitrile (such as second
Nitrile etc.), C6-20Aromatic hydrocarbon (such as benzene,toluene,xylene and isopropylbenzene), C6-10Alkane (such as n-hexane, hexamethylene and petroleum
Ether), C1-6Aliphatic alcohol (such as methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C2-20Halogenated hydrocarbons (such as two
Chloromethanes, carbon tetrachloride, chlorobenzene and 1,2- dichloro-benzenes), C3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C3-10
Amide (such as dimethylformamide, dimethyl acetamide and N-Methyl pyrrolidone) etc..One kind can be used only in these solvents,
It can also be used with combination of two or more.
According to the present invention, in the preparation method of the shielding phenolic compounds, in the additional step B (as individual
When step carries out) in, it can be added without catalyst, catalyst can also be added.As the catalyst, for example nothing can be enumerated
Machine acid catalyst and organic acid catalyst.As the inorganic acid catalyst, for example hydrochloric acid, sulfuric acid and phosphoric acid can be enumerated etc..
As the organic acid catalyst, for example methane sulfonic acid, ethylsulfonic acid, sulfamic acid and p-methyl benzenesulfonic acid can be enumerated etc..Make
For the dosage of the catalyst, can be not particularly limited directly referring to the conventional amount used of the prior art.
According to the present invention, in the preparation method of the shielding phenolic compounds, to the additional step B (as individual
When step carries out) there is no particular limitation reaction time, but generally 0.1h-24h, preferably 0.2h-12h, most preferably 0.5h-
6h。
According to the present invention, in the preparation method of the shielding phenolic compounds, to the additional step B (as individual
When step carries out) reaction temperature there is no particular limitation, but generally 0 DEG C -250 DEG C, preferably 20 DEG C -180 DEG C, most preferably 60
℃-120℃。
According to the present invention, in the preparation method of the shielding phenolic compounds, in the additional step B (as individual
When step carries out) terminate after, the reaction that is obtained by conventionally known separation method (such as evaporation etc.) from additional step B
After removing the volatile materials such as solvent that may be present in mixture, the reaction product of additional step B, Huo Zheye can be obtained
Subsequent reaction step can be directly used in without the separation (than additional step A as the aforementioned).
It is known in the art, aforementioned all reaction step (including the first step, the additional step A and
The additional step B) generally carried out under the protection of inert gas atmosphere.As the inert gas, for example nitrogen can be enumerated
Gas and argon gas etc., are not particularly limited.
According to the present invention, it is described shielding phenolic compounds preparation method in, as the first step reaction product,
The reaction product of the reaction product of the additional step A or the additional step B can be a kind of single shielding phenolic compounds
(for example shielding phenolic compounds shown in aforementioned formula (I)) is also possible to the mixture comprising a variety of shielding phenolic compounds.These
Reaction product is all desired by the present invention, and the difference of existence form has no effect on the realization of effect of the present invention.Therefore, this theory
These reaction products are collectively termed as to shielding phenolic compounds of the invention without distinction in bright book context.In consideration of it, according to
The present invention, and be not present and these reaction products are further purified, or be further separated out a certain spy from these reaction products
Determine the absolute necessity of the shielding phenolic compounds of structure.Certainly, the purifying or separation are for the further of desired effect of the present invention
It is sometimes preferred for promotion, but for the present invention not necessarily.Even so, as the purifying or separation method,
For example it can enumerate and the reaction product is purified or separated by the methods of column chromatography method or preparation chromatography.
The present invention is further illustrated for embodiment below, but is not intended to limit the present invention.Following embodiment
In, dropping point is measured using 3498 method of GB/T, and cone penetration is measured using 269 method of GB/T, and oxidation stability uses GB/T
13464 methods measure, and Stencil oil-dividing is measured using 0324 method of SH/T, and anticorrosive property is measured using 018 method of GB/T5, water
Leaching number of dropouts is measured using 0109 method of SH/T, and tetra-ball machine test PB is measured using 0202 method of SH/T, tetra-ball machine test PD
It is measured using SH/T0202 method, copper corrosion performance is measured using 7326 method of GB/T.
Embodiment 1
Shield the preparation of phenolic compounds (structure sees below formula):
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
31.65 grams of (133mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 1.86 grams of (62mmol) formaldehyde, 28.15 grams
(153mmol) 4-aminodiphenylamine, 0.75 gram of (7.5mmol) hydrochloric acid and 150mL isopropanol stir rapidly, react at 25 DEG C
24h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and obtains structure as above by column chromatography for separation
Shielding phenol product.
