CN106590820A - Sodium-based lubricating grease and preparation method thereof - Google Patents
Sodium-based lubricating grease and preparation method thereof Download PDFInfo
- Publication number
- CN106590820A CN106590820A CN201510664744.8A CN201510664744A CN106590820A CN 106590820 A CN106590820 A CN 106590820A CN 201510664744 A CN201510664744 A CN 201510664744A CN 106590820 A CN106590820 A CN 106590820A
- Authority
- CN
- China
- Prior art keywords
- group
- straight
- hydrogen
- branched alkyl
- independently selected
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 CC(*)*(*C=C)N1CC1 Chemical compound CC(*)*(*C=C)N1CC1 0.000 description 4
Landscapes
- Lubricants (AREA)
Abstract
The present invention provides a sodium-based lubricating grease, which comprises, by weight, 0.01-10% of a shielded phenol compound, 5-35% of a sodium-based thickener, and a main amount of a lubricating base oil, wherein the structure of the shielded phenol compound is defined in the specification. According to the present invention, the sodium-based lubricating grease has advantages of good colloidal stability, excellent mechanical stability, long service life, excellent oxidation resistance, excellent rust resistance, excellent water leaching resistance and excellent extreme pressure performance, and can be used under harsh working conditions such as high temperature, high speed, high load, more water, and the like.
Description
Technical field
The present invention relates to a kind of lubricating grease, more particularly to a kind of sodium base grease.
Background technology
Sodium base grease is usually by natural animal-plant grease soda soap or fatty acid sodium soap thickening ore deposit
Thing oil and be obtained, with higher dropping point, good colloid stability, shear stability.
By changing raw materials for production and preparation process condition in production process, can be obtained different outward appearances and
The product of different performance.CN 102021546A report a kind of antirust for firm product antirust
Water；CN 101153236 is added to the pressed powder that different-grain diameter is distributed in lubricating grease, no
The water repelling property of lubricating grease is only enhanced, extreme pressure anti-wear is also improved；CN 1557922 leads to
Cross the addition clean water in sodium base grease and be prepared for the aqueous sodium base containing 8-30% clean waters
Lubricating grease, the fat is substantially pollution-free to environment, high lubricating effect, has thermal balance to make friction pair
With and it is with low cost can be applied to heavy load sliding bearing lubriation material；CN
102021068A is prepared for a kind of sodium aluminate soap grease for ship, it is adaptable to marine propeller and
Floating Crane and dredger, more than 75 DEG C of dropping point, with good water-resistance, protective
And rust-preventing characteristic, existing proper lubrication effect, there is corrosion-resisting function again, and make an uproar with machinery is lowered
The function of sound.
Lubricating grease keeps its property not occur forever in storage with the effect of air is resisted when using
Long the ability of change is referred to as oxidation stability, is to cause lubricating grease as the metal soap of thickening agent
The major reason of oxidation deterioration.In order to suppress the oxidation deterioration of lubricating grease, anti-oxidation product
Cause the corrosion of metal surface, to add appropriate antioxidant additive.At present, conventional antioxygen
Agent is broadly divided into amine and the class of phenols two.Phenolic antioxidant generally comprises 2,6- di-t-butyls to first
Phenol, 2,6- di-tert-butylphenols etc., but it uses temperature relatively low, typically within 150 DEG C.Amine
Kind antioxidant is mainly alkylated diphenylamine, or alkylating phenyl-naphthylamines etc..
The content of the invention
The invention provides a kind of sodium base grease and preparation method thereof.
Content of the present invention including the following aspects：
1. a kind of sodium base grease, on the basis of lubricating grease gross weight, including following components：
The shielding phenolic compounds of 0.01%-10%, the sodium base thickening agent and major amount of lubrication of 5%-35%
Base oil；
The structure of the shielding phenolic compounds is as shown in logical formula (I)：
In logical formula (I), each group R is same to each other or different to each other, be each independently selected from hydrogen,
C1-300Straight or branched alkyl (preferred C1-10Straight or branched alkyl or number-average molecular weight
Mn is the polyolefin-based of 300-3000), the group shown in logical formula (II) and logical formula (III) institute
The group for showing, on condition that at least one group R is the group shown in logical formula (II)；Each group
R' is same to each other or different to each other, and is each independently selected from hydrogen and C1-20Straight or branched alkyl is (preferably
It is each independently selected from hydrogen and C1-4Straight or branched alkyl),
In aforementioned each logical formula (II), (III) and (IV), each group L is same to each other or different to each other,
It is independently of one another groupWherein group R " is selected from hydrogen, C1-20Alkyl is (excellent
Select C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl, be preferably selected from hydrogen,
C1-10Straight or branched alkyl and C3-10Straight or branched miscellaneous alkyl；Each group R2It is mutually the same
Or it is different, it is each independently selected from hydrogen, C1-20Shown in straight or branched alkyl, logical formula (IV)
Group and logical formula (V) shown in group (be preferably each independently selected from hydrogen, C1-10Straight chain
Or branched alkyl and the group shown in logical formula (IV))；Each group RbIt is same to each other or different to each other,
It is each independently selected from hydrogen and C1-20Straight or branched alkyl (is preferably each independently selected from hydrogen
And C1-10Straight or branched alkyl)；Each group RcIt is same to each other or different to each other, selects independently of one another
From hydrogen, C1-20Straight or branched alkyl and C1-20Straight or branched alkyl epoxide is (preferably each
Independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10Straight or branched alkyl epoxide,
It is more preferably in cyclic groupThe contraposition of upper nitrogen-atoms)；Y be 0 to 3 integer it is (excellent
Select 0 or 1)；Z is 0 to 3 integer (preferably 0 or 1)；N be 1 to 8 integer it is (excellent
Select 1 or 2)；N' is 0 to 7 integer (preferably 0,1 or 2), on condition that n'+n≤8 are (excellent
Select n'+n=1 or n'+n=2)；Each group RdIt is same to each other or different to each other, is each independently selected from
Group (preferred hydrogen) shown in hydrogen and logical formula (V)；Each cyclic groupIt is mutually the same
Or it is different, phenyl ring and naphthalene nucleus (preferred phenyl ring) are each independently selected from, wherein adjacent two
Cyclic groupIt is optionally former with the N for bridging the two rings by additional S atom each other
Son and formed phenthazine ring, and/or, two adjacent cyclic groupsOptionally lead to each other
Cross additional group(wherein group R " it is selected from hydrogen, C1-20Alkyl is (preferably
C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl, is preferably selected from hydrogen and C1-10
Straight or branched alkyl) and bridge the N atoms of the two rings and form 9,10- acridan rings,
In logical formula (V), each group R is same to each other or different to each other, be each independently selected from hydrogen,
C1-300Straight or branched alkyl (preferred C1-10Straight or branched alkyl or number-average molecular weight
Mn is the polyolefin-based of 300-3000), the group shown in logical formula (II) and logical formula (III) institute
The group for showing (is preferably each independently selected from hydrogen and C1-300Straight or branched alkyl)；Each group
R' is same to each other or different to each other, and is each independently selected from hydrogen and C1-20Straight or branched alkyl is (preferably
It is each independently selected from hydrogen and C1-4Straight or branched alkyl)；Group L is groupWherein group R " is selected from hydrogen, C1-20Alkyl (preferred C1-20Straight chain is propped up
Alkyl group) and C3-20Straight or branched miscellaneous alkyl, is preferably selected from hydrogen, C1-10Straight or branched
Alkyl and C3-10Straight or branched miscellaneous alkyl；A is 0 or 1, and two group R and one
Group-(S)a- L- occupies respectively three positions of residue on phenyl ring,
Wherein, the straight or branched miscellaneous alkyl is inside straight or branched alkyl molecular structure
One or more (such as 1 to 4,1 to 3,1 to 2 or 1) bases
Group-CH2- (R' is H or C to be selected from-O- ,-S- and-NR'-1-4Straight or branched alkyl) it
Group and straight or branched alkyl molecular structure that one substituting group is directly substituted and obtained
One or more internal (such as 1 to 3,1 to 2 or 1) group-CH<
By substituting group-N<The group for directly substituting and obtaining, wherein the shielding phenolic compounds is at it
At least one group R in whole molecular structuredIt is hydrogen.
2. according to the shielding phenolic compounds described in any preceding aspect, selected from following concrete
The mixture of compound or its arbitrary proportion：
3. the preparation method of aforementioned shielding phenolic compounds, including the phenol made shown in logical formula (X)
Amines shown in compound and formula (Y) is (excellent in the aldehyde compound shown in formula (Z)
Select formaldehyde) in the presence of the first step that reacts, optionally also include making the first step
Product and vulcanizing agent (preferred sulphur) react and/or close with the hydroformylation shown in formula (Z)
The additional step of thing (preferred formaldehyde) reaction,
In logical formula (X), each group R0Be same to each other or different to each other, be each independently selected from hydrogen,
-SH
And C1-300Straight or branched alkyl (preferred C1-10Straight or branched alkyl or number are divided equally
Son amount Mn is the polyolefin-based of 300-3000), on condition that at least one group R0It is-SH；
Each group R' is same to each other or different to each other, and is each independently selected from hydrogen and C1-20Straight or branched alkane
Base (is preferably each independently selected from hydrogen and C1-4Straight or branched alkyl),
In formula (Y), group R'2Selected from hydrogen, C1-20Straight or branched alkyl and groupEach group RbBe same to each other or different to each other, be each independently selected from hydrogen and
C1-20Straight or branched alkyl (is preferably each independently selected from hydrogen and C1-10Straight or branched alkane
Base)；Each group RcIt is same to each other or different to each other, is each independently selected from hydrogen, C1-20Straight chain is propped up
Alkyl group and C1-20Straight or branched alkyl epoxide (is preferably each independently selected from hydrogen, C1-10
Straight or branched alkyl and C1-10Straight or branched alkyl epoxide, 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)；N1 is 1 to 8 integer (preferably 1 or 2)；Respectively
Cyclic groupIt is same to each other or different to each other, is each independently selected from phenyl ring and naphthalene nucleus is (excellent
Select phenyl ring),
In formula (Z), group R " it is selected from hydrogen, C1-20Alkyl (preferred C1-20Straight chain is propped up
Alkyl group) and C3-20Straight or branched miscellaneous alkyl, is preferably selected from hydrogen, C1-10Straight or branched
Alkyl and C3-10Straight or branched miscellaneous alkyl,
Wherein, the straight or branched miscellaneous alkyl is inside straight or branched alkyl molecular structure
One or more (such as 1 to 4,1 to 3,1 to 2 or 1) bases
Group-CH2- (R' is H or C to be selected from-O- ,-S- and-NR'-1-4Straight or branched alkyl) it
Group and straight or branched alkyl molecular structure that one substituting group is directly substituted and obtained
One or more internal (such as 1 to 3,1 to 2 or 1) group-CH<
By substituting group-N<The group for directly substituting and obtaining.