The characterize data of the product is as follows:
1H NMR (300MHz, CDCl3): δ 1.36-1.54 (18H), 3.75 (1H), 4.80 (2H), 5.32 (1H), 6.80
(2H), 6.97 (5H), 7.17 (2H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,51.2,119.4,121.8,126.5,129.5,131.4,
136.6,144.5,153.4；
C27H34N2OS calculated value C 74.61, H 7.88, N 6.45, O 3.68, S 7.38；Measured value: C 74.52, H
7.84, N 6.51, O 3.73, S 7.40.
The preparation of complex lithium grease:
Material component: shielding phenolic compounds 8kg；(100 DEG C of viscosity are 10mm to 500SN lubricating base oil 1464kg2/s)；One
Water lithium hydroxide 32.78kg；12- hydroxy stearic acid 75.9kg；Azelaic acid 47.54kg；
Rouge kettle processed first is added in the 12- hydroxy stearic acid and 47.54kg azelaic acid of 732kg lubricating base oil and 75.9kg
In, heating stirring, be warming up to 85 DEG C of addition lithium hydroxide aqueous solutions (wherein 32.78kg containing lithium hydroxide, water 262.24kg) into
Row saponification 0.5h is warming up to 190 DEG C of progress high temperature refining 5min；After addition 732kg lubricating base oil cools to 100 DEG C,
The shielding phenolic compounds (structure is shown in above formula) of 8kg is added, stirs evenly；2 times are ground into rouge by three-roller.Properties of product such as table
Shown in 1.
It is calculated according to inventory, in the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows:
4.8 weight % of 12- hydroxy lithium stearate；3.2 weight % of azelaic acid lithium；91.5 weight % of lubricating base oil；Shield phenolic compounds
0.5 weight %.
Embodiment 2
Shield the preparation of phenolic compounds (structure sees below formula):
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
8.57 grams of (36mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 0.45 gram of (15mmol) formaldehyde, 10.14 grams (39mmol)
N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL toluene stir rapidly, in 90 DEG C of reaction 4h.To after reaction, be evaporated under reduced pressure
A small amount of water of solvent and generation is removed, and the shielding phenol product of structure as above is obtained by column chromatography for separation.
The characterize data of the product is as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 5.23 (2H), 6.80-7.02 (10H), 7.17 (2H), 7.26
(4H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,55.2,117.1,121.8,126.2,129.5,136.6,
143.6,153.4；
C33H38N2OS calculated value C 77.60, H 7.50, N 5.48, O 3.13, S 6.28；Measured value: C 77.71, H
7.52, N 5.53, O 3.10, S 6.23.
The preparation of complex lithium grease:
Material component: (100 DEG C of viscosity are 30mm to 150BS lubricating base oil 1044kg2/s)；Lithium hydroxide monohydrate
28.52kg；Stearic acid 133.98kg；Terephthalic acid (TPA) 15.64kg；2.4kg shields phenolic compounds；
First the stearic acid and 15.64kg terephthalic acid (TPA) of 744kg lubricating base oil and 133.98kg are added in rouge kettle processed,
Heating stirring is warming up to 95 DEG C of addition lithium hydroxide aqueous solutions (wherein 28.52kg containing lithium hydroxide, water 171.12kg) and carries out soap
Change reaction 0.8h, is warming up to 210 DEG C of progress high temperature refining 5min；After addition 300kg lubricating base oil cools to 120 DEG C, it is added
2.4kg shields phenolic compounds (structure is shown in above formula), stirs evenly；2-3 times is ground into rouge by three-roller.Properties of product such as table 1
It is shown.
It is calculated according to inventory, in the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows:
11.4 weight % of lithium stearate；1.4 weight % of terephthalic acid (TPA) lithium；87 weight % of lubricating base oil；Shield 0.2 weight of phenolic compounds
Measure %.
Embodiment 3
Shield the preparation of phenolic compounds (structure sees below formula):
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
20.23 grams of (85mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 3.45 grams of (115mmol) formaldehyde, 18.49 grams
(69mmol) N- (1,3- dimethylbutyl)-N'- diphenyl-para-phenylene diamine and 150mL benzene stir rapidly, in 85 DEG C of reaction 3h.To
After reaction, vacuum distillation removes a small amount of water of solvent and generation, and obtains the shielding of structure as above by column chromatography for separation
Phenol product.
The characterize data of the product is as follows:
1H NMR (300MHz, CDCl3): δ 0.80 (6H), 1.11-1.21 (4H), 1.36 (18H), 1.67 (2H), 3.47
(1H), 4.80 (2H), 5.32 (1H), 6.80 (2H), 6.97 (5H), 7.17 (2H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 17.9,22.4,29.6,34.6,45.2,52.7,58.6,119.4,121.8,
126.2,129.5,131.2,136.6,144.1,146.1,153.4；
C33H46N2OS calculated value: C 76.40, H 8.94, N 5.40, O 3.08, S 6.18；Measured value: C 76.48, H
8.96, N 5.35, O 3.09, S 6.12.
The preparation of complex lithium grease:
Material component: (100 DEG C of viscosity are 5.8mm to PAO6 synthesized hydrocarbon fluid base oil 983kg2/s)；Lithium hydroxide monohydrate
56.48kg；Stearic acid 148.58kg；Adipic acid 57.18kg；3.6kg shields phenolic compounds；
First the stearic acid and 57.18kg adipic acid of 738kg lubricating base oil and 148.58kg are added in rouge kettle processed, heating
Stirring is warming up to 88 DEG C of addition lithium hydroxide aqueous solutions (wherein 56.48kg containing lithium hydroxide, water 45.19kg) and be saponified instead
0.6h is answered, 195 DEG C of progress high temperature refining 8min are warming up to；After addition 245kg lubricating base oil cools to 110 DEG C, 3.6kg is added
It shields phenolic compounds (structure is shown in above formula), stirs evenly；3 times are ground into rouge by three-roller.Properties of product are as shown in table 1.
It is calculated according to inventory, in the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows:
12.64 weight % of lithium stearate；5.16 weight % of lithium adipate；81.9 weight % of lubricating base oil；Shield 0.3 weight of phenolic compounds
Measure %.
Embodiment 4
Shield the preparation of phenolic compounds (structure sees below formula):
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
4.99 grams of (21mmol) 2,6- di-t-butyl -4- mercapto-phenols, 1.59 grams of (53mmol) formaldehyde, 5.70 grams of (31mmol) N- are added
Diphenyl-para-phenylene diamine and 150mL ethyl alcohol stir rapidly, after 60 DEG C of reaction 2.5h, are down to room temperature, 2.55 grams (85mmol) is added
Formaldehyde is warming up to 85 DEG C of reaction 2.5h.To which after reaction, vacuum distillation removes a small amount of water of solvent and generation, and passes through column
Chromatography obtains the shielding phenol product of structure as above.
The characterize data of the product is as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 3.74 (1H), 4.12 (2H), 4.59 (1H), 4.83 (2H),
5.32 (1H), 6.97-7.11 (5H), 7.17 (2H), 7.24 (2H)；
13C NMR (75MHz, CDCl3): δ 29.6,33.1,34.6,50.6,119.4,123.3,126.2,126.7,
127.9,136.6,140.5,142.9,153.4；
C26H34N2OS calculated value C 75.29, H 7.67, N 6.27, O 3.58, S 7.18；Measured value: C 75.20, H
7.59, N 6.29, O 3.65, S 7.22.
The preparation of complex lithium grease:
Material component: (100 DEG C of viscosity are 13mm to 500SN and 150BS mixed lubrication base oil 1358kg2/s)；One water hydrogen
Lithia 50.2kg；12- hydroxy stearic acid 175.6kg；Decanedioic acid 58.68kg；1.6kg shields phenolic compounds；
Rouge kettle processed first is added in the 12- hydroxy stearic acid and 58.68kg decanedioic acid of 678kg lubricating base oil and 175.6kg
In, heating stirring is warming up to 92 DEG C of addition lithium hydroxide aqueous solutions (wherein 50.2kg containing lithium hydroxide, water 200.8kg) and carries out
Saponification 1h is warming up to 205 DEG C of progress high temperature refining 8min；After addition 680kg lubricating base oil cools to 105 DEG C, it is added
1.6kg shields phenolic compounds (structure is shown in above formula), stirs evenly；2 times are ground into rouge by three-roller.Properties of product such as 1 institute of table
Show.
It is calculated according to inventory, in the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows:
11.11 weight % of 12- hydroxy lithium stearate；3.89 weight % of decanedioic acid lithium；84.9 weight % of lubricating base oil；Phenolate is shielded to close
0.1 weight % of object.