4. according to the preparation method that phenolic compounds is shielded described in any preceding aspect, wherein in institute
In stating first step, the phenolic compounds shown in the logical formula (X) and the formula (Y) institute
The mol ratio of the amines for showing is 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0,
Phenolic compounds shown in the logical formula (X) and the aldehyde compound shown in the formula (Z)
Mol ratio is 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0, in the extra step
In rapid, the amines shown in the formula (Y) is 1 with the mol ratio of the vulcanizing agent:1-10,
It is preferred that 1:1.2-6.0, more preferably 1:1.5-3.0, the amines shown in the formula (Y) with
The mol ratio of the aldehyde compound shown in the formula (Z) is 1:0.1-10, preferably 1:0.5-5.0,
More preferably 1:0.8-2.0.
5. the sodium base grease described in any preceding aspect, wherein the shielding phenolic compounds is accounted for
The 0.01%-10% of the sodium base grease composition total weight, preferred 0.05%-5%, it is more excellent
Select 0.1%-0.5%.
The foregoing sodium base thickening agent of the present invention can be anti-with NaOH by polymer acid
Should generate, the polymer acid is C12-C25 aliphatic acid and/or hydroxy fatty acid, Ke Yishi
One or more mixture in laurate, palmitic acid, stearic acid and 12- hydroxy stearic acids,
It is preferred that stearic acid and/or 12- hydroxy stearic acids.
The lubricating base oil can be one kind in mineral oil, vegetable oil and artificial oil or many
Kind, preferably 100 DEG C kinematic viscosity are 5-60mm2The lubricating base oil of/s, most preferably
10-30mm2The lubricating base oil of/s.The vegetable oil can be castor oil, rapeseed oil, peanut
One or more in oil and soya-bean oil.The artificial oil can be poly-a-olefin oil (PAO), ester
One or more in class oil, fluorocarbon oil and silicone oil.
Various additives, such as extreme pressure anti-wear additives, antirust agent can also be contained in lubricating grease of the present invention
Deng.Wherein, extreme pressure anti-wear additives account for the 0.5-12% of lubricating grease gross weight, preferred 0.5-5%, can
Being two thio Acidic phosphates zinc, two thio dialkyl amido formic acid molybdenums, two thio dialkyl group
Lead carbamate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, curing
Molybdenum, polytetrafluoroethylene (PTFE), D2EHDTPA molybdenum, chlorinated paraffin, dibutyl dithiocaarbamate antimony,
At least one in tungsten disulfide, selenium disulfide, fluorographite, calcium carbonate and zinc oxide；It is anti-
Rust agent accounts for 0.01-4.5%, the preferred 0.1-2% of lubricating grease gross weight, can be barium mahogany sulfonate,
In petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid extremely
Few one kind.
In the present invention, the content of each component is calculated according to inventory in grease composition.
Wherein, the weight of content=100% of sodium base thickening agent × polymer acid sodium/lubricating grease gross weight.
The invention provides a kind of preparation method of sodium base grease, including：By sodium base thickening agent
It is well mixed with partial lubrication base oil, in 180-230 DEG C of constant temperature refining, cooling, adds surplus
Remaining lubricating base oil, adds foregoing shielding phenolic compounds, grinds to form fat.
The preparation method of the preferred sodium base grease of the present invention, including：
By partial lubrication base oil and polymer acid mixing, heating, 80-105 DEG C is warming up to, plus
Enter the aqueous solution of NaOH, carry out saponification, after reaction completely 190-220 DEG C is warming up to
Refined, add remaining lubricating base oil to be cooled to 100-120 DEG C, added noted earlier
Shielding phenolic compounds, grind to form fat.The polymer acid is preferably C12-C25 aliphatic acid
And/or hydroxy fatty acid.Mol ratio between the polymer acid and NaOH is preferably complete
Into the equivalent ratio of saponification.
Wherein, the temperature of the saponification is preferably 80-95 DEG C, and the time of saponification is excellent
Elect 0.2-1.5 hours, more preferably 0.5-1 hours as.
The content of water is so that saponification can be smoothed out in the aqueous solution of the NaOH
It is defined.The usually 0.1-10 times of weight of sodium hydroxide concentration, preferred 2-8 times of weight.
The time of the refining is preferably 5-25 minutes.
According to the present invention, the ratio between the partial lubrication base oil and remaining lubricating base oil
Example is 50-75：25-50.
There is the sodium base grease of the present invention good colloid stability, splendid machinery to stabilize
Property, long-life, non-oxidizability, rust-preventing characteristic, anti-water drenching and extreme pressure property, can be competent in
The harshness working condition such as high temperature, high speed, high load capacity, many water.
Specific embodiment
In the sodium base grease of the present invention, the shielding phenolate being related to shown in a kind of logical formula (I)
Compound.
According to the present invention, in logical formula (I), when having multiple, each group R phases each other
It is same or different, it is each independently selected from hydrogen, C1-300Straight or branched alkyl, logical formula (II) institute
Group shown in the group for showing and logical formula (III), on condition that at least one group R is formula
(II) group shown in.
According to the present invention, in logical formula (I), as the C1-300Straight or branched alkyl,
C can such as be enumerated1-20Straight or branched alkyl (preferred C1-10Straight or branched alkyl, more
It is preferred that C1-4Straight or branched alkyl) or it is polyolefin-based.As described polyolefin-based, specifically
Number-average molecular weight Mn can such as be enumerated for the polyolefin-based of 300-3000.Now, as
Polyolefin-based number-average molecular weight Mn, more preferably preferred 500-2000,500-1500.
According to the present invention, polyolefin-based (substantially) is that saturation (is rendered as chain alkyl knot
Structure), but depending on the polyolefinic species as initiation material or the process for preparing polyolefins
It is likely in difference, the polyolefin-based strand containing a small amount of olefinic double bond (such as poly-
Remain in alkene manufacture process or introduce), but this has no effect on the realization of effect of the present invention,
The present invention also has no intention to carry out clearly the amount, and the present invention still polyolefin-based returns this
Class is " alkyl ".
, in logical formula (I), there are multiple group R in an embodiment of the invention,
One of group R is to lead to the group shown in formula (II), in two other group R
It is described polyolefin-based, another is hydrogen, C1-20Straight or branched alkyl (preferred C1-10Directly
Chain or branched alkyl) or logical formula (III) shown in group.
An embodiment of the invention, in logical formula (I), when group R is described
When polyolefin-based, the polyolefin-based contraposition for being preferably placed at phenolic hydroxyl group in logical formula (I).
According to the present invention, in logical formula (I), when having multiple, each group R' phases each other
It is same or different, it is each independently selected from hydrogen and C1-20Straight or branched alkyl.
An embodiment of the invention, in logical formula (I), when having multiple,
Each group R' is same to each other or different to each other, and is each independently selected from hydrogen and C1-4Straight or branched alkane
Base.
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 " it is selected from
Hydrogen, C1-20Alkyl (preferred C1-20Straight or branched alkyl) and C3-20The miscellaneous alkane of straight or branched
Base.
An embodiment of the invention, in logical formula (II), in the definition of group L
In, group R " it is selected from hydrogen, C1-10Straight or branched alkyl and C3-10Straight or branched miscellaneous alkyl.
According to the present invention, in logical formula (II), group R2Selected from hydrogen, C1-20Straight or branched
Group and the group shown in logical formula (V) shown in alkyl, logical formula (IV).
An embodiment of the invention, in logical formula (II), group R2Selected from hydrogen,
C1-10Group shown in straight or branched alkyl and logical formula (IV).
According to the present invention, in logical formula (II), when having multiple, each group RbPhase each other
It is same or different, it is each independently selected from hydrogen and C1-20Straight or branched alkyl, preferably each solely
On the spot selected from hydrogen and C1-10Straight or branched alkyl.
An embodiment of the invention, in logical formula (II), when having multiple,
Each group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-6Straight or branched alkane
Base, preferred hydrogen.
According to the present invention, in logical formula (II), when having multiple, each group RcPhase each other
It is same or different, it is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight chain or
Branched alkyl epoxide.
An embodiment of the invention, in logical formula (II), when having multiple,
Each group RcIt is same to each other or different to each other, is each independently selected from hydrogen, C1-10Straight or branched alkane
Base and C1-10Straight or branched alkyl epoxide.
An embodiment of the invention, in logical formula (II), preferably one group Rc
In cyclic groupUpper N atoms are (that is, with group RdThe N atoms 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), n is 1 to 8 integer, preferably 1 or 2.
According to the present invention, in logical formula (II), when having multiple, each group RdPhase each other
With or it is different, be each independently selected from hydrogen and the group shown in logical formula (V), preferred hydrogen.
According to the present invention, in logical formula (II), when having multiple, each cyclic group
(being rendered as divalent group in the inside configuration of logical formula (II)) is same to each other or different to each other, each
Independently selected from phenyl ring (inside configuration preferably in logical formula (II) is rendered as 1,4- phenylenes)
With naphthalene nucleus (inside configuration preferably in logical formula (II) is rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene), its
In preferred phenyl ring.
An embodiment of the invention, in logical formula (II), two adjacent ring groups
GroupAdditional S atom (not showing in structural formula) and bridge joint can be passed through each other
The N atoms of the two rings are (that is, with group RdThe N atoms of bonding) and phenthazine ring is formed,
I.e.
, in logical formula (II), there is two or more in the embodiment of the invention
Cyclic groupWhen, as long as wherein at least two (adjacent) cyclic groupForm the phenthazine ring, it is not necessary that require these cyclic groupsIn each with another adjacent cyclic groupForm the fen
Thiazine ring.