Embodiment 5
Shield the preparation of phenolic compounds (structure sees below formula):
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
19.52 grams of (82mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 3.63 grams of (121mmol) formaldehyde, 19.93 grams
(94mmol) 4- amino -4'- ethyl diphenylamines and 150mL dimethylbenzene stir rapidly, after 90 DEG C of reaction 3h, are down to room temperature, add
Enter 10.11 grams of (316mmol) sulphur and 0.04 gram of (0.35mmol) iodine, is warming up to 150 DEG C of reaction 8h.To after reaction, depressurize
A small amount of water of solvent and generation is distilled off, and the shielding phenol product of structure as above is obtained by column chromatography for separation.
The characterize data of the product is as follows:
1H NMR (300MHz, CDCl3): δ 1.23 (1H), 1.36 (18H), 2.61 (2H), 3.77 (1H), 4.84 (2H),
5.32 (1H), 5.70 (1H), 6.98 (5H), 7.17 (2H), 7.49 (1H)；
13C NMR (75MHz, CDCl3): δ 15.60,29.6,34.6,50.7,118.9,121.8,126.2,129.7,
136.6,141.2,146.1,153.4；
C29H36N2OS2Calculated value C 70.69, H 7.36, N 5.69, O 3.25, S 13.02；Measured value: C 70.77, H
7.41, N 5.67, O 3.17, S 12.93.
The preparation of complex lithium grease:
Material component: shielding phenolic compounds 2.6kg；(100 DEG C of viscosity are 10mm to 500SN lubricating base oil 522kg2/s)；
Lithium hydroxide monohydrate 32.78kg；12- hydroxy stearic acid 75.9kg；Azelaic acid 47.54kg；
Rouge kettle processed first is added in the 12- hydroxy stearic acid and 47.54kg azelaic acid of 322kg lubricating base oil and 75.9kg
In, heating stirring, be warming up to 85 DEG C of addition lithium hydroxide aqueous solutions (wherein 32.78kg containing lithium hydroxide, water 262.24kg) into
Row saponification 0.7h is warming up to 190 DEG C of progress high temperature refining 5min；After addition 200kg lubricating base oil cools to 100 DEG C,
The shielding phenolic compounds (structure is shown in above formula) of 2.6kg is added, stirs evenly；2 times are ground into rouge by three-roller.Properties of product are such as
Shown in table 1.
It is calculated according to inventory, in the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows:
11.76 weight % of 12- hydroxy lithium stearate；7.84 weight % of azelaic acid lithium；90.5 weight % of lubricating base oil；Phenolate is shielded to close
1.5 weight % of object.
Comparative example 1
Complex lithium grease is prepared according to the method for embodiment 4, unlike, the preparation process of complex lithium grease
In be added without shielding phenolic compounds.Properties of product are as shown in table 1.
Comparative example 2
Complex lithium grease is prepared according to the method for embodiment 4, unlike, it is the tertiary fourth of 2,6- bis- of following formula by structure
Phenolic compounds is covered in base p-cresol substitution screen embodiment 4, obtains the comparative example 2 of lubricant composition.Properties of product such as table 1
It is shown.
Comparative example 3
Complex lithium grease is prepared according to the method for embodiment 4, unlike, it is the N- phenyl-α-of following formula by structure
Phenolic compounds is covered in naphthylamines substitution screen embodiment 4, obtains the comparative example 3 of lubricant composition.Properties of product are as shown in table 1.
Comparative example 4
Complex lithium grease is prepared according to the method for embodiment 4, unlike, the shielding phenolate that structure is following formula is closed
Shielding phenolic compounds in object alternate embodiment 4 obtains the comparative example 4 of lubricant composition.Properties of product are as shown in table 1.
Shield the preparation of phenolic compounds (structure sees below formula):
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
20.23 grams of (85mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 2.61 grams of (87mmol) formaldehyde, 14.37 grams (85mmol)
Diphenylamines and 150mL methanol stir rapidly, in 60 DEG C of reaction 2h.To which after reaction, vacuum distillation removes solvent and generation
A small amount of water, and the shielding phenol product of structure as above is obtained by column chromatography for separation.
The characterize data of the product is as follows:
1H NMR (300MHz, CDCl3): δ 1.36 (18H), 5.21 (2H), 5.32 (1H), 6.99 (6H), 7.17 (2H),
7.27(4H)；
13C NMR (75MHz, CDCl3): δ 29.6,34.6,55.2,120.4,123.3,125.9,126.2,129.2,
136.6,150.0,153.5；
C27H33NOS calculated value C 77.28, H 7.93, N 3.34, O 3.81, S 7.64；Measured value: C 77.22, H
7.89, N 3.31, O 3.83, S 7.67.
Comparative example 5
Complex lithium grease is prepared according to the method for embodiment 4, unlike, the shielding phenolate that structure is following formula is closed
Shielding phenolic compounds in object alternate embodiment 4 obtains the comparative example 5 of lubricant composition.Properties of product are as shown in table 1.
Shield the preparation of phenolic compounds (structure sees below formula):
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
10.71 grams of (52mmol) 2,6- di-t-butyl -4- mercapto-phenols of addition, 1.89 grams of (63mmol) formaldehyde, 17.42 grams (65mmol)
N- (1,3- dimethylbutyl)-N'- diphenyl-para-phenylene diamine and 150mL methanol stir rapidly, in 70 DEG C of reaction 4h.Wait react knot
Shu Hou, vacuum distillation remove a small amount of water of solvent and generation, and obtain the shielding phenol product of structure as above by column chromatography for separation.
The characterize data of the product is as follows:
1H NMR (300MHz, CDCl3): δ 0.80 (6H), 1.11 (3H), 1.29 (1H), 1.36 (18H), 3.45 (1H),
4.53 (2H), 5.32 (2H), 6.97-7.07 (9H), 7.26 (2H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 17.9,22.40,24.6,30.4,34.3,45.7,54.5,56.7,116.6,
120.4,121.8,125.9,128.9,129.5,135.6,146.1,153.5,154.8；
C33H46N2O calculated value C 81.43, H 9.53, N 5.76, O 3.29；Measured value: C 81.38, H 9.51, N
5.79, O 3.31.
Comparative example 6
Complex lithium grease is prepared according to the method for embodiment 4, unlike, the shielding phenolate that structure is following formula is closed
Shielding phenolic compounds in object alternate embodiment 4 obtains the comparative example 6 of lubricant composition.Properties of product are as shown in table 1.
Shield the preparation of phenolic compounds (structure sees below formula):
Under nitrogen protection atmosphere, in the 250ml four-hole boiling flask equipped with blender, thermometer, condenser pipe and dropping funel,
9.24 grams of (33mmol) 2,6- di-t-butyl -4- (3- mercaptopropyi) phenol of addition, 1.11 grams of (37mmol) formaldehyde, 11.71 grams
(45mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL benzene stir rapidly, in 80 DEG C of reaction 4h.To after reaction, subtract
A small amount of water of solvent and generation is distilled off in pressure, and obtains the shielding phenol product of structure as above by column chromatography for separation.
The characterize data of the product is as follows:
1H NMR (300MHz, CDCl3): δ 1.40 (18H), 1.99 (1H), 2.61-2.80 (6H), 4.63 (2H), 5.32
(1H), 6.97-7.02 (12H), 7.26 (4H), 7.55 (1H)；
13C NMR (75MHz, CDCl3): δ 28.7,31.1,34.3,35.7,54.1,117.1,119.4,123.3,
124.8,129.2,131.8,136.0,142.8,144.9,146.1,151.9；
C36H44N2OS calculated value C 78.22, H 8.02, N 5.07, O 2.89, S 5.80；Measured value: C 78.27, H
7.96, N 4.98, O 2.92, S 5.83.
The assessment of performance of 1 lubricating grease of table
From the results shown in Table 1, complex lithium grease of the invention has excellent high temperature antioxidant, antirust
Property, heat-resisting quantity, water-resistance and adhesiveness, colloid stability, extreme pressure anti-wear, lubricating life, anticorrosive property and resistance to saltfog
Etc. performances.