An embodiment of the invention, in logical formula (II), two adjacent ring groups
GroupAdditional group can be passed through each other(do not show in structural formula
Show) and the N atoms of the two rings are bridged (that is, with group RdThe N atoms of bonding) and shape
Into 9,10- acridan rings, i.e.,
According to the present invention, in groupIn, group R " it is selected from hydrogen, C1-20Alkyl
(preferred C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl.
An embodiment of the invention, in groupIn, group R " choosing
From hydrogen and C1-10Straight or branched alkyl.
, in logical formula (II), there is two or more in the embodiment of the invention
Cyclic groupWhen, as long as wherein at least two (adjacent) cyclic groupForm 9, the 10- acridans ring, it is not necessary that require these cyclic groupsIn each 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 " choosing
From hydrogen, C1-20Alkyl (preferred C1-20Straight or branched alkyl) and C3-20Straight or branched is miscellaneous
Alkyl.
An embodiment of the invention, in logical formula (III), in the definition of group L
In, group R " it is selected from hydrogen, C1-10Straight or branched alkyl and C3-10Straight or branched miscellaneous alkyl.
According to the present invention, in logical formula (III), group R2Selected from hydrogen, C1-20Straight chain is propped up
Group and the group shown in logical formula (V) shown in alkyl group, logical formula (IV).
An embodiment of the invention, in logical formula (III), group R2Selected from hydrogen,
C1-10Group shown in straight or branched alkyl and logical formula (IV).
According to the present invention, in logical formula (III), when having multiple, each group RbEach other
It is identical or different, it is each independently selected from hydrogen and C1-20Straight or branched alkyl, preferably each
Independently selected from hydrogen and C1-10Straight or branched alkyl.
An embodiment of the invention, in logical formula (III), when having multiple,
Each group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-6Straight or branched alkane
Base, preferred hydrogen.
According to the present invention, in logical formula (III), when having multiple, each group RcEach other
It is identical or different, it is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight chain
Or branched alkyl epoxide.
An embodiment of the invention, in logical formula (III), when having multiple,
Each group RcIt is same to each other or different to each other, is each independently selected from hydrogen, C1-10Straight or branched alkane
Base and C1-10Straight or branched alkyl epoxide.
An embodiment of the invention, in logical formula (III), preferably one group
RcIn cyclic groupUpper N atoms are (that is, with group RdThe N atoms 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), n is 1 to 8 integer, preferably 1 or 2.
According to the present invention, in logical formula (III), when having multiple, each group RdEach other
It is identical or different, it is each independently selected from hydrogen and the group shown in logical formula (V), preferred hydrogen.
According to the present invention, in logical formula (III), when having multiple, each cyclic group
(being rendered as divalent group in the inside configuration of logical formula (III)) is same to each other or different to each other, each
Independently selected from phenyl ring (inside configuration preferably in logical formula (III) is rendered as 1,4- phenylenes)
With naphthalene nucleus (inside configuration preferably in logical formula (III) is rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene),
Wherein preferred phenyl ring.
An embodiment of the invention, in logical formula (III), two adjacent ring groups
GroupAdditional S atom (not showing in structural formula) and bridge joint can be passed through each other
The N atoms of the two rings are (that is, with group RdThe N atoms of bonding) and phenthazine ring is formed,
I.e.
, in logical formula (III), there is two or more in the embodiment of the invention
Cyclic groupWhen, as long as wherein at least two (adjacent) cyclic groupForm the phenthazine ring, it is not necessary that require these cyclic groupsIn each with another adjacent cyclic groupForm the fen
Thiazine ring.
An embodiment of the invention, in logical formula (III), two adjacent ring groups
GroupAdditional group can be passed through each other(do not show in structural formula
Show) and the N atoms of the two rings are bridged (that is, with group RdThe N atoms of bonding) and shape
Into 9,10- acridan rings, i.e.,
According to the present invention, in groupIn, group R " it is selected from hydrogen, C1-20Alkyl
(preferred C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl.
An embodiment of the invention, in groupIn, group R " choosing
From hydrogen and C1-10Straight or branched alkyl.
, in logical formula (III), there is two or more in the embodiment of the invention
Cyclic groupWhen, as long as wherein at least two (adjacent) cyclic groupForm 9, the 10- acridans ring, it is not necessary that require these cyclic groupsIn each with another adjacent cyclic groupBeing formed should
Acridan ring.
According to the present invention, in logical formula (IV), when having multiple, each group RbEach other
It is identical or different, it is each independently selected from hydrogen and C1-20Straight or branched alkyl, preferably each
Independently selected from hydrogen and C1-10Straight or branched alkyl.
An embodiment of the invention, in logical formula (IV), when having multiple,
Each group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-6Straight or branched alkane
Base, preferred hydrogen.
According to the present invention, in logical formula (IV), when having multiple, each group RcEach other
It is identical or different, it is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight chain
Or branched alkyl epoxide.
An embodiment of the invention, in logical formula (IV), when having multiple,
Each group RcIt is same to each other or different to each other, is each independently selected from hydrogen, C1-10Straight or branched alkane
Base and C1-10Straight or branched alkyl epoxide.
An embodiment of the invention, in logical formula (IV), preferably one group
RcIn cyclic groupUpper N atoms are (that is, with group RdThe N atoms 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), n' is 0 to 7 integer, preferably 0,1
Or 2, on condition that n'+n≤8.An embodiment of the invention, n'+n=1 or n'+n=2.
Here, n is identical with the definition in aforementioned formula (II).
According to the present invention, in logical formula (IV), when having multiple, each group RdEach other
It is identical or different, it is each independently selected from hydrogen and the group shown in logical formula (V), preferred hydrogen.
According to the present invention, in logical formula (IV), when having multiple, each cyclic group
(being rendered as divalent group in the inside configuration of logical formula (IV)) is same to each other or different to each other, each
Independently selected from phenyl ring (inside configuration preferably in logical formula (IV) is rendered as 1,4- phenylenes)
With naphthalene nucleus (inside configuration preferably in logical formula (II) is rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene), its
In preferred phenyl ring.
An embodiment of the invention, in logical formula (IV), two adjacent ring groups
GroupAdditional S atom (not showing in structural formula) and bridge joint can be passed through each other
The N atoms of the two rings are (that is, with group RdThe N atoms of bonding) and phenthazine ring is formed,
I.e.
, in logical formula (IV), there is two or more in the embodiment of the invention
Cyclic groupWhen, as long as wherein at least two (adjacent) cyclic groupForm the phenthazine ring, it is not necessary that require these cyclic groupsIn each with another adjacent cyclic groupForm the fen
Thiazine ring.
An embodiment of the invention, in logical formula (IV), two adjacent ring groups
GroupAdditional group can be passed through each other(do not show in structural formula
Show) and the N atoms of the two rings are bridged (that is, with group RdThe N atoms of bonding) and shape
Into 9,10- acridan rings, i.e.,
According to the present invention, in groupIn, group R " it is selected from hydrogen, C1-20Alkyl
(preferred C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl.
An embodiment of the invention, in groupIn, group R " choosing
From hydrogen and C1-10Straight or branched alkyl.
, in logical formula (IV), there is two or more in the embodiment of the invention
Cyclic groupWhen, as long as wherein at least two (adjacent) cyclic groupForm 9, the 10- acridans ring, it is not necessary that require these cyclic groupsIn each with another adjacent cyclic groupBeing formed should
Acridan ring.
According to the present invention, in logical formula (V), when having multiple, each group R phases each other
It is same or different, it is each independently selected from hydrogen, C1-300Straight or branched alkyl, logical formula (II) institute
Group shown in the group for showing and logical formula (III).
An embodiment of the invention, in logical formula (V), when having multiple,
Each group R is same to each other or different to each other, and is each independently selected from hydrogen and C1-300Straight or branched alkane
Base.
According to the present invention, in logical formula (V), as the C1-300Straight or branched alkyl,
C can such as be enumerated1-20Straight or branched alkyl (preferred C1-10Straight or branched alkyl, more
It is preferred that C1-4Straight or branched alkyl) or it is polyolefin-based.As described polyolefin-based, specifically
Number-average molecular weight Mn can such as be enumerated for the polyolefin-based of 300-3000.Now, as
Polyolefin-based number-average molecular weight Mn, more preferably preferred 500-2000,500-1500.
According to the present invention, polyolefin-based (substantially) is that saturation (is rendered as chain alkyl knot
Structure), but depending on the polyolefinic species as initiation material or the process for preparing polyolefins
It is likely in difference, the polyolefin-based strand containing a small amount of olefinic double bond (such as poly-
Remain in alkene manufacture process or introduce), but this has no effect on the realization of effect of the present invention,
The present invention also has no intention to carry out clearly the amount, and the present invention still polyolefin-based returns this
Class is " alkyl ".
, in logical formula (V), there are multiple group R in an embodiment of the invention,
One of group R is described polyolefin-based, and another is hydrogen or C1-20Straight or branched
Alkyl (preferred C1-10Straight or branched alkyl, more preferably C1-4Straight or branched alkyl).
An embodiment of the invention, in logical formula (V), when group R is described
When polyolefin-based, the polyolefin-based contraposition for being preferably placed at phenolic hydroxyl group in logical formula (V).
According to the present invention, in logical formula (V), when having multiple, each group R' phases each other
It is same or different, it is each independently selected from hydrogen and C1-20Straight or branched alkyl.
An embodiment of the invention, in logical formula (V), when having multiple,
Each group R' is same to each other or different to each other, and is each independently selected from hydrogen and C1-4Straight or branched alkane
Base.
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 " choosing
From hydrogen, C1-20Alkyl (preferred C1-20Straight or branched alkyl) and C3-20Straight or branched is miscellaneous
Alkyl.
An embodiment of the invention, in logical formula (V), in the definition of group L
In, group R " it is selected from hydrogen, C1-10Straight or branched alkyl and C3-10Straight or branched miscellaneous alkyl.
According to one preferred embodiment of the invention, in logical formula (V), group L's
In definition, group R " selected from hydrogen and C1-10Straight or branched alkyl.