Claims (22)
1. a kind of complex lithium grease, on the basis of lubricating grease total weight, including following components: the shielding of 0.01%-10%
Phenolic compounds, the compound lithium base thickening agent and major amount of lubricating base oil of 5-%35%；
The structure of the shielding phenolic compounds is as shown in logical formula (I):
In logical formula (I), each group R is same or different to each other, and is each independently selected from hydrogen, C1-300Linear or branched alkyl group, general formula
(II) group shown in group shown in and logical formula (III), on condition that at least one group R is group shown in logical formula (II)；
Each group R' is same or different to each other, and is each independently selected from hydrogen and C1-20Linear or branched alkyl group,
In aforementioned each logical formula (II), (III) and (IV), it is group each independently that each group L, which is same or different to each other,Wherein group R " is selected from hydrogen, C1-20Alkyl and C3-20Linear chain or branched chain miscellaneous alkyl；Each group R2It is mutually the same
Or it is different, it is each independently selected from hydrogen, C1-20Shown in group shown in linear or branched alkyl group, logical formula (IV) and logical formula (V)
Group；Each group RbIt is same or different to each other, is each independently selected from hydrogen and C1-20Linear or branched alkyl group；Each group RcEach other
It is identical or different, it is each independently selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup；Y is 0 to 3
Integer；Z is 0 to 3 integer；The integer that n is 1 to 8；The integer that n' is 0 to 7, on condition that n'+n≤8；Each group RdEach other
It is identical or different, it is each independently selected from group shown in hydrogen and logical formula (V)；Each cyclic groupIt is mutually the same or
Difference is each independently selected from phenyl ring and naphthalene nucleus, wherein two adjacent cyclic groupsEach other optionally by additional
S atom and bridge the two rings N atom and form phenthazine ring, and/or, two adjacent cyclic groups
Optionally pass through additional group each otherWith bridge the two rings N atom and form 9,10- acridan ring,
Wherein group R " is selected from hydrogen, C1-20Alkyl and C3-20Linear chain or branched chain miscellaneous alkyl,
In logical formula (V), each group R is same or different to each other, and is each independently selected from hydrogen, C1-300Linear or branched alkyl group, general formula
(II) group shown in group shown in and logical formula (III)；Each group R' is same or different to each other, be each independently selected from hydrogen and
C1-20Linear or branched alkyl group；Group L is groupWherein group R " is selected from hydrogen, C1-20Alkyl and C3-20Directly
Chain or branched heteroalkyl groups；A is 0 or 1, and two group R and a group-(S)a- L- occupies the residue three on phenyl ring respectively
A position,
Wherein, the linear chain or branched chain miscellaneous alkyl is selected from one or more groups-inside linear or branched alkyl group molecular structure
CH2The group and linear or branched alkyl group that the substituting group for being selected from one of-O- ,-S- and-NR'- is directly substituted and obtained divide
One or more group-CH inside minor structure <by substituting group-N < are directly substituted and the group of acquisition, wherein in-NR'-
R' is H or C1-4Linear or branched alkyl group, the shielding phenolic compounds at least one group R in its entire molecular structuredIt is
Hydrogen.
2. lubricating grease described in accordance with the claim 1, which is characterized in that each group R is each independently selected from hydrogen, C1-10Straight chain or
Group and logical formula (III) institute shown in polyolefin-based, the logical formula (II) of branched alkyl or number-average molecular weight Mn for 300-3000
The group shown；Each group R' is each independently selected from hydrogen and C1-4Linear or branched alkyl group；
Group R " is selected from hydrogen, C1-20Linear or branched alkyl group and C3-20Linear chain or branched chain miscellaneous alkyl；Each group R2It selects each independently
From hydrogen, C1-10Group shown in linear or branched alkyl group and logical formula (IV)；Each group RbIt is each independently selected from hydrogen and C1-10Straight chain
Or branched alkyl；Each group RcIt is each independently selected from hydrogen, C1-10Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygen
Base；Y is 0 or 1；Z is 0 or 1；N is 1 or 2；N' is 0 or 1, on condition that n'+n=1 or n'+n=2；Each group RdFor hydrogen；Each ring
GroupSelected from phenyl ring.
3. lubricating grease according to claim 2, which is characterized in that group R " is selected from hydrogen, C1-10Linear or branched alkyl group and
C3-10Linear chain or branched chain miscellaneous alkyl.
4. lubricating grease according to claim 2, which is characterized in that each group RcIn cyclic groupUpper nitrogen is former
The contraposition of son.
5. lubricating grease described in accordance with the claim 1, which is characterized in that the shielding phenolic compounds materialization selected from the following
Close object or the mixture of its arbitrary proportion:
6. lubricating grease described in accordance with the claim 1, which is characterized in that the preparation method of the shielding phenolic compounds includes making to lead to
Occur in the presence of amine compounds aldehyde compound shown in general formula (Z) shown in phenolic compounds shown in formula (X) and general formula (Y)
The first step of reaction, optionally further include make the reaction product of the first step reacted with vulcanizing agent and/or with general formula (Z) institute
The additional step for the aldehyde compound reaction shown,
In logical formula (X), each group R0It is same or different to each other, is each independently selected from hydrogen ,-SH and C1-300Linear chain or branched chain alkane
Base, on condition that at least one group R0It is-SH；Each group R' is same or different to each other, and is each independently selected from hydrogen and C1-20Straight chain
Or branched alkyl,
In general formula (Y), group R'2Selected from hydrogen, C1-20Linear or branched alkyl group and groupEach group Rb
It is same or different to each other, is each independently selected from hydrogen and C1-20Linear or branched alkyl group；Each group RcIt is same or different to each other, respectively
From independently selected from hydrogen, C1-20Linear or branched alkyl group and C1-20Linear or branched alkyl group oxygroup；Y is 0 to 3 integer；Z be 0 to
3 integer；The integer that n1 is 1 to 8；Each cyclic groupBe same or different to each other, be each independently selected from phenyl ring and
Naphthalene nucleus,
In general formula (Z), group R " is selected from hydrogen, C1-20Alkyl and C3-20Linear chain or branched chain miscellaneous alkyl,
Wherein, the linear chain or branched chain miscellaneous alkyl is selected from one or more groups-inside linear or branched alkyl group molecular structure
CH2The group and linear or branched alkyl group that the substituting group for being selected from one of-O- ,-S- and-NR'- is directly substituted and obtained divide
One or more group-CH inside minor structure <by substituting group-N < are directly substituted and the group of acquisition, wherein in-NR'-
R' is H or C1-4Linear or branched alkyl group.
7. lubricating grease according to claim 6, which is characterized in that aldehyde compound shown in general formula (Z) is formaldehyde；The sulphur
Agent is sulphur；
Each group R0It is each independently selected from hydrogen ,-SH and C1-10Linear or branched alkyl group or number-average molecular weight Mn are 300-3000
It is polyolefin-based；Each group R' is each independently selected from hydrogen and C1-4Linear or branched alkyl group；
Each group RbIt is each independently selected from hydrogen and C1-10Linear or branched alkyl group；Each group RcIt is each independently selected from hydrogen, C1-10
Linear or branched alkyl group and C1-10Linear or branched alkyl group oxygroup；Y is 0 or 1；Z is 0 or 1；N1 is 1 or 2；Each cyclic groupSelected from phenyl ring；Group R " is selected from hydrogen, C1-20Linear or branched alkyl group and C3-20Linear chain or branched chain miscellaneous alkyl.
8. lubricating grease according to claim 7, which is characterized in that each group RcIn cyclic groupUpper nitrogen is former
The contraposition of son.
9. lubricating grease according to claim 7, which is characterized in that group R " is selected from hydrogen, C1-10Linear or branched alkyl group and
C3-10Linear chain or branched chain miscellaneous alkyl.
10. lubricating grease according to claim 6, which is characterized in that wherein in the first step, the logical formula (X)
Shown in the molar ratios of amine compounds shown in phenolic compounds and the general formula (Y) be 1:0.1-10, shown in the logical formula (X)
The molar ratio of phenolic compounds and aldehyde compound shown in the general formula (Z) is 1:0.1-10, described logical in the additional step
The molar ratio of amine compounds shown in formula (Y) and the vulcanizing agent is 1:1-10, amine compounds and institute shown in the general formula (Y)
The molar ratio for stating aldehyde compound shown in general formula (Z) is 1:0.1-10.
11. lubricating grease according to claim 6, which is characterized in that wherein in the first step, the logical formula (X)
Shown in the molar ratios of amine compounds shown in phenolic compounds and the general formula (Y) be 1:0.5-5.0, shown in the logical formula (X)
Phenolic compounds and the general formula (Z) shown in aldehyde compound molar ratio be 1:0.5-5.0, in the additional step, institute
The molar ratio for stating amine compounds shown in general formula (Y) and the vulcanizing agent is 1:1.2-6.0, amination shown in the general formula (Y)
The molar ratio for closing aldehyde compound shown in object and the general formula (Z) is 1:0.5-5.0.
12. lubricating grease according to claim 6, which is characterized in that wherein in the first step, the logical formula (X)
Shown in the molar ratios of amine compounds shown in phenolic compounds and the general formula (Y) be 1:0.8-2.0, shown in the logical formula (X)
Phenolic compounds and the general formula (Z) shown in aldehyde compound molar ratio be 1:0.8-2.0, in the additional step, institute
The molar ratio for stating amine compounds shown in general formula (Y) and the vulcanizing agent is 1:1.5-3.0, amination shown in the general formula (Y)
The molar ratio for closing aldehyde compound shown in object and the general formula (Z) is 1:0.8-2.0.
13. lubricating grease described in accordance with the claim 1, which is characterized in that the shielding phenolic compounds accounts for the compound lithium base profit
The 0.05%-5% of grease composition total weight.