According to the present invention, in logical formula (V), two group R and group-(S)a-L-
Three positions of residue in logical formula (V) on phenyl ring are occupied respectively.
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 mentioned (such as such as logical formula (I)
Or further as shown in logical formula (V)), it is necessary to comprising structureAs phenol unit.
According to one preferred embodiment of the invention, the shielding phenolic compounds is tied in its whole molecule
At most 5, at most 3, at most 2 or at most 1 phenol unit are included in structure.
According to the present invention, the shielding phenolic compounds is defined as previously mentioned (such as such as logical formula (II)
Or further as shown in logical formula (III) or (IV)), it is necessary to comprising structureAs amine unit.According to one preferred embodiment of the invention,
It is described shielding phenolic compounds in its whole 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 in its whole molecular structure
One (preferably 2,3 or 4 or more) group RdIt is hydrogen.Specifically, institute
Shielding phenolic compounds is stated preferably in its whole molecular structure containing selected from following hydrogen amine unit
(1), at least one of hydrogen amine unit (2) and hydrogen amine unit (3).In these hydrogen amine lists
In unit, cyclic groupWith group R " it is identical with the definition in logical formula (II).
A preferred embodiment of the invention, the shielding phenolic compounds entirely divides at it
Contain hydrogen amine unit (1) described at least one in minor structure.
Specifically, shielding phenolic compoundsAs a example by, the compound exists
Comprising 2 phenol units and 2 amine units in its whole molecular structure, and comprising 1
The individual hydrogen amine unit (1).
According to the present invention, as the shielding phenolic compounds, such as following change can be enumerated
The mixture of compound or its arbitrary proportion, but the present invention is not limited to this.
According to the present invention, the shielding phenolic compounds shown in aforementioned formula (I) can be with single one
In the form of kind (pure) compound, manufacture or use, it is also possible to wherein two or more
Mixture (in any proportion) in the form of, manufacture or use, this has no effect on this
The realization of obvious results fruit.
According to the present invention, the shielding phenolic compounds shown in aforementioned formula (I) can pass through following
Preparation method manufactured, but be not limited to this sometimes.
Preparation method of the invention, including the phenolic compounds made shown in logical formula (X)
With the amines shown in formula (Y) in the presence of the aldehyde compound shown in formula (Z)
The first step for reacting.
According to the present invention, in leading to formula (X), when having multiple, each group R0It is mutually the same or not
Together, hydrogen ,-SH and C are each independently selected from1-300Straight or branched alkyl, on condition that at least
One group R0It is-SH.
According to the present invention, in logical formula (X), as the C1-300Straight or branched alkyl,
C can such as be enumerated1-20Straight or branched alkyl (preferred C1-10Straight or branched alkyl, more
It is preferred that C1-4Straight or branched alkyl) or it is polyolefin-based.As described polyolefin-based, specifically
Number-average molecular weight Mn can such as be enumerated for the polyolefin-based of 300-3000.Now, as
Polyolefin-based number-average molecular weight Mn, more preferably preferred 500-2000,500-1500.
According to the present invention, polyolefin-based (substantially) is that saturation (is rendered as chain alkyl knot
Structure), but depending on the polyolefinic species as initiation material or the process for preparing polyolefins
It is likely in difference, the polyolefin-based strand containing a small amount of olefinic double bond (such as poly-
Remain in alkene manufacture process or introduce), but this has no effect on the realization of effect of the present invention,
The present invention also has no intention to carry out clearly the amount, and the present invention still polyolefin-based returns this
Class is " alkyl ".
, in logical formula (X), there are multiple group R in an embodiment of the invention0,
One of group R0It is-SH, two other group R0In one be it is described polyolefin-based,
Another is hydrogen or C1-20Straight or branched alkyl (preferred C1-10Straight or branched alkyl).
An embodiment of the invention, in logical formula (X), in group R0It is described
When polyolefin-based, the polyolefin-based contraposition for being preferably placed at phenolic hydroxyl group in logical formula (X).
According to the present invention, in logical formula (X), when having multiple, each group R' phases each other
It is same or different, it is each independently selected from hydrogen and C1-20Straight or branched alkyl.
An embodiment of the invention, in logical formula (X), when having multiple,
Each group R' is same to each other or different to each other, and is each independently selected from hydrogen and C1-4Straight or branched alkane
Base.
According to the present invention, as the phenolic compounds shown in the logical formula (X), can directly make
With commercially available product, it is also possible to manufactured by conventionally known in the art method, not
It is special to limit.In addition, as the phenolic compounds shown in the logical formula (X), can only make
With one kind, it is also possible to which combination of two or more is used.
According to the present invention, as the preparation method of the phenolic compounds shown in the logical formula (X),
Such as can enumerate in the presence of catalyst for alkylation reaction, make the phenolate shown in formula (X')
(number-average molecular weight Mn is 300-3000, preferred 500-2000, more preferably for compound and polyolefin
The method that alkylated reaction 500-1500) occurs.
According to the present invention, in formula (X'), group R' have with aforementioned formula (X) in
Identical implication.
According to three group R' of presence in the present invention, formula (X')0, one of group R'0
It is-SH, another group R'0It is H, the 3rd group R'0It is hydrogen ,-SH or C1-20Directly
Chain or branched alkyl (preferred C1-10Straight or branched alkyl).
An embodiment of the invention, in formula (X'), at least one group
R'0It is H, and group R'0The contraposition of phenolic hydroxyl group in formula (X').
According to the present invention, the polyolefin preferably passes through ethene, propylene or C4-C10Alpha-olefin
Homopolymerization or by polyolefin obtained from two or more copolymerization in these alkene.As institute
State C4-C10Alpha-olefin, such as can enumerate n-butene, isobutene, n-pentene, n-hexylene,
Positive octene and positive decene.
According to the present invention, and at least 20wt% in these polyolefin (preferably at least 50wt%, more
Preferably at least 70wt%) polymer chain contain olefinic double bond in its end.The olefinic double bond one
As be in the form of the ethenylidene or vinyl of high reaction activity.
According to the present invention, as the polyolefin, more preferably polybutene.Unless otherwise stated,
Term as used herein " polybutene " broadly includes being obtained by 1- butylene or isobutylene homopolymerisation
The polymer for arriving, and by two or three in 1- butylene, 2- butylene and isobutene by altogether
Poly- and obtained polymer.The commercially available prod of such polymer is likely to its containing negligible quantity
Its olefinic component, but this has no effect on the enforcement of the present invention.
According to the present invention, as the polyolefin, further preferred polyisobutene (PIB),
Referred to as high-activity polyisobutylene.In this kind of polyisobutene, at least 20wt% is (preferably extremely
Few 50wt%, more preferably at least 70wt%) total terminal ethylenic double bond be by methyl Asia ethene
What base was provided.
As the catalyst for alkylation reaction, such as Lewis acid catalysts can be enumerated, than
Such as selected from alchlor, boron trifluoride, butter of tin, titanium tetrabromide, boron trifluoride phenol,
One or more in boron trifluoride alcohol complex and boron trifluoride ether complex, wherein it is preferred that
Boron trifluoride etherate and/or boron trifluoride methanol complex compound.These alkylated reactions are urged
Agent can directly use commercially available product.
According to the present invention, in the alkylated reaction, the polyolefin, the formula (X')
Mol ratio between shown phenolic compounds, 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
Sometimes it is not limited to this.
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 this is not limited to sometimes.
According to the present invention, the reaction temperature of the alkylated reaction is such as 0 DEG C -200 DEG C, excellent
Select 10 DEG C -150 DEG C, most preferably 20 DEG C -100 DEG C, but this is not limited to sometimes.
According to the present invention, the alkylated reaction can be carried out in the presence of the solvent.As institute
Solvent is stated, such as can enumerate C6-10Alkane (such as hexane, heptane, octane, nonane or
Decane etc.).Wherein, hexane and heptane are preferably used, more preferably using hexane.
According to the present invention, after the alkylated reaction terminates, by conventional methods from finally obtaining
Catalyst for alkylation reaction, unreacted reactant are removed in the reactant mixture for obtaining and may be made
After solvent, that is, obtain the phenolic compounds shown in the logical formula (X).
According to the present invention, in formula (Y), group R'2Selected from hydrogen, C1-20Straight chain is propped up
Alkyl group and group
According to the present invention, in formula (Y), when having multiple, each group RbPhase each other
It is same or different, it is each independently selected from hydrogen and C1-20Straight or branched alkyl, preferably each solely
On the spot selected from hydrogen and C1-10Straight or branched alkyl.
An embodiment of the invention, in formula (Y), when having multiple,
Each group RbIt is same to each other or different to each other, is each independently selected from hydrogen and C1-6Straight or branched alkane
Base, preferred hydrogen.
According to the present invention, in formula (Y), when having multiple, each group RcPhase each other
It is same or different, it is each independently selected from hydrogen, C1-20Straight or branched alkyl and C1-20Straight chain or
Branched alkyl epoxide.
An embodiment of the invention, in formula (Y), when having multiple,
Each group RcIt is same to each other or different to each other, is each independently selected from hydrogen, C1-10Straight or branched alkane
Base and C1-10Straight or branched alkyl epoxide.
An embodiment of the invention, in formula (Y), preferably one group Rc
In cyclic groupUpper N atoms are (that is, with group RdThe N atoms of bonding)
Contraposition.
According to the present invention, in formula (Y), y is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in formula (Y), z is 0 to 3 integer, preferably 0 or 1.
According to the present invention, in formula (Y), n1 is 1 to 8 integer, preferably 1 or 2.
According to the present invention, in formula (Y), when having multiple, each cyclic group
(being rendered as divalent group in the inside configuration of formula (Y)) is same to each other or different to each other, each
Independently selected from phenyl ring (inside configuration preferably in formula (Y) is rendered as 1,4- phenylenes)
With naphthalene nucleus (inside configuration preferably in formula (Y) is rendered as Isosorbide-5-Nitrae-or 2,6- naphthylene), its
In preferred phenyl ring.
According to the present invention, as the amines shown in the formula (Y), can directly make
With commercially available product, it is not particularly limited.In addition, as the formula (Y) Suo Shi
Amines, can only using one kind, it is also possible to combination of two or more is used.
According to the present invention, in formula (Z), group R " it is selected from hydrogen, C1-20Alkyl is (excellent
Select C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl.
An embodiment of the invention, in formula (Z), group R " selected from hydrogen,
C1-10Straight or branched alkyl and C3-10Straight or branched miscellaneous alkyl.
According to one preferred embodiment of the invention, in formula (Z), group R " it is selected from
Hydrogen and C1-10Straight or branched alkyl.
According to the present invention, as the aldehyde compound shown in the formula (Z), such as can lift
Go out C1-6Aliphatic aldehyde and benzaldehyde.
An embodiment of the invention, as the C1-6Aliphatic aldehyde, such as can be with
Enumerate C1-6Straight or branched saturated aliphatic aldehyde, specifically such as acetaldehyde or formaldehyde, more preferably formaldehyde.
As the formaldehyde, such as its aqueous solution, paraformaldehyde or paraformaldehyde form can be used,
It is not particularly limited.
According to the present invention, as the aldehyde compound shown in the formula (Z), can only use
It is a kind of, it is also possible to which that combination of two or more is used.
According to the present invention, in the preparation method of the shielding phenolic compounds, in the first step
In rapid, the phenolic compounds shown in the logical formula (X) and the amination shown in the formula (Y)
The mol ratio of compound is generally 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0.
According to the present invention, in the preparation method of the shielding phenolic compounds, in the first step
In rapid, the phenolic compounds shown in the logical formula (X) and the hydroformylation shown in the formula (Z)
The mol ratio of compound is generally 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0.
According to the present invention, in the preparation method of the shielding phenolic compounds, the first step
Can carry out in the presence of the solvent.As the solvent, such as can enumerate C2-10Fat
Race's nitrile (such as acetonitrile 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 first
Alcohol, ethanol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C2-20Halogenated hydrocarbons is (such as
Dichloromethane, carbon tetrachloride, chlorobenzene and 1,2- dichloro-benzenes), C3-10Ketone (such as acetone, fourth
Ketone and methyl iso-butyl ketone (MIBK)) or C3-10Acid amides (such as dimethylformamide, dimethyl second
Acid amides and 1-METHYLPYRROLIDONE) etc..These solvents can only using one kind, it is also possible to two
Plant or multiple combination is used.
According to the present invention, in the preparation method of the shielding phenolic compounds, in the first step
In rapid, catalyst can be added without, it is also possible to add catalyst.As the catalyst, than
Inorganic acid catalyst and organic acid catalyst can such as be enumerated.As the inorganic acid catalyst,
Hydrochloric acid, sulfuric acid and phosphoric acid etc. can such as be enumerated.As the organic acid catalyst, such as may be used
To enumerate pyrovinic acid, ethylsulfonic acid, sulfamic acid and p-methyl benzenesulfonic acid etc..
As the consumption of the catalyst, can directly with reference to the conventional amount used of prior art, and
There is no particular limitation.
According to the present invention, in the preparation method of the shielding phenolic compounds, to the first step
The rapid reaction time, there is no particular limitation, but generally 0.1h-24h, preferred 0.2h-12h,
Most preferably 0.5h-6h.
According to the present invention, in the preparation method of the shielding phenolic compounds, to the first step
There is no particular limitation for rapid reaction temperature, 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, in the first step
Suddenly after terminating, by conventionally known separation method (such as evaporation etc.) from the first step
Removing in the reactant mixture (the hereinafter referred to as reactant mixture of first step) of acquisition to deposit
The volatile materials such as solvent after, you can obtain the product of first step.
An embodiment of the invention, the preparation method of the shielding phenolic compounds is optional
Also include making the product of the first step and vulcanizing agent reaction (forming phenthazine ring)
Additional step (hereinafter referred to as additional step A).
An embodiment of the invention, the preparation method of the shielding phenolic compounds is optional
Also include making the product of the first step and the aldehyde compound shown in aforementioned formula (Z)
The additional step (hereinafter referred to as additional step B) of reaction (forming acridan ring).
According to the present invention, in the preparation method of the shielding phenolic compounds, institute can be only carried out
State additional step A, it is also possible to only carry out the additional step B, it is also possible to both carried out described attached
Plus step A carries out the additional step B again.Carry out the additional step A is not only carried out
Priority time during the additional step B, to the additional step A and the additional step B
There is no particular limitation for sequence, the additional step A can be first carried out, in additional step A
Carry out the additional step B after end again, or first carry out the additional step B, at this
Additional step B carries out again the additional step A after terminating.In addition, between each additional step
There can be product (that is, from the product of previous additional step) separating step, it is also possible to
Without product separating step, it is not particularly limited.
An embodiment of the invention, in the preparation method of the shielding phenolic compounds
In, the additional step A is carried out after the first step terminates.Now, described
The product of one step is as previously mentioned from the reactant mixture of the first step point
Separate out and.Or, the product of the first step can also be and straight without the separation
To connect be used in the form of the reactant mixture of the first step and carry out the additional step A.Or
Person, the additional step A can also be carried out after the additional step B terminates.Work as institute
Additional step A is stated when carrying out after the additional step B terminates, the additional step B
Product it is as described herein from the reactant mixture of the additional step B separate
Out.Or, the product of the additional step B can also without the separation, and
Directly it is used to carry out the additional step in the form of the reactant mixture of the additional step B
A。
An embodiment of the invention, in the preparation method of the shielding phenolic compounds
In, in the additional step A, as the vulcanizing agent, such as can enumerate sulphur and two
Sulfur chloride etc., wherein it is preferred that sulphur.As the sulphur, such as can enumerate sulphur or sublimed sulfur.
According to the present invention, in the preparation method of the shielding phenolic compounds, in the extra step
In rapid A, the amines shown in the formula (Y) is general with the mol ratio of the vulcanizing agent
For 1:1-10, preferably 1:1.2-6.0, more preferably 1:1.5-3.0.
According to the present invention, in the preparation method of the shielding phenolic compounds, the additional step
A can be carried out in the presence of the solvent.As the solvent, such as can enumerate C2-10Fat
Fat race nitrile (such as acetonitrile etc.), C6-20Aromatic hydrocarbon (such as benzene,toluene,xylene and isopropyl
Benzene), C6-10Alkane (such as n-hexane, hexamethylene and petroleum ether), C1-6Aliphatic alcohol (ratio
Such as methyl alcohol, ethanol, normal propyl alcohol, isopropanol, n-butanol and ethylene glycol), C2-20Halogenated hydrocarbons (ratio
Such as dichloromethane, carbon tetrachloride, chlorobenzene and 1,2- dichloro-benzenes), C3-10Ketone (such as acetone,
Butanone and methyl iso-butyl ketone (MIBK)) or C3-10Acid amides (such as dimethylformamide, dimethyl
Acetamide and 1-METHYLPYRROLIDONE) etc..These solvents can only using one kind, it is also possible to
Combination of two or more is used.
According to the present invention, in the preparation method of the shielding phenolic compounds, the additional step
A is typically carried out in the presence of a catalyst.As the catalyst, such as can enumerate existing
The technology conventional catalyst for adopting for this purpose, specifically such as iodine.As the catalyst
Consumption, can directly with reference to the conventional amount used of prior art be not particularly limited.
According to the present invention, in the preparation method of the shielding phenolic compounds, to the extra step
The reaction time of rapid A, there is no particular limitation, but generally 0.1h-24h, preferred 0.2h-12h,
Most preferably 0.5h-4h.
According to the present invention, in the preparation method of the shielding phenolic compounds, to the extra step
There is no particular limitation for the reaction temperature of rapid A, 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, in the extra step
It is additional from this by conventionally known separation method (such as evaporation etc.) after rapid A terminates
Remove after the volatile materials such as solvent that may be present in the reactant mixture that step A is obtained,
The product of additional step A can be obtained, or can also be without the separation, directly
For follow-up reactions steps (than additional step B as the aforementioned).
An embodiment of the invention, in the preparation method of the shielding phenolic compounds
In, the additional step B can be carried out (as independent after the first step terminates
The step of), it is also possible to carry out simultaneously with the first step, be not particularly limited.When
The additional step B when carrying out after the first step terminates, the first step
Product is separated from the reactant mixture of the first step as previously mentioned.Or
Person, the product of the first step can also be without the separation, and directly with described the
The form of the reactant mixture of one step is used to carry out the additional step B.Or, it is described attached
Plus step B can also be carried out after the additional step A terminates.When the additional step
B when carrying out after the additional step A terminates, the product of the additional step A
It is as described herein to separate from the reactant mixture of the additional step A.Or,
The product of the additional step A can also be without the separation, and directly with described attached
Plus the form of the reactant mixture of step A is used to carry out the additional step B.In addition, working as institute
Additional step B is stated with the first step while when carrying out, directly to the first step
(such as carried out in the beginning of the first step or in the first step in reaction system
In journey) add the aldehyde compound shown in the formula (Z) according to hereinafter provided consumption.
According to the present invention, in the preparation method of the shielding phenolic compounds, in the extra step
In rapid B, as the aldehyde compound shown in the formula (Z), such as C can be enumerated1-6Fat
Fat race aldehyde and benzaldehyde.As the C1-6Aliphatic aldehyde, such as can enumerate C1-6Straight chain or
Chain is saturated fatty aldehyde, specifically such as acetaldehyde or formaldehyde, more preferably formaldehyde.As the formaldehyde,
Its aqueous solution, paraformaldehyde or paraformaldehyde form can be such as used, is not particularly limited
It is fixed.
According to the present invention, in the preparation method of the shielding phenolic compounds, in the extra step
In rapid B, the amines shown in the formula (Y) and the aldehyde shown in the formula (Z)
The mol ratio of compound is generally 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0.
According to the present invention, in the preparation method of the shielding phenolic compounds, the additional step
B (when carrying out as independent step) can be carried out in the presence of the solvent.As described molten
Agent, such as can enumerate C2-10Aliphatic nitrile (such as acetonitrile etc.), C6-20Aromatic hydrocarbon is (such as
Benzene,toluene,xylene and isopropylbenzene), C6-10Alkane (such as n-hexane, hexamethylene and stone
Oily ether), C1-6Aliphatic alcohol (such as methyl alcohol, ethanol, normal propyl alcohol, isopropanol, n-butanol
And ethylene glycol), C2-20Halogenated hydrocarbons (such as dichloromethane, carbon tetrachloride, chlorobenzene and 1,2- bis-
Chlorobenzene), C3-10Ketone (such as acetone, butanone and methyl iso-butyl ketone (MIBK)) or C3-10Acid amides (ratio
Such as dimethylformamide, dimethyl acetamide and 1-METHYLPYRROLIDONE).These solvents
Can only using one kind, it is also possible to which combination of two or more is used.