14. lubricating grease described in accordance with the claim 1, which is characterized in that the compound lithium base thickening agent passes through acid and hydrogen-oxygen
Change lithium reaction to generate, the acid is the mixed acid containing polymer acid and low molecular acid, and the polymer acid is C12-C25Fat
Acid and/or hydroxy fatty acid, the low molecular acid are C2-C11Organic carboxyl acid, the molar ratio of the polymer acid and low molecular acid
For 1:0.1-1.
15. lubricating grease according to claim 14, which is characterized in that the polymer acid is lauric acid, palmitinic acid, tristearin
Acid and one of 12- hydroxy stearic acid are a variety of, the low molecular acid be acetic acid, propionic acid, ethanedioic acid, adipic acid, azelaic acid,
One of decanedioic acid and terephthalic acid (TPA) are a variety of.
16. lubricating grease described in accordance with the claim 1, which is characterized in that the lubricating base oil is mineral oil, vegetable oil and conjunction
At one of oil or a variety of, 100 DEG C of kinematic viscosity are 5-60mm2/s。
17. the preparation method of complex lithium grease described in claim 1, comprising: by compound lithium base thickening agent and lubrication base
Plinth oil is uniformly mixed, and is refined in 180-230 DEG C of constant temperature, cooling, and the shielding phenolic compounds is added, is ground into rouge.
18. the preparation method of complex lithium grease described in claim 1, comprising: by partial lubrication base oil, polymer acid
With low molecular acid mixing, heating, it is warming up to 85-95 DEG C, the aqueous solution that lithium hydroxide is added carries out saponification, after fully reacting
It is warming up to 190-210 DEG C, high temperature refining is carried out, remaining lubricating base oil is added and is cooled to 100-120 DEG C, the shielding is added
Phenolic compounds is ground into rouge.
19. according to the method for claim 18, which is characterized in that the polymer acid is C12-C20Fatty acid and/or C12-
C20Hydroxy fatty acid, the low molecular acid are C2-C11Organic carboxyl acid, the molar ratio of the polymer acid and low molecular acid is 1:
0.1-1。
20. according to the method for claim 18, which is characterized in that the partial lubrication base oil and remaining lubrication base
The dosage of oil is respectively 50%-75%, 25%-50% of the total dosage of lubricating base oil.
21. according to the method for claim 18, which is characterized in that the time of the saponification is 0.2-1.5 hours.
22. according to the method for claim 18, which is characterized in that the time of the refining is 5-25 minutes.
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| CN109679713B (en) * | 2017-10-18 | 2022-06-28 | 中国石油化工股份有限公司 | Lithium-based lubricating grease and preparation method thereof |
| CN109679716B (en) * | 2017-10-18 | 2022-06-28 | 中国石油化工股份有限公司 | Composite lithium-based lubricating grease and preparation method thereof |
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|---|---|---|---|---|
| CA1219584A (en) * | 1983-02-10 | 1987-03-24 | John D. Spivack | N-substitute (4-hydroxyphenylthiomethyl) amine or ureide stabilizers |
| US4946610A (en) * | 1989-08-03 | 1990-08-07 | Ethyl Petroleum Additives, Inc. | Sulfur-bridged phenolic antioxidants |
| CN1534084A (en) * | 2003-03-28 | 2004-10-06 | 中国石油化工股份有限公司 | Preparation method of antioxidation antifriction lubricating oil additive |
| CN102839041A (en) * | 2012-08-23 | 2012-12-26 | 中国石油化工股份有限公司 | Composition of composite lithium grease and preparation method |
| CN103320198A (en) * | 2012-03-22 | 2013-09-25 | 中国石油天然气股份有限公司 | Thioether-containing hindered phenol antioxidant and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080090742A1 (en) * | 2006-10-12 | 2008-04-17 | Mathur Naresh C | Compound and method of making the compound |
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|---|---|---|---|---|
| CA1219584A (en) * | 1983-02-10 | 1987-03-24 | John D. Spivack | N-substitute (4-hydroxyphenylthiomethyl) amine or ureide stabilizers |
| US4946610A (en) * | 1989-08-03 | 1990-08-07 | Ethyl Petroleum Additives, Inc. | Sulfur-bridged phenolic antioxidants |
| CN1534084A (en) * | 2003-03-28 | 2004-10-06 | 中国石油化工股份有限公司 | Preparation method of antioxidation antifriction lubricating oil additive |
| CN103320198A (en) * | 2012-03-22 | 2013-09-25 | 中国石油天然气股份有限公司 | Thioether-containing hindered phenol antioxidant and preparation method thereof |
| CN102839041A (en) * | 2012-08-23 | 2012-12-26 | 中国石油化工股份有限公司 | Composition of composite lithium grease and preparation method |
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