According to the present invention, in the preparation method of the shielding phenolic compounds, in the extra step
In rapid B (when carrying out as independent step), catalyst can be added without, it is also possible to add
Catalyst.As the catalyst, such as can enumerate inorganic acid catalyst and organic acid catalysis
Agent.As the inorganic acid catalyst, such as can enumerate hydrochloric acid, sulfuric acid and phosphoric acid etc..Make
For the organic acid catalyst, such as can enumerate pyrovinic acid, ethylsulfonic acid, sulfamic acid
With p-methyl benzenesulfonic acid etc..As the consumption of the catalyst, can directly with reference to prior art
Conventional amount used, is not particularly limited.
According to the present invention, in the preparation method of the shielding phenolic compounds, to the extra step
The reaction time of rapid B (when carrying out as independent step), there is no particular limitation, but typically
For 0.1h-24h, most preferably preferred 0.2h-12h, 0.5h-6h.
According to the present invention, in the preparation method of the shielding phenolic compounds, to the extra step
There is no particular limitation for the reaction temperature of rapid B (when carrying out as independent step), but typically
For 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, in the extra step
After rapid B (when carrying out as independent step) terminates, by conventionally known separation method
Remove in the reactant mixture that (such as evaporation etc.) is obtained from additional step B and there may be
The volatile materials such as solvent after, you can obtain the product of additional step B, or
Without the separation follow-up reactions steps can also be directly used in (than extra step as the aforementioned
Rapid A).
It is known in the art, aforementioned all of reactions steps (including the first step,
The additional step A and additional step B) typically enter under the protection of inert gas atmosphere
OK.As the inert gas, such as nitrogen and argon gas etc. can be enumerated, not particularly
Limit.
According to the present invention, in the preparation method of the shielding phenolic compounds, as described first
The product of step, the product of the additional step A or the additional step B
Product, can be a kind of single shielding phenolic compounds (such as aforementioned formula (I) institute
The shielding phenolic compounds for showing), or the mixture comprising various shielding phenolic compounds.This
A little product are all that desired by the present invention, the difference of its existence form has no effect on the present invention
The realization of effect.Therefore, it is without distinction that these product are equal in this specification context
It is referred to as the shielding phenolic compounds of the present invention.In consideration of it, according to the present invention, not existing into one
Step purifies these product, or is further separated out from these product a certain specific
The absolute necessity of the shielding phenolic compounds of structure.Certainly, the purifying or separation are for the present invention
It is sometimes preferred for the further lifting of Expected Results, but for the present invention not necessarily
Need.Even so, as the purifying or separation method, such as can enumerate by column chromatography
The method such as method or preparative chromatography is purified or separated to the product.
The present invention is further illustrated for below example, but and is not so limited this
It is bright.In following examples, dropping point is measured using the methods of GB/T 3498, and cone penetration adopts GB/T
269 methods are measured, and oxidation stability is measured using the methods of SH/T 0325, and extreme pressure property adopts SH/T
0202 method is measured, and anticorrosive property is measured using the methods of GB/T 5018, and water drenches number of dropouts to be adopted
Measured with the methods of SH/T 0109, copper corrosion performance is measured using the methods of GB/T 7326.
Embodiment 1
The preparation of shielding phenolic compounds (structure sees below formula)：
Under nitrogen protection atmosphere, agitator, thermometer, condenser pipe and dropping funel are being housed
In 250ml four-hole boiling flasks, 31.65 grams of (133mmol) 2,6- di-t-butyl -4- sulfydryl benzene are added
Phenol, 1.86 grams of (62mmol) formaldehyde, 28.15 grams of (153mmol) 4-aminodiphenylamines,
0.75 gram of (7.5mmol) hydrochloric acid and 150mL isopropanols, rapid stirring, in 25 DEG C of reactions
24h.After question response terminates, vacuum distillation removes solvent and a small amount of water for generating, and by post
Chromatography obtains the shielding phenol product of constituted above.
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 values 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 sodium base grease：
Material component：(100 DEG C of viscosity are 10mm to 500SN lubricating base oil 875kg2/s)；
NaOH 16.45kg；Stearic acid 113.39kg；Shielding phenolic compounds 0.5kg；
First the stearic acid of 438kg lubricating base oils, 113.39kg is added in fat kettle processed, heating
Stirring.Temperature adds sodium hydrate aqueous solution 148.05kg (wherein containing hydrogen-oxygen when rising to 85 DEG C
Change sodium 16.45kg, water 131.6kg) saponification 30min, being continuously heating to 190 DEG C is carried out
High temperature refines 5min；After adding 437kg lubricating base oils to cool to 120 DEG C, 0.5kg is added
Shielding phenolic compounds, stir；By three-roller 2 times are ground into fat.Properties of product are such as
Shown in table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, consist of：It is stearic
Weight % of sour sodium 12；Weight % of lubricating base oil 87.5；Shielding weight % of phenolic compounds 0.5.
Embodiment 2
The preparation of shielding phenolic compounds (structure sees below formula)：
Under nitrogen protection atmosphere, agitator, thermometer, condenser pipe and dropping funel are being housed
In 250ml four-hole boiling flasks, 8.57 grams of (36mmol) 2,6- di-t-butyl -4- mercapto-phenols are added,
0.45 gram of (15mmol) formaldehyde, 10.14 grams of (39mmol) N, N'- diphenyl-Isosorbide-5-Nitrae-benzene two
Amine and 150mL toluene, rapid stirring, at 90 DEG C 4h is reacted.After question response terminates, decompression
Solvent and a small amount of water for generating are distilled off, and the screen of constituted above is obtained by column chromatography for separation
Cover phenol product.
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 values 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 sodium base grease：
Material component：150BS lubricating base oil 718kg (100 DEG C of viscosity are 31mm2/s)；
NaOH 36.47kg；Stearic acid 260.9kg；Shielding phenolic compounds 0.2kg；
First the stearic acid of 538kg lubricating base oils, 260.9kg is added in fat kettle processed, heating
Stirring.Temperature adds sodium hydrate aqueous solution 109.41kg (wherein containing hydrogen-oxygen when rising to 85 DEG C
Change sodium 36.47kg, water 72.94kg) saponification 60min, being continuously heating to 190 DEG C is carried out
High temperature refines 5min；After adding 180kg lubricating base oils to cool to 120 DEG C, 0.2kg is added
Shielding phenolic compounds, stir；By three-roller 2 times are ground into fat.Properties of product are such as
Shown in table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, consist of：It is stearic
Weight % of sour sodium 28；Weight % of lubricating base oil 71.8；Shielding weight % of phenolic compounds 0.2.
Embodiment 3
The preparation of shielding phenolic compounds (structure sees below formula)：
Under nitrogen protection atmosphere, agitator, thermometer, condenser pipe and dropping funel are being housed
In 250ml four-hole boiling flasks, 20.23 grams of (85mmol) 2,6- di-t-butyl -4- sulfydryl benzene are added
Phenol, 3.45 grams of (115mmol) formaldehyde, 18.49 grams of (69mmol) N- (1,3- dimethyl butyrates
Base)-N'- diphenyl-para-phenylene diamines and 150mL benzene, rapid stirring reacts 3h at 85 DEG C.Treat anti-
After should terminating, vacuum distillation removes solvent and a small amount of water for generating, and is obtained by column chromatography for separation
To the shielding phenol product of constituted above.
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 values: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 sodium base grease：
Material component：(100 DEG C of viscosity are PAO6 synthesized hydrocarbon fluid base oil 817kg
5.8mm2/s)；NaOH 23.44kg；Stearic acid 167.72kg；The shielding phenolate of 0.3kg
Compound；
First the stearic acid of 417kg lubricating base oils, 167.72kg is added in fat kettle processed, heating
Stirring.Temperature adds sodium hydrate aqueous solution 164.08kg (wherein containing hydrogen-oxygen when rising to 85 DEG C
Change sodium 23.44kg, water 140.64kg) saponification 50min, being continuously heating to 190 DEG C is carried out
High temperature refines 5min；After adding 400kg lubricating base oils to cool to 120 DEG C, 0.3kg is added
Shielding phenolic compounds, stir；By three-roller 2 times are ground into fat.Properties of product are such as
Shown in table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, consist of：It is stearic
Weight % of sour sodium 18；Weight % of lubricating base oil 81.7；Shielding weight % of phenolic compounds 0.3.
Embodiment 4
The preparation of shielding phenolic compounds (structure sees below formula)：
Under nitrogen protection atmosphere, agitator, thermometer, condenser pipe and dropping funel are being housed
In 250ml four-hole boiling flasks, 4.99 grams of (21mmol) 2,6- di-t-butyl -4- mercapto-phenols are added,
1.59 grams of (53mmol) formaldehyde, 5.70 grams of (31mmol) 4-aminodiphenylamines and 150mL
Ethanol, rapid stirring after reacting 2.5h at 60 DEG C, is down to room temperature, adds 2.55 grams (85mmol)
Formaldehyde, is warming up to 85 DEG C of reaction 2.5h.After question response terminates, vacuum distillation remove solvent and
The a small amount of water for generating, and the shielding phenol product of constituted 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), 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 values 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 sodium base grease：
Material component：(100 DEG C of the mixed lubrication base oil 769kg of 500SN and 150BS
Viscosity is 13mm2/s)；NaOH 31.52kg；Stearic acid 213.49kg；The screen of 0.1kg
Cover phenolic compounds；
First the stearic acid of 513kg lubricating base oils, 213.49kg is added in fat kettle processed, heating
Stirring.Temperature adds sodium hydrate aqueous solution 157.60kg (wherein containing hydrogen-oxygen when rising to 85 DEG C
Change sodium 31.52kg, water 126.08kg) saponification 40min, being continuously heating to 190 DEG C is carried out
High temperature refines 5min；After adding 256kg lubricating base oils to cool to 120 DEG C, 0.1kg is added
Shielding phenolic compounds, stir；By three-roller 2 times are ground into fat.Properties of product are such as
Shown in table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, consist of：It is stearic
Weight % of sour sodium 23；Weight % of lubricating base oil 76.9；Weight % of antioxidant 0.1.
Embodiment 5
The preparation of shielding phenolic compounds (structure sees below formula)：
Under nitrogen protection atmosphere, agitator, thermometer, condenser pipe and dropping funel are being housed
In 250ml four-hole boiling flasks, 19.52 grams of (82mmol) 2,6- di-t-butyl -4- sulfydryl benzene are added
Phenol, 3.63 grams of (121mmol) formaldehyde, 19.93 grams of (94mmol) 4- amino -4'- ethyls two
Aniline and 150mL dimethylbenzene, rapid stirring after reacting 3h at 90 DEG C, is down to room temperature,
10.11 grams of (316mmol) sulphur and 0.04 gram of (0.35mmol) iodine are added, 150 DEG C are warming up to
Reaction 8h.After question response terminates, vacuum distillation removes solvent and a small amount of water for generating, and leads to
Cross the shielding phenol product that column chromatography for separation obtains constituted above.
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 sodium base grease：
Material component：(100 DEG C of viscosity are 10mm to 500SN lubricating base oil 876kg2/s)；
NaOH 16.45kg；Stearic acid 113.39kg；The shielding phenolic compounds of 0.4kg；
First the stearic acid of 476kg lubricating base oils, 113.39kg is added in fat kettle processed, heating
Stirring.Temperature adds sodium hydrate aqueous solution 148.05kg (wherein containing hydrogen-oxygen when rising to 85 DEG C
Change sodium 16.45kg, water 131.6kg) saponification 30min, being continuously heating to 190 DEG C is carried out
High temperature refines 5min；After adding 400kg lubricating base oils to cool to 120 DEG C, 0.4kg is added
Shielding phenolic compounds, stir；By three-roller 2 times are ground into fat.Properties of product are such as
Shown in table 1.
In the lubricating grease that the present embodiment is obtained, on the basis of lubricating grease weight, consist of：It is stearic
Weight % of sour sodium 12；Weight % of lubricating base oil 87.6；Weight % of antioxidant 0.4.
Comparative example 1
Method according to embodiment 4 prepares sodium base grease, except for the difference that, sodium base grease
It is added without shielding phenolic compounds in preparation process.Properties of product are as shown in table 1.
Comparative example 2
Method according to embodiment 4 prepares sodium base grease, except for the difference that, by the tertiary fourths of 2,6- bis-
Shielding phenolic compounds in base p-cresol (structure sees below formula) alternate embodiment 4, is moistened
The comparative example 2 of grease composition.Properties of product are as shown in table 1.
Comparative example 3
Method according to embodiment 4 prepares sodium base grease, except for the difference that, by N- phenyl-α-
Shielding phenolic compounds in naphthylamines (structure sees below formula) alternate embodiment 4, obtains lubricating grease group
The comparative example 3 of compound.Properties of product are as shown in table 1.
Comparative example 4
Method according to embodiment 4 prepares sodium base grease, is following formula by structure except for the difference that
Shielding phenolic compounds alternate embodiment 4 in shielding phenolic compounds, obtain lubricant composition
Comparative example 4.Properties of product are as shown in table 1.
The preparation of shielding phenolic compounds (structure sees below formula)：
Under nitrogen protection atmosphere, agitator, thermometer, condenser pipe and dropping funel are being housed
In 250ml four-hole boiling flasks, 20.23 grams of (85mmol) 2,6- di-t-butyl -4- sulfydryl benzene are added
Phenol, 2.61 grams of (87mmol) formaldehyde, 14.37 grams of (85mmol) diphenylamines and 150mL
Methyl alcohol, rapid stirring, at 60 DEG C 2h is reacted.After question response terminates, vacuum distillation removes molten
Agent and a small amount of water for generating, and the shielding phenol product of constituted 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 values 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
Method according to embodiment 4 prepares sodium base grease, is following formula by structure except for the difference that
Shielding phenolic compounds alternate embodiment 4 in shielding phenolic compounds, obtain lubricant composition
Comparative example 5.Properties of product are as shown in table 1.
The preparation of shielding phenolic compounds (structure sees below formula)：
Under nitrogen protection atmosphere, agitator, thermometer, condenser pipe and dropping funel are being housed
In 250ml four-hole boiling flasks, 10.71 grams of (52mmol) 2,6- di-t-butyl -4- sulfydryl benzene are added
Phenol, 1.89 grams of (63mmol) formaldehyde, 17.42 grams of (65mmol) N- (1,3- dimethylbutyl)-N'-
Diphenyl-para-phenylene diamine and 150mL methyl alcohol, rapid stirring, at 70 DEG C 4h is reacted.Question response is tied
Shu Hou, vacuum distillation remove solvent and generate a small amount of water, and by column chromatography for separation obtain as
The shielding phenol product of upper structure.
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 values 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
Method according to embodiment 4 prepares sodium base grease, is following formula by structure except for the difference that
Shielding phenolic compounds alternate embodiment 4 in shielding phenolic compounds, obtain lubricant composition
Comparative example 6.Properties of product are as shown in table 1.
The preparation of shielding phenolic compounds (structure sees below formula)：
Under nitrogen protection atmosphere, agitator, thermometer, condenser pipe and dropping funel are being housed
In 250ml four-hole boiling flasks, 9.24 grams of (33mmol) 2,6- di-t-butyl -4- (3- sulfydryls are added
Propyl group) phenol, 1.11 grams of (37mmol) formaldehyde, 11.71 grams of (45mmol) N, N'- bis-
Phenyl-Isosorbide-5-Nitrae-phenylenediamine and 150mL benzene, rapid stirring, at 80 DEG C 4h is reacted.Question response is tied
Shu Hou, vacuum distillation remove solvent and generate a small amount of water, and by column chromatography for separation obtain as
The shielding phenol product of upper structure.
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 values 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 the lubricating grease of table 1
From the results shown in Table 1, sodium base grease of the invention has excellent anti-oxidant
Property, rust-preventing characteristic, heat-resisting quantity, water-resistance and adhesiveness, colloid stability, extreme pressure anti-wear,
The performances such as lubricating life, anticorrosive property and resistance to saltfog.
Claims (14)
1. a kind of sodium base grease, on the basis of lubricating grease gross weight, including following components：
The shielding phenolic compounds of 0.01%-10%, the sodium base thickening agent and major amount of lubrication of 5%-35%
Base oil；
The structure of the shielding phenolic compounds is as shown in logical formula (I)：
In logical formula (I), each group R is same to each other or different to each other, be each independently selected from hydrogen,
C1-300Straight or branched alkyl (preferred C1-10Straight or branched alkyl or number-average molecular weight
Mn is the polyolefin-based of 300-3000), the group shown in logical formula (II) and logical formula (III) institute
The group for showing, on condition that at least one group R is the group shown in logical formula (II)；Each group
R' is same to each other or different to each other, and is each independently selected from hydrogen and C1-20Straight or branched alkyl is (preferably
It is each independently selected from hydrogen and C1-4Straight or branched alkyl),
In aforementioned each logical formula (II), (III) and (IV), each group L is same to each other or different to each other,
It is independently of one another groupWherein group R " is selected from hydrogen, C1-20Alkyl is (excellent
Select C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl, be preferably selected from hydrogen,
C1-10Straight or branched alkyl and C3-10Straight or branched miscellaneous alkyl；Each group R2It is mutually the same
Or it is different, it is each independently selected from hydrogen, C1-20Shown in straight or branched alkyl, logical formula (IV)
Group and logical formula (V) shown in group (be preferably each independently selected from hydrogen, C1-10Straight chain
Or branched alkyl and the group shown in logical formula (IV))；Each group RbIt is same to each other or different to each other,
It is each independently selected from hydrogen and C1-20Straight or branched alkyl (is preferably each independently selected from hydrogen
And C1-10Straight or branched alkyl)；Each group RcIt is same to each other or different to each other, selects independently of one another
From hydrogen, C1-20Straight or branched alkyl and C1-20Straight or branched alkyl epoxide is (preferably each
Independently selected from hydrogen, C1-10Straight or branched alkyl and C1-10Straight or branched alkyl epoxide,
It is more preferably in cyclic groupThe contraposition of upper nitrogen-atoms)；Y be 0 to 3 integer it is (excellent
Select 0 or 1)；Z is 0 to 3 integer (preferably 0 or 1)；N be 1 to 8 integer it is (excellent
Select 1 or 2)；N' is 0 to 7 integer (preferably 0,1 or 2), on condition that n'+n≤8 are (excellent
Select n'+n=1 or n'+n=2)；Each group RdIt is same to each other or different to each other, is each independently selected from
Group (preferred hydrogen) shown in hydrogen and logical formula (V)；Each cyclic groupIt is mutually the same
Or it is different, phenyl ring and naphthalene nucleus (preferred phenyl ring) are each independently selected from, wherein adjacent two
Cyclic groupIt is optionally former with the N for bridging the two rings by additional S atom each other
Son and formed phenthazine ring, and/or, two adjacent cyclic groupsOptionally lead to each other
Cross additional group(wherein group R " it is selected from hydrogen, C1-20Alkyl is (preferably
C1-20Straight or branched alkyl) and C3-20Straight or branched miscellaneous alkyl, is preferably selected from hydrogen and C1-10
Straight or branched alkyl) and bridge the N atoms of the two rings and form 9,10- acridan rings,
In logical formula (V), each group R is same to each other or different to each other, be each independently selected from hydrogen,
C1-300Straight or branched alkyl (preferred C1-10Straight or branched alkyl or number-average molecular weight
Mn is the polyolefin-based of 300-3000), the group shown in logical formula (II) and logical formula (III) institute
The group for showing (is preferably each independently selected from hydrogen and C1-300Straight or branched alkyl)；Each group
R' is same to each other or different to each other, and is each independently selected from hydrogen and C1-20Straight or branched alkyl is (preferably
It is each independently selected from hydrogen and C1-4Straight or branched alkyl)；Group L is groupWherein group R " is selected from hydrogen, C1-20Alkyl (preferred C1-20Straight chain is propped up
Alkyl group) and C3-20Straight or branched miscellaneous alkyl, is preferably selected from hydrogen, C1-10Straight or branched
Alkyl and C3-10Straight or branched miscellaneous alkyl；A is 0 or 1, and two group R and one
Group-(S)a- L- occupies respectively three positions of residue on phenyl ring,
Wherein, the straight or branched miscellaneous alkyl is inside straight or branched alkyl molecular structure
One or more (such as 1 to 4,1 to 3,1 to 2 or 1) bases
Group-CH2- (R' is H or C to be selected from-O- ,-S- and-NR'-1-4Straight or branched alkyl) it
Group and straight or branched alkyl molecular structure that one substituting group is directly substituted and obtained
One or more internal (such as 1 to 3,1 to 2 or 1) group-CH<
By substituting group-N<The group for directly substituting and obtaining, wherein the shielding phenolic compounds is at it
At least one group R in whole molecular structuredIt is hydrogen.
2. according to the lubricating grease described in claim 1, it is characterised in that described shielding
Mixture of the phenolic compounds selected from following particular compound or its arbitrary proportion：
3. according to the lubricating grease described in claim 1, it is characterised in that the shielding phenol
The preparation method of compound includes making the phenolic compounds shown in logical formula (X) and formula (Y) institute
The amines for showing is sent out in the presence of the aldehyde compound (preferred formaldehyde) shown in formula (Z)
The first step of raw reaction, optionally also includes making the product and vulcanizing agent of the first step
(preferred sulphur) reacts and/or reacts with the aldehyde compound (preferred formaldehyde) shown in formula (Z)
Additional step,
In logical formula (X), each group R0Be same to each other or different to each other, be each independently selected from hydrogen,
-SH
And C1-300Straight or branched alkyl (preferred C1-10Straight or branched alkyl or number are divided equally
Son amount Mn is the polyolefin-based of 300-3000), on condition that at least one group R0It is-SH；
Each group R' is same to each other or different to each other, and is each independently selected from hydrogen and C1-20Straight or branched alkane
Base (is preferably each independently selected from hydrogen and C1-4Straight or branched alkyl),
In formula (Y), group R'2Selected from hydrogen, C1-20Straight or branched alkyl and groupEach group RbBe same to each other or different to each other, be each independently selected from hydrogen and
C1-20Straight or branched alkyl (is preferably each independently selected from hydrogen and C1-10Straight or branched alkane
Base)；Each group RcIt is same to each other or different to each other, is each independently selected from hydrogen, C1-20Straight chain is propped up
Alkyl group and C1-20Straight or branched alkyl epoxide (is preferably each independently selected from hydrogen, C1-10
Straight or branched alkyl and C1-10Straight or branched alkyl epoxide, 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)；N1 is 1 to 8 integer (preferably 1 or 2)；Respectively
Cyclic groupIt is same to each other or different to each other, is each independently selected from phenyl ring and naphthalene nucleus is (excellent
Select phenyl ring),
In formula (Z), group R " it is selected from hydrogen, C1-20Alkyl (preferred C1-20Straight chain is propped up
Alkyl group) and C3-20Straight or branched miscellaneous alkyl, is preferably selected from hydrogen, C1-10Straight or branched
Alkyl and C3-10Straight or branched miscellaneous alkyl,
Wherein, the straight or branched miscellaneous alkyl is inside straight or branched alkyl molecular structure
One or more (such as 1 to 4,1 to 3,1 to 2 or 1) bases
Group-CH2- (R' is H or C to be selected from-O- ,-S- and-NR'-1-4Straight or branched alkyl) it
Group and straight or branched alkyl molecular structure that one substituting group is directly substituted and obtained
One or more internal (such as 1 to 3,1 to 2 or 1) group-CH<
By substituting group-N<The group for directly substituting and obtaining.
4. according to the lubricating grease described in claim 3, it is characterised in that wherein described
In first step, the phenolic compounds shown in the logical formula (X) with the formula (Y) Suo Shi
Amines mol ratio be 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0,
Phenolic compounds shown in the logical formula (X) and the aldehyde compound shown in the formula (Z)
Mol ratio is 1:0.1-10, preferably 1:0.5-5.0, more preferably 1:0.8-2.0, in the extra step
In rapid, the amines shown in the formula (Y) is 1 with the mol ratio of the vulcanizing agent:1-10,
It is preferred that 1:1.2-6.0, more preferably 1:1.5-3.0, the amines shown in the formula (Y) with
The mol ratio of the aldehyde compound shown in the formula (Z) is 1:0.1-10, preferably 1:0.5-5.0,
More preferably 1:0.8-2.0.
5. according to the lubricating grease described in claim 1, it is characterised in that the shielding phenolate
Compound accounts for the 0.05%-5% of the sodium base grease composition total weight.
6. according to the lubricating grease described in claim 1, it is characterised in that described sodium base is thick
Agent is generated by polymer acid with NaOH reaction, and the polymer acid is C12-C25
Aliphatic acid and/or hydroxy fatty acid.
7. according to the lubricating grease described in claim 6, it is characterised in that the polymer acid
For one or more in laurate, palmitic acid, stearic acid and 12- hydroxy stearic acids.
8. according to the lubricating grease described in claim 1, it is characterised in that the lubrication base
Oil is one or more in mineral oil, vegetable oil and artificial oil, and its 100 DEG C of kinematic viscosity are
5-60mm2/s。
9. the preparation method of the sodium base grease described in claim 1, including：Sodium base is thick
Agent and partial lubrication base oil are well mixed, and in 180-230 DEG C of constant temperature refining, cool down, plus
Enter remaining lubricating base oil, add the shielding phenolic compounds, grind to form fat.
10. the preparation method of the sodium base grease described in claim 1, including：Part is moistened
Sliding base oil and polymer acid mixing, heating, are warming up to 80-105 DEG C, add NaOH
The aqueous solution, carries out saponification, is warming up to 190-220 DEG C after reaction completely and is refined, plus
Enter remaining lubricating base oil and be cooled to 100-120 DEG C, add the shielding phenolic compounds, grind
Wear into fat.
11. in accordance with the method for claim 10, it is characterised in that the polymer acid
For C12-C25 aliphatic acid and/or hydroxy fatty acid.
12. in accordance with the method for claim 10, it is characterised in that the saponification
Time be 0.2-1.5 hours.
13. in accordance with the method for claim 10, it is characterised in that the refining when
Between be 5-25 minutes.
14. in accordance with the method for claim 10, it is characterised in that the partial lubrication
Ratio between base oil and remaining lubricating base oil is 50-75：25-50.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510664744.8A CN106590820B (en) | 2015-10-15 | 2015-10-15 | Sodium base grease and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510664744.8A CN106590820B (en) | 2015-10-15 | 2015-10-15 | Sodium base grease and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106590820A true CN106590820A (en) | 2017-04-26 |
| CN106590820B CN106590820B (en) | 2019-08-16 |
Family
ID=58552254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510664744.8A Active CN106590820B (en) | 2015-10-15 | 2015-10-15 | Sodium base grease and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106590820B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114672360A (en) * | 2022-04-26 | 2022-06-28 | 中国石油化工股份有限公司 | High-temperature high-speed flexible gyroscope motor bearing lubricating grease and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20080090742A1 (en) * | 2006-10-12 | 2008-04-17 | Mathur Naresh C | Compound and method of making the compound |
| 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 |
| CN104560315A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Composite sodium-based lubricating grease and preparation method thereof |
-
2015
- 2015-10-15 CN CN201510664744.8A patent/CN106590820B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20080090742A1 (en) * | 2006-10-12 | 2008-04-17 | Mathur Naresh C | Compound and method of making the compound |
| 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 |
| CN104560315A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Composite sodium-based lubricating grease and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114672360A (en) * | 2022-04-26 | 2022-06-28 | 中国石油化工股份有限公司 | High-temperature high-speed flexible gyroscope motor bearing lubricating grease and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106590820B (en) | 2019-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2737740C2 (en) | Benzotriazole derivative, a method for production and use thereof | |
| CN111100738B (en) | Oxidation-resistant long-life zinc-free hydraulic fluid composition and preparation method thereof | |
| CN112940832A (en) | Coal-based anti-wear hydraulic oil and preparation method thereof | |
| CN112126497A (en) | Turbine oil composition, preparation method and application thereof | |
| CN106590886B (en) | Complex calcium lubricating grease and preparation method thereof | |
| CN106590822B (en) | Complex lithium-calcium base grease and preparation method thereof | |
| CN106590821B (en) | Composite aluminum base grease and preparation method thereof | |
| CN103060059B (en) | Antioxidant composition and lubricating oil composition | |
| CN109233980B (en) | Lubricating grease and preparation method thereof | |
| CN106590820A (en) | Sodium-based lubricating grease and preparation method thereof | |
| CN106590819B (en) | Complex lithium grease and preparation method thereof | |
| CN105505525A (en) | Phenolic amine antioxidant and preparation method and application thereof | |
| CN105524698B (en) | Excellent composite barium-base grease composition of a kind of Wear vesistance and preparation method thereof | |
| CN106590885B (en) | Bentonite grease and preparation method thereof | |
| CN106590825B (en) | Lubricating grease and preparation method thereof | |
| CN106590883B (en) | Anhydrous calcium-base grease and preparation method thereof | |
| CN106590824B (en) | Composite barium-base grease and preparation method thereof | |
| CN106590884B (en) | Lithium base grease and preparation method thereof | |
| CN106590823B (en) | Composite sodium-based lubricating grease and preparation method thereof | |
| WO2010016127A1 (en) | Additive for lubricating fluid, lubricating fluid composition and method for producing sulfurized polyolefin | |
| CN109679743B (en) | Fully synthetic industrial gear lubricating oil composition and preparation method thereof | |
| CN109679731B (en) | Composite aluminum-based lubricating grease and preparation method thereof | |
| EP0846750B1 (en) | Tin stabilizers for aviation lubricants | |
| CN109679714B (en) | Composite sodium-based lubricating grease and preparation method thereof | |
| CN112522017A (en) | Composite barium-based lubricating grease and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |